JPH10251215A - Higher secondary alkyl ether sulfate ester salt composition, and detergent and emulsifier containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain higher secondary alkyl ether sulfate ester salt composition, capable of being readily treated because of having a low viscosity and hardly gelling, good in surface tension and osmotic force, further good in break of foam and excellent in detergency and emulsifying properties. SOLUTION: This higher secondary alkyl ether sulfate ester salt composition comprises a compound of the formula [R<1> and R<2> are each an alkyl group with the proviso that the total number of carbons of R<1> and R<2> is 7-29 and R<1> <=R<2> ; A is a lower alkylene group; (n) is 1-20 in average; M is an alkali metal atom, an alkaline earth metal ion, ammonia or a substituted ammonium group], and consists of 30-90mol% alkyl ether sulfate ester salt in which R<1> is methyl, and 70-10mol% alkyl ether sulfate ester salt in which R<1> is the alkyl group larger than the methyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a higher secondary alkyl ether sulfate composition and a detergent and an emulsifier containing the same.

[0002]

BACKGROUND OF THE INVENTION Anionic surfactants include alkyl allyl sulfonates, higher primary alcohol sulfates, higher primary alkyl ether sulfates, and the like.

[0003] Of these, alkyl allyl sulfonates,
In particular, linear alkylbenzene sulfonates are being regulated because they have poor biodegradability and thus have an adverse effect on the environment.

[0004] Alkyl allyl sulfonates, higher primary alcohol sulfates, and the like are easily affected by the hardness of water and have poor water solubility.

[0005] Higher primary alkyl ether sulfates not only have high viscosities and are easily gelled, but also have insufficient surface activity such as surface tension and osmotic power, and have sufficient detergency and emulsifying power. Absent.

[0006] Other anionic surfactants also include
There is not enough performance.

[0007]

As a result of various studies, the present inventors have found that a specific higher secondary alkyl ether sulfate composition is low in viscosity and hard to gel, so that it is easy to handle, and has a high surface tension, The present inventors have found that a surfactant having good penetration power, good foam removal, excellent detergency and emulsifying power can be obtained, and the present invention has been completed.

That is, an object of the present invention is to provide (i) a general formula (1)

[0009]

Embedded image

(Wherein R ¹ and R ² are alkyl groups, the total number of carbon atoms in R ¹ + R ² is 7 to 29, and R ¹ ≦
R ² , A is a lower alkylene group, and n is an average of 1 to 20. However, when n is 2 or more, AO
The type of the oxyalkylene group represented by
When the number of the oxyalkylene groups is two or more, it indicates that the number of various oxyalkylene groups is n on average. M is an alkali metal atom, an alkaline earth metal ion, ammonia or a substituted ammonium group. A higher secondary alkyl ether sulfate composition represented by the formula ( ¹⁾ , wherein R ¹ is a methyl group: 30 to 90 mol%
And a higher secondary alkyl ether sulfate composition comprising 70 to 10 mol% of an alkyl ether sulfate wherein R ¹ is an alkyl group larger than a methyl group.

Another object of the present invention is achieved by (ii) a detergent comprising the above (i) higher secondary alkyl ether sulfate composition.

Further, another object of the present invention is achieved by (iii) an emulsifier characterized in that it contains the higher secondary alkyl ether sulfate composition of the above (i).

[0013]

DETAILED DESCRIPTION OF THE INVENTION The higher secondary alkyl ether sulfate composition according to the present invention has the general formula (1):

[0014]

Embedded image

(Wherein R ¹ and R ² are alkyl groups, the total number of carbon atoms of R ¹ + R ² is 7 to 29, and R ¹ ≦
R ² , A is a lower alkylene group, and n is an average of 1 to 20. However, when n is 2 or more, AO
The type of the oxyalkylene group represented by
When the number of the oxyalkylene groups is two or more, it indicates that the number of various oxyalkylene groups is n on average. M is an alkali metal atom, an alkaline earth metal ion, ammonia or a substituted ammonium group. A higher secondary alkyl ether sulfate composition represented by the formula ( ¹⁾ , wherein R ¹ is a methyl group: 30 to 90 mol%
And 70 to 10 mol% of an alkyl ether sulfate salt in which R ¹ is an alkyl group larger than a methyl group.

In the above formula (1), the lower alkylene group represented by A is an alkylene group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. Therefore, examples of the oxyalkylene group represented by AO include an ethoxy group, a propoxy group, and a butoxy group. Further, as defined by AO in the general formula (1), these oxyalkylene groups may be composed of only one kind, or may be composed of two or more kinds. In that case, two or more types of oxyalkylene groups may be randomly arranged, or each may be arranged in a block. For example, a configuration in which a part of the long chain of an ethoxy group is a propoxy group may be employed.

In the above formula (1), the alkyl groups represented by R ¹ and R ² are preferably straight-chain alkyl groups.
¹ + total number of carbon atoms in R ² is 7 to 29, preferably 9 to 19
And R ¹ ≦ R ² . N in the general formula (1) is 1 to 20 on average.

The higher secondary alkyl ether sulfate composition according to the present invention is a higher secondary alkyl ether sulfate composition represented by the general formula (1), wherein R ¹ is a methyl group. 30 to 90 mol% of an ether sulfate 70 and an alkyl ether sulfate 70 wherein R ¹ is an alkyl group larger than a methyl group
-10 mol%.

The higher secondary alcohol alkoxylate used as a raw material for the higher secondary alkyl ether sulfate composition of the present invention can be synthesized by the following reaction.

Reacting a long chain olefin having 8 to 30 carbon atoms with a (poly) alkylene glycol in the presence of an acid catalyst;
It is obtained by separating the product by distillation, extraction or other methods.

The long-chain olefin used for obtaining the higher secondary alcohol alkoxylate is preferably a hydrocarbon having 8 to 30 carbon atoms having an ethylenically unsaturated bond, preferably an ethylenically unsaturated bond. Acyclic hydrocarbon having 10 to 20 carbon atoms. Specifically, octene, decene, dodecene, tetradecene,
Hexadecene, octadecene, eicosene and the like.
These may be used alone or as a mixture of two or more.

Specific examples of the (poly) alkylene glycol include monoethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, , 2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, para-xylene glycol, 1,4-cyclohexanemethanediol, and the like. These may be used alone or as a mixture of two or more.

Specific examples of the acid catalyst used in the reaction between the long-chain olefin and the (poly) alkylene glycol include:
Strongly acidic ion exchange resins, crystalline aluminosilicates, dodecylbenzenesulfonic acid, etc., are preferred from the viewpoint of reactivity, and are preferably crystalline aluminosilicates, and among them, BEA zeolite is particularly desirable.

The acid catalyst is used in an amount of 1 to 50% by weight, preferably 2 to 30% by weight, based on the long-chain olefin. When the amount of the catalyst is less than 1% by weight, sufficient catalytic activity cannot be obtained and the addition reaction cannot be promoted.
If the amount is more than 10% by weight, it is not preferable because the effect corresponding to the further addition cannot be obtained and it becomes uneconomical.

The higher secondary alcohol alkoxylate can be used as a raw material for a higher secondary alkyl ether sulfate composition as it is, and further, can be used as an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide or styrene oxide. The reaction can be carried out in the presence of an alkali catalyst to give a higher secondary alcohol alkoxylate, which can also be used as a raw material for a sulfate ester salt.

The molar ratio of the alkylene oxide to the higher secondary alcohol alkoxylate is not particularly limited, but is preferably 1 to 30, more preferably 4 to 4.
20. As the conditions for adding the alkylene oxide, the reaction temperature is usually 50 to 250 ° C., preferably 100 to 200 ° C., and the reaction pressure may be either normal pressure or pressurized. / Cm ²
Is desirable. When the reaction temperature is lower than 50 ° C., the reaction rate is slow. On the other hand, when the reaction temperature is higher than 250 ° C., it is not preferable because decomposition and an increase in by-products occur.

Examples of the alkali catalyst include hydroxides of elements belonging to alkali metals or alkaline earth metals, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide,
Barium hydroxide and the like can be mentioned. From the viewpoint of availability and reactivity, preferred are sodium hydroxide and potassium hydroxide. These may be powdered, granular, or added as an aqueous solution to perform dehydration. The amount of the alkali catalyst used is preferably from 0.01 to 2.0% by weight, and more preferably from 0.02 to 0.5% by weight, based on the starting alkoxylate.

For the sulfation of the higher secondary alcohol alkoxylate, sulfation is performed using chlorosulfonic acid or sulfuric anhydride.

When chlorosulfonic acid is used, higher secondary
Chlorosulfonic acid is dropped into the secondary alcohol alkoxylate by a known method, for example, directly or accompanied by air, an inert gas, or the like, or JP-B1-36823.
According to the method described in Japanese Patent Application Laid-Open Publication No. H10-163, the mixture is mixed using a sulfation apparatus equipped with an external circulation equipped with a line mixer, thereby performing batch-type sulfation. The dropping time of chlorosulfonic acid is 1 to 2 hours, and the reaction temperature is -20 to 30C, particularly 0 to 20C.

When sulfuric anhydride is used, the higher secondary alcohol alkoxylate is allowed to flow down into a thin film using a co-current thin film reactor by a known method, for example, the method described in Japanese Patent Publication No. Sho 51-17538. By bringing sulfuric anhydride gas diluted with active gas into parallel flow and gas-liquid contact,
Sulfation is carried out continuously. Inert gas speed is 20 ~ per second
70 m, the concentration of sulfuric anhydride in gas is preferably 1 to 10% by volume, and the molar ratio of sulfuric anhydride to higher secondary alcohol alkoxylate is preferably 0.95 to 1.2. Reaction temperature is -2
0-60 degreeC, especially 0-30 degreeC are desirable.

By using a solvent in the sulfation step, it is possible to produce the higher secondary alkyl ether sulfate composition of the present invention with higher yield and higher quality. As the type of the solvent used, chloroform, carbon tetrachloride, ethyl chloride, ethylene chloride, 1,1,
Chlorine solvents such as 1-trichloroethane and 1,1,1,2-tetrachloroethane, hydrocarbon solvents such as n-pentane, n-hexane, n-heptane and cyclohexane, ether solvents such as diethyl ether and isopropyl ether And the like. The solvent concentration is desirably 10 to 90% by weight in the reaction solution. Solvent concentration is 10% by weight
If the amount is less than 90%, the effect of using a solvent cannot be obtained. If the amount exceeds 90% by weight, the reaction efficiency is deteriorated and the yield is lowered.

After the sulfation, the obtained reaction solution is neutralized with a basic substance, and if a solvent is used, the solvent is removed to obtain the desired higher secondary alkyl ether sulfate composition. it can.

Suitable bases for the neutralization step are alkali metal hydroxides, more preferably sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal oxides and hydroxides, more preferably Magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, alkanolamines, more preferably mono-, di- and triethanolamine,
And primary, secondary and tertiary alkylamines containing from 1 to 4 carbon atoms per alkyl group.

Next, the higher secondary alkyl ether sulfate composition of the present invention may be used alone as a detergent, or may be used in combination with a conventionally known detergent surfactant. Examples of such surfactants include nonionic surfactants such as alkylphenol ethoxylate, higher primary alcohol ethoxylate, higher secondary alcohol ethoxylate, and fatty acid ethoxylate;
Examples include cationic surfactants such as alkylamine salts and quaternary ammonium salts, and zwitterionic surfactants such as alkyl betaines.

Conventional anionic surfactants such as, for example,
Alkyl allyl sulfonates, higher primary alcohol sulfates, higher primary alkyl ether sulfates, and the like can also be used in combination as long as the performance of the detergent of the present invention is not impaired.

Further, various additives used in ordinary cleaning agents can be added to the cleaning agent of the present invention. Such additives include, for example, alkaline agents,
Examples include builders, fragrances, optical brighteners, coloring agents, foaming agents, foam stabilizers, polishing agents, bactericides, bleaching agents, enzymes, preservatives, dyes, solvents, and the like.

The cleaning agent of the present invention can be used for clothing, textiles, tableware, containers, sundries, food, building maintenance products,
Cleaning agents for houses, furniture, cars, aircraft, metal products, etc.
It can be used effectively as shampoo, body shampoo and the like.

On the other hand, the higher secondary alkyl ether sulfate composition of the present invention may be used alone as an emulsifier, but may contain other conventionally known emulsifiers as necessary. . For example, anionic surfactants, cationic surfactants commonly used as emulsifiers,
A nonionic surfactant or a zwitterionic surfactant can be used in combination.

The oily substance used in the emulsifier of the present invention is not particularly limited, and mineral oil, animal and vegetable oil, synthetic oil and the like can be used. These can be used alone or in combination of two or more. Examples of mineral oils include, for example, spindle oil, machine oil, liquid paraffin, and the like. Examples of animal and vegetable oils include beef tallow, lard, fish oil, whale oil, rapeseed oil, sesame oil, coconut oil, soybean oil, palm oil, camellia oil, castor oil and the like.

The emulsifier of the present invention can be used in agricultural chemicals, metal working oils, paints, emulsifiers for emulsion polymerization, and the like.

[0041]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis Method) Example 1 Secondary dodecyl ether sulfate ester composition 1-dodecene was converted to a BEA type zeolite (trade name: manufactured by PQ)
VALFOR CP811 BL-25) 5% by weight, obtained by treating at 150 ° C. for 10 hours.
Dodecene isomer mixture (1-dodecene 25 mol%,
810 g (consisting of 75 mol% of inner decene)
(4.82 mol), monoethylene glycol 900
g (14.52 mol), and PQ B as a catalyst
EA type zeolite (trade name: VALFOR CP 81)
1BL-25) was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser, and the gas phase was replaced with nitrogen.
Next, while stirring at a rotation speed of 600 rpm, 1
After the temperature was raised to 50 ° C., and the reaction was carried out at the same temperature for 3 hours, the reaction solution was cooled to room temperature, the upper layer of the dodecene phase was separated and distilled. After distilling off unreacted dodecene, the pressure was reduced to 2 mmH.
155 g of secondary dodecanol monoethoxylate was obtained in a boiling point range of 129 to 131 ° C.

This secondary dodecanol monoethoxylate was used in a reaction tube forming an annular reaction zone having an inner diameter of 5 mm and a length of 100 cm. 16.2 per minute along the inner wall of
It flowed down in a thin film at a speed of g. At the same time, sulfuric anhydride diluted with nitrogen gas was flowed in from a nozzle provided at the top of the reaction tube. The flow rate of the flowed total nitrogen gas in the reaction tube was 30 m / sec, and the concentration of sulfuric anhydride in the flowed total mixed gas was 4% by volume. The molar ratio of the sulfuric anhydride dropped and the secondary dodecanol ethoxylate dropped was 1.1. Reaction heat generated by the reaction between ethoxylate and sulfuric anhydride was removed by a refrigerant flowing outside the reaction tube, and kept at 15 ° C. The fluid exiting the reaction tube was separated into nitrogen gas and reaction products by a cyclone. The reaction product was immediately neutralized with an aqueous sodium hydroxide solution to obtain an approximately 25% aqueous solution of a sulfate salt.

The addition position of the alkyl chain carbon of the sulfate ester salt of the obtained secondary dodecyl ether sulfate ester composition was determined from the proton ratio of the alkyl terminal methyl group by ¹ H-NMR analysis (FIG. 1). As a result, the secondary dodecyl ether sulfate in which the position 2 was sulfated was 66 mol%.

[0045] (protons of the methyl group of R ¹ is R ¹ is a methyl group) integral value of double lines near 1.15 ppm <calculation method of the position of the sulfate>: triplets around a 0.9 ppm integrated value (R ¹ is and terminal methyl group of R ¹ above methyl group, protons of methyl group at the end of all R ²⁾ of: the proportion of sulfated alkyl ether sulfate of the position of b 2: c c = 2a / (a + b) <NMR measurement method> Model: Varian Unity Plus400 (4
00 MHz) Solvent: CDCl ₃ + 0.03% TMS: SAMPLE =
99: 1 The number of times of integration: The conditions displayed after 16 ¹ H-NMR measurement were as follows.

FREQUENCY 399.958 MHz SPECIAL WIDTH 7998.4 Hz ACQUISITION TIME 4.001 sec RELAXATION DELAY 3.000 sec PULSE WIDTH 10.0usec AMBIENT TEMPERAT. REPETITIONS16 DOUBLE PRECISION ACQUISIT
ION DATA PROCESSING FT SIZE 65536 TOTAL ACQUISITION TIME 1m
inutes. .

Example 2 Secondary Dodecyl Ether Sulfate Composition 155 g (0.67 mol) of secondary dodecanol ethoxylate, which is an intermediate product of Example 1, and 0.2 g of sodium hydroxide as a catalyst in a stainless steel autoclave. And after replacing with nitrogen, the pressure in the reactor was increased to 1.0 with nitrogen.
and kg / cm ² G, temperature was raised to 0.99 ° C., was introduced ethylene oxide 62g of (1.41 mol) to an autoclave at 3hrs. After the introduction, the temperature was further maintained at 150 ° C. for 1 hour, cooled to room temperature, and the internal pressure was purged. Thus, a secondary dodecanol ethoxylate having an average of 3.1 mol of oxyethylene groups was obtained.

217 g (0.67 mol) of the secondary dodecanol ethoxylate added with the ethylene oxide was added to 5
It was charged into a 00 ml flask and cooled to 10 ° C. To this, 86.3 g (0.74 mol) of chlorosulfonic acid was added dropwise over about 1 hour. During the dropwise addition, the liquid temperature was maintained at 10 to 15 ° C. After dropping chlorosulfonic acid, nitrogen gas was flowed into the reaction solution to remove hydrogen chloride gas as a by-product.
While maintaining the temperature below ℃, the reaction solution was dropped into sodium hydroxide solution to neutralize it, and about 25%
An aqueous solution was obtained.

The addition position of the alkyl chain carbon of the sulfate salt of the resulting secondary dodecyl ether sulfate salt composition was determined from the proton ratio of the alkyl terminal methyl group by ¹ H-NMR analysis (FIG. 2). As a result, the secondary dodecyl ether sulfate in which the position 2 was sulfated was 75 mol%. The method for calculating the position of the sulfate ester salt and the method for NMR measurement were performed in the same manner as in Example 1.

Example 3 Secondary hexadecyl ether sulfate composition 1-hexadecene was treated at 150 ° C. for 13 hours with 5% by weight of BEA type zeolite (trade name: VALFOR CP 811 BL-25) manufactured by PQ. Hexadecene isomer mixture (1-hexadecene 2
810 g (3.62 mol), 900 g (14.52 mol) of monoethylene glycol, and BEA type zeolite manufactured by PQ (trade name: VALFO) as a catalyst.
RCP 811 BL-25) (100 g) was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser, and the gas phase was replaced with nitrogen. Then, the temperature was raised to 150 ° C. while stirring at a rotation speed of 600 rpm, and the reaction was carried out at the same temperature for 3 hours. After that, the reaction solution was cooled to room temperature, and the upper hexadecene phase was separated and distilled. After distilling off unreacted hexadecene, 95 g of secondary hexadecanol ethoxylate was obtained at a reduced pressure of 2 mmHg and a boiling point range of 160 to 165 ° C.

80 g (0.28 mol) of this secondary hexadecanol ethoxylate and 400 g of ethylene chloride as a solvent were charged into a 1 liter flask and cooled to 10 ° C. 36 g of chlorosulfonic acid (0.31 m
ol) was added dropwise over about 1 hour. During dropping, the liquid temperature is 10
Maintained at １５15 ° C. After the chlorosulfonic acid was dropped, nitrogen gas was flowed into the reaction solution to remove hydrogen chloride gas as a by-product, and then the reaction solution was dropped into a sodium hydroxide solution while maintaining the temperature at 20 ° C or lower. Then, ethylene chloride was removed to obtain an approximately 25% aqueous solution of a sulfate salt.

The alkyl chain carbon addition position of the sulfate salt of the obtained secondary hexadecyl ether sulfate composition was determined by ¹ H-NMR analysis (FIG. 3).
As a result of calculating from the proton ratio of the alkyl terminal methyl group, 2
Was 61 mol% of the secondary hexadecyl ether sulfate in which the position of was sulfated. The method for calculating the position of the sulfate ester salt and the method for NMR measurement were performed in the same manner as in Example 1.

Comparative Example 1 Primary alkyl ether sulfate ester 593 g (3.08 mol) of primary alcohol (mixture of n-dodecanol and n-tetradecanol) and 0.2 g of sodium hydroxide as a catalyst were placed in a stainless steel autoclave. After charging and purging with nitrogen, the pressure in the reactor was adjusted to 1.0 kg / cm ² G with nitrogen, and after raising the temperature to 150 ° C., 407 g (9.25 mol) of ethylene oxide was introduced into the autoclave over 3 hours. One hour after introduction, 150 hours
After maintaining at 0 ° C., the mixture was cooled to room temperature, and after purging the internal pressure, a primary alcohol ethoxylate to which 3.0 mol of ethylene oxide was added on average was obtained.

The primary alcohol ethoxylate 20
0 g (0.62 mol) was charged into a 500 ml flask and cooled to 10 ° C. In this, chlorosulfonic acid 79.0
g (0.68 mol) was added dropwise over about 1 hour. During the dropwise addition, the liquid temperature was maintained at 10 to 15 ° C. After the chlorosulfonic acid was dropped, nitrogen gas was flowed into the reaction solution to remove hydrogen chloride gas as a by-product, and then the reaction solution was dropped into an aqueous sodium hydroxide solution while maintaining the temperature at 20 ° C. or lower. About 25% of primary alkyl ether sulfate
An aqueous solution was obtained.

Comparative Example 2 Secondary dodecyl ether sulfate composition 1-dodecene 810 g (4.82 mol), monoethylene glycol 900 g (14.52 mol), and BEA type zeolite manufactured by PQ (trade name: VA) as a catalyst
100 g of LFOR CP 811 BL-25) was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser. After the gas phase was replaced with nitrogen, the atmosphere was kept under a nitrogen atmosphere at normal pressure. Subsequently, the temperature was raised to 150 ° C. while stirring at a rotation speed of 600 rpm, and the reaction was carried out at the same temperature for 3 hours. After that, the reaction solution was cooled to room temperature, and the upper layer of the dodecene phase was separated and distilled. After distilling off unreacted dodecene, 255 g of secondary dodecanol ethoxylate was obtained at a reduced pressure of 2 mmHg in a boiling point range of 129 to 131 ° C.

This secondary dodecanol ethoxylate 2
55 g (1.11 mol) and 510 g of ethylene chloride as a solvent were charged into a 1-liter flask and cooled to 10 ° C. 142 g of chlorosulfonic acid (1.22 m
ol) was added dropwise over about 1 hour. During dropping, the liquid temperature is 10
Maintained at １５15 ° C. After the chlorosulfonic acid was dropped, nitrogen gas was flowed into the reaction solution to remove hydrogen chloride gas as a by-product, and then the reaction solution was dropped into an aqueous sodium hydroxide solution while maintaining the temperature at 20 ° C. or lower. Then, about 25% aqueous solution of a sulfate salt was obtained.

The addition position of the alkyl chain carbon of the sulfate salt of the resulting secondary dodecyl ether sulfate composition was determined from the proton ratio of the alkyl terminal methyl group by ¹ H-NMR analysis (FIG. 4). As a result, the secondary dodecyl ether sulfate in which the position 2 was sulfated was 94 mol%. The method for calculating the position of the sulfate ester salt and the method for NMR measurement were performed in the same manner as in Example 1.

(Physical Properties / Interface Properties) The following measurements were performed on the materials obtained in Examples 4 to 6 and Comparative Examples 3 and 4 (Examples 4 to 6). Similarly, the following measurement was performed on the substances obtained in Comparative Examples 1 and 2 (Comparative Example 3,
4). The results of these measurements are shown in Table 1 below.

Measurement method (1) The liquid range was determined from the aqueous solution viscosity measured with a Brookfield-type rotational viscometer at 25 ° C. (2) Surface tension The surface tension was measured at 25 ° C using a surface tensiometer manufactured by Kyowa Kagaku based on the Wilhelmy method.
(Activator concentration: 0.1% by weight) (3) Penetration cotton: canvas 6 at 25 ° C by the campus disk method.
No. was measured. (Activator concentration: 0.25% by weight) (4) Foam property According to JIS K-3362 (Rosmiles method), 2
It was measured at 5 ° C. (Activator concentration: 0.1% by weight)

[0060]

[Table 1]

Examples 7 to 9 The substances obtained in Examples 1 to 3 were evaluated for the following detergency (Examples 7 to 9). The results are shown in Table 2 below.

(Evaluation method) In accordance with JIS K-3362, a stirring type detergency tester (Terg-O-tome) was used.
ter) was tested under the following conditions. <Washing condition> Soiled cloth: size 5 × 5 cm Soil (%) Oleic acid 28.3 Triolein 15.6 Cholesterol oleate 12.2 Liquid paraffin 2.5 Squalene 1.6 Cholesterol 7.0 Gelatin 29.8 Carbon Black 0.5 Water used: Tap water Temperature: 25 ° C Time: Washing 5 minutes / Rinse 5 minutes Bath ratio: 3 sheets / 1 pot (1 L) Activator concentration: 0.03% <Evaluation method of detergency> Reflectance meter The reflectance of the original cloth, the artificially-contaminated cloth, and the washed cloth after cleaning are measured at three locations for each cloth of each test piece, and the detergency (%) is calculated from the average value using the following formula. did.

[0063]

(Equation 1)

[0064] In the above formulas, R _O is the reflectance of the original cloth, R _S is the reflectivity of the artificially stained cloth, R _W represents reflectance of the cloth, respectively.

[0065]

[Table 2]

Examples 10 to 12 The substances obtained in Examples 1 to 3 were evaluated for the following emulsifying power. The results are shown in Table 3 below.

(Evaluation method) 5 ml of the synthesized sample was added to a mixture of 55 ml of water and 40 ml of oil, mixed well, and allowed to stand. After 5 minutes, the state of separation of the water or oil layer is observed. Evaluation was made as follows according to the emulsified state. ：: Good emulsified state △: Slightly separated ×: Completely separated

[0068]

[Table 3]

[0069]

The high-grade secondary alkyl ether sulfate composition of the present invention is particularly easy to handle because it has a low viscosity and does not easily gel, has good surface tension and penetrating power, has good foam removal, and has good cleaning properties. It has the characteristic of excellent power and emulsifying power.

[Brief description of the drawings]

FIG. 1 is ¹ H-NMR analysis data used for calculating the alkyl chain carbon addition position of a sulfate of the secondary dodecyl ether sulfate obtained in Example 1.

FIG. 2 shows ¹ H-NMR analysis data used for calculating an alkyl chain carbon addition position of a sulfate salt of a secondary dodecyl ether sulfate salt composition obtained in Example 2.

FIG. 3 is ¹ H-NMR analysis data used for calculating the alkyl chain carbon addition position of the sulfate of the secondary hexadecyl ether sulfate composition obtained in Example 3.

FIG. 4 is ¹ H-NMR analysis data used for calculating the alkyl chain carbon addition position of the sulfate salt of the secondary dodecyl ether sulfate composition obtained in Comparative Example 2.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiyuki Onda 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd.

Claims (3)

[Claims] 1. A compound of the general formula (1) (Wherein R ¹ and R ² are alkyl groups, and R ¹ + R ²
Has a total carbon number of 7 to 29, and R ¹ ≦ R ² ,
Represents a lower alkylene group, and n is an average of 1 to 20. However, when n is 2 or more, the kind of oxyalkylene group represented by AO may be one kind or two kinds or more, and when there are two or more kinds of oxyalkylene groups, various oxyalkylene groups are used. Indicates that there are an average of n groups in total. M is an alkali metal atom, an alkaline earth metal ion, ammonia or a substituted ammonium group. A higher secondary alkyl ether sulfate salt composition represented by the formula: wherein R ¹ is a methyl group, 30 to 90 mol% of an alkyl ether sulfate salt, and R ¹ is an alkyl group larger than a methyl group. A higher secondary alkyl ether sulfate composition comprising 70 to 10 mol% of an ether sulfate salt. 2. A cleaning agent comprising the higher secondary alkyl ether sulfate composition according to claim 1. 3. An emulsifier comprising the higher secondary alkyl ether sulfate composition according to claim 1.