US3773056A

US3773056A - Compositions and methods of improving the quality of human hair with stable methylol compounds

Info

Publication number: US3773056A
Application number: US00121515A
Authority: US
Inventors: G Kalopissis; J Abegg; H Debeaulie; G Ghilardi
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1971-03-05
Filing date: 1971-03-05
Publication date: 1973-11-20
Anticipated expiration: 1990-11-20

Abstract

Methylol compounds which do not liberate free formol and are therefore suitable for cosmetic use, compositions including said compounds, and methods of using said compositions to improve the cosmetic properties of human hair. Exemplary methylol compounds are the methylolureas, and they may be prevented from liberating harmful amounts of free formol by including therein an electrophile group selected from among those responding to the formula:

IN WHICH X is selected from the group consisting of an oxygen atom and a sulfur atom and R'''' is selected from the group consisting of a hydrogen atom, an alkyl radical and an NH2 group.

Description

United States atent 1 Kalopissis et al.

[ Nov. 20, 1973 COMPOSITIONS AND METHODS OF IMPROVING THE QUALITY OF HUMAN HAIR WITH STABLE METHYLOL COMPOUNDS [75] Inventors: Gregoire Kalopissis, Paris; Jean Louis Abegg, Le Perreus; Henry DeBeaulie; Giuliana Ghilardi, both of Paris, all of France [73] Assignee: Societe Anonyme Dite: LOreal [22] Filed: Mar. 5, 1971 [21] Appl. No.: 121,515

Related US. Application Data [63] Continuation of Ser. No. 631,156, April 17, 1967,

abandoned.

[52] US. Cl. 132/7, 8/127.51, 8/127.6, 424/DIG. 1, 424/47, 424/70, 424/71 [51] Int. Cl. A45d 7/04, A45d 7/06 [58] Field of Search 424/76, 71, 47; 132/7 [56] References Cited UNITED STATES PATENTS 1,871,087 8/1932 Schneevoigt et a1 117/139.4 X 2,235,141 3/1941 Dreyfus et a1. 91/70 2,254,001 8/1941 Conaway 91/70 2,342,785 2/1944 Bock et a1 117/161 2,836,185 5/1958 Hervey 424/72 2,836,543 5/1958 Watson 424/72 3,116,967 l/1964 Goldstein et a1 8/1 15.6

9/1964 Habicht et al. 424/70 10/1967 Joos 424/70 X OTHER PUBLICATIONS Sagarin, Cosmetic Science and Technology, Interscience Pub., lnc., N.Y., p. 609, (1957) Wells & Lubowe, Cosmetics and the Skin, Reinhold Pub., Corp., N.Y., p. 475, (1964) Primary ExaminerAlbert T. Meyers Assistant ExaminerFrederick E. Waddell Attorney-Cushman, Darby & Cushman [5 7] ABSTRACT Methylol compounds which do not liberate free formol and are therefore suitable for cosmetic use, compositions including said compounds, and methods of using said compositions to improve the cosmetic properties of human hair. Exemplary methylol compounds are the methylolureas, and they may be prevented from liberating harmful amounts of free formol by including therein an electrophile group selected from among those responding to the formula:

from the group consisting of a hydrogen atom, an alkyl radical and an NI-I group.

23 Claims, N0 Drawings COMPOSITIONS AND METHODS OF IMPROVING THE QUALITY OF HUMAN HAIR WITH STABLE METHYLOL COMPOUNDS This is a continuation of US. Pat. application Ser. No. 631,156, filed Apr. 17, 1967.

This invention relates to a cosmetic composition for improving the cosmetic properties of human hair which has become degraded, and thereby confer on the hair the strength and appearance which it possessed before degradation.

It is well known that hair undergoes more or less substantial degradation when exposed to atmospheric agents such as sea water and the sun, or when subjected to chemical treatments such as permanent waves and blcaches.

The effects of such degradations may be to a large extent eliminated by using the compositions according to the invention.

It has already been suggested that the strength and elasticity of the hair be improved by treating it with compositions which contain solutions of dimethylolurea and dimethylolthiourea so as to obtain the desired result by the polymerization or condensation of these active compounds on the keratine.

This method cannot, however, be applied in practice because, as is well known, compositions having a dimethylolurea or a dimethylolthiourea base are relatively unstable and soon release substantial quantities of free formol. As the cumulative effect of this liberation of formol during storage of the composition and during its application to the hair, the composition contains a relatively high concentration of free formol, which is disadvantageous because the free formol is in contact with the scalp.

Since formol is known to be a toxic substance which cannot be applied to the scalp in substantial quantities without producing undesirable effects, legislation in force in most countries prohibits the application to the skin or scalp of compositions containing more than a very weak concentration of formol, usually of the order of 0.2 percent.

For this reason, the above-mentioned compositions, based on dimethylolurea and dimethylolthiourea, cannot be used in practice, since, when applied to the head, they contain concentrations of formol substantially greater than those permitted by law.

Moreover, dimethylolurea and dimethylolthiourea, which are powders when in the pure state, are difiicult to dissolve in water, which makes it inconvenient to prepare compositions containing them at the moment of use.

These dimethylolurea and dimethylolthiourea powders are also difficult to keep, even while taking the customary precautions relative to their storage, so that the degradation which occurs during storage increases the difficulties encountered in dissolving them in water.

The present invention relates to compositions for strengthening the hair which contain methylol compounds having characteristics to some extent analogous to those of dimethylolurea and dimethylolthiourea. However, due to the choice of the particular active compounds which they contain, the compositions according to the invention have the advantage that they liberate only small quantities of formol, so that they conform to legislative requirements and are safe to use.

Moreover, the compositions according to the invention have certain advantages over those previously described which will be hereinafter set forth.

Several interrelated approaches to the problem of preparing such compositions have been discovered. Each approach has lead to the development of a plurality of satisfactory compounds, and in many cases one or more of the compounds developed by research along one line of approach has also been found when proceeding along another line of approach.

In a first embodiment of the invention there is provided a new article of manufacture which consists of a cosmetic composition characterized by the fact that it contains, in a suitable cosmetic vehicle, at least one partially polymerizable compound which forms bonds with the keratin of the hair, and which is of to the following formula:

lt-N-CIIzOII in which:

R represents a substituent which is sufiiciently electrophile to prevent the immediate release of a formol molecule,

R represents a hydrogen atom, an alkyl radical, a hydroxyalkyl radical, or a substituent of the same type as R, and

R and R may form part of a nitrogenous heterocyclic ring which may have a methylol group attached to the nitrogen.

In a particular embodiment of the invention the substituent R of the formula (I) is a group of the formula:

in which: 7

X represents an oxygen atom or a sulfur atom,

R" represents a hydrogen atom, an alkyl radical, or an alkoxy radical, and these radicals may have an amidic or carbamic group having a methylol group attached to the nitrogen.

X represents an NH radical, and

R represents an -NH-R" group, in which R is a hydrogen atom, a hydroxymethyl radical, or an C E N radical.

In another embodiment of the invention the substituent R of the formula (I) is a group of the formula:

in which R represents an alkyl group, and aryl group, or an alkylaryl group.

Among the methylol compounds defined above which may be selected for introduction into the composition according to the invention are the following, but this is by no means exhaustive:

monomethylol ethyl carbamate having the formula:

dimethylol methylene ethyl bis-carbamate having the formula:

HgOH H OH 5 dimethylol succinamide having the formula:

non c-Nir-j(H2)zc-N1I-cn 0n W monomethylol guanidine carbonate having the formula: l

[NII;-(]?NIIJ+:|CO3-[NII3+%FNHCH;OH]

Il NII I N-methylol paratoluene sulfamide having the formula:

CH3SO;NHCH;OH

- dimethylol adipamide having the formula:

1IOII CNHC(CH;)4CNHCHzO1I 3O N ,N '-dimethy]ol-( Z-methyLZ-propyl )-propylene bis-carbamade having the formula:

i H0H2CNHo0CH -c-O1I op-NHcH30H monomethylol dimethylhydantoin having the formula:

C-CO

113C N-CHOII NH--CO monomethylol ethyleneurea having the formula:

CHzOH CH2N \CO H,Nfi

monomethylolethylene thiourea having the formula:

/CH20H OH N 5 CH2NH dimethylol ethylene thiourea having the formula:

The composition according to this embodiment of the invention may advantageously contain 0.1 to 10 percent and preferably from I to 3 percent by weight of the methylol compounds.

In a preferred form of this embodiment of the invention the composition also contains an acid catalyst, which may be an acid or an acid mineral or organic salt suitable for use in cosmetic products.

The composition according to this embodiment of the invention may consist of an aqueous or hydroalcoholic solution of methylol compounds. It may also take the form of a gel or cream, or aerosol.

The composition according to this embodiment of the invention may also contain other ingredients conventionally used in cosmetics, such as perfumes, dyes, surface-active agents, swelling agents, resins, etc.

The compositions according to this embodiment of the invention offer the advantage of having satisfactory stability and of releasing free formol only in quantities so small that they are not injurious when the composition is applied to the hair.

Moreover, the compositions according to this embodiment of the invention have the advantage of yielding better cosmetic results with respect to the appearance and springiness of the hair than the abovementioned compositions based on dimethylolurea and dimethylolthiorea.

It appears that this results from a slower speed of polymerization and, doubtless, from a different polymerization process, in which the active compounds of the compositions according to the invention seem to have a more marked tendency to form bonds with the keratin than to undergo condensation or polymerization as strictly defined.

Moreover, the compositions according to the embodiment of the invention may be easily packaged in the form of a powder which may then be dissolved in an aqueous or hydroalcoholic liquid medium. This is made easy by the fact that the methylol compounds used in the invention have the great advantage of dissolving much more easily in aqueous media than do dimethylolurea or dimethylolthiourea, which have a tendency to remain in suspension, which is incompatible with their use for cosmetic purposes.

Finally, the methylol compounds used in accordance with the invention have the advantage of being generally chemical compositions which are relatively easy to prepare in the pure state, which makes it possible to insure a constant quality in production and reproducible results.

These advantages are in addition to the fact that, as has already been indicated, the compositions according to this embodiment of the invention have no marked tendencies to liberate free formol.

The present invention also relates to a method of treating the hair characterized by the fact that the hair is impregnated by one of the compositions hereinbefore described, and is then dried, preferably by applying external heat.

In a first method of carrying out the foregoing invention the cosmetic composition does not itself contain the acid catalyst necessary to polymerize the methylol compounds in the keratinic fiber, this catalyst being applied independently to the hair before or after the composition according to the invention.

In another method of carrying out the invention, the cosmetic composition, with the polymerization catalyst already incorporated thereinto is applied directly to the air, which is then dried in the manner which has just been described.

The cosmetic characteristics of hair which have been degraded or altered, by bleaching for example, may thus be efficaciously restored.

In order that the foregoing invention may be better understood, several exemplary methods of carrying out the invention will now be described, purely by way of illustration and example:

EXAMPLE A1 The first step of a permanent wave is carried out in a conventional manner, using the following composition:

Thioglycolic acid 8 g Monoethanolamine q.s.p. pH 9.5 Monomethylol dimethyl hydantoin 6 g Water q.s.p. 100

The hair is impregnated with this solution, the impregnated locks of hair are rolled up on curlers of a normal diameter, the hair is again saturated with the solution and left for 15 minutes under a plastic cap at the ambient temperature. The hair is then rinsed and an aqueous solution of hydrogen peroxide at 6 volumes, the pH of which has been adjusted to 1.5 by the addition of phosphoric acid, is applied.

The hair is then placed under a hood and dried in a conventional manner.

EXAMPLE A2 After having bleached the hair in a conventional manner, the following composition is applied:

Monomethylol ethylene urea 4 g Monosodium phosphate 0.3 g Water q.s.p. 100 cc The hair is then set in a conventional manner and excellent results are obtained, especially with respect to its springiness and holding power.

EXAMPLE A3 A solution having the following composition is applied, as in Example A2 to hair which has first been bleached and washed:

Monmethylol ethylene thiourea 5 g Phosphoric acid q.s.p. pH 2.5 Water q.s.p. 100 cc The hair is left under a hood for about minutes, remoistened, and permanently waved in a conventional manner. The hair is then found to be in excellent condition, particularly with respect to its tips, and both the appearance and life of the permanent wave are increased.

EXAMPLE A4 Bleached hair is first shampooed with a cationic acid shampoo. It is then rinsed and carefully dried, after which the following solution is applied:

Dimethylol ethylene thiourea 4 g Polyvinylpyrrolidone vinyl acetate copolymer 2 g Ethyl alcohol 25 cc Perfume 0.1 g Water, q.s.p. cc

The hair is then dried in a conventional manner for 30 minutes at 50 C.

EXAMPLE A5 A solution having the following composition is applied to hair which has first been given a conventional permanent wave, and then rinsed and dried:

Monomethylol ethylene thiourea 8 g Monomethylol ethyl carbamate 2 g 10% lactic acid 3 cc Water 97 cc The entire head of hair is then set in a conventional manner.

EXAMPLE A6 A solution having the following composition is applied to hair which has been bleached, just before setting it:

Dimethylol methylene ethyl bis-carbamate 0.5 g Citric acid q.s.p. pH =3.5 Water q.s.p. 100 cc EXAMPLE A 7 Under the same conditions as in Example A6, a solution having the following composition is applied to the EXAMPLE A8 A solution having the following composition is applied to hair which has previously been bleached:

N,N'-dimethylol (2-methyl-2-propyl)-pnopylene bis-carbamate l g Dimethylol ethylene thiourea 0.3 g 10% phosphoric acid q.s.p. 1.5 Water q.s.p. 100 cc The hair is then set in a conventional manner.

EXAMPLE A9 A gel having the following composition is applied, before setting it in a conventional manner to hair which has first been bleached, and then washed and rinsed in a citric acid solution having a pH of 3.5:

Oleic alcohol 10 moles O.E. (Bn'j 96) 23 g Parafim oil 22 g Dimethylol adipamide 2 g Perfiune 0.2 3 Water 55 g EXAMPLE A10 A gel having the following composition is applied to hair just before setting it, under the same conditions as in Example A6:

Oleic acid 10 moles 015. 27 g Paraffin oil 23 g Monomethylol ethylene urea 0.5 g Pure acetic acid qsp pH 3.5 Water 50 cc EXAMPLE Al 1 10 cc of a phosphoric acid solution having a pH value of 2 are applied to hair which has previously been given a permanent wave, rinsed, and dried. A cream having the following composition is then applied:

Lanette AO wax Oleic alcohol Cetyl trimethylammonium bromide Monomethylol ethyl carbamate Water 8 The hair is then set in a conventional manner.

EXAMPLE A12 A solution having the following composition is applied to a head of hair under the same conditions as in Example A6:

Monomethylol paratoluene sulfarnide l g 10% lactic acid l cc Ethyl alcohol 30 cc Perfume 0.1 g Water 99 cc EXAMPLE A13 A solution having the following composition is ap plied to a head of hair under the same conditions as in Example A6:

Monomethyl guanidine carbonate 3 g Compound having the formula:

Cw i: z a

CH -CON-(CH2)3-N 0.2 g.

RNH-CH-COONa 11 i "I (R =Copraj Sulfuric acid, q.s.p. pH L5 Water q.s.p. 100

By using the compositions according to the invention in the ways described in the examples set forth above the hair is made brighter and springier.

Moreover, and especially when the hair has been bleached, the hair becomes more pleasant to touch and easier to comb.

Waves which have been made according to the invention also have greater holding power.

Finally, no undesirable cumulative effects have been found to result from repeating treatments in accordance with the invention as often as necessary for normal hair care.

In the second approach to the problem, it has been found particularly effective to employ a cosmetic composition characterized by the fact that it comprises in combination at least one at least partialiy polymerizable composition which will form bonds with the keratin of the hair and comprising at least one group of the formula in which R represents a hydrogen atom, a lower alkyl radical, a hydroxymethyl radical, or an alkoxymethyl radical and R represents a hydrogen atom or a lower alkyl radical; the nitrogen atom of the group being attached to a group which is sufficiently electrophile to insure the chemical stability of the group, that is to say, to avoid any immediate release of a formol molecule together with at least one nitrogen derivative comprising at least one group of the following formula in which X represents an oxygen atom, a sulfur atom, or an NH radical, and in which both X and the carbon atom may form part of a heterocyclic ring In the compositions according to the invention, the number of NH groups supplied by the nitrogen derivatives is between 0.1 and 1.0 times and preferably between 0.1 and 0.3 times the number of methylol groups supplied to the composition by the methylol com pounds.

Among the methylol compounds which may be used in carrying out the invention are:

Monomethylol dimethylhydantoin Monomethylol ethylene urea Dimethylol ethylene thiourea Monomethylol ethyl carbarnate Dimethylol ethylene ethyl bis-carbamate Dimethylol succinamide Monomethylolethylene thiourea (The formula for each of the above compounds has already been given during the description of the first embodiment.

Dimethylolthiourea of the formula:

- Dimethylolurea of the formula:

It should be noted that these two prior art compounds are suggested only for use in conjunction with the nitrogen compounds disclosed in this embodiment of the invention. It is not recommended that they be used as the sole active ingredient as the compounds listed in connection with the first embodiment may be used.

- Monomethylolurea of the formula:

Monomethylolthiourea of the formula:

CHZOH +11 /C Homo-NH N NHCHOH M Monomethyloldicyandiamlde of the formula:

NECNHC-NHCHZOH N U: h

15 Bismethoxymethylurea of the formula:

oHaooH -NH-p-NHcHoHa .mummwa at. 20

- Monomethylol guanidine of the formula:

H N-C-NH-CHzOH I II N,N-dimethylol (2-methyl-2-propyl) propylene biscarbamate of the formula:

(IJHS 0 HOH2CNH-(|JOCHZ(FCH2OFNHOH2OH 3 when." V .WFiEL, 7* Dimethylol adipamide of the formula:

' HOII CNII-C(CIIz)4CNHCH OII N,N-diethyl N-methylolurea of the formula: 40

N-C-NH-CHzOH N,N-dimethylol ethyleneurea of the fornula:

/omolt CH2N\ /C=O CHz-N\ w m P3 WHWHM Dimethylol ethyl carbamate of the formula:

CH2OH EtO-C-N @9592. an mt- Tetramethylol acetylenediurea of the formula:

HOHzC-N-CH-N-CHzOH 0:0 0:0

Among the nitrogen compounds which may be used in carrying out the invention are: Urea of the formula:

Melamine of the formula:

Dicyandiamide of the formula:

NEG-NH-C-NHz N,N diethyl urea of the formula:

Ethylene urea of the formula: V

-- lsopropyl carbamate of the formula:

- Dimethyl hydantoin of the formula:

NI l

Nll-(JO Ethylene thiourea of theformula:

Guanidine carbonate of the formula:

Succinamide of the formula:-

in a preferred form of this second embodiment of the invention, the composition comprises a nitrogen derivative mixed with the corresponding methylol derivative, that is to say, one obtained by reacting formol with said nitrogen derivative.

in accordance with the preferred form of this second embodiment of the invention the concentration of the methylol derivatives may vary within broad limits, but remains generally between 0.5 and 12 percent. This concentration is dependent in part on the solubility of these derivatives in water and in part on the state of the hair to be treated. Bleached hair is preferably treated with lower concentrations than hair which has not been bleached.

The new cosmetic composition may take the form of an aqueous or hydro-alcoholic solution and may serve as a setting lotion in which case it may contain any of the cosmetic additives conventionally included in such lotions.

The new cosmetic composition may also be used as a neutralizing lotion for permanent waves, in which case it will also comprise at least one oxidizing agent and the additives conventional in such lotions.

The composition may also take the form of a gel, cream, or aerosol, and contain surface-active agents, swelling agents, dyes or perfumes.

Another object of this second embodiment of the invention is to provide a method of storing the said composition, characterized by the fact that the methylol products are in the solid state and the nitrogen derivatives are in a solution which also contains an acid.

The methylol products may then be dissolved, at the time of use on the hair, in the acid solution which already contains the nitrogen derivative.

ln accordance with the embodiment of the invention the methylol compounds may also be mixed with the nitrogen derivatives and a separate acid catalyst prepared, which may be in solution, or in solid form. This catalyst may be mixed with the solution containing the methylol compounds and the nitrogen derivatives at the time the composition is to be used on the hair.

The cosmetic compositions according to this embodiment of the invention have the advantage of liberating less formol than those methylol-containing compositions heretofore known, such a dimethylolurea and dimethylolthiourea. It has been established that the addition of the nitrogen compounds according to the invention will in general reduce by more than 50 percent the amount of free formal present at the time the cosmetic compositions containing the methylol derivatives are used.

Moreover, the addition of nitrogen derivatives to the cosmetic compositions containing the methylol compounds makes it possible to store these compositions more easily in solution, since the release of formol, which normally takes place under these conditions, is prevented by the presence of the nitrogen compounds.

A further object of this second embodiment of the isnvention is to provide a method of treating hair, which method is characterized by the fact that the hair is impregnated with a cosmetic solution such as that hereinafter described, that an acid polymerization catalyst is then added if the solution does not already include it, and the hair is dried by applying external heat, after having been rinsed, if desired.

This brings about a group of reactions within the keratinic fibers of the hair which tend to create bonds between the fibers and to strengthen the inner parts of the fibers themselves by polymerization of the methylol compounds.

in order that the invention may be better understood, several methods of carrying out the invention will now be described, purely by way of illustration:

EXAMPLE Bl After having first bleached and dyed the hair in a conventional manner, a solution having the following composition is applied:

Dimethylolurea 2 g Urea 1,5 g Citric acid 0.2 cm Water q.s.p. cm

EXAMPLE B2 At the moment at which it is to be used a solution having the following composition is prepared:

Monomethylolurea 9 g Urea 6 g Acetic acid q.s.p. pH 3 Water q.s.p. 100 cc After washing and drying the hair, this solution is applied in a conventional manner as a setting lotion and the hair is dried for 30 minutes at about 50 C. The result is a wave which is springy ab initio and the hair holds the wave well over the course of time, even when exposed to humid air.

EXAMPLE B3 After having bleached the hair in a conventional manner, a solution having the following composition is applied:

Dimethylolurea [.2 g Ethyleneurea 0.5 g Citric acid q.s.p. pH 3 Water q.s.p. 100 cc The hair is then set in a conventional manner and excellent results are obtained with respect to the springiness of the hair and the durability of the wave.

EXAMPLE B4 Under the same conditions as in Example B3 the following solution is applied:

Dimethylolthiourea 2 g Urea 0.9 g 10% lactic acid q.s.p. pH 1.5 Water q.s.p. 100 cc Equally good results are obtained.

EXAMPLE B The following solution is prepared just before use:

Trimethylolmelamine 4.2 g Ethyleneurea 1.6 g Acetic acid q.s.p. pH 3 Water q.s.p. 100 cc This is applied in a conventional manner as a setting lotion to hair which has first been given a permanent wave. The hair is then dried for 40 minutes at 50 C. The hair which has been thus treated is found to be springy ab initio and holds the wave well over a substantial period of time.

EXAMPLE B6 A solution having the following composition is applied to hair which has first been bleached and dyed:

Monomethylol dicyandiamide Urea Cetyltrimethylammonium bromide phosphoric acid q.s.p.

Water q.s.p.

The hair is then set in a conventional manner, and dried under a drying hood at a temperature of 4550 C. It is found that hair treated in this manner is brighter, combs easily and is more agreeable to the touch than hair which has been bleached, dyed, and set under identical conditions except that the process according to the invention was not used.

EXAMPLE B7 Under the same conditions as in Example B6, a solution having the following composition is applied to the hair:

Equally good results are obtained.

EXAMPLE B8 Under the same conditions as in Example B3, a solution having the following composition is applied to the hair:

Dimethylolethyleneurea 2.9 g Urea .07 g Ext. violet DC No. 2 (CJ. acid violet No. 43) 0.004 g Sulfuric acid q.s.p. pH 2 Water q.s.p. 100 cc Equally good results are obtained with respect to the quality of the hair and the durability of the wave.

All of the compositions according to this second embodiment of the invention which have been hereinbefore described are clearly more stable than compositions which do not include the nitro derivatives which are added by the invention. In particular, experience has shown that when the compositions which have been described are kept at a temperature of 50 C. for 30 minutes, they contain at least 2 to 4 times less free formol than the same compositions when they do not contain nitro derivatives.

In generaly, the addition of nitro compounds according to this embodiment of the invention greatly facilitates the storing and the conditions of application of the methylol composition in that they make it possible to substantially reduce the concentration of free formol, which concentration is thereby reduced within perfectly acceptable limits.

It will be noted that monomethylol dicyandiamide is among the methylol compounds suggested for use according to the second embodiment of this invention in combination with a nitro compound.

In accordance with a third embodiment of the invention it has been found that not only monomethyloldicyandiamide but other compounds of the formula:

in which R represents either a hydrogen atom or an alkyl remainder, may be used without the nitro compound. Methoxymethyloldicyandiamide, for example, is suitalbe, and it is within the scope of the invention to employ ethers thereof corresponding to the above formula.

A particular disadvantage of the dimethylolurea and dimethylolthiourea suggested by the prior art stems from the fact that since they are substantially insoluble in water they have a cumulative effect so that when repeatedly applied they render the hair hard and brittle. The compositions according to this third embodiment of the invention, however, may be removed by simply washing the hair so as to avoid any undesirable cumulative effect.

The compounds of the foregoing formula are also sufficiently stable to prevent the release of more than a small quantity of formol, so that they may be safely employed in cosmetic compositions, and impart an improved brightness, fluffyness, and feel to the hair.

Monomethyloldicyandiamide keeps well when in powder form, and is easy to dissolve at the moment of use. It is also stable in aqueous solution, so that a 20 percent aqueous solution of monomethyloldicyandiamide may be stored for substantial lengths of time and then diluted as required at the moment of use, with an acid solution which serves as a catalyst, for example.

The ethers of monomethylolcyandiamide, and particularly methoxy methyldicyandiamide may also be used but are less water-soluble than monomethylolcyandiamide itself. These ethers may, however, be rendered sufficiently soluble to permit their use for cosmetic purposes by employing water which has been heated to about 50 C. Solutions of monomethyloldicyandiamide ethers having a concentration of several percent may be obtained in this manner, and the ethers do not reprecipitate out when the solution is cooled to room temperature.

The solubility of these ethers may also be increased without any adverse effect on their cosmetic properties, by proceeding in the following manner:

The alkoxymethylol derivative of the product is reacted with not more than 0.5 mol of hydrochloric acid per mol of the alkoxymethyldicyandiamide and the produce isolated therefrom is used in powder form. Under these circumstances the product is sufficiently soluble in either water or alcohol to make it fully practical to prepare solutions having a concentration of the order of 2 percent.

Three representative solubilizing methods will now be described Method I 100 g of methoxymethyldicyandiamide in suspension in 100 cc of absolute ethyl alcohol are added to 25 cc of 12 N hydrochloric acid. The mixture is then heated to 40 C and agitated until dissolution. The result is a 20 percent ethanolic solution of the methoxymethylol product. This solution may be directly used after dilution in acidulated water at the moment of use, as will be hereinafter indicated.

Method ll 1 14 g Ci moi/g) of monomethyloldicyandiamide are dissolved in a liter of methyl alcohol in the presence of cc (0.06 mols) of 12 N hydrochloric acid. The mixture is brought to 30 C until dissolution. The corresponding methyl ether is obtained. The excess methanol is then driven off by heating under vacuum.

The result is a powder which can be used either as is, after dissolution in water at the moment of use, or dissolved in a suitable alcohol, such as ethanol, and used in the form of this solution, as will be hereinafter set forth.

Method III 114 g 1 mol/g) of monomethyloldicyandiamide are dissolved in 700 cc of ethanol in the presence of 35 cc of hydrochloric 12 N acid. The mixture is heated at 30 C until dissolution. The result is an ethyl alcohol solution containing 20 percent of a derivative of the ethyl ether of monomethyloldicyandiamide.

This ethyl solution may be used in accordance with the invention in the preparation of cosmetic compositions.

Such compositions may advantageously contain from 0.2 to percent and preferably from I to 4 percent by weight of the active compounds described above.

These compositions may take the form of aqueous or hydroalcoholic solutions, gels, creams, emulsions or aerosols.

They may of course contain any additives conventionally used in cosmetics such as perfume, dyes, surface-active agents, swelling agents, etc.

This third embodiment of the invention also includes the new method of improving the properties of degraded hair, which method is essentially characterized by the fact that a composition such as described above is applied to the hair with an acid catalyst, that the product is left to act on the hair for from to 40 minutes, for example, while the hair is being dried.

In a first method of carrying out this third form of the invention, the acid catalyst is included in the composition before it is applied to the hair.

In a second method the acid catalyst is applied separately to the hair, either before or after the composition according to the invention.

Any substance compatible with cosmetic use, and which permits the pH to be lowered sufficiently to permit the polymerization or condensation of the active products according to the invention may be used as the catalyst.

It is also possible to use organic acids such as acetic acid, lactic acid, citric acid or even mineral acids and acid salts such as phosphoric acid and sulphuric acid.

The results achieved are particularly impressive when treating hair which has been previously bleached or bleached and dyed with an oxydation dye.

In this case the hair may advantageously be treated during the course of a setting process. The hair becomes brighter, more manageable, easier to arrange, and easier to comb. The hair also becomes harder and fluffier. Furthermore, when the products according to the invention are applied to the hair they impart thereto an improved holding power, regardless of whether the hair has first been bleached or not. Finally, it is found that any color imparted by a dye is more marked and the sets are longer lasting.

In order that this third form of the invention may be better understood, several examples thereof will now be given, purely by way of illustration:

EXAMPLE Cl A solution having the following composition is applied to hair which has been repeatedly bleached:

Monomethyloldicyandiamide l0 g Cetylpyridinium bromide 0.l g Phosphoric acid q.s.p. pH 2.5 Water q.s.p. g

The hair is dried under a hood for about 30 minutes at 45 C and then permanently waved in a conventional manner, using a reducing solution containing ammonium thioglycolate.

After this the hair is set in a conventional manner and it is found that hair treated in this manner is very springy, fluffy, bright, and has cosmetic qualities clearly superior to those of hair which has been permanently waved, but not treated in accordance with the invention.

EXAMPLE C2 The following composition is applied to hair which has first been bleached, rinsed and dried:

Monomethyloidicyandiamide 2 g Cetylpyridinium bromide 0.l g Polyvinylpyrrolidone/vinylactate copolymer 0.5 g Acetic acid q.s.p. pH 3.5 Water q.s.p. 100 g The hair is then wound up on curlers and set in a conventional manner. The resulting coifi'ure is long-lasting and attractive in appearance.

EXAMPLE C3 A solution having the following composition is applied to hair which has first been bleached and dyed:

Monomethyloldicyandiamide methyl ether 1 g Alcohol 10 cc Cetylpyridinium bromide 0.15 g Phosphoric acid q.s.p. pH 2.5 Water q.s.p. 100 g Equally good results with respect to springiness and long life of the wave are obtained.

EXAMPLE C5 A solution having the following composition is ap- Monomethyloldicyandiamide methyl ether 6 g Cetylpyridinium bromide O.l g Vinyl acetate/polyvinylpyrrolidone copolymer 0.5 g Acetic acid q.s.p. pH 3 Water q.s.p. 100 g The hair is set in a conventional manner. The hair becomes hard and bright and the coiffure is fluffier than when given a permanent wave without treatment in accordance with the invention.

EXAMPLE C5 A solution having the following composition is applied as in Example C2 to hair which has previously been bleached:

Monomethyloldicyandiamide 3.5 g Cetyl trimethylammonium bromide 0.1 g Alcohol cc Acetic acid q.s.p. pH 3 Water q.s.p. 100 cc The resulting set is more stable than those imparted to hair which has not been treated in accordance with the invention.

EXAMPLE C6 Hair which has first been bleached and rinsed is washed with an acid shampoo, and rinsed again. A gel having the following composition is applied thereto:

Paraffin oil 23 g Oleic alcohol, 10 moles O.E. (sold under the tradename Brij 96") 25 g Monomethyloldicyandiamide l g Perfume 0.2 g Water 52 g The hair is then wound up on curlers and set in a conventional manner. After drying, the hair is easy to comb, bright, and springy.

EXAMPLE C7 A solution having the following composition is applied to bleached hair:

After having set the hair in a conventional manner, it is found that the treated hair has a more attractive appearance and feel, and that the resulting coiffure is flufly and long lasting.

EXAMPLE C8 A solution having the following composition is applied under the same conditions as in Example C7:

Monomethyloldicyandiamide ethyl ether 2 g Alcohol cc Perfume 0.1 g Monopotassium phosphate 0.3 g Water q.s.p. 100 cc Equally good results are obtained.

EXAMPLE C9 In order to produce an aerosol composition suitable for use as a setting lotion 50 grams of a 20 percent alcoholic solution prepared as described under Method I is prepared. A propellant gas is then added, which may be nitrogen at a pressure of 1.5 kg, or 2.7 g of dichlorodifluoromethane, which is sold under the trade-name Freon 12.

A quantity of this aerosol composition sufficient to adequately impregnate all its locks is sprayed onto hair which has first been washed, rinsed, and wound up on rollers. The hair is then dried under a heated hood and it is found that the set is springy and the hair is attractive, fluffy, and has an excellent feel.

The compositions set forth in Examples C1-C9 may be obtained by mixing a concentrated alcoholic solution of the active compounds according to the invention at the moment of use with an aqueous solution which suitably dilutes the concentrated aqueous solution.

The active compounds according to the invention may also be stored in the form of a powder which is dissolved at the moment of use in the other components of the product.

In the case of the compositions according to this third embodiment of the invention and particularly in the case of those mentioned in the foregoing examples, there is no cumulative hardening of the hair since the condensation products of these methylol derivatives are easily removed by simply shampooing the hair.

It has also been found that those of the active compounds described in the second embodiment of the invention in which R represents an alkoxymethyl radical will produce satisfactory results even if not mixed with a nitro derivative. The fourth form of the invention is accordingly characterized by the fact that it comprises at least one at least partially polymerizable compound capable of forming a bond by addition or condensation with the keratin of the hair and having at least one group of the formula:

R 1 I-CH 0 R in which:

R represents a hydrogen atom, a lower alkyl radical or an alkoxymethyl radical, and

R represents a lower alkyl radical.

The nitrogen atom in the group is attached to a remainder which is sufficiently electrophile to insure the chemical stability of the group.

In the present application the term lower alkyl radical is used to mean an alkyl radical having a number of carbon atoms small enough to render the alkoxymethyl compounds according to the invention sufficiently soluble in the cosmetic carrier in which they are to be incorporated. In general, alkyl radicals having fewer than five carbon atoms will serve this purpose.

Among the sufficiently electrophile groups to which the nitrogen atom may be attached are those having a group, the carbon atom of which is directly attached to the nitrogen atom of the above formula.

The alkoxymethyl compounds according to the invention may be prepared by reacting the corresponding methylol compounds in a conventional manner with alcohols in the presence of an acid catalyst such as hydrochloric acid.

Methanol, ethanol, propano], isopropanol and butanol, for example, may be employed.

According to the invention the compositions are preferably used in the form of hydroalcoholic solutions which, at the moment of use, contain a concentration of active ingredients ranging from 0.2 to 10 percent and preferably between 1 and 4 percent, by weight.

At the moment of use the compositions according to the invention may have an acid pH, between 2 and 5 for example, obtained by adding an organic or mineral acid. These compositions may also be applied to the hair at a higher pH, when the acid catalyst is independently applied to the hair either before or after the compositions according to the invention.

Suitable acid catalysts include mineral acids such as phosphoric and sulfuric acid, acid salts such as monometallic phosphates, or even organic acids such as acetic, citric, and lactic acid.

The stability of these compositions is such that almost no release of formol occurs during their application, even when the hair is dried by the application of heat.

In a preferred embodiment of the invention, the alkoxymethyl compounds are kept in the form of a concentrated solution such as those listed above, the concentration of the active ingredients being between and 30 percent by weight.

Such concentrated alcoholic solutions are stable and may be stored.

At the moment of use, the addition of a given quantity of an aqueous liquid will produce the composition ready for use.

In accordance with the invention it is possible to use in the composition the same alcohol as that used to etherify the methylol compound. However, the alkoxymethy] compound which has been prepared in predetermined alcohol may be isolated and then redissolved in another alcohol if, for example, this alcohol has more valuable cosmetic properties than the one used to produce the compound according to the invention.

Of course, the compositions according to the invention may also contain any ingredients customarily used in cosmetics, such as perfumes, dyes, penetrating agents, surface-active agents, etc.

The compositions according to the invention may take the form of aqueous or hydroalcoholic solutions, creams, emulsions or gels.

These compositions may also be packaged in the form of aerosols.

Among the active compounds according to the above Formula 1 which may be used in accordance with the invention, are the following, but this list is not allinclusive:

Bis methoxymethylurea, of the formula:

Methoxymethylurea, of the formula:

Ethoxymethylurea, of the formula:

- i.propyloxymethylurea, of the formula:

Trimethoxymethylmelamine, of the formula:

N rncornotmf w vnon ocni ,l N

NH-CH;OCH:

Ethyl dimethoxymethylcarbamate, of the formula:

CH OCH H C OOCN CH OOH;

Bismethoxymethyladipamide, of the formula:

Bis-butoxy-methylurea of the formula:

The fourth embodiment of the present invention also envisages a new process for strengthening hair which process is essentially characterized by the fact that a composition as hereinbefore defined is applied to the hair and that said hair is then heated to a temperature between 25 and 45 C. This heat may be supplied while drying the hair which has first been impregnated with the composition according to the invention.

In a first method of utilizing this fourth embodiment of the invention the acid catalyst is mixed into the composition containing the active compounds.

In a second method of utilizing this fourth embodiment of the invention, the acid catalyst and the composition containing the active compounds are applied separately, with the catalyst applied to the hair either before or after the composition according to the invention.

In order that this fourth embodiment of the invention may be better understood, several methods of carrying it out will now be described, purely by way of illustration and example.

This lotion is applied to hair which has been strongly bleached. Then, after having wound the hair on setting rollers, it is dried by blowing hot air against it. After re- 21 moving the rollers and combining the hair, it is found that the hair is fluffier, softer, and brighter than when set with a conventional lotion.

Moreover, the set lasts longer.

EXAMPLE D2 A composition having the following composition is prepared at the moment of use:

Bismethoxymethylurea 0.2 g Trimethylcetylammonium bromide 0.1 g Water q.s.p. 100 g Acetic acid q.s.p. pH 3.5

This lotion is applied to hair which has been treated with a mild bleach, and the hair is then wound up on setting rollers.

The hair is dried by applying hot air and after combing, the result is a set of good quality, the hair having recovered its original flufiiness and brightness.

EXAMPLE D3 A solution having the following composition is prepared:

Trimethoxymethylmelamine 30 g Ethanol 70 cc Water 20 cc EXAMPLE D4 0.5 cc of normal hydrochloric acid is added to a suspension of 90 g of monomethylolurea in 180 cc of absolute methanol. The mixture is then heated to reflux and under agitation for 15 minutes.

It is then neutralized, while hot, with sodium carbonate, cooled and filtered. The filtrate is evaporated under vacuum at a temperature below 40-45 C. The result is thick syrup which is highly soluble in water and in alcohol. An ethanol solution containing about 20 percent of methoxymethylurea is prepared and diluted at the moment of use with an aqueous solution of phosphoric acid having a pH value of 3, so as to reduce the concentration of the active compound to 4 percent. This solution is applied to hair which has been strongly bleached in the same manner as a conventional setting lotion. The hair thus treated is springy and bright, and the resulting set lasts longer than a conventional set EXAMPLE D 0.5 cc of normal hydrochloric acid is added to a suspension of 90 g of monomethylolurea in 400 cc of absolute ethanol and the mixture is then heated to reflux under agitation for minutes. It is neutralized while hot with sodium carbonate, permitted to cool, and filtered.

A setting lotion is prepared at the moment of use by adding the following solution to the concentrated alcoholic solution of ethoxymethylurea:

Polyvinylpyrrolidone/vinyl acetate copolymer 0.5 g Trimethylcetylammonium bromide 0.1 g Perfume 0.1 g acetic acid 10 cc Water q.s.p. 100 cc This brings the concentration of the resulting solution to 8 percent in terms of ethoxymethylurea. This solution is applied to hair which has been permanently waved and the hair is then set in a conventional manner. Excellent results with respect to the quality, appearance and fluffiness of the hair are obtained.

EXAMPLE D6 Hair which has previously been bleached is carefully washed and dried and a detergent solution of citric acid at a pH of 3.5 is applied. The hair is then impregnated with a solution having the following composition:

Bismethoxymethylurea 3 g Trimethylcetylammonium bromide 0. g Polyvinylpyrrolidone/vinyl acetate copolymer 0.5g Perfume 0.] g Alcohol 25 cc Water q.s.p. 100 u:

The hair is then wound up on curlers, again saturated with this solution and dried under a hood for to minutes at about C. The hair is then found to be springy and the set is long lasting.

EXAMPLE D7 A setting lotion having the following composition is applied to hair which has first been bleached and dyed,

under the same conditions as in Example D2:

Ethyl dimethoxymethylcarbamate 2 g Polyvinylpyn'olidone/vinyl acetate copolymer 2 g Perfume 0.l g Acetic acid q.s.p. pH 2.5 Water q.s.p. 10 cc The hair is dried by applying hot air thereto while it is still wound up on the curlers, and a set having excellent holding power results.

EXAMPLE D8 Hair which has been washed and dried is impregnated with a 2 percent lactic acid solution. A cream having the following composition is then applied:

Lanette A.0. wax 4 g Oleic alcohol 4 g Trimethylcetylammonium bromide 2 g Bis-methoxymethyladipamide l g Water 89 g The hair is then wound up on curlers and dried under a hood for about 30 minutes at 45 C. The result is a springy, long-lasting set.

The fifth form of our invention results from the suprising discovery that while dimethylolurea and dimethylolthiourea have the disadvantages hereinbefore set forth with respect to the release of free formol and solubility, monomethylolurea and monomethylolthiourea do not.

Specifically these particular monomethylols release from 2 to 3 times less free formol than the corresponding dimethylols, and are at least 4 or 5 times as soluble in water. Moreover, when in powder form, these monomethylols dissolve about 10 times as rapidly in water as the corresponding dimethylols. On the other hand both monomethylolurea and monomethylolthiourea compositions have the same characteristic of improving the quality of degraded hair possessed by the active com pounds described in connection with the first four embodiments of this invention. In particular, when applied in conjunction with dyes, these compositions cause the dye to color the hair uniformly, even though previously bleached.

The fifth form of our invention accordingly relates to a cosmetic composition for improving the quality of degraded hair, said composition being essentially characterized by the fact that it comprises in solution in a cosmetic recipient at least one active compound selected from the group consisting of monomethylolurea and monomethylolthiourea.

These compositions may advantageously contain from 0.2 to 10 percent and preferably from 2 to 5 percent by weight of the active compound. They may take the form of aqueous or hydro-alcoholic solutions, emulsions, creams, gels, or aerosols, and may include any of the additives such as perfumes, surface active agents, etc. conventionally used in cosmetics These compositions may also contain an acid polymerization catalyst consisting, for example, of a mineral acid such as phosphoric or sulfuric acid, or any of the organic acies or acid salts hereinbefore mentioned. The acid catalyst should be introduced in an amount sufficient to bring the pH value of the composition to between about 1.5 and 5.

The fifth form of our invention also relates to a method of improving the cosmetic properties of hair which comprises the step of applying thereto a composition such as has just been described, and then heating the hair for 20 to 40 minutes at a temperature of from 35 to 50 C. This heating may advantageously take place during drying.

The acid catalyst may form part of the composition according to the invention or be applied separately either before or after said composition.

The invention makes it possible to bleach and permanently wave hair in rapid succession, or to permanently wave it twice in a relatively short period of time, without damaging the hair.

Several examples showing how the invention may be carried out will now be described, purely by way of illustration:

EXAMPLE E1 The hair is completely bleached in a conventional manner, and a solution having the following composition is then applied for 30 minutes at a temperature of 45 C:

Monomethylolurea 3.5 g Cetylpyridiniurn bromide 0.] g 20% acetic acid cc Water q.s.p. 100 cc The pH of this solution is about 3.

The hair is then dyed and dried in a conventional manner. The color takes well, and the springiness and brightness of the hair are increased, a result which is not found in the case of bleached hair which has not been treated in accordance with the invention before dyeing.

EXAMPLE E2 Under the same conditions as in Example El, a solution having the following composition is applied to bleached hair:

Monomethylolthiourea 1.5 g 10% phosphoric acid 5 cc Polyvinylpyrrolidone/vinyl acetate copolymer 0.5 g Water q.s.p. cc

The pH of this solution is about 1.6.

The hair is then set in a conventional manner and dried under a hood at 45-50 C. It is found that the hair treated in this way has an agreeable feel," is quite springy, and is easy to comb.

EXAMPLE E3 Hair which has been previously bleached is shampooed with an acid cationic shampoo, rinsed, and dried. it is then saturated with a solution having the following composition:

Monomethylolurea 3 g compound having the formula:

( ll CON(CII )i-N 0.2 R.

ltNll(3lIC()ONu C2115 It =Copm) Water q.s.p. 100 cc The hair is then dried for 35 minutes at about 45 C.

l. is then permanently waved in a conventional manner and the moistened hair is strong and of good quality. After being set in a conventional manner the hair is springy, fluffy and shiny, and holds the set well over a period of time.

EXAMPLE E4 A solution having the following composition is applied to hair which has first been permanently waved:

Monomethylolthiourea 4 g 10% phosphoric acid 4 cc Ext. violet DC. No. 2 (Cl violet No. 43) 0.005 g Ethyl alcohol 25 cc Water q.s.p. I00 cc The pH of this solution is about 1.8.

The hair is dried in a conventional manner and excellent results with respect to springiness and brightness are obtained.

EXAMPLE E5 EXAMPLE E6 A lotion consisting of a solution having the following composition is applied to the hair:

Monomethylolurea 6 g Monomethylolthiourea 3 g Trimethylcetylammonium bromide 0.1 g Water 90 cc The hair is then wound up on setting rollers and impregnated with a 20 percent lactic acid solution. It is dried under a hood and the resulting set is springy and long lasting. The hair is substantially stiffened.

EXAMPLE E7 A solution having the following composition is applied to hair which has first been bleached and washed:

Monomethylolurea 10 g Phosphoric acid q.s.p. pH 2.5 Water q.s.p. 100 cc The hair is left under a hood for about 10 minutes, remoistened, and permanently waved in a conventional manner.

The hair is then in excellent condition all the way to its tips, and the life of the permanent wave is substantially increased.

We claim:

1. A method for treating degraded hair to improve the strength and appearance thereof comprising applying to said hair in amounts effective to improve the strength and appearance thereof a cosmetic composition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a methylol compound of the formula R-lf-CHzOH wherein R is selected from the group consisting of hydrogen and -H,o-Nc 000,115

wherein R" is selected from the group consisting of i.

- wherein is tQl h q R and ethr tm id v lent radical selected from the group consisting of b. -CH -CH -NH-CO; c. -CH -CH -NH-CS and (1.

,. H29 W v said compound being present in amounts of about 0.1-10 percent by weight of said composition, polymerizing said methylol compound on said hair by applying thereto an acidic catalyst in amounts sufficient to cause polymerization of said methylol compound, said catalyst being selected from the group consisting of phosphoric acid, acetic acid, lactic acid, sulfuric acid, citric acid and monosodium phosphate, and drying said hair.

2. The method of claim 1 wherein said acidic catalyst is applied simultaneously with said methylol compound.

3. The method of claim 1 wherein said acid catalyst is applied before application of said methylol compound.

4. The method of claim 1 wherein said acid catalyst is applied subsequent to the application of said methylol compound.

5. A method for treating degraded hair to improve the strength and appearance thereof comprising applying to said. hair in amounts effective to improve the strength and appearance thereof a cosmetic composition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a methylol compound selected from the group consisting of monomethylol ethyl carbamate, dimethylol methylene ethyl bis-carbamate, dimethylol succinamide, monomethylol guanidine carbonate, N- methylol paratoluene sulfamide, dimethylol adipamide, N,N-dimethylol-(2-methyl-2-propyl)-propylene biscarbamate, monomethylol dimethyl hydantoin, monomethylol ethyleneurea, monomethylol ethylene thiourea and dimethylol ethylene thiourea, said compound being present in amounts of about 0.1-10 percent by weight of said composition, polymerizing said methylol compound on said hair by applying thereto an acidic catalyst in amounts sufficient to cause polymerization of said methylol compound, said catalyst being selected from the group consisting of phosphoric acid, acetic acid, lactic acid, sulfuric acid, citric acid and monosodium phosphate and drying said hair.

6. A method for treating degraded hair to improve the strength and appearance thereof comprising applying to said hair in amounts effective to improve the strength and appearance thereof a cosmetic composition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a mixture of (a) a methylol compound se lected from the group consisting of monomethylol dimethylhydantoin, monomethylol ethylene urea, dimethylol ethylene thiourea, monomethylol ethyl carbamate, dimethylol ethylene ethyl bis-carbamate, dimethylol succinamide, monomethylolethylene thiourea, dimethylolthiourea, dimethylolurea, monomethylolurea, monomethylolthiourea, trimethylol melamine, monomethyloldicyandiamide, bismethoxymethylurea, monomethylol guanidine, N,N'-dimethylol- (2-methyl,2-propyl) propylene bis-carbamate, dimethylol adipamide, N,N-diethyl-N-methylolurea, N,N- dimethylol ethyleneurea, dimethylol ethyl carbamate and tetramethylol acetylenediurea and (b) a nitrogen derivative selected from the group consisting of urea, melamine, dicyandiamide, N,N-diethylurea, ethyleneurea, isopropyl carbamate, dimethyl hydantoin, ethylene thiourea, guanidine carbonate and succinamide, said methylol compound being present in amounts of 05-12 percent by weight of said composition, said nitrogen derivative being present in amounts such that the number of NH groups supplied by said nitrogen derivative is between 0. ll .0 times the number of methylol groups supplied by said methylol compound, polymerizing said methylol compound on said hair by applying thereto an acidic catalyst in amounts sufficient to cause polymerization of said methylol compound, said catalyst being selected from the group consisting of phosphoric acid, acetic acid, lactic acid, sulfuric acid, citric acid and sodium acid phosphate, and drying said hair.

7. The method of claim 6 wherein said acidic catalyst is applied simultaneously with said methylol compound.

8. The method of claim 6 wherein said acidic catalyst is applied before application of said methylol compound.

9. The method of claim 6 wherein said acidic catalyst is applied subsequent to the application of said methylol compound.

10. A cosmetic composition for treating degraded hair to improve the strength and appearance thereof, said composition comprising a solution in a solvent selected from the gorup consisting of water and aqueous ethyl alcohol solution of a mixture of (a) a methylol compound selected from the group consisting of monomethylol dimethylhydantoin, monomethylol ethylene urea, dimethylol ethylene thiourea, monomethylol ethyl carbamate, dimethylol ethylene ethyl biscarbamate, dimethylol succinamide, monomethylolethylene thiourea, dimethylolthiourea, dime thylolurea, monomethylolurea, monomethylolthiourea, trimethylol melamine, monomethyloldicyandiamide, bismethoxymethylurea, monomethylol guanidine, N,N- -dimethylol-(2-rnethyl,2-propyl)propylene biscarbamate, dimethylol adipamide, N,N-diethyl N- methylolurea, N,N-dimethylol ethyleneurea, dimethylol ethylcarbamate and tetramethylol acetylenediurea and (b) a nitrogen derivative selected from the group consisting of urea, melamine, dicyandiarnide, N,N diethylurea, ethylene urea, isopropyl carbamate, dimethyl hydantoin, ethylene thiourea, guanidline carbonate and succinamide, said methylol compound being present in amounts of 05-12 percent by weight of said composition and said nitrogen derivative being present in amounts such that the number of NH groups supplied by said nitrogen derivative is between 0. ll .0 times the number of methylol groups supplied by said methylol compound.

11. A method for treating degraded hair to improve the strength and appearance thereof comprising applying to said hair in amounts effective to improve the strength and appearance thereof a cosmetic omposition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a compound of the formula wherein R is selected from the group consisting of hydrogen, methyl and ethyl, said compound being present in amounts of 02-10 percent by weight of said composition, polymerizing said compound on said hair by applying thereto an acidic catalyst in amounts sufficient to cause polymerization of said compound, said catalyst being selected from the group consisting of acetic, lactic, citric, phosphoric and sulfuric acid and monopotassium phosphate, and drying said hair.

12. The method of claim 11 wherein said acidic cata lyst is applied simultaneously with said methylol compound.

13. The method of claim 1 1 wherein said acidic catalyst is applied before application of said methylol compound.

14. The method of claim 1 1 wherein said acidic catalyst is applied subsequent to the application of said methylol compound.

15. A pressurized sprayable aerosol composition for treating degraded hair to improve the strength and appearance thereof comprising an ethanolic solution of a compound of the formula wherein R is selected from the group consisting of hydrogen, methyl and ethyl, said compound being present in amounts of 20 percent by weight of said solution and an aerosol propellant selected from the group consisting of nitrogen and dichlorodifluoromethane.

16. A method for treating degraded hair to improve the strength and appearance thereof comprising applying to said hair in amounts effective to improve the strength and appearance thereof a cosmetic composition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a compound selected from the group consisting of bis-methoxymethylurea, methoxymethylurea, ethoxymethylurea, isopropyloxymethylurea, trimethoxymethylmelamine, ethyl dimethoxymethylcarbamate, bismethoxymethyladipamide and bisbutoxy-methylurea, said composition containing 0.2l0 percent by weight of said compound, polymerizing said compound on said hair by applying thereto an acidic catalyst in amounts sufficient to cause polymerization of said compound, said catalyst being selected from the group consisting of phosphoric, acetic, lactic, sulfuric and citric acid and drying said hair.

17. The method of claim 16 wherein said acidic catalyst is applied simultaneously with said compound.

18. The method of claim 16 wherein said acidic catalyst is applied before application of said compound.

19. The method of claim 16 wherein said acidic catalyst is applied subsequent to the application of said compound.

20. A method for treating degraded hair to improve the strength and appearance thereof comprising applying to said hair in amounts effective to improve the strength and appearance thereof a cosmetic composition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a compound selected from the group consisting of monomethylolurea and monomethylolthb ourea, said compound being present in amounts of 0.2- percent by weight of said composition, polymerizing said compound on said hair by applying thereto an acidic catalyst in amounts sufficient to cause polymerization of said compound, said catalyst being selected from the group consisting of phosphoric, sulfuric, acetic, citric and lactic acid, and heating said hair at a temperature between 3550 C for a period of about 204O minutes.-

21. The method of claim 20 wherein said acidic catalyst is admixed with said composition, the pH of said composition ranging between 1.5-5.0.

22. The method of claim 20 wherein said acidic catalyst is applied before application of said composition.

23. The method of claim 20 wherein said acidic catalyst is applied subsequent to the application of said composition and prior to heating said hair.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. [772 OI ,6 Dated mg h r 2Q 1913 Gregoire Kalopissis, Jean Louis Abegg, Henri Inventor(s) d l d It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading:

Name of third inventor should be changed from "Henry DeBeaulie" to --Henri deBeaulieu-.

Please add --C1a1ms priority, application Iuxembourg 5 ,9 3: p i 19, l966--,

Signed and sealed this 2nd day of July 1974.

(SEAL) Attest:

EDWARD M. FLETCHER,JR. C.MARSHALL DANN Attesting Officer Commissioner of Patents M PO-1050 (10-69) USCOMM-DC 603764 69 u 5. aovnnuzuv "mums onlci nu o-su-u4

Claims

2. The method of claim 1 wherein said acidic catalyst is applied simultaneously with said methylol compound.
3. The method of claim 1 wherein said acid catalyst is applied before application of said methylol compound.
4. The method of claim 1 wherein said acid catalyst is applied subsequent to the application of said methylol compound.
5. A method foR treating degraded hair to improve the strength and appearance thereof comprising applying to said hair in amounts effective to improve the strength and appearance thereof a cosmetic composition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a methylol compound selected from the group consisting of monomethylol ethyl carbamate, dimethylol methylene ethyl bis-carbamate, dimethylol succinamide, monomethylol guanidine carbonate, N-methylol paratoluene sulfamide, dimethylol adipamide, N,N''-dimethylol-(2-methyl-2-propyl)-propylene bis-carbamate, monomethylol dimethyl hydantoin, monomethylol ethyleneurea, monomethylol ethylene thiourea and dimethylol ethylene thiourea, said compound being present in amounts of about 0.1-10 percent by weight of said composition, polymerizing said methylol compound on said hair by applying thereto an acidic catalyst in amounts sufficient to cause polymerization of said methylol compound, said catalyst being selected from the group consisting of phosphoric acid, acetic acid, lactic acid, sulfuric acid, citric acid and monosodium phosphate and drying said hair.
6. A method for treating degraded hair to improve the strength and appearance thereof comprising applying to said hair in amounts effective to improve the strength and appearance thereof a cosmetic composition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a mixture of (a) a methylol compound selected from the group consisting of monomethylol dimethylhydantoin, monomethylol ethylene urea, dimethylol ethylene thiourea, monomethylol ethyl carbamate, dimethylol ethylene ethyl bis-carbamate, dimethylol succinamide, monomethylolethylene thiourea, dimethylolthiourea, dimethylolurea, monomethylolurea, monomethylolthiourea, trimethylol melamine, monomethyloldicyandiamide, bismethoxymethylurea, monomethylol guanidine, N,N''-dimethylol-(2-methyl,2-propyl) propylene bis-carbamate, dimethylol adipamide, N,N-diethyl-N''-methylolurea, N, N-dimethylol ethyleneurea, dimethylol ethyl carbamate and tetramethylol acetylenediurea and (b) a nitrogen derivative selected from the group consisting of urea, melamine, dicyandiamide, N,N-diethylurea, ethyleneurea, isopropyl carbamate, dimethyl hydantoin, ethylene thiourea, guanidine carbonate and succinamide, said methylol compound being present in amounts of 0.5-12 percent by weight of said composition, said nitrogen derivative being present in amounts such that the number of NH2 groups supplied by said nitrogen derivative is between 0.1-1.0 times the number of methylol groups supplied by said methylol compound, polymerizing said methylol compound on said hair by applying thereto an acidic catalyst in amounts sufficient to cause polymerization of said methylol compound, said catalyst being selected from the group consisting of phosphoric acid, acetic acid, lactic acid, sulfuric acid, citric acid and sodium acid phosphate, and drying said hair.
7. The method of claim 6 wherein said acidic catalyst is applied simultaneously with said methylol compound.
8. The method of claim 6 wherein said acidic catalyst is applied before application of said methylol compound.
9. The method of claim 6 wherein said acidic catalyst is applied subsequent to the application of said methylol compound.
10. A cosmetic composition for treating degraded hair to improve the strength and appearance thereof, said composition comprising a solution in a solvent selected from the gorup consisting of water and aqueous ethyl alcohol solution of a mixture of (a) a methylol compound selected from the group consisting of monomethylol dimethylhydantoin, monomethylol ethylene urea, dimethylol ethylene thiourea, monomethylol ethyl carbamate, dimethylol ethylene ethyl bis-carbamate, dimethylol succinamide, monomethylolethylene thiourea, dimethylolthiourea, dimethylolurea, monometHylolurea, monomethylolthiourea, trimethylol melamine, monomethyloldicyandiamide, bismethoxymethylurea, monomethylol guanidine, N,N''-dimethylol-(2-methyl,2-propyl)propylene bis-carbamate, dimethylol adipamide, N, N-diethyl N''-methylolurea, N,N-dimethylol ethyleneurea, dimethylol ethylcarbamate and tetramethylol acetylenediurea and (b) a nitrogen derivative selected from the group consisting of urea, melamine, dicyandiamide, N,N-diethylurea, ethylene urea, isopropyl carbamate, dimethyl hydantoin, ethylene thiourea, guanidine carbonate and succinamide, said methylol compound being present in amounts of 0.5-12 percent by weight of said composition and said nitrogen derivative being present in amounts such that the number of NH2 groups supplied by said nitrogen derivative is between 0.1-1.0 times the number of methylol groups supplied by said methylol compound.
11. A method for treating degraded hair to improve the strength and appearance thereof comprising applying to said hair in amounts effective to improve the strength and appearance thereof a cosmetic omposition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a compound of the formula
12. The method of claim 11 wherein said acidic catalyst is applied simultaneously with said methylol compound.
13. The method of claim 11 wherein said acidic catalyst is applied before application of said methylol compound.
14. The method of claim 11 wherein said acidic catalyst is applied subsequent to the application of said methylol compound.
15. A pressurized sprayable aerosol composition for treating degraded hair to improve the strength and appearance thereof comprising an ethanolic solution of a compound of the formula
16. A method for treating degraded hair to improve the strength and appearance thereof comprising applying to said hair in amounts effective to improve the strength and appearance thereof a cosmetic composition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a compound selected from the group consisting of bis-methoxymethylurea, methoxymethylurea, ethoxymethylurea, isopropyloxymethylurea, trimethoxymethylmelamine, ethyl dimethoxymethylcarbamate, bismethoxymethyladipamide and bis-butoxy-methylurea, said composition containing 0.2-10 percent by weight of said compound, polymerizing said compound on said hair by applying thereto an acidic catalyst in amounts sufficient to cause polymerization of said compound, said catalyst being selected from the group consisting of phosphoric, acetic, lactic, sulfuric and citric acid and drying said hair.
17. The method of claim 16 wherein said acidic catalyst is applied simultaneously with said compound.
18. The method of claim 16 wherein said acidic catalyst is applied before application of said compound.
19. The method of claim 16 wherein said acidic catalyst is applied subsequent to the application of said compound.
20. A method for treating degraded hair to improve the strength and appearance thereof comprising applying to said hair in amounts effective to improve the strength and appearance thereof a cosmetic composition comprising a solution in a solvent selected from the group consisting of water and aqueous ethyl alcohol solution of a compound selected from the group consisting of monomethylolurea and monomethylolthiourea, said compound being present in amounts of 0.2-10 percent by weight of said composition, polymerizing said compound on said hair by applying thereto an acidic catalyst in amounts sufficient to cause polymerization of said compound, said catalyst being selected from the group consisting of phosphoric, sulfuric, acetic, citric and lactic acid, and heating said hair at a temperature between 35*-50* C for a period of about 20-40 minutes.
21. The method of claim 20 wherein said acidic catalyst is admixed with said composition, the pH of said composition ranging between 1.5-5.0.
22. The method of claim 20 wherein said acidic catalyst is applied before application of said composition.
23. The method of claim 20 wherein said acidic catalyst is applied subsequent to the application of said composition and prior to heating said hair.