Permanent waving solutions and method

2,736,323

Patented Feb. 28, 1956

United States Patent Office

2,736,323

PERMANENT WAVING SOLUTIONS AND METHOD o

Everett G. McDonough, Yonkers, N. Y., assignor, by mesne assignments, to Tide Water Patent Development Company, Incorporated,^ Norfolk, Va., a corporation of Virginia

No Drawing. Application August 13, 1949, ¹⁰

Serial No. 110,239

Claims. (CI. 132—7)

This invention relates generally to the art of permanent- 15 ly altering the physical form or shape of hair, and, more particularly, to the art of permanently waving hair. This application is a continuation-in-part of my copending application Serial No. 398,235, filed June 16, 1941 now Pat. No. 2,577,710. 20

It is known that the physical form or shape of hair can be permanently altered without injury to the hair structure by utilizing three forces, namely, a mechanical force, a chemical or softening force, and a fixing or setting force. More particularly, in permanent waving the 25 mechanical force is set up by winding the hair in curls as on mandrels. A chemical medium is then (or previously) applied to create the chemical or softening force adapted to place the wound tresses in condition to be permanently molded and altered to their new form as ³⁰determined by the winding. Finally, means are utilized to fix the wound tresses in their new form, which latter means may consist of an application of heat, generated electrically, chemically or in any other way followed by cooling or a second chemically reactive force to neu- ³³tralize the chemical waving medium.

The present invention is concerned with the chemical medium which provides the chemical or softening force above referred to, this being identified hereinafter for descriptive purposes only as the waving solution, and com- ⁴⁰prising an aqueous solution containing the waving agent or agents.

Heretofore, the practice has been to use a waving agent for such solutions which is an alkaline material, for example, borax, various carbonates and phosphates of ⁴⁵alkaline materials, ammonia and ammonium salts, such as the carbonates. Furthermore, soluble sulfites of alkalies and ammonia have been utilized for the waving agent, and sulfides have also been provided for this purpose.

However, with respect to the sulfites and to all other ⁵⁰heretofore utilized waving agents excepting sulfides, relatively high concentrations are necessary in order to obtain any satisfactory permanent wave in the hair. Especially with fine hair, there is difficulty in providing a suitable waving solution for obtaining an altered form or shape ⁵⁵for the hair which can be termed permanent.

I have found that there is a limiting concentration of these materials above which either hair destruction Or injury occurs with less satisfactory wave. It is probably this upward limiting effect on concentration of these wav- ⁶⁰ing agents that make it impossible to obtain satisfactory results in a short time where the hair is set by a chemical force, for the solution containing these waving agents must be left in contact with the hair for periods ranging from four to twenty-four hours before a satisfactory wave ⁶⁵may be obtained.

The sulfides do not require as long a time nor need quite as great a concentration as the sulfites and a satisfactory solution may be made therefrom for most types of hair and even fine hair under some conditions, but many disadvantages appear when using sulfides, the first of which is the characteristic odor of rotten eggs possessed by such sulfides resulting from generation and liberation of free hydrogen sulfide by hydrolysis. All attempts to mask this odor result in failure and the use of heavy perfumes only serve to minimize the objectionable odor. Secondly, these sulfides have a tendency to cause tarnishing and blackening on metal, particularly jewelry, silverware, and the like, which is a further objection to their use in the waving lotion. Furthermore, the disgusting odor which accompanies the use of such hydrogen sulfide salts is toxic to breathe and although normally the amount of hydrogen sulfide produced thereby is not dangerous, when in a confined booth or room such as a beauty shop cubicle often used in hair waving establishments, the concentration of the gas may become so high as to seriously affect both operator and patron, unless expensive ventilating equipment is installed and maintained to remove this gas.

Thus, it will be seen that, while these sulfides are satisfactory in use in waving solutions from the point of view of performance or results in the finished permanent wave, they are wholly unsatisfactory because of the combined effect of toxicity, nauseating odor, and metallic coating effect.

More specifically, one of the best waving agents known for use when carrying out a permanent change of form or shape of the hair is ammonium hydrogen sulfide; but, despite its relatively greater waving power, the use thereof is limited by liberation of hydrogen sulfide gas, together with ammonia gas. These evolved gases make this compound very objectionable and perhaps dangerous, unless special precautions to remove the vapors, for instance, by suction ventilators, are taken.

Another objection to use of ammonium hydrogen sulfide and other sulfides is that the hair tends to retain the sulfide in spite of repeated rinsings even when using a chemical setting solution. The result is a mal-odor to the hair, particularly oh each re-wetting. More important, however, is the fact that this retention by the hair of the sulfide affords a continuous “relaxing” effect on the permanent wave with the result that the wave becomes less tight with each re-wetting.

It is the general objective of this invention to provide an agent for use in altering the permanent form or shape of hair which will be similar in its effect to that of the sulfides referred to above and yet will not possess the great disadvantages mentioned.

It is a further object of this invention to provide a lotion for the permanent waving of hair containing an entirely novel ingredient as the waving agent which will give the solution a wide range of adaptability for permanent waving of any type or texture of hair.

It is a further object of this invention to provide a non-odorous, non-toxic hair waving solution adapted to more rapidly and more successfully place hair in a condition to be altered in form or shape permanently, irrespective of whether codling subsequent to heating or chemical meins is used after applying the waving solution in order to fix the hair in its new configuration.

It is a further object of this invention to provide a waving solution suitable for that type of permanent waving of hair which utilizes a chemical action for the fixing of· the hair in its wound forni, such waving solution containing a waving agent as powerful, rapid and satisfactory as ammonium hydrogen sulfide, but free from the limitations of ammonium hydrogen sulfide, particularly the bad odor and toxicity.

It is a further object of this invention to provide a waving solution powerful enough to wave hair without the need of added heat and which can be neutralized or completely removed by water alone; or, in other words, the wave can be fixed in the hair by washing out the waving agent’with water alone.

2,736,323 ³

By this invention there is provided an agent for use in the permanent reforming of hair which is fast in action, satisfactory in use for all types of hair and yet is free from objectionable odors or toxicity or the like.

I have discovered that I can obtain these objects by providing as a waving agent a mercaptan, or a mixture of mercaptans, whether the fixing of the new form for the hair be by cooling subsequent to heating, or by using chemical rinses or by any other method, and, further, that an effective waving solution can be obtained by proper formulation including a mercaptan in water. The mercaptans are represented by the formula R—SH where R is an organic group such as the ethyl group in

Hthyl mercaptan or the benzyl group in

A-C-SH U^H

Benzyl mercaptan

Such simple mercaptans will function adequately as waving agents, but they still have the disadvantage of sulfides, such as ammonium hydrogen sulfide as far as bad odor is concerned.

I have discovered that bad odor, and other disadvantages can be entirely obviated by having the molecule contain other groups which are carefully selected, as hereinafter set forth, to give the optimum desired results. For instance, the mercaptan molecule may contain polar groups, which may be acidic groups. Examples of preferred compounds and groups of compounds belonging under the general heading of polar acidic substituted mercaptans are: mercaptans containing the carboxylic groups, as for example, the simple mercapto-alkanoic acid, mercapto-acetic acid (thioglycollic). It is to be noted that any homologues could be used—also derivatives of these compounds such as salts, esters, amides, and the like.

I have discovered that all of the materials mentioned above function satisfactorily as hair waving agents when used in solutions. The concentration is usually less than 15%. I have found that the mercaptans are especially effective when the pH range is from 7.0 to 10.0, the preferred pH being about 9.2.

I have found that all alkaline materials are satisfactory for adjusting these pH, but that particularly effective with less hair destructive effect are bases having a dissociation constant less than 5χ 10”³ and preferably about 10~⁵. In the “cold” waving process also I have found the volatile bases, such as ammonia, methylamine, and ethylamine are to be preferred with the mercaptans, since at the same pH value and mercaptan concentration solutions containing these volatile bases give tighter waves. Ammonia, therefore, is particularly to be preferred with the mercaptans since its ionization constant is satisfactory, its odor blends pleasantly with the mercaptans and it has a relatively non-irritating action in the desired pH range of 7.0 to 10.0.

This pH range is particularly critical when the waving agent is used for that type of waving employing a chemical setting agent, as in the so-called “cold waving” method, since in that system the necessary requirement of speed without hair destruction demands a high concentration of the waving agent in the waving solution. If the pH value is not high enough slow waving action will result and if too high the hair will be destroyed or badly damaged. While with sulfite a shorter waving time may require a pH of 10 or above—with these more powerful waving agents, the use of pH’s higher than 9.5 must be watched very carefully for with pH of 10 or above, hair destruction or injury may occur before a satisfactory wave is obtained.

It is to be noted that organic sulfides and disulfides are not effective waving agents.

I have discovered that whereas all the mercaptans function very effectively in permanent waving where the final set is accomplished by heating and then cooling, when used in the so-called “cold waving” method requiring a chemical setting solution, unusual and startling dif10 ferences from the prior art become apparent.

Furthermore, I have found that mercaptans containing polar groups are difficult to remove from the hair and whenever the hair becomes damp, for instance, in bathing, shampooing, or at sports such as skiing, the residual 15 odor tends to offend. This is most observable with mercaptans containing polar alkaline groups such as B-amino ethyl mercaptan.

The odor effect is of tremendous importance, not only during the processing of the wave, but for a long time 20 after the wave has been given. I have found that certain groups such as polar groups tend to reduce the vapor pressure of the mercaptan and thus make the resulting mercaptan less objectionable.

I have also discovered that as the molecular weight in25 creases, the mercapto-alkanoic acids become less effective as waving agents, particularly if the increase is due to a polar acid group or to a polar alkaline group. For example, in the homologous series of simple mercapto-alkanoic acids, mercapto-acetic acid is more effective than 30 mercapto-propionic acid which in turn is more effective than mercapto-butyric acid; and the simple mercapto alkanoic acid, mercapto-hexanoic acid, is far more effective than the dicarboxylic acid, thiomalic acid, although these two mercaptans have almost identical molecular weights; 35 and mercapto-butyric acid is far for efficient as a waving agent than cysteine which has almost the same molecular weight but contains the polar alkaline group, the amino group, in addition to the polar carboxyl group.

As illustrations of waving solutions using the new 40 waving agents according to this invention, the following specific example is given:

EXAMPLE

Polar type-acidic

Mercapto-acetic_________________________gms—10

Ammonium Hydroxide--------------------cc—10

Water q. s.________________________ cc__100

The waving solution in the above example may be ⁵⁰ utilized for effecting a “cold wave” by soaking the hair therein and applying thereafter a rinse, say, of sodium hypochlorite or other suitable rinse such as hydrogen peroxide, tartaric acid or the like. I have found that __ it is desirable to remove as much of the solution of the ⁰⁰ waving agent as possible by first rinsing with water.

In the example given above the treatments resulted in satisfactory curls of medium tightness.

If the above example is used for waving where heat is employed, the concentration of the waving agent ⁶⁰ may be materially decreased, approximately to onethird or one-fifth of the concentration given in the example. .-.

Thus, the concentration of the waving agent given in the above example, so decreased, would be:

Mercapto-acetic__________________gms. about 2 to 3.3

In considering this invention, it must also be borne in mind that a purpose is to provide a waving agent for use in a solution, the concentration of the waving agent '° being much lower than heretofore effective commensurate with the desired effect of waving the hair.

As a comparison of the reduction of concentration of the waving ingredient provided by the instant inven__ tion as against that of one of the standard waving agents ^la used in this art, namely, sodium sulfite, I. have found that

2,736,323 the. same wave, under the same? conditions-of procedure can be given with about, one-fifth of: the concentration of my new, waving agent. Thus, by the instant? invention, I can use. the same, time of· operation! but, greatly reduce the concentration ofi the waving ingredient, Alter- 5 nately, I can? shorten the: time: of waving by using, a stronger concentration but, still below the concentrations, heretofore used; for instance, the sodium, sulfite above mentioned. I,, therefore,, provide a complete control, of. the waving process by the: waving agent. ₁₀

Utilizing the waving solution: of any of the examples, the. following procedure, or one similar thereto, may be employed in giving a permanent wave: The head, of hair, is blocked off into sections and each of the sectioned strands is: then well, soaked in the waving solu- 75 tion. Thereafter, each-section: of hair is wound, on the mandrel to the form desired and heat is then, applied, as by a chemical heating· pad. arranged over the wound section , or by an electrical heating unit, the temperature being raised to about 212. F.,,and the hair, upon, cooling, go sets into its new configuration.

In giving: a “cold wave,” procedures similar to- the following, which may be variously, modified; may be used: The head of hair is again sectioned, off into strands which are preferably wound on mandrels, the 25 waving solution being applied: before or after winding by soaking the· hair in any desired manner. After a.suitable. lapse of time for the reaction, the hair is water rinsed,. and: then a chemical rinse, such as chlorine, water may be-applied. which removes the last trace of the 30 waving agent and thus assures, the fixing? of the. hair, in its, new configuration, whereafter the hair will have a, permanent wave.

I have found that in order to reduce the. time of waving by. this chemical method, i. e., without heat, to a figure 33 comparable to the time of waving by heat it is necessary to increase the concentration of-mercaptans in the waving solution, about three to five times.

Thus, the concentrations of mercaptans in the. above examples, when so increased from the concentrations 40 suitable, for waving with heat, would be. as follows:

Mercapto-acetic------------------gms. about 6 to 10

Thus,, it is possible to so: select the- concentration· of my novel waving agent in the waving solution that¹ the 45 desired, time of actual. treatment becomes feasible, ranging from a low, concentration, with longer, time, of application as is desired in some .methods of cold! waving; ,or a low. concentration in continuous intimate contact with shorter time of application, or a low concentration with 50 shorter time using heat, to higher concentrations with decrease in time whether the fixation is by chemical, or by cooling subsequent to heating. Since the time of waving is greater with lower concentrations and less with higher concentrations of mercaptans and' since, as described 55 above, the time of waving it greater with a lower pH value and less with a higher pH value, it follows that the concentration? of the mercaptan and the pH of' the solution, can be adjusted within: the ranges given above to obtain a permanent change'in· the configuration : of 60 human-hair during· a-given time of application without damage to the.hair structure by having the concentration of mercaptan in the higher portion of. the concentration range for a lower pH and having the concentration of mercaptan in the lower portion of. said concentration 65 range for a higher pH: But I do not under any conditions use concentrations higher than heretofore used. On. the contrary, comparing the time-concentration factors, of my. novel waving agent with, waving: agents of the prior art for equivalent purposes, it will, be found 70 that under all analogous conditions I provide a distinct reduction in concentration while attaining optimum-results in the final waving.

While’throughout this specification I have specifically mentioned the.waving:of,hair,,I do not wish to limit myself thereto,, since: by this, invention- it is possible to permanently alter or reform the. form, shape or configuration of the hair as desired. Thus, my invention contemplates also the reverse of waving, such as de-kinking, removal of curls, or waves, imparting of creases and the like. The waving solution according to this invention may be applied to the hair at any desired time; either, before or after winding or otherwise mechanically placing the hair in its reformed desired shape or form and by any desired means, such as soaking, spraying, continuous circulation or the like, and the claims are to be. so construed' Furthermore, while I have described examples of our invention and have outlined advantages thereof over the prior art, I do not wish to limit myself to. the exact materials or proportions given hereinbefore since a.variety of like or similar materials may be used in lieu of those specified and the proportions thereof may be widely varied without departing from the spirit of my invention or the intended scope of the appended claims.