DE1011580B - Cationic shampoos - Google Patents

Description

GERMAN

It is known that cation-active compounds can be used for the production of shampoos. They generally have the advantage over anionic detergents that they hold the hair in its Influence properties favorably. The grip, softness and combability of the hair become essential improved; the hair gets a nice shine, and weakened and damaged hair is strengthened, that it can be further processed more easily. In addition to these advantages, those previously used for this purpose have Cation-active compounds compared to the anion-active products have the disadvantage that their solutions too little foam.

The invention now relates to good-foaming, cation-active shampoos, which are characterized in that that they have at least one imidazoline, which is at least one non-aromatic carbon radical with 7 to 14 carbon atoms and has at least one nitrogen-containing side chain in the form of its water-soluble Salts, including water-soluble, quaternary ammonium salts, and also at least one acidic compound and optionally other compounds known as additives to shampoos, in particular nonionic compounds Detergents included.

Among the imidazoline derivatives that correspond to the definition given and for the preparation of the invention Shampoo can be used, especially compounds of the general formula

R.

CH ₂ - CH ₂

CHXH ₉ N -

-CH ₂ CH ₂ NHR ₂

contemplated in which R is a non-aromatic hydrocarbon _{radical having 7 to 14 carbon atoms, R 1} and R _{2 are} hydrogen, the same radical as R or the atomic grouping

- C —R,

(R ₃ = alkyl radical with at most 6 carbon atoms), with the proviso that R, R ₁ and R ₂ together have no more than 14 carbon atoms, and where η is a small integer.

Particularly advantageous products are those in which the sum of the carbon atoms present in the radicals R, R ₁ and R _{2 is} between 10 and 14.

The imidazoline derivatives are prepared from polyalkylenepolyamines by methods known per se

Applicant: CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dipl.-Ing. E. Splanemann, patent attorney, Hamburg 36, Neuer Wall 10

Claimed priority: Switzerland of November 17, 1953

Dr. Otto Albrecht, New World, Basel (Switzerland), has been named as the inventor

and non-aromatic, relatively high molecular weight carboxylic acids of the general form R-COOH or their reactive derivatives.

Those to be used as starting materials for the production of the products to be used according to the invention In addition to hydrocarbon radicals and basic nitrogen atoms, polyamines can contain other Have substituents. For example, the following can be used: diethylenetriamine, triethylenetetramine or tetraethylenepentamine, also polyamines, such as are available if you Äthyle.ndihalogenide with ammonia or Amines heated.

As non-aromatic carboxylic acids that can be used for the preparation of the imidazoline derivatives are called: caprylic acid, capric acid, lauric acid and myristic acid. The functional derivatives are halides, Esters or anhydrides are possible.

Inorganic acids can be used for salt formation, such as. B. hydrochloric acid, sulfuric acid, Methyl sulfuric acid; organic acids are preferably used, such as acetic acid, lactic acid, formic acid or citric acid. Organic compounds that are capable of forming salts can also be used for salt formation. react with amines, forming salts, including quaternary ammonium salts. Such connections are z. B. benzyl chloride or dimethyl sulfate.

The salts of the imidazolines are easily soluble in water and give the solution a stable foam when it reacts acidic. To set a suitable p _H -value is at least incorporated into an acid-reacting compound the · shampoos invention. As such, acidic salts such as primary phosphates can be used; however, the organic ones customary in cosmetics for such purposes are preferred

• 709 586/380

3 4

Acids, ζ. B. aliphatic oxycarboxylic acids, such as glycol. A soft mass is obtained, which with water a

acid or citric acid, but especially lactic acid, provides a highly foaming solution,

to use. . .

It can also be advantageous in addition to the imide. Example

azoline derivatives the shampoos not yet iono- 5 Mix 10 parts of that described in Example 1

add generous detergents. As such, lactates make do with 10 parts of the condensation product

preferably the known Äthylenoxydkondensations- 1 mole of p-tert-octylphenol and 8 moles of ethylene oxide,

products of fatty alcohols, fatty amines, höhermole- 15 parts of 89.4 ° / ₀ hydrochloric lactic acid and 55 parts of water,

külaren Alkylmercäptanen or Alkylphenolen in Be obtained a solution, which when diluted with water

costume; these connections can be e.g. B. of io results in a strong foaming solution.

Octadecyl alcohol, oleylamine, dodecyl mercaptan, octyl, instead of the above-mentioned addition product of

Derive nonyl- or dodecylphenol. Ethylene oxide on p-tert-octylphenol can also do that

The production of the hair washing condensation product according to the invention from 1 mol of tert-dodecyl mercaptan

medium is done by simply mixing and dissolving and using 8 to 10 moles of ethylene oxide.

Components; a single representative 15. .

of a compound class can be used. Example <±

Mixtures of two or more compounds of one Mix 10 parts of the items described below

Class can be used. Furthermore, even lactate with 15 parts of 89.4 ° / ₀ strength lactic acid and 75 parts

Additions to other water commonly used for shampoos.

Substances such as perfume, dyes, bleaching agents, agents

thickeners. The new funds can proceed as follows:

produced in solid, pasty or liquid form 60 parts of lauric acid, 31 parts of diethylenetriamine,

will. They are used in the known 0.6 parts of boric acid and 50 parts of xylene in the im

Way in hair treatment. The treated hair Example 1 specified manner under reflux for

are generally well degreased, are heated to a boil until the elimination of water is complete.

soft handle and a nice shine and can be The reaction time is about 5 hours, according to

Brush lightly because their tendency to electrostatic which time is 2 moles of water, based on 1 mole

Charge is greatly reduced. · Lauric acid, have split off.

In the following examples, parts by weight mean 13.4 parts of the imidazoline thus obtained are in the

share. The ratio of weight part to part by volume is stirred for 30 heat with 5.1 parts 89.4 ° / ₀ sodium lactic acid,

the same as from kilogram to liter. The tempera- whereby you get a soft mass that is easy in water

Doors are given in degrees Celsius. is soluble.

Example 1 Example 5

Mix 10 parts of the 35 described below. Mix 10 parts of the below described

Lactate with 15 parts of 89.4 ° / ₀ hydrochloric lactic acid and 75 parts of the acetate with 15 parts of 89.4 ° / ₀ hydrochloric acid and 75 parts of milk

Water. Water.

For the production of the above-mentioned lactate, one can use For the production of the above-mentioned acetate

proceed as follows: proceed as follows:

200 parts of distilled coconut fatty acid, 103 parts of diethy 40 26.7 parts of the imide described in Example 4

lentriamine, 0.2 parts boric acid and 150 parts xylene azolines of the formula are placed on the reflux condenser until the water

cleavage heated. You leave that out of the back y

Xylene flowing off from the flow cooler before being returned to the C ₁₁ H ₂₃ - C, pass the reaction vessel through a water separator, in 45
which the water is continuously separated
can. The implementation is completed after about 8 hours,
and the solvent is distilled under reduced pressure

Pressure off. are at 80 to 85 ° in small portions with 10.2 parts

16.8 parts of the imidazoline thus obtained are mixed with 50 acetic anhydride, whereupon the reaction

6 parts of 89.4 ° / ₀ hydrochloric lactic acid on a water mixture for 2 hours under stirring in a

Stir heated until a homogeneous mixture formed a heated boiling water bath. The acetate thus obtained

is. A soft mass is obtained, which from water to the acetylated imidazoline of the formula a strong foaming solution is absorbed.

₅₅ , N-CH ₂

Example 2. /?

Mix 10 parts of the \ _ _ "_ described below

Lactate with 15 parts of 89.4% lactic acid and 75 parts of N - LH ₂ O

Water. 1 ''

For the production of the lactate mentioned above, one can proceed as follows: _{60 CH 2} --CH ₂ - NH - C - CH _3:

239 parts technical myristic acid, 103 parts diethylene- forms a viscous oil, which from water to a

triamim, 2 parts boric acid and 150 parts xylene are taken up in foaming solution,

the manner described in Example 1 at the reflux. .

cooler heated until the elimination of water is complete. The 65 example 6

Implementation is completed after 8 hours. It is distilled. 10 parts of that described below are mixed

the solvent from under reduced pressure. Lactatsmit 15 parts of 89.4 ° / ₀ hydrochloric acid and 75 parts of milk

15.3 parts of the imidazoline thus obtained are mixed with water.

5.1 parts of 89.4% lactic acid on a water bath. For the preparation of the lactate mentioned above, one can

stirred until a homogeneous mixture is formed. 70 proceed as follows:

1 Oil

14.4 parts of caprylic acid, 10.3 parts of diethylenetriamine, 0.1 part of boric acid and 50 parts of xylene are refluxed in the manner described in Example 1 heated until the elimination of water is complete. Then 14.4 parts of caprylic acid are allowed to flow in and again heated to the boil on the water separator until no more water is split off. To distilling off the xylene gives 33.7 parts of reaction product.

10 parts of the imidazoline of the formula thus obtained

- C

yN-CH ₂

^ N-CH ₂

CH ₂ -CH ₂ -NH-

CO-C ₇ H

15th

will ° / ₀ hydrochloric acid heated milk with 3.1 parts of 89.4 with stirring to give a thick oil, ao captured by water to a high foaming solution.

Example 7

10 parts of the quaternary ammonium salt described below are mixed with 5 parts of 89.4% strength Lactic acid and 85 parts of water. For the preparation of the above-mentioned quaternary ammonium salt one can proceed as follows:

10 parts of the imidazoline of the formula described in Example 6

120 °, whereupon 44 parts of ethylene oxide are introduced at up to 125 ° as a finely divided gas stream.

175 parts of the imidazoline thus obtained are heated with 45.8 parts of 89.4 ° / ₀ hydrochloric lactic acid on a water bath, until a homogeneous mixture is formed. A viscous mass is obtained, which is absorbed by the water to form a strongly foaming solution.

Claims (10)

Patent claims: 1. Cation-active shampoos, characterized in that that they have at least one imidazoline, which is at least one non-aromatic hydrocarbon radical has 7 to 14 carbon atoms and at least one nitrogen-containing side chain, in the form of its water-soluble salts, including water-soluble, quaternary ammonium salts, also at least one acidic compound and possibly other than additives to shampoos known compounds, in particular non-ionic cleaning agents. 2. Shampoo according to claim 1, characterized in that it is one of an imidazoline the general formula r ' , N-CH, ^ N-CH, CH ₂ -CH ₂ -NH- 35 -CO-C ₇ H ₁ are heated with 3.8 parts of dimethyl sulfate for 4 hours to 50 to 55 °, the quaternary ammonium salt is obtained as a thick oil. It dissolves easily in water with the formation of a strong foaming Solution. Example 8 45 Mixing 10 parts of the lactate as described below with 15 parts of 89.4 ° / ₀ hydrochloric lactic acid and 75 parts of water. To prepare the above-mentioned lactate, one can proceed as follows: 93 parts of the product described in the penultimate paragraph of Example 1 are dissolved in a stream of nitrogen 120 to 130 ° C heated, whereupon 43 parts of propylene oxide as a finely divided gas stream at the specified Temperature initiates. 39.5 parts of the imidazoline thus obtained are heated with 15.7 parts of 89.4 ° / ₀ hydrochloric lactic acid on a water bath, until a homogeneous mixture is formed. A viscous mass is obtained, which is absorbed by the water to form a strongly foaming solution. Example 9 10 parts of the lactate described below are mixed with 15 parts of 89.4% strength lactic acid and 75 parts Water. To prepare the above-mentioned lactate, one can proceed as follows: 148.5 parts of the product described in the penultimate paragraph of Example 1 are dissolved in a stream of nitrogen N - - CHo -CH ₉ CH ₉ N- -CH ₂ CH ₂ NHR ₂ n-l Derived salt contain, in which formula R for a non-aromatic hydrocarbon _{radical having 7 to 14 carbon atoms, R 1} and R ₂ for hydrogen, an identical radical as R or the atomic grouping -CR ₃ (R ₃ = alkyl radical with at most 6 carbon atoms), with the proviso that R, R ₁ and R ₂ together have no more than 14 carbon atoms, and where η is a small integer. 3. Shampoo according to Claims 1 and 2, characterized in that it is a salt of an imidazoline contain, which has alkyl side chains whose carbon number together between 10 to 14 lies. 4. Shampoo according to Claims 1 to 3, characterized in that it is a salt of an imidazoline contain, by condensation of 1 mole of a fatty acid having 12 to 14 carbon atoms with 1 mole of diethylenetriamine is obtained. 5. Shampoo according to Claims 1 to 4, characterized in that it contains the lactate of the Imidazolines of the formula contain. , N-CH ₂ N-CH, CH, CH, - NH, 1 Oil 6. Shampoo according to Claims ^ to 3, characterized in that it contains the lac'tat of the imidazoline of the formula ^: , N-CH ₉ 'N-CH ₅ , CxAg - ^ Ή.2 NH-CO-C ₇ H ₁₅ contain. 7. Shampoo according to Claims 1 to 3, characterized in that it consists of dimethyl sulfate and the imidazoline of the formula C ₇ H ₁₅ , N-CH, ^ N-CH ₂ 8. Shampoo according to Claims 1 to 7, characterized in that they contain an aliphatic oxycarboxylic acid as the acidic compound ^{1 '.} 9. Shampoo according to Claims 1 to 8, characterized in that it is used as an acidic compound Contain lactic acid. 10. Shampoo according to claims 1 to 9, characterized in that they contain the condensation product of 1 mole of p-tert-octylphenol and 8 moles of ethylene oxide or that of 1 mole of tert-dodecyl mercaptan and 8 to 10 moles of ethylene oxide as a nonionic cleaning agent. CH ₂ -CH ₂ -NH-CO-C ₇ H ₁₅ available quaternary ammonium salt contain. Considered publications: Belgian Patent No. 506 094;
U.S. Patent Nos. 2,211,001, 2,355,837;
H. Janistyn: Fragrances, Soaps, Cosmetics, 1950, Vol. II, p. 128; Schwartz-Perry: Surface Active Agents, 1949, p. 196. -