WO2016204277A1 - Α-sulfofatty acid ester salt-containing solution - Google Patents

Abstract

An α-sulfofatty acid ester salt-containing solution that contains an α-sulfofatty acid ester salt (a) having 16-18 carbon atoms in the fatty acid residue, a fatty acid polyoxyalkylene alkyl ether (b) and water, characterized in that: the total content of (a) and (b) is more than 30 mass% and not more than 40 mass% relative to the total liquid; and the ratio by mass [(a)/(b)] is 1.5-9.0 inclusive. When allowed to stand, this α-sulfofatty acid ester salt-containing solution maintains high homogeneity of the liquid and scarcely causes separation or precipitation.

Description

Liquid containing α-sulfo fatty acid ester salt

The present invention relates to an α-sulfo fatty acid ester salt-containing liquid.
This application claims priority on June 18, 2015 based on Japanese Patent Application No. 2015-122903 for which it applied to Japan, and uses the content here.

α-Sulfo fatty acid ester salts (hereinafter sometimes referred to as α-SF salts) have conventionally been distributed in the form of solids (flakes, powders, etc.), and are mainly used as cleaning components for powder detergents. However, when α-SF salt is used as a liquid detergent, a liquid in which flaky α-SF salt solids are dissolved or dispersed in water or the like is prepared in advance before blending into the main blending tank. There was a need.

As the cleaning component of the cleaning agent, in addition to the α-SF salt, linear alkylbenzene sulfonate (LAS), polyoxyethylene alkyl ether sulfate (AES) and the like are widely used. These LAS and AES are already distributed in the form of highly concentrated liquid (concentrated liquid).
The α-SF salt aqueous solution is preferably used or stored at a high concentration in terms of efficiency, but in the case of the α-SF salt single aqueous solution, the viscosity increases as the concentration increases, and the concentration is about 30% by mass or more. Then, a hexagonal structure is formed and the gel state is lost.

On the other hand, as a method for improving the fluidity of a high-concentration α-SF salt aqueous solution, the example of Patent Document 1 includes α-sulfo fatty acid methyl ester sodium salt powder having a fatty acid composition of 14 to 16 carbon atoms. And a method of preparing an α-SF salt aqueous solution by dissolving a solution of fatty acid polyoxyethylene (EOp = 15) methyl ether having 18 carbon atoms in water at a predetermined ratio.

JP-A-6-128588

According to the knowledge of the present inventors, the α-SF salt aqueous solution prepared by the method described in Patent Document 1 may undergo separation or precipitation when stored at rest, and such separation or precipitation occurs. The α-SF salt aqueous solution in a wet state has a non-uniform fatty acid composition in the liquid.

An object of the present invention is to provide an α-sulfo fatty acid ester salt-containing liquid that maintains good liquid uniformity even when stored at a standstill and is less likely to cause separation or precipitation.

The present invention has the following aspects.
<1>
The α-sulfo fatty acid ester salt-containing liquid of the present invention comprises an α-sulfo fatty acid ester salt (a) having a fatty acid residue of 16 to 18 carbon atoms, a fatty acid polyoxyalkylene alkyl ether (b), and water. Contains,
The total content of (a) and (b) is more than 30% by mass and 40% by mass or less with respect to the total (total mass of the α-sulfo fatty acid ester salt-containing liquid), and (a) / (b) The mass ratio is 1.5 or more and 9.0 or less.

<2>
(A) is a mixture of an α-sulfo fatty acid ester salt (C16) in which the fatty acid residue has 16 carbon atoms and an α-sulfo fatty acid ester salt (C18) in which the fatty acid residue has 18 carbon atoms. , (C16): (C18) 45:55 to 95: 5 <1> α-sulfo fatty acid ester salt-containing liquid.
<3>
An α-sulfo fatty acid ester salt-containing liquid of <1>, wherein (b) is a compound represented by the following general formula (II).
R ³ —CO (OR ⁴ ) mOR ⁵ (II)
[Wherein R ³ is a saturated or unsaturated hydrocarbon group having 9 to 18 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and R ⁵ is a hydrocarbon group having 1 to 3 carbon atoms. M represents the average added mole number of OR ⁴ and is 5 to 25. ]

According to the present invention, an α-sulfo fatty acid ester salt-containing liquid is obtained that maintains good liquid uniformity even when stored at rest, and that hardly causes separation or precipitation.

The α-SF salt-containing liquid of the present invention comprises (a) component: an α-SF salt having a fatty acid residue having 16 to 18 carbon atoms, (b) component: a fatty acid polyoxyalkylene alkyl ether, and water. contains.

<(A) component: α-sulfo fatty acid ester salt in which fatty acid residue has 16 to 18 carbon atoms>
The α-SF salt can be obtained by a known production method, for example, by using a tank reactor equipped with a stirrer, etc. by a conventional method, and bringing the fatty acid ester of the raw material into contact with sulfuric anhydride or the like for sulfonation. A product obtained by preparing an α-sulfo fatty acid ester (α-SF acid) and then neutralizing the α-SF acid with sodium hydroxide or the like can be used. In addition, what was bleached with hydrogen peroxide etc. before and after neutralization may be used.
The component (a) is a compound represented by the following general formula (I).
The number of carbon atoms of the fatty acid residue of the α-SF salt is the number of carbon atoms of the portion derived from the fatty acid (acyl group portion). For example, in the case of a compound represented by the following formula (I), the number of carbon atoms of R ¹ is +2. .

[Wherein, 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. R ¹ has 14 to 16 carbon atoms. When the carbon number of R ¹ is 14 or more, the surface activity is increased and the cleaning power is improved as a cleaning component. On the other hand, when the carbon number of R ¹ is 16 or less, the appearance stability of the α-SF salt-containing liquid is improved.

In the formula (I), the hydrocarbon group represented by 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, the methyl group, ethyl group, and n-propyl group are A methyl group is preferable, and a methyl group is particularly preferable.

In the formula (I), M is a counter ion and may be any one that can form a water-soluble salt with R ¹ CH (COOR ² ) SO ₃ ^— . Examples of the counter ion include alkali metal ions, protonated amines, ammonium and the like. Examples of the alkali metal that can be the counter ion include sodium.
The amine that can be the counter ion may be any of primary to tertiary amines, and preferably has 1 to 6 carbon atoms in total. The amine may have a hydroxy group, and it preferably has a hydroxy group because the solubility of the α-SF salt-containing liquid in water increases under low temperature conditions. Examples of such amines include alkanolamines, and the alkanol group preferably has 1 to 3 carbon atoms. Specific examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine and the like.
M is preferably an alkali metal ion and particularly preferably a sodium ion because it is easily available and the appearance stability of the α-SF salt-containing liquid is improved.

Among the components (a), a compound that is an α-sulfo fatty acid ester salt in which the fatty acid residue has 16 to 18 carbon atoms is preferable. Specifically, 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 ² is methyl. Particularly preferred are compounds that are groups.
(A) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.

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.
As the component (a), an α-SF salt having a fatty acid residue having 16 carbon atoms (sometimes abbreviated as “C16” in the present specification) and an α- fatty acid residue having 18 carbon atoms. It is preferable to use a mixture with an SF salt (sometimes abbreviated as “C18” in this specification). Specifically, an α-SF salt (C16) in which R ¹ in the formula (I) is a hydrocarbon group having 14 carbon atoms and an α-SF salt (C18 in which R ¹ is a hydrocarbon group having 16 carbon atoms). It is preferable to use a mixture thereof.
The mixing ratio (mass ratio) of C16 and C18 is preferably C16: C18 = 45: 55 to 95: 5, more preferably 60:40 to 90:10, and still more preferably 80:20 to 85:15. When the mass ratio is within the above-described preferable range, the detergency, solubility in water, and appearance stability are further improved.

In the α-SF salt-containing liquid of the present invention, the content of the component (a) is 18 to 36% by mass, preferably 23 to 36% by mass, based on the total mass of the α-SF salt-containing liquid. More preferably, it is 25 to 32% by mass.
If content of (a) component is more than a lower limit, the effect of the present invention will notably be exhibited. On the other hand, if the content of the component (a) is not more than the upper limit, the uniformity of the liquid is easily maintained and separation and precipitation are difficult to occur.

The α-SF salt-containing liquid of the present invention may contain an α-SF salt other than the component (a). Other α-SF salts are preferably those in which the fatty acid residue has 12 to 14 carbon atoms. By containing another α-SF salt having a fatty acid residue having 12 to 14 carbon atoms, the appearance stability and fluidity of the α-SF salt-containing liquid are further improved.
Since the effects of the present invention are more exerted and the detergency increases as a cleaning component, (a) relative to the total mass of the α-SF salt (the sum of the component (a) and other α-SF salts) The component is preferably 67% or more, more preferably 80% or more, still more preferably 90% or more, and may be 100%.

<(B) component: fatty acid polyoxyalkylene alkyl ether>
Component (b) is obtained by a known production method, for example, a method in which an alkylene oxide is addition-polymerized to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (see JP-A-2000-144179). ) Can be easily manufactured.
As a preferable example of such a surface-modified composite metal oxide catalyst, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co 1) surface-modified with a metal hydroxide or the like are used. ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) are added to a composite metal oxide catalyst such as magnesium oxide, or a calcined catalyst of hydrotalcite surface-modified with a metal hydroxide and / or metal alkoxide, etc. is there.
Further, in the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is changed to metal hydroxide with respect to 100 parts by mass of the composite metal oxide. The ratio of the product and / or metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.

(B) As a component, the compound represented by the following general formula (II) is mentioned as a preferable thing.
R ³ —CO (OR ⁴ ) mOR ⁵ (II)
[Wherein R ³ is a saturated or unsaturated hydrocarbon group having 9 to 18 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and R ⁵ is a hydrocarbon group having 1 to 3 carbon atoms. M represents the average added mole number of OR ⁴ and is 5 to 25. ]
In the formula (II), R ³ is a saturated or unsaturated hydrocarbon group having 9 to 18 carbon atoms. When the number of carbon atoms is within the above range, the cleaning performance and appearance stability are excellent. The saturated or unsaturated hydrocarbon group preferably has 10 to 18 carbon atoms, more preferably 11 to 17 carbon atoms. The saturated or unsaturated hydrocarbon group is preferably linear or branched, respectively.
Among them, (b) component, wherein R ³ in (II) is a fatty acid polyoxyethylene ether is a straight chain alkyl group having 11 or 13 carbon atoms, and formula (II) in R ³ is derived from palm oil It preferably contains one or more selected from the group consisting of fatty acid polyoxyethylene methyl ethers, which are unsaturated hydrocarbon groups having 17 carbon atoms.
In particular, the component (b) contains at least one selected from the group consisting of fatty acid polyoxyethylene methyl ethers in which R ³ in formula (II) is a linear alkyl group having 11 or 13 carbon atoms. This is particularly preferable.

R ⁴ is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group. A plurality of R ⁴ in the formula may be the same or different. That is, as the alkylene group for R ⁴ , only one type may be used alone, or a plurality of types may be combined. For example, (OR ⁴ ) m in the formula may be a mixture of EO and PO.
The addition method of OR ^{4 in} the case of combining a plurality of types is not particularly limited. For example, the addition method when (OR ⁴ ) m includes EO and PO may be random addition or block addition. As a block addition method, for example, a method of adding PO after adding EO, a method of adding EO after adding PO, a method of adding PO after adding EO, and further adding EO Is mentioned.
Since the component (b) has good foaming at the time of washing and is inexpensive, the m OR ⁴ in the formula is an EO adduct in which all of the OR ⁴ are EO, or the m OR ⁴ in the formula is EO. It is preferably an EO / PO adduct which is a mixture of NO and PO.

m represents the average added mole number of OR ⁴ (alkylene oxide) and is 5 to 25. When m is within the above range, the cleaning power, particularly the cleaning power against sebum dirt is improved. Moreover, the solubility of a cleaning composition improves.
In the case of an EO adduct, m is preferably 10 to 20, more preferably 12 to 20, and particularly preferably 12 to 18. When m is 10 or more, the effect of suppressing separation of the α-SF salt-containing solution or reforming hexagonal into a micelle phase is high.
R ⁵ is an alkyl group having 1 to 3 carbon atoms, and a methyl group is preferable from the viewpoint of cleaning performance.

In the component (b), the narrow ratio indicating the proportion of the distribution of alkylene oxide adducts having different numbers of added moles of alkylene oxide is usually 20% by mass or more and 80% by mass or less.
The higher the narrow rate, the better the cleaning power. Further, when the narrow ratio is 20% by mass or more, particularly 30% by mass or more, it becomes easy to obtain a liquid detergent composition with less raw material odor of the surfactant. This is because, after the production of the component (b), the fatty acid ester which is the raw material of the component (b) coexisting with the component (b) and the alkylene oxide adduct having 1 or 2 in the above formula are reduced.
Here, the “narrow ratio” in this specification is a value indicating the distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide, and is represented by the following mathematical formula (1).

In the formula (1), n _max represents the number of added moles of alkylene oxide of the alkylene oxide adduct most present in the entire alkylene oxide adduct.
i represents the number of added moles of alkylene oxide.
Yi represents the proportion (mass%) of the alkylene oxide adduct having an added mole number of alkylene oxide present in the entire alkylene oxide adduct.
The narrow rate can be controlled by, for example, the manufacturing method of the component (b).
In the α-SF salt-containing liquid of the present invention, the component (b) may be used alone or in combination of two or more.

In the α-SF salt-containing solution of the present invention, the total content of the α-sulfo fatty acid ester salt (a) having a fatty acid residue of 16 to 18 carbon atoms and the fatty acid polyoxyalkylene alkyl ether (b) is α- More than 30% by mass and 40% by mass or less, preferably more than 30% by mass and 37% by mass or less, more preferably 33% by mass or more and 37% by mass or less, based on the total mass of the SF salt-containing liquid. It is.
If the total content of the component (a) and the component (b) is not less than the lower limit value, the effects of the present invention are remarkably exhibited. On the other hand, if the total content of the component (a) and the component (b) is not more than the upper limit value, the uniformity of the liquid is easily maintained and separation and precipitation are unlikely to occur.

Further, (a) / (b) representing the mass ratio of the content of the component (a) to the content of the component (b) is 1.5 to 9.0, preferably 2.0 to 9.0. 3.0 to 7.0 is more preferable. If the mass ratio of (a) / (b) is not less than the lower limit value, it is preferable in terms of productivity, and if it is not more than the upper limit value, workability during production is improved.

The water content with respect to the total mass of the α-SF salt-containing liquid is 60% by mass or more and less than 70% by mass, preferably 63% by mass or more and less than 70% by mass, and more preferably 63% by mass or more and 67% by mass or less. More preferred. When it is at least the lower limit, it is preferable from the viewpoint of appearance stability, and when it is at most the upper limit, it is preferable from the viewpoint of productivity.
The total content of the component (a), the component (b) and water does not exceed 100% by mass with respect to the total mass of the α-SF salt-containing liquid.

The α-SF salt-containing liquid of the present invention may contain impurities inevitable in the production of component (a). Examples of impurities include alkali metal sulfates (such as sodium sulfate), alkali metal alkyl sulfates (such as sodium methyl sulfate), α-sulfo fatty acids, α-sulfo fatty acid dialkali salts (such as α-sulfo fatty acid disodium salts). It is done.

The α-SF salt-containing liquid of the present invention contains other components that do not fall under any of the components (a), (b), and impurities inevitable in the production thereof, as long as the effects of the present invention are not impaired. (Optional component) may be blended.
Examples of such other components include alcohols having 1 to 3 carbon atoms, pH buffering agents, preservatives, chelating agents and the like.
The fluidity of the α-SF salt-containing liquid of the present invention is further improved by containing an alcohol having 1 to 3 carbon atoms. Examples of the alcohol having 1 to 3 carbon atoms include monohydric alcohols such as methanol, ethanol, n-propanol and isopropanol; polyhydric alcohols such as ethylene glycol and propylene glycol. Monohydric alcohols are preferable, and ethanol is more preferable.

Examples of pH buffering agents include carbonates; sulfates; fatty acid salts; phosphates; organic acid salts; inorganic acids such as phosphoric acid and sulfuric acid; organic acids such as citric acid and fatty acids; alkanolamines and the like. These may be used alone or in combination of two or more.
As preservatives, benzoic acid compounds such as sodium benzoate, isobutyl paraoxybenzoate, and isopropyl paraoxybenzoate; sorbic acid compounds such as sorbic acid and potassium sorbate; dehydroacetic acids; propionic acids; isopropylmethylphenol, orthophenyl Phenols such as phenol and triclosan; thiabenzol; isothiazoline compounds and the like. These may be used alone or in combination of two or more.
As chelating agents, hydroxycarboxylates such as sodium malate and sodium citrate; aminoacetates such as sodium nitrilotriacetate and sodium ethylenediaminetetraacetate; condensed phosphates such as potassium pyrophosphate and sodium tripolyphosphate; polyacrylic acid, Examples thereof include polymer chelating agents such as polymaleic acid, copolymers of polyacrylic acid and maleic acid, and salts thereof. These may be used alone or in combination of two or more.

When the α-SF salt-containing liquid contains the other components, the total mass thereof is preferably more than 0% by mass and 4% by mass or less, based on the total mass of the α-SF salt-containing liquid. Is more preferable.
When the other component is contained in the α-SF salt-containing liquid, the total of the contents of the component (a), the component (b), water, and the other component is 100 masses with respect to the total mass of the α-SF salt-containing liquid. % Does not exceed.

The viscosity at 30 ° C. of the α-SF salt-containing liquid of the present invention is preferably 0.1 to 10 Pa · s, more preferably 0.5 to 10 Pa · s, and further preferably 0.5 to 7.5 Pa · s. . When it is at least the lower limit of the above range, the viscosity of the composition when blended into the detergent composition is maintained moderately, and when it is at most the upper limit, the handling properties when blending the composition are improved.
The viscosity of the α-SF salt-containing liquid can be adjusted by the content of water.
The viscosity of the α-SF salt-containing liquid in the present invention is a value measured 30 seconds after the sample is adjusted to 30 ° C., the B-type viscometer is used, the rotor is rotated at 30 rpm, and the rotation is started. It is. The rotor used for measurement is rotor No. 1 or 2 (when the viscosity is 0.1 Pa · s or less), rotor No. 3 (when the viscosity is more than 0.1 Pa · s and less than 5 Pa · s), or rotor no. 4 (when the viscosity is 5 Pa · s or more).

The pH at 30 ° C. of the α-SF salt-containing liquid of the present invention is preferably 5.0 to 9.0, more preferably 5.5 to 8.0. If the pH of the α-sulfo fatty acid ester salt-containing liquid is within the above preferred range, hydrolysis of the α-SF salt (a) and the fatty acid polyoxyalkylene alkyl ether (b) in the α-sulfo fatty acid ester salt-containing liquid Is suppressed, and the liquid can be stabilized.
The pH of the α-SF salt-containing solution can be adjusted by the amount of pH buffer added.

The α-SF salt-containing liquid of the present invention can be produced by mixing the components (a), (b) and water. For example, it can manufacture by adjusting (a) component, (b) component, and arbitrary components as needed to predetermined | prescribed pH, melt | dissolving in the water which is a solvent. As the component (a), for example, any of a paste or a solid after neutralization or bleaching can be used.

The α-SF salt-containing liquid of the present invention can be used for the production of a cleaning agent.
For example, a liquid detergent can be produced by a method in which an α-SF salt-containing liquid is mixed with other components. Since the α-SF salt-containing liquid does not need to be dissolved or dispersed in a solvent in advance, the mixing operation with other components is easy.
Further, for example, a powder cleaning agent by a method of spray drying a slurry containing an α-SF salt-containing liquid and a powder detergent raw material, or a method of granulating a powder detergent raw material using an α-SF salt-containing liquid as a binder Can be manufactured.

The present invention has the following preferred embodiments.
α-sulfo fatty acid ester salt (a), fatty acid polyoxyalkylene alkyl ether (b), and water,
(A) is a mixture of an α-sulfo fatty acid ester salt (C16) in which the fatty acid residue has 16 carbon atoms and an α-sulfo fatty acid ester salt (C18) in which the fatty acid residue has 18 carbon atoms. Yes, the mass ratio of C16: C18 is 60:40 to 85:15,
The content of the component (a) is 18 to 36% by mass with respect to the whole, the total content of (a) and (b) is more than 30% by mass and 40% by mass or less, (a) / ( An α-sulfo fatty acid ester salt-containing liquid having a mass ratio of b) of 1.5 or more and 9.0 or less and a viscosity at 30 ° C. of 0.1 to 10 Pa · s.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the examples, “%” means “% by mass” unless otherwise specified.

The raw materials shown in Table 1 were used.
In addition, the α-sulfo fatty acid methyl ester sodium salt (hereinafter sometimes abbreviated as “α-SF-Na”), which is the component (a), is added to the flaky sodium salt of α-sulfo fatty acid methyl ester. A solid (hereinafter referred to as “α-SF salt solid”) was used. The α-SF salt solid was prepared by producing a paste-like α-SF salt concentrate as follows, and cooling and crushing it.

(Production Example 1) Production of Pasty α-SF-Na Salt (a1) In this example, as a fatty acid ester as a raw material, methyl palmitate (trade name: Pastel M-16 manufactured by Lion Corporation) and stearic acid A fatty acid methyl ester mixture in which methyl (trade name: Pastel M-180, manufactured by Lion Corporation) was mixed in advance so that the mass ratio of methyl palmitate: methyl stearate was 85:15 was used.
Injecting 330 kg of 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) 115 diluted to 8% by volume with nitrogen gas .6 kg (1.2 times mol with respect 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 was supplied as a lower alcohol, and esterification was performed at a temperature condition of 80 ° C. and an aging time of 75 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.
Next, this neutralized product was poured into a bleaching agent mixing line, and 35% by volume of hydrogen peroxide solution was supplied in terms of pure content at 1% by mass with respect to the AI content, mixed, and bleached while maintaining at 80 ° C. To obtain α-SF-Na salt (a1).
The molecular weight of the α-SF-Na salt contained in the obtained α-SF-Na salt (a1) was calculated from the carbon chain length ratio (mass ratio) of the raw materials to be 377.

(Production Example 2) Production of Pasty α-SF-Na Salt (a2) In this example, as a fatty acid ester as a raw material, methyl palmitate (same as Production Example 1) and methyl stearate (Production Example 1 and The same) and a fatty acid methyl ester mixture in which methyl palmitate: methyl stearate was mixed at a mass ratio of 6: 4 was used.
Injecting 330 kg of the fatty acid methyl ester mixture into a 1 kL reactor equipped with a stirrer and stirring the solution, the reaction temperature was 80 ° C., and the SO ₃ gas (sulfonated gas) diluted to 8% by volume with nitrogen gas was 112.8 kg ( 1.2 times moles of the fatty acid methyl ester mixture) was blown at a constant rate 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, α-SF-Na salt (a2) was obtained in the same manner as in the production of α-SF-Na salt (a1).
The molecular weight of the α-SF-Na salt contained in the obtained α-SF-Na salt (a2) was calculated from the carbon chain length ratio (mass ratio) of the raw material to be 384.

Concentration of pasty α-SF-Na salt:
The paste-like α-SF-Na salts (a1) and (a2) obtained in Production Examples 1 and 2, respectively, were rotated at a rotational speed of 1060 rpm and a blade tip speed of about 11 m / s (transmission thin film evaporator) Hot surface: 0.5 m ² , inner diameter of cylindrical processing part: 205 mm, clearance between heat transfer surface and blade tip as scraping means: 3 mm, trade name “Exeva”, manufactured by Shinko Pantech Co., Ltd.) 35 kg / Hr, and concentrated under the conditions of inner wall heating temperature (heat transfer surface temperature) of 135 ° C. and degree of vacuum (pressure in the processing section) of 0.007 to 0.014 MPa. The temperature of the obtained concentrate was 115 ° C., and the water content was 2.5% by mass.

Production of α-SF salt solids:
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-SF salt solids (a1) and (a2) were obtained, respectively.

Anionic surfactant concentration in solid α-SF salt (total concentration (AI) of α-sulfo fatty acid methyl ester sodium salt (α-SF-Na) and α-sulfo fatty acid disodium salt (di-Na salt)) ) Was measured as follows.
<AI measurement method>
The total content (AI) of α-sulfo fatty acid methyl ester sodium salt (α-SF-Na) and α-sulfo fatty acid disodium salt (di-Na salt) was measured as follows.
A 0.2 g sample 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 with ultrasound. 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 was used) was performed, and the content of AI in the sample was calculated from the following formula from the difference in titration of the sodium alkylbenzenesulfonate solution.
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 measurement, the anionic surfactant concentration (AI) in the α-SF salt solid (a1) was 90.0% by mass, and the anionic surfactant concentration (AI) in the α-SF salt solid (a2). Was 88.1% by mass.

<Method for measuring content of α-sulfo fatty acid disodium salt>
The content of α-sulfo fatty acid disodium salt (di-Na salt) in the α-SF salt solid was measured as follows.
Standard standards of α-sulfo fatty acid disodium salt (0.02 g, 0.05 g, 0.1 g) were accurately weighed into 200 mL volumetric flasks, respectively, and dissolved by adding about 50 mL of water and about 50 mL of ethanol. After dissolution, the mixture was cooled to about 25 ° C., and methanol was accurately added up to the marked line to obtain a standard solution. About 2 mL of this standard solution was filtered using a 0.45 μm chromatographic disk, then analyzed by high performance liquid chromatography under the following measurement conditions, and a calibration curve was created from the peak area.
[Measurement conditions for high performance liquid chromatography analysis]
・ Device: LC-6A (manufactured by Shimadzu Corporation)
Column: Nucleosil 5SB (manufactured by GL Sciences)
-Column temperature: 40 ° C
・ Detector: Differential refractive index detector RID-6A (manufactured by Shimadzu Corporation)
Mobile phase: 0.7% sodium perchlorate in H ₂ O / CH ₃ OH = 1/4 (volume ratio) solution Flow rate: 1.0 mL / min.
・ Injection volume: 100 μL
Next, 1.5 g of α-SF salt solid as a pure AI was accurately weighed into a 200 mL volumetric flask and dissolved by adding about 50 mL of water and about 50 mL of ethanol. After dissolution, the mixture was cooled to about 25 ° C., and methanol was accurately added up to the marked line to make a test solution. About 2 mL of the test solution was filtered using a 0.45 μm chromatographic disk and then analyzed by high performance liquid chromatography under the same measurement conditions as described above. Using the calibration curve, the α-sulfo fatty acid disodium salt in the sample solution was analyzed. The concentration was determined.
As a result of the measurement, the di-Na salt concentration in the α-SF salt solid (a1) was 4.2% by mass, and the di-Na salt concentration in the α-SF salt solid (a2) was 3.6% by mass. Met.
From the above, α-sulfo fatty acid methyl ester sodium salt (α-SF-Na) in α-SF salt solid (a1) was 85.8% by mass, α-sulfo salt in α-SF salt solid (a2). Fatty acid methyl ester sodium salt (α-SF-Na) was calculated to be 84.5% by mass, and in this example, these values were used for the content of component (a).

The fatty acid polyoxyalkylene alkyl ether used in this example was synthesized according to the production example in the examples described in JP-A No. 2000-144179.

(Production Example 3) Production of fatty acid polyoxyethylene methyl ether (m = average 15, narrow ratio 33% by mass) (b1) Alumina-magnesium hydroxide whose chemical composition is 2.5 MgO.Al ₂ O ₃ .nH ₂ O (Product name: KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.) was calcined at 600 ° C. for 1 hour in a nitrogen atmosphere, and calcined alumina / magnesium hydroxide (unmodified) catalyst (2.2 g) Then, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 262.5 g of lauric acid methyl ester and 87.5 g of myristic acid methyl ester were charged into a 4 liter autoclave, and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 1048 g of ethylene oxide was introduced and reacted while stirring. Further, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added respectively, and then the catalyst was filtered off to obtain (b1). The amount of alkali added to the catalyst was adjusted so that the narrow ratio of (b) was 33% by mass.

(Production Example 4) Production of fatty acid polyoxyethylene methyl ether (m = average 11, narrow ratio 33% by mass) (b2) The same purpose as in Production Example 3 except that the amount of ethylene oxide added was 768 g. I got a thing.

(Production Example 5) Production of fatty acid polyoxyethylene methyl ether (m = average 15, narrow ratio 33% by mass) (b3) Carbon number derived from palm oil containing methyl oleate or methyl linoleate as a main component as a raw material The target product was prepared in the same manner as in Production Example 3, except that a fatty acid methyl ester mixture derived from 18 fractions (trade name: Pastel M182, manufactured by Lion Corporation) was used and the amount of ethylene oxide added was 780 g. Obtained.

<Method for measuring number of moles of ethylene oxide added to fatty acid polyoxyalkylene alkyl ether>
Under the following measurement conditions, the distribution of ethylene oxide adducts with different numbers of moles of ethylene oxide added was measured, and the narrow ratio (% by mass) was calculated according to the formula (1).
[Conditions for measuring distribution of ethylene oxide adducts by HPLC]
Apparatus: LC-6A (manufactured by Shimadzu Corporation),
Detector: SPD-10A,
Measurement wavelength: 220 nm
Column: Zorbax C8 (manufactured by Du Pont)
Mobile phase: acetonitrile / water = 60/40 (volume ratio),
Flow rate: 1 mL / min,
Temperature: 20 ° C.

(Examples 1 to 14, Comparative Examples 1 to 5)
According to the compositions shown in Tables 2 to 4, the components (a) and (b) were added to water, mixed, stirred at 70 ° C. until uniform and transparent, then allowed to cool, and Examples 1 to 14 and Comparative Example 2 Α-5-SF salt-containing liquids of ˜5 were obtained. Further, an α-SF salt-containing liquid of Comparative Example 1 was obtained in the same manner as described above except that the component (b) was not added.
In the table, the content of the compounding component indicates a pure conversion amount, and the unit is mass%.
“Balance” indicating the content of water (purified water) means the balance added so that the total amount (% by mass) of all the components included in the α-SF salt-containing liquid is 100% by mass. .
The pH (30 ° C.) of the obtained α-SF salt-containing liquid was in the range of 5.5 to 7.5 in all examples.

The appearance of each α-sulfo fatty acid ester salt-containing liquid in each example was evaluated by the following method and the viscosity at 30 ° C. was measured. The evaluation results are shown in Tables 2-4.

<Appearance evaluation method>
In preparing the α-SF salt-containing solution, the mixture was stirred at 70 ° C. until uniform and transparent, and then allowed to stand in an atmosphere at 30 ° C. for 1 day, and then visually observed. Evaluation was made according to the following criteria. The state in which separation occurred was observed in a state in which a large number of small spheres floated in the solution and became slightly cloudy, or in a state in which some transparent and large lumps floated.
A: Uniform and transparent.
B: Separation occurred.
C: Precipitation occurred.

<Measurement method of viscosity>
The sample was adjusted to 30 ° C. and measured by the above method using a B-type viscometer (manufactured by TOKIMEC). In addition, when the appearance evaluation result was C or B, the viscosity was not measured (“−” was shown in the table that the viscosity was not measured).

As shown in the results of Tables 2 to 4, Comparative Examples 3, 5 and (a) / a in which the total content of α-SF salt (a) and fatty acid polyoxyethylene methyl ether (b) exceeds 40% by mass Comparative Example 4 having a large mass ratio of (b) was separated when stored at 30 ° C.
In particular, when Example 5 and Comparative Example 3 are compared, the mass ratio of (a) / (b) is the same, and the total content of component (a) and component (b) is increased by only 2% by mass, Appearance evaluation decreased from A to B.
In Comparative Example 1 that does not contain fatty acid polyoxyethylene methyl ether (b), and in Comparative Example 2 in which the total content of component (a) and component (b) is 45% by mass, precipitation occurs when stored at rest. It was.
Comparing Examples 1 to 4 and 8 to 11, when the total content of the component (a) and the component (b) is the same, the smaller the mass ratio of (a) / (b), the lower the viscosity. It was.

Claims (3)

1. An α-sulfo fatty acid ester salt having a fatty acid residue having 16 to 18 carbon atoms (a), a fatty acid polyoxyalkylene alkyl ether (b), and water;
   The total content of (a) and (b) is more than 30% by mass and 40% by mass or less, and the mass ratio of (a) / (b) is 1.5 or more and 9.0 or less with respect to the whole. An α-sulfo fatty acid ester salt-containing liquid characterized by being.
2. (A) is a mixture of an α-sulfo fatty acid ester salt (C16) in which the fatty acid residue has 16 carbon atoms and an α-sulfo fatty acid ester salt (C18) in which the fatty acid residue has 18 carbon atoms. The liquid containing an α-sulfo fatty acid ester salt according to claim 1, wherein (C16) :( C18) is 45:55 to 95: 5.
3. The α-sulfo fatty acid ester salt-containing liquid according to claim 1, wherein (b) is a compound represented by the following general formula (II).
   R ³ —CO (OR ⁴ ) mOR ⁵ (II)
   [Wherein R ³ is a saturated or unsaturated hydrocarbon group having 9 to 18 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and R ⁵ is a hydrocarbon group having 1 to 3 carbon atoms. M represents the average added mole number of OR ⁴ and is 5 to 25. ]