JPWO2019124486A1 - Liquid cleaning agent composition for clothing - Google Patents

Abstract

In the present invention, component (A): an anionic surfactant excluding higher fatty acid salts, component (B): nonionic surfactant, component (C): bicarbonate, and component (D): chelating agent. The present invention relates to a liquid detergent composition for clothing, which contains the above component (C) and has a mass ratio represented by the component (D) of 0.6 or more and 20 or less.

Description

The present invention relates to a liquid cleaning composition for clothing.
The present application claims priority based on Japanese Patent Application No. 2017-245556 filed in Japan on December 21, 2017, the contents of which are incorporated herein by reference.

When thickening a liquid detergent composition having a low surfactant concentration, an acrylic acid-based polymer or a combination of an anionic surfactant and an inorganic salt is used.
However, when an acrylic acid-based polymer is used, there is a concern that the coating cleanability may be deteriorated. The coating detergency is the detergency in a method in which a liquid cleaning agent composition is directly applied to an object to be washed such as clothes, left for an arbitrary time, and then ordinary washing is performed. In addition, when an acrylic acid-based polymer is used, there is a concern that the liquid stability at a low temperature (5 ° C. or lower) (difficulty of solidification, precipitation, white turbidity and separation after storage for a certain period of time) may be lowered.
When sodium sulfate is used as the inorganic salt in the combination of the anionic surfactant and the inorganic salt, there is a problem that needle-like or plate-like crystals are precipitated under low-temperature storage conditions (liquid stability at low temperature is poor).
To solve such a problem, Patent Document 1 proposes a liquid cleaning agent composition containing a specific solvent and a surfactant. The liquid cleaning agent composition of Patent Document 1 has an appropriate viscosity, and the liquid stability at a low temperature is improved.

Japanese Unexamined Patent Publication No. 2014-37503

However, the liquid cleaning agent composition is required to have liquid stability at a lower temperature.
Therefore, an object of the present invention is a liquid cleaning agent composition for clothing, which has an appropriate viscosity and is more excellent in liquid stability at a low temperature.

As a result of repeated diligent studies, the present inventors have found that the liquid stability of the liquid cleaning agent composition at low temperature is improved by combining the bicarbonate and the chelating agent in a specific ratio.
That is, the present invention has the following aspects.

[1] Component (A): anionic surfactant excluding higher fatty acid salt, component (B): nonionic surfactant, component (C): bicarbonate, component (D): chelating agent. A liquid detergent composition for clothing, which contains and has a mass ratio of the component (C) / the component (D) of 0.6 or more and 20 or less.
[2] The composition of a liquid cleaning agent for clothing according to [1], wherein the content of the component (C) is 1% by mass or more and 4% by mass or less with respect to the total mass of the liquid cleaning agent composition for clothing. Stuff.
[3] In [1] or [2], the content of the component (D) is 0.15% by mass or more and 1.5% by mass or less with respect to the total mass of the liquid cleaning agent composition for clothing. The liquid cleaning agent composition for clothing described.
[4] Any one of [1] to [3], wherein the mass ratio represented by the component (A) / (component (A) + component (B)) is 0.2 or more and less than 1. The liquid cleaning agent composition for clothing according to.
[5] The liquid cleaning agent composition for clothing according to any one of [1] to [4], further containing the component (E): enzyme.
[6] The liquid cleaning agent composition for clothing according to any one of [1] to [5], which further contains a component (F): a fatty acid having 8 to 22 carbon atoms.
[7] The liquid cleaning agent composition for clothing according to any one of [1] to [6], which further contains an alkaline agent excluding the component (C).
[8] The liquid cleaning agent composition for clothing according to any one of [1] to [7], further containing the component (H): an antioxidant.
[9] The liquid cleaning agent composition for clothing according to any one of [1] to [8], which has a viscosity at 25 ° C. of 30 mPa · s or more and 1500 mPa · s or less.

According to the liquid cleaning agent composition for clothing of the present invention, it has an appropriate viscosity and is superior in liquid stability at low temperature.

[Liquid cleaning agent composition for clothing]
The liquid cleaning agent composition for clothing of the present invention (hereinafter, also simply referred to as a liquid cleaning agent) is a composition containing a component (A), a component (B), a component (C), and a component (D).
The composition of the present invention is a liquid at 25 ° C. and is suitably used as a cleaning agent for clothing.
In the present specification, "clothing" is a concept that includes cloth and synthetic fibers to be washed (object to be washed) such as towels, sheets, and cushion covers, in addition to clothes such as clothes and underwear.

<Ingredient (A)>
The component (A) is an anionic surfactant excluding higher fatty acid salts. By containing the component (A), the liquid cleaning agent of the present invention exerts a cleaning power against stains on clothes. In the present specification, the higher fatty acid is a fatty acid having 8 to 22 carbon atoms. The fatty acid refers to a carboxylic acid having one carboxyl group at the end of a chain hydrocarbon group. As used herein, the higher fatty acid salt is a salt of a fatty acid having 8 to 22 carbon atoms.

Examples of the component (A) include the following (1) to (10).
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) α-sulfofatty acid ester salt (MES) having 10 to 20 carbon atoms.
(3) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(4) Polyoxyethylene monoalkyl phosphate, polyoxyethylene dialkyl phosphate or polyoxyethylene sesquialkyl phosphate.
(5) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (the molar ratio of EO / PO is 0.1 / 9.9 to 9.9 / 0.1). An alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with an average of 0.5 to 10 mol.
(6) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (where the molar ratio of EO / PO is 0.1 / 9.9 to 9.9 / 0.1) is 3 to 30 on average. A molar-added alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(7) Any of the alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (where the molar ratio of EO / PO is 0.1 / 9.9 to 9.9 / 0.1) is 0.5 on average. An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 moles of carbon atoms.
(8) An alkyl polyhydric alcohol ether sulfate such as an alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms. Here, the polyhydric alcohol refers to an alcohol having two or more hydroxyl groups in the molecule.
(9) Long-chain monoalkyl phosphate, long-chain dialkyl phosphate or long-chain sesquialkyl phosphate. Here, the long-chain alkyl means an alkyl group having 12 to 26 carbon atoms.
(10) An alkyl sulfate having 10 to 20 carbon atoms or an alkenyl sulfate salt having 10 to 20 carbon atoms (AS).

As the component (A), an anionic surfactant other than those exemplified above may be used. For example, carboxylic acid type anionic surfactants such as polyoxyalkylene ether carboxylate, alkylamide ether carboxylate or alkenylamide ether carboxylate, acylaminocarboxylate; alkyl phosphate ester salt, polyoxyalkylene alkyl phosphorus. Examples thereof include phosphoric acid ester-type anionic surfactants such as acid ester salts, polyoxyalkylene alkylphenyl phosphate ester salts, and glycerin fatty acid ester monophosphate ester salts.
Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt; alkanolamine salts such as monoethanolamine salt and diethanolamine salt; and ammonium salts. Be done. Of these, alkali metal salts are preferable.

As the component (A), one type may be used alone, or two or more types may be used in combination.
As the component (A), at least one selected from the group consisting of the above (1), (2), (3) and (5) because better detergency can be easily obtained among the above. It is preferable to contain the anionic surfactant of (1), (2), (3) and (5), (1), (3) and (5), (1), (2). It is more preferable to contain an anionic surfactant which is at least one combination selected from the group consisting of the combination of (5) and (1) and (5).

The content of the component (A) is preferably 2% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 18% by mass or less, and 5% by mass or more and 16% by mass or less with respect to the total mass of the liquid cleaning agent. Is even more preferable. When the content of the component (A) is at least the above lower limit value, a thickened liquid cleaning agent can be easily obtained. It is easy to obtain a liquid cleaning agent with excellent protein detergency. In addition, it is easy to obtain a liquid cleaning agent having excellent anti-recontamination properties. Further, when the content of the component (A) is not more than the above upper limit value, a liquid cleaning agent having good fluidity can be easily obtained.
In the present specification, the protein detergency means the detergency against protein stains. Further, the anti-recontamination property means a property of preventing the dirt removed from the object to be washed by the washing treatment from adhering to the object to be washed again.

In one aspect of the present invention, the component (A) may contain the above-mentioned (2). Further, (2) is preferably an α-sulfofatty acid salt ester represented by the following general formula (a1) (hereinafter, also referred to as a component (a)).
R ¹ CH (SO ₃ M) COOR ² ... (a1)
(In the general formula (a1), R ¹ is a hydrocarbon group having 10 to 16 carbon atoms, R ² is a hydrocarbon group having 1 to 6 carbon atoms, and M is a counterion.)

((A) component)
In the general formula (a1), the carbon number of the hydrocarbon group ^{R 1} is 10-16. That is, the number of carbon atoms of the fatty acid residue contained in the component (a) is 12 to 18. The fatty acid residue refers to an acyl group moiety. When the number of carbon atoms of R ¹ is 10 or more, the surface activity is strong and the coating cleanability becomes better.
When the carbon number of R ¹ is 16 or less, the liquid stability of the liquid cleaning agent at a low temperature is excellent.

The hydrocarbon group of R ¹ may be linear, may be branched, or may contain a cyclic structure. The hydrocarbon group of R ¹ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or more preferably a linear or branched alkenyl group, and a linear alkyl. Groups or linear alkenyl groups are more preferred.
Examples of R ¹ include a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group and the like.

In the general formula (a1), R ² has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
Hydrocarbon group R ² may be linear, may be branched, may contain a cyclic structure. Hydrocarbon group R ² is preferably an aliphatic hydrocarbon group, a linear or branched alkyl group, or a linear or branched chain alkenyl group is more preferably a straight chain alkyl A group or a branched alkyl group is more preferable.
The R ^2, since the coating detergency is further improved, a methyl group, an ethyl group, n- propyl group, an isopropyl group are preferable, methyl group, ethyl group, is n- propyl group, and particularly preferably a methyl group ..

In the general formula (a1), as the counterion of M, those capable of forming a water-soluble salt together with R ¹ CH (COOR ² ) SO ₃ ⁻ are preferable, and examples thereof include alkali metal ions, protonated amines, and ammonium ions. Can be mentioned. Examples of the alkali metal that can be the counterion include sodium and the like. Examples of the amine that can be the counter ion include primary to tertiary amines. The total carbon number of the amine is preferably 1 to 6. Examples of the amine include methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and the like. Moreover, the amine may have a hydroxy group. The amine preferably has a hydroxy group because the component (a) becomes more soluble in water. Examples of the amine having a hydroxy group include alkanolamine, and the alkanol group preferably has 1 to 3 carbon atoms. Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine and the like.
As M, alkali metal ions are preferable, and sodium ions are particularly preferable, because they are easily available and the liquid stability of the liquid cleaning agent at low temperatures can be more easily enhanced.
As the component (a), R ¹ in the general formula (a 1) is a linear or branched alkyl group having 14 to 16 carbon atoms, or a linear or branched alkenyl group, and R ² Compounds in which is a methyl group are particularly preferred.

As the component (a), one type may be used alone, or two or more types may be used in combination.
The component (a) is preferably a mixture in which compounds having different carbon numbers of fatty acid residues are mixed because the coating detergency is improved and the solubility in water is improved. In particular, the compound (a-1) in which R ¹ in the general formula (a1) is a hydrocarbon group having 14 carbon atoms and the compound (a-) in which R ¹ in the general formula (a1) is a hydrocarbon group having 16 carbon atoms. A mixture with 2) is preferable. In such a mixture, the mass ratio of compound (a-1) to compound (a-2) is preferably (a-1) :( a-2) = 45: 55-95: 5, and is preferably 60:40 to 90. : 10 is more preferable, and 80:20 to 85:15 is even more preferable. When the mass ratio is within the above numerical range, the coating cleanability, the solubility in water, and the liquid stability of the liquid cleaning agent at a low temperature tend to be better.

As the component (a), those obtained by a known production method may be used. For example, an α-sulfo fatty acid ester (α-SF acid) is prepared by contacting the raw material fatty acid ester with anhydrous sulfuric acid or the like and sulfonated using a tank-type reactor equipped with a stirrer or the like by a conventional method. Then, the one obtained by neutralizing the α-SF acid with sodium hydroxide or the like may be used. As the component (a), a commercially available product may be used. Before and after neutralization, bleaching may be performed with hydrogen peroxide or the like.

The content of the component (a) is preferably 0% by mass or more and 6% by mass or less, more preferably 0.5% by mass or more and 5.0% by mass or less, and 1.0% by mass, based on the total mass of the liquid cleaning agent. % Or more and 3.0% by mass or less are more preferable. When the content of the component (a) is within the above numerical range, it becomes easy to obtain a liquid cleaning agent having excellent coating cleaning property, recontamination prevention property, dispersion stability, and enzyme stability. In addition, it becomes easier to maintain the degree of freedom in blending other components.
The ratio of the component (a) to the component (A) ((a) / (A)) is preferably 0/100 or more and 50/100 or less, more preferably 5/100 or more and 40/100 or less, and 10 /. More preferably, it is 100 or more and 30/100 or less.

<Ingredient (B)>
The component (B) is a nonionic surfactant. By containing the component (B), the liquid cleaning agent of the present invention can improve liquid stability, defoaming property, and sebum cleaning power. As used herein, the defoaming property refers to the ability to eliminate bubbles of a liquid cleaning agent. Sebum detergency refers to the detergency against sebum stains.

Examples of the component (B) include the following (11) to (15).
(11) An average of 3 to 30 mol, preferably 3 to 20 mol, and further preferably 5 to 10 mol of an alkylene oxide having 2 to 4 carbon atoms is added to a monohydric aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. The added polyoxyalkylene alkyl (or alkenyl) ether. Of these, polyoxyethylene alkyl (or alkenyl) ethers and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ethers are preferable. Examples of the monohydric aliphatic alcohol used here include primary alcohols and secondary alcohols. Moreover, the alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable. Examples of the primary alcohol include 1-dodecanol, 1-tetradecanol, 1-octadecanol and the like.
(12) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(13) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long chain fatty acid alkyl ester. Here, the long chain fatty acid refers to a fatty acid having 12 to 26 carbon atoms.
(14) Polyoxyethylene fatty acid ester.
(15) Polyoxyethylene cured castor oil.

As the component (B), one type may be used alone, or two or more types may be used in combination.
As the component (B), those of the above (11) or (13) are preferable, and among them, those represented by the following general formula (b1) or (b2) are preferable.
R ^3- C (= O) O-[(EO) _s / (PO) _t ]-(EO) _u- R ⁴ ... (b1)
R ^5- O-[(EO) _v / (PO) _w ]-(EO) _x- H ... (b2)
(In the general formula (b1), R ³ is a hydrocarbon group having 7 to 22 carbon atoms, R ⁴ is an alkyl group having 1 to 6 carbon atoms, and s represents the average number of repetitions of EO, 6 to 20. , T represents the average number of repetitions of PO, 0-6, u represents the average number of repetitions of EO, 0-20, EO represents an oxyethylene group, PO. Represents an oxypropylene group.
In the general formula (b2), R ⁵ is a hydrocarbon having 6 to 22 carbon atoms, v represents the average number of repetitions of EO, 3 to 20, and w represents the average number of repetitions of PO, which is 0. It is a number of ~ 6, x represents the average number of repetitions of EO, is a number of 0 to 20, EO represents an oxyethylene group, and PO represents an oxypropylene group. )

In the general formula (b1), R ³ is a hydrocarbon group having 7 to 22 carbon atoms. The carbon number of R ³ is preferably 9 to 21, and more preferably 11 to 21.
R ³ is preferably an alkyl group or an alkenyl group.
R ³ may be either straight chain or branched chain.
From the viewpoint of further improving the detergency, R ³ is a straight-chain or branched-chain alkyl group having a carbon number of 7-22, or a linear or alkenyl group having a carbon number of 7-22 branched chain.
Examples of R ³ include dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and the like.
In the general formula (b1), R ⁴ is an alkyl group having 1 to 6 carbon atoms, and may be either a straight chain or a branched chain. Of these, a methyl group or an ethyl group is preferable.
In the general formula (b1), s and u are numbers that independently represent the average number of repetitions of EO.
s + u is preferably 6 to 20, more preferably 6 to 18, and even more preferably 11 to 18. When it is at least the above lower limit value, the liquid stability is more likely to be improved. If it is not more than the above upper limit value, the detergency is more likely to be improved.
In the general formula (b1), t is a number representing the average number of repetitions of PO.
t is a number from 0 to 6, preferably 0 to 3. If it is not more than the above upper limit value, the liquid stability is more likely to be improved.
When t is 1 or more, in [(EO) _s / (PO) _t ], the oxyethylene group and the oxypropylene group may be bonded in a random manner or in a block shape.
In the present specification, the average number of repetitions can be measured by gas chromatography or the like.

In the general formula (b2), ^{R 5} is a hydrocarbon group having 6 to 22 carbon atoms.
In the general formula (b2), the number of carbon atoms of ^{R 5} may, from the viewpoint of further improving the detergency, preferably 10 to 22, more preferably from 10 to 20, more preferably 10 to 18.
R ⁵ may be a straight chain or a branched chain.
The R ^5, dodecyl group, an alkyl group of primary alcohol-derived 12 to 14 carbon atoms, such as tetradecyl group.
In the general formula (b2), v and x are numbers that independently represent the average number of repetitions of EO.
v + x is preferably 3 to 20, more preferably 5 to 18, further preferably 6 to 15, particularly preferably 7 to 12, and most preferably 7 to 10. When it is at least the above lower limit value, the defoaming property and the liquid stability are more likely to be improved. If it is not more than the above upper limit value, the detergency is more likely to be improved.
In the general formula (b2), w is a number representing the average number of repetitions of PO.
w is a number from 0 to 6, preferably 0 to 3. If it is not more than the above upper limit value, the liquid stability is more likely to be improved.
When w is 1 or more, in [(EO) _v / (PO) _w ], the oxyethylene group and the oxypropylene group may be bonded in a random manner or in a block shape.

The distribution of EO or PO in the general formula (b2) varies depending on the reaction method at the time of production.
For example, when ethylene oxide or propylene oxide is added to a raw material using a general alkaline catalyst such as sodium hydroxide or potassium hydroxide, the distribution of v or w becomes relatively wide. A specific alkoxylation catalyst such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ²⁺ described in JP-A-6-15038 are added. When ethylene oxide or propylene oxide is added to the raw material in use, the distribution of v or w becomes relatively narrow.

The nonionic surfactant represented by the general formula (b1) (hereinafter, also referred to as the component (b1)) preferably has a narrow ratio of 20% by mass or more, and more preferably 25% by mass or more. The higher the narrow ratio, the better the detergency can be obtained. Further, when the narrow ratio is 20% by mass or more, particularly 25% by mass or more, it becomes easy to obtain a cleaning agent composition having less raw material odor of the surfactant.
When the component (b1) is produced by a conventional method, the product contains the component (b1) and a component that does not contribute to detergency, for example, a fatty acid ester that is a raw material of the component (b1), or the general formula (b1). An ethylene oxide adduct having an s of 1 or 2 in the nonionic surfactant represented by is coexisting to reduce the narrow ratio. Therefore, when the narrow ratio is high, the number of coexisting components is sufficiently small, and the problems of deterioration of detergency and raw material odor are less likely to occur.
The same applies to the nonionic surfactant represented by the general formula (b2) (hereinafter, also referred to as the component (b2)).
The upper limit of the narrow ratio is not particularly limited, but it is practically preferable that the narrow ratio is 80% by mass or less.
The narrow ratio is more preferably 20% by mass or more and 50% by mass or less, and further preferably 20% by mass or more and 40% by mass or less, in order to improve liquid stability and solubility.
Here, in the present specification, the "narrow ratio" indicates the ratio of the distribution of ethylene oxide adducts having different numbers of moles of EO, and is represented by the following mathematical formula (S).

In the formula (S), s _max indicates the number of moles of EO of the ethylene oxide adduct that is most abundant in the total ethylene oxide adduct. i indicates the number of moles of EO added. Yi indicates the proportion (mass%) of the ethylene oxide adduct in which the number of moles of EO added is i, which is present in the whole ethylene oxide adduct.

The narrow ratio can be controlled by, for example, a method for producing the component (b1) or the component (b2). The method for producing the component (b1) is not particularly limited, but for example, a method of addition-polymerizing ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (Japanese Patent Laid-Open No. 2000-). It can be easily manufactured according to (see JP-A-144179). As a method for producing the component (b2), for example, it can be produced by a method of addition-polymerizing ethylene oxide to an alcohol having 6 to 22 carbon atoms using a surface-modified composite metal oxide catalyst.
Suitable surface-modified composite metal oxide catalysts used in such methods include, specifically, surface-modified metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , In ³⁺ , etc.) with metal hydroxides and the like. Hydro modified by one or more selected from composite metal oxide catalysts such as magnesium oxide to which Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc. are added, and metal hydroxides and metal alkoxides. Examples thereof include a calcined product catalyst for tarcite.
In the surface modification using the composite metal oxide catalyst, it is preferable to use the composite metal oxide in combination with one or more selected from the metal hydroxide and the metal alkoxide. In this case, the ratio of one or more selected from the metal hydroxide and the metal alkoxide to 100 parts by mass of the composite metal oxide is preferably 0.5 parts by mass or more and 10 parts by mass or less, and 1 part by mass or more. More preferably, it is 5 parts by mass or less.

As another method for producing the component (b1), there is a method of 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 oxyacid or the like. The above-mentioned alkoxylation catalyst is disclosed in Japanese Patent No. 04977609, WO1993004030, WO20020328269, WO2012028435 and the like. For example, an alkaline earth metal salt of a carboxylic acid and an alkali of a hydroxycarboxylic acid. Examples thereof include an alkoxylation catalyst prepared from a mixture of one or more selected from earth metal salts and sulfuric acid or the like.

As the component (B), a commercially available product may be used, or a product produced by a known synthetic method may be used. As a known synthetic method, the component (b1) can be produced, for example, by addition-polymerizing one or more selected from ethylene oxide and propylene oxide to a fatty acid alkyl ester. The component (b2) can be produced, for example, by a method of addition-polymerizing one or more selected from ethylene oxide and propylene oxide to alcohol having 6 to 22 carbon atoms.

The content of the component (B) is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, and 3% by mass or more and 10% by mass or less with respect to the total mass of the liquid cleaning agent. Is even more preferable. When the content of the component (B) is at least the above lower limit value, it is easy to improve liquid stability, defoaming property, and sebum detergency. When the content of the component (B) is not more than the above upper limit value, a sufficient amount of other components can be contained, and a synergistic effect with the component (A) can be easily obtained.

The total content of the component (A) and the component (B) is preferably 3% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 33% by mass or less, and 8% by mass, based on the total mass of the liquid cleaning agent. % Or more and 30% by mass or less are more preferable. When the total content of the component (A) and the component (B) is at least the above lower limit value, a liquid cleaning agent having thickening and excellent protein detergency can be easily obtained. When the total content of the component (A) and the component (B) is not more than the above upper limit value, it is easy to obtain a liquid cleaning agent having good fluidity and excellent liquid stability at low temperature.

The mass ratio represented by (A) component / ((A) component + (B) component) (hereinafter, also referred to as (A) / ((A) + (B)) ratio) is 0.2 or more and less than 1. Is preferable, 0.3 or more and 0.9 or less is more preferable, and 0.4 or more and 0.8 or less is further preferable. When the (A) / ((A) + (B)) ratio is at least the above lower limit value, it is easy to improve the protein detergency and the recontamination prevention property. When the (A) / ((A) + (B)) ratio is not more than the above upper limit value, the defoaming property is likely to be improved.

<Component (C)>
The component (C) is a bicarbonate. By containing the component (C), the liquid cleaning agent of the present invention can improve the viscosity, detergency and liquid stability at low temperature.
Examples of the component (C) include sodium hydrogen carbonate, potassium hydrogen carbonate, sodium sesquicarbonate and the like.
As the component (C), one type may be used alone, or two or more types may be used in combination.

The content of the component (C) is preferably 1.0% by mass or more and 4.0% by mass or less, more preferably 1.6% by mass or more and 3.6% by mass or less, based on the total mass of the liquid cleaning agent. It is more preferably 1.8% by mass or more and 3.2% by mass or less. When the content of the component (C) is at least the above lower limit, the thickening effect can be easily obtained, and the pH of the diluted solution after diluting the liquid cleaning agent with tap water is weakly alkaline (pH 8 to 11 or less). ) Is easy to keep and the cleaning power is easy to improve. When the content of the component (C) is not more than the above upper limit value, it becomes easy to obtain a good liquid cleaning agent having a uniform and transparent liquid appearance at a low temperature. In particular, it is easy to maintain a good appearance in the cycle test described later.

<Ingredient (D)>
The component (D) is a chelating agent. By containing the component (D), the liquid cleaning agent of the present invention can improve the liquid stability at low temperatures.
The component (D) is considered to capture multivalent metal ions mainly contained in tap water, raw materials, or dirt, and when it is dissolved in water, it has an action of capturing polyvalent metal ions. It has.

The component (D) includes at least one compound having a molecular weight of less than 550 and selected from the group consisting of an aminocarboxylic acid, a salt of an aminocarboxylic acid, a hydroxycarboxylic acid, and a salt of a hydroxycarboxylic acid.
Aminocarboxylic acid means a compound having a nitrogen atom and a carboxyl group in one molecule.
The hydroxycarboxylic acid means a compound having a carboxyl group and an alcoholic hydroxy group in one molecule, which does not correspond to an aminocarboxylic acid.
The molecular weight of the component (D) is less than 550, preferably 50 or more and 400 or less, and more preferably 100 or more and 400 or less. When the molecular weight of the component (D) is within the above numerical range, the liquid stability at low temperature is more likely to be improved.

As the component (D), an aminocarboxylic acid-based chelating agent or a hydroxycarboxylic acid-based chelating agent is preferable.
Examples of the aminocarboxylic acid-based chelating agent include methylglycine diacetic acid or a salt thereof, L-glutamate diacetic acid or a salt thereof, nitrilotriacetic acid or a salt thereof, ethylenediaminetetraacetic acid or a salt thereof, diethylenetriaminepentaacetic acid or a salt thereof, β-alanine diacetic acid. Or a salt thereof, L-aspartate diacetic acid or a salt thereof, iminodisuccinic acid or a salt thereof, an aminocarboxylic acid such as ethylenediaminedisuccinic acid or a salt thereof or a salt thereof; serine diacetic acid or a salt thereof, hydroxyiminodicohacetic acid or a salt thereof. , Hydroxyethylethylenediamine triacetic acid or a salt thereof, hydroxyaminocarboxylic acid such as dihydroxyethylglycine or a salt thereof or a salt thereof.

Examples of the hydroxycarboxylic acid chelating agent include lactic acid or a salt thereof, malic acid or a salt thereof, citric acid or a salt thereof, tartaric acid or a salt thereof, glycol or a salt thereof, gluconic acid or a salt thereof and the like.
Among these components (D), citric acid or a salt thereof, methylglycine diacetic acid or a salt thereof, hydroxyiminodisuccinic acid or a salt thereof is preferable from the viewpoint of improving liquid stability at low temperature.
Examples of the salt constituting the component (D) include alkali metal salts such as sodium salt and potassium salt; monoethanolamine salt (monoethanolamine), diethanolamine salt (diethanolamine), triethanolamine salt (triethanolamine) and the like. Alkanolamine salt; ammonium salt and the like can be mentioned.
As the component (D), one type may be used alone, or two or more types may be used in combination.

The content of the component (D) is preferably 0.15% by mass or more and 1.5% by mass or less, more preferably 0.2% by mass or more and 0.9% by mass or less, based on the total mass of the liquid cleaning agent. More preferably, it is 0.3% by mass or more and 0.7% by mass or less. When the content of the component (D) is at least the above lower limit value, it is easy to obtain a good liquid cleaning agent having a uniform and transparent liquid appearance at a low temperature, and it is easy to improve the cleaning power. When the content of the component (D) is not more than the above upper limit value, it becomes easy to obtain a good liquid cleaning agent having a uniform and transparent liquid appearance at a low temperature. In particular, it is easy to maintain a good appearance in the cycle test described later. Further, when the content of the component (D) is not more than the above upper limit value, the stability of the enzyme becomes good and the thickening effect can be easily obtained.

The mass ratio represented by the component (C) / component (D) (hereinafter, also referred to as (C) / (D) ratio) is 0.6 or more and 20 or less, preferably 2.0 or more and 18 or less, 2 .5 or more and 11 or less are more preferable. When the (C) / (D) ratio is at least the above lower limit value, the liquid stability at low temperature is more likely to be improved. In particular, it is easy to maintain a good appearance in the cycle test described later. When the ratio (C) / (D) is not more than the above upper limit value, the thickening effect can be easily obtained and the detergency can be easily improved.

<Arbitrary ingredient>
The liquid cleaning agent of the present invention may contain any component other than the component (A), the component (B), the component (C), and the component (D) as long as the effects of the present invention are not impaired. ..
Optional components include, for example, an enzyme (component (E)), a higher fatty acid or a salt thereof (component (F)), an alkaline agent (component (G)) excluding component (C), and an antioxidant (component (H)). ), Colorant (component (I)), surfactant other than component (A) and component (B), water, water-miscible organic solvent, thickener, thickener, solubilizer, preservative, enzyme Stabilizers (eg calcium chloride, sodium lactate, etc.), texture improvers, storage stability improvers, fluorescent agents, stain transfer inhibitors, recontamination inhibitors (soil release agents), pearls, flavoring agents, emulsions Examples thereof include turbidants and extracts of natural products.

(Component (E))
The component (E) is an enzyme. By containing the component (E), the liquid cleaning agent of the present invention can further improve the detergency against sebum stains and protein stains.
Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase and the like.
As the component (E), one type may be used alone, or two or more types may be used in combination.

When the liquid cleaning agent of the present invention contains the component (E), the content of the component (E) is preferably 0.01% by mass or more and 1.0% by mass or less based on the total mass of the liquid cleaning agent as an enzyme preparation. , 0.03% by mass or more and 0.9% by mass or less is more preferable, and 0.05% by mass or more and 0.8% by mass or less is further preferable. When the content of the component (E) is at least the above lower limit value, the detergency is more likely to be improved. When the content of the component (E) is not more than the above upper limit value, the liquid stability at low temperature is more likely to be improved.

((F) component)
The component (F) is a higher fatty acid or a salt thereof. The liquid cleaning agent of the present invention can enhance the defoaming property by containing the component (F). The defoaming property is a property of suppressing foaming of the liquid cleaning agent.
The component (F) includes, for example, single fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, and behenic acid, or salts thereof, and coconut. Examples thereof include mixed fatty acids such as oil fatty acids and beef fatty acids, or salts thereof.
Examples of the salt constituting the component (F) include salts similar to the salt constituting the component (D).
As the component (F), one type may be used alone, or two or more types may be used in combination. By using two or more kinds of the component (F) in combination, it is easy to improve the defoaming property.

When the liquid cleaning agent of the present invention contains the component (F), the content of the component (F) is preferably 0.2% by mass or more and 2.0% by mass or less with respect to the total mass of the liquid cleaning agent. It is more preferably 4% by mass or more and 1.8% by mass or less, and further preferably 0.6% by mass or more and 1.5% by mass or less. When the content of the component (F) is at least the above lower limit value, the defoaming property is more likely to be enhanced. When the content of the component (F) is not more than the above upper limit value, the liquid stability at low temperature is more likely to be improved.

((G) component)
The component (G) is an alkaline agent excluding the component (C). By containing the component (G), the liquid cleaning agent of the present invention can adjust the pH of the liquid cleaning agent to a higher level. That is, the component (G) functions as a pH adjuster.
Examples of the component (G) include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; sodium hydroxide, potassium hydroxide and the like.
As the component (G), one type may be used alone, or two or more types may be used in combination.

When the liquid cleaning agent of the present invention contains the component (G), the content of the component (G) is preferably 0.01% by mass or more and 2.0% by mass or less with respect to the total mass of the liquid cleaning agent. When the content of the component (G) is within the above numerical range, the pH of the liquid cleaning agent can be easily adjusted to be higher.

((H) component)
The component (H) is an antioxidant. When a liquid cleaning agent is stored and used in a plastic container, a gas space called a head space is formed in the container. Deformation of the container can occur as the gas in the headspace decreases. The liquid cleaning agent of the present invention contains the component (C). The liquid cleaning agent containing the component (C) easily absorbs oxygen in the headspace. When the liquid cleaning agent absorbs oxygen in the headspace, the gas in the headspace is reduced, which may cause deformation of the container. The liquid cleaning agent of the present invention can easily suppress the absorption of oxygen in the head space of the container containing the liquid cleaning agent by blending the component (H). Therefore, it is easy to reduce the possibility of deformation of the container.
In addition, when the liquid cleaning agent contains the component (I) described later, the inclusion of the component (H) makes it easy to suppress discoloration when the liquid cleaning agent is exposed to light or heat.

Examples of the component (H) include ascorbic acid, dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), cresol distyrene, sodium sulfite, sodium hydrogen sulfite and the like. The component (H) preferably contains one or more selected from the group consisting of ascorbic acid, BHT, and BHA, and BHT is easy to suppress absorption of oxygen in the headspace and easily suppress fading. More preferable.

When the liquid cleaning agent of the present invention contains the component (H), the content of the component (H) is 0.005% by mass or more and 1% by mass or less, and 0.008% by mass, based on the total mass of the liquid cleaning agent. % Or more and 0.8% by mass or less is preferable, and 0.01% by mass or more and 0.6% by mass or less is more preferable. When the content of the component (H) is at least the above lower limit value, the effect of suppressing a decrease in oxygen concentration in the headspace and the effect of suppressing fading due to light or heat can be sufficiently obtained. When the content of the component (H) is not more than the above upper limit value, the liquid stability at low temperature is more likely to be improved.
As the component (H), one type may be used alone, or two or more types may be used in combination.

The mass ratio represented by the component (C) / component (H) (hereinafter, also referred to as (C) / (H) ratio) is preferably 3 or more and 1000 or less, more preferably 6.5 or more and 750 or less, and 20 More than 200 or less is more preferable. When the (C) / (H) ratio is at least the above lower limit value, a liquid cleaning agent having excellent detergency can be easily obtained. When the (C) / (H) ratio is not more than the above upper limit value, the effect of suppressing a decrease in oxygen concentration in the headspace and the effect of suppressing fading due to light or heat can be sufficiently obtained.

((I) component)
The component (I) is a colorant. The liquid cleaning agent of the present invention can be colored by containing the component (I). The component (I) is not particularly limited, and examples thereof include dyes described in the "Legal Dye Handbook" (Japan Cosmetic Industry Association) and those obtained by chemically modifying the end of the structure of the chromophore with a water-soluble polymer or the like. Be done.
As the component (I), C.I. I. Acid Red 138, C.I. I. Acid Red 260, C.I. I. Acid Red 106, Acid Yellow 203 (Yellow 203), Acid Blue 9, Blue 1, Blue 205, Green 3, Levanyl® Violet (Levanyl® Violet), Liquitint® BLUE SE (Liquitint® Blue SE), Liquitint® BLUE HP (Liquitint® Blue HP), Liquitint® BLUE MC (Liquitint® Blue MC), Liquitint® VIOLET CT (Liquitint® Violet CT), Liquitint® VIOLET LS (Liquitint® Violet LS), Liquitint® VIOLET DD (Registered Trademark) Violet D ) GREEN SA (Liquitint® Green SA), Liquitint® Bright Yellow (Liquitint® Bright Yellow), Liquitint® YELLOW SY (Registered Trademark) Yellow SY (Registered Trademark) Trademarks) YELLOW LP (Liquitint® Yellow LP), Liquitint® BRILLIANT ORANGE (Liquitint® Brilliant Orange), Liquitint® PINK AL (Liquitint® Pink AL) Examples thereof include general-purpose dyes and pigments such as RED ST (Liquitint (registered trademark) Red ST) and Liquitint (registered trademark) RED MX (Liquitint® Red MX). In addition, in this specification, "CI" is an abbreviation for a color index.

When the liquid cleaning agent of the present invention contains the component (I), the content of the component (I) is preferably 0.00005% by mass or more and 0.01% by mass or less with respect to the total mass of the liquid cleaning agent. When the content of the component (I) is at least the above lower limit value, the liquid cleaning agent can be sufficiently colored. When the content of the component (I) is not more than the above upper limit value, pigmentation on the object to be washed is difficult, and a liquid cleaning agent having excellent dispersion stability can be easily obtained.
As the component (I), one type may be used alone, or two or more types may be used in combination.

(Surfactants other than component (A) and component (B))
The liquid cleaning agent of the present invention may contain a surfactant other than the component (A) and the component (B) (hereinafter, also referred to as another surfactant).
Examples of other surfactants include salts of higher fatty acids (soap, component (F)), cationic surfactants, amphoteric surfactants and the like.

The content of the other surfactant is preferably 0% by mass or more and 10% by mass or less with respect to the total mass of the liquid cleaning agent.
The total content of the component (A) and the component (B) with respect to the total mass of the surfactant is preferably 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, and 100% by mass. There may be.

(water)
The liquid cleaning agent of the present invention preferably contains water. The content of water is preferably 10% by mass or more and 95% by mass or less, more preferably 20% by mass or more and 90% by mass or less, and further preferably 40% by mass or more and 90% by mass or less, based on the total mass of the liquid cleaning agent. When the water content is at least the above lower limit, the ease of handling during production and the solubility in water during use are more excellent. When the water content is not more than the above upper limit value, the detergency is more excellent.

Examples of the water-mixable organic solvent include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, 3-methoxy-3-methyl-1-butanol (Solfit, trade name); propylene glycol (PG). , Butylene glycol, hexylene glycol and other glycols; diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of about 200 to 1000, polyglycols such as dipropylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Examples thereof include alkyl ethers such as monobutyl ether (butyl carbitol) and diethylene glycol dimethyl ether.
Among these, ethanol, 3-methoxy-3-methyl-1-butanol, propylene glycol, polyethylene glycol having a molecular weight of 200 to 1000, etc. from the viewpoints of low odor, availability, fluidity of liquid cleaning agent, etc. , Diethylene glycol monobutyl ether (butyl carbitol) is preferable.
As the water-miscible organic solvent, one type may be used alone, or two or more types may be used in combination.
In the present specification, the water-miscible organic solvent means an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.
In the present specification, the molecular weight of polyglycols means the mass average molecular weight.

When the liquid cleaning agent of the present invention contains a water-miscible organic solvent, the content of the water-miscible organic solvent is preferably 0.1% by mass or more and 10% by mass or less with respect to the total mass of the liquid cleaning agent. More preferably, it is 0.1% by mass or more and 5% by mass or less.

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), octanediol, benzyl alcohol, phenoxyethanol, sodium benzoate and the like.
One type of preservative may be used alone, or two or more types may be used in combination.
When the liquid cleaning agent of the present invention contains a preservative, the content of the preservative is preferably 0.001% by mass or more and 1% by mass or less with respect to the total mass of the liquid cleaning agent.

Examples of the fragrance include fragrances. Examples of the fragrance include the fragrance compositions A, B, C and D shown in Tables 11 to 18 of JP-A-2002-146399.
When the liquid cleaning agent contains a flavoring agent, the content of the flavoring agent is preferably 0.1% by mass or more and 1.5% by mass or less with respect to the total mass of the liquid cleaning agent.

Examples of the emulsifying agent include polystyrene emulsions and polyvinyl acetate emulsions, and emulsions having a solid content of 30 to 50% by mass are usually preferably used. Specific examples include polystyrene emulsion (trade name: Cybinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Saiden Chemical Co., Ltd.), Opulin 301, Acusol OP 301, and the like.
One type of emulsifying agent may be used alone, or two or more types may be used in combination.
When the liquid cleaning agent of the present invention contains an emulsifying agent, the content of the emulsifying agent is preferably 0.001% by mass or more and 0.5% by mass or less with respect to the total mass of the liquid cleaning agent.

The total amount of the components constituting the liquid cleaning agent of the present invention does not exceed 100% by mass. That is, the total amount of the components (A) to (D) and the optional components does not exceed 100% by mass.

One aspect of the present invention is that the liquid cleaning agent composition for clothing contains a polyoxyethylene alkyl ether sulfate (alkyl group having 12 to 14 carbon atoms, average mass addition of ethylene oxide: 2, content) as the component (A). : 2% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, still more preferably 4% by mass or more and 10% by mass or less with respect to the total mass of the liquid cleaning agent) and linear alkylbenzene sulfonic acid ( The number of carbon atoms of the alkyl group is 10 to 14, and the content: 2% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, still more preferably 2% by mass or more and 7% by mass with respect to the total mass of the liquid cleaning agent. (Mass% or less) as the component (B) is polyoxyethylene alkyl ether (alkyl group having 12 to 14 carbon atoms, average number of moles of ethylene oxide added: 5 to 15, more preferably 5 to 9, content: liquid cleaning agent. 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, still more preferably 3% by mass or more and 10% by mass or less) as the component (C) of sodium hydrogen carbonate (C). Content: 1.0% by mass or more and 4.0% by mass or less, more preferably 1.6% by mass or more and 3.6% by mass or less, still more preferably 1.8% by mass or more, based on the total mass of the liquid cleaning agent. 3.2% by mass or less) as the component (D) of citric acid (content: 0.15% by mass or more and 1.5% by mass or less, more preferably 0.2% by mass with respect to the total mass of the liquid cleaning agent). More than 0.9% by mass, more preferably 0.3% by mass or more and 0.7% by mass or less) as the component (E) of protease (content: 0.01% by mass with respect to the total mass of the liquid cleaning agent). More than 1.0% by mass, more preferably 0.03% by mass or more and 0.9% by mass or less, still more preferably 0.05% by mass or more and 0.8% by mass or less) as the component (F) of lauric acid (F). Content: 0.2% by mass or more and 2.0% by mass or less, more preferably 0.4% by mass or more and 1.8% by mass or less, still more preferably 0.6% by mass or more, based on the total mass of the liquid cleaning agent. (1.5% by mass or less), palmitic acid (content: 0.1% by mass or more and 0.5% by mass or less with respect to the total mass of the liquid cleaning agent) and stearic acid (content: total mass of the liquid cleaning agent) On the other hand, 0.1% by mass or more and 0.5% by mass or less) is used as the component (G) in a 48% by mass aqueous solution of sodium hydroxide (content: 0.01% by mass or more with respect to the total mass of the liquid cleaning agent. (0% by mass or less) as the component (H) is dibutylhydroxytoluene (content: liquid washing) 0.005% by mass or more and 1% by mass or less, more preferably 0.008% by mass or more and 0.8% by mass or less, still more preferably 0.01% by mass or more and 0.6% by mass or less with respect to the total mass of the agent) (I) Liquitint® BLUE HP (content: 0.00005% by mass or more and 0.01% by mass or less with respect to the total mass of the liquid cleaning agent) as a component, and JP-A-2002 as a flavoring agent. Perfume composition A (content: 0.1% by mass or more and 1% by mass or less with respect to the total mass of the liquid cleaning agent) described in Japanese Patent Publication No. 146399 as water to purify water (content: total mass of the liquid cleaning agent). On the other hand, it contains 10% by mass or more and 95% by mass or less, more preferably 20% by mass or more and 90% by mass or less, still more preferably 40% by mass or more and 90% by mass or less (however, the total content of each component is liquid. Does not exceed 100% by mass based on the total mass of the cleaning agent).

Another aspect of the present invention is that the liquid cleaning agent composition for clothing has a polyoxyethylene alkyl ether sulfate (alkyl group having 12 to 14 carbon atoms, average mass addition of ethylene oxide: 2, content) as the component (A). : 2% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, still more preferably 4% by mass or more and 10% by mass or less with respect to the total mass of the liquid cleaning agent) and linear alkylbenzene sulfonic acid ( The number of carbon atoms of the alkyl group is 10 to 14, and the content: 2% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, still more preferably 2% by mass or more and 7% by mass with respect to the total mass of the liquid cleaning agent. (Mass% or less) as the component (B) is polyoxyethylene alkyl ether (alkyl group having 12 to 14 carbon atoms, average number of moles of ethylene oxide added: 5 to 15, more preferably 5 to 9, content: liquid cleaning agent. 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, still more preferably 3% by mass or more and 10% by mass or less) as the component (C) of sodium hydrogen carbonate (C). Content: 1.0% by mass or more and 4.0% by mass or less, more preferably 1.6% by mass or more and 3.6% by mass or less, still more preferably 1.8% by mass or more, based on the total mass of the liquid cleaning agent. 3.2% by mass or less) as the component (D) of citric acid (content: 0.15% by mass or more and 1.5% by mass or less, more preferably 0.2% by mass with respect to the total mass of the liquid cleaning agent). More than 0.9% by mass, more preferably 0.3% by mass or more and 0.7% by mass or less) as the component (E) of protease (content: 0.01% by mass with respect to the total mass of the liquid cleaning agent). More than 1.0% by mass, more preferably 0.03% by mass or more and 0.9% by mass or less, still more preferably 0.05% by mass or more and 0.8% by mass or less) as the component (F) of lauric acid (F). Content: 0.2% by mass or more and 2.0% by mass or less, more preferably 0.4% by mass or more and 1.8% by mass or less, still more preferably 0.6% by mass or more, based on the total mass of the liquid cleaning agent. 1.5% by mass or less) and palmitic acid (content: 0.1% by mass or more and 0.5% by mass or less with respect to the total mass of the liquid cleaning agent) as the component (G) in a 48% by mass aqueous solution of sodium hydroxide. (Content: 0.01% by mass or more and 2.0% by mass or less with respect to the total mass of the liquid cleaning agent) and monoethanolamine (Content: 0.01% by mass or more with respect to the total mass of the liquid cleaning agent 2 (0.0% by mass or less) as the component (I) of Liquitint (registered trademark) BLUE HP (content: 0.00005 mass% or more and 0.01 mass% or less with respect to the total mass of the liquid cleaning agent) is used as a flavoring agent in the perfume composition A (content) described in JP-A-2002-146399. : 0.1% by mass or more and 1% by mass or less with respect to the total mass of the liquid cleaning agent, and sodium benzoate as an antiseptic (content: 0.001% by mass or more and 1% by mass with respect to the total mass of the liquid cleaning agent) % Or less) as a water-miscible organic solvent with a molecular weight of 1000 polyethylene glycol (content: 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5) with respect to the total mass of the liquid cleaning agent. Purified water (content: 10% by mass or more and 95% by mass or less, more preferably 20% by mass or more and 90% by mass or less, still more preferably 40% by mass with respect to the total mass of the liquid cleaning agent) as water. (More than 90% by mass or less) is included (however, the total content of each component does not exceed 100% by mass with respect to the total mass of the liquid cleaning agent).

Yet another aspect of the present invention is that the component (A), the component (B), the component (C) and the component (D) are contained, and the mass ratio represented by the component (C) / component (D) is 0. Includes use for clothing of liquid cleaning compositions of .6 to 20.

[Manufacturing method of liquid cleaning agent]
The liquid cleaning agent of the present invention is produced by mixing the components (A) to (D) and, if necessary, an arbitrary component by a conventionally known method. In order to prevent foaming, it is preferable not to mix the acid component such as citric acid after mixing the component (C).
The pH of the finally obtained liquid cleaning agent at 25 ° C. is preferably 7 or more and 10 or less, and more preferably 8 or more and 10 or less. When the pH is within the above numerical range, the stability of the enzyme (component (E)) is high, and the detergency is easily improved.
The pH can be adjusted by adding an appropriate amount of the component (G), which is a pH adjuster.
The pH in the present specification means a value measured by a pH meter (product name: HM-30G, manufactured by DKK-TOA CORPORATION) with a measurement target of 25 ° C.

The viscosity of the liquid cleaning agent at 25 ° C. is preferably 40 mPa · s or more and 1500 mPa · s or less, more preferably 60 mPa · s or more and 1100 mPa · s or less, and further preferably 100 mPa · s or more and 600 mPa · s or less. When the viscosity is at least the above lower limit value, it is easy to improve the ease of application to clothing, the feeling of richness of the liquid, and the feeling of luxury. When the viscosity is not more than the above upper limit value, it is easy to improve the ease of pouring into the cap, the liquid dripping property, and the liquid drainage property.
In the present specification, the viscosity at 25 ° C. is a value measured 30 seconds after setting the rotation speed of the rotor to 30 rpm with a Brookfield type (B type) viscometer.

[How to use liquid cleaning agent]
The method of using the liquid cleaning agent is, for example, a method of putting the liquid cleaning agent into water together with the object to be washed at the time of washing, or a method of immersing the object to be washed in a cleaning agent aqueous solution prepared by dissolving the liquid cleaning agent in water in advance. The method of doing this can be mentioned. Alternatively, the liquid cleaning agent may be applied directly to the object to be washed, left for 3 minutes to 24 hours, and then subjected to normal washing.
The content of the liquid cleaning agent in the aqueous cleaning agent solution is not particularly limited. The amount of the liquid cleaning agent added to water is preferably 2 to 30 mL per 10 L of water, for example.

The method of adding the liquid cleaning agent to the water together with the object to be washed at the time of washing is the process of adding the object to be washed into the washing machine, the process of adding water to the washing machine in which the object to be washed is added, and the process of adding water. It includes a step of charging a liquid cleaning agent into the loaded washing machine. After pouring water into the washing machine, the object to be washed may be thrown into the washing machine filled with water.

The method of immersing the object to be washed in the cleaning agent aqueous solution prepared by dissolving the liquid cleaning agent in water in advance is a step of dissolving the liquid cleaning agent in water to obtain a cleaning agent aqueous solution and a cleaning agent aqueous solution for the object to be washed. Including the step of immersing in.

The method of directly applying the liquid cleaning agent to the object to be washed (coating cleaning) is the process of applying the liquid cleaning agent to the dirt of the object to be washed and the process of applying the liquid cleaning agent to the object to be washed. It includes a step of leaving it for a certain period of time, a step of putting the left-behind object into a washing machine, and a step of performing normal washing. In the step of leaving for a certain period of time, it is preferable to leave it for 1 minute to 24 hours, more preferably 3 minutes to 12 hours, and further preferably 5 minutes to 1 hour. When the time for leaving the object to be washed to which the liquid cleaning agent is applied is equal to or longer than the above lower limit, it is easier to clean the object to be washed more cleanly. When the time for leaving the object to be washed to which the liquid cleaning agent is applied is not more than the above upper limit value, it is easy to efficiently wash the object to be washed.

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

[Ingredients used]
<Ingredient (A)>
AES-EO2: Polyoxyethylene alkyl ether sulfate (alkyl group having 12 to 14 carbon atoms, average number of moles of ethylene oxide added: 2), manufactured by Kao Corporation, trade name "EMAL270N".
LAS-H: Linear alkylbenzene sulfonic acid (alkyl group having 10 to 14 carbon atoms), manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lypon LH-200".

<Ingredient (B)>
AE-EO9: Polyoxyethylene alkyl ether (12 to 14 carbon atoms of alkyl group, average number of moles of EO added 9), manufactured by ECOGREEN OLEOCHEMICALS, trade name "ECOLAT24-9".
AE-EO7: Polyoxyethylene alkyl ether (12 to 14 carbon atoms of alkyl group, average number of moles of EO added 7), manufactured by ECOGREEN OLEOCHEMICALS, trade name "ECOLAT24-7".
AE-EO5: Polyoxyethylene alkyl ether (1214 carbon atoms of alkyl group, average number of moles of EO added 5), manufactured by ECOGREEN OLEOCHEMICALS, trade name "ECOLAT24-5".

<Component (C)>
NaHCO ₃ : Sodium hydrogen carbonate, manufactured by Kanto Chemical Co., Ltd., trade name "sodium hydrogen carbonate".

<(C') component (comparative component of (C) component)>
Na ₂ SO ₄ : Sodium sulfate, manufactured by Kanto Chemical Co., Ltd., trade name "sodium sulfate".

<Ingredient (D)>
Citric acid: Citric acid, manufactured by Kanto Chemical Co., Inc., trade name "citric acid".

<Ingredient (E)>
Protease 1: Enzyme, manufactured by Novozymes, trade name "Savinase Ultra 16L".
Protease 2: Enzyme, manufactured by Novozymes, trade name "Savinase Evity 16L".

<(F) component>
Lauric acid: A fatty acid having 12 carbon atoms, manufactured by Wako Pure Chemical Industries, Ltd., trade name "lauric acid".
Palmitic acid: Fatty acid with 16 carbon atoms, manufactured by Wako Pure Chemical Industries, Ltd., trade name "palmitic acid".
Stearic acid: Fatty acid with 18 carbon atoms, manufactured by Wako Pure Chemical Industries, Ltd., trade name "stearic acid".

<(G) component>
MEA: Monoethanolamine, manufactured by Nippon Shokubai Co., Ltd., trade name "monoethanolamine".
48% NaOH aqueous solution: pH adjuster (48% by mass aqueous solution of sodium hydroxide), manufactured by Kanto Chemical Co., Ltd., trade name "48% sodium hydroxide solution".

<(H) component>
BHT: Dibutylhydroxytoluene, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "2,6-Di-tert-butyl-p-cresol".

<Ingredient (I)>
Dye: Dye, manufactured by Milliken, trade name "Liquitint (registered trademark) BLUE HP".

<Other optional ingredients>
Sodium benzoate: Made by Toagosei Co., Ltd., trade name "Sodium benzoate".
Polyethylene glycol: PEG1000, polyethylene glycol having a molecular weight of 1000, manufactured by Mitsui Chemicals, Inc., trade name "PEG # 1000-L60".
Fragrance: Perfume composition A described in JP-A-2002-146399.
Water: Purified water, manufactured by Kanto Chemical Co., Inc., trade name "purified water".

[Examples 1 to 18, Reference Example 1, Comparative Examples 1 to 5]
According to the composition of Tables 1 to 5, components (A) to (I) and other optional components were added to water and mixed to obtain a mixed solution. The temperature of the mixed solution was 25 ° C., and an appropriate amount of a pH adjusting agent was added so that the pH of the mixed solution was 9, and a liquid cleaning agent was obtained.
The viscosity, liquid stability, and detergency of the obtained liquid cleaning agent were evaluated by the following evaluation methods. Further, with respect to Examples 2, 17 and 18, oxygen absorption and appearance stability were further evaluated. Reference Example 1 is a composition that serves as a reference for appearance stability. The results are shown in Tables 1-5.
The unit of the blending amount of each component in the table is "mass%", which indicates the net conversion amount. "Balance" means that water is blended so that the total blending amount (mass%) of all the blended components contained in the composition of each example is 100% by mass.

<Evaluation of viscosity>
60 g of the liquid cleaning agent of each example was placed in a bottle (manufactured by Nichiden Rika Glass Co., Ltd., product name: SV50A), allowed to stand in a water bath at 25 ° C. for 1 hour, and then the viscosity was measured with a B-type viscometer. Viscosity measurement conditions were 25 ° C., 30 rpm, 30 seconds, No. The rotor of 2 was used.
From the measured values of viscosity, the evaluation of viscosity was judged based on the following evaluation criteria.
"Evaluation criteria"
⊚: Viscosity 60 mPa · s or more and 1100 mPa · s or less.
◯: Viscosity 40 mPa · s or more and less than 60 mPa · s, or viscosity 1100 mPa · s more than 1500 mPa · s or less.
X: Viscosity less than 40 mPa · s or more than 1500 mPa · s.

<Evaluation of liquid stability>
(Cycle test)
30 mL of the liquid cleaning agent was placed in a cylindrical glass bottle, and the lid was closed to seal it. In this state, the mixture was allowed to stand at −15 ° C. for 12 hours and then allowed to stand at 5 ° C. for 12 hours, and stored in a constant temperature bath set to repeat the conditions for 3 days.
Then, the cylindrical glass bottle was taken out from the constant temperature bath, the transparency uniformity of the liquid cleaning agent was visually observed, and the liquid stability of the liquid cleaning agent was evaluated based on the following evaluation criteria.
"Evaluation criteria"
◯: It was transparent and uniform.
X: Solidification, precipitation or cloudiness was observed.

(Stability at -5 ° C and 0 ° C)
30 mL of the liquid cleaning agent was placed in a cylindrical glass bottle, and the lid was closed to seal it. In this state, it was stored for 1 month in a constant temperature bath set at −5 ° C. and 0 ° C.
Then, the cylindrical glass bottle was taken out from the constant temperature bath, the transparency uniformity of the liquid cleaning agent was visually observed, and the liquid stability of the liquid cleaning agent was evaluated based on the following evaluation criteria.
"Evaluation criteria"
◯: It was transparent and uniform.
X: Solidification, precipitation or cloudiness was observed.

(Judgment)
In the evaluation of liquid stability, the above cycle test and the evaluation of storage stability at −5 ° C. and 0 ° C. were comprehensively judged. In the following evaluation criteria, ◎ and ○ were accepted.
"Evaluation criteria"
⊚: The evaluation of the cycle test is “○”, and the evaluation of -5 ° C storage stability and 0 ° C storage stability is “○”.
◯: The evaluation of the cycle test is “×”, and the evaluation of -5 ° C storage stability and 0 ° C storage stability is “○”.
X: Evaluation of -5 ° C storage stability or 0 ° C storage stability is "x".

<Evaluation of detergency>
(Cleaning power against sebum stains)
With a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name: SE-2000), the reflectance R of 10 wet artificial contaminated cloths (purchased from the Laundry Science Association, hereinafter referred to as contaminated cloths) before cleaning was measured ( Calculated from the hunter whiteness Z as a reflectance R = Z / 100. The same shall apply hereinafter). Using a Terg-O-Tometer (manufactured by US Testing) as a cleaning tester, 10 contaminated cloths, a charge cloth (a knitted cloth that has been finely cut, thoroughly washed and rinsed, and dried) and a washing liquid Was weighed so as to have a bath ratio of 30 times (total mass of cleaning liquid / charged cloth) and placed in a cleaning tank. As the cleaning liquid, the compositions of Examples and Comparative Examples were dissolved in 900 mL of tap water at 15 ° C. so as to have a concentration of 1000 ppm.
After washing at a rotation speed of 120 rpm and a temperature of 15 ° C. for 10 minutes, rinsing was performed twice with 900 mL of tap water at 15 ° C. for 3 minutes. After rinsing and drying, the reflectance R of the contaminated cloth after washing was measured using a 460 nm filter, and the washing rate (%) was calculated by the following formula.

In the above formula, the washing cloth means the cloth after washing the contaminated cloth, and the unstained cloth means the original white cloth (original cloth) to which no dirt is attached. Further, K represents an absorption coefficient, S represents a scattering coefficient, and R represents a reflectance.
The larger the value of the obtained cleaning rate, the higher the cleaning power. The cleaning rate (%) was calculated for 10 contaminated cloths, and the average value was used to evaluate the cleaning power against sebum stains based on the following evaluation criteria.
In the following evaluation criteria, ◎ and ○ were accepted.
"Evaluation criteria"
⊚: Cleaning rate 85% or more.
◯: Cleaning rate is 80% or more and less than 85%.
X: Cleaning rate is less than 80%.

(Cleaning power against protein stains)
The evaluation was performed in the same manner as the detergency against sebum stains, except that EMPA117 (purchased from Swisstest Testmaterialian AG) was used as the contaminated cloth.

<Evaluation of oxygen absorption>
15 mL of the liquid cleaning agent of each example was placed in a headspace crimp vial having a capacity of 22 mL, and the lid was closed with a septum to seal the vial. The crimp vial was stored in a constant temperature bath set at 50 ° C. for 1 month. Then, the crimp vial was taken out from the constant temperature bath and cooled at room temperature (25 ° C.). Then, the air in the headspace was taken with a syringe, and the amount of oxygen (μl) was measured by gas chromatography. The oxygen absorption amount (μl) and the oxygen absorption ratio (volume%) were calculated by the following formulas, and the oxygen absorption was evaluated based on the following evaluation criteria. In the following evaluation criteria, ◎ or ○ was regarded as acceptable.
(Oxygen absorption amount (μl)) = (Oxygen amount in air (μl))-(Oxygen amount in headspace after storage (μl))
(Percentage of oxygen absorbed (volume%)) = (Oxygen absorption amount (μl)) / (Oxygen amount of air (μl)) × 100
"Evaluation criteria"
⊚: The ratio of absorbing oxygen is less than 1.5% by volume.
◯: The ratio of absorbing oxygen is 1.5% by volume or more and less than 2.5% by volume.
X: The ratio of absorbing oxygen is 2.5% by volume or more.

<Evaluation of appearance stability>
50 mL of the liquid cleaning agent was placed in a cylindrical glass bottle, and the lid was closed to seal it. In this state, it was allowed to stand in a place exposed to sunlight (near the window in the laboratory) for one week.
Then, the color of the liquid cleaning agent was visually observed, and the appearance stability (degree of fading) of the liquid cleaning agent was evaluated based on the following evaluation criteria. In the following evaluation criteria, the liquid cleaning agent of Reference Example 1 containing no component (C) was used as a reference for comparison. In the following evaluation criteria, ◎ or ○ was regarded as acceptable.
"Evaluation criteria"
⊚: Equivalent to the standard liquid cleaning agent.
◯: The color is slightly faded compared to the standard liquid cleaning agent.
X: The color is more clearly faded than the standard liquid cleaning agent.

As shown in Tables 1 to 5, Examples 1 to 18 to which the present invention is applied have a viscosity, liquid stability at low temperature and detergency of "⊚" or "○", have an appropriate viscosity, and are washed. It was found to be excellent in force and liquid stability at low temperatures. In addition, Examples 17 to 18 further containing the component (H) were found to be excellent in oxygen absorption and appearance stability.
On the other hand, in Comparative Example 1 containing no component (B), the liquid stability at low temperature and the detergency against sebum stains were "x".
In Comparative Example 2 containing no component (A), the viscosity and detergency against protein stains were "x".
In Comparative Example 3 in which the (C) / (D) ratio was outside the scope of the present invention, the liquid stability at low temperature was “x”.
In Comparative Example 4 containing no component (C), the viscosity and detergency against protein stains were "x".
In Comparative Example 5 in which the component (C') was used instead of the component (C), the liquid stability at low temperature and the detergency against protein stains were "x".

According to the liquid cleaning agent composition for clothing of the present invention, it has been found that it has an appropriate viscosity and is superior in liquid stability at low temperature.

Claims (9)

Ingredient (A): Anionic surfactant excluding higher fatty acid salts,
(B) Ingredients: Nonion surfactant and
(C) Ingredients: bicarbonate and
Ingredient (D): Contains a chelating agent and
A liquid cleaning agent composition for clothing, wherein the mass ratio represented by the component (C) / the component (D) is 0.6 or more and 20 or less. The liquid cleaning agent composition for clothing according to claim 1, wherein the content of the component (C) is 1% by mass or more and 4% by mass or less with respect to the total mass of the liquid cleaning agent composition for clothing. The clothing liquid according to claim 1 or 2, wherein the content of the component (D) is 0.15% by mass or more and 1.5% by mass or less with respect to the total mass of the liquid cleaning agent composition for clothing. Cleaning agent composition. The clothing product according to any one of claims 1 to 3, wherein the mass ratio represented by the component (A) / (component (A) + component (B)) is 0.2 or more and less than 1. Liquid cleaning agent composition. (E) The liquid cleaning composition for clothing according to any one of claims 1 to 4, further containing an enzyme. (F) The liquid cleaning composition for clothing according to any one of claims 1 to 5, further containing a fatty acid having 8 to 22 carbon atoms. The liquid cleaning agent composition for clothing according to any one of claims 1 to 6, further comprising an alkaline agent excluding the component (C). The liquid cleaning composition for clothing according to any one of claims 1 to 7, further comprising a component (H): an antioxidant. The liquid cleaning agent composition for clothing according to any one of claims 1 to 8, wherein the viscosity at 25 ° C. is 30 mPa · s or more and 1500 mPa · s or less.