JP2001328996A - Alkylglycoside and method for producing alkylglycoside - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkylglycoside having good hue and stability thereof. SOLUTION: This alkylglycoside for surfactant or cosmetic base has <-5 Gardner hue of 30 wt.% aqueous solution of an alkylglycoside having pH 12 to 14 exhibited after the solution is allowed to stand for three days at 25 deg.C. This method for producing an alkylglycoside comprises reacting saccharides with monohydric alcohol in the presence of an acid catalyst and then treating the reaction product with an absorbent containing a complex metal oxide in an amount of 0.5-50 wt.% based on total weight of saccharides, monohydric alcohol and components other than the above components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkyl glycoside useful as a surfactant, a cosmetic base and the like, and a method for producing an alkyl glycoside having a good hue and its stability. .

[0002]

BACKGROUND OF THE INVENTION Alkyl glycosides, which are useful as surfactants, have become indispensable due to interesting physical properties, excellent biodegradability and high safety to the human body. These alkyl glycosides need to have good hue and odor in order to be used in household products, especially in the cosmetics field. In addition, although they are also used in the field of detergents based on their excellent properties such as foaming properties and permeability, since detergents are mostly alkaline, they tend to be strongly colored when an alkylglycoside is added as an alkaline detergent. Was. Conventional methods for producing alkyl glycosides include a method of directly reacting a saccharide with an alcohol in the presence of an acid catalyst, as typified by EP132046, and a method of typified by JP-A-64-47796, The method can be broadly divided into a method in which a lower alkyl glycoside obtained by reacting with a lower alcohol such as butanol is subjected to an acetal exchange reaction with a higher alcohol. However, the hue of the alkyl glycoside obtained by any of these methods was not satisfactory.

[0003] For this reason, the hue has been improved by combining various purification methods before and after the reaction. JP-A-61-33193 discloses a method in which the obtained alkyl glycoside is bleached with hydrogen peroxide or the like. JP-A-64-71895 discloses a method in which the obtained alkyl glycoside is treated with activated carbon. -29069
In JP-A-2-88593, a method of hydrogenating the obtained alkyl glycoside, in JP-A-2-88593, a method of removing a coloring substance from the obtained alkylglycoside by extraction with an organic solvent, and in JP-A-4-124196, A method of reacting an alcohol with a saccharide in the presence of an adsorbent, and the like are disclosed. However, none of these methods
There were problems such as unsatisfactory hue improvement, lack of storage stability, complicated processes, and the necessity of large-scale dedicated equipment, which were not satisfactory.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to an alkyl glycoside useful as a surfactant or a cosmetic base and a method for producing an alkyl glycoside, and to provide an alkyl glycoside having a good hue and its stability. Aim.

[0005]

That is, the present invention provides:
(1) After an elapse of 3 days at 25 ° C. with a 30% by weight aqueous solution of an alkyl glycoside having a pH of 12 to 14, the hue becomes Gardner 5
(2) A method for producing an alkyl glycoside by reacting a saccharide and a monohydric alcohol in the presence of an acid catalyst, wherein the alkyl glycoside for a surfactant or a cosmetic base is characterized by the following: , Sugars, monohydric alcohol and other components other than water.
A method for producing an alkyl glycoside to be treated with an adsorbent containing 5 to 50% by weight of a composite metal oxide, (3) a metal oxide of the adsorbent containing a composite metal oxide is 20 to 80% by weight of magnesium oxide, And aluminum oxide 10
(2) The method for producing an alkyl glycoside according to (2), which contains 60% by weight, and (4) the treatment of the adsorbent containing the composite metal oxide, with respect to the total weight of components other than water and the adsorbent, from 1 to 300 Performed in the presence of water by weight (2)
Or (3) a method for producing an alkyl glycoside.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the production method of the present invention, a saccharide, a monohydric alcohol and an acid catalyst are put into a reaction vessel, and the reaction is allowed to proceed under reflux or reduced pressure while removing by-produced water. The product is treated with an adsorbent containing a substance to obtain an alkyl glycoside. As saccharides, monosaccharides, oligosaccharides and the like can be used. Specific examples include monosaccharides such as glucose, mannose, galactose, talose, fructose, sorbose, tagalose, arabinose, xylose, ribose, ribulose and lyxose, and maltose, lactose, maltotriose,
Oligosaccharides such as cellobiose can be mentioned, and among them, reducing sugars of hexacarbon sugars such as glucose, mannose and galactose are preferable.

The monohydric alcohol includes saturated alcohols such as methanol, ethanol, isopropanol, butanol, hexanol, 2-ethylhexanol, octanol, decanol, dodecanol, tridecanol, tetradecanol, hexadecanol, octadecanol, and oleyl alcohol. And unsaturated alcohols such as icosyl alcohol, natural alcohols derived from coconut oil, palm oil, palm kernel oil, sunflower oil, tallow, lard, and the like, and mixtures thereof. In this case, the alkyl group may be linear or branched. Preferably,
It is a linear alcohol having 1 to 12 carbon atoms. The ratio of the saccharide to the alcohol in the reaction is 1 to 20 mol, preferably 2 to 10 mol of the alcohol per 1 mol of the saccharide. 1
When the amount is less than the mole, the reaction rate decreases, and when the amount is more than 20 mole, the production is difficult.

As the acid catalyst, for example, hydrochloric acid, phosphoric acid,
Examples include sulfuric acid, paratoluenephosphonic acid, paratoluenesulfonic acid, strong cation exchange resins, or mixtures thereof, with paratoluenesulfonic acid being preferred. The amount of the acid catalyst used is 1 to 200 mmol per 1 mol of saccharide,
Preferably it is 5 to 50 mmol. When the amount is less than 1 mmol, the reaction rate is low, and when the amount is more than 200 mmol, coloring may be caused.

The reaction temperature is 80 to 200 ° C., preferably 1 to
00 ° C to 150 ° C. If the temperature is lower than 80 ° C., the reaction rate is low, and if it is higher than 200 ° C., it causes coloring. In general, the reaction of the alkyl glycoside proceeds by removing generated water to the outside of the system at the above-mentioned temperature. However, if necessary, the reaction can be further progressed by removing water to the outside of the system at a vacuum pressure at which alcohol does not evaporate.

The adsorbent containing a composite metal oxide is generally, for example, a silica / alumina adsorbent, zeolite, hydrotalcite, etc. Among them, magnesium oxide as a metal oxide is 20 to 80% by weight. Further, an adsorbent containing 10 to 60% by weight of aluminum oxide is preferable, and an adsorbent containing 40 to 70% by weight of magnesium oxide and 20 to 50% by weight of aluminum oxide is more preferable, which is effective in improving hue. The adsorbent containing the composite metal oxide is more effective when activated by firing. The firing activation temperature is 200 to 1000 ° C. and 2
It is common to treat for ~ 6 hours. Adsorbents containing composite metal oxides are commercially available, for example, Kyowad 300 and Kyowad 50 manufactured by Kyowa Chemical Industry Co., Ltd.
0, KYOWARD 1000, KYOWARD 2000, TOMIX AD300 manufactured by Tomita Pharmaceutical Co., Ltd., and the like.

The amount of the adsorbent containing the composite metal oxide is 0.5 to 50% by weight, preferably 1 to 2% by weight based on the total weight of the saccharide, the monohydric alcohol and other components other than water.
0% by weight, more preferably 2 to 10% by weight. 0.
If the amount is less than 5% by weight, the hue is not sufficiently improved even if the treatment is carried out. Usually, the processing temperature is 30 to 100
° C, preferably 50 to 90 ° C. If the temperature is lower than 30 ° C., it takes too much processing time, and if it is higher than 100 ° C., coloring may be caused. Usually, the processing time is 30 minutes to 2 hours. Further, this treatment step is more effective when performed in the presence of water. The water content is 1 to 300% by weight, preferably 10 to 100% by weight, based on the total weight of components other than water and the adsorbent. After the treatment, it is preferable to remove the adsorbent by filtration, centrifugation or the like. Components other than water and the adsorbent are saccharides, monohydric alcohols, acid catalysts, and solvents other than water.

The production method of the present invention is not limited to the direct method described above. First, a lower alkyl glycoside obtained by reacting with an alcohol having 1 to 4 carbon atoms is converted to a lower alkyl glycoside having 1 carbon atom.
The method is also applicable to a method of acetal exchange reaction with an alcohol of 0 to 18 (acetal exchange method). After the reaction of the higher alkyl glycoside is completed, it can be treated with an adsorbent containing a composite metal oxide.

Further, after the alkyl glycoside reaction and before the adsorbent treatment, the acid catalyst is neutralized with an alkali metal or alkaline earth metal hydroxide, carbonate, alcoholate or the like, or unreacted alcohol or solvent is decompressed. It can also be removed below. Further, after the adsorbent is separated by the adsorption treatment, neutralization and removal of unreacted alcohol can be performed.
In the production method of the present invention, it is necessary to perform the adsorbent treatment after reacting the saccharide and the monohydric alcohol in the presence of an acid catalyst. In the pre-reaction treatment, there is no decolorizing effect, and in the reaction in the presence of the adsorbent, the catalyst is deactivated and the reaction does not proceed. In addition, when the reaction is continued without stopping after the reaction is completed, by-products are likely to be generated. By performing the adsorbent treatment after the reaction is completed, an alkyl glycoside having excellent hue and stability can be obtained.

The alkyl glycoside obtained by the production method of the present invention can be used as a surfactant, a cosmetic base and the like. Preferably, it can be used as a surfactant. Among them, a surfactant comprising a 30% by weight aqueous solution of an alkyl glycoside having a pH of 12 to 14 and an alkyl glycoside having a hue of 5 or less Gardner after 25 days at 25 ° C. is particularly preferable, and is useful as a surfactant having excellent hue stability. It is. As a method for evaluating the storage stability in an alkaline aqueous solution, a 30% by weight aqueous solution of an alkyl glycoside was prepared, and 5 g of sodium hydroxide was added thereto.
For 3 days, and then measure the hue. The pH at that time is 12-14.

[0015]

EFFECT OF THE INVENTION The alkyl glycoside produced by the production method of the present invention has excellent color stability immediately after production and long-term color stability even in an alkaline solution, so that it is suitably used as a surfactant or a cosmetic base. it can.

[0016]

Next, the present invention will be described with reference to examples and comparative examples. Example 1 Synthesis of butyl glucoside 518 g (7 mol) of n-butanol, glucose 180
g (1 mol), p-toluenesulfonic acid monohydrate 2.8
5 g (15 mmol) was charged into a four-necked flask, and stirred while blowing in nitrogen, and the temperature was raised to 120 ° C. The temperature was maintained at normal pressure, and the mixture was refluxed for 4 hours while removing by-product water out of the system. After the reaction, 20 g of Kyoward 2000 (content: 59.2% by weight of magnesium oxide, 33.0% by weight of aluminum oxide) manufactured by Kyowa Chemical Industry Co., Ltd. (total of components other than saccharides, monohydric alcohol and water) 2.85% by weight).
After treatment at 80 ° C. for 1 hour, the mixture was filtered to remove the adsorbent. Thereafter, in order to remove the contained n-butanol, the pressure was reduced to -0.0.
The mixture was treated at 092 MPa (50 mmHg) and 120 ° C. for 1 hour, and the remaining solid was dissolved in water to obtain a 30% butylglucoside aqueous solution.

Example 2 Synthesis of butyl glucoside After reacting butyl glucoside under the conditions of Example 1, water 1
40 g (20.0% by weight based on the total weight of components other than water and the adsorbent) and 20 g of Kyowa 2000 manufactured by Kyowa Chemical Industry Co., Ltd. (to the total weight of components other than sugars, monohydric alcohol and other water) 2.85% by weight), treated at 80 ° C. for 1 hour, and filtered to remove the adsorbent. Thereafter, the pressure was reduced to remove the contained n-butanol.
The mixture was treated at 0.092 MPa (50 mmHg) and 120 ° C. for 1 hour, and the remaining solid was dissolved in water to obtain a 30% butylglucoside aqueous solution.

Example 3 Synthesis of decylglucoside 1106 g (7 mol) of n-decanol, glucose 18
0 g (1 mol), paratoluenesulfonic acid monohydrate
8 g (20 mmol) was charged into a four-necked flask, and stirred while blowing nitrogen, and the temperature was raised to 120 ° C. Decompression-
Keep the above temperature at 0.07 MPa (200 mmHg),
The system was refluxed for 6 hours while removing by-product water out of the system. After completion of the reaction, 200 g of water (15.5% by weight based on the total weight of components other than water and the adsorbent) and 35 g of Kyoward 2000 manufactured by Kyowa Chemical Industry Co., Ltd. (excluding sugars, monohydric alcohols and other water) (2.71% by weight based on the total weight of the components), and the mixture was treated at 80 ° C. for 1 hour and filtered to remove the adsorbent. Thereafter, the pressure was reduced to -0.99 MPa (10 mmH) to remove the contained n-decanol.
g), and treated at 150 ° C. for 1 hour, and the remaining solid content was dissolved in water to obtain a 30% aqueous solution of decylglucoside.

Example 4 Synthesis of decylglucoside 1106 g (7 mol) of n-decanol, 787 g (1 mol) of the aqueous butylglucoside solution obtained in Example 1, 3.8 g (20 mmol) of paratoluenesulfonic acid monohydrate
Was charged into a four-necked flask, and stirred while blowing in nitrogen, and the temperature was raised to 120 ° C. Decompression -0.07 MPa (20
The temperature was maintained at 0 mmHg), and the mixture was refluxed for 6 hours while removing water and butanol out of the system. After completion of the reaction, 200 g of water (14.4% by weight based on the total weight of components other than water and the adsorbent) and 35 g of Kyoward 2000 manufactured by Kyowa Chemical Industry Co., Ltd. (sugars, monohydric alcohols and other components other than water) (2.60% by weight based on the total weight of the components), and the mixture was treated at 80 ° C. for 1 hour and filtered to remove the adsorbent. Thereafter, in order to remove the contained n-decanol, the pressure was reduced to -0.99 MPa (10 mmHg) at 150 ° C. for 1 hour.
After a time treatment, the remaining solid content was dissolved in water to obtain a 30% aqueous solution of decylglucoside.

Example 5 After the reaction of decyl glucoside under the conditions of Example 4, water 2
00g (14.9% by weight based on the total weight of components other than water and the adsorbent) and Tomix AD3 manufactured by Tomita Pharmaceutical Co., Ltd.
35 g (content: 13.2% by weight of magnesium oxide, 31% by weight of aluminum oxide, 30.5% by weight of silicon dioxide) based on the total weight of components other than saccharides, monohydric alcohol and water. 60% by weight)
After treatment at 80 ° C. for 1 hour, the mixture was filtered to remove the adsorbent. Thereafter, the pressure was reduced to -0.1 to remove the contained n-decanol.
The mixture was treated at 099 MPa (10 mmHg) and 150 ° C. for 1 hour, and the remaining solid was dissolved in water to obtain a 30% aqueous solution of decylglucoside.

Comparative Example 1 After reacting butyl glucoside under the conditions of Example 1, the mixture was neutralized with an appropriate amount of a 1 mol / L aqueous sodium hydroxide solution, and the solid matter in the reaction vessel was filtered. N contained in the filtrate
-Reduced pressure to remove butanol-0.092 MPa
(50 mmHg) at 120 ° C. for 1 hour, and the remaining solid was dissolved in water to obtain a 30% aqueous butylglucoside solution.

Comparative Example 2 After reacting butyl glucoside under the conditions of Example 1, neutralized with an appropriate amount of 1 mol / L aqueous sodium hydroxide solution, added 20 g of activated carbon, treated at 80 ° C. for 1 hour, and filtered to remove the activated carbon. Removed. Thereafter, to remove the n-butanol contained in the filtrate, the pressure was reduced to -0.092 MPa (50 mmH).
g) and treated at 120 ° C. for 1 hour, and the remaining solid content was dissolved in water to obtain a 30% butylglucoside aqueous solution.

Comparative Example 3 n-Butanol 518 g (7 mol), glucose 180
g (1 mol), p-toluenesulfonic acid monohydrate 2.8
5 g (15 mmol) and 20 g of activated carbon were charged into a four-necked flask, and heated to 120 ° C. while stirring and blowing nitrogen. The temperature was maintained at normal pressure, and the mixture was refluxed for 4 hours while removing by-product water out of the system. Thereafter, the activated carbon was removed by filtration and neutralized with an appropriate amount of a 1 mol / L aqueous sodium hydroxide solution. Reduced pressure -0.092 MPa (50 mmHg), 120 to remove contained n-butanol
C. for 1 hour, dissolve the remaining solids in water, 30%
An aqueous butylglucoside solution was obtained.

Comparative Example 4 After reacting decyl glucoside under the conditions of Example 3, 35 g of highly active magnesium oxide (Kyowa Mag 150 manufactured by Kyowa Chemical Industry Co., Ltd.) (total of components other than saccharides, monohydric alcohol and water) was used. (2.71% by weight based on the weight), treated at 80 ° C. for 1 hour, and filtered to remove the adsorbent.
Then, the pressure was reduced to remove the contained n-decanol.
The mixture was treated at 0.099 MPa (10 mmHg) and 150 ° C. for 1 hour, and the remaining solid was dissolved in water to obtain a 30% aqueous solution of decylglucoside.

[0025]

[Table 1]

0.5 g of sodium hydroxide was dissolved in 100 g of each aqueous solution of the alkyl glucoside and the hue of the aqueous solution of the alkyl glucoside immediately after production in Examples 1 to 5 and Comparative Examples 1 to 4. The hue after standing for 3 days was compared and observed. Hue is APHA: JIS K-1
557 6.2, Gardner: JIS K-6901
Comparing Examples 1 to 5, which were measured in accordance with 4.2, with Comparative Examples, Examples 1 to 5, which are alkyl glycosides produced by the production method of the present invention, except for Comparative Example 3, immediately after production, The hue after 3 days is excellent. Comparative Example 3 was at the same level as the Example immediately after the production, but was inferior in hue stability in an aqueous alkaline solution. The alkyl glycoside produced by the production method of the present invention showed a hue immediately after the production and storage stability in an aqueous alkaline solution. It can be seen that both properties are excellent.

Claims (4)

[Claims] 1. An alkyl glycoside 30 having a pH of 12 to 14.
An alkylglycoside for a surfactant or a cosmetic base, which has a hue of not more than 5 Gardner after 3 days at 25 ° C. in a weight% aqueous solution. 2. A process for producing an alkyl glycoside by reacting a saccharide with a monohydric alcohol in the presence of an acid catalyst, wherein after the reaction, the total weight of the saccharide, monohydric alcohol and other components other than water is reduced to 0. A method for producing an alkyl glycoside, which is treated with an adsorbent containing 0.5 to 50% by weight of a composite metal oxide. 3. The method for producing an alkyl glycoside according to claim 2, wherein the metal oxide of the adsorbent containing the composite metal oxide contains 20 to 80% by weight of magnesium oxide and 10 to 60% by weight of aluminum oxide. 4. The method according to claim 1, wherein the treatment of the adsorbent containing the composite metal oxide is performed in an amount of 1 to 5% based on the total weight of the components other than water and the adsorbent.
The method for producing an alkyl glycoside according to claim 2 or 3, wherein the method is carried out in the presence of 300% by weight of water.