JPH04288092A - Production of sugar esters - Google Patents

Abstract

PURPOSE:To produce a novel sugar ester excellent in emulsifiability, foamability, water solubility. etc., and useful as an emulsifier, colloid-protecting agent, etc., by reacting a saccharide with an alkenyl succinic anhydride in the presence of an alkali catalyst. CONSTITUTION:A saccharide such as glucose is reacted with an alkenyl succinic anhydride such as octenyl succinic anhydride in the presence of an alkali catalyst such as NaOH to produce the objective alkenyl succinic anhydride. Concretely, the reaction is carried out by the steps of dissolving the saccharide in water, in a mixture of the water with an alcohol, etc.; adding the alkenyl succinic anhydride to the solution; further adding the alkali catalyst to the solution; and subsequently stirring the solution preferably at a pH of 6-8.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to novel saccharide esters composed of alkenyl succinates of saccharides, more specifically, saccharide esters having surface-active properties that can be used as emulsifiers, detergents, protective colloids, or cosmetic base materials. It is related to.

0002

BACKGROUND OF THE INVENTION Conventionally, sucrose fatty acid esters have been known as sugar esters. For example, Tokuko Sho 58-216
No. 37 discloses a method for producing mono-, di-, or tri-esters of sucrose and fatty acids by transesterification of sucrose and lower alcohol esters of fatty acids.

0003

[Problem to be solved by the invention] Sucrose fatty acid ester is a nonionic surfactant useful as an edible dispersant, an emulsifier, or a detergent, but when the content of fatty acid ester becomes high, it becomes insoluble in water. It was difficult to use in water systems. In view of these circumstances, an object of the present invention is to provide a novel saccharide ester that has excellent emulsifying properties with oil and the like and excellent water solubility.

0004

[Means for Solving the Problems] As a result of various studies to achieve the above object, the present invention has developed an alkenyl succinic acid ester of a sugar obtained by reacting a sugar with an alkenyl succinic anhydride in the presence of an alkali catalyst. The inventors have found that the object of the invention can be achieved and have completed the present invention.

Specifically, the present invention provides glucose, mannose, allose, altrose, talose, galactose, idose, gulose, fructose, tagatose,
Monosaccharides such as ribose, arabinose, xylose, lyxose, sorbose, ribulose, xylulose, aldohexose, ketohexose, psicose, rhamnose, sucrose, maltodextrins, cyclodextrins, isomaltodextrins, cellooligosaccharides, galactooligosaccharides, Oligosaccharides such as mannooligosaccharides,
Enzyme-modified dextrin, hydrolyzed starch such as roasted dextrin, amino sugars such as glucosamine, galactosamine, chondrosamine, mannosamine, glossamine, canosamine, acidic sugars such as glucuronic acid, guluronic acid, galacturonic acid, mannuronic acid, glycerin, erythritol, ribitol, etc. , sugar alcohols such as arabit, mannitol sorbit, glucit, dulcit, boremit, reduced starch saccharified products (reduced starch syrup), reduced malt starch syrup, etc. are used as raw materials, and the sugars include octenyl succinic anhydride, decenyl succinic anhydride, Alkenyl succinic anhydride such as dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, and octadecenyl succinic anhydride is used as a reaction reagent.

Then, the above saccharide is dissolved in an appropriate amount of water alone or a mixed solvent of water and an organic solvent such as alcohol or acetone, and alkenyl succinic anhydride is added, and sodium hydroxide, potassium hydroxide, and hydroxide are added. Hydroxides of alkali metals such as lithium, sodium carbonate, potassium carbonate,
Alkali metal carbonates such as lithium carbonate, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, ammonia, methylamine, dimethylamine, trimethylamine,
Monos having alkyl groups such as ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, isobutylamine, secondary butylamine, tertiary butylamine, amylamine, secondary amylamine, tertiary amylamine, hexylamine,
Mono-, di-, or triethanolamine having an alcohol group such as di- or trialkylamine, triethanolamine, triisopropanolamine, or diethanolamine is added as a catalyst, and the mixture is stirred and mixed while maintaining the pH at 6 or more, preferably 6 to 8. react by. Since the pH of the reaction solution decreases during the reaction, the above-mentioned alkali catalyst is added in solid or solution form to maintain the pH. The reaction temperature is not particularly limited, but may be appropriately adjusted to a temperature at which the alkenyl succinic anhydride is dissolved in the reaction solution. The alkenyl succinic acid ester of a saccharide of the present invention is one in which an alkenyl succinic anhydride undergoes a ring-opening reaction using the alkali catalyst described above, and is ester-bonded to the saccharide as one ester, and the other carboxylic acid is bonded to an alkali metal by the alkali catalyst used. Obtained as a solution as a salt or amine salt. The maximum number of alkenyl succinic esters to be introduced is determined according to the number of hydroxyl groups in the sugar, but the desired effect can be achieved even if not all hydroxyl groups are introduced, so the amount of alkenyl succinic anhydride added to the sugar is You can choose as appropriate. In addition, the saccharide alkenyl succinate ester of the present invention may optionally contain preservatives and antifungal agents, various surfactants, oily substances such as long chain fatty acid esters and hydrocarbons, hydrolyzed proteins, lanolin, lipids, etc. , vitamins, fragrances, pigments, various thickeners, etc. can be blended.

[0007]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples. Example 1 100 parts by weight of glucose (hereinafter simply referred to as parts) was mixed with 80 parts by weight of water.
50 parts of octenyl succinic anhydride was added,
While stirring at 30° C., the pH was adjusted to 7.5 with a 50% aqueous solution of sodium hydroxide, and the reaction was carried out for 8 hours. After the reaction, the water content was adjusted to make the product a 60% aqueous solution. Example 2 A product was obtained in the same manner as in Example 1 except that triethanolamine was used as the alkali catalyst. Example 3 A product was obtained in the same manner as in Example 1 except that sorbitol was used instead of glucose. Example 4 A product was obtained in the same manner as in Example 3 except that triethanolamine was used as the alkali catalyst. Example 5 A product was obtained in the same manner as in Example 1 except that glycerin was used instead of glucose. Example 6 A product was obtained in the same manner as in Example 1, except that enzyme-modified dextrin (Amicol No. 1, manufactured by Nippon Star Chemical Co., Ltd.) was used instead of glucose. Example 7 A product was obtained in the same manner as in Example 1 except that the amount of octenyl succinic anhydride was changed to 100 parts. Example 8 A product was obtained in the same manner as in Example 1 except that the amount of octenyl succinic anhydride added was changed to 150 parts. Example 9 A product was obtained in the same manner as in Example 1 except that dodecenyl succinic anhydride was used instead of octenyl succinic anhydride. Example 10 A product was obtained in the same manner as in Example 1 except that tetradecenyl succinic anhydride was used instead of octenyl succinic anhydride. Example 11 A product was obtained in the same manner as in Example 1 except that octenyl succinic anhydride was changed to octadecenyl succinic anhydride and the reaction temperature was changed to 50°C.

Example 12 A 2% solution of the products obtained in Examples 1 to 11, undenatured glucose, sorbitol, glycerin, and enzyme-modified dextrin was prepared and tested for emulsifying power and foaming power and foam stability. was tested. For the emulsifying power test, put 60g of the sample solution in a 500ml beaker and add 60g of white squeezed oil.
g and stirred at 9000 rpm for 1 minute with a homomixer. Immediately after stirring, transfer to a 100 ml graduated cylinder and increase the volume to 100 ml. After 24 hours, the state of separation of each phase was observed. The results are shown in Table 1. Tests for foaming power and foam stability were conducted in accordance with the method specified in JIS 3362-1990. The results are shown in Table 2.

[Table 1]

[Table 2] Example 13 25 parts of the products obtained in Examples 1 to 11, 1 part of hydroxypropylcellulose and 74 parts of water were mixed, and the pH was adjusted to 6 with dilute hydrochloric acid or aqueous sodium hydroxide solution to obtain a detergent composition. . As a result of conducting a hand-washing test with this detergent composition in warm water, it was found that the detergent composition had a creamy foam quality, had good foam breakage after washing, and had a good feel.

Example 14 Transparent shampoos shown in Table 3 were prepared using the products obtained in Examples 1 to 11.

[Table 3] This shampoo was found to have significantly improved performance in terms of smoothness and moisturizing of the hair, compared to shampoos that do not contain the saccharide alkenyl succinate of the present invention.

0010

Effects of the Invention The saccharide alkenyl succinate ester of the present invention is excellent in emulsifying property, foaming power and foam stability. When used as a cleaning composition, the foam quality, foam breakage, and feel were good. When used as a cosmetic base material, it can provide a good feeling of use and finish. Furthermore, the saccharide ester of the present invention has a feature of superior biodegradability compared to synthetic surfactants.

Claims (1)

[Claims] 1. A method for producing alkenyl succinic esters of sugars, which comprises reacting sugars and alkenyl succinic anhydrides in the presence of an alkali catalyst.