JP2018177870A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition which suppresses recontamination and is excellent in rinsability and liquid stability. SOLUTION: (A) component: an alkylene oxide adduct of polyalkylene amine, (B) component: a nonionic surfactant, (C) component: an anionic surfactant, and (D) component: the following general formula ( It contains at least one selected from the organic solvent represented by d1) and the organic solvent represented by a specific structure, and the mass ratio represented by the component (B) / component (C) is 0.5. The above is the liquid detergent composition. (In the formula (d1), R1 to R3 are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and R4 is a hydrogen atom or acetyl group.) [Chemical formula 1] [Selection diagram] None.

Description

  The present invention relates to liquid detergent compositions.

In recent years, for the purpose of resource saving and reduction of environmental load (reduction of the amount of waste), miniaturization of the cleaning agent container has been achieved, and along with this, concentration of liquid cleaning agent (high concentration of surfactant) Is required.
The more concentrated the liquid detergent, the lower the liquid stability of the liquid detergent, and the more likely it is to form a film or cause gelation. When the liquid detergent forms a film or causes gelation, it becomes difficult to pour out the liquid detergent from the container, and the dispersibility in water and the permeability to the object to be washed are impaired.
In order to prevent film formation and gelation of a liquid detergent, a liquid detergent containing a specific organic solvent is proposed in which a nonionic surfactant and an anionic surfactant are used in combination (Patent Document 1).

International Publication No. 2014/050710

By the way, the water saving type washing machine has become mainstream because of environmental awareness. In a water-saving washing machine, the amount of water is small, so the concentration of dirt in the washing liquid tends to increase. Therefore, it is easy for the recontamination that the stain | pollution | contamination removed during washing | cleaning adhere to clothes etc. (to-be-washed thing) again arise.
In addition, when a liquid detergent concentrated by a water-saving washing machine is used, it is difficult to wash out the liquid detergent attached to the object to be washed, and the rinse property is likely to be deteriorated.
In order to suppress recontamination, it is advantageous to increase the amount of anionic surfactant. On the other hand, when the nonionic surfactant is reduced in the liquid detergent and the amount of the anionic surfactant is increased, the rinse property is lowered.
Although the invention of Patent Document 1 described above well prevents film formation and gelation and improves the liquid stability, the suppression of recontamination and the rinse property are not sufficient yet.
Accordingly, the present invention is directed to a liquid detergent composition that suppresses recontamination and is more excellent in rinseability and liquid stability.

The present invention has the following aspects.
[1] Component (A): alkylene oxide adduct of polyalkylene amine, (B) component: nonionic surfactant, (C) component: anionic surfactant, and (D) component: General Formula (d1) And at least one selected from organic solvents represented by the following general formula (d2), and the mass ratio represented by (B) component / (C) component is 0 .5. A liquid detergent composition that is greater than or equal to 5;

(In formula (d1), R ^{1 to} R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or an acetyl group.)

R ⁵ O (C ₂ H ₄ O) _X (C ₃ H ₆ O) _Y R ⁶ (d2)
(In formula (d2), R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ and R ⁶ are not simultaneously a hydrogen atom. X is 0 ≦ An integer of X ≦ 3, Y is an integer of 0 ≦ Y ≦ 3, and X and Y can not be 0 simultaneously.)

[2] Component (E): at least one selected from monohydric alcohols having 2 to 3 carbon atoms and polyhydric alcohols having 2 to 4 carbon atoms, and (E) component / (D) component The liquid detergent composition as described in [1] whose mass ratio represented is more than 0 and 3 or less.
[3] The liquid detergent composition according to [1] or [2], wherein the total content of the surfactant is 15 to 85% by mass with respect to the total mass of the liquid detergent.
[4] The liquid detergent composition according to any one of [1] to [3], wherein the mass ratio represented by (D) component / (A) component is 0.2 or more and 500 or less.
[5] The liquid detergent composition according to any one of [1] to [4], wherein a mass ratio represented by (D) component / (B) component is 0.04 or more and 1.0 or less.
[6] The liquid detergent composition according to any one of [1] to [5], wherein the mass ratio represented by (D) component / (C) component is 0.01 or more and 50 or less.
[7] The liquid detergent composition according to any one of [1] to [6], which has a pH of 5 to 9 at 25 ° C.

  According to the liquid detergent composition of the present invention, recontamination is suppressed, and the rinse performance and the liquid stability are excellent.

[Liquid cleaner composition]
The liquid detergent composition of the present invention (hereinafter sometimes referred to simply as liquid detergent) contains (A) component, (B) component, (C) component, and (D) component.

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

((A1) component)
The component (a1) is an alkylene oxide adduct of a polyalkyleneimine. The polyalkyleneimine of component (a1) is represented, for example, by the following general formula (I).
^{_{NH 2 -R 21 - (NA-}} R 21) n -NH 2 ··· (I)
In formula (I), R ²¹ is each independently an alkylene group having 2 to 6 carbon atoms, A represents a hydrogen atom or a branched polyamine chain, and n is a number of 1 or more. However, all of the aforementioned A is not a hydrogen atom.
That is, the polyalkyleneimine represented by the formula (I) has a branched polyamine chain in the structure.

R ²¹ is a C 2 to C 6 linear alkylene group or a C 3 to C 6 branched alkylene group. R ²¹ is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
The polyalkyleneimine is obtained by polymerizing one or two or more kinds of alkyleneimine 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 the polyalkyleneimine, polyethyleneimine (PEI) and polypropyleneimine are preferable, and PEI is more preferable. PEI is obtained by polymerizing ethyleneimine and has in its structure a branched structure containing primary, secondary and tertiary amine nitrogen atoms.

  200-2000 are preferable, as for the mass mean molecular weight of polyalkyleneimine, 300-1500 are more preferable, 400-1000 are more preferable, and 500-800 are especially preferable.

  As a polyalkyleneimine, what has 5-30 active hydrogen in 1 molecule is preferable, what has 7-25 is more preferable, and what has 10-20 is still more preferable.

The component (a1) is obtained by adding an alkylene oxide to a polyalkyleneimine. As this method, for example, addition of an alkylene oxide such as ethylene oxide at 100 to 180 ° C. to the starting material polyalkyleneimine in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methylate And the like.
As an alkylene oxide, a C2-C4 alkylene oxide is mentioned. 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 ethylene oxide adducts of polyalkyleneimines, propylene oxide adducts of polyalkyleneimines, ethylene oxide-propylene oxide adducts of polyalkyleneimines, and the like. The ethylene oxide-propylene oxide adduct of the polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to a polyalkyleneimine, and the addition order or addition form (block shape, random shape) of ethylene oxide and propylene oxide to the polyalkyleneimine ) Is optional.
As the component (a1), ethylene oxide adducts of polyalkyleneimines and ethylene oxide-propylene oxide adducts of polyalkyleneimines are preferable, and ethylene oxide adducts of polyalkyleneimines are more preferable.

  The component (a1) is preferably one having an average of 5 to 40 alkylene oxides added to one active hydrogen atom of the starting material polyalkyleneimine, and an average of 10 to 30 alkylene oxides added. Is more preferred. That is, one having an average of 5 to 40 moles of alkylene oxide added per mole of active hydrogen contained in the starting material polyalkyleneimine is preferable, and one having an average of 10 to 30 moles of alkylene oxide added is more preferable.

1000-80,000 are preferable, 2000-50000 are more preferable, 5000-30000 are more preferable, and, as for the mass mean molecular weight of (a1) component, 10000-20000 are especially preferable.
In addition, a mass mean 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 (I-a).

In formula (I-a), R ²² is each independently an alkylene group having 2 to 6 carbon atoms, and m is each 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 an average repeat number of (R ²² O), preferably 5 to 40, and more preferably 10 to 30.
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 Corporation etc. is mentioned, for example.

((A2) component)
The component (a2) is an alkylene oxide adduct of a polyalkylene amine represented by the following formula (II).
NH ₂ (R ³¹ NH) _l 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 C 2-6 linear alkylene group or a C 3-6 branched alkylene group. 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 polyalkylene amine, polyethylene amine is preferable. Examples of polyethylene amines include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and the like. These polyethylene amines can be obtained by a known production method, for example, by reacting ammonia and ethylene dichloride.

  60-1800 are preferable, as for the mass mean molecular weight of a polyalkylene amine, 60-1000 are more preferable, and 60-800 are more preferable.

  As the polyalkylene amine, one having 6 to 30 active hydrogens in one molecule thereof is preferable, and one having 7 to 20 active hydrogens is more preferable.

  The component (a2) is obtained by adding an alkylene oxide to a polyalkylene amine. This reaction can be carried out in the same manner as the component (a1). As an alkylene oxide, a C2-C4 alkylene oxide is mentioned. 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 ethylene oxide adducts of polyalkylene amines, propylene oxide adducts of polyalkylene amines, and ethylene oxide-propylene oxide adducts of polyalkylene amines.
As the alkylene oxide adduct of polyalkylene amine, an ethylene oxide adduct of polyalkylene amine and an ethylene oxide-propylene oxide adduct of polyalkylene amine are preferable, and an ethylene oxide adduct of polyalkylene amine is more preferable.

  The component (a2) is preferably one having an average of 5 to 40 alkylene oxides added to one active hydrogen atom of the starting material polyalkyleneamine, and an average of 10 to 30 alkylene oxides added. Is more preferred. That is, it is preferable that an average of 5 to 40 moles of alkylene oxide is added per 1 mole of active hydrogen of the starting material polyalkyleneamine, and more preferably, an average of 10 to 30 moles of alkylene oxide is added.

  1000-80,000 are preferable, 2000-50000 are more preferable, 5000-30000 are more preferable, and, as for the mass mean molecular weight of (a2) component, 10000-20000 are especially preferable.

  As the component (A), the component (a1) is preferable. Among the components (a1), ethylene oxide adducts of polyethyleneimine represented by the formula (I-a) are 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, more preferably 0.05 to 3% by mass, and further preferably 0.1 to 1.5% by mass, with respect to the total mass of the liquid detergent. preferable.
If the content of the component (A) is equal to or less than the upper limit value, it is easy to maintain the degree of freedom of blending the other components. When the content of the component (A) is equal to or more than the lower limit value, the recontamination prevention property can be easily enhanced, and the storage stability can be easily enhanced.

<(B) component>
The component (B) is a nonionic surfactant. As the component (B), any component conventionally used in liquid detergents may be used. For example, alkylene oxide adducts such as polyoxyalkylene type nonionic surfactants, alkylphenols and higher amines, polyoxyethylene polyoxyethylenes Propylene block copolymer, fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or alkylene oxide adduct thereof, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester , N-alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like.
In addition, a higher amine means the amine which has a C8-C22 hydrocarbon group.

Among the above-mentioned components, polyoxyalkylene type nonionic surfactants are preferable as the component (B) from the viewpoint of viscosity and liquid stability. As a polyoxyalkylene type nonionic surfactant, the compound (Hereinafter, it may be mentioned a compound (b1).) Represented by the following general formula (III) is mentioned.
R ⁴¹ -X-(EO) _s (PO) _t- R ⁴² (III)
In formula (III), R ⁴¹ is a hydrocarbon group having 8 to 22 carbon atoms, -X- is a divalent linking group, R ⁴² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the carbon number It is an alkenyl group of 2-6. EO is an oxyethylene group, s is a number of 3 to 20 representing the average number of repetition of EO. PO is an oxypropylene group, and t is a number from 0 to 6, which represents the average number of repetition of PO.

In the formula (III), the carbon number of the hydrocarbon group of R ⁴¹ is preferably 10 to 18. The hydrocarbon group of R ⁴¹ may be linear or branched, and may or may not have an unsaturated bond.
As -X-, -O-, -COO-, -CONH- and the like can be mentioned.
The carbon number of the alkyl group in R ⁴² is 1 to 6, preferably 1 to 3.
The carbon number of the alkenyl group in R ⁴² is 2 to 6, preferably 2 to 3.

Wherein (III), -X- is -O -, - COO- or -CONH-, compound (b1) is a primary or secondary higher alcohols ^(R 41 -OH), higher fatty acids ^{(R 41} - resulting COOH) or a higher fatty acid amide ^(R 41 -CONH) as a raw material.
The “higher” compound means a “having a hydrocarbon group having 8 to 22 carbon atoms”.

In formula (III), s is a number of 3 to 20 representing an average number of repetition of EO (that is, an average added mole number of ethylene oxide), and 5 to 18 is preferable. Above the upper limit, the HLB value may be too high, which may lower the detergency against sebum, and below the lower limit, the odor may be deteriorated.
t is a number of 0 to 6 representing an average number of repetition of PO (i.e., an average number of moles of propylene oxide added), preferably 0 to 3. Above the upper limit, the liquid stability of the liquid detergent at a high temperature tends to decrease.
When t is 1 or more, that is, when the compound (b1) has EO and PO, the addition method of ethylene oxide and propylene oxide is not particularly limited, and may be, for example, a random addition method or a block addition method. As a block addition method, for example, a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, adding ethylene oxide, adding propylene oxide and further adding ethylene oxide The method etc. of adding are mentioned.

The added mole number distribution of ethylene oxide or propylene oxide is not particularly limited.
The distribution of added moles tends to vary depending on the reaction method in producing the nonionic surfactant. For example, when ethylene oxide or propylene oxide is added to a hydrophobic raw material using a common alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution of ethylene oxide or propylene oxide with a relatively wide distribution of added moles is relatively wide distribution Tend to be In addition, specific alkoxylations such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ²⁺ are added as described in Japanese Patent Publication No. 6-15038. When ethylene oxide or propylene oxide is added to the hydrophobic base material by using a catalyst, the distribution of added moles of ethylene oxide or propylene oxide tends to be a relatively narrow distribution.

As the compound (b1), particularly, a compound in which -X- is -O- (alcohol type nonionic surfactant), or -X- is -COO-, and R ⁴² is an alkyl having 1 to 6 carbon atoms The compound (fatty acid alkyl (alkenyl) ester type nonionic surfactant) which is a group or a C2-C6 alkenyl group is preferable.

When -X- is -O-, the carbon number of R ⁴¹ is preferably 10-22, more preferably 10-20, and still more preferably 10-18.
When -X- is -O-, R ⁴² is preferably a hydrogen atom.

If -X- is ^-COO-, the carbon number of ^{R 41} is preferably 9 to 21, 11 to 21 is more preferable.
When -X- is -COO-, R ⁴² is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

  As a compound (b1) in which -X- is -O- or -COO-, for example, Diadol (trade name, C13 (C indicates the number of carbon atoms. The same applies to the following.)) Manufactured by Mitsubishi Chemical Corporation, Shell Equivalent to 12 moles or 15 moles of ethylene oxide with respect to alcohols such as Neodol (trade name, a mixture of C12 and C13) and Sasol Safol 23 (a trade name, mixture of C12 and C13) Additive; 12 moles equivalent or 15 moles equivalent ethylene oxide added to natural alcohol such as Procor & Gamble CO-1214 or CO-1270 (trade name); butene is trimerized 7 moles of ethylene oxide are added to the C13 alcohol obtained by subjecting the resulting C12 alkene to the oxo method. Things (trade name: Lutensol TO7, manufactured by BASF); those obtained by adding pentaol equivalent ethylene oxide to C10 alcohol obtained by subjecting pentanol to a garbet reaction (trade name: Lutensol XP90, manufactured by BASF); 7 moles of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to a garbet reaction (trade name: Lutensol XL70, manufactured by BASF); C10 alcohol obtained by subjecting pentanol to a garbage reaction On the other hand, 6 mol equivalent of ethylene oxide added (trade name: Lutensol XA60, manufactured by BASF); 9 mol equivalent or 15 mol equivalent of ethylene oxide added to secondary alcohol having 12 to 14 carbon atoms Things (brand name: Seo Phthalol 90, Softanol 150, manufactured by Nippon Shokubai Co., Ltd .; Cosil fatty acid methyl (lauric acid / myristic acid = 8/2) to which 15 mol equivalent of ethylene oxide is added using an alkoxylation catalyst Ethylene palm fatty acid methyl ester (EO 15 mol) etc. are mentioned.

As the compound (b1), among the above, a compound in which -X- is -COO-, R ⁴² is an alkyl group having 1 to 6 carbon atoms, and t is 0, ie, a polyoxyethylene fatty acid alkyl ester Preferably, polyoxyethylene fatty acid methyl ester (hereinafter sometimes referred to as MEE) in which R ⁴² is a methyl group is more preferable.
By using polyoxyethylene fatty acid alkyl ester as the nonionic surfactant, the solubility of the liquid detergent in water can be enhanced, and the detergency can be enhanced. In addition, even if the content of the component (B) in the liquid detergent is increased, a viscosity increase (gelation) hardly occurs, and a concentrated liquid detergent having good fluidity can be obtained.
Polyoxyethylene fatty acid alkyl esters, in particular MEE, are nonionic surfactants in which the orientation of molecules is weak in aqueous solution systems and micelles are unstable. Therefore, it is presumed that the polyoxyethylene fatty acid alkyl ester does not cause gelation or the like at a high concentration, and the solubility in water can be enhanced even if one type alone is blended in a large amount in the liquid detergent. Therefore, when the liquid detergent containing the polyoxyethylene fatty acid alkyl ester is dispersed in water, the concentration of the polyoxyethylene fatty acid alkyl ester in the washing liquid quickly becomes uniform, and contacts the object to be washed at an arbitrary concentration from the initial stage of washing. Is considered to exert a high cleaning power.

  In the polyoxyethylene fatty acid alkyl ester, the narrow ratio indicating the distribution ratio of the compounds having different addition moles of ethylene oxide is preferably 20% by mass or more. The upper limit value of the narrow ratio is preferably substantially 80% by mass or less. The narrow ratio is more preferably 20 to 60% by mass. The higher the narrow ratio, the better the detergency. However, if it is too high, the liquid stability at low temperature may be reduced, so 30 to 45% by mass is more preferable.

  The narrow ratio of a polyoxyalkylene type nonionic surfactant such as polyoxyethylene fatty acid alkyl ester is a value determined by the following formula (S).

In the formula (S), S _max represents the number of added moles (value of s + t) of the alkylene oxide in the alkylene oxide adduct which is most abundant in the polyoxyalkylene type nonionic surfactant.
i represents the number of moles of alkylene oxide added.
Yi shows the ratio (mass%) of the alkylene oxide adduct which is i in addition mole number of the alkylene oxide which exists in the whole component represented by (S) Formula.

The narrow ratio can be controlled, for example, by the method for producing polyoxyethylene fatty acid alkyl ester.
The method for producing the polyoxyethylene fatty acid alkyl ester is not particularly limited, but, for example, a method in which ethylene oxide is addition-polymerized to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst JP 2000-144179)).
Preferred examples of the surface-modified composite metal oxide catalyst include metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ which are surface-modified with, for example, a metal hydroxide or the like. , Complex metal oxide catalysts such as magnesium oxide to which Sc ³⁺ , La ³⁺ , Mn ²⁺ etc. are added, and catalysts of calcined hydrotalcites surface-modified with metal hydroxides and / or metal alkoxides etc. Can be mentioned.
In surface modification of the composite metal oxide catalyst, the ratio of metal hydroxide and / or metal alkoxide is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the composite metal oxide, It is more preferable to set to 5 parts by mass.

  Another method for producing the component (B) is a method of adding an alkylene oxide to a fatty acid alkyl ester by an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and an oxy acid or the like. The alkoxylation catalyst is disclosed, for example, in Patent Nos. 049777609, WO 1993/004030, WO 2002/038269, WO 2012/028435, and examples thereof include alkaline earths of carboxylic acids. An alkoxylation catalyst etc. which were prepared from mixtures of a metal salt and / or an alkaline earth metal salt of hydroxycarboxylic acid and sulfuric acid etc. may be mentioned.

As the component (B), one type may be used alone, or two or more types may be used in combination.
For example, as the component (B), MEE and an alcohol ethoxylate obtained by adding ethylene oxide to an alcohol may be used in combination.
When MEE and a primary alcohol ethoxylate are used in combination, the mass ratio represented by (MEE) / (alcohol ethoxylate) in the component (B) is preferably 1/9 or more and less than 10/0, 2 / 8 or more and less than 10/0 are more preferable, and 3/7 or more and less than 10/0 are more preferable.
When the mass ratio represented by (MEE) / (alcohol ethoxylate) is equal to or more than the lower limit value, gelling of the liquid detergent hardly occurs, and additionally, the rinse property is improved.

The content of the component (B) is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and still more preferably 30 to 45% by mass, with respect to the total mass of the liquid detergent. When the content of the component (B) is within the above range, it is easy to obtain a liquid detergent which is excellent in detergency against oil stains and excellent in liquid stability.
If content of (B) component is more than the said lower limit, high cleaning performance can be provided to a liquid detergent. When the content of the component (B) is equal to or less than the upper limit value, gelation is less likely to occur and the liquid stability is likely to be improved.

<(C) component>
The component (C) is an anionic surfactant. As the component (C), an anionic surfactant generally used for liquid detergents for clothing and the like can be used. Examples of the component (C) include the following components (c1) and (c2).

((C1) component)
The component (c1) is polyoxyalkylene alkyl ether sulfuric acid or a salt thereof (AES). The AES of the component (c1) is represented by, for example, the following general formula (IV).
R ⁵¹ -O-[(EO) _u / (PO) _v ] -SO ₃ -M ⁺ (IV)
In formula (IV), R ⁵¹ is a linear or branched alkyl group having 8 to 20 carbon atoms. EO represents an oxyethylene group, and PO represents an oxypropylene group. u represents the average number of repetitions of EO and is a number of 0 or more. v represents the average number of repetitions of PO and is a number from 0 to 6. It is 0 <u + v. M ⁺ is a counter cation.

As the polyoxyalkylene alkyl ether sulfate, one having a linear or branched alkyl group having 10 to 20 carbon atoms and having an average of 1 to 5 moles of an alkylene oxide added is preferable.
As carbon number of an alkyl group, 10-20 are preferable and 12-14 are more preferable. Specifically, dodecyl group, tridecyl group, tetradecyl group and the like can be mentioned. Among these, dodecyl is preferable.

The average repetition number of EO is preferably 0 to 5, more preferably 0.5 to 3, and particularly preferably 0.5 to 1.5. The average repeat number of PO is preferably 0 to 3, and more preferably 0.
Examples of the salt include alkali metal salts with sodium, potassium etc., alkaline earth metal salts with magnesium etc., alkanolamine salts with monoethanolamine, diethanolamine etc., and the like.
By using polyoxyalkylene alkyl ether sulfuric acid or a salt thereof as the component (c1), denaturation of the enzyme by the anionic surfactant in the liquid detergent can be suppressed.

  A commercial item may be used as a component (c1), and you may manufacture with a well-known synthetic | combination method. Examples of known synthetic methods include a method in which polyoxyalkylene alkyl ether is reacted with sulfuric anhydride or a method in which chlorosulfonic acid is reacted, and these can be produced by these methods.

((C2) ingredient)
The component (c2) is linear alkyl benzene sulfonic acid or a salt thereof (LAS). As the component (c2), linear alkyl groups having 8 to 16 carbon atoms are preferable, and those having 10 to 14 carbon atoms are more preferable. If it is in the said range, recontamination prevention property can be improved. Examples of the linear alkyl group include decyl group, undecyl group, dodecyl group, tridecyl group and tetradecyl group. Examples of the salt include alkali metal salts with sodium, potassium etc., alkaline earth metal salts with magnesium etc., alkanolamine salts with monoethanolamine, diethanolamine etc., and the like.

  A commercial item may be used as a component (c2), and you may manufacture with a well-known synthetic | combination method. Examples of known synthetic methods include methods of sulfonation of alkylbenzenes with sulfuric anhydride, which can be produced by this method.

  Examples of the component (C1) and the component (C) other than the component (c2) include monoethanolamine salt of polyoxyalkylene alkyl ether sulfate (AEPS) and the like.

As component (C), in addition to this, for example, α-olefin sulfonates; linear or branched alkyl sulfates; alkyl ether sulfates; alkenyl ether sulfates; alkanes having an alkyl group Sulfonates; α-sulfo fatty acid ester salts; higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkylamide ether carboxylates, alkenylamide ether carboxylates, acylamino carboxylates, etc. Carboxylic acid type anionic surfactant; Phosphate type anionic surfactant such as alkyl phosphoric acid ester salt, polyoxyalkylene alkyl phosphoric acid ester salt, polyoxyalkylene alkyl phenyl phosphoric acid ester salt, glycerin fatty acid ester mono phosphoric acid ester salt and the like Sex agents and the like can be mentioned.
Examples of the salt form of component (C) include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; and alkanolamine salts such as monoethanol ammonium and diethanol ammonium.

As an alpha-olefin sulfonate, a C10-C20 alpha-olefin sulfonate is preferable.
As an alkyl sulfuric ester salt, a C10-C20 alkyl sulfuric ester salt is preferable.
As the alkyl ether sulfuric acid ester salt or alkenyl ether sulfuric acid ester salt, it has a linear or branched alkyl group having 10 to 20 carbon atoms or a linear or branched alkenyl group having 10 to 20 carbon atoms. And alkyl ether sulfates or alkenyl ether sulfates (i.e., polyoxyethylene alkyl ether sulfates or polyoxyethylene alkenyl ether sulfates) to which 1 to 10 moles of ethylene oxide have been added on average. In addition, any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio is ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1), the average is 0.5 to 0.5. Alkyl ether sulfate ester salt having a linear or branched alkyl group having 10 to 20 carbon atoms, or alkenyl ether having a linear or branched alkenyl group having 10 to 20 carbon atoms, to which 10 moles is added Sulfate ester salts are preferred.

As an alkanesulfonic acid salt, a C10-C20 alkanesulfonic acid salt is mentioned, A C14-C17 alkanesulfonic acid salt is preferable, and a secondary alkanesulfonic acid salt is especially preferable.
As an alpha-sulfo fatty acid ester salt, a C10-C20 alpha-sulfo fatty acid ester salt is preferable.
The higher fatty acid salt is preferably a higher fatty acid salt having a hydrocarbon group of 10 to 20 carbon atoms.
These (C) components are easily available in the market. Moreover, you may use what was synthesize | combined by the well-known method.

As the component (C), one type may be used alone, or two or more types may be used in combination.
For example, as the component (C), the component (c1) (any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio of ethylene oxide / propylene oxide = 0.1 / 9.9-9. 9). 9 / 0.1) is added on average 0.5 to 10 moles of alkyl ether sulfate ester salt (alkyl group is 10 to 20 carbon atoms, linear or branched), or alkylene oxide of 2 to 4 carbon atoms Or alkenyl ether sulfate ester salt (average molar ratio of ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1) added with ethylene oxide and propylene oxide (molar ratio of ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1) The alkenyl group has 10 to 20 carbon atoms, and is linear or branched)); (c2) component; alkane sulfonate; Olefin sulfonates; at least one selected from the group consisting of and higher fatty acid salts are preferred. Among these, at least one selected from the group consisting of the component (c2) and the higher fatty acid salt is more preferable.

  The mass ratio represented by (c1) component / (c2) component (hereinafter sometimes referred to as (c1) / (c2) ratio) is preferably 1/9 to 9/1, and 1/9 to 8/2. Is more preferable, and 1/9 to 7/3 is more preferable. When the (c1) / (c2) ratio is equal to or more than the lower limit value, the recontamination prevention property is more easily improved. If the (c1) / (c2) ratio is equal to or less than the upper limit value, the liquid stability is more easily improved.

The content of the component (C) is preferably 0.5 to 60% by mass, more preferably 0.5 to 50% by mass, and still more preferably 0.5 to 40% by mass with respect to the total mass of the liquid detergent.
When the content of the component (C) is equal to or more than the above lower limit, the cleaning performance, particularly the recontamination prevention property is likely to be improved. When the content of the component (C) is equal to or less than the upper limit value, gelation is less likely to occur, and liquid stability is likely to be improved.

The total of the content of the component (B) and the content of the component (C) is preferably 15 to 80% by mass, more preferably 15 to 75% by mass, based on the total mass of the liquid detergent, and 30 to 70 % By mass is more preferred.
If the sum of the content of the component (B) and the content of the component (C) is equal to or more than the lower limit value, the liquid detergent can be provided with high cleaning performance, and the recontamination prevention property can be easily improved. If the sum of the content of the component (B) and the content of the component (C) is equal to or less than the upper limit, the liquid stability is likely to be improved.

  0.5-30 are preferable and 0.5-20 are more preferable, as mass ratio (Hereinafter, it may be mentioned (B) / (C) ratio) represented by (B) component / (C) component. 0.5 to 10 are more preferable. If (B) / (C) ratio is more than the said lower limit, rinse property will become easier to improve. If the (B) / (C) ratio is less than or equal to the upper limit value, the recontamination prevention property is more easily improved.

<(D) component>
The component (D) is at least one selected from an organic solvent represented by the following general formula (d1) and an organic solvent represented by the following general formula (d2).

(In formula (d1), R ^{1 to} R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or an acetyl group.)

R ⁵ O (C ₂ H ₄ O) _X (C ₃ H ₆ O) _Y R ⁶ (d2)
(In formula (d2), R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ and R ⁶ are not simultaneously a hydrogen atom. X is 0 ≦ An integer of X ≦ 3, Y is an integer of 0 ≦ Y ≦ 3, and X and Y can not be 0 simultaneously.)

  The organic solvent represented by General Formula (d1) is a component (d1), and the organic solvent represented by General Formula (d2) is a component (d2). As the component (d1), for example, 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, 3-methoxy-2 -Methylbutanol, 3-methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol, 3-methoxy-1 -Propylbutanol, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-ethylbutyl acetate, 3-methoxy-3-propylbutyl acetate, 3-methoxy-2-methylbutyl acetate , 3-methoxy-2-ethylbutyl acetate, 3-methoxy-2-propylbutyl acetate 3-methoxy-1-methylbutyl acetate, 3-methoxy-1-ethylbutyl acetate, 3-methoxy-1-propylbutyl acetate, etc., 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3 -Methoxy-2 methyl butanol, 3 methoxy 1-methyl butanol, 3-methoxy 3- methyl butyl acetate are preferable, and 3- methoxy 3- methyl butanol is more preferable.

  Examples of the component (d2) include ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, polyoxyethylene polyoxypropylene glycol monobutyl ether and the like.

As the component (D), one type may be used alone, or two or more types may be used in combination.
Component (D) is preferably used in combination with component (E) described later. Among them, it is preferable to use in combination with ethanol.
The content of the component (D) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 15% by mass, with respect to the total mass of the liquid detergent.
When the content of the component (D) is not less than the lower limit value, gelation is suppressed, flowability of the liquid detergent is further maintained, and rinse performance is likely to be improved. If content of (D) component is below the said upper limit, liquid fluidity does not increase too much, it is easy to aim at the improvement of usability, and cost can be held down.

  0.2-500 are preferable and 0.2-300 are more preferable, as mass ratio (Hereinafter, it may be mentioned the ratio of (D) / (A)) represented by (D) component / (A) component. 0.5 to 50 are more preferable. When the (D) / (A) ratio is at least the lower limit value, gelation is suppressed, the fluidity of the liquid detergent is more maintained, and the rinse property is likely to be improved. If the (D) / (A) ratio is less than or equal to the upper limit value, it is easy to improve the recontamination prevention property.

  The mass ratio represented by (D) component / (B) component (hereinafter sometimes referred to as (D) / (B) ratio) is preferably 0.04 to 1.0, and 0.04 to 0.8. Is more preferably 0.04 to 0.5. When the (D) / (B) ratio is at least the lower limit value, gelation is suppressed, the fluidity of the liquid detergent is further maintained, and the rinse property is likely to be improved. If (D) / (B) ratio is below the said upper limit, it will be easy to aim at the improvement of washing | cleaning performance.

  The mass ratio represented by (D) component / (C) component (hereinafter sometimes referred to as (D) / (C) ratio) is preferably 0.01 to 50, and more preferably 0.01 to 30, 0.1 to 10 is more preferable. When the (D) / (C) ratio is not less than the lower limit value, gelation is suppressed, the fluidity of the liquid detergent is more maintained, and the rinse property is likely to be improved. If (D) / (C) ratio is below the said upper limit, it will be easy to aim at the improvement of washing | cleaning performance.

<(E) component>
The component (E) is at least one selected from a C2-C3 monohydric alcohol and a C2-C4 polyhydric alcohol.
As a C2-C3 monohydric alcohol among (E) components, ethanol, 1-propanol, 2-propanol is mentioned, for example.
As a C2-C4 polyhydric alcohol among (E) components, ethylene glycol, propylene glycol, butylene glycol, glycerol etc. are mentioned, for example.
Among these alcohols, ethanol is preferred.

As the component (E), one type may be used alone, or two or more types may be used in combination.
The content of the component (E) is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 15% by mass with respect to the total mass of the liquid detergent.
When the content of the component (E) is at least the lower limit value, gelation is suppressed, the fluidity of the liquid detergent is further maintained, and the rinse property is likely to be improved. If content of (E) component is below the said upper limit, liquid fluidity does not increase too much, usability can be improved and cost can be held down.

  1-30 mass% is preferable with respect to the total mass of a liquid detergent, and, as for the sum total of content of (D) component and content of (E) component, 2-25 mass% is more preferable, and 2-20 mass % Is more preferred. When the sum of the content of the component (D) and the content of the component (E) is not less than the lower limit value, gelation is suppressed, the fluidity of the liquid detergent is further maintained, and the rinse property is improved. Cheap. If the sum of the content of the component (D) and the content of the component (E) is equal to or less than the upper limit, the liquid flowability does not increase excessively, the usability can be improved, and the cost can be suppressed.

  The mass ratio represented by (E) component / (D) component (hereinafter sometimes referred to as (E) / (D) ratio) is preferably more than 0 and 3 or less, more preferably more than 0 and 1 or less, and more than 0 0.8 or less is more preferable. When the (E) / (D) ratio is at least the lower limit value, gelation is suppressed, the fluidity of the liquid detergent is more maintained, and the rinse property is likely to be improved. When the (E) / (D) ratio is equal to or less than the upper limit value, the liquid fluidity does not increase excessively, and the usability is easily improved.

  The liquid detergent of the present invention may contain any surfactant other than the (B) component and the (C) component. Examples of the optional surfactant include cationic surfactants, amphoteric surfactants and the like.

(Cationic surfactant)
As a cationic surfactant, a cationic surfactant generally used for liquid detergents for clothing etc. can be used, for example, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylamino Long-chain aliphatic amido alkyl tertiary amines or propylamino, propyl myristate dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide, etc. Aliphatic ester alkyl tertiary amines such as palmitate ester propyldimethylamine, stearate ester propyldimethylamine or salts thereof; palmitic acid diethanolaminopropylamide , Diethanol aminopropyl amide stearate; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyl benzyl dimethyl ammonium salts, quaternary compound such as such as alkyl pyridinium salts.

As the cationic surfactant, long-chain aliphatic amidoalkyl tertiary amines or salts thereof are preferred, and caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristate dimethylaminopropylamide, More preferred are palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide or salts thereof.
One of these cationic surfactants may be used alone, or two or more thereof may be used in combination.

(Ampholytic surfactant)
As the amphoteric surfactant, amphoteric surfactants generally used in liquid detergents for clothing etc. can be used. For example, alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfonic acid type, Amphoteric surfactants such as alkylaminocarboxylic acid type, alkylamidocarboxylic acid type, amide amino acid type or phosphoric acid type can be mentioned.
One of these amphoteric surfactants may be used alone, or two or more thereof may be used in combination.

The total content of the (B) component, the (C) component and the optional surfactant (total content of surfactant) is preferably 15 to 85% by mass with respect to the total mass of the liquid detergent, and 15 to 80 % By mass is more preferable, and 30 to 75% by mass is further preferable.
When the total content of the surfactant is equal to or more than the lower limit value, it is easy to achieve high concentration of the surfactant. If the total content of the surfactant is equal to or less than the upper limit value, the rinse property is likely to be improved.
80 mass% or more is preferable, as for the ratio of content of (B) component and (C) component with respect to the total content of surfactant, 90 mass% or more is more preferable, and 100 mass% may be sufficient.
If the ratio of the content of the (B) component and the (C) component to the total content of the surfactant is equal to or more than the above lower limit, the liquid detergent is given high cleaning performance, and the recontamination prevention property is It is easy to improve.

<Optional component>
In addition to the components (A) to (E), the liquid detergent according to the present invention may, if necessary, be blended with components generally used in liquid detergents as long as the effects of the present invention are not impaired.
Such optional components include, for example, enzymes, hydrotropes (eg, polyethylene glycol, aromatic sulfonic acids or salts thereof), detersive builders, stabilizers, alkaline agents (eg, monoethanolamine, diethanolamine, etc.) Alkanolamines such as triethanolamine etc.) Metal ion capture agents, texture improvers such as silicone, preservatives, fluorescent agents, dye transfer inhibitors, pearls, antioxidants, dyes or pigments generally used as colorants, milk Turbidifying agents, perfumes, pH adjusters and the like can be mentioned.

(enzyme)
The liquid detergent of the present invention may contain an enzyme conventionally incorporated in detergents and the like for clothing and the like. By containing the enzyme, the application cleaning power when the liquid detergent is directly applied to the object to be washed is further improved.
Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase and the like.

As the protease, a protease having serine, histidine and aspartic acid in the molecule, such as serine protease, is preferable.
In general, preparations containing proteases (protease preparations) are commercially available. When preparing a liquid detergent, a protease is usually formulated using this protease preparation.
As a protease preparation, for example, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX available from Novozymes, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Licanase 2.5L Liquanase Ultra 2.5 L, Liquanase Ultra 2.5 XL, Coronase 48 L; trade names Purafect L, Purafect OX, Properase L, etc. available from Genencor Corporation.

  As the amylase preparation, for example, trade name Termamyl 300L, tradename Ultra300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L available from Novozymes; trade name Maxamyl available from Genencor, trade name Pululanase available from Amano Enzyme Co., Ltd. Amano; trade name DB-250 available from Seikagaku Corporation, etc. may be mentioned.

Examples of the lipase preparation include, for example, trade names Lipex 100 L and Lipolase 100 L available from Novozymes.
As the cellulase preparation, for example, Carezyme 4500 L (trade name, manufactured by Novozymes), Carezyme Premium 4500 L (trade name, manufactured by Novozymes), Endolase 5000 L (trade name, manufactured by Novozymes), Cell Clean 4500 T (trade name, Novozymes) Company) and the like.
Examples of mannanase preparations include, for example, trade name Mannaway 4L available from Novozymes.

One of the enzymes may be used alone, or two or more of the enzymes may be used in combination.
The content of the enzyme in the liquid detergent is preferably 0.1 to 3% by mass as the enzyme preparation with respect to the total mass of the liquid detergent.

(PH adjuster)
In order to bring the pH of the liquid detergent of the present invention to a desired value, a pH adjuster may be blended. However, when the liquid detergent has a desired pH only with the above-described components, it is not necessary to use a pH adjuster.
Examples of pH adjusters include acidic compounds such as sulfuric acid and hydrochloric acid; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and alkaline compounds such as sodium hydroxide and potassium hydroxide. From the viewpoint of enhancing the liquid stability of the liquid detergent, sulfuric acid, sodium hydroxide, potassium hydroxide or alkanolamine is preferable, and sulfuric acid or sodium hydroxide is more preferable.
These pH adjusters may be used alone or in combination of two or more. The content of the pH adjuster in the liquid detergent is appropriately selected according to the target pH.

The liquid detergent according to the present invention dissolves, for example, the components (A) to (E) and, if necessary, optional components in water as a solvent, and adjusts the pH to a predetermined value using a pH adjuster. It can be manufactured by
5-9 are preferable and, as for pH at 25 degreeC of the liquid detergent of this invention, pH 6-8 are more preferable.
When the pH of the liquid detergent at 25 ° C. is within the above range, the storage stability of the liquid detergent is better maintained.
In the present invention, the pH of the liquid detergent is a liquid detergent adjusted to 25 ° C. and shows a value measured by a pH meter or the like.

  In addition, the sum total of content of all the components contained in a liquid detergent shall be 100 mass%.

  The liquid detergent of the present invention described above contains a specific amount of (A) component, (B) component, (C) component and (D) component, and is represented by (B) component / (C) component Since the mass ratio is 0.5 or more, recontamination is suppressed, and the rinse property and liquid stability are excellent. In particular, when the liquid detergent contains the component (E), the gelation can be suppressed, and the fluidity of the liquid detergent is more maintained.

The liquid detergent of the present invention can be used in any of household, commercial and industrial applications. Above all, it can be suitably used for household use, and is particularly suitable as a liquid cleaner for clothes.
The types of objects to be washed include those similar to those to be washed by domestic laundry, and examples thereof include textiles such as clothes, cloths, towels, sheets and curtains, and the like.

The method of using the liquid detergent is, for example, a method of putting the liquid detergent into the water together with the article to be washed, and immersing the article in a detergent aqueous solution prepared by previously dissolving the liquid detergent in water. And the like. Alternatively, the liquid detergent may be applied directly to the object to be washed and left for a certain period of time, and then normal washing may be performed (application washing).
The content of the liquid detergent in the detergent aqueous solution is not particularly limited. The amount of liquid detergent added to water is, for example, preferably 2 to 10 mL per 10 liters of water.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited by the following description.
The raw materials and measurement / evaluation methods used in each of the examples and comparative examples are as follows.

[Used raw material]
<(A) component>
A-1: Ethylene oxide adduct of polyethyleneimine, manufactured by BASF, trade name "Sokalan HP20". In the formula (I-a), compounds wherein R ²² is an ethylene group and m is 20.
<Comparative component ((A ') component)
A'-1: Polyethyleneimine (PEI), manufactured by BASF, trade name "Lupazol P". Weight average molecular weight about 750000.

<(B) component>
B-1: MEE (polyoxyethylene fatty acid methyl ester). Methyl coconut fatty acid (mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) with addition of ethylene oxide equivalent to 15 moles using an alkoxylation catalyst. In the general formula (III), R ⁴¹ = alkyl group having 11 carbon atoms and alkyl group having 13 carbon atoms, R ⁴² = methyl group, s = 15, t = 0, narrow ratio 33%.
(Method of producing B-1)
In a 1 L separable flask, 525 g of isopropyl alcohol (IPA) (primary reagent, made by Kanto Chemical Co., Ltd.) and 150 g of calcium acetate monohydrate (special grade reagent, made by Kanto Chemical Co., Ltd.) are placed, and 20 ° C with a disper stirring blade. To obtain a dispersion (dispersion step). While stirring the dispersion at 3000 rpm, 75 g of sulfuric acid (special grade reagent, manufactured by Kanto Chemical Co., Ltd.) was added over 60 minutes by means of a dropping funnel and mixed (mixing step). The reaction temperature was controlled to 15 to 25 ° C. in a warm bath with a separable flask, since heat is generated by the addition of sulfuric acid in the mixing step. After the addition of sulfuric acid, the mixture was further stirred for 2 hours while maintaining the temperature at 20 ° C. (catalyst aging step) to obtain an alkoxylation catalyst.
In an autoclave, 2.1 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 autoclave is purged with nitrogen, the temperature is raised to 160 ° C., and 1876 g of ethylene oxide (EO) (15 moles of the total of methyl laurate and methyl myristate) under the conditions of 0.1 to 0.5 MPa Was introduced and stirred (addition reaction step). The reaction mixture was further stirred at an addition reaction temperature for 0.5 hours (aging step) and then cooled to 80 ° C. to obtain 2516 g of a reaction crude product (fatty acid methyl ester ethoxylate (MEE), average added mole number of EO = 15). The reaction crude was filtered to remove the catalyst to obtain B-1.
(How to measure the narrowing rate)
The narrow ratio of B-1 was measured by the following procedures.
Under the following measurement conditions, the distribution of ethylene oxide adducts different in addition mole number of ethylene oxide was measured, and the narrow ratio (mass%) was calculated by the above-mentioned numerical formula (S).
[Conditions for measuring distribution of ethylene oxide adducts by HPLC]
Device: LC-6A (manufactured by Shimadzu Corporation).
Detector: SPD-10A.
Measurement wavelength: 220 nm.
Column: Zorbax C8 (manufactured by Du Pont Co., Ltd.).
Mobile phase: acetonitrile / water = 60/40 (volume ratio).
Flow rate: 1 mL / min.
Temperature: 20 ° C.

B-2: AE (15 EO). What added ethylene oxide equivalent to 15 mol to a C12 and C14 natural alcohol (primary alcohol). In general formula (III), R ⁴¹ = alkyl group having 12 carbon atoms and alkyl group having 14 carbon atoms, R ⁴² = hydrogen atom, s = 15, t = 0.
(Method of producing B-2)
861.2 g of CO-1214 (trade name) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of a 30% by mass aqueous solution of NaOH were charged in a pressure resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Next, after dehydrating at a temperature of 100 ° C. and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160 ° C. Then, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution while stirring the reaction solution. At this time, ethylene oxide was added by a blow-in tube while controlling the addition rate so that the reaction temperature did not exceed 180 ° C.
After completion of the addition of ethylene oxide, the mixture was aged for 30 minutes at a temperature of 180 ° C. and a pressure of 0.3 MPa or less, and then unreacted ethylene oxide was distilled off for 10 minutes at a temperature of 180 ° C. and a pressure of 6.0 kPa or less. Next, after the temperature is cooled to 100 ° C. or less, 70% by mass p-toluenesulfonic acid is added to neutralize so that the pH of a 1% by mass aqueous solution of the reaction product becomes about 7, to obtain B-2 The

B-3: AE (7EO). What added 7 mol equivalent ethylene oxide to the C12 and C14 natural alcohol (primary alcohol). In the general formula (III), R ⁴¹ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, R ⁴² = a hydrogen atom, s = 7, t = 0.
B-4: EO / PO nonion. One obtained by block addition of 8 moles of ethylene oxide, 2 moles of propylene oxide, and 8 moles of ethylene oxide in this order to a natural alcohol (C12 alcohol / C14 alcohol = 7/3 by mass ratio). In the following general formula (V), R ⁶¹ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, p = 8, q = 2, r = 8.
R ⁶¹ -O-[(EO) _p / (PO) _q ]-(EO) _r -H (V)
[In formula (V), R ⁶¹ is a hydrocarbon having 6 to 22 carbon atoms, p is the average number of repetitions of EO, is a number of 3 to 20, q is the average number of repetitions of PO, 0 It is a number of -6, r represents the average repeat number of EO, is a number of 0-20, EO represents an oxyethylene group, PO represents an oxypropylene group. ]
B-5: Softanol. One obtained by adding ethylene oxide equivalent to 7 moles to a secondary alcohol having 12 to 14 carbon atoms, Softanol 70 (trade name), manufactured by Nippon Shokubai Co., Ltd. In general formula (V), R ⁶¹ = alkyl group having 12 carbon atoms and alkyl group having 14 carbon atoms, p = 7, q = 0, r = 0.
B-6: Rutensol (C13 oxo alcohol ethoxylate). What added ethylene oxide equivalent to 10 mol with respect to C13 alcohol obtained by using the C12 alkene obtained by trimerizing butene for the oxo method (brand name: Lutensol TO10, BASF company make). In the following general formula (VI), m = 6, n = 10.
R ⁷¹ -CH (R ⁷² ) -CH ₂ -O- (CH ₂ CH ₂ O) _n -H (VI)
[In formula (VI), R ⁷¹ is represented by C _m H _{2m + 1} , R ⁷² is represented by C _(m−2) H _{2 (m−2) +1} , m = 4 to 6, and n = 3 To 10. ]
The raw material which supplies such a component is obtained, for example by the Garbett reaction. Here, the Garbett reaction refers to a reaction in which, when the primary alcohol is heated in the presence of metallic sodium or metallic potassium, bimolecular condensation occurs to form a primary alcohol branched to the β-position. The alcohol obtained by the Garbett reaction has a structure of the following general formula (VII).
R ⁷³ -CH (R ⁷⁴ ) -CH ₂ -OH (VII)
[In Formula (VII), R ⁷³ is represented by C _m H _{2m + 1} , and R ⁷⁴ is represented by C _(m-2) H _{2 (m-2) +1} . ]

<(C) component>
C-1: AES, polyoxyethylene alkyl ether sulfate (natural alcohol (trade name "CO-1270" manufactured by P & G Co., Ltd.) compound obtained by adding 1 mol equivalent of EO) (manufactured by Lion Corporation), trade name : BRES (1)).
C-2: LAS, linear or branched alkyl benzene sulfonate having an alkyl group having 10 to 14 carbon atoms (manufactured by Lion Corporation, trade name: Lipon (registered trademark) LH-200).
C-3: AEPS, monoethanolamine salt of polyoxyalkylene alkyl ether sulfate ester (1-dodecanol with propylene oxide having an average added mole of 1.0 mol and ethylene oxide having an average added mole of 2.0 mol added in this order) Then, it is produced by neutralizing it with sulfated monoethanolamine).
C-4: coconut fatty acid sodium, manufactured by NOF Corporation, trade name "Pascal fatty acid".

<(D) component>
D-1: 3-methoxy-3-methylbutanol (manufactured by Kuraray Co., Ltd., trade name "Solfit"). In general formula (d1), R ¹ = methyl group, R ² = R ³ = R ⁴ = hydrogen atom.
D-2: butyl carbitol (diethylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd.). In the general formula (d2), R ⁵ = hydrogen atom, X = 2, Y = 0, R ⁶ = butyl group.

<(E) component>
E-1: ethanol, manufactured by Nippon Alcohol Sales Co., Ltd., trade name "specific alcohol 95 degree synthesis".

<PH adjuster>
Sodium hydroxide or sulfuric acid: appropriate amount (amount required to adjust to pH 7). The total of pH adjusters in the liquid detergent of each example was 0 to 3% by mass.
<Water>
Water: distilled water, manufactured by Kanto Chemical Co., Ltd. Balance (the amount to make the total amount of liquid detergent 100% by mass).

<Optional component>
Hereinafter, “mass%” described at the end of each component is the content in the finally adjusted liquid detergent of each example.
MEA (manufactured by Nippon Shokubai Co., Ltd., trade name: "monoethanolamine") 0.5% by mass.
Alcalase (manufactured by Novozymes, trade name: “Alcalase 2.5 L”) 0.5% by mass.
Para-toluenesulfonic acid, PTS (manufactured by Kyowa Hakko Kogyo Co., Ltd., trade name "PTS acid"), 0.2% by mass.
TexCare SRN-170C (trade name, manufactured by Clariant Japan, mass average molecular weight: 2000 to 3000, pH (5% by mass aqueous solution at 20 ° C): 4, viscosity (20 ° C): 300 mPa · s). TexCare SRN-170C is 0.5 mass% which is a 70 mass% aqueous solution of trade name: TexCare SRN-100 (manufactured by Clariant Japan, mass average molecular weight: 2000 to 3000).
PPG: polyoxypropylene glyceryl ether, Actocol T-4000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 4000, 1% by mass.
Methyl glycine diacetate trisodium, manufactured by BASF, trade name "Trilon M Liquid", 0.5% by mass.
Sodium benzoate, manufactured by Toagosei Co., Ltd., trade name "sodium benzoate", 0.3% by mass.
Calcium chloride, manufactured by Kanto Chemical Co., Ltd., trade name "calcium chloride", 0.01% by mass.
Sodium lactate, manufactured by Kanto Chemical Co., Ltd., trade name "sodium lactate", 0.5% by mass.
Fragrance, 0.5% by mass of perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.
Dye, manufactured by Tsuji Kasei Co., Ltd., trade name "Green No. 3", 0.0005% by mass.

[Examples 1 to 25, Comparative Examples 1 to 5]
The components (A) to (D), the component (E) and the optional components were added to water and mixed according to the compositions in Tables 1 to 3 to obtain a liquid detergent. About the obtained liquid detergent, the rinse property, the recontamination prevention property, and liquid stability in 5 degreeC or 25 degreeC were evaluated by the following evaluation methods. The results are shown in Tables 1 to 3.
In addition, the unit of the content in a table | surface is "mass%", and shows the pure equivalent amount. The optional component indicates that a predetermined amount of optional component other than the pH adjuster and water is added. The pH adjuster indicates that an appropriate amount has been added. "Balance" means that water is blended such that the total blending amount (% by mass) of all the blending components contained in the composition of each example is 100% by mass.

<Evaluation method>
[Evaluation of rinseability]
0.5 g of the liquid cleaner shown in each example of Tables 1 to 3 was dissolved in tap water adjusted to 25 ° C. to prepare a cleaning solution. 20 mL of this washing solution was placed in an Epton tube, and this Epton tube was shaken by hand 20 times at 1 stroke / sec. One minute after the end of shaking, the height of each foam (the volume from the boundary between the foam and the washing solution and the volume from the upper end face of the foam) was read, and the rinse property was evaluated according to the following evaluation criteria. In the following evaluation criteria, ◎, ◎, ◎, ○, を, and 合格 were accepted.
(Evaluation criteria)
◎ ◎: The height of the foam is less than 30 mm.
◎ :: The height of the foam is 30 mm or more and less than 50 mm.
:: The height of the foam is 50 mm or more and less than 70 mm.
○: The height of the foam is 70 mm or more and less than 90 mm.
○: The height of the bubble is 90 mm or more and less than 120 mm.
Δ: The height of the bubble is 120 mm or more and less than 150 mm.
X: The height of the bubble is 150 mm or more.

[Evaluation of recontamination prevention property]
Using the liquid detergent of each example, the washing process shown below was repeated three times in the order of washing, rinsing and drying steps.
(Washing process)
The following cotton cloth, wet artificial soil cloth and skin shirt were used as objects to be washed.
-Cotton: 5 pieces of 5 cm x 5 cm of cotton knitwear (made by Tanigami Store) as a recontamination judgment cloth.
Wet artificial soiled cloth: Contaminated cloth manufactured by Japan Foundation for the Laundry Science (28.3% by weight of oleic acid, 15.6% by weight of triolein, 12.2% by weight of cholesterol oleate, 2.5% by weight of liquid paraffin, squalene 2 .20 cloths with a soiled composition of 5% by mass, 1.6% by mass of cholesterol, 7.0% by mass of gelatin, 29.8% by mass of mud, and 0.5% by mass of carbon black.
-Skin shirt: 150 pieces of a skin shirt (LL size, manufactured by DVD) finely cut (about 3 cm x 3 cm).
In a Terg-o-tometer (manufactured by UNITED STATES TESTING Co., Ltd.), 900 mL of 3 ° DH hard water at 25 ° C. was placed, and 0.6 g of a liquid detergent was added thereto. Then, the material to be washed was added to adjust the bath ratio to 20 times and washed at 120 rpm and 25 ° C. for 10 minutes.

(Rinse process)
After washing, the material to be washed was dehydrated for 1 minute, and then 900 mL of 3 ° DH hard water at 25 ° C. was added, and rinsed at 120 rpm for 3 minutes at 25 ° C. This operation (dehydration, rinse) was repeated twice. In the second time, a predetermined amount of softener was added to 900 mL of 3 ° DH hard water at 25 ° C. for rinsing. As a softener, room-dried Soflan (manufactured by Lion Corporation) was used.

(Drying process)
After the rinsed material was dewatered for 1 minute, only the recontamination test cloth (cotton cloth) was taken out, sandwiched with filter paper, and dried with an iron.

(Measurement of reflectance)
The reflectance (Z value) of the recontamination determination cloth before and after the laundry treatment was measured using a reflectometer (spectral color difference meter SE2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and ΔZ was determined from the following formula.
Δ Z = (Z value before laundry treatment)-(Z value after laundry treatment)
An average value of five sheets was determined for ΔZ in the cotton cloth recontamination determination cloth. And the recontamination prevention property to the cotton cloth by liquid cleaning agent was evaluated according to the following judgment standard which made this average value the index. In the following evaluation criteria, ◎ and を were accepted.

(Evaluation criteria)
◎: 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 solution stability]
In a transparent glass bottle (wide-mouth standard bottle, PS-NO. 11), 100 mL of the liquid detergent of each example was filled, and the lid was closed and sealed. In this state, it was stored in a thermostat at 5 ° C. or 25 ° C. for 7 days.
After the storage, the appearance of the liquid was visually observed, and the liquid stability of the liquid detergent was evaluated according to the following evaluation criteria.以上 or more was accepted.

(Evaluation criteria)
○: No sediment is observed at the bottom of the glass bottle, and the liquid is fluid.
Δ: Precipitated material is observed at the bottom of the glass bottle, but when the glass bottle is gently shaken, 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 gently, the precipitated substance does not disappear, or gelation or clouding occurs immediately after the production of the liquid detergent.

As shown in Tables 1 to 3, it can be confirmed that Examples 1 to 25 to which the present invention is applied are excellent in the rinse property and the recontamination prevention property, and the solution stability is also good.
On the other hand, the comparative example 1 which does not contain (A) component was "(DELTA)" recontamination prevention property. The comparative example 2 which does not contain (D) component was "(triangle | delta)" rinse property. Comparative Example 3 in which the component (A ') was used instead of the component (A), the recontamination resistance was "Δ". The comparative example 4 which does not contain the (B) component was "x" in rinse property. The rinse property was "(triangle | delta)" in comparative example 5 whose mass ratio represented by (B) component / (C) component is less than 0.5.

  From these results, it was found that according to the liquid detergent composition of the present invention, recontamination is suppressed and the rinse performance and liquid stability are superior.

Claims (2)

Component (A): an alkylene oxide adduct of a polyalkylene amine,
(B) component: nonionic surfactant,
Component (C): An anionic surfactant,
Component (D): containing at least one selected from an organic solvent represented by the following general formula (d1) and an organic solvent represented by the following general formula (d2),
The liquid detergent composition whose mass ratio represented by (B) component / (C) component is 0.5 or more.

(In formula (d1), R ^{1 to} R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or an acetyl group.)
R ⁵ O (C ₂ H ₄ O) _X (C ₃ H ₆ O) _Y R ⁶ (d2)
(In formula (d2), R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ and R ⁶ are not simultaneously a hydrogen atom. X is 0 ≦ An integer of X ≦ 3, Y is an integer of 0 ≦ Y ≦ 3, and X and Y can not be 0 simultaneously.)   Furthermore, it contains at least one selected from (E) component: C2-C3 monohydric alcohol and C2-C4 polyhydric alcohol, and is represented by (E) component / (D) component The liquid detergent composition according to claim 1, wherein the mass ratio is more than 0 and 3 or less.