JP7641738B2 - Liquid cleaning agents - Google Patents

Description

The present invention relates to a liquid cleaning agent.

There are two general types of detergents for textile products, namely powder detergents and liquid detergents, which are used to clean clothing, etc. Demand for liquid detergents is growing because there is no risk of residual detergent remaining and they can be applied to clothing, etc.
Detergents for textile products are required to have excellent detergency. To address this issue, liquid detergents have been proposed that combine an alkaline agent with an enzyme to enhance their detergency.

However, when an alkaline agent is added to a liquid detergent and the pH of the liquid detergent increases, the enzyme activity decreases during storage of the liquid detergent, which may result in a decrease in the detergency of the liquid detergent. Therefore, it is necessary to suppress the decrease in the enzyme activity in the liquid detergent (i.e., to increase the enzyme stability).
As an example of a liquid detergent with enhanced enzyme stability, Patent Document 1 discloses a liquid detergent containing a surfactant, at least one of (meth)acrylic acid and a (meth)acrylic acid ester copolymer, polyethylene glycol, an enzyme, and an alkaline agent.

Japanese Patent Application Publication No. 11-193398

However, there is still room for improvement in enzyme stability in liquid detergents.
In addition, when a solid enzyme is used, if a part or all of the enzyme exists in a solid state in the liquid detergent, the enzyme stability tends to be higher, but the enzyme may disintegrate or dissolve depending on the water content and pH of the liquid detergent. Therefore, the enzyme existing in a solid state is also required to maintain the particle appearance without disintegrating or dissolving in the liquid detergent (visual stability of the enzyme).
An object of the present invention is to provide a liquid detergent which is alkaline yet has excellent appearance stability and enzyme stability of the enzyme and has a high detergency.

The present invention has the following aspects.
[1] Component (A): an inorganic alkaline agent,
(B) component: an enzyme;
A liquid cleaning agent comprising:
In the liquid detergent, at least a part of the component (B) is present in a solid state,
The water content is more than 7% by mass and less than 30% by mass based on the total mass of the liquid detergent,
A liquid cleaning agent having a pH of 8.5 or more at 25°C.
[2] Component (C): Further containing a surfactant,
The liquid detergent according to [1], wherein the content of the component (C) is 15 to 85 mass% based on the total mass of the liquid detergent.
[3] Further containing a water-miscible organic solvent,
The liquid cleaning agent according to [1] or [2], wherein the content of the water-miscible organic solvent is 5 to 50 mass % based on the total mass of the liquid cleaning agent.
[4] The liquid cleaning agent according to [3], wherein the water-miscible organic solvent comprises one or more selected from the group consisting of ethanol, glycerin and propylene glycol.
[5] The liquid detergent according to any one of [1] to [4], wherein at least a part of the component (A) is present in a solid state.
[6] The liquid detergent according to any one of [1] to [5] above, further comprising a component (D): a structuring agent.
[7] The liquid detergent according to any one of [1] to [6] above, which is for use in textile products.

The present invention provides a liquid detergent that is alkaline yet has excellent enzyme appearance stability and enzyme stability, and has a high cleaning power.

The present invention will be described in detail below.
The liquid detergent of the present invention contains the following components (A), (B), and water. The liquid detergent preferably further contains one or more of the following components (C) and (D). The liquid detergent may contain components (optional components) other than the components (A), (B), (C), (D), and water.
In this specification, the term "enzyme appearance stability" refers to the state in which component (B), which exists in a solid state in a liquid detergent, maintains its particulate appearance without disintegrating or dissolving.
In addition, the ability of an enzyme in a liquid detergent to remain active is called "enzyme stability."

<Component (A)>
The component (A) is an inorganic alkaline agent.
Component (A) is a component that imparts cleaning power, particularly cleaning power against sebum stains (sebum cleansing power), to the liquid detergent.
In the liquid detergent, it is preferable that at least a part of the (A) component exists in a solid state. That is, some of the (A) component is dissolved in the liquid detergent, while some of the (A) component exists in a solid state without dissolving, and it is preferable that the liquid detergent contains an amount of the (A) component that exceeds the solubility. Hereinafter, in this specification, the (A) component that is dissolved in the liquid detergent is also referred to as the "(A1) component," and the (A) component that exists in a solid state in the liquid detergent is also referred to as the "(A2) component."
The entire amount of component (A) may be blended directly into the liquid detergent, or an amount of component (A) not exceeding its solubility may be blended and dissolved in the liquid detergent, and the remaining amount may then be blended into the liquid detergent.

The inorganic alkaline agent is a component that dissolves in whole or in part in water to exhibit basicity, and the pH of a 1% by mass aqueous solution at 25° C. is 8 or higher.
Specific examples of such components include carbonates such as sodium carbonate, sodium bicarbonate, a double salt of sodium carbonate and sodium bicarbonate (sodium sesquicarbonate), potassium carbonate, potassium bicarbonate, etc.; and silicates such as sodium metasilicate, layered sodium silicate, etc. Among these, sodium carbonate, potassium carbonate, sodium metasilicate, and layered sodium silicate are preferred from the viewpoint of further enhancing the detergency.
The inorganic alkaline agent may be used alone or in combination of two or more kinds.

The surface of the (A2) component may be modified. If the surface of the (A2) component is modified, the (A2) component does not dissolve, and the particle appearance (number of particles, particle size, etc.) can be maintained well, and the appearance stability of the (A2) component is improved. In addition, the (A2) component is less likely to precipitate, and the dispersion stability is improved. Furthermore, the dissolution rate of the (A2) component can be controlled.
The surface of the component (A2) can be modified, for example, by calcining an inorganic alkali agent.
In this specification, the inorganic alkaline agent whose surface has been modified is also referred to as a “modified alkaline agent.” In the present invention, sodium carbonate that partially contains sodium hydrogen carbonate and sodium sesquicarbonate is also considered to be a modified alkaline agent.

The surface of the (A2) component may be coated with a coating agent. If the surface of the (A2) component is coated with a coating agent, the (A2) component does not dissolve, and the particle appearance (number of particles, particle size, etc.) can be maintained well, and the appearance stability of the (A2) component is improved. In addition, the (A2) component is less likely to precipitate, and the dispersion stability is improved. Furthermore, the dissolution rate of the (A2) component 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, it is preferable that the surface of the (A2) component is not coated with a coating agent from the viewpoint of preventing clogging of the dispenser pipe, syringe pump, etc.
In this specification, an inorganic alkaline agent whose surface is coated with a coating agent is also referred to as a "coated alkaline agent".

The coating agent is preferably one that is difficult to dissolve in a liquid detergent and easily adheres to an inorganic alkaline agent, but is easily dissolved, swelled, disintegrated or dispersed in a washing liquid obtained by diluting the liquid detergent with water, and is easily detached from the inorganic alkaline agent. Examples of the coating agent include hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxyethylcellulose, polyacrylic acid or a salt thereof, acrylic acid-maleic acid copolymer or a salt thereof, acrylic acid-maleic anhydride copolymer or a salt thereof, fatty acid or a salt thereof, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, calcium carbonate, aluminosilicate (zeolite, etc.), titanium oxide, etc. Among these, from the viewpoints of controlling the solubility in a liquid detergent and maintaining the particle appearance, hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxyethylcellulose, polyacrylic acid or a salt thereof, acrylic acid-maleic acid copolymer or a salt thereof, acrylic acid-maleic anhydride copolymer or a salt thereof, fatty acid or a salt thereof, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, and calcium carbonate are preferred, and hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, polyacrylic acid or a salt thereof, acrylic acid-maleic acid copolymer or a salt thereof, acrylic acid-maleic anhydride copolymer or a salt thereof, and sodium sulfate are more preferred.
The coating agent may be used alone or in combination of two or more kinds.

The coated alkali agent can be obtained by a fluidized bed granulation method in which a coating agent is sprayed onto an inorganic alkali agent while fluidizing the inorganic alkali agent to form a granule and coat it; an agitation granulation method in which a coating agent is sprayed onto an inorganic alkali agent and the inorganic alkali agent is agitated with an agitator blade to form a granule and coat it; an immersion agitation granulation method in which an inorganic alkali agent is agitated by immersing the inorganic alkali agent in a coating agent and distilling off the solvent to obtain a granulated or coated material; an extrusion granulation method in which a coating agent is added to an inorganic alkali agent, kneaded, and extruded with an extruder; a tumbling granulation method in which a coating agent is sprayed onto the inorganic alkali agent while it is tumbling to form a granule and coat it; and a spray drying type granulation method in which a slurry containing an inorganic alkali agent and a coating agent is sprayed and dried.
The coating agent may be used in the form of a solution by dissolving or dispersing it in any solvent.

Furthermore, a salt that sensitizes the coating agent (a sensitizing salt) may be added to and mixed with the granules obtained by the above-mentioned method using any machine such as a mixer, a granulator, or a fluidized bed to produce a coated alkali agent.
Here, the term "salt that sensitizes the coating agent" refers to a salt that increases the viscosity of the coating agent, gels the coating agent, or forms a film. Preferred examples of such sensitizing 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; and sodium tetraborate.
The sensitizing salt may be used alone or in combination of two or more kinds.

The particle size of component (A) is preferably 10 to 2000 μm, more preferably 100 to 1500 μm, and even more preferably 200 to 1000 μm. When the particle size of component (A) is equal to or greater than the lower limit, the dissolution rate is easily controlled, and the particle appearance is excellent. When the particle size of component (A) is equal to or less than the upper limit, the dissolution rate in water is improved.
On the other hand, when the dissolution rate control of the (A) component is not required, the particle size of the (A) component is preferably 200 μm or less, more preferably 100 μm or less. In particular, the particle size of the (A) component whose surface is not coated is preferably less than 200 μm, more preferably less than 100 μm. If the particle size of the (A) component is equal to or less than the upper limit, the (A2) component dissolves quickly when the liquid detergent is diluted with water. In addition, the solid (A2) component is unlikely to remain in the inlet of the washing machine or on the clothes after washing. Therefore, if the particle size of the (A) component is 200 μm or less, it is suitable for use in a washing machine or an automatic dispenser 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, and even more preferably 200 to 1000 μm. If the particle size of the coated alkaline agent is equal to or greater than the lower limit, the dissolution rate is easily controlled and the particle appearance is excellent. If the particle size of the coated alkaline agent is equal to or less than the upper limit, the dissolution rate in water is improved.
On the other hand, when control of the dissolution rate of the coated alkaline agent is not required, the particle size of the coated alkaline agent is preferably 200 μm or less, and more preferably 100 μm or less.

The particle size of component (A) and the particle size of the coated alkali agent are volume-based median sizes measured by a laser diffraction scattering method using a particle size distribution measuring device (e.g., Beckman Coulter, Inc., product name "LS 13 320"). The particle size may be measured by a dry method in which component (A) or the coated alkali agent is measured as is, or by a wet method in which component (A) or the coated alkali agent is dispersed in a solvent and measured.

The content of component (A) is preferably 1 to 20 mass %, more preferably 2 to 15 mass %, and even more preferably 3 to 10 mass %, based on the total mass of the liquid detergent. If the content of component (A) is equal to or greater than the lower limit, the detergency is further enhanced. If the content of component (A) is equal to or less than the upper limit, the fluidity of the liquid detergent can be well maintained.
The proportion of the component (A2) relative to the total mass of the component (A) is preferably from 10 to 80 mass %, more preferably from 20 to 70 mass %, and even more preferably from 30 to 60 mass %.

<Component (B)>
Component (B) is an enzyme. Here, "enzyme" refers to an enzyme preparation.
Component (B) is an ingredient that enhances the cleaning power of the liquid detergent against sebum stains, protein stains, and food stains.
In the liquid detergent, at least a part of the component (B) exists in a solid state. That is, some of the component (B) is dissolved in the liquid detergent, while some is not dissolved and exists in a solid state, and the liquid detergent contains an amount of the component (B) that exceeds its solubility. Hereinafter, in this specification, the component (B) that is dissolved in the liquid detergent is also referred to as the "component (B1)," and the component (B) that exists in a solid state in the liquid detergent is also referred to as the "component (B2)."
When at least a portion of component (B) is present in a solid state in the liquid detergent, the enzyme stability is increased.
The entire amount of component (B) may be blended directly into the liquid detergent, or an amount of component (B) not exceeding its solubility may be blended and dissolved in the liquid detergent, and the remaining amount may then be blended into the liquid detergent.

As the component (B), a solid (granular) enzyme preparation is preferred. A liquid enzyme preparation may also be used in combination.
A liquid enzyme preparation corresponds to component (B1). Among solid enzyme preparations, an enzyme preparation dissolved in a liquid detergent corresponds to component (B1), and an enzyme preparation in an amount exceeding the solubility of the liquid detergent corresponds to component (B2).
From the viewpoint of further increasing solubility and enzyme stability, the particle size of the solid enzyme preparation is preferably 100 to 1500 μm, more preferably 150 to 1000 μm. In consideration of use in a washing machine or automatic dispenser equipped with an automatic detergent dispensing function, the particle size of the solid enzyme preparation is preferably less than 350 μm, more preferably 200 μm or less.
The particle size of the solid enzyme preparation is measured in the same manner as for the particle size of component (A).

The surface of the solid enzyme preparation may be coated with a coating agent.
In addition, as a solid enzyme preparation, a granulated product with a stabilizer, a filler, an extender, a brightener, a binder, a coating agent, etc. based on a normal granulation method can be used. In addition, when granulating two or more kinds of enzymes, they may be granulated separately, or the enzymes may be mixed and made into the same granulated product. There is no particular limitation on the method for granulating the enzyme, and any known method can be used.

Examples of the enzyme include protease, amylase, lipase, cellulase, and mannanase.
Examples of proteases include protease preparations available from Novozymes under the trade names of Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Savinase Evity 16L, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, and Progress Uno. 100L, Deozyme, Savinase Evity 12T, Kannase Evity 24T; and trade names EFFECTENZ P150, EFFECTENZ P100, and PREFERENZ P100 available from DuPont.
Examples of amylase include amylase preparations available from Novozymes under the trade names Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, Amplify 12L, Amplify Prime 100L, and Stainzyme Plus 12T; available from DuPont under the trade name EFFECTENZ S100; available from Amano Enzyme Co., Ltd. under the trade name Pullulanase Amano; and available from Seikagaku Corporation under the trade name DB-250.
Examples of lipase include lipase preparations available from Novozymes under the trade names Lipex 100L, Lipolase 100L, Lipex 100T, and the like.
Examples of cellulases include cellulase preparations available from Novozymes under the trade names Endolase 5000L, Celluzyme 0.4L, Carezyme 4500L, and Celluclean 4500T, and those available from DuPont under the trade name REVITALENTZ 2000.
Examples of mannanase include mannanase preparations available from Novozymes under the trade names Mannaway 4L and Mannaway 4.0T.
Examples of multi-enzymes that contain two or more types of enzymes include 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, and Medley Boost. 200T, Medley SuperioR 100T, etc.
The enzymes may be used alone or in combination of two or more.

The content of component (B) is preferably 0.1 to 5 mass %, more preferably 0.3 to 3 mass %, and even more preferably 0.4 to 2.5 mass %, based on the total mass of the liquid detergent. If the content of component (B) is within the above range, the cleaning power is further increased and it is also economically advantageous.
The proportion of the component (B2) is preferably from 30 to 90 mass %, more preferably from 40 to 85 mass %, and even more preferably from 50 to 80 mass %, based on the total mass of the component (B).

<Component (C)>
The component (C) is a surfactant.
If the liquid cleaner contains a surfactant, it will have better cleaning power.
The surfactant is not particularly limited as long as it is a surfactant used in conventional liquid detergents, and examples thereof include nonionic surfactants, non-soap anionic surfactants, cationic surfactants, amphoteric surfactants, and semi-polar surfactants.
As the component (C), one type of surfactant may be used, or two or more types of surfactants may be used in combination.
From the viewpoint of further enhancing the cleaning power, it is preferable that the component (C) contains a nonionic surfactant and a non-soap anionic surfactant.
As the component (C), a nonionic surfactant and a non-soap anionic surfactant may be used in combination with one or more of a cationic surfactant, an amphoteric surfactant, and a semi-polar surfactant.

Examples of the nonionic surfactant include polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts of 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 alkylene oxide adducts thereof, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides.
The nonionic surfactants may be used alone or in combination of two or more kinds.
As the nonionic surfactant, a polyoxyalkylene type nonionic surfactant is preferable, and among them, in particular, a compound represented by the following general formula (1) (hereinafter also referred to as "compound (1)") and a compound represented by the following general formula (2) (hereinafter also referred to as "compound (2)") are more preferable, and compound (1) is even more preferable.

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

The hydrocarbon group of R ¹¹ has 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and more preferably 12 to 16 carbon atoms.
R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
When u is 0, s is preferably an integer of 4 to 20, more preferably an integer of 5 to 16, and even more preferably an integer of 6 to 10. t is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably an integer of 0.
When u is 1 or more, s is preferably 4 to 16, more preferably 6 to 12, and still more preferably 8 to 10. t is preferably 1 to 4, and more preferably 2 or 3. u is preferably 4 to 16, more preferably 6 to 12, and still more preferably 8 to 10.
When t is 1 or more, the distribution (arrangement order) of EO and PO, EO and BO, or EO, PO and BO in [(EO) _s /( ^A11O ) _t ] is not particularly limited, and these may be arranged in a block form or randomly.

R ¹³ -X-[(EO) _p /(A ¹² O) _q ]-(EO) _r -R ¹⁴ ...(2)
(In general formula (2), 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 having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. p is a number from 3 to 25 indicating the average number of EO repetitions. A ¹² represents at least one of PO (oxypropylene group) and BO (oxybutylene group). q is a number from 0 to 6 indicating the average number of A ¹² O repetitions. r is a number from 0 to 20 indicating the average number of EO repetitions.)

The hydrocarbon group of R ¹³ has 7 to 21 carbon atoms, preferably 9 to 19 carbon atoms, and more preferably 11 to 17 carbon atoms.
As —X—, —COO— is preferable.
R ¹⁴ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms.
When r is 0, p is preferably 6 to 22, more preferably 9 to 20, and even more preferably 12 to 18. q is preferably 0 to 4, more preferably 0 to 2, and even more preferably 0.
When r is 1 or more, p is preferably 4 to 16, more preferably 6 to 12, and still more preferably 8 to 10. q is preferably 1 to 4, and more preferably 2 or 3. r is preferably 4 to 16, more preferably 6 to 12, and still more preferably 8 to 10.
When q is 1 or more, the distribution (arrangement order) of EO and PO, EO and BO, or EO, PO and BO in [(EO) _p /(A ¹² O) _q ] is not particularly limited, and these may be arranged in a block form or randomly.

The content of the nonionic surfactant is preferably 10 to 60 mass % relative to the total mass of the liquid detergent, more preferably 15 to 50 mass %, and even more preferably 20 to 40 mass %. If the content of the nonionic surfactant is equal to or greater than the lower limit, the cleaning power is further increased. If the content of the nonionic surfactant is equal to or less than the upper limit, the liquid stability at low temperatures is improved.

Examples of non-soap anionic surfactants include carboxylic acid type anionic surfactants such as linear alkylbenzenesulfonic acid or a salt thereof (LAS), α-olefinsulfonic acid or a salt thereof (AOS), linear or branched alkyl sulfate or a salt thereof (AS), polyoxyalkylene alkyl(alkenyl)ether sulfate or a salt thereof (AES), alkanesulfonic acid having an alkyl group or a salt thereof, α-sulfofatty acid ester or a salt thereof, internal olefinsulfonic acid or a salt thereof (IOS), alkyl ether carboxylic acid or a salt thereof, polyoxyalkylene ether carboxylic acid or a salt thereof, alkylamide ether carboxylic acid or a salt thereof, alkenylamide ether carboxylic acid or a salt thereof, and acylamino carboxylic acid or a salt thereof; and phosphate type anionic surfactants such as alkyl phosphate ester or a salt thereof, polyoxyalkylene alkyl phosphate ester or a salt thereof, polyoxyalkylene alkylphenyl phosphate ester or a salt thereof, and glycerin fatty acid ester monophosphate ester or a salt thereof.
Examples of the salt form of the non-soap anionic surfactant include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), and alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.).
The non-soap anionic surfactant may be used alone or in combination of two or more kinds.
As the non-soap anionic surfactant, LAS, AOS, AS, AES, and IOS are preferred, and among them, LAS, AES, and IOS are more preferred from the viewpoint of further enhancing the detergency. The liquid detergent preferably contains at least AES, and more preferably contains both LAS and AES.

The polyoxyalkylene alkyl(alkenyl) ether sulfate or its salt (AES) is represented by the following general formula (3).
R ¹⁵ -O- [(EO) _m / (PO) _n ]-SO ₃ ^- M ⁺ ... (3)
(In general formula (3), 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 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. 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 limitation on the order of arrangement of EO and PO, and M ⁺ is a counter cation.)

Internal olefin sulfonic acid or its salt (IOS) is a mixture of an alkene sulfonic acid represented by the following general formula (4) (hereinafter also referred to as "compound (4)") and a hydroxyalkane sulfonic acid represented by the following general formula (5) (hereinafter also referred to as "compound (5)"). An internal olefin refers to an olefin in which the double bond is located inside the 2-position.

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

The carbon number of compound (4) is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 14 to 18. If the carbon number is equal to or greater than the lower limit, the lipophilicity of IOS is increased, and the function as a surfactant is enhanced. If the carbon number is equal to or less than the upper limit, the hydrophilicity of IOS is increased, and the function as a surfactant is enhanced.

In the formula (4), R ¹⁶ represents an alkyl group. R ¹⁶ preferably has 1 to 21 carbon atoms, more preferably 3 to 17 carbon atoms, and further preferably 7 to 15 carbon atoms.
In the formula (4), R ¹⁷ represents an alkyl group having 1 to 5 carbon atoms. The number of carbon atoms in R ¹⁷ is preferably 1 to 3.
In formula (4), x is an integer of 0 to 4, and preferably 0 to 2. When x is equal to or greater than the lower limit, the cleaning power is further increased. When x is equal to or less than the upper limit, the liquid stability is further increased.
Examples of M in the formula (4) include a sodium ion, a potassium ion, a magnesium ion, and an ammonium ion.

R ¹⁸ -CH(OH)(CH ₂ ) _y CH(SO ₃ M)-R ¹⁹ ...(5)
(In formula (5), R ¹⁸ is an alkyl group, R ¹⁹ is an alkyl group having 1 to 5 carbon atoms, and the total number of carbon atoms is 8 to 24. y is a number from 0 to 4, and M represents a counter ion.)

Compound (5) is a hydroxy form of compound (4).
The carbon number of the compound (5) is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 14 to 18. When the carbon number is equal to or more than the lower limit, the lipophilicity of the IOS is increased, and the function as a surfactant is enhanced. When the carbon number is equal to or less than the upper limit, the hydrophilicity of the IOS is increased, and the function as a surfactant is enhanced.

In the formula (5), R ¹⁸ represents an alkyl group. R ¹⁸ preferably has 2 to 22 carbon atoms, more preferably has 4 to 18 carbon atoms, and further preferably has 8 to 16 carbon atoms.
In the formula (5), R ¹⁹ represents an alkyl group having 1 to 5 carbon atoms. The number of carbon atoms in R ¹⁹ is preferably 1 to 3.
In formula (5), y is 0 to 4, and preferably 0 to 2. When y is equal to or more than the lower limit, the cleaning power is further increased. When y is equal to or less than the upper limit, the liquid stability is further increased.
Examples of M in the formula (5) include a sodium ion, a potassium ion, a magnesium ion, and an ammonium ion.

The mass ratio ((IO-2S)/(IO-1S) ratio) of IOS in which a sulfonic acid group is present at the 2nd to 4th positions ((IO-1S) component) to IOS in which a sulfonic acid group is present at the 5th position or higher is preferably 0.3 to 5, more preferably 1 to 3. When the (IO-2S)/(IO-1S) ratio is not less than the above lower limit, the slipperiness of the object to be cleaned is further improved. When the (IO-2S)/(IO-1S) ratio is not more than the above upper limit, the liquid stability is further improved.
The (IO-1S) component is an IOS in which R ¹⁷ in formula (4) and R ¹⁹ in formula (5) each have 1 to 3 carbon atoms. The (IO-2S) component is an IOS in which R ¹⁷ in formula (4) and R ¹⁹ in formula (5) each 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, and even more preferably 14 to 18.
An internal olefin can be obtained, for example, by isomerizing a 1-olefin obtained by dehydrating a 1-alcohol. When an internal olefin is sulfonated, β-sultone is quantitatively produced, and a part of the β-sultone is converted to γ-sultone and olefin sulfonic acid, which are then converted to compound (4) and compound (5) in a neutralization hydrolysis step (for example, J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxy group of the obtained compound (5) is located inside the alkane chain, and the double bond of the obtained compound (4) is located inside the olefin chain. The obtained product is mainly a mixture of these, and may contain a trace amount of hydroxyalkanesulfonate having a hydroxy group at the end of the carbon chain or α-olefinsulfonate having a double bond at the end of the carbon chain. In this specification, these products and their mixtures are collectively referred to as IOS.

The mass ratio of compound (4) to the mass of compound (5) relative to 100% by mass of IOS, i.e., the mass ratio represented by compound (4)/compound (5) (compound (4)/compound (5) 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. If the compound (4)/compound (5) ratio is equal to or greater than the lower limit, the liquid stability is further improved. If the compound (4)/compound (5) ratio is equal to or less than the upper limit, the cleaning power is further improved.

The content of the non-soap anionic surfactant is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass, based on the total mass of the liquid detergent. If the content of the non-soap anionic surfactant is equal to or greater than the lower limit, the cleaning power is further increased. In addition, the prevention of re-soiling is improved. If the content of the non-soap anionic surfactant is equal to or less than the upper limit, the liquid stability at low temperatures is improved.

The mass ratio of the nonionic surfactant to the mass of the non-soap anionic surfactant, i.e., the mass ratio expressed as nonionic surfactant/non-soap anionic surfactant (nonionic/anionic ratio), is preferably 0.25 to 3, more preferably 0.5 to 2, and even more preferably 0.8 to 1.5. When the nonionic/anionic ratio is within the above range, the liquid stability at low temperatures is improved. In addition, the liquid detergent is less likely to gel, and the fluidity can be better maintained.
In addition, if the liquid detergent contains a non-soap anionic surfactant as component (C), the enzyme stability may decrease. However, if the nonionic/anionic ratio is within the above range, the enzyme stability can be maintained well.

Examples of cationic surfactants include long-chain aliphatic amidoalkyl tertiary amines or salts thereof, such as caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, and oleic acid dimethylaminopropylamide; aliphatic ester alkyl tertiary amines or salts thereof, such as palmitate ester propyl dimethylamine and stearate ester propyl dimethylamine; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide; tetramethylammonium salts, tetraethylammonium salts, and the like. short-chain tetramethylammonium (alkyl having 1 to 4 carbon atoms) ammonium salts such as tetrapropylammonium salt, tetrabutylammonium salt, etc.; 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, long chain (alkyl having 8 to 18 carbon atoms) tri-short chain (alkyl having 1 or 2 carbon atoms) ammonium salts such as ammonium salts, decyl diethylmethyl ammonium salts, dodecyl diethylmethyl ammonium salts, tetradecyl diethylmethyl ammonium salts, cetyl diethylmethyl ammonium salts, and stearyl diethylmethyl ammonium salts; dioctyl dimethyl ammonium salts, didecyl dimethyl ammonium salts, N,N-didecyl-N-methyl-poly(oxyethyl) ammonium salts, didodecyl dimethyl ammonium salts, ditetradecyl dimethyl ammonium salts, dicetyl dimethyl ammonium salts, distearyl dimethyl ammonium salts, dioctyl methyl ethyl ammonium salts, didecyl methyl ethyl ammonium salts, didodecyl methyl ethyl ammonium salts, ditetradecyl dimethyl ammonium salts, Examples of such ammonium salts include di-long chain (alkyl having 8 to 18 carbon atoms) di-short chain (alkyl having 1 or 2 carbon atoms) ammonium salts such as decylmethylethylammonium salt, dicetylmethylethylammonium salt, and distearylmethylethylammonium salt; long chain (alkyl having 8 to 18 carbon atoms) di-short chain (alkyl having 1 or 2 carbon atoms) hydroxyalkyl (1 or 2 carbon atoms) ammonium salts such as stearyldimethylhydroxyethylammonium; di-short chain (alkyl having 1 or 2 carbon atoms) long chain (alkyl having 8 to 18 carbon atoms) ammonium salts having trialkoxysilylalkyl groups (having 4 to 10 carbon atoms) such as [3(trimethoxysilyl)]propyl(dimethyl)octadecylammonium salt; amine nitrates; benzyltrimethylammonium salts; benzalkonium salts; and benzethonium salts.
Examples of the salt form of the cationic surfactant include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), and alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.).
The cationic surfactant may be used alone or in combination of two or more kinds.

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

Examples of amphoteric surfactants include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactants.
The amphoteric surfactant may be used alone or in combination of two or more kinds.

Examples of semi-polar surfactants include alkylamine oxides and alkylamidopropyldimethylamine oxides.
The semi-polar surfactant may be used alone or in combination of two or more kinds.

The content of component (C) is preferably 15 to 80% by mass, more preferably 25 to 75% by mass, even more preferably 35 to 65% by mass, and particularly preferably 45 to 55% by mass, based on the total mass of the liquid detergent. If the content of component (C) is equal to or greater than the lower limit, the cleaning power is further increased. If the content of component (C) is equal to or less than the upper limit, the liquid detergent is less likely to gel, and the fluidity can be better maintained. In particular, gelling of the liquid detergent can be further suppressed even if the liquid detergent is left in an open system.

<Component (D)>
Component (D) is a structuring agent.
The liquid detergent is structured by containing component (D), and therefore when the liquid detergent contains insoluble particles (such as the above-mentioned components (A2) and (B2)), the dispersion stability of the insoluble particles is improved, and the insoluble particles can be uniformly dispersed in the liquid detergent and maintained in a good state.
In this specification, the term "structuring" refers to a state in which the viscosity changes before and after the application of force.

Examples of structuring agents include bacterial cellulose, non-bacterial cellulose, and the following compound (6).
The structuring agent may be used alone or in combination of two or more.

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 in a mesh-like manner and interdigitate with each other to form a network.

At least a portion of the bacterial cellulose may be coated with or mixed with a thickening agent.
Examples of thickening agents include 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, tamarind gum, and locust bean gum.
The thickener may be used alone or in combination of two or more kinds.

Commercially available bacterial cellulose can be used, such as CELLULON (registered trademark) manufactured by CPKelco U.S., Inc.

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

As non-bacterial cellulose, commercially available products can be used, such as "Avicel (registered trademark)" manufactured by FMC Corporation, "Citri-Fi" manufactured by Fiberstar Corporation, and "Betafib" manufactured by Cosun Corporation.

Compound (6) is a compound (triglyceride component) represented by the following general formula (6):

In formula (6), Z ¹ to Z ³ each independently represent a hydrogen atom, a hydroxyl group, or a carboxyl group, and Z ¹ to Z ³ may be the same or different.
In formula (6), 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, and more preferably a + b = 13 to 15, c + d = 13 to 15, and e + f = 13 to 15. If a + b, c + d, and e + f are each 7 or more, the volume of the hydrophobic group portion becomes sufficiently bulky, and the coating cleaning power becomes high. On the other hand, if a + b, c + d, and e + f are each 19 or less, the risk of solidification due to the volume of the hydrophobic group portion becoming bulky is reduced.

Examples of the compound (6) include a compound (6-1) in which Z ¹ to Z ³ are hydroxy groups, and a compound (6-2) in which Z ¹ to Z ³ are hydrogen atoms.
As the compound (6-1), hydrogenated castor oil is particularly preferred, and as the compound (6-2), hydrogenated palm oil is particularly preferred.
Hydrogenated castor oil can include glycerides, particularly triglycerides, that contain an alkyl or alkenyl moiety having 10 to 22 carbon atoms incorporating a hydroxyl group, such as trihydroxystearin, dihydroxystearin, and the like.
Hydrogenated castor oil is obtained by hydrogenating castor oil to convert double bonds that may be present in the starting oil as ricinoleyl moieties, which are converted to saturated hydroxyalkyl moieties, such as hydroxystearyl.
The hydrogenated castor oil may be processed in any suitable starting form, including but not limited to, being used in a solid state, a melt, or a mixture thereof.

As the hydrogenated castor oil, commercially available products can be used, such as "THIXCIN (registered trademark)" manufactured by Rheox, Inc. and "Custerwax A Flake" manufactured by NOF Corporation.
As the hardened palm oil, commercially available products can be used, for example, the product name "Extremely Hardened Palm Oil A" manufactured by New Japan Chemical Co., Ltd.

As component (D), bacterial cellulose and non-bacterial cellulose are preferred, with bacterial cellulose being more preferred, since even a small amount can sufficiently enhance the dispersion stability of insoluble particles such as components (A2) and (B2), and a highly transparent liquid appearance is easily obtained.

The content of component (D) is preferably 0.02 to 2 mass %, more preferably 0.04 to 1.7 mass %, and even more preferably 0.05 to 1.5 mass %, based on the total mass of the liquid detergent.
Furthermore, for example, when a bacterial cellulose preparation such as the commercially available product "CELLULON (registered trademark)" is used as component (D), the content of component (D) in the as-is form of the product is preferably 1 to 10 mass %, more preferably 2 to 8 mass %, and even more preferably 2.5 to 7 mass %, relative to the total mass of the liquid detergent.
When the content of component (D) is equal to or greater than the lower limit, the dispersion stability of the insoluble particles of components (A2) and (B2) is improved. When the content of component (D) is equal to or less than the upper limit, the viscosity of the liquid detergent is lowered, and the usability and storage stability are improved.

<Water>
As the water, purified water, ion-exchanged water, distilled water, tap water, etc. can be used.
The water content is more than 7% by mass and less than 30% by mass, preferably 10 to 29% by mass, and more preferably 15 to 28% by mass, based on the total mass of the liquid detergent. If the water content is equal to or greater than the lower limit, the enzyme stability is improved. If the water content is equal to or less than the upper limit, the appearance stability of the enzyme is improved.

The mass ratio of component (C) to the mass of water, i.e., the mass ratio expressed as component (C)/water (C/water ratio), is preferably 1 to 5, more preferably 1.5 to 4, and even more preferably 1.5 to 3. If the C/water ratio is within the above range, the fluidity of the liquid detergent can be well maintained. In addition, the appearance stability and enzyme stability (residual activity) of the enzyme are also improved.

<Optional ingredients>
Examples of optional components include water-miscible organic solvents, builder components other than component (A), chelating agents, pH adjusters, viscosity reducers and solubilizing agents, antibacterial agents, thickeners other than component (D), higher fatty acids or salts thereof, preservatives, antioxidants, inorganic reducing agents, enzyme stabilizers, texture improvers, fluorescent brightening agents, dye transfer inhibitors, redeposition inhibitors, colorants, opacifying agents, discoloration inhibitors, hydrotropes, bleaching agents, fluorescent agents, pearling agents, fragrances, and extracts of natural products and the like.
The optional components may be used alone or in combination of two or more.

The water-miscible organic solvent refers to an organic solvent that dissolves at least 25 g in 1 L of water at 25°C.
Examples of the water-miscible organic solvent include alcohols such as ethanol, glycerin, 1-propanol, 2-propanol, 1-butanol, and 3-methoxy-3-methyl-1-butanol (Solfit, product name); glycols such as propylene glycol (PG), butylene glycol, and hexylene glycol; polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols having a molecular weight of about 200 to 1000, and dipropylene glycol; and alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), and diethylene glycol dimethyl ether. Among these, from the viewpoints of low odor, ease of availability, and fluidity of the liquid detergent, ethanol, glycerin, 3-methoxy-3-methyl-1-butanol, propylene glycol, polyethylene glycols having a molecular weight of about 200 to 1000, and diethylene glycol monobutyl ether (butyl carbitol) are preferred, and ethanol, glycerin, and propylene glycol are more preferred.
The water-miscible organic solvent may be used alone or in combination of two or more. From the viewpoints of enzyme stability (residual activity), appearance stability, and fluidity of the liquid detergent, it is preferable to use propylene glycol in combination with glycerin.
The content of the water-miscible organic solvent is preferably 5 to 50 mass %, more preferably 10 to 30 mass %, and even more preferably 10 to 20 mass %, based on the total mass of the liquid detergent.

The total content of water and the water-miscible organic solvent is preferably 15 to 60% by mass, more preferably 25 to 50% by mass, and even more preferably 30 to 40% by mass, based on the total mass of the liquid detergent. If the total content of water and the water-miscible organic solvent is within the above range, the liquid detergent composition has excellent fluidity even if it contains a sufficient amount of component (C) to ensure detergency.
The mass ratio of water to the mass of the water-miscible organic solvent, i.e., the mass ratio expressed as water/water-miscible organic solvent (water/organic solvent ratio), is preferably 0.2 to 3, more preferably 0.8 to 2.5. When the water/organic solvent ratio is within the above range, the appearance stability of the enzyme is further improved. In addition, the fluidity of the liquid detergent is excellent.

Builder components other than component (A) (hereinafter also referred to as "other builder components") include, for example, sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium sulfite, potassium sulfite, sodium hydrogensulfite, ammonium chloride, ammonium sulfate, sodium tetraborate, sodium pyrophosphate, sodium tripolyphosphate, sodium hydroxide, potassium hydroxide, aluminosilicates (e.g., zeolite, etc.), and the like.
The other builder components may be used alone or in combination of two or more.
Other builder ingredients may be dissolved in the liquid detergent or may be 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.

The chelating agent is preferably, for example, a chelating agent having a trivalent or tetravalent carboxylic acid group or a salt thereof. Specific examples include citric acid or a salt thereof, and an aminocarboxylic acid-based chelating agent or a salt thereof. An aminocarboxylic acid refers to a compound containing at least one primary, secondary or tertiary amino group and at least one carboxyl group in one molecule, and an aminocarboxylic acid-based chelating agent refers to a chelating agent that is an aminocarboxylic acid.
The aminocarboxylic acid chelating agent may be any known one in the field of cleaning agents. Specific examples include methylglycine diacetate (MGDA), methylglycine diacetate, L-glutamic acid diacetate (GLDA), L-glutamic acid diacetate, diethylenetriamine pentaacetic acid (DTPA), diethylenetriamine pentaacetate, ethylenediamine succinic acid (EDDS), ethylenediamine succinate, 3-hydroxy-2,2'-iminodisuccinic acid (HIDS), 3-hydroxy-2,2'-iminodisuccinic acid, L-aspartic acid-N,N-diacetic acid (ASDA), and L-aspartic acid-N,N-diacetate. Among these, citric acid or a salt thereof, and MGDA or a salt thereof are preferred, and trisodium methylglycine diacetate is more preferred.
The chelating agent may be used alone or in combination of two or more kinds.
The content of the chelating agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, based on the total mass of the liquid detergent. When the content of the chelating agent is equal to or more than the lower limit, the cleaning power improving effect, the storage stability improving effect, and the discoloration preventing effect are easily obtained.

Examples of pH adjusters include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, isopropanolamine, and diisopropanolamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; basic amino acids such as arginine and lysine; ammonia; and acid agents such as sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid. Among these, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, sodium hydroxide, sulfuric acid, and hydrochloric acid are preferred.
The pH adjusters may be used alone or in combination of two or more.
The amount of pH adjuster added may be appropriately determined so as to adjust the liquid detergent to a predetermined pH.

Examples of the viscosity reducing agent and solubilizing agent include aromatic sulfonic acid or its salt. Specifically, examples of the aromatic sulfonic acid include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and their salts. Examples of the aromatic sulfonic acid salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, and alkanolamine salt.
The viscosity reducing agent and the solubilizing agent may be used alone or in combination of two or more kinds.
The content of the viscosity reducer and solubilizer is preferably 0.1 to 15% by mass based on the total mass of the liquid detergent.

Antibacterial agents include, for example, diclosan and triclosan.
The antibacterial agent may be used alone or in combination of two or more kinds.
The content of the antibacterial agent is preferably 0.001 to 10 mass %, more preferably 0.01 to 3 mass %, and even more preferably 0.03 to 2 mass %, based on the total mass of the liquid detergent.

Examples of thickeners other than component (D) (hereinafter also referred to as "other thickeners") include acrylic polymers, xanthan gum, and carrageenan.
Commercially available acrylic polymers include, for example, the Carbopol (registered trademark) series manufactured by Lubrizol Corp. Examples of the Carbopol series include Carbopol ETD 2623, Carbopol EZ3, Carbopol EZ4, Carbopol Ultrez 20, Carbopol Ultrez 21, and Carbopol Aqua 30.
The other thickeners may be used alone or in combination of two or more.
The content of the other thickener is preferably 6 mass % or less, more preferably 0.2 to 4 mass %, based on the total mass of the liquid detergent.

If a liquid detergent contains a higher fatty acid or its salt, the defoaming property is enhanced. Note that "defoaming property" refers to the property of suppressing foaming when the liquid detergent is used for washing, specifically when the liquid detergent is diluted with tap water or the like before use.
Examples of 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, and behenic acid; mixed fatty acids or salts thereof, such as coconut oil fatty acid and beef tallow fatty acid; and the like.
As the higher fatty acid, lauric acid, myristic acid, palmitic acid, and coconut oil fatty acid are preferred, and coconut oil fatty acid is more preferred.
Examples of salt forms of higher fatty acids include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), and alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.).
The higher fatty acid or the salt thereof may be used alone or in combination of two or more kinds.
The content of the higher fatty acid or its salt is preferably 0.5 to 10 mass %, more preferably 2 to 8 mass %, and even more preferably 3 to 5 mass %, based on the total mass of the liquid detergent. If the content of the higher fatty acid or its salt is equal to or more than the above lower limit, the defoaming property is improved. If the content of the higher fatty acid or its salt is equal to or less than the above upper limit, the liquid stability at low temperatures is improved.

Examples of preservatives include 2-bromo-2-nitropropane-1,3-diol, 3-iodopropynyl butylcarbamate, 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, and sodium benzoate.
The preservatives may be used alone or in combination of two or more.
The content of the preservative is preferably 0.001 to 2% by mass based on the total mass of the liquid detergent.

If the liquid detergent contains an antioxidant, it can suppress the absorption of oxygen in the head space of the container in which the liquid detergent is stored, and it can also suppress fading and discoloration due to light and heat.
Examples of the antioxidant include monophenol-based antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; bisphenol-based antioxidants such as 2,2'-methylenebis(4-methyl-6-t-butylphenol); and polymeric phenol-based antioxidants such as dl-α-tocopherol. Of these, monophenol-based antioxidants and polymeric antioxidants are preferred. Of the monophenol-based antioxidants, dibutylhydroxytoluene is particularly preferred. Of the polymeric phenol-based antioxidants, dl-α-tocopherol is particularly preferred.
The antioxidants may be used alone or in combination of two or more.
The content of the antioxidant is preferably 0.01 to 2 mass % based on the total mass of the liquid detergent.

If the liquid detergent contains an inorganic reducing agent, it can suppress fading and discoloration caused by light and heat.
Examples of the inorganic reducing agent include sulfites such as sodium sulfite and potassium sulfite, pyrosulfites such as sodium pyrosulfite and potassium pyrosulfite, and hydrogen sulfites such as sodium hydrogen sulfite and potassium hydrogen sulfite. Among these, sodium sulfite is preferred from the viewpoint of excellent storage stability.
The inorganic reducing agent may be used alone or in combination of two or more kinds.
The content of the inorganic reducing agent is preferably 0.01 to 3 mass %, more preferably 0.02 to 1 mass %, and even more preferably 0.05 to 0.5 mass %, based on the total mass of the liquid detergent. If the content of the inorganic reducing agent is equal to or more than the lower limit, the effect of suppressing coloring due to light is easily obtained, and if it is equal to or less than the upper limit, storage stability is improved.

Examples of the enzyme stabilizer include boric acid, borax, formic acid or a salt thereof, lactic acid or a salt thereof, calcium chloride, calcium sulfate, and other calcium salts.
The enzyme stabilizer may be used alone or in combination of two or more kinds.
The content of the enzyme stabilizer is preferably 2 mass % or less based on the total mass of the liquid detergent.

Examples of the feel improver include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone.
The texture improver may be used alone or in combination of two or more kinds.
The content of the texture improver is preferably 5% by mass or less based on the total mass of the liquid detergent.

The fluorescent whitening agent may, for example, be a distyrylbiphenyl type fluorescent whitening agent.
The fluorescent whitening agent may be used alone or in combination of two or more kinds.
The content of the fluorescent whitening agent is preferably 1% by mass or less based on the total mass of the liquid detergent.

Examples of dye transfer inhibitors include polyvinylpyrrolidone, carboxymethylcellulose, and polyalkyleneamines.
The dye transfer inhibitor may be used alone or in combination of two or more kinds.
The content of the dye transfer inhibitor is preferably 3% by mass or less based on the total mass of the liquid detergent.

Examples of the anti-redeposition agent include water-soluble polymers having 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. Specific examples of such water-soluble polymers include products under the trade name "TexCare SRN-100" (manufactured by Clariant, mass average molecular weight 2000 to 3000), "TexCare SRN-300" (manufactured by Clariant, mass average molecular weight 7000), "Repel-O-Tex Crystal" (manufactured by Rhodia), and "Repel-O-Tex QC" (manufactured by Rhodia). Among these, TexCare SRN-100 is preferred because of its high solubility in water and excellent storage stability. From the viewpoint of ease of handling, it is preferable to use, as the re-soiling inhibitor, a product name TexCare SRN-170 (manufactured by Clariant) which is commercially available as a 70% aqueous solution of the above-mentioned TexCare SRN-100.
In addition to the above, examples of the anti-redeposition agent that can be used include an alkylene oxide adduct of a polyalkyleneimine and an alkylene oxide adduct of a polyalkyleneamine. Specific examples include the product name "Sokalan HP20" (manufactured by BASF).
The anti-redeposition agent may be used alone or in combination of two or more kinds.
The content of the anti-redeposition agent is preferably 0.01 to 5% by mass based on the total mass of the liquid detergent.

The colorant is not particularly limited, and examples thereof include dyes described in the "Legal Dyes Handbook" (Japan Cosmetic Industry Association) and dyes chemically modified with water-soluble polymers at the end of the chromophore structure. Specific examples thereof include C.I. Acid Red 138, C.I. Acid Red 260, C.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 (R) BLUE SE (Liquitint (R) Blue SE), Liquitint (R) BLUE HP (Liquitint (R) Blue HP), Liquitint (R) BLUE MC (Liquitint (R) Blue MC), Liquitint (R) VIOLET CT (Liquitint (R) Violet CT), Liquitint (R) VIOLET LS (Liquitint (R) Violet LS), Liquitint (registered trademark) VIOLET DD, Liquitint (registered trademark) GREEN SA, Liquitint (registered trademark) Bright Yellow, Liquitint (registered trademark) YELLOW SY, Liquitint (registered trademark) YELLOW LP, Liquitint (registered trademark) BRILLIANT ORANGE, Liquitint (registered trademark) PINK AL (Liquitint (registered trademark) Pink AL), Liquitint (registered trademark) RED ST (Liquitint (registered trademark) Red ST), Liquitint (registered trademark) RED MX (Liquitint (registered trademark) Red MX) L-280 BLUE U, WA-S Color Green, Labracol 040 (F) Red, PIGMOSOL (registered trademark), and other general-purpose dyes and pigments. In this specification, "C.I." is an abbreviation for Color Index.
The colorant may be used alone or in combination of two or more kinds.
The content of the colorant is preferably 0.00005 to 1.0% by mass, more preferably 0.00005 to 0.01% by mass, based on the total mass of the liquid detergent. If the content of the colorant is equal to or more than the lower limit, the liquid detergent can be sufficiently colored, and if the content is equal to or less than the upper limit, pigmentation on the washed items is unlikely to occur, making it easier to obtain a liquid detergent with excellent dispersion stability.

Examples of the emulsifier include polystyrene emulsion and polyvinyl acetate emulsion, and typically, emulsions with a solid content of 30 to 50% by mass are preferably used. Specific examples include polystyrene emulsion (product name: Saibinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Saiden Chemical Industry Co., Ltd.), Opulyn 301, Acusol OP 301, etc.
The emulsifier may be used alone or in combination of two or more kinds.
The content of the emulsifier is preferably 0.001 to 0.5% by mass based on the total mass of the liquid detergent.

Examples of the flavoring agent include those described in "Synthetic Fragrances: Chemistry and Product Knowledge" by Indo Genichi, published by The Chemical Daily in 1996, and "Perfume and Flavor Chemicals" by STEFFEN ARCTANDER, published by MONTCLAIR, N.J. in 1969. More specific examples include synthetic fragrances, natural fragrances derived from animals or plants, blended fragrances containing natural fragrances and/or synthetic fragrances, and fragrance components described in JP-A-2002-146399.
The flavoring agent may be incorporated as a capsule flavoring encapsulated in a capsule formed of a polymer compound.
The flavoring agent may be used alone or in combination of two or more kinds.
The content of the fragrance is preferably 0.01 to 2% by mass based on the total mass of the liquid detergent.

<Physical Properties>
(pH)
The pH of the liquid detergent at 25° C. is 8.5 or more, preferably 8.5 to 11, more preferably 8.5 to 10.5, and even more preferably 8.5 to 10. If the pH of the liquid detergent is equal to or more than the lower limit, the cleaning power is further increased. If the pH of the liquid detergent is equal to or less than the upper limit, damage to textile products such as clothing can be prevented.
The pH of the liquid cleaner can be adjusted, if necessary, by adding a pH adjuster.
The pH of the liquid detergent is measured at 25° C. using a pH meter (manufactured by DKK-TOA Corporation, product name "HM-30G").

<Production Method>
The method for producing the liquid detergent is not particularly limited, and the liquid detergent can be produced in accordance with a conventional method.
For example, the liquid detergent can be produced by mixing the above-mentioned component (A), component (B), water, and, as necessary, one or more optional components other than component (C), component (D), and the pH adjuster.

When the liquid detergent contains a water-miscible organic solvent, it is preferable to adjust the total mass of the liquid detergent to 100 mass % by the water-miscible organic solvent.
An example of a method for producing a liquid detergent containing components (A), (B), (C), (D), water, and a water-miscible organic solvent will be described below.
First, component (C), water, a portion of the water-miscible organic solvent, and optional components other than the pH adjuster as necessary are mixed, and the pH is adjusted to a predetermined value, preferably 6.5 to 7.5, using a pH adjuster as necessary. Next, component (D) is added and mixed. Next, components (A) and (B) are added and mixed, and the remaining water-miscible organic solvent is added and mixed to obtain a liquid detergent.

<How to use>
Methods for using liquid detergents include, for example, putting the liquid detergent into the liquid detergent inlet of a washing machine and then running the washing machine, putting the liquid detergent into water together with the items to be washed when washing, immersing the items to be washed in a cleaning liquid prepared by dissolving the liquid detergent in water in advance, applying the liquid detergent directly to the items to be washed and leaving it for, for example, 3 minutes to 24 hours, and then washing as usual.

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. The automatic detergent dispenser is a device that automatically dispenses liquid detergent from a tank containing the liquid detergent into the washing tub via a dust filter installed at the bottom of the tank and a dispenser pipe. A measuring means such as a syringe pump is installed in the dispenser pipe, so that a fixed amount set according to the amount of laundry, etc. can be transferred from the tank to the washing tub.
Using an automatic detergent dispenser not only saves you the trouble of measuring out the detergent, but also prevents liquid detergent from getting on your hands when measuring out the detergent, or from spilling and soiling the washing machine or surrounding area.

It is also preferable to use an automatic dispenser that can automatically dispense a predetermined amount of liquid. When an automatic dispenser is used, it is also preferable because it is possible to accurately measure even a small amount of liquid detergent, making it easier to achieve sufficient cleaning power and avoiding waste due to overuse.
Some automatic dispensers on the market use infrared sensors to automatically dispense liquid detergent without the need to touch a switch, etc. By using such an automatic dispenser, the user can measure out the liquid detergent simply by holding the container in one hand, greatly reducing the burden on the user.

In addition, when using an automatic dispenser, it is also preferable to receive the liquid detergent dispensed into a soft container and then put the soft container directly into the washing machine, so that the entire amount of the dispensed liquid detergent can be reliably dissolved in the cleaning liquid.
Examples of materials for the soft container that can be directly put into the washing machine include silicone resin, polyvinyl chloride, elastomer, soft polyester, soft polypropylene, polyurethane, and the like.

Examples of items to be washed include textile products such as clothing, dishcloths, towels, sheets, curtains, etc. The material of the textile products is not particularly limited, and may be any of natural fibers such as cotton, silk, wool, etc., and chemical fibers such as polyester, polyamide, etc.
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 liquor ratio, which is the amount of water per amount of clothes (mass of washing liquid during washing/mass of clothes), is preferably 5 or more for a drum type washing machine and 10 or more for a vertical washing machine.
The liquid detergent is suitable as a detergent for textile products. In particular, if the liquid detergent contains an uncoated component (A), the particle size of the component (A) is less than 200 μm, more preferably less than 100 μm, and the particle size of the component (B) is less than 350 μm, more preferably 200 μm or less, it is suitable for use in a washing machine or an automatic dispenser equipped with an automatic detergent dispensing function.

<Action and effect>
The liquid detergent of the present invention described above contains components (A) and (B), and therefore has high detergency.
In addition, the liquid detergent of the present invention has excellent enzyme stability despite its alkaline nature, specifically, its pH being 8.5 or higher, because at least a part of component (B) exists in a solid state and the water content is more than 7% by mass and less than 30% by mass. Moreover, component (B) existing in a solid state is unlikely to disintegrate or dissolve in the liquid detergent, and the appearance stability of the enzyme is also excellent.
In addition, when the liquid detergent is used for washing, the liquid detergent is diluted with water, so that the (B) component present in a solid state gradually dissolves in the washing liquid, increasing the concentration of the (B) component around it, allowing it to act at a high concentration on dirt and textile products, and thus exert a high cleaning power.

Furthermore, if at least a portion of component (A) is present in a solid state in the liquid detergent, the liquid detergent will contain an amount of component (A) that exceeds its solubility, thereby further enhancing the cleaning power.
In addition, when the liquid detergent is used for washing, the liquid detergent is diluted with water, so that the (A) component present in a solid state gradually dissolves in the washing liquid, increasing the concentration around the (A) component, allowing it to act at a high concentration on dirt and textile products, and thereby exert a high cleaning power.

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

"Ingredients used"
As the component (A), the compound shown below was used.
A-1: Sodium carbonate (manufactured by Soda Ash Japan Co., Ltd., product name "grain ash").
A-2: Sodium metasilicate (anhydrous sodium metasilicate, manufactured by Nippon Chemical Industry Co., Ltd.).

As the component (B), the compound shown below was used.
B-1: Protease preparation (manufactured by Novozymes Japan Co., Ltd., trade name "Savinase Evity 12T", a green-colored enzyme granule preparation).
B-2: Multi-enzyme containing two or more types of enzymes (manufactured by Novozymes Japan Co., Ltd., product name "Medley Core 200T", a red-colored enzyme granule preparation).
B-3: Multi-enzyme containing two or more types of enzymes (manufactured by Novozymes Japan Co., Ltd., product name "Medley Boost 200T", a blue-colored enzyme granule preparation).

As the component (C), the compound shown below was used.
C-1: polyoxyethylene alkyl ether (manufactured by Lion Specialty Chemicals Co., Ltd., product name "Rheox CL-70", a compound (1) in which, in the general formula (1), R ¹¹ is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), the carbon atom of R ¹¹ bonded to an oxygen atom is a primary carbon atom, R ¹² is a hydrogen atom, s is 7, t is 0, and u is 0).
C-2: Polyoxyethylene alkyl ether (manufactured by Lion Chemical Co., Ltd., trade name "LMAO-90", compound (1) in which, in the general formula (1), R ¹¹ is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), the carbon atom of R ¹¹ bonded to an oxygen atom is a primary carbon atom, R ¹² is a hydrogen atom, s is 15, t is 0, and u is 0).
C-3: Linear alkylbenzene sulfonic acid having an alkyl group having 10 to 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipon (registered trademark) LH-200").
C-4: Polyoxyalkylene alkyl ether sulfate (a compound (3) in which, in the general formula (3), R ¹⁵ is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), m is 1, n is 0, M is sodium, and the proportion of compounds in which m is 0 and n is 0 relative to the total amount of AES is 43 mass%. Synthesized by the following synthesis method.).
C-5: IOS. Sodium internal olefin sulfonate synthesized by the following synthesis method, hydroxy content is 85% by mass. Synthesized by the following synthesis method.

(Synthesis of C-4)
Into a 4 L autoclave, 400 g of Procter &Gamble's trade name CO1270 alcohol (a mixture of an alcohol having 12 carbon atoms and an alcohol having 14 carbon atoms in a mass ratio of 75/25) was charged as a raw material alcohol, and 0.8 g of potassium hydroxide catalyst was charged as a reaction catalyst. The atmosphere inside the autoclave was replaced with nitrogen, and the temperature was raised with stirring.
Subsequently, 91 g of ethylene oxide was introduced while maintaining the temperature at 180° C. and the pressure at 0.3 MPa or less, and reacted to obtain an alcohol ethoxylate.
Analysis using a gas chromatograph: GC-5890 manufactured by Hewlett-Packard, a detector: a flame ionization detector (FID), and a column: Ultra-1 (manufactured by HP, L25m×φ0.2mm×T0.11μm) showed that the average number of moles of ethylene oxide added in the obtained alcohol ethoxylate was 1.0. In addition, the amount of compounds to which ethylene oxide was not added (those that ultimately became component (b-0)) was 43% by mass based on the total amount of the obtained alcohol ethoxylate.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after replacing with nitrogen, 96 g of liquid sulfuric anhydride (sulfane) was slowly added dropwise while maintaining the reaction temperature at 40° C. After the dropwise addition was completed, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfate. This was then neutralized with an aqueous sodium hydroxide solution to obtain C-4.

(Synthesis of C-5)
An internal olefin mixture containing 2.0 mass% of paraffin components and 3 mass% of C14 or less, 33 mass% of C15, 39 mass% of C16, 24 mass% of C17, and 1 mass% of C18 or more was used as the internal olefin. This internal olefin mixture was sulfonated in a glass thin-film sulfonation apparatus having an inner diameter of 6 mmφ and a length of 1.2 m with nitrogen-diluted _SO3 gas (SO3 concentration: 5% by volume) at a reactor temperature of 10°C and a molar ratio of SO3/internal olefin of 1.1 in a conventional manner to obtain an internal olefin sulfonic acid. The obtained reaction product, internal olefin sulfonic acid, was aged at 5° C. for 1 hour, and then 1.11 times by mole (relative to the internal olefin sulfonic acid) of a 15% aqueous sodium hydroxide solution was added and the mixture was stirred at 30° C. for 30 minutes to carry out a neutralization reaction, thereby obtaining a neutralized product. Thereafter, this neutralized product was heated at 160° C. for 40 minutes in an autoclave and hydrolyzed to obtain C-5.

As the component (D), the compound shown below was used.
D-1: Bacterial cellulose (manufactured by CPKelco U.S., product name "CELLULON (registered trademark) R27", moisture content 80% by mass).
The moisture content of D-1 was measured using an automatic moisture measuring device (manufactured by Hiranuma Sangyo Co., Ltd., product name "AQUACOUNTER AQV-2200").

Water and the compounds shown below were used as optional components.
・Water: Ion-exchanged water.
- Monoethanolamine: Manufactured by Nippon Shokubai Co., Ltd., product name "Monoethanolamine".
Ethanol: Manufactured by Japan Alcohol Sales Co., Ltd., product name "Specific Alcohol 95% Synthetic".
- Glycerin: Manufactured by Fujifilm Wako Pure Chemical Industries, product name "Glycerin".
- Propylene glycol: Manufactured by The Dow Chemical Company, trade name "Propylene Glycol."
・Palm fatty acid: Manufactured by NOF Corporation, product name "Palm Fatty Acid".
- Trisodium citrate.2H ₂ O: product name "Liquid Citric Acid", manufactured by Ipposha Yushi Kogyo Co., Ltd.
Dichrosan: BASF Corporation, product name "Tinosan HP100".
Sodium sulfite: manufactured by Mitsui Chemicals, Inc., trade name "Sodium sulfite".
Fragrance: Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399.
・Pigment: Manufactured by Kinmi Kasei Co., Ltd., product name "Green No. 3".

"Measurement and evaluation methods"
(Evaluation of Enzyme Appearance Stability)
A transparent glass bottle (screw-cap bottle, S-5) was filled with 10 g of the liquid detergent of each example, and stored in a thermostatic chamber at 50° C. with the lid closed and sealed for 4 weeks. The liquid detergent after storage was stirred, and the appearance of the enzyme granule preparation (component (B)) in the liquid detergent was visually observed, and the appearance stability of the enzyme was evaluated based on the following evaluation criteria. ◎ and ○ were deemed to be acceptable.
Evaluation Criteria
◎: The appearance of the enzyme granule preparation remains almost unchanged compared to before storage.
○: A part of the enzyme granule preparation has slightly disintegrated or dissolved compared to before storage.
×: The entire enzyme granule preparation has disintegrated or dissolved compared to before storage.

(Evaluation of Enzyme Stability)
10 g of the liquid detergent of each example was filled into a transparent glass bottle (screw-cap bottle, S-5), and stored in a sealed state with the lid closed for 4 weeks at 37° C. and −5° C. Protease activity was measured as shown below for the liquid detergent stored at 37° C. for 4 weeks (product stored at 37° C.) and the liquid detergent stored at −5° C. for 4 weeks (product stored at −5° C.).

Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free/Calbiochem (registered trademark)) was dissolved in 1N sodium hydroxide (1 mol/L sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Ltd.), the pH was adjusted to 10.5, and the solution was diluted with an aqueous solution of 0.05M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Ltd.) so that the milk casein concentration became 0.6%, to prepare a protease substrate.
In addition, 10 g of each of the samples stored at 37°C and -5°C in each example was diluted with calcium chloride (calcium chloride (special grade), manufactured by Kanto Chemical Co., Ltd.) and 3° DH hard water to make a total of 1000 mL, and 60 mL was then measured out of the diluted solution and further diluted to 100 mL to prepare a sample solution.

5 g of the above protease substrate was added to 1 g of sample solution, stirred for 10 seconds with a vortex mixer, and then allowed to stand at 37° C. for 30 minutes to allow the enzyme reaction to proceed. 5 g of a 0.44 M aqueous solution of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Ltd.), an enzyme reaction stopper, was then added to the solution, and stirred for 10 seconds with a vortex mixer. The resulting solution was then allowed to stand at 37° C. for 30 minutes, and the precipitated unreacted substrate was removed with a 0.45 μm filter, and the filtrate was collected.
The absorbance (absorbance A) of the recovered filtrate at a wavelength of 275 nm was measured using an ultraviolet-visible spectrophotometer UV-160 (product name) manufactured by Shimadzu Corporation.

In order to eliminate the influence of absorption by components other than the target components, 5 g of TCA, an enzyme reaction stopper, was added to 1 g of each sample solution, and the mixture was stirred for 10 seconds with a vortex mixer. Then, 5 g of a protease substrate was added, and the mixture was stirred for 10 seconds with a vortex mixer. The resulting solution was allowed to stand at 37°C for 30 minutes. Insoluble components were then removed with a 0.45 μm filter, and the filtrate was collected. The absorbance (absorbance B) of the filtrate at a wavelength of 275 nm was then measured using UV-160.
The larger the difference between absorbance A and absorbance B, the greater the amount of tyrosine (produced by the protease decomposing the protease substrate) present in the filtrate.

From the results of the above-mentioned measurement of protease activity, the residual rate (%) of protease activity was calculated according to the following formula (i).
In addition, the absorbance value at 275 nm of each filtrate substituted into the following formula (i) was used after subtracting the absorbance value at 600 nm measured at the same time in order to exclude scattered light due to bubbles, etc. from the absorbance.
Protease activity residual rate={(absorbance A of sample stored at 37° C.)−(absorbance B of sample stored at 37° C.)}/{(absorbance A of sample stored at −5° C.)−(absorbance B of sample stored at −5° C.)}×100 (i)

Using the residual protease activity (%) as an index, the enzyme stability was evaluated according to the following evaluation criteria: ⊚ and ◯ were deemed acceptable.
Evaluation Criteria
◎: Protease activity remaining is 75% or more.
◯: Protease activity remaining rate is 55% or more and less than 75%.
×: Residual protease activity is less than 55%.

(Evaluation of cleaning power)
A commercially available protein-stained cloth (manufactured by Swissatest, product name "EMPA117") was cut into a size of 5 cm x 5 cm to prepare a soiled cloth.
The cleaning tester used was a Terg-O-Tometer (manufactured by UNITED STATES TESTING).
The cleaning liquid used was prepared by adding the liquid cleaning composition of each example to 900 mL of tap water (15° C., 5° DH) so as to give a concentration of 333 ppm by mass, and stirring for 30 seconds.

The cleaning solution, 10 of the above soiled fabrics, and the cleaned knitted fabric were placed in a cleaning tester, and the bath ratio (washing water/total mass of items to be washed) was adjusted to 20, and the items were washed for 10 minutes at 120 rpm and 15° C. Thereafter, the items were transferred to a twin-tub washing machine (manufactured by Mitsubishi Electric Corporation, product name "CW-C30A1-H1"), spin-dried for 1 minute, rinsed in 30 L of water for 3 minutes, and air-dried.
The reflectance of the unsoiled cloth and the soiled cloth before and after cleaning was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SE7700 type"), and the cleaning rate (%) was calculated using the following formula (ii).
Cleaning rate (%)=(K/S of soiled cloth before cleaning−K/S of soiled cloth after cleaning)/(K/S of soiled cloth before cleaning−K/S of unsoiled cloth)×100 (ii)
In formula (ii), "K/S" is a value calculated by (1-R/100) ² /(2R/100) (where R represents the reflectance (%) of an unsoiled cloth and a soiled cloth before and after washing).
The unstained cloth means the original white cloth (raw cloth) to which no stain is attached, and the R of the raw cloth is set to 80.

The cleaning rate (%) was calculated for 10 pieces of soiled cloth, and the average value was used to evaluate the cleaning power for sebum stains based on the following evaluation criteria.
Evaluation Criteria
◎: Cleaning rate (average value) is 60% or more.
◯: The cleaning rate (average value) was 55% or more and less than 60%.
×: The cleaning rate (average value) is less than 55%.

"Examples 1 to 12, Comparative Examples 1 to 3"
In a 500 mL beaker, component (C), ion-exchanged water, a portion of glycerin, and optional components other than the pH adjuster and glycerin were added according to the formulation in Tables 1 and 2, and thoroughly stirred with a Three-One Motor Stirrer (manufactured by AS ONE Corporation) to obtain a mixture. At this point, it was confirmed that the pH of the mixture at 25°C was 7. For convenience, the total amount of ion-exchanged water used in preparing the mixture and the amount of water contained in D-1 was recorded as the amount of water (mass%) in Tables 1 and 2. Therefore, the amount of ion-exchanged water added here is the amount obtained by subtracting the amount of water contained in D-1 from the amount of water listed in Tables 1 and 2.
Next, component (D) was added to the mixture and thoroughly stirred. Furthermore, components (A) and (B) were added and thoroughly stirred, and the remaining glycerin was then added so that the total amount became 100% by mass, thereby obtaining a liquid detergent.
In the liquid detergents obtained in Examples 1 to 12 and Comparative Examples 2 and 3, a portion of component (A) and component (B) were present in a solid state.
In the liquid detergent obtained in Comparative Example 1, a part of component (B) was present in a solid state.
The pH of the resulting liquid detergent at 25° C. was measured using a pH meter (manufactured by Tokyo Keiki Co., Ltd., product name "HM-30G") The results are shown in Tables 1 and 2.
The obtained liquid detergent was evaluated for the appearance stability of the enzyme, the enzyme stability and the detergency. The results are shown in Tables 1 and 2.

In Tables 1 and 2, the amount (mass%) of each component is the percentage relative to the total mass of the liquid detergent, and unless otherwise specified, the value is expressed as a pure content. The value in parentheses for the amount (mass%) of D-1 is the amount in its pure form (formulation). The amount (mass%) of water includes the amount (mass%) of water contained in D-1. A blank column for the amount means that the component is not included (amount 0 mass%).
Furthermore, the "nonionic/anionic ratio" is the mass ratio of the nonionic surfactant to the mass of the non-soap anionic surfactant. The "C/water ratio" is the mass ratio of component (C) to the mass of water. The "water/organic solvent ratio" is the mass ratio of water to the mass of the water-miscible organic solvent.

As is clear from Tables 1 and 2, the liquid detergents obtained in the respective Examples were alkaline but had excellent appearance stability and enzyme stability of the enzyme, and had strong detergency.
On the other hand, the liquid detergent of Comparative Example 1, which did not contain the component (A), had poor detergency.
The liquid detergent of Comparative Example 2, which had a water content of 35% by mass, was poor in the appearance stability of the enzyme.
The liquid detergent of Comparative Example 3, which had a water content of 7 mass %, was poor in enzyme stability.

Claims (7)

(A) component: an inorganic alkaline agent,
(B) component: an enzyme;
A water-miscible organic solvent;
Water,
A liquid cleaning agent comprising:
In the liquid detergent, at least a part of the component (B) is present in a solid state,
The content of the water is more than 7% by mass and less than 30% by mass based on the total mass of the liquid detergent,
the mass ratio of the water to the water-miscible organic solvent is 0.4 to 3;
A liquid cleaning agent having a pH of 8.5 or more at 25°C. Component (C): Further containing a surfactant,
The liquid detergent according to claim 1, wherein the content of the component (C) is 15 to 85 mass % based on the total mass of the liquid detergent. The liquid detergent according to claim 2, wherein the component (C) comprises a nonionic surfactant and a non-soap anionic surfactant, and the mass ratio represented by the nonionic surfactant/the non-soap anionic surfactant is 0.25 to 3. The liquid detergent according to any one of claims 1 to 3, wherein the content of the water- miscible organic solvent is 5 to 50 mass % based on the total mass of the liquid detergent. The liquid cleaning agent according to claim 4 , wherein the water-miscible organic solvent comprises at least one selected from the group consisting of ethanol, glycerin and propylene glycol. The liquid detergent according to any one of claims 1 to 5 , further comprising a component (D): a structuring agent. At least a part of the component (A) is a component (A2) that exists in the form of solid particles,
The liquid detergent according to any one of claims 1 to 6, wherein the surface of the component (A2) has been modified.