DE1208450B - Preparations for shaping human hair - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

A61k

German class: 30 h - 13/07

Number: 1208 450

File number: M 58257IV a / 30 h

Filing date: September 19, 1963

Opened on: January 5, 1966

The usual procedures currently used for reshaping hair by chemical means are, have a first stage in which the hair is impregnated with an aqueous solution, the one or contains several sulfhydryl compounds as reducing agents for the disulfide bridges of the keratin, to make the hair plastic and allow it to be reshaped. The sulfhydryl compound Thioglycolic acid is the only compound in this class that has a substantial degree of practicality Has found application because of its low cost and the fact that the undesirable properties of the thiols emerge least in this connection.

Nonetheless, the currently available permanent waving compositions have significant disadvantages. The main disadvantages are their foul odor and their aggressive effect on human skin and to name the hair. Often allergic reactions occur. The lack of a universal Applicable to the hair of any person, depending on the different sensitivity of the Hair to thioglycolic acid is due, is also an unsolved problem.

The aggressive nature of thioglycolate based hair waving lotions, which leads to damage to the hair, which manifests itself in a loss of tensile strength, is a certain degrees on the properties of the thioglycoalt component traced back. Furthermore, such lotions are unstable in the presence of air, and often a large excess of material is required. One of the reasons for the unusability certain other thiol compounds with the desired effect is that on the treated one Hair is left with unwanted deposits or that the hair has an undesirable appearance or appearance. takes on an undesirable odor.

It has now been found that by using lower N-alkanoylcysteines with up to 10 carbon atoms and N-aroylcysteines having up to 12 carbon atoms as thiol reducing agents Hair deformation is accompanied by a number of unexpected benefits, especially when one considers that the cysteine itself, as is well known, has only a very limited capacity to make hair plastic and its applicability in such processes continues to be due to its inconstancy as opposed to oxidation in air and its property, in the case of oxidation, a precipitate or leaving a deposit is limited.

The cosmetic advantage or the cosmetic

Preparations for shaping human hair

Applicant:

Mead Johnson & Company,

Evansville, Ind. (V. St. A.)

Representative:

Dr.-Ing. H. Ruschke and Dipl.-Ing. H. Agular,

Patent Attorneys, Munich 27, Pienzenauer Str. 2

Named as inventor:
Aaron Leonard Sheffner,
Ivansville, Ind. (V. St. A.)

Claimed priority:

V. St. v. America September 21, 1962

(225 392),

dated August 13, 1963

(301 843)

"Elegance" of compiled using lower N-alkanoylcysteines and N-aroylcysteines Hair preparations associated with their physiologically acceptable properties and their Ability to reduce keratin makes these agents special for use in hair shaping suitable. Lower N-alkanoylcysteines also provide and N-aroylcysteines are only water-soluble oxidation products and therefore leave after rinsing Do not oxidize a film back on the hair, nor do they otherwise impart to the hair an undesirable appearance.

According to one embodiment of the invention, the hair is treated with a solution of an N-alkanoylcysteine or N-aroylcysteine treated and then shaped. In another embodiment of the Invention clean human hair while maintaining it in the desired, predetermined shape is, with a 3 to 20% aqueous solution of one lower N-alkanoylcysteine or an N-aroylcysteine having a pH of about 7.0 to 9.5 in Brought in touch. The contact time is about 10 minutes to about 12 hours, depending on the properties of the treated hair, the temperature, the pH of the solution and the

509 777/409

3 4

Concentration and the type of low concentration used in the process according to the invention are those in

N-alkanoylcysteine or N-aroylcysteine. The fixing agents customary in the hair wave technique can be used,

choice of the optimal time period is left to the specialist. These means either consist of the hair

left to man. exposed to air for a long time or with

Preferred lower N-alkanoylcysteines in a solution of an inorganic oxidizing agent include, inter alia, N-acetylcysteine, N-propionyl- is brought into contact. For this purpose vercysteine, N-butyrylcysteine, N-valerylcysteine, N-capro- used and according to the invention suitable oxydationsylcysteine and N-heptanoylcysteine, including hydrogen peroxide, which are valid, whether in the D or L configuration or into alkali bromates and iodates, the alkali perborates, etc. in the form of a mixture of the optical antipodes. Since the cysteine derivatives described are an acid-preferred N-aroylcysteines, among other things, they have a strength similar to that of acetic acid N-benzoylcysteine, N-toluoylcysteine, N-ethylbenzoyl-, their solutions are preferably with cysteine and N-propylbenzoylcysteine. According to the invention, the hair waving agent which is preferred to neutralize a suitable base to the pH value is N-acetyl to a level within that for permanent waving L-cysteine. Adjust the advantageous properties of the area required for treatment. The compounds used according to the invention, bases used for pH adjustment, should be embodied sufficiently by this compound in an optimal manner. be strong to neutralize the cysteine derivative, the L-shape is economical and should be cosmetically acceptable. Both preferred, since L-cysteine, from which the connection is challenged by sodium hydroxide or, is technically fulfilled from materials such as feathers, ammonia or ammonium hydroxide. Other hooves etc. is obtained. N-acetyl-DL-cysteine is useful substances are among others which are equally effective and may be preferred to use sodium, potassium and ammonium salts of kos if it is cheaper, such as. For example, by total synthesis, hermetically acceptable acids with pK _a values can be obtained from. over 3.2. Furthermore, the cosmetically appropriate

It has been found that N-acetyl-L-cysteine in acceptable organic amines, the basicity of which, with regard to damage to the hair, offers an advantage over thioglycolate preparations that is substantially comparable or greater than that of ammonia. is suitable and even preferred. The pKt, values in the diagram are the elongations of various of these amines are below 5.0.
Hair samples that have been treated according to the invention or with a number of thioglycolate preparations, as described in Example 9 for pH adjustment of the bases used according to the invention, are indicated as a function of the hair waving solutions: Na tensile stress shown. The diagram shows that with trium hydroxide, potassium hydroxide, ammonia, Meeiner 10% (0.6 molar) aqueous solution of ethylamine, ethylamine, propylamine, butylamine, di-N-acetyl-L-cysteine with a pH of 9.3 bemethylamine, diethylamine, monoethylamine, ethylene-treated hair (sample C) compared to sample A, 35 diamine, piperazine, tetramethylene diamine, and that of the untreated lock of hair does not have any significant sodium, potassium or ammonium salts of the milk damage. The monoethanolamine with a 0.6 molar solution acid, acetic acid, carbonic acid, citric acid, etc. of thioglycolic acid with a pH value of 9.3 is the sample pretreated for pH adjustment (sample B) is, however, significantly added base. The preferred pH range is 9.0 to 9.5. been harmed. 4 ° As can be seen, most of the

When administered orally, N-Acetyl-L-cysteine has the bases listed above to be water-soluble substances,

or when inhaling an aerosol, from which it can be deduced that such bases

contains binding, proven to be practically non-toxic. be preferred.

It has no adverse effect on the blindfold on the ingredients of the invention skin or the mucous membrane of the nasal passages and also the term "cosmetically acceptable" used. not to the activity of the cilia in the air - refers to certain functional properties tube out. Both in the guinea pig and the substances. Among cosmetically acceptable amibeim People showed themselves with repeated annen and salts are z. B. use of such substances no symptoms of sensitization. that stood in the concentrations used

As usual in the manufacture of perms, 50 do not exert any aggressive effects, a low one

the hair, if it is exposed to toxicity through contact and does not irritate or sensitize

Size N-alkanoylcysteine or N-aroylcysteine solution. Furthermore, these components should be based on the

Sufficiently plasticized in order not to excessively or irreversibly emollient to the desired hair

To be able to take shape, oxidizing conditions have an effect. You should be familiar with the sulfhydryl

exposed to the cystine disulfide bridges of the keratin 55 groups of the lower N-alkanoylcysteines resp.

■ restore. In technical terms, this level bears N-aroylcysteine under storage and use conditions.

various terms, such as "fixing" or not in an irreversible or destructive way

"Neutralize". The former expression appears for respond, such as B. by oxidation, condensation

the use in the present description or precipitation. Furthermore, they should not have any undesirable

more suitable, since the expression "neutralization" also causes color reactions that lead to the

includes pH adjustment. If in the present appearance of the remedy as a whole or with it

Description of the term "fixative" used could worsen treated hair,

it refers to the stage at which the hair, When performing the inventive method

that by touching a solution of a low driving, permanent waving solutions are preferred in which

N-alkanoylcysteine or N-aroylcysteine plasticizes 65 the described cysteine derivative in one concentration

Has been exposed to oxidative conditions from about 7 to 10% when the treatment is included

is carried out to restore the cystine disulfide at room temperature, as is done e.g. B.

to allow bonds of the keratin. is the case with the so-called cold wave. The excellent

recorded physiological compatibility which has been described above, however, present even in solutions with a concentration of up to 20 ° / _0th If higher temperatures are used when treating the hair with an N-alkanoylcysteine or N-, a_roylcysteine preparation, it may be desirable to use the compounds in a concentration of less than 7%.

The auxiliary substances used in the hair wave technique are also suitable according to the invention. Such tools include opaque means and thickening agents to avoid the otherwise transparent solution of the cysteine derivative described to give a milky or creamy, lotion-like consistency. For this purpose you can Substances such as carboxymethyl cellulose, polyacrylates, polystyrene latex, emulsified oils, chlorinated hydrocarbons, Pectins, gums, etc. can be used. Furthermore, cosmetically acceptable ones can optionally be used Perfumes and dyes are added.

Additives of a functional nature can also be incorporated. He was found in that Agents used according to the invention can advantageously be incorporated with wetting agents and swelling agents. Suitable wetting agents include the ionic and nonionic synthetic wetting agents and in particular Detergent actives such as the sodium and potassium salts of the alkylsulfuric acids and alkylsulfonic acids and aralkyl sulfonic acids having at least 12 carbon atoms, the polyoxyethylenes and polyoxypropylenes and their ethers and esters. The wetting agents are used in concentrations of about 0.1 to 1.0 percent by weight used.

As substances which, in a known manner, cause the hair sheath to swell on contact with water cause urea, thiourea, methylurea, ethylurea and the mineral acid salts called of guanidine. These substances are added to the masses in an amount of about 1 to 15 percent by weight incorporated into the hair wave solution, depending on the function and for the end product "Elegance" desired properties.

Other additives that can be used include agents to prevent a Over-treatment of the hair. Known substances suitable for this purpose include Ammonium chloride, ammonium sulfate, ammonium phosphate and various other salts of weak Bases and strong acids.

The invention is further illustrated by the following examples.

example 1

A heavily waved or bent lock of hair was immersed in a 7% strength aqueous solution at room temperature for 1 hour Solution of N-acetyl-L-cysteine, which had been adjusted to pH = 9 with aqueous sodium hydroxide solution, immersed. The curl was then removed from the solution with a weighted down in a small clamp and allowed to hang down from a horizontal rod. That way the curl was left hanging for 5 minutes and during this time once with the N-acetyl-L-cysteine solution flushed. The tress was then washed with tap water and placed in a hanging position allowed to air dry. The treatment resulted in a complete removal of the corrugation or Curvature of the hair and a strand of completely straight, undamaged hair was obtained.

Example 2

In an experiment using identical curls of human hair, the following Hair wave solutions compared. The compositions of these solutions are given below in percent by weight of the final solution. A fixing solution of 4.2 g of sodium perborate monohydrate and 1.0 g of sodium hexametaphosphate was obtained used in 475 ecm of water.

Solution # 1
Water (serves as a blank sample).

Solution # 2

7% N-acetyl-L-cysteine, adjusted to pH = 9.15 with ammonium hydroxide.

Solution # 3

7% N-acetyl-L-cysteine, adjusted to pH = 9.15 with sodium hydroxide.

Solution # 4

7% N-acetyl-L-cysteine and 15% urea, adjusted to pH == 9.15 with sodium hydroxide.

Solution No. 5

3% N-acetyl-L-cysteine and 15 ° / ₀ urea, adjusted with sodium hydroxide to pH = 9.15.

Five practically identical locks of hair were put on conventional permanent curlers, such as those for household use used, wound and separately saturated with any of the above hair waving solutions 1 to 5. After 10 minutes of exposure, the excess hair waving solution was rinsed off the curls with water. The curlers with the wet curls on them were kept for 30 minutes at room temperature, and then each curled curl was saturated with the fixing solution. The curls were then Rinsed with warm water, removed from the curlers and rinsed again with warm water. To After rinsing with water it was found that the curl treated with solution No. 1 (water) had assumed a straight shape, while the remaining samples had a wavy or curl shape but the sample treated with solution no. 5 was less pronounced than the samples treated with solutions 2, 3 and 4.

Similar results as with solution no. 4 were obtained if instead of urea in the same amount by weight of thiourea, methylurea, ethylurea or guanidine acid addition salts, such as the sulfate, phosphate, hydrochloride or hydrobromide were used.

Example 3

Comparative tests were carried out using the hair waving solutions specified below and identical curls or strands of fresh human hair 15.3 cm in length and weighing about 1 g each.
Solution # 1

10% N-acetyl-L-cysteine, adjusted to pH = 9.3 with ammonium hydroxide.

Solution # 2

10% N-acetyl-L-cysteine, adjusted to pH = 9.3 with sodium hydroxide.

I 208 450

Solution # 3

10% N-acetyl-L-cysteine, with monoethanolamine adjusted to pH = 9.3.

The curls were first moistened with the test solution, wound on conventional hair-curling sticks, moistened again with the same test solution and kept in this state for 10 minutes. The curls on the bars were then rinsed and carefully saturated with a fixing solution made from 1.5%. aqueous hydrogen peroxide existed. Similar results are obtained when aqueous hydrogen peroxide in place of l% strength sodium perborate or ^e l, 5% aqueous Natriumbromatlösungen be used as a fixing solution. The curls were then unwound, saturated again with the fixing solution, rinsed again with warm water and tested. It was found that all of the curls retained a pronounced curl when wet. The curl that had been treated with Solution # 3 was superior in texture and slightly firmer curl.

Example 4

A hair wave solution that contains 10% N-acetyl-L-cysteine and 0.1% ethylene oxide-propylene oxide polymer a molecular weight of 1750 ("Pluronic F-68", Wyandotte Chemicals Corporation, Wyandotte, Michigan) Contained was compared in their effectiveness with a commercially available hair wave lotion that after the analysis showed 5.52% ammonium thioglycolate as a waving agent and a pH of 9.25. Of the The experiment was carried out on separate curls or strands of fresh human hair as in the preceding Example, but with a treatment time of 15 minutes. In each case there were undulations obtained equivalent strength, but the curl curled with the N-acetylcysteine solution was softer and showed a more natural texture. Similar results were obtained with an N-acetylcysteine solution, which contained the following wetting agents: 1 percent by weight »Pluronic F-68«, 0.1% sodium lauryl sulfate, or 0.5% "Polysorbate 80", and 1% sodium dodecylbenzenesulfonate.

Example 5

Following the procedure described in Example 3, a further experiment was carried out using individual Hair curls or strands carried out. In this experiment, three hair curling solutions were used the same composition given below, but adjusted to pH = 7, pH = 8 or pH = 9 had been adjusted.

N-acetyl-L-cysteine 20.0 g

Urea 5.0 g

Ethylene oxide-propylene oxide copolymer ("Pluronic F-68") 1.0 g

Monoethanolamine how to adjust the

required pH value

Distilled water like to top up

100 ecm required

Exposure times of 15 minutes were used. The curl treated at pH = 7 pointed showed a weak undulation, while the undulation produced at pH == 8 was more pronounced. With the curl treated with the solution adjusted to pH = 9 had a firm, receding or elastic shape Curl on.

Example 6
5

A hair waving lotion is produced with the composition given below. The mineral oil and the liquid lanolin are used to enhance the cosmetic "elegance" of the

ίο To give a cream-like appearance by means of. The polyoxyethylene components are nonionic wetting agents that improve the effectiveness the corrugation and for the purpose of helping to emulsify the oils. That Silicone antifoam is used for ease of manufacture, and the ethylenediaminetetraacetic acid disodium salt is a chelating agent that increases the shelf life of the finished composition. N-acetyl-L-cysteine is the waving agent, monoethanolamine is used to adjust the pH, as established it was found that agents containing this compound produce corrugations of better quality or deliver a better structure. Distilled water is the carrier. Optionally, a perfume can also be incorporated will.

I mineral oil 3.0 g

Liquid lanolin 0.75 g

Polyoxyethylene (4) lauryl ether 0.5 g

Polyoxyethylene (20) lauryl ether 0.5 g

Silicone antifoam agent 0.01 g

N-acetyl-L-cysteine 10.0 g.

Ethylenediaminetetraacetic acid

Disodium salt 0.05 g

B <monoethanolamine, as for setting
required to pH = 9.3

Distilled water as required to make up to 100.0 ecm.

The preparation of the composition consists of the following steps: There are separately prepared solutions of the designated A and B, oil-soluble and water-soluble ingredients and heated to 70 ⁰ C. These solutions are then combined and the silicone antifoam agent added. The pH of the mixture is then adjusted further, if necessary, and finally topped up with water.

Example 7

Perms were made on seven people. It became according to the usual, when using The procedure used by permanent waving lotions consists of the following stages: Shampooing of the hair, saturation with the hair wave solution, winding the hair on hair curling rods, again Saturate on the rods with the hair curling solution, wait for a while, at the discretion of the hairdresser Rinse and "neutralize" with 1.5% igaa is sufficient to create a wave in the hair Hydrogen peroxide solution that serves as a fixing solution. It was the hair wave lotion of Example 6 with the the following exposure times are used:

3 people 15 minutes

1 person 17 minutes

1 person 20 minutes

1 person 30 minutes

1 person 60 minutes

After saturating the hair on the winding bars with the fixing solution, it was removed from the winding bars removed, saturated again with fixing solution, rinsed, wound on curlers and dry calmly. After the hair curlers had been removed, there were perms made by the. Hairdresser and all were considered satisfactory.

Example 8

A hair wave lotion similar to that of Example 6 was compared in effectiveness with a commercially available Hair wave lotion, as it is used to create permanent waves in the home, compared. The usual one Medium had a pH of 9.25 and after analysis 5.52% ammonium thioglycolate as Corrugating agent on. Five people were given a lotion to make permanent waves on the left Head side applied while the perm is made on the right side of the head with the other lotion became. The perms were made by hand by a licensed hairdresser according to the usual, in the method described in Example 7 prepared. The most noticeable difference, that of that The hairdresser found in all cases was the greater ease with which the lotion was used Hair treated by Example 6 could be combed. Knots or intertwining of the hair ends, that occurred when using the commercially available product were completely absent.

Example 9

Individual curls or strands of freshly grown human hair 15.3 cm in length and one Weight of about 1 g each were separately in a loose, unwound state for 30 minutes in one of the immersed in the following means. The hair waving solution was then rinsed off the hair and the tresses or curls were saturated with a 1.5% solution of hydrogen peroxide as a fixing solution. The tresses or curls were rinsed again and dried.

A. Untreated control sample.

B. thioglycolic acid, 0.6 molar, adjusted to pH = 9.3 with monoethanolamine.

C. N-acetyl-L-cysteine, 0.6 molar, with monoethanolamine adjusted to pH = 9.3.

Twenty-five to thirty individual hairs were selected from each lock a single load on an Instron tensile tester to ultimate break exposed. This is a machine that does a stretch at a constant speed causes and has a load measuring system, which consists of a load cell, at the voltage and Distance coupled, and an electronic amplifier device consists. It became the following Instron test conditions applied:

Map or diagram speed 25.4 cm / minute

Clamp speed 5.08 cm / minute

Length of the distance to which the load cell is adjusted .. 10.16 cm

Speed of increase
of tension 50% / minute

Full load at the above-mentioned settings 100 and 200 g

Temperature 21 ° C

Relative humidity 65%

The values obtained for the individual hair from the various strands or curls were averaged and the obtained average values of the

ίο Tension in grams per denier and with the associated Average values of elongation, expressed as a percentage of the original length, in a graphic representation compiled. The curves obtained are shown in the diagram. Of the The course of the curves according to the yield point for each strand was then derived from these curves according to the Method of Harris and Brown, Textile Research Journal, 17, p. 323 (1947). These authors have shown that with decreasing Number of disulfide bonds the slope of the curve after exceeding the yield point accordingly decreased. From the data summarized in the following table, it was concluded that the course the curve after exceeding the yield point for sample C, which contains the N-acetyl-L-cysteine agent treated sample, from the course of the curve of the untreated control sample, sample A, statistical is not different. Furthermore, it was concluded that sample B, which was processed with the Thioglycolate agent treated sample, due to the treatment as a result of the destruction of a number of Cysteine bridges have been severely damaged.

Table I.

Curve shape after exceeding the yield point in stress-strain tests
on hair samples

sample
40 Rise in curves after
Exceeding the yield point default
deviation A.
B.
C. 3.50
1.91
3.31 0.40
0.56
0.42

Example 10

To further measure the hair damage caused by the chemical treatment described, stress-strain tests were also carried out on the wet hair samples in accordance with the method described in Example 9. About ten individual hairs from each sample were subjected to stress-elongation tests using the device described in Example 9 while they were immersed in water at 21 ° C. There were the same speed increase of the voltage, namely 50% P ^ro minute, and to which the load cell is set to the same path length, selected nämlieh 10.16 cm, as in Example 9. Using the Instron Prüfdynamometer was connected an integrator, in order to be able to automatically calculate the area under the stress-strain curve as a measure of the work done in stretching each individual hair thread up to an elongation of 20 and 30%. The "work index" (Speakman, Journal of the Textile Institute, Vol. 37 T, p. 102 (1947) is the ratio of work involved in stretching the treated

509 777/409

Hair thread to a given stretch value is required to do the work required to stretch the untreated Material to the same elongation value is required. The results obtained are in Table II compiled.

Table II

From strain-tension tests
treated hair samples (under water from 2Γ
determined working indices

C)

rehearse
relationship index
for 20% elongation index
for 30% elongation B / A
C / A 0.245
0.841 0.265
0.837

Examples 12 and 13

The experiment described in Example 3 was carried out under

Replacement of the N-acetyl-L-cysteine used in this example by N-propionyl-L-cysteine or N-butyryl-L-cysteine repeated. Virtually the same results were obtained.

Example 14

LO The experiment described in Example 3 was repeated using N-benzoyl-L-cysteine instead of N-acetyl-L-cysteine. Virtually the same results were obtained.

The conclusion can be drawn from the values that the sample treated with the thioglycolate agent, sample B, has significantly poorer properties than sample C, which contains the N-acetyl-L-eysteine agent has been treated.

Example 11

After shampooing, the hair of an adult woman was moistened while still moist with a 7% strength ^e n aqueous solution of N-acetyl-L-cysteine, which had a pH of 7.0 (adjusted with sodium hydroxide), and was applied Curlers wound. The hair on each curler was then re-moistened with the solution. The procedure was stopped shortly before bedtime and the hair on the rollers remained damp during the night. The hair was then dried, the curlers removed and the hair combed. The desired wavy or curly texture was achieved, which was of much longer duration than if water alone was used to produce the wave. In addition, the hair had a better overall texture or body and a better shine.

Claims (7)

Patent claims: 1. Means for deforming human hair, characterized in that it from a 3 to 20% aqueous solution of a lower N-alkanoylcysteine with up to 10 carbon atoms or an N-aroylcysteine with up to 12 carbon atoms that has a pH from about 7 to 9.5 and contains at least one swelling agent or wetting agent. 2. Composition according to claim 1, characterized in that the solution contains about 1 to 15 ⁰ J ₀ urea, thiourea, Methylurstoff.ätthylurstoff or a guanidine acid addition salt as swelling agent. 3. Means according to claim 1 or 2, characterized in that the solution is about 0.1 to 1% contains a wetting agent. 4. Composition according to claim 1 to 3, characterized in that it contains N-acetyl-L-cysteine. 5. Composition according to claim 1 to 3, characterized in that it contains N-acetyl-DL-cysteine. 6. Composition according to claim 1 to 3, characterized in that it contains N-benzoyl-L-cysteine. 7. Means according to claim 1 to 3, characterized in that that it contains N-benzoyl-DL-cysteine. 1 sheet of drawings 509 777/409 12.65 © Bundesdruckerei Berlin