JP2017014425A - Liquid detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent containing α-SF salt excellent in low temperature stability.SOLUTION: There is provided a liquid detergent containing an α-sulfo fatty acid alkyl ester salt represented by the following general formula (I) (a) and alkyl glycoside having an alkyl group having 8 to 10 carbon atoms (b). R-CH(SOM)-COOR(I), Ris a hydrocarbon group having 14 to 16 carbon atoms, Ris a hydrocarbon group having 1 to 6 carbon atoms and M is a counter ion.SELECTED DRAWING: None

Description

  The present invention relates to a liquid cleaning agent.

In recent years, α-sulfo fatty acid alkyl ester salts (α-SF salts) have been washed because they are excellent in hard water resistance, biodegradability, have high detergency, and are reproducible plant-derived natural raw materials that have little impact on the environment. Cleaning agents contained as components are widely used.
However, in a liquid detergent containing an α-SF salt having a fatty acid residue having a large number of carbon atoms (an α-SF salt having a fatty acid residue having 16 or more carbon atoms), the liquid cleaning is performed when stored in a low temperature environment. In some cases, the agent solidifies or precipitates are formed, and liquid stability is impaired (that is, low-temperature stability is impaired).
It is known that the low temperature stability of the liquid detergent can be improved by adding linear alkylbenzene sulfonate (LAS) to the liquid detergent containing the α-SF salt.
However, LAS is a petroleum-derived raw material and has a benzene ring, compared with surfactants such as α-SF salt, alkyl ether sulfate (AES), polyoxyalkylene alkyl ether (AE) and the like. Due to the poor biodegradability and the like, there may be a need for a detergent with a reduced LAS content or no LAS. Furthermore, LAS may not exhibit sufficient detergency in regions where the water resistance is low and the water hardness is high compared to surfactants such as α-SF salts.
Patent Document 1 discloses a liquid detergent containing an α-SF salt and an alkyl glucoside having an alkyl group having 12 to 14 carbon atoms.

JP2013-203775A

  The present invention has been made in view of the above circumstances, and an object thereof is an α-SF salt-containing liquid detergent excellent in low-temperature stability.

As a result of intensive studies, the present inventors have found that the following liquid cleaning agents can solve the above problems.
That is, the present invention has the following configuration.
[1] α-sulfo fatty acid alkyl ester salt (a) represented by the following general formula (I):
A liquid detergent containing an alkyl glycoside (b) having an alkyl group having 8 to 10 carbon atoms.
R ¹ —CH (SO ₃ M) —COOR ² (I)
However, in 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 liquid detergent according to [1], wherein a mass ratio represented by the component (b) / the component (a) is 1.5 or more.

  According to the present invention, it is possible to provide an α-SF salt-containing liquid detergent having excellent low-temperature stability.

(Liquid cleaning agent)
The liquid detergent of the present invention is a liquid composition containing the component (a) and the component (b).

<(A) component>
The component (a) is an α-sulfo fatty acid alkyl ester salt (α-SF salt) represented by the following general formula (I).
R ¹ —CH (SO ₃ M) —COOR ² (I)
However, in 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. Since the detergency is further improved as a cleaning component, a methyl group, an ethyl group, and an n-propyl group are A methyl group is preferable, and a methyl group is particularly preferable.
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 include an alkali metal ion, a protonated amine, and ammonium. Examples of the alkali metal that can serve as the counter ion include sodium and potassium. Examples of the amine that can be the counter ion 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 is increased, 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.
M is preferably an alkali metal ion and particularly preferably a sodium ion because it is easily available and the low-temperature stability of the liquid detergent can be further enhanced.

Among the components (a), R ¹ in the formula (I) is a linear or branched alkyl group having 14 to 16 carbon atoms, or a linear or branched alkenyl group, and R A compound in which ² is a methyl group is particularly preferred.
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, the α-SF salt represented by the general formula (I) includes an α-SF salt (a1) having 14 carbon atoms in R ¹ and an α-SF salt having 16 carbon atoms in R ^1. (A2) is preferably a mass ratio of a1: a2 = 45: 55 to 95: 5, more preferably 60:40 to 90:10, and 80:20 to 85:15 Is more preferable. When the mass ratio is within the above-described preferable range, the detergency, solubility in water, and appearance stability are further improved.

The content of the component (a) is preferably 3 to 15% by mass, more preferably more than 3% by mass and 10% by mass or less, still more preferably more than 3% by mass and 7% by mass or less based on the total mass of the liquid detergent. .
When the content of the component (a) is equal to or higher than the lower limit, the effect of the present invention obtained by using the component (a) and the component (b) described later in combination can be more easily enjoyed. When the content of the component (a) is not more than the above upper limit, the low temperature stability is further improved.

Further, the content of the component (a) is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less with respect to the total mass of the surfactant (including the component (b)). . When the content of the component (a) is equal to or lower than the above upper limit, a liquid detergent having excellent low-temperature stability is easily obtained.
The content of the component (a) is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more with respect to the total mass of the surfactant. When the content of the component (a) is equal to or higher than the lower limit, it becomes easier to enjoy the effects of the present invention obtained by using the component (a) and the component (b) together. Furthermore, it becomes easy to obtain a liquid detergent in which the detergency is not easily lowered even when used under conditions of high water hardness.

<(B) component>
The component (b) is an alkyl glycoside having an alkyl group having 8 to 10 carbon atoms.
The liquid detergent of the present invention is improved in low-temperature stability by containing the component (b).
(B) As a component, the compound represented by the following general formula (II) is mentioned.

R ³ (OR ⁴ ) _x G _y (II)
However, in formula (II), R ³ is a linear or branched alkyl group having 8 to 10 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and G is a reduction It is a residue derived from sugar. x is the average number of repetitions of (OR ⁴ ) and is a number from 0 to 5, and y is the average degree of condensation of sugars and is a number from 1 to 5.

R ³ is a linear or branched alkyl group having 8 to 10 carbon atoms.
R ⁴ is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
Examples of G include a residue derived from a monosaccharide, disaccharide, or trisaccharide or more reducing sugar. Examples of reducing sugars of monosaccharides include glucose, galactose, xylose, mannose, lyxose, arabinose, fructose, or a mixture thereof. Examples of reducing sugars greater than disaccharides or trisaccharides include maltose, xylobiose, isomaltose, cellobiose, gentibiose, lactose, sucrose, nigerose, tulanose, raffinose, gentianose, and mixtures thereof.
Among these, G is preferably a residue derived from glucose, fructose, maltose, or sucrose, and more preferably a residue derived from glucose.
x is the average number of repetitions of (OR ⁴ ), is a number of 0 to 5, is preferably a number of 0 to 2, and is more preferably 0.
y is the average degree of condensation of sugars, and is a number of 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1 to 1.5.

As the component (b), a synthetic product may be used, or a commercial product may be used. As a commercial item, the brand name "Glucopon215UP" etc. by BASF Corporation etc. are mentioned, for example.
As the component (b), any one type may be used alone, or two or more types may be used in combination.

(B) As for content of a component, 3-27 mass% is preferable with respect to the total mass of a liquid detergent, 6-20 mass% is more preferable, 6-15 mass% is further more preferable.
When the content of the component (b) is in the above preferred range, it becomes easy to obtain a liquid detergent that is excellent in low-temperature stability.

  The total content of the component (a) and the component (b) in the liquid detergent is preferably 6 to 30% by mass, and more preferably 10 to 20% by mass. When the total content of the component (a) and the component (b) is equal to or higher than the lower limit, a liquid detergent having excellent low-temperature stability is easily obtained. Moreover, it becomes easy to maintain the freedom degree of the mixing | blending of another component as the total content of (a) component and (b) component is below the said upper limit.

The total content of the component (a) and the component (b) with respect to the total mass of the surfactant is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and 70% by mass. % Or more is particularly preferable, and may be 100% by mass.
When the total content of the component (a) and the component (b) with respect to the total mass of the surfactant is equal to or more than the above lower limit value, a liquid detergent having excellent low-temperature stability is easily obtained.

The mass ratio represented by (b) component / (a) component [the mass ratio of the mass of component (b) to the mass of the component (a), hereinafter also referred to as “b / a ratio”] is 0.5. The above is preferable, 1.0 or more is more preferable, and 1.5 or more is more preferable.
When the b / a ratio is not less than the above lower limit, the low-temperature stability is further improved.

<Water>
The liquid detergent of the present invention preferably contains water from the viewpoints of ease of handling during production, solubility in water when used, and the like.
Although content of the water in a liquid cleaning agent is not specifically limited, 50-95 mass% in a liquid cleaning agent is preferable, 55-90 mass% is more preferable, 60-85 mass% is further more preferable.

<Other ingredients>
The liquid detergent of this invention may contain the other component normally used for a liquid detergent other than the said (a) component and (b) component.
As other components, for example, surfactants other than the components (a) and (b), solvents, hydrotropes, chelating agents, bactericides, antiseptics, antifungal agents, dyes, antioxidants, ultraviolet absorption Agents, fragrances, pH adjusters and the like.

Examples of the surfactant other than the component (a) and the component (b) include anionic surfactants other than the component (a), nonionic surfactants other than the component (b), and amphoteric surfactants.
Examples of the anionic surfactant other than the component (a) include linear alkylbenzene sulfonates; alkyl sulfates; alkyl ether sulfates or alkenyl ether sulfates; α-olefin sulfonates; alkane sulfonates; Α-SF salt having 8 to 14 carbon atoms: higher fatty acid salt (soap) having 8 to 24 carbon atoms, alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkyl (or alkenyl) amide ether carboxylic acid Carboxylic acid type anionic surfactants such as salts and acylaminocarboxylates; alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkylphenyl phosphate ester salts, glycerin fatty acid ester monophosphate ester salts Phosphate ester type Examples include nonionic surfactants.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt, and ammonium salts. Of these, alkali metal salts are preferred.

Among these, as the linear alkylbenzene sulfonate, those having 8 to 20 carbon atoms in the linear alkyl group are preferable, and those having 10 to 14 carbon atoms are more preferable.
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.
As the alkenyl ether sulfate, polyoxyethylene alkenyl ether sulfate having a linear or branched alkenyl group having 10 to 20 carbon atoms and having an average of 1 to 10 moles of ethylene oxide added is preferable.
As an alpha olefin sulfonate, a C10-C20 thing is preferable and a C10-C16 thing is more preferable.
As the alkane sulfonate, a secondary alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 18 carbon atoms is preferable.
As the polyoxyalkylene ether carboxylate, a polyoxyethylene alkyl ether carboxylate having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and added with an average of 1 to 10 moles of ethylene oxide or Polyoxyethylene alkenyl ether carboxylates are preferred.

Nonionic surfactants other than the component (b) include polyoxyalkylene type nonionic surfactants obtained by adding alkylene oxide to higher alcohols, alkylphenols, higher fatty acids, higher fatty acid esters or higher amines, and polyoxyethylene polyoxypropylene blocks. Copolymer, fatty acid alkanolamide, 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 Examples thereof include polyhydroxy fatty acid amides, alkyl glycosides having an alkyl group having 12 or more carbon atoms, and glyceryl ether. 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.

  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.

As the surfactant other than the component (a) and the component (b), those other than the compound containing an aromatic ring such as LAS are preferable. Among these, polyoxyethylene alkyl ether sulfate and polyoxyalkylene alkyl ether are preferable.
Any one of the surfactants other than the components (a) and (b) may be used alone, or two or more thereof may be used in combination.
In the liquid detergent of the present invention, the total content of the surfactant is preferably 50% by mass or less, more preferably 35% by mass or less, and further preferably 25% by mass or less based on the total mass of the liquid detergent. Moreover, 6 mass% or more is preferable with respect to the total mass of a liquid detergent, and, as for the total content of surfactant, 10 mass% or more is more preferable.
When the total content of the surfactant is within the above preferable range, a liquid detergent having excellent low-temperature stability is easily obtained.

In the present invention, the LAS content is preferably reduced. The LAS content is preferably less than 6% by mass, more preferably less than 3% by mass, even more preferably less than 1.5% by mass, particularly preferably less than 1% by mass, based on the total mass of the liquid detergent. Mass% is most preferred. When the content of LAS is not more than the above upper limit value, a liquid detergent that is superior in biodegradability can be obtained. Furthermore, the content of LAS is reduced, and the hard water resistance is increased by using a liquid detergent mainly composed of (a) component, surfactant such as AES, AE, etc., for example, used in areas with high water hardness Even if it is carried out, the liquid cleaning agent which is hard to reduce a cleaning power is obtained.
The LAS content is preferably less than 10% by mass, more preferably less than 5% by mass, still more preferably less than 3% by mass, particularly preferably less than 1.5% by mass, based on the total mass of the surfactant. Less than mass% is particularly preferred, and 0 mass% is most preferred.
As described above, it is known that the addition of LAS can improve the low temperature stability of a liquid detergent containing an α-SF salt. In the present invention, the combination of the component (a) and the component (b) enables low temperature stability while containing the component (a) even if the content of LAS is reduced or LAS is not contained. A liquid cleaning agent excellent in the above can be obtained.

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, and a weight average molecular weight of about 200 to 1000 polyglycols such as polyethylene glycol and dipropylene glycol, alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and diethylene glycol dimethyl ether, 2-phenoxyethanol, phenoxy-2-propanol, benzyl alcohol and the like Aromatics and the like.
As the solvent, those other than aromatics are preferable.

A hydrotrope agent may be blended in the liquid cleaning agent of the present invention. As a hydrotrope agent, aromatic sulfonic acid or its salt is mentioned. Examples of the aromatic sulfonic acid or a salt thereof include toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, or a salt thereof.
Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.

  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.

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 preferable range, when the liquid detergent is stored for a long period of time, the α-SF salt is more stabilized, and thus 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.

The viscosity at 25 ° C. of the liquid cleaning agent of the present invention is not particularly limited, but is, for example, 10 to 1000 mPa · s. When the viscosity is within the above range, the liquid cleaning agent can be easily measured with a measuring cap or the like. Further, when used for application cleaning, the liquid cleaning agent can be easily applied to the object to be cleaned.
The viscosity at 25 ° C. of the liquid detergent in the present invention is a value measured using a B-type viscometer (manufactured by TOKIMEC) after adjusting the sample to 25 ° C. (an example of measurement conditions: rotor No. 2. Measure the viscosity at 30 rpm after rotation of 30 rpm).

In the liquid detergent of the present invention, it is preferable that the content of aromatic compounds having an aromatic ring such as LAS, 2-phenoxyethanol, and toluenesulfonic acid is reduced.
The total content of aromatic compounds is preferably less than 6% by mass, more preferably less than 3% by mass, even more preferably less than 1.5% by mass, and particularly preferably less than 1% by mass with respect to the total mass of the liquid detergent. Preferably, 0% by mass is most preferable. When the total content of the aromatic compounds is not more than the above upper limit value, a liquid detergent that is superior in biodegradability can be obtained.

(Method for producing liquid detergent)
The liquid detergent of the present invention can be produced, for example, by dissolving the above components (a) and (b) and optional components as necessary in water.

  The liquid cleaning agent of the present invention is, for example, a liquid cleaning agent for textile products whose clothes are to be cleaned, a liquid cleaning agent for kitchens which is to be cleaned of tableware, vegetables, etc., and a hard target which is to be cleaned of toilet bowls, walls, bathrooms, etc. It can be used as a liquid detergent for the surface, a liquid detergent for the human body such as body soap and shampoo for washing the skin and hair. Especially, it is used suitably as a liquid cleaning agent for textiles.

  As described above, the liquid cleaning agent of the present invention has good low-temperature stability because the component (a) and the component (b) are used in combination. The liquid cleaning agent of the present invention may not contain an aromatic compound such as LAS.

The liquid detergent of the present invention may be, for example, the following aspect.
[1] α-sulfo fatty acid alkyl ester salt (a) represented by the following general formula (I):
A liquid detergent comprising an alkyl glycoside (b) having an alkyl group having 8 to 10 carbon atoms.
R ¹ —CH (SO ₃ M) —COOR ² (I)
However, in 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 liquid detergent according to [1], wherein a mass ratio represented by the component (b) / the component (a) is 1.5 or more.
[3] The liquid detergent according to [1] or [2], wherein the component (b) is a compound represented by the following general formula (II).
R ³ (OR ⁴ ) _x G _y (II)
However, in formula (II), R ³ is a linear or branched alkyl group having 8 to 10 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and G is a reduction It is a residue derived from sugar. x is the average number of repetitions of (OR ⁴ ) and is a number from 0 to 5, and y is the average degree of condensation of sugars and is a number from 1 to 5.
[4] The liquid cleaning agent according to any one of [1] to [3], wherein the content of the component (a) is 3 to 10% by mass.
[5] The liquid cleaning agent according to any one of [1] to [4], wherein the total content of the component (a) and the component (b) is 6 to 30% by mass.
[6] The liquid cleaning agent according to any one of [1] to [5], wherein the LAS content is less than 6% by mass.
[7] The liquid cleaning agent according to any one of [1] to [6], wherein the content of the aromatic compound is less than 6% by mass.

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: MES salt (sodium salt of sulfonated product of methyl palmitate / methyl stearate = 85/15 by mass ratio) Synthesized by the following synthesis method.
a-2: MES salt (sodium salt of sulfonated mixture of methyl palmitate / methyl stearate = 60/40 by mass ratio) Synthesized by the following synthesis method.

<(B) component>
b-1: Alkyl glycoside having an alkyl group having 8 to 10 carbon atoms (BASF, trade name “Glucopon 215UP”).

<(B ′) Component: Comparative Component of (b) Component>
b′-1: Alkyl glycoside having an alkyl group having 12 to 14 carbon atoms (manufactured by BASF, trade name “Glucopon225DK”).
b′-2: Alkyl glycoside having an alkyl group having 16 to 18 carbon atoms (manufactured by Evonik, trade name “Tego Care CG90”).

<Optional component>
AES: Polyoxyethylene alkyl (carbon number 12 to 14) sodium ether sulfate [average added mole number of ethylene oxide 2]. Product name “EMAL270N” manufactured by Kao Corporation.
AE: Polyoxyethylene alkyl (carbon number 12-14) ether (average addition mole number of ethylene oxide 7), manufactured by Lion Co., Ltd., trade name “Leox CL-70”.
LAS: linear alkyl (C10-C14) sodium benzenesulfonate (manufactured by Lion Co., Ltd., trade name “Lypon LH-200” sodium hydroxide neutralized product).
Water: Purified water.

[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, and 35% by volume of hydrogen peroxide solution was supplied and mixed, and bleaching was performed while maintaining the temperature at 80 ° C. to obtain paste a-1.

[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 paste a-2.

<Examples 1-11, Comparative Examples 1-5>
According to the composition shown in Table 1, the components (a), (b) and optional components were added to water and mixed to obtain liquid detergents of Examples 1-11. Moreover, the liquid cleaning agent of Comparative Examples 1-3 was obtained like the above except not adding (b) component. Liquid detergents of Comparative Examples 4 and 5 were obtained in the same manner as described above except that the component (b ′) was used instead of the component (b).
Table 1 shows the composition (formulation component, content (mass%)) of the obtained liquid cleaning agent in each example.
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 equivalent amount.
“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%.
In the table, “b / a ratio” in Comparative Examples 4 and 5 indicates the mass ratio of the component (b ′) to the component (a).

  About the liquid detergent of each example, low temperature stability was evaluated as follows. The evaluation results are shown in Table 1.

[Evaluation of low-temperature stability]
To a colorless and transparent sample bottle, 50 mL of the liquid detergent of each example was added, and the lid was closed and sealed. In this state, the sample bottles were left in a thermostatic bath at 5 ° C. and 10 ° C., respectively, and stored for 1 month. Thereafter, the appearance of the liquid was visually observed, and the low temperature stability of the liquid detergent was evaluated based on the following criteria. ○ and △ were regarded as acceptable.
○: At a storage temperature of 5 ° C., the liquid detergent does not solidify, and no precipitate is observed in the liquid detergent.
Δ: Solidification of the liquid cleaning agent occurs at a storage temperature of 5 ° C., or sediment is observed in the liquid cleaning agent, but no solidification of the liquid cleaning agent occurs at a storage temperature of 10 ° C. and the liquid cleaning agent. No sediment is observed in it.
X: Solidification of the liquid detergent occurs at a storage temperature of 10 ° C., or sediment is observed in the liquid detergent.

From the results shown in Table 1, it was confirmed that the liquid detergents of Examples 1 to 11 to which the present invention was applied were excellent in low temperature stability.
On the other hand, liquid detergents (Comparative Examples 1 to 3) containing no component (b) and liquid detergents (Comparative Examples 4 and 5) using the component (b ′) instead of the component (b) are stable at low temperatures. Could not be obtained sufficiently.

Next, about the liquid detergent of Examples 1-11 which passed in the evaluation of the said low-temperature stability, the following detergency evaluation which assumed the area where water hardness is high was performed. The evaluation results are shown in Table 1.
[Detergency evaluation]
Artificial dirt cloth (manufactured by Laundry Science Association) produced by impregnating artificial dirt with oily co-fabricated cloth (unstained cloth) was cut into 5 × 5 cm to make a dirty cloth. As a cleaning tester, Terg-O-meter (manufactured by UNITED STATES TESTING) was used. The washing liquid was prepared by adding a liquid detergent to 200 ppm with respect to 900 mL of water (25 ° C., 5 ° DH) and stirring for 30 seconds.
The washing liquid, 5 pieces of the artificial dirt cloth and the washing knitted cloth were put into the washing tester, and washed at 120 rpm and 25 ° C. for 10 minutes according to the bath ratio of 30 times. Then, it moved to the 2 tank type washing machine (Mitsubishi Electric Corp. make: product name CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 L of water for 3 minutes, and air-dried.
The reflectance was measured with a color difference meter (manufactured by Nippon Denshoku Co., Ltd .: product name SE2000 type) for the unstained fabric and the artificial soiled fabric before and after cleaning, and the cleaning rate (%) was determined by the following formula. However, K / S is (1-R / 100) ² / (2R / 100) (R represents the reflectance (%) of the unsoiled cloth and the artificial soil cloth before and after washing).
Washing rate (%) = (K / S of artificial soil cloth before washing−K / S of artificial soil cloth after washing) / (K / S of artificial soil cloth before washing−K of unsoiled cloth) / S) × 100.

The washing rate was calculated for each of the five artificial dirt cloths, and the average value was calculated as the washing rate of the liquid detergent. And detergency was evaluated based on the following reference | standard.
A: The cleaning rate is 70% or more.
○: The cleaning rate is 60% or more and less than 70%.
Δ: The cleaning rate is 50% or more and less than 60%.
X: The cleaning rate is less than 50%.

  As shown in Table 1, all of the liquid detergents of Examples 1 to 11 had a cleaning rate of 50% or more. Moreover, evaluation is (circle) (cleaning rate 67%) in the liquid cleaning agent of Example 1, and evaluation (triangle | delta) is 58 (cleaning rate) in the liquid cleaning agent of Example 11, and the liquid cleaning agent of Example 1 is (alpha). -Hard water resistance was superior to the liquid detergent of Example 11 in which a part of the SF salt was replaced with LAS. Furthermore, since the liquid detergent of Example 1 does not contain LAS, it is superior in biodegradability to the liquid detergent of Example 11.

Claims (2)

Α-sulfo fatty acid alkyl ester salt (a) represented by the following general formula (I):
A liquid detergent containing an alkyl glycoside (b) having an alkyl group having 8 to 10 carbon atoms.
R ¹ —CH (SO ₃ M) —COOR ² (I)
However, in 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 liquid detergent of Claim 1 whose mass ratio represented by said (b) component / said (a) component is 1.5 or more.