JP5779392B2 - Liquid cleaning agent - Google Patents

Description

  The present invention relates to a liquid cleaning agent.

In recent years, the development of products in consideration of the global environment has been demanded also in the field of daily necessities such as household cleaners. From the environmental aspect of carbon neutral, it is preferable to use an alcohol having a linear alkyl group derived from an oil and fat raw material as a detergent raw material. When the linear alcohol ethoxy sulfate made from this alcohol as a raw material is blended in a hard surface cleaner, the persistence of the foam is improved.
A composition containing a specific linear alcohol ethoxy sulfate, a secondary alkane sulfonate, a semipolar surfactant, and a higher alcohol or fatty acid has been proposed as a liquid detergent having excellent foam persistence. (See Patent Document 1).

JP 2007-332305 A

However, since linear alcohol ethoxy sulfate has high intermolecular orientation, liquid detergents containing it are likely to precipitate under low temperature conditions, and it is difficult to ensure storage stability. In addition, there is a problem that foaming is slow.
In the liquid cleaning agent described in Patent Document 1, it is said that the foam is well foamed by pouring the sponge into the dishwashing sponge and then manually swiping the sponge ten times. However, in practice, a sufficient amount of foam is further added. There is a demand for foaming quickly.
This invention is made | formed in view of the said situation, and makes it a subject to provide a liquid detergent with quick foaming while having low-temperature stability favorable.

As a result of intensive studies, the present inventors have found that an anionic surfactant having a specific structure from among branched-chain compounds that are generally difficult to form an association state and are suitable components for low foaming compositions. And using the combination of the anionic surfactant, linear alcohol ethoxysulfate, and a specific hydrotrope, found that the above-mentioned problems were solved, and the present invention was completed. .
That is, the liquid detergent of the present invention includes a compound (a) represented by the following general formula (a1), a compound (b) represented by the following general formula (b1), toluenesulfonic acid, cumenesulfonic acid, At least one hydrotrope selected from the group consisting of xylenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, or aromatic sulfonates thereof , benzoic acid or salts thereof , and alcohols having 2 to 4 carbon atoms (c And a mass ratio represented by (a) component / (b) component is 6 or less.

［式（ａ１）中、Ｒ^１は炭素数８〜２４の直鎖状のアルキル基、又は炭素数８〜２４の直鎖状のアルケニル基である。ＥＯはオキシエチレン基を表す。ｎはＥＯの平均繰返し数を表し、１〜５の数である。Ｍ_１はアルカリ金属、アルカリ土類金属、アンモニウム又はアルカノールアミンを表す。式（ｂ１）中、ｘとｙはそれぞれ１〜７の整数であり、ｘ＋ｙ＝８である。ＰＯはオキシプロピレン基、ＥＯはオキシエチレン基を表す。ｐはＰＯの平均繰返し数、ｑはＥＯの平均繰返し数を表し、ｐ＋ｑは１〜１０である。Ｍ_２はアルカリ金属、アルカリ土類金属、アンモニウム又はアルカノールアミンを表す。］

[In Formula (a1), R ¹ is a linear alkyl group having 8 to 24 carbon atoms or a linear alkenyl group having 8 to 24 carbon atoms. EO represents an oxyethylene group. n represents the average number of repetitions of EO and is a number from 1 to 5. M ₁ represents an alkali metal, alkaline earth metal, ammonium or alkanolamine. In the formula (b1), x and y are each an integer of 1 to 7, and x + y = 8. PO represents an oxypropylene group, and EO represents an oxyethylene group. p represents the average number of repetitions of PO, q represents the average number of repetitions of EO, and p + q is 1 to 10. M ₂ represents an alkali metal, alkaline earth metal, ammonium or alkanolamine. ]

  The liquid detergent of the present invention preferably further contains an amphoteric surfactant and / or a semipolar surfactant (d).

  According to the present invention, it is possible to provide a liquid cleaning agent having good low-temperature stability and quick foaming.

The liquid detergent of the present invention comprises a compound (a) represented by the general formula (a1), a compound (b) represented by the general formula (b1), an aromatic sulfonic acid, and an aromatic sulfonate. And at least one (c) selected from the group consisting of aromatic carboxylic acids, aromatic carboxylates, and alcohols having 2 to 4 carbon atoms.
Hereinafter, these components are also referred to as component (a), component (b), and component (c), respectively.
The liquid detergent of the present invention can be suitably used as a hard surface detergent. Here, the “hard surface” means a surface made of a hard material such as pottery, porcelain, glass, hard plastic, metal, painted metal, or tile. Specific examples thereof include tableware, cooking utensils, toilet bowls, window glass, vehicle glass, glasses, transparent plastic, mirrors; bathtubs, bathroom walls and floors, sinks, washstands, and the like. Especially, the liquid cleaning agent of this invention can be utilized especially suitably as cleaning agents for kitchens, such as tableware and cooking utensils.

<Compound (a)>
In the liquid detergent of the present invention, the compound (a) is a linear anionic surfactant (linear alcohol ethoxy sulfate) represented by the following general formula (a1). By containing the component (a), the persistence of foam and the cleaning power are mainly provided.

［式（ａ１）中、Ｒ^１は炭素数８〜２４の直鎖状のアルキル基、又は炭素数８〜２４の直鎖状のアルケニル基である。ＥＯはオキシエチレン基を表す。ｎはＥＯの平均繰返し数を表し、１〜５の数である。Ｍ_１はアルカリ金属、アルカリ土類金属、アンモニウム又はアルカノールアミンを表す。］

[In Formula (a1), R ¹ is a linear alkyl group having 8 to 24 carbon atoms or a linear alkenyl group having 8 to 24 carbon atoms. EO represents an oxyethylene group. n represents the average number of repetitions of EO and is a number from 1 to 5. M ₁ represents an alkali metal, alkaline earth metal, ammonium or alkanolamine. ]

In the formula (a1), R ¹ is a linear alkyl group having 8 to 24 carbon atoms or a linear alkenyl group having 8 to 24 carbon atoms, and a linear chain having 8 to 24 carbon atoms. Alkyl groups are preferred.
In the alkyl group and alkenyl group of R ¹ , the carbon number is 8 to 24, preferably 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, and particularly preferably 12 to 14 carbon atoms.
R ¹ is preferably a linear alkyl group derived from an oil or fat raw material from the standpoint of foam persistence, detergency and environmental aspects. Suitable fats and oils include palm kernel oil, coconut oil and the like.

In the formula (a1), EO represents an oxyethylene group, and n represents the average number of repetitions of EO.
n is a number from 1 to 5, and if n is less than 1, the low-temperature stability of the liquid detergent may be reduced, and if n is more than 5, the durability of foam and the cleaning power may be reduced. is there.

In the formula (a1), M ₁ is an alkali metal, an alkaline earth metal, ammonium or alkanolamine, and can form a water-soluble salt with R ¹ —O— (EO) n—SO ₃ ^—. I just need it.
Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.

Specific examples of the component (a) include polyoxyethylene (1) linear alkyl (C12) sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12) sulfate sodium salt, polyoxyethylene (3) Linear alkyl (C12) sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) sulfate sodium salt, polyoxyethylene (3) linear alkyl (C12 / 14 = 75/25; derived from natural oils and fats) sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) sulfate triethanolamine salt, and the like.
Among them, polyoxyethylene (2) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) sulfate sodium salt is preferable because the effects of the present invention are particularly easily obtained.
Here, for example, “polyoxyethylene (2)” means that the average number of repeating oxyethylene groups is 2 (the average number of added moles of ethylene oxide is 2).
“C12 / 14 = 75/25; derived from natural fats and oils” means a mixture of a compound having a linear alkyl group having 12 carbon atoms and a compound having a linear alkyl group having 14 carbon atoms (mixing ratio: by mass ratio). 75/25) and a linear alkyl group derived from natural fats and oils.

(A) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
In the liquid detergent, the amount of component (a) is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, based on the total mass of the liquid detergent.
When the blending amount of the component (a) is less than the lower limit value, the foam persistence may be lowered. On the other hand, if the upper limit is exceeded, foaming tends to be slow. Moreover, it becomes difficult to obtain the effect of improving the rinsing properties and the low temperature stability.

<Compound (b)>
In the liquid detergent of the present invention, the compound (b) is an anionic surfactant having a branched alkyl group represented by the following general formula (b1).
By using the compound (b) in combination with the component (a), foaming is mainly accelerated. In addition, good rinsing properties and high detergency against oil stains can be obtained.

［式中、ｘとｙはそれぞれ１〜７の整数であり、ｘ＋ｙ＝８である。ＰＯはオキシプロピレン基、ＥＯはオキシエチレン基を表す。ｐはＰＯの平均繰返し数、ｑはＥＯの平均繰返し数を表し、ｐ＋ｑは１〜１０である。Ｍ_２はアルカリ金属、アルカリ土類金属、アンモニウム又はアルカノールアミンを表す。］

[Wherein, x and y are each an integer of 1 to 7, and x + y = 8. PO represents an oxypropylene group, and EO represents an oxyethylene group. p represents the average number of repetitions of PO, q represents the average number of repetitions of EO, and p + q is 1 to 10. M ₂ represents an alkali metal, alkaline earth metal, ammonium or alkanolamine. ]

In the formula (b1), x and y are each an integer of 1 to 7, and x + y = 8. When x + y = 8, the bubbles are likely to rise quickly.
_{Examples of} C _x H _{2x + 1} and C _y H _{2y + 1} include a linear alkyl group or a branched alkyl group, and a linear alkyl group is preferable from the viewpoint of easy foam formation. Among them, C _x H _{2x + 1} and C _y H _{2y + 1} are particularly preferably a combination of a propyl group and a pentyl group (one of x and y is 3 and the other is 5).

In the formula (b1), PO represents an oxypropylene group, EO represents an oxyethylene group, p represents the average number of repetitions of PO, and q represents the average number of repetitions of EO.
p + q is 1 to 10, preferably 1 to 5, and particularly preferably 3 to 4. When p + q is within the above range, bubbles are likely to rise quickly. In addition, the rinsing properties (goodness of foaming, no nulliness) are good. Furthermore, the storage stability under low temperature conditions is further improved. In addition, when used in combination with the component (d) described later, if dirt is removed from the dishes, etc. even during washing, friction will occur between the sponge and the dishes, resulting in a feeling of being washed. It is easy to be done.
q is preferably from 1 to 10, and more preferably from 1 to 5.
p is preferably from 0 to 9, more preferably from 0 to 4, from the viewpoint of ease of foam formation.
When PO and EO are mixed, the arrangement state of PO and EO is not particularly limited, and may be mixed in a random manner or in a block shape.
Note that p and q indicate the “average” number of repetitions of PO and EO, respectively. That is, the compound represented by the formula (b1) is an aggregate of molecules having different repeating numbers of PO and EO (including molecules having no PO or EO). Further, it may be an assembly of molecules having different combinations of C _x H _{2x + 1} and C _y H _{2y + 1} .

In the formula (b1), M ₂ is an alkali metal, an alkaline earth metal, ammonium, or an alkanolamine, and (C _x H _{2x + 1} ) (C _y H _{2y + 1} ) CH—CH ₂ O— (PO) p— ( Any material that can form a water-soluble salt with EO) q-SO ₃ ^— may be used.
Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.

(B) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
Among these, the component (b) is preferably a sulfate of an alkylene oxide adduct of an alcohol having a branched structure at the β-position obtained by bimolecular condensation by a gerbet reaction.
As the component (b), an alkylene oxide adduct of gerbet alcohol is mixed with, for example, liquid sulfuric anhydride or SO ₃ using a tank type reaction system, a film type reaction system, a tubular gas-liquid mixed phase reaction system, or the like. It can be produced by sulfating by contact with a gas or the like and then neutralizing with an alkali metal compound, an alkaline earth metal compound, ammonium or alkanolamine or the like.
Specific examples of gerbet alcohol alkylene oxide adducts include BASF's Rutensol XP30 (average number of moles of ethylene oxide added 3), Rutensol XP40 (average number of moles of ethylene oxide added 4), Rutensol XL40 (average of propylene oxide added) The number of moles is 1, and the average number of moles of ethylene oxide added is 3) (above, trade name).

In the liquid cleaning agent, the amount of component (b) is preferably 1 to 35% by mass, more preferably 4 to 20% by mass, based on the total mass of the liquid cleaning agent.
When the amount of component (b) is less than the lower limit, foaming tends to be delayed. Moreover, it becomes difficult to obtain the effect of improving the rinsing properties and the low temperature stability. On the other hand, if the upper limit value is exceeded, the rinsing properties tend to decrease.

In the liquid cleaning agent of the present invention, the total of the component (a) and the component (b) is preferably 15 to 50% by mass with respect to the total mass of the liquid cleaning agent, and is 20 to 45% by mass. Is more preferable.
When the total of the component (a) and the component (b) is equal to or higher than the lower limit, high cleaning performance is easily imparted to the liquid cleaning agent. On the other hand, if the sum of the component (a) and the component (b) exceeds the preferable upper limit, the effect of improving the rinsability becomes difficult to obtain.

In the present invention, “mass ratio represented by (a) component / (b) component” means the ratio (mass ratio) of the content of (a) component to the content of (b) component in the liquid detergent. Represents.
In the liquid detergent of the present invention, the mixing ratio of the component (a) and the component (b) is such that the mass ratio represented by the component (a) / component (b) is 6 or less, preferably 0.5 to 6, more preferably 1-5.
When the said mass ratio is more than a lower limit, it is excellent especially in the sustainability of the foam by (a) component mixing | blending, and a rinse property also improves. On the other hand, when it is at most the upper limit value, the low-temperature stability becomes better. In addition, bubbles are easier to stand up.

<At least one (c) selected from the group consisting of aromatic sulfonic acid, aromatic sulfonate, aromatic carboxylic acid, aromatic carboxylate, and alcohol having 2 to 4 carbon atoms>
In this invention, by containing (c) component as a hydrotrope agent, the storage stability (especially low temperature stability) of a liquid cleaning agent improves, and a transparent external appearance can be ensured more stably.

Examples of the aromatic sulfonic acid in the component (c) include toluene sulfonic acid, cumene sulfonic acid, xylene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, and among them, toluene sulfonic acid and cumene sulfonic acid are preferable.
Toluene sulfonic acid and cumene sulfonic acid may be any of the three isomers, o-form, m-form and p-form, respectively, and since they are easily available, p-form is preferred. Among them, p- Toluenesulfonic acid is more preferred.
Examples of the aromatic carboxylic acid include benzoic acid.
Salt forms of aromatic sulfonates and aromatic carboxylates include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium and calcium; ammonium salts; monoethanolamine, diethanolamine, Examples include alkanolamine salts such as ethanolamine. Of these, alkali metal salts are preferable, and sodium salts are more preferable.
Among the alcohols having 2 to 4 carbon atoms, examples of the monohydric alcohol include ethanol, 1-propanol, 2-propanol, and 1-butanol. Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.

(C) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
As the component (c), since it is excellent in storage stability even under a low temperature condition, aromatic sulfonic acid, aromatic sulfonate, aromatic carboxylic acid, aromatic carboxylate, and C2-4 It is preferable to use at least two selected from the group consisting of alcohols. Among them, it is more preferable to use at least two selected from the group consisting of toluenesulfonic acid, toluenesulfonic acid salt, cumenesulfonic acid, cumenesulfonic acid salt, benzoic acid, benzoic acid salt, and ethanol. It is particularly preferable to use ethanol in combination with at least one selected from the group consisting of toluenesulfonic acid, toluenesulfonic acid salt, cumenesulfonic acid, cumenesulfonic acid salt, benzoic acid and benzoic acid salt.

In the liquid detergent, the amount of the component (c) is preferably 5 to 20% by mass, more preferably 6 to 10% by mass with respect to the total mass of the liquid detergent.
(C) When the compounding quantity of a component is more than a preferable lower limit, the low temperature stability of a liquid detergent improves more. On the other hand, when the preferred upper limit is exceeded, the blending effect of the component (c) reaches saturation, and when blended in a large amount exceeding the upper limit, other cleaning components are reduced, and foaming properties (ease of foaming, There is a risk that the amount of foam) and detergency may be reduced.

<Solvent: Water>
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of preparation of the liquid detergent, solubility in water when used, and the like.
The amount of water in the liquid detergent is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, and still more preferably 50 to 80% by mass with respect to the total mass of the liquid detergent.
When the blending amount of water is at least the lower limit, the liquid stability of the liquid detergent with time will be better, and when it is not more than the upper limit, the liquid viscosity will be moderately low and good from the viewpoint of usability. .

<Other ingredients>
In the liquid cleaning agent of the present invention, other components other than the above-described components may be arbitrarily blended as necessary within the range not impairing the effects of the present invention.
The other components are not particularly limited, and components used in cleaning agents for hard surfaces or clothing can be blended, and specific examples include the following.

(Amphoteric surfactant and / or semipolar surfactant (d))
The liquid detergent of the present invention preferably further contains an amphoteric surfactant and / or a semipolar surfactant (d) (hereinafter also referred to as “component (d)”).
By further containing the component (d), mainly when the stains are removed from the dishes during cleaning, friction is generated between the sponge and the dishes and the like, giving a feeling of being cleaned. Furthermore, it becomes easy to obtain a high detergency against oil stains.

Amphoteric surfactants include betaine types such as aminoacetic acid betaines (such as alkylbetaines and alkylamidobetaines) and sulfobetaines (such as alkylhydroxysulfobetaines); glycine-based (such as imidazolinium betaines), and aminopropion. Amino acid type ones such as acid type ones can be mentioned.
Specific examples of amphoteric surfactants include betaine aminoacetates such as lauryldimethylaminoacetic acid betaine and amidopropyldimethylaminoacetic acid betaine; N-lauryl-N, N-dimethylammonium-N-propylsulfobetaine, N-lauryl Sulfobetaines such as -N, N-dimethylammonium-N- (2-hydroxypropyl) sulfobetaine, N-lauryl-N, N-dimethyl-N- (2-hydroxy-1-sulfopropyl) ammonium sulfobetaine; 2 -Glycines such as lauryl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and sodium lauryldiaminoethylglycine; aminopropionic acids such as sodium laurylaminopropionate and sodium laurylaminodipropionate Include those of.

In the present invention, the “semipolar surfactant” is a surfactant having a semipolar bond (a bond having an intermediate property between a nonpolar bond and a polar bond), and the semipolar surfactant is dissolved therein. Depending on the pH of the solution or dispersion system to be dispersed, it means that it becomes cationic, anionic, or bipolar.
Suitable examples of the semipolar surfactant include amine alkylene oxide surfactants and amine oxide surfactants. Of these, amine oxide surfactants are preferred because of their good detergency against oil stains and good foaming.
Examples of amine oxide type surfactants include alkylamine oxide and alkylamidopropyldimethylamine oxide. Among them, compounds represented by the following general formula (d1) are preferable.

［式中、Ｒ^２は炭素数８〜１８の直鎖状若しくは分岐鎖状のアルキル基又はアルケニル基であり、Ｒ^３、Ｒ^４はそれぞれ独立して炭素数１〜３のアルキル基又はヒドロキシアルキル基であり、Ｒ^５は炭素数１〜４のアルキレン基である。Ｂは−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−又は−Ｏ−である。ｒは０又は１の数である。］

[Wherein, R ² is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, and R ³ and R ⁴ are each independently an alkyl group or hydroxyalkyl having 1 to 3 carbon atoms. R ⁵ is an alkylene group having 1 to 4 carbon atoms. B is —CONH—, —NHCO—, —COO—, —OCO— or —O—. r is a number of 0 or 1; ]

In the formula (d1), R ² is a linear or branched alkyl group having 8 to 18 carbon atoms, or a linear or branched alkenyl group having 8 to 18 carbon atoms, 8-18 linear or branched alkyl groups are preferred.
In the alkyl group and the alkenyl group of R ^2, the number of carbon atoms is 8 to 18, and the effect of imparting detergency to oil stains and a washed feeling is further improved.
R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. R ³ and R ⁴ are more preferably methyl groups.
R ⁵ is an alkylene group having 1 to 4 carbon atoms.
B is —CONH—, —NHCO—, —COO—, —OCO— or —O—.
r is a number of 0 or 1, and 0 is preferable.

  Specific examples of the amine oxide type surfactant include alkyl dimethyl amine oxides such as lauryl dimethyl amine oxide, coconut alkyl dimethyl amine oxide, and lauryl diethyl amine oxide; And the like. Especially, since the detergency with respect to oil stain | pollution | contamination and the provision effect of the wash | cleaned feeling are especially favorable, the thing of an alkyl dimethylamine oxide type is more preferable.

(D) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
Among these, as the component (d), the detergency against oil stains and the effect of imparting a washed feeling in combination with the component (b) are particularly good. Therefore, aminoacetic acid betaine, sulfobetaine, alkyldimethylamine An oxide type or an alkanoylamide alkyldimethylamine oxide type is preferable, and an alkyldimethylamine oxide type is particularly preferable.

In the liquid detergent, the blending amount of the component (d) is preferably 2 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 4 with respect to the total mass of the liquid detergent. -10 mass%.
(D) When the compounding quantity of a component is more than a preferable lower limit, detergency will increase and a bubble will stand up more easily. On the other hand, when the preferable upper limit is exceeded, the viscosity of the liquid cleaning agent may increase excessively, and the rinsing property may decrease.

In the liquid detergent of the present invention, the blending ratio of the component (a), the component (b), and the component (d) is a mass ratio represented by [(a) component + (b) component] / (d) component. Is preferably 1.5 to 7.5, and 4 to 6.
When the mass ratio is equal to or higher than the lower limit, a feeling of being washed during washing can be obtained. In addition, bubbles are easily formed and rinsing properties are further improved. On the other hand, if it is less than or equal to the upper limit value, in addition to the feeling of being cleaned during cleaning, the cleaning power against oil stains is further improved.
In the present invention, the “mass ratio represented by [(a) component + (b) component] / (d) component” refers to (a) component and ( b) The ratio (mass ratio) of the total content with the component is represented.

(Fatty acid monoethanolamide compound (e))
The liquid detergent of the present invention preferably further contains a fatty acid monoethanolamide compound (e) (hereinafter referred to as “component (e)”). By containing the component (e), the persistence of the foam during cleaning is mainly increased.
Preferred examples of the component (e) include compounds represented by the following general formula (e1).

［式中、Ｒ^６は炭素数５〜１９のアルキル基を表す。ｍはオキシエチレン基（−Ｃ_２Ｈ_４Ｏ−）の平均繰返し数を表し、０〜９の数である。］

[Wherein R ⁶ represents an alkyl group having 5 to 19 carbon atoms. m represents the average number of repetitions of the oxyethylene group (—C ₂ H ₄ O—), and is a number from 0 to 9. ]

In the formula (e1), R ⁶ represents an alkyl group having 5 to 19 carbon atoms, and may be linear or branched.
In the alkyl group of R ⁶ , the carbon number is 5 to 19, and the detergency against oil stains and the persistence of foam are improved, and therefore, the number of carbon atoms is preferably 7 to 13.
m represents the average number of repetitions of the oxyethylene group (—C ₂ H ₄ O—), is a number from 0 to 9, is preferably a number from 0 to 4, and is a number from 0 to 2. More preferred.

Specific examples of the component (e) include polyoxyethylene (2) lauric acid monoethanolamide (R ⁶ in formula (e1) = a linear alkyl group having 11 carbon atoms, m = 2), polyoxyethylene (2) Capric acid monoethanolamide (R ⁶ in formula (e1) = a linear alkyl group having 9 carbon atoms, m = 2) and the like. Of these, polyoxyethylene (2) capric acid monoethanolamide is more preferable.

(E) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
In the liquid detergent, the amount of component (e) is preferably 1 to 20% by mass, more preferably 2 to 16% by mass, based on the total mass of the liquid detergent.
When the blending amount of the component (e) is less than the preferred lower limit value, it may be difficult to obtain the effect of improving the foam persistence. On the other hand, when the preferred upper limit value is exceeded, the foam persistence increases, May be difficult to stand.

In the liquid detergent of the present invention, the mass ratio represented by (e) component / [(a) component + (b) component] is preferably 0.6 or less, and preferably 0.01 to 0.55. Is more preferable, and 0.05 to 0.55 is particularly preferable.
When the mass ratio is equal to or lower than the upper limit value, bubbles are likely to rise more quickly. In addition, the amount of foaming and rinsing properties are also improved. On the other hand, if it is at least the lower limit value, the sustainability of the foam is further improved.
In the present invention, “mass ratio represented by (e) component / [(a) component + (b) component]” means the total content of the (a) component and the (b) component in the liquid detergent. The ratio (mass ratio) of the content of the component (e) with respect to.

  In the liquid cleaning agent of the present invention, as other components than the above-described components, divalent metal salts, pH adjusters (sodium hydroxide, sulfuric acid, glycolic acid, etc.), chelating agents, antioxidants, coloring agents, enzymes In addition, fragrances and the like can be arbitrarily blended.

The liquid cleaning agent of the present invention mainly contains a divalent metal salt (hereinafter also referred to as “component (f)”), whereby the cleaning power is mainly increased.
As the component (f), magnesium salts such as magnesium chloride, magnesium sulfate, magnesium iodide, magnesium nitrate and magnesium bromide; calcium salts such as calcium chloride, calcium iodide, calcium bromide and calcium nitrate; zinc nitrate and sulfide Examples thereof include zinc salts such as zinc, zinc sulfate, zinc chloride, zinc acetate, ammonium zinc chloride, zinc gluconate, zinc tartrate, zinc perchlorate and zinc oxide.
Among these, zinc salts are preferable, and zinc sulfate and zinc oxide are particularly preferable because they can provide a sterilizing effect and an antibacterial effect in addition to the effect of improving detergency.
(F) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
When the component (f) is, for example, a zinc salt, the component (f) is preferably blended in the liquid detergent so that zinc ions are 0.01% by mass or more, and 0.02% by mass or more. It is more preferable to blend in. If zinc ions are blended in at least the preferred lower limit, the effect of improving detergency is likely to be obtained, and the sterilization effect and antibacterial effect are also likely to be obtained.

The concentration of the divalent metal ion derived from the component (f) with respect to the total mass of the liquid detergent can be determined as follows.
For example, when 1 mass% of zinc sulfate heptahydrate (molecular weight 287.61) is contained in the liquid detergent, the content (mass%) of zinc ions in the liquid detergent is as follows.
Content of zinc ion in liquid detergent = blending amount of zinc sulfate heptahydrate in liquid detergent x (molecular weight of zinc / molecular weight of zinc sulfate heptahydrate)
= 1% by mass x (65.39 / 287.61)
= 0.23 mass%

The pH of the liquid cleaning agent of the present invention is preferably 5 to 8 at 25 ° C., more preferably 6.5 to 7.5.
When the pH of the liquid detergent is 5 or more, the transparent appearance of the liquid detergent can be easily maintained more stably. In addition, gelation or solidification of the liquid detergent is less likely to occur. On the other hand, when the pH is 8 or less, foaming properties (ease of foaming, foam amount) are further improved. Moreover, the detergency with respect to oil stains and the persistence of foam are further improved.
The pH of the liquid detergent (controlled at 25 ° C.) is a value measured by a method based on JIS K3362-1998 using a pH meter (product name: Horiba F-22, manufactured by Horiba, Ltd.). .

The liquid detergent of the present invention has good low temperature stability and quick foaming. The reason why such an effect is obtained is not certain but is presumed as follows.
As described above, a liquid detergent containing a linear alcohol ethoxy sulfate is likely to precipitate under low temperature conditions, and it is difficult to ensure storage stability. Furthermore, there is a problem that foaming is slow.
In the liquid detergent of the present invention, the linear alcohol ethoxysulfate (a) and the component (b) which is a sulfate ester salt having a specific branched structure have a specific blending ratio ((a) component / (b ) The mass ratio represented by the component is 6 or less). Due to the branched structure at the β-position of the component (b), the molecular arrangement of the component (a) is easily disturbed. Furthermore, by using the specific hydrotrope agent (c) in combination, precipitation of the component (a) under low temperature conditions is suppressed. For this reason, it is considered that the stability at low temperature is good.
In addition, the component (b) having a specific structure branched at the β-position has a higher dynamic interfacial tension reducing ability than a general linear or branched anionic surfactant. As a result, when the (b) component newly forms an interface, it can be quickly oriented to the interface, and a surfactant molecular film can be formed quickly together with the (a) component. For this reason, it is thought that foaming is quick.

In addition, the liquid detergent of the present invention has high detergency and good foam persistence and rinsing properties. The reason is presumed as follows.
As described above, since the component (b) has a high ability to reduce the dynamic surface tension, the component (b) is quickly adsorbed to oil stains and the like, and the component (a) is quickly adsorbed to oil stains. As a result, the decomposition (dispersion, dissolution) of the oil stain is promoted, and the durability of the foam is also improved. Furthermore, in the branched structure only at the β-position, the hydrophobic group tends to be bulky as compared with a general branched anionic surfactant. For this reason, it is presumed that rinsing properties (goodness of bubble breakage, non-nullness) are improved by being difficult to orientate densely at the gas-liquid interface and easily rupturing when the cleaning liquid is diluted.

Furthermore, the liquid detergent of the present invention contains amphoteric surfactant and / or semipolar surfactant (d), so that the tableware and the like can be covered with foam during washing while maintaining foaming power. Even if it is broken, you can feel that the dirt has been removed. The reason is presumed as follows.
It is considered that the component (b) can form a stable association state by mixing with the component (a) and the component (d). In addition, since the component (b) has a high ability to reduce dynamic interfacial tension, the component (b) has a high diffusion speed in the cleaning liquid, and accordingly, the components (a), (b) and (d) are , Do not stay long between sponge and tableware. As a result, when oil stains are removed while washing dishes with a sponge containing a liquid cleaning agent, a feeling of friction is felt between the sponge and the dishes. . From the above, according to the liquid detergent of the present invention further containing the component (d), it is possible to realize that the dirt has been removed even if the dishes are covered with foam while maintaining the foaming power. Guessed.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

<Preparation of liquid detergent>
According to the blending composition shown in the table, each of the liquid detergents of each example was prepared by the following production method (when there is an unblended component, the component is not blended).
The unit of the blending amount in the table is “mass%”, and all the components indicate the equivalent amount of pure component.
In addition, the liquid cleaning agent of each example was prepared by balancing with water so that the total of each component described in the table was 100% by mass. Each component used was kept at 50 ° C.

[Method for producing liquid detergent]
First, in a 200 mL beaker, (a) component, (b) component or (b ′) component, (c) component or (c ′) component, and (e) component were added and stirred with a magnetic stirrer. . Next, the component (d) was added and stirred.
Next, water was added and stirred so that the total amount (the total amount was 100 parts by mass) was 93 parts by mass. Thereafter, glycolic acid and sodium hydroxide were added to adjust the pH, and the remaining water was added and balanced so that the total amount became 100 parts by mass, thereby producing each of the liquid detergents of each example.
In addition, the “balance” indicating the blending amount of water means the balance added so that the total blending amount (% by mass) of all the blending components contained in the liquid detergent is 100% by mass.
“Suitable amount” indicating the blending amount of sodium hydroxide indicates the amount of sodium hydroxide blended in order to adjust the pH (25 ° C.) of the liquid detergent to 7.0 after blending a predetermined amount of glycolic acid. .
The pH was measured by adjusting the liquid detergent to 25 ° C. and using a glass electrode type pH meter (product name: Horiba F-22, manufactured by Horiba, Ltd.). The measuring method was performed based on JIS K3362-1998.

In the table, (a) / (b) means the ratio (mass ratio) of the content of component (a) to the content of component (b) in the liquid detergent.
[(A) + (b)] / (d) is the ratio (mass ratio) of the total content of the component (a) and the component (b) to the content of the component (d) in the liquid detergent. Means.
(E) / [(a) + (b)] is the ratio (mass ratio) of the content of component (e) to the total content of component (a) and component (b) in the liquid detergent. Means.
Below, the component shown in the table | surface is demonstrated.

(A) Component a-1: C12 linear AES, polyoxyethylene alkyl ether sodium sulfate, R ¹ in the above formula (a1) = C12 linear alkyl group, n = 2, M ₁ = sodium .
[Preparation example of a-1]
In a 4 L autoclave, 400 g of P &G's trade name CO1270 alcohol (C12 / C14 = 75% / 25%, mass ratio) and 0.8 g of potassium hydroxide catalyst were charged, and the autoclave was purged with nitrogen and stirred. While raising the temperature. Thereafter, 181 g of ethylene oxide was introduced while maintaining a temperature of 180 ° C. and a pressure of 0.3 mPa, to obtain a reaction product having an average addition mole number of ethylene oxide of 2. In addition, said "C12 / C14" means the mixture of C12 alcohol and C14 alcohol.
Next, 282 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 78 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, this was neutralized with an aqueous sodium hydroxide solution to obtain a-1.

(B) Component b-1: Polyoxyethylene mono (2-propylheptyl) ether sulfate Na, C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8 in the above formula (b1) Corresponds to p = 0, q = 3, M ₂ = sodium.
[Preparation example of b-1]
290 g of “Lutensol XP30” manufactured by BASF was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, this was neutralized with an aqueous sodium hydroxide solution to obtain b-1.

b-2: Polyoxyethylene mono (2-propylheptyl) ether sulfate Na, C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p = 0, q in the above formula (b1) = 4, M ₂ = corresponding to sodium.
[Preparation example of b-2]
It was prepared in the same manner as b-1 except that 334 g of “Lutensol XP40” manufactured by BASF was used instead of “Lutensol XP30” manufactured by BASF.

b-3: Polyoxyethylene polyoxypropylene mono (2-propylheptyl) ether sulfate Na, C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p in the above general formula (b1) = 1, q = 3, M ₂ = sodium equivalent.
[Preparation example of b-3]
It was prepared in the same manner as b-1 except that 349 g of “Lutensol XL40” manufactured by BASF was used instead of “Lutensol XP30” manufactured by BASF.

-Comparison component of component (b) [hereinafter referred to as "component (b ')". ]
b′-1: polyoxyethylene mono (2-butyloctyl) ether sulfate Na, C _x H _{2x + 1} = butyl group, C _y H _{2y + 1} = hexyl group, x + y = 10, p = 0 in the above formula (b1) Corresponds to q = 2, M ₂ = sodium.
[Preparation example of b′-1]
In a 4 L autoclave, 372 g of a trade name “ISOFOL12” (C _x H _{2x + 1} = butyl group, C _y H _{2y + 1} = hexyl group in the above formula (b1)) manufactured by Sasol and 0.8 g of potassium hydroxide catalyst The autoclave was charged with nitrogen and the temperature was raised while stirring. Thereafter, 181 g of ethylene oxide was introduced while maintaining a temperature of 180 ° C. and a pressure of 0.3 mPa, to obtain a reaction product having an average addition mole number of ethylene oxide of 2. Next, 274 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, this was neutralized with an aqueous sodium hydroxide solution to obtain b′-1.

b′-2: mono (2-propylheptyl) ether sulfate Na, C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p = 0, q = 0 in the above formula (b1) , M ₂ = corresponding to sodium.
[Preparation example of b′-2]
Hexylaldehyde was subjected to gel condensation (dimerization) with alkali, and 158 g of 2-propylheptanol obtained in this manner was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfane) It was dripped slowly, keeping at 40 degreeC. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired alkyl ether sulfuric acid. Further, this was neutralized with an aqueous sodium hydroxide solution to obtain b′-2.

b'-3: Sulfur oxide of an ethylene oxide average 3 mol addition product of C13 branched alcohol.
[Preparation Example of b′-3]
BASF “Lutensol TO3” (332 g) was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Further, this was neutralized with an aqueous sodium hydroxide solution to obtain b′-3.

b′-4: Sulfur oxide of an ethylene oxide average 3 mol addition product of a synthetic alcohol having 12 to 13 carbon atoms.
[Preparation Example of b′-4]
A 4 L autoclave was charged with 400 g of a trade name “Safol23” manufactured by Sasol and 0.8 g of a potassium hydroxide catalyst. The autoclave was purged with nitrogen and heated while stirring. Thereafter, 271 g of ethylene oxide was introduced while maintaining a temperature of 180 ° C. and a pressure of 0.3 mPa, to obtain a reaction product having an average added mole number of ethylene oxide of 3. Next, 334 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Further, this was neutralized with an aqueous sodium hydroxide solution to obtain b′-4.

-(C) component c-1: p-toluenesulfonic acid, the Kyowa Hakko Chemical Co., Ltd. make, p-toluenesulfonic acid abbreviation p-TSH.
c-2: Sodium cumene sulfonate, manufactured by Teika Co., Ltd., trade name “Taikatox N5040”.
c-3: Sodium benzoate, manufactured by Fushimi Pharmaceutical Co., Ltd., food additive Sodium benzoate.
c-4: Ethanol, manufactured by Pure Chemical Co., Ltd., reagent grade.

Component (c) Comparative component [hereinafter referred to as “(c ′) component”. ]
c′-1: Polyethylene glycol, manufactured by Lion Corporation, trade name “PEG # 1000”.

-(D) component d-1: AX, C12 alkyl dimethylamine oxide (The product made from Lion Akzo, brand name "Aromox DM12D-W").
d-2: HSB, N-lauryl-N, N-dimethyl-N- (2-hydroxy-1-sulfopropyl) ammonium sulfobetaine, abbreviation C12 hydroxysulfobetaine (trade name “Amphithol 20HD” manufactured by Kao Corporation) .

· (E) component e1: C12MEA (2), polyoxyethylene lauric acid monoethanolamide, a straight-chain alkyl group ^{R 5} = 11 carbon atoms in the formula (e1), m = 2. Abbreviation LME (2).
[Preparation Example of e-1]
214 g of methyl laurate (product name “Pastel M-12”, manufactured by Lion Corporation), 64.1 g of monoethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and sodium methylate (product name, manufactured by Nippon Shokubai Co., Ltd.) “SM-28”, 28 mass% product) 7.7 g (1.0 mass% to fatty acid methyl ester) was added, and methanol by-product was heated and stirred while distilling off under reduced pressure (40 Pa to 1.3 kPa, When the reaction pressure reached 1.3 kPa, the mixture was aged at a reaction temperature of 90 ° C. for 3 hours to prepare 240 g of lauric acid monoethanolamide.
The obtained lauric acid monoethanolamide was charged into a 1 L autoclave, 1.0 mol of ethylene oxide was charged with respect to lauric acid monoethanolamide, and an addition reaction was performed at 90 ° C. for 2 hours to obtain C12MEA (2). It was.

e-2: C10MEA (2), polyoxyethylene capric acid monoethanolamide, R ⁵ in the above formula (e1) = a linear alkyl group having 9 carbon atoms, m = 2. Abbreviation CME (2).
[Example of preparation of e-2]
C10MEA (2) was prepared in the same manner as C12MEA (2), except that methyl caprate (manufactured by Lion Corporation, trade name “Pastel M-10”) was used instead of methyl laurate.

Other components Glycolic acid: Product name “Grip Pure 70” manufactured by DuPont.
Na hydroxide: sodium hydroxide, manufactured by Tsurumi Soda Co., Ltd.
Water: tap water.

<Evaluation of liquid detergent>
Each liquid cleaning agent in each example was evaluated by the following evaluation methods, and the results were also shown in the table.

[Evaluation of low-temperature stability]
100 mL of the liquid cleaning agent of each example was filled in a cylindrical glass bottle having a diameter of 50 mm and a height of 100 mm, and the lid was closed and sealed. In this state, the appearance of the liquid detergent after being stored for 1 month in a thermostatic bath at -5 ° C. (low temperature condition) is visually observed and based on the following evaluation criteria (◎ to ○ are acceptable ranges). The low temperature stability (appearance) of the liquid detergent was evaluated.
(Evaluation criteria)
A: Uniform and transparent.
A: Although precipitation occurred, the amount of the precipitate present in the cylindrical glass bottle was a trace amount to less than 5% of the total volume of the cylindrical glass bottle.
Δ: Precipitation occurred, and the amount of the precipitate present in the cylindrical glass bottle was 5% or more and less than 10% of the total volume of the cylindrical glass bottle.
X: Precipitation occurred, and the amount of the precipitate present in the cylindrical glass bottle was 10% or more of the total volume of the cylindrical glass bottle.

[Evaluation of foaming speed]
Take 18.5cm x 7.5cm x 3cm high sponge for dishwashing (product name: Scotch Bright, Sumitomo 3M Co., Ltd.) with 38g of water and 2g of the liquid cleaning agent in each case. The state after foaming (the state of foam formation) was evaluated based on the following evaluation criteria. When the evaluation results were ◎, ◎, and ○, the foaming speed was considered good.
(Evaluation criteria)
A: Bubbles overflowed from the entire surface of the sponge.
A: Foam covered the entire surface of the sponge.
○: The ratio of foam covering the sponge surface was 80% or more and less than 100% of the surface area of the sponge.
Δ: The ratio of foam covering the sponge surface was 50% or more and less than 80% of the surface area of the sponge.
X: The ratio of the foam covering the sponge surface was less than 50% of the surface area of the sponge.

[Rinse evaluation]
Take a sponge for dishwashing (product name: Scotch Bright, Sumitomo 3M Co., Ltd., product name: Scotch Bright) measuring 11.5 cm in length × 7.5 cm in width × 3 cm in height. Frozen and foamed by hand 5 times. With a foamed sponge, 5 pieces of a ceramic dish (φ = 23 cm) were rubbed 5 times so as to draw a circle on the surface of the ceramic dish. Next, while rinsing the pottery plate in which bubbles remained, tap water (flow rate 100 mL / s, 25 ° C.) was used to measure the time from when bubbles disappeared until the fingers no longer felt null.
And the rinse property was evaluated based on the following evaluation criteria. The samples with ◎ and ○ were considered to have good rinsing properties.
(Evaluation criteria)
A: Within 30 seconds.
A: Within a range of 31 to 35 seconds.
(Triangle | delta): It was in the range of 36 to 40 seconds.
X: It was 41 seconds or more.

[Evaluation of foam persistence]
Take a sponge for washing dishes (product name: Scotch Bright, 11.5 cm long x 7.5 cm wide x 3 cm high) with 38 g of water and 2 g of the liquid cleaning agent in each case. I got in. Thereafter, the sponge and a ceramic dish (φ = 23 cm) on which 1 g of olive oil and 5 g of water were placed were brought into contact with each other, so that the dirt and the sponge became familiar.
Then, with the sponge pressed against the earthenware dish, it was scrubbed by moving it so as to draw a circle twice on the surface of the earthenware dish. And the time when foam | bubble became 5% of the whole surface of a ceramic dish was made into the end point, the number of the ceramic dishes which finished washing by the said end point was calculated | required, and the sustainability of foam was evaluated.

[Evaluation of washed feeling]
Into a dishwashing sponge (product name: Scotch Bright, 11.5 cm long × 7.5 cm wide × 3 cm high), 38 g of water and 2 g of the liquid cleaning agent in each example were taken, 1 g of olive oil, A ceramic dish (φ = 23 cm) on which 5 mL of water was placed was washed while being rubbed with the sponge. The cleaning is done by rubbing around the pottery plate once and with a sponge so as to draw a circle five times on one side of the pottery plate (φ = 23 cm) and then a circle twice on the other side. By the method.
And about the washed feeling of the earthenware dish under washing | cleaning, evaluation by 10 panelists was performed based on the following evaluation criteria, and the average value of the 10 persons was computed.
(Evaluation criteria)
Two points: During the cleaning, the dirt from the ceramic dish was clearly felt by the change in friction between the sponge and the ceramic dish.
1 point: During cleaning, it was felt that dirt was removed from the pottery plate due to a change in friction between the sponge and the pottery plate.
0 point: No change in friction between sponge and earthenware dish was felt during washing.
In addition, in the case of 2 points and 1 point of the evaluation standard, scrubbing is interrupted when friction is felt between the sponge and the ceramic dish, and the ceramic dish in which bubbles remain is treated with tap water (flow rate 100 mL / s, 25 ° C. ) For 5 seconds to check whether dirt is removed from the ceramic dish. As a result, in all cases, there was no oil film, no stickiness when touched by hand due to residual oil, and the dirt was removed from the ceramic dish.

From the results shown in the table, it can be seen that the liquid detergents of Examples 1 to 25 to which the present invention is applied have good low-temperature stability and quick foaming.
In addition, it turns out that the liquid detergents of Examples 1 to 25 have good rinsing properties.

From the results shown in Table 4, it can be seen from the results of evaluation of the liquid detergents of Examples 20, 21 to 23 that a washed feeling can be obtained by further containing the component (d).
It can be seen that the liquid detergents of Examples 24 and 25 further containing component (e) have better foam persistence.
In addition, a dishwashing sponge (Sumitomo 3M Co., Ltd., trade name: Scotch Bright) measuring 11.5 cm long x 7.5 cm wide x 3 cm high was charged with 38 g of 25 ° C. tap water and 2 g of liquid detergent. After scouring by hand, using this foamed sponge, as a result of performing a test to wash the dirt model in which beef tallow was applied to the inner surface of the tapper container in the same manner as usual at home, any example The liquid detergent also had a good detergency against oil stains.

Claims (2)

A compound (a) represented by the following general formula (a1);
A compound (b) represented by the following general formula (b1);
Selected from the group consisting of toluenesulfonic acid, cumenesulfonic acid, xylenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, or aromatic sulfonates thereof , benzoic acid or salts thereof , and alcohols having 2 to 4 carbon atoms. Containing at least one hydrotrope agent (c),
(A) Liquid cleaning agent characterized by mass ratio represented by component / (b) component being 6 or less.

[In Formula (a1), R ¹ is a linear alkyl group having 8 to 24 carbon atoms or a linear alkenyl group having 8 to 24 carbon atoms. EO represents an oxyethylene group. n represents the average number of repetitions of EO and is a number from 1 to 5. M ₁ represents an alkali metal, alkaline earth metal, ammonium or alkanolamine. In the formula (b1), x and y are each an integer of 1 to 7, and x + y = 8. PO represents an oxypropylene group, and EO represents an oxyethylene group. p represents the average number of repetitions of PO, q represents the average number of repetitions of EO, and p + q is 1 to 10. M ₂ represents an alkali metal, alkaline earth metal, ammonium or alkanolamine. ]   The liquid detergent according to claim 1, further comprising an amphoteric surfactant and / or a semipolar surfactant (d).