JP2023008435A - Liquid detergent and cleaning liquid - Google Patents

Abstract

To provide a liquid detergent and a cleaning liquid that has high detergency and suppressed coloration when exposed to light.SOLUTION: Provided is a liquid detergent that contains component (A): a phenolic antibacterial agent, component (B): one or more selected from fluorescent whitening agent and ultraviolet absorber, and component (C): an inorganic alkaline agent. The liquid detergent preferably further contains at least one of component (D): a surfactant and component (E): an inorganic reducing agent.SELECTED DRAWING: None

Description

The present invention relates to liquid detergents and cleaning fluids.

Two types of detergents, ie, powder detergents and liquid detergents, are generally used as detergents for textile products for washing clothes and the like. Demand for liquid detergents is increasing because there is no concern that they will remain undissolved and they can be used by applying them to clothing and the like.
In recent years, due to the increasing awareness of cleanliness, liquid detergents have the ability to remove dirt adhering to the items to be washed (detergency), as well as to remove unpleasant odors generated from the items to be washed. It is required to prevent unpleasant odors from being emitted from the air. Unpleasant odors are generated from the articles to be washed mainly due to the growth of microorganisms adhering to the fibers during drying and storage of the articles to be washed.
In order to prevent the growth of such microorganisms, liquid detergents containing antibacterial agents are known.

However, liquid detergents containing phenolic antimicrobial agents such as diclosan are not sufficiently light stable and may develop coloration when exposed to light. Specifically, a liquid detergent containing a phenol-based antibacterial agent is colored under fluorescent light or sunlight, and may change color from orange to red.
Therefore, as a liquid cleaning agent whose coloration is suppressed even when exposed to light, for example, Patent Document 1 discloses a liquid cleaning agent containing a phenol-based antibacterial agent, an inorganic reducing agent, and a surfactant. there is

WO2016/159368

However, there is still room for improvement in light stability of liquid detergents containing phenolic antibacterial agents. In particular, liquid detergents are often mixed with alkaline agents for the purpose of enhancing their detergency. Easier to color.
SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid detergent and a cleaning liquid that have high detergency and are less colored when exposed to light.

The present invention has the following aspects.
[1] (A) component: a phenol-based antibacterial agent,
(B) component: one or more selected from fluorescent brighteners and ultraviolet absorbers;
(C) component: an inorganic alkaline agent;
A liquid detergent containing
[2] The liquid detergent of [1] above, wherein the component (A) contains at least one of diclosan and triclosan.
[3] Component (D): The liquid detergent of [1] or [2], further containing a surfactant.
[4] Component (E): The liquid detergent according to any one of [1] to [3], further containing an inorganic reducing agent.
[5] The liquid detergent according to any one of [1] to [4], wherein the weight ratio of the component (B) to the weight of the component (A) is 0.1-60.
[6] The liquid detergent according to any one of [1] to [5], wherein at least part of the component (C) is present in a solid state in the liquid detergent.
[7] Component (F): The liquid detergent according to any one of [1] to [6], further containing a structuring agent.
[8] The liquid detergent according to any one of [1] to [7], which has a pH of 8.5 or higher at 25°C.
[9] The liquid detergent according to any one of [1] to [8], which is for textile products.
[10] A cleaning liquid that is an aqueous solution containing the liquid cleaning agent according to any one of [1] to [9],
The content of the component (A) is 0.03 ppm by mass or more relative to the total mass of the cleaning liquid,
A cleaning liquid in which the content of the component (B) is 0.17 ppm by mass or more relative to the total mass of the cleaning liquid.

According to the present invention, it is possible to provide a liquid detergent and a cleaning liquid that have high detergency and suppress coloring when exposed to light.

The present invention will be described in detail below.
The liquid detergent of the present invention is a composition containing the following components (A), (B) and (C). The liquid detergent preferably further contains one or more of the following components (D), (E) and (F). The liquid detergent may further contain water. The liquid detergent may contain components (optional components) other than (A) component, (B) component, (C) component, (D) component, (E) component, (F) component and water.

<(A) Component>
(A) Component is a phenolic antibacterial agent.
Component (A) is a component that has an antibacterial effect and imparts antibacterial properties to textile products such as clothes after washing.
A phenolic compound means having a structure in which one or more hydrogen atoms of an aromatic hydrocarbon nucleus are substituted with a hydroxy group. As component (A), compounds having 1 to 2 benzene nuclei are preferred. Among them, a compound having a structure in which one or more hydrogen atoms in the benzene nucleus are substituted with a hydroxy group is particularly preferable as the component (A).

As the component (A), phenol derivatives or diphenyl compounds known as antibacterial agents can be preferably used. Specific examples of the phenol derivative include 4-isopropyl-3-methylphenol and parachlorometaxylenol. Specific examples of the diphenyl compound include 2-hydroxydiphenyl ether compounds represented by the following formula (1) (hereinafter also referred to as “compound (1)”).
(A) Component may be used individually by 1 type, and may be used in combination of 2 or more types.

In formula (1), Y is an oxygen atom or an alkylene group having 1 to 4 carbon atoms. V is a chlorine atom or a bromine atom. W is —SO ₂ H, —NO ₂ , or an alkyl group having 1 to 4 carbon atoms. z, g, and h are each independently an integer of 0 or 1-3. i is 0 or 1; j is 0 or 1; k is 0 or 1; The sum of h, i and j is 4 or less.
-(V)g means that g hydrogen atoms in the benzene ring are replaced with V. The same applies to -(V)h, -(W)i, -(OH)j and -(OH)k.

(A) Component preferably contains compound (1). Compound (1) is particularly prone to coloration when exposed to light, and is therefore preferable in that the application of the present invention has a large effect.
As the compound (1), Y is an oxygen atom or a methylene group, V is a chlorine atom or a bromine atom, j is 0, k is 0 or 1, z is 1, g is 0 , 1 or 2, h is 0, 1 or 2, and i is 0 are more preferred.
A more preferred specific example of compound (1) is a monochlorohydroxydiphenyl ether (Y is an oxygen atom, z is 1, V is a chlorine atom, one of g or h is 1 and the other is 0, compounds in which i is 0, j is 0, and k is 0, common name: chlorophene), dichlorohydroxydiphenyl ether (Y is an oxygen atom, z is 1, V is a chlorine atom, compound in which g is 1, h is 1, i is 0, j is 0, and k is 0, trichlorohydroxydiphenyl ether (Y is an oxygen atom, z is 1, V is a chlorine atom, one of g or h is 1 and the other is 2, i is 0, j is 0, and k is 0, triclosan) , benzyl chlorophenol (Y is a methylene group, z is 1, V is a chlorine atom, g is 0, h is 1, i is 0, j is 0, k is 0).

Particularly preferred compounds (1) are each described according to the IUPAC nomenclature: 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: chlorophen), 5-chloro-2-(2,4-dichlorophenoxy)phenol (common name: triclosan), 4, 4'-Dichloro-2-hydroxydiphenyl ether (common name: diclosan) is more preferred, and 4,4'-dichloro-2-hydroxydiphenyl ether (common name: diclosan) is most preferred.
The content of compound (1) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and may be 100% by mass with respect to the total mass of component (A). .
Compound (1) may be used alone or in combination of two or more.

The content of component (A) is preferably 0.01 to 2% by mass, more preferably 0.03 to 1% by mass, and further preferably 0.05 to 0.5% by mass, relative to the total mass of the liquid detergent. Preferred is 0.05 to 0.4% by weight, most preferred is 0.05 to 0.25% by weight. (A) If content of a component is more than the said lower limit, the antibacterial property of a liquid detergent will be more excellent. If the content of component (A) is equal to or less than the above upper limit, coloration when exposed to light can be further suppressed. Moreover, it is excellent in cost.

<(B) Component>
Component (B) is one or more selected from fluorescent brighteners and ultraviolet absorbers.
If the liquid detergent contains the (B) component, even if the pH of the liquid detergent is high, it is possible to suppress coloration when the liquid detergent is exposed to light. The reason for this is considered as follows.
When a liquid detergent containing component (A) is exposed to light, a reaction occurs between phenyl groups in component (A), causing coloration. If the liquid detergent contains component (B), the component (B) absorbs the light striking the liquid detergent, thereby suppressing the reaction between phenyl groups and improving the stability against light. It is believed that coloration can be suppressed when exposed to light.
(B) component may be used individually by 1 type, and may be used in combination of 2 or more types.

Fluorescent brighteners include, for example, stilbenes, pyrazolines, coumarins, carboxylic acids, methinecyanines, dibenzothiophene-5-dioxide, azoles, and derivatives of five- and six-membered heterocyclic compounds. Specifically, particularly preferred examples include 4,4'-bis(2-sulfostyryl)biphenyl disodium salt, 4,4'-bis-(4-chloro-3-sulfostyryl)-biphenyl disodium salt, and the like. 4,4′-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2′-disulfonate, 4,4 '-Bis((4-toluidino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate and other stilbene type fluorescent brighteners.
These fluorescent brightening agents may be used singly or in combination of two or more.

As the fluorescent brightening agent, commercially available products can be used, for example, trade names "Whitex SA" and "Whitex SKC" manufactured by Sumitomo Chemical Co., Ltd.; trade names "Tinopal (registered trademark) AMS-GX" manufactured by BASF. , "Tinopal (registered trademark) DBS-X", "Tinopal (registered trademark) CBS-X", "Tinopal (registered trademark) CBS-CL"; trade name "Lemonite CBUS-3B" manufactured by Khyati Chemicals; manufactured by ARCHROMA and the trade name "Leucophor (registered trademark) DMA-X Conc". Among these, Tinopal (registered trademark) CBS-X, Tinopal (registered trademark) CBS-CL, Tinopal (registered trademark) AMS-GX and Leucophor (registered trademark) DMA-X Conc are preferred.

Examples of UV absorbers include 2H-benzotriazole, s-triazine, benzophenone, α-cyanoacrylate, oxanilide, benzoxazinone, benzoate and α-alkylcinnamate. Particularly preferred are 2-hydroxy-4-n-octyloxybenzophenone, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone-type UV absorbers such as benzophenone; 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzo benzotriazole types such as triazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole UV absorber; 2,4-bis(2-hydroxy-4-butyroxyphenyl)-6-(2,4-bis-butyroxyphenyl)-1,3,5-triazine, 2-[4-[( 2-Hydroxy-3-(2′-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and other triazine-type UV absorbers agents and the like.
These ultraviolet absorbers may be used singly or in combination of two or more.

As the component (B), a fluorescent whitening agent is preferable from the viewpoint of increasing the detergency against yellow stains.
When using an ultraviolet absorber as the component (B), a benzophenone-type ultraviolet absorber is preferable from the viewpoint of excellent solubility.
Benzotriazole-type ultraviolet absorbers and triazine-type ultraviolet absorbers are inferior in solubility. Therefore, when the liquid detergent contains at least one of the benzotriazole-type ultraviolet absorber and the triazine-type ultraviolet absorber as the component (B), the liquid detergent may become cloudy. If the liquid detergent becomes cloudy, a light-shielding effect can be obtained, which is preferable from the viewpoint of suppressing the reaction occurring between phenyl groups.

The content of component (B) is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, even more preferably 0.1 to 1% by mass, relative to the total mass of the liquid detergent. 0.1 to 0.5% by weight is particularly preferred. If the content of component (B) is at least the above lower limit, the stability of the liquid detergent against light is further improved, and coloration when exposed to light can be further suppressed. (B) If content of a component is below the said upper limit, it will be excellent in liquid stability and cost.
The term "liquid stability" as used herein refers to the property that solidification, precipitation, and separation of components are unlikely to occur when the liquid detergent is stored.

The mass ratio of component (B) to the mass of component (A), that is, the mass ratio represented by component (B)/component (A) (B/A ratio) is preferably 0.1 to 60, and 0.1 to 60. 25 to 60 are more preferred, 1 to 30 are more preferred, 1 to 10 are particularly preferred, and 2 to 10 are most preferred. When the B/A ratio is at least the above lower limit, the stability of the liquid detergent against light is further improved, and coloration when exposed to light can be further suppressed. When the B/A ratio is equal to or less than the above upper limit, a sufficient antibacterial effect is likely to be obtained.

<(C) Component>
(C) Component is an inorganic alkaline agent.
The component (C) is a component that imparts detergency to the liquid detergent, particularly detergency against sebum stains (sebum detergency).
The inorganic alkaline agent is a component that dissolves in whole or in part in water and exhibits basicity, and the pH of a 1% by mass aqueous solution at 25° C. is 8 or higher. In the present invention, the inorganic alkaline agent does not contain an inorganic reducing agent, which is the component (E) described below.
Specific examples of component (C) include sodium carbonate, sodium hydrogen carbonate, double salts of sodium carbonate and sodium hydrogen carbonate (sodium sesquicarbonate), carbonates such as potassium carbonate and potassium hydrogen carbonate; sodium metasilicate, layered silicon and silicates such as sodium phosphate. Among these, sodium carbonate, potassium carbonate, sodium metasilicate, and lamellar sodium silicate are preferable from the viewpoint of further increasing detergency.
(C) Component may be used individually by 1 type, and may be used in combination of 2 or more types.

In the liquid detergent, all of the component (C) may be dissolved, or at least part of the component (C) may exist in a solid state. In other words, component (C) may be dissolved in the liquid detergent or may exist in a solid state without being dissolved. may be included. If at least part of the component (C) exists in a solid state in the liquid detergent, the light-shielding effect of the component (C) present in a solid state further improves the stability of the liquid detergent against light, Coloration when exposed to light can be further suppressed.
Hereinafter, of the components (C), the component (C) dissolved in the liquid detergent is also referred to as "component (C1)", and the component (C) present in the liquid detergent in a solid state is referred to as "component (C1)". Also referred to as "(C2) component".
The entire amount of component (C) may be blended in the liquid detergent as it is, or an amount not exceeding the solubility of the total amount of component (C) may be blended in the liquid detergent and dissolved. may be incorporated into the liquid detergent.

The surface of component (C2) may be modified. If the surface of the component (C2) is modified, the component (C2) does not dissolve and the particle appearance (number of particles, particle size, etc.) can be maintained well, and the appearance stability of the component (C2) is enhanced. . In addition, the component (C2) is less likely to precipitate, improving dispersion stability. Furthermore, the dissolution rate of component (C2) can be controlled.
As a method for modifying the surface of the component (C2), for example, a method of baking an inorganic alkaline agent may be used.
In this specification, the surface-modified inorganic alkaline agent is also referred to as "modified alkaline agent". In the present invention, sodium carbonate partially containing sodium bicarbonate and sodium sesquicarbonate is also regarded as a modified alkaline agent.

Moreover, the surface of the component (C2) may be coated with a coating agent. That is, a coating layer may be formed on the surface of the component (C2). If the surface of the component (C2) is coated with a coating agent, the component (C2) does not dissolve and the particle appearance (particle number, particle size, etc.) can be maintained well, and the appearance stability of the component (C2) increases. In addition, the component (C2) is less likely to precipitate, improving dispersion stability. Furthermore, the dissolution rate of component (C2) can be controlled. However, when the liquid detergent of the present invention is used in a washing machine or an automatic dispenser equipped with an automatic detergent dispenser, the surface of the component (C2) is It is preferably not coated with a coating.
In this specification, an inorganic alkaline agent whose surface is coated with a coating agent is also referred to as a "coated alkaline agent".

As a coating agent, it is difficult to dissolve in a liquid detergent and easily adheres to an inorganic alkaline agent, but in a washing liquid obtained by diluting a liquid detergent with water, it dissolves, swells, disintegrates, or disperses easily, and is removed from an inorganic alkaline agent. A material that can be easily separated is preferable. Coating agents include, for example, hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxyethylcellulose, polyacrylic acid or salts thereof, acrylic acid-maleic acid copolymers or salts thereof, acrylic acid-maleic anhydride copolymers or salts thereof. , fatty acid or its salt, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, calcium carbonate, aluminosilicate (zeolite, etc.), titanium oxide, and the like. Among these, hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxyethylcellulose, polyacrylic acid or a salt thereof, acrylic acid-maleic acid copolymer, are used from the viewpoint of controlling the solubility in the liquid detergent and maintaining the appearance of the particles. Combined or its salt, acrylic acid-maleic anhydride copolymer or its salt, fatty acid or its salt, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, calcium carbonate are preferred, hydroxypropyl methylcellulose, hydroxypropyl cellulose , methylcellulose, polyacrylic acid or its salt, acrylic acid-maleic acid copolymer or its salt, acrylic acid-maleic anhydride copolymer or its salt, and sodium sulfate are more preferred.
A coating agent may be used individually by 1 type, and may be used in combination of 2 or more type.

The coating alkali agent is granulated and coated by spraying the coating agent while fluidizing the inorganic alkali agent. Immersion and stirring granulation method in which an inorganic alkaline agent is immersed and stirred in a coating agent, and the solvent is distilled off to obtain granules and coated products. Extrusion granulation method of mixing and extruding this with an extruder, rolling granulation method of granulating and coating by spraying coating agent while rotating inorganic alkaline agent, spraying slurry containing inorganic alkaline agent and coating agent It can be obtained by a spray-drying granulation method or the like.
The coating agent may be dissolved or dispersed in any solvent and used in the form of a solution.

Furthermore, a salt that makes the coating agent sensitive (sensitive salt) is added to the granules obtained by the above-described method using any machine such as a mixer, granulator, or fluidized bed, and mixed, A coated alkaline agent may be produced.
As used herein, the term "salt that sensitizes the coating agent" refers to a salt that increases the viscosity of the coating agent, causes gelation, or forms a film. Preferred examples of such sensitive salts include polyvalent chlorides such as calcium chloride, magnesium chloride and aluminum chloride; polyvalent sulfates such as magnesium sulfate and aluminum sulfate; polyvalent nitrates such as calcium nitrate and magnesium nitrate; Polyvalent organic acid salts such as calcium acetate and calcium citrate; calcium oxide; calcium hydroxide; sodium tetraborate and the like.
One type of sensitive salt may be used alone, or two or more types may be used in combination.

The ratio of the coating layer to 100 parts by mass of component (C2) is preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 40 parts by mass. When the ratio of the coating layer is at least the above lower limit, the effect of component (C2) covering the surface can be sufficiently obtained. If the ratio of the coating layer is not more than the above upper limit, the coating layer quickly dissolves, swells, disintegrates, or disperses in the washing liquid, and undissolved components (C2) can be prevented. In addition, the amount of component (C2) per unit weight can be increased.

The particle size of component (C) is preferably 10 to 2000 μm, more preferably 100 to 1500 μm, even more preferably 200 to 1000 μm. When the particle size of the component (C) is at least the above lower limit, the dissolution rate can be easily controlled, and the appearance of the particles can be excellent. If the particle size of component (C) is equal to or less than the above upper limit, the rate of dissolution in water will improve.
On the other hand, when it is not necessary to control the dissolution rate of component (C), the particle size of component (C) is preferably 200 μm or less, more preferably 100 μm or less. In particular, the particle size of component (C) whose surface is not coated is preferably less than 200 μm, more preferably less than 100 μm. If the particle size of the component (C) is equal to or less than the above upper limit, the component (C2) dissolves quickly when the liquid detergent is diluted with water. In addition, the solid component (C2) is less likely to remain on the inlet of a washing machine or on clothes after washing. Therefore, if the particle size of component (C) is 200 µm or less, it is suitable for use in washing machines and automatic dispensers equipped with an automatic detergent injection function.

The particle size of the coated alkaline agent is preferably 10 to 2000 μm, more preferably 100 to 1500 μm, even more preferably 200 to 1000 μm. When the particle diameter of the coated alkaline agent is at least the above lower limit, the dissolution rate can be easily controlled, and the appearance of the particles is excellent. If the particle size of the coated alkaline agent is equal to or less than the above upper limit, the dissolution rate in water is improved.
On the other hand, when the dissolution rate control of the coated alkaline agent is not required, the particle size of the coated alkaline agent is preferably 200 μm or less, more preferably 100 μm or less.

The particle size of the component (C) and the particle size of the coated alkaline agent are measured by a laser diffraction scattering method using a particle size distribution analyzer (for example, manufactured by Beckman Coulter, Inc., product name "LS 13 320"). This is the standard median diameter. The particle size may be measured by a dry method in which the component (C) or the coated alkaline agent is measured as it is, or by a wet method in which the component (C) or the coated alkaline agent is dispersed in a solvent and measured.

The content of component (C) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 3 to 10% by mass, relative to the total mass of the liquid detergent. (C) If content of a component is more than the said lower limit, detergency will increase more. (C) If content of a component is below the said upper limit, the fluidity|liquidity of a liquid detergent can be maintained favorably. Moreover, it is also excellent in liquid stability at low temperatures.
Further, when at least part of the component (C) exists in a solid state in the liquid detergent, the ratio of the component (C2) is 10 to 80% by mass with respect to the total mass of the component (C). Preferably, 15 to 70% by mass, and even more preferably 20 to 60% by mass. If the ratio of component (C2) to the total mass of component (C) is equal to or less than the above upper limit, fluidity of the liquid detergent and beautiful appearance of particles can be obtained.

<(D) Component>
(D) Component is a surfactant.
If the liquid detergent contains the (D) component, the detergency will be enhanced.
Component (D) is not particularly limited as long as it is a surfactant used in conventional liquid detergents. Examples include nonionic surfactants, non-soap anionic surfactants, cationic surfactants, amphoteric surfactants, Semipolar surfactants and the like are included.
As component (D), one surfactant may be used, or two or more surfactants may be used in combination.
From the viewpoint of increasing detergency, the component (D) preferably contains a nonionic surfactant and a non-soap anionic surfactant.
As component (D), a nonionic surfactant, a non-soap anionic surfactant, and one or more of a cationic surfactant, an amphoteric surfactant and a semipolar surfactant may be used in combination.

Examples of nonionic surfactants include polyoxyalkylene type nonionic surfactants, alkylphenols, alkylene oxide adducts such as fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, polyoxyethylene polyoxypropylene block copolymers, Fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, hydrogenated castor oil alkylene oxide adducts, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like.
A nonionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more types.
As the nonionic surfactant, a polyoxyalkylene-type nonionic surfactant is preferable, and among them, in particular, a compound represented by the following general formula (2) (hereinafter also referred to as "compound (2)"), the following general formula A compound represented by (3) (hereinafter also referred to as "compound (3)") is more preferred, and compound (2) is even more preferred.

R ¹¹ —O—[(EO) _s /(A ¹¹ O) _t ]—(EO) _u —R ¹² (2)
(In general formula (2), R ¹¹ is a straight or branched hydrocarbon group having 8 to 22 carbon atoms; R ¹² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a is an alkenyl group, EO is an oxyethylene group, s is a number representing the average repeating number of EO from 3 to 25, and A ¹¹ O is at least one of PO (oxypropylene group) and BO (oxybutylene group); t is a number from 0 to 6 representing the average number of repetitions of A ¹¹ O. u is a number from 0 to 20 representing the average number of repetitions of EO.)

The number of carbon atoms in the hydrocarbon group of R ¹¹ is 8-22, preferably 10-18, more preferably 12-18.
R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
When u is 0, s is preferably 4-20, more preferably 5-16, even more preferably 6-10. t is preferably 0 to 4, more preferably 0 to 2, even more preferably 0.
When u is 1 or more, s is preferably 4-16, more preferably 6-12, even more preferably 8-10. t is preferably 1 to 4, more preferably 2 to 3. u is preferably 4 to 16, more preferably 6 to 12, even more preferably 8 to 10.
When t is 1 or more, in [(EO) _s /(A ¹¹ O) _t ], there is no particular limitation on the distribution (order of arrangement) of EO and PO, EO and BO, or EO, PO and BO. may be arranged in blocks or may be arranged randomly.

R ¹³ —X—[(EO) _p /(A ¹² O) _q ]—(EO) _r —R ¹⁴ (3)
(In general formula (3), R ¹³ is a hydrocarbon group having 7 to 21 carbon atoms; —X— is —COO— or —CONH—; R ¹⁴ is a hydrogen atom; an alkyl group or an alkenyl group having 2 to 6 carbon atoms; EO is an oxyethylene group; p is a number of 3 to 25 indicating the average number of repetitions of EO; A ¹² is PO (oxypropylene group) and BO ( oxybutylene group), q is a number from 0 to 6 representing the average number of repetitions of A ¹² O, and r is a number from 0 to 20 representing the average number of repetitions of EO.)

The number of carbon atoms in the hydrocarbon group of R ¹³ is 7-21, preferably 9-19, more preferably 11-17.
-X- is preferably -COO-.
R ¹⁴ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms.
When r is 0, p is preferably 6-22, more preferably 9-20, even more preferably 12-18. q is preferably 0 to 4, more preferably 0 to 2, even more preferably 0.
When r is 1 or more, p is preferably 4-16, more preferably 6-12, even more preferably 8-10. q is preferably 1 to 4, more preferably 2 to 3. r is preferably 4 to 16, more preferably 6 to 12, even more preferably 8 to 10.
When q is 1 or more, there is no particular limitation on the distribution (order of arrangement) of EO and PO, EO and BO, or EO, PO and BO in [(EO) _p /(A ¹² O) _q ]. may be arranged in blocks or may be arranged randomly.

The content of the nonionic surfactant is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, still more preferably 10 to 45% by mass, and 15 to 40% by mass with respect to the total mass of the liquid detergent. Especially preferred. If the content of the nonionic surfactant is at least the above lower limit, the detergency will be enhanced. If the content of the nonionic surfactant is equal to or less than the above upper limit, liquid stability at low temperatures is improved.

Examples of non-soap anionic surfactants include linear alkylbenzene sulfonic acid or its salt (LAS), α-olefin sulfonic acid or its salt (AOS), linear or branched alkyl sulfate ester or its salt ( AS), polyoxyalkylene alkyl (alkenyl) ether sulfate or its salt (AES), alkanesulfonic acid having an alkyl group or its salt, α-sulfo fatty acid ester or its salt, internal olefin sulfonic acid or its salt (IOS) , alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide ether carboxylic acid or its salt, acylaminocarboxylic acid or its salt, carboxylic acid type anion Surfactants; phosphoric acid ester types such as alkyl phosphates or salts thereof, polyoxyalkylene alkyl phosphates or salts thereof, polyoxyalkylene alkylphenyl phosphates or salts thereof, glycerin fatty acid ester monophosphates or salts thereof Examples include anionic surfactants.
Salt forms of non-soap anionic surfactants include, for example, alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). ) and the like.
The non-soap anionic surfactants may be used singly or in combination of two or more.
As the non-soap anionic surfactant, LAS, AOS, AS, AES, and IOS are preferable, and LAS, AES, and IOS are more preferable from the viewpoint of further increasing detergency. Preferably, the liquid detergent contains at least AES, more preferably both LAS and AES.

A polyoxyalkylene alkyl (alkenyl) ether sulfate or a salt thereof (AES) is represented by the following general formula (4).
R ¹⁵ —O—[(EO) _m /(PO) _n ]—SO ₃ ⁻ Ma ⁺ (4)
(In general formula (4), R ¹⁵ is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms. EO is is an oxyethylene group, PO is an oxypropylene group, m is a number of 0.1 or more representing the average number of repetitions of EO, and n is a number of 0 to 6 representing the average number of repetitions of PO.[ (EO) _m /(PO) _n ] indicates that there is no restriction on the arrangement order of EO and PO, and Ma ⁺ is a countercation.)

The internal olefin sulfonic acid or its salt (IOS) is an alkene sulfonic acid represented by the following general formula (5) (hereinafter also referred to as "compound (5)") and a general formula (6) below. It is a mixture with hydroxyalkanesulfonic acid (hereinafter also referred to as "compound (6)"). An internal olefin represents an olefin in which a double bond exists inside from the 2-position.

R ¹⁶ —CH═CH(CH ₂ ) _x CH(SO ₃ Mb)—R ¹⁷ (5)
(In formula (5), R ¹⁶ is an alkyl group, R ¹⁷ is an alkyl group having 1 to 5 carbon atoms, the total number of carbon atoms is 8 to 24, x is a number of 0 to 4, Mb represents a counter ion.)

The number of carbon atoms in compound (5) is 8 to 24, preferably 10 to 20, more preferably 12 to 18, even more preferably 14 to 18. If the number of carbon atoms is at least the above lower limit, the lipophilicity of IOS increases, and the function as a surfactant increases. If the number of carbon atoms is equal to or less than the above upper limit, the hydrophilicity of IOS increases, and the function as a surfactant increases.

R ¹⁶ in formula (5) represents an alkyl group. The number of carbon atoms in R ¹⁶ is preferably 1-21, more preferably 3-17, even more preferably 7-15.
R ¹⁷ in formula (5) represents an alkyl group having 1 to 5 carbon atoms. The number of carbon atoms in R ¹⁷ is preferably 1-3.
x in formula (5) is 0 to 4, preferably 0 to 2. If x is more than the said lower limit, detergency will increase more. If x is below the said upper limit, liquid stability will improve more.
Examples of Mb in formula (5) include sodium ion, potassium ion, magnesium ion, and ammonium ion.

R ¹⁸ —CH(OH)(CH ₂ ) _y CH(SO ₃ Mc)—R ¹⁹ (6)
(In formula (6), R ¹⁸ is an alkyl group, R ¹⁹ is an alkyl group having 1 to 5 carbon atoms, the total number of carbon atoms is 8 to 24, y is a number of 0 to 4, Mc represents a counterion.)

Compound (6) is the hydroxy form of compound (5).
The number of carbon atoms in compound (6) is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 14 to 18. If the number of carbon atoms is at least the above lower limit, the lipophilicity of IOS increases, and the function as a surfactant increases. If the number of carbon atoms is equal to or less than the above upper limit, the hydrophilicity of IOS increases, and the function as a surfactant increases.

R ¹⁸ in formula (6) represents an alkyl group. The number of carbon atoms in R ¹⁸ is preferably 2-22, more preferably 4-18, even more preferably 8-16.
R ¹⁹ in formula (6) represents an alkyl group having 1 to 5 carbon atoms. The number of carbon atoms in R ¹⁹ is preferably 1-3.
y in formula (6) is 0 to 4, preferably 0 to 2. If y is at least the above lower limit, the detergency will be enhanced. When y is equal to or less than the above upper limit value, the liquid stability is further improved.
Examples of Mc in formula (6) include sodium ion, potassium ion, magnesium ion, and ammonium ion.

Mass of IOS ((IO-1S) component) having sulfonic acid groups at positions 2 to 4 and IOS ((IO-2S) component) having sulfonic acid groups at positions 5 and higher among IOS The ratio ((IO-2S)/(IO-1S) ratio) is preferably 0.3-5, more preferably 1-3. When the (IO-2S)/(IO-1S) ratio is at least the above lower limit, the slipperiness of the object to be washed is further enhanced. If the (IO-2S)/(IO-1S) ratio is equal to or less than the above upper limit, the liquid stability is further enhanced.
The (IO-1S) component is IOS in which R ¹⁷ in formula (5) and R ¹⁹ in formula (6) have 1 to 3 carbon atoms. The (IO-2S) component is an IOS in which R ¹⁷ in formula (5) and R ¹⁹ in formula (6) have 4 or more carbon atoms.

IOS is obtained by sulfonating an internal olefin. The total number of carbon atoms in the internal olefin is 8 to 24, preferably 10 to 20, more preferably 12 to 18, even more preferably 14 to 18.
Internal olefins can be obtained, for example, by isomerizing 1-olefins obtained by dehydrating 1-alcohols. When the internal olefin is sulfonated, β-sultone is generated quantitatively, and a part of β-sultone is converted to γ-sultone and olefin sulfonic acid, which are then converted into compounds ( 5) and compound (6) (for example, J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxy group of the resulting compound (6) is inside the alkane chain and the double bond of compound (5) is inside the olefin chain. In addition, the resulting product is mainly a mixture of these, and a part thereof includes a hydroxyalkanesulfonate having a hydroxy group at the end of the carbon chain, or a double bond at the end of the carbon chain. A trace amount of α-olefin sulfonate may also be contained. Each of these products and mixtures thereof are collectively referred to herein as IOS.

The mass ratio of compound (5) to the mass of compound (6) with respect to 100% by mass of IOS, that is, the mass ratio represented by compound (5)/compound (6) (compound (5)/compound (6) ratio) is preferably 1/99 to 50/50, more preferably 1/99 to 30/70, even more preferably 5/95 to 20/80, and particularly preferably 10/90 to 15/85. When the compound (5)/compound (6) ratio is at least the above lower limit, the liquid stability is further enhanced. If the compound (5)/compound (6) ratio is equal to or less than the above upper limit, the detergency will be enhanced.

The content of the non-soap anionic surfactant is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, even more preferably 10 to 30% by mass, further preferably 15 to 30% by mass, relative to the total mass of the liquid detergent. % by weight is particularly preferred. If the content of the non-soap anionic surfactant is at least the above lower limit, the detergency will be enhanced. In addition, anti-soil redeposition property is improved. When the content of the non-soap anionic surfactant is equal to or less than the above upper limit, the fluidity of the liquid detergent is excellent and the liquid stability at low temperatures is improved.

Further, the mass ratio of the nonionic surfactant to the mass of the non-soap anionic surfactant, that is, the mass ratio represented by nonionic surfactant/non-soap anionic surfactant (nonion/anion ratio) was 0.00. 1 to 3 are preferred, 0.15 to 2 are more preferred, 0.2 to 1.5 are even more preferred, and 0.25 to 1.3 are particularly preferred. If the nonion/anion ratio is within the above range, liquid stability at low temperatures is improved. In addition, the liquid detergent is less prone to gelation, and better fluidity can be maintained.
When the liquid detergent contains an enzyme, the enzyme stability may decrease if the liquid detergent contains a non-soap anionic surfactant as component (D). Enzyme stability can be maintained well.

Examples of cationic surfactants include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristate dimethylaminopropylamide, palmitate dimethylaminopropylamide, stearic acid dimethylaminopropylamide, Long-chain fatty amidoalkyl tertiary amines such as behenic acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide or their salts; fatty ester alkyl tertiary amines such as palmitate ester propyl dimethylamine and stearate ester propyl dimethylamine or salts thereof; diethanolaminopropylamide palmitate, diethanolaminopropylamide stearate; tetra short chain (alkyl of 1 to 4 carbon atoms) such as tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt Ammonium salts; octyltrimethylammonium salt, decyltrimethylammonium salt, dodecyltrimethylammonium salt, tetradecyltrimethylammonium salt, lauryltrimethylammonium salt, cetyltrimethylammonium salt, palmityltrimethylammonium salt, stearyltrimethylammonium salt, octyldimethylethylammonium salt , decyldimethylethylammonium salt, dodecyldimethylethylammonium salt, tetradecyldimethylethylammonium salt, lauryldimethylethylammonium salt, cetyldimethylethylammonium salt, stearyldimethylethylammonium salt, octyldiethylmethylammonium salt, decyldiethylmethylammonium salt, Long-chain (alkyl having 8 to 18 carbon atoms) trishort-chain (alkyl having 1 or 2 carbon atoms) ammonium such as dodecyldiethylmethylammonium salt, tetradecyldiethylmethylammonium salt, cetyldiethylmethylammonium salt, stearyldiethylmethylammonium salt Salt; dioctyldimethylammonium salt, didecyldimethylammonium salt, N,N-didecyl-N-methyl-poly(oxyethyl)ammonium salt, didodecyldimethylammonium salt, ditetradecyldimethylammonium salt, dicetyldimethylammonium salt, di Stearyldimethylammonium salt, dioctylmethylethylammonium salt, didecylmethylethylammonium salt di-long chain (alkyl having 8 to 18 carbon atoms) di-short chain (carbon Number 1 or 2 alkyl) ammonium salts; Long-chain (C 8-18 alkyl) dishort-chain (C 1 or 2 alkyl) hydroxyalkyl (C 1 or 2) ammonium such as stearyldimethylhydroxyethylammonium Salt; dishort chain (alkyl having 1 or 2 carbon atoms) long chain (alkyl having 1 or 2 carbon atoms) having a trialkoxysilylalkyl group (4 to 10 carbon atoms) such as [3(trimethoxysilyl)]propyl(dimethyl)octadecyl ammonium salt 8-18 alkyl)ammonium salts; amine nitrates; benzyltrimethylammonium salts; benzalkonium salts;
Examples of the salt form of the cationic surfactant include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.), and the like. mentioned.
A cationic surfactant may be used individually by 1 type, and 2 or more types may be combined and used.

The content of the cationic surfactant is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, relative to the total mass of the liquid detergent. If the content of the cationic surfactant is within the above range, it is possible to further enhance the softening, antibacterial and deodorizing effects of clothes.

Examples of amphoteric surfactants include alkylbetaine-type, alkylamidobetaine-type, imidazoline-type, alkylaminosulfone-type, alkylaminocarboxylic acid-type, alkylamidocarboxylic acid-type, amideaminoacid-type, and phosphoric acid-type amphoteric surfactants. mentioned.
An amphoteric surfactant may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of semipolar surfactants include alkylamine oxides, alkylamidopropyldimethylamine oxides, and the like.
Semi-polar surfactants may be used singly or in combination of two or more.

The content of component (D) is preferably 15 to 80% by mass, more preferably 15 to 70% by mass, even more preferably 20 to 60% by mass, and 40 to 55% by mass relative to the total mass of the liquid detergent. Especially preferred. (D) If content of a component is more than the said lower limit, detergency will increase more. (D) If the content of the component is equal to or less than the above upper limit, the liquid cleaning agent is less likely to gel, and the fluidity can be maintained more satisfactorily.

<(E) component>
(E) Component is an inorganic reducing agent.
If the liquid detergent contains the component (E), coloration can be further suppressed when the liquid detergent is exposed to light. The reason for this is considered as follows.
As described above, when a liquid detergent containing component (A) is exposed to light, a reaction occurs between phenyl groups in component (A), causing coloration, but the reaction is suppressed by component (E). and component (E) does not color even if it is oxidized.
In addition, the reducing agent means an agent that has a function of reducing a substance and itself oxidizes. By inorganic reducing agent is meant a reducing agent that does not contain carbon atoms.

Examples of component (E) include sulfites such as sodium sulfite and potassium sulfite; pyrosulfites such as sodium pyrosulfite and potassium pyrosulfite; and bisulfites such as sodium hydrogensulfite and potassium hydrogensulfite. Among these, sodium sulfite and potassium sulfite are preferred, and sodium sulfite is more preferred, from the viewpoint of excellent liquid stability.
(E) component may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of component (E) is preferably 0.001 to 3% by mass, more preferably 0.02 to 1% by mass, and further preferably 0.05 to 0.5% by mass, relative to the total mass of the liquid detergent. preferable. If the content of component (E) is at least the above lower limit, the stability of the liquid detergent against light is further improved, and coloration when exposed to light can be further suppressed. In addition, it is possible to suppress the coloring of the composition due to storage at high temperature. If the content of the component (E) is equal to or less than the above upper limit, the liquid stability at low temperatures is enhanced.

The total content of components (B) and (E) is preferably 0.06 to 5% by mass, more preferably 0.1 to 2% by mass, more preferably 0.3 to 0.3% by mass, relative to the total mass of the liquid detergent. 1% by mass is more preferred. If the total content of the component (B) and the component (E) is at least the above lower limit, the stability of the liquid detergent against light is further improved, and coloration when exposed to light can be further suppressed. If the total content of the component (B) and the component (E) is equal to or less than the above upper limit value, excellent liquid stability and cost are obtained.

The mass ratio of component (B) to the mass of component (E), that is, the mass ratio represented by component (B)/component (E) (B/E ratio) is preferably 0.1 to 150, and 0.1 to 150. 2 to 50 are more preferred, and 0.4 to 20 are even more preferred. When the B/E ratio is at least the above lower limit, the stability of the liquid detergent against light is further improved, and coloration when exposed to light can be further suppressed. When the B/E ratio is equal to or less than the above upper limit, the liquid stability is enhanced, and coloring of the composition due to storage at high temperatures can be suppressed.

<(F) Component>
(F) Component is a structuring agent.
The liquid detergent is structured by containing the component (F). Therefore, when the liquid detergent contains insoluble particles (for example, the above-described component (C2)), the dispersion stability of the insoluble particles can be enhanced, the insoluble particles can be uniformly dispersed in the liquid detergent, and the state can be maintained satisfactorily. can.
In this specification, the term “structured” refers to a state in which the viscosity changes before and after force is applied.

Examples of structuring agents include bacterial cellulose, non-bacterial cellulose, and the following compound (7).
A structuring agent may be used individually by 1 type, and may be used in combination of 2 or more types.

Bacterial cellulose is cellulose produced by fermentation of bacteria of the genus Acetobacter.
Examples of bacterial cellulose include so-called mesh-like bacterial cellulose, in which water-insoluble fibers are branched into a network and mesh with each other to form a network.

At least part of the bacterial cellulose may be coated or mixed with a thickening agent.
Thickeners include, for example, carboxymethylcellulose (CMC), modified CMC, xanthan products, pectin, alginates, gellan gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, gum ghatti, gum karaya, gum tragacanth, Examples include tamarind gum and locust bean gum.
A thickener may be used individually by 1 type, and may be used in combination of 2 or more type.

Commercially available bacterial cellulose can be used, for example, CPKelco U.S.A. S. company's product name "CELLULON (registered trademark)".

Non-bacterial cellulose is cellulose obtained from vegetables, fruits and wood and is also called cellulose fiber.

As the non-bacterial cellulose, commercially available products can be used, for example, the trade name "Avicel (registered trademark)" manufactured by FMC, the trade name "Citri-Fi" manufactured by Fiberstar, the trade name "Betafib" manufactured by Cosun, etc. mentioned.

Compound (7) is a compound (triglyceride component) represented by the following general formula (7).

In formula (7), Z ¹ to Z ³ are each independently a hydrogen atom, a hydroxy group, or a carboxy group. Z ¹ to Z ³ may be the same or different.
In formula (7), a + b = 7 to 19, c + d = 7 to 19, and e + f = 7 to 19, preferably a + b = 11 to 15, c + d = 11 to 15, and e + f = 11 to 15, More preferably, a+b=13-15, c+d=13-15, and e+f=13-15. When each of a+b, c+d, and e+f is 7 or more, the volume of the hydrophobic group portion becomes sufficiently bulky, and the coating detergency is enhanced. On the other hand, if each of a+b, c+d, and e+f is 19 or less, the risk of solidification due to bulkiness of the hydrophobic group portion is reduced.

Examples of compound (7) include compound (7-1) in which Z ¹ to Z ³ are hydroxy groups, compound (7-2) in which Z ¹ to Z ³ are hydrogen atoms, and the like.
Hydrogenated castor oil is particularly preferred as compound (7-1), and hydrogenated palm oil is particularly preferred as compound (7-2).
Hydrogenated castor oils may include glycerides, particularly triglycerides, containing alkyl or alkenyl moieties with 10 to 22 carbon atoms incorporating hydroxyl groups, specifically trihydroxystearin, dihydroxystearin, and the like.
Hydrogenated castor oil is obtained by hydrogenating castor oil to convert double bonds that may be present as ricinoleyl moieties in the starting oil. Transformation of the double bond converts the ricinoleyl moiety to a saturated hydroxyalkyl moiety such as hydroxystearyl.
Hydrogenated castor oil can be processed in any suitable starting form, including, but not limited to, which can be used in the solid state, the melt state, or mixtures thereof.

Commercially available hydrogenated castor oil can be used, for example, Rheox, Inc.; product name "THIXCIN (registered trademark)" manufactured by NOF Corporation, and product name "Caster Wax A Flake" manufactured by NOF Corporation.
As the hardened palm oil, commercially available products can be used.

As the component (F), bacterial cellulose and non-bacterial cellulose are preferable because even a small amount thereof can sufficiently exhibit the effect of enhancing the dispersion stability of insoluble particles such as the component (C2), and a highly transparent liquid appearance can be easily obtained. , bacterial cellulose is more preferred.

The content of component (F) is preferably 0.02 to 2% by mass, more preferably 0.04 to 1.5% by mass, and further preferably 0.05 to 1% by mass, relative to the total mass of the liquid detergent. preferable.
Further, for example, when using a commercially available bacterial cellulose preparation such as "CELLULON (registered trademark)" as the component (F), the content of the component (F) is the actual content of the product. , preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and even more preferably 2.5 to 7% by mass, relative to the total mass of the liquid detergent.
Here, the "content of the product as it is" means the content of the product itself, including the water contained in the product.
If the content of the component (F) is at least the above lower limit, the dispersion stability of the insoluble particles such as the component (C2) is enhanced. If the content of the component (F) is equal to or less than the above upper limit, the viscosity of the liquid detergent becomes lower, and usability and liquid stability are further enhanced.

<Water>
Purified water, ion-exchanged water, distilled water, tap water, and the like can be used as water.
One type of water may be used alone, or two or more types may be used in combination.
The content of water is not particularly limited, but in the case of a liquid detergent having a high concentration of surfactant, the content of water is preferably 7 to 40% by weight, preferably 10 to 30% by weight, based on the total weight of the liquid detergent. % by mass is more preferred, and 15 to 28% by mass is even more preferred. In particular, when the liquid detergent contains component (C2), if the water content is less than the above upper limit, component (C2) is difficult to dissolve in the liquid detergent, and particle appearance (particle number, particle size, etc.) can be maintained well, and the appearance stability of the (C2) component is improved.
In the case of a liquid detergent with a low surfactant concentration, the water content is preferably 60-85% by mass, more preferably 65-83% by mass, even more preferably 70-80% by mass.
If the content of water is at least the above lower limit, the viscosity of the liquid cleaning agent can be lowered, thereby improving usability and making it less flammable. Furthermore, the compatibility between the components is improved, and the manufacturability and liquid stability are further enhanced. If the content of water is equal to or less than the above upper limit, detergency and liquid stability will be enhanced.
In addition, "the surfactant concentration is high" means that the total content of the surfactant in the liquid cleaning agent is 40% by mass or more with respect to the total mass of the liquid cleaning agent. "Low surfactant concentration" means that the total content of surfactants in the liquid detergent is less than 40% by mass with respect to the total mass of the liquid detergent.

<Optional component>
Optional components include a water-miscible organic solvent, a builder component other than components (C) and (E), a chelating agent, a pH adjuster, a viscosity reducer and a solubilizer, an enzyme, and a thickener other than component (F). agents, alkali agents other than component (C), higher fatty acids or salts thereof, preservatives, antioxidants, enzyme stabilizers, texture improvers, dye transfer inhibitors, anti-soil redeposition agents, coloring agents, emulsifying agents , flavoring agents, discoloration inhibitors, hydrotropic agents, bleaching agents, pearl agents, extracts of natural products, and the like.
Optional components may be used singly or in combination of two or more.

A water-miscible organic solvent refers to an organic solvent that dissolves 25 g or more in 1 L of water at 25°C.
Water-miscible organic solvents include alcohols such as ethanol, glycerin, 1-propanol, 2-propanol, 1-butanol, 3-methoxy-3-methyl-1-butanol (Solfit, trade name); propylene glycol; (PG), butylene glycol, hexylene glycol and other glycols; diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of about 200 to 1000, dipropylene glycol and other polyglycols; diethylene glycol monomethyl ether, diethylene glycol monoethyl Alkyl ethers such as ether, diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, and the like are included. Among these, ethanol, glycerin, 3-methoxy-3-methyl-1-butanol, propylene glycol, and a molecular weight of about 200 to 1000 are preferred from the viewpoints of low odor, availability, fluidity of liquid detergents, and the like. of polyethylene glycol and diethylene glycol monobutyl ether (butyl carbitol) are preferred, and ethanol, glycerin and propylene glycol are more preferred.
The water-miscible organic solvents may be used singly or in combination of two or more. It is preferable to use propylene glycol and glycerin in combination from the viewpoints of enzyme stability (residual activity), appearance stability, and fluidity of the liquid detergent.
The content of the water-miscible organic solvent is preferably 5-50% by mass, more preferably 10-40% by mass, and even more preferably 10-25% by mass, relative to the total mass of the liquid detergent.

Examples of builder components other than components (C) and (E) (hereinafter also referred to as "other builder components") include sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, ammonium chloride, ammonium sulfate, tetraborate, sodium, sodium pyrophosphate, sodium tripolyphosphate, sodium hydroxide, potassium hydroxide, aluminosilicate (eg, zeolite, etc.), and the like.
Other builder components may be used singly or in combination of two or more.
Other builder components may be dissolved in the liquid detergent or present in solid form.
The content of other builder components is preferably 20% by mass or less, more preferably 0.5 to 10% by mass, based on the total mass of the liquid detergent.

As the chelating agent, for example, a chelating agent having a tri- or tetravalent carboxylic acid group or a salt thereof is preferred. Specific examples thereof include citric acid or its salts, aminocarboxylic acid-based chelating agents or its salts. Aminocarboxylic acid refers to a compound containing at least one primary to tertiary amino group and at least one carboxyl group in one molecule, and an aminocarboxylic acid-based chelating agent is a chelating agent that is an aminocarboxylic acid. say.
Aminocarboxylic acid-based chelating agents that are known in the field of detergents can be used. Specific examples include methylglycine diacetate (MGDA), methylglycine diacetate, L-glutamic acid diacetic acid (GLDA), L-glutamic acid diacetate, diethylenetriamine pentaacetic acid (DTPA), diethylenetriamine pentaacetate, and ethylenediamine succinic acid. (EDDS), ethylenediamine succinate, 3-hydroxy-2,2'-iminodisuccinic acid (HIDS), 3-hydroxy-2,2'-iminodisuccinate, L-aspartic acid-N,N-2 acetic acid (ASDA) ), L-aspartic acid-N,N-2 acetate and the like. Among these, citric acid or its salts, MGDA or its salts are preferred, and trisodium methylglycine diacetate is more preferred.
A chelating agent may be used individually by 1 type, and may be used in combination of 2 or more types.
The content of the chelating agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the total mass of the liquid detergent. 0.1% by mass or more is more preferable. If the content of the chelating agent is at least the above lower limit, the detergency improving effect, liquid stability improving effect, and discoloration preventing effect can be sufficiently obtained.

Examples of pH adjusters include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; basic amino acids such as arginine and lysine; ammonia; acid agents such as sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid. . Among these, sodium hydroxide, sulfuric acid and hydrochloric acid are preferred.
The pH adjusters may be used singly or in combination of two or more.
The amount of the pH adjuster to be added may be appropriately set so as to adjust the pH of the liquid detergent to a predetermined value.

Viscosity reducers and solubilizers include, for example, aromatic sulfonic acids or salts thereof. Specific examples include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and salts thereof. Salts of aromatic sulfonic acids include sodium salts, potassium salts, calcium salts, magnesium salts, ammonium salts, alkanolamine salts, and the like.
The viscosity reducers and solubilizers may be used singly or in combination of two or more.
The content of the viscosity reducer and the solubilizer is preferably 0.1 to 15% by weight with respect to the total weight of the liquid detergent.

If the liquid detergent contains an enzyme, the cleaning power against sebum stains, protein stains, and spilled food stains is enhanced.
Here, the enzyme means an enzyme preparation.
As the enzyme, a liquid enzyme preparation may be used, or a solid (granular) enzyme preparation may be used. When a solid enzyme preparation is used, it is preferred that a part or the whole of it is present in the liquid detergent in a solid state from the viewpoint of enzyme stability.

Examples of enzymes include protease, amylase, lipase, cellulase, mannanase and the like.
As the protease, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Savinase Evity 16L, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 5L, Alcalase 5L, 2L, Alcalase, 2L, Alcalase, 2L, 2L, Alcalase, 16XL, Savinase Evity 16L, Savinase Ultra 16XL, Savinase Evity 16L, and Alcalase are available as protease preparations from Novozymes. Ｌｉｑｕａｎａｓｅ ２．５Ｌ、Ｌｉｑｕａｎａｓｅ Ｕｌｔｒａ ２．５Ｌ、Ｌｉｑｕａｎａｓｅ Ｕｌｔｒａ ２．５ＸＬ、Ｃｏｒｏｎａｓｅ ４８Ｌ、Ｐｒｏｇｒｅｓｓ Ｕｎｏ １００Ｌ、Ｄｅｏｚｙｍｅ、Ｓａｖｉｎａｓｅ Ｅｖｉｔｙ １２Ｔ、Ｋａｎｎａｓｅ Ｅｖｉｔｙ ２４Ｔ；デュポン社から入手できる商品名ＥＦＦＥＣＴＥＮＺ Ｐ１５０、ＥＦＦＥＣＴＥＮＺ Ｐ１００、ＰＲＥＦＥＲＥＮＺ Ｐ１００などis mentioned.
アミラーゼとしては、アミラーゼ製剤としてノボザイムズ社から入手できる商品名Ｔｅｒｍａｍｙｌ ３００Ｌ、Ｔｅｒｍａｍｙｌ Ｕｌｔｒａ ３００Ｌ、Ｄｕｒａｍｙｌ ３００Ｌ、Ｓｔａｉｎｚｙｍｅ １２Ｌ、Ｓｔａｉｎｚｙｍｅ Ｐｌｕｓ １２Ｌ、Ａｍｐｌｉｆｙ １２Ｌ、Ａｍｐｌｉｆｙ Ｐｒｉｍｅ １００Ｌ、Ｓｔａｉｎｚｙｍｅ Ｐｌｕｓ １２Ｔ；デュポン社から入手できる商品名ＥＦＦＥＣＴＥＮＺ S100; trade name pullulanase Amano available from Amano Enzyme Co.; trade name DB-250 available from Seikagaku Corporation;
Examples of lipase include Lipex 100L, Lipolase 100L, Lipex 100T (trade names) available from Novozymes as lipase preparations.
Examples of cellulase include Endolase 5000L, Celluzyme 0.4L, Carezyme 4500L and Celluclean 4500T available from Novozymes as cellulase preparations, and REVITALENTZ 2000 available from DuPont.
Examples of mannanase include Mannaway 4L, Mannaway 4.0T and the like available from Novozymes as mannanase preparations.
酵素が２種以上配合されたマルチ酵素としては、Ｍｅｄｌｅｙ Ｃｏｒｅ ２１０Ｌ、Ｍｅｄｌｅｙ Ｃｏｒｅ ２００Ｌ、Ｍｅｄｌｅｙ Ｂｏｏｓｔ ３００Ｌ、Ｍｅｄｌｅｙ Ａｄｖａｎｃｅ ２００Ｔ、Ｍｅｄｌｅｙ Ｇｌｏｗ ２００Ｌ、Ｍｅｄｌｅｙ Ｂｒｉｌｌｉａｎｔ １００Ｌ、Ｍｅｄｌｅｙ Ｅｓｓｅｎｔｉａｌ １５０Ｌ、Ｍｅｄｌｅｙ Ｃｏｒｅ ２００Ｔ、Ｍｅｄｌｅｙ ＣｌｅａｎＲ、Ｍｅｄｌｅｙ Ｅｓｓｅｎｔｉａｌ 200T, Medley SmartR, Medley Advance 200T, Medley Boost 200L, Medley Boost 200T, Medley SuperioR 100T and the like.
An enzyme may be used individually by 1 type, and 2 or more types may be combined and used.

The enzyme content is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, even more preferably 0.4 to 2.5% by mass, relative to the total mass of the liquid detergent. If the content of the enzyme is within the above range, the detergency will be enhanced and it will be economically advantageous.

Examples of thickeners other than component (F) (hereinafter also referred to as "other thickeners") include acrylic polymers, xanthan gum, and galageenan.
Examples of commercially available acrylic polymers include the Carbopol (registered trademark) series manufactured by Lubrizol. The Carbopol series includes, for example, Carbopol ETD 2623, Carbopol EZ3, Carbopol EZ4, Carbopol Ultrez20, Carbopol Ultrez21, Carbopol Aqua 30 and the like.
Other thickeners may be used singly or in combination of two or more.
The content of other thickening agents is preferably 6% by mass or less, more preferably 0.2 to 4% by mass, relative to the total mass of the liquid detergent.

Examples of alkaline agents other than component (C) (hereinafter also referred to as “other alkaline agents”) include monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino Alkanolamine such as 2-methyl-1,3-propanediol, isopropanolamine and diisopropanolamine. Among these, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and diisopropanolamine are preferred.
Other alkaline agents may be used singly or in combination of two or more.
The content of other alkaline agents is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, relative to the total mass of the liquid detergent.
In addition, you may use another alkaline agent as a pH adjuster.

If the liquid detergent contains a higher fatty acid or its salt, the antifoaming property will be enhanced. The term "antifoaming" refers to the property of suppressing foaming when washing with a liquid detergent, specifically when the liquid detergent is diluted with tap water or the like.
Higher fatty acids or salts thereof include single fatty acids or salts thereof such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, behenic acid; Fatty acids, mixed fatty acids such as beef tallow fatty acids, salts thereof, and the like are included.
Preferred higher fatty acids are lauric acid, myristic acid, palmitic acid and coconut oil fatty acid, and more preferred is coconut oil fatty acid.
Salt forms of higher fatty acids include, for example, alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). .
Higher fatty acids or salts thereof may be used singly or in combination of two or more.
The content of the higher fatty acid or its salt is preferably 0.5 to 10% by mass, more preferably 2 to 8% by mass, even more preferably 3 to 5% by mass, relative to the total mass of the liquid detergent. If the content of the higher fatty acid or salt thereof is at least the above lower limit, antifoaming properties are enhanced. If the content of the higher fatty acid or salt thereof is equal to or less than the above upper limit, liquid stability at low temperatures is improved.

Examples of antiseptics include 2-bromo-2-nitropropane-1,3-diol, 3-iodopropynylbutylcarbamate, zinc pyrithione, sodium pyrithione, octylisothiazolin-3-one, 1,2-benzisothiazolin-3-one. (BIT), 5-chloro-2-methylisothiazolin-3-one (CMIT), 2-methylisothiazolin-3-one (MIT), ethoxylated cocoamine, octanediol, benzyl alcohol, phenoxyethanol, sodium benzoate, and the like. be done.
The preservatives may be used singly or in combination of two or more.
The content of the preservative is preferably 0.001 to 2% by mass with respect to the total mass of the liquid detergent.

If the liquid detergent contains an antioxidant, oxygen absorption in the headspace of the container containing the liquid detergent can be suppressed. In addition, fading and discoloration due to light and heat can be suppressed.
Examples of antioxidants include monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; bisphenolic antioxidants such as 2,2′-methylenebis(4-methyl-6-t-butylphenol; dl-α -polymeric phenolic antioxidants such as tocopherol, etc. Among these, monophenolic antioxidants and polymeric antioxidants are preferable.Among the monophenolic antioxidants, dibutylhydroxytoluene Among the polymeric phenolic antioxidants, dl-α-tocopherol is particularly preferred.
An antioxidant may be used individually by 1 type, and 2 or more types may be combined and used.
The content of the antioxidant is preferably 0.01-2% by mass with respect to the total mass of the liquid detergent.

Enzyme stabilizers include, for example, boric acid, borax, formic acid or salts thereof, lactic acid or salts thereof, calcium salts such as calcium chloride and calcium sulfate.
An enzyme stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the enzyme stabilizer is preferably 2% by mass or less with respect to the total mass of the liquid detergent.

Examples of the texture improver include silicones such as dimethylsilicone, polyether-modified silicone and amino-modified silicone.
The texture improver may be used singly or in combination of two or more.
The content of the texture improver is preferably 5% by mass or less with respect to the total mass of the liquid detergent.

Examples of dye transfer inhibitors include polyvinylpyrrolidone, carboxymethylcellulose, and polyalkyleneamine.
The dye transfer inhibitor may be used singly or in combination of two or more.
The content of the dye transfer inhibitor is preferably 3% by mass or less with respect to the total mass of the liquid detergent.

Examples of anti-soil redeposition agents include at least one repeating unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one repeating unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. and a water-soluble polymer having Specific examples of such water-soluble polymers include the trade name “TexCare SRN-100” (manufactured by Clariant, weight average molecular weight 2000 to 3000), the trade name “TexCare SRN-300” (manufactured by Clariant, weight average molecular weight 7000), trade name “Repel-O-Tex Crystal” (manufactured by Rhodia), trade name “Repel-O-Tex QC” (manufactured by Rhodia), and the like. Among these, TexCare SRN-100 is preferred because of its high solubility in water and excellent liquid stability. Further, from the viewpoint of excellent handleability, it is preferable to use TexCare SRN-170 (manufactured by Clariant Co., Ltd.), which is commercially available as a 70% aqueous solution of TexCare SRN-100, as an anti-soil redeposition agent.
As the anti-soil redeposition agent, in addition to those described above, for example, an alkylene oxide adduct of polyalkyleneimine, an alkylene oxide adduct of polyalkyleneamine, and the like can be used. BASF Corporation) and the like.
The anti-soil redeposition agents may be used singly or in combination of two or more.
The content of the anti-soil redeposition agent is preferably 0.01 to 5% by mass with respect to the total mass of the liquid detergent.

The coloring agent is not particularly limited, and examples thereof include dyes described in "Legal Dyes Handbook" (Japan Cosmetic Industry Association) and those chemically modified with a water-soluble polymer or the like at the end of the chromophore structure. be done. Specifically, C.I. I. Acid Red 138, C.I. I. Acid Red 260, C.I. I. Acid Red 106, Acid Yellow 203 (Yellow No. 203), Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Levanyl® Violet (Levanyl® Violet), Liquitint® BLUE SE (Liquitint® Blue SE), Liquitint® BLUE HP (Liquitint® Blue HP), Liquitint® BLUE MC (Liquitint® Blue MC), Liquitint® VIOLET CT (Liquitint® Violet CT), Liquitint® VIOLET LS (Liquitint® Violet LS), Liquitint® VIOLET DD (Liquitint® Violet DD), Liquitint® ) GREEN SA (Liquitint (Registered Trademark) Green SA), Liquitint (Registered Trademark) Bright Yellow (Liquitint (Registered Trademark) Bright Yellow), Liquitint (Registered Trademark) YELLOW SY (Liquitint (Registered Trademark) Yellow SY), Liquitint (Registered Trademark) Trademark) YELLOW LP (Liquitint (registered trademark) yellow LP), Liquitint (registered trademark) BRILLIANT ORANGE (Liquitint (registered trademark) brilliant orange), Liquitint (registered trademark) PINK AL (Liquitint (registered trademark) pink AL), Liquitint (registered trademark) RED ST (Liquitint® Red ST), Liquitint® RED MX (Liquitint® Red MX), C.I. I. 77007 (Pigment Blue 29, L-280 BLUE U), C.I. I. 74160 (Pigment Blue 15), C.I. I. 77346 (Pigment Blue 28), C.I. I. 77343 (Pigment Blue 36), C.I. I. 74260 (Pigment Green 7), C.I. I. 74265 (Pigment Green 36), WA-S Color Green, C.I. I. 21090 (Pigment Yellow 12, Yellow No. 205), C.I. I. 56110 (Pigment Red 254), C.I. I. general-purpose dyes and pigments such as 12490 (Pigment Red 5), Labracor 040 (F) Red, and PIGMOSOL (registered trademark); In this specification, "C.I." is an abbreviation for color index.
Colorants may be used singly or in combination of two or more.
The content of the colorant is preferably 0.00005 to 1.0% by mass, more preferably 0.00005 to 0.01% by mass, relative to the total mass of the liquid detergent. If the content of the coloring agent is at least the above lower limit value, the liquid detergent can be sufficiently colored, and if it is at most the above upper limit value, pigmentation on the object to be washed is less likely to occur, resulting in excellent dispersion stability. It becomes easier to obtain a liquid detergent.

Examples of emulsifying agents include polystyrene emulsions and polyvinyl acetate emulsions, and usually emulsions having a solid content of 30 to 50% by mass are preferably used. Specific examples include polystyrene emulsion (trade name: Saibinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Saiden Chemical Co., Ltd.), Opulyn 301, Acusol OP 301, and the like.
Emulsifying agents may be used singly or in combination of two or more.
The content of the emulsifying agent is preferably 0.001 to 0.5% by mass with respect to the total mass of the liquid detergent.

Examples of flavoring agents include, for example, Kagaku Kogyo Nippousha, 1996, Genichi Indo, "Synthetic Perfume, Chemistry and Product Knowledge"; Montclair, 1969; J. published by STEFFEN ARCTANDER, "Perfume and Flavor Chemicals". More specific examples include synthetic fragrances, natural fragrances derived from animals or plants, mixed fragrances containing natural and/or synthetic fragrances, and fragrance ingredients described in, for example, JP-A-2002-146399.
The flavoring agent may be formulated as a capsule fragrance encased in a capsule formed of a polymer compound.
Flavoring agents may be used singly or in combination of two or more.
The content of the flavoring agent is preferably 0.01 to 2% by mass with respect to the total mass of the liquid detergent.

<Physical properties>
(pH)
The pH of the liquid detergent at 25° C. is preferably 8.5 or higher, more preferably 8.5-11, even more preferably 8.5-10.5, and particularly preferably 8.5-10. If the pH of the liquid detergent is equal to or higher than the above lower limit, the detergency will be enhanced. If the pH of the liquid detergent is equal to or less than the above upper limit, damage to textile products such as clothes can be prevented.
The pH of the liquid detergent can be adjusted by adding a pH adjuster, if necessary.
The pH of the liquid detergent is a value measured with a pH meter (manufactured by Toa DKK Co., Ltd., product name "HM-30G") at 25°C.

<Manufacturing method>
The method for producing the liquid detergent is not particularly limited, and the liquid detergent can be produced according to a conventional method.
For example, a liquid detergent is prepared by mixing components (A), (B), (D), a portion of water, and one or more optional components other than a pH adjuster, and optionally After adjusting to a predetermined pH using a pH adjuster, it can be produced by mixing the component (C), the component (E), the component (F) and the remaining water as necessary.

<How to use>
Liquid detergents can be used, for example, by putting the liquid detergent into the liquid detergent inlet of the washing machine and then running the washing machine, or by putting the liquid detergent into the water together with the object to be washed during washing. a method of immersing the object to be washed in a cleaning solution prepared by dissolving a liquid detergent in advance in water; and the like.

A cleaning liquid is an aqueous solution containing a liquid cleaning agent. That is, the cleaning liquid contains the above-described components (A), (B), (C), water, and optionally (D), (E), (F), and optional components. is an aqueous solution comprising one or more
The content of each component in the cleaning liquid is as follows.
The content of component (A) is preferably 0.03 ppm by mass or more, more preferably 0.03 to 6.7 ppm by mass, and even more preferably 0.1 to 3.3 ppm by mass, relative to the total mass of the cleaning liquid. , more preferably 0.17 to 1.7 mass ppm, particularly preferably 0.17 to 1.3 mass ppm, and most preferably 0.17 to 0.8 mass ppm.
The content of component (B) is preferably 0.17 mass ppm or more, more preferably 0.17 to 17 mass ppm, still more preferably 0.3 to 10 mass ppm, and 0.3 mass ppm, relative to the total mass of the cleaning liquid. ~3.3 ppm by mass is even more preferable, and 0.3 to 1.7 ppm by mass is particularly preferable.
The mass ratio of component (B) to the mass of component (A), that is, the mass ratio represented by component (B)/component (A) (B/A ratio) is preferably 0.1 to 60, and 0.1 to 60. 25 to 60 are more preferred, 1 to 30 are more preferred, 1 to 10 are particularly preferred, and 2 to 10 are most preferred.
The content of component (C) is preferably 3.3 to 67 ppm by mass, more preferably 6.7 to 50 ppm by mass, and even more preferably 10 to 33 ppm by mass relative to the total mass of the cleaning liquid.
The mass ratio of the nonionic surfactant to the mass of the non-soap anionic surfactant, that is, the mass ratio represented by nonionic surfactant/non-soap anionic surfactant (nonion/anion ratio) is 0.1 to 3 is preferred, 0.15 to 2 is more preferred, 0.2 to 1.5 is even more preferred, and 0.25 to 1.3 is particularly preferred.
The content of component (D) is preferably 50 to 700 ppm by mass, more preferably 100 to 500 ppm by mass, and even more preferably 150 to 300 ppm by mass relative to the total mass of the cleaning liquid.

It is also preferable to use a washing machine equipped with an automatic detergent dispenser, which has been put into practical use in recent years. An automatic detergent dispenser is a device that automatically injects liquid detergent from a tank containing liquid detergent into the washing tub via a filter for dust removal provided at the bottom of the tank and an injection pipe. is. A metering means such as a syringe pump is provided in the middle of the loading pipe so that a fixed amount set according to the amount of laundry can be transferred from the tank to the washing tub.
Using an automatic detergent dosing device not only saves you the trouble of weighing, but also prevents liquid detergent from sticking to your hands or spilling out and staining the washing machine and its surroundings.

It is also preferable to use an automatic dispenser that can automatically dispense a predetermined amount of liquid. Even when an automatic dispenser is used, even a small amount of the liquid detergent can be measured accurately, so it is easy to exhibit sufficient detergency and waste due to overuse can be avoided, which is preferable.
Some automatic dispensers on the market use an infrared sensor or the like to automatically dispense without touching a switch or the like. If such an automatic dispenser is used, the amount of liquid detergent can be measured simply by holding out the container held in one hand, which greatly reduces the burden on the user.

Moreover, when using an automatic dispenser, it is also preferable to receive the liquid detergent discharged into a soft container and to put the soft container into the washing machine as it is. As a result, the entire amount of the discharged liquid cleaning agent can be reliably dissolved in the cleaning liquid.
Examples of the material of the soft container that can be thrown into the washing machine as it is include silicone resin, polyvinyl chloride, elastomer, soft polyester, soft polypropylene, and polyurethane.

Examples of articles to be washed include clothing (clothes), cloths, towels, sheets, and textile products such as curtains. The material of the textile product is not particularly limited, and may be any of natural fibers such as cotton, silk and wool, and chemical fibers such as polyester and polyamide.
When the liquid detergent is used by dissolving it in water, it is preferable to dilute it, for example, 5 to 6000 times (by volume).
The bath ratio (mass of washing liquid during washing/mass of clothes), which is the amount of water per amount of clothes, is preferably 5 or more for a drum-type washing machine, and 10 or more for a vertical washing machine.
Liquid detergents are suitable as detergents for textiles. In particular, if the liquid detergent contains the uncoated component (A) and the particle size of the component (A) is less than 200 μm, preferably less than 100 μm, the washing machine or the automatic washing machine equipped with an automatic detergent injection function can be used. Suitable for use in dispensers.

<Effect>
Since the liquid detergent of the present invention described above contains the components (A), (B) and (C), it is excellent in detergency and antibacterial properties. Moreover, since the liquid detergent of the present invention has excellent stability to light, it is less likely to be colored even when exposed to light, and can maintain aesthetics over a long period of time. In addition, when the component (B) is a fluorescent whitening agent, it is possible to impart a white appearance to the clothing.
In particular, if at least part of the component (C) exists in a solid state in the liquid detergent, the liquid detergent contains the component (C) in an amount exceeding its solubility, Increases detergency. When the liquid detergent is used for washing, the liquid detergent is diluted with water, so the component (C) existing in a solid state gradually dissolves in the washing liquid, and the concentration around the component (C) becomes thicker, it acts on dirt and textiles at a high concentration, and can demonstrate high detergency.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited by the following description.
The raw materials used in this example are as follows.

"Raw materials used"
(A) The compound shown below was used as a component.
A-1: Diclosan (4,4′-dichloro-2-hydroxydiphenyl ether) (manufactured by BASF, trade name “TINOSAN (registered trademark) HP100”).

(B) The compound shown below was used as a component.
· B-1: 4,4′-bis(2-sulfostyryl)biphenyl disodium salt (manufactured by BASF, trade name “Tinopal (registered trademark) CBS-X”).
· B-2: 4,4'-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate (manufactured by ARCHROMA, trade name "Leucophor® DMA-X Conc").
· B-3: 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (manufactured by BASF, trade name "Uvinul (registered trademark) 3049").
· B-4: Sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate (manufactured by Sankyo Kasei Co., Ltd., trade name “Dislizer S”).
· B-5: 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole (manufactured by BASF, trade name “Tinuvin (registered trademark) 326”).
· B-6: 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyroxyphenyl)-1,3,5-triazine (manufactured by BASF, trade name "Tinuvin® 460").

As the component (C), the compounds shown below were used.
· C-1: Sodium carbonate (manufactured by Soda Ash Japan Co., Ltd., trade name "granular ash").
· C-2: Sodium hydrogen carbonate (manufactured by Qingdao Kaiwan Co., Ltd., trade name "sodium hydrogen carbonate").
· C-3: layered sodium silicate (manufactured by Tokuyama Co., Ltd., trade name "Prefeed").

(D) The compound shown below was used as a component.
D-1: Polyoxyethylene alkyl ether (manufactured by Lion Specialty Chemicals Co., Ltd., product name "Rheox CL-70", in general formula (2), R ¹¹ is a linear alkyl group having 12 carbon atoms ( C12) and a linear alkyl group having ¹⁴ carbon atoms (C14) (C12:C14 = 75:25 in mass ratio), the carbon atom of R11 bonded to the oxygen atom is a primary carbon atom, A compound (2) wherein ^R12 is a hydrogen atom, s is 7, t is 0 and u is 0).
D-2: Polyoxyethylene alkyl ether (manufactured by Lion Chemical Co., Ltd., product name “LMAO-90”, in general formula (2), R ¹¹ is a linear alkyl group having 12 carbon atoms (C12) and carbon A linear alkyl group (C14) of number 14 (C12:C14 = 75:25 in mass ratio), the carbon atom of R ¹¹ bonded to the oxygen atom is a primary carbon atom, and R ¹² is hydrogen A compound (2) wherein s is 15, t is 0, and u is 0).
D-3: natural alcohol (mass ratio of primary alcohol having 12 carbon atoms/primary alcohol having 14 carbon atoms = 7/3), 8 mol ethylene oxide, 2 mol propylene oxide, 8 mol ethylene oxide A nonionic surfactant obtained by block addition in the order of
D-4: A linear alkylbenzenesulfonic acid having an alkyl group with 10 to 14 carbon atoms (Lion Specialty Chemicals Co., Ltd., trade name “Lipon (registered trademark) LH-200”).
D-5: polyoxyalkylene alkyl ether sulfate (in the general formula (4), R ¹⁵ is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (C12:C14 = 75:25 in mass ratio), m is 1, n is 0, Ma is sodium, and the ratio of compounds with m = 0 and n = 0 to all AES is 43 % by mass of compound (4), which was synthesized by the following synthesis method).
・D-6: IOS. The content of sodium internal olefin sulfonate and hydroxy form synthesized by the following synthesis method is 85% by mass. Synthesized by the synthesis method described below.
D-1, D-2 and D-3 are nonionic surfactants, and D-4, D-5 and D-6 are non-soap anionic surfactants.

(Synthesis of D-5)
In an autoclave with a capacity of 4 L, 400 g of CO1270 alcohol manufactured by Procter & Gamble Co. as a raw material alcohol (a mixture of alcohol having 12 carbon atoms and alcohol having 14 carbon atoms in a mass ratio of 75/25), and a catalyst for reaction 0.8 g of a potassium hydroxide catalyst was added as a catalyst, and after the inside of the autoclave was replaced with nitrogen, the temperature was raised while stirring.
Subsequently, while maintaining the temperature at 180° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted to obtain an alcohol ethoxylate.
Gas chromatograph: GC-5890 manufactured by Hewlett-Packard, detector: flame ionization detector (FID), column: Ultra-1 (manufactured by HP, L25 m × φ0.2 mm × T0.11 μm), As a result of analysis using , the obtained alcohol ethoxylate had an average added mole number of ethylene oxide of 1.0. In addition, the amount of the compound to which ethylene oxide was not added (the one that finally became the component (b-0)) was 43% by mass with respect to the entire alcohol ethoxylate obtained.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer and purged with nitrogen. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Then, D-5 was obtained by neutralizing this with an aqueous sodium hydroxide solution.

(Synthesis of D-6)
An internal olefin mixture containing a total of 26% by mass of double bonds at the 2-position, a cis/trans isomer mass ratio of 27/73, and a paraffin component of 2.0% by mass. used as This internal olefin is an internal olefin mixture consisting of 3% by mass of C14 and below, 33% by mass of C15, 39% by mass of C16, 24% by mass of C17 and 1% by mass of C18 and above. Using this internal olefin mixture, using a glass thin-film sulfonation apparatus with an inner diameter of 6 mmφ and a length of 1.2 m, nitrogen _- diluted SO gas (SO concentration: 5% by volume) was added to the reactor at a temperature of 10 °C. , under the conditions of a SO3/internal olefin molar ratio of 1.1, a sulfonation reaction was carried out in a conventional manner to obtain an internal olefin sulfonic acid. The resulting reaction product, internal olefinsulfonic acid, was aged at 5°C for 1 hour, then added with 1.11 mol (relative to internal olefinsulfonic acid) of 15% sodium hydroxide aqueous solution, and heated at 30°C for 30 minutes. A neutralization reaction was carried out by stirring to obtain a neutralized product. The neutralized product was then heated in an autoclave at 160° C. for 40 minutes and hydrolyzed to give D-6.

(E) The compound shown below was used as a component.
E-1: Sodium sulfite (manufactured by Mitsui Chemicals, Inc., trade name "sodium sulfite").

(F) The compound shown below was used as a component.
· F-1: Bacterial cellulose (manufactured by CPKelco US, trade name “CELLULON (registered trademark) R27”, water content 80% by mass).
The moisture content of F-1 was measured using an automatic moisture measuring device (manufactured by Hiranuma Sangyo Co., Ltd., product name "AQUACOUNTER AQV-2200").

The following compounds were used as water and optional components.
- Water: Purified water.
- Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd., trade name "monoethanolamine".
- Propylene glycol: manufactured by Dow Chemical Company, trade name "propylene glycol".
- Glycerin: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "glycerin".
- Ethanol: manufactured by Japan Alcohol Sales Co., Ltd., trade name "specific alcohol 95 degree synthesis".
- Coconut fatty acid: manufactured by NOF Corporation, trade name "coconut fatty acid".
- Enzyme: Mixed formulation (liquid) of protease and amylase (manufactured by Novozymes Japan, trade name "Medley Core 210L").
· Antioxidant: dibutylhydroxytoluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "dibutylhydroxytoluene").
Perfume: Perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.
- Pigment: manufactured by Kisumi Kasei Co., Ltd., trade name "Green No. 3".
- Sodium hydroxide: manufactured by Toagosei Co., Ltd., trade name "sodium hydroxide".

"Measurement/evaluation method"
(Confirmation of liquid appearance)
100 mL of the liquid detergent was placed in a transparent glass bottle (wide mouth standard bottle PS-NO.11), and the lid was closed and sealed. This state was allowed to stand at room temperature (25° C.) for 4 weeks. Visually observe the liquid appearance of the liquid cleaning agent after it has been left to stand. If it is transparent and uniform and no foreign matter is observed, it is “clear”; The case where there was a cloudiness was defined as "white turbidity".

(Evaluation of stability against light)
100 mL of the liquid detergent was placed in a transparent glass bottle (wide mouth standard bottle PS-NO.11), and the lid was closed and sealed. In this state, it was allowed to stand in a place exposed to sunlight for one week. The color tone of the liquid detergent after standing was visually observed, and the stability to light was evaluated based on the following evaluation criteria. ⊚ and ◯ were regarded as passed.
"Evaluation criteria"
A: Equivalent to the color tone of the liquid detergent before exposure to sunlight.
◯: Slightly colored compared to the liquid detergent before being exposed to sunlight.
x: Strongly colored compared to the liquid detergent before being exposed to sunlight.

(Evaluation of detergency)
A commercially available protein-stained cloth (manufactured by Swissatest, product name “EMPA117”) was cut into a size of 5 cm×5 cm and used as the stained cloth.
A Terg-O-Tometer (manufactured by UNITED STATES TESTING) was used as a cleaning tester.
As a cleaning liquid, one prepared by adding the liquid cleaning composition of each example to 900 mL of tap water (15° C.) so as to make 333 mass ppm and stirring for 30 seconds was used.

Put the cleaning solution, 10 of the above-mentioned contaminated cloths, and the washed knitted cloth into a washing tester, and wash at 120 rpm and 15° C. for 10 minutes at a bath ratio (wash water/total mass of washed item) of 20 times. bottom. After that, it was transferred to a two-tank washing machine (manufactured by Mitsubishi Electric Corporation, product name "CW-C30A1-H1"), dehydrated for 1 minute, rinsed in 30 L of water for 3 minutes, and air-dried.
For the unstained cloth and the stained cloth before and after washing, the reflectance was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SE7700 type"), and the washing rate (%) was calculated by the following formula (i). asked.
Cleaning rate (%) = (K/S of contaminated cloth before washing - K/S of contaminated cloth after washing) / (K/S of contaminated cloth before washing - K/S of unstained cloth) x 100 (i)
In formula (i), "K/S" is a value obtained by (1−R/100) ² /(2R/100) (where R is the reflectance of the unstained cloth and the stained cloth before and after washing ( %).).
In addition, the unstained cloth means the original white cloth (original cloth) to which dirt is not adhered, and the R of the original cloth is set to 80.

Detergency (%) was calculated for 10 soiled cloths, and the average value was used to evaluate detergency against sebum stains based on the following evaluation criteria. ⊚ and ◯ were regarded as passed.
"Evaluation criteria"
A: Cleaning rate (average value) is 80% or more.
◯: Cleaning rate (average value) is 55% or more and less than 80%.
x: Cleaning rate (average value) is less than 55%.

"Examples 1 to 7, 9, 10, 12 to 18, 20 to 22, Comparative Examples 1 and 2"
Into a 500 mL beaker, ingredients (A), (B), (D), a portion of water, and optional ingredients other than pH adjusters and enzymes are added according to the formulations shown in Tables 1 to 3. Then, the mixture was sufficiently stirred with a three-one motor stirrer (manufactured by AS ONE Co., Ltd.) to obtain a mixture.
A pH adjuster (sodium hydroxide) was then added to the mixture as needed so that the mixture had a pH of 7 at 25°C. After that, the component (C), optionally the component (E), and the enzyme were added, and the rest of the water was added so that the total amount was 100% by mass, to obtain a liquid detergent.
The pH of the obtained liquid detergent at 25° C. was measured using a pH meter (manufactured by Toa DKK Co., Ltd., product name “HM-30G”). The results are shown in Tables 1-3.
The appearance of the obtained liquid detergent was confirmed, and the stability against light and detergency were evaluated. These results are shown in Tables 1-3. In addition, Tables 1 to 3 show the contents of each component in the cleaning solution prepared in the evaluation of detergency.

"Examples 8, 11, 19"
Into a 500 mL beaker, ingredients (A), (B), (D), a portion of water, and optional ingredients other than pH adjusters and enzymes are added according to the formulations shown in Tables 2 and 3. Then, the mixture was sufficiently stirred with a three-one motor stirrer (manufactured by AS ONE Co., Ltd.) to obtain a mixture.
A pH adjuster (sodium hydroxide) was then added to the mixture as needed so that the mixture had a pH of 7 at 25°C. After that, the component (E) and the enzyme were added, and the remaining water was added so that the total amount excluding the component (F) was 100% by mass. Subsequently, the component (F) was added to the mixture and thoroughly stirred, and then the component (C) was further added and thoroughly stirred to obtain a liquid cleaning agent.
In the liquid detergents obtained in Examples 8, 11 and 18, part of the component (C) existed in a solid state.
The pH of the obtained liquid detergent at 25° C. was measured using a pH meter (manufactured by Toa DKK Co., Ltd., product name “HM-30G”). Tables 2 and 3 show the results.
The appearance of the obtained liquid detergent was confirmed, and the stability against light and detergency were evaluated. These results are shown in Tables 2 and 3. In addition, Tables 2 and 3 show the contents of each component in the cleaning solution prepared in the evaluation of detergency.

In Tables 1 to 3, the blending amount (% by mass) of each component is the ratio to the total mass of the liquid detergent, and unless otherwise specified, indicates the value in terms of pure content. The compounding amount (% by mass) of F-1 is the amount as a physical form (preparation). The water content (% by mass) includes the amount (% by mass) of water contained in F-1. “Appropriate amount” means that the pH adjuster (sodium hydroxide) is blended so that the pH of the liquid detergent at 25° C. becomes the value shown in Tables 1-3. "Balanced" means that water is blended so that the total amount (% by mass) of all compounding components contained in the liquid detergent of each example is 100% by mass. In addition, a blank for the blending amount means that the component is not blended (the blending amount is 0% by mass).
Also, the "B/A ratio" is the mass ratio of the component (B) to the mass of the component (A). "B/E ratio" is the weight ratio of component (B) to the weight of component (E). "Nonionic/anionic ratio" is the weight ratio of nonionic surfactant to weight of non-soap anionic surfactant. "B+E" is the total content (% by mass) of the components (B) and (E) relative to the total mass of the liquid detergent.

As is clear from Tables 1 to 3, the liquid detergent obtained in each example had high detergency, excellent stability to light, and excellent suppression of coloration when exposed to light. .
On the other hand, the liquid detergent obtained in Comparative Example 1, which did not contain the component (B), had poor stability to light and tended to be colored when exposed to light.
The liquid detergent of Comparative Example 2, which did not contain component (C), was inferior in detergency.

Claims (6)

(A) component: a phenolic antibacterial agent;
(B) component: one or more selected from fluorescent brighteners and ultraviolet absorbers;
(C) component: an inorganic alkaline agent;
A liquid detergent containing The liquid detergent according to claim 1, wherein the component (A) contains at least one of diclosan and triclosan. (D) Component: The liquid detergent according to claim 1 or 2, further comprising a surfactant. (E) Component: The liquid detergent according to any one of claims 1 to 3, further comprising an inorganic reducing agent. The liquid detergent according to any one of claims 1 to 4, wherein the mass ratio of said component (B) to said component (A) is 0.1-60. A cleaning liquid that is an aqueous solution containing the liquid cleaning agent according to any one of claims 1 to 5,
The content of the component (A) is 0.03 ppm by mass or more relative to the total mass of the cleaning liquid,
A cleaning liquid in which the content of the component (B) is 0.17 ppm by mass or more relative to the total mass of the cleaning liquid.