DE2001351A1 - New surface-active agents which can be used in cosmetics and processes for their preparation - Google Patents

Description

PATENT LAWYERS

DR.DR.-J. RE1TSTÖTTER DR.-1NG. W. BUNTE DR. K. G. LÖSCH

B-8 MUNCHEM 13.

M / 11003 series 91 bis

L ¹ OREAL 14 Rue Royale, Paris (France)

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BATH

Surfactants usable today in cosmetics and methods of making them

[Addition to patent application P 15 93 215.7]

P-ie additive present application relates to novel surfactant i fittel with the same general formula as the main patent (Patent Application P 15 93 215.7) described means, but the definition of the radicals is expanded.

In the main patent (patent application P 15 93 215.7) are from one Sulphate amide of the general formula I

R-CO-NH- (GH ₂ CH ₂ O) ₂ -SO ₃ M (I)

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existing anionic surfactants described, where R is a saturated or unsaturated alkyl radical, the is derived from copra and has 11 to 17 carbon atoms, and M is an alkali metal, ammonium ion, or a short chain Mean alkylammonium radical. In the main patent are also cosmetic compositions described which contain at least one compound of general formula I in aqueous solution contain, these compositions being in particular hair shampooing agents. There is also a in the main patent Preparation process for the compounds of general formula I described, according to which in a first stage the Amide of a fatty acid derived from copra and, in a second stage, a sulfate of this amide.

The cosmetic compositions according to the main patent have the purpose of avoiding the disadvantages of fatty alcohol sulfates, i.e., the aggressiveness and poor touch properties of the hair after shampooing. on the other hand these manufacturing products do not have the lack of stability that the already known amide sulfates have.

New compounds have now been found that have analogous properties like the compounds described in the main patent and which correspond to the general formula of the main patent, however, its definition is expanded.

The present invention therefore relates to a suI-fatamid with the general formula I.

R-CO-NH- (CH ₂ CH ₂ O) ₂ -SO M (I)

existing new anionic surfactants, where R is saturated or unsaturated, branched or not

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branched alkyl radical with 11 to 26 carbon atoms and M an alkali metal, ammonium ion, a short-chain alkylammonium residue, mean a short-chain hydroxyalkylammonium radical or an alkaline earth metal.

It has also been found that in the compounds of the formula I according to the invention in which M denotes an ion of an alkaline earth metal, M in the case of the cations Ca ⁺⁺ and Mg ⁺⁺ can correspond to half an equivalent.

The present invention also encompasses compositions containing at least one compound of the formula I, as well as that Process for the preparation of these compounds.

In the formula I according to the present application, the acyl radical RCO mixtures of acids of various origins, such as tallow fatty acids, dwarf palm fatty acids (acidic gras de palmiste), palm fatty acids and generally fatty acids obtained from oils and fats of animal or vegetable origin will.

The RGO radical can also be an acyl radical, the "iso acids" with the general formula:

CH- (CH ₂ ) _n COOH

OH,

CH ₃

and "anti-iso acids" with the general formula:

_x0 -CH- (CH ₀₎ "COOH

J c- t c. Jl

OH,

corresponds, where η values from 14 "to 22 and from 12 to 22 be indicates.

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These acids are produced in the form of mixtures by saponifying lanolin. In particular, it can be the mixture of fatty acids used by the Unilever-Emery company under the name "isostearic acid" according to the USA patent 2 812 342 is manufactured.

Branched fatty acids such as those manufactured by Enjay Chemical Company and under the term "neo acids" are known, such as the neotridecanoic acids with the formula:

CH,

CH, - (CH ₉ ) -C-COOH

where η has the V.'ert 3 to 8, and in particular the acid in which η is 8. These neo-acids can be converted into acid chlorides according to known procedures, which are obtained by reaction result in hydroxylated amides which can be sulfated with diglycolamine.

The acyl group RCO can be derived from fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid. These acids can be used in the pure state or in a mixture, as they are obtained, for example, by fractional distillation from copra. If it is desired to achieve foaming detergents in the production of the shampooing agents, it is preferred to use lauric acid and myristic acid or mixtures which contain at least 50 % of these acids. Acids with an odd number of carbon atoms can also be used, such as pelargonic acid and undecylenic acid.

Tn of the formula I according to the present application, M not only means, as in the main patent, (1) an alkali ion, (2) an ammonium ion, (3) an alkylammonium such as

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H ₃ N ⁺ CH ₂ CH ₅

CH

CH ₂ GH ₃ CH ₂ CH ₃ CH ₂ CH ₃

but also (4) a hydroxylalkylammonium and in particular the following radicals:

H ₃ N - CH ₂ CH ₂ OH: 2-hydroxyethylammonium H ₃ N - CH ₂ CHOHCH ₃ : 2-hydroxypropylammonium

CH ₂ CH ₂ OH N.

CH ₂ CH ₂ OH

: Bis (2-hydroxyethyl) ammonium

CH ₀ CHOH-CH,

: Bis (2-hydroxypropyl) ammonium

CH ₂ CHOH-CH ₃

CH ₂ CH ₂ OH CH ₂ CH ₂ OH CII ₂ CH ₂ OH

: Tris (2-hydroxyethyl) ammonium

CH ₂ CHOH-CH ₃

CII ₂ CrIOH-CH ₃ : Tris (2-hydroxypropyl) ammonium CH ₂ CHOH-CH ₃

The present invention also comprises cosmetic compositions which, in particular in aqueous solution, contain at least one compound of the general formula I in which R

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and / or M have the extended meanings given above. These compositions are particularly useful as shampoos usable for the hair. These compositions can of course also contain other products and auxiliaries, as commonly used in cosmetics, such as thickeners or other ionic or nonionic surface-active compounds.

The cosmetic compositions according to the invention contain generally 5 to 40 parts by weight and preferably about 10 parts by weight per 100 parts by volume of the compounds according to the invention I as defined above, the pH of these compositions being 6 to 9 and preferably about 7.

The present invention also includes a method of manufacture of the compounds of the formula I, where R and / or M have the extended meanings given above, according to which one an acid with the general formula R-COOH with diglycolamine converts and the alcohol function of the resultant Amides sulfated, the sulfation optionally followed by salt formation.

The compounds according to the invention have the perfect hydrolytic stability of the compounds of the main patent, the represents one of their essential properties. The new comparison test given below confirms this fact and makes it clear that only the process of the invention is a well-defined compound and not a reaction mixture results, which has the unfavorable property of still subject to hydrolysis.

In this experiment, on the one hand, the lauric acid diglycolamide with the formula A

^C 11 ^H 23 ^CONH " ^CH 2 ^CH 2 ^OCH 2 ^CH 2 ^OH ^

by means of the process according to the invention and, on the other hand, a compound of the formula B

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C ₁₁ H ₂₃ CONHCH ₂ CH ₂ O- (CH ₂ CH ₂ O) _n -H (B)

produced, where τι represents a statistical mean value of 1.

The preparation of the compound A by means of the method according to the invention takes place as follows:

With the help of diglycolamine with the formula

H N-CH ₂ CH ₂ O-CH ₂ CH ₂ OH,

used with an excess of $ 100, the | Aminolysis of lauric acid methyl ester, the mixture of the reactants being ^{heated progressively up to 160 °} C. and the methanol formed being removed. The excess diglycolamine is then evaporated in vacuo. The crude product thus obtained is recrystallized from ethyl acetate.

The production of the product B according to a process of the state of the art takes place as follows:

Ethylene oxide is combined with the lauric acid monoethanolamide of the formula

C ₁₁ H ₂₅ CONHCH ₂ CH ₂ OH

condensed, the latter compound being obtained by aminolysis of methyl laurate with the aid of monoethanolamine. Its melting point is 85 ^° C. after recrystallization

The condensation of the ethylene oxide is carried out in the following way:

3.5 g of a solution of 24.8 56 CH, ONa in methanol are added to 75 g of lauric acid monoethanolamide, which is then evaporated off in vacuo. In 73.3 g of the thus obtained and heated ^{to 135 0 C}

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th mixture is passed in ethylene oxide after the apparatus has been flushed with a stream of nitrogen. After 45 minutes of reaction at 135 to 145 ⁰ C, the condensation of 12.8 g of ethylene oxide or 0.96 mole per mole Äthanolamid is reached.

The condensation product is obtained in the form of a yellowish-white wax with a hydroxyl number of 207.

If, after silylation according to the method of Suffis and co-workers (J. Soc. Cosm. Chemists 76, 783-794 (1965)), chromatography is carried out in the gas phase, it is found that the condensation product is the compounds of the formulas C ₁₁ H ₂₃ CONH-CH ₂ CH ₂ OH and C ₁₁ H ₂₃ CONH-CH ₂ CH ₂ OCH ₂ CH ₂ Oh in essentially equal amounts.

Result :

This comparative experiment clearly shows that mixtures are obtained when working in accordance with known procedures which contain a significant proportion of monoethanol araids, which are known to be the sulfated derivatives are unstable to hydrolysis. You can of course reduce the proportion of these monoethanolamides by using the The degree of condensation with the ethylene oxide is increased, but in this case the products obtained are very pronounced because of them hydrophilic character less active.

The use of the diglycolamine, which in the reaction according to the present invention yields diglycolamides, allows this Avoidance of these disadvantages, since the starting product already has the degree of condensation η = 2, while with the already known Process the condensation of ethylene oxide with a substituted monoethanolamide takes place and during the degree of condensation of the group (CHpCHpO) only a statistical mean has, which is why the product B is actually a mixture in which a large part of non-oxyethylene Ethanolamide continues to be subject to the effects of hydrolysis.

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The procedure is carried out in two stages in the same way as in the main patent and according to the same variants.

The following examples are intended to illustrate the invention further, but not to limit it.

example 1

Production of the magnesium salt of Dodecanoylaminoäthoxyätha nolsulfat with the Pormel

This hydroxylated amide is produced by aminolysis of methyl laurate with the aid of diglycolamine in an excess of 100 μ , the mixture of the reactants being ^{heated progressively to 160 °} C. and the methanol being removed. The excess diglycolamine is then evaporated in vacuo. The crude product thus obtained is then recrystallized from ethyl acetate.

This compound is then replaced by sulfamic acid under the conditions sulfated from example 1 of the main patent.

50 g of the Sulfatierungsprodukts are dissolved in 150 ml of water and to this solution 2.25 g of pulverized and sieved \ tes magnesium oxide is added in small portions. This mixture is then heated on the boiling water bath, releasing ammonia. After heating on a water bath for 24 hours, the mixture is filtered to remove the remaining magnesium oxide.

The determination of the magnesium ions in the Piltrat shows that 59 % of the ammonium salt of diglycolamide sulfate in magnesium

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salt have been converted.

This filtrate has good foaming properties, whereby the surface active agent thus obtained has the following formula:

_{2 3} CONH- (CH ₂ -CH ₂ -O)

Example 2

Production of the magnesium salt of dodecanoylaminoethoxyethanol sulfate in the form of a "powder.

57.4 g of dodecanoylaminoethoxyethanol, prepared as in Example, game 1, are dissolved in 100 ml of chloroform. 25.6 g of chlorosulfonic acid are added dropwise over the course of 20 minutes to this solution, which has previously been ^{cooled to 15 ° C., with vigorous stirring, the temperature being kept below 25 °} C. The reaction mixture is left stirring for 1 hour at ambient temperature and the hydrochloric acid is driven off under reduced pressure by passing a stream of nitrogen into the reaction mixture.

The sulfation product obtained in this way is neutralized in the following way:

A magnesia milk is made by adding 9 g of magnesia dispersed in 20 ml of water, and this magnesium oxide dispersion is stirred into a chloroformic acid solution of the sulfation product introduced. After 1 1/2 hours If the mixture still shows a strongly acidic reaction, another 2 g of powdered magnesium oxide are added.

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The mixture is left to stand overnight and the excess magnesium oxide is separated off by filtration "Then" the chloroform and the water are driven off by evaporation "The yield is 80 <? <>. ·

The product obtained is recrystallized in acetone and filtered through Precipitation is the magnesium salt with the formula according to the example 1 obtained, which is easily separated off by filtration will.

After drying it becomes an atomizable or pulverizable obtained white pesticide that dissolves very easily in water. The solution obtained has good foaming properties ^

- ■■ - ■■ -; ■,. - ^: ■ "■". ^: - ^l ·. 'i

By S ν i e 1 5

First, the hydroxylated amides are prepared, which result from the aminolysis of the methyl esters of copra fatty acids, which is carried out with diglycolamine in an excess of 100 % . ,.,. ......-.-- .. "" ■,. .

To .diesem Zy / eck heated the mixture of the reactants progressively to 160 ⁰ O, wherein the methanol is removed and then evaporated the excess diglycolamine in vacuo.

The crude product thus obtained is then made with the help of chlorosulfonic acid sulfated under the conditions of Example 2. The sulfation product is then neutralized with monoethanolamine. .

By S; ρ - - i e 1 4

If you work as in Example 5, but the Kopraderivat " is replaced by methyl ester of tallow fatty acid and neutralization with monoisopropanolamine takes place, so a compound is with the formula I.

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obtained, where R is a tallow fatty acid residue and M is a 2-hydroxypropylammonium ion mean.

Example 5

A bubble bath powder is produced with the following composition:

Magnesium salt with the formula:

C ₁₁ H ₂₃ CONH- (CH ₂ -CH ₂ -O) ₂

SO ₃ C ₁₁ H ₂₃ COlTH- (CH ₂ -CH ₂ -O) J _{gQ g}

Monosodium phosphate 6 g

Perfume 4 g

Example 6

A shampoo is made with the following composition:

Magnesium salt with the formula:

SO,

Mg

C ₁₁ H ₂₃ CONH- (CH ₂ -CH ₂ -O) ₂ 30

Lauric acid diethanolamide 3 %

Perfume 0.5

Water as much as necessary for 100

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Claims (23)

£ »£ β & H / U0O9 P A T E NT A N S P RU C Ή E 1. Novel anionic surfactants Compounds with the general formula I. R-GO-NH- (CH ₂ CH ₂ O) ₂ -SO ₃ M (I) where R is a saturated or unsaturated, branched or unbranched alkyl radical with 11 to 26 carbon atoms and M is an alkali metal, the ammonium ion, a short-chain alkylammonium radical, a short-chain hydroxyalkylammonium radical or an alkaline earth metal ", where M in the case of Ca ⁺⁺ and Mg ^{+ +} half a, equivalent means. 2. Surface-active agent according to claim 1, wherein R is an alkyl radical of an acyl group RCO, which is one of copra-derived, equivalent to fatty acid. 3. A surfactant according to claim 1, wherein R denotes Alkyl radical of an acyl group RCO means the acids of vegetable origin, such as lauric acid, myristic acid, pälmitic acid, Oleic acid and lenolic acid. . 4. Surface-active agent according to claim 1, wherein R is the alkyl radical of an · acyl group RCO, the fatty acids animalisehen Origin, such as tallow fatty acids, stearic acid, caprylic acid and capric acid. 5. The surfactant of claim 1, wherein R denotes Alkyl radical of an acyl group RCO means, the Isosäureti the all common formula CH ₅ ^^ CH- (CH ₉ ) -— COOH - GH, ^ _ ■■ '■■■. ■ ■■■■■ ,. - 13 - '- s ■ 209809/1720 1351 «/ 1X003 where η is a number νοΏ 14 to 22, corresponds. 6. The surfactant of claim 1, wherein R
denotes the alkyl radical of an acyl group, the anti-iso acids of the general formula ) GOOH where η is a number from 12 to 22, corresponds to. 7. Surface-active agent according to claim 1, wherein R denotes the 'alkyl radical of an acyl group, the neo-acids of the general formula OH, CH, - (CH ₉ ) -C-COOH OH, ' where η is a number from 3 to 8, corresponds to. 8. A surfactant according to claim 1, wherein M is the sodium or potassium ion. 9. The surfactant of claim 1, wherein M is one-half equivalent of calcium and magnesium ions. 10. The surfactant according to claim 1, wherein M is the methylammonium ion, the dimethylammonium ion or the triethylammonium ion means. 11. Surface-active agent according to claim 1, wherein M is 2-hydroxyethylammonium, 2-hydroxypropylammonium, bis (2-hydroxyethyl) ammonium, Bis (2-hydroxypropyl) ammonium, Tris (2-hydroxyethyl) ammonium or tris (2-hydroxypropyl) ammonium ion means. - 14 209809/1720 M / 11005. '·' ■. '. K 12. Cosmetic composition that can be used as a shampoo, characterized by a content of at least one Surface-active agents according to any one of claims 1 TdIs 11. 13. Cosmetic composition according to claim 12, characterized characterized in that it also contains a second surfactant according to any one of claims 1 to 11. '- / ■' 14. Cosmetic composition, characterized in that it contains the surface-active agents according to all claims "II. 15. Cosmetic composition according to claim 12 to 14 » characterized in that they contain surface-active agents of the formula I in an amount of 5 to 40 parts by weight per 100 parts by volume contains. 16. Cosmetic composition according to one of the claims 12 to 15, characterized by a content of others in the Ko; -sme tik- used components. "_".-.--- 17. Cosmetic composition according to one of the claims 11 to 16, characterized by a content of other surface-active substances Means. ■ 18. Cosmetic composition according to one of the claims 12 to 17 in the form of an aqueous solution. . "" 19 · Cosmetic composition according to claim 18 with a pH of 6 to 9 * ..... . ■. ■ 20. Cosmetic usable as foaming bath powder. Composition, characterized by a. Content of at least, one surfactants according to a depc :. Expectations.,.... ... 1 to 11. "'■ - ■ - - - ^15th T 203809/1720 M / 11005 W 21. A process for the preparation of surface-active agents according to claim 1 with the general formula I. R-CO-NH- (CH ₂ CH ₂ O) ₂ -SO M (I) characterized in that diglycolamine with an acid having the general formula R-COOH, where R is for the formula I has given meanings, converts the alcohol group of the amide thus obtained sulfated and the salt formation of the sulfatamide with the help of a salt-forming agent, which contains a radical M with the meanings given for the formula I. 22. The method according to claim 21, characterized in that there is used as sulfating agent sulfamic acid, wherein M means the ammonium ion. 23. The method according to claim 21, characterized in that the salt formation of the sulfatamide with 'pulverized Magnesium oxide carries out. - 16 2098U9 / 1720