US3694141A

US3694141A - Method of hair conditioning

Info

Publication number: US3694141A
Application number: US749278A
Authority: US
Inventors: Gregorie Kalopissis; Jean-Louis Abegg; Guiliana Ghilardi; Henri Philippe De Beaulieu
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1967-08-02
Filing date: 1968-08-01
Publication date: 1972-09-26
Anticipated expiration: 1989-09-26

Abstract

IN WHICH:
COSMETIC COMPOSITION COMPRISING, IN A SUITABLE CARRIER, AT LEAST ONE ACTIVE COMPOUND INCLUDING BOTH AT LEAST ONE DISULFIDE FUNCTION AND AT LEAST ONE GROUP RESPONDING TO THE FORMULA:

-N(-R)-CH2-O-R''

THE NITROGEN ATOM IN SAID GROUP BEING ATTACHED TO A REMAINDER WHICH IS SUFFICIENTLY ELECTROPHILE TO PREVENT THE IMMEDIATE RELEASE OF FORMOL.

R IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, A LOWER ALKYL, A HYDROXY-METHYL OR AN ALKOXY METHYL RADICAL; R'' IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, AND A LOWER ALKYL RADICAL;

Description

United States Patent once 3,694,141 Patented Sept. 26, 1972 3,694,141 METHOD OF HAIR CONDITIONING Gregorie Kalopissis, Paris, Jean-Louis Abegg, Le Perreux,

and Guiliana Ghilardi and Henri Philippe de Beaulieu,

Paris, France, assignors to Societe Anonyme dite:

lOreal N Drawing. Filed Aug. 1, 1968, Ser. No. 749,278

Int. Cl. A61k 7/10, 7/06 US. Cl. 8-127.51 3 Claims ABSTRACT OF THE DISCLOSURE Cosmetic composition comprising, in a suitable carrier, at least one active compound including both at least one disulfide function and at least one group responding to the formula:

t -N-oHtoR' in which:

R is selected from the group consisting of hydrogen, a lower alkyl, a hydroxy-methyl or an alkoxy methyl radical;

R is selected from the group consisting of hydrogen, and

a lower alkyl radical;

the nitrogen atom in said group being attached to a remainder which is sufliciently electrophile to prevent the immediate release of formol.

Keratinic fibers known to consist of chemical substances having a high molecular weight and having a large number of transverse disulfide bonds. It is considered that these disulfide bonds impart a group of characteristic physiochemical properties to the fibers.

It is also known that the disulfide bonds play an important role in the chemical treatment undergone by hair in order to impart permanent deformation thereto.

In order to produce such permanent deformation is is necessary to first open up the disulfide SS bonds of the keratin, and then, after having imparted the desired deformation to the hair, to reconstitute the S-S bonds, usually by means of oxidizing compounds.

On the other hand the chemical processes for imparting a permanent deformation to the hair, which cause opening of the SS bonds, substantially reduce the percentage of cystine, while other chemical treatments such as bleaches or combinations of bleaches and dyes, which are carried out by using rather strong oxidizing agents, also reduce the number of SS bonds in the keratin.

Moreover, atmospheric agents, such as exposure to the sun or sea water, also degrade the hair, to a very substantial extent in some cases.

Such a reduction in the quantity of SS bonds in the hair produces an irreversible alteration in the keratinic structure, which amounts to a change in the strength and cosmetic properties of the hair.

It is for these various reasons that attempts have been made to improve by a cosmetic treatment the quality of hair which has been thus degraded.

It has already been proposed to strengthen the hair by using polysulfhydryl polymers which make it possible to attach polymers of relatively high molecular weight to the natural keratinic fibers. These polymers attach themselves solidly to the keratin because they have a certain number of SH groups which can form mixed disulfides with cystein.

It has also been suggested that degraded hair be treated with cosmetic compositions containing such substances as formaldehyde or other compounds of this family which attach themselves to the keratin by reticulation, or polycondensation.

The present invention relates to new cosmetic compositions based on active compounds which increase the percentage of disulfide bonds in the hair.

It is an object of the present invention to provide as a new article of manufacture a cosmetic composition characterized by the fact that it contains at least one compound comprising at least one disulfide function and at least one group responding to the formula:

in which:

R represents hydrogen, a lower alkyl radical, a hydroxymethyl radical, or an alkoxy-methyl radical. R represents hydrogen or a lower alkyl radical.

The nitrogen atom of said group is attached to a remainder sufliciently electrophile to insure the chemical stability of the group, that is to say, to avoid the immediate release of a formol molecule.

In the present description the term lower alkyl radical is used to identify alkyl radicals having 4 or less carbon atoms.

In certain particular embodiments, the compositions according to the invention may contain compounds responding to the general formula:

HOH CQ-(H C) -SS(CH ),,'-Q'--CH OH in which Q and Q, which may be identical or diiferent, represent nitrogenous groups capable of being methylolized, such as ureas, thioureas, amides and carbamates,

n and n, which may be identical or different, each represent a whole number less than or equal to 6.

In certain particular embodiments of the invention, the cosmetic compositions according to the invention may contain at least one of the following compounds:

l;l,N'-dimethylol-dithiodiglycolamide having the for mu a:

N,N' dimethylol-dithiodi(ethylurea) having the formula:

Di(hydroxymethyl acetamido)-dimethyl cystamine am- In this latter method of producing a self-neutralizing mom'um dichloride having the formula: permanent, or long-lasting set, the compounds according (CHsh (CHM Di(hydroxymethyl-ethylurea)-dimethyl cystamine amto the invention have the advantage over known commonium dichloride having the formula: pounds of avoiding the formation of mixed disulfides, one

CO (CH3)1 H92 b IH oHloE In a first embodiment of the invention, the cosmetic part of which does not become attached to the keratin. compositions are in'the form of setting lotions which may In effect, by utilizing the disulfides according to the inalso contain an acid catalyst which facilitates the convention, all the disulfides, that is to say, both the disulfides densation of the methylol groups on the hair. according to the invention, and the mixed disulfides ob- The new compositions have the advantage of increasing tained from the disulfides and keratin are bonded to the the number of SS bonds in the keratinic fibers by means keratin at each side of the SS bond through their of compounds which penetrate into the keratinic fiber and, methylol groups. because of the methylol groups in the active compounds The cosmetic compositions according to the invention according to the invention, become chemically attached may take the form of a liquid containing the active comto the substance of the hair itself. This addition to the pounds in a simple aqueous or hydroalcoholic solution. number of SS bonds permits the formation of mixed These compositions may also take the form of a cream disulfides between the compounds according to the inor gel with the active compounds dispersed or dissolved vention and cystine, which also strengthens the hair. in one of the phases of the composition.

Both the SS bonds added by the compositions ac- The compositions according to the invention may also cording to the invention, and the SS bonds of the contain any other ingredients conventionally used in mixed disulfides may be used in permanent waving proccosmetology, such as dyes, perfumes, swelling agents, suresses. face-active agents, etc.

Finally, the compositions according to the invention They may also be packaged as aerosols. have, independently of the additional SS bonds, the ad- The compositions according to the invention contain, vantage of strengthening the hair because of the phein general, from 1 to 10% and preferably 2 to 4% of the nomenon of condensation or reticulation which is due to active compounds. the presence of the methylol groups. It is a further object of the invention to provide as In another preferred embodiment of the compositions a new article of manufacture a chemical compound which according to the invention, the active compounds are inmay be used in cosmetology characterized by the fact that troduced into fixing lotions designed to carry out the it corresponds to the following formula:

second step of a permanent Wave. In this case, particular reliance is placed on the oxidizing properties of the SS functions in the active compounds according to the invention.

In one particular method of using these compositions, they are employed as fixing lotions when permanently setting the hair, which permits the hair, after having been first reduced, rolled up on setting rollers and then impregnated with such a lotion to be dried directly.

In this case, the composition according to the invention makes it possible to not only reconstitute the SS bonds of the keratin, but also to strengthen the hair by reticulation or condensation of the methylol functions, while Q and Q, which may be identical or different, represent either an aminoalcoylamide remainders which may be quaternized, or a remainders containing urea, thio-urea, or carbamate groups, which may also contain an eventually quaternized amine function, the -CH OH groups being attached to the amide nitrogen of these remainders.

simultaneously increasing the quality of sulfur attached The Pmsfint invflnfiofl has its Particular i the to the hair. following chemical compounds:

In another embodiment, the compositions according to N,N'- im thylol dithi0di(ethylurea) having the the invention are compositions which make it possible to formula; produce a long-lasting deformation of the hair in a single step, with the reducing and oxidizing phases being carried 0 out simultaneously.

It has already been suggested that permanent waves be OHZ-OHPNHCNHCH1OH produced by using compositions containing a mixture of thiols and disulfides, in which the molar concentration of the disulfides is greater than that of the thiols. Di(hydroxymethyl acetamido)-dimethyl crystamine In accordance with the present invention, it is adammonium dichloride having the formula:

vantageous to use in such compositions the new disulfide Di(hydroxymethyl-ethylurea)-dimethyl cystamine amcompounds hereinbefore described. monium dichloride A further object of the present invention is to provide several methods of preparing the chemical compounds which have just been described.

In accordance with the invention, by starting with a compound already having a disulfide bond and at least one amine function, and reacting this with a cyanate which transforms the amine function into a urea function, which is then methylolized with a solution of formaldehyde, a chemical compound according to the invention is obtained.

In an alternative method of preparing a compound according to the invention, the process starts with a halogen derivative having an amine function which is transformed into sodium S-amino-alkyl-thiosulfate by reacting it with sodium thiosulfate. This salt may then be hydrolyzed to produce a disulfide which comprises, like the starting product, at least one amine function. This amine may be transformed into urea by reacting it with a cyanate, as has just been described, and methylolized by a solution of formaldehyde. The disulfide having a tertiary amine function may be quaternized with a compound which is itself methylolized or capable of becoming so, such as chloracetamide or N-methylol-chloracetamide. In both cases a chemical compound according to the invention results.

In order that the invention may be better understood, several examples of the preparation and use of the active compounds according to the invention will now be described purely by way of illustration.

EXAMPLE I Preparation of N,N'-dirnethyloldithiodi(ethylurea) An aqueous solution of cystamine dihydrochloride is reacted with a stoichiometric quantity of potassium cyanate for 2 hours at 80 C.

The reaction yields dithiodi(ethylurea) which is extracted and recrystallized in absolute ethanol. The melting point of the resulting product is between 152 and 153 C. and the yield is 77% A solution is then prepared which contains one mole of dithiodi(ethylurea) per liter of water, to which 187.5 g. of formaldehyde in the form of a 40% aqueous solution is added. The pH value of the mixture is adjusted to 8 by adding an N/ 10 sodium hydroxide solution and heated while stirring to a temperature of 50 C., while maintaining the pH at a value near 8. The reactants are completely dissolved at the end of about 30 minutes.

The reaction mixture is then cooled to C. and a white crystalline product having a melting point of about 100 C. results.

The yield of the reaction is 70% and the product contains about 20% combined formol.

EXAMPLE II Preparation of di(hydroxymethyl-acetamido), dimethyl cystamine ammonium dichloride Beginning with N dimethyl bromoethylamine hydrobromide, sodium S-dimethylaminoethyl thiosulfate is prepared by reaction with sodium thiosulfate, which is then hydrolized to obtain the disulfide, that is to say, tetramethyl cystamine.

The reaction produces a yield of 50% and a liquid is obtained having a boiling point of 100 C. under a pressure of 1 millimeter, and containing 99% of the theoretical quantity of tertiary amines.

The tetramethyl cystamine is then quaternized with a stoichiometric quantity of N methylol chloracetamide.

The reaction is carried out at 100 C. for 30 minutes and a colorless paste is obtained which contains no tertiary amines. The yield of the reaction is 100%.

EXAMPLES OF APPLICATIONS Example I A solution having the following composition is applied to hair which has first been washed and dried:

G. Thioglycolic acid 2.5 Di-(hydroxymethyl acetamido) dimethyl cystamine ammonium dichloride 7 Monoethanolamine, q.s.p., pH 9.5. Water, q.s.p., c.

The following composition is applied to hair which has previously been bleached:

G. N,N'-dimethylol dithiodi(ethylurea) 2 Polyvinylpyrrolidone/vinyl acetate copolymer 0.4 Trimethyl cetyl ammonium bromide 0.1

Acetic acid q.s.p., pH 3. Water, q.s.p., 100 cc.

The hair is set in a conventional manner and it is found that the hair is harder and cleaner, and its tips are less dry than when bleached hair is set using a process other than one according to the invention. Moreover, the wave set exhibits excellent resilience.

Example III -A long lasting set is produced in a generally conventional manner, using the following composition:

Thioglycerol, 3 g. Ammonia, q.s.p., pH 9.5. Water, q.s.p., 100 cc.

The hair is impregnated with this solution, wound upon setting rollers of the usual diameter, and again saturated with the solution before being left for 15 minutes under a plastic cap at room temperature.

The hair is then rinsed and the following solution is applied:

N,N-dimethylol dithiodiglycolamide, 4 g. Phosphoric acid q.s.p., pH 2.5. Water, q.s.p., 100 cc.

The hair is then placed under a hood and dried in a conventional manner. The resulting wave is of excellent quality and exhibits excellent stability in time.

Example IV The first step of a long lasting set is carried out as in Example II'I after which the following solution is applied to the hair:

N,N'-dimethylol dithio dipropionamide, 4 g. Phosphoric acid q.s.p., pH 2.5. Water, q.s.p., 100 cc.

Example V The following composition is applied to hair which has first been washed and dried:

Thioglycolic acid 2.5 Di(hydroxymethyl ethylurea) dimethyl cystamiue ammonium dichloride 7 Monoethanolamine, q.s.p., pH 9.5.

The hair is then wound upon rollers and left under a hood for 15 minutes at a temperature of 35 to 40 C., rinsed with running water, and impregnated with a solution comprising citric acid to bring its pH to 2.5. The waving process is then completed in a conventional manner by drying it at a temperature of about 45 to 50 C.

The hair exhibits excellent resilience, and the wave is very stable in time.

What is claimed is:

1. A method for strengthening hair comprising applying to said hair in amounts effective to strengthen said hair a composition having a pH of 2.5 to 3 and comprising a solution in a solvent selected from the group consisting of water and aqueous alcohol solution of an active compound selected from the group consisting of N,N'-dimethylol-dithiodiglycolamide,

N,N'-dimethylol-dithiodi (ethylurea) di(hydroxymethyl acetamido)-dimethyl cystamine ammonium dichloride, di(hydroxymethyl-ethylurea)-dimethyl cystamine ammonium dichloride, and

N,N-dimethyloldithiodipropionamide, said active compound being present in amounts ranging from 110% by weight of said composition, and an acid catalyst selected from the group consisting of acetic acid, phosphoric acid and citric acid, and then drying said hair.

2. A method for permanently setting hair comprising applying to hair previously chemically reduced, rinsed and then mechanically shaped, an effective amount of a composition having a pH of 2.5 to 3, said composition comprising a solution in a solvent selected from the group consisting of water and aqueous alcohol solution of an active compound selected from the group consisting of N,N'-dimethylol-dithiodiglycolamide,

N,N'-dimethylol-dithiodi(ethylurea) di(hydroxymethyl acetamido)-dimethyl cystamine ammonium dichloride, di(hydroxymethyl-ethylurea)-dimethyl cystamine ammonium dichloride, and

N,N-dimethylol dithio dipropionamide, said active compound being present in amounts ranging from 110% by weight of said composition, and an acid catalyst selected from the group consisting of acetic acid, phosphoric acid and citric acid, and then drying said hair.

3. A method for permanently setting hair comprising applying to hair a composition having a basic pH and comprising a solution in a solvent selected from the group consisting of water and aqueous alcohol solution of (a) a thiol hair reducing agent in amounts effective to reduce said hair and (b) an active compound selected from the group consisting of N,N'-dirnethylol-dithiodiglycolarnide,

N,N'-dimethylol dithio dipropionamide, said active compound being present in amounts ranging from 110% by weight of said composition, heating the air, rinsing the hair with water, impregnating said rinsed hair with a pH 2.5 to 3 solution comprising an acid catalyst selected from the group consisting of acetic acid, phosphoric acid and citric acid and then drying said hair.

References Cited UNITED STATES PATENTS 3,642,429 2/ 1972 Kalopissis et al. 8-127.51 3,485,815 12/1969 Oroslan et al 8-1163 X 2,351,718 6/1944 Speakman 8-128 X 2,723,213 11/1955 Powers et al 8-128 X 3,149,042 9/ 1964 Habicht et al 424- 3,349,000 10/1967 Joos 8127.6 X

GEORGE F. LESMES, Primary Examiner H. WOLMAN, Assistant Examiner U.S. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,694,141 pated. September 26, 1972 Gregoire Kalopissis; Jean-Louis Abegg; Giuliana Inventor(s) Ghilardi; and Henri Philippe de Beaulieu 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, add

P y, pplication Luxembourg- 5 b 33, .August 2, 196

Signed and sealed this 3rd day of December 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. cw. MARSHALL DANN At-testing Officer Cmmnissioner of Patents *cmM 5 0-1050 (10-69) uscomm-oc wan-pan