JP7061845B2 - Liquid detergent composition for clothing - Google Patents

Description

The present invention relates to a liquid detergent composition for clothing.

As a cleaning agent for clothing, an anionic surfactant having excellent detergency and good foaming is widely used. When such an anionic surfactant is used as a main surfactant as a cleaning agent, there is a concern that bubbles may overflow during washing in a drum-type washing machine. Therefore, the cleaning agent used in the drum-type washing machine is required to have low foaming resistance (low foaming property). Further, it is desired that the rinsing can be completed quickly (good rinsing property) because the bubbles disappear quickly at the time of rinsing (foam breaking property).
Patent Document 1 introduces a liquid detergent composition having a nonionic surfactant as a main surfactant and a small amount of an anionic surfactant, which has low foaming property at the time of washing and good rinsing property. ..

Japanese Unexamined Patent Publication No. 2002-167600

However, Patent Document 1 uses a nonionic surfactant as a main surfactant, and although it improves low foaming property and rinsing property during washing, it uses an anionic surfactant as a main surfactant in order to enhance the detergency. If so, no improvement in low foaming property is seen.
Therefore, an object of the present invention is a liquid detergent composition for clothing, which has higher detergency and is excellent in low foaming property and defoaming property.

The present invention has the following aspects.
[1] Component (A): Anionic surfactant excluding soap, Component (B): Fatty acid having 12 carbon atoms or a salt thereof, Component (C): Fatty acid having 14 to 18 carbon atoms or a salt thereof, ( D) component: contains a nonionic surfactant, and the mass ratio represented by (A) component / ((A) component + (D) component) is 0.2 or more and less than 0.9, and (C). A liquid cleaning agent composition for clothing, wherein the mass ratio represented by the component (component) / component (B) is 0.03 or more and 0.5 or less.
[2] The liquid detergent composition for clothing according to [1], which further contains the component (E): an enzyme.
[3] The liquid detergent composition for clothing according to [1] or [2], which further contains the component (F): a chelating agent.
[4] The liquid detergent composition for clothing according to any one of [1] to [3], further containing a component (G): a defoaming aid.
[5] Any of [1] to [4], wherein the total content of the component (A) and the component (D) is 5 to 60% by mass with respect to the total mass of the liquid detergent composition for clothing. The liquid detergent composition for clothing according to the above.
[6] The method according to any one of [1] to [5], wherein the mass ratio represented by (A) component / ((B) component + (C) component) is 1.5 or more and less than 13.8. Liquid detergent composition for clothing.
[7] The clothing according to any one of [1] to [6], wherein the mass ratio represented by (D) component / ((B) component + (C) component) is 0.8 or more and less than 30. Liquid detergent composition.

According to the present invention, it is possible to provide a liquid detergent composition for clothing, which has higher detergency and is excellent in low foaming property and defoaming property.

[Liquid detergent composition for clothing]
The liquid detergent composition for clothing of the present invention (hereinafter, may be simply referred to as a liquid detergent) contains (A) component, (B) component, (C) component, and (D) component. ..
The liquid detergent of the present invention mainly contains an anionic surfactant. Here, the fact that the anionic surfactant is the main surfactant means that the mass ratio of the anionic surfactant to the total mass of the anionic surfactant and the nonionic surfactant is 0.2 or more. say.

<Ingredient (A)>
The component (A) is an anionic surfactant excluding soap. The liquid detergent contains the component (A), so that the cleaning power can be enhanced. Examples of the anionic surfactant 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).
(3) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(4) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(5) Any of the 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 with an average of 0.5 to 10 mol added.
(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. An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by mole.
(7) 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 0.5 on average. An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(8) An alkyl polyhydric alcohol ether sulfate such as an alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(9) Long-chain monoalkyl, dialkyl or sesquialkyl phosphate.
(10) An alkyl sulfate or an alkenyl sulfate (AS) having 10 to 20 carbon atoms.

Anionic surfactants other than those exemplified above may be used. For example, carboxylic acid type anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkylamide ether carboxylates or alkenylamide ether carboxylates, acylaminocarboxylates; alkyl phosphate ester salts. , Polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkylphenyl phosphate ester salt, glycerin fatty acid ester monophosphate ester salt and other phosphate ester type anionic surfactants and the like can be mentioned.
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.

The component (A) may be used alone or in combination of two or more.
As the component (A), at least one selected from the group consisting of the above (1), (2), (3) and (5) because it is easy to obtain better detergency among the above. It is preferable to contain the anionic surfactant of (1), (2), the combination of (3) and (5), the combination of (1), (2) and (5), (1), (3). It is more preferable to contain at least one anionic surfactant selected from the group consisting of the combination of (5) and (5) and the combination of (1) and (5).

The content of the component (A) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, still more preferably 3 to 15% by mass, based on the total mass of the liquid detergent. When the content of the component (A) is at least the above lower limit value, a liquid detergent having excellent protein detergency can be easily obtained. In addition, it becomes easy to obtain a liquid detergent having excellent anti-recontamination properties. Further, when the content of the component (A) is not more than the upper limit value, it is easy to obtain a liquid detergent having good fluidity.
Here, the "recontamination preventive property" is a property of preventing the dirt removed from the object to be washed (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 formula (a1) (hereinafter, referred to as a component (a)).
R ³ CH (SO ₃ M) COOR ⁴ ... (a1)
(In the formula (a1), R ³ is a hydrocarbon group having 10 to 16 carbon atoms, R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms, and M is a counterion.)

((A) component)
In the formula (a1) ^, the hydrocarbon group of R3 has 10 to 16 carbon atoms. 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 ³ is 10 or more, the surface activity is strong and the detergency is better. When the carbon number of R ³ is 16 or less, the low temperature stability of the liquid detergent is excellent.

The hydrocarbon group of R ³ may be linear, may be branched, or may contain a cyclic structure. The hydrocarbon group of R ³ 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.

In the formula (a1), the number of carbon atoms of ^R4 is 1 to 6, preferably 1 to 3.
The hydrocarbon group of ^R4 may be linear, may be branched, or may contain a cyclic structure. The hydrocarbon group of ^R4 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. A group or a branched alkyl group is more preferable.
As ^R4 , 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 detergency is further improved.

In the formula (a1), as M, those capable of forming a water-soluble salt together with R ³ CH (COOR ⁴ ) SO ₃ ⁻ are preferable, and examples thereof include alkali metal ions, protonated amines, and ammonium ions. Examples of the alkali metal that can be M include sodium and the like. Examples of the amine that can be M include primary to tertiary amines and the like. The total carbon number of the amine is preferably 1 to 6. Further, the amine may have a hydroxy group. It is preferable that the amine has a hydroxy group because the solubility of the component (a) in water is increased. 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 the M, alkali metal ions are preferable, and sodium ions are particularly preferable, because they are easily available and the low temperature stability of the liquid detergent can be more easily enhanced.
As the component (a), R ³ in the above formula (a1) is a linear or branched alkyl group having 14 to 16 carbon atoms, or a linear or branched alkenyl group having 14 to 16 carbon atoms. A compound in which ^R4 is a methyl group is particularly preferable.

As the component (a), any one of them may be used alone, or two or more of them may be used in combination.
As the component (a), a mixture of compounds having different carbon atoms of fatty acid residues is preferable because the detergency is enhanced and the solubility in water is enhanced. In particular, the compound (a- ¹ ) in which R3 in the formula (a1) is a hydrocarbon group having 14 carbon atoms and the compound (a-) in which R3 in the formula ⁽ a1) is a hydrocarbon group having 16 carbon atoms. A mixture with 2) is preferable. 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 even more preferable. When the mass ratio is within the above-mentioned suitable range, the detergency, the solubility in water, and the low temperature stability of the liquid detergent tend to be better.

The component (a) is obtained by a known production method, for example, a tank-type reactor equipped with a stirrer is used by a conventional method, and the fatty acid ester as a raw material is sulfonated by contacting it with anhydrous sulfuric acid or the like. A product obtained by preparing an α-sulfofatty acid ester (α-SF acid) and then neutralizing the α-SF acid with sodium hydroxide or the like may be used, and a commercially available product is used. It is also good. Before and after neutralization, bleaching may be performed with hydrogen peroxide or the like.
The content of the component (a) is preferably 0 to 6.0% by mass, more preferably 0.5 to 4.0% by mass, and 1.0 to 3.0% by mass with respect to the total mass of the liquid detergent. % Is more preferable. When the content of the component (a) is within the above range, it becomes easy to obtain a liquid detergent having excellent detergency, anti-recontamination property, dispersion stability, and enzyme stability. In addition, it becomes easier to maintain the degree of freedom in blending other ingredients.
The ratio of the component (a) to the component (A) (hereinafter, may be referred to as (a) / (A) ratio) is preferably 0/100 or more and 50/100 or less, and 5/100 or more and 40/100. The following is more preferable, and 10/100 or more and 30/100 or less are further preferable.

(Soap)
Soap is a higher fatty acid salt represented by the following formula (a2).
R ⁵ -COOX ... (a2)
However, in the formula (a2), R5 is a linear or branched alkyl group having ⁷ to 17 carbon atoms, or a linear or branched alkenyl group. X in the formula (a2) is an alkali metal salt, an amine salt, an ammonium salt, an alkanolamine salt or the like.
In the present invention, the component (B) and the component (C) described later may correspond to the formula (a2), and in this case, the soap corresponds to the component (B) or the component (C). Therefore, soap is removed from the component (A).

<Ingredient (B)>
The component (B) is a fatty acid having 12 carbon atoms or a salt thereof (hereinafter, also simply referred to as a fatty acid (salt)). Examples of the component (B) include at least one selected from fatty acids represented by the following general formula (I) and alkali metal salts, amine salts, ammonium salts, alkanolamine salts and the like thereof. The liquid detergent contains the component (B) to enhance low foaming property.
R ⁶ -COMM ... (I)
(However, in the formula (I), R ⁶ is a saturated hydrocarbon group or an unsaturated hydrocarbon group having 11 carbon atoms. R ⁶ may be linear or branched. It may contain a cyclic structure. M is hydrogen, alkali metal, amine, ammonia, alkanolamine, etc.)
As (B), a linear saturated hydrocarbon group is preferable for ^R6 , and a hydrogen atom, an alkali metal, and an alkanolamine are preferable for R6, because low foaming property is enhanced and compatibility with a detergent is enhanced.
As the component (B), any one of them may be used alone, or two or more of them may be used in combination.

<Ingredient (C)>
The component (C) is a fatty acid (salt) having 14 to 18 carbon atoms. Examples of the component (C) include at least one selected from fatty acids represented by the following general formula (II) and alkali metal salts, amine salts, ammonium salts, alkanolamine salts and the like thereof. The liquid detergent contains the component (C) to enhance the foam breaking property.
R ⁷ -COMM ... (II)
(However, in the formula (II), R ⁷ is a saturated hydrocarbon group or an unsaturated hydrocarbon group having 13 to 17 carbon atoms. R ⁷ is preferably hydrogen or an alkali. Metals, amines, ammonia, alkanolamines, etc.)
By combining the component (B) and the component (C), the foam breaking property can be further enhanced.
As the component (C), any one of them may be used alone, or two or more of them may be used in combination. When two or more kinds are combined, it is preferable to use a fatty acid (salt) having R ⁷ having 15 carbon atoms and a fatty acid (salt) having R ⁷ having 17 carbon atoms in combination. By combining two or more types, the appearance stability is improved.

In the liquid detergent, the mass ratio represented by (A) component / ((B) component + (C) component) (hereinafter, may be referred to as (A) / (B + C) ratio) is, for example, 1.5. More than 13.8 is preferable, 2 or more and less than 13 is more preferable, and 3 or more and less than 9 is even more preferable. Within the above range, the foam breaking property can be further enhanced and the appearance stability can be further enhanced.
In the liquid detergent, the mass ratio represented by (D) component / ((B) component + (C) component) (hereinafter, may be referred to as (D) / (B + C) ratio) is, for example, 0.8. More than 30 is preferable, 1 or more and less than 20 is more preferable, and 1.5 or more and less than 9 is further preferable. Within the above range, the foam breaking property can be further enhanced and the appearance stability can be further enhanced.
By combining a higher fatty acid (salt) in which R ⁶ has 11 carbon atoms and a higher fatty acid (salt) in which R ⁷ has 13 to 17 carbon atoms, low foaming property and foam breaking property can be further enhanced.

In the liquid detergent, the mass ratio represented by the component (C) / component (B) (hereinafter, may be referred to as (C) / (B) ratio) is 0.03 or more and 0.5 or less, and 0. It is preferably 05 or more and 0.38 or less, and more preferably 0.06 or more and 0.3 or less. When the ratio (C) / (B) is within the above range, the foam breaking property and the appearance stability can be further enhanced.
The reason why the low foaming property, the foam breaking property and the appearance stability can be further improved by setting the (C) / (B) ratio within the above range is considered as follows. That is, the number of particles of the complex particles generated by the reaction between the polyvalent metal ion and the fatty acid in tap water increases, the particle shape and surface hydrophobicity change, and the state suitable for breaking the foam film is obtained. Is.

The total content of the component (B) and the component (C) in the liquid detergent is preferably 0.1% by mass or more and less than 2% by mass, and 0.5% by mass or more, based on the total mass of the liquid detergent. Less than 1.8% by mass is more preferable, and 1.1% by mass or more and less than 1.7% by mass is further preferable.
When the total content of the component (B) and the component (C) is at least the above lower limit value, it becomes easy to obtain a liquid detergent having excellent low foaming property and foam breaking property. When the total content of the component (B) and the component (C) is not more than the upper limit, it becomes easy to maintain a transparent and uniform liquid appearance.

<(D) component>
The component (D) is a nonionic surfactant. The liquid detergent of the present invention is excellent in appearance stability, foam breaking property, and sebum cleaning property by containing the component (D) as a surfactant other than the component (A).
The content of the component (D) is preferably 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and 2% by mass or more and 10% by mass with respect to the total mass of the liquid detergent. The following is more preferable.

The total content of the component (A) and the component (D) is preferably 80% by mass or more and 100% by mass or less, and 85% by mass or more and 100% by mass, based on the total mass of the surfactant (excluding soap). % Or less is more preferable, 90% by mass or more and 100% by mass or less is further preferable, and 100% by mass may be used.
Further, the mass ratio represented by (A) component / ((A) component + (D) component) (hereinafter, may be referred to as (A) / (A + D) ratio) is 0.2 or more and less than 0.9. Yes, 0.3 or more and 0.8 or less are preferable, and 0.4 or more and 0.7 or less are more preferable. When the (A) / (A + D) ratio is at least the above lower limit value, it is easy to suppress deterioration of protein detergency and anti-recontamination property, and when it is at least the above upper limit value, low foaming property and foam breaking property are good. It is easy to become. Of the surfactants, the ones that mainly contribute to the detergency are the anionic surfactant and the nonionic surfactant. The (A) / (A + D) ratio represents the content ratio of the anionic surfactant in the surfactant that contributes to the detergency.

Examples of the component (D) include the following (1) to (5).
(1) An average of 3 to 30 mol, preferably 3 to 20 mol, more preferably 5 to 20 mol of an alkylene oxide having 2 to 4 carbon atoms in a monohydric fatty alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. The added polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the monohydric aliphatic alcohol used here include primary alcohols and secondary alcohols. Further, the alkyl group may have a branched chain. As the aliphatic alcohol, primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between the ester bonds of a long-chain fatty acid alkyl ester.
(4) Polyoxyethylene fatty acid ester.
(5) Polyoxyethylene hydrogenated castor oil.

As the nonionic surfactant, those of the above (1) or (3) are preferable, and among them, those represented by the following general formula (III) or (IV) are preferable.
R ⁸ -C (= O) O-[(EO) _s / (PO) _t ]-(EO) _u -R ⁹ ... (III)
R ¹⁰ -O-[(EO) _v / (PO) _w ]-(EO) _x -H ... (IV)
(In formula (III), R ⁸ is a hydrocarbon group having 7 to 22 carbon atoms, R ⁹ is an alkyl group having 1 to 6 carbon atoms, and s represents the average number of repetitions of EO, which is 6 to 20. It is a number, t represents the average number of repetitions of PO, is a number of 0 to 6, u represents the average number of repetitions of EO, is a number of 0 to 20, EO represents an oxyethylene group, and PO represents an oxyethylene group. Represents an oxypropylene group.
In formula (IV), R ¹⁰ 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, 0 to 0. It is a number of 6, x represents the average number of repetitions of EO, is a number from 0 to 20, EO represents an oxyethylene group, and PO represents an oxypropylene group. )

In formula (III), R8 is a hydrocarbon group having ⁷ to 22 carbon atoms. The carbon number of R ⁸ is preferably 9 to 21, and more preferably 11 to 21.
R ⁸ is preferably an alkyl group or an alkenyl group.
R ⁸ may be either straight chain or branched chain.
From the viewpoint of further improving the detergency, R8 is preferably an alkyl group having ⁷ to 22 carbon atoms in a straight chain or a branched chain, or an alkenyl group having 7 to 22 carbon atoms in a straight chain or a branched chain.
R ⁹ 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 and an ethyl group are preferable.
In formula (III), 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. When it is not more than the upper limit value, the detergency is more likely to be improved.
In formula (III), t is a number representing the average number of repetitions of PO.
t is a number of 0 to 6, preferably 0 to 3. When it is not more than the 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 formula (IV), R ¹⁰ is a hydrocarbon group having 6 to 22 carbon atoms.
In the formula (IV), the carbon number of R ¹⁰ is preferably 10 to 22, more preferably 10 to 20, and even more preferably 10 to 18 from the viewpoint of further improving the detergency.
R ¹⁰ may be a straight chain or a branched chain.
Preferred R10 ^— O— includes groups represented by the following general formula (V).
(R ¹⁰¹ ) (R ¹⁰² ) CH-O -... (V)
(In the formula (V), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a chain hydrocarbon group, and the total carbon number of R ¹⁰¹ and R ¹⁰² is 5 to 21.)
The total number of carbon atoms of R ¹⁰¹ and R ¹⁰² is preferably 9 to 21, more preferably 9 to 19, and even more preferably 9 to 17.
R ¹⁰¹ and R ¹⁰² may be linear or branched.
The R ¹⁰ is preferably an alkyl group having 12 to 14 carbon atoms, and the carbon bonded to the oxygen atom is preferably an alkyl group which is a secondary carbon.
In formula (IV), 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 18, particularly preferably 7 to 18, and most preferably 12 to 15. When it is at least the above lower limit value, the foam breaking property and the appearance stability are more likely to be improved. When it is not more than the upper limit value, the detergency is more likely to be improved.
In formula (IV), w is a number representing the average number of repetitions of PO.
w is a number of 0 to 6, preferably 0 to 3. When it is not more than the 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 formula (III) 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. Specific alkoxylation catalysts 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 formula (III) (hereinafter, also referred to as the component (d11)) and the nonionic surfactant represented by the formula (IV) (hereinafter, also referred to as the component (d12)) have a narrow ratio. Is preferably 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 detergent composition having less raw material odor of the surfactant.
When the component (d11) is produced by a conventional method, the product contains the component (d11), a component that does not contribute to detergency, for example, a fatty acid ester that is a raw material of the component (d11), and is represented by the formula (III). Ethylene oxide adducts having an s of 1 or 2 in the nonionic surfactant are coexistent 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 component (d12).
The upper limit of the narrow ratio is not particularly limited, but is preferably 80% by mass or less.
The narrow ratio is more preferably 20 to 50% by mass, still more preferably 20 to 40% by mass, because liquid stability and solubility are improved.
Here, the "narrow ratio" in the present specification indicates the ratio of the distribution of ethylene oxide adducts having different numbers of moles of EO, and is expressed by the following mathematical formula (S).

[In the formula, p _max indicates the number of moles of EO of the ethylene oxide adduct that is most abundant in the whole ethylene oxide adduct. i indicates the number of moles of EO added. Yi indicates the proportion (% by 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 (d11) or the component (d12). The method for producing the component (d11) 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. 2000-144179). It can be easily manufactured by (see Japanese Patent Publication No.). As a method for producing the component (d12), for example, it can be produced by a method of addition-polymerizing ethylene oxide to an alcohol having 6 to 22 carbon atoms by 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⁺ , etc.) with metal hydroxides and the like. Of composite metal oxide catalysts such as magnesium oxide to which Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ²⁺ , etc. are added, and hydrotalcite surface-modified with metal hydroxides and / or metal alkoxides, etc. Examples include calcined material catalysts.
In the surface modification using the composite metal oxide catalyst, it is preferable to use the composite metal oxide in combination with the metal hydroxide and / or the metal alkoxide. In this case, the ratio of the metal hydroxide and / or the metal alkoxide to 100 parts by mass of the composite metal oxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass. ..
Further, as a method for producing the other component (d11), 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 oxyacid. The above alkoxylation catalyst is disclosed in Japanese Patent No. 04977609, WO1993004030, WO20020328269, WO20102028435, etc., for example, an alkaline earth metal salt of a carboxylic acid and / or an alkali of a hydroxycarboxylic acid. Examples thereof include an alkoxylation catalyst prepared from a mixture of an earth metal salt and sulfuric acid.

As the nonionic surfactant, a commercially available product may be used, or a product produced by a known synthetic method may be used. As a known production method, the component (d11) can be produced by, for example, addition polymerization of ethylene oxide and / or propylene oxide to a fatty acid alkyl ester. The component (d12) can be produced, for example, by a method of addition-polymerizing ethylene oxide and / or propylene oxide to an alcohol having 6 to 22 carbon atoms.
As the component (D), one type may be used alone, or two or more types may be used in combination.

The content of the surfactant (excluding soap) with respect to the total mass of the liquid detergent is, for example, preferably 5 to 60% by mass, more preferably 5 to 50% by mass, still more preferably 10 to 40% by mass.

The mass ratio represented by (A) component / ((B) component + (C) component) (hereinafter, may be referred to as (A) / (B + C) ratio) is 1.5 or more and less than 13.8. 2 or more and 13 or less are preferable, and 3 or more and 9 or less are more preferable. When the (A) / (B + C) ratio is at least the above lower limit value, it is easy to suppress deterioration of protein detergency and recontamination prevention property, and when it is at least the above upper limit value, foam breaking property is likely to be good.

The mass ratio represented by (D) component / ((B) component + (C) component) (hereinafter, may be referred to as (D) / (B + C) ratio) is 0.8 or more and less than 30, and 1 or more. 20 or less is preferable, and 1.5 or more and 9 or less are more preferable. When the (D) / (B + C) ratio is at least the above lower limit value, it is easy to suppress deterioration of protein detergency and recontamination prevention property, and when it is at least the above upper limit value, foam breaking property is likely to be good.

<(E) component>
The component (E) is an enzyme. The liquid cleaning agent of the present invention further contains the component (E) to further enhance the cleaning power.
As the component (E), an enzyme used for laundry detergent applications and the like can be used, and examples thereof include protease, amylase, lipase, cellulase, and mannanase.
As the protease, trade names Savinase 16L, Savinase Ultra 16L, and Savinase, which are available as protease preparations from Novozymes, Inc.
Ultra 16XL, SubtilisEvity 16L, Everlase 16L TypeEX, Everlase Ultra 16L, Coronase 48L, Esperase 8L, Alcalase 2.5L, Alcalase 2.5L, Alcalase Ultra 2.5L, Alcalase Ultra 2.5L, Alcalase Ultra 2.5L Examples thereof include trade names Purafect L, Purafect OX, Properase L and the like that can be obtained from the company.
As amylase, trade names Termamyl 300L, Termamyl Ultra 300L, and Duramyl, which are available as amylase preparations from Novozymes, Inc.
300L, Steinzyme 12L, Steinzyme Plus 12L, Amplify 12L; Product name Maxamyl available from Genecore, Pullulanase Amano available from Amano Enzyme Co., Ltd .; Product name DB-250 available from Seikagaku Corporation. ..
Examples of the lipase include Lipex 100L, Lipex Evity 100L, Lipase 100L and the like, which can be obtained from Novozymes as a lipase preparation.
Examples of the cellulase include trade names Endolase 5000L, Cellulizeme 0.4L, and Carezyme 4500L, which can be obtained from Novozymes as a cellulase preparation.
Examples of the mannanase include the trade name Mannaway 4L available from Novozymes as a mannanase preparation.
As the component (E), any one of them may be used alone, or two or more of them may be used in combination.

The content of the component (E) is preferably 0.01 to 1.0% by mass, more preferably 0.03 to 0.8% by mass, and 0.05 to 0% by mass with respect to the total mass of the liquid detergent. 5% by mass is more preferable. When the content of the component (E) is at least the above lower limit value, the cleaning effect of the protein stain by the component (E) is satisfactorily obtained, and when it is at least the above upper limit value, calcium which is a stabilizer in the enzyme preparation is obtained. Precipitation of the complex of the component (B) and the component (C) is suppressed, and the appearance stability is further enhanced. In addition, a sufficient blending effect of the component (E) can be obtained while suppressing an increase in cost. Further, the generation of the base material odor is also satisfactorily suppressed.

<(F) component>
The component (F) is a chelating agent. The liquid cleaning agent of the present invention further contains the component (F), so that the cleaning power is further enhanced.
The component (F) is at least one compound having a weight average molecular weight of less than 550 and selected from the group consisting of an aminocarboxylic acid, a salt of aminocarboxylic acid, a hydroxycarboxylic acid, and a salt of 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 and does not correspond to an aminocarboxylic acid.
The weight average molecular weight of the component (F) is less than 550, preferably 400 or less, preferably 50 or more, and more preferably 100 or more.
The component (F) is considered to capture polyvalent metal ions mainly contained in tap water or dirt, and has an action of capturing polyvalent metal ions when it is dissolved in water. Is.
As the component (F), an aminocarboxylic acid-based chelating agent and a hydroxycarboxylic acid-based chelating agent are preferable.
The aminocarboxylic acid-based chelating agent means a chelating agent having a nitrogen atom and a carboxyl group in one molecule.
The hydroxycarboxylic acid-based chelating agent means a chelating agent having a carboxyl group and an alcoholic hydroxy group in one molecule, which does not correspond to an aminocarboxylic acid-based chelating agent.
Examples of the aminocarboxylic acid-based chelating agent include nitrilotriacic acid or a salt thereof, ethylenediaminetetraacetic acid or a salt thereof, diethylenetriaminepentaacetic acid or a salt thereof, β-alaninediacetic acid or a salt thereof, diacetic acid aspartate or a salt thereof, methylglycinediacetic acid or a salt thereof. Aminocarboxylic acid or a salt thereof such as the salt, iminodysuccinic acid or a salt thereof, ethylenediaminedisuccinic acid or a salt thereof; Examples thereof include hydroxyaminocarboxylic acids such as ethylglycine or salts thereof or salts thereof.
Examples of the hydroxycarboxylic acid-based chelating agent include lactic acid or a salt thereof, malic acid or a salt thereof, citric acid or a salt thereof, tartrate acid or a salt thereof, glycol or a salt thereof, gluconic acid or a salt thereof.
Of these, citric acid or a salt thereof, malic acid or a salt thereof, gluconic acid or a salt thereof is preferable from the viewpoint of high solubility of the complex with polyvalent metal ions in water.
Examples of the salt constituting the component (F) include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; monoethanolamine salt (monoethanolammonium) and diethanolamine salt (diethanolammonium). ), Alkanolamine salts such as triethanolamine salt (triethanolammonium); ammonium salts and the like.
As the component (F), any one of them may be used alone, or two or more of them may be used in combination.
The content of the component (F) is preferably 0.03% by mass or more and 3.0% by mass or less, more preferably 0.05% by mass or more and 1.0% by mass or less, based on the total mass of the liquid detergent. More preferably, it is 0.08% by mass or more and 0.5% by mass or less.
When the content of the component (F) is not more than the lower limit value, it becomes easy to obtain a good detergent composition having a uniform and transparent liquid appearance, and it becomes easy to improve the cleaning power.
When the content of the component (F) is not more than the upper limit value, it is easy to obtain a detergency commensurate with the blending cost, and the stability of the component (E) is likely to be good.

<(G) component>
The component (G) is a defoaming aid. The liquid detergent of the present invention further contains the component (G) to further enhance the defoaming effect.
As the component (G), fatty acid 2-ethylhexyl (pastel 2H-08, trade name), polyoxypropylene glyceryl ether (Actol T-3000, trade name), polyoxypropylene glyceryl ether (Actol T-4000, product name). Name), polyoxypropylene glyceryl ether (Actcol T-5000, trade name) and one or more selected from silicon preparations.
The component (G) may be used alone or in combination of two or more.
The content of the component (G) is preferably 0.01 to 20% by mass with respect to the total mass of the liquid detergent.

<Arbitrary ingredient>
In addition to the above-mentioned components (A) to (G), the liquid cleaning agent of the present invention may contain other components usually used for cleaning agents as long as the effects of the present invention are not impaired.
Other components include, for example, water, a water-miscible organic solvent, a thickener, a thickener, a solubilizer, an alkaline agent such as monoethanolamine, an antioxidant, a preservative, calcium chloride, sodium lactate and the like. Enzyme stabilizer, texture improver, storage stability improver, fluorescent agent, stain transfer inhibitor, recontamination inhibitor, pearl agent, solvent release agent, flavoring agent, colorant, emulsion agent, natural product, etc. Extract, pH adjuster, texture improver and the like.

The content of water with respect to the total mass of the liquid detergent is, for example, preferably 10 to 95% by mass, more preferably 20 to 90% by mass, still more preferably 40 to 90% by mass.

Examples of the water-miscible 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 weight average molecular weight of about 200 to 1000, polyglycols such as dipropylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monobutyl ether (butyl carbitol), alkyl ethers such as diethylene glycol dimethyl ether and the like.
Among these, ethanol, 3-methoxy-3-methyl-1-butanol, propylene glycol, weight average molecular weight of about 200 to 1000 are considered from the viewpoint of low odor, availability, fluidity of liquid detergent, etc. Polyethylene glycol and diethylene glycol monobutyl ether (butyl carbitol) are preferable.
The water-miscible organic solvent may be used alone or in combination of two or more.
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 to 10% by mass, preferably 0.1, based on the total mass of the liquid detergent. ~ 5% by mass is more preferable.
In the present invention, the water-miscible organic solvent means an organic solvent that dissolves in 1 L of ion-exchanged water at 25 ° C. in an amount of 50 g or more.

As the antioxidant, butylhydroxytoluene, disstyrene cresol, sodium sulfite, sodium hydrogen sulfite and the like can be contained, for example, in an amount of 0.01 to 2% by mass based on the total mass of the liquid detergent. The antioxidant may be used alone or in combination of two or more.

Preservatives include 2-bromo-2-nitropropane-1,3-diol, 3-iodopropynylbutylcarbamate, zincpyrythion, sodiumpyrythion, 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.

Colorants include Acid Red 138, Polar Red RLS, Liquidtin PINK AL, Acid Yellow 203, LiquidBright.
Examples thereof include general-purpose dyes and pigments such as Yellow, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Turquoise P-GR, Liquidint BLUE SE, Levanyl Violet, and Red 106 (all trade names). As the colorant, any one of them may be used alone, or two or more of them may be used in combination.
When the liquid detergent of the present invention contains a colorant, the content thereof is preferably 0.00005 to 0.005% by mass with respect to the total mass of the liquid detergent.

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 thereof include polystyrene emulsion (trade name: Cybinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Saiden Chemical Co., Ltd.), Opoolin 301, Acusol OP 301 and the like. As the emulsifying agent, any one of them may be used alone, or two or more of them may be used in combination.
When the liquid detergent of the present invention contains an emulsifying agent, the content thereof is preferably 0.001 to 0.5% by mass with respect to the total mass of the liquid detergent.

It is assumed that the total content of all the components contained in the liquid detergent is 100% by mass.

(PH)
The pH of the liquid detergent at 30 ° C. is preferably 7 to 10 from the viewpoint of further enhancing the detergency. In particular, when the liquid detergent contains the component (E), if the pH is within the above range, it is possible to suppress the decrease in the activity of the enzyme.
The pH of the cleaning agent may be adjusted by using an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine, or a pH adjuster such as sodium hydroxide, potassium hydroxide or sodium carbonate.

(viscosity)
The viscosity of the liquid detergent of the present invention at 25 ° C. is preferably 1 to 2500 mPa · s. When the viscosity of the liquid detergent is within the above range, it becomes easy to measure the liquid detergent with a measuring cap or the like. In addition, when the liquid detergent is directly applied to the object to be washed for cleaning, the liquid detergent can be easily applied to the object to be washed. In addition, it tends to be easy to obtain a sense of quality.
The viscosity of the liquid detergent in the present specification at 25 ° C. indicates a value measured by adjusting the sample to 25 ° C. and using a B-type viscometer. The measurement condition is a rotation speed of 30 rpm, and the viscosity after rotation is measured for 30 seconds.

The liquid detergent of the present invention dissolves, for example, the above-mentioned components (A) to (D) and, if necessary, the components (E), (F), (G) and optional components in water. It is manufactured by adjusting the pH to a desired level with a pH adjuster.

The liquid detergent of the present invention can be contained in a commonly used container. Such containers include, for example, a nozzle-type container or an inner plug type container equipped with a measuring cap, a squeeze container or a pump container equipped with an automatic measuring mechanism or a simple measuring mechanism, a trigger container or a squeeze to be sprayed or applied in a foam shape. Examples include containers, coating containers having a coating surface on which liquid is applied, refill containers (pouches, thin-walled bottles, replacement bottles, etc.).

Since the liquid detergent of the present invention described above contains a specific amount of the component (A), the component (B), the component (C) and the component (D), it is excellent in foaming property and foam breaking property. In particular, if the liquid detergent contains the component (E), the component (F) and the component (G), the cleaning power is further enhanced and the enzyme stability is also excellent.

The liquid detergent of the present invention can be used for any of household, commercial and industrial purposes. Among them, it can be suitably used for home use, and is particularly suitable as a liquid detergent for clothing.
Examples of the type of the object to be washed include those similar to those targeted for washing in household washing, and examples thereof include clothing, cloths, towels, sheets, textile products such as curtains, and the like.

The method of using the liquid detergent for clothing is, for example, a method of putting the liquid detergent into water together with the object to be washed at the time of washing, or a method of dissolving the liquid detergent in water in advance to prepare an aqueous detergent solution. Examples include a method of immersing the water. Further, the liquid detergent may be directly applied to the object to be washed and left for a certain period of time, and then normal washing may be performed (coating washing).

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.
The raw materials, measurement / evaluation methods used in each Example and Comparative Example are as follows.

[Ingredients used]
<Ingredient (A)>
AES-EO2: Polyoxyethylene alkyl ether sulfate, manufactured by Kao Corporation, trade name: "EMAL270N", average number of moles of ethylene oxide added: 2.
LAS-H: Linear alkyl (10 to 14 carbon atoms) Sodium benzenesulfonate (trade name: "Lypon LH-200" manufactured by Lion Specialty Chemicals Co., Ltd.).
MES-Na: Sodium salt of α-sulfofatty acid ester (in formula (a1), α-sulfofatty acid ester salt (C16) in which R3 is an alkyl group having 14 carbon atoms ^, and in formula (a1) ^, R3 is Mixture of α-sulfofatty acid ester salt (C18) which is an alkyl group having 16 carbon atoms (mixed mass ratio C16 / C18 = 8/2) (manufactured by Lion Eco Chemicals Sdn. Bhd., Trade name: MIZULA®) FL-80).

<Ingredient (B)>
Lauric acid: Made by Wako Pure Chemical Industries, Ltd., Product name: "Lauric acid".

<Ingredient (C)>
Myristic acid: Made by Wako Pure Chemical Industries, Ltd., Product name: "Myristic acid".
Palmitic acid: Made by Wako Pure Chemical Industries, Ltd., Product name: "Palmitic acid".
Stearic acid: Made by Wako Pure Chemical Industries, Ltd., Product name: "Stearic acid".

<(D) component>
AE-EO15: Polyoxyethylene alkyl ether. ECOGREEN OLEOCHEMICALS, trade name: "ECOLAT24-15".
AE-EO9: Polyoxyethylene alkyl ether. ECOGREEN OLEOCHEMICALS, trade name: "ECOLAT24-9".
AE-EO7: Polyoxyethylene alkyl ether. ECOGREEN OLEOCHEMICALS, trade name: "ECOLAT24-7".
AE-EO5: Polyoxyethylene alkyl ether. Made by THAI ETHOXYLATE, trade name: "DEHYDOL LS5 TH".

<(E) component>
Protease 1: Made by Novozymes, trade name: "Savinase Ultra 16L".
Protease 2: Made by Novozymes, trade name: "Savinase Evity 16L".
Protease 3: Made by Novozymes, trade name: "Coronase 48L".

<(F) component>
Citric acid: Made by Kanto Chemical Co., Inc., Product name: "Citric acid".

<(G) component>
Silicon formulation: Manufactured by Momentive, trade name: "SAG 689".
2H08: Fatty acid 2-ethylhexyl, manufactured by Lion Specialty Chemicals Co., Ltd., trade name: "Pastel 2H-08".
PPG: Polyoxypropylene glyceryl ether, manufactured by Mitsui Chemicals, Inc., trade name: "Actcol T-4000", weight average molecular weight 4000.

<Arbitrary ingredient>
MEA: Monoethanolamine, manufactured by Nippon Shokubai Co., Ltd., trade name: "Monoethanolamine".
DEA: Diethanolamine, manufactured by Nippon Shokubai Co., Ltd., trade name: "Diethanolamine".
Sodium benzoate: Made by Toagosei Co., Ltd., Product name: "Sodium benzoate".
Paratoluenesulfonic acid: manufactured by Meitomo Sangyo Co., Ltd., trade name: "paratoluenesulfonic acid aqueous solution (70% solution)".
Ethanol: Made by Japan Alcohol Trading Co., Ltd., Product name: "Specific alcohol 95 degree synthesis".
Dye: Made by Milliken, Product name: "Liquitint Blue HP".
Perfume: Perfume composition A according to Tables 11 to 18 of JP-A-2002-146399.
48% by mass aqueous solution of sodium hydroxide: manufactured by Kanto Chemical Co., Inc., trade name: "48% sodium hydroxide solution".
Water: Purified water.

[Examples 1 to 23, Comparative Examples 1 to 9]
According to the compositions of Tables 1 to 6, the components (A) to (D), the components (E) to (H) and the optional component were added to water and mixed to obtain a liquid detergent. The obtained liquid detergent was evaluated for appearance stability at 0 ° C. and 5 ° C., foaming mL,% foam breaking property, detergency against sebum stains, and detergency against protein stains by the following evaluation methods. The results are also shown in Tables 1 to 6.
The unit of the content in the table is "mass%", which indicates the amount converted to pure content. "Balance" means that water is blended so that the total blending amount (mass%) of all the blending components contained in the composition of each example is 100% by mass. In addition, Examples 4, 7, 10, 12, 19, and 23 are reference examples.

[Evaluation method of bubble height]
In a glass specific color tube (with 1 mL scale) having a height of 250 mm, an outer diameter of 28 mm, and a capacity of 100 mL, a cleaning liquid diluted with 2700 ppm (1000 ppm in Example 19) of tap water at 40 ° C. up to the marked line of 20 mL. I put it in. It was shaken 20 times in 10 seconds and allowed to stand on a flat table. Measure the foam volume mL immediately after shaking and the foam volume mL after 3 minutes of standing, and subtract the value of the initial liquid level 20mL from the value of the foam volume mL immediately after shaking or the foam volume mL after 3 minutes of standing. The value was calculated. Based on this value, the foaming property mL and the foam breaking property% were calculated according to the following formula, and the foaming property and the foam breaking property of the liquid detergent were evaluated based on the following criteria. The smaller the value of foaming mL, the better the low foaming property. Further, the larger the value of% foam breaking property, the better the foam breaking property.
Foamable mL = (foam volume immediately after shaking)-(initial liquid level 20 mL)
Foam breaking property% = ((foam volume immediately after shaking)-(foam volume mL after 3 minutes of standing)) / ((foam volume immediately after shaking)-(initial liquid level 20 mL)) x 100
(Evaluation of foaming mL)
◯: 30 mL or less.
Δ: More than 30 mL and 40 mL or less.
×: Over 40 mL.
(Evaluation of% foam breaking property)
◯: 60% or more.
Δ: 40% or more and less than 60%.
×: Less than 40%.

[Evaluation method of appearance stability]
Two cylindrical glass bottles were prepared, 50 mL of liquid detergent was taken into each cylindrical glass bottle, and the lid was closed and sealed. In this state, each cylindrical glass bottle was left in a constant temperature bath at 0 ° C. and a constant temperature bath at 5 ° C., and stored for 1 month. Then, each cylindrical glass bottle was taken out from the constant temperature bath, the transparency uniformity of the liquid detergent was visually observed, and the appearance stability of the liquid detergent was evaluated based on the following criteria.
(Evaluation of appearance stability)
◯: Transparent and uniform.
X: Solidification or precipitation was observed.

[Evaluation method of detergency]
In this method, the reflectance of the cloth was measured by using an integrating sphere spectrophotometer Color-Eye7000A (manufactured by GretagMacbeth), and the reflectance R was calculated from the hunter whiteness Z by the following formula.
R = Z / 100
First, as the contaminated cloth before washing, the reflectances of 10 wet artificially contaminated cloths (sebum stains, purchased from the Laundry Science Association) and EMPA116 (protein stains, purchased from Swissist Testmaterian AG) were measured. A drum-type washing machine TROM WD-965RD (manufactured by LG) was used as a washing tester, and the steps of washing (setting at 40 ° C.) → dehydration → rinsing → dehydration → rinsing → dehydration → rinsing → dehydration were set.
The amount of the liquid detergent composition for clothing used is 36 g (13 g in Example 19), put it in the slot of the washing machine, cotton cloth 1 m x 0.8 m, and one artificially contaminated cloth and one EMPA116 for each piece. Ten pieces of sewn cotton cloth were sewn one by one and put into a washing machine.
After washing, the contaminated cloth was removed from the cotton cloth and dried. The reflectance R of the contaminated cloth after drying (hereinafter, also referred to as a washing cloth) is measured using a 460 nm filter, and the washing rate (unit:%, rounded to the nearest whole number is rounded off) according to the following formulas (i) and (ii). ) Was calculated.
Cleaning rate (%) = ((contaminated cloth K / S)-(cleaning cloth K / S)) / ((contaminated cloth K / S)-(standard white cloth K / S)) x 100 ... (i)
K / S = (1-R / 100) ² / (2R / 100) ... (ii)
In the formula, K represents the absorption coefficient, S represents the scattering coefficient, and R represents the reflectance. The standard white cloth is the original white cloth (raw cloth) that has not been soiled, and the reflectance R of the standard white cloth is calculated as 80% for the artificially contaminated cloth and 82% for the EMPA116.

The larger the value of the cleaning rate obtained by the above formulas (i) and (ii), the higher the cleaning power. The average value of the cleaning rates of 10 artificially contaminated cloths and 10 EMPA116s was obtained and evaluated according to the following evaluation criteria.
(Cleaning power (artificial contaminated cloth, sebum stains))
◎, ○, △ were accepted.
⊚: 85% or more.
◯: 80% or more and less than 85%.
Δ: 75% or more and less than 80%.
×: Less than 75%.
(Detergency (EMPA116, protein stains))
◎, ○, △ were accepted.
⊚: 70% or more.
◯: 68% or more and less than 70%.
Δ: 65% or more and less than 68%.
×: Less than 65%.

As shown in Tables 1 to 6, Examples 1 to 23 to which the present invention was applied were "○" or "Δ" in foaming property mL and foam breaking property%, and it was confirmed that they were excellent in low foaming property. did it. It was also confirmed that the appearance stability was excellent. In addition, the detergency was also good.
On the other hand, in Comparative Examples 1 to 4 containing no component (B) or component (C), the% foam breaking property and the detergency (sebum stain) were "x". In Comparative Examples 5 to 7 in which the ratio (C) / (B) was out of the predetermined range, the foaming property mL or the foaming property% was "x". In Comparative Example 8 containing no component (B) and component (C), the foam breaking property% and the detergency (sebum stain) were "x". In Comparative Example 9 in which the value of (A) / ((A) + (D)) is out of the predetermined range, the foaming property mL, the foam breaking property%, and the detergency (sebum stain) are all “x”. rice field.

From these results, it was found that according to the present invention, it is possible to provide a liquid detergent composition for clothing, which has higher detergency and is excellent in low foaming property and foam breaking property.

Claims (7)

(A) Ingredients: Anionic surfactants other than soap and
(B) Component: A fatty acid having 12 carbon atoms or a salt thereof,
(C) Component: Fatty acid having 14 to 18 carbon atoms or a salt thereof,
Ingredient (D): Containing a nonionic surfactant,
The content of the component (A) is 2.7% by mass or more and 8.5% by mass or less with respect to the total mass.
The content of the component (D) is 2% by mass or more and 10% by mass or less with respect to the total mass.
The mass ratio represented by (A) component / ((A) component + (D) component) is 0.3 or more and 0.8 or less , and the mass ratio represented by ( C) component / (B) component is It is 0.05 or more and 0.38 or less ,
Moreover, the total content of the component (B) and the component (C) is 0.5% by mass or more and less than 1.8% by mass with respect to the total mass.
The nonionic surfactant comprises a compound represented by the following general formula (IV).
Liquid detergent composition for clothing.
R ¹⁰ -O-[(EO) _v / (PO) _w ]-(EO) _x -H ... (IV)
[In formula (IV), R ¹⁰ is a hydrocarbon having 6 to 22 carbon atoms, v represents the average number of repetitions of EO, 3 to 15, and w represents the average number of repetitions of PO, 0. It is a number of ~ 6, x represents the average number of repetitions of EO, is a number of 0-12, (v + x) is 6-15 , EO represents an oxyethylene group, PO represents an oxypropylene group. show. ] The liquid detergent composition for clothing according to claim 1, further comprising the component (E): an enzyme. The liquid detergent composition for clothing according to claim 1 or 2, wherein the component (A) comprises a combination of the following (1) and the following (5).
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(5) Any of the 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 with an average of 0.5 to 10 mol added. The liquid detergent composition for clothing according to any one of claims 1 to 3, further comprising a component (F): a chelating agent. The item according to any one of claims 1 to 4, wherein the mass ratio represented by the component (A) / (component (B) + component (C)) is 1.5 or more and less than 13.8. Liquid detergent composition for clothing. The clothing product according to any one of claims 1 to 5, wherein the mass ratio represented by the component (D) / (component (B) + component (C)) is 0.8 or more and less than 30. Liquid detergent composition. Claims 1 to 100, wherein the total content of the component (A) and the component (D) is 80% by mass or more and 100% by mass or less with respect to the total mass of the surfactant (however, excluding soap). The liquid detergent composition for clothing according to any one of 6 .