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Publication numberUS3882114 A
Publication typeGrant
Publication dateMay 6, 1975
Filing dateApr 17, 1972
Priority dateOct 26, 1967
Publication numberUS 3882114 A, US 3882114A, US-A-3882114, US3882114 A, US3882114A
InventorsJean-Louis Abegg, Beaulieu Henri Philippe De, Guiliana Ghilardi, Gregoire Kalopissis
Original AssigneeOreal
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
N-(morpholinomethyl carbamyl) cysteamine and glycine
US 3882114 A
Abstract
Polycondensable compound and a process for treating hair employing a composition containing said polycondensable compound having the formula WHEREIN X is O or S; R1 and R2 are ethyl or together form the divalent radical -CH2-CH2-O-CH2-CH2-, -CH 2-CH2-CH2-CH2-CH2- or R3 and R'3 are hydrogen or taken together form the divalent radical -CH2-CH2-, Y is hydrogen, -CH2-CH2-S-S-CH2-CH2-NHCONH2, -CH2-CH2HS, -CH2COOH, -C12H25 and -C18H37 and an acid catalyst in an amount effective to polymerize the compound on the hair and then drying the hair.
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United States Patent 191 Kalopissis et al.

1 May6, 1975 N-(MORPHOLINOMETHYL CARBAMYL) CYSTEAMINE AND GLYCINE [75] Inventors: Gregoire Kalopissis, Paris;

Jean-Louis Abegg, Le Perreux; Guiliana Ghilardi; Henri Philippe de Beaulieu, both of Paris. all of France [73] Assignee: Societe Anonyme dite: LOreal, Paris, France [22] Filed: Apr. 17, 1972 [2]] Appl. No: 244,906

Related 0.8. Application Data [63] Continuation-impart of Ser. No, 770,074, Oct. 23,

1968, Pat. No. 3,678,157.

[30] Foreign Application Priority Data Oct. 26, 1967 Luxembourg 54745 [52] US. Cl "260/2471 R; 8/127.51; 8/1276;

260/246 B; 260/2472 A; 260/268 H; 260/268 R; 260/293.7; 260/293.85; 260/293.86; 260/309.7; 260/552 R; 260/553 R; 424/248; 424/70; 424/71; 424/72; 424/47 OTHER PUBLICATIONS Welcome 1. Weaver et a1, Chemical Abstracts Vol. 38, pages 1507-1508, (1944). Gregoire Kalopissis et al., Chemical Abstracts Vol. 71, 739565, (1969).

Primary Examiner-Donald G. Daus Assistant Examiner-Jose Tovar Attorney, Agent, or Firm-Cushman, Darby & Cushman [57] ABSTRACT Polycondensable compound and a process for treating hair employing a composition containing said polycondensable compound having the formula wherein X is O or S; R and R are ethyl or together form the divalent radical CH CH OCH- ,-CH, CH CH,-CH -CH CH or CH -NHCONi-I R and R are hydrogen or taken together form the divalent radical CH CH Y is hydrogen,

C H CH (37 2 5 6 3 -CH CH -N .1 CB -CH -N c1 C H CH copra CH cu cu NC CH CH rm H N 2 2 H2- -cir-crt -ri 3,

C, H and C ;H and an acid catalyst in an amount effective to polymerize the compound on the hair and then drying the hair.

2 Claims, N0 Drawings N( MURPHOLINOMETHYL CARBAMYL) CYSTEAMINE AND GLYCINE This application is a continuation-in-part of our earlier application Ser. No. 770,074, filed Oct. 23, W68, now US Pat. No. 3,678,157.

This invention relates to a cosmetic composition for improving the condition of human hair and imparting thereto properties which are advantageous when the hair is to be subsequently subjected to a cosmetic treatment.

It is known that the hair is more or less degraded by the action of atmospheric agents such as the sun and sea water, and by chemical treatments to which they are subjected, for example, during permanent waving and bleaching.

The effects of such degradation may be to a large extend eliminated by using the compositions according to the present invention.

It has already been proposed to increase the strength and elasticity of the hair by treating it with compounds which can be polymerized inside the keratin fiber, and at the same time become attached to the reactive groups of the keratin.

Among the compounds heretofore suggested for this purpose are dimethylolurea and dimethylolthiourea. which have, however, the disadvantage of causing the release of a substantial quantity of free formol, the presence of which in contact with the scalp cannot be tolerated.

It has also been suggested to use for this same purpose compounds which are more stable than dime thylolurea and dimethylolthiourea. that is to say, com pounds which release much less free formol.

However, these compounds exhibit the common characteristic of having hydroxymethyl group substituents which prevent them from being completely stable. Moreover, these products are difficult to prepare in a very pure state and consequently the process for preparing them does not lead to rigorously reproducible results.

Furthermore, a great many of these compounds are difficult to dissolve in aqueous solvents which are generally used in the cosmetic field.

In order to at least partially eliminate these disadvantages, it has been suggested that one use, instead of the hydroxymethyl derivatives themselves. particular derivatives of these compounds obtained in a known manner by condensing them with secondary amines in accordance with the Mannich reaction.

The compounds produced in accordance with this reaction are more soluble, more stable, and easier to prepare than the corresponding hydroxymethyl compounds and are thus appreciably more satisfactory when used for the cosmetic purpose of strengthening the hair.

Specifically, cosmetic compounds having disulfide bonds have been chemically attached to the hair. This supplement to the SS bonds improve the behavior of the hair and affects the action of the fiber with respect to the chemical reactants customarily used in the cosmetic field, such as reducing solutions containing mercaptans or sulfites, or oxidizing agents containing hydrogen peroxide, for example.

In like manner cosmetic compounds having carboxylic groups have been attached inside the hair. These additional acid groups greatly increase the affinity of the fiber for basic dyes.

On the other hand, basic groups, or even fatty chains, have been introduced into the hair in order to increase the affinity of the hair for acid dyes, or improve the sheen and feel of the hair over a substantial period of time.

It has now been discovered that these different purposes can be served by using compounds having in their molecule both a function capable of causing polycondensation and a function serving the other cosmetic purposes outlined above. In this manner, when this type of product is poly-condensed in a conventional manner inside the keratin, the result is to achieve simutaneously both the desired cosmetic effect and iproved properties with respect to their mechano-elastic behavior.

It is therefore an object of the present invention to provide a process for treating or modifying the keratin of the hair comprising applying to the hair an effective amount of a composition containing in a solvent selected from the group consisting of water and an aque ous alcoholic solution (l.5l 2 weight percent of a polycondensable compound having the formula:

| Y N it N c N 1 CH --CH -IilCH -CH 3 CH -NHCONH R and R are selected from the group consisting of hydrogen and, when taken together, a divalent radical having the formula CH -CH Y is selected from the group consisting of hydrogen,

wherein R and R have the meaning given above,

wherein copra is a mixture of alkyl and alkenyl having 6-18 carbon atoms,

ED Z S -ca -N CH -CH CH -N-CH 'CH S-CH CH CH 2 The solvent, as stated, can be water or an aqueous alcoholic solution and when the latter is chosen the alcohol generally employed is either ethanol or isopropanol present in amounts up to about 70 percent by weight of said aqueous alcoholic solution.

ln combination with said polycondensable compound there is employed an acid catalyst in amounts effective to polymerize said compound on the hair. Thereafter, the hair is dried.

Representative of such polycondensable compounds are monomorpholinomethylurea dimorpholinomethylurea, dimorpholinomethylthiourea, monomorpholinomethylthiourea, monomorpholinomethylethyleneurea, l,4-bis(carbamidomethyl) piperazine, diethylaminomethylurea, monomorpholinomethylethylene diurea, dimorpholinomethylene diurea, piperidinomethylurea, (N-carbamyl-N'- morpholinomethylcarbamyl)cystamine, N,N'- (morphol inomethylcarbamyl )cystamine, N- (morpholinomethylcarbamyl)cysteamine, N-(morpholinomethylcarbamyl) glycine, (diethylmethylmorpholinomethyl ureidoethyl)ammonium iodide, (dimethylcopra-morpholinomethyl ureidoethyl )ammonium chloride, [N-(morpholinomethyl)ethylurea diethyl ethylurea] ammonium chloride, methylpropylurea N-(morpholinomethyl) propylurea amine, methyl di-[ N-(morpholinomethyl )propylurea amine], (N-dimethyl ethylurea-N'-dimethyl morpholinomethyl ureidoethyl)cystamine dichloride, N-dodecyl, N'- (morpholinomethyl)urea and N-octadecyl, N'- (morpholinomethyl )urea.

Of particular interest in the present invention is the use of a polycondensable compound having the formula wherein Y is selected from the group consisting of hydrogen and -CH OCH R, and R; together represent a member selected from the group consisting of 1 a divalent radical having the formula CH --CH- -OCH CH in which case R' is methyl and (2) together with R';, represent a member having the formula -CH=CH-CH=CHCH=, and A represents an anion selected from the group consisting of iodide and chloride.

Representative of such compounds are morpholinomethylurea quaternized with methyliodide and methoxymethylureidomethyl pyridinium chloride.

As the acid catalyst employed with the polycondensable compound in the process of the present invention the following are representative of those usefully employed: sulfuric, hydrochloric, phosphoric, citric, lactic, formic, acetic, p-toluenesulfonic, tartaric, succinic, glycolic, salicyclic, oxalic, malic, phenylacetic and nicotinic acids. Particularly effective catalysts are sodium and potassium monophosphates.

The cosmetic composition utilized in the present invention generally has a pH ranging between 1-5 and ordinarily is applied to the hair in amounts of about [0-30 cc. It will be appreciated, however, that the amount of the composition applied to the hair can vary depending on, for instance, the amount of hair to be treated.

Further, the cosmetic compositions employed in the present invention can also contain one or more ureins, such as those having the following formula:

ll Y (NH 0 m wherein X is selected from the group consisting of O, S and NH,

n 1 or 2 and Y is a chemical group which has cosmetic properties and is selected from the group consisting of disulfide, carboxylic acid, tertiary amine, quaternary amine, fatty chain and SH groups.

The cosmetic composition employed in the present invention can be provided in the form ofa gel, a cream, or an aerosol. It can also contain cnventional cosmetic additives, such as surface-active agents, penetrating agents, perfumes, resins and the like.

Moreover, the cosmetic composition can be provided in the form of a two-package assembly, the contents of said packages designed to be mixed just prior to use on the hair. One of said packages contains the polycondensable compound in solid form while the other package contains the aqueous or aqueous alcoholic solvent together with the acid catalyst, as well as any convenient cosmetic additive desired to be included in the overall composition.

In particular, the solid or aqueous phase of the cosmetic composition packages in this manner can also contain a salt of sulfurous acid, such as sodium metabisulfite.

A further object of the present invention is to provide a new process for treating hair characterized by the fact that the hair is impregnated with the above composition, and dried by the application of heat. If desired, the hair can be rinsed prior to drying the same.

In a first method of carrying out this process, the cosmetic composition does not itself contain the acid catalyst necessary to cause polycondensation of the polycondensable compounds in the keratinic fiber, and this acid catalyst is instead applied directly to the hair either before or after applying the cosmetic composition of this invention.

In another method of carrying out this process, a cosmetic composition which does contain the acid catalyst is applied directly to the hair, which is then dried as previously described.

The treatment according to the invention makes it possible to substantially strengthen the keratinic fiber of the hair by forming a polycondensate inside the hair which also becomes attached to the reactive groups of the keratin. This treatment makes it possible to obtain sets of excellent quality when the hair is treated while wound up on setting rollers.

On the other hand, when the polycondensable compounds also contain other cosmetic constituents, the treatment according to the invention also makes it possible to carry out subsequent cosmetic treatments, such as bleachings, dyeings, permanent wavings and the like under greatly improved conditions.

It is a further object of the present invention to provide as a new article of manufacture, a compound corresponding to the formula:

Z NH NH CH N O Representative of such compounds are: (N-carbamyl N-morpholinomethylcarbamyl )cysteamine N,N (morpholinomethylcarbamyl)cysteamine; N- (morpholinomethylcarbamyl )cysteamine; N-

R NH C NH This type of compound is prepared by reacting an alkali cyanate (Na or K) with a primary amino hydrochloride R NH +HCl O =CNA,R -NH NH A Na or K In a second step, a reaction of Mannich type such as described in Organic Reaction" Vol. I, Ch. 10, p. 303 and Houban Weyl XIV/2, p. 342 -354 is carried out by reacting the above urein (ll) which has thus been formed with a secondary amine (in the present case with morpholine) in the presence of formol in stoichiometric quantity or in slight excess.

The reaction is carried out in aqueous solution either at room temperature or at a temperature of about 20C to 60C. In some cases the reaction is exothermic.

The yield of the Mannich reaction is generally comprised between 80 to 100 EXAMPLES OF PREPARATION Example 1 Preparation of dimorpholinomethylthiourea 1 mol of thiourea is dissolved in 2 mols of formol in an aqueous 30% solution, at a temperature of 40-50C.

This mixture is cooled below 20C and 2 mols of morpholine are added slowly while keeping the temperature between and C. This resulting mixture is then cooled to -l0C until the dimorpholinomethyl thiourea crystallizes out, which takes at least 24 hours.

The resulting product is a white crystalline solid which melts at 130C. The yield of the reaction is 90%.

Example 2 Preparation of (N-carbamyl-N'-morpholinomethyl carbamyl )cystamine s CH2 CH2 rm K N112 S-CH-CH-NH-C-NH-C 1 mol of N,N' -dicarbamyl-cystamine, 1 mol of formol in an aqueous 30% solution, 1 mol of morpholine and 50 cc of distilled water are mixed while stirring.

While the resulting reaction is exothermic, it is nevertheless necessary to heat the above mixture to 50-55C so as to dissolve the reagents. The mixture is then permitted to revert to ambient temperature and is then cooled to l5C. The reaction product solidifies, and is dried under vacuum on P 0 It is a white crystalline product. The yield of the reaction is better than 90%.

Total amines 3.0 meq/g. Theoretical 2.96 meq/g.

Tertiary amines 2.7 meq/g. Theoretical 2.96 meq/g.

Example 3 Preparation of N,N(morpholinomethylcarbamyl)cystamine.

8 S-CH -CH -NH-CO-NH-CH -fi p CH -NH-CO-NH-CH g) 1 mol of N,N-dicarbamyl cystamine, 2 mols of formol in an aqueous 30% solution, 2 mols of morpholine and 50 cc of distilled water are mixed together while stirring.

The resulting mixture is heated to about 55-60C until the reactants are completely dissolved. After cooling, the mixture is evaporated under vacuum at a temperature below 40C. The residue is a white crystalline product. The yield of the reaction is greater than Tertiary amines 4.0 meq/g. Theoretical 4.6 meq/g.

S CH

Example 4 opra.

l mol of (dimethyl, morpholinomethylcarbamyl)- cysteamine; chloride, prepared by quaternization of dimethyl copra with chloroethylurea, is dissolved in distilled water. 1 mol of formol in an aqueous 30% solution is then added. Morpholine is then added slowly, while stirring. The reaction is exothermic. The temperature is kept near 50C. When the temperature falls, the reaction mixture is evaporated until dry and it is then redissolved by heating it in 2400 cc of ethanol. This mixture is then again evaporated until dry. The resulting product is a yellow oil, which after mixing with ether and vacuum drying, forms a translucent lightcolored paste. The yield of the reaction is 87%.

Example 5 Preparation of N-methyl-di(morpholinomethyl )propylurea Example 6 Preparation of N-( morpholinomethyl carbamyl cysteamine The residue is a white colored paste. The yield of the ascn cn NHcoNH-c1a N\ Jo reaction is 98 Total amines 4.28 meq/g. Theoretical 4.60 meq/g. 1 mol of N-carbamyl cysteamine, 1 mol of formol in an aqueous 3U solution, 1 mol of morpholine and 5 E l 8 lOcc of distilled water are mixed while stirring.

The reaction is exothermic (52C.) After cooling to Preparation of (diethyl methyl about 30C, 10cc of water is added and the mixture morpholinomethyureidoethyl)ammonium iodide 59 c a ,--a I N CH CH NH CO NH CH N O CH heated to 60C until the reactants are completely disl mol of (diethyl methyl ureidoethyl)ammonium, solved. The mixture is then evaporated and redissolved prepared according to the following scheme, is disby heating it in ethanol. This mixture is then again solved in distilled water.

C H C H N (CH2) 2 NH2, HCl KCNO N (CH2) 2 NHCONH2 z s z s 2 s ICH3 Ii] (CH2) 2 NH CO NH2 I c H ca evaporated until dry and after washing with 50cc of To this solution 1 mol offormol in an aqueous 30% soether and vacuum drying on P 0 the result is a yellow lution is added and then slowly and under stirring l mol colored paste (hydroscopic). The yield of the reaction of morpholine. The reaction is exothermic. The temis lOO perature is kept near 50C. When the temperature falls,

Total amines 4.60 meq/g. Theoretical 4.57 meq/g the reaction mixture is evaporated until dry. The result- Example 7 gig product is a paste. The yield of the reaction IS 96 Preparation of N-(morpholinomethylcarbamyl)glycine Total amines 2.32 meq/g. Theoretical 2.50 meq/g.

Tertiary amines 1.96 meq/g. HO-C-CH -NH- -N t 2 co H CH N o Example 9 O Preparation of N-( morpholinomethyl)ethylurea diethyl 1 mol of N-earbamyl glycine and 1 mol of formol are ethylurea ammonium chloride LT) C2H5\ 1 Cl N CH CH NH CO NH CH N O 2 2 2 VJ c l mixed while stirring. This mixture is cooled with an ice- This compound is prepared accoding to the following bath and 1 mol of morpholine is added slowly while scheme:

C II

N- (CH2) 2-NH-CO-NH2+HCHO+HN O C H 2 5 Cl- (CH NH-CONH N (CH2) 2-NH-cO-NH-cH2-N O C H e 2 5 Cl N- (CH -NH-CO-NH-CH -N O 2 2 2 C H U CH2-CH2-NHCONH2 keeping the temperature at about 15C during 30 min- I mol of diethyl amino ethylurea and 1 mol of formol utes and at about 50C during the same time. After are mixed and the reaction temperature raised from cooling the resulting mixture is evaporated until dry. 24C. to 37C.

To this mixture 1 mol of morpholine is then slow y according to organic synthesis Vol. 3 l963 page 515 added. The reaction is exothermic (50C). The mixture and then carrying out a Mannich reaction in the presis then ct .iled and stirred dining half an hour. ence of 1 mol of formol and 1 mol of morpholine ac- To the aqueous solution ethanol and quickly chloroecording to one of the preceding examples. thylurea are added while stirring. 5

The rcsult'ng iixture is heated until the reactants are EXAMPLES OF USE completely dissolved and the heating is maintained dur- Example 12 ing 2h 30 to 3h at ll/80C.

After evaporation to dryness the resulting residue is dried on P A yellow colored viscous product is ob- A head of hair is first bleached with a conventional oxidizing composition, rinsed, and dried. The hair is then impregnated with the following solution:

tained.

The yield of the reaction is 97.5 monomorpholinomethyl thiourea 2 g Total amines 2.63 meq/g Theoretical 2.63 mcq/g 1mgfg z ggfggg l z {232 32 chunol solution) -50 0.4 g Example 10 [5 acetic acid, qsp. pH 2.8 Preparation of N-methylpropylurea 100 cc (morpholinomethyl )propylurea The hair is then set and dried under a hood for 30 to m (CH 3 NH CO NH CH N 0 CH3 N (CH 3 NH co Nit l mol of N-methyl dipropylurea and l mol of formol 40 minutes at a temperature of about 50C. The in aqueous 30 solution are mixed. To this solution 1 hair is markedly hardened and is easily arranged. The mol of morpholine is slowly added while cooling. The tips of the hair appear to be in good condition. The set stirring is maintained 1 hour after the end of the N- is springy, and lasts well. methyl dipropylurea addition. After evaporation to Exa l 13 dryness a crystalline product is obtained which melts at 30 mp e 1 10C, Th i ld f th r ti i 98 Example 12 is repeated except that the solution con- Total amines: 5.69 meq/g Theoretical 6,06 meq/g, tains 2 g Of dimorpholinomethylurea rather than 2 g of Tertiary amines: 5.80 meq/g. monomorpholinomethyl thiourea and the acetic acid is replaced by sulfuric acid in amounts effective to impart Example 11 35 a pH of l to said solution. Preparation of E l I 4 (N -dimethyl-ethylurea-N'- xamp e dimethylmorpholinomethylureidoethyl)cysteamine A solution having the following composition is apdichloride plied to natural hair which has first been washed and CH CH l (CH -N-(CH -NHCO-NH-CH-N O S l 2C1.

(ca i 22/N\(CH l 2 NH CO NH CH H l mol of (N-N' dimethyl N-N ethylurea) cysteamine dried: dichloride, obtained by quaternization of N-N' di- A g V methyl cysteamine with 2 moles of chloroethylurea. is lflibslcurhum'domethyllp'pemzme 4 g ater 100 cc dissolved in distilled water.

To this solution 1 mol of formo] in aqueous 3O The hair iS then wound up On setting rollers and carelution and subsequently 1 mol of morpholine are fully impregnated with a 2% lactic acid solution. The added. The reaction is exothermic (30C). The solvent hair is left to dry under a hood at about 45C and a set is then evaporated to dryness and a white colored paste of excellent quality results. is obtained. E I 5 The yield of the reaction if 90 Tertiary amines: L68 meq/g. Theoretical L81 Example l4 is repeated except that the [,4- meq/g. bis(carbamidomethyl)piperazine is replaced by an es- N-dodecyl. N (morpholinomethyl)urea and N- sentially equivalent amount of dimorpholinomethylthiocetadecyl N-(morpholinomethyl)urea are obtained ourea and the 2% lactic acid solution is replaced by a by first preparing N-dodecyl urea and N-octadecylure'a 2% citric acid solution.

Example In Hair which has been strongly bleached is impregnated with a solution obtained by mixing, just before use, a powder containing:

monomorpht linomcihylurca 6 g urea l g with 100 cc of a phosphoric acid solution diluted to a pH of 2.5.

The hair is dried while keeping the temperature between 40 and 45C for about 30 minutes.

Hair which has thus been treated is permanently waved in a conventional manner. The results of this permanent are excellent, whereas it is usually impossible to give a satisfactory permanent wave immediately after bleaching.

Example 17 Example 16 is repeated except that the monomorpholinomethylurea is replaced with an essentially equivalent amount of monomorpholinomethylethyleneurea and the phosphoric acid is replaced with formic acid in amounts sufficient to impart to the solution a pH of 3.5.

Example 18 The following composition is applied to hair which has just been bleached in a conventional manner.

(dimethyl-copra-morpholinomethyl-ureido ethyl) ammonium chloride 1 g methykpropylurea N(morpholinomethyl) propylurea amine l g acetic acid, q.s.p. pH 2.5 water 100 cc The hair is then set in a conventional manner and excellent results are obtained with respect to resilience and holding power, as well as the condition, feel and sheen of the treated hair.

Example 19 Example 20 Example l9 is repeated except that the methylpropylurea N-(morpholinomethyl)propylurea amine is replaced with an essentially equivalent amount of methyl-di-{N-(morpholinomethyl)propylurea] amine and the acetic acid is replaced with tartaric acid in amounts sufficient to impart to the composition a pH of 4.5.

Example 2l A solution having the following composition is applied th hair which is to be strongly bleached.

N N-(morpholinomethyl carhamyl) cystamine 4 g phosphoric acid q.s.p. pH 2.5 water, qsp. I cc The hair is then dried under a hood for about 30 minutes at a temperature of about 45C.

Afterwards the hair is bleached with a conventional oxidizing agent. The quality of hair which has been thus bleached after being first treated in accordance with the invention is excellent, under both humid and dry conditions.

Example 22 Example 21 is repeated except that the N,N- (morpholinomethyl carbamyl)cystamine is replaced with an essentially equivalent amount of (N-dimethyL ethylurea N'-dimethylmorpholinomethyl ureidoethyl)- cystamine dichloride and the phosphoric acid is replaced with succinic acid in amounts sufficient to impart to the solution a pH of 5.

Example 23 The first step of a conventional permanent wave is carried out using the following composition:

N-(morpholinomethyl carbamyl) cysteamine L3 g N,N'-(morpholinomethyl carbamyl) cysteamine 4 g monoethanolamine, qsp. pH water, q.s.p. I00 cc The hair is impregnated with this solution, wound up on rollers of the usual diameter, and again saturated with this solution. It is then left for IS minutes under a plastic cap at room temperature. The hair is then rinsed after which an aqueous solution of hydrogen peroxide at 6 volumes is applied. This solution has been brought to a pH of 1.5 by adding phosphoric acid.

The hair is then put under a hood and dried in a conventional manner. The result is a set of excellent quality which lasts well, with the hair shiny with a very soft feel."

Example 24 Example 23 is repeated except that the N- (morpholinomethylcarbamyl)cysteamine is replaced with an essentially equivalent amount of diethylaminomethylurea and the phosphoric acid is replaced with glycolic acid.

Example 25 Example 24 is repeated except that the N,N'- (morpholinomethyl carbamyl)cysteamine is replaced with an essentially equivalent amount of monomorpholinomethylethylenediurea, and the water is replacced with a water/ethyl alcohol 50/50 mixture.

Example 26 Natural hair, or hair which has first been bleached, is permanently waved, using the following selfneutralizing composition:

thioglycolic acid 2 g (N-carhamyl N'-morpholinomethyl carbamyl) cysteamine 7 g ammonia, qsp. pH 9.5

water. q.s.p.

Example 27 Example 26 is repeated except that the (N-carbamyl N'-morpholinomethyl carbamyl)cysteamine is re placed with an essentially equivalent amount of N- (morpholinomethylcarbamyl)glycine and the water is replaced with a water/isopropyl alcohol 60/40 mixture.

Example 28 Example 12 is repeated except that the monomorpholinomethyl thiourea is replaced with an essentially equivalent amount of dimorpholinomethylene diurea and the acetic acid is replaced by salicylic acid.

Example 29 Example 12 is repeated except that the monomorpholinomethy] thiourea is replaced with an essentially equivalent amount of piperidinomethylurea and the acetic acid is replaced by oxalic acid.

Example 30 Example 18 is repeated except that the (dimethylcopra morpholinomethyl-ureido ethyl)ammonium chloride is replaced with an essentially equivalent amount of [N-(morpholinomethyl)ethylurea, diethyl, ethylurealammonium chloride and the acetic acid is replaced by malic acid.

Example 31 Example 2l is repeated except that the N.N- (morpholinomethyl carbamyhcystamine is replaced with an essentially equivalent amount of N-dodecyl. N '-(morpholinomethyl )urea and the phosphoric acid is replaced by phenylacetic acid in amounts sufficient to impart to the solution a pH of 1.0.

Example 32 Example 21 is repeated again except that the NM- (morpholinomethyl carhamyhcystamine is replaced with an essentially equivalent amount of Noctadecyl N(morpholinomethyl)urea and the phosphoric acid is replaced by nicotinic acid in amounts sufficient to impart to the solution a pH of 4.0.

Example 33 Example 14 is repeated except that the 1,4- bis(carbamid0methyl)piperazine is replaced with an essentially equivalent amount of morpholinome thylurea quaternized with methyl iodide. and the water is replaced with a water/ethyl alcohol /30 mixture.

Example 34

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Citing PatentFiling datePublication dateApplicantTitle
US3957774 *Feb 6, 1975May 18, 1976L'orealN-morpholinomethyl-n-'-substituted ethyl and propylureas
US4011331 *Feb 28, 1975Mar 8, 1977John Wyeth & Brother LimitedPiperidine derivatives
US4038303 *Feb 20, 1976Jul 26, 1977Colgate-Palmolive CompanyQuaternary ammonium carbamide compounds
US4348202 *Jun 10, 1980Sep 7, 1982L'orealHair dye or bleach supports
US4579732 *Aug 6, 1982Apr 1, 1986L'orealHair dye or bleach supports
US4774075 *Jul 2, 1985Sep 27, 1988L'orealCompositions containing bis-(quaternary ammonium) derivatives for the treatment of keratin materials and natural non-keratin materials or synthetic textile materials
US4777040 *Mar 28, 1986Oct 11, 1988L'orealProcess and composition for protecting the hair from the degradation effects of a permanent wave
US4795629 *Jul 16, 1987Jan 3, 1989Chesebrough-Pond's Inc.Crosslinking of hair thiols using cystamine
US4828819 *Jun 16, 1988May 9, 1989L'orealCompositions containing bis-(quaternary ammonium) derivatives for the treatment of keratin materials and natural non-keratin or synthetic textile materials
US5026910 *May 22, 1990Jun 25, 1991Societe AtochemPolyfluoroalkyl nitrogen compounds, processes for their preparation and their use
US5107021 *Apr 12, 1991Apr 21, 1992Societe AtochemPolyfluoroalkyl nitrogen compounds, processes for their preparation and their use
US5466878 *Oct 18, 1991Nov 14, 1995L'orealReducing composition for the permanent deformation of hair containing as a reducing agent, an amino mercaptoalkylamide or a salt thereof
US7981167Jul 22, 2009Jul 19, 2011The Procter & Gamble CompanyMethod and composition for maintaining hair dye color
US8486942Nov 21, 2011Jul 16, 2013Gilead Sciencs, Inc.Modulators of pharmacokinetic properties of therapeutics
US9139541Jan 20, 2015Sep 22, 2015Gilead Sciences, Inc.Modulators of pharmacokinetic properties of therapeutics
US9358197Jun 14, 2013Jun 7, 2016The Procter & Gamble CompanyMethod employing polyols when chemically modifying the internal region of a hair shaft
US20080187506 *Feb 5, 2007Aug 7, 2008Jose Antonio CarballadaHair care composition
US20090022681 *Jul 31, 2008Jan 22, 2009Jose Antonio CarballadaHair Care Composition
US20100028279 *Jul 22, 2009Feb 4, 2010Jose Antonio CarballadaMethod and Composition for Maintaining Hair Dye Color
US20100120871 *Nov 9, 2009May 13, 2010Dawson Jr Thomas LarryHair care compositions, methods, and articles of commerce that can increase the appearance of thicker and fuller hair
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WO1999023195A1 *Nov 2, 1998May 14, 1999The Procter & Gamble CompanyMulti-purpose liquid aqueous bleaching compositions
Classifications
U.S. Classification544/159, 564/59, 544/400, 544/82, 564/30, 8/127.6, 544/86, 546/233, 546/210, 544/139, 544/160, 544/357, 544/168, 8/127.51, 546/190, 424/70.51, 544/370, 424/47, 424/70.17, 546/187
International ClassificationC07D295/13, A61Q5/04, A61K8/49, A61Q5/06
Cooperative ClassificationA61Q5/04, A61Q5/06, A61K8/49, C07D295/13
European ClassificationA61Q5/06, A61K8/49, A61Q5/04, C07D295/13