JPH05984A - Glyceryl etherified polyhydric alcohol and its production - Google Patents

Abstract

(57) [Summary] [Structure] The following general formula (1) G [(AO) _x B] _y (1) [wherein G represents a polyhydric alcohol residue, and at least one of B is A branched alkyloxyglyceryl group, the rest of which represent hydrogen atoms], and a method for producing the same. [Effect] Form a thermotropic liquid crystal in water dispersion system,
It has extremely excellent lubricity and has the property of easily dispersing almost uniformly when mixed with water, so it is a detergent, emulsifier, dispersant, wetting agent for toiletries and cosmetics.
It is extremely useful as a solubilizer and a liquid crystal forming agent.

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 lubricant, a liquid crystal forming agent and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Polyol ethers such as polyoxyalkylene alkyl ethers and polyoxyalkylene ethers of sorbitan esters have been used as emulsifiers, solubilizers and lubricants for cosmetics and cosmetics. However, these polyol ethers are produced by the addition reaction of alkylene oxides such as ethylene oxide and propylene oxide, but the products obtained are mixtures having various polyoxyalkylene chain lengths, and high purity products are synthesized. It is difficult to obtain such a composition, and when used in cosmetics and cosmetics, sufficient performance may not be obtained.

In the natural world, there are many derivatives of polyhydric alcohols having an ether bond. Among them, monoalkyl ether of glycerin (referred to as glyceryl ether) is particularly well known. For example, fish lipids include palmityl glyceryl ether, stearyl glyceryl ether and oleyl glyceryl ether.

Such glyceryl ether has the W
Utilizing the / O type emulsifying property, it has been widely used as a cosmetic base and the like (JP-A-49-87612 and JP-A-49-92239).
No. JP-A-52-12109). Further, paying attention to the fact that such glyceryl ether is a nonionic surfactant having many characteristics, attempts have been made to derive a polyol ether compound having a molecular structure similar to that of glyceryl ether from a polyhydric alcohol. (US Patent No. 2258
No. 892, Japanese Patent Publication No. 52-18170, Japanese Patent Publication No. 53-137905, Japanese Patent Publication No.
54-145224 etc.). Among these glyceryl ether derivatives, branched alkyl glyceryl ethers having a branched alkyl group such as isostearyl group (Oil Chemistry, Vol. 36, No. 8, pp. 588-598 (1987)) and diglycerin are branched. Branched alkyl ether of diglycerin having an alkyl group (Japanese Patent Publication No. 63-24496, JP-A-59-175445)
Have been used in cosmetics and cosmetics as nonionic surfactants having excellent W / O type emulsifying properties.

However, while the branched alkyl glyceryl ether and the branched alkyl ether of diglycerin have excellent W / O type emulsifying properties, they are used for perfume cosmetics having a high water content such as shampoo, rinse or lotion. In this case, since the hydrophilicity is low, the dispersibility in water may be poor to cause poor emulsification, and there is a problem that a sufficient effect cannot be expected because the amount used is limited.

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

[0007]

Under the circumstances, as a result of intensive investigations by the present inventors, the novel glyceryl etherified polyhydric alcohol represented by the general formula (1) described below is thermodynamically dispersed in an aqueous dispersion system. It has the properties of forming a tropic liquid crystal, showing extremely excellent lubricity, being compatible with almost all solvents, and being easily dispersed almost uniformly when mixed with water. Base,
The present invention has been completed by discovering that it has extremely excellent performance as an emulsifier, a lubricant, and a liquid crystal forming agent, which has never been obtained.

That is, the present invention provides the following general formula (1) G [(AO) _x B] _y (1) [wherein, G: polyhydric alcohol having four or more hydroxyl groups (sucrose, fructofuranose, full (Excluding octopyranose and glucopyranose) in which all the hydrogen atoms of the hydroxyl groups are removed. A: an alkylene group having 2 to 4 carbon atoms, one end of which is an oxygen atom derived from a hydroxyl group of a polyhydric alcohol having 4 or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose and glucopyranose) It has an ether bond and the other end is bonded to an oxygen atom. B: a group that binds to a terminal oxygen atom in the -AO- group or a group that binds to an oxygen atom derived from a hydroxyl group of a polyhydric alcohol having four or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose and glucopyranose) And a hydrogen atom or

[0009]

[Chemical 9]

And / or

[0011]

[Chemical 10]

Is shown. Here, R represents a branched alkyl group having 16 to 36 carbon atoms. However, at least one of the y B groups is

[0013]

[Chemical 11]

And / or

[0015]

[Chemical 12]

[0016]

X: [total moles of alkylene oxide added to hydroxyl groups of polyhydric alcohol having four or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose and glucopyranose)] / y, 0 to 10 Is the number of. y: Indicates the number of hydroxyl groups in a polyhydric alcohol having 4 or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose and glucopyranose). ] A glyceryl etherified polyhydric alcohol represented by the following and a method for producing the same are provided.

The glyceryl etherified polyhydric alcohol (1) of the present invention is, for example, a polyhydric alcohol (sucrose, fructofuranose, fructopyranose) having four or more hydroxyl groups represented by the general formula (5) according to the following formula. And glucopyranose) or an alkylene oxide adduct thereof and a branched alkyl glycidyl ether represented by the general formula (6) in the presence of a basic catalyst.

[0019]

[Chemical 13]

[In the formula, A, B, G, x, y and R have the above-mentioned meanings. H in the formula (5) is a hydroxyl group of a polyhydric alcohol (excluding sucrose, fructofuranose, fructopyranose and glucopyranose) having 4 or more hydrogen atoms or hydroxyl groups bonded to the terminal oxygen atom in the -AO- group. It is a hydrogen atom that is bonded to the oxygen atom of origin. ]

As the polyhydric alcohol having four or more hydroxyl groups used in the present invention (excluding sucrose, fructofuranose, fructopyranose and glucopyranose),
For example, pentaerythritol, sorbitol, mannitol, maltitol, glycosides, polyglycerin represented by the following general formula (2), erythritol,
Inositol, xylitol, dipentaerythritol, tripentaerythritol, heptitol, octitol, 1,2,3,4-pentanetetrol, 1,
3,4,5-hexanetetrol, sorbitan, mannitan, raffinose, gentianose, xylose, galactose, mannose, maltose, sorbiose,
Examples thereof include maltotriose, maltotetraose, maltopentaose, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and their alkylene oxide adducts.

[0022]

[Chemical 14]

(In the formula, a represents a number of 2 to 20.)

The polyhydric alcohol having four or more hydroxyl groups used in the present invention may contain impurities other than the intended polyhydric alcohol. These polyhydric alcohols may be used while containing impurities unless they are practically problematic, and if they are problematic, they can be purified by a known purification method before use.

For example, pentaerythritol may contain dipentaerythritol or tripentaerythritol condensed with pentaerythritol as impurities, and a small amount of a glycidyl ether adduct of dipentaerythritol and tripentaerythritol is by-produced. However, if it does not affect the performance and quality of the product, it may be used as it is, and if it does not, it is preferable to use pentaerythritol purified as a raw material by crystallization. Also, sorbitol and mannitol may contain a small amount of reducing sugars such as glucose, and a small amount of these glycidyl ether adducts of reducing sugars are by-produced, but this does not affect the product performance and quality. If so, it is preferable to use sorbitol or mannitol purified by a crystallization operation or the like if there is any trouble. In addition, alkylene oxide adducts (average addition mole number 1 to 10 moles) such as pentaerythritol, sorbitol, mannitol and the like may be used as the polyhydric alcohol, and examples thereof include polyoxyethylene sorbitol, polyoxypropylene sorbitol and polyoxyethylene.・ Polyoxypropylene sorbitol, polyoxyethylene pentaerythritol, polyoxypropylene pentaerythritol, polyoxyethylene / polyoxypropylene pentaerythritol, polyoxyethylene mannitol, polyoxypropylene mannitol, polyoxyethylene / polyoxypropylene mannitol, polyoxyethylene Maltitol, polyoxypropylene maltitol, polyoxyethylene / polyoxypropylene maltitol, polio Shi sorbitol, polyoxypropylene sorbitol, polyoxyethylene-polyoxypropylene sorbitol

An example of the reaction for obtaining a 1 mol adduct of glycidyl ether of pentaerythritol is as follows.

[0027]

[Chemical 15]

Examples of the glycosides used in the present invention include (a) monosaccharides such as glucose, galactose, fructose, mannose and xylose, disaccharides such as maltose, isomaltose, lactose and sucrose, or cellulose, starch and amylose. A polysaccharide such as
(B) Obtained by a known means for reacting lower alcohols such as methanol, ethanol, propanol or the like or polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, erythritol, sorbitol in the presence of an acid catalyst. Can be mentioned. Specifically, alkyl glucosides such as methyl glucoside, ethyl glucoside, propyl glucoside, octyl glucoside, decyl glucoside, dodecyl glucoside, oleyl glucoside, 2-ethylhexyl glucoside, methyl maltoside, ethyl maltoside; 2-
Hydroxyalkyl glycosides such as hydroxypropyl glucoside, 2,3-dihydroxypropyl glucoside and 2-hydroxyethyl glucoside; alkyl ether glycosides such as methoxyethyl glucoside and ethoxyethyl glucoside; reducing ends such as maltitol and lactitol were reduced Examples thereof include oligosaccharides, which may be used alone or as a mixture of two or more kinds.

Further, these alkylene oxide adducts (average number of moles added: 1 to 10 moles) may be used, for example, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, polyoxyethylene / polyoxypropylene methyl glucoside. Etc.

The polyglycerin represented by the general formula (2) is a polyglycerin obtained by condensing glycerin by a known method, represented by diglycerin, triglycerin, tetraglycerin and pentaglycerin. As the polyglycerin used in the present invention,
Generally, the average degree of condensation (a) of glycerin is polyglycerin of 2 to 20, but when polyglycerin having a high degree of condensation is used, hydrophilicity may become too high and sufficient performance may not be obtained. It is desirable to use polyglycerin in which a is 2 to 10, more preferably a is 2 to 4. These polyglycerins may be used alone or as a mixture if they are suitable for actual use. Further, in the polyglycerin used in the present invention, unreacted glycerin may be mixed,
If there is no problem in actual use, it can be used in a state of being mixed with glycerin. Further, an alkylene oxide adduct of polyglycerin may be used as the polyhydric alcohol.

The branched alkyl glycidyl ether used in the present invention is represented by the above general formula (6) and has the formula (6)
In the formula, R represents a branched alkyl group having 16 to 36 carbon atoms, preferably 18 to 24 carbon atoms. The branched alkyl group R has the following general formula (3):

[0032]

[Chemical 16]

(Wherein p and q each represent an integer of 0 to 33, and the sum of p and q is 13 to 33) or the following general formula (4):

[0034]

[Chemical 17]

(In the formula, r and s each represent an integer of 0 to 31, and the sum of r and s is 11 to 31). In addition, these branched alkyl groups may be a mixture of two or more kinds. Preferred branched alkyl glycidyl ethers include, for example, methyl pentadecyl glycidyl ether, methyl hexadecyl glycidyl ether, methyl heptadecyl (isostearyl) glycidyl ether, methyl octadecyl glycidyl ether, methyl behenyl glycidyl ether, ethyl hexadecyl glycidyl ether, ethyl octadecyl glycidyl ether. Ether, ethyl behenyl glycidyl ether, butyl dodecyl glycidyl ether, butyl hexadecyl glycidyl ether, butyl octadecyl glycidyl ether, hexyl decyl glycidyl ether, heptyl undecyl glycidyl ether, octyl dodecyl glycidyl ether, decyl dodecyl glycidyl ether, decyl tetradecyl glycidyl ether, Dodecyl Hexadecyl glycidyl ether, tetradecyl octadecyl glycidyl ether. The branched alkyl glycidyl ether used in the present invention may contain a linear alkyl group as long as it does not interfere with the actual use.

The reaction molar ratio between the polyhydric alcohol used (excluding sucrose, fructofuranose, fructopyranose and glucopyranose) or its alkylene oxide adduct (5) and the branched alkyl glycidyl ether (6) is It can be appropriately selected depending on the degree of etherification of the glyceryl etherified polyhydric alcohol. For example, in order to obtain the target product having a high content of 1 mol adduct of glyceryl etherified polyhydric alcohol, it is usually 1.2: 1.
The polyhydric alcohol may be used in excess at a ratio of 0 to 10.0: 1.0, and a ratio of 1.5: 1.0 to 5.0: 1.0 is preferable in consideration of the production amount of 1 mol adduct and the recovery of the polyhydric alcohol. In addition, in order to obtain a desired glyceryl etherified polyhydric alcohol having a high content of 2 mol adduct,
Usually, the branched alkyl glycidyl ether may be used in excess at a ratio of 0.3: 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.

The 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 polyhydric alcohol and the branched alkyl glycidyl ether. Examples of such an organic solvent include dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, etc.
It is preferable to use 10.0 times the amount.

As the catalyst, an acid or basic catalyst generally known as an epoxy group reaction catalyst can be used, but when an acid catalyst is used, as a side reaction,
It is not preferable because a decomposition reaction of the ether bond or a dehydration reaction of the hydroxyl group of the generated glyceryl etherified polyhydric alcohol occurs, and it is preferable to use a basic catalyst. The basic catalyst used is not particularly limited, but sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium hydride and the like can be mentioned from the viewpoint of reactivity and economy. These basic catalysts are
0.01-20.0% by weight, especially 0.1-
It is preferably used in the range of 10.0% by weight.

The reaction is carried out at 50 to 200 ° C, preferably 80 to 150 ° C.
Done in. If the reaction temperature is less than 50 ° C, the reaction rate is slow,
If the temperature exceeds 200 ° C, the product will be colored, which is not preferable.

In this reaction, when water is present in the reaction system, the epoxy group of the branched alkyl glycidyl ether reacts with water to form glyceryl ether as a by-product.
It is preferable to dissolve or disperse a polyhydric alcohol in an organic solvent, heat it to blow dry nitrogen gas, or heat dehydration under reduced pressure to remove water, and then add a branched alkyl glycidyl ether to react. .

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

The glyceryl etherified polyhydric alcohol (1) of the present invention is usually a 1-mol addition product obtained by adding 1 molecule of a branched alkyl glycidyl ether (6) to 1 molecule of a polyhydric alcohol or its alkylene oxide adduct (5). It can be obtained as a mixture of a polyhydric alcohol or its alkylene oxide adduct (5) and a polymorphic adduct in which three or more molecules of a branched alkyl glycidyl ether (6) are added to one molecule of the polyhydric alcohol or its alkylene oxide adduct (5) . The glyceryl etherified polyhydric alcohol (1) thus obtained is
Usually, they are used as a mixture of these 1-mole adducts, 2-mole adducts, or poly-mole adducts, but if there is a problem due to performance or compounding reasons, publicly known methods such as silica gel column and solvent extraction It can be purified using the purification method of. In the glyceryl etherified polyhydric alcohol (1) of the present invention, the desired 1 mol adduct, 2 mol adduct,
Alternatively, an unreacted glycoside may be contained in addition to the polymorphic adduct. Such unreacted glucoside is
If there is no problem in practical use, it can be used as it is contained, but if there is a problem, a two-layer extraction solvent system using an organic solvent such as ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, or chloroform is used. It can be removed by a method or a known purification method such as Smith thin film distillation. However, the mixture of 1 mol adduct, 2 mol adduct, polymol adduct of the glyceryl etherified polyhydric alcohol of the present invention is a mixture as it is without performing such a purification operation unless there is a problem in use. It can be used as a surfactant.

[0043]

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

[0044]

EXAMPLES Next, 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, the ¹ H-NMR spectrum is
Using a BRUKER AC-200P NMR SPECTROMETER, CDCl ₃ (D
_{(In the} presence of ₂ O) as a solvent, concentration 3%, internal standard TMS, 25
It was measured under the condition of ° C. The IR spectrum was measured by the KBr liquid film method at 25 ° C using a Hitachi 270-30 infrared spectrophotometer.

Example 1 Pentaerythritol 82 g, dimethyl sulfoxide 200
g and 1 g of sodium hydroxide in a 500 ml flask,
It was heated to 105 ° 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. After 39 g of isostearyl glycidyl ether was added dropwise thereto over 1 hour, the mixture was reacted at 105 ° 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, and dimethyl sulfoxide was completely distilled off at 80 ° C under reduced pressure.
Unreacted pentaerythritol precipitated by adding ethanol was filtered off. 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 pale yellow pentaerythritol. 63 g of a crude purified product of an adduct of isostearyl glycidyl ether was obtained. This crude product was separated and purified by silica gel column chromatography with an elution solvent of acetone: hexane = 2: 1 to obtain the target pentaerythritol.
The 1 mol adduct of isostearyl glycidyl ether was eluted, and the eluate fractions were collected and the solvent was distilled off to obtain 16 g of the desired 1 mol adduct of pentaerythritol isostearyl glycidyl ether (yield 30%). Obtained. In addition,
Figure 1 shows the obtained NMR spectrum and Figure 2 shows the IR spectrum.
, Respectively. Hydroxyl value 482 (calculated value 486) NMR (CDCl ₃ ): δ (ppm) 3.95 (1H, m, -OCH ₂ -C H OH-CH ₂ O-), 3.67 (6H, s, -C (C H ₂ O
H) ₃ ), 3.46 (8H, m, -OCH _2- ), 1.30 ~ 1.59 (29H, b, -CH ₂ -,-CH
-), 0.88 (6H, m, -CH ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 to 3400; ν _CH (stretching) (-CH-,-CH ₂ -,-CH ₃ ) 2850,2920; ν _CH (Deflection) (-CH-,-CH ₂ -,-CH ₃ ) 1375,1460; ν _CO (-CO-) 1110,1035,1010

Example 2 91 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 the flask to mix them with water and N-.
About 10 g of methylpyrrolidone was distilled off to remove water in the reaction system. Isostearyl glycidyl ether 33
After g was added dropwise over 2 hours, the mixture was reacted at 110 ° 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, N-methylpyrrolidone was completely distilled off at 80 ° C. under reduced pressure, and acetone 500 was added to the residue.
g was added and the precipitated unreacted sorbitol was filtered off. Acetone was distilled off from the resulting filtrate under reduced pressure to obtain 42 g of a crudely purified adduct of sorbitol / isostearyl glycidyl ether. This crude product was subjected to silica gel column chromatography, and chloroform: methanol =
Separation and purification with a 5: 1 elution solvent elutes the target 1-mol adduct of sorbitol-isostearyl glycidyl ether, and the elution fractions are collected and the solvent is distilled off. 20 g (yield 39%) of a 1 mol adduct of isostearyl glycidyl ether was obtained. Hydroxyl value 664 (calculated value 663) NMR (CDCl ₃ ): δ (ppm) 3.35 to 3.94 (15H, m, -O-CH _2- , O-CH-), 1.34 to 1.58 (29H, b,-
CH ₂ -,-CH-), 0.86 (6H, m, -CH ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200-3400; ν _CH (stretching) (-CH-,-CH ₂ -,-CH ₃ ) 2840,2910; ν _CH (bend) (-CH-,-CH ₂ -,-CH ₃ ) 1370,1455; ν _CO (-C
-O-) 1030-1110

Example 3 91 g of mannitol, 50 g of dimethyl sulfoxide and 0.8 g of sodium hydroxide were placed in a 300 ml flask and dissolved by heating at 120 ° C., dry nitrogen gas was blown in, and about 10 g of water and dimethyl sulfoxide were distilled off. Water in the reaction system was removed. 35 g of 2-octyldodecyl glycidyl ether was added dropwise thereto over 2 hours, and then reacted at 120 ° C. for 6 hours with stirring. After the reaction was completed, acetic acid was added to the reaction mixture.
1.2 g of the catalyst was added to neutralize the catalyst, dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, 500 ml of water was added to the residue, and the mixture was extracted with 1000 ml of methyl ethyl ketone (500 ml × 2).
The obtained methyl ethyl ketone layer was dried with Glauber's salt, filtered and the solvent was distilled off to obtain a crude product of an adduct of mannitol 2-octyldodecyl glycidyl ether 53
g was obtained. This crude product was separated and purified using silica gel column chromatography with an elution solvent of chloroform: methanol = 5: 1 to elute the target 1-mole adduct of mannitol 2-octyldodecylglycidyl ether. The elution fractions are collected and the solvent is distilled off,
29 g (yield: 46%) of the desired 1-mole adduct of mannitol 2-octyldodecylglycidyl ether was obtained. Hydroxyl value 625 (calculated value 628) NMR (CDCl ₃ ): δ (ppm) 3.34 to 3.96 (15H, m, -O-CH _2- , O-CH-), 1.33 to 1.59 (33H, b,
-CH ₂ -,-CH-), 0.87 (6H, m, -CH ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200-3400; ν _CH (stretching) (-CH-,- CH ₂ -,-CH ₃ ) 2860,2930; ν _CH (bending angle) (-CH-,-CH ₂ -,-CH ₃ ) 1380,1440; ν _CO (-C
-O-) 1030 ~ 1120

Comparative Example 1 Pentaerythritol 70 g, dimethyl sulfoxide 200
g and 1 g of sodium hydroxide in a 500 ml flask,
Water was dissolved by heating at 100 ° C., dry nitrogen gas was blown thereinto, and about 20 g of water and dimethyl sulfoxide were distilled off to remove water in the reaction system. 33 g of stearyl glycidyl ether was added dropwise thereto over 2 hours, and then reacted at 110 ° C. for 5 hours with stirring. After the reaction was completed, acetic acid was added to the reaction mixture.
1.5 g of the catalyst was added to neutralize the catalyst, dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, and 500 g of acetone was added to the residue, and the unreacted pentaerythritol deposited was filtered off. Acetone was distilled off from the obtained filtrate under reduced pressure to obtain 45 g of a crude extract of an adduct of pentaerythritol / stearyl glycidyl ether. This crude purified product was subjected to silica gel column chromatography using hexane:
Separation and purification with an elution solvent of acetone = 2: 1 elutes the target 1-molar adduct of pentaerythritol stearyl glycidyl ether, and the elution fractions are collected and the solvent is distilled off to Pentaerythritol
22 g (yield 47%) of 1 mol adduct of stearyl glycidyl ether was obtained. From the NMR and IR spectrum analysis, it was confirmed that the obtained compound was a 1 mol adduct of pentaerythritol stearyl glycidyl ether.

Test Example 1 With respect to the glyceryl etherified polyhydric alcohols of the present invention obtained in the examples and conventionally known compounds, the properties at room temperature and the dispersibility in water (concentration: 5% by weight) were examined. .
The results are shown in Table 1. (Evaluation method) The properties at room temperature were examined by visual observation.
For the dispersibility in water, 1 g of the sample was sampled in a 30 ml volume sample bottle, ion-exchanged water was added thereto so that the sample concentration was 5% by weight, and the sample bottle was shaken for 1 minute and allowed to stand for 5 minutes. After that, the dispersed state was visually observed.

[0050]

[Table 1]

Test Example 2 Using the compounds of the present invention obtained in the examples, hair rinse agents having the compositions shown in Table 2 were produced, and the rinse performance was examined. The results are shown in Table 2. (Manufacturing method) To water heated to 70 ° C, components dissolved by heating to the same temperature were added, stirred and mixed, and then cooled to room temperature with stirring to obtain a hair rinse agent. (Evaluation method) 20 g of hair of a Japanese woman (length of which has never been subjected to cosmetic treatment such as cold perm or bleach)
15 cm) and this hair bundle is washed with a commercial shampoo containing an anion activator as the main component, 2 g of the hair rinse agent shown in Table 2 is evenly applied, and then rinsed under running water for 30 seconds and then towel dried. went. This wet hair bundle was sensory evaluated for softness, smoothness and oiliness. The evaluation criteria are shown as ⊚ for excellent, ◯ for good, Δ for normal, and x for inferior.

[0052]

[Table 2]

Example 4 97 g of methyl glucoside, 200 g of dimethyl sulfoxide and 1 g of sodium hydroxide were placed in a 500 ml flask and heated to 105 ° C. to dissolve them, and dry nitrogen gas was blown thereinto to distill about 20 g of water and dimethyl sulfoxide. Then, the water content in the reaction system was removed. 33 g of isostearyl glycidyl ether was added dropwise to the flask over 4 hours, and then reacted at 105 ° C. for 5 hours while stirring. After the reaction was completed, 1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and then dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, and 99% ethanol was added to the residue for precipitation. The reaction methyl glucoside was filtered off. 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 pale yellow methyl glucoside / iso. 49 g of a crude product of a stearyl glycidyl ether adduct was obtained. When this crudely purified product is separated and purified using silica gel column chromatography, acetone: hexane =
The target methyl glucoside / isostearyl glycidyl ether is eluted with a 4: 1 elution solvent, and the 1 mol adduct of the target methyl glucoside / isostearyl glycidyl ether is eluted. 16 g of a 1-mole adduct of ether was obtained. Hydroxyl value 436 (calculated value 432) NMR (CDCl ₃ ): δ (ppm) 4.75 (1H, d, -OC H -OCH ₃ ), 3.95 (1H, m, -OCH ₂ -C H OH-CH ₂ O
-), 3.77 ~ 3.35 (12H, m, -OC H ₂ -,-OC H- ), 3.24 (3H, s, -OC
H ₃ ), 1.30 to 1.59 (29H, b, -C H ₂ -,-C H- ), 0.85 (6H, m, -C H ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 to 3400; ν _CH (stretching) (-CH-,-CH ₂ -,-CH ₃ ) 2840,2915; ν _CH (bending angle) (-CH-,-CH ₂ -,-CH ₃ ) 1375,1460 ; Ν _CO (-C
-O) 1110,1035,1005

Example 5 104 g of ethyl glucoside, 100 g of N-methylpyrrolidone and 1 g of sodium hydroxide were placed in a 300 ml flask and heated to 110 ° C.
The mixture was heated to dissolve and dry nitrogen gas was blown in to distill about 10 g of water and N-methylpyrrolidone to remove water in the reaction system. 33 g of isostearyl glycidyl ether was added dropwise to the reaction solution over 2 hours, and then reacted at 110 ° C. for 4 hours with stirring. After the reaction was completed, 1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and then N-methylpyrrolidone was completely distilled off at 80 ° C. under reduced pressure, and 500 g of acetone was added to the residue for precipitation. Unreacted ethyl glucoside was filtered off. Acetone was distilled off from the obtained filtrate under reduced pressure to obtain 50 g of a crude purified adduct of ethyl glucoside / isostearyl glycidyl ether. When this crude product was separated and purified using silica gel column chromatography, the desired 1 mol adduct of ethyl glucoside / isostearyl glycidyl ether was eluted with an elution solvent of hexane: acetone = 5: 1. The elution fractions were collected and the solvent was distilled off to obtain 20 g of a 1 mol adduct of ethyl glucoside / isostearyl glycidyl ether. Hydroxyl value 420 (calculated value 420) NMR (CDCl ₃ ): δ (ppm) 4.82 (1H, d, -OC H -OCH ₃ ), 3.94 (1H, m, -OCH ₂ -C H OH-CH ₂ O
-), 3.77 ~ 3.50 (12H, m, -OC H ₂ -,-OC H- ), 3.40 (2H, q, -OC H ₂
CH ₃ ), 1.30 to 1.60 (32H, b, -C H ₂ -,-C H- ), 0.85 (6H, m, -C H ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 ~ 3400; ν _CH (expansion / contraction) (-CH-,-CH ₂ -,-CH ₃ ) 2840,2910; ν _CH (bend) (-CH-,-CH ₂ -,-CH ₃ ) 1370,1455 ; Ν _CO (-C
-O-) 1030,1110

Example 6 Methyl glucoside (194 g), dimethyl sulfoxide (400 g) and potassium hydroxide (2.8 g) were placed in a 300 ml flask and heated to 120 ° C. to dissolve them, and dry nitrogen gas was blown thereinto to distill about 50 g of water and dimethyl sulfoxide. Then, the water content in the reaction system was removed. 33 g of 2-heptylundecyl glycidyl ether was dropped into the flask over 2 hours, and then 12
The reaction was carried out at 0 ° C. for 6 hours with stirring. After the reaction,
After adding 3 g of acetic acid to the reaction mixture to neutralize the catalyst,
After dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, 1000 ml of ethanol was added to the residue and the precipitated methyl glucoside was filtered off. Ethanol was distilled off by filtration to obtain 56 g of a crude product of an adduct of methyl glucoside-2-heptylundecyl glycidyl ether. When this crude product is separated and purified using silica gel column chromatography, the target 1 mol adduct of methyl glucoside 2-heptylundecyl glycidyl ether is eluted with an elution solvent of hexane: acetone = 4: 1. Then
The eluate fractions were collected and the solvent was distilled off to obtain 20 g of a 1 mol adduct of methyl glucoside 2-heptylundecyl glycidyl ether. Hydroxyl value 438 (calculated value 432) NMR (CDCl ₃ ): δ (ppm) 4.90 (1H, d, -OC H -OCH ₃ ), 3.88 (1H, m, -OCH ₂ -C H OH-CH ₂ O
-), 3.74 to 3.36 (12H, m, -OC H ₂ -,-OC H- ), 3.20 (3H, s, -OC
H ₃ ), 1.68 to 1.23 (29H, b, -C H ₂ -,-C H- ), 0.79 (6H, m, -C H ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 to 3400; ν _CH (expansion / contraction) (-CH-,-CH ₂ -,-CH ₃ ) 2860,2930; ν _CH (bend) (-CH-,-CH ₂ -,-CH ₃ ) 1380,1440 ; Ν _CO (-C
-O-) 1130,1040

Example 7 18 g of methyl maltoside, 200 g of dimethyl sulfoxide and 1 g of sodium hydroxide were placed in a 500 ml flask and heated to 105 ° C.
It was heated to dissolve it, and dry nitrogen gas was blown into it to distill about 20 g of water and dimethyl sulfoxide to remove water in the reaction system. 35 g of 2-octyldodecyl glycidyl ether was added dropwise to the flask over 4 hours, and then 10
The reaction was carried out at 5 ° C. for 5 hours with stirring. After the reaction,
After adding 1.5 g of acetic acid to the reaction mixture to neutralize the catalyst,
Dimethylsulfoxide was completely distilled off at 80 ° C. under reduced pressure, 99% ethanol was added to the residue, and the precipitated unreacted methylmaltoside was filtered off. Ethanol was distilled off from the obtained filtrate under reduced pressure to obtain a crude product of an adduct of methylmaltoside 2-octyldodecylglycidyl ether.
19 g were obtained. When this crude product was separated and purified using silica gel column chromatography, chloroform:
The target 1-methyl adduct of methyl maltoside 2-octyldodecyl glycidyl ether was eluted with an elution solvent of methanol = 2: 1, and the elution fractions were collected and the solvent was distilled off to obtain the desired methyl ester. 8 g of a 1 mol adduct of maltoside 2-octyldodecyl glycidyl ether was obtained. Hydroxyl value 560 (calculated value 553) NMR (CDCl ₃ ): δ (ppm) 5.01 to 4.85 (2H, m, -OC H -OCH ₃ ), 3.93 (1H, m, -OCH ₂ -C H OH-
CH ₂ O-), 3.75-3.40 (17H, m, -OC H ₂ -,-OCH-), 3.25 (3H, s,-
OC H ₃ ), 1.65 ~ 1.20 (33H, b, -C H ₂ -,-C H- ), 0.80 (6H, m, -C
H ₃ ), IR (liquid film) cm ⁻¹ : ν _OH (-OH) 3200 to 3400; ν _CH (stretching) (-CH-, -CH ₂ -,-CH ₃ ) 2850,2920; ν _CH (variable Angle) (-CH-,-CH ₂ -,-CH ₃ ) 1375,1460; ν _CO (-C
-O-) 1110,1035,1010

Example 8 69 g of maltitol, 400 g of N-methylpyrrolidone and 2 g of sodium hydroxide were placed in a 300 ml flask and heated to 110 ° C. to dissolve them, and dry nitrogen gas was blown thereinto to obtain water and N-.
About 10 g of methylpyrrolidone was distilled off to remove water in the reaction system. 38 g of 2-decyl tetradecyl glycidyl ether was added dropwise to the reaction solution over 2 hours, and then at 4 ° C at 110 ° C.
The reaction was carried out with stirring for an hour. After completion of the reaction, 5 g of phosphoric acid was added to the reaction mixture to neutralize the catalyst, and then N-methylpyrrolidone was completely distilled off at 80 ° C. under reduced pressure, and 500 g of acetone was added to the residue for precipitation. Unreacted maltitol was filtered off. Acetone was distilled off from the obtained filtrate under reduced pressure to obtain 83 g of a crudely purified adduct of maltitol.2-decyltetradecylglycidyl ether. When this crudely purified product is separated and purified using silica gel column chromatography, chloroform: methanol =
The target 1 mol adduct of maltitol 2-decyl tetradecyl glycidyl ether was eluted with a 2: 1 elution solvent, and the elution fractions were collected and the solvent was distilled off to give maltitol 2-decyl. 20 g of a 1 mol adduct of tetradecyl glycidyl ether was obtained. Hydroxyl value 663 (calculated value 670) NMR (CDCl ₃ ): δ (ppm) 4.90 (1H, d, -OC H -OCH ₃ ), 3.96 (1H, m, -OCH ₂ -C H OH-CH ₂ O
-), 3.78 ~ 3.42 (20H, m, -OC H ₂ -,-OC H- ), 1.30 ~ 1.59 (41H,
b, -C H ₂ -,-C H- ), 0.81 (6H, m, -C H ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 to 3400; ν _CH (stretch) ( -CH-,-CH ₂ -,-CH ₃ ) 2830,2910; ν _CH (Variation) (-CH-,-CH ₂ -,-CH ₃ ) 1370,1450; ν _CO (-C
-O-) 1030,1110

Example 9 300 g of 2,3-dihydroxypropyl glucoside (25 g), dimethyl sulfoxide (50 g) and potassium hydroxide (1.4 g) were added.
Put in a flask, heat to 120 ℃ to dissolve, blow dry nitrogen gas and water and dimethylsulfoxide about 5g.
The water in the reaction system was removed by distilling. 16 g of isostearyl glycidyl ether was dropped into the flask over 2 hours, and then reacted at 120 ° C. for 6 hours while stirring. After completion of the reaction, 3 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and dimethylsulfoxide was depressurized at 80 ° C.
After completely distilling off with, the residue was extracted with 500 ml of water and 1000 ml of methyl ethyl ketone. 17 g of a crude product of an adduct of 2,3-dihydroxypropyl glucoside / isostearyl glycidyl ether was obtained by distilling off methyl ethyl ketone from the obtained methyl ethyl ketone layer under reduced pressure.
Got This crude product was separated and purified using silica gel column chromatography to obtain the desired 1-mol adduct of 2,3-dihydroxypropyl glucoside / isostearyl glycidyl ether with an elution solvent of hexane: acetone = 2: 1. Was eluted, and the eluted fractions were collected and the solvent was distilled off to obtain 7 g of a 1 mol adduct of 2,3-dihydroxypropyl glucoside / isostearyl glycidyl ether. Hydroxyl value 578 (calculated value 580) NMR (CDCl ₃ ): δ (ppm) 4.88 (1H, d, -OC H -OCH ₃ ), 4.01 to 3.86 (2H, m, -OCH ₂ -C H OH-
CH ₂ O-), 3.75 ~ 3.46 (17H, m, -OC H ₂ -,-OCH-), 1.27 ~ 1.73
(29H, b, -C H ₂ -,-C H- ), 0.85 (6H, m, -C H ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 to 3400; ν _CH ( Expansion / contraction) (-CH-,-CH ₂ -,-CH ₃ ) 2860,2920; ν _CH (bend) (-CH-,-CH ₂ -,-CH ₃ ) 1370,1440; ν _CO (-C
-O-) 1040,1120

Comparative Example 2 97 g of methyl glucoside, 200 g of dimethyl sulfoxide and 1 g of sodium hydroxide were placed in a 500 ml flask and heated to 105 ° C.
It was heated to dissolve it, and dry nitrogen gas was blown into it to distill about 20 g of water and dimethyl sulfoxide to remove water in the reaction system. Stearyl glycidyl ether
After dropping 33g into the flask over 4 hours, 5g at 105 ℃
The reaction was carried out with stirring for an hour. After the reaction was completed, 1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and then dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, and 99% ethanol was added to the residue for precipitation. The reaction methyl glucoside was filtered off. Ethanol was distilled off from the resulting 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 pale yellow methylglucoside stearyl. 47 g of a crude product of an adduct of glycidyl ether was obtained. When this crude product was separated and purified using silica gel column chromatography, the target 1 mol adduct of methyl glucoside stearyl glycidyl ether was eluted with an elution solvent of acetone: hexane = 4: 1, and the elution was performed. Fractions are collected and the solvent is distilled off to obtain the desired 1 mol adduct of methyl glucoside stearyl glycidyl ether 15
g was obtained.

Test Example 3 Properties of the glyceryl etherified polyhydric alcohols of the present invention obtained in Examples 4 to 9 and the compound obtained in Comparative Example 2 at room temperature and dispersibility in water (concentration 5 wt%) I checked about. The results are shown in Table 3.

[0061]

[Table 3]

Test Example 4 Using the compounds of the present invention obtained in Examples 4 to 9 and the compound obtained in Comparative Example 2, a hair rinse composition having the composition shown in Table 4 was prepared in the same manner as in Test Example 2, and The rinse performance was investigated.
The results are shown in Table 4.

[0063]

[Table 4]

Example 10 83 g of diglycerin, 50 g of dimethyl sulfoxide and 0.8 g of sodium hydroxide were placed in a 300 ml flask and heated to 110 ° C. to dissolve them, and dry nitrogen gas was blown thereinto to distill about 10 g of water and dimethyl sulfoxide. Then, the water content in the reaction system was removed. Isostearyl glycidyl ether
After dropping 33g into the flask over 1 hour,
The reaction was carried out with stirring for an hour. After the reaction was completed, 1.2 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and then dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, and 500 ml of water and 500 ml of ethyl acetate were added to the residue. Ethyl acetate extraction was performed, and the solvent was distilled off from the ethyl acetate soluble fraction to obtain 51 g of a pale yellow diglycerin / isostearyl glycidyl ether adduct. When this crude product was separated and purified using silica gel column chromatography, the desired 1 mol adduct of diglycerin / isostearyl glycidyl ether was eluted with an elution solvent of acetone: hexane = 2: 1. The eluate fractions were collected and the solvent was distilled off to obtain 16 g of the desired 1 mol adduct of diglycerin / isostearyl glycidyl ether. Hydroxyl value 451 (calculated value 456) NMR (CDCl ₃ ): δ (ppm) 3.95 to 3.85 (3H, m, -OCH ₂ -C H OH-CH ₂ O-), 3.67 to 3.45 (14H,
m, -OC H _2- ), 1.30 to 1.59 (29H, b, -C H ₂ -,-CH-), 0.88 (6H, m,
-C H ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 to 3400; ν _CH (stretching) (-CH-,-CH ₂ -,-CH ₃ ) 2850,2920; ν _CH ( Deflection) (-CH-,-CH ₂ -,-CH ₃ ) 1375,1460; ν _CO (-C
-O-) 1110,1035,1010

Example 11 Tetraglycerin (157 g), N-methylpyrrolidone (100 g) and potassium hydroxide (1.0 g) were placed in a 300 ml flask and heated to 100 ° C. to dissolve the mixture.
-About 10 g of methylpyrrolidone was distilled off to remove water in the reaction system. 33 g of isostearyl glycidyl ether was added dropwise to the reaction solution over 5 hours, and the mixture was reacted at 110 ° C. for 4 hours with stirring. After the reaction was completed, acetic acid was added to the reaction mixture.
After adding 1.5 g to neutralize the catalyst, N-methylpyrrolidone was completely distilled off at 80 ° C. under reduced pressure, and 500 ml of methyl ethyl ketone and 1000 ml of water were added to the residue for extraction with ethyl acetate. Ethyl acetate was distilled off from the obtained ethyl acetate-soluble portion under reduced pressure to obtain 61 g of a crude product of an adduct of tetraglycerin / isostearyl glycidyl ether. When this crude product was separated and purified using silica gel column chromatography, the target tetraglycerin / isostearyl glycidyl ether 1 mol adduct was eluted with an eluting solvent of chloroform: methanol = 4: 1. The eluted fractions were collected and the solvent was distilled off to obtain 19 g of a 1 mol adduct of tetraglycerin / isostearyl glycidyl ether. Hydroxyl value 532 (calculated value 526) NMR (CDCl ₃ ): δ (ppm) 3.95 to 3.75 (5H, m, -OCH ₂ -C H OH-CH ₂ O-), 3.67 to 3.45 (22H,
m, -OC H _2- ), 1.30 to 1.59 (29H, b, -C H ₂ -,-CH-), 0.88 (6H, m,
-C H ₃ ) IR (liquid film) cm ⁻¹ : ν _OH (-OH) 3200 to 3400; ν _CH (stretching) (-CH-,-CH ₂ -,-CH ₃ ) 2835 to 2910; ν _CH ( Deflection) (-CH-,-CH ₂ -,-CH ₃ ) 1370,1445; ν _CO (-C
-O-) 1030-1110

Example 12 83 g of diglycerin, 50 g of dimethyl sulfoxide and 0.8 g of sodium hydroxide were placed in a 300 ml flask and heated to 120 ° C. to dissolve them, and dry nitrogen gas was blown thereinto to distill about 10 g of water and dimethyl sulfoxide. Then, the water content in the reaction system was removed. 35 g of 2-octyldodecyl glycidyl ether was dropped into the flask over 2 hours, and then 120 ° C.
The mixture was reacted for 6 hours with stirring. After the reaction was completed, 1.2 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and dimethylsulfoxide was completely distilled off at 80 ° C. under reduced pressure. 500 ml of water was added to the residue, and methyl ethyl ketone 1
It was extracted with 000 ml (500 ml × 2). The obtained methyl ethyl ketone layer was dried with Glauber's salt, filtered, and the solvent was distilled off to obtain 53 g of a crude product of an adduct of diglycerin-2-octyldodecylglycidyl ether. When this crudely purified product was separated and purified by silica gel column chromatography, the target 1 mol adduct of diglycerin-2-octyldodecylglycidyl ether was eluted with an elution solvent of chloroform: methanol = 5: 1. The eluate fractions were collected and the solvent was distilled off to obtain 29 g of a 1 mol adduct of diglycerin-2-octyldodecylglycidyl ether. Hydroxyl value 527 (calculated value 529) NMR (CDCl ₃ ): δ (ppm) 3.95 to 3.78 (3H, m, -OCH ₂ -C H OH-CH ₂ O-), 3.65 to 3.45 (14H,
m, -OC H _2- ), 1.30 to 1.59 (33H, b, -C H ₂ -,-CH-), 0.87 (6H, m,
-C H ₃ ) IR (liquid film) cm ⁻¹ : ν _OH (-OH) 3200 to 3400; ν _CH (stretching) (-CH-,-CH ₂ -,-CH ₃ ) 2860,2930; ν _CH ( Deflection) (-CH-,-CH ₂ -,-CH ₃ ) 1380,1440; ν _CO (-C
-O-) 1030 ~ 1120

Comparative Example 3 According to the reaction conditions of Example 1, 33 g of stearyl glycidyl ether instead of isostearyl glycidyl ether were used.
Was used to synthesize an adduct of diglycerin / stearyl glycidyl ether, and the reaction mixture was purified by silica gel column chromatography to obtain 15 g of a 1 mol adduct of diglycerin / stearyl glycidyl ether.

Test Example 5 The compounds of the present invention obtained in Examples 10 to 12 and Comparative Example 3
The properties of the compound obtained in 1 above at room temperature and the dispersibility in water (concentration 5 wt%) were examined. The results are shown in Table 5.

[0069]

[Table 5]

Test Example 6 The compounds of the present invention obtained in Examples 10 to 12 and Comparative Example 3
A hair rinse agent having a composition shown in Table 6 was prepared in the same manner as in Test Example 2 by using the compound obtained in 1., and the rinse performance was examined. The results are shown in Table 6.

[0071]

[Table 6]

[Brief description of drawings]

1 is the NMR spectrum of the 1-mole adduct of pentaerythritol isostearyl glycidyl ether obtained in Example 1. FIG.
It is drawing which shows a spectrum.

FIG. 2 is a drawing showing an IR spectrum of a 1-mol addition product of pentaerythritol isostearyl glycidyl ether obtained in Example 1.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 6, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] And / or

[Chemical 2] Indicates. Here, R represents a branched alkyl group having 16 to 36 carbon atoms. However, at least one of the y B groups is

[Chemical 3] And / or

[Chemical 4] Is. X: [Polyhydric alcohol having 4 or more hydroxyl groups (sucrose,
Fructofuranose, fructopyranose , polyglyce
Total number of moles of alkylene oxide added to hydroxyl groups (excluding phosphorus and glucopyranose)] / y, 0 to 1
It is a number of zero. y: Polyhydric alcohol having 4 or more hydroxyl groups (sucrose, fructofuranose, fructopyranose , polyglycerin)
Group and glucopyranose). ]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 8

[Correction method] Change

[Correction content]

[Chemical 8] The glyceryl etherification according to claim 1, wherein the glycidyl branched alkyl ether represented by the formula (wherein R represents a branched alkyl group having 16 to 36 carbon atoms) is reacted in the presence of a basic catalyst. Manufacturing method of polyhydric alcohol.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 9

[Correction method] Change

[Correction content]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

That is, the present invention provides the following general formula (1) G [(AO) _x B] _y (1) [wherein, G is a polyhydric alcohol having four or more hydroxyl groups (sucrose, fructofuranose, fulucose). Topyranose , Po
( Excluding reglycerin and glucopyranose) is a residue obtained by removing hydrogen atoms of all hydroxyl groups. A: an alkylene group having 2 to 4 carbon atoms, one end of which is a polyhydric alcohol having 4 or more hydroxyl groups (sucrose, fructofuranose, fructopyranose , polyglycerin)
( Excluding benzene and glucopyranose) ether bond with the oxygen atom derived from the hydroxyl group, and the other end bonds with the oxygen atom. B: Hydroxyl group of a polyhydric alcohol having 4 or more hydroxyl groups or a group bonded to a terminal oxygen atom in the -AO- group (excluding sucrose, fructofuranose, fructopyranose , polyglycerin and glucopyranose). A group that is bonded to an oxygen atom derived from a hydrogen atom or

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

X: [total number of moles of alkylene oside added to hydroxyl groups of polyhydric alcohol having 4 or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose , polyglycerin and glucopyranose)] / y
Is shown and is a number from 0 to 10. y: Polyhydric alcohol having 4 or more hydroxyl groups (sucrose, fructofuranose, fructopyranose , polyglycerin)
Group and glucopyranose). ] A glyceryl etherified polyhydric alcohol represented by the following and a method for producing the same are provided.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

The glyceryl etherified polyhydric alcohol (1) of the present invention is, for example, a polyhydric alcohol (sucrose, fructofuranose, fructopyranose) having four or more hydroxyl groups represented by the general formula (5) according to the following formula. , Polyg
(Except lyserine and glucopyranose) or an alkylene oxide adduct thereof and a branched alkyl glycidyl ether represented by the general formula (6) in the presence of a basic catalyst.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

[In the formula, A, B, G, x, y and R have the above-mentioned meanings. H in the formula (5) is a polyhydric alcohol having four or more hydrogen atoms or hydroxyl groups bonded to the terminal oxygen atom in the -AO- group (excluding sucrose, fructofuranose, fructopyranose , polyglycerin and glucopyranose). ) Is a hydrogen atom bonded to an oxygen atom derived from the hydroxyl group. ]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

The polyhydric alcohol having 4 or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose , polyglycerin and glucopyranose) used in the present invention includes, for example, pentaerythritol, sorbitol, mannitol, maltitol, Glycosides,
Erythritol toll is I table by the following general formula (2), inositol, xylitol, dipentaerythritol, tripentaerythritol, heptitol, Okuchitoru, 1,2,3,4 pen Thante trawl, 1,3,
4,5-Hesantetrol, sorbitan, mannitan, raffinose, gentianose, xylose, galactose, mannose, maltose, sorbiose, maltotriose, maltotetraose, maltopentaose, α-cyclodextrin, β-cyclodextrin, γ -Cyclodextrin or alkylene oxide adducts thereof and the like can be mentioned.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

Polyhydric alcohols used (excluding sucrose, fructofuranose, fructopyranose , polyglycerin and glucopyranose) or their alkylene oxide adducts (5) and branched alkyl glycidyl ethers (6) The reaction molar ratio of can be appropriately selected depending on the degree of etherification of the desired glyceryl etherified polyhydric alcohol. For example, in order to obtain a desired glyceryl etherified polyhydric alcohol having a high content of 1 mol adduct, the polyhydric alcohol is usually added in excess at a ratio of 1.2: 1.0 to 10.0: 1.0. It suffices to use, considering the production amount of 1 mol adduct and the recovery of polyhydric alcohol,
A ratio of 1.5: 1.0 to 5.0: 1.0 is preferable. Further, in order to obtain the desired product having a high content of 2 mol adduct of glyceryl etherified polyhydric alcohol, it is usually 0.3:
The branched alkyl glycidyl ether may be used in excess at a ratio of 1.0 to 1.1: 1.0, and in view of the production amount of the 2 mol adduct, 0.4: 1.0 to 0.8: A ratio of 1.0 is preferred.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // C07B 61/00 300 7419-4H

Claims (9)

[Claims] 1. A glyceryl etherified polyhydric alcohol represented by the following general formula (1). G [(AO) _x B] _y (1) [wherein G: hydrogen atoms of all hydroxyl groups in a polyhydric alcohol having four or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose and glucopyranose)] The residues except for are shown. A: an alkylene group having 2 to 4 carbon atoms, one end of which is an oxygen atom derived from a hydroxyl group of a polyhydric alcohol having 4 or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose and glucopyranose) It has an ether bond and the other end is bonded to an oxygen atom. B: a group that binds to a terminal oxygen atom in the -AO- group or a group that binds to an oxygen atom derived from a hydroxyl group of a polyhydric alcohol having four or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose and glucopyranose) And is a hydrogen atom or And / or [Chemical formula 2] Indicates. Here, R represents a branched alkyl group having 16 to 36 carbon atoms. Provided that at least one of y groups B is And / or [Chemical formula 4] Is. X: [Polyhydric alcohol having 4 or more hydroxyl groups (sucrose,
Fructofuranose, fructopyranose, and glucopyranose), and the total number of moles of alkylene oxide added to the hydroxyl group] / y is 0 to 10. y: Indicates the number of hydroxyl groups in a polyhydric alcohol having 4 or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose and glucopyranose). ] 2. In the general formula (1), G is pentaerythritol, sorbitol, mannitol, glycosides, polyglycerin represented by the following general formula (2) or an alkylene oxide adduct of at least one of them. The glyceryl etherified polyhydric alcohol according to claim 1, which is a residue obtained by removing hydrogen atoms of all hydroxyl groups in the polyhydric alcohol. [Chemical 5] (In the formula, a represents a number of 2 to 20.) 3. Glycosides having an alkyl group having 1 to 22 carbon atoms, which may have a linear or branched hydroxyl group, an alkenyl group or an alkyl ether group as G aglycone in the general formula (1). 3. The glyceryl etherified polyhydric alcohol according to claim 2, which is a residue obtained by removing hydrogen atoms of all the hydroxyl groups in 3. 4. In the general formula (1), G is a sugar condensation degree of 1.
4. The glyceryl etherified polyhydric alcohol according to claim 3, which is a residue obtained by removing hydrogen atoms from all the hydroxyl groups of the glycosides of .about.2. 5. In the general formula (1), G is methyl glucoside, ethyl glucoside, methyl maltoside, maltitol or 2,3-dihydroxypropylene glucoside, which is a residue obtained by removing hydrogen atoms from all hydroxyl groups. 4. The glyceryl etherified polyhydric alcohol according to 4. 6. In the general formula (1), R is the following general formula (3): (In the formula, p and q each represent an integer of 0 to 33, and the sum of p and q is 13 to 33.) The glyceryl etherified polyhydric alcohol according to claims 1 to 5. 7. In the general formula (1), R is the following general formula (4): (In the formula, r and s each represent an integer of 0 to 31, and the sum of r and s is 11 to 31.) The glyceryl etherified polyhydric alcohol according to claims 1 to 5. 8. A polyhydric alcohol having four or more hydroxyl groups represented by the general formula (5) (excluding sucrose, fructofuranose, fructopyranose and glucopyranose).
Alternatively, an alkylene oxide adduct thereof and G [(AO) _x H] _y (5) [wherein G, A, x, and y have the above-mentioned meanings]. H is -A
A hydrogen atom bonded to the terminal oxygen atom in the O-group or a hydrogen atom bonded to the oxygen atom derived from the hydroxyl group of a polyhydric alcohol having four or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose and glucopyranose). is there. ] General formula (6) (In the formula, R represents a branched alkyl group having 16 to 36 carbon atoms.)
The glycidyl branched alkyl ether represented by the formula (1) is reacted in the presence of a basic catalyst.
A method for producing the glyceryl etherified polyhydric alcohol described. 9. A polyhydric alcohol having 4 or more hydroxyl groups (excluding sucrose, fructofuranose, fructopyranose and glucopyranose), pentaerythritol,
The method for producing a glyceryl etherified polyhydric alcohol according to claim 8, which is at least one selected from sorbitol, mannitol, glycosides, polyglycerin represented by the general formula (2), and alkylene oxide adducts thereof.