JP2018002824A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition which is excellent in film formation preventive property and is also excellent in washing performance.SOLUTION: A liquid detergent composition contains a nonionic surface active agent (A), an alkylene oxide adduct (B) of polyalkyleneamine and a compound (C) represented by expression (I): RO-(EO)-H. A mass ratio represented by component (A)/(component (B)+component (C)) is preferably 20 or less, and the liquid detergent composition preferably contains an anionic surface active agent (D) having 10 to 20 carbon atoms excluding fatty acid salt.SELECTED DRAWING: None

Description

  The present invention relates to a liquid detergent composition.

  It is known that a liquid detergent composition for textile products such as clothing (hereinafter sometimes referred to as a liquid detergent) is blended with a nonionic surfactant as a detergent base for the purpose of obtaining good cleaning performance. ing. When the blending amount of the nonionic surfactant in the liquid detergent is increased in order to further improve the cleaning performance, a film is easily formed on the liquid detergent. Such a film is particularly easily formed when the liquid detergent is left in an open system for a long time. For example, when a laundry process is performed using a reservation function of a washing machine, the liquid cleaning agent is left at the inlet of the washing tub for a long time. In this case, a film is formed on the left liquid cleaning agent, causing a problem that a target amount of the liquid cleaning agent is difficult to be input into the washing tub or the input port is clogged. For this reason, in the liquid cleaning agent containing such a nonionic surfactant, compatibility between the cleaning performance and the film formation prevention performance is required.

As a conventional technique for preventing film formation of a liquid detergent, a method of adding a water-miscible organic solvent such as butyl carbitol is known. Since butyl carbitol has a peculiar odor, fragrances such as fragrances blended to impart a scent to liquid cleaning agents and objects to be washed are likely to be damaged, and the odor adheres to the objects to be washed. There is a problem.
With respect to such a problem, Patent Document 1 has two types of nonionic surfactants obtained by adding a specific amount of ethylene oxide to a hydrophobic group having a specific carbon number, and a specific mass average molecular weight. A liquid detergent composition containing polyethylene glycol and having a specific range of content and blending ratio of the two types of nonionic surfactants is described. According to the invention of Patent Document 1, it is possible to obtain a liquid detergent that is excellent in cleaning performance and hardly forms a film (excellent in film formation prevention).

Japanese Patent Laid-Open No. 2001-3100

However, in the invention of Patent Document 1, the film formation preventing property of the liquid detergent is not sufficient.
Then, this invention aims at the liquid detergent composition which is excellent in film formation prevention property, and is excellent also in cleaning performance.

The present invention has the following aspects.
[1] A liquid detergent composition comprising a nonionic surfactant (A), an alkylene oxide adduct (B) of a polyalkyleneamine, and a compound (C) represented by the following general formula (I).
R ¹ O— (EO) _n —H (I)
[In Formula (I), R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms, EO represents an oxyethylene group, and n represents a number of 1 to 30000 representing an average number of repeating oxyethylene groups. is there. ]
[2] The liquid detergent composition according to [1], wherein a mass ratio represented by the component (A) / (the component (B) + the component (C)) is 20 or less.
[3] The liquid detergent composition according to [1] or [2], further comprising an anionic surfactant (D) excluding a fatty acid salt having 10 to 20 carbon atoms.
[4] The liquid detergent composition according to any one of [1] to [3], further comprising water.
[5] The liquid detergent composition according to any one of [1] to [4], wherein the mass ratio represented by the component (C) / the component (B) is 50 or less.
[6] The liquid detergent composition according to any one of [1] to [5], wherein a mass ratio represented by the component (A) / the component (B) is 10 to 300.
[7] The liquid detergent composition according to any one of [1] to [6], wherein a mass ratio represented by the component (A) / the component (C) is 20 or less.

  According to the liquid detergent composition of the present invention, the film formation prevention property is excellent and the cleaning performance is also excellent.

(Liquid detergent composition)
The liquid detergent composition of the present invention is a composition containing the following components (A) to (C).

<(A) component>
The component (A) is a nonionic surfactant. The component (A) imparts cleaning performance to the liquid cleaning agent of the present invention.
Examples of the component (A) include a polyoxyalkylene type nonionic surfactant represented by the following general formula (a1) and a polyoxyalkylene type nonionic surfactant represented by the following general formula (a2).
^{_{R 11 -X - [(EO)}} s / (PO) t] -R 12 ··· (a1)
[In the formula (a1), R ¹¹ represents a hydrocarbon group having 8 to 18 carbon atoms, X represents O, COO or CONH, R ¹² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number Represents 2 to 6 alkenyl groups. s represents the average number of repetitions of EO, and is a number from 6 to 20. t represents the average number of repetitions of PO and is a number from 0 to 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

In the formula (a1), R ¹¹ is preferably a hydrocarbon group having 10 to 18 carbon atoms because of good cleaning performance, and may be linear or branched. . Examples of the hydrocarbon group include those derived from raw materials such as primary or secondary higher alcohols, higher fatty acids, and higher fatty acid amides.
As the alkyl group for R ¹² , an alkyl group having 1 to 3 carbon atoms is preferable. The alkenyl group for R ¹² is preferably an alkenyl group having 2 to 3 carbon atoms. X is preferably O or COO.
In the formula (a1), when X is O, the component (A) is an alkyl ether type nonionic surfactant. When X is O, R ¹¹ is preferably a hydrocarbon group having 10 to 18 carbon atoms from the viewpoint of further improving the cleaning performance. R ¹¹ may have an unsaturated bond. Moreover, it is preferable that s is 10-20, and 14-18 are more preferable. R ¹² is preferably a hydrogen atom.

In the formula (a1), when X is COO, the component (A) is a fatty acid ester type nonionic surfactant. When X is COO, R ¹¹ is preferably a hydrocarbon group having 9 to 18 carbon atoms, and more preferably a hydrocarbon group having 11 to 18 carbon atoms, from the viewpoint of further improving the cleaning performance. R ¹¹ may have an unsaturated bond. R ¹² is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

In said formula (a1), s is a number of 6-20, 10-18 are preferable and 14-18 are more preferable. When s is within the above range, the cleaning performance is further improved.
In said formula (a1), t is a number of 0-6, 0-3 are preferable and 0 is more preferable. If t is within the above range, the storage stability at high temperatures tends to be good.
In [(EO) _s / (PO) _t ] in the formula (a1), EO and PO may be mixed and arranged. When EO and PO are mixed and arranged, they may be in a random shape or a block shape.

In the component (A) represented by the formula (a1), the distribution of the EO repeat number s (that is, the average added mole number of ethylene oxide) or the PO repeat number t (that is, the average added mole number of propylene oxide) is As long as it has the effect of the present invention, it is not particularly limited. The added mole number distribution varies depending on the reaction method in producing the component (A). For example, the addition mole number distribution of ethylene oxide or propylene oxide is obtained by using ethylene oxide or propylene oxide as a hydrocarbon raw material (primary or secondary higher alcohol) using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. , Higher fatty acids, higher fatty acid amides, etc.) tend to have a relatively wide distribution. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to the hydrocarbon group raw material using a catalyst, the distribution tends to be relatively narrow.

  The component (A) represented by the formula (a1) may be a commercially available product. Specific examples of commercially available products include Diadol (registered trademark) manufactured by Mitsubishi Chemical Corporation (trade name, C13 and C indicate the number of carbon atoms; the same applies hereinafter), Neodol (registered trademark) manufactured by Shell (trade name). , A mixture of C12 and C13), an alcohol such as Sasol (registered trademark) 23 (trade name, a mixture of C12 and C13) manufactured by Sasol, or the like, 12 mol equivalent or 15 mol equivalent ethylene oxide was added. A product obtained by adding 12 moles or 15 moles of ethylene oxide to a natural alcohol such as CO-1214 (trade name) or CO-1270 (trade name) manufactured by P &G; A product obtained by adding 15 moles of ethylene oxide to secondary alcohol (Sophanol (registered trademark) 150 (trade name) manufactured by Nippon Shokubai Co., Ltd.) And the like. Furthermore, to the palm fatty acid methyl (lauric acid / myristic acid = 8/2), using an alkoxylation catalyst, 15 mol equivalent of ethylene oxide was added (polyoxyethylene palm fatty acid methyl ester (EO 15 mol)) ).

^{_{R 13 -O - [(EO)}} p / (PO) q] - (EO) r -H ··· (a2)
[In the formula (a2), R ¹³ represents a hydrocarbon group having 8 to 18 carbon atoms. p represents the average number of repetitions of EO, q represents the average number of repetitions of PO, r represents the average number of repetitions of EO, p, q, r are p ≧ 1, r ≧ 7, 0 <q ≦ 3 , P + r = 8-20. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]
In the formula ^{(a2), R 13} is a hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl or alkenyl group having 8 to 18 carbon atoms. These may be linear or branched.

In the formula (a2), the ratio of EO and PO is preferably 0.1 to 0.5, and preferably 0.1 to 0.3, as expressed by q / (p + r). More preferred. When the ratio represented by q / (p + r) is equal to or greater than the lower limit, it is easy to optimize the foaming of the liquid detergent. When it is not more than the above upper limit, an appropriate viscosity is easily obtained, and gelation is easily suppressed.
EO and PO in [(EO) _p / (PO) _q ] may be mixed and arranged. In that case, EO and PO may be random or may be block.

The component (A) represented by the formula (a2) can be produced by a known method. Specifically, after adding ethylene oxide and propylene oxide in this order to an alcohol having an R ¹³ hydrocarbon group derived from natural fats and oils, ethylene oxide and propylene oxide were mixed and added (random addition). Thereafter, it can be produced by adding ethylene oxide again.
When the component (A) represented by the formula (a2) is used, the liquid detergent can easily obtain an appropriate viscosity, and gelation is also suppressed. Moreover, foamability improves and biodegradability also becomes better.
(A) A component may be used individually by 1 type and may be used in combination of 2 or more type.

As the component (A), a nonionic surfactant represented by the formula (a1) is preferable from the viewpoint of improving the cleaning performance of the liquid detergent, and among them, polyoxyethylene alkyl ether and polyoxyethylene fatty acid alkyl ester are more preferable. preferable.
The content of the component (A) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 8 to 20% by mass with respect to the total mass of the liquid detergent. If content of (A) component is more than the said lower limit, it will be easy to improve cleaning performance, and if it is below the said lower limit, film formation prevention property will increase more.

<(B) component>
The component (B) is an alkylene oxide adduct of polyalkyleneamine. (B) By containing a component, the film formation preventive property of the liquid detergent of this invention improves.
As a component (B), the following (b1) component and (b2) component are mentioned, for example.

[(B1) component]
The component (b1) is an alkylene oxide adduct of polyalkyleneimine.
The polyalkylenimine as the component (b1) is represented by the following general formula (b1), for example.
^{_{NH 2 -R 21 - (NA-}} R 21) n2 -NH 2 ··· (b1)
In formula (b1), each R ²¹ independently represents an alkylene group having 2 to 6 carbon atoms, A represents a hydrogen atom or another polyamine chain by branching, and n2 is a number of 1 or more. . However, not all of the A are hydrogen atoms.
That is, the polyalkyleneimine represented by the formula (b1) has a branched polyamine chain in the structure.

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 can be obtained by polymerizing one or more of 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, 1,1-dimethylethyleneimine and the like.
As 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 the structure.

  The mass average molecular weight of the polyalkyleneimine is preferably 200 to 2000, more preferably 300 to 1500, still more preferably 400 to 1000, and particularly preferably 500 to 800.

  As polyalkyleneimine, those having 5 to 30 active hydrogens in one molecule are preferable, those having 7 to 25 are more preferable, and those having 10 to 20 are more preferable.

The component (b1) is obtained by adding an alkylene oxide to a polyalkyleneimine. As this method, for example, an alkylene oxide such as ethylene oxide is added to a polyalkyleneimine which is a starting material in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methylate at 100 to 180 ° C. 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. Ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.

Examples of the component (b1) include an ethylene oxide adduct of polyalkyleneimine, a propylene oxide adduct of polyalkyleneimine, and an ethylene oxide-propylene oxide adduct of polyalkyleneimine. In addition, 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 of ethylene oxide and propylene oxide to polyalkyleneimine (block shape, random shape). ) Is optional.
As the component (b1), 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 component (b1), an average of 5 to 40 alkylene oxides are preferably added to an active hydrogen atom of the polyalkyleneimine as a raw material, and an average of 10 to 30 alkylene oxides are added. Those are more preferred. That is, an average of 5 to 40 moles of alkylene oxide added is preferable per mole of active hydrogen of the polyalkyleneimine as a raw material, and an average of 10 to 30 moles of alkylene oxide is more preferable.

1000-80000 are preferable, as for the mass average molecular weight of (b1) component, 2000-50000 are more preferable, 5000-30000 are further more preferable, and 10000-20000 are especially preferable.
In addition, a mass average molecular weight shows the value which converted the value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent based on the calibration curve in PEG (polyethylene glycol).
Examples of the component (b1) include compounds represented by the formula (b1-a).

In formula (b1-a), R ²² is each 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, and more preferably 10 to 30.
As the component (b1), a synthetic product may be used, or a commercially available product may be used.
As a commercial item, the brand name "Sokalan HP20" by BASF, etc. are mentioned, for example.

<(B2) component>
The component (b2) is an alkylene oxide adduct of polyalkyleneamine represented by the following formula (b2).
NH ₂ (R ³¹ NH) ₁ H (b2)
In the formula (b2), 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 polyethyleneamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. These polyethyleneamines can be obtained by a known production method, for example, by reacting ammonia and ethylene dichloride.

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

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

  The component (b2) is obtained by adding alkylene oxide to polyalkyleneamine. This reaction can be carried out 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. Ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.

Examples of the component (b2) include an ethylene oxide adduct of polyalkyleneamine, a propylene oxide adduct of polyalkyleneamine, and an ethylene oxide-propylene oxide adduct of polyalkyleneamine.
The alkylene oxide adduct of polyalkyleneamine is preferably an ethylene oxide adduct of polyalkyleneamine or an ethylene oxide-propylene oxide adduct of polyalkyleneamine, more preferably an ethylene oxide adduct of polyalkyleneamine.

  As the component (b2), an average of 5 to 40 alkylene oxides is preferably added to one active hydrogen atom of the polyalkyleneamine as a raw material, and an average of 10 to 30 alkylene oxides are added. Those are more preferred. That is, an average of 5 to 40 moles of alkylene oxide added per mole of active hydrogen contained in the polyalkyleneamine as a raw material, and an average of 10 to 30 moles of alkylene oxide added is more preferable.

  (B2) As for the mass mean molecular weight of a component, 1000-80000 are preferable, 2000-50000 are more preferable, 5000-30000 are more preferable, 10000-20000 are especially preferable.

  As the component (B), the component (b1) is preferable. Among the components (b1), an ethylene oxide adduct of polyethyleneimine represented by the formula (b1-a) is particularly preferable.

(B) A component may be used individually by 1 type and may be used in combination of 2 or more type.
The content of the component (B) in the liquid detergent is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, and 0.8 to 3% by mass with respect to the total mass of the liquid detergent. Is more preferable.
When the content of the component (B) is equal to or higher than the lower limit, a liquid cleaning agent having excellent film formation preventing ability is easily obtained. Moreover, it becomes easy to maintain the freedom degree of the mixing | blending of another component as content of (B) component is below the said upper limit.

<(C) component>
The component (C) is a compound represented by the following general formula (I).
R ¹ O— (EO) _n —H (I)
[In Formula (I), R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms, EO represents an oxyethylene group, and n represents a number of 1 to 30000 representing an average number of repeating oxyethylene groups. is there. ]

In the formula (I), examples of the compound in which R ¹ is a hydrogen atom and n is 1 to 30000 include polyethylene glycol.
As the polyethylene glycol, those in which n in the formula (I) is 5 or more are preferable. Moreover, 200-1320000 are preferable, as for the mass average molecular weight of polyethyleneglycol, 200-5000 are more preferable, 200-2000 are more preferable, 200-1000 are especially preferable. Among these, polyethylene glycol having a mass average molecular weight of 1000 (n is 22 to 24) is particularly preferable. In addition, the mass average molecular weight of polyethylene glycol shows the value calculated based on the calibration curve in polyethylene glycol, the value measured by GPC (gel permeation chromatography) using methanol as a solvent.
In the formula (I), examples of the compound in which R ¹ is an alkyl group having 1 to 3 carbon atoms include glycol monoether, diglycol monoether, polyethylene glycol monoether, and the like. Among these, methoxypolyethylene glycol (having a mass average molecular weight of 1000) in which R ¹ is a methyl group and n is 22 to 24 is particularly preferable.
As the component (C), polyethylene glycol is preferable, and polyethylene glycol having a mass average molecular weight of 1000 is particularly preferable.
(C) A component may be used individually by 1 type and may be used in combination of 2 or more type.

  As content of (C) component in a liquid cleaning agent, 1-10 mass% is preferable with respect to the total mass of a liquid cleaning agent, 2-8 mass% is more preferable, 3-5 mass% is especially preferable. . If content of (C) component is more than the said lower limit, film formation prevention property will increase more. Moreover, if content of (C) component is below the said upper limit, the liquid stability of a liquid detergent will not fall easily.

In the liquid cleaning agent of the present invention, by using the component (B) and the component (C) in combination, the intermolecular interaction of the component (A) can be further prevented and the formation of the film can be efficiently suppressed. . As a result, the film formation preventing property of the liquid cleaning agent is enhanced.
The mass ratio (C) / (B) of the component (C) and the component (B) in the liquid detergent is preferably 50 or less, more preferably 1 to 30, and still more preferably 2 to 10. If (C) / (B) is 50 or less, the film formation preventing property tends to be better.
Moreover, 1-10 mass% is preferable with respect to the total mass of a liquid cleaning agent, and, as for the total amount of (B) component in a liquid cleaning agent, and (C) component, 3.5-6.5 mass% is more. preferable.

  Mass ratio of (A) component and the total amount of (B) component and (C) component in the liquid detergent of the present invention (that is, (A) component / ((B) component + (C) component)) In the following, A / (B + C) may be 20 or less, preferably 18 or less, more preferably 10 or less, and 6 or less. It is particularly preferred. Further, the lower limit value of A / (B + C) is preferably 2 or more, more preferably 4 or more, from the viewpoint of liquid stability. That is, A / (B + C) is preferably 2 to 20, more preferably 4 to 18, and still more preferably 4 to 10. When A / (B + C) is within the above range, the film formation preventing property is further enhanced.

  Further, the mass ratio of the component (A) and the component (B) in the liquid cleaning agent (that is, the mass ratio represented by the component (A) / (B) component, hereinafter may be referred to as A / B). Is preferably 10 to 300, more preferably 50 to 250, and still more preferably 100 to 200. When A / B is within the above range, the film formation preventing property tends to be better.

  Furthermore, the mass ratio of the component (A) and the component (C) in the liquid detergent (that is, the mass ratio represented by the component (A) / (C). Hereinafter, it may be referred to as A / C). Is preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less. Further, the lower limit of A / C is preferably 3 or more, more preferably 5 or more, from the viewpoint of liquid stability. That is, 3-20 are preferable, as for A / C, 5-18 are more preferable, and 5-15 are more preferable. When A / C is within the above range, the film formation preventing property is further enhanced.

<(D) component>
Component (D) is an anionic surfactant excluding a fatty acid salt having 10 to 20 carbon atoms (that is, a non-soap anionic surfactant). When the liquid cleaning agent of the present invention contains the component (D), the cleaning performance and the film formation preventing property are further improved.
The component (D) can be appropriately selected from known non-soap anionic surfactants.
The component (D) preferably used in the present invention includes, for example, a linear alkylbenzene sulfonic acid or a salt thereof; an α-olefin sulfonate; a linear or branched alkyl sulfate ester salt; an alkyl ether sulfate ester or an alkenyl ether. Examples thereof include sulfate ester salts; alkane sulfonates having alkyl groups; α-sulfo fatty acid ester salts and the like. Examples of salts in these anionic surfactants include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
Among these, as a linear alkylbenzenesulfonic acid or its salt, the C8-C16 thing of a linear alkyl group is preferable, and a C10-C14 thing is especially preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
The alkyl sulfate ester salt is preferably an alkyl group having 10 to 20 carbon atoms.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average of 1 to 10 moles of ethylene oxide added thereto (ie, , Polyoxyethylene alkyl ether sulfates or polyoxyethylene alkenyl ether sulfates) are preferred.
As the alkane sulfonate, those having 10 to 20 carbon atoms in the alkyl group are preferable, and those having 14 to 17 are more preferable. Among these, those in which the alkyl group is a secondary alkyl group (that is, secondary alkane sulfonate) are particularly preferable.
The α-sulfo fatty acid ester salt is preferably a fatty acid residue (that is, ^a group represented by R ^a —C (H) —COO; R ^a represents ^a hydrocarbon group) having 10 to 20 carbon atoms. .
Among these, at least one anionic surfactant selected from linear alkyl benzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate ester salt, and α-olefin sulfonate is more preferable. Oxyethylene alkyl ether sulfate salts are particularly preferred.

As the component (D), other non-soap anionic surfactants other than those described above may be used. Examples of other non-soap anionic surfactants include carboxylic acid type anions such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, and acylaminocarboxylates. Surfactant: Phosphate ester type anionic surfactants such as alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkylphenyl phosphate ester salt, glycerin fatty acid ester monophosphate ester salt, etc. .
A commercial item may be used for these anionic surfactants.
(D) A component may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the component (D) in the liquid detergent is preferably 1 to 20 mass%, more preferably 2 to 10 mass%, and more preferably 3 to 8 mass% with respect to the total mass of the liquid detergent. When the content of the component (D) in the liquid detergent is within the above range, the cleaning performance and the film formation preventing property are likely to be better.

  The mass ratio of the component (A) to the component (D) in the liquid cleaning agent (that is, the mass ratio represented by the component (A) / (D). Hereinafter referred to as A / D) is sebum. 1 or more is preferable, 2 or more is more preferable, and 3 or more is more preferable. In addition, the upper limit of A / D is preferably 50 or less, more preferably 30 or less, and particularly preferably 10 or less, from the viewpoints of better film formation prevention and better liquid stability. That is, A / D is preferably 1 to 50, more preferably 2 to 30, and particularly preferably 3 to 10.

  The liquid detergent of the present invention has a viscosity of 10 to 200 mPa when measured after 60 seconds using a B-type viscometer (manufactured by TOKIMEC, rotor No. 2) at a measurement temperature of 25 ° C. and a rotation speed of 60 rpm. -It is preferable that it is s. If the viscosity is within the above range, the liquid detergent can be easily measured with a measuring cap or the like. Further, when used for application cleaning, it becomes easy to apply a liquid cleaning agent to a textile product or the like.

<Optional component>
The liquid detergent of this invention can contain arbitrary components other than the said (A)-(D) component in the range which does not impair the effect of this invention as needed.
Examples of optional components include water, surfactants other than the components (A) and (D) (optional surfactants), water-miscible organic solvents, metal ion scavengers, stabilizers, antioxidants, and cleaning performance. Examples include improvers / stability improvers, colorants / emulsifiers, pH adjusters, and fragrances.

  For example, the content of water with respect to the total amount of the liquid detergent is preferably 20 to 90% by mass, more preferably 40 to 80% by mass, and still more preferably 60 to 80% by mass.

<Optional surfactant>
The optional surfactant is a cleaning component, and a known surfactant can be used in the liquid cleaning agent. For example, a fatty acid salt having 10 to 20 carbon atoms (higher fatty acid salt, soap), a cationic surfactant, an amphoteric surfactant, and a semipolar surfactant can be used alone or in combination.

[Cationic surfactant]
Conventionally known cationic surfactants can be appropriately selected and used. Specifically, dodecyltrimethylammonium chloride, cetyltrimethylammonium salt, cetostearyltrimethylammonium salt, stearyltrimethylammonium salt, behenyltrimethylammonium salt, myristyldimethylethylammonium chloride, didecyldimethylammonium salt, benzalkonium chloride, etc. Can be mentioned. Among these, dodecyltrimethylammonium chloride and myristyldimethylethylammonium chloride are preferable from the viewpoint of liquid stability. When the liquid detergent of this invention contains a cationic surfactant, the compounding quantity is preferably 0.01 to 5% by mass with respect to the total mass of the liquid detergent from the viewpoint of liquid stability.

[Amphoteric surfactant]
Examples of amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactant. It is done. When the liquid detergent of this invention contains an amphoteric surfactant, the compounding quantity is preferably 0.1 to 10% by mass with respect to the total mass of the liquid detergent from the viewpoint of liquid stability.

[Semipolar surfactant]
As the semipolar surfactant, a conventionally known one can be appropriately selected and used. Specifically, dodecyl dimethylamine oxide, lauric acid amide propylamine oxide, etc. are mentioned. When the liquid detergent of this invention contains a semipolar surfactant, the compounding quantity is preferably 0.1 to 10% by mass with respect to the total mass of the liquid detergent from the viewpoint of liquid stability.

The liquid detergent of the present invention preferably contains a water-miscible organic solvent.
Examples of water-miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol, glycols such as propylene glycol, butylene glycol and hexylene glycol, polyglycols such as dipropylene glycol, and diethylene glycol. Examples thereof include alkyl ethers such as monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, and 3-methoxy-3-methyl-1-butanol.
Among these, ethanol, propylene glycol, diethylene glycol monobutyl ether (butyl carbitol), 3-methoxy-3-methyl-1-butanol due to availability, liquid stability when used as a liquid detergent, fluidity, and the like. Is preferred.
A water-miscible organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the water-miscible organic solvent is preferably 0.1 to 15% by 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 metal ion scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid, hydroxyetadisulfonic acid (HEDP), and trisodium methylglycine diacetate (MGDA). The content of the metal ion scavenger is preferably 0.01 to 10% by mass with respect to the total mass of the liquid detergent. A metal ion capture agent may be used individually by 1 type, and 2 or more types may be used in combination.

Examples of the stabilizer include boric acid, borax, formic acid or a salt thereof, benzoic acid, lactic acid or a salt thereof, and calcium salts such as calcium chloride and calcium sulfate. These may be used alone or in combination of two or more.
The content of the stabilizer is preferably 0 to 2% by mass with respect to the total mass of the liquid detergent.

  As antioxidant, butylhydroxytoluene, dibutylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogensulfite, etc. can be contained 0.01-2 mass% with respect to the total mass of a liquid cleaning agent, for example. An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.

  For the purpose of improving washing performance and stability, enzymes (proteases, lipases, cellulases, amylases, mannanases, etc.), texture improvers, alkali builders such as alkanolamines, hydrotropes, fluorescent agents, dye transfer inhibitors, Antifouling agents, pearl agents, soil release agents and the like can be included.

  As colorants, Acid Red 138, Polar Red RLS, Liquid PINK AL, Acid Yellow 203, Liquid Bright Yellow, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Turquoise P-GR, Liquid Blue BL, SE General-purpose dyes and pigments such as Levanyl Violet (both are trade names) can be included, for example, in an amount of about 0.00005 to 0.1% by mass with respect to the total mass of the liquid detergent.

  Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples include polystyrene emulsion (trade name: Cybinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Seiden Chemical Co., Ltd.), Opulyn 301, Acusol OP 301, etc. 0.001-1 mass% can be included with respect to the total mass of.

  As a fragrance | flavor for fragrance, a conventionally well-known thing can be selected suitably and can be used. As for the compounding quantity of the said fragrance | flavor, 0.1-1 mass% is preferable with respect to the total mass of a liquid detergent.

The liquid cleaning agent of the present invention preferably has a pH at 25 ° C. of 4 to 10, more preferably 6 to 9. When the pH is in such a range, the appearance stability of the liquid detergent is easily maintained well.
The pH of the liquid detergent can be adjusted by blending a pH adjuster as necessary. The pH adjuster is optional as long as the effects of the present invention are not impaired, but sulfuric acid, hydrochloric acid, paratoluenesulfonic acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of enzyme stability. .

(Production method)
The liquid detergent of the present invention is produced by a conventionally known production method.
The manufacturing method of a liquid detergent is obtained by disperse | distributing (A)-(D) component and another component as needed to the water which is a dispersion medium, for example.

(how to use)
As a method of using the liquid detergent, for example, a liquid detergent alone or in a water together with a known bleaching agent or softening agent is used as a washing liquid. Or a method of applying a liquid cleaning agent to an object to be washed and washing it with a washing machine.
Examples of the articles to be washed include textiles such as clothes, fabrics, sheets, curtains, and carpets.
The content of the liquid cleaning agent in the cleaning liquid is not particularly limited. The amount of liquid detergent added to water is preferably 3 to 10 mL per 10 L of water, for example.

  The liquid cleaning agent of the present invention contains components (A) to (D) and water, and the component (A) is a polyoxyalkylene type nonionic surfactant represented by the formula (a1). The component B) is preferably an ethylene oxide adduct of polyethyleneimine, and the component (C) is preferably polyethylene glycol having a mass average molecular weight of 1000. Moreover, it is preferable that A / (B + C) is 3-12. Moreover, it is more preferable that C / B is 0.5-15.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Raw materials used)
Abbreviations in Table 1 represent the following.
<(A) component>
A-1: LMAO: polyoxyethylene alkyl ether (EO addition mole number 15) (product name “LMAO-90” manufactured by Lion Chemical Co., Ltd.) (in formula (a1), R ¹¹ has 12 to 14 carbon atoms A compound in which X is O, s is 15, t is 0, and R ¹² is a hydrogen atom).
A-2: a compound obtained by adding 5 mol of ethylene oxide to a secondary alcohol having 12 carbon atoms and a secondary alcohol having 14 carbon atoms (in the formula (a1), R ¹¹ is a secondary alkyl having 12 carbon atoms. And a mixture of a compound in which s is 5, t is 0, R ¹² is a hydrogen atom, and a compound in which R ¹¹ is a secondary alkyl group having 14 carbon atoms, s is 5, t is 0, and R ¹² is a hydrogen atom (Nippon Shokubai Co., Ltd., trade name "Softanol 50").
A-3: LMAF: polyoxyethylene alkyl ether (EO added mole number 6) (product name “LMAF-90” manufactured by Lion Chemical Co., Ltd.) (in formula (a1), R ¹¹ has 12 to 14 carbon atoms A compound in which X is O, s is 6, t is 0, and R ¹² is a hydrogen atom).
A-4: MEE: palm fatty acid methyl (mixture of methyl laurate / methyl myristate = 8/2 in mass ratio) with 15 mol equivalent of ethylene oxide added using an alkoxylation catalyst (MEE) (In the formula (a1), R ¹¹ is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R ¹² is a methyl group, X is COO, s is 15, and t is 0. Compound, narrow rate 33%, manufactured by the following manufacturing method).
(Manufacturing method of A-4)
The compound was synthesized according to the production method described in JP-A No. 2000-144179.
Alumina / magnesium hydroxide having a composition of 2.5 MgO.Al ₂ O ₃ .wH ₂ O (manufactured by Kyowa Chemical Industry Co., Ltd., trade name “KYOWARD (registered trademark) 300”) at 600 ° C. for 1 hour, nitrogen Calcination was performed in an atmosphere to obtain a calcined alumina / magnesium hydroxide (unmodified) catalyst. A 4 L autoclave was charged with 2.2 g of calcined alumina / magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide in ethanol, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester, Catalyst reforming was performed in an autoclave. Next, after the inside of the autoclave was replaced with nitrogen, 1052 g of ethylene oxide was introduced and reacted while stirring while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa.
The obtained reaction liquid was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added and mixed, and then the catalyst was filtered off to obtain A-4.
A-5: MEE: Methyl coconut fatty acid (mixture of methyl laurate / methyl myristate = 8/2 in mass ratio) to which 15 moles of ethylene oxide was added using an alkoxylation catalyst (formula (a1)) A compound in which R ¹¹ is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R ¹² is a methyl group, X is COO, s is 15 and t is 0. 33% manufactured by the following manufacturing method).
(Manufacturing method of A-5)
In a 1 L separable flask, 525 g of isopropyl alcohol (IPA) (primary reagent, manufactured by Kanto Chemical Co., Ltd.) and 150 g of calcium acetate monohydrate (special grade reagent, manufactured by Kanto Chemical Co., Ltd.) are placed, and a disperser impeller To obtain a dispersion (dispersing step). While stirring the dispersion at 3000 rpm, 75 g of sulfuric acid (special grade reagent, manufactured by Kanto Chemical Co., Inc.) was added and mixed with a dropping funnel over 60 minutes (mixing step). In the mixing step, heat was generated by the addition of sulfuric acid, so the separable flask was controlled with a warm bath and the reaction temperature was controlled at 15-25 ° C. After addition of sulfuric acid, the mixture was further stirred for 2 hours while maintaining at 20 ° C. (catalyst aging step) to obtain an alkoxylation catalyst.
In an autoclave, 2.1 g of the above alkoxylation catalyst, 462 g of methyl laurate (Lion Chemical Co., Ltd., trade name “Pastel (registered trademark) M12”), and methyl myristate (Lion Chemical Co., Ltd., trade name “ Pastel M14 ") 166g was added and stirred. While stirring, the inside of the autoclave was purged with nitrogen, heated to 160 ° C., and under conditions of 0.1 to 0.5 MPa, ethylene oxide (EO) 1876 g (15 times mol of the total of methyl laurate and methyl myristate) And stirred (addition reaction step). Furthermore, after stirring at the addition reaction temperature for 0.5 hour (aging step), the mixture was cooled to 80 ° C. to obtain 2516 g of a crude reaction product (fatty acid methyl ester ethoxylate (MEE), EO average addition mole number: 15). The reaction crude product was filtered to remove the catalyst to obtain A-5.

<(B) component>
B-1: Ethylene oxide adduct of polyethyleneimine (manufactured by BASF, trade name “Sokalan HP20”).

<(C) component>
C-1: Polyethylene glycol (mass average molecular weight 1000) (product name “PEG # 1000” manufactured by Lion Chemical Co., Ltd.).
C-2: Polyethylene glycol (mass average molecular weight 4000) (product name “PEG # 4000” manufactured by Lion Chemical Co., Ltd.).

<(D) component>
D-1: Linear alkylbenzene sulfonic acid (manufactured by Lion Corporation, trade name “Lypon (registered trademark) LH-200”) (C10-14, average molecular weight 322).
D-2: Polyoxyethylene alkyl ether sodium sulfate (AES) represented by the following general formula (d1-1) produced by the following production method.
R ⁵¹ —O— (EO) _j —SO ₃ M (d1-1)
[In the formula (d1-1), R ⁵¹ is a linear alkyl group having 12 to 14 carbon atoms, j is a number of 1.0, and M is sodium. EO is an oxyethylene group, and j is the average number of repetitions of EO. ]
(Manufacturing method of D-2)
In an autoclave having a capacity of 4 L, 400 g of CO1270 (trade name) manufactured by P & G as a raw material alcohol (a mixture of a 12 carbon alcohol and a 14 carbon alcohol in a mass ratio of 75/25) and hydroxylation as a reaction catalyst After charging 0.8 g of potassium and replacing the inside of the autoclave with nitrogen, the temperature was raised with stirring. Subsequently, 91 g of ethylene oxide was introduced and reacted while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less to obtain an alcohol ethoxylate.
The obtained alcohol ethoxylate was gas chromatograph mass spectrometer (manufactured by Hewlett-Packard, product name “GC-5890”, detector: flame ionization detector (FID), column: Ultra-1 (manufactured by HP). , L25m × φ0.2mm × T0.11 μm)), the average added mole number of ethylene oxide was 1.0. Moreover, content of the compound which ethylene oxide has not added was 43 mass% with respect to the total mass of the obtained alcohol ethoxylate.
Next, 237 g of the alcohol ethoxylate obtained above was collected in a 500 mL flask equipped with a stirrer, and after the flask was replaced with nitrogen, 96 g of liquid anhydrous sulfuric acid (sulfane) was slowly added while maintaining the reaction temperature at 40 ° C. It was dripped. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Subsequently, this was neutralized with an aqueous sodium hydroxide solution to obtain sodium polyoxyethylene alkyl ether sulfate (D-2).
D-3: Sodium polyoxyethylene alkyl ether sulfate (AEPS) represented by the following general formula (d1-2) produced by the following production method.
_{^{R 61 -O- (PO) j2 -}} (EO) k -SO 3 M ··· (d1-2)
[In the formula (d1-2), R ⁶¹ is a linear alkyl group having 12 to 14 carbon atoms, j2 is a number of 1.0, k is a number of 2.0, and M is sodium. Compound. PO is an oxypropylene group, EO is an oxyethylene group, k is the average number of repetitions of PO, and j2 is the average number of repetitions of EO. ]
(Manufacturing method of D-3)
In an autoclave equipped with a stirrer, a temperature controller and an automatic introduction device, a carbon number of 12
Linear alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., trade name “1-dodecanol” (molecular weight 1
86.33), purity> 99%) 640 g and potassium hydroxide 1.0 g were charged, and dehydration was performed at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, nitrogen substitution was performed, and after heating up to 120 ° C., 199 g of propane-1,2-diyl oxide was charged. Subsequently, after addition reaction and aging at 120 ° C., the temperature was raised to 145 ° C., and 303 g of ethylene oxide was charged. Subsequently, after addition reaction and aging at 145 ° C., the mixture 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 to the autoclave, and the mixture was stirred for 30 minutes at 80 ° C. and then extracted. The average added mole number of propylene oxide was 1.0, and the average added mole number of ethylene oxide was An alkoxylate with a value of 2.0 was obtained.
The resulting alkoxylate was sulfated in a falling film reactor using SO ₃ gas. The resulting sulfate was neutralized with monoethanolamine to obtain sodium polyoxyalkylene alkyl ether sulfate (D-3).

<Common component (X)>
Higher fatty acid salt: coconut fatty acid salt (manufactured by NOF Corporation, trade name “coconut fatty acid (PKO) TC”, 0.8 mass% based on the total amount of liquid detergent).
Water-miscible organic solvent: 95% ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., trade name “specific alcohol 95 degree synthesis”. 0.5% by mass based on the total mass of the liquid detergent)
Metal ion scavenger: Trisodium citrate dihydrate (manufactured by Fuso Chemical Industry Co., Ltd., trade name “Trisodium citrate dihydrate”, AI (pure content) = 100%, based on the total mass of the liquid detergent 0.1% by mass), trisodium methylglycine diacetate (MGDA) (trade name “Trilon M” manufactured by BASF AG. 0.3% by mass based on the total mass of the liquid detergent).
Enzyme: Coronase 48L (manufactured by Novozyme. 0.3% by mass based on the total mass of the liquid detergent).
Stabilizer: Sodium benzoate (Fushimi Pharmaceutical Co., Ltd., trade name “Fuminal”. 0.5% by mass based on the total mass of the liquid detergent), sodium lactate (Pureak Co., Ltd., trade name “ “Fermented sodium lactate”. 0.8% by mass based on the total mass of the liquid detergent, calcium chloride (made by Tokuyama Corporation, trade name “granular calcium chloride.” For the total mass of the liquid detergent, 0.01% by mass).
Antioxidant: Dibutylhydroxytoluene (manufactured by Sumitomo Chemical Co., Ltd., trade name “SUMILIZER (registered trademark) BHT-R”). 0.05% by mass based on the total mass of the liquid detergent.
Perfume: perfume composition A described in Tables 7 to 14 of JP 2003-268398 A. 0.4% by mass based on the total mass of the liquid detergent).
Colorant: Colorant (manufactured by Hatake Kasei Co., Ltd., trade name “Green No. 3”. 0.0002% by mass based on the total mass of the liquid detergent).
pH adjuster: sulfuric acid (manufactured by Toagosei Co., Ltd., required amount), sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd., required amount).
Solvent: water (purified water) (balance).

<Common component (Y)>
Higher fatty acid salt: Coconut fatty acid salt (manufactured by NOF Corporation, trade name “Zushi Fatty Acid (PKO) TC”) 1.6% by mass based on the total amount of liquid detergent.
Enzyme: Coronase 48L (manufactured by Novozyme. 0.3% by mass based on the total mass of the liquid detergent).
Antioxidant: Dibutylhydroxytoluene (manufactured by Sumitomo Chemical Co., Ltd., trade name “SUMILIZER BHT-R”. 0.05% by mass based on the total mass of the liquid detergent).
Water-miscible organic solvent: 95% ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., trade name “specific alcohol 95-degree synthesis”, 6.0% by mass based on the total mass of the liquid detergent), propylene glycol (BASF) (Compounded 2.0% by mass with respect to the total mass of the liquid detergent).
Stabilizer: Sodium benzoate (Fushimi Pharmaceutical Co., Ltd., trade name “Fuminal”. 0.4% by mass based on the total mass of the liquid detergent), sodium lactate (Pureak, trade name “ Fermented sodium lactate ”. 0.4% by mass based on the total mass of the liquid detergent
Fragrance | flavor: The fragrance | flavor composition A of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399. 0.5% by mass based on the total mass of the liquid detergent).
Colorant: Colorant (manufactured by Hatake Kasei Co., Ltd., trade name “Green No. 3”. 0.0005% by mass based on the total mass of the liquid detergent).
pH adjuster: sulfuric acid (manufactured by Toa Gosei Co., Ltd., required amount), monoethanolamine (manufactured by Nippon Shokubai Co., Ltd., required amount).
Solvent: water (purified water) (balance).
The water content “balance” is an amount necessary to make the liquid detergent 100% by mass as a whole. Further, the content “necessary amount” of the pH adjusting agent is an amount required to bring the liquid detergent to the pH (25 ° C.) in the table.

(Examples 1-16, Comparative Examples 1-3)
In accordance with the composition shown in Table 1, all the components (A) to (D) and optional components and water are stirred and mixed, and a pH adjuster is added as necessary to obtain the pH in the table, and a liquid detergent. Got.
In addition, the compounding quantity in a table | surface is a pure part conversion value. Moreover, the component whose compounding quantity is not described in the table | surface is not mix | blended.

<Evaluation method>
(Evaluation of prevention of film formation)
5 g of the liquid cleaning agent of each example was weighed into a 5 cm diameter petri dish and left in a room at 25 ° C. and a relative humidity of 40%. The degree of film formation on the liquid surface was evaluated according to the following criteria. In the following evaluation criteria, A to C were regarded as acceptable. The results are shown in Table 1.
[Evaluation criteria for prevention of film formation]
A: Formation of a film is not observed after 12 hours.
B: When 12 hours have elapsed, no film formation is observed, but a decrease in fluidity is observed.
C: Slight film formation is observed at 12 hours, and a decrease in fluidity is observed.
D: When 12 hours have elapsed, formation of a film is recognized and there is no fluidity.

(Evaluation of cleaning performance)
As a soiled cloth, wet artificially contaminated cloth (manufactured by the Association of Laundry Science, 28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene Cholesterol 1.6%, gelatin 7.0%, mud 29.8%, carbon black 0.5%) were cut into 5 cm × 5 cm squares. As a cleaning tester, Terg-O-meter (manufactured by UNITED STATES TESTING) was used. As the cleaning liquid, 750 μL of the liquid cleaning agent of each example was added to 900 mL of water (300 μL in Examples 14 to 16), and the liquid prepared by stirring for 30 seconds was used.
Into the cleaning tester, the cleaning liquid 900 mL, the 10 soiled cloths, and the cleaning knitted cloth were added, and the bath ratio (washing water / washed cloth total mass) was adjusted to be 20 times, Washing was performed at 120 rpm and 15 ° C. for 10 minutes. After that, it was transferred to a two-tank washing machine (product name “VH-30S” manufactured by Toshiba Corporation), dehydrated for 1 minute, and then rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes. Treatment was performed, and further dehydration treatment was performed for 1 minute, followed by air drying. The reflectivity of each of the uncleaned cloth, the uncleaned cloth, and the uncleaned cloth (the uncleaned cloth refers to the original white cloth (raw cloth) that has not been soiled), respectively. It was measured with a color difference meter (manufactured by Nippon Denshoku Co., Ltd., product name “SE200 type”), and the cleaning rate (%) was determined by the following formula (i).
Washing rate (%) = (K / S of soiled cloth before washing−K / S of soiled cloth after washing) / (K / S of soiled cloth before washing−K / S of unstained cloth) ) × 100 (i)
[In the formula (i), K / S is (1-R / 100) ² / (2R / 100), and R is a dirt cloth before washing, a dirt cloth after washing, or an unstained cloth. Represents the reflectance (%). K represents an extinction coefficient, S represents a scattering coefficient, and R represents an absolute reflectance. ]
The average value of the cleaning rate of 10 soiled cloths was determined, and this average value was evaluated according to the following evaluation criteria to evaluate the cleaning performance of the liquid cleaning agent in each example. In the following evaluation criteria, A and B were considered acceptable. The results are shown in Table 1.
[Evaluation criteria for cleaning performance]
A: The cleaning rate is 70% or more.
B: The cleaning rate is 60% or more and less than 70%.
C: The cleaning rate is 50% or more and less than 60%.
D: The cleaning rate is less than 50%.

As shown in Table 1, the liquid detergents of Examples 1 to 16 containing all the components (A) to (C) were excellent in film formation prevention properties and good cleaning performance.
On the other hand, the liquid detergents of Comparative Example 1 containing no component (B) or (C), Comparative Example 2 containing no component (B), and Comparative Example 3 containing no component (C) have good cleaning performance. Although there was, it was inferior to film formation prevention property.
From the above results, it was confirmed that the liquid cleaning agent of the present invention was excellent in film formation preventive properties and good cleaning performance.

Claims (3)

A liquid detergent composition comprising a nonionic surfactant (A), an alkylene oxide adduct of polyalkyleneamine (B), and a compound (C) represented by the following general formula (I).
R ¹ O— (EO) _n —H (I)
[In Formula (I), R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms, EO represents an oxyethylene group, and n represents a number of 1 to 30000 representing an average number of repeating oxyethylene groups. is there. ]   The liquid detergent composition according to claim 1, wherein a mass ratio represented by (A) component / ((B) component + (C) component) is 20 or less.   Furthermore, the liquid detergent composition of Claim 1 or 2 containing the anionic surfactant (D) except a C10-C20 fatty acid salt.