JPH0565267A - Alpha-sulfo fatty acid ester salt composition and its production - Google Patents

Abstract

PURPOSE:To obtain a new useful alpha-sulfo fatty acid ester salt composition having both excellent solubility and cleaning properties. CONSTITUTION:A compound comprising (1) (A) an alpha-sulfo fatty acid (8-22C) alkyl (1-2C) ester salt and (B) an alpha-sulfo fatty acid (8-22C) alkyl (3-4C) ester salt in the ratio of the component A/B (weight standard)=2/3-9/1. (2) 8-22C fatty acid alkyl (1-2C) ester is sulfonated with sulfuric anhydride and then 10-60wt.% of the sulfonated substance is subjected to ester exchange with 3-4C aliphatic alcohol to produce the composition industrially.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an α-sulfofatty acid ester salt composition and a method for producing the same.

[0002]

2. Description of the Related Art α-Sulfo fatty acid ester salt (hereinafter referred to as "α
-SFE ". ) Is a compound known as a surfactant having good detergency, hard water resistance and biodegradability, and in particular, α consisting of a single or mixed fatty acid having 16 to 18 carbon atoms.
-Lower alkyl (C1 to C2) ester salts such as methyl ester salt and ethyl ester salt of sulfo fatty acid have good detergency. However, this product has a high Kraft point and, when applied to a liquid detergent, has a drawback that it causes a precipitate at room temperature. On the other hand, carbon number 6 to 1
It is known that the α-sulfofatty acid lower alkyl (C1 to C2) ester salt of 4 or a single or mixed fatty acid has a low Kraft point but inferior detergency.

As a composition having α-SFE as a main surfactant component and improved solubility and detergency, attention has been paid to the carbon number of a fatty acid residue, and (a) a carbon number of 12
High bulk containing α-SFE having 14 to 14 fatty acid residues and (b) α-SFE having 16 to 18 fatty acid residues in a predetermined weight ratio and in a predetermined total amount. A density granular detergent composition has been proposed (Japanese Patent Laid-Open No. 2-103).
293). However, α-SFE in the composition
However, when the above was considered as a constituent of the liquid detergent composition, it was still not sufficiently satisfactory.

The Kraft point of α-SFE is affected not only by the carbon number of the fatty acid residue but also by the carbon number of the alcohol component, and generally decreases as the alcohol residue becomes longer (that is, the solubility improves). There is a tendency. However, α-SFE having a long-chain alcohol residue is
At the same time, the detergency tends to decrease (Tenside, 27 , 2
43 (1990)), it is difficult to use them alone as the main surfactant in liquid detergents.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have an alcohol component having 1 to 2 carbon atoms, which has a high detergency but a high Kraft point and is difficult to use as a main surfactant of a liquid detergent. The inventors have conducted earnest studies to develop a surfactant composition containing α-SFE as an essential component, which has good detergency and solubility and is useful not only as a powder detergent but also as a component of a liquid detergent. As a result, the present inventors have found the following facts in the examination conducted by focusing on the alcohol component which has not been sufficiently examined so far.

(1) By combining α-SFE obtained from an alcohol having 1 to 2 carbon atoms with α-SFE obtained from an alcohol having 3 to 4 carbon atoms, the Kraft point can be lowered, In addition, a composition having good detergency can be obtained.

(2) In the above composition, the α-sulfo fatty acid ester obtained from an alcohol having 1 to 2 carbon atoms is partially transesterified within a specific range by using an aliphatic alcohol having 3 to 4 carbon atoms. Then, it can be produced under industrially advantageous conditions by neutralization. That is, the present invention is an invention completed based on such findings, and an object thereof is to provide a novel and useful composition of α-SFE and a method for producing the same.

[0008]

The α-sulfofatty acid ester salt composition according to the present invention comprises an α-sulfofatty acid ester salt represented by the general formula (I).
-Sulfo fatty acid ester salt (hereinafter referred to as "A component")
And an α-sulfo fatty acid ester salt represented by the general formula (II) (hereinafter referred to as “component B”), and component A /
B component (weight basis) is 2/3 to 9/1, preferably 1 /
It is characterized by being 1 to 5/1.

[In the formula, R ¹ represents a linear or branched alkyl group having 6 to 20 carbon atoms, and R ² represents 1 to 10 carbon atoms.
2 represents an alkyl group. M represents an alkali metal, an alkaline earth metal, an alkanolamine residue or ammonium. ]

[In the formula, R ³ represents a linear or branched alkyl group having 6 to 20 carbon atoms, and R ⁴ represents 3 to 3 carbon atoms.
4 represents a linear or branched alkyl group. M is the same as in general formula (I). ]

The weight ratio of the A component to the B component is 2/3.
If it is less than less than 1, the detergency is lowered, and if it exceeds 9/1, the craft point becomes high, which is not preferable.

In the α-SFE composition according to the present invention, the components A and B are separately prepared by a known method, for example, having 8 to 22 carbon atoms.
Can be obtained by sulfonating a fatty acid ester of sulfuric acid with anhydrous sulfuric acid, aging, and then neutralizing with a predetermined alkali to prepare, and appropriately mixing each of the obtained components in a predetermined ratio. By applying the following method, the desired composition can be industrially obtained efficiently in one step.

That is, the method for producing an α-SFE composition according to the present invention is a generic term for a methyl ester or ethyl ester of a linear or branched fatty acid having 8 to 22 carbon atoms (hereinafter referred to as "fatty acid lower alkyl ester"). ) Is sulfonated with sulfuric acid anhydride, and then 10 to 60 of such sulfonated product.
It is characterized in that wt% is transesterified with one or more alcohols selected from linear or branched aliphatic alcohols having 3 to 4 carbon atoms and then neutralized.

The fatty acid lower alkyl ester used as a raw material is transesterified from animal fats and oils such as beef tallow, lard and fish oil, vegetable fats and oils such as palm oil, coconut oil and palm kernel oil with methanol or ethanol, Alternatively, it can be obtained by esterifying the higher fatty acid having the above chain length by adding methanol or ethanol in the presence or absence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid.

[Sulfonation step] By contacting these fatty acid lower alkyl esters with sulfuric anhydride diluted with 5 to 20 times the amount of dried inert gas (eg, dry air, dry nitrogen gas). A sulfone group is introduced at the α-position to obtain the desired α-sulfofatty acid lower alkyl ester. At this time, the lower the iodine value of the raw material ester, the better. Specifically, it is preferably 1 or less. This is because when the raw material ester has an unsaturated bond, sulfuric anhydride reacts with the unsaturated bond, and as a result, a sulfone group is introduced in addition to the α-position, resulting in a decrease in the yield of the target product. is there.

The preferred amount of sulfuric anhydride is usually 1.1 to 1.7 with respect to 1 mol of the fatty acid lower alkyl ester.
The amount is more preferably about 1.2 to 1.5 mol.
If it is less than 1.1 mol, the yield will be significantly reduced, and if it is added in excess of 1.7 mol, the hue of the sulfonated product obtained will be significantly deteriorated.

The sulfonation is carried out at a temperature of about 60 to 90 ° C., preferably about 70 to 80 ° C., usually for 40 minutes to 2 minutes.
It will be completed in about time.

The reaction is a compound which is inactive to sulfuric anhydride,
For example, a chlorine-based compound such as carbon tetrachloride or 1,2-dichloroethane or a fluorine-based compound may be used as a solvent, but it is preferably performed without a solvent from the industrial, economical and environmental viewpoints.

After completion of the reaction, excess sulfuric acid in the sulfonated product produced by topping or by circulating an inert gas such as air in the product is removed as necessary, or water, methanol or the like is used. The sulfuric anhydride is deactivated, and if necessary, it is bleached with a bleaching agent such as hydrogen peroxide.

[Transesterification Step] The sulfonated product obtained in the above-mentioned step contains 0.1 to 1 mol of the sulfonated compound.
About 2.0 mol, preferably about 0.5-1.5 mol of a linear or branched aliphatic alcohol having 3 to 4 carbon atoms is added all at once or in a divided amount. In an atmosphere of active gas, the melting temperature of the sulfonated product is higher than, for example, 50.
~ 150 ° C, preferably about 70-130 ° C 5
The reaction is carried out for about 3 minutes to about 3 hours, preferably about 30 minutes to 2 hours to transesterify 10 to 60% by weight of the sulfonated product. The end time of this transesterification step is determined using high performance liquid chromatography (HPLC) described later. When the temperature is lower than the above temperature, the sulfonated material is solidified, the reaction time becomes long and the productivity is lowered, and on the contrary, coloring or a side reaction occurs at a high temperature, which is not preferable. Transesterification is not sufficiently carried out in a time shorter than 5 minutes, while long-term reaction is economically undesirable. If the transesterification rate is less than 10% by weight, the Kraft point is high, while if it exceeds 60% by weight, the detergency is lowered, and in any case, the effect of the present invention cannot be obtained.

Examples of the linear or branched aliphatic alcohols having 3 to 4 carbon atoms include propanol, isopropanol, butanol, isobutanol and sec-butanol, and particularly isopropanol, butanol and isobutanol are effective. is there.

In this step, methanol, while circulating an inert gas such as air, nitrogen, or argon in the system or continuously adding alcohol under reduced pressure,
The transesterification rate can be increased by distilling off the alcohol component derived from the raw material ester such as ethanol.

[Neutralization Step] In this step, a predetermined alkaline aqueous solution is added to the transesterification reaction product, and the temperature is usually from room temperature to 60.
It is performed under heating at about ℃.

Examples of the predetermined alkali include alkali hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide, ethanolamine,
Examples are alkanolamines such as diethanolamine and triethanolamine, and ammonia.

Further, after neutralization, if necessary, the unreacted alcohol is distilled off, and when decolorization is required, it is 60 to 8
Bleaching is performed at 0 ° C. with hydrogen peroxide or sodium dichlorite to obtain an α-SFE aqueous solution having a concentration of about 10 to 40% by weight.

The composition of α-SFE thus obtained is
It has good detergency and low Kraft point (that is, good solubility) and is useful as a main surfactant in powder or liquid laundry detergents or kitchen detergents.

Further, other surfactants (for example, straight chain alkylbenzene sulfonate, alkyl ether sulfate, alkyl sulfate, sec-
Alkane sulfonate, α-olefin sulfonate,
Used in combination with anionic surfactants such as fatty acid soaps, amphoteric surfactants such as lauryldimethyl acetic acid betaine and coconut alkylamidopropyl acetic acid betaine, and nonionic surfactants such as lauryl dimethylamine oxide, coconut alkyl diethanolamide, and coco alkyl glucoside. You can also In addition, well-known builders, chelating agents, anti-redeposition agents, hydrotropes, stabilizers, enzymes, bleaching agents, fragrances, dyes, fluorescent agents and the like can be appropriately contained.

[0026]

EXAMPLES The present invention will be described in detail below with reference to examples. The composition, Kraft point, and cleaning power (cleaning rate) of the α-SFE composition in each example were measured and evaluated by the following methods.

Compositional HPLC method of α-SFE composition [shampoo analysis, J.Soc.Cosmet.Chem.Ja
pan, 21 (1), 5 (1987)]. The conditions are described below. Equipment: High Performance Liquid Chromatograph LC-3A (Shimadzu) Column: Shimpack CLC-ODS (6φ x 150 mm)
(Manufactured by Shimadzu Corporation) Mobile phase: methanol / water = 80/20 (v / v), 0.0.
25M-Natrium perchlorate, adjusted to pH = 2.5 with phosphoric acid Flow rate: 1.0 ml / min Column temperature: 45 ° C. Detector: RID-6A

100 g of an aqueous surfactant solution (surfactant concentration 1.0% by weight) was put into a 100 ml beaker having a Kraft point, allowed to stand at room temperature for 24 hours, and then cooled at -5 ° C for 40 to 50 hours. A thermometer is fixed at the center of the beaker, the aqueous solution in which crystals are precipitated is heated at a rate of 1 ° C./minute, and the temperature at which the solution begins to be rapidly dissolved is taken as the craft point. The Kraft point of the test article in which crystals were not precipitated at -5 ° C was 0 ° C or lower.

Cleaning rate : The method was based on the Hitachi-Lion artificial soil method. That is, using a Terg-O-Tometer, a predetermined contaminated cloth was washed in an aqueous detergent solution (surfactant concentration 1.0% by weight) for 10 minutes (rotation speed 100 rpm / min, washing temperature 30 ° C.), and then Rinse for 3 minutes. This operation was performed 4 times, after air-drying, ironing was performed to measure the whiteness, and the detergency was calculated according to the following formula.

[0030]

[Equation 1] [In the formula, Rw represents the whiteness of the contaminated cloth after washing, Rs represents the whiteness of the contaminated cloth, and Ro represents the whiteness of the original white cloth. ]

Example 1 214 g (1 mol) of methyl laurate was placed in a 2-liter four-necked flask equipped with a stirrer, a thermometer, a condenser and a gas inlet.
Was added, and anhydrous sulfuric acid diluted to 5% with dry air was added.
Blow 4 g (1.3 mol) into the ester at 70 ° C,
Then, it was aged at 80 ° C. for 1 hour. Then, 74 g (1 mol) of isobutanol was added, and transesterification was carried out at 70 ° C. for 150 minutes. Then, after cooling to room temperature, it was neutralized with a 15% aqueous sodium hydroxide solution. After fine adjustment to pH 7, the mixture was aged at 60 ° C for 1 hour. Then, the reaction was completed while distilling off methanol and unreacted isobutanol under reduced pressure. A predetermined amount of water was added to obtain a 30 wt% α-SFE mixed aqueous solution having the following composition. Sodium salt of methyl α-sulfolaurate 51% by weight Sodium salt of isobutyl α-sulfolaurate 47% by weight α-sulfofatty acid di salt 2% by weight As a result of the measurement, the Kraft point of the above composition was 0 ° C. or lower and washing The rate was 72%.

Comparative Example 1 Each constituent was separately prepared by the conventional method (J. Am. Chem. Soc., 75, 4859 (19
53), the same applies hereinafter) to obtain an α-SFE composition having the following composition. α-sulfolauric acid sodium salt 25% by weight α-sulfolauric acid isobutyl sodium salt 70% by weight α-sulfolauric acid di-salt 5% by weight As a result of the measurement, the Kraft point of the composition is 0 ° C. or lower, The cleaning rate was 65%.

Example 2 284 g of ethyl palmitate was placed in the same reactor as in Example 1.
(1 mol) was charged and sulfonated under the same conditions as in Example 1. Then, 30 g of n-propanol (0.5
Mol) and transesterified at 90 ° C. for 90 minutes. Then, after cooling to room temperature, it was neutralized with a 15% aqueous sodium hydroxide solution. After fine adjustment to pH7, 1 at 60 ℃
Aged for hours. Then, the reaction was completed while distilling off methanol and unreacted n-propanol under reduced pressure. 30% by weight of α having the following composition by adding a predetermined amount of water
-SFE mixed aqueous solution was obtained. Sodium salt of ethyl α-sulfopalmitate 63 wt% Sodium salt of n-propyl α-sulfopalmitate 32 wt% α-sulfopalmitate di salt 5 wt% As a result of the measurement, the Kraft point of the above composition is 0 ° C or lower. The cleaning rate was 75%.

Comparative Example 2 Each component was separately prepared according to a conventional method to obtain an α-SFE composition having the following composition. Sodium salt of ethyl α-sulfopalmitate 35 wt% Sodium salt of n-propyl α-sulfopalmitate 63 wt% α-sulfopalmitate di salt 2 wt% As a result of the measurement, the Kraft point of the above composition is 0 ° C or lower. The cleaning rate was 63%.

Example 3 Hardened coconut oil fatty acid methyl 25 was placed in the same reactor as in Example 1.
8 g (1 mol) was charged and sulfonated under the same conditions as in Example 1. Then, 18.5 g of n-butanol
(0.25 mol) was added and transesterification was carried out at 110 ° C. for 40 minutes. Then, after cooling to room temperature, it was neutralized with a 15% aqueous sodium hydroxide solution. After fine adjustment to pH 7, the mixture was aged at 60 ° C for 1 hour. Then, the reaction was completed while distilling off methanol and unreacted n-butanol under reduced pressure. 30 having the following composition by adding a predetermined amount of water
A wt% α-SFE mixed aqueous solution was obtained. α-sulfo-cured coconut fatty acid methyl sodium salt 78% by weight α-sulfo-cured coconut fatty acid n-butyl sodium salt 19% by weight α-sulfo-cured coconut acid di-salt 3% by weight As a result of the measurement, the Kraft point of the above composition was At 0 ° C or lower, the cleaning rate was 70%.

Comparative Example 3 Each constituent was separately prepared according to a conventional method to obtain an α-SFE composition having the following composition. α-sulfo-cured coconut fatty acid methyl sodium salt 92% by weight α-sulfo-cured coconut acid n-butyl sodium salt 6% by weight α-sulfo-cured coconut fatty acid di-salt 2% by weight As a result of the measurement, the Kraft point of the above composition was determined. At 15 ° C., the cleaning rate was 68%.

Example 4 295 g (1 mol) of hardened palm stearin fatty acid ethyl was charged into the same reactor as in Example 1 and sulfonated under the same conditions as in Example 1. Then, 56 g (0.75 mol) of sec-butanol was added, and transesterification was carried out at 90 ° C. for 40 minutes. Then, after cooling to room temperature, it was neutralized with a 15% aqueous sodium hydroxide solution. After fine adjustment to pH 7, the mixture was aged at 60 ° C for 1 hour. Then, the reaction was completed while distilling off methanol and unreacted sec-butanol under reduced pressure. A predetermined amount of water was added to obtain a 30 wt% α-SFE mixed aqueous solution having the following composition. Sodium salt of α-sulfo-cured palm stearate fatty acid ethyl 59% by weight Sodium salt of α-sulfo-cured palm stearate fatty acid sec-butyl 37% by weight
α-sulfo-hardened palm stearin fatty acid di-salt
As a result of 4% by weight measurement, the composition had a Kraft point of 0 ° C. or lower and a cleaning rate of 75%.

Comparative Example 4 Each constituent was separately prepared according to a conventional method to obtain an α-SFE composition having the following composition. Sodium salt of α-sulfo-cured palm stearic acid fatty acid 20% by weight Sodium salt of α-sulfo-cured palm stearic acid sec-butyl 76% by weight
α-sulfo-hardened palm stearin fatty acid di-salt
As a result of 4% by weight measurement, the Kraft point of the above composition was 0 ° C. or lower, and the cleaning rate was 60%.

[0039]

The α-sulfofatty acid ester salt composition according to the present invention has an excellent cleaning performance, a low Kraft point and a greatly improved liquidity. Furthermore, by applying the method according to the present invention, the present composition can be produced under industrial conditions.

Claims (2)

[Claims] 1. An α-sulfo fatty acid ester salt represented by the general formula (I) (hereinafter referred to as “component A”) and an α-sulfo fatty acid ester salt represented by the general formula (II) (hereinafter referred to as “B”). Component)), and A component / B component (weight basis) is 2/3 to 9/1.
Sulfo fatty acid ester salt composition. [Chemical 1] [In the formula, R ¹ represents a linear or branched alkyl group having 6 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 2 carbon atoms. M represents an alkali metal, an alkaline earth metal, an alkanolamine residue or ammonium. ] [Chemical 2] [In the formula, R ³ represents a linear or branched alkyl group having 6 to 20 carbon atoms, and R ⁴ represents a linear or branched alkyl group having 3 to 4 carbon atoms. M is the same as in general formula (I). ] 2. A methyl ester or ethyl ester of a linear or branched fatty acid having 8 to 22 carbon atoms is sulfonated with sulfuric anhydride, and then 10 to 10 of such sulfonated product is obtained.
60% by weight is transesterified with one or more alcohols selected from linear or branched aliphatic alcohols having 3 to 4 carbon atoms, and then neutralized. A method for producing the described α-sulfofatty acid ester salt composition.