WO2008001797A1 - Liquid detergent composition - Google Patents

Abstract

A liquid detergent composition comprising 50 to 80% by mass of an ethylene oxide adduct (A) and an anti-oxidant (B) and having a pH value ranging from 5 to 8 at 25˚C, wherein the ethylene oxide adduct (A) is represented by the general formula (I) and has a narrow ratio (which represents a fractional distribution of ethylene oxide adducts having different numbers of moles of ethylene oxide units added) of 30% by mass or higher. R1CO-(OCH2CH2)n'-OR2 (I) wherein R1 represents a linear or branched alkyl or alkenyl group having 11 to 13 carbon atoms; R2 represents an alkyl group having 1 to 3 carbon atoms; and n' means an average number of moles of ethylene oxide units added and is a numerical number ranging from 10 to 20.

Description

 Specification

 Liquid detergent composition

 Technical field

 [0001] The present invention relates to a liquid detergent composition.

 Background art

 [0002] In order to reduce the amount of liquid detergent composition used, or to reduce the size of the container in which the liquid detergent composition is contained, etc., the surfactant composition has a high surfactant concentration. A so-called “concentrated type” liquid detergent composition has been proposed.

 [0003] For example, a liquid detergent composition for clothing comprising a specific nonionic surfactant and a polyoxyalkyleneamine has been proposed (see Patent Document 1).

 In addition, the anti-gelling agent and the amphoteric surfactant that promotes gelation are premixed in the stirring device, and then an anionic surfactant and a nonionic surfactant are added. A method for producing a liquid detergent is proposed (see Patent Document 2).

 Further, a concentrated liquid detergent composition comprising a nonionic surfactant obtained by adding ethylene oxide and propylene oxide to a higher alcohol having 8 to 18 carbon atoms by a specific addition method has been proposed. (See Patent Document 3).

 Further, a concentration comprising a nonionic surfactant obtained by reacting a fatty acid alkyl ester and an alkylene oxide in the presence of a catalyst comprising magnesium oxide to which one or more of specific metal ions are added. A liquid detergent composition has been proposed (see Patent Document 4).

 [0004] Patent Document 1: Japanese Patent Application Laid-Open No. 2005-171195

 Patent Document 2: Japanese Patent Laid-Open No. 2003-238999

 Patent Document 3: Japanese Unexamined Patent Publication No. 2003-105377

 Patent Document 4: JP-A-5-222396

 Disclosure of the invention

 Problems to be solved by the invention

[0005] Polyoxyethylene alkyl used as a cleaning ingredient in a liquid detergent composition General-purpose surfactants such as ruether increase the viscosity (gelation) with increasing surfactant concentration. Further, since the range of the concentration of the surfactant that causes the gelation is wide, a concentrated liquid detergent composition containing a large amount (for example, 50% by mass or more) of one kind of powerful general-purpose surfactant alone. It is difficult to manufacture.

 Therefore, a conventional concentrated liquid detergent composition needs to contain a certain amount of solubilizer (hydrotrope) in order to suppress the gelation. In addition, in the liquid detergent composition described in Patent Documents 1 and 2, it is essential to use two or more surfactants in combination, and a large amount of one surfactant alone is contained in the liquid detergent composition. It is not included in.

 In the concentrated liquid detergent composition described in Patent Document 3, a special nonionic surfactant having a complicated reaction process is used, which is economically disadvantageous.

 In addition, the specific nonionic surfactant described in Patent Document 4 has a remarkably wide distribution of alkylene oxide adducts (AO adducts) having different numbers of added moles of alkylene oxide. Therefore, the concentrated liquid detergent composition described in Patent Document 4 has a problem that the odor of the unreacted raw material ester remains in the liquid detergent composition. In addition, there is a problem in that the cleaning power and rinsing properties of the liquid detergent composition are reduced due to the influence of the addition of the alkylene oxide having a high amount, the AO adduct, or the low addition AO adduct. is there.

 [0006] By the way, according to the study of the present inventor, a conventional concentrated liquid detergent composition cannot obtain a sufficient cleaning power, for example, in the case of washing using a washing machine.

 Furthermore, as a result of investigations by the present inventors, the conventional concentrated type liquid detergent composition does not dissolve quickly after being poured into the water in the washing machine tub, and becomes a lumpy state for a while. It was found that due to the low dissolution rate in water, such as the presence, sufficient detergency cannot be exerted within the limited washing time of washing using a washing machine.

 [0007] The present invention has been made in view of the above circumstances, and includes a liquid detergent composition containing a single surfactant in a large amount, excellent in solubility in water, and having high detergency. The challenge is to provide It is another object of the present invention to provide a liquid detergent composition having a low raw material odor of a surfactant.

Means for solving the problem [0008] In order to solve the above-mentioned problems, in the present invention, the following component (A) contains 50 to 80% by mass and an antioxidant (B), and the pH at 25 ° C is 5 to 8. A liquid detergent composition is proposed.

 (A) Narrow ratio indicating the distribution ratio of ethylene oxide adducts represented by the following general formula (I), wherein the number of moles of attached ethylene oxide is different. Oxide adduct.

[0009] [Chemical 1]

R'CO ™ COCH ₂ GH ₂ ) _n .- OR ² (I)

[In the formula (I), R ¹ is a linear or branched alkyl group or alkenyl group having 11 to 13 carbon atoms; R ² is an alkyl group having 1 to 3 carbon atoms; n ′ Indicates the average number of moles of ethylene oxide added, and is 10-20. ]

 [0010] According to the above configuration, a liquid detergent composition containing a large amount of a single surfactant alone, having excellent solubility in water and high detergency can be obtained. Furthermore, according to the above configuration, a liquid detergent composition having a low raw material odor of the surfactant can be obtained.

 [0011] The liquid detergent composition of the present invention may further contain a compound (D) represented by the following general formula (IV).

 [0012] [Chemical 2]

R ¹¹ — N— R ¹³ — Y

R ¹² ~ ( _IV)

[In the formula (IV), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group; R ¹³ is a straight chain having 1 to 4 carbon atoms; A chain or branched alkylene group; —Y is a group represented by the following general formula (V) and Z or general formula (VI). ]

[0013] [Chemical 3]

[In the formulas (V) to (VI), R ¹⁴ and R ¹⁵ are each independently a linear or branched alkyl or alkenyl group having 7 to 23 carbon atoms. ]

[0014] In this case, in addition to the above-described effects, a liquid detergent composition having a further excellent flexibility imparting effect can be obtained.

 In addition, the liquid detergent composition of the present invention is represented by the following general formula (VII) and / or general formula (VIII), in addition to the compound (D) represented by the general formula (IV). The polyether-modified silicone (E) may be further contained.

 [0016] [Chemical 4]

[In the formulas (VII) to (VIII), R is a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms, or a hydrogen atom, and each R may be the same. It may be different. R ¹⁶ is a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and each R ¹⁶ may be the same or different. Z represents a polyoxyalkylene group. The order of each structural unit marked with 1, _m , n may be different 1 ίMA 0 ~ 50, mi MA 10 ~: 10000, ηίMA:! ~ 1000, and represents an integer of m> n. Moreover, ai is 5 to 10000, b is an integer of 2 to 10000. ]

In this case, the flexibility imparting effect is further improved.

 * 10

 [0018] The liquid detergent composition of the present invention may further contain an antibacterial compound (C) represented by the following general formula (II) and / or general formula (III).

[0019] [Chemical 5]

RR ¹ X

 ■■ (II)

[In the formula (II), two or more of R ^{3 to} R ⁶ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group; the other is a straight chain having 8 to 22 carbon atoms. Or it is a branched alkyl group or alkenyl group. In formula (III), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group; R ⁹ is a linear or branched alkyl group having 8 to 22 carbon atoms. R ^1Q is an alkylene group having from 3 to 3 carbon atoms. X— is a halogen ion or an alkyl sulfate ion. ]

 [0020] In this case, in addition to the above-described effects, a liquid detergent composition having an excellent deodorizing effect can be obtained.

 [0021] Here, in the present specification and claims, the “narrow ratio indicating the distribution ratio of ethylene oxide adducts having different addition mole numbers of ethylene oxide” is represented by the following mathematical formula (S). Show things.

[0022] [Equation 1] i = n _m max +2

 Narrow rate = Z Yi ... (s)

'= ^-2

[In the formula (S), n is the most abundant ethylene max in the entire ethylene oxide adduct

 The number of moles of ethylene oxide added in the oxide adduct is shown. i represents the number of moles of ethylene oxide added. Yi indicates the ratio (mass%) of the ethylene oxide adduct having the number of moles of ethylene oxide present in the total ethylene oxide adduct being i.

₀ ]

 [0023] In the present specification, the "concentrated type" liquid detergent composition means that the total surfactant concentration in the liquid detergent composition is high, and the surfactant concentration is In the liquid detergent composition, it is 50% by mass or more, preferably 55% by mass or more. The invention's effect

 [0024] According to the present invention, it is possible to provide a liquid detergent composition containing a large amount of a single surfactant alone, having excellent solubility in water and high detergency.

 Furthermore, according to the present invention, it is possible to provide a liquid detergent composition with less surfactant raw material odor.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0025] The liquid detergent composition of the present invention is an ethylene oxide adduct represented by the above general formula (I), and shows a distribution ratio of ethylene oxide adducts having different numbers of moles of ethylene oxide added. And an ethylene oxide adduct (A) (hereinafter referred to as “component (A)”) having a ratio of 30% by mass or more and an antioxidant (hereinafter also referred to as “component (B)”). The pH at C is 5-8.

 The liquid detergent composition of the present invention further contains an antibacterial compound (C) (hereinafter referred to as component (C)) represented by the general formula (II) and / or the general formula (III). I prefer it.

 In addition, the liquid detergent composition of the present invention preferably further contains a compound (D) represented by the general formula (IV) (hereinafter referred to as “component (D)”).

In addition to the component (D), the liquid detergent composition of the present invention includes the general formula (VII) And / or a polyether-modified silicone (E) represented by the general formula (VIII) (hereinafter referred to as “component (E)”).

[0026] <(A) component>

 In the present invention, the component (A) is an ethylene oxide adduct represented by the above general formula (I) and has a narrow ratio of 30 indicating the distribution ratio of ethylene oxide adducts having different numbers of added moles of ethylene oxide. It is an ethylene oxide adduct having a mass% or more. By using the component (A), the liquid detergent composition of the present invention does not significantly increase (gel) the viscosity even if it contains a high concentration of surfactant, and one surfactant alone. Can contain a large amount of

 Here, “containing one surfactant alone in a large amount” means that one surfactant alone is contained in a liquid detergent composition in an amount of 50% by mass or more.

 In addition, the liquid detergent composition of the present invention contains the component (A), so that it has excellent solubility in water and a high detergency can be easily obtained. Further, a liquid detergent composition having a low raw material odor for the surfactant can be obtained. Furthermore, even if a high concentration surfactant is contained, gelation or the like does not occur, and a concentrated liquid detergent composition having good fluidity can be produced.

In the above general formula (I), R ¹ is a linear or branched alkyl group having 11 to 13 carbon atoms or an arnolekenino group.

In R ¹ , the number of carbon atoms of the alkyl group and alkenyl group is preferably 11 from the viewpoint of improving detergency against sebum dirt and mud dirt.

R ² is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.

 n ′ represents the average added mole number of ethylene oxide, and is 10-20. Preferably, it is 12 to 18 from the viewpoint of improving the detergency against sebum dirt, mud dirt, etc. and the liquid stability of the liquid detergent composition (for example, stability over time at low temperature).

[0028] The narrow ratio is 30% by mass or more, preferably 55% by mass or more, and more preferably 65% by mass or more. A higher narrow ratio is preferable, but the upper limit is substantially 80% by mass or less. When the narrow ratio is 30% by mass or more, preferably 55% by mass or more, the odor and liquid stability of the liquid detergent composition are improved. Furthermore, Detergency is also improved by increasing the desired component (ethylene oxide adduct having the desired number of moles of ethylene oxide added).

 [0029] The narrow rate can be controlled by, for example, the production method of the component (A).

 The method for producing the component (A) is not particularly limited. For example, a method in which ethylene oxide is added to a fatty acid alkyl ester by polymerization using a surface-modified composite metal oxide catalyst (JP 2000-2000A). — Refer to publication No. 144179).

Specific examples of suitable composite metal oxide catalysts having a surface modification include metal ions (Al ³⁺ , Ga ³⁺ , In ^{3 +} , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) and mixed metal oxide catalyst such as magnesium oxide, metal hydroxide and Z or metal alkoxide This is a modified catalyst for calcined hydrated talcite.

 Further, in the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is set to 100 parts by weight of the composite metal oxide with respect to the metal water. The ratio of oxide and / or metal alkoxide is preferably 0.5 to 10 parts by mass, more preferably! To 5 parts by mass.

 [0030] The component (A) used in the present invention has a high narrow rate. In addition, the component (A) has no hydrophilic group at the end of the molecule (end-capped type) in its molecular structure and has a highly polar carbonyl group in the molecule.

 As a result, the component (A) is a nonionic surfactant in which micelles with weak molecular orientation in an aqueous solution system are unstable, so gelation or the like does not occur at a high concentration. It is presumed that it can be incorporated into a liquid detergent composition. In addition, the solubility in water is estimated to improve. Furthermore, it is thought that it contributes to good fluidity at high concentrations. Therefore, after the component (A) is poured into the water in the washing machine tub, the concentration of the component (A) in the washing liquid becomes uniform quickly and can contact the object to be washed at a predetermined concentration from the initial stage of cleaning. Therefore, it is considered that high detergency can be obtained.

[0031] Further, when the narrow ratio is 30% by mass or more, after the production of the (A) component, The fatty acid ester which is the raw material of the component (A) and the ethylene oxide adduct of n ′ = 1 and 2 in the general formula (I) are reduced, so that the liquid detergent with a low raw material odor of the surfactant It is believed that a composition is obtained.

 In component (A), the total proportion of ethylene oxide adducts in which the number of moles of ethylene oxide present in the entire ethylene oxide adduct is 0, 1 and 2 mol (hereinafter said ratio is referred to as “Y”). ) Is preferably 0.5% by mass or less.

 0-2

 It is more preferable that it is% or less. If the cocoon content is 0.5% by mass or less,

 0-2

 A liquid detergent composition with less odor is obtained.

[0032] The component (ii) can be used alone or in combination.

 The content of component (ii) is 50 to 80% by mass, preferably 55 to 65% by mass, in the liquid detergent composition. By being the said range, the effect of this invention becomes easy to be acquired. Moreover, it becomes easy to use as a concentrated type liquid detergent composition. Moreover, when the content of component (ii) is 50% by mass or more, preferably 55% by mass or more, a concentrated liquid detergent composition containing a high concentration of surfactant can be obtained. Further, the effectiveness (commercial value) as a concentrated liquid cleaning composition is increased. On the other hand, when the content is 80% by mass or less, preferably 65% by mass or less, an increase in the viscosity of the liquid detergent composition at a low temperature is suppressed.

 In the liquid detergent composition of the present invention, when the component (C) is contained, the content of the component (ii) is 50% by mass or more, preferably 55% by mass or more. (C) Adsorbability of component is improved.

 Further, in the liquid detergent composition of the present invention, when the component (D), or the component (D) and the component (i) (hereinafter these components are also referred to as flexibility-imparting components), Ii) When the content of the component is 50% by mass or more, preferably 55% by mass or more, the adsorptivity of the flexibility-imparting component to the article to be washed is improved.

[0033] <(Β) component>

In the present invention, the component (ii) is an antioxidant. By containing the component (ii), a high detergency can be easily obtained. In addition, the liquid detergent composition can contain a large amount of the component (ii) alone. Further, when the liquid detergent composition contains the component (C), the component (B) contributes to the improvement of the deodorizing effect.

 In addition, when the liquid detergent composition contains the component (D), or the component (D) and the component (E), the component (B) contributes to an improvement in flexibility.

[0034] The component (B) is not particularly limited, and an antioxidant that can be generally used in a liquid detergent composition can be used. Among them, monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxydisol are preferred because of their good detergency and liquid stability, and phenolic antioxidants. 1J; 2, 2'-methylenebis (4- Bisphenolic antioxidants such as methyl 1_t_butylphenol; Monophenolic antioxidants, polymer type antioxidants such as dl_α-tocopherolole are more preferred, Polymeric phenolic oxidations An inhibitor is more preferred.

 Of the monophenolic antioxidants, dibutylhydroxytoluene is particularly preferred. Of the polymeric phenolic antioxidants, dl-a tocopherol is particularly preferred.

 [0035] Component (B) may be used alone or in combination of two or more.

 The content of the component (B) in the liquid detergent composition is preferably 0.01 to 1% by mass, more preferably 0.02 to 0.8% by mass. By being at least the lower limit of the above range, the liquid stability of the liquid detergent composition is improved, and good detergency is easily obtained. On the other hand, when the amount is not more than the upper limit value, a sufficient effect of improving the liquid stability can be obtained, which is economically significant IJ. Further, by being in the above range, the liquid stability of the liquid detergent composition (suppression of coloration, prevention of pH reduction, aroma stabilization, etc.) is further improved.

 [0036] <(C) component>

 In the present invention, the component (C) is an antibacterial compound represented by the general formula (II) and / or the general formula (III). By containing the component (C), a deodorizing effect can be obtained. Further, in the liquid detergent composition of the present invention, a good deodorizing effect can be obtained even if the amount of the component (C) is small in the washing liquid.

Here, in the present invention, the “antibacterial compound” is a quaternary ammonium salt represented by the general formula (Π) and Z or the general formula (III), and has an action of suppressing bacterial growth. All things to do are included.

 The “laundry liquid” means, for example, a mixed liquid of a large amount of water stored in a washing machine tub and a liquid detergent composition.

 “Even if the amount of the component (C) is small” means that the concentration of the component (C) in the washing liquid is 9.9 ppm or less, preferably 1.7 to 5. Oppm. Conventionally, when using a detergent composition that promotes the “deodorizing effect”, the concentration of the antibacterial compound in the washing liquid is generally about 30 ppm.

[0037] In the general formula (II), two or more of R ^{3 to} R ⁶ are each independently an alkyl group or a hydroxyalkyl group having carbon numbers:! To 3; It is a linear or branched alkyl group or alkenyl group of ˜22.

Preferred examples of the component (C) represented by the general formula (II) include, for example, R ^{3 to} R 5 are each independently an alkyl group having 1 to 3 carbon atoms or 1 to 3 carbon atoms. An antibacterial compound wherein R ⁶ is a linear or branched alkyl group having 8 to 22 carbon atoms or a linear or branched alkenyl group having 8 to 22 carbon atoms ( C 1) (hereinafter referred to as component (C 1)); R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, R ⁵ And R ⁶ are each independently a linear or branched alkyl group having 8 to 22 carbon atoms or a linear or branched alkenyl group having 8 to 22 carbon atoms (C 2 ) (Hereinafter referred to as component (C2)).

[0038] In the component (C-1), R ^{3 to} R ⁵ are each preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. It is particularly preferred that

In the alkyl group or alkenyl group of R ⁶ , the carbon number is 8 to 22, and 10 to 22 is preferable, and 16 to 18 is more preferable. R ⁶ is more preferably a linear alkyl group, preferably a linear or branched alkyl group.

[0039] In the component (C-2), R ³ and R ⁴ are each preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. In It is particularly preferable.

In the alkyl group or alkenyl group of R ⁵ and R ⁶ , the number of carbon atoms is 8 to 22, and 8 to 12 is preferable, and 8 to 10 is more preferable. R ⁵ and R ⁶ are each preferably a linear or branched alkyl group, more preferably a linear alkyl group, and both are linear. Particularly preferred is an alkyl group.

In the general formula (III), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ⁹ is a straight chain having 8 to 22 carbon atoms. Alternatively, it is a branched alkyl group or alkenyl group, and R ^{1 ()} is an alkylene group having 1 to 3 carbon atoms. In the component (C) represented by the general formula (III) (hereinafter referred to as the component (C-3)), R ⁷ and R ⁸ are each preferably an alkyl group having 1 to 3 carbon atoms. More preferably, each of them is more preferably a methyl group.

In the alkyl group or alkenyl group of R ⁹ , the carbon number is 8 to 22, and 10 to 18 is preferable, and 12 to 14 is more preferable. R ⁹ is more preferably a linear alkyl group, preferably a linear or branched alkyl group.

R ^1Q is an alkylene group having 1 to 3 carbon atoms, and is preferably a methylene group.

[0041] X- is a halogen ion or an alkyl sulfate ion.

 Examples of X constituting the halogen ion include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

 X having an alkyl sulfate ion is preferably one having an alkyl group having 1 to 3 carbon atoms.

 Of these, halogen ions are preferred.

[0042] Specific examples of the preferred component (C) include salt and alkyl (preferably having 16 to 1 carbon atoms).

8) Ingredients (C-1) such as trimethylammonium (for example, trade name “ARCARD T-800”, manufactured by Lionaxo, etc.); (C-2) component such as 210 ”, manufactured by Lion Akuzo, etc .; (C-3) component such as benzanoreconium chloride (eg, product name“ ARCARD CB ”, manufactured by Lion Akuzo, etc.) wear.

 [0043] The component (C) can be used alone or in combination.

 The content of component (C) in the liquid detergent composition is preferably from 0.:! To 3% by mass, and more preferably from 0.5 to: 1.5% by mass. The deodorizing effect is improved by being above the lower limit of the above range. On the other hand, by being below the upper limit, transfer and recontamination of the object to be washed are suppressed. In addition, the liquid stability of the liquid detergent composition (inhibition of coloring, the effect of preventing viscosity reduction, aroma stabilization, etc.) is further improved. Furthermore, it becomes economically advantageous.

 [0044] The liquid detergent composition of the present invention (when the component (C) is used in combination) is excellent in the deodorizing effect.

 The reason for this is not clear, but the liquid detergent composition of the present invention is likely to contain a large amount of component (A), so that it is concentrated in the micelle of component (A) that is rich in less free water (comparison). (C) component is considered to be incorporated in (lowly oriented). Therefore, it is estimated that the component (C) is highly adsorbed quickly and effectively in the initial stage of the cleaning process, so that the deodorizing effect is excellent.

 [0045] Ku (D) component>

 In the present invention, the component (D) is a compound represented by the general formula (IV). By containing the component (D 1), a flexibility imparting effect can be obtained. Further, in the liquid detergent composition of the present invention, a good flexibility-imparting effect can be obtained even if the amount of the component (D) is small in the washing liquid.

 Here, the washing liquid means, for example, a mixed liquid of a large amount of water stored in the washing machine tub and a liquid detergent composition.

 “Even if the component (D) is in a small amount” means that the concentration of the component (D) in the washing liquid is 16.7 ppm or less, preferably 1.7 to:! Oppm.

In the general formula (IV), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a linear chain having 1 to 4 carbon atoms. Or a branched-chain hydroxyalkyl group. Preferably, both R ¹¹ and R ¹² are linear alkyl groups having 1 to 4 carbon atoms, and it is preferable that both R ¹¹ and R ¹² are methyl groups.

R ¹³ is a linear or branched alkylene group having 1 to 4 carbon atoms, preferably a propylene group. [0047] Y is a group represented by the general formula (V) and / or the general formula (VI). In the general formula (V), R ¹⁴ is a linear or branched alkyl group having 7 to 23 carbon atoms, or a linear or branched alkenyl group having 7 to 23 carbon atoms. The carbon number of the alkyl group is preferably 7-21. The carbon number of the alkenyl group is preferably 7-21.

In the general formula (VI), R ¹⁵ is the same as R ¹⁴ described above.

[0048] Specific examples of the compound represented by the general formula (IV) include force amidopropyl dimethylamine, force amidopropyl dimethylamine, amidopropyl dimethylamine laurate, amidopropyl dimethylamine myristate, Long-chain aliphatic amidoalkyl tertiary amines such as amine, amidopropyl dimethylaminoamine palmitate, amidopropyl dimethylamine stearate, amidopropyl dimethylenomine behenate, amidopropyl dimethylamine oleate, etc .; palmitate Aliphatic ester alkyl tertiary amines such as ester propyldimethylamine and stearate ester propyldimethylamine or their salts; amidopropyl diethanolamine palmitate, amidopropyl diethanolamine stearate, etc. It is below.

 Among them, long-chain aliphatic amidoalkyl tertiary amines or salts thereof are more preferable. Amidopropyldimethylamine caprylate, Amidopropyldimethylamine purinate, Amidopropyldimethylamine laurate, Amidopropyl myristate Particularly preferred are dimethylamine, amidopropyldimethylamine palmitate, amidopropyldimethylamine stearate, amidopropyldimethylamine behenate, amidopropyldimethylamine oleate or salts thereof.

 [0049] "Long-chain aliphatic amidoalkyl tertiary amine" in the above examples includes, for example, fatty acid or fatty acid lower alkyl ester or fatty acid derivatives such as animal and vegetable oils, and dialkyl (or alkanol) aminoalkylamine. It is obtained by condensing with the amine and then distilling off the unreacted dialkyl or alkylenol) aminoalkylamine under reduced pressure or nitrogen blowing.

On the other hand, “aliphatic ester alkyl tertiary amine” means, for example, fatty acid or fatty acid lower alkyl ester or fatty acid derivatives such as animal and vegetable oils and fats and dialkylaminoamines. It is obtained by an esterification reaction that condenses with alcohol.

 Here, specific examples of fatty acids or fatty acid derivatives include strength prillic acid, strength purine acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, L strength acid, and 12-hydroxystearic acid. Acids, coconut oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oil or animal oil fatty acid, etc. Examples include methyl ester, ethyl ester, glyceride and the like. Among these, strong prillic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like are particularly preferable.

 These fatty acids or fatty acid derivatives may be used alone or in combination of two or more.

 [0050] Specific examples of “dialkyl or allyol) aminoalkylamine” include dimethylaminopropylamine, dimethylaminoethylamine, jetylaminopropylamine, and dimethylaminoethylamine. Among them, dimethylaminopropylamine is particularly preferable.

 Examples of the “dialkylamino alcohol” include dimethylaminoethanol, jetamino alcohol and the like. As the jetylamino alcohol, jetylaminoethanol is preferred. Of these, dimethylaminoethanol is particularly preferred.

[0051] In the production of the long-chain aliphatic amidoalkyl tertiary amine, the amount of dialkyl or alkananol) aminoalkylamine used is from 0.9 to 2.0 times mol of the fatty acid or derivative thereof. Preferred 1. 0 to: 1. 5 times mole is particularly preferred.

 The reaction temperature is usually 100 to 220 ° C, preferably 150 to 200 ° C. If the reaction temperature is less than 100 ° C, the reaction will be too slow, and if it exceeds 220 ° C, the resulting tertiary amine may become markedly colored.

[0052] The amount of dialalkylamino alcohol used in the esterification reaction in the production of the aliphatic ester alkyl tertiary amine is from 0.:! To 5.0 times monoreca S, preferably 0, compared to the fatty acid or derivative thereof. 3 to 3.0 times monolith power is preferable to S, 0.9 to 2.0 times monoreka is more preferable 1.0 to 1.5: 5 times mole is particularly preferable.

 The reaction temperature is usually 100 to 220 ° C, preferably 120 to 180 ° C. If the reaction temperature and force are less than S100 ° C, the reaction will be too slow, and if it exceeds 220 ° C, the resulting tertiary amine may become prominently colored.

[0053] The production conditions of the long-chain aliphatic amidoalkyl tertiary amine and aliphatic ester alkyl tertiary amine are the same except for the above, and the pressure during the reaction may be normal pressure or reduced pressure. It is also possible to introduce the active gas by blowing it.

 When fatty acids are used, acid catalysts such as sulfuric acid and p-toluenesulfonic acid, and when fatty acid derivatives are used, alkaline catalysts such as sodium methylate, caustic potash and caustic soda can be used for a short time at a low reaction temperature. The reaction can proceed efficiently.

 In addition, when the resulting tertiary amine is a long chain amine having a high melting point, it is preferable to form it into flakes or pellets after the reaction in order to improve the nodling property or ethanol. It is preferable to dissolve in an organic solvent such as

[0054] The component (D) can be used alone or in combination of two or more.

 The content of component (D) is preferably from 0.:! To 5% by mass, more preferably from 0.5 to 3% by mass, in the liquid detergent composition. By being at least the lower limit of the above range, the effect of imparting flexibility is improved. On the other hand, if it is less than the upper limit, recontamination and the like for the object to be washed can be suppressed. In addition, the liquid stability of the liquid detergent composition (suppression of coloring, prevention of viscosity reduction, fragrance stabilization, etc.) is further improved. Furthermore, it becomes economically advantageous.

[0055] <(E) component>

 In the present invention, the component (E) is a polyether-modified silicone (E) represented by the general formula (VII) and Z or the general formula (VIII). By containing the component (E) in addition to the component (D), the flexibility imparting effect is further improved.

[0056] In the general formulas (VII) and (VIII), R is a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, or a hydrogen atom, R may be the same or different.

R ¹⁶ is a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms. Yes, each R may be the same or different.

 Z represents a polyoxyalkylene group. In the polyoxyalkylene group, the alkylene group preferably has 2 to 5 carbon atoms, and the repeating number thereof is 1 to 50.

[0057] 1 is an integer of 0 to 50, and there may be no structural unit to which 1 is attached, but preferably 1 is 0 to

 10.

 m is 10 to 10,000, n is:! to 1000, and represents an integer of m> n.

 The order of the structural units to which 1, m and n are attached may be different.

 Here, “the order of each structural unit with 1, m, n may be different,” means _Si〇 (H) (CH)-(the structural unit with 1),- SiO (CH)-(the structural unit with m),

 3 3 2

-SiO (CH) (R ¹⁶ -Z-0-R)-(Structural unit with n) arranged in any order

 Three

 It shows that it is placed.

 The component (E) may be a block copolymer or a random copolymer. For example, 1J may be arranged in the order of a structural unit marked with 1, a structural unit marked with m, a structural unit marked with n, or a structural unit marked with 1, n They may be arranged in the form of blocks in the order of the structural unit marked with and the structural unit marked with m. In addition, a structural unit marked with 1, a structural unit marked with n, a structural unit marked with m, a structural unit marked with 1, a structural unit marked with m, a construction marked with n Like a unit, each structural unit may be arranged at random.

 A represents an integer of 5 to 10000, and b represents an integer of 2 to 10000.

 [0058] Among the polyether-modified silicones represented by the general formula (VII) and the general formula (VIII), alkyl (1 to 3 carbon atoms) siloxane and polyoxyalkylene (alkylene group having 2 to 2 carbon atoms). A copolymer with 5) is preferred. Furthermore, a copolymer of dimethylsiloxane and polyoxyalkylene (such as polyoxyethylene, polyoxypropylene, random or block copolymer of ethylene oxide and propylene oxide) is particularly preferred.

[0059] The method for producing the polyether-modified silicone represented by the general formula (VII) generally includes an organohydrodiene polysiloxane having a Si_H group and a carbon-carbon double carbon such as polyoxyalkylene ether. It can be produced by addition reaction with a polyoxyalkylene alkyl ether having a bond at the terminal. The method for producing the polysiloxane polyoxyalkylene block copolymer represented by the general formula (VIII) includes a polyoxyalkylene compound having a reactive terminal group and a terminal group that reacts with the reactive terminal group of the compound. It can be produced by reacting it with dihydrocarbylsiloxane.

 [0060] Specific examples of the component (E) include CF1188H V, SH3748, SH3749, SH3772M, SH3775M, SF8410, SH8700, BY22 — 008, BY22 — 012, SILWET L — manufactured by Toray Dow Cowing Silicone Co. 7001, SILWET L- 7002, SILWET L-7602, SILWET L— 7604, SILWET FZ— 2104, SILWET FZ— 2120, SILWET FZ— 2161, SILWET FZ— 2162, SILWET FZ— 2164, SILWE T FZ-2171, ABN SILWET FZ— Fl— 009— 01, ABN SILWET FZ— F 1— 009— 02, ABN SILWET FZ— Fl— 009— 03, ABN SILWET FZ_F 1— 009— 05, ABN SILWET FZ— Fl— 009— 09, ABN SILWET FZ_F 1— 009— 11, ABN SILWET FZ— Fl— 009— 13, ABN SILWET FZ— F 1 009— 54, ABN SILWET FZ— 2222; X—20—80 10B, KF352A, manufactured by Shin-Etsu Chemical Co., Ltd. KF6008, KF615A, KF6012, KF6016, KF6017; TSF4450, TSF4452, TSF4445 (above, trade names) manufactured by GE Toshiba Silicone Co., Ltd.

 The above polyether-modified silicone oils may be used alone or in combination of two or more.

 [0061] The component (E) using the polyether-modified silicone oil can be used singly or in combination of two or more.

 The content of the component (E) in the liquid detergent composition is preferably from 0.:! To 5% by mass, and more preferably from 0.5 to 3% by mass. By being at least the lower limit of the above range, the effect of imparting flexibility is further improved. On the other hand, if the amount is less than the upper limit, recontamination and the like are suppressed if the dye is transferred to the object to be washed. In addition, the liquid stability of the liquid detergent composition (inhibition of coloring, the effect of preventing viscosity reduction, aroma stabilization, etc.) is further improved.

By containing the component (E), it is possible to obtain a slipperiness-imparting effect on the item to be washed (in particular, clothing made of a polyester material in particular). The slipperiness-imparting effect is an amino modification. It is better than other silicones such as silicone. In addition, it is excellent in stability over time without causing yellowing (coloring) of the liquid detergent composition, which is a problem particularly when amino-modified silicone is used.

 [0062] The liquid detergent composition of the present invention (when the component (D) is used in combination) is excellent in the effect of imparting flexibility. The reason for this is not clear, but in the liquid detergent composition of the present invention, the (A) component in a large amount of free water is contained in the micelle of the concentrated (A) component with a small amount of free water ( (D) component is taken into (relatively weak, orientation). For this reason, it is presumed that component (D) is highly adsorbed on the object to be cleaned quickly and effectively in the initial stage of the cleaning process.

 Moreover, in the liquid detergent composition of the present invention, the flexibility imparting effect is further improved by further containing the component (E). The reason for this is not clear, but the (D) component and the (E) component form a complex, so that the (D) component is different from the washing object related to the washing process. This is presumed to have resulted in high adsorptivity.

[0063] Further, when the liquid cleaning composition of the present invention is combined with the component (C) and the component (D), both the deodorizing effect and the flexibility-imparting effect are excellent. For this reason, it is not certain, but it is presumed that the component (C) and the component (D) can be dissolved stably in the liquid detergent composition.

[0064] <Optional component>

 In addition to the components (A) to (E), other optional components can be blended in the liquid detergent composition of the present invention as necessary.

Specific examples of hydrotropes include alcohols such as glycol solvents such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol. Among these, polyethylene glycol having a weight average molecular weight of 400 to 5000 (preferably about 1000) is preferred because the liquid stability is further improved. Further, ethanol is also preferable because liquid stability and antiseptic power are further improved. Hydrotropes can be used alone or in combination. The content of the hydrotrope agent is preferably 0.5 to 10% by mass in the liquid detergent composition. [0065] Further, the liquid detergent composition of the present invention may contain one or more selected from benzenesulfonic acid, alkylbenzenesulfonic acid, benzenesulfonate, and alkylbenzenesulfonate strength.

 In the alkylbenzene sulfonic acid and the alkylbenzene sulfonate, the number of alkynole groups (substituents) is preferably 1 to 3, more preferably 1 to 2. The alkyl group preferably has 1 to 3 carbon atoms, more preferably a methyl group or an isopropyl group, and still more preferably a methyl group.

 Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; ammonium salt; alkanolamines such as monoethanolamine salt, diethanolamine salt and triethanolamine salt Examples include salt. Of these, sodium salt, monoethalamine salt and diethanolamine salt are preferable.

 Of these, preferred are compounds represented by the following general formula (IX).

[0066] [Chemical 6]

[In the formula, X ", Y" and Z "are each independently a hydrogen atom, C Η (η" is an integer of! ~ 3 η "2η" + 1

 is there. ) Or (CH) CH; M is a hydrogen atom, an alkali metal atom, an alkaline earth

 3 2

 Indicates a metal atom, NH + or an aranolamine. ]

 Four

 In the general formula (IX), X ", Y", and Ζ "each independently represent a hydrogen atom, C Η (η"

 η "2η" + 1 is an integer from 1 to 3. ) Or (CH) CH, preferably CH, (CH) CH

 More preferably, it is CH.

 Three

Μ is a hydrogen atom; an alkali metal atom such as sodium or potassium; an alkaline earth metal atom such as magnesium or calcium; ΝΗ +; or monoethanolamine, diethanolamine And alcohols such as triethanolamine, preferably sodium, monoethanolamine and diethanolamine.

 Specific examples of compounds include benzenesulfonic acid, sodium benzenesulfonate, potassium benzenesulfonate, ammonium benzenesulfonate, magnesium benzenesulfonate, calcium benzenesulfonate, monoethanolamine benzenesulfonate , Benzenesulfonic acid diethanolamine salt, benzenesulfonic acid triethanolamine salt, p-toluenesulfonic acid, p-toluenesulfonic acid sodium salt, p-toluenesulfonic acid potassium salt, p-toluenesulfonic acid ammonium salt, p-toluenesulfone Magnesium salt, p-toluenesulfonic acid calcium salt, p-toluenesulfonic acid monoethanolamine salt, p-toluenesulfonic acid diethanolamine salt, p_tonoleenesulfonic acid triethanolate Luamine salt, o- or m- or p-xylene sulfonic acid, o _ or m- or p-xylene sulfonic acid sodium salt, o _ or m- or p xylene sulphonic acid potassium salt, o or m or p Phosphoric acid ammonium salt, o or m- or p-xylene sulfonic acid magnesium salt, o or m-or p-xylene sulfonic acid calcium salt, o- or m-or p-xylene sulfonic acid monoethanolamine salt, o or m —Or p-xylenesulfonic acid ethanolamine salt, o or m—or p-xylenesulfonic acid triethanolamine salt, cumenesulfonic acid, cumenesulfonic acid sodium salt, cumenesulfonic acid potassium salt, cumenesulfonic acid ammonium salt, cumenesulfone Magnesium acid salt, cumens Acid calcium salt, particulate members acid monoethanolamine salt, particulate members acid diethanolamine salt, particulate members acid triethanolamine salt and the like. Of these, p-toluenesulfonic acid, m-xylenesulfonic acid, cumenesulfonic acid or monoethanolamine salts thereof are preferred. P-toluenesulfonic acid, cumenesulfonic acid and m-xylenesulfonic acid are more preferred.

 These can be used alone or in combination.

These contents are preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass in the liquid detergent composition. Within this range, the formation of a film formed when the liquid detergent composition gels on the liquid surface of the liquid detergent composition. The control effect is improved.

 [0069] In addition, an alkaline agent can be blended in the liquid detergent composition of the present invention.

 Examples of the alkali agent include alkanolamine, and monoethanolamine, diethanolamine, and triethanolamine are preferable.

 Alkaline agents can be used alone or in combination of two or more.

 The content of these alkali agents is preferably 0.5 to 15% by mass in the liquid detergent composition.

[0070] Further, the liquid detergent composition according to the present invention comprises 0 to 2% by mass of a recontamination inhibitor such as polybulur pyrrolidone or carboxymethylcellulose for the purpose of preventing recontamination; a lipase or cellulase for the purpose of improving detergency. Enzymes such as amylase and protease 0 ~ :! / ₀ ; 0-3 mass% of calcium salts such as boric acid, borax, formic acid or salts thereof, calcium chloride, calcium sulfate for the purpose of enzyme stabilization; dimethyl silicone, amino modified silicone, etc. for the purpose of improving the texture acid for the purpose of coloring the liquid detergent composition; silicone 0-5 mass _^0/0; fluorescent whitening agent distyryl ruby phenylalanine type such purpose on ShirodoMuko white clothing 0 :! wt% Add pigments such as dyes to 0.0001 to 0.001% by mass; add 0.001 to 1% by mass of preservatives such as sodium benzoate and caisson CG (trade name) for the purpose of liquid stability and antiseptic properties. be able to.

 Examples of the fragrance for aroma include a fragrance composition described in JP-A-2002-146399, a fragrance composition containing a solvent and a stabilizer, and the like in the liquid detergent composition of the present invention. 01 to 1% by mass can be blended.

 [0071] Further, in the liquid detergent composition according to the present invention, the content of water is preferably 15 to 45 mass% in the liquid detergent composition, more preferably 30 to 40 mass%. It is. Within the above range, a stable liquid detergent composition as a “concentrated type” can be easily obtained.

 [0072] Further, examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide and ammonia, among others. From the viewpoint of the effect of pH buffering, organic acids are preferred.

Specific examples of the organic acid include succinic acid, maleic acid, fumaric acid, and salts thereof. Polyhydric carboxylic acids; hydroxycarboxylic acids such as citrate, malic acid, glycolic acid, p-hydroxybenzoic acid or salts thereof are exemplified, and among them, citrate or a salt thereof is particularly preferable.

 The pH adjuster can be used alone or in combination.

The pH adjuster is appropriately added in an amount that adjusts the pH of the liquid detergent composition at 25 ° C to 5-8. It specifically content of the pH adjusting agent, for example, in a liquid detergent composition, it forces S preferably 0.05 to 3 mass _^0/0, a 0.:!～ 1.5 wt% Is more preferable. By being above the lower limit of the above range, it becomes easy to keep the pH constant. On the other hand, by being below the upper limit value, a pH adjustment effect for adjusting the pH to 5 to 8 can be sufficiently obtained, which is advantageous economically.

 [0073] The pH of the liquid detergent composition of the present invention is 5 to 8, preferably 6 to 7, at 25 ° C.

 In the present invention, it contains the component (Β) and has a pH of 5 to 8, and in particular, the component (さ れ る) contained in a large amount in the liquid detergent composition can be dissolved stably, Since the liquid stability of the liquid detergent composition (suppression of coloring, the effect of preventing pH reduction, aroma stabilization, etc.) is improved, it is estimated that a high detergency can be obtained.

 For adjusting the pH, for example, a certain amount of an organic acid (preferably citrate or a salt thereof) is added, and an inorganic acid (preferably hydrochloric acid or sulfuric acid) or sodium hydroxide or potassium hydroxide is added for fine adjustment of pH. Furthermore, it can control by adding.

 The pH of the liquid detergent composition (temperature adjusted to 25 ° C.) is a value measured by a pH meter (product name: HM-30G, manufactured by Toa D-keke Co., Ltd.).

[0074] The liquid detergent composition of the present invention can be produced with water as a solvent, based on a conventional method.

The usage method is a normal usage method, that is, a method in which the liquid detergent composition of the present invention (product of the present invention) is poured into water together with the laundry during washing, and the product of the present invention is directly applied to mud and sebum soil. And a method of immersing clothing by dissolving the product of the present invention in water in advance. Also preferred is a method in which the product of the present invention is applied to the laundry and allowed to stand as appropriate, followed by normal washing using a normal washing solution. At that time, the amount of the product of the present invention is the same as that of the conventional liquid. The amount can be reduced to substantially half or less than the amount of the cleaning composition used.

[0075] According to the present invention, it is possible to provide a liquid detergent composition containing a large amount of a single surfactant alone, having excellent solubility in water and high detergency.

 Furthermore, according to the present invention, it is possible to provide a liquid detergent composition with less surfactant raw material odor.

 [0076] The liquid detergent composition of the present invention can exhibit a high detergency even within a limited washing time such as using a washing machine or washing.

 In addition, the liquid detergent composition of the present invention can provide a high detergency with a small amount of use.

[0077] Further, according to the present invention, by using the antibacterial compound (C), a liquid detergent composition containing a large amount of a single surfactant and having an excellent deodorizing effect is provided. be able to.

 According to this liquid detergent composition, a liquid detergent composition having both “detergency” and “deodorizing effect” can be provided.

 Moreover, according to this liquid cleaning composition, a deodorizing effect is also acquired.

 Further, this liquid detergent composition can provide an excellent deodorizing effect even if the amount of the antibacterial compound contained in the washing liquid is smaller than before. Therefore, it is economically advantageous.

[0078] Further, according to the present invention, by using the polyether-modified silicone (E) in addition to the compound (D) represented by the general formula (IV) or the compound (D), It is possible to provide a liquid detergent composition containing a large amount of a single surfactant alone and having an excellent flexibility imparting effect.

 According to this liquid detergent composition, a 2inl type liquid detergent composition having both “detergency” and “flexibility imparting effect” can be provided.

 In addition, this liquid detergent composition can provide an excellent softening effect even if the amount of the softening component contained in the washing liquid is smaller than the conventional amount. Therefore, it is economically advantageous.

[0079] Further, according to the present invention, by using the component (C) and the component (D), a single surfactant is contained in a large amount, excellent in solubility in water, and high. A liquid detergent composition that has a detergency and excellent flexibility and deodorant effect. Can provide power S.

 [0080] The liquid detergent composition of the present invention has good fluidity even when the surfactant concentration is high, and also has good liquid stability (low temperature to high temperature storage stability).

 In addition, the liquid detergent composition of the present invention can contain a large amount of a single surfactant alone, even if the solubilizer (hydrotrope) is small. Since a small amount of the agent is sufficient, it is economically advantageous because the environmental load is small.

 In addition, the liquid detergent composition of the present invention is less susceptible to transfer between objects to be washed and yellowing of objects to be washed.

 In addition, according to the liquid detergent composition of the present invention, a compact container having a container size in which the liquid detergent composition is accommodated is possible.

 The liquid detergent composition of the present invention is particularly suitable as a so-called “concentrated type” liquid detergent composition for clothing.

 Example

 [0081] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In Examples, “%” represents “% by mass” unless otherwise specified.

 Examples:! -11, Examples 31-39, Example 43, Examples 51-59, Example 63, and Examples 71-76 are examples.

 Examples 21 to 26, Example 41, Example 42, Examples 44 to 46, Example 61, Example 62, Examples 64 to 66, and Example 77 are comparative examples.

<Manufacture of liquid detergent composition>

 Liquid detergent compositions having the compositions shown in Table 1 to Table 7 were produced as follows according to a conventional method.

First, the component (A) was placed in a cylindrical glass bottle (diameter 50 mm, height 100 mm) containing a 2 cm stir bar. Next, a mixed solution of the component (B) and the optional component was added, and the stirrer was stirred at 400 rpm. Next, the component (C), the component (D), and the component (E) were blended according to the composition shown in the table. After that, add purified water so that the total amount (the total amount is 100 parts by mass) is 95 parts by mass, mix with stirring, adjust the pH, add the remaining purified water, and add the liquid detergent. A composition was prepared.

 The pH was finely adjusted by appropriately adding a pH adjuster (sodium hydroxide or sulfuric acid) so that the pH at 25 ° C. of the liquid detergent composition was the pH shown in the table.

 However, the unit of the blending amount in the table is% by mass, and represents a pure equivalent amount. In addition, the amount of water was adjusted so that the total amount was 100% by mass. Below, the narrow ratio of component (A) and Y

 0-2 The measurement method and the components shown in the table will be described.

[0083] <Narrow ratio of component (A) and method for measuring Y>

 0-2

 The distribution of ethylene oxide adducts with different numbers of moles of ethylene oxide was measured under the following measurement conditions. And the narrow ratio (mass%) of (A) component was computed based on the said Numerical formula (S). In addition, the total proportion of ethylene oxide adducts in which the number of moles of ethylene oxide present in the entire ethylene oxide-added casing is 0, 1, and 2 moles is determined as Y (mass%) of component (A) It was.

 0-2

 [Measurement conditions for the distribution of ethylene oxide adducts by HPLC]

 Equipment: LC-6A (manufactured by Shimadzu Corporation)

 Detector: SPD—10A

 Measurement wavelength: 220nm

 Column: Zorbax C8 (Du Pont)

 Mobile phase: Acetonitrile / water = 60/40 (volume ratio)

 Flow rate: lmL, min

 Temperature: 20 ° C

[0084] <Description of components shown in the table>.

 • (A) component

A- 1: CH CO (OC H ) 〇_CH, narrow ratio 65 mass _^0/0, Y 0 mass _^0/0; synthetic

 11 23 2 4 15 3 0-2

 P

PPo

 A- 2: Mass ratio of C H CO (〇C H) 〇CH and C H CO (〇C H) 〇CH

 11 23 2 4 15 3 13 27 2 4 15 3

 8/2 mixture, narrow ratio 65% by mass, 丫 0% by mass; synthetic product.

 0-2

 A-3 (Comparative product): C H CO (OC H) 〇CH, Narrow rate 65% by mass, Y 0 quality

17 33 2 4 15 3 0-2 Amount%; synthetic product. A- 4 (comparative product): CHO (CHO) H, narrow ratio of 30 mass _^0/0, Y 2 · 0 Weight ^_0/0

 12 25 2 4 15 0- 2

 A synthetic product.

 A-5: A mixture of 85 g of 0-1 and 0.02 g of dibutylhydroxytoluene in purified water to make a total amount of 100 g.

A-6: CH CO (OC H) 〇_CH, narrow ratio 37 mass _^0/0, Y 0. 1 mass ^_0/0;

 11 23 2 4 15 3 0- 2

 a Naruro.

A_ 7 (comparative product): CH CO (OC H) 〇_CH, narrow ratio of 25 mass _^0/0, Y 1. 5

 11 23 2 4 15 3 0-2 mass%; synthetic product.

 [0085] However, A_l and A_3 (comparative products) are synthetic products manufactured according to the synthesis method described in JP-A-2000-144179 (A_1 is described in JP-A-2000-144179). Corresponding to sample D; similarly, A-3 (comparative product) corresponds to sample Nore F described in the publication).

 A-2 is the same as the synthesis method of A-1, except that in the synthesis method of A-1, 280 g of methinoreesterol laurate and 70 g of myristic acid methyl ester were used, respectively, and 1052 g of ethylene oxide was introduced. Produced by the method.

[0086] A-4 (comparative product) was synthesized as follows.

 186 g of lauryl alcohol and 2.0 g of 30 mass ° ^ & ◯ ^ 1 aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen.

 Next, after dehydrating for 30 minutes at a temperature of 100 ° C and a pressure of 2. OkPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 660 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid while adjusting the feed rate so that the reaction temperature did not exceed 180 ° C using a blowing tube.

 After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C and a pressure of 6. OkPa or less for 10 minutes. Next, after cooling the temperature to 100 ° C or lower, neutralize by adding ρ-toluenesulfonic acid (70% by weight aqueous solution) so that the pH of the 1% by weight aqueous solution of the reaction solution becomes about 7. A_4 (Comparative product) was obtained.

[0087] Synthesis of A-6 was performed as follows. Alumina hydroxide with a chemical composition of 2.5 MgO -Al O · η

 2 3 2

 Wagaku Kogyo Co., Ltd., trade name: Kiyo Ward 300) 25g was calcined at 700 ° C for 3 hours under a nitrogen atmosphere to obtain 14g of calcined alumina / magnesium hydroxide. Calcined alumina hydroxide Magnesium (unmodified) catalyst 1.2 g, 0.4 g of 5% by weight potassium hydroxide methanol solution, and 350 g of methyl laurate were charged into a 4 liter autoclave, and the catalyst was reformed in the autoclave. It was. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and 1079 g of ethylene oxide was introduced while the temperature was maintained at 180 ° C. and the pressure was maintained at 3 atm, and the reaction was carried out with stirring.

 The average number of moles of ethylene oxide added to the resulting polyoxyethylene methyl ether of lauric acid was 15, and the narrow ratio was 37% by mass. Further, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added respectively, and the catalyst was filtered off to obtain A_6.

 The narrow ratio is calculated by measuring the distribution of ethylene oxide adducts with different numbers of moles of ethylene oxide in the resulting polyoxyethylene methyl ether of lauric acid.

 [0088] A-7 (comparative product) is a synthetic product produced using a catalyst produced according to Example 1 described in JP-A-4 279552 (sample A1 described in JP-A-5-222396). Corresponding to the above).

 [0089] * Component (B)

B—1: Dibutylhydroxytoluene, manufactured by Degussa, trade name “K—N × X”. B-2: dl- _α— Tocopheronore, manufactured by Junsei Chemical Co., Ltd., trade name “DL—a— TocopherolJ, reagent.

[0090] 'Component (C)

 C-1: Alkyl chloride (C16-C18) trimethylammonium, manufactured by Lion Akuzo, trade name “ARCARD T_800”.

 C_ 2: Didecylmethylammonium chloride, manufactured by Lionakuzo, trade name "AR CARD 21

0 ".

C—3: Benzalkonium chloride, manufactured by Lion Akzo, trade name “AR CARD CB”. [0091] * (D) component

 D- 1: C H C〇NH (CH) N (CH) (m / m '= 15 and m' = 17 in mass ratio 3 / m '2m' + 1 2 3 3 2

 7), manufactured by Toho Chemical Co., Ltd., trade name “Kachinar MPAS-R”.

 D-2: C H CONH (CH) N (CH), Amidopropyldimethylamine stearate

 17 35 2 3 3 2

 '' α Naruguchi etc

 [0092] Synthesis of D_2 was performed as follows.

 A 1-liter four-flask flask equipped with a reflux condenser was charged with 360 g of stearic acid (molecular weight 284) and heated to 80 ° C. to melt the stearic acid. After performing nitrogen substitution twice, the temperature was raised to 150 ° C., and 123 g of dimethylaminopropylamine (molecular weight 102) (mole ratio to stearic acid: 0.95) was added dropwise over 1 hour.

 Next, after maintaining at 150 to 160 ° C. for 1 hour, the temperature was raised to 185 ° C. over 1 hour, and 45 g of dimethylaminopropinoleamine was added dropwise over 1 hour.

 After completion of the dropwise addition, the temperature was maintained at 185 to 190 ° C. and aged for 7 hours to distill off by-product water out of the system. Further, the pressure was reduced (4. OkPa) while maintaining at 170 to 190 ° C., and the mixture was allowed to stand for 1 hour to distill off unreacted dimethylaminopropylamine to obtain C-2.

 The conversion rate of stearic acid calculated from the acid value was 99.6%.

[0093] * (E) component

 E-1: Polyether-modified silicone, manufactured by Toray Dow Corning Silicone Co., Ltd., trade name “SH3775M”.

E—2: Polyether-modified silicone, in the general formula (VII), R = H, R ¹⁶ = CH

 3 6

, Z = (OC H), 1 = 0, m = 210, n = 9; synthetic product.

 2 4 9

 [0094] The synthesis of E_2 was performed as follows.

Into a 1-liter four-flask equipped with a stirrer, condenser, thermometer and nitrogen inlet, 100 g of organohydropolysiloxane represented by the following formula (VII-1), 50 g of isopropyl alcohol, and the following formula (VII— 2) Polyoxyalkylene compound llg represented by 2), 0.2g of catalyst for addition reaction, and 0.3g of 2 mass% sodium acetate in isopropyl alcohol were added, and these were added at 90 ° C under a nitrogen atmosphere. For 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain E_2. [0095] [Chemical 7]

[In the formula (VII-1), α = 210, = 9. ]

[0096] [Chemical 8]

CH ₂ = CHCH ₂ 0— (C ₂ H ₄ O) ₁₀ — CH ₃ … (VI 1-2)

[0097] 'Optional ingredients

 Ethanol: Product name “95vol% synthetic ethanol” manufactured by NEDO.

 PEG # 1000: Polyethylene glycol (weight average molecular weight 1000), manufactured by NOF Corporation, trade name “PEG # 1000”.

 p-Toluenesulfonic acid: manufactured by Kyowa Hakko Kogyo Co., Ltd.

 Cenaic acid trisodium dihydrate: Made by Miles (USA), trade name “Taenoic acid soda”.

 Sodium benzoate: Toagosei Co., Ltd., trade name “Sodium benzoate”.

 Perfume composition: The perfume composition described in Tables 11 to 18 of JP-A-2002-146399. Dye: Product name “Green 201”, manufactured by Hatake Kasei Co., Ltd.

 Caisson CG: Made by Rohm 'and' Haas.

 Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.

 Sulfuric acid: Toho Zinc Co., Ltd.

[0098] <Evaluation>

 The obtained liquid detergent composition was evaluated by the following methods and evaluation criteria, and the results are also shown in Tables 1-7.

[0099] <Evaluation of solubility in water>

In an lOOmL beaker containing a 2 cm stir bar, 80 mL of ion-exchanged water adjusted to 15 ° C. was added, and the stir bar was stirred at 400 rpm. In each lOOmL beaker, the liquid of each example 2 g of the detergent composition was added, and the dissolution state after 10 minutes was visually observed, and the solubility in water was evaluated based on the following criteria. The results are shown in Tables 1-7.

 (Double-circle): It melt | dissolved uniformly.

 ◯: Some insoluble liquid detergent composition was present.

 (Triangle | delta): It gelatinized and it was in the shape of lumps.

[0100] <Evaluation of cleaning power>

 (Cleaning method)

 No. 100 cotton plain weave fabric was cut into 10cm squares, and these were fixed to the surface of a small container with a hemispherical surface with a radius of about 3cm, and sebum dirt was adhered by rubbing it against the hands and face. .

 Next, the cotton plain woven fabric with sebum soil adhered was cut into four equal parts to obtain a sebum soiled fabric.

 Next, use Terg_〇_tometer as a cleaning tester, 10 pieces of the above-mentioned sebum-stained cloth, Sebum cloth and cleaning knitted cloth, the liquid detergent composition of each example, and water into the cleaning tester. The sample was washed at 120 i "pm and 15 ° C for 10 minutes according to the bath ratio of 30 times.

 The concentration of the cleaning liquid was adjusted so that the liquid cleaning composition in each example had a ratio of 10 mL to 30 L of the cleaning liquid (liquid cleaning composition and water). However, the liquid detergent composition in each example was stored at 50 ° C for 1 month.

 Then, it moved to the two tank type washing machine (Mitsubishi Electric Corp. make, product number: CW-C30A1-HI), and dehydrated for 1 minute. Thereafter, it was rinsed with running water for 1 minute, dehydrated for 1 minute, and then air-dried.

[0101] (Evaluation method of detergency)

 The reflectance of the sebum-stained cloth after the washing treatment was measured with a color difference meter (trade name: SE200 type, manufactured by Nippon Denshoku Co., Ltd.), and the washing rate (%) was calculated according to the following formula.

 Cleaning rate (Q / o) = (KZS of sebum soiled cloth before cleaning—K / S of sebum soiled cloth after cleaning) Z (K / S of sebum soiled cloth before cleaning—KZS of unsoiled cloth) X 100

 Where K / S = (l -R / 100) (2R / 100). However, R indicates reflectance (%).

The evaluation criteria were based on the cleaning rate (%) calculated by the above formula, and the cleaning power was evaluated based on the following criteria. As the cleaning rate (%), the average value of 10 sheets of sebum-stained cloth was used. So The results are shown in Tables 1-7.

 (Standard)

 A: The cleaning rate is 80% or more.

 ○: Cleaning rate is 70% or more and less than 80%.

 Δ: Cleaning rate is less than 70%.

[0102] <Evaluation of raw material odor>

 Sensory evaluation was performed by a method of directly sniffing the liquid detergent composition of each example, and the raw material odor was evaluated according to the following evaluation criteria. The evaluation was performed by five researcher panelists, and it was determined that the raw material odor was small if ◯ and ◎. The results are shown in Tables 1-7.

 (Evaluation criteria)

 ◎: There were 0 panelists who felt a strange odor.

 〇: One or two panelists who felt a strange odor.

 Δ: 3 to 5 panelists who felt a strange odor.

[0103] <Measurement of hydrolysis rate>

 Using a liquid chromatograph mass spectrometer, the amount of fatty acid in the liquid detergent composition of each example after storage at 50 ° C for 1 month was measured, and the fatty acid was determined by hydrolysis of component (A). The mass ratio of the fatty acid and the component (A) (fatty acid / component (A)) was determined as the hydrolysis rate (mass%). The amount of fatty acid was measured under the following conditions.

 Apparatus: NANOSPACE SI-2 (manufactured by SHISEIDO).

 Detector: FINNIGEN LCQ DUO Mass Spectrometer System (Thermo Quest).

 Column: PEGASIL ○ DS (diameter 2 mm x length 150 mm) (manufactured by Senshu Science Co., Ltd.). Mobile phase: purified water / methanol = 85/15 (volume ratio).

 Flow rate: 0.1 mL / min.

 Temperature: 40 ° C.

 Injection volume: lO z Lo

Based on the obtained hydrolysis rate, it evaluated according to the evaluation criteria shown below. The evaluation is good if the hydrolysis rate is less than 0.5% by mass (that is, the liquid detergent composition is stable (A ) Component is dissolved). The results are shown in Tables 1-7.

 (Evaluation criteria)

 Good: hydrolysis rate less than 0.5% by mass.

 Slightly poor: hydrolysis rate 0.5% by mass or more and less than 1.0% by mass.

 Poor: Hydrolysis rate 1.0% by mass or more.

[0104] <Evaluation of deodorizing effect>

 Garments that are heavily soiled, such as sebum stains, will produce off-flavors and odors originating from bacteria when they are washed and dried in a humid room.

 In this evaluation, the deodorizing effect was evaluated according to the following evaluation method that models the above phenomenon (reproduced at the laboratory level).

 (Washing method)

 A semi-finished cotton towel with very accumulated dirt (reused / washed for half a year at home) and the liquid detergent composition in each case using the usage amount shown in Table 1 and a bath ratio of 15 Wash with double tank washing machine (Mitsubishi Electric Corp., part number: CW—C30A1—H) (Temperature 20 °) C, tap water 30L, washing 10 minutes, rinsing 3 minutes + dehydration 1 minute X 2 times).

[0105] (Evaluation method of deodorizing effect)

 After washing, it was dried in a constant temperature and humidity room at 25 ° C and a humidity of 90% or more for 12 hours. At that time, the “smelling smell” for each of the clothes in the almost dry stage (drying time 5 hours: during drying) and the clothes in the completely dry stage (drying time 12 hours: after drying) The sensory evaluation was performed according to the following six-level evaluation criteria. The evaluation was performed by calculating the average value of 10 expert panelists.

 (Evaluation criteria)

 0 points: Odorless.

 1 point: The smell that can finally be detected.

 2 points: Odor, which shows what odor is.

 3 points: Smell that can be easily detected.

4 points: Strong smell. 5 points: Strong smell.

 Then, based on the evaluation results based on the six evaluation criteria, the deodorizing effect was evaluated based on the following criteria. If the average score of the evaluation was less than 3.0, the deodorizing effect was judged to be good. The results are shown in Tables 3-4 and 7.

 (Standard)

 : 1. Less than 5 points.

 0: 1. 5 points or more and less than 3.0 points.

 △: 3.0 points or more and less than 4.0 points.

 X: 4.0 or higher.

Evaluation of the effect of imparting flexibility>

 Put 30L of tap water into a two-tank washing machine, put 7 sheets of commercially available T-shirts (100% cotton, manufactured by BV D) and the amount of liquid detergent composition shown in Table 1 and wash with a weak water flow. The washing operation was performed with 10 minutes for 1 minute, 1 minute for dehydration, rinsing (repeated twice, 5 minutes each) and 1 minute for dehydration as one step. The temperature of the tap water used was adjusted to 25 ° C.

 The T-shirt treated in the washing operation process was shaded and dried for 12 hours. After that, it was left in a constant temperature and humidity room at 25 ° C and 65% RH for 2 days. The T-shirt treated above was used as a test cloth to evaluate the flexibility-imparting effect.

 On the other hand, a 20% by weight aqueous solution of a nonionic surfactant (alcohol ethoxylate added with an average of 15 moles of ethylene oxide per mole of lauryl alcohol) as a liquid detergent composition was used in the above washing operation step. Evaluation of the flexibility-imparting effect using T-shirts as an evaluation control cloth was performed by sensory comparison with the evaluation control cloth according to the following evaluation criteria, and calculating the average value of 10 professional panelists. The results are shown in Tables 5-7.

 (Evaluation criteria)

 1 point: Equivalent to control cloth.

 2 points: Slightly softer than the control cloth.

3 points: Softer than the control cloth. ^

^ 5 :.

 Table: From the results of! ~ 2, the examples 1 to 11 are effective in the present invention. Each of Examples 1 to 11 contains a single surfactant in a large amount, has excellent solubility in water, and has a high detergency. It could be confirmed.

 Furthermore, it was confirmed that the examples according to the present invention:! To 11 had little raw material odor of the surfactant.

 On the other hand, it was confirmed that both Example 21 and Example 22 containing a nonionic surfactant different from the component (A) used in the present invention were inferior in both solubility in water and detergency. . Further, Example 24 containing a nonionic surfactant (A-7) having a narrow rate of less than 30% by mass, which is a case with an ethylene oxide case represented by the above general formula (I), has a detergency and It was confirmed that both raw material odors were inferior.

 Further, it was confirmed that Example 23 containing no component (B) used in the present invention was inferior in detergency. In addition, Example 23 was confirmed to have a poor hydrolysis rate.

In addition, it was confirmed that Examples 25 and 26 in which the pH of the liquid detergent composition was outside the range of 5 to 8 had a poor hydrolysis rate and inferior cleaning power.

su illo

 From the results shown in Table 3-4, the present invention is excellent in the present invention: Example 3:! 39 and Example 43 contain a large amount of a single surfactant, have excellent solubility in water, and have high detergency. I was able to confirm that. Furthermore, Examples 3139 and 43 according to the present invention were confirmed to have a low raw material odor of the surfactant.

 In addition, it was confirmed that Example 31 39 containing the component (C) was superior in deodorizing effect compared to Example 43 containing no component (C).

 Further, it was confirmed that Example 31 39, which is useful in the present invention, can provide an excellent deodorizing effect even when the concentration of the component (C) in the washing liquid is low.

 On the other hand, Example 41 and Example 42 in which the content of the component (A) used in the present invention is less than 50% by mass are different from the so-called “concentrated type” liquid detergent composition.

 In addition, it was confirmed that Example 41 and Example 42 were inferior in deodorizing effect to Example 31 33 even though the concentration of component (C) in the washing liquid was the same.

In addition, Examples 44 and 45 containing a nonionic surfactant different from the component (A) used in the present invention were confirmed to be inferior in water solubility, detergency, and deodorizing effect. did it. Further, Example 46 containing a nonionic surfactant (A-7) having a narrow rate of less than 30% by mass, which is a case with an ethylene oxide case represented by the general formula (I), has a detergency and It was confirmed that both raw material odors were inferior.

[0113] [Table 5]

[0114] [Table 6]

 From the results of 5 to 6, Examples 51 to 59 and Example 63, which are effective in the present invention, contain a large amount of a single surfactant individual agent, have excellent solubility in water, and have high detergency. I was able to confirm that. Further, it was confirmed that Examples 51 to 59 and Example 63, which are effective in the present invention, have little raw material odor of the surfactant.

 In addition, it was confirmed that Examples 51 to 59 containing the component (D) were superior in the flexibility imparting effect compared to Example 63 not containing the component (D).

 Further, it was confirmed that Examples 51 to 59, which are effective in the present invention, have an excellent flexibility imparting effect even when the concentration of the component (D) in the washing liquid is low.

 It was confirmed that Example 53, Example 54, Example 56 and Example 57, which further contain the component (E) in addition to the component (D), can provide a more excellent flexibility-imparting effect.

 On the other hand, Example 61 and Example 62 in which the content of the component (A) used in the present invention is less than 50% by mass are different from so-called “concentrated type” liquid detergent compositions.

 In addition, it was confirmed that Example 61 and Example 62 were inferior to Examples 51 to 53 in spite of having the same concentration of component (D) in the washing liquid, but the effect of imparting flexibility was inferior.

Further, an example containing a nonionic surfactant different from the component (A) used in the present invention 6 4 and Example 65 were all confirmed to be inferior in water solubility, detergency, and flexibility imparting effect.

 In addition, Example 66, which is an ethylene oxide adduct represented by the above general formula (I) and contains a nonionic surfactant (A-7) having a narrow ratio of less than 30% by mass, has a detergency and a raw material odor. It was confirmed that both were inferior.

[0116] [Table 7]

 [0117] From the results in Table 7, it was confirmed that Example 71 76, which is useful in the present invention, contains a single surfactant in a large amount, has excellent solubility in water, and has high detergency. did it.

 Furthermore, it was confirmed that Example 71 76, which is useful in the present invention, has little raw material odor of the surfactant.

 Further, it was confirmed that Example 71 and Example 73 76 containing both the component (C) and the component (D) were excellent in both the flexibility-imparting effect and the deodorizing effect.

 Further, from the comparison with Example 71 73, it was confirmed that Example 73 further containing the component (E) in addition to the component (D) was most excellent in imparting flexibility.

On the other hand, Example 7 containing a nonionic surfactant different from the component (A) used in the present invention It was confirmed that No. 7 was inferior in water solubility, detergency, deodorizing effect, and flexibility imparting effect.

Industrial applicability

 According to the present invention, it is possible to provide a liquid detergent composition containing a large amount of a single surfactant alone, having excellent solubility in water and high detergency.

 Furthermore, according to the present invention, it is possible to provide a liquid detergent composition with less surfactant raw material odor.

 The liquid detergent composition of the present invention is particularly suitable as a so-called “concentrated type” liquid detergent composition for clothing.

Claims

Claims [1] A liquid detergent composition comprising 50 to 80% by mass of the following component (A) and an antioxidant (B) and having a pH of 5 to 8 at 25 ° C. (A) Narrow ratio indicating the distribution ratio of ethylene oxide adducts represented by the following general formula (I), wherein the number of moles of attached ethylene oxide is different. Oxide adduct.

 [Chemical 1]

R'CO-COCH ₂ CH _t ) „.- OR ² * .. ί Π

[In the formula (I), R ¹ is a linear or branched alkyl group or alkenyl group having 11 to 13 carbon atoms; R ² is an alkyl group having 1 to 3 carbon atoms; n ′ Indicates the average number of moles of ethylene oxide added, and is 10-20. ]

[2] The liquid detergent composition according to claim 1, further comprising a compound (D) represented by the following general formula (IV):

 [Chemical 2]

[In the formula (IV), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group; R ¹³ is a straight chain having 1 to 4 carbon atoms; A chain or branched alkylene group; —Y is a group represented by the following general formula (V) and Z or general formula (VI). ]

[Chemical 3]

[In the formulas (V) to (VI), R ¹⁴ and R ¹⁵ are each independently a linear or branched alkyl or alkenyl group having 7 to 23 carbon atoms. ]

 3. The liquid detergent composition according to claim 2, further comprising a polyether-modified silicone (E) represented by the following general formula (VII) and / or general formula (VIII).

[Chemical 4]

[In the formulas (VII) to (VIII), R is a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms, or a hydrogen atom, and each R may be the same. It may be different. R ¹⁶ is a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and each R ¹⁶ may be the same or different. Z represents a polyoxyalkylene group. The order of each component unit with 1, m, n may be different. 1 f to 0 to 50, mf to 10 to 10000, nf to! To 1000, and an integer of m> n Show. Moreover, af is 5 to 10000, b is an integer of 2 to 10000. ]

A liquid detergent composition according to any one of claims 1 to 3, wherein the following general formula (II) And / or a liquid detergent composition further comprising an antibacterial compound (C) represented by the general formula (III).

 [Chemical 5]

R ³ —— N— R ⁶

 … (Π)

[In the formula (II), two or more of R ^{3 to} R ⁶ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group; the other is a straight chain having 8 to 22 carbon atoms. Or it is a branched alkyl group or alkenyl group. In formula (III), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group; R ⁹ is a linear or branched alkyl group having 8 to 22 carbon atoms. R ^1G is an alkylene group having from 3 to 3 carbon atoms. X— is a halogen ion or an alkyl sulfate ion. ]