JP5568447B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition.

Conventionally, liquid detergent compositions using polyoxyethylene alkyl ether sulfate (AES) as a cleaning ingredient, which is made from natural alcohol (linear alcohol) as a raw material, have storage stability under low temperature conditions (hereinafter referred to as “low temperature stability”). It was difficult to secure.
When this AES is produced, a product having a wide distribution of the number of moles of ethylene oxide added is obtained by a reaction of adding ethylene oxide to an alcohol. By sulfating the product, about 30% by mass of an alkyl sulfate ester is obtained. Salt (AS) coexists. The reason why it is difficult to ensure the low temperature stability was thought to be that the complex of the AS and the alkaline earth metal in the composition was precipitated under low temperature conditions.
On the other hand, polyoxyethylene alkyl ether sulfate ester salt (AES (p)) produced by first adding a small amount of propylene oxide to alcohol and then adding ethylene oxide as a cleaning component of the liquid cleaning composition. By using it, excellent low temperature stability is ensured. This is presumed to be because the reaction proceeds without reducing the proportion of 1 mol of adduct and 2 mol of adduct of ethylene oxide, which contributes to detergency, by adding propylene oxide to alcohol first. Yes.
Patent Document 1 discloses a liquid detergent composition containing such AES (p), an inorganic water-soluble alkaline earth metal compound, a phase stabilizer selected from a hydrotrope agent and an organic solvent, and water. Has been proposed. According to this liquid detergent composition, it is said that high detergency and excellent low-temperature stability can be expressed.

JP 2009-155611 A

However, the liquid detergent composition containing AES (p) as a cleaning component has a problem that foamability is poor.
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 cleanability against oil stains, kitchen cleaning agents are also required to have foaming properties (good foaming at the beginning of washing, persistence of the amount of foam from the start of washing to the end of washing).

  The present invention has been made in view of the above circumstances, has excellent detergency against oil stains, has good storage stability at low temperature conditions, and has a foam amount from the beginning of washing even when used in the presence of oil. Therefore, a problem is a liquid detergent composition having a large amount of bubbles and a good sustainability of the amount of bubbles.

As a result of intensive studies, the present inventors have found that a washing component produced by first adding a small amount of propylene oxide to an alcohol and then adding ethylene oxide is generally less likely to form an association state and is used for a low foaming composition. As a result, it has been found that the above-mentioned problems can be solved by using together with a compound having a specific structure from among the branched compounds suitable as the present invention, 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), a compound (b) represented by the following general formula (b1), an amphoteric surfactant and / or Or a semipolar surfactant (c).

［式（ａ１）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。］

[In the formula (a1), 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. ]

［式（ｂ１）中、Ｒ^５は炭素数８〜１８の直鎖状のアルキル基を表す。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、０＜ｐ＜１、０＜ｑ≦３である。Ｍは陽イオンである。］

[In formula (b1), R ⁵ represents a linear alkyl group having 8 to 18 carbon atoms. 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 0 <p <1 and 0 <q ≦ 3. M is a cation. ]

In the liquid detergent composition of the present invention, in the compound (a), 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 preferably 5.
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, good storage stability under low temperature conditions, and even when used in the presence of oil, the amount of foam is large from the start of washing, and the sustainability of the amount of foam Can provide a good liquid detergent composition.

≪Liquid detergent composition≫
The liquid detergent composition of the present invention comprises a compound (a) represented by the general formula (a1), a compound (b) represented by the general formula (b1), an amphoteric surfactant and / or a semipolar interface. And an active agent (c).

<Compound (a)>
The compound (a) in the present invention is represented by the following 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), both the foaming and the persistence of the amount of foam are mainly good even when the liquid detergent composition is used in the presence of oil. In addition, when the liquid detergent composition is included in a sponge and gripped, a feeling of elasticity can be felt. By feeling this elasticity, as will be described later, when cleaning tableware, 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.

［式（ａ１）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。］

[In the formula (a1), 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 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 group and oxypropylene group, foaming and persistence of the amount of foam when used in the presence of oil, and a liquid detergent composition included in the sponge In view of excellent elasticity at the time, the average number of repeating oxypropylene groups is preferably 3 or less, and more preferably 1 or 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, the detergency against oil stains is good. Further, when the liquid detergent composition is included in the sponge and gripped, a feeling of elasticity can be felt. When m is 9 or 10, the foaming and the sustainability of the amount of foam are excellent, and a feeling of elasticity is more felt when the liquid detergent composition is included 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, 6 ≦ x + y ≦ 10 is preferable, 6 ≦ x + y ≦ 8 is more preferable, and x + y = 8 is particularly preferable because the foaming of the liquid cleaning composition and the persistence of the foam amount are further improved.
When x + y is 6 or more, surface activity is exhibited and the adsorptivity to the liquid surface is increased. Further, when the liquid detergent composition is included in the sponge and gripped, a feeling of elasticity can be felt. When x + y is 12 or less, the foaming and the sustainability of the foam amount are excellent even when used in the presence of oil.
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 these, as the component (a), AO in the formula (a1) is an oxyethylene group, m is 9 or 10, one of x and y is 3, and the other is 5. preferable.
Further, as the component (a), an ethylene oxide adduct of alcohol having a branched structure at the β-position obtained by bimolecular condensation by a 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 at least the lower limit, the foaming of the liquid detergent composition and the sustainability of the foam amount are further improved, and the low temperature stability is further improved. On the other hand, if it is not more than the upper limit value, the detergency against oil stains is further improved.

<Compound (b)>
The compound (b) in the present invention is represented by the following general formula (b1) (hereinafter referred to as “component (b)”).
By containing the component (b), mainly, the detergency against oil stains is excellent, and the storage stability under low temperature conditions is good.

［式（ｂ１）中、Ｒ^５は炭素数８〜１８の直鎖状のアルキル基を表す。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、０＜ｐ＜１、０＜ｑ≦３である。Ｍは陽イオンである。］

[In formula (b1), R ⁵ represents a linear alkyl group having 8 to 18 carbon atoms. 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 0 <p <1 and 0 <q ≦ 3. M is a cation. ]

In the formula (b1), R ⁵ is a linear alkyl group having 8 to 18 carbon atoms, and the carbon atom of R ⁵ bonded to the oxygen atom in “R ⁵ O—” is only one It is bonded to other carbon atoms. R ⁵ preferably has 10 to 16 carbon atoms, and more preferably 12 to 14 carbon atoms.

In the formula (b1), 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 0 <p <1 and 0 <q ≦ 3.
When 0 <p <1, the content ratio of the alkyl sulfate ester salt (AS) is limited, and the low-temperature stability is improved. When 0 <q ≦ 3, the detergency against oil stains is good, and even when used in the presence of oil, the foaming and the amount of foam are excellent.
Here, p and q indicate the “average” number of repetitions of PO and EO, respectively. Therefore, the compound represented by the formula (b1) is an aggregate of molecules (including molecules having no PO or EO) having different numbers of repetitions of PO and EO. The number of carbon atoms of R ⁵ may be a collection of different molecules.

In the formula (b1), M is a cation, and examples thereof include alkali metal ions, alkaline earth metal ions, and ammonium ions.
Examples of the alkali metal that provides the alkali metal ion include sodium and potassium. Examples of alkaline earth metals that provide alkaline earth metal ions include calcium and magnesium. Examples of those that provide ammonium ions include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

  The component (b) is obtained by adding propylene oxide to a linear primary alcohol to obtain a propylene oxide adduct, adding ethylene oxide to the propylene oxide adduct to obtain an alkoxylate, It can be produced by sulfation and then neutralization.

(B) A component can be used individually by 1 type or in mixture of 2 or more types.
The content of the component (b) in the liquid detergent composition is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, and further preferably 15 to 25% by mass.
(B) When content of a component is more than a lower limit, the detergency with respect to oil dirt improves more, and low-temperature stability becomes more favorable. 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 at most the upper limit value, it becomes easier to maintain a transparent appearance especially under low temperature conditions.

<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 the component (c), a semipolar surfactant is preferable because it has a particularly good detergency against oil stains in combination with the component (b).
Specifically, the component (c) is preferably an aminoacetic acid betaine, a sulfobetaine, an alkyldimethylamine oxide type or an alkanoylamide alkyldimethylamine oxide type, particularly preferably an alkyldimethylamine oxide type.

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. Furthermore, when the liquid detergent composition is included in a sponge and gripped, a good feeling of 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 preferably 2 to 10, more preferably 3 to 9.5. preferable.
When the mass ratio is 2 or more, the cleaning power against oil stains is further improved. In addition, when the liquid detergent composition is included in a sponge and gripped, good elasticity can be obtained. On the other hand, when the mass ratio is 10 or less, the foaming of the liquid detergent composition and the sustainability of the foam amount are further improved. In addition, an increase in viscosity is suppressed, and when the liquid detergent composition is included in a sponge and gripped, an appropriate elasticity can be obtained and the amount of foam can be maintained.
Thus, by using the component (a) at a specific mass ratio with the component (b) and the component (c), the detergency against oil stains is increased, and foaming does not occur even if continuous cleaning is continued. The amount of foam is easy to sustain without fading.

<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. 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 cleaning composition of the present invention, as a hydrotrope other than the component (d), water-soluble solvents such as propylene glycol, polyethylene glycol, and phenyl glycol; xylene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, and the like An aromatic sulfonic acid or a salt thereof, an aromatic carboxylic acid or a salt thereof (excluding benzoic acid or a salt thereof) and the like can also be blended.

In the liquid detergent composition of the present invention, a nonionic surfactant other than the component (a) and an anionic surfactant other than the component (b) can be blended as optional components.
Nonionic surfactants other than component (a) include polyoxyalkylene alkyl ethers, ester-type polyoxyalkylene alkyl ethers, alkyl polyglycosides, alkyl glucosides, alkyl monoglyceryl ethers; fatty acids such as fatty acid alkanolamides and alkylmethyl glucamides Amide derivatives; long chain fatty acid ester compounds such as sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, fatty acid glycoside ester, fatty acid methyl glycoside ester, and the like. By further containing these nonionic surfactants, hand roughness is less likely to occur, and high hand skin mildness is imparted.
(B) As an anionic surfactant other than the component, sulfonate type (alkylbenzene sulfonate, alkyl sulfate, alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl) Ester salt, sulfosuccinate, etc.), sulfate ester type (alkyl sulfate ester salt, alkenyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkenyl ether sulfate ester salt, etc.), carboxylate type (alkyl) Ether carboxylates, amide ether carboxylates, sulfosuccinates, amino acid anionic surfactants, etc.), phosphate ester types, and the like.

  Further, the liquid detergent composition of the present invention includes, as optional components, a pH adjuster (sodium hydroxide, sulfuric acid, glycolic acid, etc.), a chelating agent, an antioxidant, a coloring agent, an enzyme, a disinfectant (water-soluble). Silver salts, water-soluble copper salts, water-soluble zinc salts, etc.), perfumes, alkaline earth metal salts, and the like can also be blended.

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.

As described above, the liquid detergent composition of the present invention includes a compound (a) having a branched structure represented by the general formula (a1) and a sulfate ester containing an oxypropylene group represented by the general formula (b1). A salt compound (b) and an amphoteric surfactant and / or a semipolar surfactant (c) are contained.
In the conventional liquid detergent composition using the component (b) and the component (c) as the cleaning component, the foaming property is inferior, but the foaming property is remarkably improved by using the component (a) together. The reason why such an effect is obtained is not certain but is presumed as follows.
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, 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. The component (a)
(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.
From the above, it is considered that the liquid detergent composition of the present invention has a large amount of foam from the start of washing even when used in the presence of oil, has a good sustainability of the amount of foam, and is excellent in foaming properties.

In addition, according to the present invention, a feeling of elasticity is felt when the liquid detergent composition is included in a sponge and gripped.
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 addition, when it was felt that there was no elasticity when grasping the sponge, it was found that the sponge could not be efficiently pressed against tableware during washing, so that it was difficult to rub off oil stains.
In the dishwashing sponge containing the liquid detergent composition of the present invention, the creamy foam formed by associating the components (a) to (c) is felt as a feeling of elasticity. It is thought that it can feel that the thing is fully contained.

According to the liquid detergent composition of the present invention, for example, when washing dishes and cooking utensils, even if used in the presence of oil, foaming is good in the first half of washing, and the amount of foam is maintained even in the latter half of washing. In addition, since 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 (1)]
(Examples 1-18, Comparative Examples 1-10)
First, (a) component or (a ') component, (b) component, (d) component, and PEG1000 were put into a 200 mL beaker, and it stirred with the 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.

[Method for producing liquid detergent composition (2)]
(Examples 19 to 26)
First, (a) component, (b) component, (d) component, and PEG1000 were put into a 200 mL beaker, and it stirred with the magnetic stirrer. Next, component (c) was added and stirred. Next, nonion 1, nonion 2, phenyl glycol and Mg sulfate heptahydrate are added and stirred, and then zinc sulfate heptahydrate is added and stirred. did.
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.
In Examples 19 to 21, the pH is adjusted by blending a predetermined amount of glycolic acid so that the pH at 25 ° C. of the liquid detergent composition (stock solution) of each example becomes the value shown in the table. This was performed by adding an appropriate amount of 0.1N sodium hydroxide. In Examples 22 to 26, it was carried out only by adding an appropriate amount of 0.1N sodium hydroxide so that the pH at 25 ° C. of the liquid detergent composition (stock solution) of each example would be the value shown in the table. . The pH measurement was performed in the same manner as described above.

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
a′-6: Alkyl glucoside, manufactured by Kao Corporation, trade name “Mydoll 12”.
a′-7: 2-ethylhexyl monoglyceryl ether.

Component (b): b-1: a primary alcohol (C12OH) having a linear alkyl group having 12 carbon atoms and a primary alcohol (C14OH) having a linear alkyl group having 14 carbon atoms are C12OH : C14OH = 73: 27 (mass ratio) natural alcohol mixed with 0.4 mol of PO on average and 1.5 mol of EO added on average, then sulfated with sulfur trioxide and neutralized with sodium hydroxide (Diluted with water and neutralized until the pH of the 10% by weight aqueous solution was 11).
b-2: A primary alcohol (C12OH) having a linear alkyl group having 12 carbon atoms and a primary alcohol (C14OH) having a linear alkyl group having 14 carbon atoms are C12OH: C14OH = 73: After adding 0.5 mol of PO and 1.5 mol of EO to natural alcohol mixed at 27 (mass ratio), it was sulfated with sulfur trioxide and neutralized with sodium hydroxide (diluted with water). And neutralized until the pH of the 10 mass% aqueous solution becomes 11.
b-3: A primary alcohol (C12OH) having a linear alkyl group having 12 carbon atoms and a primary alcohol (C14OH) having a linear alkyl group having 14 carbon atoms are C12OH: C14OH = 73: After adding an average of 0.6 mol of PO and an average of 1.5 mol of EO to natural alcohol mixed at 27 (mass ratio), it was sulfated with sulfur trioxide and neutralized with sodium hydroxide (diluted with water). And neutralized until the pH of the 10 mass% aqueous solution becomes 11.
The natural alcohol is composed only of a compound having a linear alkyl group.

-(C) component c-1: C12 alkyl dimethylamine oxide, the product made from Lion Akzo, brand name "Aromox DM12D-W".
c-2: Amidopropyldimethylamine oxide laurate, manufactured by Kawaken Fine Chemical Co., Ltd., trade name “SOFTAZOLINE LAO”.

-(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.
Nonion 1: Same as a'-6.
Nonion 2: Same as a′-7.
Phenyl glycol: manufactured by Nippon Emulsifier Co., Ltd., trade name “PhG-H”.
Zinc sulfate heptahydrate: Made by Jun Chemical Co., Ltd., reagent grade.
Fragrance: Fragrance composition A described in JP-A No. 2002-327194.
Mg sulfate heptahydrate: Magnesium sulfate heptahydrate, manufactured by Wako Pure Chemical Industries, Ltd.

≪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]
0.8 g of beef tallow was applied uniformly on the entire inner surface of the 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 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 5% by volume of the entire volume of the cylindrical glass bottle.
(Triangle | delta): The deposit was recognized and the quantity which has deposited was 5 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.

[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.

From the results of Tables 1 to 3, the liquid detergent compositions of Examples 1 to 18 according to the present invention have excellent detergency against oil stains, good storage stability at low temperature conditions, and in the presence of oil. It was confirmed that the amount of foam was large from the start of washing and the sustainability of the amount of foam was also good.
Moreover, from the results of Tables 1 and 2, it can be seen that the low temperature stability is further improved by further containing the component (d) in addition to the components (a) to (c).
Also in the liquid detergent compositions of Examples 19 to 26 shown in Table 4, good evaluation results were obtained for all of the detergency against oil stains, low temperature stability, foamability, and sponge feel.

Claims (3)

1 to 15% by mass of the compound (a) represented by the following general formula (a1), 5 to 50% by mass of the compound (b) represented by the following general formula (b1), an amphoteric surfactant and / or half A liquid detergent composition containing 1 to 15% by mass of a polar surfactant (c).

[In the formula (a1), 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 . ]

[In formula (b1), R ⁵ represents a linear alkyl group having 8 to 18 carbon atoms. 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 0 <p <1 and 0 <q ≦ 3. M is a cation. ] The compound (a), the AO in the general formula (a1) is an oxyethylene group, the liquid detergent composition according to claim 1, wherein m is 9 or 10.
  Claim 1 or Claim further containing at least one hydrotrope agent (d) selected from the group consisting of toluenesulfonic acid, toluenesulfonic acid salt, cumenesulfonic acid, cumenesulfonic acid salt, benzoic acid, benzoic acid salt and ethanol. Item 3. A liquid detergent composition according to Item 2.