JPH08243374A - Glycolipid type surfactant - Google Patents

Abstract

PURPOSE: To obtain a safety glycolipid type surfactant large in biodegradability and useful as a surfactant by preparing surfactant from a mixture of a specific acylglucose and a specific fructose compound. CONSTITUTION: In the glycolipid surfactant useful for foods, cosmetics, drugs, toiletry products or the like, the surfactant is prepared by using the mixture of an acylglucose expressed by formula 1 and a fructose compound expressed by formula 11. The mixture is produced by hydrolyzing glycoside bond of a sucrose fatty acid ester by enzymatic decomposition or under an acidic condition. In formula 1, R expresses a 6-24C alkyl group or alkenyl group and in formula 11, X expresses hydrogen or an acyl group having a 6-24C alkyl group or alkenyl group. As the alkyl group or alkenyl group, octyl, decyl, dodecyl, stearly, eicosyl, octynyl, decenyl and the like are mentioned.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a glycolipid-type surfactant and a surface-active compound thereof which can be widely used in various industrial fields related to foods, cosmetics, quasi drugs, pharmaceuticals, toiletry products, detergents and the like. The present invention relates to a manufacturing method of.

[0002]

2. Description of the Related Art In recent years, glycolipid-type surfactants are mildly biodegradable in the living body, and because they are non-ionic, they have a large emulsifying / dispersing effect, and have a colloid-stabilizing effect and acid / salt resistance It is attracting attention because it is shown. Among these are sucrose fatty acid esters [Toshinobu Yamada, Nobuyuki Kawase, Kenji Ogimoto,
Oil Chemistry, 29, 543 (1980)] and, maltotriose fatty acid ester (JP-54-25930), alkyl glycoside [Toshiyuki Sakakibara, oil chemistry, 39, 451 (1
990); Shuichi Matsumura, Kazuyasu Imai, Sadao Yoshikawa, Kazuo Kawada,
Takeshi Uchibori, J. Am. Oil Chem. Soc. , 6
7 , 996 (1990)], dextrin fatty acid ester (JP-A-56-81301), gluconolactone derivative (JP-A-3-251580), acyl hyaluronic acid (JP-B-5-77450), enzymatically synthesized acyl glucose [G. Ljuger, P.M. Adlecreuz.
B. Mattiasson, Biotechnol.
Lett. , 16 , 1167 (1994)], and methyl or ethyl-α-D-glycoside stearate [Karime Takao, "Talking about food additives", Kenseisha (1993)]. Furthermore, trehalose lipid, rhamnose lipid, etc. are known as biosurfactants derived from microorganisms [Yugami Ishigami, Surface, 27 , 457 (1989)]. Based on such studies, the present inventors have earnestly studied the correlation between the chemical structure of sucrose fatty acid ester and its property, and as a result, hydrolyzing the sucrose fatty acid ester results in a good surfactant action. It was found that a glycolipid type surfactant having

[0003]

The present invention provides a glycolipid type surfactant useful as a safe and highly biodegradable surfactant, and a method for producing the surfactant compound. It is an issue.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an acyl glucose and a fructose compound obtained by hydrolyzing a glycoside bond of a sucrose fatty acid ester are obtained. The mixture is excellent in surface tension lowering action, interfacial tension lowering action, foamability, foam stability, emulsification action, aqueous solution thickening action, membrane protein extraction action, protein denaturation prevention action, safety against biological cells, etc. It was found that the above effects are exhibited, and the present invention has been completed. That is, according to the present invention, there is provided a surfactant comprising a mixture of an acyl glucose represented by the following general formula (I) and a fructose compound (II) represented by the following general formula (II). Further, according to the present invention, an acyl glucose represented by the following general formula (I) and the following general formula (I
A method for producing a mixture of fructose compounds represented by I), wherein the glycoside bond of the sucrose fatty acid ester represented by the following general formula (III) is hydrolyzed.

Embedded image (In the formula, R represents an alkyl group or an alkenyl group having 6 to 24 carbon atoms)

Embedded image (In the formula, X represents hydrogen or an acyl group having an alkyl group or an alkenyl group having 6 to 24 carbon atoms)

Embedded image (In the formula, R and X have the same meanings as described above.)

R in the above general formulas (I), (II) and (III) represents an alkyl group or an alkenyl group, the carbon number of which is 6 to 24, preferably 8 to 22. Examples of such alkyl group or alkenyl group include octyl, decyl, dodecyl, stearyl, eicosyl, octynyl, decenyl, dodecenyl, heptadecenyl, eicosenyl and the like. The surfactant of the present invention comprises a mixture of acyl glucose and a fructose compound,
When used, their total concentration should be 0.01-5.
It may be added to the target liquid so that the amount of the amount is preferably 0.1 to 2% by weight. The ratio of the acyl glucose to the fructose compound is 1/1 to 1/0, preferably 1/1 to 1 / 0.5, and more preferably 1/1 to 1/0 by weight ratio.
It is 1 / 0.8.

The surfactant of the present invention is a nonionic surfactant whose lipophilic group is composed of fatty acid monoester and hydrophilic group is composed of glucose or fructose, and which is obtained by hydrolysis of glycoside bond of sucrose fatty acid ester. It can be manufactured. Hydrolysis of the glycoside bond of the sucrose fatty acid ester can be carried out by a conventionally known method, for example, enzymatic hydrolysis or hydrolysis under acidic conditions. For example, a sucrose fatty acid ester is added in an aqueous medium having a pH of 3 to 6 by adding a glycoside bond-hydrolyzing enzyme such as invertase as an enzyme to 70%.
It can be carried out by stirring at a temperature of not higher than 0 ° C. for several hours to react.

The reaction raw material used in the present invention is a sucrose fatty acid ester represented by the above general formula (III) or a fatty acid esterified product of sucrose containing this as a main component.
Fatty acid esterification products of sucrose include monoesterification products, diesterification products and triesterization products of sucrose,
The reaction raw material used in the present invention preferably contains a monoester compound in an amount of 50% by weight or more, and preferably 60% by weight or more. The surfactant of the present invention is obtained by hydrolyzing the sucrose fatty acid ester, but in this case, unreacted sucrose fatty acid ester contained in the reaction product,
Glucose triesters and the like do not necessarily have to be separated.

[0008]

INDUSTRIAL APPLICABILITY The glycolipid type surfactant of the present invention is useful as a surfactant which is safe for living organisms and excellent in environmental compatibility.
Further, the surfactant of the present invention is excellent in surface tension lowering action, interfacial tension lowering action, foamability, foam stability, emulsifying action, thickening action of an aqueous solution, and the like, and is also biodegradable. It has solubilization and denaturation-preventing actions for membrane proteins, and has a small hemolytic action, and is safe for living organisms and can be applied to foods and pharmaceuticals.

[0009]

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

Example 1 1.0 g of sucrose lauric acid ester [Ryoto L-1695 (76% monoester content, manufactured by Mitsubishi Chemical Co., Ltd.) in a volume of 100 ml with a stopper containing 20 ml of 80 mM acetate buffer (pH 4, 5)] The solution was added to the Erlenmeyer flask and dissolved with stirring using a magnetic stirrer, and the flask was further immersed in a constant temperature water bath heated to 50 ° C. to continue stirring, and the invertase [ Candi manufactured by Seikagaku Corporation was used.
da utilis- derived product] 10 mg, and 50 ° C
I reacted for one day. After the reaction was completed, 60 ml of chloroform was added to the reaction mixture to extract a chloroform-soluble matter.
Then, silica gel column chromatography (inner diameter 2
A column of 0 mmφ and a length of 50 cm was packed with 40 g of Wako Gel C-200), and the chloroform-soluble component was put in the column, and the composition of chloroform: methanol as a developing solvent was 10: 0, 9: 1, 8: 2, 7: 3, 6: 4, 5:
While changing to 5, divide the elution fraction into 20 ml portions and
Was collected. Then, it was confirmed that the glycoside bond of sucrose laurate was cleaved by the action of invertase to generate acyl glucose. First, 2 ml of each of 16 fractions was put into a test tube, and a silver mirror reaction was tried. That is, when 2 ml of 0.1 M silver nitrate aqueous solution was added to each fraction, a brown precipitate was formed, so 8% ammonia water was added to make it transparent, and the mixture was heated to 60 ° C. in a water bath. When left to cool, No. 5 and No.
In the case of fraction 6, the silver mirror was most often deposited on the inner wall of the test tube. Fraction No. 3 to No. Since a silver mirror was deposited on No. 8, these were united and No. 8 was used. 1 fraction (yield 5
00 mg). Fraction No. 9 and No. 10
Had a weak silver mirror reaction. Furthermore, fraction N
o. 11-No. There is a weak silver mirror reaction in No. 16, and these are combined to No. 16. Two fractions were made (yield 500 mg).
FAB / MS spectrum (sample glycerin / water suspension was electrosprayed to JEOL H
X-100 type mass spectrometer)),
No. A fragment 352 corresponding to lauryl glucose was newly found in one fraction. Also, 400 MHz ¹³ C
An anomer peak was observed from the ¹ H NMR spectrum. In addition, DS by differential scanning calorimeter (DSC)
No. 1 from the C spectrum. 1 and No. The spectra of the two fractions were similar to those of the starting material (sucrose laurate), but endothermic peaks of different sizes were found at different positions. That is, the base peak at 197 ° C. of the starting material was No. No. 1 fraction, no. The base peak of one fraction was 86 ° C.

The above No. 1 fraction and No. The composition of the two fractions is as follows.

[Table 1]

Example 2 No. 1 obtained in Example 1 1 fraction and No. The surface activity of the aqueous solution of the two fractions was compared with the surface activity of the aqueous solution of sucrose lauric acid ester (L-1695) used as a reaction raw material, and the results are shown in Tables 2 to 6. No. 1
The fractions are No. The two fractions and the original sucrose laurate showed lower surface tension and interfacial tension lowering action, and greater foam stability than the original one. Further, it had an action as a surfactant such as an emulsifying action for cottonseed oil, a dispersing action for carbon black, and a dipping action for felt cloth.

[0013]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

Example 3 1.0 g of sucrose, 0.9 g of lauric acid, and 2.29 g of triphenylphosphine, which had been thoroughly ground and dried, were added to 100 parts.
It was placed in a round bottom flask with a stopper of ml volume, dried dimethylformamide (DMF) was added and dissolved, and it was immersed in a water bath kept at 0 ° C with ice water. Then, a dropping funnel was attached to the flask via Abzatz, and a dry calcium chloride tube with a pickle was connected to the upper end of the funnel. 1.53 g of diisopropyl azodicarboxylate was placed in the dropping funnel, and the contents of the flask were added dropwise over 20 minutes while magnetically stirring. After completion of dropping, stirring was continued at room temperature (about 20 ° C.) for 24 hours. After the reaction, the solvent was removed using a rotary evaporator, and silica gel column chromatography was carried out in the same procedure as in Example 1 to separate 20 fractions into 10 fractions. Then T each fraction
Analyzed by LC [TLC plate: Merck 574
5; Composition of developing solvent (volume ratio): CHCL ₃ , 79, C
H ₃ OH, 11; CH ₃ COOH, 8; H ₂ O, 2],
1.4 g of a sucrose monolaurate fraction was obtained. 80m of 1.0g of the obtained sucrose monolaurate ester
The mixture was added to a 100 ml Erlenmeyer flask with a stopper containing M acetate buffer (pH 4.5), and dissolved with stirring using a magnetic stirrer. Furthermore, while immersing the flask in a constant temperature water bath heated to 50 ° C. and continuing stirring,
Invertase (10 mg) was added and reacted at 50 ° C. After the reaction was completed, 60 ml of chloroform was added to the reaction mixture to extract a chloroform-soluble matter. Then, the chloroform-soluble component was put into the column by silica gel column chromatography, and the eluate fraction was collected by changing the composition of chloroform: methanol as a developing solvent. It was confirmed by the silver mirror reaction that the glycosidic bond was cleaved to generate acyl glucose. The surface tension of the 0.1% aqueous solution was 28.2 mN / m (30 ° C.).

Example 4 No. 1 obtained in Example 1 The hemolytic action of one fraction of the aqueous solution was measured. That is, red blood cells were obtained by collecting blood from the ears of rabbits, adding isoton buffer, and repeating centrifugation. Against the suspension of red blood cells,
Nos. As acyl glucose and acyl fructose.
Add 1 fraction to 1 × 10 ^-5 M and add 30 at 37 ℃.
Stir for minutes. When the absorbance was measured at 543 nm using a colorimeter, it was the same as when water was added to erythrocytes, but with sucrose ester (L-1695) 1 × 10 ⁻⁵ M, a large increase in absorbance due to hemolysis was observed. It was The absorbance of the SDS aqueous solution was increased at 4 × 10 ⁻⁴ M. Therefore, it is clear that the surfactant of the present invention has a small hemolytic action and thus is safe and exhibits a large surface activity. Also, no denaturing effect on hemoglobin in red blood cells was detected.

Example 5 No. 1 obtained in Example 1 The effect of extracting the physiologically active protein from the aqueous solution of one fraction, the denaturation-inhibiting effect of the extracted protein, and the higher-order structure protecting effect were measured, and an excellent effect was found. That is, the retina part detached from the eyes of the firefly squid was ground, added with a 40% sucrose aqueous solution and centrifuged, and the upper surface was taken to obtain a love dome membrane containing a large amount of rhodopsin protein. In order to perform the extraction of rhodopsin protein from this Labdome membrane, No. One fraction or a 2% aqueous solution of sucrose ester was added, and the mixture was shaken and allowed to stand for 5 minutes for spectroscopic measurement. Both have absorption peaks at 275 and 480 nm, and it was found that the extracted rhodopsin did not deteriorate and the protein structure corresponding to the physiologically active expression of rhodopsin was retained. In particular, No. The absorbance of the membrane dispersion containing one fraction is 4 than that of sucrose ester.
Since it became 0% larger, No. One fraction was shown to have a large stabilizing / protecting effect on rhodopsin. In addition,
In the system containing no SDS or the control, no two absorption peaks disappeared rapidly, and rhodopsin was denatured.

Example 6 1.0 g of dried sucrose, 1.6 g of decanoic acid, and 2.29 g of triphenylphosphine were placed in a 100 ml round bottom flask with a stopper, and dried with dimethylformaldehyde (D
15 ml of MF) was added and dissolved, and it was immersed in a water bath kept at 0 ° C. with ice water. Then, a dropping funnel was attached to the flask via Abzatz, and a dry calcium chloride tube with a pickle was connected to the upper end of the funnel. 1.53 g of diisopropyl azodicarboxylate was put in the dropping funnel, and the contents of the flask were added dropwise over 20 minutes while magnetically stirring.
After completion of dropping, stirring was continued at room temperature (about 20 ° C.) for 24 hours. After the reaction, the solvent was removed using a rotary evaporator, and silica gel column chromatography was carried out in the same procedure as in Example 1 to separate 20 fractions into 10 fractions. Then, each fraction was analyzed by TLC [TLC plate: Merck 5745; composition of developing solvent (volume ratio): CHCl ₃ , 79; CH ₃ OH, 11; CH ₃ COOH, 8; H ₂ O, 2], and sucrose. 1.3 g of dilaurate ester fraction was obtained. ¹³ C NMR and ¹ H NMR (JEOL GX-400), FAB / MS
And it was confirmed from the DSC spectrum that it was sucrose didecanoate. 1.0 g of the obtained sucrose didecanoate ester was added to a 100 ml Erlenmeyer flask with a stopper containing 80 mM acetate buffer (pH 4.5), and dissolved while stirring using a magnetic stirrer. further,
While the flask was immersed in a constant temperature water bath heated to 70 ° C. and stirring was continued, 15 mg of the invertase of Example 1 was added and reacted at 70 ° C. After completion of the reaction, 60 ml of a mixed solution of chloroform 50 / methanol 50 was added to the reaction mixture to extract soluble matter. The extract was developed by TLC [TLC plate: Merck 5745; composition of developing solvent (volume ratio): CHCl ₃ , 7
9; CH ₃ OH, 11; CH ₃ COOH, 8; H ₂ O, 2], the TLC plate was dried, and then a 1% diphenylamine solution (diphenylamine 2.
Dissolve 0 g in 20 ml of ethanol and add 100 ml of 36
% Hydrochloric acid 100 ml and glacial acetic acid 80 ml were added to prepare)
Was sprayed and left at 105 ° C. for 25 minutes, the spots of acyl glucose and acyl fructose were colored blue gray. The substrate was in a position where Rf was high. Preparative TL
C plate (Marck Kieselgel 60, thickness 2mm, length and width 20c each
m) was used to separate the spots of acyl glucose and acyl fructose. Surface tension of 0.1% aqueous solution is 3
It was 3.6 mN / m (30 ° C.).

The characteristic values relating to the performance of the above-mentioned surfactants are measured as follows. (1) Surface tension Wilhelmy surface tension meter (manufactured by Shimadzu Corporation, ST-
1) was used and the measurement was performed at 30 ° C. (2) Interfacial tension Spinning drop type interfacial tension meter (Core Labo
Model 500) manufactured by Ratories,
The interfacial tension to decane was measured at room temperature (about 25 ° C). (3) Foaming power It was measured by a semi-trace improved TK method. Ie height 4
A cylindrical container with a glass jacket having a diameter of 0 cm and a diameter of 70 mm was set vertically, 30 ° C. hot water was circulated in the outer temperature-adjusting cylinder, and an inner 400 ml foam container with a graduated scale had a volume of 0.
Add 5 ml of 3% sample aqueous solution. And, except for the glass tube for blowing air into the solution at the bottom of the foam container, the inside of the foam container is shielded from the outside air and water is 300 m.
It is connected to an aspirator that stores l. Since a pinch cock at the lower end of the aspirator was opened to cause water to flow down, air was introduced into the sample solution to cause foaming. Therefore, the volume of the foam was read immediately after the end of the flow (0 min) to after 5 min. Also, foam stability (%) = [foam volume at 0 min-
After 5 min) x 100/0 min]
The foam stability was calculated and determined. (4) Penetration force Using a square felt having a thickness of 0.2 cm and 2 cm × 2 cm as a test piece, measurement was carried out at 30 ± 1 ° C. by a spontaneous sedimentation method. That is, both ends of the test cloth are lightly sandwiched with tweezers and gently dropped from above the water surface of 5 mm and dropped. From the moment when the cloth touched the surface of the 0.1% aqueous solution of the sample, the stopwatch was pressed to measure the time, and the number of seconds until the cloth completely separated from the liquid surface was read. (5) Emulsifying power 3 ml of 0.3% sample aqueous solution in a 30 ml graduated test tube
And 2 ml of ethylbenzene are added, and the mixture is put in water at 95 ° C and brought to the same temperature. Shake this with a shaker (30 sec
Immediately after shaking vertically 120 times with an amplitude of 25 cm)
Place in a constant temperature water bath at 5 ° C., and read the separated oil layer, emulsion layer, and separated water layer with time (from 5 minutes after shaking to 120 minutes after). The intermediate layer between the upper layer (oil) and the lower layer is the emulsion layer. The height of the oil-water layer was read before shaking, and the amount of emulsified oil in the oil was determined as the percentage of the emulsified oil layer relative to the total oil, and this was calculated as the emulsification rate (%). (6) Dispersion power 50 mg of carbon black is placed in a 30 ml graduated test tube, 20 ml of a 0.1% aqueous sample solution is added, and the mixture is shaken horizontally with a shaker, and allowed to stand at 30 ° C for 5 hours. Then, insert the tip of the pipette from the liquid surface of the test tube to the 5 ml scale stopper, suck 2 ml from that portion, and transfer it to another test tube. The diluted solution (A) in which 25 ml of water was added was measured using an integrating sphere type haze meter (Nippon Denshoku Digital Turbidity Meter NDH-20D), and the dispersive power was calculated by the following formula. Dispersing power (%) = (To−Ts) × 100 / Ts, where To represents the transmittance of an aqueous solution obtained by adding 25 ml of water to 2 ml of the test solution, and Ts represents the transmittance of the above (A).

Claims (2)

[Claims] 1. A surfactant comprising a mixture of an acyl glucose represented by the following general formula (I) and a fructose compound (II) represented by the following general formula (II). Embedded image (In the formula, R represents an alkyl group or an alkenyl group having 6 to 24 carbon atoms) (In the formula, X represents hydrogen or an acyl group having an alkyl group or an alkenyl group having 6 to 24 carbon atoms) 2. A sucrose fatty acid ester represented by the following general formula (III) in a method for producing a mixture of an acyl glucose represented by the following general formula (I) and a fructose compound represented by the following general formula (II). The method as described above, which comprises hydrolyzing the glycoside bond of Embedded image (In the formula, R represents an alkyl group or an alkenyl group having 6 to 24 carbon atoms) (In the formula, X represents hydrogen or an acyl group having an alkyl group or an alkenyl group having 6 to 24 carbon atoms.) (In the formula, R and X have the same meanings as described above.)