JP6684558B2 - Liquid detergent for clothing - Google Patents

Description

  The present invention relates to a liquid detergent for clothes.

In recent years, the use of water-saving washing machines has become mainstream due to increasing environmental awareness. In the case of washing with a water-saving washing machine, the soil concentration in the washing liquid increases, so that the soil removed during washing is likely to be redeposited again on the article to be washed.
By using a liquid detergent containing a high concentration of anionic surfactant, recontamination can be easily suppressed. However, in this case, if the liquid detergent contains an enzyme, the enzyme is denatured by the anionic surfactant, and it becomes difficult to maintain the enzyme activity. That is, the enzyme stability is impaired.
Further, when providing a liquid detergent, appearance stability is required so that precipitation of a compound such as an enzyme or precipitation does not occur.
In Patent Document 1, 40% by mass or more of a nonionic surfactant, at least one component selected from the group consisting of an aminocarboxylic acid or a salt thereof, and a phosphonic acid or a salt thereof, an α-hydroxy-monocarboxylic acid or A liquid detergent composition containing the salt and an enzyme and having excellent enzyme stability is disclosed.
Patent Document 2 discloses a detergent composition containing a surfactant, a detergency builder, an enzyme and polyethyleneimine.

International Publication No. 2012/144601 Japanese Patent Publication No. 2013-530266

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent for clothes, which is excellent in recontamination resistance, enzyme stability, and appearance stability.

As a result of intensive studies, the present inventors have found that the following liquid detergent for clothes can solve the above problems.
That is, the liquid detergent of the present invention has the following aspects, for example.
[1] Component (A): a non-soap-based anionic surfactant, and component (B): at least one selected from an alkylene oxide adduct of polyalkyleneimine and an alkylene oxide adduct of polyalkyleneamine, and (C). Component: contains at least one selected from the carboxylic acids represented by the following general formula (I) and salts thereof, and the component (D): an enzyme, and is represented by the component (B) / the component (C). A liquid detergent for clothes, characterized in that the mass ratio is 0.1 to 20.
X-R ¹ -COOH (I)
However, in formula (I), R ¹ is a divalent hydrocarbon group having 1 to 4 carbon atoms or an arylene group, and X is —H, —OH, —CH ₃ , or —COOH.
[2] The liquid detergent for clothes according to [1], which further contains a component (E): a nonionic surfactant.
[3] The liquid detergent for clothing according to [2], wherein the mass ratio represented by the component (E) / the component (A) is 0.1 to 10.

  The liquid detergent for clothing of the present invention is excellent in recontamination resistance, enzyme stability, and appearance stability.

(Liquid detergent for clothing)
The liquid detergent for clothing of the present invention (hereinafter, also simply referred to as “liquid detergent”) is a composition containing components (A) to (D).

<(A) component>
The component (A) is a non-soap type anionic surfactant. The liquid detergent of the present invention contains the component (A), whereby the anti-redeposition effect is enhanced.
In the present invention, the non-soap anionic surfactant is an anionic surfactant excluding a saturated or unsaturated fatty acid salt having 8 to 24 carbon atoms (so-called soap).
Examples of the component (A) include known non-soap anionic surfactants used for detergents such as clothing.
Examples of the component (A) include linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; alkane sulfone. Acid salt; α-sulfo fatty acid ester salt; Carboxylic acid type anionic surfactant such as alkyl ether carboxylic acid, polyoxyalkylene ether carboxylic acid, alkyl (or alkenyl) amido ether carboxylic acid, acylamino carboxylic acid or salts thereof A phosphate ester type anionic surfactant such as alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkylphenyl phosphate ester salt, glycerin fatty acid ester monophosphate ester salt Can be mentioned.
Examples of these salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, and alkanolamine salts such as monoethanolamine salts and diethanolamine salts.

Among the above, as the linear alkylbenzene sulfonic acid or a salt thereof, a linear alkyl group having 8 to 16 carbon atoms is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate preferably has 10 to 20 carbon atoms.
The alkyl sulfate ester salt preferably has 10 to 20 carbon atoms.
As the alkyl ether sulfate ester salt or the alkenyl ether sulfate ester salt, a polyoxyalkylene alkyl ether sulfate ester salt or a polyoxyalkylene alkenyl ether sulfate ester salt is preferable, and a linear or branched alkyl group or alkenyl having 10 to 20 carbon atoms is used. A polyoxyalkylene alkyl ether sulfuric acid ester salt or a polyoxyalkylene alkenyl ether sulfuric acid ester salt having a group and having an average of 1 to 5 mol of alkylene oxide (ethylene oxide and / or propylene oxide) added thereto is more preferable.
As the alkane sulfonate, a secondary alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms is preferable.
As the α-sulfo fatty acid ester salt, an α-sulfo fatty acid ester salt having a fatty acid residue having 10 to 20 carbon atoms is preferable.

As the component (A), one type may be used alone, or two or more types may be used in combination.
Among them, linear alkylbenzene sulfonic acid or a salt thereof, α-olefin sulfonic acid salt, alkyl sulfuric acid ester salt, alkyl ether sulfuric acid ester salt or alkenyl ether sulfuric acid ester salt, alkane sulfonic acid, from the viewpoint of excellent recontamination resistance. One or more selected from salts and α-sulfo fatty acid ester salts are preferable, and one or more selected from linear alkylbenzene sulfonic acid or salts thereof, alkyl ether sulfate ester salts or alkenyl ether sulfate ester salts are more preferable, and alkyl ether sulfates Ester salts are more preferred.
As the component (A), one type may be used alone, or two or more types may be used in combination.

  Further, the content of the component (A) in the liquid detergent is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and further preferably 8 to 20% 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, the effect of preventing recontamination will be easily enhanced. When the content of the component (A) is at most the above upper limit value, the enzyme stability will be easily enhanced.

  As the component (A), a linear alkylbenzene sulfonic acid and / or a salt thereof (hereinafter, also referred to as a component (a1)), and an alkyl ether sulfate ester salt and / or an alkenyl ether sulfate ester salt (hereinafter a component (a2)). It is also preferable to be used in combination. In this case, the mass ratio [mass ratio of the content of the (a1) component to the content of the (a2) component] represented by the (a1) component / the (a2) component is preferably 0.5 to 2, 0.5-1 is more preferable. When the mass ratio represented by (a1) / (a2) is within the above-mentioned preferred range, the effect of preventing redeposition is likely to be enhanced. Furthermore, enzyme stability is likely to be enhanced.

<(B) component>
The component (B) is at least one selected from an alkylene oxide adduct (b1) of polyalkyleneimine and an alkylene oxide adduct (b2) of polyalkyleneamine.
In the liquid detergent of the present invention, the enzyme stability is further enhanced by using the component (B) and the component (C) described later in combination.

The component (b1) is an alkylene oxide adduct of polyalkyleneimine.
The polyalkyleneimine is represented by the following general formula (II).
^{_{NH 2 -R 21 - (NA-}} R 21) n -NH 2 ··· (II)
In the formula (II), R ²¹ is each independently an alkylene group having 2 to 6 carbon atoms, A represents a hydrogen atom or another polyamine chain by branching, and n is a number of 1 or more. However, all of the above A are not hydrogen atoms.

R ²¹ is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. R ²¹ is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
The polyalkyleneimine is obtained by polymerizing one or more alkyleneimines having 2 to 6 carbon atoms by a conventional method. Examples of the alkyleneimine having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine.
As the polyalkyleneimine, polyethyleneimine (PEI) and polypropyleneimine are preferable, and PEI is more preferable. PEI is obtained by polymerizing ethyleneimine, and has a branched chain structure containing primary, secondary, and tertiary amine nitrogen atoms in its structure.

200-2000 are preferable, as for the weight average molecular weight of polyalkyleneimine, 300-1500 are more preferable, 400-1000 are more preferable, and 500-800 are especially preferable.
In addition, the weight average molecular weight in this specification means the value calculated | required by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance.

  The polyalkyleneimine preferably has 5 to 30 active hydrogen atoms in its molecule, more preferably 7 to 25 active hydrogen atoms, and even more preferably 10 to 20 active hydrogen atoms.

The component (b1) is obtained by adding alkylene oxide to polyalkyleneimine. As this method, for example, alkylene oxide such as ethylene oxide is added at 100 to 180 ° C. to polyalkyleneimine as a starting material in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide and sodium methylate. And the like.
Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferred, and ethylene oxide being more preferred.

Examples of the alkylene oxide adduct of polyalkyleneimine include ethylene oxide adduct of polyalkyleneimine, propylene oxide adduct of polyalkyleneimine, and ethylene oxide-propylene oxide adduct of polyalkyleneimine. The ethylene oxide-propylene oxide adduct of polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to polyalkyleneimine, and the addition order and addition form (block shape, random shape) of ethylene oxide and propylene oxide to polyalkyleneimine. ) Is optional.
As the alkylene oxide adduct of polyalkyleneimine, an ethylene oxide adduct of polyalkyleneimine and an ethylene oxide-propylene oxide adduct of polyalkyleneimine are preferable, and an ethylene oxide adduct of polyalkyleneimine is more preferable.

  As the alkylene oxide adduct of polyalkyleneimine, it is preferable that an average of 5 to 40 alkylene oxides are added to one active hydrogen atom of the polyalkyleneimine as a raw material, and an average of 10 to 30 alkylene oxides. Those to which is added are preferable. That is, one having an average of 5 to 40 moles of alkylene oxide added thereto is preferable, and one having an average of 10 to 30 moles of alkylene oxide added per 1 mole of active hydrogen contained in the raw material polyalkyleneimine is preferable.

The weight average molecular weight of the alkylene oxide adduct of polyalkyleneimine is preferably from 1,000 to 80,000, more preferably from 2,000 to 50,000, even more preferably from 5,000 to 30,000, particularly preferably from 10,000 to 20,000.
Examples of the alkylene oxide adduct of polyalkyleneimine include a compound represented by the formula (II-a).

In formula (II-a), R ²² is independently an alkylene group having 2 to 6 carbon atoms, and m is independently a number of 1 or more.
R ²² is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
m is the average number of repetitions of (R ²² O), preferably 5 to 40, more preferably 10 to 30.
As the alkylene oxide adduct of polyalkyleneimine, a synthetic product or a commercially available product may be used.
Examples of commercially available products include the product name “Sokalan HP20” manufactured by BASF.

The component (b2) is an alkylene oxide adduct of polyalkyleneamine.
The polyalkylene amine is represented by the following general formula (III).
NH ₂ (R ³¹ NH) ₁ H ... (III)
In formula (III), R ³¹ is an alkylene group having 2 to 6 carbon atoms, and l is a number of 1 or more.

R ³¹ is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. R ³¹ is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
As the polyalkyleneamine, polyethyleneamine is preferable. Examples of polyethyleneamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like. In addition, these polyethylene amines can be obtained by a known production method, for example, by reacting ammonia and ethylene dichloride.

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

  As the polyalkyleneamine, those having 6 to 30 active hydrogen atoms in one molecule are preferable, and those having 7 to 20 active hydrogen atoms are more preferable.

  The component (b2) is obtained by adding alkylene oxide to polyalkylene amine. This reaction can be performed in the same manner as the component (b1). Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferred, and ethylene oxide being more preferred.

Examples of alkylene oxide adducts of polyalkylene amines include ethylene oxide adducts of polyalkylene amines, propylene oxide adducts of polyalkylene amines, ethylene oxide-propylene oxide adducts of polyalkylene amines, and the like.
As the alkylene oxide adduct of polyalkyleneamine, an ethylene oxide adduct of polyalkyleneamine and an ethylene oxide-propylene oxide adduct of polyalkyleneamine are preferable, and an ethylene oxide adduct of polyalkyleneamine is more preferable.

  As the alkylene oxide adduct of polyalkyleneamine, one having an average of 5 to 40 alkylene oxides added to 1 atom of active hydrogen of the polyalkyleneamine as a raw material is preferable, and an alkylene oxide of 10 to 30 averages. Those to which is added are preferable. That is, one having an average of 5 to 40 moles of alkylene oxide added thereto is preferable, and one having an average of 10 to 30 moles of alkylene oxide added per 1 mole of active hydrogen contained in the polyalkylene amine as a raw material is preferable.

  The weight average molecular weight of the alkylene oxide adduct of polyalkyleneamine is preferably from 1,000 to 80,000, more preferably from 2,000 to 50,000, further preferably from 5,000 to 30,000, particularly preferably from 10,000 to 20,000.

As the component (B), the component (b1) is preferable. Among the components (b1), an ethylene oxide adduct of polyethyleneimine is preferable.
As the component (B), any one type may be used alone, or two or more types may be used in combination.

  The content of the component (B) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and even more preferably 0.1 to 2% by mass, based on the total mass of the liquid detergent. . When the content of the component (B) is at least the above lower limit value, it becomes easy to adjust the mass ratio of the component (B) and the component (C) within the range specified in the present application, and a liquid detergent excellent in appearance stability is obtained. It will be easier to obtain. Further, when the content of the component (B) is not more than the upper limit value, it becomes easy to maintain the degree of freedom in blending the other components.

<(C) component>
The component (C) is at least one selected from carboxylic acids represented by the following general formula (I) and salts thereof.
X-R ¹ -COOH (I)
However, in formula (I), R ¹ is a divalent hydrocarbon group having 1 to 4 carbon atoms or an arylene group, and X is —H, —OH, —CH ₃ , or —COOH.
In the liquid detergent of the present invention, the enzyme stability is enhanced by using the component (B) and the component (C) together.

In formula (I), R ¹ is a divalent hydrocarbon group having 1 to 4 carbon atoms or an arylene group. The divalent hydrocarbon group having 1 to 4 carbon atoms and the arylene group may or may not have a substituent. A hydroxy group etc. are mentioned as a substituent.
The divalent hydrocarbon group having 1 to 4 carbon atoms may be saturated or unsaturated, and may be linear, branched, or cyclic. Good. Examples of such a divalent hydrocarbon group having 1 to 4 carbon atoms include a divalent group obtained by removing one hydrogen atom from an alkyl group having 1 to 4 carbon atoms, and one from an alkenyl group having 1 to 4 carbon atoms. And a divalent group obtained by removing one hydrogen atom from an alkynyl group having 1 to 4 carbon atoms.
A phenylene group is mentioned as an arylene group.
X is -H, -OH, -CH _3, or -COOH.

Examples of the carboxylic acid represented by the formula (I) include benzoic acid, acetic acid, propionic acid, butyric acid, hydroxybutyric acid, hydroxyisobutyric acid, lactic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid. , Malic acid, glutaric acid and the like.
Examples of the carboxylic acid salt include sodium salt, potassium salt, calcium salt, monoethanolamine salt, diethanolamine salt and triethanolamine salt.
Among these, as the component (C), benzoic acid, lactic acid or a salt thereof is preferable, and lactic acid or a salt thereof is more preferable, since the enzyme stability is further enhanced. Further, the sodium salt is preferable as the component (C) from the viewpoint of further improving the appearance stability.
As the component (C), sodium lactate is preferable from the viewpoint of further enhancing enzyme stability and appearance stability.
As the component (C), any one type may be used alone, or two or more types may be used in combination.

The content of the component (C) is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.2 to 2% by mass, based on the total mass of the liquid detergent. .
When the content of the component (C) is at least the above lower limit, it becomes easy to adjust the mass ratio of the component (B) and the component (C) within the range specified in the present application, and a liquid detergent having excellent appearance stability is obtained. It is easy to be affected. Further, when the content of the component (C) is not more than the above upper limit, it becomes easy to maintain the degree of freedom in blending the other components.

<(D) component>
The component (D) is an enzyme.
The liquid detergent of the present invention further contains the component (D) to enhance the detergency.
As the component (D), enzymes used for clothing detergents and the like can be used, and examples thereof include protease, amylase, lipase, cellulase, and mannanase.
In addition, in this specification, an "enzyme" means an enzyme preparation.

Proteases include trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type Alex 2.5L, 2.5L, 2.5L, 2.5L, 2.5L, and 2.5L, which are available from Novozymes as protease preparations. , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, trade names Purafect L, Purafect OX, Properase L and the like available from Genencor Corporation.
Amylases include, as amylase preparations, trade names Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus Plus 12L, tradenames available from Genencor Co., Ltd. under the trade name Maxaman brand name, Maxaman brand name, Maxa available from Novozymes. , Trade name DB-250 available from Seikagaku Corporation.
Examples of the lipase include Lipex 100L and Lipolase 100L, which are trade names available from Novozymes as lipase preparations.
Examples of cellulases include Endolase 5000L, Celluzyme 0.4L, and Carzyme 4500L, which are trade names available from Novozymes as cellulase preparations.
Examples of mannanases include the product name Mannaway 4L, which is available from Novozymes as a mannanase preparation.

The component (D) preferably contains a protease. By adding a protease, the detergency against protein stains can be further enhanced.
Among the above-mentioned proteases, among the above-mentioned proteases, Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L, Everlase Ultra 16Lit, Alkalase Ultra 2.5L, Alcalase UltraLan, 2.5L, Alcalase UltraLan, 2.5L, 2.5L, Alcalase UltraLu, 2.5L, 2.5L, Alcalase, UltraLan, 2.5L, 2.5L, and 2.5L. Ultra 2.5XL and Coronase 48L are preferable, and Alcalase 2.5L, Everlase 16L, Savinase 16L and Coronase 48L are particularly preferable.
As the component (D), any one type may be used alone, or two or more types may be used in combination.

The content of the component (D) is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and 0.1 to 1.5% by mass based on the total mass of the liquid detergent. More preferable. When the content of the component (D) is at least the lower limit value of the above-mentioned preferred range, the detergency will be further enhanced. When the content of the component (D) is at most the upper limit of the above-mentioned preferred range, the precipitation of the enzyme will be suppressed and the appearance stability will be further enhanced.
In the present specification, the amount of the enzyme incorporated in the liquid detergent is the amount of the formulation. The blending amount can be obtained by a general method, for example, by back-calculating the amount of the raw material used or the amount of enzyme protein in the liquid detergent.

Mass ratio represented by the above-mentioned (B) component / the above-mentioned (C) component [The mass ratio of the content of the (B) component to the content of the (C) component, hereinafter also referred to as "B / C ratio". ] Is 0.1-20.
When the B / C ratio is less than 0.1 or more than 20, the appearance stability is impaired.
The B / C ratio is preferably 0.3 to 10, more preferably 0.5 to 7, and further preferably 1 to 5.

  The total content of the components (B) and (C) is preferably 0.1 to 4% by mass, more preferably 0.5 to 3% by mass, and 1-2. 5% by mass is more preferable. When the total content of the component (B) and the component (C) is at least the lower limit value described above, it is easy to adjust the B / C ratio within the range specified by the present application, and it becomes easy to obtain a liquid detergent having excellent appearance stability. Further, when the total content of the component (B) and the component (C) is not more than the upper limit value, it becomes easy to maintain the degree of freedom in blending the other components.

<Water>
The liquid detergent of the present invention preferably contains water from the viewpoint of ease of handling during production, solubility in water when used, and the like.
The content of water in the liquid detergent is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 50% by mass in the liquid detergent.

<Other ingredients>
The liquid detergent of the present invention may contain, in addition to the above components (A) to (D), other components usually used in detergents.
Examples of other components include surfactants other than component (A), water-miscible organic solvents, viscosity reducing agents and solubilizing agents, alkaline agents, antioxidants, preservatives, enzyme stabilizers (provided that (B ) And (C) component are not included), texture improver, storage stability improver, fluorescent agent, dye transfer inhibitor, redeposition inhibitor (however, component (B) is not included), chelating agent (however). (Component (C) is not included), pearlescent agents, soil release agents, flavoring agents, coloring agents, emulsifying agents, extracts of natural products, pH adjusting agents, defoaming agents and the like.

Examples of the surfactant other than the component (A) include a nonionic surfactant (component (E)), a cationic surfactant, and an amphoteric surfactant.
<(E) component>
The component (E) is a nonionic surfactant. The liquid detergent of the present invention preferably contains the component (E) from the viewpoint of further enhancing the detergency.
Examples of the component (E) include higher alcohols, alkylphenols, higher fatty acids, higher fatty acid esters, higher amines, polyoxyalkylene type nonionic surfactants obtained by adding alkylene oxides, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines. , Fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like. The term “higher grade” as used herein means a compound having 8 to 24 carbon atoms.

Examples of the component (E) include a polyoxyalkylene type nonionic surfactant represented by the following general formula (IV-1) (hereinafter, also referred to as “compound (e1)”) and a general formula (IV-2) below. The polyoxyalkylene type nonionic surfactant represented (hereinafter, also referred to as “compound (e2)”) is preferable.
^{_{R 41 -COO - [(EO)}} s / (PO) t] - (EO) u -R 42 ··· (IV-1)
(In the formula (IV-1), R ⁴¹ is a hydrocarbon group having 7 to 21 carbon atoms, R ⁴² is a methyl group or an ethyl group. S is a number of 6 to 20 and t is 0 to 6; And u is a number from 0 to 20. EO represents an ethyleneoxy group, PO represents a propyleneoxy group, s and u represent the average repetition number of EO, and t represents the average repetition number of PO. Represents.)

R ⁴¹ is preferably a linear or branched alkyl group or a linear or branched alkenyl group because the detergency is further enhanced. The number of carbon atoms in ^{R 41} is preferably 9 to 21, 11 to 21 is more preferable.
The number of 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, the hydrophilicity does not become too low, the increase of free water in the system can be suppressed, and the enzyme stability is further enhanced. When it is at most the above upper limit, the hydrophilicity does not become too high, and good detergency is easily obtained.
t is a number of 0 to 6, and preferably a number of 0 to 3. When it is at most the upper limit value, the appearance stability will be easily enhanced.
When t is more than 0, the addition form of EO and PO in [(EO) _s / (PO) _t ] may be a block form or a random form. Further, either EO or PO may be added first.

The compound (e1) is preferably a compound in which t in formula (IV-1) is 0 (that is, a polyoxyethylene fatty acid alkyl ester), and further, a polyoxyethylene fatty acid methyl ester (wherein R ⁴² is a methyl group ( Hereinafter, also referred to as “MEE”) is more preferable.

^{_{R 43 -O - [(EO)}} v / (PO) w] - (EO) y -H ··· (IV-2)
(In the formula ^{(IV-2), R 43} is a hydrocarbon group having 8 to 22 carbon atoms, v is the number of 3 to 20, w is a number of Less than six, y is from 0 to 20 EO represents an ethyleneoxy group, PO represents a propyleneoxy group, v and y represent the average repeating number of EO, and w represents the average repeating number of PO.

R ⁴³ is preferably a linear or branched alkyl group or a linear or branched alkenyl group because the detergency is further enhanced. The carbon number of R ⁴³ is preferably 10 to 22, more preferably 12 to 22.
The number of v + y is preferably 3 to 20, more preferably 5 to 18, even more preferably 6 to 18, and particularly preferably 11 to 18. When it is at least the above lower limit, the hydrophilicity does not become too low, the increase of free water in the system can be suppressed, and the enzyme stability is further enhanced. When it is at most the above upper limit, the hydrophilicity does not become too high, and good detergency is easily obtained.
w is a number of 0 to 6, and 0 to 3 is preferable. If it exceeds the upper limit, the appearance stability may decrease.
When w is greater than 0, the addition form of EO and PO in [(EO) _v / (PO) _w ] may be a block form or a random form. Further, the addition form of EO and PO may be a block form or a random form. Further, either EO or PO may be added first.

The component (E) preferably contains a polyoxyethylene fatty acid alkyl ester from the viewpoint of solubility in water and detergency. Further, the liquid detergent of the present invention can be made into a concentrated type having good fluidity without causing a significant increase in viscosity (gelation) even if it contains a high concentration of a surfactant.
Polyoxyethylene fatty acid alkyl ester, especially MEE, is a nonionic surfactant in which the orientation of molecules in the aqueous solution system is weak and the micelle is unstable. It is speculated that a large amount can be incorporated into the liquid detergent. It is also presumed that the solubility in water is improved. Further, it is considered that it contributes to good fluidity at high concentration. Therefore, when the polyoxyethylene fatty acid alkyl ester is poured into the water in the washing machine tub, the concentration of the polyoxyethylene fatty acid alkyl ester in the washing liquid quickly becomes uniform, and the washing liquid comes into contact with the object to be washed at a predetermined concentration from the initial stage of washing. Therefore, it is considered that high detergency can be obtained.

In the polyoxyethylene fatty acid alkyl ester, the narrow ratio showing the distribution ratio of the compounds (ethylene oxide adducts) having different repeating numbers of oxyethylene groups is preferably 20% by mass or more. The upper limit of the narrow rate is preferably substantially 80% by mass or less. The narrow rate is more preferably 25 to 50% by mass, and further preferably 25 to 45% by mass from the viewpoint of further improving storage stability and solubility in water.
The higher the narrow rate, the easier it is to obtain good detergency. Further, when the narrow rate is 20% by mass or more, and particularly 25% by mass or more, it is easy to obtain a detergent having a small amount of raw material odor derived from the compound (e1). This is because the compound (e1) having a high narrow ratio has a small amount of the fatty acid alkyl ester as the raw material and the ethylene oxide adduct having s of 1 or 2. From the viewpoint of obtaining a detergent with a low raw material odor, the total content of the fatty acid alkyl ester and the ethylene oxide adduct having s of 1 or 2 is 0.5 with respect to the total amount of the polyoxyethylene fatty acid alkyl ester. It is preferably at most% by mass, more preferably at most 0.2% by mass.

  The “narrow ratio” of the polyoxyethylene fatty acid alkyl ester is represented by the following formula (S), and indicates the distribution ratio of the ethylene oxide adduct having different numbers of repeating oxyethylene groups.

In the above formula (S), p _max represents the number of repeating oxyethylene groups in the ethylene oxide adduct which is most abundant in the ethylene oxide adduct. i represents the number of repeating oxyethylene groups. Yi represents the ratio (% by mass) of the ethylene oxide adducts in which the number of repeating oxyethylene groups is i, which is present in all the ethylene oxide adducts.
The narrow rate can be controlled by, for example, a method for producing a polyoxyethylene fatty acid alkyl ester. Such a production method is not particularly limited, and examples thereof include a method of addition-polymerizing ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (see JP-A-2000-144179).

As the component (E), any one type may be used alone, or two or more types may be used in combination.
As the component (E), the compound (e1) is preferable. Further, as the component (E), it is preferable to use the compound (e1) and the compound (e2) together. In this case, the mass ratio of the content of the compound (e1) to the content of the compound (e2) [the mass ratio represented by the compound (e1) / the compound (e2)] is preferably 0.1 to 30, 0.5-20 is more preferable, and 1-10 is still more preferable. When the mass ratio represented by the compound (e1) / the compound (e2) is in the above-mentioned preferred range, the cleaning power and the appearance stability of the liquid detergent are more likely to be enhanced.

  When the liquid detergent of the present invention contains the component (E), the content of the component (E) is preferably more than 0 mass% and not more than 70 mass% with respect to the total mass of the liquid detergent, and is 0.5 to. 70 mass% is more preferable, 5 to 50 mass% is further preferable, and 20 to 40 mass% is particularly preferable. If it is at least the above lower limit, the cleaning power of the liquid detergent will be more likely to be improved, and if it is at most the above upper limit, the appearance stability of the liquid detergent will be more easily enhanced.

  When the liquid detergent of the present invention contains the component (E), it is represented by a mass ratio of the content of the component (E) to the content of the component (A) (the component (E) / the component (A)). The mass ratio) is preferably 0.1 to 10, more preferably 0.5 to 5, and further preferably 1 to 3. When the mass ratio represented by the component (E) / the component (A) is within the above-mentioned preferred range, the cleaning power and the appearance stability of the liquid detergent can be more easily enhanced.

  Examples of the cationic surfactant include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl benzyl dimethyl ammonium salt, alkyl pyridinium salt and the like.

  Examples of the amphoteric surfactant include alkylbetaine type, alkylamidobetaine type, imidazoline type, alkylaminosulfonic acid type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amideamino acid type, phosphoric acid type and the like. Is mentioned.

  In the liquid detergent of the present invention, the total content of surfactants is preferably 1 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 65% by mass, based on the total mass of the liquid detergent. 30-60 mass% is especially preferable, and 40-55 mass% is the most preferable.

The liquid cleaning agent of the present invention preferably contains a water-miscible organic solvent from the viewpoints of improving coating cleaning performance, lowering viscosity and improving usability.
Examples of the water-miscible organic solvent include alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol, glycols such as propylene glycol, butylene glycol and hexylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol, Polyglycols such as polyethylene glycol and dipropylene glycol having a weight average molecular weight of about 200 to 1,000, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), alkyl ethers such as diethylene glycol dimethyl ether, etc. may be mentioned.
Among these, ethanol, propylene glycol, polyethylene glycol having a weight average molecular weight of about 200 to 1,000, and diethylene glycol monobutyl ether (butyl carbitol) are used because of their low odor, availability, and fluidity of the liquid detergent. Is preferred.
As the water-miscible organic solvent, 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 a water-miscible organic solvent, the content of the water-miscible organic solvent is preferably 0.1 to 15 mass% with respect to the total mass of the liquid detergent.
In the present invention, the water-miscible organic solvent means an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.

Examples of the viscosity reducer and the solubilizer include aromatic sulfonic acids and salts thereof, such as toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid and salts thereof.
Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, and alkanolamine salt.
These aromatic sulfonic acids or salts thereof may be used alone or in combination of two or more.
When the liquid detergent of the present invention contains a viscosity reducing agent and a solubilizing agent, the content of the viscosity reducing agent and the solubilizing agent is preferably 0.01 to 15 mass% with respect to the total weight of the liquid detergent. .

Examples of the alkaline agent include monoethanolamine, diethanolamine, triethanolamine and the like. As the alkaline agent, 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 an alkaline agent, the content of the alkaline agent is preferably 0.5 to 5 mass% with respect to the total weight of the liquid detergent.

The antioxidant is not particularly limited, but a phenolic antioxidant is preferable because of its good detergency and compounding stability, and a monophenolic antioxidant such as dibutylhydroxytoluene or butylhydroxyanisole, 2 , 2'-methylenebis (4-methyl-6-t-butylphenol and other bisphenol antioxidants, dl-α-tocopherol and other polymeric phenolic antioxidants are more preferred, monophenol antioxidants and high A molecular type antioxidant is more preferable.
Among the monophenol antioxidants, dibutyl hydroxytoluene is particularly preferable. Among the polymeric phenolic antioxidants, dl-α-tocopherol is particularly preferable.
As the antioxidant, 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 an antioxidant, the compounding amount of the antioxidant is preferably 0.01 to 2% by mass based on the total mass of the liquid detergent composition.

  As the antiseptic, for example, Rohm and Haas Co .: trade name Caison CG may be contained in an amount of, for example, 0.001 to 1% by mass.

As an enzyme stabilizer (however, the components (B) and (C) are not included), boric acid, borax, formic acid or a salt thereof, and calcium salts such as calcium chloride and calcium sulfate are contained in an amount of 0 to 2% by mass. May be.
Silicone such as dimethyl silicone, polyether-modified silicone and amino-modified silicone may be contained in an amount of 0 to 5 mass% for the purpose of improving the texture.
For the purpose of improving whiteness of white clothing, a fluorescent whitening agent such as distyryl biphenyl type may be contained in an amount of 0 to 1% by mass.
A dye transfer inhibitor and a recontamination inhibitor such as polyvinylpyrrolidone and carboxymethyl cellulose may be contained in an amount of 0 to 2% by mass for the purpose of preventing recontamination.
You may also contain a pearlescent agent, a soil release agent, etc.

A flavoring agent, a coloring agent, an emulsifying agent, an extract such as a natural product, or the like may be contained for the purpose of improving the added value of the product.
As a typical flavoring agent, the fragrance compositions A, B, C and D described in Tables 11 to 18 of JP-A-2002-146399 can be used. The content of the flavoring agent is preferably 0.1 to 1 mass% with respect to the total mass of the liquid detergent, for example.
As the colorant, general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Turquoise P-GR (all are trade names) Is mentioned. The content of the colorant is preferably about 0.00005 to 0.005 mass% with respect to the total mass of the liquid detergent.
Examples of the emulsifying agent include polystyrene emulsions and polyvinyl acetate emulsions. Usually, emulsions having a solid content of 30 to 50 mass% are preferably used. Specific examples thereof include polystyrene emulsion (manufactured by Saiden Chemical Co., Ltd .: trade name Cybinol RPX-196 PE-3, solid content 40% by mass). The content of the emulsifying agent is preferably 0.01 to 0.5 mass% with respect to the total mass of the liquid detergent, for example.

Examples of the extract of natural products include Inenju, Uchiha, Echinacea, Scutellaria, Yellowfin, Coptis, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Caigai, Kei, Bayesque, Honoki, Burdock, Comfrey, Jasho, Waremoko, Peony, ginger, goldenrod, sambucus, sage, mistletoe, prickly pear, thyme, rapeseed, clove, citrus unshiu, tea tree, barberry, dokudami, nanten, nyukou, yoragusa, shirogaya, bow-fuu, netherlands burdock, hops, honpe, honpaku, honpaku , Murasaki tagayasan, yamahakka, halibut, yamajizo, eucalyptus, lavender, rose, rosemary, balun, cedar, giant balsam tree Ringworm, kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, plant extracts, such as St. John's Wort.
The blending amount of the extract such as a natural product is preferably about 0 to 0.5 mass% with respect to the total mass of the liquid detergent.

Examples of the pH adjuster include sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and ammonia. Among these, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid, sodium hydroxide, and alkanolamine are more preferable, because the stability of the liquid detergent over time is easily enhanced.
As the pH adjuster, one type may be used alone, or two or more types may be used in combination.

4-9 are preferable and, as for pH at 25 degreeC of the liquid detergent of this invention, 6-9 are more preferable. When the pH is within the above-mentioned preferred range, the appearance stability of the liquid detergent tends to be favorably maintained.
The pH of the liquid detergent of the present invention at 25 ° C. is a value measured by adjusting the sample to 25 ° C. and using a pH meter (for example, a product name “HM-30G” manufactured by Toa DKK Co., Ltd. is used). Indicates.

The liquid detergent of the present invention has a viscosity at 25 ° C of preferably 10 to 300 mPa · s, more preferably 25 to 300 mPa · s. When the viscosity is within the above-mentioned preferred range, it becomes easy to measure the liquid detergent with a measuring cap or the like. In addition, when used for application cleaning, it becomes easy to apply the liquid cleaning agent to textile products and the like.
The viscosity of the liquid detergent of the present invention at 25 ° C is a value measured by using a B-type viscometer (manufactured by TOKIMEC) after adjusting the sample to 25 ° C (example of measurement conditions: rotor No. .2, the rotation speed is 60 rpm, and the viscosity 1 minute after the start of rotation is measured).

  The liquid detergent of the present invention is manufactured by a conventionally known manufacturing method. Examples of the method for producing the liquid detergent include a method in which components (A) to (D) and, if necessary, optional components are added to water and then mixed.

  The liquid detergent of the present invention can be stored in a commonly used container. As the container, a nozzle type container or a medium stopper type container having a measuring cap, a squeeze container or a pump container having an automatic measuring mechanism or a simple measuring mechanism, a trigger container or a squeeze container for spraying or foaming a liquid, Examples thereof include an application container having an application surface for applying the liquid and a refill container (pouch, thin-walled bottle, refill bottle, etc.).

(How to use liquid cleaner)
The method of using the liquid detergent of the present invention includes, for example, a method of adding the liquid detergent to water together with an article to be washed at the time of washing, a method of previously dissolving in water and immersing the article to be washed, a liquid detergent. Examples of the method include a method of applying it to the article to be washed, allowing it to stand for a certain period of time, and then performing normal washing.

As described above, the liquid detergent of the present invention contains the components (A) to (D), and the components (B) and (C) have a specific mass ratio. Excellent in stability, enzyme stability and appearance stability.
In the liquid detergent of the present invention, the enzyme stability is enhanced by using the component (B) and the component (C) together. Although the details of the reason are not clear, the nitrogen atom of the component (B) has a cationic property and is adsorbed on the fiber surface of the laundry. At this time, the nitrogen atom of the component (B) also interacts with the anionic surfactant and acts so as to suppress enzyme denaturation by the anionic surfactant. Further, the component (C) is adsorbed on the surface of the enzyme and acts so as to protect the structure of the enzyme. Therefore, it is presumed that a liquid detergent excellent in enzyme stability can be obtained even if it contains an anionic surfactant.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In this example, "%" indicates "mass%" unless otherwise specified.
The raw materials used in this example are as follows.
In addition, Examples 7 and 8 are reference examples.

<A component>
A-1: Sodium polyoxyethylene alkyl ether sulfate (AES). A compound represented by the following general formula (a1-1), wherein R ⁵¹ = a straight-chain alkyl group having 12 to 14 carbon atoms, j = 1.0, and M = sodium. However, in the formula (a1-1), EO is an ethyleneoxy group, and j is the average number of repetitions of EO. A-1 was synthesized as follows.
_{^{R 51 -O- (EO) j -SO}} 3 M ··· (a1-1)

<< Synthesis Example >> Synthesis of A-1 400 g of a product name CO1270 alcohol manufactured by P & G Co. (a mixture of an alcohol having 12 carbon atoms and an alcohol having 14 carbon atoms in a mass ratio of 75/25) as a raw material alcohol in an autoclave having a capacity of 4 L. Then, 0.8 g of potassium hydroxide was charged as a reaction catalyst, the inside of the autoclave was replaced with nitrogen, and then the temperature was raised with stirring. Subsequently, while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted to obtain an alcohol ethoxylate.
Gas chromatograph mass spectrometer: GC-5890 manufactured by Hewlett-Packard, detector: hydrogen flame ionization type detector (FID), column: Ultra-1 (manufactured by HP, L25m × φ0.2 mm × T0.11 μm) ) And was used, the obtained alcohol ethoxylate had an average addition mole number of ethylene oxide of 1.0. Moreover, the compound to which ethylene oxide was not added was 43 mass% with respect to the total mass of the obtained alcohol ethoxylates.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after substituting with nitrogen, 96 g of liquid anhydrous sulfuric acid (sulfane) was slowly added dropwise while keeping the reaction temperature at 40 ° C. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Then, A-1 was obtained by neutralizing this with an aqueous sodium hydroxide solution.

A-2: Sodium linear alkylbenzene sulfonate (LAS), manufactured by Lion Corporation, trade name "Lipon LH-200".
A-3: Monoethanolamine salt of polyoxyalkylene alkyl ether sulfate (AEPS). The one synthesized as follows.

<< Synthesis Example >> Synthesis of A-3 In a autoclave equipped with a stirrer, a temperature controller and an automatic introduction device, a linear primary alcohol having 12 carbon atoms [manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 1-dodecanol ( A molecular weight of 186.33), a purity of> 99%] of 640 g and KOH of 1.0 g were charged and dehydration was performed at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the atmosphere was replaced with nitrogen, the temperature was raised to 120 ° C., and then 199 g of propane-1,2-diyl oxide was charged. Then, after addition reaction and aging at 120 ° C., the temperature was raised to 145 ° C. and 303 g of ethylene oxide was charged. Then, after carrying out an addition reaction and aging at 145 ° C., it was cooled to 80 ° C. and unreacted ethylene oxide was removed at 4.0 kPa. After removing unreacted ethylene oxide, 1.0 g of acetic acid was added into the autoclave, stirred at 80 ° C. for 30 minutes and then withdrawn, the average addition mole number of propylene oxide was 1.0, and the average addition mole number of ethylene oxide was To obtain an alkoxylate having a value of 2.0.
The resulting alkoxylate was sulphated using SO ₃ gas in a falling thin film reactor. A-3 was obtained by neutralizing the obtained sulfated substance with monoethanolamine.

<B component>
B-1: Ethylene oxide adduct of polyethyleneimine, manufactured by BASF, trade name "Sokalan HP20". A compound represented by the above formula (II-a), wherein R ²² is an ethylene group and m is 20.
<Comparison component of B'component and B component>
B'-1: Polyethyleneimine, manufactured by BASF, trade name "Lupazole P". (Weight average molecular weight about 750000).
B'-2: Polyethylene glycol # 10000 (weight average molecular weight 10000), manufactured by Kanto Chemical Co., Inc.

<C component>
C-1: Sodium lactate, manufactured by Kanto Chemical Co., Inc., trade name "sodium lactate".

<D component>
D-1: Alcalase 2.5L, manufactured by Novozymes.
D-2: Coronase 48L, manufactured by Novozymes.

<E component>
E-1: Fatty acid methyl ester ethoxylate (C12 to C14 of fatty acid, average number of moles of EO added 15), in the general formula (IV-1), R ⁴¹ = alkyl group having 11 carbons and having 13 carbons Alkyl group, R ⁴² = methyl group, s = 15, t = 0, u = 0. It was synthesized by the following synthesis method.

<< Synthesis Example >> Synthesis of E-1 Synthesis was carried out according to the synthesis method described in JP-A-2000-144179.
Composition alumina hydroxide magnesium is _{2.5MgO · Al 2 O 3 · zH} 2 O ( Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) for 1 hour at 600 ° C., and calcined in a nitrogen atmosphere Thus, a calcined alumina hydroxide / magnesium (unmodified) catalyst was obtained. 2.2 g of calcined alumina / magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester were charged into a 4 L autoclave, and then autoclaved. The catalyst was reformed inside. Next, after replacing the inside of the autoclave with nitrogen, 1052 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa, and the reaction was performed while stirring.
The obtained reaction liquid was cooled to 80 ° C., 159 g of water and 5 g of each of activated clay and diatomaceous earth as filter aids were added and mixed, and then the catalyst was separated by filtration to obtain E-1. The narrow rate of E-1 was 30 mass%.

E-2: Natural alcohol added with 15 mol of ethylene oxide. In the general formula (IV-2), R ⁴³ = alkyl group having 12 carbon atoms and alkyl group having 14 carbon atoms, v = 15, w = 0, y = 0. It was synthesized by the following synthesis method.

<< Synthesis Example >> Synthesis of E-2 224.4 g of CO-1214 (trade name) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of 30 mass% NaOH aqueous solution were charged in a pressure resistant reaction vessel, and the reaction vessel The inside was replaced with nitrogen. Next, after dehydrating at a temperature of 100 ° C. and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160 ° C. Then, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added through a blowing tube while controlling the addition rate so that the reaction temperature did not exceed 180 ° C.
After the addition of ethylene oxide was completed, the mixture was aged at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added and neutralized so that the pH of a 1% by mass aqueous solution of the reaction product was about 7, to obtain E-2. It was

E-3: Block addition of 8 moles of ethylene oxide, 2 moles of propylene oxide, and 8 moles of ethylene oxide to natural alcohol (mass ratio of 12 carbons / 14 carbons = 7/3) What I did. In the general formula (IV-2), R ⁴³ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 8, w = 2, y = 8.
E-4: A secondary alcohol having 12 carbon atoms and a secondary alcohol having 14 carbon atoms, to which 7 mol of ethylene oxide has been added. Product name "Softanol 70", manufactured by Nippon Shokubai Co., Ltd. In the general formula (IV-2), R ⁴³ = a secondary alkyl group having 12 carbon atoms and a secondary alkyl group having 14 carbon atoms, v = 7, w = 0, y = 0.

<Arbitrary ingredients>
MEA: monoethanolamine (alkaline agent), trade name "monoethanolamine", manufactured by Nippon Shokubai Co., Ltd.
BHT: dibutylhydroxytoluene (antioxidant), trade name "SUMILLZER BHT-R", manufactured by Sumitomo Chemical Co., Ltd.
Ethanol: Water-miscible organic solvent, trade name "Specific alcohol 95 degree synthesis", manufactured by Nippon Alcohol Sales Co., Ltd.
Palm fatty acid: Defoaming agent, trade name "Palm fatty acid", NOF Corporation.
Calcium chloride: enzyme stabilizer, manufactured by Kanto Chemical Co., Inc., trade name "Calcium chloride (special grade)".
Fragrance: Fragrance, flavor composition A described in Tables 11 to 18 of JP-A-2002-146399.
Colorant: Colorant, trade name "Green No. 3", manufactured by Konami Kasei Co., Ltd.

(Examples 1-10, Comparative Examples 1-7)
[Manufacture of liquid detergent for clothing]
According to the compositions shown in Tables 1 and 2, components (A) to (D) and optional components were added to water and mixed to obtain liquid cleaning agents of Examples 1 to 10 and Comparative Examples 4 to 5.
Further, liquid cleaning agents of Comparative Examples 1 to 3 were obtained in the same manner as in Example 1 except that any of the components (A) to (C) was not added to water. Liquid cleaning agents of Comparative Examples 6 to 7 were obtained in the same manner as in Example 1 except that the component (B ′) was used instead of the component (B).
Tables 1 and 2 show the compositions (blending components, content (mass%)) of the obtained liquid detergents of each example.
In the table, when there is a blank compounding ingredient, the compounding ingredient is not compounded.
In the table, the content of the blending component is a pure content conversion amount. However, the component (D) indicates the content as an enzyme preparation.
“Balance” indicating the content of purified water means the balance added so that the total blending amount (mass%) of all blending components contained in the liquid detergent is 100 mass%.
In the table, “B / C ratio” of Comparative Examples 6 to 7 indicates the mass ratio of the component (B ′) to the component (C).

  With respect to the liquid detergent of each example, the anti-redeposition effect, the enzyme stability (enzyme activity residual rate), and the appearance stability were evaluated as follows. The evaluation results are shown in Tables 1 and 2.

[Evaluation of recontamination prevention effect]
The liquid cleaning agent of each example was used to perform a washing treatment in which the following washing step, rinsing step, and drying step were repeated three times in this order.

Washing process:
As the articles to be washed, the following cotton cloth, polyester (PE) cloth, wet artificially contaminated cloth, and skin shirt were used.
Cotton cloth: 5 pieces of cotton knitted cloth (manufactured by Tanigami Shoten Co., Ltd.) 5 cm × 5 cm as the redeposition determination cloth.
Polyester (PE) cloth: 5 pieces of polyester tropical (manufactured by Tanigami Shoten) 5 cm × 5 cm as the redeposition determination cloth.
Wet artificial stain cloth: A stain cloth made by the Foundation of Laundry Science Association (28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene, cholesterol) Twenty sheets of 1.6%, 7.0% gelatin, 29.8% mud, 0.5% carbon black (mass ratio) stained cloth).
Skin shirt: A skin shirt (LL size, manufactured by DVD) that is finely cut (about 3 cm × 3 cm).
In a Terg-o-meter (manufactured by UNITED STATES TESTING), 900 mL of 3 ° DH hard water at 25 ° C was placed, 0.6 g of a liquid detergent was added thereto, and then the article to be washed was placed. Thereafter, 3 ° DH hard water was added to adjust the bath ratio to 20 times, and washing was performed at 120 rpm and 25 ° C. for 10 minutes.

Rinsing process:
After washing the washed object for 1 minute, 900 mL of 3 ° DH hard water at 25 ° C was added, and rinsed at 120 rpm and 25 ° C for 3 minutes. This operation (dehydration, rinsing) was repeated twice. The second time, rinsing was performed by adding a predetermined amount of the softening agent to 900 mL of 3 ° DH hard water at 25 ° C. Room-dried Soflan (manufactured by Lion Corporation) was used as a softening agent.

Drying process:
After the rinsed article was dehydrated for 1 minute, only the redeposition determination cloth (cotton cloth, PE cloth) was taken out, sandwiched between filter papers, and dried with an iron.

A reflectance meter (spectral color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the reflectance (Z value) of the redeposition determination cloth before and after the washing treatment, and ΔZ was calculated from the following equation.
ΔZ = (Z value before washing treatment) − (Z value after washing treatment)
An average value of 5 sheets was obtained for ΔZ in each of the redeposition determination cloths of the cotton cloth and the PE cloth. Then, the effect of preventing redeposition on cotton cloth and PE cloth by the liquid detergent was evaluated according to the following criteria using the average value as an index. In the criteria below, ⊚ and ∘ were passed. The evaluation results are shown in Tables 1 and 2.

<Criteria for cotton cloth>
⊚: ΔZ is less than 5.
◯: ΔZ is 5 or more and less than 7.
Δ: ΔZ is 7 or more and less than 9.
X: ΔZ is 9 or more.

<Judgment criteria for PE cloth>
⊚: ΔZ is less than 3.
◯: ΔZ is 3 or more and less than 4.
Δ: ΔZ is 4 or more and less than 5.
X: ΔZ is 5 or more.

[Evaluation of enzyme stability (enzyme activity residual rate)]
After the liquid detergent of each example was produced, it was stored at 37 ° C. and 4 ° C. for 4 weeks. The protease activity shown below was measured for the liquid detergent stored at 37 ° C. for 4 weeks (stored at 37 ° C.) and the liquid detergent stored at 4 ° C. for 4 weeks (stored at 4 ° C.).

Measurement of protease activity:
Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free / Calbiochem (registered trademark)) was dissolved in 1N sodium hydroxide (1 mol / L sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Inc.) to adjust the pH to 10. 5, and diluted with a 0.05 M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Inc.) aqueous solution so that the concentration of milk casein was 0.6%, and used as a protease substrate.
A solution obtained by diluting 1 g of the obtained liquid detergent with 25 times of calcium chloride (calcium chloride (special grade), manufactured by Kanto Chemical Co., Inc.) 3 ° DH hard water was used as a sample solution.
5 g of the above-mentioned protease substrate was added to 1 g of the sample solution, and the mixture was stirred for 10 seconds with a vortex mixer, and then allowed to stand at 37 ° C. for 30 minutes to proceed the enzyme reaction. Then, 5 g of a 0.44 M aqueous solution of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Inc.) as an enzyme reaction terminator was added to the solution, and the mixture was stirred with a vortex mixer for 10 seconds. Then, this solution was allowed to stand at 20 ° C. for 30 minutes, the unreacted substrate that precipitated was removed with a 0.45 μm filter, and the filtrate was collected.
The absorbance (absorbance A) of the recovered filtrate at a wavelength of 275 nm was measured using an ultraviolet-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation. The larger the absorbance A, the larger the amount of tyrosine (produced by the protease decomposing the protease substrate) present in the filtrate.
To remove the influence of absorption other than the target component, separately add 5 g of TCA, which is an enzyme reaction terminator, to 1 g of each sample solution, stir with a vortex mixer for 10 seconds, then add 5 g of protease substrate, and add 10 g with a vortex mixer. The mixture was stirred for 2 seconds, removed with a 0.45 μm filter, and the filtrate was collected. Then, the absorbance (absorbance B) of the filtrate at a wavelength of 275 nm was measured using UV-160.

From the above-mentioned measurement results of protease activity, the protease activity residual rate (%) was calculated by the following formula.
In addition, the absorbance value at 275 nm of each sample substituted into the following equation was used by dividing the simultaneously measured absorbance value at 600 nm in order to exclude scattered light such as bubbles from the absorbance.
Protease activity residual ratio = (Absorbance A of 37 ° C. preserved product-Absorbance B of 37 ° C. preserved product) / (Absorbance of 4 ° C. preserved product A-4 ° C. preserved product B) × 100

The enzyme stability was evaluated based on the following criteria using the protease activity residual rate (%) as an index, and ⊚, ◯ and Δ were regarded as passing.
A: 80% or more.
◯: 70% or more and less than 80%.
Δ: 60% or more and less than 70%
X: Less than 60%.

[Evaluation method of appearance stability]
30 mL of the liquid cleaning agent was taken in a cylindrical glass bottle, and the lid was closed and sealed. In this state, it was left in a constant temperature bath at 40 ° C. and stored for 1 month.
Then, it was taken out from the constant temperature bath, the transparency uniformity and fluidity of the liquid detergent were visually observed, and the appearance stability of the liquid detergent was evaluated based on the following criteria. ○ and △ were passed.
◯: Transparent and uniform, showing fluidity.
Δ: A precipitate was observed at the bottom of the glass bottle, but the precipitate disappeared (dissolved) by gently shaking the glass bottle.
X: A precipitate was observed at the bottom of the glass bottle, and the precipitate did not disappear even if the glass bottle was shaken lightly. Alternatively, the liquid detergent has solidified.

From the results shown in Tables 1 and 2, it was confirmed that the liquid detergents of Examples 1 to 10 to which the present invention was applied were excellent in anti-soil redeposition effect, enzyme stability, and appearance stability.
On the other hand, the liquid detergent containing no component (B) or the component (C) (Comparative Examples 1 and 2), and the liquid detergent containing the component (B′-2) in place of the component (B) (Comparative Example 7). ), Enzyme stability was not sufficiently obtained. The liquid detergent containing no component (A) (Comparative Example 3) did not have a sufficient anti-soil redeposition effect. Liquid detergents (Comparative Examples 4 and 5) whose B / C ratio range did not satisfy the range of the present invention did not have sufficient appearance stability. The liquid detergent (Comparative Example 6) in which the component (B′-1) was used instead of the component (B) could not sufficiently obtain the redeposition preventing effect and the appearance stability.
From the above results, it was confirmed that the liquid detergent to which the present invention is applied is superior in the anti-redeposition effect, the enzyme stability, and the appearance stability.

Claims (1)

(A) component: a non-soap anionic surfactant,
Component (B): at least one selected from an alkylene oxide adduct of polyalkyleneimine and an alkylene oxide adduct of polyalkyleneamine,
Component (C): at least one selected from carboxylic acids represented by the following general formula (I) and salts thereof;
(D) component: enzyme
(E) component: containing a nonionic surfactant ,
The total content of the surfactant is 30 to 80% by mass based on the total mass of the liquid laundry detergent,
The content of water is 10 to 38.9 mass% with respect to the total mass of the liquid detergent for clothing,
The content of the component (E) is 20 to 50 mass% with respect to the total mass of the liquid detergent for clothes,
The mass ratio represented by the component (E) / the component (A) is 1 to 5,
A liquid detergent for clothing, characterized in that a mass ratio represented by the component (B) / the component (C) is 0.1 to 20.
X-R ¹ -COOH (I)
However, in formula (I), R ¹ is a divalent hydrocarbon group having 1 to 4 carbon atoms, or an arylene group, and X is —H, —OH, —CH ₃ , or —COOH.