WO2019124486A1

WO2019124486A1 - Liquid detergent composition for clothing material

Info

Publication number: WO2019124486A1
Application number: PCT/JP2018/046966
Authority: WO
Inventors: 聡大塚
Original assignee: ライオン株式会社
Priority date: 2017-12-21
Filing date: 2018-12-20
Publication date: 2019-06-27
Also published as: JPWO2019124486A1; KR20200100583A; JP7237012B2

Abstract

The present invention relates to a liquid detergent composition for clothing material, the composition comprising: component (A) which is an anionic surfactant except for a higher fatty acid salt; component (B) which is a nonionic surfactant; component (C) which is a hydrogen carbonate; and component (D) which is a chelating agent, wherein the weight ratio represented by component (C)/component (D) is 0.6-20.

Description

Liquid cleaning composition for clothing

The present invention relates to a liquid cleaning composition for clothing.
Priority is claimed on Japanese Patent Application No. 2017-245556, filed Dec. 21, 2017, the content of which is incorporated herein by reference.

When thickening a liquid detergent composition having a low surfactant concentration, an acrylic polymer, or a combination of an anionic surfactant and an inorganic salt is used.
However, in the case of using an acrylic acid-based polymer, there is a concern that the coating cleaning property may be reduced. The application cleaning property refers to the cleaning performance in the method of directly applying the liquid detergent composition to an article to be washed such as clothes and leaving it to stand for an arbitrary period of time, and then performing normal washing. In addition, in the case of using an acrylic acid-based polymer, there is a concern that the liquid stability at low temperature (5 ° C. or less) may be lowered (solidification, precipitation, cloudiness and difficulty in separation during storage for a fixed period).
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).
With respect to these problems, Patent Document 1 proposes a liquid detergent composition containing a specific solvent and a surfactant. The liquid detergent composition of Patent Document 1 has an appropriate viscosity, and the liquid stability at low temperatures is improved.

JP, 2014-37503, A

However, liquid detergent compositions are required to have lower liquid stability.
Therefore, the present invention is directed to a liquid detergent composition for clothing having an appropriate viscosity and being more excellent in liquid stability at low temperature.

As a result of intensive studies, the present inventors have found that the liquid stability of the liquid detergent composition at low temperature is improved by combining the hydrogen carbonate 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, (B) Component: nonionic surfactant, (C) component: hydrogen carbonate, and (D) component: chelating agent The liquid detergent composition for clothes which is contained and whose mass ratio represented by said (C) component / said (D) component is 0.6 or more and 20 or less.
[2] The liquid detergent composition for clothing according to [1], wherein the content of the component (C) is 1% by mass or more and 4% by mass or less based on the total mass of the liquid cleaning composition for clothing object.
[3] [1] or [2], wherein the content of the component (D) is 0.15% by mass or more and 1.5% by mass or less based on the total mass of the liquid cleaning composition for clothes The liquid cleaning composition for clothing as described.
[4] Any one of [1] to [3], wherein the mass ratio represented by the component (A) / (the component (A) + the component (B)) is 0.2 or more and less than 1 The liquid detergent composition for clothes according to claim 1.
[5] The liquid detergent composition for clothing according to any one of [1] to [4], which further contains an (E) component: an enzyme.
[6] The liquid detergent composition for clothing according to any one of [1] to [5], which further contains a (F) component: a fatty acid having 8 to 22 carbon atoms.
[7] The liquid detergent composition for clothing according to any one of [1] to [6], which further contains an alkali agent except the component (G): the component (C).
[8] The liquid detergent composition for clothing according to any one of [1] to [7], which further comprises (H) component: an antioxidant.
[9] The liquid detergent composition for clothing according to any one of [1] to [8], which has a viscosity of 30 mPa · s or more and 1500 mPa · s or less at 25 ° C.

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

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

<(A) component>
Component (A) is an anionic surfactant except for higher fatty acid salts. The liquid detergent of the present invention exerts a detergent power against soiling of clothes by containing the component (A). In the present specification, the higher fatty acids are fatty acids having 8 to 22 carbon atoms. A fatty acid refers to a carboxylic acid having one carboxyl group at the end of a chain hydrocarbon group. In the present specification, 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) Linear or branched alkyl benzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) α-sulfo fatty 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) And an alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms and an average of 0.5 to 10 moles of C.
(6) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (the molar ratio of EO / PO is 0.1 / 9.9 to 9.9 / 0.1), on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate salt having a linear or branched alkyl (or alkenyl) group having a carbon number of 10 to 20 and a molar amount of 10 to 20 carbon atoms;
(7) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (the molar ratio of EO / PO is 0.1 / 9.9 to 9.9 / 0.1), an average of 0.5 Alkyl (or alkenyl) ether carboxylates having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, to which 10 mols have been added.
(8) alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms. Here, polyhydric alcohol means 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, long-chain alkyl refers to an alkyl group having 12 to 26 carbon atoms.
(10) Alkyl sulfate having 10 to 20 carbon atoms or alkenyl sulfate having 10 to 20 carbon atoms (AS).

As the component (A), anionic surfactants 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, acylamino carboxylate, etc .; alkyl phosphate ester salts, polyoxyalkylene alkyl phosphorus Examples thereof include phosphate ester type anionic surfactants such as acid ester salts, polyoxyalkylene alkyl phenyl 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; ammonium salt etc. Be Among them, alkali metal salts are preferred.

As the component (A), one type may be used alone, or two or more types may be used in combination.
Among the above-described components (A), at least one selected from the group consisting of (1), (2), (3), and (5) described above, because better cleanability is easily obtained. (1), (2), a combination of (3) and (5), a combination of (1), (3) and (5), (1), (2) It is more preferable to include an anionic surfactant which is a combination of at least one selected from the group consisting of the combination of (5) and the combination of (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 Is more preferred. When the content of the component (A) is equal to or more than the above lower limit value, it is easy to obtain a thickened liquid detergent. It is easy to obtain a liquid detergent excellent in protein detergency. In addition, it is easy to obtain a liquid detergent excellent in anti-recontamination properties. In addition, when the content of the component (A) is less than or equal to the above upper limit, it is easy to obtain a liquid cleaner having good fluidity.
As used herein, protein detergency refers to detergency against protein soiling. Further, the anti-recontamination property means the property of preventing the soil removed from the object to be washed by the washing treatment from adhering again to the object to be washed.

In one embodiment of the present invention, the component (A) may contain the above-mentioned (2). Further, (2) is preferably an α-sulfo fatty acid salt ester (hereinafter also referred to as a component (a)) represented by the following general formula (a1).
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 counter ion.)

((A) ingredient)
In the general formula (a1), the carbon number of the hydrocarbon group of R ¹ is 10 to 16. That is, the carbon number of the fatty acid residue of the component (a) is 12 to 18. The fatty acid residue refers to an acyl group moiety. When the carbon number of R ¹ is 10 or more, the surface activity is strong, and the coating and cleaning properties become better.
If the carbon number of R ¹ is 16 or less, the liquid stability at low temperature of the liquid detergent is excellent.

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

In the general formula (a1), the carbon number of R ² is 1 to 6, preferably 1 to 3.
The hydrocarbon group of R ² may be linear, branched or may have a cyclic structure. The hydrocarbon group of R ² is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group or a linear or branched alkenyl group, and a linear alkyl Groups or branched alkyl groups are more preferred.
As R ² , a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like are preferable, a methyl group, an ethyl group and an n-propyl group are preferable, and a methyl group is particularly preferable because the coating cleaning properties are further improved. .

In the general formula (a1), as the counter ion of M, ^one capable of forming a water-soluble salt together with R ¹ CH (COOR ² ) SO ₃ ^— is preferable. For example, alkali metal ion, protonated amine, ammonium ion etc. Can be mentioned. Examples of the alkali metal which can be the counter ion include sodium and the like. Examples of the amine which 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. In addition, the amine may have a hydroxy group. The amine preferably has a hydroxy group because the solubility of the component (a) in water is enhanced. The amine having a hydroxy group includes an alkanolamine, and the alkanol group preferably has 1 to 3 carbon atoms. Examples of alkanolamines include monoethanolamine, diethanolamine and triethanolamine.
As M, an alkali metal ion is preferable and a sodium ion is particularly preferable, from the viewpoints of easy availability and easy improvement of liquid stability at low temperature of liquid cleaner.
As component (a), R ¹ in the general formula (a1) is a linear or branched alkyl group having 14 to 16 carbon atoms, or a linear or branched alkenyl group, and R ² Particularly preferred are compounds in which is a methyl group.

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 of compounds in which the carbon number of the fatty acid residue is different, because the coating cleaning property is enhanced and the solubility in water is enhanced. Particularly, a compound (a-1) in which R ¹ in the general formula (a1) is a hydrocarbon group having 14 carbon atoms, and a compound (a-) in which R ¹ is a hydrocarbon group having 16 carbon atoms in the general formula (a1) Mixtures with 2) are preferred. In such a mixture, the mass ratio of the compound (a-1) to the compound (a-2) is preferably (a-1) :( a-2) = 45: 55 to 95: 5, and 60:40 to 90. 10 is more preferable, and 80:20 to 85:15 is further preferable. When the mass ratio is in the above-mentioned numerical range, the coating cleaning property, the solubility in water, and the liquid stability at a low temperature of the liquid cleaner tend to be more favorable.

As the component (a), one obtained by a known production method may be used. For example, a tank type reactor equipped with a stirrer or the like is used according to a conventional method, and a fatty acid ester of a raw material is contacted with sulfuric anhydride or the like to be sulfonated to prepare an α-sulfo fatty acid ester (α-SF acid). Then, one obtained by neutralizing the α-SF acid with sodium hydroxide or the like may be used. A commercial item may be used for (a) component. In addition, you may bleach with hydrogen peroxide etc. before and after neutralization.

The content of the component (a) is preferably 0% by mass or more and 6% by mass or less, and more preferably 0.5% by mass or more and 5.0% by mass or less, with respect to the total mass of the liquid detergent. % Or more and 3.0 mass% or less are more preferable. When the content of the component (a) is within the above-mentioned numerical range, it is easy to obtain a liquid detergent which is excellent in coating cleaning properties, recontamination prevention properties, dispersion stability, and enzyme stability. Moreover, it becomes easy to maintain the freedom degree of the mixing | blending of another component.
Further, the ratio ((a) / (A)) of the component (a) in the component (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 / 100 or more and 30/100 or less are more preferable.

<(B) component>
The component (B) is a nonionic surfactant. By containing the component (B), the liquid detergent of the present invention can improve the liquid stability, the defoaming property, and the sebum detergency. In the present specification, the antifoaming property refers to the ability of liquid detergents to eliminate bubbles. Sebum detergency refers to the detergency against sebum dirt.

Examples of the component (B) include the following (11) to (15).
(11) An average of 3 to 30 moles, preferably 3 to 20 moles, more preferably 5 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms in a monohydric aliphatic alcohol having 6 to 22 and preferably 8 to 18 carbon atoms Added polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. As a monohydric aliphatic alcohol used here, a primary alcohol and a secondary alcohol are mentioned. Also, the alkyl group may have a branched chain. As aliphatic alcohol, primary alcohol is preferred. 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, long-chain fatty acids refer to fatty acids having 12 to 26 carbon atoms.
(14) Polyoxyethylene fatty acid ester.
(15) polyoxyethylene hydrogenated 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 those, 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 (b 2)
(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, s represents the average number of repetition of EO, and 6 to 20 Where t represents the average repeat number of PO, is a number from 0 to 6, u represents the average repeat number of EO, is a number from 0 to 20, and 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, is a number of 3 to 20, w represents the average number of repetitions of PO, 0 It is a number of ̃6, x represents an average repeat number of EO, 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 number of carbon atoms 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 linear or branched.
From the viewpoint of further improving the detergency, R ³ is preferably a linear or branched alkyl group having 7 to 22 carbon atoms, or a linear or branched alkenyl group having 7 to 22 carbon atoms.
Examples of R ³ include dodecyl, tetradecyl, hexadecyl, octadecyl, dodecenyl, tetradecenyl, hexadecenyl and octadecenyl.
In the general formula (b1), R ⁴ is an alkyl group having 1 to 6 carbon atoms, and may be linear or branched. Among these, a methyl group or an ethyl group is preferable.
In the general formula (b1), s and u are each independently a number representing the average number of repetitions of EO.
The s + u is preferably 6 to 20, more preferably 6 to 18, and still more preferably 11 to 18. If it is more than the said lower limit, liquid stability will become easier to improve. If it is below the said upper limit, cleaning power will become easier to improve.
In the general formula (b1), t is a number representing the average number of repetition of PO.
t is a number of 0 to 6, preferably 0 to 3. If it is below the said upper limit, liquid stability will become easier to improve.
When t is 1 or more, in [(EO) _s / (PO) _t ], the oxyethylene group and the oxypropylene group may be bonded randomly or in a block.
In the present specification, the average repetition number 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 carbon number of R ⁵ is preferably 10 to 22, more preferably 10 to 20, and still more preferably 10 to 18, from the viewpoint of further improving the detergency.
R ⁵ may be linear or branched.
As R ⁵ , an alkyl group derived from a primary alcohol having 12 to 14 carbon atoms, such as a dodecyl group or a tetradecyl group, is preferable.
In the general formula (b2), v and x are each independently a number representing the average number of repeats of EO.
v + x is preferably 3 to 20, more preferably 5 to 18, still more preferably 6 to 15, particularly preferably 7 to 12, and most preferably 7 to 10. If it is more than the said lower limit, defoaming property and liquid stability will become easier to improve. If it is below the said upper limit, cleaning power will become easier to improve.
In the general formula (b2), w is a number representing the average number of repetition of PO.
w is a number of 0 to 6, preferably 0 to 3. If it is below the said upper limit, liquid stability will become easier to improve.
When w is 1 or more, in [(EO) _v / (PO) _w ], the oxyethylene group and the oxypropylene group may be bonded randomly or in a block.

The distribution of EO or PO in the general formula (b2) varies depending on the reaction method in production.
For example, when ethylene oxide or propylene oxide is added to the raw material using sodium hydroxide or potassium hydroxide which is a common alkali catalyst, 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⁺ are added as described in Japanese Patent Publication No. 6-15038. When ethylene oxide or propylene oxide is added to the raw material to be used, the distribution of v or w becomes relatively narrow.

The nonionic surfactant (hereinafter also referred to as component (b1)) represented by general formula (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. In addition, when the narrow ratio is 20% by mass or more, particularly 25% by mass or more, it is easy to obtain a cleaning composition having a small odor of the raw material of the surfactant.
When the component (b1) is produced by a conventional method, in the product, a component not contributing to the detergency together with the component (b1), for example, a fatty acid ester which is a raw material of the component (b1), a compound represented by the general formula (b1) The ethylene oxide adduct in which s of the nonionic surfactant represented by is 1 or 2 coexists and reduces the narrowing rate. Therefore, if the narrow ratio is high, the coexisting components are sufficiently small, and the problem of the reduction of the detergency and the odor of the raw material hardly occurs.
The same applies to the case of the nonionic surfactant represented by the general formula (b2) (hereinafter, also referred to as component (b2)).
The upper limit value of the narrow ratio is not particularly limited, but substantially the narrow ratio is preferably 80% by mass or less.
The narrow ratio is more preferably 20% by mass or more and 50% by mass or less, and still more preferably 20% by mass or more and 40% by mass or less because the liquid stability and solubility are improved.
Here, in the present specification, the “narrow rate” indicates the ratio of the distribution of ethylene oxide adducts different in the molar number of addition of EO, and is represented by the following formula (S).

In the formula (S), s _max represents the number of moles of EO added to the ethylene oxide adduct which is most abundant in the whole ethylene oxide adduct. i represents the added mole number of EO. Yi represents the proportion (% by mass) of ethylene oxide adducts in which the addition mole number of EO is i, which is present in the entire ethylene oxide adducts.

The narrow ratio can be controlled, for example, by the method for producing the (b1) component or the (b2) component. The method for producing the component (b1) is not particularly limited. 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- No. 144,179) can be easily manufactured. The component (b2) can be produced, for example, by addition polymerization of ethylene oxide to an alcohol having 6 to 22 carbon atoms using a surface-modified composite metal oxide catalyst.
Specifically as a suitable thing of the surface-modified composite metal oxide catalyst used for such a method, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , surface-modified by metal hydroxide etc. Hydrometals surface-modified by at least one selected from complex metal oxide catalysts such as magnesium oxide to which Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ²⁺ etc. are added, metal hydroxides and metal alkoxides A calcined product catalyst of talcite and the like can be mentioned.
In the surface modification using the composite metal oxide catalyst, it is preferable to use the composite metal oxide and at least one selected from metal hydroxides and metal alkoxides in combination. In this case, the proportion of one or more selected from metal hydroxides and metal alkoxides is preferably 0.5 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the composite metal oxide, and preferably 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 by an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and an oxy acid and the like. The above-mentioned alkoxylation catalyst is disclosed in Japanese Patent No. 049777609, WO1993004030, WO2002038269, WO2012028435 etc. For example, alkaline earth metal salts of carboxylic acids and alkalis of hydroxycarboxylic acids And alkoxylation catalysts prepared from a mixture of one or more selected from earth metal salts and sulfuric acid and the like.

A commercial item may be used as a component (B), and what was manufactured by the well-known synthetic | combination method may be used. As a known synthesis method, the component (b1) can be produced, for example, by a method of 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 addition polymerization of one or more selected from ethylene oxide and propylene oxide to an 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 Is more preferred. When the content of the component (B) is at least the above lower limit, the liquid stability, the defoaming property, and the sebum detergency are easily improved. When the content of the component (B) is equal to or less than the above upper limit, a sufficient amount of other components can be contained, and a synergistic effect with the component (A) can be easily obtained.

3 mass% or more and 35 mass% or less are preferable with respect to the total mass of a liquid detergent, and, as for the sum total of content of (A) component and (B) component, 5 mass% or more and 33 mass% or less are more preferable, and 8 mass % Or more and 30% by mass or less is more preferable. When the total content of the component (A) and the component (B) is equal to or more than the above lower limit value, a liquid detergent which is thickened and excellent in protein detergency is easily obtained. When the total content of the components (A) and (B) is less than or equal to the above upper limit, it is easy to obtain a liquid detergent 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 are more preferable, and 0.4 or more and 0.8 or less are more preferable. When the (A) / ((A) + (B)) ratio is equal to or more than the above lower limit, protein detergency and recontamination resistance can be easily improved. When the (A) / ((A) + (B)) ratio is less than or equal to the above upper limit value, the defoaming property is likely to be improved.

<(C) component>
The component (C) is a bicarbonate. The liquid detergent of the present invention can improve viscosity, detergency and liquid stability at low temperature by containing the component (C).
Examples of the component (C) include sodium hydrogencarbonate, potassium hydrogencarbonate, 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 detergent. 1.8 mass% or more and 3.2 mass% or less are more preferable. When the content of the component (C) is at least the above lower limit, the thickening effect is easily obtained, and the pH of the diluted solution after diluting the liquid detergent with tap water is weakly alkaline (pH 8 to 11 or less) ) Easy to maintain the cleaning power. When the content of the component (C) is less than or equal to the above upper limit value, the liquid appearance at low temperature is uniform and transparent, and a good liquid detergent can be easily obtained. In particular, in the cycle test described later, it is easy to maintain a good appearance.

<(D) component>
Component (D) is a chelating agent. By containing the component (D), the liquid detergent of the present invention can improve the liquid stability at low temperature.
Component (D) is considered to capture polyvalent metal ions contained mainly in tap water, or in raw materials, or in soil, and when it is dissolved in water, it functions to capture polyvalent metal ions The

Component (D) includes at least one compound having a molecular weight of less than 550 and selected from the group consisting of aminocarboxylic acids, salts of aminocarboxylic acids, hydroxycarboxylic acids, and salts of hydroxycarboxylic acids.
The aminocarboxylic acid means a compound having a nitrogen atom and a carboxyl group in one molecule.
The term "hydroxycarboxylic acid" as used herein means a compound not having aminocarboxylic acid among compounds having a carboxyl group and an alcoholic hydroxyl group in one molecule.
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-mentioned numerical range, the liquid stability at low temperature can be more easily improved.

As the component (D), an aminocarboxylic acid chelating agent or a hydroxycarboxylic acid chelating agent is preferred.
As an aminocarboxylic acid chelating agent, methylglycine diacetic acid or a salt thereof, L-glutamic acid 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 salts thereof, L-aspartic acid diacetic acid or salts thereof, iminodisuccinic acid or salts thereof, aminocarboxylic acids such as ethylenediamine disuccinic acid or salts thereof or salts thereof; serine diacetic acid or salts thereof, hydroxyiminodisuccinic acids or salts thereof And hydroxyaminocarboxylic acids such as hydroxyethyl ethylenediamine triacetic acid or a salt thereof, dihydroxyethyl glycine 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 or the like.
Among these components (D), citric acid or a salt thereof, methylglycine diacetic acid or a salt thereof, or hydroxyiminodisuccinic acid or a salt thereof is preferable from the viewpoint of improving the liquid stability at low temperature.
As salts constituting the component (D), alkali metal salts such as sodium salts and potassium salts; monoethanolamine salt (monoethanol ammonium), diethanolamine salt (diethanol ammonium), triethanolamine salt (triethanol ammonium), etc. And alkanolamine salts; ammonium salts and the like.
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, and more preferably 0.2% by mass or more and 0.9% by mass or less, with respect to the total mass of the liquid detergent. 0.3 mass% or more and 0.7 mass% or less are more preferable. When the content of the component (D) is not less than the above lower limit value, the liquid appearance at a low temperature is uniform and transparent, and a good liquid detergent can be easily obtained, and the detergency can be easily improved. When the content of the component (D) is less than or equal to the above upper limit value, the liquid appearance at low temperature is uniform and transparent, and a good liquid detergent can be easily obtained. In particular, in the cycle test described later, it is easy to maintain a good appearance. In addition, when the content of the component (D) is less than or equal to the above upper limit, the stability of the enzyme becomes good, and the thickening effect is easily obtained.

The mass ratio (hereinafter, also referred to as (C) / (D) ratio) represented by (C) component / (D) component 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 equal to or more than the above lower limit, the liquid stability at low temperature can be more easily improved. In particular, in the cycle test described later, it is easy to maintain a good appearance. When the (C) / (D) ratio is less than or equal to the above upper limit, the thickening effect is easily obtained, and the detergency is easily improved.

<Optional component>
The liquid detergent of the present invention may contain optional components other than the components (A), (B), (C), and (D), as long as the effects of the present invention are not impaired. .
As an optional component, for example, an enzyme ((E) component), a higher fatty acid or a salt thereof ((F) component), an alkaline agent excluding the (C) component ((G) component), an antioxidant ((H) component ), Coloring agents (component (I)), surfactants other than components (A) and (B), water, water-miscible organic solvents, thickeners, thickeners, solubilizers, preservatives, enzymes Stabilizers (eg, calcium chloride, sodium lactate etc.), texture improver, storage stability improver, fluorescent agent, dye transfer inhibitor, anti-soiling agent (soil release agent), pearl agent, flavoring agent, milk Turbidifying agents, extracts of natural products and the like can be mentioned.

((E) ingredient)
The component (E) is an enzyme. By containing the component (E), the liquid detergent of the present invention can further improve the detergency against sebum dirt and protein dirt.
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 detergent 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 detergent as an enzyme preparation. 0.03 mass% or more and 0.9 mass% or less are more preferable, and 0.05 mass% or more and 0.8 mass% or less are more preferable. When the content of the component (E) is equal to or more than the above lower limit value, the detergency is easily improved. When the content of the component (E) is less than or equal to the above upper limit, the liquid stability at low temperature can be more easily improved.

((F) ingredient)
The component (F) is a higher fatty acid or a salt thereof. The liquid detergent of the present invention can enhance the defoaming property by containing the component (F). The defoaming property is the property of suppressing the foaming of the liquid detergent.
As the component (F), for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, single fatty acids such as oleic acid, behenic acid or the like, salts thereof, palm Oil fatty acids, mixed fatty acids such as beef tallow fatty acids, or salts thereof can be mentioned.
As a salt which comprises (F) component, the salt similar to the salt which comprises (D) component is mentioned.
As the component (F), one type may be used alone, or two or more types may be used in combination. By combining two or more types of the component (F), the defoaming properties can be easily enhanced.

When the liquid detergent 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 detergent, 0. 4 mass% or more and 1.8 mass% or less are more preferable, and 0.6 mass% or more and 1.5 mass% or less are more preferable. When the content of the component (F) is equal to or more than the above lower limit value, the defoaming property is more easily enhanced. When the content of the component (F) is less than or equal to the above upper limit, the liquid stability at low temperature can be more easily improved.

((G) ingredient)
The component (G) is an alkaline agent excluding the component (C). The liquid detergent of the present invention can adjust the pH of the liquid detergent to a higher level by containing the component (G). 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 detergent 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 detergent. When the content of the component (G) is within the above numerical range, it is easy to adjust the pH of the liquid detergent to a higher level.

((H) ingredient)
The component (H) is an antioxidant. When the liquid detergent is stored in a plastic container for storage and use, a gas space called a head space is formed in the container. Depletion of gas in the head space can cause deformation of the container. The liquid detergent of the present invention contains the component (C). The liquid detergent containing the component (C) tends to absorb oxygen in the head space. When the liquid cleaning agent absorbs oxygen in the head space, the gas in the head space may be reduced to cause deformation of the container. The liquid detergent according to the present invention can easily suppress the absorption of oxygen in the head space of the container containing the liquid detergent, by blending the component (H). For this reason, it is easy to reduce the possibility of causing deformation of the container.
In addition, when the liquid detergent contains a component (I) described later, the component (H) makes it easy to suppress discoloration when the liquid detergent is exposed to light or heat.

As the component (H), ascorbic acid, dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), distyrenated cresol, sodium sulfite, sodium bisulfite and the like can be mentioned. The component (H) preferably contains one or more selected from the group consisting of ascorbic acid, BHT, and BHA, and from the viewpoint of easily suppressing the absorption of oxygen in the head space and suppressing fading, BHT is preferred. More preferable.

When the liquid detergent according to the present invention contains the (H) component, the content of the (H) component is 0.005% by mass or more and 1% by mass or less based on the total mass of the liquid detergent, 0.008% by mass % Or more and 0.8 mass% or less are preferable, and 0.01 mass% or more and 0.6 mass% or less are more preferable. When the content of the component (H) is at least the above lower limit, the effect of suppressing the decrease in the oxygen concentration in the head space, and the effect of suppressing the fading due to light or heat are easily obtained. When the content of the component (H) is less than or equal to the above upper limit, the liquid stability at low temperature can be more easily improved.
As the component (H), one type may be used alone, or two or more types may be used in combination.

3 or more and 1000 or less are preferable, and, as for mass ratio (Hereinafter, it is also mentioned (C) / (H) ratio.) Represented by (C) component / (H) component, 6.5 or more and 750 or less are more preferable, 20 More preferably, it is 200 or less. When the (C) / (H) ratio is not less than the above lower limit value, it is easy to obtain a liquid detergent having excellent detergency. When the (C) / (H) ratio is less than or equal to the above upper limit, the effect of suppressing the decrease in the oxygen concentration in the head space and the effect of suppressing the fading due to light or heat are easily obtained.

((I) component)
The component (I) is a colorant. The liquid detergent of the present invention can be colored by containing the component (I). The component (I) is not particularly limited, and mention may be made of the dyes described in the "Legal Dyes Handbook" (Japan Cosmetics Industry Association) and those obtained by chemically modifying a water-soluble polymer or the like at the end of the chromophore structure. Be
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 No. 1, Blue No. 205, Green No. 3, Levanyl (R) Violet (Levanyl (R) Violet), Liquitint (R) BLUE SE (Liquitint (R) Blue SE), Liquitint (R) BLUE HP (Liquitint (R) Blue HP), Liquitint (R) Blue MC (Liquitint (R) Blue MC), Liquitint (R) VIOLET CT (Liquitint (R) Violet CT), Liquitint (R) VIOLET LS (Liquitint (R) Violet LS Liquitint (R) VIOLET DD (Liquitint (R) Violet DD), Liquitint (R) GREEN SA (Liquitint (R) Green SA), Liquitint (R) Bright Yellow (Liquitint (R) Bright Yellow ), Liquitint (registered trademark) YELLOW SY (Liquitint (registered trademark) yellow SY), Liquitint (registered trademark) YELLOW LP (Liquitint (registered trademark) yellow LP), Liquitint (registered trademark) BRILLIANT ORANGE (Liquitint (registered trademark) brilliant) Orange), Liquitint® PINK AL (Li General-purpose dyes and pigments such as uitint (registered trademark) pink AL), Liquitint (registered trademark) RED ST (Liquitint (registered trademark) red ST), Liquitint (registered trademark) RED MX (Liquitint (registered trademark) red MX), etc. Can be mentioned. In the present specification, "CI" is an abbreviation of color index.

When the liquid detergent 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 based on the total mass of the liquid detergent. When the content of the component (I) is not less than the above lower limit value, the liquid detergent can be sufficiently colored. When the content of the component (I) is less than or equal to the above upper limit value, it is difficult to cause pigmentation on the to-be-washed material, and a liquid detergent 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 (A) component and (B) component)
The liquid detergent of the present invention may contain a surfactant other than the (A) component and the (B) component (hereinafter, also referred to as another surfactant).
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 based on the total mass of the liquid detergent.
80 mass% or more is preferable, as for content of the sum total of (A) component and (B) component with respect to the total mass of surfactant, 85 mass% or more is more preferable, 90 mass% or more is more preferable, and 100 mass% It may be.

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

Examples of water-miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, 3-methoxy-3-methyl-1-butanol (sorbite, trade name); propylene glycol (PG) , Glycols such as butylene glycol and hexylene glycol; 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, from the viewpoints of low odor, availability, fluidity of liquid detergent, etc. , Diethylene glycol monobutyl ether (butyl carbitol) is preferred.
The water-miscible organic solvents may be used alone or in combination of two or more.
In addition, in this specification, a water-miscible organic solvent means the organic solvent melt | dissolved 50 g or more in 1L of ion-exchange water of 25 degreeC.
As used herein, the molecular weight of polyglycols means mass average molecular weight.

When the liquid detergent 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 based on the total mass of the liquid detergent, 0.1 mass% or more and 5 mass% or less are more preferable.

As preservatives, 2-bromo-2-nitropropane-1,3-diol, 3-iodopropynyl butyl carbamate, 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.
The preservative may be used alone or in combination of two or more.
When the liquid detergent 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 based on the total mass of the liquid detergent.

Flavoring agents include flavorings. Examples of the perfume include perfume compositions A, B, C and D described in Tables 11 to 18 of JP-A-2002-146399.
When the liquid detergent contains a flavoring agent, the content of the flavoring agent is preferably 0.1% by mass or more and 1.5% by mass or less based on the total mass of the liquid detergent.

The emulsifying agent may, for example, be a polystyrene emulsion, a polyvinyl acetate emulsion or the like, and usually, an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples thereof include polystyrene emulsions (trade name: Sybinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Ciden Chemical Co., Ltd.), Opulyn 301, Acusol OP 301, and the like.
The emulsifying agents may be used alone or in combination of two or more.
When the liquid detergent of the present invention contains a emulsifying agent, the content of the emulsifying agent is preferably 0.001% by mass or more and 0.5% by mass or less based on the total mass of the liquid detergent.

In addition, the total amount of the component which comprises the liquid cleaning agent of this invention does not exceed 100 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 detergent composition for clothing comprises, as component (A), polyoxyethylene alkyl ether sulfate (having 12 to 14 carbon atoms of alkyl group, average addition mole number of ethylene oxide: 2, content : 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 based on the total mass of the liquid detergent 10 to 14 carbon atoms in the alkyl group, content: 2% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, still more preferably 2% by mass to 7% by mass relative to the total mass of the liquid detergent Polyoxyethylene alkyl ether (carbon number of alkyl group: 12 to 14, average number of moles of added ethylene oxide: 5 to 15, More preferably, 5 to 9, content: 1% by mass to 20% by mass, more preferably 2% to 15% by mass, and still more preferably 3% to 10% by mass with respect to the total mass of the liquid detergent Sodium hydrogencarbonate (content: 1.0 mass% or more and 4.0 mass% or less, more preferably 1.6 mass% or more and 3.6 mass% or less based on the total mass of the liquid detergent as the component (C)) Citric acid (content: 0.15 mass% or more with respect to the total mass of the liquid detergent) as the (D) component as the mass% or less, more preferably 1.8 mass% or more and 3.2 mass% or less. 5% by mass or less, more preferably 0.2% by mass or more and 0.9% by mass or less, still more preferably 0.3% by mass or more and 0.7% by mass or less) as a component (E) (content: liquid 0.01 mass% or more 1.0 based on the total mass of the cleaning agent % Or less, more preferably 0.03% to 0.9% by mass, and still more preferably 0.05% to 0.8% by mass) as the component (F) (lauric acid (content: liquid) 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 and 1.5% by mass with respect to the total mass of the cleaning agent %, Palmitic acid (content: 0.1% to 0.5% by mass with respect to the total mass of the liquid detergent) and stearic acid (content: 0.1% with respect to the total mass of the liquid detergent). Sodium hydroxide 48 mass% aqueous solution (content: 0.01 mass% or more and 2.0 mass% or less with respect to the total mass of the liquid detergent as a component (G)) of 1 mass% or more and 0.5 mass% or less) ) As the (H) component (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 based on the total mass of the cleaning agent And 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 detergent) as the component (I); No.-146399 gazette perfume composition A (content: 0.1 mass% or more and 1 mass% or less with respect to the total mass of a liquid detergent) as purified water (content: total mass of a liquid detergent) To 10% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, still more preferably 40% by mass to 90% by mass (however, the total content of the respective components is Total quality of liquid cleaning agents Not exceeding 100% by weight relative).

Another aspect of the present invention is that the liquid detergent composition for clothing comprises, as component (A), polyoxyethylene alkyl ether sulfate (having 12 to 14 carbon atoms of alkyl group, average addition mole number of ethylene oxide: 2, content) : 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 based on the total mass of the liquid detergent 10 to 14 carbon atoms in the alkyl group, content: 2% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, still more preferably 2% by mass to 7% by mass relative to the total mass of the liquid detergent The polyoxyethylene alkyl ether (having a carbon number of 12 to 14 of the alkyl group, the average addition mole number of ethylene oxide: 5 to 15, Preferably, the content is 5 to 9, the content is 1% to 20% by mass, more preferably 2% to 15% by mass, and still more preferably 3% to 10% by mass, based on the total mass of the liquid detergent. Sodium bicarbonate (content: 1.0 mass% or more and 4.0 mass% or less, more preferably 1.6 mass% or more and 3.6 mass% or less, based on the total mass of the liquid detergent) % Or less, more preferably 1.8% by mass or more and 3.2% by mass or less as citric acid (content: 0.15% by mass or more based on the total mass of the liquid detergent) as the component (D) Protease (content: liquid cleaning) as the component (E), with mass% or less, more preferably 0.2 mass% or more and 0.9 mass% or less, more preferably 0.3 mass% or more and 0.7 mass% or less) 0.01 mass% or more 1.0 quality to the total mass of % Or less, 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) (content: liquid cleaning 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 and 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 detergent) as a component (G) of 48% by mass aqueous solution of sodium hydroxide (content: liquid 0.01% by mass or more and 2.0% by mass or less based on the total mass of the cleaning agent and monoethanolamine (content: 0.01% by mass or more and 2.0% by mass or less based on the total mass of the liquid cleaning agent ), As component (I), Liquitint® BLUE HP (content: 0.00005 mass% or more and 0.01 mass% or less based on the total mass of the liquid detergent) as a flavor and fragrance composition A described in JP-A-2002-146399 (content : 0.1% by mass or more and 1% by mass or less with respect to the total mass of the liquid detergent, and sodium benzoate as a preservative (content: 0.001% by mass or more with respect to the total mass of the liquid detergent % Or less) as a water-miscible organic solvent: polyethylene glycol having a molecular weight of 1000 (content: 0.1 to 10% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the liquid detergent Purified water (content: 10% by weight or more and 95% by weight or less, more preferably 20% by weight or more and 90% by weight or less, still more preferably 40% by weight, based on the total weight of the liquid detergent More than 9 Mass%) containing (provided that the total of the content of each component does not exceed 100% by weight relative to the total weight of the liquid detergent).

Still another aspect of the present invention contains (A) component, (B) component, (C) component and (D) component, and the mass ratio represented by (C) component / (D) component is 0. The use for clothing of the liquid detergent composition being greater than or equal to 6 and less than or equal to 20;

[Method of producing liquid detergent]
The liquid detergent of the present invention is produced by mixing the components (A) to (D) and, if necessary, optional components, by a conventionally known method. In order to prevent foaming, it is preferable not to mix acid components such as citric acid after mixing the component (C).
7 or more and 10 or less are preferable, and, as for the pH in 25 degreeC of the liquid detergent finally obtained, 8 or more and 10 or less are more preferable. When the pH is within the above numerical range, the stability of the enzyme (component (E)) is high, and the detergency can be easily improved.
The pH can be adjusted by adding an appropriate amount of the component (G) which is a pH adjuster.
The term "pH" as used herein refers to a value measured by a pH meter (product name: HM-30G, manufactured by Toa DK Co., Ltd.) at 25 ° C.

The viscosity of the liquid detergent 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 still more preferably 100 mPa · s or more and 600 mPa · s or less. It is easy to improve the ease of application to clothes, the thick feeling of a liquid, and a luxury feeling as viscosity is more than the above-mentioned lower limit. It is easy to improve the ease of pouring to a cap, liquid dripping property, and liquid cutting property as a viscosity is below the said upper limit.
In the present specification, the viscosity at 25 ° C. is a value measured after 30 seconds by setting the rotational speed of the rotor to 30 rpm with a Brookfield type (B-type) viscometer.

[How to use liquid cleaner]
The method of using the liquid detergent is, for example, a method of putting the liquid detergent into the water together with the article to be washed, and immersing the article in a detergent aqueous solution prepared by previously dissolving the liquid detergent in water. And the like. Alternatively, the liquid detergent may be applied directly to the object to be washed, for example, left for 3 minutes to 24 hours, and then subjected to normal washing.
The content of the liquid detergent in the detergent aqueous solution is not particularly limited. The amount of liquid detergent added to water is, for example, preferably 2 to 30 mL per 10 liters of water.

The method of introducing the liquid detergent into the water together with the object to be washed in washing includes the steps of: inserting the object into the washing machine; injecting the water into the washing machine into which the object is being washed; And a step of charging a liquid detergent into the loaded washing machine. After water is introduced into the washing machine, the object to be washed may be introduced into the washing machine into which water has been introduced.

The method of immersing the object to be washed in a detergent aqueous solution prepared by dissolving the liquid detergent in water in advance comprises the steps of: dissolving the liquid detergent in water to obtain a detergent aqueous solution; And the step of

The method of applying the liquid cleaning agent directly to the object to be washed and cleaning the object to be washed (coating and cleaning) comprises the steps of applying the liquid cleaning agent to the dirt of the object to be washed and the object to be washed to which the liquid cleaning agent has been applied. The method includes a step of leaving for a fixed time, a step of putting the left-to-be-washed material into a washing machine, and a step of performing a normal washing. In the step of leaving for a fixed time, it is preferable to leave for 1 minute to 24 hours, more preferably for 3 minutes to 12 hours, and still more preferably for 5 minutes to 1 hour. It is easy to clean the to-be-washed | cleaned material more cleanly when the time which leaves the to-be-washed | cleaned material which apply | coated the liquid cleaning agent is more than the said lower limit. It is easy to wash | clean a to-be-washed thing efficiently that the time which leaves the to-be-washed thing which apply | coated the liquid cleaning agent is below the said upper limit.

EXAMPLES The present invention will be described in more detail using the following examples, but the present invention is not limited to these examples.
The raw materials used in this example are as shown in the following [Use raw materials].

[Used raw material]
<(A) component>
AES-EO2: polyoxyethylene alkyl ether sulfate (carbon number of alkyl group: 12 to 14, average number of added ethylene oxide moles: 2), manufactured by Kao Corporation, trade name "EMAL 270N".
LAS-H: straight-chain alkyl benzene sulfonic acid (alkyl carbon number of 10 to 14), manufactured by Lion Specialty Chemicals Co., Ltd., trade name "RIPON LH-200".

<(B) component>
AE-EO9: polyoxyethylene alkyl ether (alkyl carbon number of 14 to 14, average addition mole number of EO: 9), ECOGREEN OLEOCHEMICALS company, trade name "ECOLAT 24-9".
AE-EO7: polyoxyethylene alkyl ether (carbon number of alkyl group: 12 to 14, average added mole number of EO: 7), manufactured by ECOGREEN OLEOCHEMICALS, trade name "ECOLAT 24-7".
AE-EO5: polyoxyethylene alkyl ether (carbon number of alkyl of 1214, average added mole number of EO: 5), ECOGREEN OLEOCHEMICALS company make, brand name "ECOLAT 24-5".

<(C) component>
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”.

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

<(E) component>
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: fatty acid having 12 carbon atoms, manufactured by Wako Pure Chemical Industries, Ltd., trade name "lauric acid".
Palmitic acid: fatty acid having 16 carbon atoms, manufactured by Wako Pure Chemical Industries, Ltd., trade name "palmitic acid".
Stearic acid: fatty acid having 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".
NaOH 48% aqueous solution: pH adjuster (sodium hydroxide 48% by mass aqueous solution), manufactured by Kanto Chemical Co., Ltd., trade name "48% sodium hydroxide solution".

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

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

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

[Examples 1 to 18, Reference Example 1, Comparative Examples 1 to 5]
According to the compositions 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 mixture was 25 ° C., and an appropriate amount of a pH adjuster was added to obtain a liquid detergent so that the pH of the mixture became 9.
The viscosity, the liquid stability, and the washability of the obtained liquid detergent were evaluated by the following evaluation method. Moreover, about Example 2, 17, 18, the oxygen absorbability and appearance stability were further evaluated. Reference Example 1 is a composition serving as a standard of appearance stability. The results are shown in Tables 1-5.
In addition, the unit of the compounding quantity of each component in a table | surface is "mass%", and shows the pure equivalent conversion amount. "Balance" means that water is blended such that the total blending amount (% by mass) of all the blending components contained in the composition of each example is 100% by mass.

<Evaluation of viscosity>
60 g of the liquid detergent 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 its viscosity was measured with a B-type viscometer. The measurement conditions of viscosity were 25 ° C., 30 rpm, 30 seconds, No. Used 2 rotors.
Based on the following evaluation criteria, evaluation of viscosity was judged from the measured value of viscosity.
"Evaluation criteria"
◎: viscosity of 60 mPa · s or more and 1100 mPa · s or less.
○: viscosity of 40 mPa · s or more and less than 60 mPa · s, or viscosity of more than 1100 mPa · s and 1500 mPa · s or less.
X: The viscosity is less than 40 mPa · s, or the viscosity is more than 1500 mPa · s.

<Evaluation of liquid stability>
(Cycle test)
30 mL of the liquid detergent was taken in a cylindrical glass bottle, the lid was closed and sealed. In this state, after standing at -15 ° C. for 12 hours, it was kept for 5 days in a thermostatic bath set to repeat standing conditions at 5 ° C. for 12 hours.
Thereafter, the cylindrical glass bottle was taken out from the thermostatic chamber, and the transparent uniformity of the liquid detergent was visually observed, and the liquid stability of the liquid detergent was evaluated based on the following evaluation criteria.
"Evaluation criteria"
○: Transparent and uniform.
X: Solidification, precipitation or cloudiness was observed.

(-5 ° C, 0 ° C storage stability)
30 mL of the liquid detergent was taken in a cylindrical glass bottle, the lid was closed and sealed. In this state, it was stored for 1 month in a constant temperature bath set to -5 ° C and 0 ° C.
Thereafter, the cylindrical glass bottle was taken out from the thermostatic chamber, and the transparent uniformity of the liquid detergent was visually observed, and the liquid stability of the liquid detergent was evaluated based on the following evaluation criteria.
"Evaluation criteria"
○: Transparent and uniform.
X: Solidification, precipitation or cloudiness was observed.

(Judgement)
In the evaluation of liquid stability, the above cycle test and the evaluation of storage stability at −5 ° C. and 0 ° C. were collectively determined. In the following evaluation criteria, ◎ and を were accepted.
"Evaluation criteria"
◎: The evaluation of the cycle test is “o”, and the evaluation of storage stability at −5 ° C. and 0 ° C. is “o”.
○: Evaluation of cycle test is “x”, and evaluation of storage stability at −5 ° C. and storage stability at 0 ° C. is “o”.
X: Evaluation of storage stability at -5 ° C or storage stability at 0 ° C is "x".

<Evaluation of washability>
(Detergency against sebum stains)
The reflectance R of 10 sheets of wet-type artificial soiled cloth (purchased from the Association of Laundry Science, hereinafter referred to as soiled cloth) before cleaning was measured with a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name: SE-2000) Calculated from Hunter Whiteness Z as reflectance R = Z / 100. Using a Terg-O-Tometer (manufactured by U.S. Testing) as a cleaning tester, 10 contaminated cloths and 10 charged cloths (the cloths are finely cut, sufficiently washed and rinsed) and the washing liquid Were weighed to a bath ratio of 30 times (total weight of washing solution / charge cloth) and placed in the washing tank. The washing solution was prepared by dissolving the composition of the example and the comparative example in 900 mL of 15 ° C. tap water to a concentration of 1000 ppm.
After washing for 10 minutes at a rotation speed of 120 rpm and a temperature of 15 ° C., rinsing was performed twice with 900 mL of 15 ° C. tap water for 3 minutes. After rinsing and drying, the reflectance R of the soiled fabric after washing was measured using a 460 nm filter, and the washing ratio (%) was calculated by the following equation.

In the above formula, the washing cloth means the cloth after washing the contaminated cloth, and the unstained cloth means the original white cloth (raw cloth) to which the stain is not attached. Also, 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 pieces of the soiled cloth, and the average value was used to evaluate the detergency against sebum stain based on the following evaluation criteria.
In the following evaluation criteria, ◎ and を were accepted.
"Evaluation criteria"
◎: 85% or more of the cleaning rate.
○: The cleaning rate is 80% or more and less than 85%.
X: Less than 80% of the cleaning rate.

(Washing power for protein stains)
Evaluation was made in the same manner as detergency against sebum stain except using EMPA 117 (purchased from Swissatest Testmaterialien AG) as a stain.

<Evaluation of oxygen absorbency>
15 mL of the liquid cleaner of each example was taken in a 22 mL volume headspace crimp vial and sealed with a septum closed. The crimped vial was stored in a thermostat set at 50 ° C. for one month. Thereafter, the crimp vial was removed from the thermostat and cooled at room temperature (25 ° C.). Thereafter, air in the head space was taken by a syringe and the amount of oxygen (μl) was measured by gas chromatography. The oxygen absorption amount (μl) and the ratio of oxygen absorption (volume%) were calculated by the following formula, and the oxygen absorbability was evaluated based on the following evaluation criteria. In the following evaluation criteria, ◎ or を was accepted.
(Oxygen absorption amount (μl)) = (oxygen amount of air (μl))-(oxygen amount of head space after storage (μl))
(Proportion of absorbing oxygen (volume%)) = (oxygen absorption amount (μl)) / (oxygen amount of air (μl)) × 100
"Evaluation criteria"
◎: The ratio of absorption of oxygen is less than 1.5% by volume.
○: The proportion of absorbed oxygen is 1.5% by volume or more and less than 2.5% by volume.
X: The ratio of absorption of oxygen is 2.5% by volume or more.

<Evaluation of appearance stability>
50 mL of the liquid cleaner was taken in a cylindrical glass bottle and the lid was closed and sealed. In this state, it was left for 1 week in a place exposed to sunlight (by a window in the laboratory).
Thereafter, the color of the liquid detergent was visually observed, and the appearance stability (degree of fading) of the liquid detergent was evaluated based on the following evaluation criteria. In the following evaluation criteria, it compared on the basis of the liquid detergent of the reference example 1 which does not contain (C) component. In the following evaluation criteria, ◎ or を was accepted.
"Evaluation criteria"
◎: Equivalent to the standard liquid detergent.
○: Slightly faded than the standard liquid detergent.
X: The color is clearly discolored than the reference liquid detergent.

As shown in Tables 1 to 5, in Examples 1 to 18 to which the present invention is applied, the viscosity, the liquid stability at low temperature, and the cleaning property are “◎” or “」 ”, and have appropriate viscosity, and cleaning It was found that the force and the liquid stability at low temperature were excellent. In addition, it was found that Examples 17 to 18 further containing the (H) component were excellent in oxygen absorbability and appearance stability.
On the other hand, in Comparative Example 1 which does not contain the component (B), the liquid stability at low temperature and the detergency with respect to sebum stain were "x".
The comparative example 2 which does not contain (A) component was "x" in the viscosity and the cleaning power with respect to protein stain | pollution | contamination.
In Comparative Example 3 in which the (C) / (D) ratio is out of the scope of the present invention, the liquid stability at low temperature was “×”.
The comparative example 4 which does not contain the (C) component was "x" in the viscosity and the cleaning power with respect to protein stain | pollution | contamination.
Comparative Example 5 using the component (C ') instead of the component (C) had a liquid stability at low temperature and a detergency against protein stain of "x".

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

Claims

(A) Component: An anionic surfactant except for higher fatty acid salts,
(B) component: nonionic surfactant,
(C) component: bicarbonate and
(D) component: containing a chelating agent,
The liquid detergent composition for clothes whose mass ratio represented by said (C) component / said (D) component is 0.6 or more and 20 or less.
The liquid detergent composition for clothes according to claim 1 whose content of said (C) ingredient is 1 mass% or more and 4 mass% or less to the total mass of the liquid detergent composition for clothes.
The liquid for clothing according to claim 1 or 2 whose content of the above-mentioned (D) ingredient is 0.15 mass% or more and 1.5 mass% or less to the total mass of the liquid detergent composition for clothes. Cleaning composition.
The clothing according to any one of claims 1 to 3, wherein the mass ratio represented by the component (A) / (the component (A) + the component (B)) is 0.2 or more and less than 1. Liquid detergent composition.
The liquid detergent composition for clothing according to any one of claims 1 to 4, further comprising (E) component: an enzyme.
The liquid detergent composition for clothing according to any one of claims 1 to 5, further comprising (F) component: fatty acid having 8 to 22 carbon atoms.
The liquid detergent composition for clothing according to any one of claims 1 to 6, further comprising (G) component: an alkaline agent excluding the (C) component.
The liquid detergent composition for clothing according to any one of claims 1 to 7, further comprising (H) component: an antioxidant.
The liquid detergent composition for clothing according to any one of claims 1 to 8, which has a viscosity of 30 mPa · s or more and 1500 mPa · s or less at 25 ° C.