DE1050507B - Process for the preparation of ready-to-use hair curling liquids and means for its implementation - Google Patents

Description

Process for the preparation of ready-to-use hair curling liquids and means of carrying it out in spite of various interesting proposals it has not yet been possible to produce indefinitely durable, d. H. can be stored practically unlimited Manufacture Kaitweli preparations. The cold wave fluids are still sensitive against atmospheric oxygen, especially in the presence of heavy metal ions. That I Well proven ammonia is also with good closures with longer storage of the bottles volatile at higher temperatures, and at very low temperatures are cold wave fluids. if endangered. For the manufacturer itself is it is uneconomical to transport a lot of liquids. The pursuit of this Mitigating evil is expressed, among other things, in the fact that one cold wave concentrates generated. There has therefore been no lack of efforts to find connections which are solid and which yield thioglycolate by cleavage or other reactions. Shortcomings, e.g. B. the need for the hairdresser, the chemical conversion by observing the instructions, possibly by warming up, to do it yourself, more difficult Use.

It has now been found that the hairdresser is in a sense a chemical Can provide cold wave fluid reservoir; if you have the ability of ion exchange resins, 'to bind acids or bases and when treated with to give up neutral salts again, recycled. The procedure is carried out by loading an anion exchange resin with thioglycocic acid and a cation exchange resin with a base, e.g. B. ammonia, these components in the solid state over, the components subsequently can be mixed with each other as desired. Mixing is done in the ratio of Composition of that to be obtained by eluting with a neutral salt solution Cold wave liquid.

Experiments have shown, however, that free thioglycolic acid can do this is therefore not very suitable because the HS groups anchored to the resin via the CH COOH radical are particularly sensitive to oxidation.

It has now also been found that this disadvantage can be avoided can, if such compounds are used for loading, whose mercapto group in is protected in any manner amenable to division. Has under division one here to understand conversions through which in the displacement of the exchange resin the mercapto group is exposed at the same time. The mercaptocarboxylic acid with protected Sulfhydryl group, which usually contains the group -5 - CO -, and the base made free from the ion exchanger mixture by an eluting liquid, and at the same time the sulfhydryl group, e.g. B. hydrolytically, exposed. Also enzymatic Operations belong here.

By using an esterase complex in the elution liquid, as is found in dry liver extract, a cleavage of the - 5 - CO - -binding causes. These implementations can be carried out by the Ion exchanger apparently are considerably promoted.

For elution use a heated to 50 to 60 "C, if possible, suitable saline solution, e.g. B. a solution of potassium citrate.

For the purposes of the invention, for. B. the compounds carbaminothioglycolic acid (H2N CO - 5 CH COOH), carbethoxy-thioglycolic acid (C2H5. 0 CO S CH, COOH), carbonyl-bis-thioglycolic acid (HOOC. CH2. S. CO. S. CH2. COOH), thiocarbonyl-bis-thioglycolic acid (HOOC CH2-S CS CH 'COOH) and the S-acyl mercaptocarboxylic acids, such as S-acetylthioglycolic acid (CH3 CO S CH2 COOH).

Thiocarbonylglycolic acid thioglycolic acid amide (HOOC CH2, 0 CS 5 CH2 CO NH suitable. The anion exchangers are advantageously loaded with the preferably aqueous or aqueous alcoholic solutions of the acids in question, which are the cation exchangers with the solutions of the free base.

Although basically all types of ion exchangers can be used can, such as sulfonated phenolic resins or polystyrenes or methacrylic acid products, which have C O O H groups, as well as polystyrene resins with quaternary ammonium groups or phenol-formaldehyde resins with amino groups, so are the weakly acidic, COOH groups containing or weakly basic exchangers containing amino groups are preferable, for example the weakly basic one, under the protected one description AMBERLITE NE 59 commercially available product and the weakly acidic product under the protected name ASIBERLITE NE 64 commercially available resin because of its capacity is better than that of the strongly acidic or strongly basic resins.

The ion exchange resins are loaded as follows: A weakly acidic ion exchange resin, e.g. B. under the trade name AMBERLITE XE 64 known resin, it is washed three times with hydrochloric acid to transfer it to the HiForm, then with distilled water until the reaction is neutral. On 35 parts by volume of the The resin pretreated in this way is left in 175 parts by volume of normal ammonia solution for 30 minutes act, sucks off and dries.

The weakly basic ion exchange resin, e.g. B. under the trade name AMBERLITE XE 59, known resin, is washed three times to convert it into the OH 'form with ammonia and then washed neutral with distilled water. 50 parts by volume of the resin pretreated in this way is left with 250 parts by volume of the solution of one of the aforementioned Compounds, optionally in a water-alcohol mixture for 30 minutes in the Contact, washes off well after suction and dries.

When mixing the resins loaded in this way, it must be ensured that the Proportion of the ammonia carrier is dimensioned so that the displaced ammonia later not only neutralizes the displaced acid, but also that at the same time ongoing cleavage, e.g. B. hydrolysis, the sulfur compound exposing the Mercapto group ensures and still elutes the desired amount of free ammonia will.

The wet, weakly basic resin AMBERLITE XE 59 takes z. B. per liter 2.5 equivalents of S-acetyl-thioglycolic acid, the wet, slightly acidic resin AMBERLITE XE 64 e.g. B. binds 3 equivalents of ammonia. Here, under "equivalents" the Understanding the exchange capacity (see Prof. Dr. J. Büchi, ion exchanger in pharmacy und Medizin «in Arzneimittel-Forschung, 1, 6: pp. 247 to 257, especially p. 251 [1951]). In the simplest case, about 89.4 g correspond to a mixture of 1283 parts by weight loaded resin AMBERLITE XE 64 and 1414 parts by weight loaded amberlite resin XE 59 of a cold wave liquid of 5.1 g of thioglycolic acid as ammonium thioglycolate and 1.7 g of free ammonia in 100 ml of liquid.

In principle, it is possible to use the exchanger loaded with ammonia to waive and instead with an additional portion of an unloaded, d. H. to work in the O H 'form of the anion exchanger.

It is then eluted with an ammonium salt. Of course the The concentration of salts in the eluting solution is such that the one required for the desired Amount of cold wave solution required amounts of thioglycolate and base are released.

The mixture of the loaded ion exchange resins is in a suitable Given container. The amount is measured in such a way that from it several times with the same in each case Quantities of eluting solution taken from several cold wave liquids of the same composition can be.

By changing the composition of the eluting solution is the same When filling the container, a variation of the resulting cold wave liquid is possible. The container is expedient with a sintered plate on which the mixture is placed as a column is abandoned, a collecting vessel and see a nozzle that leads to a good .1rflow pump leads. The eluent liquid is used as a column of the resin mixture brought and (cheap (hlrcllgtsucks. The eluate has the composition of the desired Causing liquid and should be used immediately.

100 ml of t0 molar lialium citrate solution are used for the elution Contains 3240 g in 1000 ml of water. When performing an enzymatic cleavage add the esterases shortly before eluting with the aforementioned salt solution containing cod liver extract in an amount of 8.4 g. If you elute with 200 ml of 5 molar potassium citrate solution and 4.2 g of dry liver extract, one obtains one Curling liquid for the mild wave with about 2.5 g thioglycolic acid and 0.85 g free ammonia per liter.

If 894 g of the loaded ion exchanger mixture are filled into the container mentioned, in this way you can get about ten solutions for one cold wave or twenty Take solutions for one mild wave each.

Or you mix 1 part by weight of anion exchange resin, which the contains the required amount of thioglycolic acid, and 2 parts by weight of the same exchanger, but in the O H 'form, and eluted with an ammonium citrate or acetate solution sufficiently high molarity.

If the capacity of the ion exchangers is known, a person skilled in the art can Calculate and practically prepare the appropriate mixtures for all the cases mentioned.

The hairdresser z. B. in plastic bags the container fillings, the required individual amounts of salt and, if necessary, dry liver extract given at hand. Distilled water is generally available.

Claims (6)

PATENT CLAIMS: 1. Process for the production of ready-to-use hair curling liquids, characterized in that an anion exchange resin is used with a mercaptocarboxylic acid or with a compound forming a mercaptocarboxylic acid by cleavage and a Cation exchange resin loaded with a base and the loaded ion exchange resins with a suitable saline solution, e.g. B. an aqueous solution of potassium citrate, eluted. 2. The method according to claim 1, characterized in that the ion exchange resins be mixed after loading. 3. The method according to claims 1 and 2, characterized in that that an esterase complex is added to the salt solution used. 4. Means for performing the method according to claims 1 to 3, characterized by a mixture of weakly acidic, containing carboxyl groups Anion and weakly basic cation exchange resins containing amino groups, being on the anion exchange resin acidic compounds with protected, but through Reactions or cleavage of the exposed mercapto groups and on the cation exchange resin Bases are bound. 5. Means according to claim 4, characterized by a content of the Ion exchange mixture on unloaded anion exchange resin. 6. Agent according to claims 4 and 5, consisting of an aqueous Solution of potassium citrate containing an esterase complex.