MIXTURE OF ALKYLETHER SULPHATE AND ALKYLPOLYGLYCOL ETHER CARBOXYLIC ACID OR SALT THEREOF

Abstract: Mixtures of alkylether sulphate and alkylpolyglycol ether carboxylic acid or salt thereof are provided, wherein the alkylpolyglycol ether carboxylic acid contains at least 7 oxyethylene residue, said mixtures containing 80-95% by weight of alkylether sulphate and 20-5% by weight of alkylpolyglycol ether carboxylic acid or salt thereof. In spite of this low percentage of polyether carboxylic acid, these compositions show a highly decreased skin toxicity. Also compositions intended for frequent or prolonged contact with human hair and skin are provided, which contain such mixtures as detergents.

Description: Mixture of alkylether sulphate and alkylpolygycol ether carYok ss i'c > or salt thereof. This invention relates to a mixture of alkylether sulphate and alkylpolyglycol ether carboxylic acid or salt thereof, particularly suitable for frequent or prolonged contact with human hair and skin. Consequently, such mixtures are particulary suitable for use in shampoos, shower and bath compositions, liquid soap particularly for hand-washing, and compositions for non-automatic dishwashing. Mixtures of alkylether sulphates and alkylpolyglycol ether carboxylic acids or salts thereof are known per se already from British patent 874,186. It appears from this patent that this kind of mixtures shows a number of synergistic effects which make them particularly suitable for use in shammpoos. In the meantime this kind of mixtures has been used already on a large scale in shampoos, showering compositions and the like. t The number of oxyethylene units in ether carboxylic component therein is generally small, particularly less than 10. A similar kind of mixture in combination with a cosmetically acceptable oil is disclosed in French patent 2,338,326. According to page 4 thereof, the ether carboxylate should constitute the major component of the mixture thereof with the ether sulphate. In an article by N.A.I. van Paassen in Seifen, Olen, Fette, Wachse, Heft 13/1983, pages 353-55, it has been shown that the skin toxicity of alkylpolyglycol ether carboxylates having an average of 10 or more oxyethylene groups is lower than that of lower compounds from this series and that mixtures of such highly ethoxylated carboxylates with sodium laurylether sulphate having an average of 2 oxyethylene groups show a high decrease of skin toxicity. In this work mixtures have been tested having a minimum of 25% ether carboxylate and at the end of the article it is mentioned as a practical possibility to replace about 25% of the sodium laurylether sulphate with an ether carboxylic acid. It has now been found that the synergistic toxicity effect is already so clearly appreciable at much lower percentages that much lower contents of polyglycolether carboxylic acid can suffice. Otherwise stated, the toxicity curve is particularly steep, exactly in the area below 25% of polyglycolether carboxylic acid, which means that exactly in that area the skin toxicity decreases to a relatively much stronger degree than in the area tested according to the article in Seifen, Ole, Fette, Wachse. In actual practice this means that with much lower percentages of alkylpolyglycolether carboxylic acid mixtures are obtained which possess a considerably lower skin toxicity than the mixtures which are usual in practice and which contain alkylpolyglycol ether carboxylic acid having a low number of oxyethylene units. Accordingly, the invention provides a mixture of alkylether sulphate and alkylpolyglycolether carboxylic ether or a salt thereof, particularly suitable for frequent or prolonged contact with humain hair and skin, wherein the alkylpolyglycol ether carboxylic acid contains at least 7 oxyethylene units, said mixture being characterized by the fact that it contains 80-95% by weight of alkyether sulphate and 20-5% by weight of alkylpolyglycol ether carboxylic acid or salt thereof. As alkylether sulphate one can use all the compounds usual for this purpose. A commercial product which is very frequently used in shampoos and the like is a lauryl ether sulphate, wherein the lauryl residvemay be replaced for up to about 30% with myristyl, the number of oxyethylene units in this product generally being an average of about 2 to 3. In the examples herein below the invention will be elucidated with the aid of the use of this product, but only because this is the most usual commercial product. It will be evident that the invention is not restricted tereto. Furthermore, this laryl ether sulphate conventionally is used as the sodium salt, but it is a matter of course that other salts can also be used, for instance potassium, magnesium and amine salts, although these are more expensive. The alkylpolyglycol ether carboxylic acid is also preferably used in the form of the sodium salt, because no particular advantages are obtained by using other and more expensive salts. These polyether carboxylic acids can be represented by the general formula fl (C2H40) .CH2COOM, wherein R is a usual high alkyl residu having 10-20 carbon atoms, preferably 12-18 carbon atoms, and x in this case is a number having an average value of 7-25, preferably 9-18. These ether carboxylic acids are known already as a class for a number of decades and their preparation has been disclosed in several patents. In connection with the principally cosmetic uses which are aimed at by the present invention, it is not the entire class of these compounds which can be used. Thus, the compounds, wherein R is an alkaryl group, generally are not suitable for cosmetic purposes, because their toxicity for the skin flora is too high. Furthermore, the low toxicity is only obtained with the compounds, wherein x has an average value of at least 7. The introduction of the oxyethylene units can be carried out in the usual way, either with a basic catalyst (NaOH), or with a tewis acid (SbC15). In the last mentioned case a mixture is obtained having a narrower distribution of the number of oxyethylene units than in the first case. However, with products having these relatively high values of x, the narrow distribution has less advantages than with a product having low values of x. In the case of the preparation of an ether carboxylic acid having only one or two oxyethylene units, the oxyethylation product of the starting alcohol in the case of basic catalysis still contains a considerable amount of non-ethoxylated product, which in the subsequent reaction with haloacetic caid accordingly yields a compound ROCH2COOH, which does not contribute much to the surfactant properties. In that case a superior product can be obtained with a catalyst like SbC15. However, in the preparation of products having a high x-value, no unethoxylated compound will occur anymore in the product, even when using basic catalysis. Alkylpolyglycol ether carboxylic acids having high x-values possess a somewhat lower foaming capacity. This also appears from the above cited article in Seifen, Ole, Fette, Wachse. Exactly for shampoos, showering compositions and the like the consumer wishes a foaming capacity which is as high as possible and for that reason it is a particular advantage that for attaining an acceptable low skin toxicity a considerably lower amount of alkylpolyglycol ether carboxylic acid will suffice than was considered necessary according to the above mentioned article. The following, non-restricting experiments elucidate the invention. The experiments were carried out according to the so-called "patch-test method". The objective thereof was to measure the primary skin irritation by the substances concerned, compared to a control. The test was carried out with a group of 25 men and women in the ages between 16 and 65. The test and control samples were applied to the skin of the upper arm with the aid of an occlusive "finn chamber". This is an occlusive 2 aluminium disc which provides a test area of 50 mm with a diameter of 8 mm and a volume of 25 us They are arranged on a non-occlusive backing tape at a standard space of 1 cm. These tapes are left in contact with the skin for 24 hours. Thereafter they are removed and the skin reaction is assessed one hour later. Immediately after this assessmentasecond identical tape with the same substance is applied to the same place on the skin and again left in contact with the skin for 24 hours. Again the reaction is assessed one hour after removal. The materials to be tested were randomly distributed over the several volunteers. All assessments were carried out under standard lighting conditions by a skilled assessor who was not aware which samples had been applied to which person. The degree of irritation is expressed according to a score varying from 0 to 5. Therein these numbers have the following meanings: 0 = no visable reaction; 1 = reaction just present; 2 = slight reaction; 3 = moderate reaction; 4 = severe reaction. Furthermore, rating of significance have also been assigned to the irritation phenomena, as follows: Phenomenon Abbreviation Rating Vesicles V 5 Edema E 4 Erythema R 3 Flakiness F 2 Dryness D 1 Wrinkling W 1 Translucency T 1 Glassy G 1 A numerical value for each skin side was obtained by multiplying the score for the reaction with the rating for the phenomena occured. The obtained values were summed and in this way a total number for the degree of irritation at that side was obtained. As an example it can be mentioned that the total score for a site. for which R3, D2 and G1 are observed, would be as follows: (3 x 3) + (2 x 1) + (1 x 1) = 12. The tested substances were lauryl polyether sulphate as sodium salt; average number of ethoxy groups 2 indicated hereinafter as "A". Lauryl-myristyl (70:30) - (OC2H4)xOCH2COONa, wherein x has an average value of 10, indicated hereinafter as "B". Five experiments were carried out with: 1. 100% A; 2. 95% A + 5% B; 3. 88% A + 12% B; 4. 80% A + 20% B; and 5. 100% B, respectively. All samples were tested in a concentration of 15% in water. The following table gives the mean results for the score of the skin irritation after 24 hours and after 48 hours for each of these experiments. In this respect it should still be remarked that a direct comparison of these results with those of the abopediscussed article from Seifen, Ole, Wachse is not possible. For it concerns here a different series of testswith different test persons. Therefore, the results are only comparable with each other within a series. Sample Mean score for skin irritation after 24 hours 48 hours 1. 1.92 2.04 2. 1.88 1.64 3. 1.48 1.48 4. 1.12 1.30 5. 0.92 1.00 As mentioned already the present mixtures are particularly suitable as active detergents in compositions which are intended for prolonged or frequent contact with humain hair or the humain skin, such as shampoos, showering and bath compositions, liquid soap and agents for non-automatic dishwashing. Consequently, the invention also encompasses such compositions which for the rest can be composed in any usual way.

Claims: Claims for the contracting states BE, CH, DE, FR, GB, IT, LI, NL, SE 1. A mixture of alkylether sulphate and alkylpolyglycol ether carboxylic acid or a salt thereof, particularly suitable for frequent or prolonged contact with human hair and skin, wherein the alkylpolyglycol ether carboxylic acid contains at least 7 oxyethylene residues, characterized by the fact that the mixture contains 80-958 by weight of alkylether sulphate and 20-5% by weight of alkylpolyglycol ether carboxylic ether or a salt thereof. 2. A mixture according to claim 1, characterized by the fact that the alkylpolyglycol ether carboxylate is a sodium salt which contains a alcohol residue having 12-18 carbon atoms and 9-18 oxyethylene residues. 3. A mixture according to claim 1 or 2, characterized that it contains sodium lauryl ether sulphate having an average of 2-3 ethoxy groups and the sodium salt of lauryl-myristyl (70:30)-(OC2H4) -OCH2COOH, wherein x has an average value of 10. 4. Composition intended for frequent or prolonged contact with human hair or skin, characterized by the fact that it contains as detergent substance a mixture according to claims 1-3. 5. Composition according to claim 4, characterized by the fact that it is a shampoo. 6. Composition according to claim 4, characterized by the fact that it is a showering or bath composition or a liquid soap. 7. Composition according to claim 4, characterized by the fact that it is an agent for non-automatic dishwashing. Claims for the contracting state AT 1. A process for preparing a mixture of alkylether sulphate and alkylpolyglycol ether carboxylic acid or salt thereof which is particularly suitable for frequent or prolonged contact with human hair and skin, wherein the alkylpolyglycol ether carboxylic acid contains at least 7 oxyethylene residues1 characterized by the fact that the mixture is prepared by at mixing 80-958 by weight of alkylether sulphate with 20-5% by weight of alkylpolyglycol ether carboxylic acid or a salt thereof. 2. A process according to claim 1, characterized by using as the alkylpolyglycol ether carboxylate a sodium salt which contains an alcohol residue of 12-18 carbon atoms and 9-18 oxyethylene residues. 3. A process according to claim 1 or 2, characterized by preparing a mixture which contains sodium laurylether sulphate having an average of 2-3 ethoxy groups and the sodium salt of lauryl-myristyl (70:30) (OC2H4)x-OCH2COOH, wherein x has an average value of 10. 4. A process for preparing a composition intended for requent or prolonged contact with human hair and skin, characterized by incorporating therein as detergent substance a mixture prepared according to any of claims 1-3. 5. A process according to claim 4, characterized by the fact that the composition is prepared in the form of a shampoo. 6. A process according to claim 4, characterized by the fact that the composition is prepared in the form of a showering or bath composition or a liquid soap. 7. A process according to claim 4, characterized by the fact that the composition is prepared in the form of an agent for non-automatic dishwashing.

Inventors: SMID, JACOB CORNELIS, VAN PAASSEN, NICOLAAS ADRIANUS IGNATIUS
Applicants: STAMICARBON B.V.
Application year: 1985
Main classification: C11D1
IPC codes: C11D1