JPH0819733A - Surfactant - Google Patents

Abstract

PURPOSE:To provide a surfactant with high water-solubility and excellent function by containing alkylglycoside whose alkyl chain is a single and which contains beta-type in a specified ratio. CONSTITUTION:A surfactant consists of glycoside having an aliphatic group expressed by a formula; R-O[m(CnH2n-1On-1)-(m-1)H2O] wherein R stands for an aliphatic group with 6-22 carbon atoms n for 5-6, and m for 1-4. The glycoside has alpha-type and beta-type in weight ratio alpha/beta, (40/60)-(0/100). Consequently, to give that specified ratio, a method in which alpha-type and beta-type are separated and refined respectively to produce highly pure alpha-type and beta-type and to mix then in a specified ratio is employed or a method in which beta-type is added to a prior art mixture of alpha-type and beta-type is empolyed. A surfactant obtained in that way is mild for human bodies and excellent in has high water-solubility and foaming property.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surfactant which is excellent in mildness to the human body, and is also excellent in basic properties such as water solubility and foam performance.

[0002]

2. Description of the Related Art Conventionally, as a method for industrially producing a glycoside having an aliphatic group (hereinafter, also simply referred to as an alkyl glycoside), a Fischer method in which a sugar and an aliphatic alcohol are reacted in the presence of an acid catalyst. [BIO IN
DUSTRY, 10, 408 (1993)] is generally adopted. The alkyl polyglycoside obtained by such a method is composed of an α-form and a β-form in which a sugar chain portion is polymerized. The weight ratio of α-form / β-form in the alkyl glycoside is about 1/1 in the initial stage of the reaction, but when the reaction is carried out for a sufficient time to achieve a high yield,
The body ratio increases, and the weight ratio of α body / β body becomes about 2/1. The alkyl polyglycoside has a surface-active action due to the hydrophilicity of the sugar residue and the hydrophobicity of the alkyl group, and has applications as an emulsifier and a detergent. But,
Conventional alkyl polyglycosides have not yet been satisfactory in their surfactant action.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a surfactant comprising an alkyl glycoside, which has good water solubility and improved surfactant activity.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that, in an alkyl glycoside having a single alkyl chain, those containing β-form at a specific ratio are good. The present invention has been completed based on the finding that it has excellent water-solubility and an excellent surface-active effect. That is, according to the present invention, the general formula R-O- _{[m (C n H 2n-1} O n-1) - (m-1) H 2 O ] (1) (wherein, R 6 carbon atoms To 22 aliphatic groups, n is a number of 5 to 6 and m is a number of 1 to 4).
Weight ratio α / β of body to β body is 40/60 to 0/100
There is provided a surfactant characterized by being in the range of.

The alkyl glycoside used as the surfactant in the present invention is represented by the above general formula (1). In the formula, -O- _{[m (C n H 2n-1} O n-1) - (m-
1) H ₂ O] represents a sugar residue. n shows the number of 5-6. m represents the number of monosaccharide bonds, and is 1 to 4, preferably 1 to
It is 2. R represents an aliphatic group having 6 to 22 carbon atoms. As the sugar residue in the general formula (1), those derived from various sugars can be used, and the following can be illustrated as typical examples of the sugar. (1) monosaccharide The monosaccharides are represented by the following general formula _{C n H 2n O n (2} ). In the above formula, n represents a number of 5 to 6. Examples of such a monosaccharide include arabinose, ribose, xylose, xylylose, ribulose, 2-deoxyribose, glucose, galactose, fructose, mannose, sorbose, talose, 2-deoxyglucose, 6-deoxygalactose, 6-deoxymannose, 2-deoxygalactose, fucose, glucoheptose, sedoheptulose, mannoheptulose, glucoheptulose, etc. can be mentioned.

(2) Oligosaccharide This oligosaccharide is represented by the following general formula. _{m (C n H 2n O n} ) - (m-1) H 2 O (3) In the formula, n is a number of 5-6. m represents a number of 1 to 4, preferably 1 to 2. Such oligosaccharides include:
Maltose, lactose, lactose, cellobiose,
Examples thereof include isomaltose, gentiobiose, laminaribiose, xylobiose, mannobiose, maltotriose, cellotriose, manninotriose, maltotetraose and the like.

As the aliphatic group R in the general formula (1), one having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms is used. The aliphatic group can be saturated or unsaturated and can be linear or branched. As such an aliphatic group, n-
Hexyl, n-heptyl, n-octyl, n-nonyl,
n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-
Linear alkyl groups such as pentadecyl, n-octadecyl, n-nonadecyl; branched chains such as 1-methyl-pentyl, 1-ethyl-butyl, 1-methyl-hexyl, 1-methyl-heptyl, 1-butyl-hexyl Alkyl group; 2
Examples thereof include alkenyl groups such as -octenyl, 4-tetradecenyl and oleyl.

In the surfactant comprising the alkyl glycoside of the present invention, the mixing weight ratio α / β of α-form and β-form is:
40 / 60-0 / 100, preferably 10 / 90-0 /
The range is 100. When the weight ratio α / β of the α-form and the β-form is lower than the above range, the water solubility of the alkyl glycoside becomes poor, and problems such as precipitation of crystals from the aqueous solution and low foam stability occur.

In order to obtain a mixture of the α-form and the β-form of the alkyl glycoside of the present invention, the α-form and the β-form containing a high content of the α-form produced by the conventional method are
And β-form are separated and purified to produce high-purity α-form and β-form, and the α-form and β-form are mixed at a predetermined ratio, or α-form and β-form with high α-form content To the mixture of the body, β
The method of adding the body in a specified ratio, α with a high content of α-body
An enzyme that selectively hydrolyzes α-alkyl glycosides, for example, α-amylase, α-
Α-Glycosidases such as glucosidase, α-galactosidase and α-mannosidase, and α such as α-transglycosidase and α-galactosyltransferase.
-A method of hydrolyzing in the presence of transglycosidase and the like can be mentioned. It is also possible to employ a method of mixing the α-form with a high-purity β-form produced in advance at a predetermined ratio.

As a method for producing β-alkyl glycoside, there can be shown a method of reacting an aliphatic alcohol with a sugar in the presence of an enzyme. In this case, the enzyme is
Those that generate an alkyl glycoside having a β bond at the anomeric position are used. Such enzymes include β
-Amylase, β-glucosidase, β-galactosidase, β-mannosidase, β-cellulase, β-glucanase and other glycosidases, β-transglycosidase, β-galactosyltransferase and other β-
Examples thereof include transglycosidase. These β-glycosidase and β-transglycosidase can be derived from microorganisms, plants and animals, and any of them can be used, but particularly β-glucosidase derived from almond having high alkylglycoside synthetic activity. It is preferable to use those derived from plants such as. These enzymes can be crude or purified enzymes. Further, these enzymes may be free enzymes, or may be immobilized by being immobilized on a carrier such as a polymer material or an inorganic material by an ionic bond method, a chemical reaction bond method, a physical adsorption method, or the like. It may be a phosphatase. When an immobilized enzyme is used, the immobilized enzyme can be separated and reused in a reaction solution, and by packing the column, it can be used as an immobilized enzyme packed column capable of continuous reaction. be able to.

When the β-alkyl glycoside is produced using an enzyme, the sugar and the aliphatic alcohol are reacted in the reaction solvent in the presence of the enzyme. The reaction temperature is 10 to 120 ° C, preferably 40 to 80 ° C. The reaction time is 2 to 60 hours, preferably 6 to 48 hours. The pH is 4-9, preferably 5-8. The water content in the reaction system is 1 to 30% by weight, preferably 2 to 15% by weight. The amount of enzyme is 0.1 to 3% by weight, especially 0.5 to 1 based on the total reaction mixture.
It is preferable to set it in the range of 0% by weight. The amount of the aliphatic alcohol may be at least equivalent to the sugar, but when the aliphatic alcohol is also used as the reaction solvent,
It is preferable to use it in a molar ratio of 50 to 400 times. As the reaction solvent, hydrocarbons such as n-hexane and n-octane; ethers such as diglyme, 1,4-dioxane and tetrahydrofuran; carbon number of t-butanol, t-amyl alcohol, diacetone alcohol, isopropanol and the like is 6 Less than secondary or tertiary alcohols; pyridine,
Nitrogen-containing compounds such as β-picoline, dimethylformamide, acetonitrile, succinonitrile, and N-methylacetamide can be used. The reaction solvent is used in a proportion of 10 to 90% by weight in the whole reaction mixture. The high-purity β-alkylglucoside thus obtained is mixed with an appropriate amount of the α-form content alkylglycoside obtained by the conventional Fischer method to prepare a surfactant composition of the present invention easily. Obtainable.

When the α-form of the alkyl glycoside having a high α-form content obtained by the conventional Fisher method is selectively hydrolyzed in the presence of an enzyme to obtain the surfactant composition of the present invention, As the enzyme, one capable of selectively hydrolyzing the α bond at the sugar anomer position is used, and examples of such an enzyme include α-amylase, α-glucosidase, α-galactosidase, α-mannosidase and the like α- Glucosidase, α-transglucosidase,
Examples include α-transglycosidases such as α-galactosyltransferase. The reaction of selectively hydrolyzing the α-form in the presence of this enzyme can be carried out in the same manner as described above for the production of β-alkyl glycosides.

[0013]

Next, the present invention will be described in more detail with reference to examples. Reference Example 1 150 parts by weight of octyl glucoside having a mixed weight ratio of α-form and β-form obtained by the Fischer method was dissolved in methanol as a solvent at a concentration of 80% by weight, and this solution was subjected to anion exchange. Resin (Brand name: Dowex 1, OH
Mold, particle size 200-400 mesh, Dow Chemical Co.)
After being adsorbed on a column packed with, methanol was passed through the adsorption column as an eluent to separate the α-form and the β-form by adsorption.
By this adsorption separation, 72 parts by weight of α form and 41 parts by weight of β form were obtained with a purity of 100%.

Example 1 The α-octylglucoside and β-octylglucoside obtained in Reference Example 1 were mixed in a weight ratio (α / β) shown in Table 1, and 10 ml of a 0.5% by weight aqueous solution of this mixture was added. After placing in an Epton tube (100 ml) and keeping the temperature constant in a water bath at 35 ° C., shaking 20 times, foaming height A 30 seconds after the end of shaking, foaming height B 5 minutes later and after 10 minutes The foam height C was measured. Furthermore, the water solubility at room temperature was evaluated. Table 1 shows the results.

[0015]

[Table 1]

Claims (2)

[Claims] 1. A general formula R-O- _{[m (C n H 2n-1} O n-1) - (m-1) H 2 O ] (1) (wherein, R 6 to 22 carbon atoms An aliphatic group, n is a number of 5 to 6 and m is a number of 1 to 4).
Weight ratio α / β of body to β body is 40/60 to 0/100
A surfactant characterized by being in the range of. 2. m in the general formula (1) is 1 or 2
The surfactant according to claim 1, which is