JP2020041074A - Liquid detergent composition for clothing - Google Patents

Abstract

To provide a liquid detergent composition for clothing which is easy to be adsorbed in clothing to be cleaned and exhibit higher antibacterial effects.SOLUTION: The liquid detergent composition for clothing includes a component (A), a component (B), and a component (C) mentioned below. The component (A) is one or more selected from the group consisting a component (a1) and a component (a2) mentioned below. The component (a1) is a cationized cellulose. The component (a2) is one or more selected from the group consisting a diallyl quaternary ammonium salt polymer and a diallyl quaternary ammonium salt-acrylamide copolymer. The component (B) is an antibacterial agent having a phenolic structure. The component (C) is an anionic surfactant.SELECTED DRAWING: None

Description

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

  In recent years, with increasing awareness of hygiene, many liquid detergents containing antibacterial agents such as cationic surfactants and cationic polymers have been put on the market. Cationic surfactants and cationic polymers have good adsorption to cotton cloth and exhibit antibacterial properties. However, cationic surfactants and cationic polymers have significantly reduced antibacterial properties in the presence of anionic surfactants. When only a nonionic surfactant is used without containing an anionic surfactant, re-staining prevention property and liquid stability are reduced. The re-contamination prevention property refers to a property of preventing dirt detached from an object to be washed (such as textiles) during washing from attaching to the object to be washed again. Liquid stability refers to a property in which solidification, precipitation, turbidity and separation hardly occur during storage for a certain period.

  In order to solve such a problem, an antibacterial agent having a high antibacterial effect (antibacterial property) in the presence of an anionic surfactant has been studied. Patent Literature 1 proposes a liquid detergent composition containing an anionic surfactant and a nonionic antibacterial agent. The liquid detergent composition of Patent Document 1 achieves both desired cleaning performance and antibacterial effect.

JP-T-2017-514967

  However, the nonionic antibacterial agent is less likely to be adsorbed on the object to be washed as compared with a cationic surfactant or a cationic polymer. In addition, the nonionic antibacterial agent is taken into the surfactant in the presence of the surfactant at a high concentration, and it is difficult to exhibit the antibacterial effect.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent composition for clothing that can be easily adsorbed to a washing object and can exhibit a higher antibacterial effect.

As a result of intensive studies, the present inventors have found that the above problem can be solved by combining a quaternary nitrogen-containing polymer with a specific antibacterial agent.
Furthermore, the present inventors have found that a liquid detergent composition for clothing that combines a quaternary nitrogen-containing polymer and a specific antibacterial agent has excellent liquid stability.
That is, the present invention has the following aspects.

[1] A liquid detergent composition for clothing, comprising the following components (A), (B) and (C).
Component (A): at least one selected from the group consisting of the following components (a1) and (a2).
Component (a1): cationized cellulose.
Component (a2): at least one selected from the group consisting of a diallyl quaternary ammonium salt polymer and a diallyl quaternary ammonium salt-acrylamide copolymer.
Component (B): an antibacterial agent having a phenol structure.
Component (C): anionic surfactant.
[2] The liquid detergent composition for clothing according to [1], wherein the component (B) is 4,4′-dichloro-2-hydroxydiphenyl ether.
[3] The liquid detergent composition for clothing according to [1] or [2], wherein the content of the component (A) is 0.1% by mass or more and 5% by mass or less based on the total mass.
[4] The liquid detergent for clothing according to any one of [1] to [3], wherein the content of the component (B) is 0.01% by mass or more and 3% by mass or less based on the total mass. Composition.
[5] The liquid detergent composition for clothing according to any one of [1] to [4], wherein the mass ratio represented by the component (A) / the component (C) is 0.002 or more and 2 or less. .
[6] The liquid detergent composition for clothing according to any one of [1] to [5], further comprising (D) a component: a water-miscible organic solvent.

  ADVANTAGE OF THE INVENTION According to the liquid detergent composition for clothing of this invention, it adsorb | sucks easily to a to-be-washed thing and can exhibit a higher antibacterial effect.

[Liquid detergent composition for clothing]
The liquid detergent composition for clothing of the present invention (hereinafter, also simply referred to as a liquid detergent) is a composition containing the component (A), the component (B), and the component (C).

<(A) component>
The component (A) is at least one selected from the group consisting of the following components (a1) and (a2). The component (A) contains quaternary nitrogen. When the liquid detergent of the present invention contains the component (A), the component (B) can be easily adsorbed to an object to be washed.
Component (a1): cationized cellulose.
Component (a2): at least one selected from the group consisting of a diallyl quaternary ammonium salt polymer and a diallyl quaternary ammonium salt-acrylamide copolymer.

((A1) component)
The component (a1) is a cationized cellulose. The component (a1) is represented by the following general formula (I) and has a substituted anhydrous glucose unit as a repeating unit.
The component (a1) is substituted with a nonionic or cationic hydrophobic substituent containing an alkyl group or an arylalkyl group having 8 to 24 carbon atoms and a cationic substituent of the following formula (II). The component (a1) has an average of 0.0003 to 0.08 mol of the above substituent per mol of the anhydrous glucose unit.

(I) In the formula, R ^{1 to} R ³ each independently include H, CH ₃ , an alkyl group having 8 to 24 carbon atoms, an alkyl group having 8 to 24 carbon atoms, or an arylalkyl group having 8 to 24 carbon atoms. It is a nonionic substituent, a cationic substituent containing an alkyl group having 8 to 24 carbon atoms or an arylalkyl group having 8 to 24 carbon atoms, or a group represented by the following formula (II). d is a number from 4000 to 10000 representing the number of repetitions.
When R ^{1 to} R ³ are an alkyl group or a substituent containing an alkyl or arylalkyl group, the alkyl group of these substituents may be linear or branched.

In the formula (II), p is 0 to 10, and R ⁴ is H, CH ₃ , an alkyl group having 8 to 24 carbon atoms, a group represented by the following formula (III), or other carbon atoms having 8 carbon atoms. To 24 including alkyl groups.
When R ⁴ is an alkyl group or a substituent containing an alkyl group, the alkyl group of these substituents may be linear or branched.

(III) In the formula, R ⁵ and R ⁶ are each independently CH ₃ , C ₂ H ₅ , and R ⁷ are H, CH ₃ , an alkyl group having 8 to 24 carbon atoms, or an arylalkyl having 8 to 24 carbon atoms. The group, R ^8, is CH ₂ CHOHCH ₂ or CH ₂ CH ₂ . Z is a water-soluble anion.
Examples of Z include a chloride ion and a bromide ion.

R ¹ is preferably a group represented by the formula (II).
When R ¹ is a group represented by the formula (II), p is preferably 0 to 3.
R ⁴ is preferably a group represented by the formula (III). In this case, R ^{5 to} R ⁷ are preferably CH ₃ , R ⁸ is preferably CH ₂ CHOCH ₂ , and Z is preferably a chloride ion or a bromide ion.

The average degree of substitution of R ¹ is preferably 0.0003 mol or more, more preferably 0.0005 mol or more, per 1 mol of anhydrous hydroglucose unit. The upper limit is preferably 0.08 mol or less, more preferably 0.07 mol or less, and even more preferably 0.05 mol or less per 1 mol of anhydrous hydroglucose unit.

R ² is preferably a group represented by the formula (II).
When R ² is a group represented by the formula (II), p is preferably 0 to 3.
R ⁴ is preferably a group represented by the formula (III). In this case, R ⁵ and R ⁶ are preferably CH ₃ , R ⁷ is C _q H _{(2q + 1)} , and q is preferably 8 to 14, more preferably 10 to 18, and particularly preferably 12. R ⁸ is preferably CH ₂ CHOHCH ₂ . Z is preferably a chloride ion or a bromide ion.

R ³ is preferably H.

The average degree of substitution of the cationic substituent of R ² is generally preferably from 0.02 to 0.9 mol, more preferably from 0.05 to 0.8 mol, and more preferably from 0.1 to 0.8 mol, per mol of the anhydrous glucose unit. -0.6 mol is more preferable, and 0.15-0.35 mol is particularly preferable.

The cationization degree of the component (a1) is preferably from 0.2 to 3.5% by mass, more preferably from 0.5 to 3.0% by mass, still more preferably from 1.0 to 2.6% by mass. 4-2.6% by weight is particularly preferred. Within the above range, a complex of the component (a1) and the component (C) is easily formed, and the action of adsorbing the component (B) to the object to be washed can be enhanced.
The term "degree of cationization" means the content (% by mass) of nitrogen atoms derived from the cationizing agent in the molecule, and represents the ratio of nitrogen atoms per glucose ring unit.
The degree of cationization of the component (a1) is calculated based on the specified chemical structure.
When the chemical structure of the component (a1) is not specified, such as when the ratio of an arbitrary monomer in the component (a1) is unknown, the degree of cationization of the component (a1) is determined from the nitrogen content obtained experimentally. Is calculated. Examples of the method for measuring the nitrogen content in the component (a1) include the Kjeldahl method.

In light of making the viscosity of the liquid detergent appropriate, the viscosity of the 1% by mass aqueous solution of the component (a1) at 25 ° C is preferably 10,000 mPa · s or less, more preferably 3000 mPa · s or less, and particularly preferably 1000 mPa · s or less. When the viscosity of the 1% by mass aqueous solution exceeds 10,000 mPa · s, the viscosity of the 0.5% by mass aqueous solution is measured. The viscosity of the 0.5% by mass aqueous solution at 25 ° C. is preferably 5000 mPa · s or less, and more preferably 2000 mPa · s or less.
The viscosity is a value obtained by measuring a measurement object (aqueous solution of the component (a1)) at 25 ° C. with a B-type viscometer (manufactured by TOKIMEC).
The conditions for measuring the viscosity are as follows.
<Measurement conditions>
[rotor]
The rotor numbers corresponding to the viscosities to be measured are as follows.
When the viscosity of the object to be measured is less than 500 mPa · s: rotor number No. 2.
When the viscosity of the object to be measured is 500 mPa · s or more and 2000 mPa · s: Rotor No. 3.
When the viscosity of the measurement target is 2000 mPa · s or more: Rotor number No. 4.
[Rotor rotation speed]
60 rpm.
[Read numerical value]
60 seconds after the start of rotor rotation.

  As the component (a1), for example, Leogard LP, GP, MGP, KGP, MLP (all are trade names, manufactured by Lion Corporation); UCARE LR-30M, JR-400, JR-30M, LK; SoftCAT SX-1300X, SX-1300H, SX-400X, SX-400H, SL-30H, SL-60H, SL-100H, SK-L, SK-M, SK-H, SK-MH (all are trade names. Commercially available products such as Dow Chemical Japan Co., Ltd.); Kachinal HC-100 (trade name, manufactured by Toho Chemical Industry Co., Ltd.). Among them, SoftCAT SX-1300X, SX-1300H, SX-400X, SX-400H, SL-30H, SL-60H, SL-100H, SK-L, SK-M, SK-H, and SK-MH are preferred. And more preferably SX-400X and SX-400H.

((A2) component)
The component (a2) is at least one selected from the group consisting of a diallyl quaternary ammonium salt polymer and a diallyl quaternary ammonium salt-acrylamide copolymer. When the liquid detergent of the present invention contains the component (a2), the action of adsorbing the component (B) to the object to be washed can be enhanced.

  The diallyl quaternary ammonium salt polymer is a homopolymer of a diallyl quaternary ammonium salt. The diallyl quaternary ammonium salt-acrylamide copolymer is a copolymer of diallyl quaternary ammonium salt and acrylamide. The diallyl quaternary ammonium salt and acrylamide may be block-polymerized, randomly polymerized, or graft-polymerized. As the component (a2), a diallyl quaternary ammonium salt-acrylamide copolymer represented by the following general formula (IV) or (V) is preferable.

In the formulas (IV) and (V), R ³³ and R ³⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, an aryl group, a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and X ₄ is an anion (chloride Ion, bromide ion, iodide ion, sulfate ion, sulfonate ion, methyl sulfate ion, nitrate ion, etc.), g is an integer of 1 to 50, h is an integer of 0 to 50, and i is an integer of 150 to 8000. .

In Formulas (IV) and (V), R ³³ and R ³⁴ are preferably an alkyl group having 1 to 3 carbon atoms.
In Formulas (IV) and (V), R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are preferably hydrogen atoms.
In the formulas (IV) and (V), X ₄ is preferably a halide ion.
The mass average molecular weight of the diallyl quaternary ammonium salt-acrylamide copolymer is preferably 30,000 to 2,000,000, more preferably 1,000,000 to 2,000,000.
The mass average molecular weight in the present specification means a value determined by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance.
Commercial products of the diallyl quaternary ammonium salt-acrylamide copolymer represented by the formula (IV) or (V) include, for example, trade names “Mercoat 100”, trade names “Mercoat 550”, “Noverite300”, and “Noverite302”. (Both manufactured by Lubrizol).

  The component (a2) may be a methacryloyloxyethyl quaternary ammonium salt-acrylamide copolymer represented by the following general formula (VI). The methacryloyloxyethyl quaternary ammonium salt-acrylamide copolymer is a copolymer of methacryloyloxyethyl quaternary ammonium salt and acrylamide. The methacryloyloxyethyl quaternary ammonium salt and acrylamide may be block-polymerized, randomly polymerized, or graft-polymerized.

In the formula (VI), R ⁴¹ , R ⁴² and R ⁴³ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, an aryl group, a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxy group. An alkyl group or a carboalkoxyalkyl group, R ⁴⁴ and R ⁴⁵ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and X is an anion (chloride ion, bromide ion, iodide ion). , Sulfate ion, sulfonate ion, methyl sulfate ion, nitrate ion, etc.), j represents an integer of 5 to 20, and k represents an integer of 80 to 95.

The mass average molecular weight of the methacryloyloxyethyl quaternary ammonium salt-acrylamide copolymer is preferably from 1,000,000 to 10,000,000, more preferably from 2,000,000 to 6,000,000.
Commercially available methacryloyloxyethyl quaternary ammonium salt-acrylamide copolymers include, for example, “Mercoat 5” (trade name, manufactured by Lubrizol).

The component (a2) may be one or more selected from the group consisting of diallyl quaternary ammonium salt-acrylic acid copolymer and acrylic acid-diallyl quaternary ammonium salt-acrylamide copolymer.
The diallyl quaternary ammonium salt-acrylic acid copolymer is a copolymer of diallyl quaternary ammonium salt and acrylic acid. The diallyl quaternary ammonium salt and acrylic acid may be block-polymerized, randomly polymerized, or graft-polymerized. The acrylic acid-diallyl quaternary ammonium salt-acrylamide copolymer is a copolymer of acrylic acid, diallyl quaternary ammonium salt and acrylamide. Acrylic acid, diallyl quaternary ammonium salt and acrylamide may be block-polymerized, randomly polymerized, or graft-polymerized.
One or more selected from the group consisting of diallyl quaternary ammonium salt-acrylic acid copolymer and acrylic acid-diallyl quaternary ammonium salt-acrylamide copolymer include acrylic acid represented by the following general formula (VII): A diallyl quaternary ammonium salt-acrylamide copolymer is preferred.

In the formula (VII), R ⁵¹ and R ⁵² each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, an aryl group, a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxyalkyl group, Or a carboalkoxyalkyl group, R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, q is an integer of 5 to 40, and r is 15 to Integer of 50, s shows the integer of 0-80.

The mass average molecular weight of the diallyl quaternary ammonium salt-acrylic acid copolymer is preferably from 600,000 to 3,000,000, more preferably from 1,000,000 to 2,000,000. The mass average molecular weight of the acrylic acid-diallyl quaternary ammonium salt-acrylamide copolymer is the same as the mass average molecular weight of the diallyl quaternary ammonium salt-acrylic acid copolymer.
Examples of one or more commercially available products selected from the group consisting of diallyl quaternary ammonium salt-acrylic acid copolymer and acrylic acid-diallyl quaternary ammonium salt-acrylamide copolymer include, for example, trade name “Mercoat 280” and commercial products And the name “Mercoat Plus 3330” (all manufactured by Lubrizol).

  The component (a2) may be an acrylic acid-methacrylamidopropyl quaternary ammonium salt-acrylic acid alkyl ester copolymer. The acrylic acid-methacrylamidopropyl quaternary ammonium salt-acrylic acid alkyl ester copolymer is a copolymer of acrylic acid, methacrylamidopropyl quaternary ammonium salt, and acrylic acid alkyl ester. Acrylic acid, methacrylamidopropyl quaternary ammonium salt and alkyl acrylate may be block-polymerized, random-polymerized, or graft-polymerized. As the acrylic acid-methacrylamidopropyl quaternary ammonium salt-alkyl acrylate copolymer, those represented by the following general formula (VIII) are preferable.

In the formula (VIII), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, an aryl group, a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxy group. An alkyl group or a carbalkoxyalkyl group, t represents an integer of 30 to 60, u represents an integer of 30 to 60, and v represents an integer of 5 to 20;

The mass average molecular weight of the acrylic acid-methacrylamidopropyl quaternary ammonium salt-acrylic acid alkyl ester copolymer is preferably from 600,000 to 3,000,000, more preferably from 1,000,000 to 2,000,000.
Examples of commercially available acrylic acid-methacrylamidopropyl quaternary ammonium salt-acrylic acid alkyl ester copolymers include "Mercoat 2001" (trade name, manufactured by Lubrizol).

As the component (A), one type may be used alone, or two or more types may be used in combination.
The content of the component (A) is preferably from 0.1% by mass to 5% by mass, more preferably from 0.1% by mass to 1.2% by mass, based on the total mass of the liquid detergent. The content is more preferably from 1% by mass to 0.6% by mass. When the content of the component (A) is equal to or more than the above lower limit, the component (B) can be easily adsorbed on the object to be washed. When the content of the component (A) is equal to or less than the upper limit, the re-contamination prevention property is easily improved.

<(B) component>
The component (B) is an antibacterial agent having a phenol structure. By containing the component (B), the liquid detergent of the present invention can impart antibacterial properties to textiles and the like after washing. Further, by combining the component (B) and the component (A), the liquid detergent easily exerts a higher antibacterial effect. The compound having a phenol structure can exert an antibacterial effect even in the presence of an anionic surfactant in a liquid detergent without impairing the detergency by the anionic surfactant.
In the present specification, the phenol structure means that the aromatic hydrocarbon nucleus has a structure in which one or more hydrogen atoms are substituted with a hydroxy group.

  As the component (B), a phenol derivative or a diphenyl compound known as an antibacterial agent can be suitably used. As the component (B), 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4′-dichloro-2-hydroxydiphenyl ether (common name: diclosan), o- Benzyl-p-chlorophenol (common name: chlorophene), isopropylmethylphenol, parachloromethaxylenol and the like can be mentioned.

The component (B) preferably contains a compound represented by the following formula (IX) (hereinafter, also referred to as compound (IX)). Further, the component (B) more preferably contains a 2-hydroxydiphenyl compound in which R ²¹ is an oxygen atom and α is 1 in the following general formula (IX) (hereinafter, also referred to as a component (b1)). . The component (b1) is preferable because it is easily adsorbed on the hydrophobic fiber and the effect of the present invention is large.

In the formula (IX), R ²¹ is an oxygen atom or an alkylene group having 1 to 4 carbon atoms, Y ₁ is a chlorine atom or a bromine atom, and Y ₂ is SO ₂ H, NO ₂ , or 1 to 4 carbon atoms. Wherein α, β, and γ are each independently an integer of 0 or 1 to 3, δ is 0 or 1, m is 0 or 1, and n is 0 or 1.

In the compound (IX), R ²¹ is an oxygen atom or a methylene group, Y ₁ is a chlorine atom or a bromine atom, m is 0, n is 0 or 1, α is 1, and β is 0. , 1 or 2; γ is 0, 1 or 2; and δ is 0.
More preferred specific examples of the compound (IX) include R ²¹ is an oxygen atom, α is 1, Y ₁ is a chlorine atom, one of β or γ is 1, the other is 0, δ is 0, m Is 0, n is 0; R ²¹ is an oxygen atom, α is 1, Y ₁ is a chlorine atom, β is 1, γ is 1, δ is 0, m is 0, n is 0 A certain dichlorohydroxydiphenyl ether; R ²¹ is an oxygen atom, α is 1, Y ₁ is a chlorine atom, one of β or γ is 1 and the other is 2, δ is 0, m is 0, and n is 0 Trichlorohydroxydiphenyl ether; benzylchlorophenol in which R ²¹ is a methylene group, α is 1, Y ₁ is a chlorine atom, β is 0, γ is 1, δ is 0, m is 0, and n is 0. .

Particularly preferred specific examples of compound (IX) include 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan) and 4,4′-dichloro-2-hydroxydiphenyl ether (common name: Diclosan), o-benzyl-p-chlorophenol (common name: chlorophene) and the like.
As the compound (IX), one type may be used alone, or two or more types may be used in combination.
The content of the compound (IX) is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and may be 100% by mass, based on the total mass of the component (B). When the content of the compound (IX) is equal to or more than the above lower limit, the liquid detergent easily exerts a higher antibacterial effect.

As the component (B), one type may be used alone, or two or more types may be used in combination.
The content of the component (B) is preferably 0.01% by mass or more and 3% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, and more preferably 0.1% by mass or less based on the total mass of the liquid detergent. % Or more and 0.5% by mass or less. When the content of the component (B) is equal to or more than the lower limit, the movement of bacteria in textiles such as clothing is easily suppressed, and the liquid detergent easily exerts a higher antibacterial effect. When the content of the component (B) is equal to or less than the upper limit, the liquid stability of the liquid detergent is easily improved.

<(C) component>
The component (C) is an anionic surfactant. When the liquid detergent of the present invention contains the component (C), it exhibits a detergency against stains on clothes, and can improve the re-contamination prevention property.
The component (C) can be appropriately selected from known anionic surfactants including higher fatty acids or salts thereof and used. In this specification, a higher fatty acid is a fatty acid having 8 to 22 carbon atoms.

  As the component (C), for example, a linear alkylbenzene sulfonic acid or a salt thereof; an α-olefin sulfonic acid salt; a linear or branched alkyl sulfate, an alkyl ether sulfate or an alkenyl ether sulfate, and an alkyl group And α-sulfofatty acid ester salts. Examples of the salt in these anionic surfactants include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

As the linear alkylbenzene sulfonic acid or a salt thereof, a linear alkyl group having 8 to 16 carbon atoms is preferable, and one having 10 to 14 carbon atoms is more preferable.
As the α-olefin sulfonate, those having 10 to 20 carbon atoms are preferable.
As the alkyl sulfate, those having 10 to 20 carbon atoms in the alkyl group are preferable.
Examples of the alkyl ether sulfate or alkenyl ether sulfate include those having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and having an average of 1 to 10 moles of ethylene oxide added thereto (namely, Polyoxyethylene alkyl ether sulfate or polyoxyethylene alkenyl ether sulfate) is preferred.
As the alkane sulfonate, those having 10 to 20 carbon atoms in the alkyl group are preferable, and those having 14 to 17 carbon atoms are more preferable. As the alkane sulfonate, those in which the alkyl group is a secondary alkyl group (ie, a secondary alkane sulfonate) are more preferable.
As the α-sulfofatty acid ester salt, those having 10 to 20 carbon atoms in the fatty acid residue are preferable.
As the component (C), among these, one or more selected from linear alkylbenzene sulfonic acids or salts thereof, alkane sulfonates, polyoxyethylene alkyl ether sulfates, and α-olefin sulfonates are particularly preferable. .

As the component (C), other anionic surfactants other than those described above may be used. Other anionic surfactants include, for example, higher fatty acids having 8 to 22 carbon atoms or salts thereof, alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkyl (or alkenyl) amide ether carboxylate, acylamino Carboxylic acid type anionic surfactants such as carboxylate salts; phosphate esters such as alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkyl phenyl phosphate ester salts, glycerin fatty acid ester monophosphate ester salts and the like Type anionic surfactant; and the like.
These anionic surfactants are readily available on the market.

As the component (C), one type may be used alone, or two or more types may be used in combination.
The content of the component (C) is preferably from 2.5% by mass to 50% by mass, more preferably from 5% by mass to 40% by mass, and more preferably from 10% by mass to 30% by mass, based on the total mass of the liquid detergent. % Is more preferable. When the content of the component (C) is equal to or more than the lower limit, it is easy to improve re-contamination prevention properties while having a detergency. When the content of the component (C) is equal to or less than the upper limit, a higher antibacterial effect is easily exerted.

  The mass ratio represented by the component (A) / component (C) (hereinafter, also referred to as the ratio (A) / (C)) is preferably 0.002 or more and 2 or less, more preferably 0.003 or more and 0.24 or less. More preferably, it is 0.004 or more and 0.06 or less. When the (A) / (C) ratio is within the above range, the liquid stability of the liquid detergent is improved, and the component (B) is easily adsorbed on the object to be washed while ensuring the property of preventing re-contamination. it can.

<Optional components>
The liquid detergent of the present invention may contain optional components other than the components (A), (B) and (C) as long as the effects of the present invention are not impaired. As the optional component, a component usually used in a liquid detergent can be blended.
Examples of the optional component include a water-miscible organic solvent (component (D)), a surfactant excluding component (C), an enzyme, water, a solubilizer, an alkali agent, a metal ion scavenger (chelating agent), and oxidation. Inhibitors, preservatives, enzyme stabilizers, texture improvers, fluorescent brighteners, anti-staining agents, pearlescent agents, soil release agents, flavoring agents, coloring agents, emulsifiers, extracts of natural products, etc., pH adjusters and the like.

((D) component)
The component (D) is a water-miscible organic solvent. When the liquid detergent of the present invention contains the component (D), the liquid stability can be improved, and the fluidity of the liquid detergent can be easily improved. In the present specification, the water-miscible organic solvent refers to an organic solvent that dissolves in 50 g or more in 1 L of ion exchange water at 25 ° C.

  Examples of the component (D) include monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, glycol ether solvents represented by the following general formula (X), and the following general formula (XI) And the like.

_{^{R 11 - (OR 12) w}} OH ··· (X)
(X) In the formula, R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ¹² is an alkylene group having 2 to 4 carbon atoms, w represents an average number of added moles, and is 1 to 5. .

CH ₃ OCR ¹³ (CH ₃ ) CHR ¹⁴ CHR ¹⁵ OR ¹⁶ (XI)
(XI) In the formula, R ^{13 to} R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁶ is a hydrogen atom or an acetyl group.

Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, and 1-butanol.
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 represented by the formula (X) 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. Can be
Examples of the solvent represented by the formula (XI) include 3-methoxymethanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, and 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-propylbuty Acetate, 3-methoxy-1-methyl-butyl acetate, 3-methoxy-1-ethyl butyl acetate, 3-methoxy-1-propyl-butyl acetate and the like.
As the component (D), among these, ethanol, propylene glycol, diethylene glycol monobutyl ether, 3-methoxy-3-methyl are preferred from the viewpoints of excellent fluidity, mild odor, and availability of raw materials. Butanol is preferred.

As the component (D), one type may be used alone, or two or more types may be used in combination.
When the liquid detergent contains the component (D), the content of the component (D) is preferably from 2.5% by mass to 25% by mass based on the total mass of the liquid detergent. When the content of the component (D) is within the above numerical range, the liquid stability can be more easily improved.

Examples of the surfactant excluding the component (C) (hereinafter, also referred to as other surfactants) include a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
As the nonionic surfactant, nonionic surfactants usually used in liquid detergents for clothing and the like can be used, for example, fatty acid alkyl esters, higher alcohols, alkylphenols, higher fatty acids, higher fatty acid alkyl esters or higher fatty acid alkyl esters. 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 And alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glucosides and the like. Among these, a compound represented by the following formula (XII) (hereinafter, also referred to as compound (XII)) is preferable as the nonionic surfactant.

R ¹⁷ -O-[(EO) _e / (PO) _f ] -H (XII)
In the formula (XII), R ¹⁷ represents a hydrocarbon group having 8 to 22 carbon atoms, EO represents an oxyethylene group (ethylene oxide), PO represents an oxypropylene group (propylene oxide), and e represents an average repetition of EO. Is a number that satisfies 2 ≦ e ≦ 20, and f is an average number of repetitions of PO and is a number that satisfies 0 ≦ f ≦ 6.

In the formula (XII), R ¹⁷ has 8 to 22 carbon atoms, preferably 11 to 18, more preferably 12 to 16, and even more preferably 12 to 14.
The hydrocarbon group for R ¹⁷ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Among them, a saturated hydrocarbon group is preferable from the viewpoint of excellent liquid stability.
The hydrocarbon group for R ¹⁷ 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 in R ¹⁷ —O— is preferably a primary carbon atom or a secondary carbon atom. This makes it difficult to inhibit the adsorption of the component (B) to the object to be washed. In particular, when the liquid detergent of the present invention is used in a method of directly applying to the stains of clothes, etc., a high application detergency is easily obtained.
As R ¹⁷ , a branched chain hydrocarbon group having 8 to 22 carbon atoms, a straight chain hydrocarbon group having 8 to 22 carbon atoms is preferable, and a straight chain hydrocarbon group having 8 to 22 carbon atoms is more preferable. When R ¹⁷ is a branched hydrocarbon group, the carbon atom bonded to the oxygen atom in R ¹⁷ —O— is preferably a primary carbon atom. When R ¹⁷ is a linear hydrocarbon group, the carbon atom bonded to the oxygen atom in R ¹⁷ —O— is preferably a secondary carbon atom.

In the formula (XII), e is a number of 2 to 20, which represents the average number of repetitions of EO (that is, the average number of moles of ethylene oxide added), preferably 2 to 18, and more preferably 5 to 16. In particular, when R ¹⁷ is a hydrocarbon group having 8 to 22 carbon atoms derived from a primary alcohol, e is 2 to 20, preferably 5 to 18, more preferably 7 to 16, and further preferably 12 to 16. preferable. When R ¹⁷ is a hydrocarbon group having 8 to 22 carbon atoms derived from a secondary alcohol, e is 2 to 20, preferably 2 to 15, more preferably 2 to 9, and still more preferably 3 to 9, 7 to 9 are particularly preferred. When e is within the above numerical range, adsorption of the component (B) to the article to be washed can be hardly inhibited.
In the formula (XII), f is a number of 0 to 6 representing the average number of repetitions of PO (that is, the average number of moles of propylene oxide added), preferably 0 to 3, more preferably 0 to 2, and 0 to 1 Is more preferred. When f is equal to or less than the upper limit, adsorption of the component (B) to the article to be washed can be hardly inhibited.

When f> 0, that is, when PO and EO are mixed, they may be mixed randomly or in blocks regardless of the order of arrangement. [(EO) _e / (PO) _f ] in the formula (XII) means that EO and PO are mixed in a random or block shape.
When PO and EO are mixed in a block shape, as a method of adding ethylene oxide and propylene oxide, for example, a method of adding propylene oxide after adding ethylene oxide, a method of adding propylene oxide and then adding ethylene oxide, a method of adding ethylene oxide, Is added, propylene oxide is added, and ethylene oxide is further added.

The addition mole number distribution of ethylene oxide or propylene oxide is not particularly limited.
The addition mole number distribution is likely to vary depending on the reaction method used for producing compound (XII). For example, when ethylene oxide or propylene oxide is added to a raw material of a hydrophobic group using an alkali catalyst such as common sodium hydroxide or potassium hydroxide, the distribution of the number of moles of ethylene oxide or propylene oxide added is relatively wide. It tends to be. Also, specific alkoxylation of magnesium oxide or the like 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 Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to a raw material of a hydrophobic group using a catalyst, the distribution of the number of moles of ethylene oxide or propylene oxide added tends to be relatively narrow.

  Specific examples of the compound (XII) include those obtained by adding 7 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms (for example, trade name “Sophthanol 70” manufactured by Nippon Shokubai Co., Ltd.), 9 to 14 moles of secondary alcohol to which 9 moles of ethylene oxide is added (for example, trade name “SOFTANOL 90” manufactured by Nippon Shokubai Co., Ltd.), 7 moles to 12 to 14 carbons of a secondary alcohol Of ethylene oxide and 2 moles of propylene oxide, and 7 moles of ethylene oxide added to an alcohol having 10 carbon atoms obtained by subjecting pentanol to a Garbet reaction (trade name "Lutensol XL70" manufactured by BASF). )), 6 moles of alcohol having 10 carbon atoms obtained by subjecting pentanol to a Garbet reaction. What Chiren'okishido are added (BASF Co., Ltd. under the trade name "Lutensol XA60"), and the like.

As the compound (XII), one type may be used alone, or two or more types may be used in combination.
When the liquid detergent contains the compound (XII), the content of the compound (XII) is preferably from 5% by mass to 35% by mass, and more preferably from 5% by mass to 25% by mass, based on the total mass of the liquid detergent. The content is more preferably 5% by mass or more and 15% by mass or less. When the content of the compound (XII) is equal to or more than the above lower limit, sebum detergency is further increased. When the content of the compound (XII) is equal to or less than the upper limit, the fluidity of the liquid detergent is further increased, and the liquid stability is easily improved. In this specification, the sebum detergency refers to the detergency for sebum dirt.

  When the liquid detergent contains a nonionic surfactant, the content of the nonionic surfactant is preferably from 5% by mass to 35% by mass, more preferably from 5% by mass to 30% by mass, based on the total mass of the liquid detergent. The content is more preferably 5% by mass or more and 25% by mass or less. When the content of the nonionic surfactant is equal to or more than the above lower limit, sebum detergency is further increased. When the content of the nonionic surfactant is equal to or less than the upper limit, the fluidity of the liquid detergent is further increased, and the liquid stability is easily improved.

Examples of the cationic surfactant include tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, etc .; tetra-short-chain (alkyl having 1 to 4 carbon atoms) ammonium salts; octyltrimethylammonium salt, decyl Trimethyl ammonium salt, dodecyl trimethyl ammonium salt, tetradecyl trimethyl ammonium salt, lauryl trimethyl ammonium salt, cetyl trimethyl ammonium salt, palmityl trimethyl ammonium salt, stearyl trimethyl ammonium salt, octyl dimethyl ethyl ammonium salt, decyl dimethyl ethyl ammonium salt, dodecyl dimethyl Ethyl ammonium salt, tetradecyl dimethyl ethyl ammonium salt, lauryl dimethyl ethyl ammonium Salt, cetyl dimethyl ethyl ammonium salt, stearyl dimethyl ethyl ammonium salt, octyl diethyl methyl ammonium salt, decyl diethyl methyl ammonium salt, dodecyl diethyl methyl ammonium salt, tetradecyl diethyl methyl ammonium salt, cetyl diethyl methyl ammonium salt, stearyl diethyl methyl ammonium salt Long-chain (alkyl having 8-18 carbon atoms) tri-short-chain (alkyl having 1 or 2 carbon atoms) ammonium salt; dioctyldimethylammonium salt, didecyldimethylammonium salt, N, N-didecyl-N-methyl-poly (Oxyethyl) ammonium salt, didodecyl dimethyl ammonium salt, ditetradecyl dimethyl ammonium salt, dicetyl dimethyl ammonium salt, distearyl dimethyl ammonium Di-long chains such as dioctylmethylethylammonium salt, didecylmethylethylammonium salt, didodecylmethylethylammonium salt, ditetradecylmethylethylammonium salt, dicetylmethylethylammonium salt, distearylmethylethylammonium salt, etc. 8-18 alkyl) di-short-chain (alkyl having 1 or 2 carbons) ammonium salt; long-chain (alkyl having 8-18 carbons) di-short chain (alkyl having 1 or 2 carbons) such as stearyldimethylhydroxyethylammonium ) Hydroxyalkyl (C1 or C2) ammonium salt; di-short chain (carbon number of 4 to 10) having trialkoxysilylalkyl group (C4 to C10) such as [3 (trimethoxysilyl)] propyl (dimethyl) octadecyl ammonium salt 1 or 2 alkyl) long chains (carbon number 8-18 alkyl) ammonium salts; amine nitrates; benzyltrimethylammonium salts; benzalkonium salts; benzethonium salts and the like.
Examples of the salt include halides such as chlorine, bromine and iodine; hydroxides; sulfonic acid esters having 1 to 5 carbon atoms, sulfuric acid esters, nitric acid esters, carboxylic acid esters and the like.

  Examples of the amphoteric surfactants include, for example, amide propyl dimethylamino acetic acid betaine octanoate, betaine decanoate dimethyl dimethyl amino acetic acid betaine, betaine laurate amide propyl dimethyl amino acetic acid betaine, myristate amide propyl dimethyl amino acetic acid betaine, amidopropyl dimethyl stearate Betaine aminoacetate, betaine amide propyldimethylaminoacetate oleate, betaine coconut fatty acid amide propyldimethylaminoacetate, betaine palm oil fatty acid amide propyldimethylaminoacetate, betaine palm oil fatty acid amide propyldimethylaminoacetate betaine, octyl dimethylamino acetate betaine, Betaine decyldimethylaminoacetate, betaine lauryldimethylaminoacetate, betaine myristyldimethylaminoacetate, stearie Betaine dimethylaminoacetate, betaine oleyldimethylaminoacetate, amidopropylhydroxysulfobetaine octanoate, amidopropylhydroxysulfobetaine decanoate, amidopropylhydroxysulfobetaine laurate, amidopropylhydroxysulfobetaine myristate, amidopropylhydroxysulfobetaine stearate Amide oleic acid hydroxypropyl sulphobetaine, palm oil fatty acid amide propyl hydroxysulfobetaine, palm oil fatty acid amide propyl hydroxysulfobetaine, palm kernel oil fatty acid amide propyl hydroxysulfobetaine, octyl hydroxysulfobetaine, decyl hydroxysulfobetaine, lauryl hydroxysulfoine Betaine, myristyl hydroxysulfobetaine, Stearyl hydroxy sulfobetaine, oleyl hydroxy sulfobetaine and the like.

  When the liquid detergent contains another surfactant, the content of the other surfactant is preferably from 5% by mass to 40% by mass, and more preferably from 5% by mass to 35% by mass, based on the total mass of the liquid detergent. It is more preferably at most 5 mass%, more preferably at least 5 mass% and at most 30 mass%.

The total mass of the surfactant is preferably from 5% by mass to 70% by mass, more preferably from 10% by mass to 60% by mass, based on the total mass of the liquid detergent. When the total mass of the surfactant is equal to or more than the lower limit, the detergency of the liquid detergent is easily increased. When the total mass of the surfactant is equal to or less than the upper limit, the liquid stability of the liquid detergent is easily improved.
The content of the component (C) with respect to the total mass of the surfactant is preferably from 15% by mass to 75% by mass, and more preferably from 25% by mass to 65% by mass. When the content of the component (C) with respect to the total mass of the surfactant is equal to or more than the lower limit, the detergency of the liquid detergent is easily increased. When the content of the component (C) with respect to the total mass of the surfactant is equal to or less than the upper limit, a higher antibacterial effect is easily exerted.

Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase and the like. In addition, in this specification, "enzyme" means an enzyme preparation.
As the protease, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase UltraLal, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, 8L , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, and trade names Purafect L, Purafect OX, and Properase L available from Genencor Corporation.
As the amylase, trade names Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, trade names available from Novozymes, Inc. as amylase preparations, and trade names available from Genencor, Maxamen available from Genencor, Inc. Pullulanase Amano, trade name DB-250 available from Seikagaku Corporation, and the like.
Examples of the lipase include Lipex 100L and Lipolase 100L, which are trade names available from Novozymes as lipase preparations.
Examples of the cellulase include Endolase 5000L, Celluzyme 0.4L, and Carzyme 4500L, which are trade names available from Novozymes as cellulase preparations.
Examples of mannanase include Mannaway 4L (trade name) available from Novozymes as a mannanase preparation.

One type of enzyme may be used alone, or two or more types may be used in combination.
When the liquid detergent contains an enzyme, the content of the enzyme is preferably from 0.01% by mass to 1.0% by mass, more preferably from 0.03% by mass to 0.9% by mass, based on the total mass of the liquid detergent. % By mass or less, more preferably 0.05% by mass or more and 0.8% by mass or less. When the content of the enzyme is equal to or more than the above lower limit, the detergency of the liquid detergent is easily increased. When the content of the enzyme is equal to or less than the upper limit, the liquid stability can be more easily improved.

  The liquid detergent of the present invention preferably contains water. The content of water is preferably from 10% by mass to 95% by mass, more preferably from 20% by mass to 90% by mass, and still more preferably from 40% by mass to 90% by mass, based on the total mass of the liquid detergent. When the content of water is equal to or more than the lower limit, ease of handling at the time of production and solubility in water at the time of use are more excellent. When the content of water is equal to or less than the above upper limit, the detergency of the liquid detergent is easily increased.

Examples of the solubilizer include aromatic sulfonic acids and salts thereof. As the aromatic sulfonic acid or a salt thereof, for example, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, toluene sulfonic acid salt, xylene sulfonic acid salt, cumene sulfonic acid salt, substituted or unsubstituted Substituted naphthalene sulfonates are mentioned.
Examples of the salt include a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an ammonium salt, and an alkanolamine salt.
As the solubilizer, one type may be used alone, or two or more types may be used in combination.

Examples of the alkali agent include monoethanolamine, diethanolamine, triethanolamine and the like.
As the alkali agent, one kind may be used alone, and two kinds or more may be used in combination.
When the liquid detergent contains an alkali agent, the content of the alkali agent is preferably 0.5% by mass or more and 5% by mass or less based on the total mass of the liquid detergent.

Examples of the metal ion scavenger (chelating agent) include, for example, malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid, HEDP (hydroxy ethazisulfonic acid), or salts thereof, and MGDA (methyl glycine diacetic acid). Trisodium) and the like.
When the liquid detergent contains a chelating agent, the amount of the chelating agent is preferably from 0.01% by mass to 20% by mass based on the total mass of the liquid detergent composition.

The antioxidant is not particularly limited, but is preferably a phenolic antioxidant because of its good detergency and liquid stability, and is preferably a monophenolic antioxidant such as dibutylhydroxytoluene or butylhydroxyanisole. Bisphenol-based antioxidants such as 2,2'-methylenebis (4-methyl-6-t-butylphenol) and high-molecular-weight phenol-based antioxidants such as dl-α-tocopherol are more preferable; Molecular antioxidants are more preferred.
Among the monophenolic antioxidants, dibutylhydroxytoluene is particularly preferred. Among the polymeric phenolic antioxidants, dl-α-tocopherol is particularly preferred.
As the antioxidant, one type may be used alone, or two or more types may be used in combination.
When the liquid detergent contains an antioxidant, the content of the antioxidant is preferably 0.01% by mass or more and 2% by mass or less based on the total mass of the liquid detergent composition.

Examples of the preservative include “Caisson CG” manufactured by Dow, “AN-1000” manufactured by Lonza, “MBS” manufactured by Saw, and “NIPACIDE BIT 20” manufactured by Clariant. And the like.
When the liquid detergent contains a preservative, the content of the preservative is preferably 0.001% by mass or more and 1% by mass or less based on the total mass of the liquid detergent.

Examples of the enzyme stabilizer include boric acid, borax, formic acid or a salt thereof, benzoic acid, lactic acid or a salt thereof, and calcium salts such as calcium chloride and calcium sulfate.
The content of the enzyme stabilizer is preferably 0% by mass or more and 2% by mass or less based on the total mass of the liquid detergent.

Examples of the texture improver include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone.
The content of the texture improver is preferably from 0% by mass to 5% by mass with respect to the total mass of the liquid detergent.

The fluorescent whitening agent is an agent added for the purpose of improving the whiteness of white clothing. Examples of the fluorescent whitening agent include a distyrylbiphenyl type fluorescent whitening agent.
The content of the fluorescent whitening agent is preferably 0% by mass or more and 1% by mass or less based on the total mass of the liquid detergent.

Examples of the anti-redeposition agent include polyvinylpyrrolidone, carboxymethylcellulose and the like.
The content of the anti-redeposition agent is preferably from 0% by mass to 2% by mass based on the total mass of the liquid detergent.

  Examples of the pearl agent include “SRN-100” (trade name) manufactured by Clariant. Examples of the soil release agent include “HP20” (trade name, manufactured by BASF).

The liquid detergent may contain a flavoring agent, a coloring agent, an emulsifier, an extract such as a natural product, etc. for the purpose of improving the added value of the product.
Examples of the flavoring agents include the flavoring compositions A, B, C, and D described in Tables 11 to 18 of JP-A-2002-146399.
When the liquid detergent contains a flavoring agent, the content of the flavoring agent is preferably 0.1% by mass or more and 1% by mass or less based on the total mass of the liquid detergent.

Examples of the colorant include trade names such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue 205, Green No. 3, and Turquoise P-GR. And pigments.
When the liquid detergent contains a colorant, the content of the colorant is preferably 0.00005% by mass or more and 0.005% by mass or less based on the total mass of the liquid detergent.

Examples of the emulsifier include a polystyrene emulsion and a polyvinyl acetate emulsion, and an emulsion having a solid content of 30 to 50% by mass is usually suitably used. Examples of commercially available products include polystyrene emulsion (trade name “Sibinol RPX-196 PE-3”, manufactured by Seiden Chemical Co., Ltd., solid content: 40% by mass).
When the liquid detergent contains an emulsifier, the content of the emulsifier is preferably from 0.01% by mass to 0.5% by mass with respect to the total mass of the liquid detergent.

Examples of extracts such as natural products include, for example, Inujuju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Kaigai, Kay, Geckage, Hoonoki, Burdock, Comfrey, Jasha, Waremokou, Peony, Ginger, Seika Awadachiso, Aedes aegypti, Sage, Mistletoe, Hosobaokera, Thyme, Hanasuge, Butterfly, Unshumikan, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yoraigusa, Shirogaya, Butterfly Mountain grape, murasaki tagayasan, yamaha mint, hyuga, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gireadval Munoki, ringworm, kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, include plant extracts such as St. John's Wort.
The content of an extract such as a natural product is preferably from 0% by mass to 0.5% by mass based on the total mass of the liquid detergent.

Examples of the pH adjuster include sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and ammonia. Among them, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid, sodium hydroxide, and alkanolamine are more preferable, from the viewpoint of easily improving the liquid stability of the liquid detergent.
One type of pH adjuster may be used alone, or two or more types may be used in combination.

  In addition, the total amount of the components constituting the liquid detergent of the present invention does not exceed 100% by mass.

[Production method of liquid detergent]
The liquid detergent of the present invention is produced by a conventionally known method by mixing the components (A), (B), and (C), and if necessary, any components.
The pH at 25 ° C. of the liquid detergent of the present invention is preferably 4 or more and 9 or less, more preferably 6 or more and 9 or less. When the pH is within the above numerical range, the liquid stability of the liquid detergent is likely to be favorably maintained.
The pH can be adjusted by adding an appropriate amount of a pH adjuster.
The pH in the present specification means a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Ltd.) with the measurement object at 25 ° C.

  The viscosity of the liquid detergent at 25 ° C. is preferably from 10 mPa · s to 500 mPa · s, and more preferably from 40 mPa · s to 300 mPa · s. When the viscosity is within the above numerical range, the liquid detergent can be easily measured with a measuring cap or the like. In addition, when used for application cleaning, it becomes easier to apply the liquid detergent to textiles and the like.

[How to use liquid detergent]
The method of using the liquid detergent is, for example, a method in which the liquid detergent is poured into water together with the object to be washed at the time of washing, and the object to be washed is immersed in an aqueous solution of the detergent which is prepared by dissolving the liquid detergent in water in advance. And the like. Alternatively, the liquid detergent may be directly applied to the object to be washed, and left for, for example, 3 minutes to 24 hours, and then normal washing may be performed.
The content of the liquid detergent in the aqueous detergent solution is not particularly limited. The amount of the liquid detergent added to water is preferably, for example, 2 to 30 mL per 10 L of water.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The raw materials used in this example are as shown in [Used raw materials] below.

[Raw materials]
<(A) component>
A-1: dimethyldiallylammonium acrylamide copolymer, manufactured by Lubrizol, trade name “Noverite300”.
A-2: Dimethyl diallyl ammonium acrylamide copolymer, manufactured by Lubrizol, trade name “Noverite 302”.
A-3: dimethyldiallylammonium polymer, manufactured by Lubrizol, trade name “Mercoat 100”.
A-4: dimethyldiallylammonium / acrylic acid copolymer, manufactured by Lubrizol, trade name “Mercoat 280”.
A-5: Dimethyldiallylammonium / acrylamide / acrylic acid copolymer, manufactured by Lubrizol, trade name “Mercoat 3330PR”.

<(A) ′ component (comparison product of (A) component)>
A′-1: Ethylene oxide adduct of polyethyleneimine, manufactured by BASF, trade name “Sokalan HP20”.
A'-2: Didecyldimethylammonium chloride, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Arcard 210".
A'-3: Dodecyltrimethylammonium chloride, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipoguard 12-37W".

<(B) component>
B-1: 4,4′-dichloro-2-hydroxydiphenyl ether (common name: diclosan), manufactured by BASF, trade name “Tinosan HP100”.
B-2: o-benzyl-p-chlorophenol (common name: chlorophen), manufactured by Clariant Japan KK, trade name "chlorophen".
B-3: 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), manufactured by BASF, trade name “Irgasan DP-300”.

<(C) component>
C-1: linear alkylbenzene sulfonic acid (alkyl group having 10 to 14 carbon atoms, average molecular weight of 322), manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Laipon LH-200".
C-2: Sodium polyoxyethylene alkyl ether sulfate (C12 to C13 in the alkyl group, average number of moles of EO added 2, trade name of raw material alcohol "Neodor 23" (manufactured by Shell)).
C-3: Sodium polyoxyethylene propylene alkyl ether sulfate (trade name of natural alcohol "CO-1270" (manufactured by P & G)).
C-4: Coconut fatty acid, manufactured by NOF Corporation, trade name "coconut fatty acid".

<Optional components>
((D) component)
D-1: 3-methoxy-3-methyl-1-butanol, manufactured by Kuraray Co., Ltd., trade name "SOLFIT".
D-2: butyl carbitol, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "butyl carbitol".
D-3: Ethanol, manufactured by Japan Alcohol Sales Co., Ltd., trade name “specific alcohol 95 ° synthesis”.
D-4: Propylene glycol, manufactured by Dow Chemical Co., Ltd., trade name "propylene glycol".

(Nonionic surfactant)
Nonionic surfactant 1: polyoxyethylene alkyl ether (15EO), which is obtained by adding 15 moles of ethylene oxide to a natural alcohol having 12 or 14 carbon atoms (primary alcohol).
Nonionic surfactant 2: polyoxyethylene alkyl ether (7EO), which is obtained by adding 7 moles of ethylene oxide to a natural alcohol having 12 or 14 carbon atoms (primary alcohol).
Nonionic surfactant 3: Polyoxyethylene fatty acid methyl ester (MEE), fatty acid having 12 to 14 carbon atoms, and EO having an average number of moles of 15 added.
Nonionic surfactant 4: EO / PO nonion, a secondary alcohol having 12 to 14 carbon atoms, which is block-added with 8 moles of ethylene oxide, 2 moles of propylene oxide, and 8 moles of ethylene oxide in this order.

(Other optional components)
Enzyme 1: Protease, manufactured by Novozymes, trade name "Coronase 48L".
Enzyme 2: Mannanase, manufactured by Novozymes, trade name "Mannaway 4.0".
Enzyme 3: Cellulase, manufactured by Novozymes, trade name "Cellclean".
Enzyme 4: Amylase, manufactured by Novozymes, trade name "Amplify Prime".
Stabilizer: polyoxypropylene glyceryl ether (PPG), manufactured by Mitsui Chemicals, Inc., trade name "Actocol T4000".
Chelating agent: Trisodium citrate dihydrate, manufactured by Fuso Chemical Industry Co., Ltd., trade name "purified sodium citrate".
Enzyme stabilizer 1: sodium benzoate, manufactured by Fushimi Pharmaceutical Co., Ltd., trade name "sodium benzoate".
Enzyme stabilizer 2: sodium lactate, manufactured by Kanto Chemical Co., Ltd., trade name "sodium lactate".
Antioxidant: dibutylhydroxytoluene, manufactured by Sumitomo Chemical Co., Ltd., trade name "SUMIZER BHT-R".
Flavoring agent: perfume, perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.
Colorant: pigment, trade name "Midori No. 3", manufactured by Kishi Kasei Corporation.
pH adjuster: sulfuric acid, manufactured by Wako Pure Chemical Industries, Ltd., trade name "sulfuric acid"; or sodium hydroxide, manufactured by Kanto Chemical Co., Ltd., trade name: "48% sodium hydroxide solution"; or monoethanolamine (MEA), manufactured by Nippon Shokubai Co., Ltd., trade name "monoethanolamine".
Water: Purified water, manufactured by Kanto Chemical Co., Ltd., trade name "purified water".

[Examples 1 to 15, Comparative Examples 1 to 4]
According to the compositions shown in Tables 1 to 3, the components (A) to (C) and optional components were added to water and mixed to obtain a mixed solution. The temperature of the mixture was 25 ° C., and an appropriate amount of a pH adjuster was added so that the pH of the mixture was 7, to obtain a liquid detergent.
The obtained liquid detergent was evaluated for liquid stability, ease of adsorption to an object to be washed (adsorbability), and antibacterial property by the following evaluation methods. The results are shown in Tables 1 to 3.
In addition, the unit of the compounding amount of each component in the table is "% by mass", and indicates a pure component conversion amount. "Balance" means that water is blended so that the total blended amount (mass%) of all the blended components contained in the composition of each example is 100% by mass.

<Evaluation of liquid stability>
A transparent glass bottle (wide-mouth standard bottle, PS-NO.11) was filled with 100 mL of the liquid detergent of each example, and the lid was closed and sealed. In this state, it was left standing for 7 days in a thermostat at 5 ° C. and stored.
After the storage, the appearance of the liquid was visually observed, and the liquid stability of the liquid detergent was evaluated according to the following evaluation criteria. ○ The above was regarded as a pass.
"Evaluation criteria"
：: No precipitated substance was observed at the bottom of the glass bottle, and there was fluidity of the liquid.
：: Precipitated substances are observed at the bottom of the glass bottle, but if the glass bottle is shaken gently, the precipitated substances disappear (dissolve).
×: Precipitated substance was observed at the bottom of the glass bottle, and the precipitated substance did not disappear even if the glass bottle was shaken lightly, or gelled or clouded immediately after the production of the liquid detergent.

<Evaluation of adsorptivity>
A cotton knit (Tanito Shoten), a liquid detergent of each example, and water were put into a Terg-O-Tometer (manufactured by US Testing Co., Ltd.) so as to have a bath ratio of 20 times. The input amount of the liquid detergent was the standard use amount (10 mL) of the detergent. The cotton knit was washed for 10 minutes to extract the bulk water after washing. The amount of the component (B) (antibacterial agent) remaining in the bulk water was quantified by high performance liquid chromatography (HPLC) under the following conditions.
(HPLC analysis conditions)
Analytical instrument: HPLC (Chrommaster, manufactured by Hitachi, Ltd.).
Column: Inertsil ODS-3 (4.6 × 250 mm, 5 μm).
Mobile phase: methanol / water = 8: 2.
Flow rate: 0.7 mL / min.
Detector: UV (278 nm).
Temperature: 40 ° C.

From the content of the component (B) of the liquid detergent added before washing (the initial content of the component (B)) and the content of the component (B) quantified by HPLC, the component (B) was added to the cotton knit. Was calculated, and the adsorption rate of the component (B) to the cotton knitted fabric (hereinafter, also simply referred to as adsorption rate) was calculated according to the following equation.
Adsorption rate (%) = ((initial content (g) of component (B)) − (content (g) of component (B) quantified by HPLC) / initial content (g) of component (B) × 100
Based on the value of the obtained adsorption rate, the adsorbability of the liquid detergent to the cotton cloth was evaluated according to the following evaluation criteria. ○ The above was regarded as a pass.
"Evaluation criteria"
A: Adsorption rate of 40% or more.
：: Adsorption rate is 30% or more and less than 40%.
Δ: Adsorption rate is 20% or more and less than 30%.
X: Adsorption rate is less than 20%.

<Evaluation of antibacterial property>
Collect cotton towels that have been used in actual homes for more than one year, and use the liquid detergent of each case to perform a washing process (JW-Z23A type, manufactured by Haier) in a normal course (water temperature of about 20). And tap water having a hardness of about 3 ° DH and a bath ratio of 20 times). At that time, the washing process was performed with the amount of the liquid detergent charged into the washing machine being 10 mL / 30 L of tap water. A new 100% cotton skin shirt (BVD (registered trademark)) was washed five times with a fully automatic washing machine (NA-F70SD1 manufactured by Panasonic Corporation) (water temperature about 20). C. and a tap water having a hardness of about 3 ° DH) were used as clothing for matching the bath ratio.
After the washing process of the cotton towel was completed, the cotton towel was dried in a room at room temperature (about 30 ° C.) and a relative humidity of 99% RH for 6 hours (room drying). Thereafter, six expert panelists smelled the smell of the cotton towel after drying (room drying) for 6 hours to perform a sensory evaluation. The sensory evaluation was performed by scoring the odor intensity display according to the following evaluation criteria. With respect to the liquid cleaning agent of each example, the average score of six specialized panelists was calculated, and using this average score as an index, it was evaluated whether the antibacterial effect was exhibited (antibacterial property). The numerical values in the table are values obtained by rounding the average score to an integer. Those having an average score of 2 or less were judged as acceptable.
《Evaluation criteria for sensory evaluation (odor intensity display)》
0 point: no off-flavor
1 point: An unpleasant odor is finally felt.
2 points: Off-flavor is felt weak.
3 points: Off-flavor is felt somewhat strong.
4: Strong smell is felt.
5 points: Off-flavor is strongly felt.

As shown in Tables 1 to 3, Examples 1 to 15 to which the present invention was applied showed that the adsorptivity was “◎” or “○”, and it was easily adsorbed on the object to be washed. In addition, it was found that Examples 1 to 15 to which the present invention was applied exhibited an antibacterial effect when the average point of the odor intensity display was 2 or less. Further, in Examples 1 to 15 to which the present invention was applied, the liquid stability was “◎” or “○”, indicating that the liquid stability was excellent.
On the other hand, in Comparative Example 1 containing no component (C), the adsorptivity was “△”, and the average point of the odor intensity display was 4 points.
In Comparative Example 2 in which the component (A) ′ was used instead of the component (A), the adsorptivity was “Δ”, and the average odor intensity display was 3 points.
In Comparative Example 3 using the component (A) ′ instead of the component (A), the adsorptivity was “×”, and the average score of the odor intensity display was 4 points.
In Comparative Example 4 using the component (A) ′ instead of the component (A), the adsorptivity was “Δ”, and the average odor intensity display was 3 points.

  According to the liquid detergent composition for clothing of the present invention, it was found that the liquid detergent composition was easily adsorbed on the article to be washed, and could exhibit a higher antibacterial effect.

Claims (2)

A liquid detergent composition for clothing, comprising the following components (A), (B) and (C).
Component (A): at least one selected from the group consisting of the following components (a1) and (a2).
Component (a1): cationized cellulose.
Component (a2): at least one selected from the group consisting of a diallyl quaternary ammonium salt polymer and a diallyl quaternary ammonium salt-acrylamide copolymer.
Component (B): an antibacterial agent having a phenol structure.
Component (C): anionic surfactant.   The liquid detergent composition for clothing according to claim 1, wherein the component (B) is 4,4'-dichloro-2-hydroxydiphenyl ether.