EP0570396A1

EP0570396A1 - Dispersions of fatty acid partial glycerides

Info

Publication number: EP0570396A1
Application number: EP19920903075
Authority: EP
Inventors: Thomas Förster; Frank Wangemann; Michael Schaaf
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1991-02-09
Filing date: 1992-01-31
Publication date: 1993-11-24
Also published as: JPH06504718A; DE4104053A1; WO1992013519A1

Abstract

Des dispersions aqueuses de glycérides partiels d'acides gras qui contiennent (A) entre 10 et 45 % en poids d'un glycéride partiel d'acide gras; (B) entre 40 et 89,9 % en poids d'eau et (C) entre 0,1 et 5 % en poids de sulfooléine se caractérisent par leur bonne fluidité et stabilité au stockage.Aqueous dispersions of fatty acid partial glycerides which contain (A) between 10 and 45% by weight of a fatty acid partial glyceride; (B) between 40 and 89.9% by weight of water and (C) between 0.1 and 5% by weight of sulfoolein are characterized by their good fluidity and storage stability.

Description

"Dispersions of Fatty Acid Partial Ivcerides"

At normal temperature, the invention relates to flowable and pumpable, storage-stable aqueous dispersions of up to 45% by weight of fatty acid partial glycerides containing 0.2 to 3% by weight of a sulfoolein.

It is known that fatty acid partial glycerides are used in the field of cosmetics as consistency agents for emulsions. Of particular importance is the glycerol mono- / distearate, hereinafter referred to as GMS for short. The incorporation of fatty substances such as GMS, which are solid, wax-like substances at normal temperature, requires melting and uniform, stable dispersion in the likewise heated solution or emulsion of the other components. When cooling, viscous lamellar gel phases form (compare e.g. K. Larsson, journal Physikalische Chemie 1967 (56) 173 - 198), which complicate the processing process. This procedure means a considerable amount of work, so that it would be advantageous for many users to have fatty substances of the GMS type in the form of a stable, flowable dispersion concentrate. Such a concentrate could be introduced homogeneously into other aqueous preparations by mere mixing.

From the teaching of DE-PS 25 11 600 and DE-PS 25 11 644 a process for the production of emulsions is known which uses aqueous GMS dispersions. DE-AS 2509255 claims fatty acid mono- / diglycerides with a content of protein-fatty acid condensates to reduce the viscosity. According to the teaching of the European patent EP 249711, low-viscosity aqueous dispersions of glycerol esters are produced by adding defined amounts of alkali soaps of long-chain fatty acids to the soap-free glycerol esters. However, the aqueous GMS dispersions of the prior art have the disadvantage of swelling to viscous gels in the course of storage. The reason for the subsequent thickening is the gel formation, which is promoted by free fatty acids and dispersants. Depending on the content of free fatty acid, crystals or la ellar gel phases are formed (see: a) N.Krog and K.Larsson, Chem. Phys. Lipids 1968 (2) 129-143; b) K.Larsson and N.Krog, Chem. Phys. Lipids 1973 (10) 177-180; c) N.Krog and APBorup, J. Sei. Fd Agric. 1973 (24) 691-701).

It has now been found that flowable, storage-stable GMS dispersions can be prepared by using small amounts of sulfo-ol.

The invention consequently relates to aqueous dispersions of fatty acid partial glycerides, characterized in that they contain

(A) 10-45% by weight, preferably 20-35% by weight, of a fatty acid partial glyceride,

(B) 40 to 89.9 weight percent water and

(C) 0.1 to 5% by weight, preferably 0.2-3% by weight, of sulfoolein in order to ensure the flowability and the storage stability of the dispersion.

Fatty acid partial glycerides (A) are technical mixtures of fatty acid ono-, di- and triglycerides of saturated or unsaturated fatty acids with 10 to 20 carbon atoms, which are esterified by esterifying 1 mole of glycerol with 1 to 2 moles of a ( Cιo-2θ) ~ ^{Fe-fctic acid 0 (} ^ ^er by transesterification of 1 mole of a (Cιo-2θ) " ^fat ^ ^uretrι 9 ^ y ^cer ' ^c ' ^s '- • - _' • ^von Rinder¬ tallow, pork lard, Palm oil, sunflower oil or soybean oil with 0.5 to 2 moles of glycerin are obtained.Commercially available are two types of partial glycerides.Partial glycerides of type I contain 35 to 60% monoglycerides, 35 to 50% diglycerides and 1 to 20% triglycerides. Partial glycerides of type II are produced by molecular distillation from those of type I and contain 90 to 96% monoglycerides, 1 to 5% diglycerides and less than 1% triglycerides (see also: a) G. Schuster and W. Adams: Zeitschrift für Lebensmitteltechnologie, 1979, Volume 30 (6), pp. 256-264; b) G.Sc huster (ed.) "Emulsifiers for Food", Springer-Ve lag, 1985). The fatty acid partial glycerides used according to the invention should contain 35 to 96% monoglycerides, 1 to 50% diglycerides and 0.1 to 20% triglycerides. Sulfooleins (C) are sulfation products of unsaturated fatty acid triglycerides with sulfur trioxide. The proportion of unsaturated fatty acids with 12 to 22 carbon atoms and 1 to 6 double bonds which is bound in the fatty acid triglycerides should be at least 50% by weight. Fatty acid triglycerides whose unsaturated fatty acid have 18 carbon atoms and 1 to 3 double bonds are preferably used to prepare the sulfoolein (C); oleic acid and elaidic acid are particularly preferred. Particularly suitable fatty acid triglycerides are olive oil, new sunflower oil, peanut oil and new rape oil. The triglycerides are converted into the sulfooleins to be used according to the invention by reaction with 1 to 2 mol of gaseous sulfur trioxide, based on the triglyceride, at temperatures of 40 to 90 ° C. and subsequent neutralization with aqueous alkali metal hydroxides. The amount of sulfur trioxide is preferably 1 to 1.5 mol, in particular 1.1 to 1.3 mol, per mol of triglyceride. If desired, the sulfoolein thus obtained can be subjected to a hydrolysis stage and / or treated with small amounts of a bleaching agent, for example hydrogen peroxide or sodium hypochlorite, to improve the color quality.

The dispersions according to the invention can be prepared in a simple manner by combining all components of the dispersion to be prepared at normal temperature (approx. 20 ° C.) and heating to 80 ° C. with stirring. After the solid constituents have melted, the mixture is left to stir for a few minutes and the dispersions thus obtained are then cooled to normal temperature.

The dispersions of fatty acid partial glycerides according to the invention are suitable, for example, for producing emulsions for use in the field of cosmetics or in the paper industry.

The following examples are intended to explain the subject matter of the invention in more detail. Examples

1. Analytical methods

The content of unsulfated water in surfactant pastes in% by weight (US content) was determined gravimetrically after acidification of the paste, petroleum ether extraction and evaporation of the solvent, and the content of sodium sulfate ionographically determined. The dry residue was determined by evaporating the water from the surfactant paste.

2. Substances used

2.1. Fatty acid ono-Zdiglyceride (A)

The glycerol used exemplarily / distearate, GMS consisted of egg _¬ nem technical partial glyceride, of a palmitic Stearinsäuregemisch (30: 70) with a proportion of 50 wt .-% of monoglyceride, 40 wt .-% and 10 wt diglycerol rid .- triglyceride.

2.2. New beet oil

New, low eruca rape oil with the following fatty acid distribution (figures in% by weight): 1% myristic acid; 4% palmitoleic acid; 1% stearic acid; 59% oleic acid; 20% linoleic acid; 9% linolenic acid; 1% arachidic acid; 2% gadoleic acid; 1% behenic acid; 1% erucic acid. The iodine number of the new beet oil was 120 and the saponification number was 190.

2.3. Sulforüböl (C)

Sulforub oil was obtained by S03 sulfonation of new rapeseed oil as follows: 5 mol of rapeseed oil at 60 to 70 ° C with 6 mol gaseous SO3 (5 vol .-% in air) implemented; this corresponds to a molar ratio of triglyceride to SO3 of 1: 1.2. The reaction was exothermic. The acidic reaction mixture was continuously neutralized at 80 ° C. with 50% by weight sodium hydroxide solution. The mixture was then bleached with 1% by weight of a 35% by weight aqueous solution of hydrogen peroxide, adjusted to a pH of 10 and heated at 80 ° C. for 120 minutes. After adjusting the pH to a value of 7.5, a clear single-phase product was obtained, which was characterized as follows: 2/13519

Dry residue: 41.9% by weight Unsulfated: 27.1% by weight Sodium sulfate: 1.4% by weight

Active substance: 40.5% by weight (calculated from the difference in dry residue minus sodium sulfate)

2.4. Lauryl ether sulfate

Commercial Texapon NSO from Henkel / Dusseldorf with an active substance content of 29% by weight. Lauryl ether sulfate is abbreviated LES in the tables.

3. Production and characterization of the dispersions All components of the dispersion to be produced were added together at normal temperature and heated to 70 to 80 ° C. with stirring. After all the solid had melted, stirring was continued for a few minutes. The dispersions thus obtained were then rapidly cooled to + 20 ° C. The dispersions were stored at normal temperature for 30 days. The viscosity was then measured at + 20 ° C. using a CARRIMED CS 200 rotary rheometer with plate-plate arrangement at a shear rate of 30 s ~. The yield point was also determined.

The compositions given in the following examples and comparative examples are always to be understood as% by weight based on the mixture as a whole. The data for sulforüb oil and lauryl ether sulfate refer to the active substance. The viscosity is given in Pa * s, the yield point in Pa.

Example 1 (Bl-A to Bl-D)

Systems made from GMS, water and sulforübüb oil were investigated according to the above procedure. The composition and characterization of these systems are summarized in Table 1. This shows very impressively that the dispersions according to the invention have only low flow limits and viscosities even after 30 days of storage and are therefore flowable and stable in storage. 2/13519

6 -

Table 1

Bl-A Bl-B Bl-C Bl-D

Systems consisting of GMS, water and sulfor rapeseed oil and an additional rapeseed oil content were investigated according to the above regulation. The composition and characterization of these systems are summarized in Table 2. It can be seen that an additional rapeseed oil content compared to Example 1 did in relation to storage rod 1 and that flowability did not result in any deterioration or improvement. It is thus shown that sulphur oil with a higher US content than in Example 1 is also suitable for the preparation of the dispersions according to the invention.

Comparative Example 1 (Vl-A to Vl-C)

Systems from GMS, water and lauryl ether sulfate (LES) were investigated according to the above regulation. The composition and characterization of these systems are summarized in Table 3. This shows that no flowable GMS dispersions are obtained with another anionic surfactant, LES. In comparison to Example 2 it is clear that sulfor rapeseed oil and not its US portion (rapeseed oil) is responsible for the excellent dispersing effect. 1 51

Table 2

B2-A B2-B B2-C

Table 3

Vl-A Vl-B Vl-C

Comparative example 2

According to the above regulation, systems were made from 30% by weight GMS, water and 0.5 to 3% by weight rapeseed oil. Two-phase systems were always obtained. Stable dispersions were not observed. This shows that the effect of the dispersions according to the invention can be attributed to sulphur oil and not to its US content.

Claims

Patent claims

1. Aqueous dispersions of fatty acid partial glycerides, characterized in that they contain

(A) 10-45% by weight, preferably 20-35% by weight, of a fatty acid partial glyceride

(B) 40 to 89.9 weight percent water and

(C) 0.1 to 5% by weight, preferably 0.2-3% by weight, sulfoolein to improve the flowability and the storage stability of the dispersion.

2. Use of the dispersions according to claim 1 for the preparation of emulsions for use e.g. in the field of cosmetics or in the paper industry.