DE1052642B - Preparations for changing the shape of hair - Google Patents

Description

Means for changing the shape of hair The invention relates to an agent for changing the shape of hair, especially living human hair.

The shape of hair can be changed without affecting its structure by first winding it into a curl shape, e.g. B. on hair curlers, then treated with a solution or agent that softens the hair, and finally fixes the new shape in various ways, e.g. B. by heat or chemicals, which cancel the effect of the agent applied first. You already have different ones Means used to change the shape of hair, e.g. B. alkalis, such as alkali carbonates, Phosphates. Borax, ammonia, ammonium carbonate, alkali sulfites, ammonium sulfite and Sulphides, especially ammonium sulphide. The sulfites and sulfides have certain disadvantages. So, z. B. sulfites are used in a relatively high concentration and the sulfides produce a satisfactory change in shape but toxic effects and unpleasant odor, e.g. B. the release of H'S. Furthermore, the sulfides are retained by the hair, which makes it uncomfortable later on Odor develops, especially when the hair gets wet.

In order to avoid these disadvantages, solutions of alkali salts are already available of thioglycolic acid or its homologues and solutions of dialkyl esters of thiocarbonic acids proposed as a means for changing the shape of hair. In particular, it is too known as a means for changing the shape of hair solutions of alkali or monoethanolamine salts of α-oxy fatty acid esters of dithiocarbamic acids, in which the hydrogen atoms the amino group can be substituted by alkyl radicals or the amino group by a morpholine residue can be replaced. When working with these dithiocarbamic acid derivatives the occurrence of the annoying hydrogen sulfide odor is avoided, however leaves the effectiveness of this means of making permanent waves in the cold much to be desired.

It has now surprisingly been found that with very similar composite dithiocarbamic acid derivatives have a very significantly higher effectiveness for making permanent waves in the cold when the amino group of the Dithiocarbamic acid is substituted by a lower oxyalkyl radical. These connections are made by reacting an aliphatic amino alcohol with 2 to 4 carbon atoms with carbon disulfide and a halogenated lower aliphatic monocarboxylic acid having 2 to 4 carbon atoms or a salt thereof or glycerol monochlorohydrin obtained and in alkaline solution at .. ainem p $ between 9.0 and 9.7, preferably of about 9.5 is applied.

The agent for changing the shape of hair, especially living human Hair, according to the invention, therefore consists of a solution, which is essential Component is the reaction product of an aliphatic amino alcohol with 2 to 4 carbon atoms with carbon disulfide and a halogenated lower aliphatic monocarboxylic acid having 2 to 4 carbon atoms or a salt thereof or glycerol monochlorohydrin and has a pH of 9.0 to 9.7.

As the aliphatic amino alcohol, one of the following compounds can be used or a compatible mixture thereof can be used: 2-amino-1-butanol, 2 = Amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, Monoethanolamine, Diethanolamine, I \ T-Methy 1-Ethanolamine, @ T-Ethyl-Ethanolamine, Butyl-Ethanolamine, Aminoethyl-ethanolamine, monoisopropanolamine, di-isopropanolamine.

As halogenated aliphatic acid, monochloroacetic acid, monobromoacetic acid, a-chloropropion Acid, α-bromopropionic acid, α-bromobutyric acid and 5-chloropropionic acid can be used.

The salt of the halogenated aliphatic acid can be Na-, K-, NH4 -1 be Ca, Mg or Ba salt; 2 # s can be from primary, secondary, tertiary amines and primary, secondary or tertiary alkanolamines.

The compounds that change the shape of the hair can be represented by the following formula: HO-ANCS-CH, CH -COOM RS R 'x HO-A denotes an alkanol group derived from an amino alcohol, R is hydrogen, alkyl or alkanol groups, R 'is hydrogen or an alkyl group, M is hydrogen or monovalent or divalent cations such as Na, K, Ca, Mg, N H4, Alkylammonium (derived from an amine) and alkanolammonium (derived from an amino alcohol). x is equal to 0 to 2. These compounds are prepared by, for example, a dithiocarbamate of the formula wherein HO-A, R and M have the above meanings, with a lower aliphatic halogen monocarboxylic acid or a salt thereof, such as the compounds listed above, expediently at not above about 25.degree. You can in an aqueous reaction medium, for. B. water, or in a substantially non-aqueous reaction medium, e.g. B. an ester or a ketone, e.g. B. ethyl acetate, isopropyl acetate, acetone or methyl ethyl ketone work.

The agent according to the invention for changing the shape of hair is produced by adding one of the above compounds together with a wetting agent and brings an opacifier into solution and adjusts the solution to a p $ of about 9.5. As wetting agents come z. B. sodium salts of alkylated aryl polyether sulfonic acids, Fatty acid partial esters of a polyhydric alcohol, in particular partial esters of higher ones Fatty acids such as lauric, myristic, stearic, palmitic and oleic acids, which e.g. B. with glycerine, the sugar alcohols such as sorbitol, mannitol and dulcitol, and the internal ones Anhydrides and ethers thereof, are esterified, salts of sulfated higher alcohols, such as the potassium and sodium salts of lauryl sulfate and myristyl sulfate, alkylaryl polyglycol ethylene ether, z. B. heptyl, octyl or nonyl phenyl polyethylene glycol ether, the diamyl ester of Sulfosuccinic acid, diisobutyl sodium succinate, isopropyl naphthalene sodium sulfonate, the dioctyl ester of sodium sulfosuccinic acid, monobutylphenylphenol sodium monosulfonate and decylbenzenesulfonate. An aqueous suspension can be used as the opacifier an acrylic acid copolymer or polystyrene which is about 25 to 30% solids contains, ethylene glycol monostearate, polyethylene glycol stearate and high molecular weight alkyl amides use.

Ammonium hydroxide is preferred for setting the alkaline pÄ value, however, other compounds can also be used, such as the hydroxides and carbonates and bicarbonates of Na and K, amines such as methyl and ethylamine, aminobutanol or Triethanodamine.

To change its shape, the hair is wound onto a hair curler and applied the agent. The duration of exposure can vary depending on the concentration be about 30 to 90 minutes. Then the hair is washed with water and neutralized, z. B. with an aqueous solution of potassium bromate, sodium perborate, ammonium persulfate or hydrogen peroxide, in the case of potassium bromate in a concentration of about 1 part by weight of bromate to 16 parts by weight of water. After 10 minutes the hair can be released from the curler, whereupon the neutralization solution is about further Leave on hair for 10 minutes. Finally, the hair is removed from the curler, washed thoroughly with water and dried. The waves obtained are very satisfactory, and the hair has pronounced elasticity, springiness, shimmer and shine.

The following examples serve to illustrate the invention without to restrict the same.

Example 1 61 g of monoethanolamine are added to 140 g of 28% ammonium hydroxide in a flask and the mixture is cooled with ice. The mixture is then stirred during the reaction. Carbon disulfide is then slowly added over the course of 2 hours. The first addition gives a milky solution that gradually turns greenish yellow. The C S2 reacts quickly. An aqueous solution of 94 g of monochloroacetic acid in 100 cms of water is added to this solution. The temperature rises to about 80 ° C. over the course of 3 hours of stirring. The solution is finally yellow and has a pg of 5.5. A hair waving agent is prepared with this solution in the following way: 50 g of solution, 53 cm3 of 28% ammonium hydroxide, 10 g of an alkylated aryl polyether sulfonate and 5 g of the aqueous suspension of an acrylic acid copolymer are mixed, a solution of pg 9.5 being formed. Hair samples are treated for 60 and 90 minutes according to the usual procedure. The hair on the curler is then washed with water and introduced into a neutralization solution which contains 30 g of potassium bromate per 1 liter of water. After 10 minutes, the hair is removed from the curler and left in the solution for a further 10 minutes. The hair is then completely removed from the curler, washed with water and dried with hot air. Good waves are achieved; the hair has pronounced elasticity, spring effect, shimmer and shine.

Example 2 70 g of the product obtained according to Example 1 from monoethanolamine and C S2 are under the conditions described there with 48 g of glycerol monochlorohydrin brought into reaction. One made with ammonium hydroxide and the other ingredients Solution gives excellent results after 90 minutes of treatment.

Example 3 89 g of 2-amino-1-butanol, 76 g of C S2 and 140 g of ammonium hydroxide are reacted. The C S2 is added to the aminobutanol-ammonium hydroxide mixture over the course of 2 hours. After one hour a clear red color has developed. 94.5 g of monochloroacetic acid in 100 cm3 of water are then added over the course of 2 hours, the temperature being kept at a maximum of 25 ° C. by cooling. The color is finally light yellow. The reaction product can be represented by the following formula: 50 cms of the reaction product are brought to p $ 9.5 with ammonium hydroxide. Excellent wave is obtained on hair samples after 90 minutes of treatment.

Example 4 179 g of 2-Amina-1-butanol, 250 g of isopropyl acetate and 76g C S2 are brought into reaction by adding to the aminobutanol to isopropyl acetate, cooling the flask with ice and gradually in the course of 2 hours, the S2 C added. The result is a white, yellow-tinged dithiocarbamate that is very vikos and has a texture similar to cream candy. The isopropyl acetate is removed by decantation and vacuum distillation. 1 mol of monochloroacetic acid, which is neutralized with N H4 OH, NaOH, K OH, methylamine, aminobutanol or triethanolamine, is placed in the flask, which is located in an ice bath. After stirring for 2 hours, a light yellow, syrupy, viscous solution has formed. The reaction product has the following composition in the form of its Na salt: It is diluted to 1 liter to produce a molar solution. 0.8, 0.6 or 0.5 molar solutions can be prepared by diluting them accordingly. A corrugating agent of molar strength can be produced from the following approach: 650 g of reaction product, 200 cm3 of water, 150 cm3 of N H4 O H, 15 g of an alkylated aryl polyether sulfonate, 10 g of a polystyrene and water up to 1000 cm3.

An 1 molar solution of the sodium salt of butanol dithiocarbamyl acetic acid is about 24.6%. Representation beyond the various mentioned salts of Butanoldithiocarbamylessigsäure in water are readily soluble and precipitate from the solution not decrease. The methylamine salt is dark in color and has the characteristic odor of the amine. The sample curls obtained by treating hair samples with different strengths of the solutions mentioned are excellent, have pronounced elasticity, resilience and strength. The angled curls are well defined and limited and are not affected by shampooing.

Example 5 178 g of 2-amino-2-methyl-1-propanol are dissolved in 300 cm 3 of isopropyl acetate and 76 g of C S2 are added over the course of 2 hours with cooling. A white dithiocarbamate is formed. Isopropyl acetate is removed and the reaction product is treated with sodium monochloroacetate. A waving agent of molar strength is produced, the pH of which is 9.5. Excellent waves are obtained with three types of hair.

Example 6 238 g of 2-amino-2-ethyl-propanediol-1,3, 76 g of C S2 and 250 cm3 of isopropyl acetate are reacted, the C S2 being added to the amino alcohol-isopropyl acetate mixture with cooling. The reaction lasts 8 hours. A solution of 1 mol of sodium monochloroacetate in 250 cm3 of water is now added. Little heat is evolved during the reaction, which takes about 2 hours with stirring. The solution is filtered and 200 cm3 of ammonium hydroxide are added. A corrugating agent is produced from the following mixture: 100 cms of the reaction product, 100 cm3 of water, 10 g of opacifier and 10 g of an alkylated aryl polyether sulfonate, the p $ being adjusted to 9.5. The curl of three different types of hair is excellent.

Example 7 89 g of 2-amino-1-butanol, 76 g of C S2 and 50 cm3 of isopropyl acetate are mixed and allowed to react in an ice bath. After 2 hours of reaction 1 mol (105g) of monoethanolamine is slowly added and the reaction mixture is 1 hour touched. The isopropyl acetate is removed and the reaction product with 1 mol of monochloroacetic acid treated in 100 cm3 of water. The temperature does not exceed a value of about 25 ° C, and the pH of the solution is about 5.3. A curling agent of imolar strength is made by adding water and 90 cm3 ammonium hydroxide. The pH of this Solution is 9.5. An excellent wave is achieved.

Example 8 210 g of diethanolamine, 76 g of CS, and 250 cm 3 of isopropyl acetate are reacted by adding the C S2 to the mixture of amino alcohol and isopropyl acetate in an ice bath over the course of 2 hours. The isopropyl acetate is removed and then a solution of 1 mol of sodium monochloroacetate in 250 cm3 of water is added. The reaction takes about 2 hours in an ice bath. A waving agent of 1 molar strength and a pH of 9.3 is prepared from the reaction product in the manner described above. It results in a very high quality wave.

Example 9 456 g of CS are added to 3 l of isopropyl acetate in a suitable vessel. The mixture is cooled to about 20 ° C., whereupon 1068 g of 2-amino-1-butanol are slowly added with stirring. When the addition is complete and the stirrer has been switched off, a pale yellow viscous material separates out, the 2-amino-1-butanol salt of 2-N- (butanol-1) dithiocarbamate. The isopropyl acetate used as solvent is decanted and the remaining solvent can be removed in vacuo.

567 g of monochloroacetic acid are dissolved in 1465 cm3 of distilled water solved. This solution is made by adding 534 g of 2-amino-1-butanol at a temperature neutralized from below about 20 ° C. When the addition of the aminobutanol has ended the dithiocarbamate is added slowly, the temperature not exceeding is around 25 ° C. When the addition is complete, the reaction mass is stirred for about 1 hour. A hair waving agent can be made from this solution by adding water and Add ammonia up to p $ 9.5 and other ingredients, as explained above.

Other dithiocarbamates can be made in a similar manner, by instead of 1068 g of 2-amino-1-butanol now 1068 g of 2-methyl-2-amino ^ 1-propanol or 732 g monoethanolamine or 1260 g diethanolamine are used. Further the 3 liters of isopropyl acetate can be replaced by 500 g of distilled water. In this case the reaction is a little slower and you have to stir longer, to get all of the CS2 into reaction. The product is an aqueous solution of the salt of dithiocarbamic acid. In addition, a triethanolamine salt of the Dithiocarbamates of 2-amino-l-butanol can be prepared by adding the C S2 solution in isopropyl acetate, a mixture of 534 g of 2-amino-1-butanol and 746 g of triethanolamine clogs. In the same way you can use half of the amino alcohol that is used to form the triethanolamine salt of the dithiocarbamate of amino alcohol is used, Replace with triethanolamine.

In addition, instead of 94.5 g each of monochloroacetic acid 106.5 Use g a- or ß-chloropropionic acid or 167 g a-bromobutyric acid. In case of α-Bromobutyric acid becomes complete because of its limited solubility in water Solution only achieved when practically all of the aminobutanol has been added, and in general, the halogenated aliphatic acid is neutralized with the amino alcohol, to make the dithiocarbamate.

Furthermore, instead of 89 g each of aminobutanol, which is used for neutralization the monochloroacetic acid are used, take 149 g of triethanolamine. In this Trap, the final solution contains a finely crystalline material of triethanolamine hydrochloride. This can either be filtered off and discarded or by adding enough Water to be dissolved to the reaction mixture.

Although the permanent waving of hair is described above, the invention but can also be used to change the hair shape in the desired manner. Thus, the means according to the invention can be used in a manner opposite to the corrugation be used, d. H. for removing curls, waves, kinks and for shaping up of kinks and the like. In addition, the remedy can not only be used for treatment of hair, such as human hair, but also to treat other fibers, which consist entirely or largely of keratin.

Claims (5)

P ti TE N T 4 NS PR V (: HE 1. Means for changing the shape of hair, in particular living human hair, consisting of a solution which, as an essential component, is the reaction product of an aliphatic amino alcohol with 2 to 4 carbon atoms with C S2 and a halogenated contains lower aliphatic monocarboxylic acid with 2 to 4 carbon atoms or their salts or glycerol monochlorohydrin and has a p11 value of 9.0 to 9.7. 2. Means according to claim 1, characterized in that it is below Using 2-amino-1-butanol as an aliphatic amino alcohol is made. 3. Composition according to claim 1, characterized in that it is made using 2-amino-2-methyl-1-propanol is made as aliphatic amino alcohol. 4. Means according to claim 1, characterized characterized in that it is using monochloro, acetic acid as halogenated aliphatic acid is produced. 5. Means according to claim 1, characterized in that that it is an essential component of the reaction product of an ethanolamine Contains carbon disulfide and monochloroacetic acid. Considered publications: U.S. Patent No. 2,600,624.