JP6591033B2 - Cleaning composition - Google Patents

Description

The present invention relates to a cleaning composition.
This application claims priority on February 16, 2016 based on Japanese Patent Application No. 2006-027293 for which it applied to Japan, and uses the content here.

In recent years, in addition to the function of removing dirt, which is a basic function, a high residual scent property (property that a scent remains in a washed object) is required for a cleaning composition.
In response to such demands, residual fragrance properties have been improved by blending perfume ingredients that are likely to remain in the object to be washed or blending cationic surfactants.

  For example, Patent Document 1 discloses a perfume delivery system suitable for delivering a perfume to a surface using a composition containing polyethyleneimine and a perfume.

JP 2010-31285 A

However, the prior art is not sufficient in terms of the fragrance that can be used or the effect.
The present invention has been made in view of the above circumstances, and relates to a cleaning composition having a high residual fragrance. Furthermore, the present invention is also excellent in recontamination prevention performance (performance for preventing dirt from re-adhering to an object to be washed).

As a result of intensive studies, the present inventors have found that the following cleaning composition can solve the above-described problems.
That is, this invention has the following aspects.
[1] An alkylene oxide adduct of polyalkyleneamine (A),
A surfactant (B) comprising a nonionic surfactant (B1) and an anionic surfactant (B2), and a fragrance (C),
The cleaning composition whose mass ratio represented by a component (B1) / component (B2) is 1.0 or more.
[2] The component (B1) contains a fatty acid methyl ester ethoxylate,
The detergent composition according to [1], wherein the content of the fatty acid methyl ester ethoxylate is 10% by mass or more based on the total mass of the component (B).
[3] Further, the component (D): containing a polymer having at least one repeating unit (d1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit (d2) [1] or The cleaning composition according to [2].
[4] Furthermore, component (E): at least one selected from carboxylic acids represented by the following general formula (VII) and salts thereof, and component (F): an enzyme containing [1] to [3] The cleaning composition according to any one of the above.
X—R ¹ —COOH (VII)
However, in formula (VII), ^{R 1} is a divalent hydrocarbon group or an arylene group, 1 to 4 carbon atoms, X is, -H, -OH, -CH _3, or -COOH.

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition which has high aftercense property can be provided.

≪Cleaning agent composition≫
The cleaning composition of the present invention contains the following components (A) to (C).

<Component (A)>
Component (A) is an alkylene oxide adduct of polyalkyleneamine.
Examples of the component (A) include the following component (a1) and component (a2).

[Component (a1)]
Component (a1) is an alkylene oxide adduct of polyalkyleneimine.
The polyalkyleneimine of component (a1) is represented by the following general formula (I), for example.
^{_{NH 2 -R 21 - (NA-}} R 21) n -NH 2 ··· (I)
In formula (I), 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 n is an integer of 1 or more. However, not all of the A are hydrogen atoms.
That is, the polyalkyleneimine represented by the formula (I) has a polyamine chain branched 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 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 (hereinafter also referred to as “PEI”) (in formula (I), R ²¹ represents an ethylene group), polypropyleneimine (in formula (I), R ²¹ represents a propylene group) Is preferred, and PEI is more preferred. PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary and tertiary amine nitrogen atoms in its structure.
n is an integer of 1 or more.

  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. Here, “active hydrogen” means a highly reactive hydrogen atom, specifically, a hydrogen atom bonded to a nitrogen atom.

Component (a1) 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 the starting polyalkyleneimine at 100 to 180 ° C. in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide or 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. Ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.

Examples of the component (a1) include polyalkyleneimine ethylene oxide adducts, polyalkyleneimine propylene oxide adducts, and polyalkyleneimine ethylene oxide-propylene oxide adducts. In addition, the ethylene oxide-propylene oxide adduct of polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to polyalkyleneimine. ) Is optional.
As the component (a1), 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 (a1), an average of 5 to 40 alkylene oxides is 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 a component (a1), 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 (a1) include compounds represented by the formula (Ia).

In formula (Ia), 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.
In formula (Ia), in — (R ²² O) _m —H, —R ²² O— may be bonded randomly or in a block form.
As the component (a1), 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.

<Component (a2)>
Component (a2) is an alkylene oxide adduct of a polyalkyleneamine represented by the following formula (II).
NH ₂ (R ³¹ NH) ₁ H (II)
In formula (II), 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.
l is a number of 1 or more.

  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.

  Component (a2) is obtained by adding an alkylene oxide to a polyalkyleneamine. This reaction can be carried out in the same manner as component (a1). 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 (a2) include polyalkyleneamine ethylene oxide adducts, polyalkyleneamine propylene oxide adducts, polyalkyleneamine ethylene oxide-propylene oxide adducts, and the like.
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 (a2), an average of 5 to 40 alkylene oxides are 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.

  1000-80000 are preferable, as for the mass average molecular weight of a component (a2), 2000-50000 are more preferable, 5000-30000 are further more preferable, and 10000-20000 are especially preferable.

  As the component (A), the component (a1) is preferable. Among the components (a1), an ethylene oxide adduct of polyethyleneimine represented by the formula (Ia) is particularly preferable.

As the component (A), one type may be used alone, or two or more types may be used in combination.
The content of the component (A) is preferably 0.01 to 5% by mass, preferably 0.05 to 3% by mass, and more preferably 0.1 to 2% by mass with respect to the total mass of the cleaning composition.
If content of a component (A) is below the said upper limit, it will become easy to maintain the freedom degree of a mixing | blending of another component.
If content of a component (A) is more than the said lower limit, it will become easy to improve residual fragrance property and will become easy to improve storage stability.

<Component (B)>
Component (B) is a surfactant containing a nonionic surfactant (hereinafter also referred to as component (B1)) and an anionic surfactant (hereinafter also referred to as component (B2)).
[Component (B1)]
Component (B1) is a nonionic surfactant.
Examples of the component (B1) include the following (1) to (8).
(1) An average of 3 to 30 moles, preferably 3 to 20 moles, more preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to a monovalent aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Added polyoxyalkylene alkyl (or alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the monohydric aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.

As a nonionic surfactant, the thing of said (1) or (3) is preferable, and what is represented by the following general formula (III) or (IV) is especially preferable.
_{^{R 2 -C (= O) O}} - [(EO) s / (PO) t] - (EO) u -R 3 ··· (III)
R ⁴ —O — [(EO) _v / (PO) _w ] — (EO) _x —H (IV)
(In the formula (III), R ² is a hydrocarbon group having 7 to 22 carbon atoms, R ³ is an alkyl group having 1 to 6 carbon atoms, s represents the average number of repeating EO, And t represents the average number of repetitions of PO and is a number from 0 to 6, u represents the average number of repetitions of EO, is a number from 0 to 20, EO represents an oxyethylene group, PO is Represents an oxypropylene group.
In the formula (IV), R ⁴ is a hydrocarbon having 6 to 22 carbon atoms, v represents an average number of repetitions of EO, 3 to 20, and w represents an average number of repetitions of PO. 6, x represents the average number of EO repeats, is a number from 0 to 20, EO represents an oxyethylene group, and PO represents an oxypropylene group. )

In the formula (III), R ² is a hydrocarbon group having 7 to 22 carbon atoms. The number of carbon atoms in R ² is preferably 9 to 21, 11 to 21 is more preferable.
R ² is preferably an alkyl group or an alkenyl group.
R ² may be linear or branched.
From the viewpoint of further improving detergency, R ² is preferably a linear or branched alkyl group having 7 to 22 carbon atoms, or a linear or branched chain alkenyl group having 7 to 22 carbon atoms.
R ³ is an alkyl group having 1 to 6 carbon atoms and may be linear or branched.
Of these, a methyl group and an ethyl group are preferable.
In formula (III), s and u are each independently a number representing the average number of repetitions of EO.
s + u is preferably 6 to 20, more preferably 6 to 18, still more preferably 11 to 18, and particularly preferably 14 to 18. If it is more than the said lower limit, liquid stability will become easy to improve more. If it is below the said upper limit, cleaning power will improve more easily.
In formula (III), t is a number representing the average number of repetitions of PO.
t is a number from 0 to 6, preferably 0 to 3, and more preferably 0. If it is below the said upper limit, liquid stability will improve more easily.
When t is 1 or more, in [(EO) _s / (PO) _t ], the oxyethylene group and the oxypropylene group may be bonded in a random manner or in a block shape.
In the present specification, the average number of repetitions can be measured by gas chromatography or the like.

In the formula (IV), R ⁴ is a hydrocarbon group having 6 to 22 carbon atoms.
In formula (IV), the number of carbon atoms in R ⁴ is preferably 10 to 22, more preferably 10 to 20, and still more preferably 10 to 18, from the viewpoint of further improving the detergency.
R ⁴ may be linear or branched.
Preferable R ⁴ —O— includes a group represented by the following general formula (V).
(R ¹⁰¹ ) (R ¹⁰² ) CH—O— (V)
(In Formula (V), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a chain hydrocarbon group, and the total carbon number of R ¹⁰¹ and R ¹⁰² is 5 to 21.)
The number of carbon atoms in the sum of R ¹⁰¹ and ^{R 102} is preferably 9 to 21, preferably from 9 to 19, more preferably 9 to 17.
R ¹⁰¹ and R ¹⁰² may be linear or branched.
Specifically, R ⁴ is preferably an alkyl group derived from a secondary alcohol having 12 to 14 carbon atoms.
In formula (IV), v and x are numbers independently representing the average number of repetitions of EO.
v + x is preferably 3 to 20, more preferably 5 to 18, still more preferably 6 to 18, particularly preferably 11 to 18, and (further) preferable. If it is more than the said lower limit, liquid stability will become easy to improve more. If it is below the said upper limit, cleaning power will improve more easily.
In formula (IV), w is a number representing the average number of repetitions of PO.
w is a number of 0 to 6, preferably 0 to 3, and more preferably 0. If it is below the said upper limit, liquid stability will improve more easily.
When w is 1 or more, in [(EO) _v / (PO) _w ], the oxyethylene group and the oxypropylene group may be bonded randomly or in a block form.
The distribution of EO or PO in the formula (III) varies depending on the reaction method in production. For example, when ethylene oxide or propylene oxide is added to a raw material using sodium hydroxide, potassium hydroxide or the like, which is a general alkali catalyst, the distribution of v or w becomes relatively wide. A specific alkoxylation catalyst such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in JP-B-615038 is added. When ethylene oxide or propylene oxide is added to the raw material, the distribution of v or w becomes relatively narrow.

The nonionic surfactant represented by formula (III) (hereinafter also referred to as component (b11)) and the nonionic surfactant represented by formula (IV) (hereinafter also referred to as component (b12)) have a narrow rate. Is preferably 20% by mass or more, and more preferably 25% by mass or more.
The higher the narrow rate, the better the cleaning power. Further, when the narrow ratio is 20% by mass or more, particularly 25% by mass or more, a detergent composition having a low raw material odor for the surfactant is easily obtained.
When the component (b11) is produced by a conventional method, the product includes a component (b11) and a component that does not contribute to detergency, for example, a fatty acid ester that is a raw material of the component (b11) or a formula (III) The nonionic surfactant s having an s of 1 or 2 coexists and reduces the narrow rate. For this reason, if the narrow ratio is high, the coexisting components are sufficiently small, and the problem of reduced cleaning power and raw material odor hardly occurs. The same applies to the component (b12).
Although it does not specifically limit as an upper limit of the said narrow rate, It is preferable that it is 80 mass% or less substantially.
As said narrow rate, since liquid stability and solubility improve, it is more preferable that it is 20-50 mass%, and 20-40 mass% is further more preferable.
Here, in this specification, the “narrow ratio” indicates a distribution ratio of ethylene oxide adducts having different EO addition mole numbers and is represented by the following formula (S).

[ _Wherein p _max represents the number of moles of EO added to the ethylene oxide adduct most present in the entire ethylene oxide adduct. i represents the number of moles of EO added. Yi represents the ratio (% by mass) of the ethylene oxide adduct present in the entire ethylene oxide adduct and having an added mole number of EO of i. ]

The narrow rate can be controlled by, for example, the production method of the component (b11) or the component (b12). The production method of the component (b11) is not particularly limited. For example, a method of addition polymerization of ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP 2000-144179 A). Can be easily manufactured. As a manufacturing method of a component (b12), it can manufacture by the method of carrying out addition polymerization of ethylene oxide to C6-C22 alcohol, for example using the surface-modified composite metal oxide catalyst.
Specific examples of the surface-modified composite metal oxide catalyst used in such a method include metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) are added to the composite metal oxide catalyst such as magnesium oxide, and the hydrotalcite surface-modified with metal hydroxide and / or metal alkoxide. A calcined product catalyst is mentioned.
In the surface modification using the composite metal oxide catalyst, it is preferable to use a composite metal oxide in combination with a metal hydroxide and / or a metal alkoxide. In this case, the ratio of the metal hydroxide and / or metal alkoxide is preferably 0.5 to 10 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the composite metal oxide. .
As another method for producing the component (b11), there is a method of adding an alkylene oxide to a fatty acid alkyl ester with an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and oxyacid. The above alkoxylation catalyst is disclosed in Japanese Patent No. 04977609, WO1993004030, WO2002028269, WO201220435, etc. For example, alkaline earth metal salts of carboxylic acids and / or hydroxycarboxylic acids And an alkoxylation catalyst prepared from a mixture of alkaline earth metal salt and sulfuric acid.

  As the nonionic surfactant, a commercially available product may be used, or a nonionic surfactant manufactured by a known synthesis method may be used. As a known production method, component (b11) can be produced, for example, by a method of addition polymerization of ethylene oxide and / or propylene oxide to a fatty acid alkyl ester. Component (b12) can be produced, for example, by a method of addition polymerization of ethylene oxide and / or propylene oxide to an alcohol having 6 to 22 carbon atoms.

As the component (B1), one type may be used alone, or two or more types may be used in combination.
Component (B1) is preferably component (b11), more preferably a compound in which t in formula (III) is 0 (ie, a polyoxyethylene fatty acid alkyl ester), and R ^{3 in} formula (III) is methyl. The group is particularly preferably polyoxyethylene fatty acid methyl ester (fatty acid methyl ester ethoxylate) (hereinafter referred to as “MEE”).
The content of the fatty acid methyl ester ethoxylate is preferably 10% by mass or more, more preferably 15 to 90% by mass, and still more preferably 20 to 80% by mass with respect to the total mass of the component (B).
When the content of the fatty acid methyl ester ethoxylate is less than or equal to the above upper limit value, the residual fragrance is easily enhanced.
When the content of the fatty acid methyl ester ethoxylate is not less than the above lower limit, the residual fragrance property is easily improved and the recontamination preventing performance is easily improved.

The cleaning composition of the present invention is preferably used in combination of component (b11) and component (b12).
0.1-65 are preferable and, as for mass ratio (henceforth b11 / b12 ratio) represented by a component (b11) / component (b12), 0.5-50 are more preferable.
When the ratio b11 / b12 is within the above numerical range, the residual fragrance property is easily improved and the recontamination preventing performance is easily improved.

20-90 mass% is preferable with respect to the total mass of a component (B), and, as for content of a component (B1), 25-80 mass% is more preferable, and 30-70 mass% is more preferable.
When the content of the component (B1) is equal to or less than the above upper limit value, the residual fragrance is easily enhanced.
When the content of the component (B1) is equal to or higher than the lower limit, it becomes easy to improve the residual fragrance and improve the recontamination prevention performance.

The content of the component (B1) is preferably 20 to 70% by mass, more preferably 20 to 60% by mass, further preferably 35 to 60% by mass, and 40 to 60% by mass with respect to the total mass of the cleaning composition. Is particularly preferred.
When the content of the component (B1) is equal to or less than the above upper limit value, the residual fragrance is easily enhanced.
When the content of the component (B1) is equal to or higher than the lower limit, it becomes easy to improve the residual fragrance and improve the recontamination prevention performance.

The mass ratio represented by component (A) / component (B1) (hereinafter also referred to as A / B1 ratio) is preferably 0.001 to 1.0, more preferably 0.005 to 0.5, and 01 to 0.25 is more preferable.
If A / B1 ratio is below the said upper limit, while remaining fragrance property will become easy, it will become easy to improve recontamination prevention performance.
If A / B1 ratio is more than the said lower limit, it will become easy to improve a residual fragrance property.

[Component (B2)]
Component (B2) is an anionic surfactant.
Examples of the anionic surfactant include the following (1) to (12).
(1) A methyl, ethyl or propyl ester salt of a saturated or unsaturated α-sulfo fatty acid having 8 to 20 carbon atoms.
(2) Linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(3) Alkane sulfonate having 10 to 20 carbon atoms.
(4) C-C20 α-olefin sulfonate (AOS).
(5) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(6) One of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) A polyoxyalkylene alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with an average of 0.5 to 10 mol.
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), an average of 3 to 30 mol An alkyl (or alkenyl) phenyl ether sulfate having an added linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(8) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), an average of 0.5 to An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with 10 moles.
(9) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(10) Long-chain (C8-20) monoalkyl, dialkyl or sesquialkyl phosphates.
(11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(12) A higher fatty acid or a salt thereof. A higher fatty acid having an average carbon number of 10 to 20 (preferably having 12 to 18 carbon atoms) or a salt thereof.

Anionic surfactants other than those exemplified above may be used. For example, carboxylic acid type anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkylamide ether carboxylates or alkenylamide ether carboxylates, acylaminocarboxylates; alkyl phosphate ester salts And phosphoric acid ester type anionic surfactants such as polyoxyalkylene alkyl phosphoric acid ester salt, polyoxyalkylene alkyl phenyl phosphoric acid ester salt and glycerin fatty acid ester monophosphoric acid ester salt.
As the anionic surfactant, the above (2) or (6) is preferable.

Specifically, the polyoxyalkylene alkyl ether sulfate (6) is preferably a compound represented by the general formula (VI).
^{_{R 40 -O - [(EO)}} m / (PO) n] -SO 3 - M + ··· (VI)
[In the formula (VI), R ⁴⁰ represents a linear or branched alkyl group having 8 to 20 carbon atoms. EO represents an oxyethylene group, and PO represents an oxypropylene group. m represents the average number of repetitions of EO and is a number of 1 or more. n represents the average number of repetitions of PO and is a number from 0 to 6. M ⁺ is a counter cation. When n is greater than 0, PO and EO in [(PO) _m (EO) _n ] may be arranged in blocks or randomly. Also, PO and EO may be bonded PO in the ^"R 40 -O-", EO may be attached to ^"R 40 -O-". ]
As the polyoxyalkylene alkyl ether sulfate, those having a linear or branched alkyl group having 10 to 20 carbon atoms and having an average of 1 to 5 moles of alkylene oxide added are preferred.
As carbon number of an alkyl group, 10-20 are preferable and 12-14 are more preferable. Specifically, a dodecyl group, a tridecyl group, a tetradecyl group, etc. are mentioned. Of these, a dodecyl group is preferable.
The average number of repeating EO is preferably 1 to 5, and more preferably 1 to 3.
The average number of PO repeats is preferably 0 to 3, more preferably 0.
It is preferable to contain 35 to 55% by mass of the compound of m = 0 and n = 0 in the above formula (VI) with respect to the whole polyoxyalkylene alkyl ether sulfate represented by the formula (VI).

  Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts; alkanolamine salts such as monoethanolamine salts and diethanolamine salts; ammonium salts and the like. It is done. Of these, alkali metal salts are preferred.

  As a method for producing an anionic surfactant, for example, in the case of LAS, alkylbenzene can be produced by sulfonating with anhydrous sulfuric acid and neutralizing with alkali. For example, in the case of AES, it can be produced by a method in which polyoxyalkylene alkyl ether is reacted with sulfuric anhydride or chlorsulfonic acid to be sulfonated and neutralized with an alkali.

  The cleaning composition of the present invention is preferably used in combination of AES, LAS and higher fatty acid or a salt thereof.

As the component (B2), one type may be used alone, or two or more types may be used in combination.
2-50 mass% is preferable with respect to the total mass of a component (B), and, as for content of a component (B2), 5-45 mass% is more preferable, and 10-40 mass% is more preferable.
If content of a component (B2) is below the said upper limit, it will become easy to improve a residual fragrance property.
If content of a component (B2) is more than the said lower limit, it will become easy to improve recontamination prevention performance, improving residual fragrance property.

The content of the component (B2) is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and further preferably 5 to 30% by mass with respect to the total mass of the cleaning composition.
If content of a component (B2) is below the said upper limit, it will become easy to improve a residual fragrance property.
If content of a component (B2) is more than the said lower limit, it will become easy to improve recontamination prevention performance, improving residual fragrance property.

The mass ratio represented by component (A) / component (B2) (hereinafter also referred to as A / B2 ratio) is preferably 0.01 to 5, more preferably 0.05 to 2, and 0.1 to 1. Further preferred.
If A / B2 ratio is below the said upper limit, it will become easy to improve the recontamination prevention performance, improving residual fragrance property.
If A / B2 ratio is more than the said lower limit, it will become easy to improve a residual fragrance property.

The mass ratio (hereinafter also referred to as B1 / B2 ratio) represented by component (B1) / component (B2) is 1.0 or more, preferably more than 1.0, more preferably 1.5 or more, and 2 0.0 or more is particularly preferable. Further, the B1 / B2 ratio is preferably 30 or less, more preferably 15 or less, and even more preferably 10 or less. Specifically, the B1 / B2 ratio is preferably 1.0 to 30, more preferably more than 1.0 and 15 or less, and further preferably 1.5 to 10.
If the B1 / B2 ratio is equal to or less than the above upper limit value, it becomes easy to improve the recontamination prevention performance while enhancing the residual fragrance.
If B1 / B2 ratio is more than the said lower limit, it will become easy to improve residual fragrance property.

[Cationic surfactant]
Examples of the cationic surfactant include an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkylbenzyldimethylammonium salt, and an alkylpyridinium salt cationic surfactant. Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

One type of cationic surfactant may be used alone, or two or more types may be used in combination.
0-10 mass% is preferable with respect to the total mass of a cleaning composition, and, as for content of a cationic surfactant, 0-5 mass% is more preferable.

[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. Can be mentioned.
One amphoteric surfactant may be used alone, or two or more amphoteric surfactants may be used in combination.
0-10 mass% is preferable with respect to the total mass of a cleaning composition, and, as for content of an amphoteric surfactant, 0-5 mass% is more preferable.

Content of a component (B) is 15-70 mass% with respect to the total mass of a cleaning composition, and 20-65 mass% is more preferable.
When the content of the component (B) is less than or equal to the above upper limit value, it becomes easy to increase the residual fragrance.
When the content of the component (B) is not less than the above lower limit value, it becomes easy to improve the recontamination preventing performance while enhancing the residual fragrance.

<Ingredient (C)>
Ingredient (C) is a fragrance.
Ingredient (C) is a fragrance. The “fragrance” contains at least one fragrance component, and a solvent (fragrance solvent) is blended as necessary. A fragrance | flavor component is suitably selected according to the desired fragrance, and a some fragrance | flavor component is combined normally.
The fragrance component is not particularly limited, and fragrance components generally used in detergents, fiber finishes, hair cosmetics, and the like can be used. Specific examples of such fragrance components include phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural fragrances as shown below, for example. And animal flavors.
The carboxylic acids are not particularly limited and may be appropriately selected depending on the intended purpose. For example, geranilic acid, citronellic acid, phenylpropionic acid, cinnamic acid, 2-methyl-2-pentenoic acid, anthranilic acid, benzoic acid Examples include acids and phenylacetic acid.
The phenols are not particularly limited and can be appropriately selected according to the purpose.For example, eugenol, isoeugenol, methylisoeugenol, ethylisoeugenol, ethyleugenol, benzyleugenol, benzylisoeugenol, acetyleugenol, Acetyl isoeugenol, methyl eugenol, raspberry ketone, vanillin propylene glycol acetal, ethyl salicylate, benzyl salicylate, and the like.
The alcohol is not particularly limited and may be appropriately selected depending on the intended purpose.For example, bacdanol, citronellol, dihydromyrcenol, dihydrolinalool, geraniol, linalool, nerol, sandalol, santarex, Terpineol, tetrahydrolinalol, phenylethyl alcohol, trans-2-hexenol, trans-3-hexenol, myrcenol, dihydromyrcenol, tetrahydromyrcenol, terpineol, farnesol, nerolidol, 1-octanol, 1-nonanol, leaf Alcohol, menthol, matsutakeol, 1,8-cineole, cabicol, carvacrol, cumin alcohol, anise alcohol, thymol, tetrahydrolinalool, Zyl alcohol, β-phenyl alcohol, β-phenyl ethyl alcohol, styryl alcohol, cinnamic alcohol, phenoxy ethyl alcohol, linalool oxide, guaiacol, hydroxycitronellal, nerol, cedrol, santalinol, ambrinol, timberol, borneol, Examples thereof include isoborneol, polysanthol, vanillin, maltol, ethyl maltol, tiveverol, patchouli alcohol, olanthol, anethole, 4-damascol, galvanam resinoid, and the like.
The aldehydes are not particularly limited and may be appropriately selected depending on the intended purpose. For example, undecylenaldehyde, lauryl aldehyde, aldehyde C-12MNA, miracaldehyde, α-amylcinnamic aldehyde, cyclamenaldehyde, citral Citronellal, ethyl vanillin, heliotropin, anisaldehyde, α-hexylcinnamic aldehyde, octanal, ligustral, lyial, rilal, tripral, vanillin, helional, nonanal, decanal, undecanal, dodecanal, cis-3-hexanal, benzaldehyde, Examples include mugealdehyde, dupical, burgeonal, cinnamic aldehyde, jasmar, ligantoral and the like.
There is no restriction | limiting in particular as said ether, According to the objective, it can select suitably, For example, cedula bar, glycalva, (beta) -naphthol methyl ether, (beta) -naphthol ethyl ether, a helium oxide, rose oxide etc. are mentioned.
The esters are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cis-3-hexenyl acetate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, p-cresate. Dil acetate, pt-butyl cyclohexyl acetate, amyl acetate, methyl dihydrojasmonate, amyl salicylate, benzyl benzoate, benzyl acetate, cedolyl acetate, citronellyl acetate, decahydro-β-naphthyl acetate, dimethylbenzylcarbinyl acetate , Erica propionate, ethyl acetoacetate, Erica acetate, geranyl acetate, geranyl formate, citronellyl formate, neryl formate, hedion, linalyl acetate, β- Phenylethyl acetate, tricyclodecenyl acetate, cinnamyl acetate, hexyl salicylate, styryl acetate, terpinyl acetate, betiberyl acetate, ot-butylcyclohexyl acetate, manzanate, allyl heptanoate, allyl amyl glycolate , Ethyl acetate, neryl acetate, isobornyl acetate, methyl anthranilate, cis-3-hexenyl anthranilate, phenylethyl anthranilate, cinnamyl anthranilate, methyl N-methylanthranylate, tricyclodecenyl propionate, propionic acid Examples include benzyl, methyl jasmonate, methyl cinnamate, ethyl cinnamate, ethyl-2,2,6-trimethylcyclohexane carbonate, and flutate.
There is no restriction | limiting in particular as said hydrocarbons, According to the objective, it can select suitably, For example, d-limonene, (alpha) -pinene, (beta) -pinene, myrcene, 3-carene, (beta) -kaliolefin, p- Cymen, cedrene, citronellyl nitrile, lemonol, indole, 6-isopropyl quinoline, isobutyl quinoline, 2-isobutyl quinoline, benzothiazole, mint sulfide and the like.
The ketones are not particularly limited and may be appropriately selected depending on the intended purpose. For example, α-ionone, β-ionone, methyl-β-naphthyl ketone, α-damascon, β-damascon, δ-damascon , Cis-jasmon, methylionone, allylionone, cashmerelan, dihydrojasmon, belt fix, isolone diforanone, coabon, rosephenone, dinascon, nootkaton, carvone, menthone, florarozone, damasenone, caron, isojasmon, yonon, methylyonon, tonalide , Beldox, Iso E Super, etc.
The lactone is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include γ-decalactone, γ-undecalactone, γ-nonalactone, γ-dodecalactone, coumarin, ambroxan, and amblet. Examples thereof include lidide, pentalide, habanolide, and traseolide.
The musk is not particularly limited and may be appropriately selected depending on the intended purpose.For example, cyclopentadecanolide, ethylene brushate, galaxolide, musk ketone, tonalid, nitromusk, musk ambullet, musk civeten, muscone, Examples thereof include ambridolide, cyclohexadecanolide, and galaxolide.
The natural perfume is not particularly limited and may be appropriately selected depending on the intended purpose. For example, orange oil, lemon oil, lime oil, petitgren oil, yuzu oil, neroli oil, bergamot oil, lavender oil, lavandin oil , Abies oil, anise oil, bay oil, bored rose oil, ylang ylang oil, citronella oil, geranium oil, peppermint oil, peppermint oil, spearmint oil, eucalyptus oil, lemongrass oil, patchouli oil, jasmine oil, rose oil, cedar oil , Vetiver oil, galvanum oil, oak moss oil, pine oil, camphor oil, sandalwood oil, melamine oil, turpentine oil, clove oil, clove leaf oil, cassia oil, nutmeg oil, cananga oil, thyme oil, mandarin oil, basil oil , Fennel oil, clary sage oil, rosemary oil, caraway seed oil, coriander oil, Ndalwood Oil, Ambret Seed Oil, Elemioleoresin, Elemi Absolute, Guayac Wood Oil, Stylax Oil, Patchouli Oil, Labdanum Oil, Mimosa Concrete, Jasmine Concrete, Rose Concrete, Rose Wax, Jasmine Wax, Orange Flower Absolute, Violet Examples include essential oils such as absolute, opopanax resinoids, castorium absolute, iris resinoids, olivenamum resinoids, copaiba balsam, trubalsam, vanilla absolute, benzoin resinoids.
There is no restriction | limiting in particular as said animal fragrance | flavor, According to the objective, it can select suitably, For example, a fragrance | flavor, a ghost cat fragrance, a sea bream incense, a dragon moth incense, etc. are mentioned.

  Examples of the perfume solvent include ethanol, acetin (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), sucrose diacetate hexaisobutyrate, ethylene glycol dibutyrate, hexylene glycol, dibutyl sebacate, Deltile extra (isopropyl myristate), methyl carbitol (diethylene glycol monomethyl ether), carbitol (diethylene glycol monoethyl ether), TEG (triethylene glycol), benzyl benzoate, propylene glycol, diethyl phthalate, tripropylene glycol, aboline (Dimethyl phthalate), deltyl prime (isopropyl palmitate), dipropylene glycol DPG-FC (dipropylene glycol) ), Farnesene, dioctyl adipate, tributyrin (glyceryl tributanoate), hydrolite-5 (1,2-pentanediol), propylene glycol diacetate, cetyl acetate (hexadecyl acetate), ethyl abiate, avalin (methyl abie) Tate), Citroflex A-2 (acetyl triethyl citrate), Citroflex A-4 (tributyl acetyl citrate), Citroflex No. 2 (triethyl citrate), Citroflex No. 4 (tributyl citrate), durafix (methyl dihydroabietate), MITD (isotridecyl myristate), polylimonene (limonene polymer), 1,3-butylene glycol, dibutylhydroxytoluene, hercoline and the like.

Component (C) preferably contains 30 to 75% by mass of a compound having at least one functional group selected from the group consisting of a hydroxyl group and a carboxyl group, based on the total mass of component (C). It is more preferable to contain -50 mass%.
Examples of the compound having at least one functional group selected from the group consisting of a hydroxyl group and a carboxyl group include carboxylic acids, phenols, alcohols and the like among the fragrance components described above.

As the component (C), one type may be used alone, or two or more types may be used in combination.
The content of the component (C) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and further preferably 0.1 to 2% by mass with respect to the total mass of the cleaning composition. preferable.
When the content of the component (C) is within the numerical range, it becomes easy to improve the residual fragrance.

0.01-100 are preferable and, as for mass ratio (henceforth A / C ratio) represented by component (A) / component (C), 0.1-50 are preferable.
When the A / C ratio is within the above numerical range, it becomes easy to enhance the residual fragrance.
The total of components (A) to (C) does not exceed 100% by mass.

<Component (D)>
Component (D) is a polymer having at least one repeating unit (d1) and oxyalkylene unit (d2) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units.
The liquid cleaning agent of the present invention has an effect of easily removing dirt adhering to the object to be cleaned by combining the component (A) and the component (D) (soil release effect, hereinafter also referred to as “SR effect”). Enhanced.
In the present specification, “repeating unit” means a monomer unit constituting a polymer.

-Specific repeating unit (d1) Among the specific repeating unit (d1), as the alkylene terephthalate unit (hereinafter, this repeating unit is also referred to as "repeating unit (d11)"), the following general formula (D1-1) The repeating unit represented by these is mentioned.

In the formula ^{(D1-1), R 41} is a lower alkylene group. The number of carbon atoms of lower alkylene group for R ⁴¹ is 1 to 5, more preferably from 1 to 4, more preferably from 2 to 4.
Specific examples of the repeating unit (d11) include an ethylene terephthalate unit, an n-propylene terephthalate unit, an isopropylene terephthalate unit, an n-butylene terephthalate unit, an isobutylene terephthalate unit, a sec-butylene terephthalate unit, and a tert-butylene terephthalate unit. It is done. Of these, isopropylene terephthalate units are preferred.
As the repeating unit (d11), one type may be used alone, or two or more types may be used in combination.

  Among the specific repeating units (d1), the alkylene isophthalate unit (hereinafter, this repeating unit is also referred to as “repeating unit (d12)”) includes the repeating unit represented by the following general formula (D1-2). It is done.

In the formula ^{(D1-2), R 42} is a lower alkylene group. The number of carbon atoms of lower alkylene group for R ⁴² is 1 to 5, more preferably from 1 to 4, more preferably from 2 to 4.
Specific examples of the repeating unit (d12) include ethylene isophthalate units, n-propylene isophthalate units, isopropylene isophthalate units, n-butylene isophthalate units, sec-butylene isophthalate units, and tert-butylene isophthalate units. Is mentioned. Of these, isopropylene isophthalate units are preferred.
As the repeating unit (d12), one type may be used alone, or two or more types may be used in combination.

Component (D) may have only one type of repeating unit (d1), or may have two or more types. That is, the component (D) may have only the repeating unit (d11) as the repeating unit (d1) in the molecule, or may have only the repeating unit (d12). You may have both a unit (d11) and a repeating unit (d12).
Moreover, you may have 2 or more types of repeating units (d11) and / or 2 or more types of repeating units (d12).
The repeating unit (d1) may be introduced as one unit in one molecule, or may be introduced as two or more units (that is, in a block form).

1-10 are preferable, as for the repeating number of the repeating unit (d1) which 1 molecule in a component (D) has, More preferably, it is 1-6, More preferably, it is 1-4.
When the number of repeating units (d1) is within the above preferred range, the cleaning effect is easily enhanced.

-Oxyalkylene unit (d2) Examples of the oxyalkylene unit (hereinafter, this repeating unit is also referred to as "repeating unit (d2)") include repeating units represented by the following general formula (D2-1).

In the formula (D2-1), R ⁴³ is a lower alkylene group. The number of carbon atoms of lower alkylene group for R ⁴³ is preferably 1 to 4, more preferably from 2 to 4, more preferably 2 or 3.
Examples of the repeating unit (d2) include an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit. Of these, oxyethylene units and oxypropylene units are preferred.

Component (D) may have only one type of repeating unit (d2), or may have two or more types. That is, the component (D) may have, for example, only an oxyethylene unit, only an oxypropylene unit, or only an oxyethylene unit as a repeating unit (d2) in one molecule. And both oxypropylene units.
In addition, the component (D) may have an oxyalkylene group (one having a repeating unit (d2) of 1) as a repeating unit (d2) in one molecule, and a polyoxyalkylene group (The number of repeating units (d2) is 2 or more) and may have both an oxyalkylene group and a polyoxyalkylene group.

The number of repeating units (d2) that one molecule in component (D) has is 1 or more, preferably 1 to 100, more preferably 1 to 80, and still more preferably 1 to 50.
When the number of repeating units (d2) is within the above-mentioned preferable range, the cleaning effect on oily soil is likely to be enhanced.

  The component (D) may be a polymer in which the repeating unit (d1) and the repeating unit (d2) are polymerized in a block shape or a polymer in which the repeating unit (d1) is polymerized in a random shape. Among these, as the component (D), a polymer polymerized in a block shape is preferable.

In addition to the repeating unit (d1) and the repeating unit (d2), the component (D) may have other repeating units. Examples of the other repeating unit include a repeating unit derived from a polymerization initiator, a polymerization terminator and the like, a repeating unit derived from a monomer copolymerizable with a monomer that provides the repeating unit (d1) or the repeating unit (d2), and the like. It is done.
When the component (D) has another repeating unit, the total of the repeating unit (d1) and the repeating unit (d2) is 80 mol% based on the total of all the repeating units constituting the component (D). Preferably, it is 90 mol% or more, and may be 100 mol%. When the sum of the repeating unit (d1) and the repeating unit (d2) is not less than the preferable lower limit value, the detergency is more likely to be increased.

Component (D) is preferably a water-soluble polymer from the standpoints of its own solubility and liquid stability when used as a liquid detergent.
The term “water-soluble polymer” as used herein means that 10 g of a polymer is added to 1000 g of water at 40 ° C. in a 1 liter beaker and stirred for 12 hours (200 rpm) with a stirrer (thickness 8 mm, length 50 mm). The one that has been dissolved after.

The weight average molecular weight of component (D) is preferably 500 to 10,000. If a weight average molecular weight is in the said range, the dispersibility to water will improve and it will become easy to improve SR effect and recontamination prevention effect more. In addition, the low temperature stability of the liquid detergent is likely to be increased. The lower limit of the weight average molecular weight is more preferably 800 or more, and even more preferably 1000 or more. On the other hand, the upper limit of the weight average molecular weight is more preferably 9000 or less, and even more preferably 8000 or less. As for the weight average molecular weight of a component (D), 800-9000 are more preferable, and 1000-8000 are more preferable.
In addition, the weight average molecular weight of a component (D) is 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). Show.

  Component (D) is a synthesis method disclosed in various documents, textbooks, patent documents, etc., for example, Journal of Polymer Science, Vol. 3, pages 609 to 630 (1948); Journal of Polymer Science, 8 Volume 1 to 22 (1951); can be produced by the method described in JP-A-61-218699.

  Preferable specific examples of component (D) include a polymer compound represented by the following general formula (D1), a polymer compound represented by the general formula (D2), or a mixture thereof. .

In the formulas (D1) and (D2), R ⁴⁰ and R ⁵⁰ are each independently a hydrogen atom or a methyl group, each preferably a methyl group, and more preferably a methyl group. .
R ⁴⁴ and R ⁴⁷ are each a methyl group or a hydrogen atom, and each is preferably a methyl group.
R ⁴⁵ , R ⁴⁶ , R ⁴⁸ and R ⁴⁹ are each independently an alkylene group having 2 to 4 carbon atoms.
Each of s1 and s2 is 0 to 10, preferably 0.5 to 5, and more preferably 0.5 to 2.5. t1, t2, u1 and u2 are each independently 1 to 100, preferably 1 to 80, more preferably 1 to 50, still more preferably 10 to 50, and particularly preferably 20 ~ 30. When s1, s2, t1, t2, u1, and u2 are in the above preferred ranges, the blending effect of component (D) is sufficiently exhibited. Moreover, the solubility with respect to water improves more, and when it mix | blends with a liquid detergent, it becomes easy to obtain the liquid detergent excellent in a transparent feeling.

In (D1), the ratio [s1: (t1 + u1)] between s1 and (t1 + u1) is preferably 1: 5 to 1:20, and more preferably 1: 8 to 1:18. When the ratio of s1 to (t1 + u1) is in the above preferred range, the cleaning power is further increased and the solubility in water is further increased.
The ratio [s2: (t2 + u2)] between s2 and (t2 + u2) in (D2) is preferably in the same range as the ratio [s1: (t1 + u1)].

As the component (D), one type may be used alone, or two or more types may be used in combination.
Moreover, as a component (D), a synthetic product may be used and a commercial item may be used.
As a commercial item of a component (D), brand name TexCare SRN-100 (made by Clariant, weight average molecular weight 2000-3000), brand name TexCare SRN-300 (made by Clariant, weight average molecular weight 7000), brand name Repel- Examples include O-Tex Crystal (manufactured by Rhodia), trade name Repel-O-Tex QC (manufactured by Rhodia), and the like.
Among these, TexCare SRN-100 is preferable because it is highly soluble in water and excellent in storage stability. Moreover, it is preferable to use the brand name TexCare SRN-170 (manufactured by Clariant), which is commercially available as a 70% aqueous solution of the TexCare SRN-100, from the viewpoint of excellent handleability.

  0.1-1.5 mass% is preferable with respect to the total mass of a cleaning agent, and, as for content of a component (D), 0.5-1 mass% is more preferable. When the content of the component (D) is equal to or greater than the lower limit, the SR effect is more easily enhanced. In addition, the effect of preventing recontamination can be further enhanced. When the content of the component (D) is not more than the above upper limit value, the blending stability into the liquid detergent is likely to be enhanced, and the low temperature stability is likely to be enhanced.

  The total content of component (A) and component (D) in the liquid detergent [hereinafter also referred to as “(A + D) total content”] is preferably 0.1 to 3.5% by mass, and 0.6 -3.3 mass% is more preferable, and 1-3 mass% is further more preferable. When the total content of (A + D) in the liquid detergent is equal to or more than the lower limit value, the SR effect is more easily enhanced. In addition, the effect of preventing recontamination can be further enhanced. When the (A + D) total content in the liquid detergent is not more than the above upper limit value, the low temperature stability is more likely to be enhanced.

The mass ratio represented by the component (A) / component (D) [the mass ratio of the content of the component (A) to the content of the component (D), hereinafter also referred to as “A / D ratio”) is 0.5 -4 are preferable and 1-3 are more preferable. When the A / D ratio is within the above-mentioned preferable range, the SR effect is more easily enhanced.
In addition, when the EO average added mole number of the nonionic surfactant (B1) is 10 or more, the SR effect is further enhanced.

<Ingredient (E)>
Component (E) is at least one selected from carboxylic acids represented by the following general formula (VII) and salts thereof.
X—R ¹ —COOH (VII)
However, in formula (VII), ^{R 1} is a divalent hydrocarbon group or an arylene group, 1 to 4 carbon atoms, X is -H, -OH, -CH ₃ or -COOH,.
In the liquid detergent of the present invention, the enzyme stability is enhanced by the combined use of the component (B) and the component (E).

In formula (VII), R ¹ is a C 1-4 divalent hydrocarbon group or an arylene group. These divalent hydrocarbon groups having 1 to 4 carbon atoms and arylene groups 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 the 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.
Examples of the arylene group include a phenylene group.
X is —H, —OH, —CH ₃ , or —COOH.

Examples of the carboxylic acid represented by the formula (VII) 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 (E), benzoic acid, lactic acid, or a salt thereof is preferable, and lactic acid or a salt thereof is more preferable because the enzyme stability is further improved. Moreover, as a component (E), a sodium salt is preferable from the point which external appearance stability is improved more.
As the component (E), sodium lactate is preferable because the enzyme stability and the appearance stability are further improved.
As the component (E), any one kind may be used alone, or two or more kinds may be used in combination.

  The content of the component (E) 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 with respect to the total mass of the liquid detergent. .

<Ingredient (F)
Component (F) is an enzyme.
The liquid cleaning agent of the present invention contains the component (F), so that the cleaning power is further enhanced.
As the component (F), enzymes used for laundry detergent applications can be used, and examples thereof include protease, amylase, lipase, cellulase, mannanase and the like.
In the present specification, “enzyme” means an enzyme preparation.

As proteases, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type 2.5, Eraase Ultra 16L, Esperase 2.5L, Esperase 2.5L, Esperase 2.5L, Esperase L , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, trade names available from Genencor, Inc., Purefect L, Purefect OX, Properase L, and the like.
As amylases, trade names available from Novozymes as amylase preparations are: Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Steinzyme Plus 12L And trade name DB-250 available from Seikagaku Corporation.
Examples of the lipase include trade names Lipex 100L and Lipolase 100L, which are available from Novozymes as lipase preparations.
Examples of the cellulase include trade names Endolase 5000L, Celluzyme 0.4L, Carzyme 4500L and the like which are available from Novozymes as cellulase preparations.
Examples of mannanase include Mannaway 4L, which is a mannanase preparation available from Novozymes.

Component (F) preferably contains a protease. By incorporating a protease, the detergency against protein soil is further enhanced.
Among the above, proteases include, among others, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L, Everase Ultra 16L, Alcalase 2.5L, Alcalase 2.5L, Alcalase Ultra 2.5L, Alcalase Ultra 2.5L, Alcalase Ultra 2.5L Ultra 2.5XL and Coronase 48L are preferable, and Alcalase 2.5L, Everase 16L, Savinase 16L, and Coronase 48L are particularly preferable.
As the component (F), any one kind may be used alone, or two or more kinds may be used in combination.

The content of the component (F) is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and 0.1 to 1.5% by mass with respect to the total mass of the liquid detergent. Further preferred. When the content of the component (D) is not less than the lower limit of the preferable range, the detergency is further increased. When the content of the component (D) is not more than the upper limit of the preferable range, the precipitation of the enzyme is suppressed and the appearance stability is further improved.
In addition, in this specification, the compounding quantity of the enzyme in a liquid detergent is a compounding quantity as a formulation. The blending amount is obtained by a general method, for example, by calculating back from the amount of raw material used or the amount of enzyme protein in the liquid detergent.

Mass ratio represented by said component (A) / component (E) [mass ratio of content of component (A) to content of component (E), hereinafter also referred to as “A / E ratio”. ] Is 0.1-20.
When the A / E ratio is less than 0.1 or more than 20, appearance stability is impaired.
The A / E ratio is preferably 0.3 to 10, more preferably 0.5 to 7, and still more preferably 1 to 5.

  0.1-4 mass% is preferable with respect to the total mass of a liquid cleaning agent, and, as for the total content of a component (A) and a component (E), 0.5-3 mass% is more preferable, 1-2. 5 mass% is more preferable. When the total content of the component (A) and the component (E) is not less than the lower limit, it is easy to adjust the A / E ratio to a specific range of the present application, and a liquid detergent excellent in appearance stability is easily obtained. Moreover, it becomes easy to maintain the freedom degree of the mixing | blending of another component as the total content of a component (A) and a component (E) is below the said upper limit.

<Optional component>
In the cleaning composition of the present invention, components usually used in the cleaning composition may be used according to the purpose within a range not impeding the effects of the present invention.
The detergent composition of the present invention comprises an enzyme such as protease, a water-miscible organic solvent such as ethanol, an alkaline agent such as monoethanolamine, an antioxidant such as dibutylhydroxytoluene, a preservative such as sodium benzoate, calcium chloride Further, an enzyme stabilizer such as sodium lactate, a colorant such as a pigment, zeolite, a detergency builder and the like may be included.

  In the cleaning composition of the present invention, the component (A) is at least one selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II). In addition, the component (B1) is at least one selected from the group consisting of the compound represented by the general formula (III) and the compound represented by the general formula (IV), and the component (C) is a phenol. , Alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural fragrances, and animal fragrances. The mass ratio represented by (B1) / component (B2) is preferably 1.0 or more.

  In the cleaning composition of the present invention, the component (A) is at least one selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II). , Component (B1), component (B1) contains fatty acid methyl ester ethoxylate, component (C) is phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, It is at least one selected from the group consisting of lactones, musks, natural fragrances, and animal fragrances, and the mass ratio represented by component (B1) / component (B2) is 1.0 or more. preferable.

  In the cleaning composition of the present invention, the component (A) is at least one selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II). , Component (B1) contains fatty acid methyl ester ethoxylate, and component (C) contains phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musk At least one selected from the group consisting of fragrances, natural fragrances, and animal fragrances, the mass ratio represented by component (B1) / component (B2) is 1.0 or more, and the fatty acid methyl ester ethoxy The content of the rate is preferably 10% by mass or more based on the total mass of the component (B).

In the cleaning composition of the present invention, the component (A) is at least one selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II). is at least one that is selected component (B1) is a compound represented by the general formula (III), and from the group consisting of compounds represented by the general formula (IV), component (B2) is the formula It is at least one selected from the group consisting of a compound represented by (VI) and a linear or branched alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms, and the component (C) is phenol , Alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural fragrances, and animal fragrances. Is one, it is preferable mass ratio represented by component (B1) / component (B2) is 1.0 or more.

  In the cleaning composition of the present invention, the component (A) is a compound represented by the general formula (Ia), the component (B1) is a compound represented by the general formula (III), and the general A compound having at least one selected from the group consisting of compounds represented by formula (IV), wherein component (B2) has a compound represented by formula (VI) and an alkyl group having 8 to 18 carbon atoms. It is at least one selected from the group consisting of linear or branched alkylbenzene sulfonates, and component (C) is phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, It is at least one selected from the group consisting of ketones, lactones, musks, natural fragrances, and animal fragrances, and the mass ratio represented by component (B1) / component (B2) is 1.0 or more. is there Door is preferable.

  In the cleaning composition of the present invention, the component (A) is a compound represented by the general formula (Ia), the component (B1) is a compound represented by the general formula (III), and the general A compound having at least one selected from the group consisting of compounds represented by formula (IV), wherein component (B2) has a compound represented by formula (VI) and an alkyl group having 8 to 18 carbon atoms. It is at least one selected from the group consisting of linear or branched alkylbenzene sulfonates, and component (C) is phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, It is at least one selected from the group consisting of ketones, lactones, musks, natural fragrances, and animal fragrances, and the mass ratio represented by component (B1) / component (B2) is 1.0-30. In It is preferable mass ratio represented by component (A) / component (B2) is 0.01 to 5.

≪Method for producing detergent composition≫
When the cleaning composition of the present invention is a liquid, it is produced by mixing the components (A) to (C) and optional components as required by a conventionally known method.
When the cleaning composition of the present invention is granular, it can be produced by a conventionally known method, for example, a dry blend method in which each raw material is powder-mixed, a dry granulation method in which powder raw materials are mixed and fluidized to granulate, Agitation granulation method in which powder raw material is mixed and fluidized while spraying and granulating by liquid binder, extrusion granulation method in which raw material is kneaded and extruded with an extruder, raw material is kneaded and pulverized Examples thereof include a pulverization granulation method and a spray drying method in which a slurry containing raw materials is spray dried.

≪How to use detergent composition≫
Examples of the method of using the cleaning composition of the present invention include a normal method of use.
When using the cleaning composition of the present invention for cleaning textile products, for example, a method of cleaning an object to be cleaned with a washing machine using a cleaning liquid in which 5 to 30 mL of the cleaning composition is added to 30 L of water, Examples include a method of immersing an object to be washed in the cleaning liquid. Alternatively, the cleaning composition may be applied directly to an object to be washed and left for a certain period of time, and then used in a normal washing method (application cleaning).
When the cleaning composition of the present invention is used for cleaning a hard surface, the cleaning composition is dissolved in water to prepare a cleaning solution, and applied to the hard surface to be cleaned by spraying or the like. A method of scrubbing with a cleaning tool such as
When the cleaning composition of the present invention is used for cleaning dishes, etc., a method of cleaning the dishes by including the cleaning composition in a sponge, a diluted cleaning solution is prepared by dissolving the cleaning composition in water And a method of rubbing with a sponge while immersing tableware or the like in the cleaning liquid.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The composition (content (mass%)) of the cleaning composition of each example is shown in Tables 6-7.
In the table, when there is a blank blending component, the blending component is not blended.
In the table, “balance” means the balance added so that the total amount of all the ingredients contained in the cleaning composition is 100% by mass.
The raw materials used in this example are as follows.

<Component (A)>
A-1: Polyethyleneimine ethylene oxide adduct, manufactured by BASF, trade name “Sokalan HP20”. In the above formula (Ia), compounds wherein R ²² is an ethylene group and m is 20.
A-2: Polyethyleneimine, manufactured by BASF, trade name “Lupazole P”, weight average molecular weight of about 75000, comparative product of component (A).

<Component (B)>
[Component (B1)]
B1-1: Fatty acid methyl ester ethoxylate (MEE) (carbon number 12 to 14 of fatty acid, average addition mole number 15 of EO), R ² = alkyl group having 11 carbon atoms and carbon number in general formula (III) 13 alkyl groups, R ³ = methyl group, s = 15, t = 0, u = 0. Synthesized by the following synthesis method.
(Synthesis of B1-1)
The synthesis was performed according to the synthesis method described in JP-A No. 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 / magnesium hydroxide (unmodified) catalyst was obtained. An autoclave was charged with 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 in a 4 L autoclave. The catalyst was reformed inside. 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 B1-1. The narrow rate of B1-1 was 30% by mass.
B1-1 ′: fatty acid methyl ester ethoxylate (MEE) (12 to 14 carbon atoms of fatty acid, average addition mole number of EO of 15), R ² = alkyl group having 11 carbon atoms and carbon in general formula (III) Formula 13 alkyl group, R ³ = methyl group, s = 15, t = 0, u = 0. Synthesized by the following synthesis method.
(Synthesis of B1-1 ′)
B1-1 ′ was synthesized according to the following synthesis method.
In a 500 mL beaker, 137 g of 2-ethylhexanol (primary reagent, manufactured by Kanto Chemical Co., Ltd.) and 41.7 g of calcium acetate monohydrate (special grade reagent, manufactured by Kanto Chemical Co., Ltd.) were placed, and the room temperature (25 (° C.) to obtain a dispersion (dispersing step). While stirring the dispersion, 20.9 g of sulfuric acid (special grade reagent, manufactured by Kanto Chemical Co., Inc.) was added and mixed for 10 minutes with a dropping funnel (mixing step). In the mixing step, heat generation was caused by the addition of sulfuric acid, so the beaker was cooled in a water bath and the reaction temperature was controlled at 30-50 ° C. After adding sulfuric acid, the mixture was further stirred for 2 hours while maintaining at 50 ° C. (catalyst aging step) to obtain an alkoxylation catalyst.
Into an autoclave, 12.5 g of the alkoxylation catalyst, 462 g of methyl laurate (Pastel M12, manufactured by Lion Chemical Co., Ltd.) and 166 g of methyl myristate (Pastel M14, manufactured by Lion Chemical Co., Ltd.) were added and stirred. While stirring, the inside of the autoclave was purged with nitrogen, heated to 100 ° C., and dehydrated under reduced pressure conditions of 1.3 kPa or less for 30 minutes. Next, the temperature was raised to 160 ° C., and 1876 g of ethylene oxide (EO) (15 times the total of methyl laurate and methyl myristate) was introduced and stirred under the condition of 0.1 to 0.5 MPa (addition reaction). Process). 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). B1-1 ′ was obtained by filtering the crude reaction product to remove the catalyst.
B1-2: Alcohol ethoxylate (AE), natural alcohol added with 15 mol equivalent of ethylene oxide. In the general formula (IV), R ⁴ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 15, w = 0, x = 0. Synthesized by the following synthesis method.
(Synthesis of B1-2)
224.4 g of CO-1214 (trade name) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of 30% by mass NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. Next, 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 the blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
After completion of the addition of ethylene oxide, aging was performed 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 to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, thereby obtaining B1-2. It was.
B1-3: alcohol ethoxylate (AE), a product obtained by adding 7 moles of ethylene oxide to natural alcohol. In the general formula (IV), R ⁴ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 7, w = 0, x = 0. Synthesized by the following synthesis method.
(Synthesis of B1-3)
224.4 g of CO-1214 (trade name) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of 30% by mass NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. Next, 355.0 g of ethylene oxide (gaseous) was gradually added to the reaction solution while stirring the reaction solution. At this time, ethylene oxide was added through the blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
After completion of the addition of ethylene oxide, aging was performed 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 to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, to obtain B1-3. It was.
B1-4: Natural alcohol (mass ratio of 12 alcohols / 14 alcohols = 7/3), 8 moles of ethylene oxide, 2 moles of propylene oxide, 8 moles of ethylene oxide blocked in this order Added one. In the general formula (IV), R ⁴ = alkyl group having 12 carbon atoms and alkyl group having 14 carbon atoms, v = 8, w = 2, x = 8.
B1-5: A product obtained by adding 7 mol of ethylene oxide to a secondary alcohol having 12 carbon atoms and a secondary alcohol having 14 carbon atoms. Product name “Softanol 70”, manufactured by Nippon Shokubai Co., Ltd. In the general formula (IV), R ⁴ = secondary alkyl group having 12 carbon atoms and secondary alkyl group having 14 carbon atoms, v = 7, w = 0, x = 0.

[Component (B2)]
-B2-1: Sodium polyoxyethylene alkyl ether sulfate (AES). In the formula (VI), a compound in which R ⁴⁰ = a linear alkyl group having 12 to 14 carbon atoms, m = 1.0, n = 0, and M = sodium. Synthesized by the following synthesis method.
(Synthesis of B2-1)
In an autoclave with a capacity of 4 L, 400 g of a product name CO1270 alcohol (mixture of 75/25 mass ratio of alcohol having 12 carbons and alcohol having 14 carbons) manufactured by P & G as raw material alcohol and potassium hydroxide as a reaction catalyst After charging 0.8 g and replacing the inside of the autoclave with nitrogen, 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: flame ionization detector (FID), column: Ultra-1 (manufactured by HP, L25m × φ0.2mm × T0.11 μm As a result, the alcohol ethoxylate obtained had an average addition mole number of ethylene oxide of 1.0. Moreover, the compound which has not added ethylene oxide was 43 mass% with respect to the total mass of the obtained alcohol ethoxylate.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer and replaced with nitrogen, and then 96 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining 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. Subsequently, B2-1 was obtained by neutralizing this with sodium hydroxide aqueous solution.
B2-2: Sodium linear alkylbenzene sulfonate (LAS), manufactured by Lion Corporation, trade name “Lypon LH-200”.
B2-3: monoethanolamine salt (AEPS) of polyoxyalkylene alkyl ether sulfate. In the formula (VI), a compound in which R ⁴⁰ = a linear alkyl group having 12 carbon atoms, m = 2.0, n = 1.0, and M = monoethanolamine. Synthesized by the following synthesis method.
(Synthesis of B2-3)
In an 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 (molecular weight 186.33), purity > 99%] 640 g and KOH 1.0 g were charged and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, nitrogen substitution was performed, the temperature was raised to 120 ° C., and 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 at 80 ° C. for 30 minutes and then extracted. The alkyl group was dodecyl group, the average added mole number of PO was 1.0, EO An alkoxylate having an average added mole number of 2.0 was obtained.
The resulting alkoxylate was sulfated in a falling film reactor using SO ₃ gas. The obtained sulfate was neutralized with monoethanolamine to obtain a composition containing a monoethanolamine salt (AEPS) of polyoxyethylene polyoxypropane-1,2-diylalkyl ether sulfate.
B2-4: Coconut fatty acid, trade name “Zushi fatty acid”, manufactured by NOF Corporation.

<Ingredient (C)>
-C-1: The fragrance | flavor shown to Tables 1-5.

<Component (D)>
D-1: A polymer having a specific repeating unit (d1) and an oxyalkylene unit (d2). Made by Clariant Co., Ltd., trade name “TexCare SRN-170”, weight average molecular weight 2000 to 3000, and polymer compound represented by the above general formula (D1). In addition, D-1 is the condition of the above-mentioned “water-soluble polymer” (that is, 10 g of polymer in a 1 liter beaker, added to 1000 g of water under the condition of 40 ° C., and a stirrer (thickness 8 mm, length 50 mm). ) To be dissolved after stirring (200 rpm) for 12 hours.
<Ingredient (E)>
-Sodium lactate (stabilizer), manufactured by Kanto Chemical Co., Ltd., trade name “sodium lactate”.
<Component (F)>
Alcalase (protease), manufactured by Novozymes, trade name “Alcalase 2.5L”.

<Optional component>
MEA: monoethanolamine (alkali agent), manufactured by Nippon Shokubai Co., Ltd., trade name “monoethanolamine”.
BHT: dibutylhydroxytoluene (antioxidant), manufactured by Sumitomo Chemical Co., Ltd., trade name “SUMILZER BHT-R”.
-Ethanol (water-miscible organic solvent), manufactured by Nippon Alcohol Sales Co., Ltd., trade name "specific alcohol 95 degree synthesis".
-Sodium benzoate (preservative), manufactured by Toa Gosei Co., Ltd., trade name “Sodium benzoate”.
・ Calcium chloride (enzyme stabilizer), manufactured by Kanto Chemical Co., Ltd., trade name “Calcium chloride (special grade)”.
-Dye (colorant), manufactured by Sakai Kasei Co., Ltd., trade name "Green No. 3".

<Method for producing cleaning composition>
(Examples 1-13, Comparative Examples 1-5)
According to the composition shown in Tables 6-7, each component was added and mixed in water, and the cleaning composition of Examples 1-13 and Comparative Examples 1-5 was obtained.
The cleaning compositions of Examples 1 to 13 and Comparative Examples 1 to 5 were evaluated for re-contamination prevention performance, residual fragrance property, and storage stability as follows.
Examples 5, 6, 7, 9 and 11 are reference examples.

<Evaluation of recontamination prevention performance>
Using the cleaning composition of each example, the washing process, the rinsing process, and the drying process shown below were performed three times in this order.

Cleaning process:
The following cotton cloth, wet artificial contamination cloth and skin shirt were used as the objects to be washed.
-Cotton cloth: 5 sheets of cotton knitted fabric (manufactured by Tanigami Shoten) 5cm x 5cm as re-contamination judgment cloth.
-Wet artificially contaminated cloth: Contaminated cloth manufactured by the Japan Laundry Science Association (oleic acid 28.3 mass%, triolein 15.6 mass%, cholesterol oleate 12.2 mass%, liquid paraffin 2.5 mass%, squalene 2 20 sheets of soil with a composition of 0.5 mass%, cholesterol 1.6 mass%, gelatin 7.0 mass%, mud 29.8 mass%, carbon black 0.5 mass%).
-Skin shirt: 150 skin shirts (LL size, manufactured by DVD) finely cut (about 3 cm x 3 cm).
In a Terg-o-meter (made by UNITED STATES TESTING), put 900 mL of 3 ° DH hard water at 25 ° C., add 0.6 g of the detergent composition, and then add the washing object to adjust the bath ratio. It was adjusted to 20 times and washed at 120 rpm and 25 ° C. for 10 minutes.

Rinsing process:
The object to be washed after washing was dehydrated for 1 minute, and then 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. In the second time, a predetermined amount of softening agent was added to 900 mL of 3 ° DH hard water at 25 ° C. to perform rinsing. As the softener, room-dried saffron (manufactured by Lion Corporation) was used.

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

Using a reflectance meter (spectral color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.), the reflectance (Z value) of the recontamination determination cloth before and after the washing treatment was measured, and ΔZ was determined from the following equation.
ΔZ = (Z value before washing process) − (Z value after washing process)
The average value of five sheets was obtained for ΔZ in the re-contamination determination cloth of the cotton cloth. Then, according to the following criteria using the average value as an index, the effect of preventing the re-contamination of the cotton fabric with the cleaning composition was evaluated. In the following evaluation criteria, “A” and “B” were acceptable. The evaluation results are shown in Tables 6-7.

[Evaluation criteria]
A: 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.

<Evaluation of residual fragrance>
(1) Treatment of cotton towel with cleaning composition (pretreatment of evaluation cloth)
A commercial cotton towel (manufactured by Toshin Co., Ltd.) was subjected to the following pretreatment three times with a commercial detergent “Top Platinum Clear” (manufactured by Lion Corporation) using a two-tank washing machine (Toshiba VH-30S). .
Pretreatment: 2 cycles of washing with standard amount of detergent, bath ratio 30 times, washing with tap water at 45 ° C. for 10 minutes and subsequent water rinsing for 10 minutes.
(Treatment with the detergent composition in the rinsing process during washing)
1.0 kg of pre-cleaned cotton towel (manufactured by Toshinsha) was washed for 10 minutes with the detergent composition shown in Tables 6-7 using a two-tank washing machine (VH-30S manufactured by Toshiba) (standard) Use amount, standard course, bath ratio 30 times, use of tap water at 25 ° C.), followed by dehydration for 1 minute, and then a first rinse for 3 minutes. After the first rinse, a 1 minute dehydration was performed, followed by a second rinse for 3 minutes followed by a 1 minute dehydration.
(2) Evaluation of treated cloth After drying for 18 hours as described above, the fragrance strength of the treated cloth (cotton towel) after storage for 5 days under the conditions of 20 ° C. and 40 RH conforms to the following 6-step odor intensity display method. And sensory evaluation. The fragrance sustainability was evaluated according to the following criteria based on the average score (calculated to the first decimal place) of 8 professional panelists. In terms of merchandise value, ○ or more was accepted. The evaluation results are shown in Tables 6-7.
<6-level odor intensity display method>
0: Odorless 1: A scent that can be finally detected 2: A scent enough to understand what scent 3: A scent that can be easily detected 4: A strong scent 5: A strong scent [Evaluation criteria]
◎◎◎: 3.0 points or more ◎◎: 2.9 to 2.5 points ◎: 2.4 to 2.0 points ○: 1.9 to 1.5 points △: 1.4 to 1.0 points ×: 0.9 point or less

<Evaluation of storage stability>
A transparent glass bottle (Hiroguchi standard bottle, PS-NO.11) was filled with 100 mL of the cleaning composition of each example, and the lid was closed and sealed. In this state, it was stored in a constant temperature bath at 5 ° C. or 25 ° C. for 7 days.
After such storage, the appearance of the liquid was visually observed, and the storage stability of the cleaning composition was evaluated according to the following evaluation criteria. △ or more was accepted. The evaluation results are shown in Tables 6-7.
[Evaluation criteria]
○: Precipitated material is not observed at the bottom of the glass bottle, and the fluidity of the liquid is present.
Δ: Precipitated material is observed at the bottom of the glass bottle, but when the glass bottle is shaken lightly, the precipitated material disappears (dissolves).
X: A precipitated substance is observed at the bottom of the glass bottle, and even if the glass bottle is shaken lightly, the precipitated substance does not disappear, or gelation or white turbidity occurs immediately after the production of the cleaning composition.

<Evaluation of SR effect>
Tet cotton cloth for evaluation (cotton / polyester = 40/60) and cotton knitted fabric were put into a fully automatic electric washing machine (AW-80VC, manufactured by Toshiba Corporation), and the bath ratio was adjusted to 20 times. Thereto, 12 g of the liquid detergents of Examples 1 and 12 were added, and a washing operation was performed in which washing, rinsing and dehydration were sequentially performed in a standard course. The washing time, rinsing, dehydration, and water volume (set to 36 L) were not adjusted at all and the standard settings of the washing machine were used. The temperature of the tap water used was 15 ° C. This washing operation was repeated 5 times. After finishing the washing operation five times, the evaluation tet cotton cloth was dried overnight in a flat lay, and the evaluation tet cotton cloth after drying was cut into 5 × 5 cm to obtain an evaluation cloth. The evaluation cloth was coated with 50 μL of fat (oleic acid, palmitic acid, myristic acid, lauric acid, triolein, tripalmitin, hexadecyl palmitate, squalene, carbon black) and dried for 24 hours. A paste cloth was produced.
The dirt cloth was subjected to a cleaning test as follows.
As a cleaning tester, Terg-O-meter (manufactured by UNITED STATES TESTING) was used. As the cleaning solution, a solution prepared by adding 300 μL of the liquid cleaning agent of Comparative Example 4 to 900 mL of water and stirring for 30 seconds was used. The cleaning tester was charged with 900 mL of the cleaning liquid, the five soiled cloths, and the cleaning knitted cloth, and was washed at 120 rpm and 15 ° C. for 20 minutes in accordance with the bath ratio of 20 times. Next, it was transferred to a two-tank washing machine (product name: CW-C30A1-H1 manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried. The reflectance of unstained cloth (evaluation cloth), uncleaned cloth, and cleaned cloth is measured with a color difference meter (manufactured by Nippon Denshoku Co., Ltd .: product name SE200 type). The washing rate (%) was determined by the formula.
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
However, K / S is (1-R / 100) ² / (2R / 100) (R is the reflectance of the dirt cloth before washing, the reflectance of the dirt cloth after washing, or unstained Indicates the reflectance (%) of the cloth). The average value of the cleaning rate of the five soiled cloths was determined, and the SR effects of the liquid cleaning agents of Examples 1 and 12 were evaluated according to the following evaluation criteria using this average value as an index. ◎ and ○ were accepted.

[Evaluation criteria for SR effect]
A: The cleaning rate is 10% or more.
○: The cleaning rate is 7% or more and less than 10%.
Δ: The cleaning rate is 4% or more and less than 7%.
X: The cleaning rate is less than 4%.

<Evaluation of enzyme stability (enzyme activity remaining rate)>
The liquid detergents of Example 1, Example 13, and Comparative Example 1 were manufactured and stored at 37 ° C. and 4 ° C. for 4 weeks, respectively. The following protease activity was measured for a liquid detergent stored at 37 ° C. for 4 weeks (stored at 37 ° C.) and a liquid detergent stored at 4 ° C. for 4 weeks (stored at 4 ° C.).

Protease activity measurement:
Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free / Calbiochem (registered trademark)) is dissolved in 1N sodium hydroxide (1 mol / L sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Inc.), and the pH is adjusted to 10. 5 was diluted with 0.05M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Ltd.) aqueous solution so that the concentration of milk casein was 0.6% to obtain a protease substrate.
A solution obtained by diluting 1 g of the obtained liquid cleaning agent 25 times with 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 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. Thereafter, 5 g of a 0.44M aqueous solution of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Inc.), an enzyme reaction terminator, was added to the solution and stirred for 10 seconds with a vortex mixer. Thereafter, 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 recovered.
The absorbance (absorbance A) at a wavelength of 275 nm of the collected filtrate was measured using an ultraviolet-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation. The greater the absorbance A, the greater the amount of tyrosine (produced by the protease degrading the protease substrate) present in the filtrate.
In order to eliminate the influence of absorption other than the target component, 5 g of TCA as an enzyme reaction stopper was separately added to 1 g of each sample solution, stirred for 10 seconds with a vortex mixer, then 5 g of protease substrate was added, and 10 times with a vortex mixer. Stir for 2 seconds and remove with a 0.45 μm filter to collect the filtrate. Thereafter, the absorbance (absorbance B) at a wavelength of 275 nm of the filtrate was measured using UV-160.

From the measurement result of the protease activity, the remaining rate of protease activity (%) was determined by the following formula.
The absorbance value at 275 nm of each sample assigned to the following formula was used by dividing the absorbance value at 600 nm measured at the same time in order to exclude scattered light such as bubbles from the absorbance.
Protease activity residual rate = (Absorbance of 37 ° C. stored product A−Absorbed B of 37 ° C. stored product) / (Absorbance of 4 ° C. stored product A−Absorbed product of 4 ° C. stored product) × 100

Using the remaining rate of protease activity (%) as an index, enzyme stability was evaluated based on the following criteria, and ◎, ○, and Δ were accepted.
A: 80% or more.
○: 70% or more and less than 80%.
Δ: 60% or more and less than 70%.
X: Less than 60%.

From the result of Tables 6-7, Examples 1-13 which applied this invention were excellent in the recontamination prevention performance, and were excellent also in residual fragrance property.
The comparative example 1 which does not contain a component (A) was inferior to residual fragrance property.
Comparative Examples 2 and 5 in which the B1 / B2 ratio was outside the numerical range of the present invention were inferior in residual fragrance properties.
The comparative example 3 which does not contain a component (A) and whose B1 / B2 ratio is outside the numerical range of this invention was inferior to a residual scent property.
The comparative example 4 which used the polyethyleneimine instead of the component (A) was inferior in the recontamination prevention performance and the remaining scent.

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition which has high aftercense property can be provided.

Claims (5)

An alkylene oxide adduct of polyalkyleneamine (A),
A surfactant (B) comprising a nonionic surfactant (B1) and an anionic surfactant (B2), and a fragrance (C),
Content of the said component (A) is 0.01-3 mass% with respect to the total mass of a cleaning composition,
The component (B1) includes a nonionic surfactant (b11) represented by the following general formula (III) and a nonionic surfactant (b12) represented by the following general formula (IV),
The component (B2) includes a polyoxyalkylene alkyl ether sulfate.
Der mass ratio is 1.0 or more represented by the component (B1) / component (B2) is,

Content of the said component (b11) is 10-80 mass% with respect to the total mass of the said component (B),
The cleaning composition whose mass ratio represented by a component (b11) / component (b12) is 0.5-65 .
^{_{R 2 -C (= O) O}} - [(EO) s / (PO) t] - (EO) u -R 3 ··· (III)
(In the formula (III), R ² is a hydrocarbon group having 7 to 22 carbon atoms, R ³ is a methyl group, s represents the average number of repetitions of EO, is a number of 6 to 20, and t is It represents the average number of repetitions of PO and is a number from 0 to 6, u represents the average number of repetitions of EO, is a number from 0 to 20, EO represents an oxyethylene group, and PO represents an oxypropylene group. )
R ⁴ —O — [(EO) _v / (PO) _w ] — (EO) _x —H (IV)
(In the formula (IV), R ⁴ is a hydrocarbon group having 6 to 22 carbon atoms, v represents the average number of repetitions of EO, 3 to 20, and w represents the average number of repetitions of PO. It is a number from 0 to 6, x represents the average number of repetitions of EO, is a number from 0 to 20, EO represents an oxyethylene group, and PO represents an oxypropylene group.) Further, component (D): washing of claim 1 comprising a polymer having at least one repeating unit (d1) and oxyalkylene units (d2) is selected from the group consisting of alkylene terephthalate units and alkylene isophthalate unit Agent composition. The repeating unit (d1) includes the alkylene terephthalate unit;
The alkylene terephthalate units, the repeating unit represented by the following formula (D1-1) (d11), or the following general formula repeating unit represented by (D1-2) (d12), according to claim 2 Cleaning composition.

(In the formula (D1-1), R ⁴¹ is an alkylene group having 1 to 5 carbon atoms.)

(In formula (D1-2), R ⁴² represents an alkylene group having 1 to 5 carbon atoms.) Furthermore, component (E): at least 1 sort (s) chosen from the carboxylic acid represented by the following general formula (VII) and its salt, and component (F): In any one of Claims 1-3 containing an enzyme. The cleaning composition as described.
X—R ¹ —COOH (VII)
However, in formula (VII), ^{R 1} is a divalent hydrocarbon group or an arylene group, 1 to 4 carbon atoms, X is, -H, -OH, -CH _3, or -COOH. The content of the said component (B1) is a cleaning composition as described in any one of Claims 1-4 which is 25-70 mass% with respect to the total mass of a cleaning composition.