JPH03262525A - Surfactant - Google Patents

Abstract

PURPOSE:To obtain a surfactant having extremely excellent capacity and relatively easy to prepare by introducing a liposoluble group into sugars having galactose-galactose-glucose type trisaccharide as a fundamental skeletal. CONSTITUTION:In a surfactant whose water-soluble part is trisaccharide or a polymer thereof, trisaccharide is set to a galactose-galactose-glucose type (4-glactosyl-lactose). This surfactant is obtained by using 4-glactosyl-lactose in a hydrophilic part and introducing an alkyl or aromatic alkyl group having oleophilicity into 4-galactosyl-lactose through in ether group (there is hexyl 4-galactosyl-beta-lactoside as an ether compound) or an ester group (there is hexanic ester of 4-galactosyl-lactose as an ester compound). This surfactant is a new one usable in all of fields and having high capacity.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention uses a novel trisaccharide derived from milk sugar (lactose) as a water-soluble moiety, and a novel trisaccharide derived from an alkyl group or an aromatic alkyl group as a fat-soluble moiety. The present invention relates to a new surfactant that is expected to be used in nonionic detergents, food additives, pesticide aids, etc.

(Prior art) Polio-bovine diethylene-type compounds have been mainly used as nonionic surfactants, but since this type of compounds are generally highly toxic, there is an ongoing need to develop compounds that can replace them. It was desired by people in the area. Therefore,
Since the saccharide is derived from natural products, surfactants with a saccharide skeleton as a hydrophilic group have attracted attention because they have low toxicity and low irritation.

Conventionally, glucose or glucose polymers are used as the saccharide skeleton of surfactants having hydrophilic saccharides [
JOURNAL OF THEAMERICAN
OIL CHEMISTS'5OCIETY, Vo
l, 47,162. (1970) Ko, maltose,
Those using maltotriose [JOURNAL
OF THE AMERICAN OIL C
HEMISTS'5OCIETY, Vol, 61, 16
51. (1984)], and those using sucrose have already been widely used in the food industry.

All of the above surfactants with saccharides as hydrophilic groups were selected because they have low toxicity and have many hydroxyl groups in their molecules, making it easy to adjust H, L, and B. It is assumed that.

However, most of the saccharides used as the water-soluble part of these surfactants consist of glucose and its oritumer, and other saccharides have not been utilized.

Therefore, the use of other saccharides has been desired for the development of industry in this field and for improving the performance of surfactants. Furthermore, surfactants using only monosaccharides or trisaccharides have disadvantages in terms of H, L, B adjustment, water solubility, and versatility as a surfactant; It was necessary to develop a surfactant using a compound.

(Problems to be Solved by the Invention) Therefore, in view of the above-mentioned prior art, the present inventor conducted various studies on the saccharide skeleton of the hydrophilic group in order to improve the performance as a surfactant, and as a result, completed the present invention. reached.

The present invention provides a novel high-performance surfactant that can be used in all fields and has a structure in which a fat-soluble group is introduced into a saccharide using trisaccharide as the basic skeleton.

(Means for Solving the Problems) That is, the present invention provides a surfactant whose water-soluble portion is trisaccharide or a polymer thereof, wherein the trisaccharide is of the galactose-galactose-glucose type. It is an activator.

The galactose-galactose-glucose trisaccharide used here has the chemical name (β-D-galactopyranosyl)-(1→4)-(βD-galactopyranosyl)-(1→4). -D-glucobylanose (hereinafter referred to as 4
-galactosyl-lactose). This trisaccharide can be produced by the method described in Japanese Patent Application No. 68-230856.

In order to produce the surfactant of the present invention, the above-mentioned 4-galactosyl-lactose is used as the hydrophilic part, and a lipophilic al-gyl group or an aromatic al-gyl group is added to this via an ether, ester group, etc. It can be obtained by introducing In this case, there is no particular problem even if a raw material containing about 30% of lactose or the like mixed in this 4-galactosyl-lactose is used.

Examples of the ether compound of the surfactant of the present invention include the following compounds.

Hexyl (β-D-galactopyranosyl)-(1→4)
-(β-D-galactopyranosyl)-(l→4)-β-
D-glucopyranoside (hereinafter referred to as 4-galactosyl-β-lactocyto) heptyl 4-galactosyl-β-lactocytooctyl 4-galactosyl-β-lactocytononyl 4-galactosyl-β-lactodidodecyl 4-galactosyl-β- Lactocytododecyl 4-galactosyl-β-
Lactocytohexadecyl 4-galactosyl-β ~ Lactocytooctadecyl 4-galactosyl-β ~ Lactocytoeicosanyl 4-galactosyl-β ~ Lactocytodocosanyl 4-galactosyl-β-lactosyto Became α-lactosyto in these compounds Although compounds can be used as well, β-lactosyto compounds are preferred.

Furthermore, a compound in which 4-galactosyl-β-lactose is oligomerized via a hydroxyl group at an arbitrary position (hereinafter referred to as oligo 4-galactosyl-lactose; hereinafter this alkyl glycoside is referred to as oligo 4-galactosyl-lactose) Alkyl etherified products of can also be used in the same manner.

In the case of an ether, any method commonly used for sugars can be used for its production, but the following 3 methods may be used.
The method is particularly advantageous therein.

Specifically, there is a production method in which 1) the above-mentioned 4-galactosyl-lactose is acetylated, then reacted with an alkanol or alkylphenol in the presence of a Lewis acid catalyst, and the product is deacetylated in a methanol solution of sodium methoxide. Next, there is 2) a production method in which 4-galactosyl-lactose is directly condensed with an alkanol or alkylphenol in the presence of an acid catalyst such as para-toluenesulfonic acid hydrate. 3) At this time,
It is also possible to first convert the anomeric position into an ether form of a lower alcohol such as methyl ether, and then introduce a long-chain alcohol or the like through ether exchange.

Among these production methods, in 2) and 3), the alkyl of the compound in which 4-galactosyl-lactose itself is polymerized,
Alkylphenyl nythermo is generated.

Further, examples of the ester compound of the surfactant of the present invention include the following compounds.

Hexanoic acid 4-galactosyl-lactose ester heptanoic acid 4-galactosyl-lactose ester octanoic acid 4-galactosyl-lactose ester decanoic acid 4-galactosyl-lactose ester dodecanoic acid 4-galactosyl-lactose ester tetradecanoic acid 4-galactosyl-lactose ester hexadecanoic acid 4-galactosyl-lactose ester octadecanoic acid 4-galactosyl-raftosester Furthermore, a compound in which two or more carboxylic acids are ester-bonded to the hydroxyl group of 4-galactosyl-lactose can also be used. Moreover, not only single substances but also mixtures of these compounds can be used as surfactants.

To produce these esters, 4-galactosyl-lactose is dissolved in a basic solvent such as pyridine, and then diluted with a solvent such as toluene, benzene, xylene, etc., or directly dissolved in fatty acid chloride, alkyl benzoic acid, etc. Obtained by reacting with chloride etc. At this time,
The ratio of the fat-soluble part can be arbitrarily changed by controlling the molar ratio of the acid chloride to sugar used, and the length of the side chain of the fat-soluble part can also be changed arbitrarily depending on the type of acid chloride. Alternatively, it can also be obtained by dehydrating and esterifying sugar and alcohol in the presence of an acid catalyst. The solvent at this time is N, N
- Preference is given to using high-boiling solvents such as dimethylformamide.

In the above-obtained surfactant, it is preferable that the alkyl group or aromatic alkyl group in the lipophilic moiety has 6 to 22 carbon atoms in both the compound having an ether bond and the compound having an ester bond with the lipophilic group. In this case, the bonding method may be chain-like or branched.

For example, a compound using a hexyl group with 6 carbon atoms as a lipophilic group has a H, L, B value of approximately 17, has high water solubility, and is an oil-in-water type (hereinafter referred to as 0/W).
Can be used to stabilize emulsions. Also, the number of carbon atoms is 2
Compounds using 2 alkyl groups are H, L, B, and the value is 12.
Therefore, it is effective for producing a water-in-oil type (hereinafter referred to as W10) emulsion. Further, a compound having a dodecyl group having 12 carbon atoms has H, L, and B values of around 15, and produces an extremely good emulsion in both O/W and Wlo types.

Even if an alkyl group or an aromatic alkyl group has less than 5 pentyl groups, it cannot be used as a surfactant, but its performance is considerably reduced. In addition, in the case of an alkyl group having 22 or more carbon atoms, it is difficult to obtain the raw material and it is not practical.

[Example] The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these Examples in any way.

Example 1 Decyl (β-D-galactopyranosyl)-(1→4)
-(β-D-galactopyranosyl)-(1→4)-D-
Synthesis of glucopyranoside 20g of (β-D-galactopyranosyl)-(1→4)
=(β-D-galactopyranosyl)-(1→4)-D-
Glucobylanose (95% purity, remaining 5% lactose) was dissolved in 100 ml of pyridine, 100 ml of acetic anhydride was added thereto, and stirred at room temperature for 24 hours. after that,
Post-processed by conventional method (β-D-galactopyranosyl)
-(1→4)-(β-D-galactopyranosyl)-(1
→4) 36g of undecaacetate of -D-glucobylanose was obtained. After dissolving this in 200 ml of methylene chloride, 10 g of anhydrous silver tetrachloride was added, 7 g of decyl alcohol was added at -20°C, and the mixture was reacted at the same temperature for 40 hours. After the reaction was completed, the reaction solution was poured into a sodium bicarbonate solution containing a large amount of ice and vigorously stirred. This solution was filtered through a Celite-coated funnel to separate an organic layer and an aqueous phase, and the organic layer was washed with water and dried with sodium sulfate. After filtering the desiccant and concentrating it, 3
2 g of residue was obtained. The product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 20 g of the desired acetate. Next, 20 g of this was gradually added to 0.1N sodium methylate/methanol solution 21 at room temperature and stirred for 5 hours.

Subsequently, a cation exchange resin was added thereto and stirred for 10 hours to remove sodium ions. After filtering the ion exchange resin, the methanol solution was concentrated to obtain 9.5 g of the target compound. The nuclear magnetic resonance spectrum of this compound revealed that the abundance ratio of alkyl chains (δ value, 0.8 to 1.7 ppm) and sugar (δ value, 3.3 to 4.5 ppm) was about 1:1. This indicates that one molecule of alkyl chain is introduced per molecule of sugar. In the Loss Miles test of a 0.25% aqueous solution of this compound, fine foam particles of 75 mm were formed and remained foamy for about 10 hours.

Example 2 Stearyl (β-D-galactopyranosyl) = (1→
4)-(β-D-galactopyranosyl)-(1→4)-
Synthesis of D-glucopyranoside 20 g of (β-D-galactopyranosyl)-(l→4)-(β-D-galactopyranosyl)-(1→4)-D-glucobyranose (purity 9
0% and the remaining 10% is lactose) was acetylated by the sodium acetate/acetic anhydride method [described in Method in Carbohydrate Chemistry Vol. 2, p. 212 (Academic Press) to obtain 16 g of undeca acetate. This acetate was dissolved in 200 ml of methylene chloride, 5 g of tin tetrachloride was added thereto, the mixture was cooled to -18° C., and then 5 g of stearyl alcohol was added and reacted for 50 hours. Post-treatment of the reaction was carried out in the same manner as in Example 1, and 10.1 g of a white solid of the target product was obtained. This compound has an alkyl chain (δ value, 0.8-1.7 ppm) from nuclear magnetic resonance spectroscopy.
The abundance ratio of sugar and sugar (δ value 3.3 to 4.5 ppm) was approximately 1:1. This indicates that one molecule of alkyl chain is introduced per molecule of sugar.

, :17) In the Ross-Miles test of a 0.25% aqueous solution of the compound, a foam of 80 mm was formed, and the presence of the foam continued for about 10 hours.

Example 3 Dodecyl (oligo 4-galactosyl lactoside)
Synthesis of 4-galactosyl-lactose 40g1 dodecanol 200ml and 1.5g para-toluenesulfonic acid-
The hydrate was reacted at 120 to 140°C under a nitrogen stream for 4.5 hours. Thereafter, excess dodecanol was distilled off under high vacuum and the residue was washed with hexane. The obtained slightly brown solid weighed 48 g, and the analysis revealed that the degree of polymerization of 4-galactosyl-lactose was approximately 1. It was 8. 0.25 of this compound
% aqueous solution, a fine foam with a diameter of 70 mm formed and remained for about 6 hours.

Example 4 (β-D-galactopyranosyl)-(1→4)-(β-
Synthesis of D-galactopyranosyl)-(1→4)-D-glucopyrano-stodecanoate 5.1 g of 4-galactosyl-lactose was dissolved in 40 ml of pyridine, and 2.5 g of dodecanoic acid chloride was added thereto at room temperature. In addition,
The mixture was stirred at room temperature for 8 hours. Thereafter, volatile matter was distilled off under reduced pressure, and then 60 ml of toluene was added thereto to dissolve the residue, which was then distilled off under reduced pressure. 50 ml of acetone was added thereto, and the resulting white precipitate was taken out by filtration and dried. Yield was 6.2g.

Nuclear magnetic resonance spectroscopy revealed that the ratio of alkyl chains to sugars was approximately 1:1. Furthermore, since ester absorption existed at a wave number of 1740 from the infrared absorption spectrum, it was determined that it had the desired structure.

When 15 mg of this compound was dissolved in 10 ml of toluene and 5 ml of water was added thereto, a homogeneous emulsion was obtained, indicating that it can be a good emulsifier.

In the Loss Miles test of a 0.25% aqueous solution, fine foam particles of 85 mm were produced, indicating excellent surfactant ability.

Example 5 (β-D-galactopyranosyl)-(1→4)-(β-
Synthesis of D-galactopyranosyl)-(l→4)-D-glucobylanose dodecanoate 5.1 g of 4-galactosyl-lactose was dissolved in 40 ml of N,N-dimethylformamide, and 2.4 g of it was dissolved therein. of dodecanoic acid and then 0.5 ml of 1N sulfuric acid.
The mixture was heated and stirred at 140° C. for 4 hours under a nitrogen stream. After cooling to room temperature, 0.5 ml of 1N aqueous sodium hydroxide solution was added and vigorously stirred. Next, N,N-dimethylformamide, water, etc. were distilled off under reduced pressure. 30 acetone here
After adding m1 and stirring, the precipitate was filtered and dried. Yield was 7.1g.

Nuclear magnetic resonance spectroscopy revealed that the ratio of alkyl chains to sugars was approximately 1:1. Furthermore, since ester absorption existed at a wave number of 1740 from the infrared absorption spectrum, it was determined that it had the desired structure.

25 mg of this compound was dissolved in 7 ml of toluene,
When 5ml of water was added to this, it became a homogeneous emulsion.
It was found to be a good emulsifier.

Example 6 paraoctylphenyl (β-D-galactopyranosyl)-(1→4)-(β-D-galactopyranosyl')-
Synthesis of (1→4)-D-glucopyranoside 20g of (β
-D-galactopyranosyl) = (1→4) = (β-D-
Galactopyranosyl)-(1→4)-D-glucobylanose (98% purity, remaining 2% is lactose) was dissolved in 100 ml of pyridine, 100 ml of acetic anhydride was added thereto, and the mixture was incubated at room temperature for 24 hours. Stir for hours. Thereafter, by post-treatment by a conventional method, (β-D-galactopyranosyl)-(1→4)
-(β-D-galactopyranosyl)-(1→4)-D-
35 g of glucobylanose undecaacetitola was obtained.

After dissolving this in 200 ml of methylene chloride, 10 g of anhydrous tin tetrachloride was added, and 8.5 g of balaroctylphenol was added at -18°C, followed by reaction at the same temperature for 55 hours.

Thereafter, post-treatment and deacetylation were carried out in the same manner as in Example 1 to obtain 10.5 g of the target compound. This compound was confirmed by examining the abundance ratio of alkyl chains and sugars using nuclear magnetic resonance spectroscopy. The ratio of alkyl chains to sugars was approximately 1:1. This indicates that one molecule of alkyl chain is introduced per molecule of sugar. 0.2 of this compound
In the Loss Miles test of a 5% aqueous solution, fine foam particles with a diameter of 68 mm were produced and the foam particles remained for about 8 hours.

Example 7 (β-D-galactopyranosyl)-(1→4)-(β-
Synthesis of D-galactopyranosyl)-(1→4)-〇-curcobylanose-balaoctylbenzoate 5.04 g of 4-galactosyl-lactose was added to 40 m
Dissolve 2.4 g of dodecanoic acid in 1 liter of N, N~ dimethylformamide, and then add 0.5 ml of 1
After adding normal sulfuric acid, the mixture was heated and stirred at 120 to 140'C under a nitrogen stream for 5 hours. After cooling to room temperature, 0.5 ml of 1N caustic soda aqueous solution was added and vigorously stirred. Next, N,N-dimethylformamide, water, etc. were distilled off under reduced pressure. A mixed solvent of 10 ml of beef sun was added to 30 ml of acetone and stirred, and the precipitate was filtered and dried.

Yield was 7.0g.

Nuclear magnetic resonance spectroscopy revealed that the ratio of alkyl chains to sugars was approximately 1:1. Furthermore, since ester absorption existed at a wave number of 1720 from the infrared absorption spectrum, it was determined that it had the desired structure.

When 25 mg of this compound was dissolved in 5 ml of toluene and 5 ml of water was added thereto, a homogeneous emulsion was obtained, indicating that it was a good emulsifier.

(Effect of the invention) As described above, the present invention provides galactose-galactose-
It is a new surfactant that has a fat-soluble group introduced into a saccharide whose basic skeleton is glucose-type trisaccharide.It has extremely excellent performance and is relatively easy to manufacture, so it is used in many applications. It can be used in the field.

Furthermore, since this surfactant is composed of lactose and galactose units, which are similar to galacto-oligomers, it has a lower calorie content compared to conventional glucose and sucrose derivatives, which are broken down in the body and serve as nutritional sources. Since it is expected to reduce the amount by half, it can also be used as a food additive for people who are required to restrict their calories.

Claims (1)

[Scope of Claims] 1. A surfactant whose water-soluble portion is a trisaccharide or a polymer thereof, wherein the trisaccharide is of the galactose-galactose-glucose type. 2. The surfactant according to claim 1, wherein the trisaccharide becomes β-D-galactoside via the hydroxyl group at the 4-position of the galactose moiety of lactose. 3. A surfactant according to claim 1, wherein the fat-soluble portion of the surfactant is an alkyl group or an aromatic alkyl group. 4. The surfactant according to claim 1 or 3, wherein the alkyl group or aromatic alkyl group is ether bonded to the trisaccharide. 5. The surfactant according to claim 1 or 3, wherein the alkyl group or aromatic alkyl group is ester bonded to the trisaccharide. 6. The surfactant according to claim 1 or 3, wherein the alkyl group or aromatic alkyl group is chain-like or branched and has 6 to 22 carbon atoms.