JP2018203923A - Liquid detergent - Google Patents

Abstract

To provide a liquid detergent excellent in sebum detergency and high in effects of suppressing generation of odors due to drying in a room from washed articles after washing.SOLUTION: The liquid detergent contains (A) to (C) components. (A) component: an anionic surfactant containing a compound (a) represented by the following general formula (1). R-O-[(EO)/(PO)]-SO1/v M(1), where Ris an alkyl group or an alkenyl group having 8 to 18 carbon atoms, p is 0 to 10, q is 0 to 5, Mis a cation other than a hydrogen ion, and v is valence of M, however p and q are not 0 at same time and satisfy 0<p≤2 when q=0. (B) component: a nonionic surfactant. (C) component: an antibacterial agent having a phenol structure (c1) and/or at least one kind selected from a group consisting of polylysine, polyhexamethylene, 2-(4-thiocyanomethylthio)benzimidazole (c2).SELECTED DRAWING: None

Description

  The present invention relates to a liquid cleaning agent.

An unpleasant odor (room-dried odor) may be generated when clothes or the like (washing object) to which sebum dirt or the like adheres are air-dried in a room with high humidity after being washed. Generation | occurrence | production of this room-drying odor originates in a microbe having propagated in the clothes after washing.
In order to prevent the growth of such bacteria, a detergent containing an antibacterial agent is known.

For example, Patent Document 1 discloses a liquid detergent composition containing a nonionic surfactant, a branched alkyl sulfate, and an antibacterial agent.
Patent Document 2 discloses a method for washing clothes using an anionic surfactant such as polyoxyethylene alkyl sulfate ester salt and linear alkylbenzene sulfonate and a diphenyl ether antibacterial agent.

JP 2001-214191 A International Publication No. 2015-172678

In order to develop a sufficient antibacterial effect, it is necessary to increase the persistence of the antibacterial agent on textiles such as clothes after washing.
However, since the cleaning agent is diluted with a large amount of water at the time of washing, most of the antibacterial agent blended in the cleaning agent is washed away by rinsing or the like. In particular, in the case of a detergent formulated with a surfactant having a high detergency against sebum soil (sebum detergency), the antibacterial agent is easily dissolved in water during washing and easily washed away by rinsing or the like. Therefore, the conventional cleaning agent has insufficient persistence of the antibacterial agent to the textiles such as clothes after washing, and the room-dried odor cannot be sufficiently suppressed.

  This invention is made | formed in view of the said situation, and it aims at provision of the liquid cleaning agent which is excellent in sebum detergency and has the high effect which suppresses generation | occurrence | production of the room drying odor from the to-be-washed article after washing.

The present invention has the following aspects.
[1] A liquid detergent containing the following component (A), component (B) and component (C).
(A) Component: An anionic surfactant containing the following component (a1).
(A1) Component: A compound represented by the following general formula (1).
^{_{R 1 -O - [(EO)}} p / (PO) q] -SO 3 - 1 / v · M + ··· (1)
(In General Formula (1), R ¹ is an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, and p represents EO. Is the number satisfying 0 ≦ p ≦ 10, q is the average number of PO repeating, 0 ≦ q ≦ 5, and M ⁺ is a cation other than hydrogen ions. , V is the valence of M ⁺ , where p and q are not 0 at the same time, and 0 <p ≦ 2 is satisfied when q = 0.)
(B) component: Nonionic surfactant.
(C) Component: At least one selected from the group consisting of the following components (c1) and (c2).
(C1) Component: an antibacterial agent having a phenol structure.
(C2) Component: At least one selected from the group consisting of polylysine, polyhexamethylene biguanide, and 2- (4-thiocyanomethylthio) benzimidazole.
[2] The liquid cleaning agent according to [1], wherein the component (C) includes at least the component (c1).
[3] The liquid cleaning agent according to [1] or [2], wherein the component (B) includes the following component (b1).
(B1) Component: A compound represented by the following general formula (2).
R ² —O — [(EO) _s / (PO) _t ] —H (2)
(In General Formula (2), R ² is a hydrocarbon group having 8 to 22 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents the average number of repetitions of EO, 2 ≦ s ≦ 20, t represents the average number of repetitions of PO, and 0 ≦ t ≦ 6.)
[4] The liquid cleaning agent according to any one of [1] to [3], further comprising the following component (D).
(D) Component: Glycolytic enzyme.
[5] The liquid cleaning agent according to [4], further comprising the following component (E):
(E) Component: Enzyme other than carbohydrase.
[6] In the general formula (2), R ² is a branched hydrocarbon group having 8 to 22 carbon atoms or a linear hydrocarbon group having 8 to 22 carbon atoms (however, a branched hydrocarbon group) In the case of a group, the carbon atom bonded to the oxygen atom is a primary carbon atom, and in the case of a linear hydrocarbon group, it is a secondary carbon atom.), The liquid detergent according to [3].
[7] The liquid detergent according to [4], wherein the content of the component (D) is 0.01 to 2% by mass with respect to the total mass of the liquid detergent.
[8] The liquid detergent according to [5], wherein the content of the component (E) is 0.01 to 2% by mass with respect to the total mass of the liquid detergent.
[9] The liquid cleaning according to [5] or [8], wherein the total content of the component (D) and the component (E) is 1.5% by mass or less with respect to the total mass of the liquid cleaning agent. Agent.
[10] The liquid detergent according to any one of [5], [8], and [9], wherein the mass ratio represented by (D) component / (E) component is 0.05 to 20.
[11] The liquid detergent according to any one of [1] to [10], wherein the content of the component (a1) is 10 to 50% by mass with respect to the total mass of the liquid detergent.
[12] The liquid cleaning agent according to any one of [1] to [11], wherein the content of the component (a1) is 10 to 100% by mass with respect to the total mass of the component (A).
[13] The liquid cleaning agent according to any one of [1] to [12], wherein the content of the component (A) is 10 to 50% by mass with respect to the total mass of the liquid cleaning agent.
[14] The liquid detergent according to any one of [1] to [13], wherein the content of the component (B) is 5 to 35% by mass with respect to the total mass of the liquid detergent.
[15] The liquid cleaning agent according to any one of [1] to [14], wherein a mass ratio represented by (A) component / (B) component is 0.1 to 10.
[16] The liquid cleaning agent according to any one of [1] to [15], wherein the content of the component (C) is 0.01 to 3% by mass with respect to the total mass of the liquid cleaning agent. .
[17] The liquid cleaning agent according to any one of [1] to [16], wherein the mass ratio represented by (A) component / (C) component is 3 to 600.
[18] The liquid cleaning agent according to any one of [1] to [17], wherein the water content is 10 to 60% by mass with respect to the total mass of the liquid cleaning agent.
[19] The liquid cleaning agent according to any one of [1] to [18], which is for clothing.

  The liquid cleaning agent of the present invention is excellent in sebum detergency and has a high effect of suppressing the generation of a room-drying odor from the washed object after washing.

Hereinafter, the present invention will be described in detail.
The liquid cleaning agent of the present invention contains the following components (A), (B) and (C). Moreover, it is preferable that a liquid cleaning agent further contains the (D) component shown below. Moreover, the liquid detergent may further contain the following component (E).
In the present invention, the “antibacterial effect” means an effect of suppressing the growth of bacteria. The higher the antibacterial effect is, the higher the effect of suppressing room drying odor when clothes or the like (objects to be washed) are dried in a room with high humidity.
The “higher fatty acid salt” means a fatty acid salt having 8 to 22 carbon atoms.

<(A) component>
The component (A) is an anionic surfactant containing the following component (a1). The component (A) may contain an anionic surfactant other than the component (a1) (hereinafter also referred to as “component (a2)”).

((A1) component)
The component (a1) is a compound represented by the following general formula (1).
^{_{R 1 -O - [(EO)}} p / (PO) q] -SO 3 - 1 / v · M + ··· (1)
(In General Formula (1), R ¹ is an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, and p represents EO. Is the number satisfying 0 ≦ p ≦ 10, q is the average number of PO repeating, 0 ≦ q ≦ 5, and M ⁺ is a cation other than hydrogen ions. , V is the valence of M ⁺ , where p and q are not 0 at the same time, and 0 <p ≦ 2 is satisfied when q = 0.)

In General Formula (1), the carbon number of R ¹ is 8 to 18, preferably 9 to 16, and more preferably 10 to 15. When the carbon number of R ¹ is within the above range, the liquid stability, the sebum detergency, and the foaming property during rinsing are improved.
The alkyl group or alkenyl group for R ¹ may be linear or branched, but is preferably linear.
R ¹ is preferably a linear alkyl group having 8 to 18 carbon atoms or a linear alkenyl group having 8 to 18 carbon atoms, more preferably a linear alkyl group having 8 to 18 carbon atoms, and a primary alcohol. A linear alkyl group having 8 to 18 carbon atoms derived from is more preferable.

In general formula (1), p is the number of 0-10 showing the average repeating number of EO (namely, average addition mole number of ethylene oxide), 1-8 are preferable and 1-5 are more preferable. If p is less than or equal to the upper limit value, the hydrophilicity does not become too high, and sufficient sebum detergency can be easily obtained. As the value of p decreases, the sebum detergency tends to increase.
In general formula (1), q is a number from 0 to 5 representing the average number of repetitions of PO (that is, the average number of moles of propylene oxide added), preferably 0 to 4, more preferably 0.2 to 4, 0.2-2 are more preferable. If q is less than or equal to the upper limit value, sufficient sebum detergency, liquid stability and biodegradability can be easily obtained.
However, p and q are not simultaneously 0, and when q is 0, p is more than 0 and 2 or less, and preferably 0.5 to 1.5. Moreover, when p is 0, q is more than 0, preferably 3 or less, and preferably 0.5 to 1.5.

In the general formula (1), in the general formula (1), M ⁺ is a cation other than a hydrogen ion, and the valence is v. Examples of M ⁺ include those capable of forming a water-soluble salt such as alkali metal ions, alkaline earth metal ions, ammonium ions, or alkanolamine ions (alkanol ammonium ions).
Examples of the alkali metal ion include sodium ion, potassium ion, lithium ion and the like.
Examples of alkaline earth metal ions include calcium ions and magnesium ions.
Examples of the alkanolamine ion include monoethanolamine ion (monoethanolammonium ion), diethanolamine ion (diethanolammonium ion), and triethanolamine ion (triethanolammonium ion).
As M ⁺ , sodium ion, potassium ion, and monoethanolamine ion are preferable, and sodium ion is more preferable.

As the component (a1), one type may be used alone, or two or more types may be used in appropriate combination.
The content of the component (a1) is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, and still more preferably 50 to 100% by mass with respect to the total mass of the component (A). If content of (a1) component in (A) component exists in the said range, the inhibitory effect of sebum cleaning power and room drying odor will increase more.
Moreover, 10-50 mass% is preferable with respect to the total mass of a liquid detergent, (a1) component content is more preferable 15-45 mass%, and 20-40 mass% is further more preferable. When the content of the component (a1) in the liquid detergent is within the above range, excellent sebum detergency and appearance stability are easily obtained.

((A2) component)
The component (a2) is an anionic surfactant other than the component (a1).
Examples of the component (a2) include linear alkyl benzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkane sulfonate having an alkyl group; α-sulfo fatty acid ester Salts; higher fatty acid salts; carboxylic acid type anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkylamide ether carboxylates, alkenyl) amide ether carboxylates and acylaminocarboxylates; Examples thereof include phosphoric acid ester type anionic surfactants such as alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phenyl phosphoric acid ester salts, and glycerin fatty acid ester monophosphoric acid ester salts. Salts in these anionic surfactants include alkali metal salts such as sodium, potassium and lithium; alkaline earth metal salts such as calcium and magnesium; ammonium salts; alkanolamine salts such as monoethanolamine, diethanolamine and triethanolamine Etc.

  Among these, as the component (a2), a saturated or unsaturated α-sulfo fatty acid methyl ester salt, ethyl ester salt or propyl ester salt having 8 to 20 carbon atoms; straight chain having an alkyl group having 8 to 18 carbon atoms Alternatively, a branched alkylbenzene sulfonate (LAS or ABS) is preferable, and an alkylbenzene sulfonate having a linear alkyl group is particularly preferable. Carbon number of this linear alkyl group is 8-18, 8-16 are preferable and 10-14 are more preferable.

As the component (a2), one type may be used alone, or two or more types may be used in appropriate combination.
The content of the component (a2) is preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less with respect to the total mass of the component (A). If the content of the component (a2) in the component (A) is within the above range, the content of the component (a1) can be sufficiently ensured, and the effect of suppressing sebum cleaning power and room drying odor is further enhanced.
The content of the component (a2) is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less with respect to the total mass of the liquid detergent. When the content of the component (a2) in the liquid detergent is within the above range, the low temperature stability is enhanced.

  By using a combination of the (a1) component and the (a2) component, it is possible to obtain a higher room drying odor suppression effect. 0.1-10 are preferable, as for the mass ratio (henceforth "a1 / a2 ratio") represented by (a1) component / (a2) component, 0.3-10 are more preferable, and 1-5 are. Further preferred. If the a1 / a2 ratio is within the above range, the sebum detergency is increased, and the effect of suppressing room drying odor is further enhanced.

  The content of the component (A) is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass with respect to the total mass of the liquid detergent. If content of the (A) component in a liquid cleaning agent is in the said range, when a liquid cleaning agent contains an enzyme, enzyme stability will increase.

<(B) component>
The component (B) is a nonionic surfactant.
(B) As a component, the nonionic surfactant normally used for liquid detergents for garments etc. can be used, for example, fatty acid alkyl ester, higher alcohol, alkylphenol, higher fatty acid, higher fatty acid alkyl ester or higher Alkylene oxide adducts such as 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, alkylamine oxides, alkenylamine oxides , Alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glucosides and the like.
These may be used alone or in combination of two or more.
Among these, as the component (B), the following component (b1) is preferable.

((B1) component)
The component (b1) is a compound represented by the following general formula (2).
R ² —O — [(EO) _s / (PO) _t ] —H (2)
(In General Formula (1), R ² is a hydrocarbon group having 8 to 22 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents the average number of repetitions of EO, 2 ≦ s ≦ 20, t represents the average number of repetitions of PO, and 0 ≦ t ≦ 6.)

In the general formula (2), the number of carbon atoms in ^{R 2} is 8 to 22, preferably from 11 to 18, more preferably 12 to 16, 12 to 14 is more preferable.
The hydrocarbon group for R ² may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Among these, a saturated hydrocarbon group is preferable from the viewpoint of suppressing the generation of a room-dried odor and the appearance stability.
The hydrocarbon group for R ² may be linear or branched. As the hydrocarbon group, an alkyl group and an alkenyl group are preferable.
The carbon atom bonded to the oxygen atom (O) in R ² —O— is preferably a primary carbon atom or a secondary carbon atom. Thereby, the permeability to a to-be-washed object becomes high. In particular, when the liquid cleaning agent of the present invention is used in a method of directly applying to the dirt or the like of clothes, high application cleaning power is easily obtained.
R ² is preferably a branched hydrocarbon group having 8 to 22 carbon atoms or a linear hydrocarbon group having 8 to 22 carbon atoms, and more preferably a linear hydrocarbon group having 8 to 22 carbon atoms. When R ² is a branched hydrocarbon group, the carbon atom bonded to the oxygen atom (O) in R ² —O— is preferably a primary carbon atom. When R ² is a linear hydrocarbon group, the carbon atom bonded to the oxygen atom (O) in R ² —O— is preferably a secondary carbon atom.

In general formula (2), s is the number of 2-20 showing the average repeating number of EO (namely, average addition mole number of ethylene oxide), 2-18 are preferable and 5-16 are more preferable. In particular, when R ² is a hydrocarbon group having 8 to 22 carbon atoms derived from a primary alcohol, s is 2 to 20, preferably 5 to 18, more preferably 7 to 16, and further preferably 12 to 16 preferable. When R ² is a hydrocarbon group having 8 to 22 carbon atoms derived from a secondary alcohol, s is 2 to 20, preferably 2 to 15, more preferably 2 to 9, still more preferably 3 to 9, 7-9 are particularly preferred. When s is within the above range, the permeability to the article to be washed is increased.
In general formula (2), t is the number of 0-6 which represents the average number of repetitions of PO (that is, the average number of moles of propylene oxide added), preferably 0-3, more preferably 0-2, 1 is more preferable. If t is below an upper limit, the permeability to a to-be-washed object will become high.

When t> 0, that is, when PO and EO are mixed, they may be mixed in a random manner or a block shape regardless of the order of arrangement. [(EO) _s / (PO) _t ] in the general formula (2) means that EO and PO are mixed in a random or block form.
When PO and EO are mixed in block form, for example, ethylene oxide and propylene oxide may be added by, for example, adding ethylene oxide, then adding propylene oxide, adding propylene oxide and then adding ethylene oxide, ethylene oxide Examples of the method include adding propylene oxide, and further adding ethylene oxide.

The addition mole number distribution of ethylene oxide or propylene oxide is not particularly limited.
The added mole number distribution is likely to vary depending on the reaction method in producing the component (b1). For example, when ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution of the number of moles of ethylene oxide or propylene oxide is relatively wide. It tends to be. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in JP-B-615038 When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a catalyst, the distribution of the number of moles of ethylene oxide or propylene oxide tends to be relatively narrow.

  Specific examples of the component (b1) include those obtained by adding 7 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms (for example, trade name “Softanol 70” manufactured by Nippon Shokubai Co., Ltd.), 9 to 14 secondary alcohol added with 9 mol of ethylene oxide (for example, trade name “Softanol 90” manufactured by Nippon Shokubai Co., Ltd.), 7 to 12 mol of ethylene oxide And 2 mol equivalent of propylene oxide, 7 mol equivalent of ethylene oxide added to 10 carbon alcohol obtained by subjecting pentanol to the gerbet reaction (trade name “Lutensol XL70” manufactured by BASF), Ethanol equivalent to 6 moles in a C10 alcohol obtained by subjecting pentanol to a garbed reaction N'okishido is obtained by adding (BASF Co., Ltd. under the trade name "Lutensol XA60"), and the like.

As the component (b1), one type may be used alone, or two or more types may be used in appropriate combination.
The content of the component (b1) is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, and still more preferably 50 to 100% by mass with respect to the total mass of the component (B). If content of (b1) component in (B) component exists in the said range, sebum detergency will increase more.
Further, the content of the component (b1) is preferably 5 to 35% by mass, more preferably 5 to 25% by mass, and further preferably 5 to 15% by mass with respect to the total mass of the liquid detergent. If the content of the component (b1) in the liquid detergent is not less than the lower limit value, the sebum detergency is further increased. In addition, the appearance stability of the liquid detergent is further improved. On the other hand, if the content of the component (b1) in the liquid detergent is not more than the upper limit value, the fluidity of the liquid detergent is further increased and the appearance stability is further improved.

  The content of the component (B) is preferably 5 to 35% by mass, more preferably 5 to 30% by mass, and further preferably 5 to 25% by mass with respect to the total mass of the liquid detergent. If content of (B) component in a liquid detergent is more than a lower limit, sebum detergency will increase more. In addition, the appearance stability of the liquid detergent is further improved. On the other hand, if the content of the component (B) in the liquid detergent is not more than the upper limit value, the fluidity of the liquid detergent is further increased and the appearance stability is further improved.

  Moreover, 0.1-10 are preferable, as for mass ratio (henceforth "A / B ratio") represented by (A) component / (B) component, 0.3-10 are more preferable, and 1- 10 is more preferable. If the A / B ratio is equal to or higher than the lower limit, the highly hydrophobic (C) component is less likely to be solubilized in the (B) component, and the (C) component is more easily adsorbed to the fiber. Can be increased. On the other hand, if the A / B ratio is not more than the upper limit value, the appearance stability of the liquid cleaning agent is further improved.

<(C) component>
The component (C) is at least one selected from the group consisting of the following components (c1) and (c2).

((C1) component)
The component (c1) is an antibacterial agent having a phenol structure.
The component (c1) is a component that imparts antibacterial properties to textile products such as clothes after washing. The component (c1) can exhibit antibacterial properties without impairing the detergency of the component (A) and the component (B) even when the component (A) and the component (B) coexist in the liquid detergent.
Here, the “phenol structure” means a structure in which one or more hydrogen atoms of the aromatic hydrocarbon nucleus are substituted with a hydroxy group.

Examples of the component (c1) include known phenol derivatives or diphenyl compounds used in antibacterial agents. Specifically, 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan) ), 4,4′-dichloro-2-hydroxydiphenyl ether (common name: dichrosan), o-benzyl-p-chlorophenol (chlorophene), isopropylmethylphenol, parachlorometaxylenol and the like.
Among these, diphenyl compounds are preferred, and specifically, 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4′-dichloro-2-hydroxydiphenyl ether (common name) : Diclosan) and o-benzyl-p-chlorophenol (chlorophene) are preferable.

  As the component (c1), a 2-hydroxydiphenyl compound represented by the following general formula (3) (hereinafter referred to as “compound (3)” has a high adsorption amount to the fiber and a large effect by applying the present invention. ) ") Is preferred.

In general formula (3), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms, Y is a chlorine atom or a bromine atom, Z is _{SO 2} H, NO 2, or alkyl of 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.
In addition,-(Y) _b means that _b hydrogen atoms of the benzene ring are substituted with Y. The same applies to-(Y) _c ,-(Z) _d ,-(OH) _m, and-(OH) _n .

  As the compound (3), 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 (3) include 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 a compound in which m is 0 and n is 0), dichlorohydroxydiphenyl ether (X is an oxygen atom, a is 1, Y is a chlorine atom, b is 1, c Is a compound in which d is 0, m is 0, and n is 0), trichlorohydroxydiphenyl ether (X is an oxygen atom, a is 1, Y is a chlorine atom, b Or one of c is 1 and the other is 2, d is 0, m is 0, and n is 0), benzylchlorophenol (X is a methylene group, a is 1; Y is a chlorine atom, b is 0, c Is 1, d is 0, m is 0, compounds wherein n is 0) and the like.

  As the compound (3), 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4′-dichloro-2-hydroxydiphenyl ether (common name: dichrosan), o- It is benzyl-p-chlorophenol (common name: chlorophene), and 4,4′-dichloro-2-hydroxydiphenyl ether (common name: dichrosan) is particularly preferred.

  60 mass% or more is preferable with respect to the total mass of (c1) component, as for content of a compound (3), 80 mass% or more is more preferable, and 90 mass% or more is further more preferable. The upper limit of the ratio of the total amount of compound (3) is 100% by mass.

As the component (c1), one type may be used alone, or two or more types may be used in appropriate combination.
(C1) As for content of a component, 10-100 mass% is preferable with respect to the total mass of (C) component, 30-100 mass% is more preferable, 50-100 mass% is further more preferable. When the content of the component (c1) in the component (C) is within the above range, the effect of suppressing the room-drying odor is further enhanced.

(Component (c2))
The component (c2) is at least one selected from the group consisting of polylysine, polyhexamethylene biguanide, and 2- (4-thiocyanomethylthio) benzimidazole.
The component (c2) is a component that imparts antibacterial properties to textile products such as clothes after washing.

(C2) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
(C2) As for content of a component, 10-100 mass% is preferable with respect to the total mass of (C) component, 30-100 mass% is more preferable, 50-100 mass% is further more preferable. When the content of the component (c2) in the component (C) is within the above range, the effect of suppressing the room drying odor is further enhanced.

  As component (C), either one of component (c1) or component (C2) may be included, or both may be included, but at least ( It is preferable that c1) component is included.

  The content of the component (C) is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, and 0.1 to 0.5% by mass with respect to the total mass of the liquid detergent. Further preferred. If content of (C) component in a liquid cleaning agent is more than a lower limit, it will be easy to acquire the favorable inhibitory effect of room drying odor. On the other hand, if the content of the component (C) in the liquid detergent is not more than the upper limit value, the liquid detergent tends to have good storage stability.

  Moreover, 3-600 are preferable, as for mass ratio (henceforth "A / C ratio") represented by (A) component / (C) component, 5-400 are more preferable, and 10-200 are more preferable. . If A / C ratio is more than a lower limit, sebum detergency and recontamination prevention property will increase more. On the other hand, if A / C ratio is below an upper limit, antibacterial property will increase more.

<(D) component>
(D) A component is a saccharide-degrading enzyme.
Generation | occurrence | production of the room-drying odor from the to-be-washed | cleaned material after washing can be suppressed more effectively because a liquid cleaning agent further contains (D) component.

Examples of the component (D) include amylase, mannanase, pectinase, xylanase, glucoamylase, glucosidase, glucanase, dextranase, chitinase, sialidase, mannosidase, saccharase, fucosidase, alginate lyase, pectin lyase and the like.
Among these, amylase, mannanase, and pectinase are preferable because an effect of suppressing the generation of room-dried odor is more easily obtained.

Component (D) may be used in the form of a preparation containing a saccharide-degrading enzyme (carbohydrate-degrading enzyme preparation).
The commercially available product of the component (D) that is specifically available is an enzyme preparation containing amylase (amylase preparation): Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stanzyme Plus 12L (available from Novozymes) Product name); trade name Maxamyl available from Genencor; trade name pullulanase Amano available from Amano Enzyme Inc .; trade name DB-250 available from Seikagaku Corporation.
Examples of the enzyme preparation containing mannanase (mannanase preparation) include trade name Mannaway 4L available from Novozymes.
Examples of the enzyme preparation containing pectinase (pectinase preparation) include trade name Xspect 1000L available from Novozymes.

(D) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
The content of the component (D) is preferably 0.01 to 2% by mass, more preferably 0.03 to 1.5% by mass, and 0.05 to 1% by mass with respect to the total mass of the liquid detergent. Further preferred. If content of (D) component in a liquid cleaning agent is more than a lower limit, a cleaning effect and the suppression effect of a room-drying odor will increase more. This effect reaches its peak when the content of the component (D) exceeds the upper limit. If content of (D) component is below an upper limit, it can suppress that (D) component precipitates during preservation | save of a liquid detergent, and suppresses the increase in cost, maintaining storage stability favorably. Can do.
In the present specification, “content of component (D) (mass%)” contained in the liquid detergent refers to “content (mass%) of saccharide-degrading enzyme preparation” contained in the liquid detergent. means.

<(E) component>
The component (E) is an enzyme other than a saccharide-degrading enzyme.
When the liquid detergent further contains the component (E), the detergency against protein soil is enhanced. Moreover, the effect of removing the odor of the object to be washed is also obtained. In addition, during the washing of the object to be washed, protein stains that become a recontamination binder are decomposed, so that recontamination to polyester and other chemical fibers and cotton is suppressed. In particular, the combined use of the component (D) and the component (E) further enhances the cleaning power against various types of dirt. In addition, it is possible to more effectively suppress the generation of a room-drying odor from the laundry after washing.

(E) As a component, the well-known enzyme conventionally used for the detergent for clothing can be used, For example, protease, a cellulase, etc. are mentioned.
The component (E) may be used in the form of a preparation containing an enzyme other than the saccharide-degrading enzyme. Hereinafter, an enzyme preparation containing protease is referred to as “protease preparation”, and an enzyme preparation containing cellulase is referred to as “cellulase preparation”.
Examples of protease preparations include, but are not limited to, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L, Everse 16L, Everse 16L, Eberse 16L, Eberse 16L .5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L; trade names available from Genencor, Inc., such as Purefect L, Purefect OX, Proper, etc.

  Among the above-mentioned components, as the component (E), trade names: Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase Ultra 16L, Equalase Ultra 16L, Liquidase 2.5L, Liquidase 2.5L, Liquidase UltraL2.5 .5L, Alcalase Ultra 2.5L, and Coronase 48L are preferred, and Everase 16L, Alcalase 2.5L, and Coronase 48L are particularly preferred.

  Examples of cellulase preparations include Endolase 5000L, Celluzyme 0.4L, Carezyme Premium 4500L (above, trade names) available from Novozymes.

  As a combination of the component (D) and the component (E), for example, a combination of amylase and protease (specifically, a combination of amylase and coronase) from the viewpoint of the effect of preventing re-contamination on polyester (PE) cloth. A combination of mannanase and protease (specifically, a combination of mannanase and coronase) and a combination of amylase and cellulase are preferable.

(E) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
(E) As for content of a component, 0.01-2 mass% is preferable with respect to the total mass of a liquid detergent, 0.03-1.5 mass% is more preferable, 0.05-1 mass% is Further preferred. If the content of the component (E) in the liquid detergent is not less than the lower limit value, the blending effect of the component (E) can be sufficiently obtained. On the other hand, if the content of the component (E) in the liquid cleaning agent is not more than the upper limit value, it is possible to suppress the precipitation of the component (E) during storage of the liquid cleaning agent while maintaining good storage stability. , Increase in cost can be suppressed. This effect reaches its peak when the content of the component (E) exceeds the upper limit.
In this specification, “content of component (E) (% by mass)” contained in the liquid detergent refers to “content of a preparation containing an enzyme other than a saccharide-degrading enzyme (mass%)” contained in the liquid detergent ( Mass%) ”.

  The total content of the component (D) and the component (E) is preferably 1.5% by mass or less based on the total mass of the liquid detergent, based on the total mass of the liquid detergent. 1.0 mass% is more preferable and 0.1-0.8 mass% is further more preferable. If the sum total of content of (D) component and (E) component is below an upper limit, aggregation of an enzyme will not occur easily and the external appearance stability of a liquid detergent will become more favorable.

In the present invention, “mass ratio represented by component (D) / component (E)” means “component (D) relative to“ content (mass%) of component (E) ”contained in the liquid detergent. "Content (% by mass)".
The mass ratio represented by component (D) / component (E) (hereinafter also referred to as “D / E ratio”) is preferably 0.05 to 20, more preferably 0.1 to 15, and 2 to 10 is more preferable, 0.25 to 5.0 is particularly preferable, and 0.25 to 2.0 is most preferable. If the D / E ratio is equal to or higher than the lower limit, the effect of preventing recontamination is further increased. On the other hand, if the D / E ratio is not more than the upper limit value, the deactivation of the (D) component by the (E) component is suppressed.

<Water>
The liquid detergent of the present invention preferably contains water from the viewpoints of ease of handling during production, solubility in water when used, and the like.
Examples of water include purified water, distilled water, ion exchange water, pure water, and ultrapure water.
The water content is preferably 10% by mass or more, more preferably 10 to 60% by mass, further preferably 25 to 55% by mass, and particularly preferably 30 to 45% by mass with respect to the total mass of the liquid detergent.

<Optional component>
As long as the liquid detergent is within the range not impairing the effects of the present invention, components other than (A) component, (B) component, (C) component, (D) component, (E) component and water (arbitrary component) ) May be contained.
As an arbitrary component, the component normally used for liquid detergents for clothes etc. can be mix | blended, For example, what is shown below is mentioned.

(solvent)
The liquid cleaning agent may contain a solvent (excluding water). As a solvent, what is necessary is just a solvent normally used for liquid detergents for clothes etc., for example, C2-C4 monohydric alcohol, C2-C4 polyhydric alcohol, glycol ether solvent, Examples thereof include water-miscible organic solvents such as alcohol having a methoxy group.

Examples of the monohydric alcohol 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, glycerin and the like.
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, diethylene glycol monobutyl ether (butyl carbitol), and the like.
Examples of the alcohol having a methoxy group include 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, 3-methoxy- 2-methylbutanol, 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-propiyl Butyl acetate, 3-methoxy-1-methyl-butyl acetate, 3-methoxy-1-ethyl butyl acetate, and 3-methoxy-1-propyl-butyl acetate.
One of these solvents may be used alone, or two or more thereof may be used in appropriate combination.
The content of the solvent is preferably 0.1 to 15% by mass with respect to the total mass of the liquid detergent.

(Thickener and solubilizer)
Thickeners and solubilizers include aromatic sulfonic acids or salts thereof, specifically, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, toluene sulfonate. Xylene sulfonate, cumene sulfonate, substituted or unsubstituted naphthalene sulfonate, and the like.
Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
These may be used alone or in combination of two or more.
The content of the thinning agent and the solubilizer is preferably 0.01 to 15% by mass with respect to the total mass of the liquid detergent. If it is in the said range, in the liquid surface of a liquid cleaning agent, the production | generation suppression effect of the film | membrane formed when this liquid cleaning agent gelatinizes will improve.

(Alkaline agent)
Examples of the alkaline agent include monoethanolamine, diethanolamine, and triethanolamine. Alkaline agents can be used alone or in combination.
These alkali agents may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
The content of the alkaline agent is preferably 0.5 to 5% by mass with respect to the total mass of the liquid detergent.

(Antioxidant)
The antioxidant is not particularly limited, but is preferably a phenolic antioxidant because of its good detergency and liquid stability. Among them, monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole are preferred. Agents, bisphenol antioxidants such as 2,2′-methylenebis (4-methyl-6-t-butylphenol), phenol antioxidants such as dl-α-tocopherol are more preferable, monophenol antioxidants, Molecular type antioxidants are more preferred.
Of the monophenolic antioxidants, dibutylhydroxytoluene is particularly preferred. Among the polymer type phenol antioxidants, dl-α-tocopherol is particularly preferable.
These antioxidants may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
As for content of antioxidant, 0.01-2 mass% is preferable with respect to the total mass of a liquid detergent.

(Preservative)
Examples of the preservative include trade name “Caisson CG” manufactured by Rohm and Haas.
The content of the preservative is preferably 0.001 to 1% by mass with respect to the total mass of the liquid detergent.

(Other)
In addition to the optional components described above, the liquid detergent may contain, for example, benzoic acid or a salt thereof (also effective as a preservative) for the purpose of improving storage stability. Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
The content of benzoic acid (salt) is preferably 0.1 to 5% by mass and more preferably 0.15 to 2% by mass with respect to the total mass of the liquid detergent.

The liquid detergent contains 0 to 2% by mass of calcium salts such as boric acid, borax, formic acid or salts thereof, calcium chloride, and calcium sulfate for the purpose of enzyme stabilization with respect to the total mass of the liquid detergent. May be.
The liquid detergent may contain 0 to 5% by mass of silicone such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone for the purpose of improving the texture with respect to the total mass of the liquid detergent.
The liquid detergent may contain 0 to 1% by mass of a fluorescent whitening agent such as a distyrylbiphenyl type for the purpose of improving the whiteness of white clothing with respect to the total mass of the liquid detergent.
The liquid detergent may contain 0 to 2% by mass of an anti-contamination agent and an anti-contamination agent such as polyvinyl pyrrolidone and carboxymethyl cellulose for the purpose of preventing recontamination with respect to the total mass of the liquid detergent.
The liquid detergent may contain a pearl agent, a soil release agent and the like.

The liquid detergent may contain a flavoring agent, a coloring agent, an emulsifying agent, an extract such as a natural product, and the like for the purpose of improving the added value of the product.
As typical examples of the flavoring agents, fragrance compositions A, B, C, D and the like described in Tables 11 to 18 of JP-A-2002-146399 can be used.
The content of the flavoring agent is preferably 0.1 to 1% by mass with respect to the total mass of the liquid detergent.

Colorants include general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, and Turquoise P-GR (all trade names) Is mentioned.
The content of the colorant is preferably 0.00005 to 0.005 mass% with respect to the total mass of the liquid detergent.

Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples include polystyrene emulsion (manufactured by Syden Chemical Co., Ltd., trade name “Cybinol RPX-196 PE-3”, solid content 40% by mass).
The content of the emulsion is preferably 0.01 to 0.5% by mass with respect to the total mass of the liquid detergent.

Examples of extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, and the like plant extracts such as St. John's Wort.
The content of extracts such as natural products is preferably 0 to 0.5% by mass with respect to the total mass of the liquid detergent.

  In addition, the sum total of content of all the components contained in a liquid detergent shall be 100 mass%.

<Manufacturing method>
The liquid cleaning agent of the present invention dissolves, for example, the above-described component (A), component (B) and component (C) and, if necessary, component (D), component (E) and optional components in water. And it can manufacture by adjusting to predetermined pH using a pH adjuster.
When the liquid detergent contains a flavoring agent, the premix may be formed by premixing the component (C) and the flavoring agent before blending them into the liquid detergent. By forming the premix, the highly hydrophobic component (C) can be more stably blended in the liquid detergent. The mixing method may be a general method, and the temperature during mixing is preferably 5 to 30 ° C. The premix can be stored for a long time, but when stored at a low temperature, the component (C) may be precipitated.

<PH>
4-9 are preferable and, as for pH at 25 degreeC of the liquid cleaning agent of this invention, 6-9 are more preferable.
If the pH of the liquid detergent at 25 ° C. is within the above range, the storage stability of the liquid detergent is maintained well.
In the present invention, the pH of the liquid detergent indicates a value measured by adjusting the liquid detergent to 25 ° C. and using a pH meter or the like.
The pH of the liquid detergent can be adjusted by blending a pH adjuster as necessary. The pH adjuster is optional as long as the effects of the present invention are not impaired, but sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of liquid stability.

<Effect>
Since the liquid detergent of the present invention described above contains the above-mentioned component (A), component (B) and component (C), it is excellent in sebum detergency. In addition, since the liquid cleaning agent of the present invention can easily adsorb the component (C) on the washed object and can impart excellent antibacterial properties, the generation of a room-drying odor from the washed object after washing. High suppression effect.

The liquid detergent of the present invention is suitable as a liquid detergent for clothing.
The method of using the liquid detergent of the present invention is the same as the method of using a normal liquid detergent. That is, the liquid detergent of the present invention (the product of the present invention) is poured into water together with the article to be washed during washing, the method of directly applying the product of the present invention to mud and sebum soil, and the product of the present invention in water. Examples include a method of dissolving and immersing clothes. Also preferred is a method in which the product of the present invention is applied to the article to be washed, and then allowed to stand as appropriate, followed by ordinary washing using ordinary washing liquid. At that time, the amount of the product of the present invention can be substantially reduced below the amount of the conventional liquid detergent.
Examples of the types of items to be cleaned include those similar to those to be cleaned by washing at home, and examples thereof include textiles such as clothes, cloths, towels, and sheets.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. In addition, the compounding quantity of the component used in each example is a pure conversion value unless there is particular notice.

"Raw material"
As the component (A), the following compounds were used.
A1-1: Polyoxyethylene propylene alkyl ether sodium sulfate (AEPS). In the general formula (1), R ¹ = a linear alkyl group having 12 to 14 carbon atoms, p = 1, q = 1, M ⁺ = sodium ion, v = 1. Synthesized by the following synthesis method.
A1-2: sodium polyoxyethylene alkyl ether sulfate (AES). In the general formula (1), R ¹ = a linear alkyl group having 12 to 14 carbon atoms, p = 1, q = 0, M ⁺ = sodium ion, v = 1. Synthesized by the following synthesis method.
A2-1: Sodium lauryl sulfate (manufactured by Wako Pure Chemical Industries, Ltd., trade name “sodium dodecyl sulfate”).
A2-2: linear alkylbenzene sulfonate (product name “Lypon LH-200”, manufactured by Lion Corporation, carbon number of alkyl group: 10-14, average molecular weight: 322).

(Synthesis method of a1-1)
224.4 g of a natural alcohol (trade name “CO-1270”, a mixture of a 12 carbon alcohol and a 14 carbon alcohol in a mass ratio of 75/25) as a raw material alcohol, and a 30% by mass NaOH aqueous solution Was charged into an autoclave having a capacity of 4 L, and the inside of the autoclave was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. Next, while stirring the reaction solution, 52 g of ethylene oxide (gaseous) was gradually added to the reaction solution for reaction. At this time, ethylene oxide was added to the reaction solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 145 ° C. and a pressure of 0.3 MPa or less for 30 minutes. Thereafter, 68 g of propylene oxide (gaseous) was gradually added to the reaction solution to cause a reaction. At this time, propylene oxide was added to the reaction solution while adjusting the addition rate using a blowing tube.
After the addition of propylene oxide, aging was performed at a temperature of 145 ° C. and a pressure of 0.3 MPa or less for 30 minutes. Thereafter, unreacted propylene oxide was distilled off.
Next, after cooling the temperature of the reaction solution to 100 ° C. or less, 70% by mass p-toluenesulfonic acid is added to neutralize the pH of the 1% by mass aqueous solution of the reaction product to about 7, and the intermediate is Obtained.
Next, 237 g of the obtained intermediate was placed in a 500 mL flask equipped with a stirrer, and the inside of the flask was replaced with nitrogen. Then, 96 g of liquid sulfuric anhydride (sulfane) 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 propylene alkyl ether sulfuric acid. Subsequently, a1-1 was obtained by neutralizing the obtained polyoxyethylene propylene alkyl ether sulfuric acid with a sodium hydroxide aqueous solution.

(Synthesis method of a1-2)
400 g of natural alcohol (trade name “CO-1270”, mixture of 12 carbons and 14 carbons in a mass ratio of 75/25) as raw material alcohol and potassium hydroxide as a reaction catalyst 0.8 g was charged into a 4 L autoclave, and the inside of the autoclave was purged with nitrogen. Then, it heated up to 180 degreeC, stirring a reaction liquid. Subsequently, 91 g of ethylene oxide (gaseous) was gradually added to the reaction solution while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less to obtain an alcohol ethoxylate.
About the alcohol ethoxylate obtained, a gas chromatograph mass spectrometer (manufactured by Hewlett-Packard, product name “GC-5890”), a flame ionization detector (FID), and a column (manufactured by HP, product name “ As a result of analysis using Ultra-1L (25 m × φ0.2 mm × T0.11 μm), the average added mole number of ethylene oxide was 1.0. Moreover, the compound which has not added ethylene oxide was 43 mass% with respect to the total mass of the obtained alcohol ethoxylate.

  Next, 237 g of the alcohol ethoxylate obtained above was put into a 500 mL flask equipped with a stirrer, and the inside of the flask was replaced with nitrogen. Then, 96 g of liquid sulfuric anhydride (sulfane) was slowly added while maintaining the reaction temperature at 40 ° C. It was dripped. After completion of the dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Subsequently, a1-2 was obtained by neutralizing the obtained polyoxyethylene alkyl ether sulfuric acid with a sodium hydroxide aqueous solution.

As the component (B), the following compounds were used.
B1-1: A product obtained by adding 7 mol of ethylene oxide to a secondary alcohol having 12 carbon atoms and a secondary alcohol having 14 carbon atoms. (Nippon Shokubai Co., Ltd., trade name “Softanol 70”). In the general formula (2), R ² = a hydrocarbon group derived from a secondary alcohol having 12 carbon atoms and a secondary alcohol having 14 carbon atoms, s = 7, t = 0.
B1-2: Polyoxyethylene alkyl ether (EO added mole number 15) (manufactured by Lion Chemical Co., Ltd., trade name “LMAO-90”). In the general formula (2), R ² = a linear alkyl group having 12 to 14 carbon atoms, s = 15, t = 0.
B1-3: polyoxyethylene alkyl ether (trade name “Rutensol XA60”, manufactured by BASF Corp.) obtained by adding 6 moles of ethylene oxide to an alcohol having 10 carbon atoms obtained by subjecting pentanol to garvet reaction . In the above general formula (2), R ² = branched chain (garvet type) alkyl group having 10 carbon atoms, s = 6, t = 0.

As the component (C) and its substitute (component (C ′)), the following compounds were used.
C1-1: 5-chloro-2- (2,4-dichlorophenoxy) phenol (trade name “Triclosan” manufactured by Wako Pure Chemical Industries, Ltd.)
C1-2: 4,4′-dichloro-2-hydroxydiphenyl ether (manufactured by BASF, trade name “Tinosan HP100”).
C2-1: Polylysine (trade name “Polylysine 25% aqueous solution” manufactured by Chisso Corporation).
C′-1: didecyldimethylammonium chloride (manufactured by Lion Specialty Chemicals, trade name “Arcade 210”).

As the component (D), the following compounds were used.
D-1: Amylase (manufactured by Novozymes, trade name “Stainzyme 12L”).

As the component (E), the following compounds were used.
E-1: Protease (manufactured by Novozymes, trade name “Coronase 48L”).

The following compounds were used as the solvent and water.
PG: Propylene glycol (water-miscible organic solvent, manufactured by Wako Pure Chemical Industries, Ltd., trade name “propylene glycol”).
BC: butyl carbitol (water-miscible organic solvent, manufactured by Tokyo Chemical Industry Co., Ltd., trade name “butyl carbitol”).
-Water: Purified water (manufactured by Kanto Chemical Co., Inc.).

"Examples 1-14, Comparative Examples 1-6"
<Preparation of liquid detergent>
According to the composition shown in Tables 1 to 3, (A) component, (B) component, (C) component or (C ′) component, (D) component, (E) component, solvent and water After mixing a part and adding a suitable amount of pH adjuster (sodium hydroxide or sulfuric acid) so that the pH of the resulting mixture at 25 ° C. is 7.0, the total amount is 100% by mass. Water was added to each to obtain a liquid detergent for each example. A pH meter (manufactured by Tokyo Keiki Co., Ltd., product name “HM-30G”) was used for pH measurement.
About the obtained liquid detergent of each example, the sebum detergency and the inhibitory effect of room drying odor were evaluated as follows. These results are shown in Tables 1-3.

<Evaluation>
(Evaluation of sebum detergency)
For the evaluation of sebum detergency, a liquid detergent immediately after production in each example (a product immediately after production) was used.
As the dirt cloth, a wet artificial dirt cloth (manufactured by the Laundry Science Association) cut into 5 cm × 5 cm square was used.
A Terg-O-meter (manufactured by UNITED STATES TESTING) was used as a cleaning tester.
As a cleaning solution, a solution prepared by adding 300 μL of a liquid cleaning agent to 900 mL of water and stirring for 30 seconds was used.

Into the cleaning tester, 900 mL of cleaning liquid, 10 pieces of dirt cloth, and cleaning knitted cloth are added, and washed at 120 rpm, 15 ° C. for 10 minutes in accordance with the bath ratio 20 times (washing water / total weight of washing object). did. Thereafter, it was transferred to a two-tank washing machine (product name “CW-C30A1-H1” manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, and then 3 in 30 L of tap water (water temperature about 15 ° C., hardness about 3 ° DH). Rinse for minutes and air dry.
The color difference meter (Nippon Denshoku Co., Ltd.) reflects the reflectance of the evaluation cloth (here, the evaluation cloth refers to a white cloth that is not adhered to a reference and is a reference white cloth), unwashed and washed dirt cloth. Manufactured, product name “SE200 type”), and the washing rate (%) was determined by the following formula. The evaluation criteria for the sebum detergency were “passed” when the cleaning rate was 50% or more, and “failed” when the cleaning rate was less than 50%.
Washing rate (%) = (K / S of soiled cloth before washing−K / S of soiled cloth after washing) / (K / S of soiled cloth before washing−K / S of cloth for evaluation) × 100
However, “K / S” is a value obtained by (1-R / 100) ² / (2R / 100) (R is the reflection of the evaluation cloth, the dirt cloth before washing, or the dirt cloth after washing). Rate (%).

(Evaluation of the effect of suppressing room odor)
Wash the cotton shirt (100% cotton) with a washing machine (product name “JW-Z23A type” manufactured by Haier) for 10 minutes (pour tap water with a water temperature of about 20 ° C. and a hardness of about 3 ° DH, bath ratio 20 Double). At that time, a commercially available synthetic detergent (product name “Top”, manufactured by Lion Corporation) was used as a cleaning agent, and the washing amount was 25 g / 30 L of tap water.
The washed cotton skin shirt was dried in a room at about 23 ° C. and a relative humidity of 90% RH for 5 hours. Next, after a cotton skin shirt was worn by 10 males in their 20s and 40s for 12 hours, a normal course of a washing machine (product name “JW-Z23A type” manufactured by Haier) using the liquid detergent of each example Then, a washing process was performed (pour tap water having a water temperature of about 20 ° C. and a hardness of about 3 ° DH, bath ratio 20 times). At that time, the washing process was performed by setting the amount of the liquid detergent to the washing machine to 10 mL / 30 L of tap water. A new 100% cotton BVD skin shirt (manufactured by Fujibo Holdings Co., Ltd.), a fully automatic washing machine (manufactured by Panasonic Corporation, product name “NA-F70SD1”) as a clothing for bath ratio matching. What was washed 5 times (injected with tap water having a water temperature of about 20 ° C. and a hardness of about 3 ° DH) was used.
After the cotton skin shirt was washed, it was dried in a room at room temperature (about 23 ° C.) and a relative humidity of 90% RH and dried for 5 hours (room drying). After that, six expert panelists each performed a sensory evaluation of sniffing the odor of the cotton shirt after drying (drying in the room) for 5 hours. The sensory evaluation was performed by scoring based on the following evaluation criteria. Specifically, a specialized panel sniffs each odor of the cotton skin shirt after drying the room, and evaluated according to the 6-level odor intensity display in the following evaluation criteria. And the average score of the cotton skin shirt was calculated, the effect which suppresses generation | occurrence | production of room-drying odor was evaluated by using this average score as an index, and the average score was 2.0 or less.
[Evaluation criteria for sensory evaluation (odor intensity display)]
0 point: There is no off-flavor.
1 point: A strange odor can be perceived at last.
2 points: The off-flavor is felt weak.
3 points: A strange odor is felt slightly stronger.
4 points: Strong odor is felt.
5 points: A strange odor is felt intensely.

In Tables 1 to 3, “balance” is the blending amount (mass%) of water (purified water) necessary to make the liquid detergent as a whole 100 mass%.
“A1 / A” is the content of the component (a1) relative to the total mass of the component (A). The “a1 / a2 ratio” is a mass ratio represented by (a1) component / (a2) component. “A / B ratio” is a mass ratio represented by (A) component / (B) component. “A / C ratio” is a mass ratio represented by (A) component / (C) component. The “A / C ′ ratio” is a mass ratio represented by (A) component / (C ′) component. "D / E ratio" is a mass ratio represented by (D) component / (E) component.

As is clear from Tables 1 and 2, the liquid detergents of each Example had a high sebum detergency and were able to suppress the occurrence of room-dried odors from the washed objects after washing.
On the other hand, as apparent from Table 3, the liquid cleaning agent of Comparative Example 1 that does not contain the component (C) and the liquid cleaning agents of Comparative Examples 2 to 6 that do not contain the component (a1) both generate room-dried odors. Could not be suppressed.

Claims (4)

Liquid detergent containing the following (A) component, (B) component, and (C) component.
(A) Component: An anionic surfactant containing the following component (a1).
(A1) Component: A compound represented by the following general formula (1).
^{_{R 1 -O - [(EO)}} p / (PO) q] -SO 3 - 1 / v · M + ··· (1)
(In General Formula (1), R ¹ is an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, and p represents EO. Is the number satisfying 0 ≦ p ≦ 10, q is the average number of PO repeating, 0 ≦ q ≦ 5, and M ⁺ is a cation other than hydrogen ions. , V is the valence of M ⁺ , where p and q are not 0 at the same time, and 0 <p ≦ 2 is satisfied when q = 0.)
(B) component: Nonionic surfactant.
(C) Component: At least one selected from the group consisting of the following components (c1) and (c2).
(C1) Component: an antibacterial agent having a phenol structure.
(C2) Component: At least one selected from the group consisting of polylysine, polyhexamethylene biguanide, and 2- (4-thiocyanomethylthio) benzimidazole.   The liquid cleaning agent according to claim 1, wherein the component (C) includes at least the component (c1). The liquid cleaning agent according to claim 1 or 2, wherein the component (B) includes the following component (b1).
(B1) Component: A compound represented by the following general formula (2).
R ² —O — [(EO) _s / (PO) _t ] —H (2)
(In General Formula (2), R ² is a hydrocarbon group having 8 to 22 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents the average number of repetitions of EO, 2 ≦ s ≦ 20, t represents the average number of repetitions of PO, and 0 ≦ t ≦ 6.) The liquid cleaning agent as described in any one of Claims 1-3 which further contains the following (D) component.
(D) Component: Glycolytic enzyme.