JPH10279553A - Production of (poly)glyceryl ether sulfate salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as an anionic surfactant by selectively sulfatizing a primary hydroxyl group existing on a (poly)glyceryl ether. SOLUTION: This (poly)glyceryl ether sulfate salt of formula I [R<1> is a 6-22C alkyl, alkenyl; R<2> is a 2-3C alkylene; (n) is 1-10 which is the average polymerization degree of glycerol; (m) is 0-30 which is the average polymerization degree of an oxyalkylene; X is a salt-forming cation] is obtained by reacting a (poly) glyceryl ether of formula II with a lower alkyl sulfate salt of the formula: R<3> -OSO3 X (R<3> is a 1-5C alkyl) as a sulfation agent. The salt of formula I is compounded as a taste-free and smell-free anionic surfactant excellent in formability and foam touch and low in skin irritancy to obtain a composition for washing bodies or a composition for oral cavities.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing (poly) glyceryl ether sulfate useful as an anionic activator, and a personal cleansing composition containing the (poly) glyceryl ether sulfate obtained by this method. And oral compositions.

[0002]

2. Description of the Related Art (Poly) glyceryl ether sulfate is
Widely used as an anionic surfactant. For example, Masaki Nakamura et al., Science and Industry, 66 (9), 400
403 (1992) describes an example of application of sodium dodecylglyceryl ether monosulfate prepared to high purity to liquid soap, and Japanese Patent Publication No. 59-1515.
No. 9 and Japanese Patent Application Laid-Open No. 7-53990,
An example of the application of a glyceryl ether sulfate mixture to a detergent composition is described. The industrial production method of (poly) glyceryl ether sulfate is described in JP-B-59-151.
No. 59 and Japanese Patent Publication No. 5-507473, however, the methods described in these publications are not yet satisfactory. For example, Japanese Patent Publication No. 59-15159 discloses that a sulfating agent such as SO ₃ gas or chlorosulfonic acid and a (poly) glyceryl ether mixture dissolved in an inert solvent have a molar ratio of 1: 1 to 1: 1.15. Mixed in the range of
A method of reacting at -15 to 75 ° C is described. In addition, Japanese Patent Publication No. 5-507473 describes a method in which glycerin ether is sulfated with SO ₃ gas and then neutralized with an aqueous base. In each of these methods, a sulfation reaction is performed by using a highly reactive sulfating agent such as SO ₃ gas and controlling the reactivity of the sulfating agent. The sulfation occurs without distinction for the plurality of primary and secondary hydroxyl groups present in the (poly) glyceryl ether, and the resulting (poly) glyceryl ether sulfate has its primary hydroxyl group and / or secondary hydroxyl group. A mixture of sulfated (poly) glyceryl ether sulfates having hydroxyl groups is obtained. Such a mixture did not exhibit a sufficient effect as an anionic surfactant.

[0003]

SUMMARY OF THE INVENTION The present invention provides a method for selectively sulphating primary hydroxyl groups present in (poly) glyceryl ether, and a (poly) glyceryl in which the primary hydroxyl groups are sulphated. An object of the present invention is to provide a (poly) glyceryl ether sulfate mixture containing a high content of ether sulfate.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, the following general formula (1)

Embedded image (Wherein, R ¹ represents an alkyl group or an alkenyl group having 6 to 22 carbon atoms, R ² represents an alkylene group having 2 or 3 carbon atoms, and n is an average degree of polymerization of glycerin, and is a number of 1 to 10). And m is the average degree of polymerization of the oxyalkylene group, from 0 to 2
And X represents a salt-forming cation) in the method for producing a (poly) glyceryl ether sulfate represented by the following general formula (2):

Embedded image (Wherein R ¹ , R ² , n and m have the same meanings as described above), to the (poly) glyceryl ether represented by the following general formula (3)

Embedded image R ³ —OSO ₃ X (3) wherein R ³ represents an alkyl group having 1 to 5 carbon atoms, and X has the same meaning as described above. The method is provided wherein the reaction is performed as an agent. Further, according to the present invention, there is provided a personal cleansing composition and an oral composition containing the (poly) glyceryl ether sulfate obtained by the above method.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (1), R ¹
Represents a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Specific examples of R ¹ include, for example, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, myristyl, pentadecyl, palmityl, stearyl, behenyl, 2-ethylhexyl, hexenyl, heptenyl, octynyl, nonenyl, decenyl, undecenyl, Dodecenyl, myristenyl, pentadecenyl, palmitenyl,
Oleyl, linole, linolenyl, arachidyl, 2-ethylhexenyl and the like can be mentioned. Examples of R ² include ethylene (—C ₂ H ₄ —) or propylene (—C ₃ H ₆ —). n represents the average degree of polymerization of glycerin,
It represents 0, preferably 1 to 5. m oxyalkylene (-OR ² -) represents an average polymerization degree of 0-20, preferably is a number of 0-8. X represents a salt-forming cation, such as a cation of an alkali metal such as sodium, potassium and lithium; a cation of an alkaline earth metal such as calcium and magnesium; an ammonium ion; Mono-, di- or trihydroxyalkyl ammonium ions having from 1 to 3 hydroxylalkyl groups; substituted ammonium ions having from 1 to 4 alkyl groups; ammonium ions derived from basic amino acids, and the like. In the general formula (3), R ³ represents an alkyl group having 1 to 5 carbon atoms, and specific examples of the alkyl group include methyl, ethyl, n-propyl, 2-propyl, n-butyl and 2-alkyl. Butyl, n-
Pentyl, 2-pentyl and the like can be mentioned.

[0006] The terms (poly) glyceryl ether and (poly) glyceryl ether sulfate as used herein mean a product containing a monoglyceryl group, a product containing a polyglyceryl group, or a product containing both of them.

The (poly) glyceryl ether of the general formula (2) used as a reaction raw material in the present invention can be produced by a conventionally known method. For example, the following general formula (4)

Embedded image (Wherein R ¹ , R ² and m have the same meaning as described above) by reacting (poly) glycidyl ether with water, glycerin or polyglycerin in the presence of an acid catalyst or a base catalyst. Obtainable. As the polyglycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin,
Heptaglycerin, octaglycerin, nonaglycerin, decaglycerin and the like can be shown as preferred.

As the acid catalyst, boron trifluoride (B
Lewis acids such as F ₃ ); Bronsted acids such as p-toluenesulfonic acid and sulfuric acid. Examples of the base catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

[0009] The reaction is carried out at 20 to 150 ° C, preferably 40 to 100 ° C. This reaction can be carried out in the presence of a solvent, if necessary. As a solvent, t-butanol, 1,4-dioxane, tetrahydrofuran (THF), dimethylformamide (DM
It is preferable to use a polar solvent such as F) and dimethyl sulfoxide (DMSO). When reacting the glycidyl ether with glycerin or polyglycerin, the use ratio of glycerin or polyglycerin is 1 to 100 mol, preferably 1 to 20 mol, per 1 mol of glycidyl ether. Excess glycerin or polyglycerin contained in the reaction product can be removed by a liquid-liquid extraction method, a crystallization method, a distillation method, or the like, whereby a high-purity (poly) glyceryl ether can be obtained.

The (poly) glyceryl ether represented by the general formula (2) is represented by the following general formula (5)

Embedded image ^{R 1 (OR 2) m-} Y (5) ( wherein, R ^1, R ² and m are as defined above, Y is a halogen atom or -OSO ₃ X (X is said Which has the same meaning) and glycerin or polyglycerin, in the presence of a base catalyst. The reaction is 100-25
It is carried out at 0 ° C, preferably at 120 to 200 ° C. This reaction can be carried out in the presence of a solvent, if necessary. As the solvent, a polar solvent such as dimethylimidazolidinone (DMI), dimethylacetamide (DMAc), dimethylformamide (DMF), or dimethylsulfoxide (DMSO) is preferably used. The use ratio of glycerin or polyglycerin is 1 to 100 mol, preferably 1 to 20 mol, per 1 mol of the compound of the general formula (5). Excess glycerin or polyglycerin contained in the reaction product can be removed by a liquid-liquid extraction method, a crystallization method, a distillation method, and the like.
Highly pure polyglyceryl ether can be obtained.

The monoglyceryl ether (in the general formula (2), n = 1) is obtained by reacting glycerin with a lower alkyl ketone in the presence of an acid catalyst.

Embedded image (Wherein R ³ and R ⁴ represent lower alkyl groups such as methyl, ethyl and propyl) with the compound of the above general formula (5), and the resulting compound is hydrolyzed. It can be obtained by decomposition.
The reaction between glycerin ketal and the compound of the general formula (5) is performed at 100 to 250 ° C, preferably 120 to 200 ° C.
Will be implemented. The reaction time is 1 to 20 hours. The use ratio of glycerin ketal is 0.1 to 10 mol, preferably 0.2 to 1 mol, per 1 mol of the compound of the general formula (5).
It is a mole ratio. In the reaction of the glycerin ketal with the compound of the general formula (5), the following general formula (7)

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ and m have the same meaning as described above), which gives a monoglyceryl ether by a hydrolysis reaction. This hydrolysis reaction is carried out at 20 to 100 ° C. in the presence of an acid catalyst, using a mixture of an organic solvent (such as THF and DMF) and water as a hydrolyzing agent.

On the other hand, the lower alkyl sulfate of the general formula (3) has a salt-forming cation X after reacting a lower alcohol with a sulfating agent such as SO ₃ gas or chlorosulfonic acid. It can be obtained by reacting a salt forming agent. The reaction product obtained by this reaction can be purified, if necessary, by a crystallization method, a chromatography method, an extraction method, or the like.

According to the present invention, the (poly) of the general formula (1)
In order to produce glyceryl ether sulfate, the (poly) glyceryl ether of the general formula (2) is reacted with a lower alkyl sulfate of the general formula (3). This reaction is performed in the presence or absence of an acid catalyst. As the acid catalyst, a Lewis acid or a Bronsted acid is used, and preferably, a Bronsted acid (protonic acid) such as sulfuric acid, hydrochloric acid, phosphoric acid, and paratoluenesulfonic acid, an acidic ion exchange resin, and a solid acid are used. . The amount of the acid catalyst used is 0.000 with respect to (poly) glyceryl ether.
It is 1 to 10% by weight, preferably 0.001 to 2% by weight. The reaction temperature is 0 to 150 when an acid catalyst is used.
° C, preferably 10 to 50 ° C, but preferably room temperature. When an acid catalyst is not used, 30 to 150 ° C,
Preferably it is 50-100 degreeC. Reaction time is 1 to 24
Hours, preferably 1 to 10 hours. The reaction is
If necessary, it can be carried out in the presence of a solvent. Examples of the solvent include ether solvents such as 1,4-dioxane and tetrahydrofuran; hydrocarbon solvents such as hexane, toluene and xylene; halogenated hydrocarbon solvents such as methylene chloride and chloroform; and nitrogen-containing solvents such as dimethylformamide and pyridine. Solvents include sulfur-containing solvents such as dimethyl sulfoxide. The proportion of the lower alkyl sulfate used in the reaction is 0.1 to 10 mol, preferably 0.5 to 2 mol, more preferably 0.9 to 1.1 mol, per 1 mol of the (poly) glyceryl ether. It is.

In the above reaction, as the reaction progresses,
Alcohol (R ³ OH) derived from the lower alkyl sulfate of the general formula (3) which is a sulfating agent is by-produced. Therefore, in this reaction, by removing this by-product alcohol out of the system, the reaction rate can be increased and the reaction can be completed quickly. As a method of removing the by-product alcohol to the outside of the system, there are a method of removing the inside of the reaction system by reducing the pressure to 0.1 to 100 Torr, a method of performing the reaction under a flow of nitrogen gas, and the like. The end point of the reaction can be known by analyzing the composition of the reaction product by a known method, for example, thin-layer chromatography, gas chromatography, liquid chromatography, or the like. The reaction is
An alkaline substance such as NaHCO ₃ , Na
It can be stopped by adding OH, KOH or the like. By removing the solvent and the like contained in the reaction product from the reaction product, the desired (poly) glyceryl ether sulfate can be obtained with high purity.

The (poly) glyceryl ether sulfate obtained by the present invention has a structure in which only the primary hydroxyl group of (poly) glyceryl ether is selectively sulfated, and has a structure in which the secondary hydroxyl group is sulfated. ) The content of glyceryl ether sulfate is from 0 to 5 mol%, in particular from 0 to 2 mol%. Therefore, the (poly) glyceryl ether sulfate obtained by the method of the present invention exhibits excellent foaming properties and foam stability by having a structure in which the primary hydroxyl group is selectively sulfated, and Produces a foam having a good foam feel. In addition, this (poly) glyceryl ether sulfate has a high mildness, is unlikely to cause protein denaturation, and has extremely low skin irritation, despite being an anionic surfactant. Furthermore, it has the characteristic of tasteless and odorless.

The (poly) glyceryl ether sulfate of the general formula (1) obtained by the present invention is used for various uses as an anionic surfactant. For such uses, for example, foaming agents for oral compositions such as dentifrice (especially with enzymes), cleaning agents such as kitchen detergents, shampoos, body shampoos, and body wash compositions such as facial cleansers. Main agents and the like are included. The (poly) glyceryl ether sulfate obtained by the present invention can be advantageously used as a surfactant component for a liquid detergent such as an enzyme-containing liquid detergent or a wool detergent. The (poly) glyceryl ether sulfate may be used alone as a surfactant component, but may be in the form of a mixture with one or more other anionic, amphoteric or nonionic surfactants. Can also be used. The surfactant preferably used in combination with the (poly) glyceryl ether sulfate is as follows:
It is a nonionic surfactant.

In the detergent composition containing the (poly) glyceryl ether sulfate, the amount of the (poly) glyceryl ether sulfate is preferably set in the range of 0.1 to 50% by weight. Specific examples of other surfactants that can be added to the composition include, as anionic surfactants, alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, α-olefin sulfonates, alkyl Phosphoric acid or alkyl ether phosphates, fatty acid salts, alkyl ether carboxylates, sulfosuccinate-based surfactants and the like, and amphoteric surfactants include betaine-based or imidazoline-based amphoteric surfactants, and the like. Examples of nonionic surfactants include surfactants such as polyoxyalkylene alkyl ether, alkyl polyglyceryl ether, alkyl polyglucoside, and alkyl (poly) glyceroglucoside. Particularly preferred are alkyl ether sulfates, alkyl ether carboxylates, sulfosuccinate surfactants, alkyl phosphoric acid or alkyl ether phosphates and imidazoline amphoteric surfactants. Furthermore, in this detergent composition, organic or inorganic builders other than those described above as long as the purpose is not impaired,
An antioxidant, an ultraviolet absorber, a chelating agent, a bactericide, a water-soluble polymer, a fragrance, an alcohol, a clay mineral, and the like can be blended.

[0018]

Next, the present invention will be described in more detail with reference to examples.

Reference Example 1 (Synthesis of dodecyl glyceryl ether) Glycerin 10
0 gr (1.08 mol), methyl ethyl ketone 15
7.0 gr (2.18 mol), sulfuric acid 1.0 gr (0.
2 mol) and 200 ml of hexane as a reactor.
The mixture was placed in a 00 ml four-necked flask and reacted at 85 ° C. for 10 hours while removing by-product water by azeotropic dehydration at a reaction temperature of 85 ° C. Then, 2.6 g of sodium hydrogencarbonate was added to stop the reaction, followed by filtration. The solvent was distilled off to obtain 2-methyl-2-ethyl-1,3-dioxolan-4-methanol (159 g).
Get r. Further, the obtained 2-methyl-2-ethyl-
To 159 gr of 1,3-dioxolane-4-methanol,
313.6 gr of sodium dodecyl sulfate and 56.7 gr of sodium hydroxide are reacted at 150 ° C. for 10 hours under a nitrogen stream. The reaction solution was neutralized by adding 16.0 gr of sulfuric acid, and further subjected to a thin-film distillation treatment to give 2-methyl-2-ethyl-1,3-dioxolan-4-methyl with a yield of 95%. 325 gr of dodecyl ether are obtained. Further, 95.2 gr of glycerin and 0.95 gr of sulfuric acid were added to 325 gr of 2-methyl-2-ethyl-1,3-dioxolan-4-methyldodecyl ether, and solvolysis was performed at 70 ° C. for 3 hours under a pressure of 3 torr. The reaction is carried out, and the obtained product is neutralized, and the solvent is distilled off.
255.6 gr of dodecyl glyceryl ether was obtained (95% yield).

Reference Example 2 (Synthesis of Dodecyl Polyoxyethylene (p = 3) Glyceryl Ether) Instead of sodium dodecyl sulfate,
The reaction was carried out in the same manner as in Reference Example 1 except that sodium dodecyl polyoxyethylene sulfate having an average addition mole number of oxyethylene p = 3 was used. Dodecyl polyoxyethylene (p = 3) glyceryl ether was obtained in a yield of 90%. I got it. Its gas chromatography purity was 99%.

Reference Example 3 484 g (2 mol) of cetyl alcohol, 48% NaO
H500g (6mol), tetrahydrofuran (TH
F) 400 g, tetrabutylammonium bromide 32
4 g was charged into a reactor, and 370 g (4 mol) of epichlorohydrin was added dropwise at 50 ° C. over 1 hour, and after aging for 5 hours, 800 g of water was added and the aqueous layer was removed. The THF was distilled off, and 398 gr of cetyl glycidyl ether (1.3 m
ol) (70% yield). Next, 2-methyl-2-
Ethyl-1,3-dioxolan-4-methanol 204
gr (1.4 mol), cetyl glycidyl ether 39
8 gr was added dropwise over 2 hours. Aged at 60 ° C 5
After an hour, the mixture was neutralized, extracted with 1.5 l of ether, washed with water, and the solvent was distilled off to obtain 594 gr of a pasty substance. 1 liter of acetone, 1 liter of water, H ₂ SO ₄
Hydrolysis was performed at 12.7 gr at 60 ° C. for 5 hours, and then 470 gr of cetyl diglyceryl ether was obtained by neutralization, extraction, and chromatographic treatment.

Reference Example 4 (Synthesis of sodium ethyl sulfate) In a 2 liter four-necked flask, 230 gr (5 mol) of ethanol was placed, and 330 ml (5 mol) of chlorosulfonic acid was placed in an ice bath.
l) was slowly added dropwise over 2 hours. HCl by-product
Was driven out of the system by nitrogen gas and neutralized by an alkali trap. After completion of the dropwise addition, the reaction solution is slowly poured into 3 liters of an ice-cooled aqueous solution of sodium hydroxide (200 gr, 5 mol). At that time, a small amount of sodium hydroxide is added for complete neutralization. Further, the solvent was distilled off to obtain 725.2 gr of sodium ethyl sulfate (yield: 98).
%).

Example 1 (Synthesis of sodium salt of dodecylglyceryl ether sulfate (sample A)) 14.8 gr of sodium ethyl sulfate
(0.1 mol), dodecyl glyceryl ether
0 gr (0.1 mol) and 200 ml of dioxane were weighed into a 1 liter flask, and 0.1 ml of concentrated sulfuric acid was added. After stirring at room temperature for 1 hour, the dioxane and methanol produced as a by-product were reduced from atmospheric pressure to 50 tones with an aspirator.
Stir at room temperature while removing over 3 hours by adjusting to rr. Finally, the suspension was solidified from the suspension state at the beginning of the reaction, and 36 gr of a white solid was obtained. Further, the solid was washed with methylene chloride to remove sulfuric acid to obtain 35.2 gr of a white solid. Yield 98%. As a result of NMR analysis shown below, it was confirmed that this was sodium dodecyl glyceryl ether sulfate in which only primary hydroxyl groups were 100% sulfated. In addition, the high performance liquid chromatography (HPLC) purity was 99%.

(1) ¹ H NMR (δ, D ₂ O solvent, internal standard: DHO, 480 ppm) analysis result 0.89 (t, 3
H), 1.15-1.47 (m, 18H), 1.62.
(M, 2H), 3.50-3.64 (m, 4H), 3.
98-4.13 (m, 3H).

Example 2 (Synthesis of sodium salt of dodecyl polyoxyethylene glyceryl ether sulfate (sample B)) Sodium methyl sulfate was used instead of sodium ethyl sulfate, and dodecyl polyoxyethylene (p) was used instead of dodecyl glyceryl ether. = 3) An experiment was conducted in the same manner as in Example 1 except that glyceryl ether was used, and dodecyl polyoxyethylene glyceryl ether sulfate (sample B)
Was obtained with a yield of 99% and HPLC purity of 99.8%.

Example 3 (cetyl glyceryl ether sulfate potassium salt (sample C)
The synthesis was performed in the same manner as in Example 1 except that potassium ethyl sulfate was used instead of sodium ethyl sulfate and cetyl diglyceryl ether was used instead of dodecyl glyceryl ether. Potassium salt (sample C) yield 97
%, 99% HPLC purity.

Comparative Example 1 (Synthesis of sodium salt of dodecyl glyceryl ether sulfate (sample D)) 130 g of dodecyl glyceryl ether and 1 liter of methylene chloride were charged into a reactor, cooled to -4 ° C, and then 58 g of chlorosulfuric acid (0.5 mol ) Was added dropwise over 1 hour. After aging at -4 ° C for 2 hours, the mixture was neutralized with NaOH, the solvent and water were distilled off, and 167 gr of a mixture of sodium dodecylglyceryl ether sulfate (sample D) was obtained.
I got Its yield is 90% and its HPLC purity is 90%
%Met.

Application Example 1 With respect to the samples A, B, C and D obtained above, their foaming properties, foam feeling, skin irritation, taste and smell were evaluated as follows. Table 1 shows the results. (Measurement of foaming performance) 20 m of 0.9% by weight aqueous solution of sample
1, lanolin / caprylic acid = 7/3 (w / w) 0.4 g
r was placed in a 100 ml Epton tube, kept at a constant temperature in a 25 ° C. water bath, shaken 20 times in 10 seconds, and then measured the foam volume (ml) after 30 seconds. (Evaluation of foam feel) A sample was dissolved in water at a concentration of 0.5% by weight, 50 ml of this aqueous solution was placed in a 100 ml sample bottle with a lid, and this was shaken 10 times at 40 ° C. Was washed and evaluated according to the following criteria. ○: Refreshing feeling △: Refreshing feeling slightly ×: Refreshing feeling weak (skin irritation) Hartley guinea pig 7 weeks old, female 5
The test was carried out using animals. Shaving the back of the guinea pig, take a 2 x 2 cm frame for each animal,
Once a day for 4 consecutive days, 40% of 5% (w / w)
Apply ml amount. According to the tracing method, edema (4 points) and erythema (out of 4 points) are visually determined, and a skin irritation score (point) is calculated. The lower the score, the better the result. (Evaluation of taste and smell) The evaluation was made based on human sensuality.

[0029]

[Table 1]

[0030]

According to the present invention, (poly) glyceryl ether sulfate having a structure in which the primary hydroxyl group of (poly) glyceryl ether is selectively sulfated can be obtained with high purity and high yield. The (poly) glyceryl ether sulfate obtained by the present invention has excellent foaming properties and foam feeling due to its structural characteristics, and has various uses as a tasteless and odorless anionic surfactant with extremely low skin irritation. Can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 1/29 C11D 1/29 (72) Inventor Haruhiko Toda 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation

Claims (3)

[Claims] [Claim 1] The following general formula (1) (Wherein, R ¹ represents an alkyl group or an alkenyl group having 6 to 22 carbon atoms, R ² represents an alkylene group having 2 or 3 carbon atoms, and n is an average degree of polymerization of glycerin, and is a number of 1 to 10). And m is the average degree of polymerization of the oxyalkylene group, from 0 to 2
In the method for producing (poly) glyceryl ether sulfate represented by the following formula (2): X represents a salt-forming cation. (Wherein R ¹ , R ² , n and m have the same meanings as described above) and (poly) glyceryl ether represented by the following general formula (3): R ³ —OSO ₃ X (3 (Wherein, R ³ represents an alkyl group having 1 to 5 carbon atoms, and X has the same meaning as described above). . 2. A personal cleansing composition comprising the (poly) glyceryl ether sulfate obtained by the method according to claim 1. 3. An oral composition containing the (poly) glyceryl ether sulfate obtained by the method of claim 1.