WO2018030399A1 - Liquid detergent - Google Patents

Abstract

A liquid detergent comprising: an α-sulfofatty acid alkyl ester salt (a) in which the fatty acid residue has 16-18 carbons; at least one (b) selected from the group consisting of sulfonic acid-type anionic surfactants other than (a), sulfate ester-type anionic surfactants, and nonionic surfactants; and an unsaturated fatty acid salt (c) having 16-22 carbons. With respect to the total mass of the liquid detergent, the content of (c) is 1.2-7.5 mass% and the total content of (a) plus (b) is 8-30 mass%. The content of (a) is not more than 50 mass% with respect to the total amount of (a) plus (b). (b) may or may not contain a linear alkylbenzenesulfonate salt (b1). If (b1) is incorporated, a (b) other than (b1) is incorporated and (b1)/{(b)-(b1)}, which is the mass ratio of (b1) with respect to the total content of (b) other than (b1), is not more than 2.0.

Description

Liquid cleaning agent

The present invention relates to a liquid cleaning agent.
This application claims priority based on Japanese Patent Application No. 2016-155688 filed in Japan on August 8, 2016, the contents of which are incorporated herein by reference.

In recent years, it has excellent hard water resistance, biodegradability, high detergency, and is a renewable plant-derived natural raw material system that has little impact on the environment. ) Is widely used as a cleaning component.
In addition, overseas liquid detergents are sometimes required to have high viscosity from the viewpoint of palatability.
In an example of Patent Document 1, a liquid detergent containing α-sulfo fatty acid methyl ester sodium salt and linear sodium C ₁₂ fatty acid sodium is disclosed.

JP-A-8-259991

For liquid detergents containing α-SF salts (alpha-SF salts with fatty acid residues having 16 or more carbon atoms), the liquid detergent solidifies and precipitates precipitate when stored in a low temperature environment Liquid stability may be impaired (that is, low temperature stability is inferior).
In order to increase the low-temperature stability of the liquid detergent, for example, it is conceivable to add a hydrotrope agent. However, in this case, the viscosity of the liquid detergent is lowered, and it is difficult to obtain a sufficient viscosity.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an α-SF salt-containing liquid detergent having excellent low-temperature stability and high viscosity.

The present invention has the following aspects.
[1] An α-sulfo fatty acid alkyl ester salt (a) represented by the following general formula (I), a sulfonic acid type anionic surfactant other than the component (a), a sulfate type anionic surfactant, and a nonionic interface At least one (b) selected from the group consisting of activators and an unsaturated fatty acid salt (c) having 16 to 22 carbon atoms,
The content of the component (c) is 1.2 to 7.5% by mass with respect to the total mass of the liquid detergent, and the component (a) and the component (b) with respect to the total mass of the liquid detergent And the total content of the component (a) and the component (b) is 50% by mass or less with respect to the total amount of the component (a) and the component (b),
When the component (b) does not contain or contains the linear alkylbenzene sulfonate (b1) and includes the component (b1), the component (b) contains the component (b) other than the component (b1), A liquid in which (b1) / {(b)-(b1)} representing a mass ratio of the content of the component (b1) to the total content of the component (b) other than the component (b1) is 2.0 or less Washing soap.
R ¹ —CH (SO ₃ M) —COOR ² (I)
[In the formula (I), R ¹ is a hydrocarbon group having 14 to 16 carbon atoms, R ² is a hydrocarbon group having 1 to 6 carbon atoms, and M is a counter ion. ]
[2] The component (b) comprises at least two selected from the group consisting of linear alkylbenzene sulfonate (b1), polyoxyethylene alkyl ether sulfate (b2), and polyoxyalkylene alkyl ether (b3). A liquid cleaning agent according to [1].
[3] The liquid detergent according to [1], wherein the content of the component (a) is 3 to 10% by mass with respect to the total mass of the liquid detergent.
[4] The liquid detergent according to [1], wherein the content of the component (b) is 5 to 27% by mass with respect to the total mass of the liquid detergent.
[5] The liquid detergent according to [1], wherein the total content of the component (a), the component (b) and the component (c) is 75 to 100% by mass with respect to the total mass of the surfactant.

[6] The liquid according to [1], wherein the content of the component (a) is 3 to 10% by mass and the content of the component (b) is 5 to 27% by mass with respect to the total mass of the liquid detergent. Washing soap.
[7] The content of the component (a) is 3 to 10% by mass and the content of the component (b) is 5 to 27% by mass with respect to the total mass of the liquid cleaning agent. The liquid detergent according to [1], wherein the total content of the component (a), the component (b), and the component (c) is 75 to 100% by mass with respect to the mass.

According to the present invention, an α-SF salt-containing liquid detergent having excellent low-temperature stability and high viscosity can be obtained.

≪Liquid cleaning agent≫
The liquid cleaning agent of the present invention is a liquid composition containing the component (a), the component (b), and the component (c).
The liquid detergent of the present invention has an embodiment in which the component (b) contains a linear alkylbenzene sulfonate (b1) and an embodiment that does not contain a linear alkylbenzene sulfonate (b1). In an embodiment in which the component (b) contains the component (b1), the liquid detergent also contains a component (b) other than (b1).

<(A) component>
The component (a) is an α-sulfo fatty acid alkyl ester salt represented by the following general formula (I) (hereinafter also referred to as α-SF salt).
R ¹ —CH (SO ₃ M) —COOR ² (I)
In the formula (I), R ¹ is a hydrocarbon group having 14 to 16 carbon atoms, R ² is a hydrocarbon group having 1 to 6 carbon atoms, and M is a counter ion.

In the formula (I), the hydrocarbon group of R ¹ may be linear or branched, or may contain a cyclic structure. Among them, the hydrocarbon group for R ¹ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group, and a linear chain And more preferably a linear alkyl group and a linear alkenyl group.
The hydrocarbon group for R ² may be linear or branched, or may contain a cyclic structure. Among these, the hydrocarbon group for R ² is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group, and a linear chain. And more preferably a branched alkyl group and a branched alkyl group. R ² has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Examples of the hydrocarbon group for R ² include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. A methyl group, an ethyl group, and an n-propyl group are preferable, and a methyl group is particularly preferable because the detergency is further improved as a cleaning component.

M is a counter ion as long as it can form a water-soluble salt with R ¹ CH (COOR ² ) SO ₃ ^— . Examples of the counter ion M include alkali metal ions, protonated amines, ammonium and the like. Examples of the alkali metal that can be the counter ion M include sodium.
Examples of the amine that can be the counter ion M include primary to tertiary amines. The total number of carbon atoms of the amine is preferably 1-6. The amine may have a hydroxy group.
Since the solubility of α-SF salt in water increases, the amine preferably has a hydroxy group. Examples of the amine include alkanolamine, and the alkanol group preferably has 1 to 3 carbon atoms. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.
As the counter ion M, an alkali metal ion is preferable and a sodium ion is particularly preferable because it is easily available and the low-temperature stability of the liquid detergent is more easily increased.

As the component (a), any one type may be used alone, or two or more types may be used in combination.
As the component (a), the cleaning power increases as a cleaning component, and the solubility in water increases. Therefore, a mixture in which fatty acid residues (referred to as acyl group moieties) having different carbon numbers are mixed is used. preferable. Specifically, an α-SF salt represented by the above general formula (I), which is an α-SF salt (a1) in which R ¹ has 14 carbon atoms, and an α-SF salt in which R ¹ has 16 carbon atoms. The salt (a2) is preferably a mixture having a mass ratio of a1: a2 = 45: 55 to 95: 5, more preferably a mixture of a1: a2 = 60: 40 to 90:10, and a1: a2 = 80 More preferably, the mixture is 20 to 85:15. When the mass ratio of a1: a2 is within the above preferable range, the detergency, solubility in water, and appearance stability become better.

The content of the component (a) with respect to the total mass of the liquid detergent is preferably 3% by mass or more from the viewpoint that the effect of the present invention can be more easily enjoyed. Moreover, 10 mass% or less is preferable from the point which is easy to obtain the liquid detergent excellent in low-temperature stability, 9 mass% or less is more preferable, and 6 mass% or less is further more preferable.

<(B) component>
The component (b) is at least one selected from the group consisting of sulfonic acid type anionic surfactants, sulfate ester type anionic surfactants and nonionic surfactants other than the component (a).
In the liquid detergent containing the component (a), the viscosity is increased and the low-temperature stability is improved by using the component (b) in combination with the component (c) described later.

[Sulphonic acid type anionic surfactant other than component (a)]
Examples of the sulfonic acid type anionic surfactant other than the component (a) include linear alkylbenzene sulfonate (LAS), α-SF salt having a fatty acid residue of 14 or less, α-olefin sulfonate (AOS) And alkane sulfonates.
As the linear alkylbenzene sulfonate, the linear alkyl group preferably has 8 to 20 carbon atoms, and more preferably 10 to 14 carbon atoms.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms, more preferably one having 10 to 16 carbon atoms.
As the α-SF salt having 14 or less fatty acid residues, the fatty acid residue preferably has 10 to 14 carbon atoms, and more preferably 12 to 14 carbon atoms.
The alkane sulfonate is preferably a secondary alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 18 carbon atoms.
Examples of these salts include alkali metal salts such as sodium and potassium, alkanolamine salts such as monoethanolamine salt, diethanolamine salt, and triethanolamine salt, alkylamine salts, and ammonium salts. Of these, alkali metal salts are preferred.

[Sulfate ester type anionic surfactant]
Examples of the sulfate type anionic surfactant include alkyl sulfates, alkyl ether sulfates, alkenyl ether sulfates (AES), and the like.
The alkyl sulfate is preferably a linear or branched chain having 10 to 20 carbon atoms, and more preferably a linear or branched chain having 10 to 16 carbon atoms.
The alkyl ether sulfate is preferably a polyoxyethylene alkyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms and having an average of 1 to 10 moles of ethylene oxide added thereto. Among these, from the viewpoint of improving the liquid stability of the liquid detergent, the carbon number of the alkyl group of the polyoxyethylene alkyl ether sulfate is more preferably 10 to 14, and from the viewpoint of improving the detergency, the average added mole number of ethylene oxide is increased. Is more preferably 1 to 4.
As the alkenyl ether sulfate, a polyoxyethylene alkenyl ether sulfate having a linear or branched alkenyl group having 10 to 20 carbon atoms and added with an average of 1 to 10 moles of ethylene oxide is preferable.
Examples of these salts include alkali metal salts such as sodium and potassium, alkanolamine salts such as monoethanolamine salt, diethanolamine salt, and triethanolamine salt, alkylamine salts, and ammonium salts. Of these, alkali metal salts are preferred.

[Nonionic surfactant]
Nonionic surfactants include polyoxyalkylene type nonionic surfactants obtained by adding alkylene oxide to higher alcohols, alkylphenols, higher fatty acids, higher fatty acid esters or higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamides, Polyhydric alcohol fatty acid ester or alkylene oxide adduct thereof, fatty acid polyglycerin ester, sugar fatty acid ester, alkyl (or alkenyl) amine oxide, amidoamine oxide, alkylene oxide adduct of hydrogenated castor oil, N-alkyl polyhydroxy fatty acid amide, alkyl Examples include glycosides, alkyl polyglycosides, and glyceryl ethers. Here, the term “higher” means a compound having 8 or more carbon atoms.

As the nonionic surfactant, a polyoxyalkylene type nonionic surfactant is preferable. Among the polyoxyalkylene type nonionic surfactants, polyoxyalkylene alkyl ether (AE) obtained by adding alkylene oxide to a saturated higher alcohol is preferable.
The number of carbon atoms of the alkyl group of the polyoxyalkylene alkyl ether is preferably 8-18, and the number of carbon atoms of the alkyl group is more preferably 10-16, and particularly preferably 10-14, from the viewpoint of improving detergency. If the carbon number of the alkyl group is 8 or more, the function as a surfactant can be sufficiently exerted, and excellent cleaning power can be imparted to the liquid cleaning agent. On the other hand, if the carbon number of the alkyl group is 18 or less, the liquid state is easily maintained, and thus the liquid stability of the liquid detergent is further improved.

The alkylene oxide may be any one of ethylene oxide, propylene oxide, or butylene oxide, or a mixture of two or more of these. Among the alkylene oxides, ethylene oxide and / or propylene oxide are preferable, and ethylene oxide is more preferable. When two or more kinds of ethylene oxide, propylene oxide, or butylene oxide are mixed, these may be mixed in a random form or in a block form. The average number of added moles of alkylene oxide is a number of 5 to 30, preferably 5 to 20, and more preferably 5 to 10 from the viewpoint of improving the stability of the liquid detergent.

As the component (b), any one type may be used alone, or two or more types may be used in combination.
As the component (b), linear alkylbenzene sulfonate (b1), polyoxyethylene alkyl ether sulfate (b2), and polyoxyalkylene alkyl ether (b3) are preferable.
It is preferable that the component (b1) is included as a part of the component (b) from the viewpoint that a liquid detergent having excellent low temperature stability and high viscosity can be easily obtained. Moreover, it is preferable that (b) component contains 2 or more types chosen from the group which consists of (b1) component, (b2) component, and (b3) component from the point which is easy to obtain the liquid cleaning agent which is more excellent in detergency, More preferably, the component (b1), the component (b2) and the component (b3) are used in combination.

The content of the component (b) is preferably 5 to 27% by mass, more preferably 7 to 25% by mass, further preferably 7 to 20% by mass, with respect to the total mass of the liquid detergent, and 10 to 20% by mass. Is particularly preferred. When the content of the component (b) is in the above preferred range, a liquid detergent that is excellent in low-temperature stability is easily obtained.

The total content of the component (a) and the component (b) in the liquid detergent (hereinafter also referred to as “(a + b) total content”) is 8 to 30% by mass. (A + b) When the total content is within the above range, the low-temperature stability is excellent, and a high-viscosity liquid detergent is easily obtained. The total content of (a + b) is preferably 10 to 25% by mass.

The content of the component (a) is 50% by mass or less with respect to the total content (a + b). When the content of the component (a) is 50% by mass or less, the low temperature stability is excellent.
The content of the component (a) is preferably 45% by mass or less and more preferably 30% by mass or less with respect to the total content (a + b). The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. When the content of the component (a) is equal to or more than the lower limit, the effect of the present invention obtained by using the component (a), the component (b), and the component (c) in combination can be easily enjoyed.

When the component (b1) is included as part of the component (b), the mass ratio represented by (b1) / {(b)-(b1)}, that is, other than the component (b1) in the component (b) The mass ratio of the content of component (b1) to the total content of components (hereinafter also referred to as “(b1) / {(b)-(b1)} ratio)” is 2.0 or less. When the (b1) / {(b)-(b1)} ratio is 2.0 or less, the low temperature stability is excellent. When the component (b) includes the component (b1), the lower limit value of the (b1) / {(b)-(b1)} ratio is greater than zero.
The ratio (b1) / {(b)-(b1)} is preferably 0.2 to 1.5, preferably 0.3 to 1. in terms of excellent low-temperature stability and easy to obtain a high viscosity liquid detergent. 3 is more preferable, and 0.5 to 1.0 is more preferable.

<(C) component>
Component (c) is an unsaturated fatty acid salt having 16 to 22 carbon atoms. In the liquid detergent containing the component (a), the viscosity is increased and the low-temperature stability is improved by using the component (b) and the component (c) together.
Examples of the component (c) include palmitate, oleate, vacsenate, linoleate, linolenate, arachidonate, and erucate. Among these, oleate and linoleate are preferable, and oleate is more preferable.
Examples of these salts include alkali metal salts such as sodium and potassium, alkanolamine salts such as monoethanolamine salt, diethanolamine salt, and triethanolamine salt, alkylamine salts, and ammonium salts. Of these, alkali metal salts or alkanolamine salts are preferred.

As the component (c), any one type may be used alone, or two or more types may be used in combination.
The content of the component (c) is 1.2 to 7.5% by mass with respect to the total mass of the liquid detergent.
When the content of the component (c) is in the above range, it is easy to obtain a liquid detergent having excellent low temperature stability and high viscosity. The content of the component (c) is preferably 1.5 to 5.0% by mass.

The total content of the component (a), the component (b), and the component (c) is preferably 75% by mass or more, more preferably 80% by mass or more, and 90% by mass or more with respect to the total mass of the surfactant. More preferably, it may be 100% by mass.
When the total content of the components (a) to (c) with respect to the total mass of the surfactant is not less than the above lower limit value, it is excellent in low-temperature stability and a high-viscosity liquid detergent is easily obtained.

<Other ingredients>
In addition to the above components (a) to (c), the liquid cleaning agent of the present invention may contain other components usually used for liquid cleaning agents.
Examples of other components include surfactants other than the components (a) to (c), water-miscible organic solvents, chelating agents, bactericides, antiseptics, antifungal agents, dyes, antioxidants, and UV absorbers. , Fragrance, pH adjuster, water and the like.

[Surfactants other than the components (a) to (c)]
Examples of the surfactant other than the components (a) to (c) include carboxylic acid type or phosphoric acid type anionic surfactants, amphoteric surfactants, and the like.
Examples of the carboxylic acid type anionic surfactant include higher fatty acid salts other than the component (c) (hereinafter also referred to as the component (d)), alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyls (or Alkenyl) amide ether carboxylate, acylaminocarboxylate and the like.
Examples of the phosphoric acid type anionic surfactants include alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkylphenyl phosphate ester salts, glycerin fatty acid ester monophosphate ester salts, and the like.
Examples of these salts include alkali metal salts such as sodium and potassium; alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt, ammonium salts and the like. Among these, alkali metal salts are preferable.

Amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfonic acid type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type. Is mentioned.

It is preferable that the liquid detergent contains a higher fatty acid salt (component (d)) other than the component (c) from the viewpoint of imparting an appropriate viscosity. Component (d) preferably has 8 to 14 carbon atoms. For example, caprate, laurate and myristate are preferable, and caprate and laurate are more preferable.
The mass ratio of the content of the component (d) to the content of the component (c) ((d) / (c)) is preferably 3.0 or less, more preferably 2.0 or less, and further preferably 1.0 or less. preferable. When the mass ratio of (d) / (c) is 3.0 or less, excellent low temperature stability and high viscosity are easily obtained.
When the liquid detergent contains the component (d), the lower limit of the mass ratio (d) / (c) is preferably 0.25 or more, and more preferably 0.66 or more.

[Water-miscible organic solvent]
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, Examples thereof include polyglycols such as polyethylene glycol and dipropylene glycol having a weight average molecular weight of about 200 to 1000, and alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and diethylene glycol dimethyl ether.
In the present invention, the water-miscible organic solvent means an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.

[water]
The liquid detergent of the present invention preferably uses water or a mixture of water or one or more water-miscible organic solvents and water as a solvent.
The total content of water and the water-miscible organic solvent with respect to the total mass of the liquid detergent is not particularly limited, but is preferably 50 to 90% by mass, more preferably 60 to 85% by mass.

[PH adjuster]
In the liquid cleaning agent of the present invention, a pH adjusting agent may be blended to bring the pH to a desired value.
However, in the case where the pH of the liquid cleaning agent becomes a desired value simply by blending the above-described components, the pH adjusting agent is not necessarily blended. Examples of the pH adjuster include acidic compounds such as sulfuric acid and hydrochloric acid, and alkaline compounds such as sodium hydroxide and potassium hydroxide. As the alkaline compound, amines other than the alkanolamine can be used. These pH adjusters may be used alone or in combination of two or more.

<PH and viscosity of liquid detergent>
The liquid detergent of the present invention preferably has a pH of 5 to 9 at 25 ° C., more preferably 7 to 9. When the pH of the liquid detergent is within the above-mentioned preferred range, when the liquid detergent is stored for a long period of time, the α-SF salt is more stabilized, so that good detergency is easily maintained. Moreover, since low temperature stability becomes easy to be improved more by making pH below the said upper limit, it is preferable.
The pH of the liquid detergent in the present invention at 25 ° C. is measured by adjusting the sample to 25 ° C. and using a pH meter (for example, using a product name “HM-30G” manufactured by Toa DKK Corporation). Indicates the value.

In the present specification, the viscosity of the liquid detergent is a value at 25 ° C. unless otherwise specified.
The viscosity of the liquid detergent of the present invention is preferably 500 mPa · s or more, and more preferably 1000 mPa · s or more. The upper limit is 20000 mPa.s. s or less is preferable, and 10000 mPa · s or less is more preferable.
When the viscosity of the liquid cleaning agent is equal to or higher than the lower limit, it can be clearly detected that the viscosity of the liquid cleaning agent has been increased, and the palatability is improved. If it is not more than the above upper limit value, for example, the liquid cleaning agent can be easily poured out from the container, and the usability is improved.
The viscosity of the liquid detergent is preferably 500 to 20000 mPa · s, more preferably 500 to 10000 mPa · s, further preferably 500 to 5000 mPa · s, particularly preferably 750 to 4000 mPa · s, and most preferably 1000 to 3000 mPa · s. .

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In this example, “%” indicates “% by mass” unless otherwise specified.
The raw materials used in this example are as follows.

<(A) component>
a-1: α-SF salt synthesized in Synthesis Example 1 below (sodium salt of sulfonated mixture of methyl palmitate / methyl stearate = 85/15 in mass ratio).
a-2: α-SF salt synthesized by Synthesis Example 2 below (sodium salt of sulfonated mixture of methyl palmitate / methyl stearate = 60/40 by mass ratio).
a-3: Composition (c12468) synthesized according to Synthesis Example 3 below (in terms of mass ratio, methyl laurate / methyl myristate / methyl palmitate / methyl stearate = 18.75 / 6.25 / 63.75 / 11) .Alpha.-SF salt derived from methyl palmitate and methyl stearate.

<(B) component>
b1-1: LAS, linear alkyl (carbon number 12-14) sodium benzenesulfonate (manufactured by Lion Corporation, trade name “Lypon LS-250”).
b2-1: AES, polyoxyethylene alkyl (carbon number 12-14) ether sodium sulfate [average number of added moles of ethylene oxide 2]. Product name “EMAL270N” manufactured by Kao Corporation.
b3-1: AE, polyoxyethylene alkyl (carbon number 12 to 14) ether (average number of added moles of ethylene oxide 7), manufactured by Lion Corporation, trade name “LEOX CL-70”.
b4-1: Composition (c12468) synthesized according to Synthesis Example 3 below (in terms of mass ratio, methyl laurate / methyl myristate / methyl palmitate / methyl stearate = 18.75 / 6.25 / 63.75 / 11) .Alpha.-SF salt derived from methyl laurate and methyl myristate.

<(C) component>
c-1: Sodium oleate, reagent, manufactured by Tokyo Chemical Industry Co., Ltd.
c-2: Sodium oleate and oleic acid (reagent, manufactured by Kanto Chemical Co., Inc.) neutralized with sodium hydroxide are used.
c-3: Sodium linoleate and linoleic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) neutralized with sodium hydroxide are used.

<(D) component: higher fatty acid salt other than (c) component>
d-1: Sodium laurate, reagent, manufactured by Kanto Chemical Co., Inc.
d-2: Sodium myristate, reagent, manufactured by Tokyo Chemical Industry Co., Ltd.
d-3: Sodium coconut fatty acid, manufactured by NOF Corporation, product name “coconut fatty acid”, coconut fatty acid neutralized with sodium hydroxide is used.

<Synthesis Example 1: Synthesis of a-1>
Methyl palmitate (trade name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (trade name: Pastel M-180, manufactured by Lion Corporation) were mixed at a mass ratio of 85:15. A fatty acid methyl ester mixture was obtained. After injecting 330 kg of this fatty acid methyl ester mixture into a 1 kL reactor equipped with a stirrer, 115.6 kg of SO ₃ gas (sulfonated gas) diluted to 4% by volume with nitrogen gas while stirring the mixture (described above) 1.2 moles relative to the fatty acid methyl ester mixture) was bubbled. The reaction temperature was 80 ° C. The sulfonated gas was blown into the fatty acid methyl ester mixture at a constant rate over 3 hours. Thereafter, 1.5 parts by mass of anhydrous sodium sulfate was added to 100 parts by mass of the fatty acid methyl ester mixture, followed by aging for 30 minutes while maintaining the temperature at 80 ° C.
Thereafter, 13.5 kg of methanol was supplied, and esterification was performed at a temperature condition of 80 ° C. and an aging time of 30 minutes. Subsequently, the esterified product extracted from the reaction apparatus was continuously neutralized by adding an equivalent amount of aqueous sodium hydroxide solution using a line mixer. This neutralized product was poured into a bleaching agent mixing line, 35% by volume of hydrogen peroxide solution was supplied and mixed, and bleaching was performed while maintaining the temperature at 80 ° C. to obtain a paste-like α-SF salt 1.
The obtained paste-like α-SF salt 1 was rotated at a rotation speed of 1060 rpm and a blade tip speed of about 11 m / s (heat transfer surface: 0.5 m ² , inner diameter of cylindrical processing section) : 205 mm, clearance between heat transfer surface and blade tip as scraping means: 3 mm, product name “Exeva”, manufactured by Shinko Pantech Co., Ltd. at 35 kg / hr, inner wall heating temperature (heat transfer surface temperature) ) Concentration was performed under conditions of 135 ° C. and a degree of vacuum (pressure in the processing section) of 0.007 to 0.014 MPa. The resulting concentrate had a temperature of 115 ° C. and a moisture content of 2.5%.
Each of the obtained concentrates was continuously supplied at 222 kg / h to a double belt type belt cooler (NR3-Lo. Cooler) manufactured by Nippon Belting Co., Ltd. in which the clearance between input pulleys was adjusted to 2 mm, and cooled. The belt moving speed at this time is 6 m / s, and the flow rate of the cooling water is 1500 L / h on the upper belt side (cooled by flowing down on the back surface of the belt in a countercurrent manner) and 1800 L / h on the lower belt side (belt back surface) The cooling water supply temperature was 20 ° C. Next, the α-SF salt-containing sheet obtained by discharging from the cooling belt is crushed at a rotation speed of 200 rpm by an attached crusher installed near the discharge pulley, thereby obtaining a flaky shape at 25 ° C. α-1 which is an α-SF salt solid was obtained.

<Synthesis Example 2: Synthesis of a-2>
Methyl palmitate (trade name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (trade name: Pastel M-180, manufactured by Lion Corporation) were mixed at a mass ratio of 6: 4. A fatty acid methyl ester mixture was obtained. After pouring 330 kg of this fatty acid methyl ester mixture into a 1 kL reactor equipped with a stirrer, while stirring the mixture, anhydrous sodium sulfate was added as a coloring inhibitor to 5 parts by mass with respect to 100 parts by mass of the fatty acid methyl ester mixture. Part. Thereafter, while the stirring was continued, 112.8 kg of SO ₃ gas (sulfonated gas) diluted to 4% by volume with nitrogen gas (1.2 times mol with respect to the fatty acid methyl ester mixture) was bubbled. The reaction temperature was 80 ° C. The sulfonated gas was blown into the fatty acid methyl ester mixture at a constant rate over 3 hours. Thereafter, aging was continued for 30 minutes while maintaining the temperature at 80 ° C.
Subsequently, esterification, neutralization and bleaching were carried out in the same manner as in a-1 to obtain a pasty α-SF salt 2. Furthermore, a-2 as an α-SF salt solid was obtained in the same manner as above except that α-SF salt 2 was used instead of α-SF salt 1.

<Synthesis Example 3: Synthesis of (c12468) composition>
In this example, an α-SF salt-containing liquid was prepared by a method of sulfonating a mixture in which fatty acid esters were mixed at a desired ratio.
First, as fatty acid esters as raw materials, methyl laurate (product name: Pastel M-12, manufactured by Lion Corporation) and methyl myristate (product name: Pastel M-14, manufactured by Lion Corporation), mass of 75:25 The mixture (henceforth c124ME) was prepared by mixing so that it might become ratio.
Methyl palmitate (trade name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (trade name: Pastel M-180, manufactured by Lion Corporation) were mixed at a mass ratio of 85:15. A mixture (hereinafter referred to as c168ME-1) was prepared.
c124ME and c168ME-1 were mixed so that the mass ratio of c124ME / c168ME was 1/3 to prepare a fatty acid methyl ester mixture.
Injecting 330 kg of the fatty acid methyl ester mixture into a 1 kL reactor equipped with a stirrer, maintaining the reaction temperature at 80 ° C. while stirring, SO ₃ gas (sulfonated gas) diluted to 8% by volume with nitrogen gas 115. 6 kg (1.15 moles relative to the fatty acid methyl ester mixture) was blown at a constant speed over 4 hours while bubbling. Thereafter, 0.25 parts by mass of anhydrous sodium sulfate was added to 100 parts by mass of the fatty acid methyl ester mixture, and aging was performed for 30 minutes while maintaining the temperature at 80 ° C. Thereafter, 13.5 kg of methanol (supplied as a lower alcohol was supplied, and esterification was carried out at a temperature of 80 ° C. and an aging time of 60 minutes. Then, the esterified product extracted from the reactor was treated with an equivalent amount of water using a line mixer. Neutralization was continued by adding aqueous sodium oxide solution.
Next, this neutralized product was poured into the bleaching agent mixing line, and 35% by volume of hydrogen peroxide solution was supplied at 1% by mass with respect to the AI content in terms of pure content, mixed, and kept at 80 ° C. Bleached.
Subsequently, methanol was removed using a vacuum thin film evaporator to obtain a paste-like (c12468) composition.

<AI measurement method>
Α-SF salt concentration in component (a) (total concentration (AI) of α-sulfo fatty acid methyl ester salt (α-SF-Na) and α-sulfo fatty acid disodium salt (di-Na salt)) is as follows: It measured as follows.
A sample having an amount of 0.2 g was accurately weighed into a 200 mL volumetric flask, ion-exchanged water (distilled water) was added up to the marked line, and the sample was dissolved in ion-exchanged water by ultrasonic waves. After dissolution, it is cooled to about 25 ° C., 5 mL of this sample aqueous solution is taken into a titration bottle with a whole pipette, 25 mL of methylene blue indicator and 15 mL of chloroform are added, and further 5 mL of 0.004 mol / L benzethonium chloride solution is added, Titration was performed with a 0.002 mol / L sodium alkylbenzenesulfonate solution. In each titration, the titration bottle was capped and shaken vigorously, then allowed to stand, and the end point was the point where both layers separated against a white plate became the same color.
Similarly, a blank test (the same test as described above except that no sample is used) is performed, and the AI content in the α-SF salt solid is calculated from the following formula from the difference in titration of the sodium alkylbenzenesulfonate solution. did.
AI content (mass%) = (Titrate in blank test (mL) −Titration (mL)) × 0.002 (mol / L) × molecular weight of α-sulfo fatty acid methyl ester salt / (sample amount ( g) × 5 (mL) / 200 (mL)) / 10
As a result of the above measurement, the α-SF salt concentration in a-1 was 90.0%, the α-SF salt concentration in a-2 was 88.1%, (c12468) Methyl palmitate and stearic acid in the composition The concentration of α-SF salt derived from methyl was calculated to be 56.5%, and the concentration of α-SF salt derived from methyl laurate and methyl myristate in the composition (c12468) was calculated to be 18.8%. In this example, these values were used for the contents of the component (a) and the component (b4-1), and a liquid detergent was prepared so that the mass% described in the examples was obtained.

<Examples 1 to 16, Comparative Examples 1 to 7>
According to the composition shown in Tables 1 and 2, the components (a) to (c) and, if necessary, the component (d) are added to and mixed with purified water, and the pH at 25 ° C. becomes 7.5 to 8.0. Thus, a pH adjusting agent was added as needed to obtain a liquid detergent.
In the table, when there is a blank blending component, the blending component is not blended.
In the table, the content of the compounding component indicates a pure conversion amount unless otherwise specified.
“Balance” indicating the content of purified water means the balance added so that the total amount (mass%) of all the ingredients contained in the liquid detergent is 100 mass%.
About the obtained liquid detergent, the viscosity and low-temperature stability were evaluated by the following method. The evaluation results are shown in Tables 1 and 2.

<Evaluation method>
[Low temperature stability]
The liquid detergent 50m was taken in a sample bottle, put in a thermostatic bath at 0 ° C. and 5 ° C., and the appearance was visually evaluated after one month.
(Criteria)
A: Transparent at 0 ° C.
B: Transparent at 5 ° C.
C: Opaque or solidified at 5 ° C.

[viscosity]
The liquid detergent 50m was placed in a sample bottle, the sample was adjusted to 25 ° C., and then measured using a B-type viscometer (manufactured by TOKIMEC). The measurement conditions are shown below.
Measurement conditions: Measure the viscosity after 30 seconds at 30 rpm.
When the viscosity is in the range of 100 to 5000 mPa · s, the rotor No. 3 is used.
When the viscosity is 100 mPa · s or less, the rotor No. Use 1 or 2.
When the viscosity is 5000 mPa · s or more, the rotor No. 4 is used.
(Criteria)
A: 1000 mPa · s or more.
B: 500 mPa · s or more and less than 1000 mPa · s.
C: Less than 500 mPa · s.
Note that the viscosity measurement was performed only when the low-temperature stability evaluation was A or B, and when the low-temperature stability evaluation was C, the viscosity was not measured, so “−” was shown in the table.

From the results shown in Tables 1 and 2, the liquid detergents of Examples 1 to 16 to which the present invention was applied had high viscosity and good low-temperature stability.
The liquid detergents of Comparative Example 1 containing no component (c) and Comparative Example 2 containing a small amount of the component (c) had low viscosity.
The liquid detergent of Comparative Example 3 having a high content of component (c) had insufficient low-temperature stability.
In Comparative Example 4 in which the content of the component (c) was reduced and the component (d) was contained instead, the low temperature stability was insufficient.
Comparative Example 5 having a large total content of the component (a) and the component (b) had insufficient low-temperature stability.
Comparative Example 6 in which the ratio of the content of the component (a) relative to the total amount of the component (a) and the component (b) was large was insufficient in low-temperature stability.
Comparative Example 7 having a large (b1) / {(b)-(b1)} ratio had insufficient low-temperature stability.

Claims (5)

Α-sulfo fatty acid alkyl ester salt (a) represented by the following general formula (I):
At least one (b) selected from the group consisting of sulfonic acid type anionic surfactants other than the component (a), sulfate ester type anionic surfactants and nonionic surfactants;
An unsaturated fatty acid salt having 16 to 22 carbon atoms (c),
The content of the component (c) is 1.2 to 7.5% by mass with respect to the total mass of the liquid detergent,
The total content of the component (a) and the component (b) is 8 to 30% by mass with respect to the total mass of the liquid detergent,
The content of the component (a) is 50% by mass or less with respect to the total amount of the component (a) and the component (b),
When the component (b) does not contain or contains the linear alkylbenzene sulfonate (b1) and includes the component (b1), the component (b) contains the component (b) other than the component (b1), A liquid in which (b1) / {(b)-(b1)} representing a mass ratio of the content of the component (b1) to the total content of the component (b) other than the component (b1) is 2.0 or less Washing soap.
R ¹ —CH (SO ₃ M) —COOR ² (I)
[In the formula (I), R ¹ is a hydrocarbon group having 14 to 16 carbon atoms, R ² is a hydrocarbon group having 1 to 6 carbon atoms, and M is a counter ion. ] The component (b) contains two or more selected from the group consisting of linear alkylbenzene sulfonate (b1), polyoxyethylene alkyl ether sulfate (b2), and polyoxyalkylene alkyl ether (b3). Item 2. A liquid cleaning agent according to Item 1. The liquid detergent according to claim 1, wherein the content of the component (a) is 3 to 10% by mass with respect to the total mass of the liquid detergent. The liquid detergent according to claim 1, wherein the content of the component (b) is 5 to 27% by mass with respect to the total mass of the liquid detergent. The liquid detergent according to claim 1, wherein the total content of the component (a), the component (b) and the component (c) is 75 to 100% by mass with respect to the total mass of the surfactant.