JP5439204B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition.

  In recent years, with the growing awareness of consumers about the environment and economy, liquid cleaning agents that can provide an excellent cleaning effect even when the amount used is reduced when cleaning tableware and cooking utensils. Is required.

Washing of tableware, cooking utensils and the like is usually performed while adding a liquid detergent to a sponge for dishwashing.
Examples of the timing for adding the liquid cleaning agent to the sponge include “when the amount of foam that can be visually recognized when the sponge is rubbed decreases”.
In conventional liquid detergents, the amount of foam is small from the start of washing until the end of washing, or even if the amount of foam is large at the beginning of washing, the foam quality becomes watery after that, and the state of high amount of foam does not continue, There was a tendency for the liquid detergent to be poured many times into the sponge. For this reason, the liquid detergent has been used excessively in excess of the amount necessary for removing oil stains and the like.
Thus, in addition to detergency, kitchen detergents are also required to have foaming properties (good foaming at the beginning of washing, sustainability of the amount of foam from the start of washing until the end of washing) as a basic performance.
In response to such demands, for example, liquid detergent compositions containing, for example, a medium-chain branched solubilized nonionic surfactant, an anionic surfactant, and a specific amine oxide have been proposed ( Patent Document 1).

JP-T-2007-511640

The present inventors have newly found “when no“ elasticity ”is felt when the sponge is gripped” as the timing of adding the liquid cleaning agent to the sponge.
According to the study by the present inventors, even when the sponge contains a cleaning agent in an amount used to remove oil stains, etc., it is soft when gripping the sponge (feels elastic). It was found that it was easy to take extra action of adding liquid detergent because it was not possible to realize that the liquid detergent was sufficiently contained in the sponge.
In the liquid detergent composition described in Patent Document 1, a feeling of elasticity is not felt when the liquid detergent composition is included in a sponge and gripped. It was.
It was also found that if the user feels that there is no elasticity when grasping the sponge, the sponge cannot be efficiently pressed against the tableware during washing, and therefore it is difficult to rub off oil stains.

Therefore, when cleaning tableware and cooking utensils, etc., the number of times the liquid detergent is added to the sponge can be reduced, and the amount of liquid detergent used can be reduced to satisfy consumers' awareness of the environment and economy. A technology that can be used is necessary.
The present invention has been made in view of the above circumstances, and has excellent detergency against oil stains, and even when used in the presence of oil, the amount of foam is large at the beginning of washing, and the sustainability of the amount of foam is good. Another object of the present invention is to provide a liquid detergent composition that feels elasticity when it is included in a sponge and gripped.

As a result of intensive studies, the present inventors generally selected a compound having a specific structure from among branched compounds suitable for use in low foaming compositions that hardly form an association state, and a cleaning component, It has been found that the above-mentioned problems can be solved by using in combination at a specific mass ratio, and the present invention has been completed.
That is, the liquid detergent composition of the present invention comprises a compound (a) represented by the following general formula (a1), an anionic surfactant (b), an amphoteric surfactant and / or a semipolar surfactant. (C) and the mass ratio represented by [(b) + (c)] / (a) is 2 to 10.

［式中、ＡＯはオキシエチレン基及び／又はオキシプロピレン基を表す。ｍはＡＯの平均繰返し数を表し、６〜１２である。ｘとｙはそれぞれ１〜６の整数であり、６≦ｘ＋ｙ≦１２である。］

[Wherein, AO represents an oxyethylene group and / or an oxypropylene group. m represents the average number of repetitions of AO and is 6-12. x and y are each an integer of 1 to 6, and 6 ≦ x + y ≦ 12. ]

In the liquid detergent composition of the present invention, AO in the general formula (a1) is an oxyethylene group, m is 9 or 10, one of x and y is 3, and the other is 5. preferable.
In the liquid detergent composition of the present invention, the anionic surfactant (b) is preferably a combination of polyoxyethylene alkyl ether sulfate and secondary alkane sulfonate.
Further, in the liquid detergent composition of the present invention, at least one hydrotrope 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 preferable to further contain an agent (d).

According to the present invention, it has excellent detergency against oil stains, and even when used in the presence of oil, it has a large amount of foam at the beginning of washing, has a good sustainability of the amount of foam, and is contained in a sponge. It is possible to provide a liquid detergent composition that feels elastic when heated.
With this liquid detergent composition, when washing dishes and cooking utensils, etc., it is possible to reduce the number of times to add to the sponge, it is possible to reduce the amount of liquid detergent used, and consumers are aware of the environment and economy. Can be satisfied.

≪Liquid detergent composition≫
The liquid detergent composition of the present invention comprises a compound (a) represented by the general formula (a1), an anionic surfactant (b), an amphoteric surfactant and / or a semipolar surfactant (c ) And.

<Compound (a)>
The compound (a) in the present invention is represented by the general formula (a1) (hereinafter referred to as “component (a)”), and an oxyethylene group and / or oxypropylene group is introduced into the alcohol, This is a compound having a structure in which a part (hydrocarbon group) is branched into C _x H _{2x + 1} and C _y H _{2y + 1} by a β-position carbon atom.
By containing the component (a), even when the liquid detergent composition is used in the presence of oil, both the foaming and the sustainability of the foam amount are good, and the elasticity when held in a sponge A feeling comes to be felt.

In the formula (a1), AO represents an oxyethylene group and / or an oxypropylene group. Among them, since the foaming of the liquid detergent composition and the sustainability of the amount of foam are further improved and a feeling of elasticity when gripped by being included in a sponge is obtained, AO contains an oxyethylene group. Those having only oxyethylene groups, those having both oxyethylene groups and oxypropylene groups, and more containing oxyethylene groups, more preferably oxyethylene groups. Those consisting only of are particularly preferred.
When AO is a mixture of oxyethylene groups and oxypropylene groups, the liquid detergent composition is contained in a sponge and feels elastic, and the foaming and the amount of foam when used in the presence of oil Therefore, the average number of repetitions of the oxypropylene group is preferably 3 or less, and more preferably 1-2.
In AO, when an oxyethylene group and an oxypropylene group are mixed, they may be mixed in a random manner or in a block shape.

In said formula (a1), m represents the average repeating number of AO, is 6-12, and it is preferable that it is 9 or 10. When m is 6 or more, even when used in the presence of oil, the foaming and the sustainability of the foam amount are excellent. When m is 12 or less, a feeling of elasticity can be felt when the liquid detergent composition is contained in a sponge and gripped.
Here, m represents the “average” repetition number of AO. Therefore, the compound represented by the formula (a1) is an aggregate of molecules having different numbers of AO repeats.

In the formula (a1), x and y are each an integer of 1 to 6, and 6 ≦ x + y ≦ 12. Among them, since the foaming of the liquid detergent composition and the sustainability of the foam amount are further improved and a feeling of elasticity when gripped by being included in a sponge can be obtained well, 6 ≦ x + y ≦ 10 is preferable, and 6 ≦ x + y ≦ 8 is more preferable, and x + y = 8 is particularly preferable.
When x + y is 6 or more, even when used in the presence of oil, the foaming and the amount of foam are excellent. Moreover, surface activity is shown and the adsorptivity to a liquid level increases. When x + y is 12 or less, a feeling of elasticity can be felt when the liquid detergent composition is included in a sponge and gripped.
Each of C _x H _{2x + 1} and C _y H _{2y + 1} includes a linear or branched alkyl group, and is preferably a linear alkyl group, such as a methyl group, an ethyl group, a propyl group, or a butyl group. Preferred examples include a group, a pentyl group and a hexyl group.
Among them, C _x H _{2x + 1} and C _y H _{2y + 1} are a combination of an ethyl group and a butyl group, and a combination of a propyl group and a pentyl group (all of these combinations may be either group). A combination of a propyl group and a pentyl group (one may be any group) is particularly preferable.

(A) A component can be used individually by 1 type or in mixture of 2 or more types.
Among the above, as the component (a), an ethylene oxide adduct of alcohol having a branched structure at the β-position obtained by bimolecular condensation by the gerbet reaction is particularly preferable.
Examples of such commercially available products include polyoxyethylene mono (2-propylheptyl) ether manufactured by BASF Corporation. Specifically, the compound represented by the above general formula (a1) with m = 6 is trade name “Lutensol”. XP60 ”, the compound of m = 9 in the general formula (a1) and the trade name“ Lutensol XP90 ”, and the compound of m = 10 in the general formula (a1) and the trade name“ Lutensol XP100 ”.
Further, polyoxyethylene polyoxypropylene mono (2-propylheptyl) ether manufactured by BASF may be mentioned. Specifically, m = 9 compound (oxyethylene group and oxypropylene group in the general formula (a1)). And a trade name “Lutensol XL90”, a compound of m = 10 in the above general formula (a1) (a mixture of oxyethylene group and oxypropylene group). .

The content of the component (a) in the liquid detergent composition is preferably 1 to 15% by mass, more preferably 1 to 10% by mass, and further preferably 3 to 8% by mass.
When the content of the component (a) is not less than the lower limit, the foaming of the liquid detergent composition and the sustainability of the amount of foam are further improved, and a feeling of elasticity when gripped by being included in a sponge can be obtained satisfactorily. On the other hand, if it is not more than the upper limit value, the detergency against oil stains is further improved.

<Anionic surfactant (b)>
The anionic surfactant (b) (hereinafter referred to as “component (b)”) is roughly classified into a sulfonate type, a sulfate ester type, a carboxylate type, and a phosphate ester. Type.
Examples of the sulfonate type include alkylbenzene sulfonate, alkyl sulfate, alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt, sulfosuccinate and the like. Of these, alkane sulfonates are preferred, and secondary alkane sulfonates (SAS) are more preferred because of their good detergency against oil stains and storage stability of the liquid detergent composition (to ensure a transparent appearance). .
Examples of the sulfate ester type include alkyl sulfate ester salts, alkenyl sulfate ester salts, polyoxyalkylene alkyl ether sulfate ester salts, polyoxyalkylene alkenyl ether sulfate ester salts, and the like. Of these, polyoxyalkylene alkyl ether sulfates (AES) are preferred because of their good detergency against oil stains and storage stability of the detergent composition (to ensure a transparent appearance). ) Is more preferable.
Examples of the carboxylate type include alkyl ether carboxylates, amide ether carboxylates, sulfosuccinates, amino acid anionic surfactants, and the like.

Among the above, as the component (b), since the detergency against oil stains is good, sulfonate type and sulfate ester type are more preferable, alkylbenzene sulfonate, alkyl sulfate, alkane sulfonate. , Α-olefin sulfonates; polyoxyalkylene alkyl ether sulfates are more preferred. Of these, the combination of AES, AES and SAS is preferable, and the combination of AES and SAS is more preferable because the detergency against oil stains is particularly good.
As AES, polyoxyethylene alkyl ether sulfate (NRES) having a narrow rate of 40% by mass or more described later is preferable.

  As the salt form of the component (b), alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; alkanolamine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts And these may be mixed. Of these, alkali metal salts are preferable, and sodium salts are more preferable.

(About NRES)
In the present invention, when NRES is used as the component (b), the detergency against oil stains is mainly good. Moreover, the storage stability of the cleaning composition is improved, and a transparent appearance can be secured stably. Excellent storage stability especially at low temperature.

  In the present specification, the “narrow ratio” means that represented by the following formula (S) indicating the distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide.

［式中、ｎ_ｍａｘは全体のアルキレンオキシド付加体中に最も多く存在するアルキレンオキシド付加体のアルキレンオキシドの付加モル数を示す。ｉはアルキレンオキシドの付加モル数を示す。Ｙｉは全体のアルキレンオキシド付加体中に存在するアルキレンオキシドの付加モル数がｉであるアルキレンオキシド付加体の割合（質量％）を示す。］

[ _Wherein n _max represents the number of moles of alkylene oxide added in the alkylene oxide adduct most abundant in the entire alkylene oxide adduct. i represents the number of added moles of alkylene oxide. Yi represents the proportion (% by mass) of the alkylene oxide adduct having an added mole number of alkylene oxide present in the entire alkylene oxide adduct. ]

In NRES, the narrow ratio is preferably 40% by mass or more, more preferably 55% by mass or more, since the detergency against oil stains is further improved and the sustainability of foam is also improved. And more preferably 65% by mass or more. The upper limit of the narrow ratio is preferably as high as possible, and is substantially 90% by mass or less from the viewpoint of manufacturability.
In the above formula (S), when n _max is zero (mole), the narrow rate is the total ratio (mass%) of Y ₀ , Y ₁ and Y ₂ ; when n _max is 1 (mole) The narrow ratio is the total ratio (mass%) of Y ₀ , Y ₁ , Y ₂ and Y ₃ .

The narrow rate can be controlled by, for example, the NRES manufacturing method.
As a method for producing NRES, for example, a polyoxyethylene alkyl ether (alcohol having a desired molecular weight range, that is, a desired number of moles of added ethylene oxide, is obtained by distillation or the like from a reaction product obtained by synthesizing a higher alcohol and ethylene oxide by a conventional method. The ethoxylate is fractionated and then subjected to sulfation reaction and neutralization.
Further, by the method described in Japanese Patent No. 3312883, that is, a method using a specific catalyst, a polyoxyethylene alkyl ether having a narrow distribution of ethylene oxide addition mole number of 55% by mass or more can be obtained. Therefore, it can also be obtained by subjecting the polyoxyethylene alkyl ether to a sulfation reaction and neutralization. The specific catalyst includes a surface-modified composite metal oxide catalyst, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) and a mixed metal oxide catalyst such as magnesium oxide, a surface-modified hydro with a metal hydroxide and / or a metal alkoxide, etc. It is a fired product catalyst of talcite.

  Preferable examples of NRES include polyoxyethylene alkyl ether sulfates represented by the following general formula (b1).

［式中、Ｒ^６は炭素数８〜１８のアルキル基又はアルケニル基であり；ｎはエチレンオキシドの平均付加モル数を示し、１〜６である。Ｍはアルカリ金属原子、アルカリ土類金属原子、アルカノールアミン又はアンモニウムを表す。］

[Wherein, R ⁶ represents an alkyl group or an alkenyl group having 8 to 18 carbon atoms; n represents an average number of added moles of ethylene oxide, and is 1 to 6. M represents an alkali metal atom, an alkaline earth metal atom, an alkanolamine or ammonium. ]

In the formula (b1), ^{R 6} is an alkyl or alkenyl group having 8 to 18 carbon atoms having 8 to 18 carbon atoms, preferably an alkyl group having 8 to 18 carbon atoms. The alkyl group or the alkenyl group may be linear or branched.
In R ⁶ , the carbon number is 8 to 18, preferably 10 to 16, and more preferably 12 to 13. When R ⁶ has 8 or more carbon atoms, the hydrophobicity increases, so that the detergency against oil stains is improved. On the other hand, when the carbon number of R ⁶ is 18 or less, the solubility of NRES itself is improved, so that precipitation during storage over time is suppressed and a transparent appearance is easily obtained.
However, R ⁶ is derived from a higher alcohol that is a raw material of NRES. Therefore, the higher alcohol is preferably selected from the following (i) to (v) which are industrially easily available.
The “branch rate” indicates the ratio (mass%) of the higher alcohol having a branched chain to the total higher alcohol. “Linear ratio” indicates the ratio (% by mass) of linear higher alcohol to the total higher alcohol.
(I) Product name “Neodol 23” manufactured by Shell Chemicals (branch rate: 20 mass%). This is produced from an n-olefin by a modified oxo method and rectified.
(Ii) A C13 alcohol obtained from a butene trimer by an oxo method (branch rate: 100% by mass).
(Iii) A higher alcohol (branch rate: 100% by mass) obtained from a medium chain alcohol by a garvet reaction.
(Iv) Product name “Safol23” (branch rate: 50 mass%) manufactured by Sasol. This is an alcohol obtained from an olefin obtained by gasification of coal by an oxo method and further hydrogenated.
(V) Product name “CO1270” (branching rate: 0% by mass) (straight chain rate: 100% by mass) manufactured by P & G. This is a natural higher alcohol synthesized from natural fats and oils.

In said formula (b1), n shows the average addition mole number of ethylene oxide, and is 1-6. Especially, since the detergency with respect to oil dirt improves, 1-5 are preferable and 1-3 are more preferable.
Here, n represents the “average” added mole number of ethylene oxide. Accordingly, the polyoxyethylene alkyl ether sulfate ester salt represented by the formula (b1) is an aggregate of ethylene oxide adducts having different addition mole numbers of ethylene oxide. The narrow ratio is obtained from the above formula (S) by setting the number of moles of ethylene oxide added to the most abundant ethylene oxide adduct (polyoxyethylene alkyl ether sulfate ester salt) in the aggregate as “n _max ”. It is done.

In the formula (b1), M represents an alkali metal atom, an alkaline earth metal atom, an alkanolamine or ammonium.
Specific examples include alkali metal atoms such as sodium, potassium and lithium; alkaline earth metal atoms such as calcium and magnesium; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; ammonium and the like. You may do it. Especially, as M, an alkali metal atom is preferable and sodium is especially preferable.

The NRES represented by the formula (b1) can be produced, for example, as follows.
A polyoxyethylene alkyl ether (alcohol ethoxylate) is obtained by adding ethylene oxide to a higher alcohol, preferably a higher alcohol selected from the above (i) to (v). As a catalyst used when adding ethylene oxide, for example, a composite metal oxide Lewis acid sintered solid catalyst composed of Al / Mg / Mn described in Japanese Patent No. 3312883 is preferable. Thereby, the thing with a narrow addition mole number distribution of ethylene oxide is obtained.
The obtained polyoxyethylene alkyl ether can be sulfonated or sulfated with sulfone to produce a polyoxyethylene alkyl ether sulfate, and further neutralized to produce a polyoxyethylene alkyl ether sulfate.

(About SAS)
In the present invention, when a secondary alkane sulfonate is used as the component (b), the detergency against oil stains is improved.
SAS is a surfactant, also called “paraffin sulfonate”, and is usually provided in the form of a mixture of secondary alkyl sulfonates having 10 to 21 carbon atoms per molecule.
In the present invention, the mixture preferably contains 80% by mass or more, and more preferably 90% by mass or more of the secondary alkyl sulfonate having 13 to 18 carbon atoms per molecule. Note that this mixture may contain a small amount of a primary alkyl sulfonate, disulfonate, or polysulfonate.

  As a suitable thing in SAS, the compound represented by the following general formula (b2) is mentioned, for example.

［式中、ｐ＋ｑ＝１０〜１４であり；Ｍはアルカリ金属原子、アルカリ土類金属原子、アルカノールアミン又はアンモニウムを表す。］

[Wherein p + q = 10 to 14; M represents an alkali metal atom, an alkaline earth metal atom, an alkanolamine or ammonium. ]

In the formula (b2), p + q = 10 to 14, that is, the component represented by the formula (b2) has 13 to 17 carbon atoms (however, excluding the carbon number in M in the formula (b2)). Secondary alkyl sulfonate.
When p + q is 10 or more, the detergency against oil stains is improved. On the other hand, when p + q is 14 or less, the solubility of the compound itself represented by formula (b2) is improved, so that precipitation during storage is suppressed.
In the formula (b2), M is the same as M in the formula (b1). Among them, an alkali metal atom is preferable, and sodium is particularly preferable.

  As commercial products that can be suitably used as SAS, HOSTAPUR SAS 30 (trade name, manufactured by Clariant Japan KK; content of sodium alkyl secondary sulfonate having 13 to 17 carbon atoms is 90% by mass or more), HOSTAPUR SAS 60 (trade name, manufactured by Clariant Japan KK; content of secondary alkyl sulfonate sodium having 13 to 17 carbon atoms is 90% by mass or more), MERSOL 80 (trade name, manufactured by Bayer; average carbon number 15 (carbon The content of the secondary alkyl sulfonate of the number 13 to 17 is 80% by mass or more), MARLON series (manufactured by SASOL; PS65, PS60, PS60W (named above, trade name), C10 to C18 (carbon number 13) ˜17 secondary alkyl sulfonate sodium content is 90% by mass or more)) And the like.

(B) A component can be used individually by 1 type or in mixture of 2 or more types.
(B) When AES and SAS are used in combination as the component, the mixing ratio of AES and SAS is preferably AES / SAS = 1 to 10 in terms of mass ratio because the detergency against oil stains is further excellent. 1 to 7 is more preferable, and 2 to 5 is more preferable.
Among these, as the component (b), NRES, a combination of NRES and SAS are particularly preferable, and among them, a combination of NRES and SAS is most preferable.

The content of the component (b) in the liquid detergent composition is preferably 5 to 30% by mass, more preferably 5 to 18% by mass, and further preferably 10 to 17% by mass.
(B) If content of a component is more than a lower limit, the cleaning power with respect to oil stains will improve more. Further, the foaming of the liquid detergent composition and the sustainability of the foam amount are further improved. On the other hand, when it is less than or equal to the upper limit value, when the liquid detergent composition is included in a sponge and gripped, a good elasticity can be obtained.

<Amphoteric surfactant and / or semipolar surfactant (c)>
In the present invention, by using the component (b) in combination with the amphoteric surfactant and / or the semipolar surfactant (c) (hereinafter referred to as “component (c)”), oil stains are mainly used. High cleaning effect can be obtained.

(Amphoteric surfactant)
Examples of amphoteric surfactants include betaine types such as aminoacetic acid betaines (such as alkylbetaines and alkylamidobetaines) and sulfobetaines (such as alkylhydroxysulfobetaines); glycine-based ones (such as imidazolinium betaines), Amino acid type ones such as aminopropionic 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.

(Semipolar surfactant)
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. This refers to those that are cationic, anionic, or bipolar depending on the pH of the solution or the dispersion in which it is dispersed.
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 the amine oxide type surfactant include alkylamine oxide and alkylamidopropyldimethylamine oxide. Among them, a compound represented by the following general formula (c1) is preferable.

［式中、Ｒ^１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^２、Ｒ^３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^４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−であり；ｒは０又は１の数である。］

[Wherein, R ¹ is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms; R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms or A hydroxyalkyl group; R ⁴ 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 (c1), R ¹ 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 alkenyl group of R ^1, the number of carbon atoms is 8 to 18, and the detergency against oil stains is further improved, so that it is preferably 10 to 14.
R ² and R ³ 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. More preferably, R ² and R ³ are all methyl groups.
R ⁴ 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 surfactant include alkyl dimethyl amine oxides such as lauryl dimethyl amine oxide, coconut alkyl dimethyl amine oxide and lauryl diethyl amine oxide; alkanoyl amide alkyl dimethyl amine oxide such as lauric acid amide propyl amine oxide. And the like. Especially, since the detergency with respect to oil dirt is especially favorable, the thing of an alkyldimethylamine oxide type is more preferable.

(C) A component can be used individually by 1 type or in mixture of 2 or more types.
Among these, as component (c), in combination with component (b), the detergency against oil stains is particularly good, so that aminoacetic acid betaines, sulfobetaines, alkyldimethylamine oxides, or alkanoyls are used. Amidoalkyldimethylamine oxides are preferred, and alkyldimethylamine oxides are particularly preferred.

The content of the component (c) in the liquid detergent composition is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and further preferably 4 to 10% by mass.
(C) If content of a component is more than a lower limit, the cleaning power with respect to oil stains will improve more. In addition, when the liquid detergent composition is included in a sponge and gripped, good elasticity can be obtained. On the other hand, if it is not more than the upper limit value, the foaming of the liquid detergent composition and the sustainability of the foam amount are further improved.

In the liquid detergent composition of the present invention, the mass ratio represented by [(b) + (c)] / (a) is 2 to 10, preferably 2.5 to 8, 6 is more preferable, and 4 to 5 is particularly preferable.
When the mass ratio is less than 2, the detergency against oil stains is low. In addition, when the liquid detergent composition is included in a sponge and gripped, elasticity cannot be obtained. On the other hand, if the mass ratio exceeds 10, the foaming of the liquid detergent composition and the sustainability of the amount of foam deteriorate. Further, the viscosity increases, and when the liquid detergent composition is included in a sponge and gripped, an appropriate elasticity cannot be obtained.
In the present invention, when the mass ratio is 2 to 10, the detergency against oil stains, the sustainability of foaming and the amount of foam, and the feeling of elasticity when included in a sponge can be satisfactorily obtained.

<Optional component>
In addition to the components (a) to (c) described above, the liquid detergent composition of the present invention usually contains components that are usually used in a detergent composition for hard surfaces or clothing. It can mix | blend suitably in the range which does not impair the effect of this invention.

(Hydrotrope agent)
In the liquid detergent composition of the present invention, at least one hydrotrope agent 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 preferable to further contain d) (hereinafter, a hydrotrope agent selected from this group is referred to as “component (d)”).
By containing the component (d), the storage stability (particularly low-temperature stability) of the liquid detergent composition is mainly improved, and it becomes easier to ensure a more stable transparent appearance.

In component (d), toluenesulfonic acid, toluenesulfonic acid salt, cumenesulfonic acid, and cumenesulfonic acid salt may be any of the three isomers of o-form, m-form, and p-form. P-form is preferable, and p-toluenesulfonic acid and p-toluenesulfonate are more preferable.
Salt forms in toluene sulfonate, cumene sulfonate, and benzoate include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium and calcium; ammonium salts; monoethanolamine, diethanolamine And alkanolamine salts such as triethanolamine. Of these, alkali metal salts are preferable, and sodium salts are more preferable.

  The component (d) is excellent in storage stability even under low temperature conditions, and therefore consists of toluenesulfonic acid, toluenesulfonic acid salt, cumenesulfonic acid, cumenesulfonic acid salt, benzoic acid, benzoic acid salt and ethanol. Preferably, at least two selected from the group, and among them, 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 ( The hydrotrope agent selected from this group is hereinafter referred to as “component (d1)”) and ethanol is more preferably used in combination.

(D) A component can be used individually by 1 type or in mixture of 2 or more types.
As the component (d), when the component (d1) and ethanol are used in combination, the mixing ratio of the component (d1) and ethanol is a mass ratio of (d1) component / ethanol = 0.05 to 2.5. It is preferable that it is, and it is more preferable that it is 0.063-1.
When the blending ratio of the component (d1) to ethanol is equal to or higher than the lower limit value, it becomes easier to maintain a transparent appearance particularly under low temperature conditions. On the other hand, when it is at most the upper limit value, the low temperature stability is further improved. Further, the viscosity of the cleaning composition is suppressed and the fluidity is improved.

The content of the component (d) in the liquid detergent composition is preferably 5 to 30% by mass, more preferably 5 to 20% by mass, and further preferably 5 to 10% by mass.
When the content of the component (d) is not less than the lower limit, the transparent appearance of the liquid detergent composition can be more stably maintained even when stored at a low temperature even under low temperature conditions. Further, when the liquid detergent composition is included in a sponge and gripped, a feeling of elasticity can be further improved. On the other hand, if it is not more than the upper limit value, the foaming of the liquid detergent composition and the sustainability of the foam amount are further improved.

  Examples of hydrotropes other than the component (d) include water-soluble solvents such as propylene glycol and polyethylene glycol; aromatic sulfonic acids such as xylene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, or salts thereof; aromatic carboxylic acids Or a salt thereof (excluding benzoic acid or a salt thereof).

  In addition, the liquid detergent composition of the present invention also contains, as other optional components, a pH adjuster such as sodium hydroxide, sulfuric acid, glycolic acid, etc .; a chelating agent, an antioxidant, a coloring agent, an enzyme, a perfume and the like can do.

The pH of the liquid detergent composition 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 composition is 5 or more, the interaction between the component (b) and the component (c) is not too strong and can be moderately suppressed, so both components dissolve well, and the liquid detergent composition This makes it easier to keep the transparent appearance of objects more stable. In addition, gelation or solidification of the liquid detergent composition is less likely to occur. On the other hand, when the pH is 8 or less, the interaction between the component (b) and the component (c) does not become too weak, and the detergency against oil stains is further improved. Further, the foaming of the liquid detergent composition and the sustainability of the foam amount are further improved.
The pH of the liquid detergent composition (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.). Indicates.

The liquid detergent composition of the present invention described above includes a compound (a) having a branched structure represented by the general formula (a1), an anionic surfactant (b), an amphoteric surfactant and / or a half A polar surfactant (c) is contained in a specific mass ratio.
Since a compound having a branched structure is generally difficult to form an associated state, it is often used to suppress foaming (for antifoaming agents, low foaming compositions, etc.).
However, in the present invention, the component (a) having a specific branched structure and the component (b) and the component (c) are used in a specific mass ratio, thereby providing excellent detergency against oil stains and coexistence of oil. Even when used underneath, the amount of foam is large at the beginning of washing, and the sustainability of the amount of foam is good, and a feeling of elasticity can be felt when gripped by being included in a sponge. The reason why such an effect is obtained is not clear, but is presumed as follows.
It has a branched structure “C _x H _{2x + 1} (C _y H _{2y + 1} ) CH—CH ₂ —” having a branched chain at the β-position, and the average repeating number (m) of the oxyalkylene group is 6 to 12 (a ) Ingredients
(I) It has the property of being rapidly oriented at the gas-liquid interface during cleaning. Thereby, the orientation of the component (b) and the component (c) to the gas-liquid interface is also accelerated, and the formation of these surfactant molecular films is promoted. Therefore, at the beginning of washing, foaming is quick even in the presence of oil, and abundant foams are quickly formed.
(Ii) After being oriented at the gas-liquid interface, stable due to the interaction between the moderate number of oxyalkylene groups in component (a) and the hydrophilic portion in components (b) and (c) New state of association is formed.
In addition, by using the component (a) with the component (b) and the component (c) at a specific mass ratio, the detergency against oil stains is increased, and the associated state is maintained even after continuous cleaning. Since it is maintained, the amount of foam is maintained without the foaming fading. In addition, in the dishwashing sponge containing the liquid detergent composition, the creamy foam formed by the association of the components (a) to (c) is felt as a feeling of elasticity. It is thought that it is possible to realize that it is sufficiently contained.
As described above, the present invention selects the component (a) having a specific branched structure among the compounds having a branched structure, and has a mass ratio represented by [(b) + (c)] / (a). By combining a specific surfactant composition with a limited range, it is only possible to obtain good detergency against oil stains, persistence of foaming and foam volume, and elasticity when held in a sponge. , Which has an extraordinary effect.

According to such a liquid detergent composition of the present invention, for example, when washing dishes or cooking utensils, even when used in the presence of oil, foaming is good in the first half of washing, Since the amount lasts and a feeling of elasticity is felt even when the sponge is gripped, it can be realized that the sponge still contains a sufficient amount of liquid detergent. This reduces the number of times the liquid detergent composition is added to the sponge. And the usage-amount of a liquid cleaning agent reduces, and the consciousness with respect to a consumer's environment and economy can be satisfied. In addition, the environmental load can be reduced.
Such a liquid detergent composition of the present invention can be particularly suitably used as a kitchen detergent.

  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 composition>
According to the blending composition shown in Tables 1 to 4, the liquid cleaning composition 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 compounding amount in Tables 1 to 4 is mass%, and all the components indicate the equivalent amount of pure component.
In addition, the liquid cleaning composition of each example was prepared so that the sum total of each component as described in a table | surface might be 100 mass%. Each component used was kept at 50 ° C.

[Method for producing liquid detergent composition]
First, the component (a) or the component (a ′), the component (b), and the components (d) and PEG 1000 for Examples 30 to 34 were placed in a 200 mL beaker and stirred with a magnetic stirrer. Next, component (c) 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, the pH was adjusted, and the remaining water was added and balanced so that the total amount became 100 parts by mass, thereby producing the liquid detergent compositions of the respective examples.
The pH is adjusted by adding a predetermined amount of glycolic acid and adding an appropriate amount of 0.1N sodium hydroxide so that the liquid detergent composition (stock solution) of each example has a pH of 7.0 at 25 ° C. Was done.
The pH was measured by adjusting the liquid detergent composition 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, [(b) + (c)] / (a) means the ratio (mass ratio) of the amount of each component.
Below, the component shown in the table | surface is demonstrated.

<Description of components shown in the table>.
-(A) component a-1: Polyoxyethylene mono (2-propyl heptyl) ether, the product made by BASF, brand name "Lutensol XP60", the compound of m = 6 in the said general formula (a1).
a-2: Polyoxyethylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XP90”, m = 9 compound in the above general formula (a1).
a-3: Polyoxyethylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XP100”, a compound of m = 10 in the above general formula (a1).
a-4: polyoxyethylene polyoxypropylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XL90”, m = 9 compound in the above general formula (a1) (oxyethylene group and oxypropylene) Mixed with group).
a-5: Polyoxyethylene polyoxypropylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XL100”, m = 10 compound in the above general formula (a1) (oxyethylene group and oxypropylene) Mixed with group).

-Comparison component of component (a) [hereinafter referred to as “component (a ′)”. ]
a′-1: polyoxyethylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XP40”, a compound of m = 4 in the above general formula (a1).
a′-2: Polyoxyethylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XP140”, compound of m = 14 in the above general formula (a1).
a′-3: Polyoxyethylene lauryl ether, manufactured by Lion Corporation, trade name “Rheox LC-90”, linear alkyl group having 12 carbon atoms, compound having an average addition mole number of ethylene oxide of 9
a′-4: polyoxyethylene decyl ether (oxo alcohol ethoxylate), manufactured by BASF, trade name “Lutensol ON80”, general formula R—O— (CH ₂ CH ₂ O) ₈ —H (where R is 2-methylnonyl group).
a′-5: Polyoxyethylene cetyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name “New Coal 1607”, linear alkyl group having 16 carbon atoms, compound having an average addition mole number of ethylene oxide of 7

(B) Component b-1: Polyoxyethylene alkyl ether sodium sulfate (NRES) (alkyl groups having 12 and 14 carbon atoms, average number of added moles of ethylene oxide of 2, narrow ratio of 43% by mass, n in the formula (S) _The ratio of the adduct of ethylene oxide in which _max = 2, the number of moles of ethylene oxide added is n _max Y _nmax = Y ₂ = 25 (mass%), the ratio of the adduct of ethylene oxide in which the number of moles of added ethylene oxide is zero Y ₀ = 13 (mass%)); raw material alcohol: CO1270 [manufactured by P & G, a mixture of C12 / C14 = 7/3 in a mass ratio of C12 alcohol (C12) and C14 alcohol (C14), linear 100% by mass (branch rate 0% by mass)].
The “linear ratio” indicates the ratio (% by mass) of the linear higher alcohol to the total higher alcohol.

[Method for synthesizing NRES]
The above CO1270 was used as a raw material alcohol.
In a 4 L autoclave, 400 g of the raw material alcohol and 0.4 g of a composite metal oxide Lewis acid sintered solid catalyst composed of Al / Mg / Mn were charged, and the autoclave was purged with nitrogen and stirred. The temperature rose. Thereafter, 54 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 mPa, to obtain a reaction product (alcohol ethoxylate).
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 dropping, stirring was continued for 1 hour to obtain the target polyoxyethylene alkyl ether sulfuric acid. Further, this was neutralized with an aqueous sodium hydroxide solution to obtain NRES.

[Narrow rate measurement method]
For NRES, the distribution of ethylene oxide adducts with different numbers of moles of ethylene oxide was measured under the following measurement conditions. And the narrow rate (mass%) of NRES was computed based on the said Numerical formula (S).
(Measurement conditions for the distribution of ethylene oxide adducts by HPLC)
Apparatus: LC-6A (manufactured by Shimadzu Corporation)
Detector: SPD-10A
Measurement wavelength: 220 nm
Column: Zorbax C8 (manufactured by Du Pont)
Mobile phase: acetonitrile / water = 60/40 (volume ratio)
Flow rate: 1 mL / min
Temperature: 20 ° C

b-2: Secondary alkane sulfonate sodium (SAS), manufactured by Clariant Japan Co., Ltd., trade name “HOSTAPUR SAS 30A”.
b-3: Sodium α-olefin sulfonate, manufactured by Lion Corporation, trade name “Lipolane LB-440”.

-(C) component c-1: C12 alkyl dimethylamine oxide, the product made from Lion Akzo, brand name "Aromox DM12D-W".
c-2: N-lauryl-N, N-dimethyl-N- (2-hydroxy-1-sulfopropyl) ammonium sulfobetaine.

-(D) component d-1: p-toluenesulfonic acid, the Teica Co., Ltd. make, brand name "Taikatox 300".
d-2: Sodium cumene sulfonate, manufactured by Teika Co., Ltd., trade name “Taikatox N5040”.
d-3: Sodium benzoate, manufactured by Fushimi Pharmaceutical Co., Ltd.
d-4: Ethanol, manufactured by Pure Chemical Co., Ltd., reagent grade.

Optional component PEG1000: Polyethylene glycol 1000, manufactured by Lion Corporation, trade name “PEG # 1000” (average molecular weight 1000).
Glycolic acid: DuPont's trade name “Grip Pure 70”.
Na hydroxide: sodium hydroxide, manufactured by Tsurumi Soda Co., Ltd.
Water: tap water.

≪Evaluation of liquid detergent composition≫
About each liquid detergent composition of each example, each evaluation was performed with the evaluation method shown below, and the result was written together in Tables 1-4.

[Evaluation of detergency against oil stains]
1 g of beef tallow was applied uniformly on the entire inner surface of a tapper container having a length of 10 cm, a width of 15 cm, and a height of 5 cm to obtain a dirt model.
Next, 38 g of 25 ° C. tap water and 2 g of the liquid detergent composition were taken in a dishwashing sponge (Sumitomo 3M Co., Ltd., trade name: Scotch Bright) measuring 11.5 cm long × 7.5 cm wide × 3 cm high. After squeezing by hand several times, the dirt model was washed in the same way as usual at home.
Next, after rinsing well with tap water at 25 ° C., the tactile sensation when touching the portion of the inner surface of the tappa container on which the beef tallow was applied was evaluated.
This evaluation was performed based on the following evaluation criteria (（to ○ are acceptable ranges), and was used to evaluate the cleaning power against oil stains.
(Evaluation criteria)
A: When touching any part of the inner surface of the tapper container, there was no oil film, and no muting due to oil residue was felt.
○: When the bottom and side surfaces inside the tappa container were touched, there was no oil film, and no sliminess due to residual oil was felt, but there was a slight stickiness at the corners inside the tappa container.
(Triangle | delta): When the bottom surface inside a tapper container was touched, there was no film | membrane with oil and the sliminess by oil residue was not felt, but the sliminess remained in the side surface and corner | angular part inside a tapper container.
X: It was found that the entire tapper container was slippery, and oil remained clearly.

[Evaluation of foaming property (sustainability of foaming and foam amount)]
As a model oil stain, a dish (21 cm in diameter) from which 1 g of olive oil and 5 g of water were collected was used as a model oil stain dish, and 30 model oil stain dishes were prepared.
Take 17.5cm x 7.5cm x 3cm height sponge for dishwashing (product name: Scotch Bright, manufactured by Sumitomo 3M Co., Ltd.) The dishwashing sponge after squeezing by hand was brought into contact with the model oil dirt dish, so that the model oil dirt and the dishwashing sponge became familiar. After that, the dishwashing sponge was pressed against the model oil-stained dish and moved to draw a circle twice to rub it.
And, without washing water and liquid detergent composition newly added to the dishwashing sponge, the model oil soiling dish is continuously scrubbed, and no bubbles remain on the model oil soiling dish after scrubbing. Washed until it was in a state (cannot be confirmed).
At this time, the liquid detergent composition in which the number of dishes that could be washed before the bubbles could not be confirmed was less than 20 was judged to be inferior in the persistence of the foam, and was excluded from the evaluation of the next foam quantity. . Tables 1 to 4 show the number of dishes that could be washed before the bubbles could be confirmed.
For example, assuming that the number of dishes to be used for one meal is a bowl, bowl, two dishes, and two small bowls, the number of dishes is 5 per person. For a general family of four, the number of dishes is 5 Since it is assumed that the number of sheets × 4 people = 20 sheets, the number of dishes less than 20 was used as a criterion for determining the persistence of bubbles.
For the liquid detergent composition in which the number of dishes that could be washed before foam could not be confirmed was 20 or more, the foam present in each model oil stain dish was transferred to a 500 mL graduated cylinder after washing, and the amount of foam (ML) was measured for each plate, and evaluated based on the following evaluation criteria (◎ to ○ are acceptable ranges).
(Evaluation criteria)
A: The number of dishes in which the amount of foam of 100 mL or more was confirmed after washing was 5 or more.
(Circle): The number of the plates which could confirm the foam volume of 100 mL or more after washing | cleaning was 3-4 sheets.
(Triangle | delta): The number of the plates which could confirm the foam amount of 100 mL or more after washing | cleaning was 1-2 sheets.
X: The number of dishes in which the amount of foam of 100 mL or more was confirmed after washing was 0.
In the table, “−” in the evaluation of foamability means that the amount of foam was not evaluated.

[Evaluation of sponge feel]
Take 38 g of tap water and 2 g of the liquid detergent composition in a sponge for dishwashing (product name: Scotch Bright, Sumitomo 3M Co., Ltd.) measuring 11.5 cm x 7.5 cm x 3 cm in height. Sponge feel felt by palms while rubbed with 10 was evaluated by 10 monitors based on the following evaluation criteria.
(Evaluation criteria)
A: A moderately strong elasticity was felt in the dishwashing sponge.
○: The dishwashing sponge felt a little elastic.
Δ: The dishwashing sponge felt slightly soft.
X: The dishwashing sponge was clearly soft.

[Evaluation of low-temperature stability]
100 mL of the liquid detergent composition 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 composition after being stored for 1 month in a thermostatic bath at −5 ° C. (low temperature condition) was visually observed and based on the following evaluation criteria (◎ to ○ are acceptable ranges). The storage stability (appearance) of the liquid detergent composition was evaluated.
(Evaluation criteria)
A: Uniform and transparent.
A: Although deposits were observed, the amount deposited was less than 1% by volume of the entire volume of the cylindrical glass bottle.
(Triangle | delta): The deposit was recognized and the amount which deposited was 1 volume% or more of the whole volume of the cylindrical glass bottle, and was less than 10 volume%.
X: Precipitates were observed, and the amount deposited was 10% by volume or more of the entire volume of the cylindrical glass bottle.

As is clear from the results in Tables 1 to 4, the liquid detergent compositions of Examples 1 to 34 according to the present invention have excellent detergency against oil stains, and even when used in the presence of oil, the liquid starts to foam. It was confirmed that the amount of foam was large and the sustainability of the amount of foam was good, and a feeling of elasticity was felt when gripped by being included in a sponge.
Therefore, according to such a liquid detergent composition, it is possible to reduce the number of times the liquid detergent is used when washing tableware, cooking utensils, etc., and to reduce the amount of liquid detergent used. Satisfies sexual awareness.

In addition, from the comparison between Example 1 and Examples 16, 21, and 22, as a component (b), a combination of polyoxyethylene alkyl ether sulfate and secondary alkane sulfonate allows the detergency against oil stains. It can be seen that is improved further.
Moreover, it turns out that low temperature stability improves further by containing the (d) component further from the result of Table 4 in addition to the (a)-(c) component.

Claims (4)

1 to 15% by mass of the compound (a) represented by the following general formula (a1),
Anionic surfactant (b) 5-30% by mass ;
Containing 1 to 15% by weight of an amphoteric surfactant and / or a semipolar surfactant (c),
A liquid detergent composition having a mass ratio represented by [(b) + (c)] / (a) of 2 to 10.

[Wherein, AO represents an oxyethylene group and / or an oxypropylene group. m represents the average number of repetitions of AO and is 6-12. One of x and y is 3 and the other is 5 . ] The AO in the general formula (a1) is an oxyethylene group, claim 1 liquid detergent composition according m is 9 or 10.
  The liquid detergent composition according to claim 1 or 2, wherein the anionic surfactant (b) is a combination of a polyoxyethylene alkyl ether sulfate and a secondary alkane sulfonate.   4. The composition further comprises at least one hydrotrope (d) selected from the group consisting of toluenesulfonic acid, toluenesulfonic acid salt, cumenesulfonic acid, cumenesulfonic acid salt, benzoic acid, benzoic acid salt and ethanol. A liquid detergent composition according to any one of the above.