JP2016108410A - Liquid detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent having excellent cleaning performance, and a good rinsing property and deodorizing effect.SOLUTION: A liquid detergent comprises a nonionic surfactant (A) comprising a compound (a1) represented by formula (a1), an anionic surfactant (B) except for a higher fatty acid salt, and a compound (C) represented by formula (c1), where a mass ratio of the compound (a1) relative to the nonionic surfactant (A), (a1)/(A), is 0.1 or more. In the formula (a1), Ris a straight-chain or branched-chain hydrocarbon group having 8 to 22 carbon atoms where, when Ris the straight-chain hydrocarbon group, the carbon atom bonded to the oxygen atom is a secondary carbon; EO is an oxyethylene group; PO is an oxypropylene group; p represents the average repeating number of EO and is a number of 2 to 9; and q represents the average repeating number of PO and is a number of 0 to 3. In the formula (c1), AO is an oxyalkylene group having 2 to 4 carbon atoms; m is an integer of 1 to 20; and M is an alkali metal or -NH. [Formula 1]SELECTED DRAWING: None

Description

  The present invention relates to a liquid cleaning agent.

In general, nonionic surfactants and anionic surfactants are used as main cleaning components for imparting detergency to liquid cleaning agents for clothing.
In recent years, due to the growing awareness of environmental impact, there is a demand for a liquid rinse with good rinsing properties that can be rinsed with a small amount of water. Especially for washing clothes, washing machines with low water consumption, such as drum-type washing machines, are used, and liquid detergents can be rinsed once even under conditions of low water usage. There is a need to promote the objects to be cleaned.

In Patent Document 1, a foam formed by foaming a nonionic surfactant or an anionic surfactant is represented by R ¹ -XY in order to quickly defoam and improve rinsing properties. A liquid detergent containing a surfactant is described. R ¹ is an alkyl group, X is —O—, —COO—, or —CONH—, Y is an alkyl group or — (R ² O) _m —R ³ (R ² is an alkylene group, m is 1 to 5) R ³ is an alkyl group, a phenyl group, or a benzyl group.
In Patent Document 2, as a liquid detergent with reduced foaming, a specific alkylene oxide adduct (nonionic surfactant) of 50 to 70% by mass, a non-soap anionic surfactant of 1 to 10% by mass, and saturation Compositions containing 0.05 to 3% by weight of fatty acids have been proposed.

JP 2013-91882 A JP 2009-173858 A

However, in the conventional technique, the rinsing property is not always satisfactory, and further improvement of the rinsing property is required so that the rinsing can be performed more quickly with a smaller amount of water.
In addition, with the recent changes in lifestyle, an increasing number of households do laundry at night, where the laundry is washed indoors and the washed items are dried indoors. The room drying is poorly ventilated and the object to be washed is difficult to dry, so that microorganisms attached to the fibers are likely to grow. For this reason, an unpleasant odor (dried room odor) is likely to be generated from the object to be washed.

  An object of this invention is to provide the liquid cleaning agent which is excellent in washing | cleaning performance, and is excellent in a rinse property and a deodorizing effect.

  In order to solve the above problems, the liquid detergent of the present invention includes a nonionic surfactant (A) containing a compound (a1) represented by the following general formula (a1) and an anionic surfactant excluding a higher fatty acid salt. (B) and the compound (C) represented by the following general formula (c1), and represents the mass ratio of the compound (a1) to the nonionic surfactant (A) (a1) / (A) Is 0.1 or more.

[Wherein, R ¹ represents a linear or branched hydrocarbon group having 8 to 22 carbon atoms. However, when R ¹ is linear, the carbon atom bonded to the oxygen atom is a secondary carbon. EO represents an oxyethylene group, and PO represents an oxypropylene group. p represents the average number of repetitions of EO, and is a number from 2 to 9. q represents the average number of repetitions of PO, and is a number from 0 to 3. ]

[Wherein, AO represents an oxyalkylene group having 2 to 4 carbon atoms, m is an integer of 1 to 20, and M represents an alkali metal or —NH ₄ . When m is 2 or more, the plurality of AOs may be the same as or different from each other. ]
Furthermore, it is preferable to contain a cationic surfactant (D).

  ADVANTAGE OF THE INVENTION According to this invention, the liquid cleaning agent which is excellent in washing | cleaning performance, and has a favorable rinse property and a deodorizing effect is obtained.

The present invention is a composition comprising a nonionic surfactant (A), an anionic surfactant (B), and a compound (C).
<(A) component>
The component (A) is a nonionic surfactant containing the compound (a1) represented by the general formula (a1) (hereinafter also referred to as “component (a1)”). (A) A component may be used individually by 1 type and may use 2 or more types together.
The component (A) may be composed of the component (a1), or may be composed of the component (a1) and a nonionic surfactant other than this (hereinafter also referred to as “component (a2)”).

≪ (a1) component≫
The component (a1) is a compound represented by the following general formula (a1).

In formula (a1), R ¹ represents a linear or branched hydrocarbon group having 8 to 22 carbon atoms.
The hydrocarbon group for R ¹ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Among these, a saturated hydrocarbon group is preferable from the viewpoint of suppressing the generation of a room-dried odor and the appearance stability.
Wherein R ¹ is the number of carbon atoms in the hydrocarbon group is from 8 to 22, preferably from 11 to 18, more preferably 12 to 16, 12 to 14 is more preferable.
R ¹ may be linear or branched. When R ¹ is linear, the carbon atom bonded to the oxygen atom (O) in R ¹ —O— is a secondary carbon. When the carbon atom bonded to the oxygen atom is a secondary carbon, the permeability to the article to be washed is likely to be improved. In particular, when used in a method of applying directly to dirt or the like on clothes, high application cleaning power is easily obtained.
Preferable R ¹ —O— includes a group represented by the following general formula (a1-r-1).

In the formula (a1-r-1), R ¹⁰¹ and R ¹⁰² each represent a chain hydrocarbon group, and the total number of carbon atoms of R ¹⁰¹ and R ¹⁰² is 7 to 21.
Each of R ¹⁰¹ and R ¹⁰² may be a linear hydrocarbon group or a branched hydrocarbon group.
The total number of carbon atoms of R ¹⁰¹ and ^{R 102} is preferably 10 to 17, more preferably from 11 to 15, 11 to 13 is more preferable.

In said formula (a1), p is a number of 2-9, and since the permeability to a to-be-washed object becomes high, 3-9 are preferable and 7-9 are more preferable.
q is a number of 0 to 3, and 0 to 2 is preferable and 0 is particularly preferable because of its high permeability to an object to be washed.

In the formula (a1), [(EO) _p / (PO) _q ] may be a mixture of EO and PO regardless of the arrangement order of EO and PO.
When q is not 0, that is, when the component (a1) has both EO and PO, EO and PO may be added in a block shape or may be added in a random shape.
Examples of the method of adding EO and PO in a block form include a method of introducing propylene oxide after introducing ethylene oxide, and a method of introducing ethylene oxide after introducing propylene oxide.
The addition mole number distribution of ethylene oxide or propylene oxide is not particularly limited.

The added mole number distribution is likely to vary depending on the reaction method in producing the component (a1). For example, when ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution of the number of moles of ethylene oxide or propylene oxide is relatively wide. It tends to be. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a catalyst, the distribution of the number of moles of ethylene oxide or propylene oxide tends to be relatively narrow.

As the component (a1), one type may be used alone, or two or more types may be used in combination.
Specific examples of the component (a1) are those obtained by adding 7 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms (for example, trade name Softanol 70 manufactured by Nippon Shokubai Co., Ltd.), 12 to 14 carbon atoms. 9 mole equivalent of ethylene oxide added to the secondary alcohol (for example, trade name Softanol 90 manufactured by Nippon Shokubai Co., Ltd.), 7 mole equivalent ethylene oxide and 2 mole equivalent to a secondary alcohol having 12 to 14 carbon atoms Propylene oxide added, 7 moles of ethylene oxide added to 10 carbon alcohol obtained by subjecting pentanol to gerbet reaction (trade name Lutensol XL70 manufactured by BASF), pentanol converted to gerbet reaction The ethylene oxide equivalent to 6 moles is obtained from the 10 carbon alcohol obtained Added ones (trade name Lutensol XA60 manufactured by BASF) and the like.

<< (a2) component >>
The component (a2) is a nonionic surfactant other than the component (a1). Any nonionic surfactant other than the component (a1) is not particularly limited. As the component (a2), one type may be used alone, or two or more types may be used in combination.
[(A2-1) component]
For example, a compound represented by the following general formula (a2-1) (hereinafter also referred to as “component (a2-1)”) can be given.

[Wherein R ² represents a hydrocarbon group. -X- is a divalent linking group. R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO represents an oxyethylene group, and PO represents an oxypropylene group. s represents the average number of repetitions of EO and is a number from 3 to 20. t represents the average number of repetitions of PO, and is a number from 0 to 6. u represents the average number of repetitions of EO, and is a number from 0 to 20. ]

In said formula (a2-1), s is a number of 3-20, and the number of 5-18 is preferable. When s exceeds 20, the HLB value becomes too high, and the detergency against oil stains such as sebum stains tends to decrease. On the other hand, when s is less than 3, the effect of preventing odor degradation tends to be reduced.
In said formula (a2-1), t is a number of 0-6, and the number of 0-3 is preferable. When t exceeds 6, the storage stability of the liquid detergent at high temperature tends to be lowered.
In said formula (a2-1), u is a number of 0-20, and the number of 0-18 is preferable. When u exceeds 20, the detergency of oil stains tends to decrease.

In the formula (a2-1), [(EO) _s / (PO) _t ] may be a mixture of EO and PO regardless of the arrangement order of EO and PO.
When t is not 0, that is, when the component (a2-1) has both EO and PO, EO and PO may be added in a block shape or may be added in a random shape.
As a method of adding EO and PO in a block form, for example, a method of introducing propylene oxide after introducing ethylene oxide, a method of introducing ethylene oxide after introducing propylene oxide, or a method of introducing propylene oxide after introducing ethylene oxide. And a method of further introducing ethylene oxide.
The addition mole number distribution of ethylene oxide or propylene oxide is not particularly limited.
The addition mole number distribution is likely to vary depending on the reaction method in producing the component (a2-1), similarly to the component (a1).

  In the formula (a2-1), the divalent linking group that is —X— is preferably —O (oxygen atom) — or —C (═O) —O—.

In the case of a compound in which —X— is —O—:
The number of carbon atoms of ^{R 2} in the formula (a2-1) in the 8 to 22, more preferably 10 to 20, more preferably 10 to 18. R ³ is preferably a hydrogen atom. In this case, the compound represented by the general formula (a2-1) is an alcohol alkoxylate (except for the compound corresponding to the component (a1)). Among these, a compound where t = 0 (ie, alcohol ethoxylate) is more preferable, and a primary alcohol ethoxylate obtained by adding ethylene oxide to a primary alcohol is more preferable.

In the case of a compound in which —X— is —C (═O) —O—:
The number of carbon atoms of ^{R 2} in the formula (a2-1) is preferably from 9 to 21, more preferably from 11 to 21, more preferably 11 to 17. R ³ is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably an alkyl group having 1 to 3 carbon atoms. The compound represented by formula (a2-1) is a polyoxyalkylene fatty acid alkyl or alkenyl ester.

  Specific examples of the compound in which —X— in the formula (a2-1) is —O— or —C (═O) —O— include a trade name Diadol (C13 alcohol, C13, manufactured by Mitsubishi Chemical Corporation). Represents the number of carbon atoms, the same applies hereinafter.), Alcohols such as Shell's brand name Neodol (C12 / C13: mixture of C12 alcohol and C13 alcohol), Sasol brand name Safol 23 (C12 / C13), etc. 12 mole equivalent or 15 mole equivalent of ethylene oxide added to the product; 12 mole equivalent or 15 mole equivalent of ethylene oxide added to a natural alcohol such as CO-1214 or CO-1270 manufactured by P & G Equivalent to 15 moles with respect to coconut fatty acid methyl (lauric acid / myristic acid = 8/2 (mass ratio)) using an alkoxylation catalyst Obtained by adding ethylene oxide (polyoxyethylene coconut fatty acid methyl ester EO15 mol), and the like.

As the component (a2), a compound represented by the general formula (a2-1) (component (a2-1)) is preferable.
Among the components (a2-1), a compound in which —X— in the formula (a2-1) is —O— and R ³ is a hydrogen atom is preferable from the viewpoint of appearance stability.
Among the components (a2-1), from the viewpoint of detergency, a compound in which —X— in the formula (a2-1) is —C (═O) —O— is preferable. A compound in which R ^{3 in} -1) is an alkyl group having 1 to 6 carbon atoms is more preferable, and a compound in which t in formula (a2-1) is 0 (that is, a polyoxyethylene fatty acid alkyl ester) is more preferable. Polyoxyethylene fatty acid methyl ester (hereinafter, referred to as “MEE”) in which R ³ in formula (a2-1) is a methyl group is particularly preferred.
By containing the polyoxyethylene fatty acid alkyl ester, the liquid detergent of the present invention is excellent in solubility in water, and high detergency is easily obtained. Moreover, even if it contains a surfactant at a high concentration, it is difficult to cause a significant increase in viscosity (gelation), and a concentrated liquid cleaning agent having good fluidity can be obtained.

  Polyoxyethylene fatty acid alkyl ester (especially MEE) is a nonionic surfactant in which the orientation of molecules in an aqueous solution system is weak and the micelle is unstable, so that gelation or the like does not occur in a high concentration region. A large amount of the seed alone can be incorporated into the liquid detergent. Moreover, the solubility to water is favorable. Furthermore, it has good fluidity even at high concentrations. Therefore, after the polyoxyethylene fatty acid alkyl ester is poured into the water in the washing machine tub, the concentration in the washing liquid becomes uniform quickly. Thereby, when a polyoxyethylene fatty acid alkyl ester is used, since it can contact with a to-be-washed object by the predetermined density | concentration from the washing | cleaning initial stage, high detergency is acquired.

  In addition, the polyoxyethylene fatty acid alkyl ester has a total content ratio of a fatty acid alkyl ester in which the number of added moles of ethylene oxide is 0 and an ethylene oxide adduct in which the number of added moles of ethylene oxide is 1 or 2, What is 0.5 mass% or less is preferable with respect to the whole ethylene fatty acid alkyl ester, and what is 0.2 mass% or less is more preferable. When the total content is 0.5% by mass or less, a liquid detergent having a lower raw material odor derived from the polyoxyethylene fatty acid alkyl ester is easily obtained.

[(A2-2) component]
The component (a2-2) is a polyoxyalkylene alkylamine type nonionic surfactant represented by the following general formula (a2-2).

[Wherein, R ⁰ represents an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms. A ¹ O and A ² O each independently represent an oxyalkylene group having 2 to 3 carbon atoms. i represents the average number of repetitions of A ¹ O, j represents the average number of repetitions of A ² O; i> 0, j> 0, and i + j is a number from 10 to 50. ]

In Formula (a2-2), R ⁰ has 10 to 20 carbon atoms, and from the viewpoint of detergency, an alkyl group having 10 to 18 carbon atoms or an alkenyl group having 10 to 18 carbon atoms is preferable. It may be a chain or a branched chain. When the carbon number of R ⁰ is 10 or more, good cleaning performance is obtained, and when it is 20 or less, good solubility is obtained.
In the formula (a2-2), each of (A ¹ O) i and (A ² O) j may have a repeating structure composed only of an oxyethylene group (EO ′), and may be composed of only an oxypropylene group (PO ′). A repeating structure may be used, and EO ′ and PO ′ may be mixed and arranged. When both are arranged in a mixed manner, EO ′ and PO ′ may be added in a random shape or may be added in a block shape. Among these, (A ¹ O) i and (A ² O) j each preferably have a repeating structure of only EO ′ in that it has a high detergency against sebum dirt.
In said formula (a2-2), i + j is a number of 10-50, 10-40 are preferable and 10-30 are more preferable. When i + j is equal to or higher than the lower limit of the range, the cleaning performance becomes better, and when i + j is equal to or lower than the upper limit of the range, the storage stability of the liquid cleaning agent is further increased.
Preferable examples of the component (a2-2) include those obtained by adding 20 (i + j = 20) moles of ethylene oxide to an alkylamine having 16 carbon atoms.

In the liquid detergent, the total content of the component (A) is preferably 10 to 60% by mass, preferably 15 to 55% by mass, and more preferably 20 to 50% by mass.
When the content of the component (A) in the liquid detergent is not less than the lower limit of the above range, a good deodorizing effect can be easily obtained, and when it is not more than the upper limit, the formation of precipitates can be satisfactorily suppressed.
The amount ratio (a2) / (A) of the component (a2) in the component (A) is preferably 0.9 to 0, more preferably 0.85 to 0.1, and particularly preferably 0.8 to 0.2. .
When the content of the component (a1) in the liquid detergent is not less than the lower limit of the above range, the sebum cleaning power is further increased. In addition, the appearance stability of the liquid detergent is further improved. On the other hand, when the amount is not more than the upper limit of the above range, the fluidity of the liquid detergent is further increased, and the appearance stability is further improved.

The component (A) is preferably composed of the component (a1) or a combination of the component (a1) and the component (a2-1), and the coating detergency is further increased. Therefore, the component (a1) and the component (a2) -1) A combination with a component is more preferable.
The combination of the component (a1) and the component (a2-1) includes a combination of the component (a1) and a polyoxyethylene fatty acid alkyl ester, and a combination of the component (a1), a polyoxyethylene fatty acid alkyl ester and an alcohol ethoxylate. Among these, a combination of the component (a1) and a polyoxyethylene fatty acid alkyl ester is more preferable.
According to the combination of the component (a1) and the component (a2-1), gelation hardly occurs even at a high concentration, so that a large amount is easily added as the component (A). In addition, since the surfactant concentration of the liquid detergent can be easily increased, washing can be performed with a small amount of use, or the detergent container can be made compact.

<(B) component: anionic surfactant excluding higher fatty acid salt>
The liquid detergent contains an anionic surfactant excluding higher fatty acid salts. By containing the component (B), the liquid cleaning agent can further improve the deodorizing property of the clothes.

As the component (B), an anionic surfactant conventionally used for liquid detergents can be used.
Preferable components (B) include, for example, linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; Alkane sulfonate having a group; α-sulfo fatty acid ester salt and the like. Examples of salts in these anionic surfactants include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

As the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms in the linear alkyl group is more preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
The alkyl sulfate ester salt is preferably an alkyl group having 10 to 20 carbon atoms.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average of 1 to 10 moles of alkylene oxide added thereto (ie, Polyoxyalkylene alkyl ether sulfates or polyoxyalkylene alkenyl ether sulfates) are preferred.
As the alkane sulfonate, an alkyl group having 10 to 20 carbon atoms is preferable, and an alkyl group having 14 to 17 carbon atoms is more preferable. Among them, the alkyl group is a secondary alkyl group (that is, secondary alkane sulfone). Acid salt) is more preferred.
As the α-sulfo fatty acid ester salt, fatty acid residues having 10 to 20 carbon atoms are preferable.
As the component (B), at least one selected from linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyalkylene alkyl ether sulfate, and α-olefin sulfonate is preferable.

As the component (B), anionic surfactants other than those described above may be used. Examples of the other anionic surfactants include carboxylic acid type anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, and acylaminocarboxylates. Agents: Phosphate-type anionic surfactants such as alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkylphenyl phosphate ester salts, glycerin fatty acid ester monophosphate ester salts, and the like.
These (B) components may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the component (B) in the liquid detergent is preferably 1 to 40% by mass, more preferably 3 to 35% by mass, further preferably 5 to 30% by mass, and particularly preferably 15 to 25% by mass. If the amount is less than the above lower limit value, the deodorizing effect may not be further improved, and if it exceeds the above upper limit value, the liquid stability may be impaired.

  Moreover, in the liquid cleaning agent of this invention, the sum total of content of (A) component and (B) component is 30-70 mass% from a viewpoint of detergency, 35-60 mass% is preferable, and 40-55 mass % Is more preferable.

<Compound (C)>
Compound (C) (hereinafter also referred to as component (C)) is a compound represented by the following general formula (c1). (C) component contributes to the improvement of a defoaming effect.
_{MO 3 S- (AO) m -SO} 3 M ··· (c1)
In formula (c1), AO represents an oxyalkylene group having 2 to 4 carbon atoms. The number of carbon atoms in AO is preferably 2 or 3.
In the formula (c1), m is an integer of 1 or more and 20 or less, and is preferably an integer of 1 to 15 and more preferably 1 to 10 from the viewpoint of the appearance stability of the liquid detergent. When m is 2 or more, the plurality of AOs may be the same as or different from each other. Preferably they are the same.
M represents an alkali metal or —NH ₄ . Examples of the alkali metal as M include sodium, potassium, lithium and the like. Sodium or potassium is preferred, and sodium is more preferred.

(C) component is ethylene glycol disulfate, diethylene glycol disulfate, triethylene glycol disulfate, tetraethylene glycol disulfate, propylene glycol disulfate, dipropylene glycol disulfate One or more selected from tripropylene glycol disulfate ester salt and tetrapropylene glycol disulfate ester salt are preferable.
The content of the component (C) with respect to the liquid detergent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.1% by mass or more from the viewpoint that the defoaming effect can be sufficiently improved. Is more preferable. Further, from the viewpoint of appearance stability of the liquid detergent, the content of the component (C) is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less.
Moreover, from the viewpoint of the defoaming effect, the value of ((A) component + (B) component) / (C) component representing the mass ratio of (C) component to the total amount of (A) component and (B) component is 20-8000 are preferable from a viewpoint of a defoaming effect, and 30-7000 are more preferable. More preferably, it is 40-7000.

<(D) component: cationic surfactant>
Examples of the component (D) include a quaternary ammonium salt type surfactant and a tertiary amine type surfactant other than the component (a2-2). Among these, the deodorizing effect is further enhanced. A quaternary ammonium salt type surfactant is preferred.

  The quaternary ammonium salt type surfactant is not particularly limited as long as it is conventionally used in liquid detergents. For example, a compound represented by the following general formula (d1) (hereinafter referred to as (d1) Component), a compound represented by the following general formula (d2) (hereinafter sometimes referred to as (d2) component), a compound represented by the following general formula (d3) (hereinafter referred to as (d3) component) Are preferred). By using the components (d1) to (d3), the deodorizing effect can be further enhanced.

[In the formula (d1), R ^{20 to} R ²³ are each independently two or three of an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and the other is a straight chain having 8 to 22 carbon atoms or A branched alkyl group or alkenyl group. Z ⁻ represents a halogen ion or an alkyl sulfate ion. ]

[In the formula (d2), R ²⁴ and R ²⁵ each independently represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, EO represents an oxyethylene group, and x and y are It is a number of 0 or more that represents the average number of added moles of oxyethylene groups, and x + y = 10 or more. Z ⁻ represents a halogen ion or an alkyl sulfate ion. ]

[In Formula (d3), R ²⁶ and R ²⁷ each independently represent an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ²⁸ represents a linear or branched alkyl group having 8 to 22 carbon atoms or An alkenyl group, and R ²⁹ is an alkylene group having 1 to 3 carbon atoms. Z ⁻ represents a halogen ion or an alkyl sulfate ion. ]

In the formula (d1), examples of the halogen ion constituting Z ⁻ include fluorine ion, chlorine ion, bromine ion, iodine ion and the like. Z ^- as alkylsulfate ions constituting the is preferably one having an alkyl group having 1 to 3 carbon atoms. Among them, as Z ⁻ , a halogen ion is preferable and a chlorine ion is more preferable. If it is a chlorine ion, liquid stability can be improved more.

As the component (d1), R ^{20 to} R ²² are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ²³ is a straight chain having 8 to 22 carbon atoms or A compound which is a branched alkyl group or a linear or branched alkenyl group having 8 to 22 carbon atoms (hereinafter referred to as component (d1-1)); R ²⁰ and R ²¹ each independently represent 1 to 3 carbon atoms Or an alkyl group having 1 to 3 carbon atoms, and R ²² and R ²³ are each independently a linear or branched alkyl group having 8 to 22 carbon atoms or a linear chain having 8 to 22 carbon atoms, or A compound that is a branched alkenyl group (hereinafter referred to as component (d1-2)) is preferred.

As the component (d1-1), R ^{20 to} R ²² are preferably each independently an alkyl group having 1 to 3 carbon atoms, more preferably any one is a methyl group, and more preferably all methyl. It is a group. If R ²⁰ to R ²² is an alkyl group as described above, it is further enhanced liquid stability.
The component ^(d1-1), the carbon number of ^{R 23} is preferably 8-22, more preferably 12-18. The number of carbon atoms of R ²³ is within the above range, it increased more deodorizing action.
As the component (d1-1), R ²³ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. When R ²³ is the above alkyl group, the deodorizing effect can be further enhanced.

As the component (d1-2), R ²⁰ and R ²¹ are preferably each independently an alkyl group having 1 to 3 carbon atoms, more preferably at least one is a methyl group, and more preferably both are methyl groups. It is. If R ²⁰ and R ²¹ is an alkyl group as described above, it is further enhanced liquid stability.
As the component (d1-2), R ²² and R ²³ preferably have 8 to 12 carbon atoms, more preferably 8 to 10 carbon atoms, independently. If the carbon number of R ²² and R ²³ is within the above range, the deodorizing action can be further enhanced.
As the component (d1-2), R ²² and R ²³ are preferably each independently a linear or branched alkyl group, more preferably any one is a linear alkyl group, and more preferably All are linear alkyl groups. If R ²² and R ²³ are the above alkyl group is enhanced more deodorizing action.

Z in formula (d2) ^- is, Z of formula (d1) ^- it is the same as.
In the formula (d2), x + y is preferably 10-50. If x + y is not less than the above lower limit, the liquid stability is better, and if it is not more than the above upper limit, the deodorizing action can be further enhanced.
As the component (d2), it is preferable that any one of R ²⁴ and R ²⁵ is a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms, and the other is a methyl group or a tolyl group. If it is said combination, a deodorizing effect can be improved more.

Z in the formula (d3) ^- is, Z in the formula (d1) ^- are the same as.
In the formula (d3), R ²⁶ and R ²⁷ are each independently preferably an alkyl group having 1 to 3 carbon atoms, and either one is more preferably a methyl group, and more preferably both are methyl groups. . If R ²⁶ and R ²⁷ is an alkyl group as described above, it is further enhanced liquid stability.
In formula (d3), the carbon number of R ²⁸ is preferably 10 to 18, and more preferably 12 to 14. When the carbon number of R ²⁸ is within the above range, the deodorizing action can be further enhanced.
R ²⁸ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. When R ²⁸ is the above alkyl group, the deodorizing effect can be further enhanced.
In the formula (d3), R ²⁹ is preferably a methylene group. When R ²⁹ is a methylene group, the liquid stability can be further improved.

Examples of the tertiary amine type surfactant other than the component (a2-2) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, Long chain aliphatic amide dialkyl tertiary amines such as palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide, palmitic acid diethanolaminopropylamide, stearic acid diethanolamino Long chain aliphatic amide dialkanol tertiary amines such as propylamide, palmitate ester propyldimethylamine, stearate ester propyldimethylamine, etc. That. Among these, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylamino Propylamide and oleic acid dimethylaminopropylamide are preferred.
The tertiary amine compound may be used as it is or as a salt. Examples of the salt include an acid salt obtained by neutralizing a tertiary amine compound with an acid. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, lactic acid, citric acid, polyacrylic acid, paratoluenesulfonic acid, cumenesulfonic acid, and the like. These tertiary amine type surfactants may be used alone or in combination of two or more.

As the component (D), a component (d1-1), a component (d1-2), and a component (d3) are preferable. By using such a component (D), the deodorizing action of the liquid cleaning agent can be further enhanced.
Examples of the component (d1-1) include alkyltrimethylammonium chlorides such as ARCARD 12-37W (trade name, manufactured by Lion Akzo Co., Ltd.) and ARCARD T-800 (trade name, manufactured by Lion Akzo Co., Ltd.). .
Examples of the component (d1-2) include didecyldimethylammonium chloride such as ARCARD 210 (trade name, manufactured by Lion Akzo Co., Ltd.).
Examples of the component (d-3) include coconut alkyldimethylbenzylammonium chloride such as ARCARD CB-50 (trade name, manufactured by Lion Akzo Co., Ltd.).
(D) component mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the component (D) in the liquid detergent is preferably 0.1% by mass or more and less than 10% by mass, more preferably 1 to 6% by mass, and further preferably 2 to 4% by mass. If it is more than the said lower limit, a deodorizing effect | action can be improved more, and if it is less than the said upper limit, the transfer, recontamination, etc. with respect to a to-be-cleaned object will be suppressed, and the liquid stability of a liquid cleaning agent will be improved more.

[Water-miscible organic solvent]
In the liquid detergent of the present invention, a water-miscible organic solvent may be used as a solvent other than water from the viewpoint of improving the stability of the liquid appearance.
“Water-miscible organic solvent” refers to an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.
Examples of water-miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol, and 1-butanol; glycols such as propylene glycol, butylene glycol, and hexylene glycol; diethylene glycol, triethylene glycol, tetraethylene glycol, Polyethylene glycol having a weight average molecular weight of about 200, polyethylene glycol having a weight average molecular weight of about 400, polyethylene glycol having a weight average molecular weight of about 1000, polyglycols such as dipropylene glycol; alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether Etc.
A water-miscible organic solvent may be used individually by 1 type, and may use 2 or more types together.
The blending amount of the water-miscible organic solvent is preferably 0.1 to 15% by mass with respect to the total mass of the liquid detergent.

[Other ingredients]
The liquid cleaning agent of the present invention is a component other than the above component (A), component (B), component (C), component (D), and water-miscible organic solvent, as necessary, as long as the effects of the present invention are not impaired. Other components may be contained. As this other component, the component normally used for a liquid detergent can be mix | blended.
For example, amphoteric surfactants, enzyme stabilizers, preservatives, alkali agents, antioxidants, water-miscible organic solvents, flavoring agents, thickeners or solubilizers, colorants, detergency builders, antifoaming agents , PH adjusters, silicones, fluorescent brighteners, dye transfer inhibitors, recontamination inhibitors, pearl agents, soil release agents, foam control agents, chelating agents, emulsifying agents, extracts and the like.

The liquid detergent of the present invention preferably has a pH at 25 ° C. of 4 to 9, more preferably pH 6 to 9. When the pH is in such a range, the storage stability of the liquid detergent can be maintained well.
The pH of the liquid detergent can be adjusted by blending a pH adjuster as necessary. The pH adjuster is optional as long as the effects of the present invention are not impaired, but sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of the stability of the component (A).

The liquid detergent may further contain water as a dispersion medium. When water is contained, the content of water in the liquid detergent can be appropriately set in consideration of balance with other components. For example, 10-80 mass% is preferable with respect to the total mass of a liquid detergent, 15-75 mass% is more preferable, 25-55 mass% is further more preferable, 30-45 mass% is especially preferable.
Examples of water include purified water, distilled water, ion exchange water, pure water, and ultrapure water.
The liquid detergent of the present invention is prepared by mixing the above components (A) to (D) and other components as necessary with water.

  The method for using the liquid detergent of the present invention may be the same as the method for using a normal liquid detergent. That is, the liquid detergent of the present invention (the product of the present invention) is poured into water together with the laundry during washing, the method of directly applying the product of the present invention to mud and sebum soil, the product of the present invention is dissolved in water in advance. And a method of immersing clothes. Also preferred is a method in which the product of the present invention is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a normal laundry solution. At that time, the amount of the product of the present invention can be substantially reduced below the amount of the conventional liquid detergent.

According to the present invention, as shown in the examples described later, the combined use of the component (A), the component (B), and the compound (C) allows cleaning, defoaming, and deodorizing effects (immediately after washing). The liquid cleaning agent satisfying (deodorization and suppression of room drying odor) can be obtained. Also, good dispersion stability of the liquid detergent can be obtained.
In the present invention, a higher fatty acid salt is not used as the anionic surfactant (B), but the liquid detergent may contain a higher fatty acid salt. For example, a higher fatty acid salt can be contained as a component for improving the detergency performance in a proportion of 20% by mass or less with respect to the liquid detergent. The content of the higher fatty acid salt is preferably 0.5% by mass or more, and preferably 1 to 15% by mass.
When the liquid detergent contains a higher fatty acid salt, the higher fatty acid salt is also included in the total as part of the surfactant when determining the total of the surfactant.

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

<Evaluation method>
The following evaluation method was used.
[Evaluation method of cleaning performance]
After storing the liquid detergent at 15 ° C. for 24 hours, the liquid detergent was applied evenly to a wet artificial soiled cloth (5 cm × 5 cm) and left for 5 minutes. The amount of liquid detergent used is 0.3 g per 10 sheets of contaminated fabric. Thereafter, the contaminated fabric and a commercially available T-shirt (100% cotton, manufactured by BVD) were put into a cleaning tester (Terg-O-Tometer, manufactured by UNITED STATES TESTING), and the cleaning operation was performed. went. The operating conditions were as follows. According to the standard course of the cleaning tester, a cleaning operation was performed once in which cleaning was performed for 10 minutes (the amount of water was 900 mL), rinsing twice, and dehydration for 3 minutes. The contaminated cloth after the washing operation was left to stand in a constant temperature and humidity room at 25 ° C. and a humidity of 65% RH for 24 hours to obtain a washed cloth.

The reflectance of each of uncontaminated cloth (cloth before attaching dirt), wet artificially contaminated cloth (hereinafter referred to as contaminated cloth) and cleaning cloth is measured with a spectroscopic color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., SE2000). The washing rate (%) was calculated from the measured reflectance (average value of 10 sheets each) using the following equation (i). The calculated cleaning rate was classified into the following evaluation criteria, and the cleaning power was evaluated.
Washing rate (%) = (K / S of contaminated cloth−K / S of washed cloth) / (K / S of contaminated cloth−K / S of uncontaminated cloth) × 100 (i)
In the formula (i), K / S is (1-R / 100) ² / (2R / 100) (where R represents the reflectance (%) of the uncontaminated cloth, the contaminated cloth, or the washed cloth). )
≪Evaluation criteria≫
○: The cleaning rate is 60% or more.
Δ: The cleaning rate is 50% or more and less than 60%.
X: The cleaning rate is less than 50%.

[Evaluation method of defoaming performance]
A liquid detergent was dissolved in purified water adjusted to 25 ° C. to a concentration of 10 g / 30 L to prepare a washing liquid. 20 minutes of this washing solution was put into an Epton tube, and the amount of foam was measured 2 minutes after shaking the Epton tube by hand. The shaking was performed 20 times at 1 stroke / second. For the measurement of the amount of foam, the volume (height) from the boundary between the foam and the cleaning liquid to the upper end surface of the foam was read with an Epton scale. Based on the height from the boundary between the foam and the cleaning liquid (bubble height, unit: mm), the following criteria were used for evaluation.
○: Less than 50 mm.
X: 50 mm or more.

[Appearance stability evaluation method]
30 mL of liquid detergent was taken in a cylindrical glass bottle and sealed with the lid closed. In this state, it was left in a thermostatic bath at 5 ° C. and stored for 1 month.
Then, it took out from this thermostat and observed the transparent uniformity and fluidity | liquidity of 5 degreeC liquid detergent visually, and evaluated the external stability of the liquid detergent based on the following reference | standard.
○: Transparent and uniform, and showed fluidity.
X: Solidification or precipitation was observed.

[Deodorizing effect evaluation method]
The test cloths were 10 hand towels used for half a year at home, each used for about 2 days in normal life. Using a liquid detergent, wash the test cloth in a normal course of a washing machine (JW-Z23A type, manufactured by Haier) (pour tap water with a water temperature of about 20 ° C. and a hardness of about 3 ° DH, 20 times the bath ratio) ) At that time, the washing process was performed by setting the amount of the liquid detergent to the washing machine to 10 mL / 30 L of tap water.
In addition, a new 100% cotton skin shirt (manufactured by BVD) is washed in a fully automatic washing machine (NA-F70SD1 manufactured by Matsushita Electric Industrial Co., Ltd.) for clothing with a bath ratio (water temperature approx. The tap water was poured 5 times at a temperature of 20 ° C. and a hardness of about 3 ° DH. The washing process at that time uses a commercially available powder detergent (trade name: Top, manufactured by Lion Co., Ltd.) as the detergent, and the washing amount is 25 g / 30 L of tap water per wash. went.
After the washing process of the hand towel was completed, the towel was dried in a room having a room temperature of about 23 ° C. and a relative humidity of 90% RH and dried for 5 hours.
For hand towels immediately after the end of the washing process (before drying) and after 5 hours of drying, 6 expert panelists each sensoryly evaluated the odor intensity, and the average score of the 6 sensory evaluations was used as the evaluation result of the deodorizing effect. .
A high odor intensity score immediately after washing (before drying) means that the deodorizing effect by washing is excellent. A high score of the odor intensity after drying means that the room drying odor generated when the room is dried is suppressed.

The sensory evaluation is a method in which each panel smells 10 towels of hand towels, evaluates the odor intensity in 6 levels based on the following evaluation criteria, and calculates the average score of 10 odor intensity for each panel I went there. The higher the odor intensity score, the weaker the odor.
Moreover, based on the average score of sensory evaluation (average score of 6 persons), the deodorizing effect was evaluated according to the following criteria.
(Evaluation of odor intensity)
5 points: No off-flavor.
4 points: A nasty smell is finally felt.
3 points: The off-flavor is felt weak.
2 points: A strange odor is felt slightly stronger.
1 point: A strange odor is felt strongly.
0 point: A strange odor is felt intensely.

(Evaluation of deodorizing effect)
[Immediately after washing is completed]
(Double-circle): The average score of sensory evaluation is 4.0 or more.
(Circle): The average score of sensory evaluation is 3.0-3.9.
(Triangle | delta): The average score of sensory evaluation is 2.5-2.9.
X: The average score of sensory evaluation is 2.4 or less.
[After drying]
(Double-circle): The average score of sensory evaluation is 3.0 or less.
(Circle): The average score of sensory evaluation is 2.5-2.9.
(Triangle | delta): The average score of sensory evaluation is 2.0-2.4.
X: The average score of sensory evaluation is 1.9 or less.

<Use ingredients>
[(A) component]
(A1): A compound (a1) represented by the formula (a1), wherein R ¹ —O— is represented by the general formula (a1-r-1). Nonionic surfactant obtained by adding 9 mol of ethylene oxide to secondary alcohol having 12 to 14 carbon atoms, Softanol 90 (trade name), manufactured by Nippon Shokubai Co., Ltd.

(A2): Nonionic surfactant (LMAO) obtained by adding 15 mol of ethylene oxide to natural alcohol. Synthesized by the following synthesis method.
Represented by formula (a2-1), R ² is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, X is an oxygen atom, R ³ is a hydrogen atom, s = 15, t = 0, u = 0 A compound that is
[Synthesis method of LMAO]
86-12 g of CO-1214 (trade name) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of 30% by mass NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. Next, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added through the blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
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 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, thereby obtaining LMAO.

(A3): Nonionic surfactant (MEE) in which ethylene oxide corresponding to 15 mol was added to methyl coconut fatty acid (mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) using an alkoxylation catalyst. ). Synthesized by the following synthesis method.
Represented by formula (a2-1), R ² is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, X is —C (═O) O—, R ³ is a methyl group, s = 15, t = 0, u = 0.
[Method of synthesizing MEE]
The synthesis was performed according to the synthesis method described in JP-A No. 2000-144179.
Alumina-magnesium hydroxide (Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO.Al ₂ O ₃ .wH ₂ O was calcined at 600 ° C. for 1 hour in a nitrogen atmosphere. Thus, a calcined alumina / magnesium hydroxide (unmodified) catalyst was obtained. An autoclave was charged with 2.2 g of calcined alumina / magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester in a 4 L autoclave. The catalyst was reformed inside. Next, after the inside of the autoclave was replaced with nitrogen, 1052 g of ethylene oxide was introduced and reacted while stirring while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa.
The obtained 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 and mixed, and then the catalyst was filtered off to obtain MEE.

(A4): obtained by block addition of 8 moles of ethylene oxide, 2 moles of propylene oxide, and 8 moles of ethylene oxide in order to natural alcohol (mass ratio of 12 alcohols / 14 alcohols = 7/3) Nonionic surfactant (EP nonionic).
Represented by formula (a2-1), R ² is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, X is an oxygen atom, R ³ is a hydrogen atom, s = 8, t = 2, u = 8 A compound that is

(A5): Natural alcohol CO-1217 manufactured by P & G Co. (trade name, monohydric alcohol having a (straight / branched) chain (saturated / unsaturated) hydrocarbon group having a carbon number of 12/14 = 7/3) Nonionic surfactant (short EO nonion) added with an average of 5 moles of ethylene oxide.
Represented by formula (a2-1), R ² is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, X is an oxygen atom, R ³ is a hydrogen atom, s = 5, t = 0, u = 0 A compound that is

[Component (B)]
(B1): AEPS
Straight chain primary alcohol having 12 carbon atoms [manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 1-dodecanol (molecular weight 186.33), purity> 99%] 640 g and KOH 1.0 g were stirred, temperature control device, automatic introduction device And dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, nitrogen substitution was performed, the temperature was raised to 120 ° C., and 199 g of propane-1,2-diyl oxide was charged. After addition reaction and aging at 120 ° C., the temperature was raised to 145 ° C., and 303 g of ethylene oxide (hereinafter referred to as “EO”) was charged. After addition reaction and aging at 145 ° C., the mixture was cooled to 80 ° C., and unreacted EO was removed at 4.0 kPa. After removal of unreacted EO, 1.0 g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes and then extracted. The average PO addition mole number p was 1.0 and the average EO addition mole number q was 2. An alkoxylate of 0 was obtained.
The resulting alkoxylate was sulfated in a falling film reactor using SO ₃ gas. The obtained sulfate was neutralized with monoethanolamine to obtain a composition containing polyoxypropane-1,2-diylalkylether sulfate [(B1)].

[Component (C)]
(C1): Dipropylene glycol sulfate ester (compound (C)).
[Synthesis of Component (C1)]
Dipropylene glycol was sulfated using SO ₃ gas in a thin film sulfation reactor. At that time, SO ₃ gas was added to dipropylene glycol so that SO ₃ was 2 mole times or more, and sulfation was performed. Therefore, the sulfate obtained in this example is a diester type. Sodium hydroxide aqueous solution was added to the obtained sulfate to obtain component (C1).
The obtained component (C1) corresponds to the compound (C) in which AO is an oxypropylene group, m is 2, and M is Na in the formula (c1).

[(D) component]
(D1): Alkyl chloride (carbon number C12) trimethylammonium, manufactured by Lion Akzo Co., Ltd., trade name: ARCARD 12-37W.
(D2): alkyl chloride (carbon number C14) trimethylammonium, commercially available product.
(D3): Alkyl chloride (C16-C18) trimethylammonium, manufactured by Lion Akzo Co., Ltd., trade name “ARCARD T-800”.

[Water-miscible organic solvent]
Ethanol: manufactured by Nippon Alcohol Sales Co., Ltd., trade name “specific alcohol 95 degree synthesis”.
Glycerin: Kanto Chemical Co., Inc.
Diethylene glycol monobutyl ether: Product name “Butyl Diglycol” manufactured by Nippon Emulsifier Co., Ltd.
Propylene glycol: 1,2-propanediol (manufactured by Dow Chemical Company).

[Other optional ingredients]
Coconut fatty acid salt (higher fatty acid salt): Coconut fatty acid (manufactured by NOF Corporation) was blended in the content shown in the table. Palm fatty acid is neutralized with sodium hydroxide to form a sodium salt.
Monoethanolamine (MEA): manufactured by Nippon Shokubai Co., Ltd.
Dibutylhydroxytoluene (BHT, phenolic antioxidant): manufactured by Sumitomo Chemical Co., Ltd., trade name “SUMILZER BHT-R”.
Dye: Product name “Green No. 3” manufactured by Hatake Kasei Co., Ltd.
Fragrance | flavor: The fragrance | flavor composition A of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.
pH adjuster: hydrochloric acid (Kanto Chemical Co., Inc.) or sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.).
Water: Purified water.

<Examples 1 to 21>
Liquid detergents were prepared according to the compositions in Tables 1-4. Examples 1 to 18 are examples, and examples 19 to 21 are comparative examples.
First, water and a water-miscible organic solvent were put into a 500 mL beaker and sufficiently stirred with a magnetic stirrer (manufactured by MITAMURA KOGYO INC.). Next, the A component, B component, C component, and D component were added and stirred, and after adding other optional components, water was added so that the total amount became 95% by mass, and further stirred. After stirring, a pH adjuster (sodium hydroxide or hydrochloric acid, not shown in the table) is added so that the pH becomes 7 (25 ° C.), and purified water is added so that the total amount becomes 100% by mass. A liquid detergent for each example was obtained.

As shown in the results of Tables 1 to 4, the liquid detergents of Examples 1 to 18 containing the component (A), the component (B), and the compound (C) have excellent cleaning performance and good antifoaming properties. Met. Moreover, it was excellent in deodorizing property.
Example 19 is a comparative example containing no component (A). The defoaming property was good, but the cleaning performance was insufficient. The effect of suppressing room-drying odor was also insufficient.
Example 20 is a comparative example containing no compound (C). The cleaning performance was good, but the defoaming property was insufficient. The effect of suppressing room-drying odor was also insufficient.
From these results, by using the component (A) and the compound (C) in combination, it is possible to obtain a liquid detergent that simultaneously satisfies the cleaning property, defoaming property, and deodorizing effect (immediately after washing and after drying in the room). Recognize.

Example 21 is a comparative example containing the component (A), the component (B) and the compound (C) but having a small content of the compound (a1). The value of (a1) / (A) is as small as 0.04, and the cleaning performance is slightly inferior. Also, the appearance stability was poor.
Example 18 is an example in which the content of the compound (C) was increased. Although the cleaning performance, defoaming property and deodorizing property were good, the appearance stability was lowered.

Claims (2)

Nonionic surfactant (A) containing compound (a1) represented by the following general formula (a1), anionic surfactant (B) excluding higher fatty acid salts, and compound represented by the following general formula (c1) (C) and (a1) / (A) showing the mass ratio of the said compound (a1) with respect to the said nonionic surfactant (A) is 0.1 or more, The liquid detergent.

[Wherein, R ¹ represents a linear or branched hydrocarbon group having 8 to 22 carbon atoms. However, when R ¹ is linear, the carbon atom bonded to the oxygen atom is a secondary carbon. EO represents an oxyethylene group, and PO represents an oxypropylene group. p represents the average number of repetitions of EO, and is a number from 2 to 9. q represents the average number of repetitions of PO, and is a number from 0 to 3. ]

[Wherein, AO represents an oxyalkylene group having 2 to 4 carbon atoms, m is an integer of 1 to 20, and M represents an alkali metal or —NH ₄ . When m is 2 or more, the plurality of AOs may be the same as or different from each other. ]   Furthermore, the liquid cleaning agent of Claim 1 containing a cationic surfactant (D).