Liquid detergent composition for textile products

Abstract

To provide a textile product liquid detergent composition that has excellent liquid appearance stability and enzyme stability.SOLUTION: Provided is a textile product liquid detergent composition that contains (A) component: at least one selected from the group consisting of sulfite (salt) and hydrogen sulfite (salt), (B) component: at least one selected from the group consisting of α-hydroxy-monocarboxylic acid (salt), (C) component: at least one selected from the group consisting of the following (C1) component and (C2) component, (D) component: enzyme, and (E) component: surfactant. (C1) Component: at least one selected from the group consisting of alkylene oxide adduct of polyalkyleneimine and alkylene oxide adduct of polyalkyleneamine. (C2) Component: a polymer having at least one unit selected from the group consisting of alkylene terephthalate unit and alkylene isophthalate unit, and one or more units selected from the group consisting of oxyalkylene unit and polyoxyalkylene unit.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a liquid detergent composition for textile products. [Background technology]

[0002] For cleaning textile products such as clothing, there are generally two types of detergents: powder detergents and liquid detergents. Liquid detergents are in high demand because they do not leave any residue and can be applied directly to clothing.

[0003] Detergents may discolor, such as yellowing, during storage. Discoloration of detergents can impair the appearance of the product and reduce its market value. Liquid detergents containing nitrogen-containing compounds, such as monoethanolamine, are particularly prone to yellowing. If liquid detergents are stored in transparent containers, discoloration is more noticeable, necessitating improvements to the liquid's appearance stability. To address the problem of discoloration of such liquid detergents, for example, Patent Document 1 discloses that yellowing of the liquid detergent can be suppressed by incorporating a color-stabilizing compound such as sulfite into the liquid detergent. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 7-500862 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Cleaning agents sometimes contain enzymes to enhance their cleaning power. However, when sulfites are added to liquid detergents containing enzymes, a new problem arises: the activity of the enzyme decreases, meaning the enzyme's stability is reduced. The present invention aims to provide a liquid detergent composition for textile products that exhibits excellent liquid appearance stability and enzyme stability. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] (A) Components: At least one selected from the group consisting of sulfites, sulfites, bisulfites and bisulfites, (B) Component: At least one selected from the group consisting of α-hydroxy-monocarboxylic acids and α-hydroxy-monocarboxylic acid salts, (C) Component: At least one selected from the group consisting of the following components (C1) and (C2), (C1) Component: At least one selected from the group consisting of alkylene oxide adducts of polyalkyleneimines and alkylene oxide adducts of polyalkyleneamines. (C2) Component: A polymer having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. (D) Ingredients: Enzymes and, (E) Ingredients: Surfactants and A liquid detergent composition for textile products containing [the specified ingredient]. [2] The liquid detergent composition for textile products according to [1], wherein the (E) component comprises a nonionic surfactant and a non-soap-based anionic surfactant, and the nonionic surfactant comprises a polyoxyalkylene-type nonionic surfactant with an average number of ethylene oxide addition moles of 10 or less. [3] The liquid detergent composition for textile products according to [2], wherein the mass ratio of the polyoxyalkylene-type nonionic surfactant to the non-soap-based anionic surfactant is 1 to 5. [4] A liquid detergent composition for textile products according to any of [1] to [3] above, wherein the mass ratio of component (C) to component (A) is 0.29 to 600. [Effects of the Invention]

[0007] According to the present invention, a liquid detergent composition for textile products is available that exhibits excellent liquid appearance stability and enzyme stability. [Modes for carrying out the invention]

[0008] The present invention will be described in detail below. The liquid detergent composition for textile products of the present invention (hereinafter also simply referred to as "liquid detergent composition") is a composition containing the following components: (A), (B), (C), (D), and (E). The liquid detergent composition preferably further contains component (F) as shown below, in addition to components (A), (B), (C), (D), and (E). Furthermore, the liquid detergent composition may contain water. In addition, the liquid detergent composition may further contain components other than (A), (B), (C), (D), (E), (F) and water (optional components) as needed.

[0009] <(A) component> (A) Component is at least one selected from the group consisting of sulfite, sulfite, bisulfite, and bisulfite. The inclusion of component (A) in the liquid detergent composition makes it less susceptible to yellowing, thereby improving the liquid appearance stability of the liquid detergent composition.

[0010] Sulfites are composed of sulfite ions (SO3 2- This refers to all compounds containing sulfites. Examples of sulfites include alkali metal salts of sulfites such as sodium sulfite and potassium sulfite; alkaline earth metal salts of sulfites such as calcium sulfite, magnesium sulfite, and barium sulfite; and ammonium sulfite. Bisulfites are composed of bisulfite ions (HSO3). - This refers to all compounds containing bisulfite. Examples of bisulfites include alkali metal salts of bisulfite such as sodium bisulfite and potassium bisulfite; alkaline earth metal salts of bisulfite such as calcium bisulfite and magnesium bisulfite; and ammonium bisulfite. Among these, as component (A), sulfites and bisulfites are preferred, sulfites are more preferred, alkali metal salts of sulfites are even more preferred, and sodium sulfite is particularly preferred. (A) Component may be used alone or in combination of two or more types.

[0011] (A) The content of component (A) is preferably 0.01 to 0.7% by mass, more preferably 0.05 to 0.6% by mass, and even more preferably 0.1 to 0.5% by mass, relative to the total mass of the liquid detergent composition. If the content of component (A) is above the lower limit, the liquid appearance stability of the liquid detergent composition can be well maintained. If the content of component (A) is below the upper limit, component (A) is less likely to precipitate even when the liquid detergent composition is stored at low temperatures (e.g., below 0°C), and stability (hereinafter also referred to as "low-temperature stability") can be well maintained. In addition, enzyme stability is further improved.

[0012] <(B) component> Component (B) is at least one selected from the group consisting of α-hydroxy-monocarboxylic acids and α-hydroxy-monocarboxylic acid salts. By using component (B) in combination with component (C) described later, components (B) and (C) adsorb onto the surface of the enzyme component (D), protecting the active site and increasing enzyme stability.

[0013] Examples of α-hydroxy-monocarboxylic acids include compounds represented by the following general formula (1). R 11 -C(OH)(R 12 )-COOH ···(1) (In formula (1), R 11 and R 12 Each of these is independently a hydrogen atom, an optionally substituted C1-C10 alkyl group, an optionally substituted C6-C10 aryl group, a nitro group, a C2-C6 ester group, a C2-C6 ether group, an optionally substituted amino group, or an amine derivative group.

[0014] R 11and R 12 Examples of the substituent which may be possessed by the alkyl group or aryl group in 12 include an aryl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a nitro group, a nitro derivative group, a hydroxyl group, an ester group having 2 to 6 carbon atoms, an ether group having 2 to 6 carbon atoms, an amino group which may have a substituent, an amine derivative group, an amide group, an amide derivative group, a halogen atom, and the like. R 11 and R 12 Examples of the substituent which may be possessed by the amino group in 12 include an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a benzyl group, a phenyl group, a pyridyl group, and the like.

[0015] Examples of the salt of α-hydroxy-monocarboxylic acid include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; ammonium salt, alkanolamine salts such as ethanolamine, and the like.

[0016] As the component (B), for example, glycolic acid, lactic acid, hydroxybutyric acid, hydroxyisobutyric acid, mandelic acid, their optical isomers, and their salts are preferable, mandelic acid, lactic acid, and their salts are more preferable, lactic acid and its salts are further preferable, and sodium lactate is particularly preferable. The component (B) may be used alone or in combination of two or more.

[0017] The content of the component (B) is preferably 0.3 to 2.0% by mass, more preferably 0.4 to 1.5% by mass, and further preferably 0.5 to 1.0% by mass based on the total mass of the liquid detergent composition. If the content of the component (B) is not less than the above lower limit value, the component (B) can be sufficiently adsorbed on the surface of the component (D), and the enzyme stability in the liquid detergent composition can be further enhanced. If the content of the component (B) is not more than the above upper limit value, the low-temperature stability of the liquid detergent composition is further improved.

[0018] <(Component (C))> Component (C) is at least one selected from the group consisting of the following components (C1) and (C2). When components (C) and (B) are used together, components (B) and (C) are adsorbed onto the surface of component (D), protecting the active site and increasing enzyme stability. Component (C) may contain only component (C1) or only component (C2), but from the viewpoint of further enhancing enzyme stability, it is preferable to contain both component (C1) and component (C2).

[0019] ((C1) component) Component (C1) is at least one selected from the group consisting of alkylene oxide adducts of polyalkyleneimines (hereinafter also referred to as "component (C11)") and alkylene oxide adducts of polyalkyleneamines (hereinafter also referred to as "component (C12)").

[0020] Component (C11) is an alkylene oxide adduct of a polyalkylene imine. Polyalkyleneimines are represented by the following general formula (2). NH2-R 21 -(NA 21 -R 21 ) n -NH2···(2) (In formula (1), R 21 Each of these is independently an alkylene group having 2 to 6 carbon atoms, and A 21 represents a hydrogen atom or another polyamine chain formed by branching, and n is a number of 1 or more. However, A 21 (Not all of them are hydrogen atoms.)

[0021] R 21 This is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. 21 The alkylene group having 2 to 4 carbon atoms is preferred, and the alkylene group having 2 carbon atoms is more preferred. Polyalkyleneimines are obtained by polymerizing one or more alkyleneimines having 2 to 6 carbon atoms by conventional methods. Examples of alkyleneimines having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. As the polyalkylene imine, polyethyleneimine (PEI) and polypropyleneimine are preferred, with PEI being more preferred. PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary, and tertiary amine nitrogen atoms in its structure.

[0022] The weight-average molecular weight of the polyalkyleneimine is preferably 200 to 2000, more preferably 300 to 1500, even more preferably 400 to 1000, and particularly preferably 500 to 800. In this specification, the weight-average molecular weight refers to the value obtained by gel permeation chromatography (GPC) using polyethylene glycol as the standard substance.

[0023] The polyalkylene imine is preferably one that has 5 to 30 active hydrogen atoms per molecule, more preferably one that has 7 to 25, and even more preferably one that has 10 to 20.

[0024] The (C11) component is obtained by adding an alkylene oxide to a polyalkylene imine. Examples of this method include adding an alkylene oxide such as ethylene oxide to the starting material, a polyalkylene imine, at 100-180°C in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methylate. Examples of alkylene oxides include alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferred, and ethylene oxide being more preferred.

[0025] (C11) Examples of components include ethylene oxide adducts of polyalkyleneimines, propylene oxide adducts of polyalkyleneimines, and ethylene oxide-propylene oxide adducts of polyalkyleneimines. The ethylene oxide-propylene oxide adducts of polyalkyleneimines are obtained by adding ethylene oxide and propylene oxide to polyalkyleneimines, and the order of addition of ethylene oxide and propylene oxide to the polyalkyleneimine, as well as the form of addition (block-like, random), are arbitrary. The (C11) component is preferably an ethylene oxide adduct of polyalkyleneimine or an ethylene oxide-propylene oxide adduct of polyalkyleneimine, with the ethylene oxide adduct of polyalkyleneimine being more preferred.

[0026] The (C11) component is preferably one in which an average of 5 to 40 alkylene oxides are added to one active hydrogen atom of the raw material polyalkyleneimine, and preferably one in which an average of 10 to 30 alkylene oxides are added. That is, it is preferably one in which an average of 5 to 40 moles of alkylene oxides are added to one mole of active hydrogen of the raw material polyalkyleneimine, and preferably one in which an average of 10 to 30 moles of alkylene oxides are added.

[0027] The weight-average molecular weight of component (C11) is preferably 1,000 to 80,000, more preferably 2,000 to 50,000, even more preferably 5,000 to 30,000, and particularly preferably 10,000 to 20,000. Examples of the (C11) component include compounds represented by the following general formula (2-1).

[0028] [ka]

[0029] In formula (2-1), R 22 Each of these is an alkylene group having 2 to 6 carbon atoms, and each of these is an independent number greater than or equal to 1. R22 The alkylene group having 2 or 3 carbon atoms is preferred, and the alkylene group having 2 carbon atoms is more preferred. m is (R 22 This is the average number of repeats of O), preferably 5 to 40, and more preferably 10 to 30. In this specification, the average number of repeats of the oxyalkylene group (alkylene oxide) is also referred to as the "average number of moles added". (C11) The component may be a synthetic product or a commercially available product. Examples of commercially available products containing component (C11) include "Sokalan HP20" manufactured by BASF.

[0030] The (C12) component is an alkylene oxide adduct of a polyalkyleneamine. Polyalkyleneamines are represented by the following general formula (3). NH2(R 31 NH) l H ···(3) (In formula (3), R 31 (where l is an alkylene group with 2 to 6 carbon atoms, and l is a number greater than or equal to 1.)

[0031] R 31 This is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. 31 The alkylene group having 2 to 4 carbon atoms is preferred, and the alkylene group having 2 carbon atoms is more preferred. Polyethyleneamines are preferred as polyalkyleneamines. Examples of polyethyleneamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. These polyethyleneamines can be obtained by known production methods, for example, by reacting ammonia with ethylene dichloride.

[0032] The weight-average molecular weight of the polyalkyleneamine is preferably 60 to 1800, more preferably 60 to 1000, and even more preferably 60 to 800.

[0033] The polyalkyleneamine is preferably one that has 6 to 30 active hydrogen atoms in one molecule, and more preferably one that has 7 to 20 active hydrogen atoms.

[0034] Component (C12) is obtained by adding an alkylene oxide to a polyalkyleneamine. This reaction can be carried out in the same manner as for component (C11). Examples of alkylene oxides include alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferred, and ethylene oxide being more preferred.

[0035] Examples of the (C12) component include ethylene oxide adducts of polyalkyleneamines, propylene oxide adducts of polyalkyleneamines, and ethylene oxide-propylene oxide adducts of polyalkyleneamines. The (C12) component is preferably an ethylene oxide adduct of polyalkyleneamine or an ethylene oxide-propylene oxide adduct of polyalkyleneamine, with the ethylene oxide adduct of polyalkyleneamine being more preferred.

[0036] The (C12) component is preferably one in which an average of 5 to 40 alkylene oxides are added to one active hydrogen atom of the raw material polyalkyleneamine, and preferably one in which an average of 10 to 30 alkylene oxides are added. That is, it is preferably one in which an average of 5 to 40 moles of alkylene oxides are added to one mole of active hydrogen of the raw material polyalkyleneamine, and preferably one in which an average of 10 to 30 moles of alkylene oxides are added.

[0037] The weight-average molecular weight of component (C12) is preferably 1,000 to 80,000, more preferably 2,000 to 50,000, even more preferably 5,000 to 30,000, and particularly preferably 10,000 to 20,000.

[0038] As component (C1), component (C11) is preferred. Among the components of (C11), the ethylene oxide adduct of polyethyleneimine is preferred. Component (C1) may be used alone or in combination of two or more types.

[0039] ((C2) component) Component (C2) is a polymer having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units (hereinafter collectively referred to as "(c21) units") and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units (hereinafter collectively referred to as "(c22) units").

[0040] Among the (c21) units that constitute the polymer of component (C2), the alkylene terephthalate unit is the unit shown in the following general formula (4-1).

[0041] [ka]

[0042] In formula (4-1), R 41 This is a lower alkylene group. R 41 The number of carbon atoms in the lower alkylene group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 2 to 4.

[0043] Specific examples of alkylene terephthalate units include ethylene terephthalate units, n-propylene terephthalate units, isopropylene terephthalate units, n-butylene terephthalate units, isobutylene terephthalate units, sec-butylene terephthalate units, and tert-butylene terephthalate units. Among these, isopropylene terephthalate units are preferred. That is, R 41Specifically, examples include ethylene, n-propylene, isopropylene, n-butylene, isobutylene, and sec-butylene, with isopropylene being preferred. (c21) As a unit, one type of alkylene terephthalate unit may be used alone, or multiple types of alkylene terephthalate units may be used in combination.

[0044] Among the (c21) units that constitute the polymer of component (C2), the alkylene isophthalate unit is the unit shown in the following general formula (4-2).

[0045] [ka]

[0046] In formula (4-2), R 42 This is a lower alkylene group. R 42 The number of carbon atoms in the lower alkylene group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 2 to 4.

[0047] Specific examples of alkylene isophthalate units include ethylene isophthalate units, n-propylene isophthalate units, isopropylene isophthalate units, n-butylene isophthalate units, sec-butylene isophthalate units, tert-butylene isophthalate units, and the like. Among these, isopropylene isophthalate units are preferred. That is, R 42 Specifically, examples include ethylene, propylene, n-butylene, sec-butylene, and tert-butylene, with propylene being preferred. (c21) As a unit, a single type of alkylene isophthalate unit may be used alone, or a combination of multiple types of alkylene isophthalate units may be used.

[0048] The (c21) unit can be selected from the alkylene terephthalate unit and alkylene isophthalate unit, either alone or in combination of two or more units. That is, the (C2) component may have only alkylene terephthalate units, only alkylene isophthalate units, or both alkylene terephthalate units and alkylene isophthalate units. (c21) The unit may be introduced as one unit per molecule, or as two or more units (i.e., in block form). The number of repeating (c21) units in one molecule of component (C2) is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0049] The units that constitute the polymer of component (C2) include the units shown in the following general formula (4-3). -(R 43 O) k - ···(4-3) (In formula (4-3), R 43 k is a lower alkylene group, and k is R 43 (This represents the average number of repetitions of O, and is an integer between 1 and 100.)

[0050] R 43 The number of carbon atoms in the lower alkylene group is preferably 1 to 4, more preferably 2 to 4, and even more preferably 2 or 3. k is R 43 k represents the average number of repeating units of O. When k is 1, the unit shown in formula (4-3) is an oxyalkylene unit, and when k is 2 or greater, the unit shown in formula (4-3) is a polyoxyalkylene unit. k is an integer from 1 to 100, preferably an integer from 1 to 80, and more preferably an integer from 1 to 50.

[0051] Specific examples of (c22) units include oxyethylene units and polyoxyethylene units; oxypropylene units and polyoxypropylene units; and polyoxyethylene-polyoxypropylene units. Among these, oxyethylene units and polyoxyethylene units are preferred. The (c22) unit can be selected from the above-mentioned oxyalkylene units and polyoxyalkylene units, either alone or in combination of two or more units. That is, the (C2) component may have only oxyalkylene units, only polyoxyalkylene units, or both oxyalkylene units and polyoxyalkylene units.

[0052] The (C2) component may be a polymer in which (c21) units and (c22) units are polymerized in a block-like manner, or a polymer in which they are polymerized in a random manner. Among these, a polymer in which (c21) units and (c22) units are polymerized in a block-like manner is preferred as the (C2) component.

[0053] Component (C2) may have units other than (c21) and (c22) units (hereinafter also referred to as "(c23) units"). Examples of (c23) units include repeating units derived from polymerization initiators and polymerization inhibitors, and repeating units derived from monomers copolymerizable with monomers that provide (c21) units or (c22) units. The total of (c21) units and (c22) units is preferably 80 mol% or more, more preferably 90 mol% or more, and may be 100 mol% with respect to all units (100 mol%) constituting component (C2).

[0054] Component (C2) is preferably a water-soluble polymer, from the viewpoint of its own solubility and liquid stability when used in a liquid detergent composition. In this context, "water-soluble polymer" refers to a polymer that dissolves when 10g of polymer is added to 1000g of water in a 1L beaker with a diameter of 12cm at a water temperature of 40°C, and stirred for 12 hours (200rpm) using a stirrer (8mm in diameter, 50mm in length).

[0055] Suitable specific examples of component (C2) include polymer compounds represented by the following general formula (4-4), polymer compounds represented by the following general formula (4-5), or mixtures thereof.

[0056] [ka]

[0057] In formula (4-4), A 41 and A 42 Each is independently a hydrogen atom or a methyl group, and R 44 , R 45 and R 46 Each of these is an alkylene group having 2 to 4 carbon atoms, s1 is 0 to 10, and t1 and u1 are each independently 1 to 100. In formula (4-5), A 43 and A 44 Each is independently a hydrogen atom or a methyl group, and R 47 , R 48 and R 49 Each of these is an alkylene group having 2 to 4 carbon atoms, s2 is 0 to 10, and t2 and u2 are each independently 1 to 100.

[0058] In formula (4-4), A 41 and A 42 Each of these is independently a hydrogen atom or a methyl group, and it is preferable that both are methyl groups. In formula (4-4), R 44 , R 45 and R 46 Each of these is independently an alkylene group having 2 to 4 carbon atoms, and preferably an alkylene group having 2 to 3 carbon atoms. In formula (4-4), s1 is between 0 and 10, preferably between 0.5 and 5, and more preferably between 0.5 and 2.5. In formula (4-4), t1 and u1 are each independently 1 to 100, preferably 1 to 80, more preferably 1 to 50, even more preferably 10 to 50, and particularly preferably 20 to 30.

[0059] In formula (4-5), A 43 and A 44 Each of these is independently a hydrogen atom or a methyl group, and it is preferable that both are methyl groups. In formula (4-5), R 47 , R 48 and R 49 Each of these is independently an alkylene group having 2 to 4 carbon atoms, and preferably an alkylene group having 2 to 3 carbon atoms. In formula (4-5), s2 is between 0 and 10, preferably between 0.5 and 5, and more preferably between 0.5 and 2.5. In formula (4-5), t2 and u2 are each independently between 1 and 100, preferably between 1 and 80, more preferably between 1 and 50, even more preferably between 10 and 50, and particularly preferably between 20 and 30.

[0060] In equation (4-4), the ratio of s1 to (t1+u1) [s1:(t1+u1)] is preferably 1:5 to 1:20, and more preferably 1:8 to 1:18. In equation (4-5), the ratio of s2 to (t2+u2) [s2:(t2+u2)] is preferably 1:5 to 1:20, and more preferably 1:8 to 1:18. If the ratio of s1 to (t1+u1) and the ratio of s2 to (t2+u2) are within the above range, the cleaning power and solubility in water will be further enhanced.

[0061] The weight-average molecular weight of component (C2) is preferably 500 to 10000, more preferably 800 to 9000, and even more preferably 1000 to 8000.

[0062] (C2) Component is readily available on the market. It can also be produced by the synthesis methods disclosed in the literature, etc.: for example, the method described in Journal of Polymer Science, Vol. 3, pp. 609-630 (1948), Journal of Polymer Science, Vol. 8, pp. 1-22 (1951), and Japanese Patent Publication No. 61-218699.

[0063] The (C2) component may be used alone or in combination of two or more types. Furthermore, the (C2) component may be a synthetic product or a commercially available product. Examples of commercially available components of (C2) include Clariant's "TexCare SRN-100" (weight-average molecular weight 2000-3000) and "TexCare SRN-300" (weight-average molecular weight 7000); and Rhodia's "Repel-O-Tex Crystal" and "Repel-O-Tex QC". Among these, "TexCare SRN-100" is preferred due to its high solubility in water and excellent storage stability. Furthermore, Clariant's "TexCare SRN-170C," which is commercially available as a 70% aqueous solution of "TexCare SRN-100," is preferred due to its ease of handling.

[0064] (Content / mass ratio) The content of component (C), i.e., the sum of the content of components (C1) and (C2), is preferably 0.2 to 6.0% by mass, more preferably 0.5 to 5.0% by mass, and even more preferably 0.8 to 4.0% by mass, relative to the total mass of the liquid detergent composition. If the content of component (C) is above the lower limit, enzyme stability can be further enhanced. If the content of component (C) is below the upper limit, it is easier to ensure flexibility in the formulation of other components in the liquid detergent composition.

[0065] The content of component (C1) is preferably 0.2 to 3.0% by mass, more preferably 0.5 to 2.5% by mass, and even more preferably 0.8 to 2.0% by mass, relative to the total mass of the liquid detergent composition. If the content of component (C1) is above the lower limit, enzyme stability can be further enhanced. If the content of component (C1) is below the upper limit, it is easier to ensure flexibility in the formulation of other components in the liquid detergent composition.

[0066] The content of component (C2) is preferably 0.2 to 3.0% by mass, more preferably 0.5 to 2.5% by mass, and even more preferably 0.8 to 2.0% by mass, relative to the total mass of the liquid detergent composition. If the content of component (C2) is above the lower limit, enzyme stability can be further enhanced. If the content of component (C2) is below the upper limit, it is easier to ensure flexibility in the formulation of other components in the liquid detergent composition.

[0067] The mass ratio expressed as (C) component / (A) component, i.e., the mass ratio expressed as ((C1) component + (C2) component) / (A) component (hereinafter also referred to as the "C / A ratio"), is preferably 0.29 to 600, more preferably 1 to 100, and even more preferably 2 to 40. If the C / A ratio is above the lower limit, the liquid detergent composition becomes less prone to yellowing, and the stability of the liquid's appearance is further improved. In addition, enzyme stability can be further enhanced. If the C / A ratio is below the upper limit, it is easier to ensure flexibility in the formulation of other components in the liquid detergent composition.

[0068] The mass ratio of component (C1) to component (A) (hereinafter also referred to as the "C1 / A ratio") is preferably 0.29 to 300, more preferably 0.5 to 50, and even more preferably 1 to 20. If the C1 / A ratio is above the lower limit, the liquid detergent composition becomes less prone to yellowing, and the stability of the liquid's appearance is further improved. In addition, enzyme stability can be further enhanced. If the C1 / A ratio is below the upper limit, it is easier to ensure flexibility in the formulation of other components in the liquid detergent composition.

[0069] The mass ratio of component (C2) to component (A) (hereinafter also referred to as the "C2 / A ratio") is preferably 0.29 to 300, more preferably 0.5 to 50, and even more preferably 1 to 20. If the C2 / A ratio is above the lower limit, the liquid detergent composition becomes less prone to yellowing, and the stability of the liquid's appearance is further improved. In addition, enzyme stability can be further enhanced. If the C2 / A ratio is below the upper limit, it is easier to ensure flexibility in the formulation of other components in the liquid detergent composition.

[0070] The mass ratio of component (C1) to component (C2) (hereinafter also referred to as the "C1 / C2 ratio") is preferably 0.07 to 15, more preferably 0.16 to 6.25, and even more preferably 0.25 to 4. If the C1 / C2 ratio is above the lower limit, enzyme stability can be further enhanced. If the C1 / C2 ratio is below the upper limit, it is easier to ensure flexibility in the formulation of other components in the liquid detergent composition.

[0071] The mass ratio of component (B) to component (C) (hereinafter also referred to as the "B / C ratio") is preferably 0.05 to 0.40, more preferably 0.05 to 0.24, even more preferably 0.08 to 0.22, and particularly preferably 0.13 to 0.20. If the B / C ratio is above the lower limit, enzyme stability can be further enhanced. If the B / C ratio is below the upper limit, low-temperature stability can be further enhanced.

[0072] The mass ratio of component (B) to component (C1) (hereinafter also referred to as the "B / C1 ratio") is preferably 0.10 to 1.00, more preferably 0.10 to 0.49, even more preferably 0.16 to 0.45, particularly preferably 0.16 to 0.40, and most preferably 0.25 to 0.30. If the B / C1 ratio is above the lower limit, enzyme stability can be further enhanced. If the B / C1 ratio is below the upper limit, low-temperature stability can be further enhanced.

[0073] The mass ratio of component (B) to component (C2) (hereinafter also referred to as the "B / C2 ratio") is preferably 0.10 to 1.00, more preferably 0.10 to 0.49, even more preferably 0.16 to 0.45, particularly preferably 0.16 to 0.40, and most preferably 0.25 to 0.30. If the B / C2 ratio is above the lower limit, enzyme stability can be further enhanced. If the B / C2 ratio is below the upper limit, low-temperature stability can be further enhanced.

[0074] <(D) component> Component (D) is an enzyme. The cleaning power of the liquid detergent composition is enhanced by the inclusion of component (D). Here, "enzyme" refers to enzyme preparations. (D) As component, a liquid enzyme preparation may be used, or a solid (granular) enzyme preparation may be used. When using a solid enzyme preparation, it is preferable for the stability of the enzyme that part or all of it is present in a solid state in the liquid detergent composition.

[0075] (D) Examples of components include proteases, amylases, lipases, cellulases, and mannanases. As for the protease, a protease having serine, histidine, and aspartic acid in its molecule, such as a serine protease, is preferred. Specifically, examples of protease preparations available from Novozymes include 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, Progress Uno 100L, Deozyme, Savinase Evity 12T, Kannase Evity 24T; products available from Genencor include Purafect L, Purafect OX, and Properase L; and products available from DuPont include EFFECTENZ P150, EFFECTENZ P100, and PREFERENZ P100.

[0076] Examples of amylases include the following amylase preparations available from Novozymes: Terhamyl 300L, Terhamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, Amplify 12L, Amplify Prime 100L, Stainzyme Plus 12T; Maxamyl from Genencor; EFFECTENZ S100 from DuPont; Pullulanase Amano from Amano Enzyme Co., Ltd.; and DB-250 from Seikagaku Corporation. Examples of lipases include Lipex 100L, Lipolase 100L, and Lipex 100T, which are available as lipase preparations from Novozymes. Examples of cellulases include Endolase 5000L, Celluzyme 0.4L, Carezyme 4500L, and Celluclean 4500T, available from Novozymes, and REVITALENTZ 2000, available from DuPont. Examples of mannanase include Mannaway 4L and Mannaway 4.0T, which are available as mannanase preparations from Novozymes. Examples of multi-enzyme supplements containing two or more 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, Medley Boost 200T, and Medley SuperioR 100T. Component (D) may be used alone or in combination of two or more types.

[0077] (D) Preferably, the component contains protease. By incorporating protease, the cleaning power against protein stains is further enhanced. Among the above, the following proteases are preferred: Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L, Everlase Ultra 16L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, and Progress Uno 100L, with Alcalase 2.5L, Everlase 16L, Savinase 16L, Coronase 48L, and Progress Uno 100L being more preferred.

[0078] The content of component (D) is preferably 0.01 to 3.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.5% by mass, relative to the total mass of the liquid detergent composition. If the content of component (D) is above the lower limit, the cleaning power is further enhanced. If the content of component (D) is below the upper limit, the precipitation of component (D) is suppressed, and the liquid appearance stability of the liquid detergent composition is further improved.

[0079] The mass ratio of component (A) to component (D) (hereinafter also referred to as the "A / D ratio") is preferably 0.1 to 70, more preferably 0.2 to 12, and even more preferably 0.3 to 5. If the A / D ratio is above the lower limit, the liquid appearance stability of the liquid detergent composition can be maintained well. If the A / D ratio is below the upper limit, the precipitation of component (D) is suppressed, and the liquid appearance stability of the liquid detergent composition is further improved.

[0080] <(E) component> Component (E) is a surfactant. The cleaning power of the liquid detergent composition is enhanced by the inclusion of component (E).

[0081] (E) The component is not particularly limited as long as it is a surfactant that can be used in conventionally known detergents, and examples include nonionic surfactants, non-soap-based anionic surfactants, cationic surfactants, amphoteric surfactants, and semipolar surfactants. (E) Component may be one type of surfactant or a combination of two or more surfactants. From the viewpoint of further enhancing cleaning power, it is preferable that component (E) contains a nonionic surfactant (hereinafter also referred to as "component (E1)") and a non-soap-based anionic surfactant (hereinafter also referred to as "component (E2)"). (E) Components (E1) and (E2) may be used in combination with surfactants other than (E1) and (E2) (hereinafter also referred to as "(E3) component").

[0082] (Component E1) Component (E1) is a nonionic surfactant. Examples of component (E1) 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 their alkylene oxide adducts, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides. Component (E1) may be used alone or in combination of two or more types.

[0083] As component (E1), polyoxyalkylene-type nonionic surfactants are preferred, and among them, compounds represented by the following general formula (5-1) (hereinafter also referred to as "compound (5-1)") and compounds represented by the following general formula (5-2) (hereinafter also referred to as "compound (5-2)") are more preferred, with compound (5-1) being even more preferred.

[0084] R 51 -O-[(EO) p1 / ( A 52 O) q1 ]-(EO) r1 -R 52 ...(5-1) (In general formula (5-1), R 51R is a hydrocarbon group having 7 to 22 carbon atoms. 52 A 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, p1 is a number from 3 to 25 indicating the average repeating number of EO, and A 52 O represents at least one of PO (oxypropylene group) and BO (oxybutylene group), and q1 is A 52 r1 is a number between 0 and 20 representing the average number of repetitions in O, and r1 is a number between 0 and 20 representing the average number of repetitions in EO.

[0085] R 51 The number of carbon atoms in the hydrocarbon group is 7 to 22, preferably 10 to 22, more preferably 10 to 20, even more preferably 10 to 18, and particularly preferably 12 to 18. 51 It may be linear or branched. Specifically, R 51 This group may be a linear hydrocarbon group, or it may be a group selected from a branched primary hydrocarbon group and a linear secondary hydrocarbon group. R 52 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. R 51 When the group is a linear hydrocarbon group, p1+r1 is preferably 3 to 30, more preferably 5 to 18, even more preferably 6 to 18, and particularly preferably 10 to 18. Q1 is preferably 0 to 6, more preferably 0 to 3. R 51 When the group is selected from a branched primary hydrocarbon group and a linear secondary hydrocarbon group, p1+r1 is preferably 3 to 10, and w is preferably 0. When r1 is 0, p1 is preferably 4 to 20, more preferably 5 to 16, and even more preferably 6 to 10. q1 is preferably 0 to 4, more preferably 0 to 2, and even more preferably 0. When r1 is 1 or greater, p1 is preferably 4 to 16, more preferably 6 to 12, and even more preferably 8 to 10. q1 is preferably 1 to 4, more preferably 2 to 3. r1 is preferably 4 to 16, more preferably 6 to 12, and even more preferably 8 to 10. If q1 is 1 or greater, [(EO)p1 / (A 52 O) q1 , there are no particular limitations on the distribution (arrangement order) of EO and PO, EO and BO, or EO, PO, and BO, and they may be arranged in a block shape or randomly. The average repeat number can be measured by gas chromatography or the like.

[0086] R 53 -X-[(EO) p2 / (A 52 O) q2 -(EO) r2 -R 54 ···(5-2) (In general formula (5-2), R 53 is a hydrocarbon group having 7 to 22 carbon atoms, -X- is -COO- or -CONH-, R 54 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, p2 is a number from 3 to 25 indicating the average repeat number of EO, A 52 represents at least one of PO (oxypropylene group) and BO (oxybutylene group), q2 is a number from 0 to 6 indicating the average repeat number of A 52 O, and r2 is a number from 0 to 20 representing the average repeat number of EO.)

[0087] R 53 has 7 to 22 carbon atoms in the hydrocarbon group, preferably 9 to 19, more preferably 11 to 17. R 53 may be linear or branched. Specifically, R 53 may be a linear hydrocarbon group or a group selected from branched primary hydrocarbon groups and linear secondary hydrocarbon groups. As -X-, -COO- is preferred. R 54 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 r2 is 0, p2 is preferably from 6 to 22, more preferably from 9 to 20, and even more preferably from 12 to 18. q2 is preferably from 0 to 4, more preferably from 0 to 2, and even more preferably 0. When r2 is 1 or more, p2 is preferably from 4 to 16, more preferably from 6 to 12, and even more preferably from 8 to 10. q2 is preferably from 1 to 4, more preferably from 2 to 3. r2 is preferably from 4 to 16, more preferably from 6 to 12, and even more preferably from 8 to 10. When q2 is 1 or more, [(EO) p2 / (A 52 O) q2 In this case, there is no particular limitation on the distribution (array order) of EO and PO, EO and BO, or EO, PO, and BO, and they may be arranged in a block shape or randomly.

[0088] As the compound (5-2), polyoxyethylene fatty acid alkyl ester is preferred. Particularly, in the formula (5-2), R 53 is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, -X- is -COO-, R 54 is a methyl group, p2 = 15, q2 = 0, and r2 = 0 (hereinafter sometimes referred to as MEE) is more preferred. Polyoxyethylene fatty acid alkyl ester, particularly MEE, is a nonionic surfactant with weak molecular orientation and unstable micelles in an aqueous solution system. Therefore, polyoxyethylene fatty acid alkyl ester does not cause gelation or the like at high concentrations, and it is presumed that even if a large amount of it is blended alone in a liquid detergent composition, the solubility in water can be increased. Therefore, it is considered that when a liquid detergent composition containing polyoxyethylene fatty acid alkyl ester comes into contact with water, it is quickly dispersed to form a cleaning solution. Also, the concentration of polyoxyethylene fatty acid alkyl ester in the cleaning solution becomes uniform quickly, and a cleaning solution with an appropriate concentration can be brought into contact with the object to be cleaned (textile products) from the initial stage of cleaning. As a result, it is considered that high detergency can be exhibited.

[0089] As for compound (5-2), among polyoxyethylene fatty acid alkyl esters, it is preferable that the narrow ratio, which indicates the proportion of compounds with different numbers of added ethylene oxide, is 20% by mass or more. The upper limit of the narrow ratio is preferably substantially 80% by mass or less. A narrow ratio of 20 to 60% by mass is more preferable. A higher narrow ratio yields better cleaning power, but if it is too high, the liquid stability at low temperatures may decrease, so a narrow ratio of 25 to 40% by mass is even more preferable. The narrowness of polyoxyalkylene-type nonionic surfactants such as polyoxyethylene fatty acid alkyl esters is a value that can be calculated using the following formula (S).

[0090]

number

[0091] In formula (S), p max This indicates the number of moles of alkylene oxide added in the alkylene oxide adduct that is most abundant in polyoxyalkylene-type nonionic surfactants. i represents the number of moles of alkylene oxide added. Yi represents the percentage (mass%) of alkylene oxide adducts in the total components represented by formula (S) where the number of moles of alkylene oxide added is i. The narrowing ratio can be controlled, for example, by a method for producing polyoxyethylene fatty acid alkyl esters.

[0092] There are no particular limitations on the method for producing polyoxyethylene fatty acid alkyl esters, but one example is a method in which ethylene oxide is added to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (see Japanese Patent Publication No. 2000-144179). Suitable examples of the surface-modified composite metal oxide catalyst include, for example, a metal ion (Al) whose surface has been modified with a metal hydroxide or the like. 3+ , Ga 3+ In 3+ , Tl 3+ Co 3+ , Sc 3+, La 3+ Mn 2+ Examples include composite metal oxide catalysts such as magnesium oxide to which (etc.) are added, and calcined hydrotalcite catalysts whose surface has been modified with metal hydroxides and / or metal alkoxides. In the surface modification of the composite metal oxide catalyst, the ratio of metal hydroxide and / or metal alkoxide to 10 parts by mass is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of composite metal oxide. The method for producing polyoxyethylene fatty acid alkyl esters is not limited to the method described above. For example, polyoxyethylene fatty acid alkyl esters can also be produced by adding an alkylene oxide to a fatty acid alkyl ester using an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and an oxy acid. Such alkoxylation catalysts are disclosed in Japanese Patent No. 04977609, International Publication No. 1993 / 004030, International Publication No. 2002 / 038269, International Publication No. 2012 / 028435, etc., and examples include alkoxylation catalysts prepared from a mixture of an alkaline earth metal salt of a carboxylic acid and / or an alkaline earth metal salt of a hydroxycarboxylic acid and sulfuric acid.

[0093] Component (E1) preferably contains a polyoxyalkylene-type nonionic surfactant with an average number of added moles of ethylene oxide of 10 or less, from the viewpoint of improving low-temperature stability, more preferably contains at least one of a compound in formula (5-1) where the sum of p1 and r1 is 10 or less, and a compound in formula (5-2) where the sum of p2 and r2 is 10 or less, and even more preferably contains at least a compound in formula (5-1) where the sum of p1 and r1 is 10 or less. In this specification, among the components (E1), polyoxyalkylene-type nonionic surfactants with an average number of added ethylene oxide moles of 10 or less are also referred to as "component (E11)".

[0094] ((E2) component) Component (E2) is a non-soap-based anionic surfactant. Examples of component (E2) include carboxylic acid-type anionic surfactants such as 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 ether sulfate ester or its salt (AES), polyoxyalkylene alkenyl ether sulfate ester or its salt, alkyl group-containing alkane sulfonic acid or its salt, α-sulfo fatty acid ester or its salt (MES), internal olefin sulfonic acid or its salt (IOS), hydroxyalkane sulfonic acid or its salt, 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; and phosphate ester-type anionic surfactants such as alkyl phosphate ester or its salt, polyoxyalkylene alkyl phosphate ester or its salt, polyoxyalkylene alkylphenyl phosphate ester or its salt, glycerin fatty acid ester monophosphate ester or its salt. Examples of salt forms of non-soap-based anionic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). The (E2) component may be used alone or in combination of two or more types. (E2) The components are preferably LAS, AOS, AS, AES, and IOS, and among these, LAS, AES, and IOS are more preferred from the viewpoint of providing better cleaning power. The liquid detergent composition preferably contains at least AES, and more preferably contains both LAS and AES.

[0095] Examples of polyoxyalkylene alkyl (alkenyl) ether sulfates or their salts (AES) include compounds represented by the following general formula (6) (hereinafter also referred to as "compound (6-1)"). R 61 -O-[(EO) v(PO) w ]-SO3Ma ···(6-1) (In general formula (6-1), R 61 (where is an alkyl group having 8 to 20 carbon atoms or an alkenyl group having 8 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, v is a number greater than or equal to 0 representing the average repeating number of EO, w is a number between 0 and 6 representing the average repeating number of PO, and Ma is the counterion.)

[0096] R 61 It may be linear or branched. 61 Preferably, the alkyl group is a linear or branched alkyl group having 10 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 12 to 14 carbon atoms. The content of the components v=0 and w=0 in equation (6-1) is preferably 35 to 55% by mass relative to the total mass of AES. v is preferably 0 to 5, more preferably 0.1 to 3, even more preferably 0.5 to 3, and particularly preferably 0.5 to 2.5. w is preferably between 0 and 3, and more preferably 0. v+w is preferably a number greater than 0, and more preferably between 1 and 5. If v and w are not both 0, that is, if compound (6-1) contains both EO and PO, then EO and PO may be added in a block-like manner or randomly. Methods for adding EO and PO in a block-like manner include introducing ethylene oxide followed by propylene oxide, or introducing propylene oxide followed by ethylene oxide. The distribution of the number of added moles of ethylene oxide and propylene oxide is not particularly limited. Examples of Ma include hydrogen atoms; alkali metal ions such as sodium and potassium; alkaline earth metal ions such as magnesium; and alkanolamines such as monoethanolamine and diethanolamine. If Ma is a counterion with a valency of 2 or higher, it is assumed that Ma is bonded to -SO3 in numbers equal to 1 multiplied by its valency. For example, if Ma is a magnesium ion, the number of Ma is 1 / 2.

[0097] Internal olefin sulfonic acid or its salt (IOS) is a mixture of alkene sulfonic acid represented by the following general formula (6-2) (hereinafter also referred to as "compound (6-2)") and hydroxyalkane sulfonic acid represented by the following general formula (6-3) (hereinafter also referred to as "compound (6-3)"). Internal olefin refers to an olefin in which the double bond is located internally beyond the 2nd position.

[0098] R 62 -CH=CH(CH2) x CH(SO3Mb)-R 63 ...(6-2) (In formula (6-2), R 62 R is an alkyl group, 63 (where x is an alkyl group with 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 Mb represents the counterion.)

[0099] The number of carbon atoms in compound (6-2) 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 above the lower limit, the lipophilicity of IOS increases, and its function as a surfactant improves. If the number of carbon atoms is below the upper limit, the hydrophilicity of IOS increases, and its function as a surfactant improves.

[0100] R in equation (6-2) 62 R represents an alkyl group. 62 It may be linear or branched. 62 The number of carbon atoms is preferably 1 to 21, more preferably 3 to 17, and even more preferably 7 to 15. R in equation (6-2) 63 R represents an alkyl group with 1 to 5 carbon atoms. 63 The number of carbon atoms is preferably 1 to 3. In equation (6-2), x is between 0 and 4, preferably between 0 and 2. If x is above the lower limit, the cleaning power is further enhanced. If x is below the upper limit, the liquid stability is further enhanced. In equation (6-2), Mb can be the same as Ma mentioned above. If Mb is a counterion with a valency of 2 or higher, it is assumed that Mb is bonded to -SO3 in a number equal to 1 multiplied by its valency. For example, if Mb is a magnesium ion, the number of Mb is 1 / 2.

[0101] R 64 -CH(OH)(CH2) y CH(SO3Mc)-R 65 ...(6-3) (In formula (6-3), R 64 R is an alkyl group, 65 is an alkyl group with 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 Mc represents the counterion.

[0102] Compound (6-3) is the hydroxy compound of compound (6-2). The number of carbon atoms in compound (6-3) 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 above the lower limit, the lipophilicity of IOS increases, and its function as a surfactant improves. If the number of carbon atoms is below the upper limit, the hydrophilicity of IOS increases, and its function as a surfactant improves.

[0103] R in equation (6-3) 64 R represents an alkyl group. 64 It may be linear or branched. 64 The number of carbon atoms is preferably 2 to 22, more preferably 4 to 18, and even more preferably 8 to 16. R in equation (6-3) 65 R represents an alkyl group with 1 to 5 carbon atoms. 65 The number of carbon atoms is preferably 1 to 3. In equation (6-3), y is between 0 and 4, preferably between 0 and 2. If y is above the lower limit, the cleaning power is further enhanced. If y is below the upper limit, the liquid stability is further enhanced. In equation (6-3), Mc can be the same as Ma mentioned above. If Mc is a counterion with a valency of 2 or higher, it is assumed that Mc is bonded to -SO3 in numbers equal to 1 multiplied by its valency. For example, if Mc is a magnesium ion, the number of Mcs is 1 / 2.

[0104] IOS is obtained by sulfonating the 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. Internal olefins can be obtained, for example, by isomerizing 1-olefins obtained by dehydrating 1-alcohols. Sulfonation of internal olefins quantitatively generates β-sartone, and some of the β-sartone is converted to γ-sartone and olefin sulfonic acid, which are then converted to compounds (6-2) and (6-3) in a neutralization hydrolysis step (e.g., J.Am. Oil Chem. Soc. 69,39 (1992)). Here, the hydroxyl group of the resulting compound (6-3) is located inside the alkane chain, and the double bond of compound (6-2) is located inside the olefin chain. The resulting product is mainly a mixture of these, and may also contain trace amounts of hydroxyalkane sulfonates having hydroxyl groups at the ends of the carbon chain, or α-olefin sulfonates having double bonds at the ends of the carbon chain. In this specification, each of these products and their mixtures are collectively referred to as IOS.

[0105] ((E3) component) Component (E3) is a surfactant other than components (E1) and (E2), and specifically includes cationic surfactants, amphoteric surfactants, semipolar surfactants, etc. The (E2) component may be used alone or in combination of two or more types.

[0106] Examples of cationic surfactants include long-chain aliphatic amide alkyl tertiary amines or their salts, such as caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, laurate dimethylaminopropylamide, myristate dimethylaminopropylamide, palmitate dimethylaminopropylamide, stearate dimethylaminopropylamide, behenate dimethylaminopropylamide, and oleate dimethylaminopropylamide; aliphatic ester alkyl tertiary amines or their salts, such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine; palmitate diethanolaminopropylamide and stearate diethanolaminopropylamide; tetra-short-chain (C1-C4 alkyl) ammonium salts, such as tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, and tetrabutylammonium salt; and octyltrimethylammonium Long-chain (C8-C18 alkyl) tri- and short-chain (C1 or C2 alkyl) ammonium salts such as ammonium salts, 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, dodecyldiethylmethylammonium salt, tetradecyldiethylmethylammonium salt, cetyldiethylmethylammonium salt, stearyldiethylmethylammonium salt, etc.Dioctyldimethylammonium salt, didecyldimethylammonium salt, N,N-didecyl-N-methyl-poly(oxyethyl)ammonium salt, didodecyldimethylammonium salt, ditetradecyldimethylammonium salt, dicetyldimethylammonium salt, distearyldimethylammonium salt, dioctylmethylethylammonium salt, didecylmethylethylammonium salt, didodecylmethylethylammonium salt, ditetradecylmethylethylammonium salt, dicetylmethylethylammonium salt, distearylmethylethylammonium salt, and other long-chain (C8-C18 alkyl) dioctyldimethylammonium salts. Examples include short-chain (C1 or C2 alkyl) ammonium salts; long-chain (C8-C18 alkyl) dishort-chain (C1 or C2 alkyl) hydroxyalkyl (C1 or C2) ammonium salts such as stearyldimethylhydroxyethylammonium; dishort-chain (C1 or C2 alkyl) long-chain (C8-C18 alkyl) ammonium salts having a trialkoxysilylalkyl group (C4-C10) such as [3(trimethoxysilyl)]propyl(dimethyl)octadecylammonium salt; amine nitrates; benzyltrimethylammonium salts; benzalkonium salts; and benzethonium salts. Examples of cationic surfactant salts include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). Cationic surfactants may be used individually or in combination of two or more types.

[0107] Examples of amphoteric surfactants include alkylbetaine type, alkylamidebetaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphate type amphoteric surfactants. Amphoteric surfactants may be used individually or in combination of two or more types.

[0108] Examples of semi-polar surfactants include alkylamine oxides and alkylamidopropyldimethylamine oxides. Semipolar surfactants may be used individually or in combination of two or more types.

[0109] (Content / mass ratio) The content of component (E), i.e., the total content of components (E1), (E3), and (E3), is preferably 30 to 65% by mass, more preferably 35 to 60% by mass, and even more preferably 40 to 55% by mass, relative to the total mass of the liquid detergent composition. If the content of component (E) is above the lower limit, the cleaning power will be higher. If the content of component (E) is below the upper limit, the liquid detergent composition will be less likely to gel, and its fluidity will be maintained more effectively.

[0110] The content of component (E1) is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and even more preferably 20 to 35% by mass, relative to the total mass of the liquid detergent composition. If the content of component (E1) is above the lower limit, the cleaning power is further enhanced. If the content of component (E1) is below the upper limit, the low-temperature stability is improved.

[0111] The content of component (E2) is preferably 5 to 20% by mass, more preferably 8 to 17% by mass, and even more preferably 11 to 15% by mass, relative to the total mass of the liquid detergent composition. If the content of component (E2) is above the lower limit, the cleaning power is further enhanced. In addition, the re-soiling prevention property is improved. If the content of component (E2) is below the upper limit, the fluidity of the liquid detergent composition is excellent, and the low-temperature stability is improved.

[0112] The mass ratio of component (E1) to component (E2) (hereinafter also referred to as the "E1 / E2 ratio") is preferably 0.5 to 8, more preferably 0.88 to 4.37, and even more preferably 1.33 to 2.72. If the E1 / E2 ratio is within the above range, low-temperature stability is improved. In addition, the liquid detergent composition is less likely to gel, and fluidity can be maintained more effectively. Furthermore, enzyme stability can be maintained more effectively.

[0113] When component (E) contains a polyoxyalkylene-type nonionic surfactant (component (E11)) with an average number of added moles of ethylene oxide of 10 or less and component (E2), the mass ratio expressed as component (E11) / component (E2) (hereinafter also referred to as the "E11 / E2 ratio") is preferably 1 to 5, more preferably 1.2 to 4, and even more preferably 1.4 to 3. If the E1 / E2 ratio is above the lower limit, the liquid detergent composition is less likely to gel and its fluidity can be maintained more effectively. If the E1 / E2 ratio is below the upper limit, low-temperature stability is improved.

[0114] <(F) component> Component (F) is a polycarboxylic acid and a polycarboxylic acid salt. The inclusion of component (F) in the liquid detergent composition makes the liquid detergent composition less prone to yellowing, thereby improving the stability of its liquid appearance.

[0115] Examples of polycarboxylic acids include compounds having divalent to tetravalent carboxylic acid groups, specifically citric acid, polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymers, copolymers of hydrocarbons with 4 to 12 carbon atoms and maleic acid, acrylic acid-methacrylic acid copolymers, and aminocarboxylic acid compounds.

[0116] Aminocarboxylic acid compounds are compounds that contain one or more primary to tertiary amino groups and two or more carboxyl groups in a single molecule. Examples of aminocarboxylic acid compounds include ethylenediaminetetraacetic acid (EDTA), triethylenetetraacetic acid (TTHA), methylglycine diacetic acid (MGDA), L-glutamic acid diacetic acid (GLDA), 1,3-propane-2-diaminetetraacetic acid (PDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), hydroxyethyliminodiacetic acid (HIDA), hydroxyiminodisuccinic acid (HIDS), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, ethylene glycol dietherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, cyclohexane-1,2-diaminetetraacetic acid, iminodisuccinic acid, aspartic acid diacetic acid, β-alaninediacetic acid, and hydroxyiminodisuccinic acid.

[0117] As the polycarboxylic acid, citric acid, polyacrylic acid, EDTA, and MGDA are preferred, citric acid, EDTA, and MGDA are more preferred, and citric acid is even more preferred. Examples of polycarboxylic acid salts include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), ammonium salts, and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). Among these, alkali metal salts of polycarboxylic acids are preferred, and sodium salts of polycarboxylic acids are more preferred. (F) Component is preferably citric acid, polyacrylic acid, EDTA, MGDA and their alkali metal salts, more preferably citric acid, EDTA, MGDA and their alkali metal salts, even more preferably citric acid and its alkali metal salts, particularly preferably citric acid and sodium citrate, and most preferably citric acid. Component (F) may be used alone or in combination of two or more types.

[0118] The content of component (F) is preferably 0.04 to 0.5% by mass, more preferably 0.06 to 0.5% by mass, and even more preferably 0.1 to 0.2% by mass, relative to the total mass of the liquid detergent composition. If the content of component (F) is above the lower limit, the liquid appearance stability is further improved. If the content of component (F) is below the upper limit, the enzyme stability can be further enhanced.

[0119] The mass ratio of component (A) to component (F) (hereinafter also referred to as the "A / F ratio") is preferably 0.03 to 17.5, more preferably 0.17 to 10, and even more preferably 0.5 to 6.25. If the A / F ratio is above the lower limit, the liquid detergent composition becomes less prone to yellowing, and the stability of the liquid's appearance is further improved. If the A / F ratio is below the upper limit, good low-temperature stability can be maintained.

[0120] The mass ratio of component (B) to component (F) (hereinafter also referred to as the "B / F ratio") is preferably 0.6 to 50, more preferably 1.0 to 25, and even more preferably 1.6 to 12.5. If the B / F ratio is above the lower limit, enzyme stability can be well maintained. If the B / F ratio is below the upper limit, low-temperature stability can be well maintained.

[0121] The mass ratio of component (C) to component (F) (hereinafter also referred to as the "C / F ratio") is preferably 0.57 to 150, more preferably 1.0 to 83.4, and even more preferably 2.5 to 40. If the C / F ratio is above the lower limit, good stability of the liquid's appearance can be maintained. If the C / F ratio is below the upper limit, good low-temperature stability can be maintained.

[0122] The mass ratio of component (C1) to component (F) (hereinafter also referred to as the "C1 / F ratio") is preferably 0.57 to 75, more preferably 1.0 to 41.7, and even more preferably 2.5 to 20. If the C1 / F ratio is above the lower limit, good stability of the liquid's appearance can be maintained. If the C1 / F ratio is below the upper limit, good low-temperature stability can be maintained.

[0123] The mass ratio of component (C2) to component (F) (hereinafter also referred to as the "C2 / F ratio") is preferably 0.57 to 75, more preferably 1.0 to 41.7, and even more preferably 2.5 to 20. If the C2 / F ratio is above the lower limit, good stability of the liquid's appearance can be maintained. If the C2 / F ratio is below the upper limit, good low-temperature stability can be maintained.

[0124] <Water> For the water used, purified water, deionized water, distilled water, or tap water can be used. Water may be used alone or in combination of two or more types.

[0125] The water content is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and more preferably 5 to 25% by mass, relative to the total mass of the liquid detergent composition. If the water content is above the lower limit, a suitable viscosity for the liquid detergent composition can be maintained well. If the water content is below the upper limit, the liquid detergent composition is less likely to gel and its fluidity can be maintained well.

[0126] <Optional ingredients> Optional ingredients include water-miscible organic solvents, higher fatty acids or their salts, pH adjusters, viscosity reducers and solubilizers, antibacterial agents, alkaline agents other than component (A), structuring agents, thickeners other than structuring agents, preservatives, antioxidants, inorganic reducing agents other than component (A), enzyme stabilizers other than components (B) and (C), texture enhancers, color transfer inhibitors, colorants, fragrances, emulsifiers, fluorescent agents, cationic polymers, discoloration inhibitors, hydrotropes, bleaching agents, pearlescent agents, and extracts of natural products. The optional components may be used individually or in combination of two or more.

[0127] A water-miscible organic solvent is an organic solvent that dissolves in 25g or more of water at 25°C in 1L of water. Examples of water-miscible organic solvents include alcohols such as ethanol, glycerin, 1-propanol, 2-propanol, 1-butanol, and 3-methoxy-3-methyl-1-butanol (Solfit, trade name); glycols such as propylene glycol (PG), butylene glycol, and hexylene glycol; polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a molecular weight of approximately 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, ethanol, glycerin, 3-methoxy-3-methyl-1-butanol, propylene glycol, polyethylene glycol with a molecular weight of approximately 200 to 1000, and diethylene glycol monobutyl ether (butyl carbitol) are preferred from the viewpoint of low odor, ease of availability, and fluidity of the liquid detergent composition, and ethanol, glycerin, and propylene glycol are more preferred. Water-miscible organic solvents may be used individually or in combination of two or more types. The content of the water-miscible organic solvent is preferably 5 to 40% by mass, more preferably 7 to 30% by mass, and even more preferably 10 to 20% by mass, based on the total mass of the liquid detergent composition.

[0128] If a liquid detergent composition contains a higher fatty acid or a salt thereof, its antifoaming properties will be enhanced. "Antifoaming properties" refer to the ability to suppress foaming when using a liquid detergent composition for laundry, specifically when the liquid detergent composition is diluted with tap water or similar. Examples of higher fatty acids or their salts include monofatty acids or their salts such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, and behenic acid; and mixed fatty acids or their salts such as coconut fatty acid and beef tallow fatty acid. Preferred high-grade fatty acids include lauric acid, myristic acid, palmitic acid, and coconut fatty acid, with coconut fatty acid being more preferred. Examples of salt forms of higher fatty acids include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), ammonium salts, and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). Higher fatty acids or their salts may be used individually or in combination of two or more types. The content of higher fatty acids or their salts is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass, and even more preferably 1.5 to 5% by mass, relative to the total mass of the liquid detergent composition. If the content of higher fatty acids or their salts is above the lower limit, the antifoaming properties are enhanced. If the content of higher fatty acids or their salts is below the upper limit, the low-temperature stability is improved.

[0129] Examples of pH adjusting agents include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; basic amino acids such as arginine and lysine; ammonia; sodium carbonate; and acidifying agents such as sulfuric acid, hydrochloric acid, and phosphoric acid. Among these, alkanolamines, sodium hydroxide, potassium hydroxide, and sodium carbonate are preferred, alkanolamines are more preferred, and monoethanolamine is even more preferred. In particular, when component (E) contains LAS or the like as component (E2), alkanolamines are preferred as pH adjusting agents. If alkanolamines are used, precipitation due to reaction with LAS or the like can be suppressed. As mentioned above, compositions containing nitrogen-containing compounds such as alkanolamines tend to yellow easily. However, since the liquid detergent composition of the present invention contains component (A), yellowing can be suppressed even if it contains nitrogen-containing compounds such as alkanolamines, and it has excellent liquid appearance stability. pH adjusters may be used individually or in combination of two or more types. The amount of pH adjuster added should be appropriately set to the amount necessary to adjust the liquid detergent composition to a predetermined pH.

[0130] Examples of viscosity reducers and solubilizers include aromatic sulfonic acids or their salts. Specifically, these include p-toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, or salts thereof. Examples of aromatic sulfonic acid salts include sodium salts, potassium salts, calcium salts, magnesium salts, ammonium salts, or alkanolamine salts. The viscosity reducer and solubilizer may be used individually or in combination of two or more types. The content of the viscosity reducer and solubilizer is preferably 0.1 to 10% by mass relative to the total mass of the liquid detergent composition.

[0131] Examples of antimicrobial agents include diclosan, triclosan, isopropylmethylphenol, polylysine, and polyhexamethylene biguanide. Among these, antimicrobial agents having a diphenyl structure are preferred, with diclosan and triclosan being more preferred. Antimicrobial agents may be used individually or in combination of two or more types. The antibacterial agent content is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.1 to 1% by mass, relative to the total mass of the liquid detergent composition.

[0132] Examples of alkaline agents other than component (A) (hereinafter also referred to as "other alkaline agents") include inorganic alkaline agents and organic alkaline agents. Inorganic alkaline agents are components that dissolve entirely or partially in water to exhibit basic properties, and whose pH of a 1% by mass aqueous solution at 25°C is 8 or higher. Examples of inorganic alkaline agents include sodium carbonate, sodium bicarbonate, sodium carbonate and sodium bicarbonate double salts (sodium sesquicarbonate), potassium carbonate, potassium bicarbonate and other carbonates; and silicates such as sodium metasilicate and layered sodium silicate. Among these, sodium carbonate, potassium carbonate, sodium metasilicate and layered sodium silicate are preferred from the viewpoint of providing higher cleaning power. Inorganic alkaline agents may be used individually or in combination of two or more types. In addition, inorganic alkaline agents may be used as pH adjusters.

[0133] In addition, as an inorganic alkaline agent, for example, sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, ammonium chloride, ammonium sulfate, sodium tetraborate, sodium pyrophosphate, sodium tripolyphosphate, sodium hydroxide, potassium hydroxide, aluminosilicate (e.g., zeolite) may be used. The inorganic alkaline agent content is preferably 20% by mass or less, and more preferably 0.5 to 10% by mass, relative to the total mass of the liquid detergent composition.

[0134] Examples of organic alkaline agents include monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, isopropanolamine, diisopropanolamine, and other alkanolamines. Among these, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and diisopropanolamine are preferred. Organic alkaline agents may be used individually or in combination of two or more types. The content of the organic alkaline agent is preferably 1.5 to 8% by mass, and more preferably 2 to 6% by mass, relative to the total mass of the liquid detergent composition. Furthermore, organic alkaline agents may be used as pH adjusters.

[0135] The liquid detergent composition becomes structured when it contains a structuring agent. Therefore, if the liquid detergent composition contains insoluble particles, the dispersion stability of the insoluble particles is enhanced, allowing the insoluble particles to be uniformly dispersed in the liquid detergent composition and maintaining that state well. In this specification, "structuring" refers to a state in which viscosity changes before and after force is applied.

[0136] Examples of structuring agents include bacterial cellulose, non-bacterial cellulose, and triglyceride components. Among these, bacterial cellulose and non-bacterial cellulose are preferred, with bacterial cellulose being more preferred, because they can sufficiently enhance the dispersion stability of insoluble particles even in small amounts, and a highly transparent liquid appearance can be easily obtained. The structuring agent may be used alone or in combination of two or more types.

[0137] Bacterial cellulose is cellulose produced by fermentation by bacteria of the genus Acetobacter. Examples of bacterial cellulose include so-called reticular bacterial cellulose, in which water-insoluble fibers branch in a net-like manner and interlock to form a network. At least a portion of the bacterial cellulose may be coated or mixed with a thickening agent. Commercially available bacterial cellulose can be used, such as the product name "CELLULON®" manufactured by CPKelco US.

[0138] Non-bacterial cellulose is cellulose obtained from vegetables, fruits, and wood, and is also called cellulose fiber. Commercially available non-bacterial cellulose products can be used, such as "Avicel®" from FMC, "Citri-Fi" from Fiberstar, and "Betafib" from Cosun.

[0139] Examples of triglyceride components include hydrogenated castor oil and hydrogenated palm oil. Examples of hydrogenated castor oil include glycerides containing a C10-C22 alkyl or alkenyl moiety incorporating a hydroxyl group, particularly triglycerides, specifically trihydroxystearin and dihydroxystearin. Hydrogenated castor oil is obtained by hydrogenating castor oil and converting the double bonds that may exist as ricinoleyl moieties in the starting oil. Through this conversion of the double bonds, the ricinoleyl moiety is converted to a saturated hydroxyalkyl moiety, such as hydroxystearyl. Hydrogenated castor oil can be used in a solid state, a molten state, or a mixture thereof, but can be processed in any suitable starting form, and is not limited to these. Commercially available hydrogenated castor oil can be used, such as "THIXCIN®" manufactured by Rheox, Inc. and "Caster Wax A Flakes" manufactured by NOF Corporation. Commercially available products can be used as hardened palm oil, such as "Palm Extreme Hardened Oil A" manufactured by Shin Nippon Rika Co., Ltd.

[0140] The content of the structuring agent is preferably 0.02 to 2% by mass, more preferably 0.04 to 1.5% by mass, and even more preferably 0.05 to 1% by mass, based on the total mass of the liquid detergent composition. Furthermore, when using a commercially available bacterial cellulose preparation such as "CELLULON®" as a structuring agent, the content of the structuring agent is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and even more preferably 2.5 to 7% by mass, based on the total mass of the liquid detergent composition. Here, "content of the product in its natural state" refers to the content of the product itself, including water and other substances contained within the product. If the structuring agent content is above the lower limit, the dispersion stability of insoluble particles will be further enhanced. If the structuring agent content is below the upper limit, the viscosity of the liquid detergent composition will be lower, resulting in improved usability and liquid stability.

[0141] Examples of thickeners other than structuring agents (hereinafter also referred to as "other thickeners") include acrylic polymers, xanthan gum, and galageenan. Examples of commercially available acrylic polymers include the Carbopol® series from Lubrizol. Examples of the Carbopol series include Carbopol ETD 2623, Carbopol EZ3, Carbopol EZ4, Carbopol Ultrez20, Carbopol Ultrez21, and Carbopol Aqua 30. Other thickening agents may be used individually or in combination of two or more. The content of other thickeners is preferably 6% by mass or less, and more preferably 0.2 to 4% by mass, relative to the total mass of the liquid detergent composition.

[0142] Examples of preservatives include 2-bromo-2-nitropropane-1,3-diol, 3-iodopropynylbutylcarbamate, zinc pyrithione, sodium pyrithione, octylisothiazolin-3-one, 1,2-benzoisothiazolin-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 preservative may be used alone or in combination of two or more types. The preservative content is preferably 0.001 to 2% by mass relative to the total mass of the liquid detergent composition.

[0143] If a liquid detergent composition contains an antioxidant, it can suppress the absorption of oxygen in the headspace of the container holding the liquid detergent composition. In addition, it can suppress fading and discoloration caused by light and heat. Examples of antioxidants include monophenol antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; bisphenol antioxidants such as 2,2'-methylenebis(4-methyl-6-t-butylphenol); and polymeric phenolic antioxidants such as dl-α-tocopherol. Among these, monophenolic antioxidants and polymeric antioxidants are preferred. Among monophenolic antioxidants, dibutylhydroxytoluene is particularly preferred. Among polymeric phenolic antioxidants, dl-α-tocopherol is particularly preferred. Antioxidants may be used individually or in combination of two or more types. The antioxidant content is preferably 0.01 to 2% by mass relative to the total mass of the liquid detergent composition.

[0144] If the liquid detergent composition contains an inorganic reducing agent other than component (A) (hereinafter also referred to as "other inorganic reducing agents"), fading and discoloration due to light and heat can be further suppressed. Other inorganic reducing agents include pyrosulfites such as sodium pyrosulfite and potassium pyrosulfite. Other inorganic reducing agents may be used individually or in combination of two or more. The content of other inorganic reducing agents is preferably 0.01 to 0.05% by mass, and more preferably 0.05 to 0.01% by mass, relative to the total mass of the liquid detergent composition.

[0145] Examples of enzyme stabilizers other than components (B) and (C) (hereinafter also referred to as "other enzyme stabilizers") include boric acid, borax, formic acid or its salts, calcium chloride, calcium sulfate and other calcium salts. Other enzyme stabilizers may be used individually or in combination of two or more. The content of other enzyme stabilizers is preferably 2% by mass or less relative to the total mass of the liquid detergent composition.

[0146] Examples of texture enhancers include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone. The texture-improving agent may be used alone or in combination of two or more types. The content of the texture-improving agent is preferably 5% by mass or less relative to the total mass of the liquid detergent composition.

[0147] Examples of anti-transfer agents include polyvinylpyrrolidone, carboxymethylcellulose, and polyalkyleneamines. The color transfer inhibitor may be used alone or in combination of two or more types. The content of the color transfer inhibitor is preferably 3% by mass or less relative to the total mass of the liquid detergent composition.

[0148] The coloring agents are not particularly limited and include, for example, pigments listed in the "Handbook of Legal Pigments" (Japan Cosmetic Industry Association) and those in which water-soluble polymers, etc., have been chemically modified at the ends of the chromophore structure. Specifically, CI Acid Red 138, CI Acid Red 260, CI Acid Red 106, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Levanyl(registered trademark) Violet, Liquitint(registered trademark) BLUE SE, Liquitint(registered trademark) BLUE HP, Liquitint(registered trademark) BLUE MC, Liquitint(registered trademark) VIOLET CT, Liquitint(registered trademark) VIOLET LS, Liquitint(registered trademark) VIOLET DD, Liquitint(registered trademark) GREEN SA Green SA), Liquitint® Bright Yellow, Liquitint® YELLOW SY, Liquitint® YELLOW LP, Liquitint® PINK AL, Liquitint® RED MX, CI77007 (Pigment Blue 29, L-280 BLUE U), CI74160 (Pigment Blue 15), CI77346 (Pigment Blue 28), CI77343 (Pigment Blue 36), CI74260 (Pigment Green 7), CI74265 (Pigment Green 36), WA-S Color Green, CIExamples include general-purpose dyes and pigments such as 21090 (Pigment Yellow 12, Yellow 205), CI56110 (Pigment Red 254), CI12490 (Pigment Red 5), Labracol 040(F) Red, PIGMOSOL®, and Liquitint® SeaGreenCC. In this specification, "CI" stands for Color Index. The coloring agent may be used alone or in combination of two or more types. The colorant content is preferably 0.001 to 1.0% by mass, and more preferably 0.01 to 0.01% by mass, relative to the total mass of the liquid detergent composition. If the colorant content is above the lower limit, the liquid detergent composition can be sufficiently colored. If the colorant content is below the upper limit, pigment deposition on the object being washed is less likely to occur, and a liquid detergent composition with excellent dispersion stability can be obtained.

[0149] Examples of fragrances include fragrance raw materials alone, or fragrance compositions comprising fragrance raw materials, fragrance solvents, fragrance stabilizers, etc., and fragrances commonly used in liquid detergent compositions can be incorporated. Capsule fragrances may also be incorporated. The amount of fragrance is preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent composition.

[0150] Examples of emulsifying agents include polystyrene emulsion and polyvinyl acetate emulsion, and emulsions with a solid content of 30-50% by mass are typically preferred. Specific examples include polystyrene emulsion (product name: Saibinol® RPX-196 PE-3, solid content 40% by mass, manufactured by Saiden Chemical Co., Ltd.), Opulyn 301, and Acusol OP 301. The emulsifying agent may be used alone or in combination of two or more types. The emulsifying agent content is preferably 0.001 to 0.5% by mass relative to the total mass of the liquid detergent composition.

[0151] Examples of fluorescent agents include biphenyl-type fluorescent agents such as 4,4'-bis-(4-chloro-3-sulfostyryl)-biphenyldisodium salt; and stilbene-type fluorescent agents such as 4,4'-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate and 4,4'-bis((4-toluidino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate. Fluorescent agents may be used individually or in combination of two or more types. The fluorescent agent content is preferably 0.05 to 1% by mass relative to the total mass of the liquid detergent composition.

[0152] Examples of cationized polymers include 4,4'-bis(2-sulfostyryl)biphenyl disodium salt, polymers of dimethyldiallylammonium chloride, dimethyldiallylammonium chloride-acrylamide copolymers, dimethyldiallylammonium chloride-acrylic acid copolymers, cationized cellulose, imidazolinium chloride-vinylpyrrolidone copolymer, polyethyleneimine, cationized polyvinyl alcohol, natural polymer derivatives having amino groups such as chitosan, and copolymers with vinyl monomers having hydrophilic groups to which diethylamino methacrylate-ethylene oxide or the like are added. Cationic polymers may be used individually or in combination of two or more types. The content of the cationized polymer is preferably 0.1 to 3% by mass relative to the total mass of the liquid detergent composition.

[0153] <Physical properties> (pH) The pH of the liquid detergent composition at 25°C is preferably 5 to 9, more preferably 5.5 to 8.5, and even more preferably 6 to 8. If the pH of the liquid detergent composition is above the lower limit, the decomposition of component (A) in the liquid detergent composition can be suppressed, and the liquid appearance stability can be well maintained. If the pH of the liquid detergent composition is below the upper limit, damage to textile products such as clothing can be prevented. In addition, the liquid appearance stability of the liquid detergent composition can be well maintained. The pH of the liquid detergent composition can be adjusted as needed by adding a pH adjuster. The pH of the liquid detergent composition is measured using a pH meter (manufactured by Toa DKK Co., Ltd., product name "HM-30G") at a temperature of 25°C.

[0154] <Manufacturing method> The method for manufacturing the liquid detergent composition is not particularly limited, and the liquid detergent composition can be manufactured in accordance with conventional methods. For example, a liquid detergent composition can be obtained by mixing the components that make up the liquid detergent composition. Alternatively, a liquid detergent composition may be produced by mixing, for example, component (A), component (B), component (C), component (D), component (E), a portion of water, component (F) as needed, and one or more optional components other than a pH adjuster, adjusting the pH to a predetermined level using a pH adjuster as needed, and then mixing in the remaining water.

[0155] <How to use> Methods of using the liquid detergent composition include, for example, putting the liquid detergent composition into the liquid detergent composition dispenser of a washing machine and then operating the washing machine; adding the liquid detergent composition to the water together with the items to be washed during washing; immersing the items to be washed in a detergent solution prepared by dissolving the liquid detergent composition in water beforehand; and applying the liquid detergent composition directly to the items to be washed, leaving it for, for example, 3 minutes to 24 hours, and then performing a normal wash.

[0156] Furthermore, it is 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 the liquid detergent composition from a tank containing the liquid detergent composition into the washing tub via a filter for removing debris located at the bottom of the tank and a dispensing pipe. A measuring means such as a syringe pump is provided in the middle of the dispensing pipe, allowing a fixed amount set according to the amount of laundry, etc., to be transferred from the tank to the washing tub. Using an automatic detergent dispenser not only eliminates the hassle of measuring, but also prevents liquid detergent from getting on your hands or spilling and staining the washing machine or surrounding area during the measuring process.

[0157] Furthermore, it is preferable to use an automatic dispenser that can automatically dispense a predetermined amount of liquid. Using an automatic dispenser is also preferable because it allows for accurate measurement of even small amounts of liquid cleaning agent composition, making it easier to achieve sufficient cleaning power and avoiding waste due to overuse. Some automatic dispensers utilize infrared sensors or other technologies to dispense liquids automatically without requiring the user to touch any switches. Using such an automatic dispenser allows users to measure out liquid detergent compositions simply by holding a container in one hand, significantly reducing the burden on the user.

[0158] Furthermore, when using an automatic dispenser, it is preferable to receive the liquid detergent composition dispensed into a flexible container and then place that flexible container directly into the washing machine. This ensures that the entire amount of the dispensed liquid detergent composition is reliably dissolved in the washing solution. Examples of materials for flexible containers that can be directly put into a washing machine include silicone resin, polyvinyl chloride, elastomer, flexible polyester, flexible polypropylene, and polyurethane.

[0159] Examples of items to be washed include clothing, dishcloths, towels, sheets, curtains, and other textile products. The material of the textile products is not particularly limited and may be any of the following: natural fibers such as cotton, silk, and wool, or synthetic fibers such as polyester and polyamide. When using a liquid detergent composition dissolved in water, it is preferable to dilute it, for example, 5 to 6,000 times (by volume). The bath ratio (mass of washing solution / mass of clothing), which is the amount of water per unit of clothing, is preferably 5 or higher for drum-type washing machines and 10 or higher for top-loading washing machines. The liquid detergent composition is suitable as a detergent for textile products.

[0160] <Effect> Since the liquid detergent composition of the present invention contains component (D) and component (E), it has high detergency. In addition, since the liquid detergent composition of the present invention contains component (A), it is less likely to yellow and has excellent liquid appearance stability, so it has excellent aesthetics when used as a detergent product. In particular, even when the liquid detergent composition of the present invention is filled in a colorless and transparent container to form a detergent product, the aesthetics can be maintained well. Moreover, for the liquid detergent composition of the present invention, since it also contains component (B) and component (C), it can suppress the decrease in the activity of the enzyme, which is component (D), despite containing component (A), and also has excellent enzyme stability.

Examples

[0161] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following description. In the present examples, "%" indicates "mass%" unless otherwise specified. Note that Example 17 is for reference only.

[0162] 「Raw materials used」 As component (A) or its substitute, the following compounds were used. · Na sulfite: Sodium sulfite (manufactured by Shenzhou Chemical Co., Ltd., trade name "Sodium sulfite"). · Na bisulfite: Sodium bisulfite (manufactured by Junsei Chemical Co., Ltd., trade name "Sodium bisulfite"). · Na thiosulfate: Sodium thiosulfate (manufactured by Junsei Chemical Co., Ltd., trade name "Sodium thiosulfate", substitute for component (A)).

[0163] As component (B), the following compounds were used. · Na lactate: Sodium lactate (manufactured by Musashino Chemical Laboratory Co., Ltd., trade name "Sodium lactate").

[0164] As component (C), the following compounds were used. · HP20: Ethylene oxide adduct of polyethyleneimine (manufactured by BASF, trade name "Sokalan HP20", in the general formula (2-1), R21 A compound in which the group is an ethylene group and m is 20 (C11 component). • SRN-170C: A 70% by mass aqueous solution of "TexCare SRN-100" manufactured by Clariant Corporation (product name "TexCare SRN-170C" manufactured by Clariant Corporation, component (C2)).

[0165] The following compounds were used as component (D). • Protease: Manufactured by Novozymes, product name "Progress Uno 100L", enzyme liquid preparation. • Amylase: Manufactured by Novozymes, brand name "Amplify Prime", enzyme liquid preparation.

[0166] The following compounds were used as component (E). • AE7: A polyoxyethylene alkyl ether obtained by adding 7 moles of ethylene oxide to an alcohol with 12 to 14 carbon atoms (manufactured by ECOGREEN OLEOCHEMICALS, trade name "ECOLAT24-7", general formula (5-1), R 51 R is an alkyl group having 12 to 14 carbon atoms. 52 Compound (5-1), (E11) component) in which is a hydrogen atom, p1 is 7, q1 is 0, and r1 is 0. ·LMAO: A polyoxyethylene alkyl ether (in general formula (5-1), R) obtained by adding 15 moles of ethylene oxide to natural alcohols (primary alcohols) having 12 and 14 carbon atoms. 51 R is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14), 52 A compound (5-1), component (E1) in which the atom is a hydrogen atom, p1 is 15, q1 is 0, and r1 is 0. Synthesized by the following synthesis method. • MEE: Fatty acid methyl ester ethoxylate (fatty acid with 12-14 carbon atoms, average number of added moles of EO is 15, in general formula (5-2), R 53 The alkyl group is a C11 alkyl group and a C13 alkyl group, and -X- is -COO-, R 54A compound (5-2) in which p2 is 15, q2 is 0, r2 is 0, and the methyl group is (E1) component, with a narrow ratio of 30% by mass. Synthesized by the following synthesis method. ·LAS-H: Linear alkylbenzene sulfonic acid having an alkyl group with 10 to 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipon LH-200", (E2) component). ·AES-1: Polyoxyalkylene alkyl ether sulfate (in the general formula (6-1), R 61 Is a linear alkyl group (C12) having 12 carbon atoms and a linear alkyl group (C14) having 14 carbon atoms (C12:C14 = 75:25 by mass ratio), v is 1, w is 0, Ma is sodium, and the proportion of the compound in which v is 0 and w is 0 with respect to the whole AES is 43% by mass (compound (6-1), (E2) component). Synthesized by the following synthesis method.

[0167] <Synthesis method of LMAO> 565.78 g of Procter & Gamble's product name CO-1214 alcohol as a raw material alcohol and 2.5 g of a 30% by mass NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Next, after dehydration at a temperature of 100 ° C and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160 ° C. Then, while stirring the reaction solution, 1933.5 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added through a blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. After completion of the addition of ethylene oxide, aging was carried out at a temperature of 180 ° C and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling the temperature to 100 ° C or less, 70% by mass p-toluenesulfonic acid was added for neutralization so that the pH of a 1% by mass aqueous solution of the reaction product became about 7, and LMAO was obtained.

[0168] <Synthesis of MEE> Synthesized according to the synthesis method described in JP-A-2000-144179. Aluminum hydroxide-magnesium hydroxide with a composition of 2.5MgO·Al2O3·zH2O (manufactured by Kyowa Chemical Industry Co., Ltd., trade name "Kyoward 300") was calcined at 600°C for 1 hour in a nitrogen atmosphere to obtain a calcined aluminum hydroxide-magnesium hydroxide (unmodified) catalyst. 2.2 g of the calcined aluminum hydroxide-magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of methyl laurate, and 70 g of methyl myristate were charged into a 4 L autoclave, and the catalyst was modified in the autoclave. Next, after replacing the inside of the autoclave with nitrogen, 1052 g of ethylene oxide was introduced while maintaining the temperature at 180°C and the pressure at 0.3 MPa, and the reaction was carried out with stirring. The obtained reaction solution was cooled to 80°C, 159 g of water, 5 g of activated clay and 5 g of diatomaceous earth as filter aids were added and mixed, and then the catalyst was filtered off to obtain MEE.

[0169] <Synthesis method of AES-1> 400 g of Procter & Gamble's product name CO1270 alcohol (a mixture of alcohol with 12 carbon atoms and alcohol with 14 carbon atoms with a mass ratio of 75 / 25) as a raw material alcohol and 0.8 g of potassium hydroxide catalyst as a reaction catalyst were charged into an autoclave with a capacity of 4 L. After replacing the inside of the autoclave with nitrogen, 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 the reaction was carried out to obtain an alcohol ethoxylate. Analysis using a gas chromatograph: GC-5890 manufactured by Hewlett-Packard, detector: hydrogen flame ionization detector (FID), column: Ultra-1 (manufactured by HP, L25m×φ0.2mm×T0.11μm) showed that the obtained alcohol ethoxylate had an average addition mole number of ethylene oxide of 1.0. Also, the amount of the compound without the addition of ethylene oxide (which finally becomes 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, replaced with nitrogen, and then 96 g of liquid anhydrous sulfuric acid (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40°C. After the addition was complete, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfate. Subsequently, this was neutralized with an aqueous sodium hydroxide solution to obtain AES-1.

[0170] (F) The following compounds were used as components. · Citric acid: manufactured by Fuso Chemical Industry Co., Ltd., trade name "Liquid Citric Acid".

[0171] The following compounds were used as optional components and water. · MEA: Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd., trade name "Monoethanolamine"). · Ethanol: manufactured by Nippon Alcohol Sales Co., Ltd., trade name "Specially Synthesized Alcohol 95 Degrees". · PEG1000: Polyethylene glycol (manufactured by Lion Corporation, trade name "PEG#1000-L60", weight average molecular weight = 1000). · pTs: p-Toluenesulfonic acid (manufactured by Meiyu Sangyo Co., Ltd., trade name "PTS Acid"). · Coconut fatty acid: manufactured by NOF Corporation, trade name "Coconut Fatty Acid". · Dichlorosan: 4,4'-dichloro-2-hydroxydiphenyl ether (manufactured by BASF, trade name "TINOSAN® HP100"). · Solfit: 3-methoxy-3-methylbutanol (manufactured by Kuraray Co., Ltd., trade name "Solfit"). · Dye: Milliken Japan Co., Ltd., trade name "Liquitint SeaGreenCC". · Fragrance: Dibodan Japan Co., Ltd., trade name "Aquatic Powdery". · Water: Ion-exchanged water.

[0172] "Measurement and Evaluation" <Evaluation of Liquid Appearance Stability> 85 mL of the liquid detergent composition was filled into a glass bottle (wide-mouth standard bottle PS-NO.11), sealed with the lid, and stored in a constant temperature bath set to 50°C for 4 weeks. During this period, the appearance of the liquid detergent composition was visually observed, and the stability of the liquid's appearance was evaluated according to the following criteria. ○ and △ were considered acceptable. (Evaluation Criteria) ○: No yellowing was observed even after 4 weeks from the start of storage. △: Yellowing progressed within two weeks of the start of storage. ×: Yellowing progressed within one week of the start of storage.

[0173] <Evaluation of low-temperature stability> 85 mL of the liquid detergent composition was filled into a glass bottle (wide-mouth standard bottle PS-No. 11), sealed with the lid, and stored in a constant temperature bath set to a cycle of 24 hours at -20°C followed by 24 hours at 0°C, and kept for 3 cycles. The appearance of the liquid detergent composition after storage was visually observed, and the liquid appearance stability was evaluated according to the following evaluation criteria. ○ and △ were considered acceptable. Note that the sodium sulfate (Glauber's salt) in the following evaluation criteria is derived from component (A). (Evaluation Criteria) ○: No sodium sulfate precipitation was observed. △: Precipitation of Glauber's salt is observed, but the Glauber's salt dissolves at room temperature (25°C). ×: Precipitation of Glauber's salt is observed, but Glauber's salt does not dissolve at room temperature (25°C).

[0174] <Evaluation of enzyme stability> 35 mL of the liquid detergent composition was filled into glass bottles (wide-mouth standard bottles PS-No.6), sealed with the lids closed, and stored for 4 weeks in a constant temperature bath set to 37°C and -5°C. The liquid detergent composition stored at 37°C (37°C stored product) and the liquid detergent composition stored at -5°C (-5°C stored product) were measured for protease activity as shown below.

[0175] (Measurement of protease activity) Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free / Calbiochem®) was dissolved in 1N sodium hydroxide (1 mol / L sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Ltd.) to adjust the pH to 10.5. The solution was then diluted with 0.05M boric acid (special grade boric acid, manufactured by Kanto Chemical Co., Ltd.) aqueous solution to a concentration of 0.6% by mass of milk casein, and used as a protease substrate. Each sample solution was prepared by diluting 1 g each of the 37°C-stored product and the -5°C-stored product 25 times (by mass ratio) with 3°DH hard water (calcium chloride (special grade), manufactured by Kanto Chemical Co., Ltd., to adjust the hardness). To each sample solution, 5 g of the above protease substrate was added and mixed for 10 seconds using a vortex mixer. The mixture was then allowed to stand at 37°C for 30 minutes to allow the enzymatic reaction to proceed. Subsequently, 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 added and mixed for 10 seconds using a vortex mixer. The mixture was then allowed to stand at 20°C for 30 minutes to stop the enzymatic reaction. The precipitate was removed using a 0.45 μm filter, and the filtrate was collected. The absorbance (absorbance A) at a wavelength of 275 nm of the recovered filtrate was measured using a UV-160 ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation. A higher absorbance A indicates a greater amount of tyrosine (produced by proteases breaking down protease substrates) present in the filtrate. To eliminate the influence of absorption by components other than the target component, 5 g of a 0.44 M aqueous solution of TCA was added to 1 g of each sample solution and stirred for 10 seconds using a vortex mixer. Then, 5 g of protease substrate was added and stirred for 10 seconds using a vortex mixer. Next, precipitates were removed using a 0.45 μm filter and the filtrate was collected. The absorbance (absorbance B) of the collected filtrate at a wavelength of 275 nm was measured using UV-160. Based on the absorbance measurement results, the residual enzyme (protease) activity percentage (%) was calculated using the following formula (i). Note that the absorbance values ​​at 275 nm for each sample substituted into formula (i) were obtained by dividing the absorbance value at 600 nm (measured simultaneously) by the absorbance value at 275 nm to exclude scattered light from bubbles, etc. Enzyme activity retention rate (%) = {(Absorbance A at 37°C) - (Absorbance B at 37°C)} / {(Absorbance A at -5°C) - (Absorbance B at -5°C)} × 100 ... (i)

[0176] (judgement) Enzyme stability was evaluated using the percentage of remaining enzyme activity as an indicator, according to the following evaluation criteria. ○ and △ were considered passing grades. (Evaluation Criteria) ◎: Enzyme activity retention rate is 50% or higher. ○: Enzyme activity retention rate is 40% or more, but less than 50%. △: Enzyme activity retention rate is 20% or more, but less than 40%. ×: Enzyme activity retention rate is less than 20%.

[0177] <Evaluation of cleaning power> The following materials were used for washing: polyester (PE) cloth, wet-process artificial soiled cloth, EMPA standard soiled cloth, and red clay soiled cloth. Polyester (PE) cloth: Five 5cm x 5cm pieces of polyester tropical cloth (manufactured by Tanigashira Shoten) were used as cloths to judge the cleaning power. Wet-process artificial soiling cloth: One soiling cloth manufactured by the Japan Laundry Science Association. EMPA standard contaminated cloths: 1 EMPA101 contaminated cloth (with carbon black / olive oil stains), 1 EMPA106 contaminated cloth (with carbon black / mineral oil stains), 1 EMPA116 contaminated cloth (with blood / milk / ink stains). Red clay stain cloth: One piece of cloth made by applying a solution of clay from Mikatagahara, dispersed in tap water using a homogenizer, onto a cotton cloth (plain weave cotton cloth, 100 count).

[0178] The items to be washed were treated using a liquid detergent composition as follows. In a washing test chamber (manufactured by UNITED STATES TESTING, product name "Terg-O-Tometer"), 900 mL of 3°DH hard water at 25°C was placed, 0.6 g of the liquid detergent composition was added, and then the object to be washed was placed in it. Subsequently, 3°DH hard water was added to adjust the bath ratio to 30 times, and washing was performed at 120 rpm and 25°C for 10 minutes (washing process). After washing, the garments were spin-dried for 1 minute, then rinsed with 900 mL of 25°C 3°DH hard water at 120 rpm for 3 minutes at 25°C. This process (spin-drying and rinsing) was repeated twice. For the second rinse, a predetermined amount of fabric softener was added to 900 mL of 25°C 3°DH hard water. Lenor Deodorizer 1Week (manufactured by Procter & Gamble) was used as the fabric softener (spin-drying and rinsing process). After rinsing the items to be washed and spinning them for 1 minute, only five pieces of PE cloth were removed to be used as test cloths, placed between filter paper, and dried with an iron (drying process).

[0179] Using a reflectometer (manufactured by Nippon Denshoku Industries Co., Ltd., product name "Spectroscopic Colorimeter SE2000"), the reflectance (Z value) of the test fabric before and after washing was measured, and ΔZ was calculated using the following formula (ii). ΔZ = (Z value before washing) - (Z value after washing) ... (ii)

[0180] The ΔZ of five test cloths (PE cloths) was calculated, and the average value was determined. Using this average value as an indicator, the cleaning power was evaluated according to the following evaluation criteria. ○ and △ were considered passing grades. (Evaluation Criteria) ◎: The average value of ΔZ is less than 3.5. ○: The average value of ΔZ is 3.5 or greater, and less than 4.5. △: The average value of ΔZ is 4.5 or higher, but less than 5.5. ×: The average value of ΔZ is 5.5 or higher.

[0181] Examples 1-21, Comparative Examples 1-4 In a 500 mL beaker, components (A), (B), (C), (D), (E), and (F), along with an optional component and water, were added according to the formulations shown in Tables 1-5. The mixture was then thoroughly stirred using a Three-One Motor Stirrer (manufactured by AS ONE Corporation) to obtain a liquid detergent composition. The pH of the obtained liquid detergent composition 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 to 5. The obtained liquid detergent compositions were evaluated for liquid appearance stability, low-temperature stability, enzyme stability, and cleaning power. These results are shown in Tables 1-5.

[0182] [Table 1]

[0183] [Table 2]

[0184] [Table 3]

[0185] [Table 4]

[0186] [Table 5]

[0187] In Tables 1-5, the amount (mass%) of each component is expressed as a percentage of the total mass of the liquid detergent composition, and unless otherwise specified, the values ​​are shown in terms of pure content. "Balance" means that water is added so that the total amount (mass%) of all components in each example liquid detergent composition equals 100% by mass. A blank space for the amount indicates that the component is not included (0% by mass). Furthermore, in Tables 1-5, the "C / A ratio" is the mass ratio of component (C) to component (A). The "C1 / A ratio" is the mass ratio of component (C1) to component (A). The "C2 / A ratio" is the mass ratio of component (C2) to component (A). The "C1 / C2 ratio" is the mass ratio of component (C1) to component (C2). The "B / C ratio" is the mass ratio of component (B) to component (C). The "B / C1 ratio" is the mass ratio of component (B) to component (C1). The "B / C2 ratio" is the mass ratio of component (B) to component (C2). The "A / D ratio" is the mass ratio of component (A) to component (D). The "E1 / E2 ratio" is the mass ratio of component (E1) to component (E2). The "E11 / E2 ratio" is the mass ratio of component (E11) to component (E2). The "A / F ratio" is the mass ratio of component (A) to component (F). The "B / F ratio" is the mass ratio of component (B) to component (F). The "C / F ratio" is the mass ratio of component (C) to component (F). The "C1 / F ratio" is the mass ratio of component (C1) to component (F). The "C2 / F ratio" is the mass ratio of component (C2) to component (F). Note that in Tables 1-5, for convenience, all mass ratios except the A / F ratio have been rounded to the third decimal place. For convenience, the A / F ratio has been rounded to the fourth decimal place.

[0188] As is clear from Tables 1-4, the liquid detergent compositions of each example exhibited excellent liquid appearance stability and enzyme stability. Furthermore, the liquid detergent compositions of each example also exhibited high cleaning power and excellent low-temperature stability. On the other hand, as is clear from Table 5, the liquid detergent composition of Comparative Example 1, which did not contain component (A), had poor liquid appearance stability. The liquid detergent compositions of Comparative Examples 2 and 3, which did not contain component (B) or component (C), exhibited poor enzyme stability. In particular, the liquid detergent composition of Comparative Example 3, which did not contain component (C), also exhibited poor cleaning power. Comparative Example 4, a liquid detergent composition containing sodium thiosulfate instead of component (A), exhibited poor liquid appearance stability.

Claims

1. (A) Components: At least one selected from the group consisting of sulfites, sulfites, bisulfites and bisulfites, (B) Component: At least one selected from the group consisting of α-hydroxy-monocarboxylic acids and α-hydroxy-monocarboxylic acid salts, (C) component: component (C1) and component (C2) below, (C1) Component: At least one selected from the group consisting of alkylene oxide adducts of polyalkyleneimines and alkylene oxide adducts of polyalkyleneamines. (C2) Component: A polymer having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units. (D) Components: Enzymes and, (E) Ingredients: Surfactants and It contains, A liquid detergent composition for textile products, wherein the mass ratio of component (C2) to component (A) is 1 to 200.

2. The liquid detergent composition for textile products according to claim 1, wherein the (E) component comprises a nonionic surfactant and a non-soap-based anionic surfactant, and the nonionic surfactant comprises a polyoxyalkylene-type nonionic surfactant with an average number of ethylene oxide addition moles of 10 or less.

3. The liquid detergent composition for textile products according to claim 2, wherein the mass ratio of the polyoxyalkylene-type nonionic surfactant to the non-soap-based anionic surfactant is 1 to 5.

4. A liquid detergent composition for textile products according to any one of claims 1 to 3, wherein the mass ratio represented by component (C) / component (A) is 0.29 to 600.

5. The liquid detergent composition for textile products according to any one of claims 1 to 3, wherein the mass ratio represented by component (C1) / component (C2) is 0.16 to 15.

6. The liquid detergent composition for textile products according to any one of claims 1 to 3, wherein the mass ratio represented by component (A) / component (D) is 0.3 to 5.

7. The liquid detergent composition for textile products according to any one of claims 1 to 3, further comprising 1 to 5% by mass of at least one selected from the group consisting of higher fatty acids and salts of higher fatty acids, based on the total mass of the liquid detergent composition for textile products.

8. The liquid detergent composition for textile products according to any one of claims 1 to 3, further comprising 5 to 20% by mass of a water-miscible organic solvent selected from the group consisting of ethanol, 3-methoxy-3-methyl-1-butanol, and polyethylene glycol having a molecular weight of about 200 to 1000, based on the total mass of the liquid detergent composition for textile products.

9. Furthermore, component (F): contains at least one selected from the group consisting of citric acid and alkali metal salts of citric acid, A liquid detergent composition for textile products according to any one of claims 1 to 3, wherein the mass ratio represented by component (A) / component (F) is 0.025 to 6.5.

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