JPH092988A - Glyceryl etherified polyhydric alcohol and its production - Google Patents

Abstract

PURPOSE: To obtain a new alcohol capable of forming a thermotropic liquid crystal in an aqueous dispersion system, exhibiting extremely excellent lubricity and useful for toiletry, etc., by reacting a polyhydric alcohol or its alkylene oxide adduct with an alkenyl glycidyl ether. CONSTITUTION: A compound of formula I [G is a residue obtained by removing H atoms from all OH groups of a polyhydric alcohol having >=3 OH groups; A is a 2-4C alkylene; the terminal carbon atom of (AO)x is bonded to the oxygen atom originated from OH group of G through ether bondand the terminal oxygen atom is bonded to B; B is H, group of formula I or group of formula II (R is an 8-24C alkenyl) or bonded to the terminal oxygen atom of (AO)x or to the oxygen atom originated from the OH group of G; at least one of (y) B groups is group of formula I or formula II; (x) is the ratio of (the total molar addition number of (AO)x )/y and is 0-10; (y) is the number of oxygen atoms originated from the OH of G] is produced by reacting a polyhydric alcohol of formula, G[(AO)x H]y or its alkylene oxide adduct with an alkenyl glycidyl ether of formula III in the presence of a basic catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel glyceryl etherified polyhydric alcohol useful as a base for cosmetics, an emulsifier, a solubilizer, a lubricant, a liquid crystal forming agent and the like, and a method for producing the same.

[0002]

2. Description of the Related Art
Polyol ester such as polyoxyalkylene ether of sorbitan ester is an emulsifier for cosmetics and cosmetics,
It has been used as a solubilizer and a lubricant. However, since such polyol esters have an ester group, their stability in an aqueous solution is not always sufficient, and when used in cosmetics and cosmetics, the stability of their performance may be insufficient. .

On the other hand, in nature, there are many derivatives of polyhydric alcohols having an ether bond. Among them, monoalkyl ether of glycerin (hereinafter referred to as "glyceryl ether") is particularly well known. .
For example, fish lipids include palmityl glyceryl ether, stearyl glyceryl ether and oleyl glyceryl ether.

Glyceryl ether is superior in stability in an aqueous solution as compared with the above-mentioned polyol esters, and by utilizing its W / O type emulsifying property, it is widely used as a cosmetic base and the like. (JP-A-49-87612, JP-A-49-92239, JP-A-52-12109, etc.).

Further, noting that such glyceryl ether is a nonionic surfactant having various useful properties, attempts to derive a polyol ether compound having a molecular structure similar to that of glyceryl ether from a polyhydric alcohol have been made. (US Pat. No. 2,258,892, Japanese Patent Publication No. 52-18170, Japanese Patent Laid-Open No. 53-137905, Japanese Patent Laid-Open No.
4-145224, etc.). Among these glyceryl ether derivatives, branched alkyl glyceryl ether having a branched alkyl group such as isostearyl group (Oil Chemistry, No. 36
Vol. 8, No. 8, pp. 588-598 (1987)), or a branched alkyl ether of diglycerin in which a branched alkyl group is introduced into diglycerin (Japanese Patent Publication No. 63-24496, Japanese Patent Publication No. 59-175445, etc.). Has been used in cosmetics and cosmetics as a nonionic surfactant having excellent W / O type emulsifying properties.

However, the branched alkyl glyceryl ethers and the branched alkyl ethers of diglycerin described above have excellent W / O type emulsifying properties, but on the other hand have low hydrophilicity, and therefore have a water content such as shampoo, rinse or lotion. When used in high cosmetics, there is a problem that the dispersibility in water is poor and emulsification failure may occur, so that the amount used is limited and a sufficient effect cannot be expected.

Therefore, it has been desired to develop a nonionic surfactant useful as a base for cosmetics, an emulsifier, a solubilizer, a lubricant and the like.

[0008]

[Means for Solving the Problems] Under such circumstances, as a result of intensive studies by the present inventors, a novel glyceryl etherified polyhydric alcohol represented by the following general formula (1) is
It forms thermotropic liquid crystals in a water dispersion system, exhibits extremely excellent lubricity, is compatible with almost all solvents, and has properties such as almost uniform dispersion when mixed with water. The present invention has been completed by discovering that they have the above-mentioned properties, and that they have extremely excellent performance as a base for cosmetics, emulsifiers, solubilizers, lubricants, liquid crystal forming agents and the like.

That is, the present invention provides a glyceryl etherified polyhydric alcohol represented by the following general formula (1) and a method for producing the same. G [(AO) _x B] _y (1) [G: shows a residue excluding hydrogen atoms of all hydroxyl groups in a polyhydric alcohol having three or more hydroxyl groups. A: represents an alkylene group having 2 to 4 carbon atoms, the terminal carbon atom _of- (A ¹ O) _x- has an ether bond with the oxygen atom derived from the hydroxyl group of G, and the terminal oxygen atom bonds with B. B: hydrogen atom or general formula (a) or (b), respectively

[0010]

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(R: a linear or branched alkenyl group having 8 to 24 carbon atoms), which is bonded to a terminal oxygen atom of-(AO) _x- or a hydroxyl group-derived oxygen atom of G. To do.
However, among y B groups, at least one is a group (a) or
It is (b). x: [total number of added moles of -AO-] / y, which is a number from 0 to 10. y: shows the number of oxygen atoms derived from the hydroxyl group of G. ]

Examples of the polyhydric alcohol residue represented by G in the general formula (1) include glycerin, pentaerythritol, sorbitol, mannitol, maltitol, glycosides, and the following general formula (2).

[0013]

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[A: Shows a number of 2 to 20. ] Polyglycerin represented by, erythritol, inositol, xylitol, dipentaerythritol, tripentaerythritol, heptitol, octitol, 1,2,3,4-pentanetetrol, 1,3,4,5-hexanetetrol, Sorbitan, mannitan, raffinose, gentianose, sucrose, fructofuranose, fructopyranose, glucopyranose, xylose, galactose, mannose,
Maltose, sorbiose, maltotriose, maltotetraose, maltopentaose, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and other polyhydric alcohols (GH _y ) from which all hydrogen atoms of hydroxyl groups have been removed Is mentioned.

Among the above polyhydric alcohols, glycosides include, for example, (a) monosaccharides such as glucose, galactose, fructose, mannose and xylose, disaccharides such as maltose, isomaltose, lactose and sucrose, or cellulose, Polysaccharides such as starch and amylose,
(b) Methanol, ethanol, lower alcohols such as propanol or polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, erythritol, sorbitol, obtained by a known means of reacting in the presence of an acid catalyst Can be mentioned.
Specifically, methyl glucoside, ethyl glucoside, propyl glucoside, octyl glucoside, decyl glucoside, dodecyl glucoside, oleyl glucoside, 2-ethylhexyl glucoside, methyl maltoside, alkyl maloside such as ethyl maltoside; 2-hydroxypropyl glucoside, Hydroxyalkyl glycosides such as 2,3-dihydroxypropyl glucoside and 2-hydroxyethyl glucoside; alkyl ether glycosides such as methoxyethyl glucoside and ethoxyethyl glucoside; oligosaccharides such as maltitol and lactitol whose reducing ends are reduced Can be mentioned.

Of the above polyhydric alcohols, polyglycerin (2) is polyglycerin obtained by condensing glycerin by a known method, as represented by diglycerin, triglycerin, tetraglycerin and pentaglycerin. is there. The average degree of condensation a of the polyglycerol (2) is 2 to 20, but if the degree of condensation is high, the hydrophilicity may become too high and sufficient performance may not be obtained. A range of 10, especially 2 to 4, is preferred.

Of these G, hydrogen atoms of all hydroxyl groups of polyhydric alcohol selected from glycerin, pentaerythritol, dipentaerythritol, trimethylolalkane, sorbitol, mannitol, glycosides and polyglycerin (2) are removed. Residues are preferred,
Especially trimethylolethane, trimethylolpropane,
A residue obtained by removing hydrogen atoms from all hydroxyl groups of a polyhydric alcohol selected from methyl glucoside, ethyl glucoside, methyl maltoside, maltitol and 2,3-dihydroxypropylene glucoside is preferable.

The number of oxygen atoms derived from the hydroxyl group of G represented by y in the general formula (1) is a number peculiar to the type of the polyhydric alcohol and is 3 or more.

In the general formula (1), examples of the alkylene group having 2 to 4 carbon atoms represented by A include ethylene, propylene and butylene, with ethylene being particularly preferable.

In the general formula (1), x represents the average number of moles of the alkyleneoxy group (-AO-) added directly to the hydroxyl group of the polyhydric alcohol per hydroxyl group and is 0 to 10,
0-3, especially 0 is preferred.

In the general formula (1), among the hydrogen atom represented by B, the group (a) or the group (b), R in the group (a) or (b) is
Is a linear or branched alkenyl group having 8 to 24 carbon atoms, and examples thereof include myristoyl group, palmitolyl group, elaidyl group, ercanyl group, brassinyl group, linoleyl group, and linoelaidyl group. 16 of these
Those of up to 22 are preferred.

It is necessary that at least one of these B's in y is a group (a) or (b), but in particular y
It is preferred that only one of the groups is group (a) or (b).

The glyceryl etherified polyhydric alcohol (1) of the present invention comprises, for example, a polyhydric alcohol having three or more hydroxyl groups represented by the general formula (3) or its alkylene oxide adduct according to the following reaction formula: It is produced by reacting an alkenyl glycidyl ether represented by the general formula (4) in the presence of a basic catalyst.

[0024]

[Chemical 6]

[G, A, B, R, x and y: The above meanings are shown. ]

By this reaction, the alkenyl glycidyl ether (4) is subjected to ring-opening addition to the polyhydric alcohol or its alkylene oxide adduct (3). At this time, depending on the ring-opening direction of the epoxy ring, the group (a) or (ro ) Is formed,
Any of them can be suitably used as the nonionic surfactant.

For example, the reaction for obtaining a 1-mol addition product of pentaerythritol glycidyl ether is as follows.

[0028]

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Among the compounds (3) which are the raw materials in the production method of the present invention, the polyhydric alcohol (GH _y ) having 3 or more hydroxyl groups can be any of those mentioned above.

The polyhydric alcohol having three or more hydroxyl groups used in the present invention may contain impurities other than the intended polyhydric alcohol, but these polyhydric alcohols have no practical problems. It may be used while containing impurities, and if there is a problem, it can be purified by a known method before use.

For example, pentaerythritol may contain dipentaerythritol or tripentaerythritol condensed with pentaerythritol, and sorbitol or mannitol may contain a small amount of reducing sugar such as glucose. In some cases, unreacted glycerin may be mixed in the polyglycerin, and if used as it is, a small amount of glycidyl ether adduct of these impurities is by-produced. These are the product performance,
If there is no problem with the quality or the like, the product may be used as it is, and if there is a problem, it is preferably purified by a crystallization operation or the like before use.

Among the compounds (3), the alkylene oxide (-AO-) adduct of the above polyhydric alcohol is
For example, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, polyoxyethylene
Polyoxypropylene methyl glucoside, polyoxyethylene sorbitol, polyoxypropylene sorbitol, polyoxyethylene / polyoxypropylene sorbitol, polyoxyethylene pentaerythritol, polyoxypropylene pentaerythritol, polyoxyethylene / polyoxypropylene pentaerythritol, polyoxyethylene Mannitol, polyoxypropylene mannitol, polyoxyethylene / polyoxypropylene mannitol, polyoxyethylene maltitol, polyoxypropylene maltitol, polyoxyethylene / polyoxypropylene maltitol, polyoxyethylene sorbitol, polyoxypropylene sorbitol, polyoxy Examples include ethylene and polyoxypropylene sorbitol. It is

The alkylene oxide adduct of the polyhydric alcohol can be prepared by a conventional method, for example, by heating the polyhydric alcohol in the presence of a base such as sodium hydroxide or the like in a suitable solvent, if necessary, in a liquid or alkylene oxide form. It can be produced by adding and reacting in a gaseous state.

These polyhydric alcohols having two or more hydroxyl groups or their alkylene oxide adducts (3) can be used alone or in combination of two or more.

The alkenyl glycidyl ether (4) can be converted into ROH according to a conventional method, for example, in a suitable solvent if necessary.
(R: has the same meaning as described above) can be synthesized by reacting it with epichlorohydrin. The alkenyl glycidyl ether (4) can be used alone or in combination of two or more kinds.

The reaction molar ratio of the polyhydric alcohol or its alkylene oxide adduct (3) and the alkenyl glycidyl ether (4) should be appropriately selected according to the degree of etherification of the desired glyceryl etherified polyhydric alcohol (1). You can For example, in order to obtain a high content of 1 mol adduct of glyceryl ether, the compound (3) may be used in excess at a ratio of 1.2: 1.0 to 10.0: 1.0, and the amount of 1 mol adduct and the compound Considering the recovery of (3), 1.5: 1.
A ratio of 0 to 5.0: 1.0 is preferred. Further, in order to obtain a product having a high content of glyceryl ether 2 mol adduct, it is usually 0
The alkenyl glycidyl ether (4) may be used in excess at a ratio of 3: 1.0 to 1.1: 1.0, and a ratio of 0.4: 1.0 to 0.8: 1.0 is preferable in consideration of the production amount of the 2 mol adduct.

This reaction is usually carried out without a solvent, but it is preferable to use an organic solvent for the purpose of assisting the mixing of the compound (3) and the compound (4). Examples of such an organic solvent include dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and the like, and it is preferable to use 0.1 to 10.0 times the volume of the compound (3).

A basic catalyst is used as the catalyst. Generally, an acid catalyst or a basic catalyst can be used as a reaction catalyst for the epoxy group, but when an acid catalyst is used in the present invention, a decomposition reaction of the ether bond of the produced glyceryl etherified polyhydric alcohol is generated as a side reaction. And a dehydration reaction of a hydroxyl group occurs, which is not preferable. The basic catalyst used in the present invention is not particularly limited, but examples thereof include sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, and sodium hydride from the viewpoint of reactivity and economy. These basic catalysts are preferably used in the range of 0.01 to 20.0% by weight, particularly 0.1 to 10.0% by weight based on the polyhydric alcohol or its alkylene oxide adduct (3).

The reaction is preferably carried out at 50 to 200 ° C, particularly 80 to 150 ° C. If the reaction temperature is less than 50 ° C, the reaction rate is slow, and if it exceeds 200 ° C, the product is colored, which is not preferable.

In this reaction, when water is present in the reaction system, the epoxy group of the alkenyl glycidyl ether (4) reacts with water to form a glyceryl ether as a by-product. Therefore, the polyhydric alcohol or its alkylene is first added to the organic solvent. The oxide adduct (3) is dissolved or dispersed, heated and blown with dry nitrogen gas, or dehydrated by heating under reduced pressure to remove water, and then alkenyl glycidyl ether.
It is preferable to add (4) and react.

After completion of the reaction, the catalyst is neutralized by adding an organic acid such as acetic acid or citric acid or an inorganic acid such as sulfuric acid, hydrochloric acid or phosphoric acid, and then removing the organic solvent used in the reaction. The organic solvent is preferably removed under reduced pressure, usually at a temperature of 120 ° C. or lower, in order to avoid thermal decomposition of the reaction product.

According to the above reaction, the glyceryl etherified polyhydric alcohol (1) of the present invention is usually prepared by adding 1 molecule of the alkenyl glycidyl ether (4) to 1 molecule of the polyhydric alcohol or its alkylene oxide adduct (3). As a mixture of a mole adduct, a 2 mole adduct with 2 molecules added, a polyhydric alcohol or its alkylene oxide adduct (3), and a polymolar adduct with 3 or more molecules of alkenyl glycidyl ether (4) added to 1 molecule. can get. The glyceryl etherified polyhydric alcohol (1) thus obtained is
Usually, such a mixture can be used as a nonionic surfactant as it is, but if there is a problem due to reasons such as performance or compounding, a known purification method such as silica gel column chromatography or solvent extraction is used. It can be purified and used.

In addition to the above, the glyceryl etherified polyhydric alcohol (1) of the present invention may contain an unreacted glycoside. Such glyceryl etherified polyhydric alcohol (1) can be used as it contains unreacted glycoside if there is no practical problem, in the case of problems, for example, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, It can be used after purification by a method using a two-layer extraction solvent system using an organic solvent such as chloroform or a known purification method such as Smith thin film distillation.

[0044]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples below, ¹ H-NMR spectrum was measured by using “AC-200P NMR SPECTROMETER” manufactured by BRUKER, using CDCl ₃ (in the presence of D ₂ O) as a solvent, a concentration of 3% and an internal standard TMS, 25. It was measured under the condition of ° C. In addition, IR spectrum was measured using Hitachi's "270-30 infrared spectrophotometer"
It was measured by the KBr liquid film method at ℃.

Example 1 Pentaerythritol 87 g, dimethyl sulfoxide 200
g and 1 g of sodium hydroxide in a 500 ml flask,
Water was dissolved by heating at 05 ° C., dry nitrogen gas was blown thereinto, and about 20 g of water and dimethyl sulfoxide were distilled out to remove water in the reaction system. Oleyl glycidyl ether 41
After g was added dropwise over 1 hour, the mixture was reacted at 105 ° C. for 4 hours with stirring. After completion of the reaction, acetic acid (1.5 g) in the reaction mixture
Was added to neutralize the catalyst, and dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure. 99% ethanol was added to the residue, and unreacted pentaerythritol precipitated was separated by filtration. Ethanol was distilled off from the obtained filtrate under reduced pressure, 500 ml of water and 500 ml of ethyl acetate were added to the residue for extraction with ethyl acetate, and the solvent was distilled off from the ethyl acetate-soluble fraction to give a pale yellow crude product. 65 g of a purified product was obtained. This crude product
The product was separated and purified by silica gel column chromatography with an elution solvent of acetone: hexane = 2: 1, the elution fractions of the target compound were collected and the solvent was distilled off, and 15 g of an oleyl glycidyl ether 1 mol adduct of pentaerythritol was collected.
(Yield 30%) was obtained.

Hydroxyl value 481 (calculated value 484) ¹ H-NMR (CDCl ₃ ): δ (ppm) 5.34 (2H, m, -C H = C H- ), 3.92 (1H, m, -C H OH- ), 3.65 (6H, s, -C
(C H ₂ OH) ₃ ), 3.48 (8H, m, -OC H _2- ), 2.03 (4H, b, -C H ₂ -C =),
1.30-1.59 (24H, b, - ( C H 2) 12 -), 0.88 (3H, m, -C H 3) IR ( liquid _{^{film) cm -1: ν OH (-OH}} ) 3200-3400 ν CH ( Alken stretch) 3048 ν _CH (stretch) (-CH ₂ -,-CH ₃ ) 2850, 2920 ν _{C = C} (stretch) 1644 ν _CH (bend) (-CH ₂ -,-CH ₃ ) 1375, 1460 ν _CO (-CO-) 1110, 1035, 1010

Example 2 89 g of sorbitol, 100 g of N-methylpyrrolidone and 1 g of sodium hydroxide were placed in a 300 ml flask and heated to 100 ° C. to dissolve them, and dry nitrogen gas was blown into them to distill about 10 g of water and N-methylpyrrolidone. Water was removed from the reaction system by letting it out. 34 g of oleyl glycidyl ether was added dropwise thereto over 2 hours, and then reacted at 110 ° C. for 4 hours while stirring. After the reaction was completed, 1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, N-methylpyrrolidone was completely distilled off at 80 ° C under reduced pressure, and 500 g of acetone was added to the residue to precipitate unreacted sorbitol. Was filtered off. The obtained filtrate is
Acetone was distilled off under reduced pressure to obtain 42 g of a crudely purified product. This crude product is separated and purified by silica gel column chromatography with an elution solvent of chloroform: methanol = 5: 1, and the elution fractions of the desired product are collected and the solvent is distilled off to give 1 mol of oleyl glycidyl ether of sorbitol. 20 g of the adduct was obtained.

Hydroxyl value 651 (calculated value 660)¹ H-NMR (CDCl_Three): Δ (ppm) 5.32 (2H, m, -CH= CH-), 3.35-3.94 (15H, m, -OCH ₂ -,-O-CH
-), 2.00 (4H, b, -CH ₂ -C =), 1.34-1.58 (24H, b,-(CH ₂ )₁₂-),
0.86 (3H, m, -CH ₃ ) IR (liquid film) cm^-1: Ν_OH(-OH) 3200-3400 ν_CH(Alken expansion / contraction) 3045 ν_CH(Expansion / contraction) (-CH_Two-,-CH_Three) 2840, 2910 ν_{C = C}(Stretch) 1642 ν_CH(Deflection) (-CH_Two-,-CH_Three) 1370, 1455 ν_CO(-C-O-) 1030-1110

Comparative Example 1 Pentaerythritol 70 g, dimethyl sulfoxide 200
g and 1 g of sodium hydroxide in a 500 ml flask,
It was heated to 00 ° C. to dissolve it, dry nitrogen gas was blown into it, and about 20 g of water and dimethyl sulfoxide were distilled out to remove water in the reaction system. Stearyl glycidyl ether
After 33 g was added dropwise over 2 hours, the mixture was reacted at 110 ° C. for 5 hours with stirring. After completion of the reaction, acetic acid was added to the reaction mixture at 1.5.
g was added to neutralize the catalyst, dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, and 50% acetone was added to the residue.
Unreacted pentaerythritol precipitated by adding 0 g was filtered off. Acetone was distilled off from the obtained filtrate under reduced pressure to obtain 45 g of a crudely purified product. This crudely purified product was subjected to silica gel column chromatography to obtain acetone: hexane =
Separation and purification were carried out with a 1: 2 elution solvent, and the elution fractions of the target compound were collected and the solvent was distilled off. 22 g (yield 47%) of pentaerythritol stearyl glycidyl ether 1 mol adduct
I got By NMR and IR spectrum analysis, it was confirmed that the obtained compound was an adduct of pentaerythritol with 1 mol of stearyl glycidyl ether.

Test Example 1 The properties at room temperature and the dispersibility in water (concentration: 5% by weight) of the glyceryl etherified polyhydric alcohols obtained in Examples and Comparative Examples and conventionally known compounds were examined. The results are shown in Table 1. (Evaluation method) The properties at room temperature were determined by visual observation. Dispersibility in water was measured by collecting 1 g of sample in a 30 ml sample bottle,
Ion-exchanged water was added thereto so that the sample concentration would be 5% by weight, the sample bottle was shaken for 1 minute, allowed to stand for 5 minutes, and then the dispersed state was visually observed.

[0051]

[Table 1]

Test Example 2 Using the glyceryl etherified polyhydric alcohol of the present invention obtained in Example, a hair rinse agent having the composition shown in Table 2 was produced, and its rinse performance was examined. Table 2 shows the results. (Manufacturing method) To a water heated to 70 ° C, components dissolved by heating to the same temperature were added, and after stirring and mixing, the mixture was cooled to room temperature with stirring to obtain a hair rinse agent. (Evaluation method) 20 g of hair of a Japanese woman who has not been subjected to beauty treatment such as cold perm or bleach (length
15 cm) and this hair bundle is washed with a commercial shampoo containing an anion activator as a main component, then 2 g of the hair rinse agent shown in Table 2 is uniformly applied, rinsed under running water for 30 seconds, and then towel dried. It was This wet hair bundle was subjected to a sensory evaluation for flexibility, smoothness and oiliness. The evaluation criteria are shown as ⊚ for excellent evaluation, ◯ for good evaluation, Δ for normal evaluation, and × for inferior evaluation.

[0053]

[Table 2]

[0054]

The glyceryl etherified polyhydric alcohol of the present invention forms a thermotropic liquid crystal in an aqueous dispersion,
It has extremely excellent lubricity, is compatible with almost all solvents, and has properties such as almost uniform dispersion when mixed with water, so it is a base or emulsifier for toiletries and cosmetics. , Dispersant, wetting agent, solubilizer,
It is extremely useful as a liquid crystal forming agent and the like.

Claims (5)

[Claims] 1. A glyceryl etherified polyhydric alcohol represented by the following general formula (1). G [(AO) _x B] _y (1) [G: shows a residue excluding hydrogen atoms of all hydroxyl groups in a polyhydric alcohol having three or more hydroxyl groups. A: represents an alkylene group having 2 to 4 carbon atoms, the terminal carbon atom of-(AO) _x- has an ether bond with the oxygen atom derived from the hydroxyl group of G, and the terminal oxygen atom bonds with B. B: hydrogen atom or general formula (a) or (b), respectively: (R: represents a linear or branched alkenyl group having 8 to 24 carbon atoms), which is bonded to a terminal oxygen atom of-(AO) _x- or a hydroxyl group-derived oxygen atom of G. However, at least one of y B groups is a group (a) or (b). x: [total number of added moles of -AO-] / y, which is a number from 0 to 10. y: shows the number of oxygen atoms derived from the hydroxyl group of G. ] 2. In the general formula (1), G is glycerin,
Pentaerythritol, dipentaerythritol, trimethylolalkane, sorbitol, mannitol, glycosides and the following general formula (2) [A: shows the number of 2-20. ] The glyceryl etherified polyhydric alcohol according to claim 1, which is a residue obtained by removing hydrogen atoms of all hydroxyl groups of at least one polyhydric alcohol selected from polyglycerin represented by 3. In the general formula (1), G is at least one selected from trimethylolethane, trimethylolpropane, methyl glucoside, ethyl glucoside, methyl maltoside, maltitol and 2,3-dihydroxypropylene glucoside. The glyceryl etherified polyhydric alcohol according to claim 1, which is a residue obtained by removing hydrogen atoms from all the hydroxyl groups of the polyhydric alcohol. 4. In the general formula (1), R is an oleyl group,
The glyceryl etherified polyhydric alcohol according to claim 1, which is a group selected from an elaidyl group, a linoleyl group and a palmitoyl group. 5. A compound represented by the general formula (3) G [(AO) _x H] _y (3) [G: a residue obtained by removing hydrogen atoms of all hydroxyl groups in a polyhydric alcohol having three or more hydroxyl groups. A: represents an alkylene group having 2 to 4 carbon atoms, the terminal carbon atom of-(AO) _x- has an ether bond with the hydroxyl group-derived oxygen atom of G, and the terminal oxygen atom bonds with a hydrogen atom. x: [total number of added moles of -AO-] / y, which is a number from 0 to 10. y: shows the number of oxygen atoms derived from the hydroxyl group of G. ] A polyhydric alcohol having 3 or more hydroxyl groups represented by the following formula or its alkylene oxide adduct and a compound represented by the general formula (4): [R: represents a linear or branched alkenyl group having 8 to 24 carbon atoms. ] The alkenyl glycidyl ether represented by these is made to react in the presence of a basic catalyst, The manufacturing method of the glyceryl etherification polyhydric alcohol in any one of Claims 1-4 characterized by the above-mentioned.