US3715429A - Deformation of hair with thiourea dioxide and activating agent therefor - Google Patents

Abstract

A COMPOSITION BASED ON THIOUREA DIOXIDE AND INCORPORATING ACTIVATING AGENTS THEREFOR SUITABLE FOR THE PREPARATION OF A SUBSTANTIALLY NEUTRAL AQUEOUS SOLUTION FOR USE IN THE TREATMENT OF HAIR.

Description

United States Patent 3,715,429 DEFORMATION OF HAIR WITH THIOUREA DI- OXIDE AND ACTIVATING AGENT THEREFOR Robert Amon, Deceased, late of London, England, by Joy Mary Amon, administratrix, 711 N. Circular Road, and Julian Jacob Tobin, joint administrator, 223 Regent St., both of London, England No Drawing. Continuation-impart of application Ser. No. 634,861, May 1, 1967. This application Nov. 24, 1969, Ser. No. 879,545 Claims priority, application Great Britain, May 2, 1966, 19,256/ 66 Int. Cl. A61k 7/10 US. Cl. 424-71 11 Claims ABSTRACT OF THE DISCLOSURE A composition based on thiourea dioxide and incorporating activating agents therefor suitable for the preparation of a substantially neutral aqueous solution for use in the treatment of hair.

CROSS REFERENCE TO RELATED APPLICATIONS This application in a continuation-in-part of application Ser. No. 634,861 filed May 1, 1967, now abandoned.

BACKGROUND OF THE INVENTION This invention relates to improvements in processes and composition for the deformation of hair and relates not only to the so-called permanent waving of hair but also to the straightening of naturally or artifically curled hair.

The accepted and most common processes now in use for the permanent waving of haid by chemical methods comprise the impregnation of the hair with an aqueous solution containing one or more sulphydryl compounds as a reducing agent for the disulphide keratin linkages so that the sulphydryl linkages formed in the hair may be allowed to reshape in the well known manner of hairdressing techniques. The sulphydryl compound generally used is thioglycollic acid and is the only member of the class that has achieved any substantial degree of practical application. This has been brought about by (a) the low cost and (b) because it largely avoids the undesirable properties of the thiols as a class which are exhibited to only a small degree by this compound. Currently available permanent waving compositions possess substantial disadvantages. These are mainly their harsh action on the hair coupled with an obnoxious odor.

Some allergy is sometimes encountered and their use is often precluded because of this.

The corrosive nature of the thioglycollate based waving lotions which is reflected in loss in tensile strength of the hair is to some etxent an unavoidable defect of the thioglycollate ingredient.

Further such lotions are unstable on exposure to the air and excess quantities of the material are required. With regard to the thiol class of keratin reducing agents, an undesirable property is that filmy deposits are left on treated hair, or the hair acquires an undesirable appearance or odor.

Generally, in the permanent waving or setting of hair, it is usual first to shampoo the hair so that there is no trace of grease, dirt or impurities left on the hair, and then to wet the hair with an alkaline solution of the thioglycollic acid, the solution having a pH of between 9 and 9.5. Instead of thioglycollic acid, a thiopolyol or a thioester has been used. The alkaline solution is allowed to permeate for a short interval of time and then the hair is set with an oxidizing solution generally consisting of a weak solution of an oxidizing material, for example, hydrogen peroxide or potassium bromate. The theory of the method is that the cystine sulphur to sulphur linkages in the keratin of the hair are broken by the reducing agent, e.g. the thioglycollate and, while in this condition, the hair is wrapped around curler devices to form a spiral wave and the sulphydryl linkages are then fixed in their new position with the oxidizing substances previously mentioned.

In US. Pat. No. 2,847,351 these undesirable properties of sulphydryl compounds have been acknowledged and the patent proposes a composition for the deformation of hair which comprises in admixture (a) the disulphide of thioglycollic acid, a water-soluble salt thereof or the disulphide of thioglycerol (b) an odorless, reducing agent selected from a group which includes thiourea dioxide and (c) a water soluble alkaline material in excess of that required to react with any acid groups present in the disulphide and the reducing agent compounds. It is pointed out in this prior patent that thiourea is relatively ineffective hair deforming agent by itself even when employed in substantial concentrations.

German Pat. No. 1,198,491 also mentions that thiourea dioxide is relatively ineffective as a hair deforming agent by itself but that in an aqueous alkali solution it becomes effective. However, at useful concentrations, the thiourea dioxide decomposes in aqueous solution and it is therefore proposed in this German patent to use a disulphide compound as a stabilizing agent.

In both these previous proposals for hair deforming or treatment compositions, the composition is decidedly alkaline and it is known that alkaline solutions constitute a risk of damage to the hair being deformed or treated.

It should be noted that thiourea dioxide is used for simplicity throughout this specification although it is also known as imino-amino-methane sulphuric acid or cformamidine sulphinic acid and includes the salts of those acids.

I have now found that thiourea dioxide can be made the base of a very satisfactory hair setting composition and, furthermore, that a shampoo can be incorporated in my hair composition so that only a single operation is required both to wash the hair and to set it, except of course for the step of setting the hair while still at least damp to the new desired configuration as, for example, by winding it around curlers.

SUMMARY According to one aspect of the present invention, a composition for the deforming of hair in waving and other operations includes from 15% to 24% of thiourea dioxide and an activating agent for the thiourea dioxide the activating agent comprising at least one compound selected from the group consisting of thiogelatin, thiobisglycollic acid, ethylene-bisthioglycollic acid, ethylene thiourea and a 2,2-dithiobis-(N-alkylamide) of an aromatic carboxylic acid, the total amount of activating agent not exceeding 5% and the composition having a pH of from 4 to 10.

According to another aspect of the present invention, there is provided a process for the deformation of hair, comprising applying to the hair an aqueous solution of the composition of the immediately preceding paragraph.

3 DESCRIPTION OF THE PREFERRED EMBODIMENTS The activating agents are preferably included in the following proportions of the composition in the dry condition and on a weight basis, these proportions relating to the individual use of the activating agentsand clearly being variable if two or more are used; thiogelatin 0.1 to 0.5%; thio-bisglycollic acid 1 to ethylene-bisthioglycollic acid 1 to 5%; ethylene thiourea 1 to 5%; 2,2-dithiobis-(N-alkylamide) of an aromatic carboxylic acid 0.1 to 5%. Thiogelatin is used in this specification to mean gelatin into which thiol groups have been introduced. Such a material is marketed under the trademark Thiogel by Schwarz BioResearch, Inc.

Depending upon the activating agent used it may be necessary to incorporate in the composition a buffering agent to maintain the pH of the composition at a value of 4 to 10, but preferably 5 to 8. A suitable buffering agent is a phosphate selected from the group disodium hydrogen phosphate, sodium orthophosphate, tetrasodium pyrophosphate and tetrapotassium pyrophosphate.

The compositions may, and preferably do, include one or more detergents or hair washing agents such as sodium lauryl sulphate, potassium lauryl sulphate and lauryl dialkylolamide which are normally solid materials. A filler material such as anhydrous sodium sulphate may also be incorporated in the composition to provide bulk to facilitate mixing of the dry ingredients and division of the mixed ingredients into batches of conveniently handleable quantities.

The composition according to the invention may be marketed in powder form or in compressed powder form, i.e. as tablets formed in conventional manner, for dissolution in water before use. Alternatively, the composition may be supplied in the form of a solution. The concentration of the composition in solution ready for use desirably does not exceed 20 gms. in 75 grams of warm water. The foregoing reference to the pH of the composition is the pH thereof in the presence of this quantity of water. When the hair is in a particularly oily, greasy and/or dirty state it may be necessary to remove this oil, grease and/or dirt with a prior shampoo of about half of the aforesaid solution. But, in general, this is not required.

One of the more important aspects of the present invention in which it substantially differs from the usual method of applying thioacid or their salts in lotion form to curled and rolled hair is that the above thiourea dioxide with an activating agent, is combined with a dry powdered detergent capable of forming a shampoo, the composition is dissolved in water and is applied to the hair and is allowed to react on the hair for a period of to 25 minutes before washing oif and curling on rollers in the usual hairdressing technique.

After the hair is rinsed and rolled onto curlers, the hair may either be warm air-dried by a warm air blowing fan for upwards of 30 minutes until dry or, after the rinsing operation, the hair may be suitably oxidized with conventional oxidizing agents and warm air-dried as before.

The conventional oxidizing or neutralizer rinsing solutions may comprise 1.5% aqueous hydrogen peroxide; or 1% sodium perborate; or 1.5% sodium bromate as fixing solutions. These oxidizing agents may be used in the final rinse in a solution of lauryl polyoxyethanol sulphate (1 to 3 mols of ethylene oxide) at a level of 0.1 to 1% to enable quicker penetration of the hair sheaths.

After the hair has been treated in accordance with the invention, by shampooing, setting, rinsing, oxidizing and drying, the final permanent wave-set hair is found to have an accompanying silkiness and lustre such that one might say that the hair becomes rejuvenated or revitalized after the treatment.

Some examples of compositions according to the present invention will now be given.

EXAMPLE I Percent w./w.

Thiourea dioxide 15.0 Thio-bisglycollic acid 0.2 Thiogelatin 0.1 Ethylene thiourea 0.2 Disodium hydrogen phosphate 15.0 Sodium lauryl sulphate 40.0 Anhydrous sodium sulphate 29.5

EXAMPLE II Percent w./w.

Thiourea dioxide 15.0 Thio-bisglycollic acid 0.2 Thiogelatin 0.1 Ethylene thiourea 1.5 Disodium hydrogen phosphate 15.0 Tetrasodium pyrophosphate 5.0 Sodium lauryl sulphate 30.0 Lauryl dialkylolamide 3.0 Anhydrous sodium sulphate 30.2

EXAMPLE III Percent w./w. Thiourea dioxide 24.0 Sodium orthophosphate 24.0 Thiogelatin 0.2 Ethylene thiourea 2.5 Sodium lauryl sulphate 25.0 Potassium lauryl sulphate 3.0 Anhydrous sodium sulphate 21.3

EXAMPLE IV Percent w./w. Thiourea dioxide 15.0 Thio-bisglycollic acid 1.0 Thiogelatin 0.1 Disodium hydrogen phosphate 15.0 Sodium lauryl sulphate 40.0 Anhydrous sodium sulphate 28.9

EXAMPLE V Percent w./w. Thiourea dioxide 15.0

Ethylene-bisthioglycollic acid 1.0 2,2 dithiobis-(N-butylbenzamide) 0.5 Ethylene thiourea 1.0 Disodium hydrogen phosphate 15.0 Tetrasodium pyrophosphate 5.0 Sodium lauryl sulphate 30.0 Lauryl dialkylolamide 3.0 Anhydrous sodium sulphate 29.5

EXAMPLE VI Percent w./w. Thiourea dioxide 24.0 Sodium orthophosphate 24.0 Thiogelatin 0.5 Sodium lauryl sulphate 25.0 Anhydrous sodium sulphate 26.5

20 grams of any one of the compositions of examples per 75 millilitres of hot water (50 C.) form a unit dose of shampoo treatment for an average head. It is desirable that the concentration of the thiourea dioxide in the final aqueous solution used for treatment should be between 2 to 7%.

Thiourea dioxide can exist as NH? O or as formamidine sulphinic acid or amino imino methane sulphinic acid It is found that the above mentioned phosphates, i.e. disodium hydrogen phosphate, tetrasodium or potassium pyrophosphate apart from their buffering effect on the pH increases the solubility of the thiourea dioxide.

It will be appreciated that the method and composition of the present invention, by elimination of at least one step enables a saving of time to be effected in the permanent waving of hair without undue expense as the compositions according to the invention are economic to manufacture and market. Furthermore, as the aqueous solution to be applied to the hair has a pH value of 4 to 10, but preferably 5 to 8, the risk of damage to the hair, as compared with conventional alkaline solutions, is materially reduced. Furthermore, the hair is left in a silky manageable and revitalized condition and therefore the application of a hair conditioner such as lanolin or lanolin substituted creams can be dispensed with, thus effecting further labor saving and other operational costs.

It has been found that the use of a 2,2-dithiobis(N-alkylamide) of an aromatic carboxylic acid, preferably 2,2-dithiobis-(N-butylbenzamide) in a composition according to the invention either as the or one of the activating agents acts to stabilize the deformation of the hair.

Thus, when 2,2-dithiobis-(N-butylbenzamide) is added to the compositions of Examples 1, II, III, IV and VI in the amount of 0.1 to 5%, preferably 0.5%, by weight, conveniently by dry mixing, it confers a more lasting permanent waving character to the compositions which is unaffected by a humidity of up to 70% relative humidity at ambient temperatures.

It is probable that the disulphide linkages add an additional catalytic activity in the breaking of the SS cystine bonds before they finally reset to reform in their new positions after the deforming process.

I claim:

1. A composition for the deforming of hair comprising from to 24% of thiourea dioxide and an activating agent for the thiourea dioxide, the activating agent comprising at least one compound selected from the group consisting of thiogelatin, thiobisglycollic acid, ethylene-bisthioglycollic acid, ethylene thiourea and 2,2-dithiobis-(N-[alkyl] butylamide) of benzoic acid, the total amount of activating agent not exceeding 5% and a pH buffering agent.

2. A composition according to claim 1 wherein said buffering agent is suitable to provide a pH of 5 to 8 in an aqueous solution.

3. A composition according to claim 1, in which thio- 6 gelatin is present in the activating agent in an amount of from 0.1 to 0.5% by weight.

4. A composition according to claim 1, in which thiobisglycollic acid is present in the activating agent in an amount of from 0.1 to 5% by weight.

5. A composition according to claim 1, in which eth ylene-bisthioglycollic acid is present in the activating agent in an amount of from 1 to 5% by weight.

6. A composition according to claim 1, in which ethylene thiourea is present in the activating agent in the amount of from 1 to 5% by weight.

7. A composition according to claim 1, in which 2,2- dithiobis-(N-[alkyl] butylamide) of benzoic acid is present in the activating agent in an amount of from 0.1 to 5% by weight.

8. A composition according to claim 7, in which the activating agent is 0.5% by weight of 2,2-dithiobis-(N- butylbenzamide) 9. A composition according to claim 1, containing as a pH buffering agent a phosphate selected from the group consisting of disodium hydrogen phosphate, sodium orthophosp'hate, tetrasodium pyrophosphate and tetrapotassium pyrophosphate.

10. A composition for the deforming of hair comprising an aqueous solution of from 15% to 24% of thiourea dioxide and at least one activating agent selected, in the percentages by weight given, from the group consisting of thiogelatin, 0.1 to 0.5%; thiobisglycollic acid, 0.1% to 5%; ethylene-bisthioglycollic acid, 0.1% to 5%; ethylene thiourea, 0.1% to 5%; and 2,2-dithiobis-(N-butylamide) of benzoic acid, 0.1 to 5%.

11. A process for the deformation of hair comprising applying to the hair an effective amount of an aqueous solution of the composition of claim 1.

References Cited UNITED STATES PATENTS 2,403,937 7/1946 Lubs 424-72 X 2,774,355 12/1956 Bell 424-71 X 2,809,150 10/1957 McDonough 424-72 2,847,351 8/1958 Brown et a1. 42472 3,171,831 3/1965 Town 42471 X 3,534,135 10/1970 Wajaroif 424-71 FOREIGN PATENTS 1,198,491 3/ 1966 Germany 424-72 OTHER REFERENCES Gialdi et al., J. Soc. Cosmetic Chemists, vol. 17, pp. 575-579 (1966).

JEROME D. GOLDBERG, Primary Examiner V. C. CLARKE, Assistant Examiner U .8. Cl. X.R.