JP6770964B2 - Liquid cleaning agent composition - Google Patents

Description

The present invention relates to a liquid cleaning agent composition.
The present application claims priority based on Japanese Patent Application No. 2015-186892 filed in Japan on September 24, 2015, the contents of which are incorporated herein by reference.

For example, liquid detergent compositions are often used as household laundry detergents. In recent years, as the size of washing machines has increased, the frequency of stuffing washing has increased, so that the liquid cleaning agent composition is required to have high detergency. In addition, when washing textile products such as clothes using a cleaning agent, recontamination (that is, a phenomenon in which some of the stains separated from the fibers of the object to be washed and dispersed in the washing liquid adhere to the fibers again. ) Is also important. It is also necessary that the liquid cleaning agent composition has excellent liquid stability.

By the way, as a liquid cleaning agent composition, one containing an antibacterial agent such as a cationic surfactant has been proposed due to heightened hygiene awareness (for example, Patent Document 1). However, when an anionic surfactant is combined with the cationic surfactant as a cleaning component in order to enhance the cleaning effect, recontamination is likely to occur during cleaning, and the cleaning effect is less likely to be exhibited. In recent years, due to the diversification of clothing products, clothing containing synthetic fibers other than cotton has become the mainstream. However, since cationic surfactants are insufficiently adsorbed on synthetic fibers, they are antibacterial against clothing containing synthetic fibers. It is difficult for the sex to be exhibited. When the antibacterial property is insufficient, microorganisms proliferate especially when the clothes and the like are dried in the room, and an unpleasant odor generated from the clothes and the like is generated.
Therefore, a liquid cleaning agent composition containing an antibacterial agent having an aromatic ring has also been proposed (for example, Patent Documents 2 to 4).

Japanese Unexamined Patent Publication No. 2014-28942 Japanese Patent Publication No. 2004-515642 Japanese Unexamined Patent Publication No. 2001-146681 Japanese Unexamined Patent Publication No. 2015-7220

However, even if a liquid cleaning agent composition containing an antibacterial agent having an aromatic ring as in Patent Documents 2 to 4 is used, stains may be recontaminated on clothing containing synthetic fibers, and excellent antibacterial properties can be obtained. Even if it can be done, it is difficult to obtain the effect of suppressing the odor of drying in the room.

INDUSTRIAL APPLICABILITY The present invention can exhibit high detergency, excellent liquid stability, and high recontamination prevention effect, can impart excellent antibacterial properties to the object to be washed, and is an excellent liquid cleaning agent having an excellent effect of suppressing the generation of room drying odor. It is an object of the present invention to provide a composition.

The present invention has the following configurations.
[1] Component (A): A nonionic surfactant containing at least one selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II), and (B). Ingredients: A liquid cleaning agent composition containing at least one selected from the group consisting of anionic surfactants and component (C): an antibacterial agent having a phenolic structure.
R ^1- C (= O) O-[(EO) _s / (PO) _t ]-(EO) _u- R ² ... (I)
R ^3- O-[(EO) _v / (PO) _w ]-(EO) _x- H ... (II)
(However, in the formula, EO is an ethyleneoxy group, PO is a propyleneoxy group. R ¹ is a hydrocarbon group having 7 to 22 carbon atoms, R ² is a methyl group or an ethyl group, and R ³ Is a hydrocarbon group having 7 to 22 carbon atoms. S, v, u, x are the average number of repetitions of EO, t and w are the average number of repetitions of PO. S is a number of 6 to 20. , T is a number from 0 to 6, u is a number from 0 to 20, v is a number from 8 to 20, w is a number from 0 to 6, and x is a number from 0 to 20. .)
[2] The liquid cleaning agent composition according to [1], wherein the (A) / (B) ratio (mass ratio) of the component (A) and the component (B) is 1 or more.
[3] The liquid cleaning agent composition according to [1] or [2], wherein the (B) / (C) ratio (mass ratio) of the component (B) and the component (C) is 3 or more.
[4] Further, a water-soluble polymer having a component (D): one or both of an alkylene terephthalate unit and an alkylene isophthalate unit and one or both of an oxyalkylene unit and a polyoxyalkylene unit can be obtained. The liquid cleaning agent composition according to any one of [1] to [3], which contains 1 to 5% by mass.
[5] Further, the component (E): a polyalkyleneamine alkylene oxide-based copolymer having an alkyleneamine structural unit containing a polyalkylene oxide chain is contained in an amount of 0.1 to 5% by mass, [1] to [4]. The liquid cleaning agent composition according to any one of.
[6] The liquid cleaning composition according to any one of [1] to [5], further containing at least one selected from the group consisting of component (F): cationic surfactant.
[7] In the component (A), R ¹ in the formula (I) is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R ² is a methyl group, s = 15, and t. The liquid cleaning agent composition according to any one of [1] to [6], which comprises a compound having = 0.
[8] The liquid cleaning agent composition according to any one of [1] to [7], wherein the content of the component (A) is 5 to 80% by mass.
[9] The component (B) is a polyoxyalkylene alkyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms, and a linear alkylbenzene having an alkyl group having 8 to 18 carbon atoms. The liquid cleaning agent composition according to any one of [1] to [8], which comprises at least one selected from the group consisting of sulfonates.
[10] The liquid cleaning agent composition according to any one of [1] to [9], wherein the content of the component (B) is 3 to 40% by mass.
[11] The liquid cleaning agent composition according to any one of [1] to [10], wherein the component (C) contains at least one selected from the group consisting of dichlorohydroxydiphenyl ether, trichlorohydroxydiphenyl ether and benzyl chlorophenol. object.
[12] The liquid cleaning agent composition according to any one of [1] to [11], wherein the content of the component (C) is 0.01 to 3% by mass.

The liquid cleaning agent composition of the present invention can exhibit high detergency, excellent liquid stability, and high recontamination prevention effect, can impart excellent antibacterial properties to the object to be washed, and has an effect of suppressing the generation of room drying odor. Is excellent.

The liquid cleaning agent composition of the present invention is a liquid cleaning agent composition containing the components (A) to (C) described later.

[(A) component]
The component (A) is a compound represented by the following formula (I) (hereinafter, also referred to as compound (I)) and a compound represented by the following formula (II) (hereinafter, also referred to as compound (II)). It is a nonionic surfactant containing at least one selected from the group consisting of.
R ^1- C (= O) O-[(EO) _s / (PO) _t ]-(EO) _u- R ² ... (I)
R ^3- O-[(EO) _v / (PO) _w ]-(EO) _x- H ... (II)

However, in the formulas (I) and (II), EO is an ethyleneoxy group and PO is a propyleneoxy group. R ¹ is a hydrocarbon group having 7 to 22 carbon atoms, R ² is a methyl group or an ethyl group, and R ³ is a hydrocarbon group having 7 to 22 carbon atoms. s, v, u, and x are the average number of repetitions of EO, and t and w are the average number of repetitions of PO. s is a number from 6 to 20, t is a number from 0 to 6, and u is a number from 0 to 20. v is a number from 8 to 20, w is a number from 0 to 6, and x is a number from 0 to 20.

The hydrocarbon group of R ¹ in the formula (I) may be linear or branched.
The hydrocarbon group of R ¹ has 7 to 22 carbon atoms. When the number of carbon atoms is equal to or higher than the lower limit, a sufficient drape maintenance effect can be obtained. When the number of carbon atoms is not more than the upper limit value, excellent liquid stability can be obtained. The number of carbon atoms of the hydrocarbon group of R ¹ is preferably 9 to 21 and more preferably 11 to 21 from the viewpoint of improving detergency.
As R ¹ , an alkyl group or an alkenyl group is preferable. Examples of the alkyl group or alkenyl group include an alkyl group derived from a raw material such as a primary or secondary higher alcohol having 7 to 22 carbon atoms, a higher fatty acid having 8 to 23 carbon atoms, and a higher fatty acid amide having 8 to 23 carbon atoms. Examples include alkenyl groups.

The s + u in the formula (I) is preferably 6 to 20, more preferably 6 to 18, and even more preferably 11 to 18. When s + u is equal to or higher than the lower limit, the hydrophilicity is sufficient and the amount of free water in the system is reduced, so that the enzyme stability is improved. When s + u is not more than the upper limit value, the hydrophilicity does not become too high, and sufficient detergency can be easily obtained.

T in the formula (I) is a number from 0 to 6, preferably 0 to 3. When t is not more than the upper limit value, the liquid stability is improved.
The ethyleneoxy group and the propyleneoxy group in [(EO) _s / (PO) _t ] may form a random chain or a block chain.

Hydrocarbon group R ³ in formula (II) may be linear, it may be branched.
The hydrocarbon group of R ³ has 7 to 22 carbon atoms. When the number of carbon atoms is equal to or higher than the lower limit, a sufficient drape maintenance effect can be obtained. When the number of carbon atoms is not more than the upper limit value, excellent liquid stability can be obtained. The carbon number of the hydrocarbon group of R ³ is preferably 10 to 22, more preferably 10 to 20, and even more preferably 10 to 18 from the viewpoint of improving detergency.
The R ^3, an alkyl group or an alkenyl group. The alkyl or alkenyl group may be the same as those mentioned in R ^1.

The v + x in the formula (II) is preferably 8 to 20, more preferably 9 to 18, further preferably 10 to 18, and particularly preferably 13 to 18. When v + x is equal to or higher than the lower limit, the hydrophilicity is sufficient, and the amount of free water in the system is reduced, so that the enzyme stability is improved. When v + x is not more than the upper limit value, the hydrophilicity does not become too high, and sufficient detergency can be easily obtained.

W in the formula (II) is 0 to 6, preferably 0 to 3. When w is not more than the upper limit value, the liquid stability is improved.
The ethyleneoxy group and the propyleneoxy group in [(EO) _v / (PO) _w ] may form a random chain or a block chain.

As the compound (I), a polyoxyethylene fatty acid alkyl ester is preferable, and a polyoxyethylene fatty acid methyl ester in which R ² is a methyl group (hereinafter, also referred to as MEE) is more preferable. By using the polyoxyethylene fatty acid alkyl ester, the solubility of the liquid cleaning agent composition in water can be enhanced, and the detergency can be enhanced. In addition, even if the content of the component (B) in the liquid cleaning agent composition is increased, a significant increase in viscosity (gelation) is unlikely to occur, and a concentrated liquid cleaning agent composition having good fluidity can be obtained. Be done.
Polyoxyethylene fatty acid alkyl esters, especially MEE, are nonionic surfactants in which the orientation of molecules is weak and micelles are unstable in an aqueous solution system. Therefore, it is presumed that the polyoxyethylene fatty acid alkyl ester does not cause gelation at a high concentration, and even if a large amount of the polyoxyethylene fatty acid alkyl ester is blended in the liquid cleaning composition by itself, the solubility in water can be enhanced. To. Therefore, when the liquid cleaning agent composition containing the polyoxyethylene fatty acid alkyl ester is dispersed in water, the concentration of the polyoxyethylene fatty acid alkyl ester in the cleaning liquid quickly becomes uniform, and the object to be washed is at an arbitrary concentration from the initial stage of cleaning. It is thought that it exerts high detergency in contact with.

In the polyoxyethylene fatty acid alkyl ester, the narrow ratio indicating the ratio of the distribution of compounds having different addition moles of ethylene oxide is preferably 20% by mass or more. The upper limit of the narrow ratio is preferably 80% by mass. The narrow ratio is more preferably 20 to 60% by mass. The higher the narrow ratio, the better the detergency can be obtained, but if it is too high, the liquid stability at a low temperature may decrease, so 30 to 45% by mass is more preferable.

The narrow ratio of the polyoxyalkylene type nonionic surfactant such as the polyoxyethylene fatty acid alkyl ester is a value obtained by the following formula (S).

In the formula (S), S _max indicates the number of moles of alkylene oxide added (value of s + t + u) in the alkylene oxide adduct most abundant in the polyoxyalkylene type nonionic surfactant.
i indicates the number of moles of alkylene oxide added.
Yi indicates the proportion (mass%) of the alkylene oxide adduct in which the number of moles of alkylene oxide added in the entire component represented by the formula (S) is i.

The narrow ratio can be controlled by, for example, a method for producing a polyoxyethylene fatty acid alkyl ester or the like.

The distribution of EO or PO in compound (I) and compound (II) varies depending on the reaction method at the time of production. For example, when ethylene oxide or propylene oxide is added to a raw material using a general alkaline catalyst such as sodium hydroxide or potassium hydroxide, the distribution of s or t becomes relatively wide. A specific alkoxylation catalyst such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ²⁺ described in JP-A-6-15038 are added. When ethylene oxide or propylene oxide is added to the raw material in use, the distribution of EO or PO becomes relatively narrow.

In addition, as another method for producing the component (A), there is a method of adding an alkylene oxide to a fatty acid alkyl ester using an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and an oxyacid or the like. The above-mentioned alkoxylation catalyst is disclosed in Japanese Patent No. 04977609, International Publication No. 1993/004030, International Publication No. 2002/0382869, International Publication No. 2012/028435, and the like. For example, alkali of a carboxylic acid. Examples thereof include an alkoxylation catalyst prepared from a mixture of an earth metal salt and / or an alkaline earth metal salt of hydroxycarboxylic acid and sulfuric acid or the like.

As the component (A), R ¹ in the formula (I) is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, and R ² from the viewpoint of improving the detergency and the solubility of the liquid cleaning agent composition. Is a methyl group, s = 15, and t = 0, a compound (MEE) is particularly preferred. Compared with other nonionic surfactants and anionic surfactants, MEE is less likely to remain on clothing, and component (C) can be efficiently adsorbed on clothing.

In addition, the component (A) may contain a nonionic surfactant other than the compound (I) and the compound (II). Examples of other nonionic surfactants include known ones used in liquid cleaning agent compositions, and examples thereof include polyoxyalkylene-type nonionic surfactants other than compound (I) and compound (II), alkylphenols, and the like. Alkylene oxide adducts such as higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amines. Examples thereof include oxides, alkylene oxide adducts of hardened castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides.
As the component (A), one type may be used alone, or two or more types may be used in combination. By combining two or more kinds of the components (A), the detergency is improved and the effect of suppressing the generation of room drying odor can be easily obtained.

The content of the component (A) in the liquid cleaning agent composition (100% by mass) of the present invention is preferably 5 to 80% by mass, more preferably 10 to 70% by mass. When the content of the component (A) is at least the lower limit value, the detergency of the liquid cleaning agent composition is enhanced. When the content of the component (A) is not more than the upper limit value, the liquid stability of the liquid cleaning agent composition is enhanced.

[(B) component]
The component (B) is at least one selected from the group consisting of anionic surfactants.

Examples of the component (B) include the following compounds (B1) to (B12).
(B1) A methyl ester salt, an ethyl ester salt or a propyl ester salt of a saturated or unsaturated α-sulfofatty acid having 8 to 20 carbon atoms.
(B2) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms. Of these, those having a linear alkyl group are preferable. The linear alkyl group preferably has 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms.
(B3) An alkane sulfonate having 10 to 20 carbon atoms.
(B4) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(B5) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.

(B6) 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 group (or alkenyl group) having 10 to 20 carbon atoms added on average 0.5 to 10 mol. The average number of moles of alkylene oxide or ethylene oxide and propylene oxide added is preferably 1 to 5.
(B7) Addition of 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. A polyoxyalkylene alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl group (or alkenyl group) having 10 to 20 carbon atoms.
(B8) 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), with an average of 0.5 to 0.5 to A polyoxyalkylene alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl group (or alkenyl group) having 10 to 20 carbon atoms with 10 molar additions.

(B9) An alkyl polyhydric alcohol ether sulfate such as an alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(B10) Long-chain monoalkyl phosphate, long-chain dialkyl phosphate, or long-chain sesquialkyl phosphate.
(B11) Polyoxyethylene monoalkyl phosphate, polyoxyethylene dialkyl phosphate, or polyoxyethylene sesquialkyl phosphate.
(B12) Soap. A higher fatty acid salt having an average carbon number of 10 to 20 (preferably 12 to 18).

As the component (B), an anionic surfactant other than the compounds (B1) to (B12) 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. , Polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkylphenyl phosphate ester salt, glycerin fatty acid ester monophosphate ester salt and other phosphoric acid ester type anionic surfactants and the like.

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; and ammonium salts. Be done. Of these, alkali metal salts are preferable.

As the component (B), a surfactant having high hard water resistance is preferable from the viewpoint of detergency, and a component having low hard water resistance is preferable from the viewpoint of improving antibacterial power.
As the component (B), one type may be used alone, or two or more types may be used in combination.

The component (B) is composed of a polyoxyalkylene alkyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms and a linear alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms. It is preferable to include at least one selected from the group. Further, from the viewpoint of detergency and enzyme stability, it is more preferable that the component (B) contains at least one or both of LAS and AES.

When both LAS and AES are used as the component (B), the LAS / AES ratio (mass ratio) of LAS and AES is preferably 0.1 to 2, and more preferably 0.5 to 1. When the LAS / AES ratio is not more than the upper limit, the enzyme stability is improved. If the LAS / AES ratio is at least the lower limit, the liquid stability is improved.

The content of the component (B) in the liquid cleaning agent composition (100% by mass) of the present invention is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, still more preferably 7 to 20% by mass. 10 to 20% by mass is particularly preferable. When the content of the component (B) is within the above range, excellent anti-recontamination property and detergency can be easily obtained. In addition, some of the anionic surfactants in the component (B) combine with calcium ions in tap water to form a salt, which increases the hydrophobicity in the detergent solution and makes the component (C) highly hydrophobic. To form a complex with. As a result, the amount of adsorption to clothing having a highly hydrophobic surface such as the surface of synthetic fibers increases, and antibacterial properties (bacteriostatic activity) are improved.

The (A) / (B) ratio (mass ratio) of the component (A) and the component (B) is preferably 0.1 to 5, more preferably 0.3 to 3, and particularly preferably 1 to 3. When the ratio (A) / (B) is equal to or higher than the lower limit, the liquid stability of the liquid cleaning agent composition is enhanced. When the ratio (A) / (B) is not more than the upper limit, the amount of the component (B) forming a complex with the component (C) increases, and the surface of the synthetic fiber or the like having a highly hydrophobic surface is applied to clothing. The amount of adsorption increases and antibacterial properties (bacteriostatic activity) improve. Further, when the ratio (A) / (B) is 1 or more, the enzyme stability is improved.

The total amount of the activator in the liquid cleaning agent composition (100% by mass) of the present invention is preferably 25 to 80% by mass, more preferably 30 to 60% by mass. When the total amount of the activator is not less than the lower limit, the detergency of the liquid detergent is further improved, the highly hydrophobic component (C) is easily solubilized, and the liquid stability is enhanced. When the total amount of the activator is not more than the upper limit, the liquid stability of the liquid cleaning agent composition is enhanced.
The total amount of the activator means the total amount of the component (A), the component (B) and the component (F).

[Component (C)]
The component (C) is an antibacterial agent having a phenolic structure. The phenol structure means a structure in which one or more hydrogen atoms of an aromatic hydrocarbon nucleus are substituted with hydroxy groups.
The component (C) is a component that imparts antibacterial properties to textile products such as clothes after washing. An antibacterial agent having a phenol structure can exhibit antibacterial properties without impairing the detergency of the anionic surfactant even when coexisting with the anionic surfactant in the liquid cleaning agent composition.

Examples of the component (C) include phenol derivatives and diphenyl compounds known as antibacterial agents. Specifically, 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4'-dichloro-2-hydroxydiphenyl ether (common name: diclosan), o-benzyl- Examples thereof include p-chlorophenol (chlorophenol), isopropylmethylphenol, parachloromethaxylenol and the like. Of these, diphenyl compounds are preferable, and specifically, 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan) and 4,4'-dichloro-2-hydroxydiphenyl ether (common name:). Diclosan) and o-benzyl-p-chlorophenol (chlorophenol) are preferred.

As the component (C), the 2-hydroxydiphenyl compound represented by the following formula (III) (hereinafter referred to as compound (III)) is represented by the following formula (III) because the amount adsorbed on the hydrophobic fiber is high and the effect of applying the present invention is large. ) Is preferable.

However, in the formula (III), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms, Y is a chlorine atom or a bromine atom, and Z is SO ₂ H, NO ₂ or 1 to 4 carbon atoms. It is an alkyl group, where a, b, and c are independently integers of 0 or 1-3, d is 0 or 1, m is 0 or 1, and n is 0 or 1.
In addition,-(Y) b means that b of hydrogen atoms of a benzene ring are substituted with Y. The same applies to − (Y) c, − (Z) d, − (OH) m and − (OH) n.

As the compound (III), X is an oxygen atom or a methylene group, Y is a chlorine atom or a bromine atom, m is 0, n is 0 or 1, a is 1, and b is 0. More preferably, the compound is 1 or 2, c is 0, 1 or 2, and d is 0.
Specific examples of the preferred compound (III) include, for example, monochlorohydroxydiphenyl 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 0. , D is 0, m is 0, n is 0), dichlorohydroxydiphenyl ether (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, n is 0), trichlorohydroxydiphenyl ether (X is an oxygen atom, a is 1 and Y is a chlorine atom). , B or c is 1 and the other is 2, d is 0, m is 0 and n is 0), benzylchlorophenol (X is a methylene group and a is 1). A compound in which Y is a chlorine atom, b is 0, c is 1, d is 0, m is 0, and n is 0).

Particularly suitable compounds (III) are 5-chloro-2- (2,4-dichlorophenoxy) phenol (trivial name: triclosan), 4,4'-dichloro-2-hydroxydiphenyl ether (trivial name: diclosan), It is o-benzyl-p-chlorophenol (trivial name: chlorophenol), and 4,4'-dichloro-2-hydroxydiphenyl ether (trivial name: diclosan) is most preferable.
As the component (C), one type may be used alone, or two or more types may be used in combination.

The ratio of the total amount of the compound (III) to the total amount (100% by mass) of the component (C) is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. The upper limit of the ratio of the total amount of the compound (III) is 100% by mass.

The content of the component (C) in the liquid cleaning agent composition (100% by mass) of the present invention is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, and 0.1 to 0. 5.5% by mass is more preferable. When the content of the component (C) is at least the lower limit value, excellent antibacterial properties can be easily obtained. When the content of the component (C) is not more than the upper limit value, it tends to be a liquid cleaning agent composition having good storage stability.

From the viewpoint of enhancing the detergency and the ability to prevent recontamination, the (B) / (C) ratio (mass ratio) of the component (B) and the component (C) is preferably 3 or more, more preferably 5 or more, and 10 or more. Is even more preferable. The (B) / (C) ratio is preferably 300 or less, more preferably 200 or less, and even more preferably 100 or less, from the viewpoint of enhancing antibacterial properties.
The ratio (B) / (C) is preferably 3 to 300.

In the present invention, the component (C) and the fragrance may be premixed before being blended into the liquid cleaning composition to form a premix. By forming the premix, the highly hydrophobic component (C) can be more stably blended in the liquid cleaning agent composition. The mixing method may be a general method, and the temperature at the time of mixing is preferably 5 to 30 ° C. There is no problem even if the premix is stored for a long time, but when it is stored at a low temperature, the component (C) may precipitate. Therefore, when it is stored, it is preferably 20 to 30 ° C.

[(D) component]
The liquid cleaning agent composition of the present invention has a component (D): one or both of an alkylene terephthalate unit and an alkylene isophthalate unit, and one or both of an oxyalkylene unit and a polyoxyalkylene unit. It is preferable that the sex polymer is further contained.
The term "water-soluble polymer" means that 10 g of the polymer was added to 1000 g of water under the condition of 40 ° C., and the mixture was stirred (200 rpm) for 12 hours with a stirrer (thickness 8 mm, length 50 mm, 1 liter beaker). Sometimes it is completely dissolved.

Hereinafter, the alkylene terephthalate unit and the alkylene isophthalate unit are collectively referred to as a unit (d1). Further, the oxyalkylene unit and the polyoxyalkylene unit are collectively referred to as a unit (d2).
The alkylene terephthalate unit is a unit represented by the following formula (IV).

However, in formula (IV), R ²¹ is a lower alkylene group.
The lower alkylene group of R ²¹ has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.

Specific examples of the alkylene terephthalate unit include ethylene terephthalate unit, n-propylene terephthalate unit, isopropylene terephthalate unit, n-butylene terephthalate unit, isobutylene terephthalate unit, sec-butylene terephthalate unit, tert-butylene terephthalate unit and the like. Be done. Of these, the isopropylene terephthalate unit is preferable.
As the unit (d1), a single type of alkylene terephthalate unit may be used, or a plurality of types of alkylene terephthalate units may be used in combination.

The alkylene isophthalate unit is a unit represented by the following formula (V).

In formula (V), R ²² is a lower alkylene group.
The lower alkylene group of R ²² has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.

Specific examples of the alkylene isophthalate unit include ethylene isophthalate unit, propylene isophthalate unit, n-butylene isophthalate unit, sec-butylene isophthalate unit, tert-butylene isophthalate unit and the like. Of these, the propylene isophthalate unit is preferable.
As the unit (d1), a single type of alkylene isophthalate unit may be used, or a plurality of types of alkylene isophthalate units may be used in combination.

The unit (d1) may be only an alkylene terephthalate unit, may be only an alkylene isophthalate unit, or may be both an alkylene terephthalate unit and an alkylene isophthalate unit.

The unit (d2) is a unit represented by the following equation (VI).
-(R ²³ O) _e -... (VI)
However, R ²³ is a lower alkylene group, and e is an integer of 1 to 100.

The lower alkylene group of R ²³ has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
In the formula (VI), when e is 1, it is an oxyalkylene unit, and when e is 2 or more, it is a polyoxyalkylene unit. e is preferably an integer of 1 to 80, and more preferably an integer of 1 to 50.

Specific examples of the unit (d2) include, for example, oxyethylene unit and polyoxyethylene unit; oxypropylene unit and polyoxypropylene unit; polyoxyethylene polyoxypropylene unit and the like. Of these, oxyethylene units and polyoxyethylene units are preferable.
The unit (d2) may be only an oxyalkylene unit, may be only a polyoxyalkylene unit, or may be both an oxyalkylene unit and a polyoxyalkylene unit.

The component (D) is preferably a polymer compound in which the unit (d1) and the unit (d2) are polymerized at random or in a block, and a polymer compound polymerized in a block is more preferable.

The component (D) may contain units other than the unit (d1) and the unit (d2). Examples of other units include units derived from a polymerization initiator, a polymerization terminator, and the like, and other copolymerizable units. When the component (D) contains other units, the total ratio of the unit (d1) and the unit (d2) to all the units of the component (D) is preferably 80 mol% or more, more preferably 90 mol% or more. ..

As the component (D), a compound represented by the following formula (VII) and a compound represented by the following formula (VIII) are preferable.

However, in the formula (VII), A ¹ and B ¹ are independently hydrogen atoms or methyl groups, and R ¹¹ and R ¹² are independently alkylene groups having 2 to 4 carbon atoms. f is the average number of repetitions of the alkylene terephthalate unit represented by -CO- (C ₆ H ₄ ) -COO-R ¹² O-, and is 0 to 10. g is the average number of repetitions of R ¹¹ O, which is 1 to 100.
Further, in the formula (VIII), A ² and B ² are independently hydrogen atoms or methyl groups, and R ¹³ and R ¹⁴ are independently alkylene groups having 2 to 4 carbon atoms. h is the average number of repetitions of the alkylene isophthalate unit represented by -CO- (C ₆ H ₄ ) -COO-R ¹⁴ O-, and is 0 to 10. i is the average number of repetitions of R ¹³ O, which is 1 to 100.

It is preferable that both A ¹ and B ¹ in the formula (VII) are methyl groups.
R ¹¹ and R ¹² are preferably alkylene groups having 2 to 3 carbon atoms.
The f is preferably 0.5 to 5, more preferably 0.5 to 2.5.
The g is preferably 1 to 80, more preferably 1 to 50, still more preferably 10 to 50, and particularly preferably 20 to 30.
The ratio of f to g in the formula (VII) is preferably 1: 5 to 1:20, more preferably 1: 8 to 1:18. When the ratio of f and g is in the above range, the soil release performance is likely to be sufficiently exhibited, and the solubility in water is improved.

It is preferable that both A ² and B ² in the formula (VIII) are methyl groups.
R ¹³ and R ¹⁴ are preferably alkylene groups having 2 to 3 carbon atoms.
h is preferably 0.5 to 5, more preferably 0.5 to 2.5.
i is preferably 1 to 80, more preferably 1 to 50, further preferably 10 to 50, and particularly preferably 20 to 30.
The ratio of h to i in the formula (VIII) is preferably 1: 5 to 1:20, more preferably 1: 8 to 1:18, for the same reason as the ratio of f to g in the formula (VII). ..

The weight average molecular weight of the component (D) is preferably 500 to 10000, more preferably 800 to 9000, and even more preferably 1000 to 8000. When the weight average molecular weight is within the above range, the solubility and dispersibility in water are improved, the effect of improving the water absorption of hydrophobic fibers (particularly polyester) is easily exhibited, and the liquid appearance of the liquid cleaning agent composition. Becomes good.
The weight average molecular weight in the present invention refers to a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent and converted using PEG (polyethylene glycol) as a calibration curve.

As the component (D), a commercially available product can be used. For example, the product name "TexCare SRN-100" (manufactured by Clariant, weight average molecular weight: 2000 to 3000), the product name "TexCare SRN-300" (manufactured by Clariant, weight average molecular weight: 7000), the product name "Repel-O". -Tex Crystal "(manufactured by Rhodia), trade name" Repel-O-Tex QC "(manufactured by Rhodia) and the like. Among them, the trade name "TexCare SRN-170" (Clariant), which is a 70% by mass aqueous solution of TexCare SRN-100 and TexCare SRN-100, is highly soluble in water and has little deterioration in cleaning performance after storage. Is preferable, and TexCare SRN-170 is particularly preferable.

The component (D) is, for example, Journal of Polymer Science, Vol. 3, pp. 609-630 (1948), Journal of Polymer Science, Vol. 8, pp. 1-22 (1951), Japanese Patent Application Laid-Open No. 61-218699. It can also be synthesized by the method described in the publication.
As the component (D), one type may be used alone, or two or more types may be used in combination.

The content of the component (D) in the liquid washed body composition (100% by mass) of the present invention is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass. When the content of the component (D) is at least the lower limit value, the stain and the amount of bacteria in the washing liquid adhering to the synthetic fiber can be suppressed, and the initial number of bacteria can be further reduced. As a result, the amount of increase in the number of bacteria during room drying can be further reduced, so that the effect of suppressing the generation of room drying odor can be easily obtained. When the content of the component (D) is not more than the upper limit value, the appearance stability of the liquid cleaning agent composition becomes better.

[(E) component]
The liquid cleaning agent composition of the present invention preferably further contains a polyalkyleneamine alkylene oxide-based copolymer having an alkyleneamine structural unit containing a component (E): a polyalkylene oxide chain.
In the present invention, by using the component (D) and the component (E) in combination, the antibacterial effect of cotton and synthetic fibers on the blended clothing and the effect of suppressing the generation of room-drying odor are particularly enhanced.

The component (E) is a polyalkyleneamine alkylene oxide-based copolymer having an alkyleneamine structural unit containing a polyalkylene oxide chain, that is, an alkylene oxide adduct of polyalkyleneimine.

Polyalkyleneimine is represented by the following formula (IX).
_{^{NH 2 -R 31 - (NA 3}} -R 32) j -NH 2 ··· (IX)
However, in the formula (IX), R ³¹ and R ³² are independently alkylene groups having 2 to 6 carbon atoms, and A ³ is another polyamine chain formed by a hydrogen atom or a branch. j is the average number of repetitions of NA ^3- R ³² , which is a number of 1 or more. All A ³ is assumed not a hydrogen atom.
The alkylene groups of R ³¹ and R ³² may be linear or branched. The alkylene group of R ³¹ and R ³² preferably has 2 to 4 carbon atoms, and 2 is particularly preferable.

Polyalkyleneimine can be obtained by polymerizing one or more of alkyleneimines having 2 to 6 carbon atoms by a conventional method. Examples of the alkyleneimine having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine and the like.
As the polyalkyleneimine, polyethyleneimine (PEI) and polypropyleneimine are preferable, and PEI is more preferable. PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary and tertiary amine nitrogen atoms in its structure.

The weight average molecular weight of the polyalkyleneimine is preferably 200 to 2000, more preferably 300 to 1500, further preferably 400 to 1000, and particularly preferably 500 to 800.
The number of active hydrogens contained in one molecule of polyalkyleneimine is preferably 5 to 30, more preferably 7 to 25, and even more preferably 10 to 20.

Examples of the alkylene oxide added to the polyalkyleneimine include an alkylene oxide having 2 to 4 carbon atoms. Of these, ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.
As a method for adding alkylene oxide to polyalkyleneimine, for example, in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate, etc., the temperature is 100 to 180 ° C. with respect to polyalkyleneimine as a starting material. A method of adding alkylene oxide such as ethylene oxide can be mentioned.

Examples of the component (E) include an ethylene oxide adduct of polyalkyleneimine, a propylene oxide adduct of polyalkyleneimine, and an ethylene oxide-propylene oxide adduct of polyalkyleneimine. The ethylene oxide-propylene oxide adduct of polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to polyalkyleneimine, and the order and form of addition of ethylene oxide and propylene oxide to polyalkyleneimine (block shape, random shape). Is optional.
As the component (E), an ethylene oxide adduct of polyalkyleneimine and an ethylene oxide-propylene oxide adduct of polyalkyleneimine are preferable, and an ethylene oxide adduct of polyalkyleneimine is more preferable.

In the alkylene oxide adduct of polyalkyleneimine, the average number of alkylene oxides added to one atom of active hydrogen contained in the raw material polyalkyleneimine is preferably 5 to 40, more preferably 10 to 30. That is, the average number of moles of alkylene oxide added per mole of active hydrogen contained in the raw material polyalkyleneimine is preferably 5 to 40 mol, more preferably 10 to 30 mol.

The weight average molecular weight of the component (E) is preferably 1000 to 80,000, more preferably 2000 to 50000, further preferably 5000 to 30000, and particularly preferably 1000 to 20000.

As the component (E), a synthetic product or a commercially available product may be used.
Examples of commercially available products include the trade name "Sokalan HP20" manufactured by BASF.
As the component (E), one type may be used alone, or two or more types may be used in combination.

The content of the component (E) in the liquid cleaning agent composition (100% by mass) of the present invention is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass. When the content of the component (E) is equal to or higher than the lower limit, the component (E) is adsorbed on the cotton fiber, so that the stain and the amount of bacteria in the adhering washing liquid are suppressed, and the number of initial bacteria is further reduced. Can be done. As a result, the amount of increase in the number of bacteria during room drying can be further reduced, so that the effect of suppressing the generation of room drying odor can be easily obtained. When the content of the component (E) is not more than the upper limit value, the appearance stability of the liquid cleaning agent composition becomes better.

[(F) component]
It is preferable that the liquid cleaning agent composition of the present invention further contains the component (F): cationic surfactant. Since the component (F) is contained, the effect of suppressing the generation of the room drying odor becomes higher. Further, by using the component (C) and the component (F) in combination, the antibacterial effect on the blended clothing of cotton and synthetic fibers and the effect of suppressing the generation of the odor of drying in the room are particularly enhanced.
As the component (F), for example, a quaternary ammonium salt can be used. Examples of the quaternary ammonium salt include conventionally known salts that are usually used in laundry detergents. Among them, preferable quaternary ammonium salts include compounds (f1), compounds (f2), and compounds (f3), which will be described later, because high antibacterial effects or bactericidal effects can be easily obtained.

(Compound (f1))
The compound (f1) is a compound represented by the following formula (f1).

However, in the formula (f1), two or more of R ^{41 to} R ⁴⁴ are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms, and other than that. Is a linear or branched alkyl group having 8 to 22 carbon atoms, or a linear or branched alkenyl group having 8 to 22 carbon atoms. Q _A ^- is a halogen ion or an alkylsulfate ion.

As the compound (f1), the following compounds (f1-1) and compound (f1-2) are preferable.

Compound (f1-1): R ^{41 to} R ⁴³ are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms, and R ⁴⁴ has 8 to 8 carbon atoms. A compound which is a linear or branched alkyl group of 22 or a linear or branched alkenyl group having 8 to 22 carbon atoms.
R ^{41 to} R ⁴³ in the compound (f1-1) are preferably alkyl groups having 1 to 3 carbon atoms, respectively, and more preferably methyl groups, respectively. Of these, it is particularly preferable that all of R ^{41 to} R ⁴³ are methyl groups.
The number of carbon atoms in the alkyl or alkenyl group R ⁴⁴ is from 8 to 22, preferably 10 to 22, 16 to 18 is more preferable. Further, R ⁴⁴ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

Compound (f1-2): R ⁴¹ and R ⁴² are independently linear or branched alkyl groups having 8 to 22 carbon atoms, or linear or branched chain chains having 8 to 22 carbon atoms. A compound in which R ⁴³ and R ⁴⁴ are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms.
The number of carbon atoms in the alkyl group or alkenyl group of R ⁴¹ and R ⁴² of the compound (f1-2) is 8 to 22, respectively, preferably 8 to 12, and more preferably 8 to 10. Further, R ⁴¹ and R ⁴² are preferably linear or branched alkyl groups, respectively, and more preferably linear alkyl groups, respectively. Of these, it is particularly preferable that both R ⁴¹ and R ⁴² are linear alkyl groups.
R ⁴³ and R ⁴⁴ are preferably alkyl groups having 1 to 3 carbon atoms, respectively, and more preferably methyl groups, respectively. Of these, it is particularly preferable that both R ⁴³ and R ⁴⁴ are methyl groups.

The formula (f1), as the Q _A constituting the halogen ion, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a chlorine atom is preferable. The Q _A constituting the alkyl sulfate ion, preferably those having an alkyl group having 1 to 3 carbon atoms, such as methyl sulfate.

Specific examples of the compound (f1) include alkyl chloride (12 to 16 carbon atoms) trimethylammonium, didecyldimethylammonium chloride and the like.

(Compound (f2))
The compound (f2) is a compound represented by the following formula (f2).

In the formula (f2), R ⁴⁵ is a linear or branched alkyl group, or a linear or branched alkenyl group having 8 to 22 carbon atoms of 8 to 22 carbon atoms. R ⁴⁶ is a methyl group or a tolyl group. p and q indicate the average number of repetitions of ethyleneoxy groups, which are independently 0 or more, and p + q is 10 or more. Q _B ^- is a halogen ion or an alkylsulfate ion.

The number of carbon atoms in the alkyl or alkenyl group ^{R 45} of the formula (f2) is from 8 to 22, preferably 10 to 18. R ⁴⁵ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
R ⁴⁶ of the formula (f2) is a methyl group or a tolyl group.
In the formula (f2), p + q is 10 or more, preferably 10 to 50. When p + q is less than 10, the effect of dispersing the dirt adhering to the object to be washed is small, and the effect of removing the dirt from the object to be washed may be difficult to obtain.
As Q _B ⁻ , the same as Q _A ⁻ in the above formula (f1) can be mentioned.

As the compound (f2), R ⁴⁵ is a linear or branched alkyl group having 10 to 18 carbon atoms, or a linear or branched alkenyl group having 10 to 18 carbon atoms, and R ⁴⁶ is a methyl group or a tolyl group, p + q is not less than 10, Q _B ^- can be cited compounds is a halogen ion or an alkylsulfate ion.

(Compound (f3))
The compound (f3) is a compound represented by the following formula (f3).

However, in the formula (f3), R ⁴⁷ and R ⁴⁸ are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms, and R ⁴⁹ has 8 to 22 carbon atoms. a linear or branched alkyl group or alkenyl group, R ⁵⁰ is an alkylene group having 1 to 3 carbon atoms. Q _C ^- is a halogen ion or an alkylsulfate ion.

R ⁴⁷ and R ⁴⁸ in the formula (f3) are preferably alkyl groups having 1 to 3 carbon atoms, respectively, and more preferably methyl groups, respectively. Of these, it is particularly preferable that both R ⁴⁷ and R ⁴⁸ are methyl groups.
The number of carbon atoms in the alkyl or alkenyl group R ⁴⁹ is from 8 to 22, preferably 10 to 18, 12 to 14 is more preferable. R ⁴⁹ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
R ⁵⁰ is an alkylene group having 1 to 3 carbon atoms, and is preferably a methylene group.
Examples of Q _C ⁻ are the same as those of Q _A ⁻ in the above formula (f1), and halogen ions are particularly preferable.

Specific examples of the compound (f3) include coconut alkyldimethylbenzylammonium chloride and the like.

As the component (F), one type may be used alone, or two or more types may be used in combination.
As the component (F), at least one selected from the group consisting of compound (f1), compound (f2) and compound (f3) is preferable. Among them, the compound (f1) is more preferable because the effect of suppressing the generation of the room-drying odor becomes higher when used in combination with the component (C).

The content of the component (F) in the liquid cleaning agent composition (100% by mass) of the present invention is preferably 0.3 to 5% by mass, more preferably 1 to 3% by mass, and 1.5 to 2% by mass. Is even more preferable. When the content of the component (F) is at least the above lower limit value, the effect of suppressing the generation of room drying odor can be more easily obtained. When the content of the component (F) is not more than the above upper limit value, the liquid stability of the liquid cleaning agent composition (suppression of coloring, effect of preventing viscosity decrease, stabilization of aroma, etc.) is further improved. In addition, dye transfer and recontamination of the object to be washed are easily suppressed. In addition, it is economically advantageous.

The (C) / (F) ratio (mass ratio) of the component (C) and the component (F) is preferably 0.002 to 5, more preferably 0.05 to 1, and preferably 0.1 to 0.75. More preferred. When the (C) / (F) ratio is at least the above lower limit value, the effect of suppressing the generation of room drying odor can be easily obtained. In addition, there is little risk of problems in terms of recontamination of the object to be washed. When the ratio (C) / (F) is not more than the upper limit value, there is little possibility that the appearance stability is impaired.
The (C) / (F) ratio (mass ratio) is the content (mass%) of the component (C) with respect to the content (mass%) of the component (F) contained in the liquid cleaning agent composition. Means the ratio.

[water]
The liquid cleaning agent composition of the present invention preferably contains water from the viewpoints of ease of handling during production, solubility in water during use, and the like.

[Arbitrary component]
In addition to the components (A) to (F), the liquid cleaning agent composition of the present invention may contain arbitrary components usually used in the liquid cleaning agent composition.
Optional components include, for example, enzymes (proteases, etc.), solvents, hydrotropes, chelating agents, bactericides, preservatives, antifungal agents, pigments, antioxidants, UV absorbers, fragrances, pH adjusters, alkaline agents. And so on.

(solvent)
The liquid cleaning agent composition of the present invention may contain a solvent. The solvent may be any solvent conventionally used in liquid cleaning composition for clothing and the like. For example, a monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms, and a glycol ether Examples include system solvents and alcohols having a methoxy group.

Examples of monohydric alcohols having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, and glycerin.
Examples of the glycol ether solvent include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol).

Examples of alcohols having a methoxy group include 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, and 3-methoxy-. 2-Methoxybutanol, 3-methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol, 3-methoxy- 1-propylbutanol, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-ethylbutyl acetate, 3-methoxy-3-propylbutyl acetate, 3-methoxy-2-methylbutyl Acetate, 3-methoxy-2-ethylbutyl acetate, 3-methoxy-2-propylbutyl acetate, 3-methoxy-1-methylbutyl acetate, 3-methoxy-1-ethylbutyl acetate, 3-methoxy-1-propylbutyl Acetate can be mentioned.
One of these solvents may be used alone, or two or more of these solvents may be used in combination as appropriate.

(Fragrance precursor)
The liquid cleaning composition of the present invention may contain a fragrance precursor. The fragrance precursor is odorless or almost odorless in itself, but means a component that generates a scent by undergoing an oxidation reaction or the like in the liquid cleaning agent composition or on the fiber.
When the liquid cleaning agent composition of the present invention contains a fragrance precursor, the intensity of the scent (fragrance intensity) perceived from the synthetic fiber clothing after washing and drying can be further enhanced. As a result, the effect of the silky feel of synthetic clothing after washing can be further enhanced, and the comfort of wearing can be easily improved. Furthermore, the fragrance derived from the fragrance precursor is gradually released, so that the actual feeling effect can be further sustained.
The fragrance precursor is not particularly limited as long as it has the above-mentioned effect, and those generally used in liquid cleaning agent compositions can be used. Examples of such a fragrance precursor include a sulfur-containing fragrance precursor (sulfur-containing fragrance precursor) and the like.

The pH of the liquid cleaning agent composition of the present invention at 25 ° C. is preferably 5 to 9, and more preferably 7 to 9. When the pH is within the above range, good detergency is likely to be maintained.
The pH of the liquid cleaning agent composition in the present invention at 25 ° C. is measured by adjusting the sample to 25 ° C. and using a pH meter (for example, using the product name "HM-30G" manufactured by DKK-TOA CORPORATION) or the like. Indicates the value to be.

In the liquid cleaning agent composition of the present invention described above, by combining the components (A) to (C), high cleaning power, excellent liquid stability, and a high anticontamination effect can be exhibited. Excellent antibacterial properties can be imparted to the object to be washed, and the generation of room drying odor can be sufficiently suppressed. Such an effect can be obtained by forming a complex of the anionic surfactant of the component (B) and the compound having a phenolic structure of the component (C) to improve the adsorption to the synthetic fiber, and (C). This is because the antibacterial activity of the component is fully exhibited.
Further, in the liquid cleaning agent composition of the present invention, the antibacterial property can be further enhanced by using the component (D), the component (E), and the component (F) in combination.

The liquid cleaning agent composition of the present invention preferably contains the components (A) to (C), the component (A) preferably contains the compound (I), and R ¹ in the formula (I) has 11 carbon atoms. It is more preferable to contain a compound which is an alkyl group and an alkyl group having 13 carbon atoms, R ² is a methyl group, s = 15, and t = 0.
The liquid cleaning agent composition of the present invention contains the components (A) to (C), and the component (B) is a polyoxyalkylene alkyl having a linear or branched alkyl group having 10 to 20 carbon atoms. It is preferable to contain at least one selected from the group consisting of an ether sulfate and a linear alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms.
The liquid cleaning agent composition of the present invention contains components (A) to (C), and the component (C) contains at least one selected from the group consisting of dichlorohydroxydiphenyl ether, trichlorohydroxydiphenyl ether and benzyl chlorophenol. Is preferable.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following description. In this embodiment, "%" indicates "mass%" unless otherwise specified.
[material]
The raw materials used in this example are as follows.
(Ingredient (A))
A-1: MEE. A compound in which 15 mol of ethylene oxide is added to methyl coconut fatty acid (mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) using an alkoxylation catalyst. In formula (I), R ¹ is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R ² is a methyl group, s = 15, and t = 0. The narrow rate was 33%.
<Synthesis method of A-1>
It was synthesized according to the synthesis method described in JP-A-2000-144179.
Composition alumina hydroxide magnesium is _{2.5MgO · Al 2 O 3 · wH} 2 O ( Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) for 1 hour at 600 ° C., and calcined in a nitrogen atmosphere A fired alumina-magnesium hydroxide (unmodified) catalyst was obtained. 2.2 g of calcined alumina-magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N 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. The catalyst was modified in. 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 carried out with stirring.
The obtained reaction solution was cooled to 80 ° C., 159 g of water, 5 g of activated clay and 5 g of diatomaceous earth as filtration aids were added and mixed, and then the catalyst was filtered off to obtain A-1.

A-1': MEE. A compound in which 15 mol of ethylene oxide is added to methyl coconut fatty acid (mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) using an alkoxylation catalyst. In formula (I), R ¹ is an alkyl group having 11 carbon atoms, an alkyl group having 13 carbon atoms, R ² = methyl group, s = 15, t = 0, and a narrow ratio of 33%. Synthesized by the following synthesis method.
<Synthesis method of A-1'>
A-1'was synthesized according to the following synthesis method.
525 g of isopropyl alcohol (IPA) (primary reagent, manufactured by Kanto Chemical Co., Inc.) and 150 g of calcium acetate monohydrate (special grade reagent, manufactured by Kanto Chemical Co., Inc.) are placed in a 1 L separable flask, and the temperature is 20 ° C. using a disperser stirring blade. To obtain a dispersion (dispersion step). While stirring the dispersion at 3000 rpm, 75 g of sulfuric acid (special grade reagent, manufactured by Kanto Chemical Co., Inc.) was added and mixed over 60 minutes by a dropping funnel (mixing step). Since heat is generated by the addition of sulfuric acid in the mixing step, the reaction temperature was controlled to 15 to 25 ° C. in a separate flask in a warm bath. After adding sulfuric acid, the mixture was further stirred for 2 hours while maintaining the temperature at 20 ° C. (catalyst aging step) to obtain an alkoxylation catalyst.
2.1 g of the above-mentioned 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. Nitrogen was substituted in the autoclave with stirring, the temperature was raised to 160 ° C., and 1876 g of ethylene oxide (EO) was used under the conditions of 0.1 to 0.5 MPa (15 times the molar amount of the total 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 crude reaction product (fatty acid methyl ester ethoxylate (MEE), EO average number of moles added = 15). The crude reaction product from which the catalyst was removed was designated as A-1'.

A-2: LMAO. A compound obtained by adding 15 mol of ethylene oxide to a polyoxyethylene alkyl ether, a natural alcohol having 12 and 14 carbon atoms (primary alcohol).
<LMAO synthesis method>
861.2 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 a 30 mass% NaOH aqueous solution are charged in a pressure resistant reaction vessel, and the reaction vessel is charged. The inside was replaced with nitrogen. Next, after dehydration 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 blow tube while adjusting 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 p-toluenesulfonic acid was added and neutralized so that the pH of the 1% by mass aqueous solution of the reaction product became about 7, to obtain LMAO.

A-3: EOPO nonion. A secondary alcohol having 12 carbon atoms and a secondary alcohol having 14 carbon atoms, to which ethylene oxide equivalent to 8 mol and propylene oxide equivalent to 2 mol are added. In formula (II), R ³ is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 8, w = 2, and x = 0.
<Synthesis method of EOPO nonion>
224.4 g of "CO-1270" manufactured by P & G and 2.0 g of a 30 mass% NaOH aqueous solution were placed in a pressure-resistant reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. Then, after dehydration 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, 352 g of ethylene oxide (gaseous) was gradually added to the alcohol solution using a blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. for the reaction. Then, 116 g of propylene oxide was introduced and further reacted.
Then, after aging at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, unreacted ethylene oxide and propylene oxide were distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes. Then, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added and neutralized so that the pH of the 1% by mass aqueous solution of the reaction product became about 7, to obtain EOPO nonionic.

(Component (B))
B-1: Polyoxyethylene alkyl ether sodium sulfate (AES). A compound represented by the following formula (b1-1), in which R ⁵¹ is a linear alkyl group having 12 to 14 carbon atoms, k = 1.0, and M is sodium. However, in the formula (b1-1), EO is an ethyleneoxy group, and k is the average number of repetitions of EO.
R ^51- O- (EO) _k- SO ₃ M ... (b1-1)
<AES synthesis method>
In an autoclave with a capacity of 4 L, 400 g of P &G's trade name CO1270 alcohol (a mixture of alcohol having 12 carbon atoms and alcohol having 14 carbon atoms in a mass ratio of 75/25) as a raw material alcohol and potassium hydroxide as a reaction catalyst 0.8 g was charged, the inside of the autoclave was replaced with nitrogen, and then the temperature was raised while stirring. Subsequently, 91 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less, and the reaction was carried out to obtain alcohol ethoxylate.
Gas chromatograph mass spectrometry (analyzer: GC-5890 manufactured by Hewlett-Packard, detector: hydrogen flame ionization detector (FID), column: Ultra-1 (manufactured by HP, L25 m × φ0.2 mm × T0.11 μm) As a result of analysis by (.), The obtained alcohol ethoxylate had an average number of molar additions of ethylene oxide of 1.0, and the compound without ethylene oxide added to the total mass of the obtained alcohol ethoxylate. On the other hand, it was 43% by mass.
Next, 237 g of the alcohol ethoxylate obtained above was taken in a 500 mL flask equipped with a stirrer, replaced with nitrogen, and then 96 g of liquid anhydrous sulfuric acid (sulfur) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Then, this was neutralized with an aqueous sodium hydroxide solution to obtain AES.

B-2: Sodium linear alkylbenzene sulfonate (LAS), manufactured by Lion Corporation, trade name "Rypon LH-200".
B-3: α-Sulphonic fatty acid methyl ester salt (MES), trade name "MIZULA F FL-80", manufactured by Lion Ecochemicals Co., Ltd.
B-4: Soap, trade name "Palm fatty acid", manufactured by NOF CORPORATION.

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

(Component (D))
D-1: TexCare SRN-170C (trade name, manufactured by Clariant Japan, weight average molecular weight: 2000 to 3000, pH (5% by mass aqueous solution at 20 ° C.): 4, viscosity (20 ° C.): 300 mPa · s). TexCare SRN-170C is a 70% by mass aqueous solution of trade name: TexCare SRN-100 (manufactured by Clariant Japan, weight average molecular weight: 2000 to 3000).

(Component (E))
E-1: Ethylene oxide adduct of polyethyleneimine (manufactured by BASF, trade name "Sokalan HP20"). The average number of moles of ethylene oxide added per mole of active hydrogen contained in polyethyleneimine is 20 mol.

((F) component)
F-1: Dodecyltrimethylammonium chloride, trade name "Lipoguard 12-37W", manufactured by Lion Specialty Chemicals Co., Ltd. (in formula (f1), R ^{41 to} R ⁴³ are methyl groups, and R ⁴⁴ has 12 carbon atoms. Compounds that are linear alkyl groups).
F-2: Didecyldimethylammonium chloride, trade name "Alucard 210", manufactured by Lion Specialty Chemicals Co., Ltd.
F-3: Cocoyl dimethylbenzylammonium chloride, trade name "Lipocard CB-50", manufactured by Lion Specialty Chemicals Co., Ltd.

(Other ingredients)
Water: Purified water Ethanol: Water-miscible organic solvent, trade name "Specific alcohol 95 degree synthesis", manufactured by Japan Alcohol Trading Co., Ltd.
BC: Butyl carbitol (water-miscible organic solvent), trade name "butyl carbitol", manufactured by Tokyo Chemical Industry Co., Ltd.
MMB: 3-Methoxy-3-methylbutanol (water-miscible organic solvent), trade name "Solfit", manufactured by Kuraray Co., Ltd.
Sodium benzoate: manufactured by Toagosei Co., Ltd.
Protease: Coronase, trade name "Coronase 48L", manufactured by Novozymes.
MEA: Monoethanolamine (alkaline agent), trade name "monoethanolamine", manufactured by Nippon Shokubai Co., Ltd.
BHT: Dibutylhydroxytoluene (antioxidant), trade name "SUMILZER BHT-R", manufactured by Sumitomo Chemical Co., Ltd.
Sodium lactate: Made by Kanto Chemical Co., Inc., trade name "sodium lactate".
Perfume: Perfume composition A according to Tables 11 to 18 of JP-A-2002-146399.

[Examples 1-28, Comparative Examples 1-3]
Each component was mixed according to the composition shown in Tables 1 to 4 to obtain a liquid cleaning agent composition.
Tables 1 to 4 show the composition (blending component, content (%)) of the liquid cleaning agent composition of each example. The blanks in Tables 1 to 4 mean that the compounding ingredients are not blended. The content of the compounding component indicates the net conversion amount. "Balance" indicating the content of purified water means the balance added so that the total blending amount (%) of all the blending components contained in the liquid cleaning agent composition is 100%.
In addition, only in Example 6, a premix in which the fragrance and C-1 were mixed in advance so as to have the mass ratio described in Example was prepared, and it was blended into the liquid cleaning agent composition. In another example, component (C) was mixed with other components without forming a premix with the fragrance.
In addition, the blending amount in the examples is described as the amount of the active ingredient.

[Evaluation method]
For the liquid cleaning agent composition of each example, "detergency", "enzyme stability", "recontamination prevention effect", "liquid stability", "antibacterial property" and "room drying odor generation" were generated by the evaluation methods shown below. "Suppressive effect of" was evaluated respectively.

(Cleaning power)
For the evaluation of the detergency, the liquid cleaning agent composition (immediately after production) immediately after production in each example was used. As the stain cloth, EMPA117 (Polyester / cotton, 65/35, soiled with blood / milk / ink, manufactured by EMPA Testatrialia), which is a protein stain cloth, was cut into 5 cm × 5 cm squares. A Terg-O-tometer (manufactured by UNITED STATES TESTING) was used as a cleaning tester. As the cleaning liquid, 300 μL of the liquid cleaning agent composition was added to 900 mL of water, and the mixture was stirred for 30 seconds.
900 mL of the cleaning liquid, 10 sheets of dirty cloth, and a cleaning knitted cloth were put into a cleaning tester, and the cleaning was performed at 120 rpm and 15 ° C. for 10 minutes at a bath ratio of 20 times. Then, it was transferred to a two-tank washing machine (manufactured by Mitsubishi Electric Corporation: product name CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried. The reflectance of uncleaned cloth (here, uncleaned cloth means a standard white cloth that is not contaminated), unwashed EMPA117, and washed EMPA117 is measured by a color difference meter (Nippon Denshoku Co., Ltd.). Made by the company: Product name SE200 type), and the cleaning rate (%) was calculated by the following formula.
Cleaning rate (%) = (K / S of dirty cloth before cleaning-K / S of dirty cloth after cleaning) / (K / S of dirty cloth before cleaning-K / S of unclean cloth) × 100
However, K / S is (1-R / 100) ² / (2R / 100) (R indicates the reflectance (%) of the unwashed cloth and EMPA117 before and after washing).
The detergency evaluation criteria were as follows: those with a detergency (%) of 55% or more were marked with ◯ (pass), and those with a detergency of less than 55% were marked with x (fail).

(Enzyme stability)
<Measurement of protease activity>
Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free / Calbiochem (registered trademark)) was dissolved in 1N sodium hydroxide (1 mol / L sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Ltd.) to adjust the pH to 10. It was set to 5, and diluted with 0.05 M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Ltd.) so that the concentration of milk casein became 0.6%, and used as a protease substrate.
A solution obtained by diluting 1 g of the liquid cleaning agent composition obtained in each example with calcium chloride (calcium chloride (special grade), manufactured by Kanto Chemical Co., Inc.) 3 ° DH hard water 25 times was used as a sample solution.
5 g of the above protease substrate was added to 1 g of the sample solution, and the mixture was stirred with a vortex mixer for 10 seconds and then allowed to stand at 37 ° C. for 30 minutes to proceed with the enzymatic reaction. Then, 5 g of a 0.44 M aqueous solution of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Inc.) as an enzyme reaction terminator was added to this solution, and the mixture was stirred with a vortex mixer for 10 seconds. Then, this solution was allowed to stand at 20 ° C. for 30 minutes, the precipitated unreacted substrate was removed with a 0.45 μm filter, and the filtrate was recovered.
The absorbance (absorbance α) of the recovered filtrate at a wavelength of 275 nm was measured using an ultraviolet visible spectrophotometer UV-160 manufactured by Shimadzu Corporation. The larger the absorbance α, the larger the amount of tyrosine (produced by the protease degrading the protease substrate) present in the filtrate.
In order to eliminate the influence of absorption other than the target component, separately add 5 g of TCA, which is an enzyme reaction terminator, to 1 g of each sample solution, stir for 10 seconds with a vortex mixer, add 5 g of a protease substrate, and 10 with a vortex mixer. The mixture was stirred for seconds and removed with a 0.45 μm filter to collect the filtrate. Then, the absorbance (absorbance β) of the filtrate at a wavelength of 275 nm was measured using UV-160.

<Evaluation of storage stability of protease activity>
After production, the protease activity was measured for a liquid cleaning agent composition (35 ° C. storage product) stored at 35 ° C. for 4 weeks and a liquid cleaning agent composition (4 ° C. storage product) stored at 4 ° C. for 4 weeks. From these measurement results, the protease activity residual rate (%) was determined by the following formula.
The absorbance value at 275 nm of each sample substituted into the following equation was used by dividing the absorbance value at 600 nm measured at the same time in order to exclude scattered light such as bubbles from the absorbance.
Protease activity residual rate = (absorbance of 35 ° C storage product α-absorbance β of 35 ° C storage product) / (absorbance of 4 ° C storage product α-4 ° C storage product absorbance β) × 100
From the obtained residual protease activity (%), the storage stability of the protease activity was evaluated according to the following evaluation criteria.
⊚: 80% or more.
◯: 70% or more and less than 80%.
Δ: 60% or more and less than 70%.
X: Less than 60%.
The evaluation results are shown in the column of enzyme stability (stability). The evaluation criteria were that those with a residual rate (%) of 60% or more passed, and those with a residual rate (%) of less than 60% were rejected.

(Recontamination prevention effect)
Using the liquid cleaning agent composition prepared in each example, a washing process was performed in which the following washing step, rinsing step, and drying step were repeated three times in this order.
<Washing process>
The following cotton cloth, polyester (PE) cloth, wet artificially contaminated cloth, and skin shirt were used as the objects to be washed.
-Cotton cloth: Five cotton knitted fabrics (manufactured by Tanito Shoten) 5 cm x 5 cm as a recontamination judgment cloth.
-Polyester (PE) cloth: Five polyester tropical (manufactured by Tanito Shoten) 5 cm x 5 cm as a recontamination judgment cloth.
-Wet artificial contaminated cloth: Contaminated cloth manufactured by the Laundry Science Association (28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene, 20 sheets of cloth with stains of 1.6% cholesterol, 7.0% gelatin, 29.8% mud, and 0.5% carbon black (mass ratio).
-Skin shirt: A skin shirt (LL size, made by DVD) cut into small pieces (about 3 cm x 3 cm).
900 mL of 3 ° DH hard water at 25 ° C. was placed in a Terg-o-tometer (manufactured by UNITED TESTES TESTING), 0.6 g of a liquid cleaning agent composition was added thereto, and then the object to be washed was placed. Then, 3 ° DH hard water was added to adjust the bath ratio 20 times, and the mixture was washed at 120 rpm and 25 ° C. for 10 minutes.
<Rinse process>
After dehydrating 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. This operation (dehydration, rinsing) was repeated twice. The second time, a predetermined amount of softener was added to 900 mL of 3 ° C. DH hard water at 25 ° C. for rinsing. Room-dried Soflan (manufactured by Lion Corporation) was used as the softener.
<Drying process>
After dehydrating the rinsed object to be washed for 1 minute, only the recontamination determination cloth (cotton cloth, PE cloth) was taken out, sandwiched between filter papers, and dried with an iron.

Using a reflectance meter (spectrophotometric color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.), the reflectance (Z value) of the recontamination determination cloth before and after the washing treatment was measured, and ΔZ was calculated from the following formula.
ΔZ = (Z value before washing treatment)-(Z value after washing treatment)
The average value of 5 sheets was calculated for ΔZ in each of the recontamination determination cloths of cotton cloth and PE cloth. Then, the effect of the liquid cleaning agent composition on cotton cloth and PE cloth was evaluated by the following judgment criteria according to the following judgment criteria using this average value as an index.
Judgment criteria for cotton cloth ◎: ΔZ is less than 5.
◯: ΔZ is 5 or more and less than 7.
Δ: ΔZ is 7 or more and less than 9.
×: ΔZ is 9 or more.
Judgment criteria for PE cloth ⊚: ΔZ is less than 3.
◯: ΔZ is 3 or more and less than 4.
Δ: ΔZ is 4 or more and less than 5.
X: ΔZ is 5 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 cleaning agent composition, and the lid was closed and sealed. In this state, it was stored in a constant temperature bath at 5 ° C. (or 25 ° C.) for 7 days.
After such storage, the appearance of the liquid was visually observed, and the liquid stability of the liquid cleaning agent composition was evaluated according to the following evaluation criteria. Those whose evaluation results were ◎ and ○ were regarded as acceptable.
Evaluation Criteria ⊚: No precipitated substance was observed at the bottom of the glass bottle even at 5 ° C, and the liquid was fluid.
◯: Precipitated substances were not observed at the bottom of the glass bottle at 5 ° C, and gelation was observed in some parts, but when left at 25 ° C for 3 hours, no gelation was observed and the entire liquid flowed. Become.
Δ: Precipitated substances are observed at the bottom of the glass bottle at 25 ° C., but when the glass bottle is shaken lightly, the precipitated substances disappear (dissolve).
X: Precipitated substances were observed at the bottom of the glass bottle even at 25 ° C., and the precipitated substances did not disappear even when the glass bottle was shaken lightly, or gelled or clouded immediately after the production of the liquid cleaning agent.

(Antibacterial)
(1) Washing treatment method Approximately 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 mass of cloth to be washed) 30 times. ]. As the cloth to be washed, about 30 g of commercially available Tetron (registered trademark) / cotton broad blend (50% polyester / 50% cotton) (hereinafter referred to as Tet cotton) cut into 5 cm x 5 cm sizes and cotton. A combination with a skin shirt (manufactured by BBD) was used.
Next, 333 ppm of each of the liquid cleaning agent compositions of each example was added to the fully automatic electric washing machine, and a washing operation was performed in which washing, rinsing, and dehydration were sequentially performed in a standard course. At that time, the washing time, rinsing, dehydration, and water volume (set to a low water level, water volume of about 12 L) were not adjusted at all, and the standard course setting of the washing machine was used as it was.
After the washing was completed, the tet cotton was taken out, and the taken out tet cotton was left in a constant temperature and humidity chamber at 25 ° C. and a relative humidity of 65% RH to dry. After drying, the Tet cotton was used as a test cloth for evaluation of antibacterial properties. Further, as the untreated cloth, Tet cotton which had not been washed was used.

(2) Evaluation of antibacterial properties against Staphylococcus aureus The instruments, water, etc. used in this evaluation were sterilized in advance by autoclave. In this evaluation, Staphylococcus aureus was used as the bacterium.
Using Staphylococcus aureus cultured according to JIS L1902, dilute the neutrient medium 20 times and prepare the Staphylococcus aureus mother liquor so that the number of bacteria is 1 ± 0.3 × 10 ⁵ cells / mL. did.
The test cloth (5 cm x 5 cm) was inoculated with 0.1 mL each of the Staphylococcus aureus mother liquor, cultured in a constant temperature bath at 37 ° C. for 18 hours, and grown or bacteriostatic on the test cloth.
Then, the bacteria were extracted from the test cloth with an extract (physiological saline for washing out described in JIS L1902), and the extract was diluted 10-fold with physiological saline. The operation of diluting the obtained diluted solution 10-fold was repeated 4 times to obtain a 100,000-fold diluted solution. In addition, "physiological saline for washing out" is made by putting 1,000 mL of purified water and 8.5 g of sodium chloride in a flask and sufficiently dissolving them, and further, polyoxyethylene sorbitan monooleate (Kanto Kagaku) as a nonionic surfactant. 2 g of a product manufactured by Co., Ltd., trade name "Polysorbate 80, Tween 80") was added and dissolved, and then high-pressure steam sterilization (autoclave treatment) was performed.
Next, 1 mL of the obtained 100,000-fold diluted solution was collected on a SCDLP agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.), sterilized in advance by an autoclave, and kept at 48 ° C. 15 mL of the SCDLP agar medium was placed on a petri dish. The mixture was mixed with and cultured in a constant temperature bath at 37 ° C. for 1 to 2 days. After culturing, the number of colonies was counted to determine the number of viable bacteria.
The viable cell count was measured for the untreated cloth in the same manner as for the test cloth, and the antibacterial activity value (A) was calculated from the following formula using these measured values.
Antibacterial activity value = log10 (number of viable bacteria on untreated cloth / number of viable bacteria on test cloth)

Next, the same operations as in (1) and (2) were performed except that a liquid cleaning agent for evaluation comparison was used instead of the liquid cleaning agent, and the viable cell count was measured on the test cloth and the untreated cloth to obtain antibacterial properties. The activity value (B) was calculated.
From the calculated antibacterial activity value (A) and antibacterial activity value (B), the difference between the antibacterial activity values {antibacterial activity value (A) -antibacterial activity value (B)} is obtained, and the antibacterial activity is evaluated according to the following evaluation criteria. went. Δ and × were rejected.
Evaluation Criteria ⊚: The difference in antibacterial activity value was 2.5 or more.
◯: The difference in antibacterial activity value was 2.0 or more and less than 2.5.
Δ: The difference in antibacterial activity value was 1.0 or more and less than 2.0.
X: The difference in antibacterial activity value was less than 1.0.

(Effect of suppressing the generation of dry odor in the room)
For blended T-shirts (60% cotton, 40% polyester), wash with a commercially available synthetic detergent top (manufactured by Lion Corporation) with a detergent usage of 25 g / 30 L of tap water (JW-Z23A type, manufactured by Haier). , Water temperature 20 ° C., 10 minutes).
Next, the blended T-shirt was worn by 10 men in their 20s and 40s for 12 hours, and then washed in a normal course of a washing machine (JW-Z23A type, manufactured by Haier) using the liquid cleaning agent composition of each example. The treatment (water temperature of about 20 ° C., hardness of about 3 ° C., tap water was injected, and the bath ratio was 20 times). At that time, the washing treatment was performed with the amount of the liquid cleaning agent composition input to the washing machine set to 10 mL / 30 L of tap water. In addition, a new 100% cotton skin shirt (made by BVD) is washed 5 times in a fully automatic washing machine (manufactured by Panasonic Corporation, NA-F70SD1) 5 times (water temperature about 20 ° C, hardness about 3 ° DH). Tap water was injected) and used as clothing for bath ratio matching.
After the washing treatment of the blended T-shirt was completed, the T-shirt was dried in a room at room temperature (about 23 ° C.) and a relative humidity of 90% RH for 5 hours (room drying). After that, 6 specialized panelists each performed a sensory evaluation of smelling the blended T-shirt after drying for 5 hours (drying in the room). The sensory evaluation was performed by scoring based on the following evaluation criteria. Specifically, a specialized panelist sniffed each odor of the blended T-shirt after drying the room, and evaluated it according to the odor intensity display of 6 levels in the following evaluation criteria. Then, the average score of the blended T-shirt was calculated, and the effect of suppressing the generation of the room drying odor was evaluated using this average score as an index. Those with an average score of 3.0 points or less were regarded as acceptable.
Evaluation criteria for sensory evaluation (odor intensity display)
0 points: No offensive odor.
1 point: A strange odor is barely perceptible.
2 points: The offensive odor is felt weak.
3 points: A strange odor is felt a little strongly.
4 points: A strong offensive odor is felt.
5 points: A strange odor is strongly felt.

The evaluation results of each example are shown in Tables 1 to 4.

As shown in Tables 1 to 4, in Examples 1 to 28 containing the components (A) to (C), high detergency, excellent liquid stability, and a high anti-recontamination effect were obtained, and the product was washed. Excellent antibacterial properties were imparted to the object, and the generation of room-drying odor was sufficiently suppressed. In addition, in Examples 1, 7, 20 to 23, sufficient enzyme stability was also obtained.
On the other hand, in Comparative Examples 1 and 2 containing no component (C), sufficient antibacterial properties could not be obtained.
In Comparative Example 3 containing no component (B), sufficient detergency was not obtained and the effect of preventing recontamination was low.

Claims (6)

Component (A): A nonionic surfactant containing at least one selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II), and component (B): anion. It contains at least one selected from the group consisting of surfactants and component (C): an antibacterial agent having a phenolic structure.
The component (C) is 4,4'-dichloro-2-hydroxydiphenyl ether.
The content of the component (B) is 10 to 20% by mass.
The content of the component (C) is 0.1 to 0.5% by mass.
A liquid cleaning agent composition in which the (B) / (C) ratio (mass ratio) of the component (B) and the component (C) is 10 or more and 100 or less.
R ^1- C (= O) O-[(EO) _s / (PO) _t ]-(EO) _u- R ² ... (I)
R ^3- O-[(EO) _v / (PO) _w ]-(EO) _x- H ... (II)
(However, in the formula, EO is an ethyleneoxy group, PO is a propyleneoxy group. R ¹ is a hydrocarbon group having 7 to 22 carbon atoms, R ² is a methyl group or an ethyl group, and R ³ Is a hydrocarbon group having 7 to 22 carbon atoms. S, v, u, x are the average number of repetitions of EO, t and w are the average number of repetitions of PO. S is a number of 6 to 20. , T is a number from 0 to 6, u is a number from 0 to 20, v is a number from 8 to 20, w is a number from 0 to 6, and x is a number from 0 to 12. , V + x is 13 to 20.) The liquid cleaning agent composition according to claim 1, wherein the (A) / (B) ratio (mass ratio) of the component (A) and the component (B) is 1 or more. The component (B) is a polyoxyalkylene alkyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms, and a linear alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms. The liquid cleaning agent composition according to claim 1 or 2, which comprises at least one selected from the group consisting of. The component (B) is a polyoxyalkylene alkyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms, and a linear alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms. The liquid cleaning agent composition according to any one of claims 1 to 3, which comprises both of the above. Polyoxyalkylene alkyl ether sulfate (AES) having a linear or branched alkyl group having 10 to 20 carbon atoms and linear alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 18 carbon atoms. The liquid cleaning agent composition according to claim 4, wherein the LAS / AES ratio (mass ratio) is 0.1 to 2. Further, a water-soluble polymer having a component (D): one or both of an alkylene terephthalate unit and an alkylene isophthalate unit, and one or both of an oxyalkylene unit and a polyoxyalkylene unit is 0.1 to 5 Contains% by mass,
Component (E): Contains 0.1 to 5% by mass of a polyalkyleneamine alkylene oxide-based copolymer having an alkyleneamine structural unit containing a polyalkylene oxide chain.
(F) The liquid cleaning composition according to any one of claims 1 to 5 , which contains at least one selected from the group consisting of cationic surfactants.