Method for reinforcement or permanent deformation of hair

A means of reinforcing and/or mechanically deforming human hair, comprising a first stage in which the hair undergoes the action of a reducing agent so as to break the disulfide linkages of the keracystine to form thiol groups, followed by the application in a second stage of a modifying agent encouraging the establishment of new chemical linkages to the thiol groups, characterized in that the aforesaid modifying agent is a polyhaloacetylated polymer whose halogen atom is capable of reacting with thiol groups.

The present invention concerns a new means of reinforcing and/or 
permanently deforming human hair and a formulation for the implementation 
of this means. 
Various means of reinforcing human hair and maintaining it in a given shape 
are known, whereby the hair is impregnated with a polymer solution which, 
after drying, leaves a film which provides the hair with enhanced cohesion 
and resistance to losing the temporary shape given to it by means of the 
procedure known as hair setting, for example. 
Polymers of this type exert a purely mechanical action by forming a 
flexible sheath around each hair, thus delaying a return to its natural 
shape. 
The use of so-called restructuring agents is also known, such as certain 
menthylol derivatives which penetrate the hair fiber and become 
polymerized therein, thus providing the hair with enhanced rigidity. 
A means called permanent hair deformation is also known, which is based on 
the combined effects of mechanical deformation and a chemical modification 
of the hair. More specifically, the hair is first subjected to an initial 
chemical modification whereby certain disulfide linkages of the keratin 
molecule are broken, thus transforming these disulfide groups to thiol 
groups, whereby the fiber is temporarily plasticized, that is to say, the 
hair made deformable but not elastic. The hair next undergoes forced 
mechanical deformation, such as being curled on rollers or smoothed and 
flattened, following which the hair undergoes a second chemical 
modification, especially consisting of reforming by means of oxidation 
disulfide bonds from thiol groups. As a result of the aforesaid forced 
deformation of the hair, new linkages are established at sites other than 
the original sites, which results in each strand of hair being set in the 
new imposed shape. 
The purpose of the present invention is to provide a new means which has 
two effects: it enables the hair to be reinforced as well as being 
subjected to permanent deformation, if required. This permanent 
deformation may consist of curling or straightening the hair as well as 
uncrimping. 
Just as in conventional cold permanent waving, the means according to the 
present invention comprises a hair reduction stage and, in the second 
stage, is characterized by the application of a polymer capable of forming 
covalent bonds are formed with the thiol groups of the chemically reduced 
hair. As a result, the polymer is chemically bound to the hair and acts as 
a reinforcing agent. Moreover, if the hair undergoes mechanical 
deformation at the same time as the polymer application, the hair will 
maintain the shape imposed on it in the course of the latter process. 
Consequently, the means according to the present invention is of particular 
interest for the treatment of fine or sensitized hair which may have 
undergone degrading procedures, such as dyeing, for example. 
Moreover, one of the advantages of using a polymer reagent is that such 
reagents are unable to penetrate the scalp and thus possible problems of 
toxicity do not arise. 
Therefore, the purpose of the present invention is to provide a means of 
reinforcing and/or permanently deforming the hair, whereby, in an initial 
stage, the hair is first acted upon by a reducing agent so as to break the 
disulfide keratocystine linkages to form thiol groups, following which, in 
a second stage, a modifying agent is applied which promotes the formation 
of new chemical linkages with the thiol groups, characterized in that the 
aforesaid agent is a polyhaloacetylated polymer whose halogen component is 
capable of reacting with the thiol groups. 
The first stage of the means according to the present invention, which 
consists of opening the S--S keratin linkages with a formulation 
containing a reducing agent, is a reaction which is known as such and the 
reducing agents which can be used for this purpose are well known to 
permanent wave experts. 
By the same token, the formulation of reducing compounds suitable for the 
achievement of this first phase is known as well and has been described in 
the cosmetological literature, such as "Problemes capillaires" (Hair 
Problems) by E. Sidi and C. Zviak, Paris (1966), for example. 
No attempt will be made to provide a detailed description here of the 
composition of reducing formulations of this type, since they do not form 
a part of the present invention. Generally speaking, these reducing 
compounds contain a reducing agent, such as a mercaptan, for example, an 
alkali metal or ammonium sulfite or bisulfite, thioglycolic acid, 
thiolactic acid or alternatively a thioglycolic or thioloactic acid ester 
(such as glycerol or glycol monothioglycolate, for example), whereby the 
pH of the latter formulation will generally lie in the 7-10 range and 
preferably in the 8-9.5 range. The reducing agent will preferably be 
present in the reducing formulation at a concentration of 2-25% by weight 
relative to the total weight of the aforesaid formulation. 
Reduction levels in the 5-30% range can be obtained in the first stage of 
this method. 
The basic pH of the aforesaid reducing formulations is generally obtained 
with the help of alkaline agents such as ammonia, monoethanolamine, 
diethanolamine, triethanolamine, and the like. 
Particular embodiments of the means according to the present invention may 
possess the following characteristics, taken individually, or in 
combination: 
The polyhaloacetylated polymer is allowed to act on the reduced hair for a 
period which may, for example, vary from 10-45 minutes; the means is 
preferably applied at a temperature of 25.degree.-70.degree. C.; the hair 
is then rinsed in water and dried, if desired; 
The polyhaloacetylated polymer is allowed to act on the reduced hair which 
is stretched, either by being wound on rollers or smoothed and flattened 
by combing, for example and, after the polymer has acted for a sufficient 
period, the hair is rinsed and dried in a stretched condition; this method 
produces a permanent hair deformation, curling or straightening, as the 
case may be. 
In a first variant of the present invention, the polyhaloacetyl polymer 
may, if desired, be applied in an admixture together with a conventional 
oxidant, such as hydrogen peroxide for example, or, according to a second 
variant, the hydrogen peroxide may be applied after the polyhaloacetyl 
polymer application, which method may be employed to complete the second 
stage of the means according to the present invention in cases where 
certain thiol groups may still remain. 
The polyhaloacetylated polymers employed in the means according to the 
present invention are essentially characterized in that they all contain a 
halogen (chlorine or bromine but preferably the former), on a carbon at 
the alpha position relative to a carbonyl group. 
These polyhaloactylated polymers, and preferably polychloracetylated 
polymers, can be obtained by various means: 
A particular means of obtaining the aforesaid polymers is by the 
homopolymerization or copolymerization of a haloacetylated monomer 
carrying a polymerizable double bond; among the possible haloacetylated 
monomers, the following may be cited in particular: vinyl chloracetate, 
allyl chloracetate, N-allyl chloracetamide, methyl chloracetamido 
2-acrylate, N-chloroacetamidomethyl acrylamide, N-chloro-acetamidomethyl 
methacrylamide, 2-(chloroacetoxy)propyl methacrylate, 
2-(chloroacetylcarbamoyloxy)propyl methacrylate, N-methacryloyl 
N'-chloroacetylurea, etc.; if copolymerization is employed, a copolymer 
will preferably be chosen which promotes favorizing solubility of the 
final copolymer in the required solvent, which will generally be water or 
a water and alcohol mixture; among the suitable comonomers, the following 
may be cited in particular: N-vinyl pyrrolidone, N,N-dimethylacrylamide, 
N-acrylomidomethyl-2-oxopyrrolidone, 3-methacrylamidopropyl, 
3-methacrylamidoproppyl-1 (N,N,N-trimethylammonium chloride, methacrylate, 
methylmethacrylate, N,N-dimethylacrylamide, etc., etc. 
The haloacetylated monomers employed are known formulations and may be 
prepared by known methods: 
The polyhaloacetylated polymers may also be obtained by attaching a 
haloacetylated group to a polymer-carrying amine or primary or secondary 
alcohol groups, whereby the haloacetyl group is attached in a known way 
(as described in the French document 1,149,161 or in the article by A. 
Carpov et al in Die Angew. Makromol. Chemie (Applied Makromolecular 
Chemistry), vol. 24, 1972, no. 322, pp. 101-120), for example, which 
consists of reacting a haloacetyl halide, preferable chloracetyl chloride 
with the aforesaid polymer carrying amine or alcohol groups; among the 
polymers which are suitable for this haloacetylation reaction, the 
following may be cited in particular: polyvinyl amine, polyvinyl alcohol, 
2-hydroxyethyl polyacrylate, polylysine, copolymers obtained by condensing 
2,2-dimethyl-1,3-diaminopropane with methylene-bisacrylamide, 
water-soluble protein hydrolysates, etc., etc. 
The molecular weight of the polyhaloacetylated polymers employed according 
to the present invention will preferably lie in the 500-50,000 range. 
Although certain of these homopolymers and copolymers are known, the 
following examples of preparation as well as a description of the 
preparation of haloacetylated monomers will be given below: 
Among the homopolymers and polyhaloacetylated copolymers especially 
preferred in the implementation of the means according to the present 
invention, the following may be cited: 
N-vinylpyrrolidone/vinyl chloroacetate copolymer 
Methyl 2-chloroacetamidoacrylate/N-acrylamido-methyl-2-oxo-pyrrolidine 
copolymer 
Methyl 2-chloroacetamidoacrylate homopolymer 
N-chloroacetamidomethyl acrylamide/N-acrylamidomethyl-2-oxo-pyrrolidine 
copolymer 
Methyl 2-chloroacetamidoacrylate/methylmethacrylamido-propyl 
trimethylammonium chloride copolymer 
N-chloroacetamidomethyl acrylamide/methyl acrylate copolymer 
N-chloroacetamidomethyl acrylamide homopolymer, and 
N-chloroacetamidomethyl acrylamide/methacrylamidopropyl trimethylammonium 
chloride copolymer 
In the means according to the present invention, the polyhaloacetylated 
polymer is applied to the reduced hair, using a composition whose pH 
preferably lies in the 8-9.5 range, or alternatively, the hair may be 
first rinsed in a buffer solution whose pH lies in the above range. 
The means according to the present means can be diagrammatically elucidated 
with the following chemical reactions: 
##STR1## 
where red. and ox. respectively represent the reduced and oxided forms of 
an oxidation-reduction system, and 
##STR2## 
where X represents the halogen and (P) denotes the remaining polymer. 
The present invention also concerns a formulation for implementing the 
means according to the above definition. This formulation is mainly 
characterized in that it includes at least one polyhaloacetylated polymer 
of the type defined above in a suitable vehicle. 
In the formulation according to the present invention the 
polyhaloacetylated polymer is present in concentrations ranging from 
0.5-10% by weight relative to the weight of the entire formulation. 
Formulations according to the present invention may take the form of 
solutions of water or water and alcohol, whereby the alcohol takes the 
form of a lower alkanol such as ethanol or isopropanol, or alternatively, 
it may take the form of creams, gels, emulsions or aerosol sprays, etc. 
Formulations according to the present invention may moreover include the 
usual common ingredients, such as pH modifiers, fragrances, colorants and 
dyestuffs, preserving agents, thickeners, surfactants or other cosmetic 
polymers, etc., etc.

The following examples will serve to exemplify the present invention in a 
nonlimitative fashion: 
I. PREATION OF HALOACETYLATED MONOMERS 
Example 1a 
Preparation of methyl chloroacetamido 2-chloroacetamidoacrylate 
##STR3## 
163.5 g of 2-chloroacetamidoacrylic acid prepared according to the 
procedure described by J. P. Greenstein in Arch. Biochem. 1947, vol. 14, 
p. 249 are added to a solution of 40 g of sodium hydroxide dissolved in 
250 ml of water over a period of 1 hour, while the temperature is 
maintained at 10.degree. C.; next, a solution of 170 g of silver nitrate 
in 1500 ml of water is then added. The white solid which forms is 
filtered, washed in water and then in acetone, dried and transferred to a 
reactor. 1000 g of methyl iodide and 1 g of hydroquinone monomethyl ether 
are then added and the mixture is refluxed for 2 hours. After filtration 
and concentration of the reaction mixture, 134 g of an oily product are 
obtained which will crystallize in a mixture of 130 ml of water and 220 ml 
of methanol (melting point: 42.degree. C.). 
Elemental analysis: 
______________________________________ 
Theoretical Actual 
______________________________________ 
C 40.56% 40.69% 
H 4.51% 4.61% 
N 7.89% 7.68% 
O 27.04% 26.77% 
Cl 20.00% 20.13% 
______________________________________ 
.sup.1 H RMN spectrum at 90 mHz in CHCl.sub.3 : --CH.sub.2 Cl d.delta.=4.1 
ppm 
Example 1b 
Preparation of N-chloroacetamidomethyl acrylamide 
EQU CH.sub.2 .dbd.CH--CONH--CH.sub.2 --NH--COCH.sub.2 Cl 
This product is prepared by reacting hydroxymethyl chloroacetamide with 
acrylamide in formic acid according to the method described by E. Mueller 
in Die Angew. Makr. Chem. (Applied Macro-chemistry), 1972, vol. 7, p. 99. 
Example 1c 
Preparation of 2-(chloroacetoxy) propyl methacrylate 
##STR4## 
This product is prepared according to the reference cited in Example 1b, by 
reacting chloroacetic acid with 2-hydroxypropyl methacrylate. 
Example 1d 
Preparation of propyl 2-(chloroacetyl carbmoyloxy)propyl methacrylate 
##STR5## 
This product is obtained starting with chloromethylcarbonyl isocyanate and 
2-hydroxypropyl methacrylate prepared according to the same reference in 
the literature as the previous example. 
Example 1e 
Preparation of N-methacryloyl-N'-chloro-acetylurea 
##STR6## 
This product is prepared, starting with methacrylamide and 
chloromethylcarbonyl isocyanate according to the method described in the 
previous reference. 
Example 2 
Preparation of the N-acrylomidomethyl-2-oxopyrrolidine comonomer 
##STR7## 
This monomer is synthesized according to the method proposed by B. Sebille, 
C.R. Acad. Sci., series C, 1969, vol. 269, p. 1513. 
Example 3 
Preparation of haloacetylated polymers by polymerization of haloacetylated 
monomers 
Example 3a 
N-vinyl pyrrolidone/vinyl chloroacetate copolymer 
63.2 g of N-vinylpyrrolidone, 36.8 g of vinyl chloroacetate, 200 g of 
ethanol and 1 g of azobis-isobutyronitrile is placed in a reactor of 1000 
ml capacity. The mixture is placed under a nitrogen blanket and is 
reflux-heated under constant stirring for 8 hours. The crude polymer 
solution is diluted in 200 g of acetone and precipitated in 5 l. of ethyl 
ether. After filtration and drying, a polymer is obtained which contains 
37.5% of vinyl chloroacetate based on chlorine determination. 
Example 3b 
Methyl 2-chloracetamidoacrylate/N-acryloamidomethyl 2-oxopyrrolidine 
copolymer 
93.8 g of methyl 2-chloracetamidoacrylate, 31.2 g of 
N-acrylamidomethyl-2-oxopyrrolidine, 3.5 l. of methanol and 50 g of a 33% 
hydrogen peroxide solution are placed in a 4 l. photochemical reactor 
equipped with a 2000 W type Q 2020 original Hanau-type lamp. The solution 
is heated to 50.degree. C. and irradiated for 6 hours. The reaction 
mixture is then filtered and the solution is concentrated to 400 g and 
poured into 5 l. of ethyl ether. The resulting 93 g of polymer is then 
dried. The water-soluble fraction is extracted with 1.8 l. of water at 
50.degree. C. 68 g of water-soluble polymer are obtained. 
Elemental analysis: 
______________________________________ 
Actual 
______________________________________ 
C 42.22% 
H 6.08% 
N 12.21% 
O 28.47% 
Cl 10.15% 
______________________________________ 
The above result indicates that the yield includes 54% of chlorinated 
monomer. 
Example 3c 
Methyl 2-chloroacetamidoacrylate homopolymer 
The following ingredients are placed in a Hanovia-type photochemical 
reactor equipped with a medium pressure 100 W lamp supplied by Prolabo 
Inc: 
25 g of methyl 2-chloroacetamidoacrylate 
33.2 g of 33% hydrogen peroxide solution 
610 g of methanol 
The solution is maintained at 20.degree. C. and is irradiated for 8 hours. 
The reaction mixture is filtered, concentrated to 100 g and poured into 2 
l. of ethyl ether under constant stirring; after filtration the resulting 
polymer is dried and the expected 4.3 g of polymer are in fact obtained. 
Elemental analysis: 
______________________________________ 
Actual Theoretical 
______________________________________ 
C 40.35% 40.56% 
H 4.61 4.51 
N 7.80 7.89 
O 26.92 27.04 
Cl 20.34 20.00 
______________________________________ 
Example 3d 
Methyl 2-chloroacetamidoacrylate/methylacryloamidopropyl trimethylammonium 
chloride copolymer (supplied by Texaco, USA under the trade name of 
Maptac) 
The following constituants are placed in a tubular photochemical reactor 
equipped with a Hannovia 100 W medium pressure lamp: 
4 g of methyl 2-chloroacetamidoacrylate 
2 g of a 50% solution of Maptac in water 
6.66 g of a 50% hydrogen peroxide solution 
122 g of methanol 
The solution is maintained at 20.degree. C. and is irradiated for 6 hours. 
The reaction mixture is filtered, concentrated to 15 g and precipitated in 
500 ml of ethyl ether. A yield of 3.2 g of water-soluble polymer is 
obtained, characterized by a .sup.1 H RMN spectroscopy at 250 MHz (DMSO 
solvent). 
Characteristic peak integration indicates that the yield contains 30% of 
chlorinated monomer. 
Example 3e 
N-chloroacetamidomethyl acrylamide/methyl acrylate copolymer 
10 g of N-chloroacetamidomethyl acrylamide, 40 g of methyl acrylate, 400 g 
of a mixture of equal parts of water and ethanol and 0.25 g of 
azobis-iso-butyronitrile are placed in a reactor. The pH of the solution 
is adjusted to 2.5 with 0.1N hydrochloric acid and it is heated at 
70.degree. C. for 6 hours. After phase separation, the polymer is 
redissolved in 200 g of ethyl acetate and precipitated in 5 l. of hexane. 
After filtration and drying, 24 g of polymer is obtained which is soluble 
in a solution of 90 parts of ethanol and 10 parts of water. 
Elemental analysis: 
______________________________________ 
Actual 
______________________________________ 
C 51.38% 
H 6.67 
N 7.71 
O 24.24 
Cl 6.70 
______________________________________ 
which indicates that the yield contains 33% of chlorinated monomer. 
Example 3f 
N-chloroacetamidomethyl acrylamide homopolymer 
2 g of N-chloroacetamidomethyl acrylamide, 8 g of absolute ethanol and 8 g 
of water are placed in a reactor; the pH of this solution is adjusted to 
2.4 with 0.1M HCl; 0.1 g of azobis-iso-butronitrile is added and the 
mixture which is heated for 2 hours and the solvent refluxes. The polymer, 
which is soluble in the hot reaction medium, precipitates on cooling to 
20.degree. C. The precipitate is then recovered and dried. 
Elemental analysis: 
______________________________________ 
Actual 
______________________________________ 
C 40.83% 
H 5.34 
N 14.19 
O 24.62 
Cl 14.92 
______________________________________ 
Example 3g 
N-chloroacetamidomethyl acrylamide/methylacrylamidopropyl trimethylammonium 
chloride copolymer (Maptac) 
144 g of N-chloroacetamidomethyl acrylamide, 72 g of a 50% solution of 
Maptac in water, 720 g of ethanol, 648 g of water and 9 g of 
azobis-iso-butyronitrile are placed in a reactor. 
The mixture is heated with constant stirring under a nitrogen blanket for 4 
hours until the solvent is refluxed; on completion of polymerization, the 
solvent is removed with a rotary evaporator until a syrup is obtained, 
which is precipitated in 10 l. of acetone. The solid residue is dried in 
an oven at 40.degree. C. under reduced pressure. A yield of 180 g of pure 
polymer is obtained: 
Elemental analysis: 
______________________________________ 
Actual 
______________________________________ 
C 42.2% 
H 6.5 
N 14.4 
O 19.7 
Cl 16.9 
______________________________________ 
which indicates that the yield includes 67.5% of the chlorinated monomer 
and 32.5% of Maptac. 
Example 3h 
N-chloroacetamidomethyl acrylamide/N-acrylamidomethyl-2-oxopyrrolidine 
copolymer 
18 g of N-chloroacetamidomethyl acrylamide, 18 g of acrylamidomethyl 
2-oxopyrrolidine, 144 g of ethanol, 144 g of water and 1.8 g of 
azobis-iso-butyronitrile are placed in a reactor. The mixture is heated 
under a nitrogen blanket for 2 hours with constant stirring. 
After cooling, the mixture is concentrated to 110 g in a rotary evaporator 
and then diluted in 70 ml of acetone; the resulting solution is 
precipitated in 5 l. of acetone and the polymer is fitered and oven-dried 
under vacuum at 40.degree. C. 
Elemental analysis: 
______________________________________ 
Actual 
______________________________________ 
C 47.8% 
H 6.5 
N 15.2 
O 21.4 
Cl 8.9 
______________________________________ 
which indicates that the yield includes 50.4% of the chlorinated monomer 
and 49.6% of the comonomer. 
Example 3i 
N-chloroacetamidomethyl acrylamide/methacrylamidopropyl trimethylammonium 
chloride copolymer (Maptac) 
80 g of N-chloroacetamidomethyl acrylamide, 40 g of a 50% solution of 
Maptac in water, 3 l. of methanol and a 50 g of a 33% hydrogen peroxide 
solution are placed in a 4 l photochemical reactor equipped with a 2000 W 
lamp (ref. Q 2020 original Hanau). 
The solution is heated to 45.degree. C. and irradiated for 4 hours. The 
reaction mixture is concentrated to 175 g and poured into 4 l. of acetone. 
The recovered polymer, which is completely water-soluble, is then dried. 
Elemental analysis: 
______________________________________ 
Actual 
______________________________________ 
C 41.45% 
H 6.10 
N 21.85 
O 13.23 
Cl 16.82 
______________________________________ 
which indicates that the yield includes 63% of the chlorinated monomer and 
37% of Maptac. 
Example 3j 
N-chloroacetamidomethyl acrylamide/N,N-dimethyl acrylamide copolymer 
21 g of N-chloroacetamidomethyl acrylamide, 14 g of N,N-dimethyl 
acrylamide, 850 g of methanol and 42 ml of a 33% hydrogen peroxide 
solution are placed in a Hanovia-type photochemical reactor equipped with 
a 100 W medium pressure lamp. 
The reaction solution is maintained at 20.degree. C. and irradiated for 6 
hours. The reaction mixture is then concentrated to 50 g and poured into 1 
l. of diethyl ether. The recovered polymer, which is completely 
water-soluble, is then dried. 
Elemental analysis: 
______________________________________ 
Actual 
______________________________________ 
C 45.90% 
H 6.90 
N 13.64 
O 23.19 
Cl 10.41 
______________________________________ 
which indicates that the yield includes 52% of the chlorinated monomer. 
Example 3k 
N-chloroacetamidomethyl acrylamide/methacrylaminopropyl trimethylammonium 
chloride copolymer (Maptac) 
40 g of chloroacetamidomethyl acrylamide, 20 g of a 50% solution of Maptac 
in water, 15 g of a 33% hydrogen peroxide solution, 37.5 g of water and 
100 g of isopropanol are placed in a reactor. 
The solution is reflux heated and 40 ml of a solution of 5 g of ascorbic 
acid in 400 g of water is then added over a period of 40 min. The solvent 
is next reflux heated for a further four hours. The reactive mixture is 
next concentrated to one third of its orginal weight and the resulting 
polymer is precipitated in 3 l. of acetone. The polymer yield is dried 
under vacuum at 40.degree. C. 
Elemental analysis: 
______________________________________ 
Actual 
______________________________________ 
C 42.38% 
H 6.35 
N 14.02 
O 21.97 
Cl 15.43 
______________________________________ 
which indicates that the yield includes 74% of the chlorinated monomer and 
26% of Maptac. 
Example 3l 
N-chloroacetamidomethyl acrylamide/propyl methacrylamidopropyl 
trimethylammonium chloride copolymer (Maptac) 
28.8 g of chloroacetamidomethyl acrylamide, 14.4 g of a 50% solution of 
Maptac in water, 685 g of isopropanol, 3.6 g of azobis-iso-butyronitrile 
and 3.6 g of dodecylmercaptan are placed in a reactor. 
The solvent is reflux heated for 16 hours. The polymer which partially 
precipitates on the walls of the reactor vessel and the precipitated 
polymer is dissolved in 100 ml of methanol. 
The reaction mixture is concentrated and the resulting polymer is 
precipitated in 2 l. of acetone. 
Elemental analysis: 
______________________________________ 
Actual 
______________________________________ 
C 45.09% 
H 6.52 
N 13.70 
O 16.88 
Cl 17.70 
______________________________________ 
which indicates that the yield includes 82% of the chlorinated monomer and 
18% of Maptac. 
Example 4 
Preparation of a haloactylated polymer by binding a haloactylated halide to 
a polymer 
6.4 g of polycondensate obtained by the polyaddition of 
1.1-dimethyl-1,3-diaminopropane and methylenebisacrylamide according to 
the procedure described in French document 85.10,158, Example 2 are 
dissolved in 45 g of N-methyl pyrrolidone and heated to 50.degree. C. 6 g 
of freshly distilled chloroactyl chloride are slowly added to the 
aolution. The reaction is completed in 10 hours. The resulting mixture is 
precipitated in 1 l. of acetone, the pH of the polymer recovered in an 
acqueous solution is adjusted to 9 with sodium bicarbonate, thus bringing 
about precipitation. The precipitate is then filtered, washed and dried. 
This process yields 5 g of polymer soluble in a 50/50 mixture of water and 
ethanol. 
Elemental analysis: 
______________________________________ 
Actual 
______________________________________ 
C 48.60% 
H 6.24 
N 14.00 
O 17.40 
Cl 12.70 
______________________________________ 
which indicates that the yield includes 75% of the chlorinated monomer. 
Example 5 
Reaction of the polymer on reduced hair 
Example 5a 
Preparation of reduced hair 
Natural hair is reduced in a 2% solution of thioglycol acid at a pH of 9.5 
(ammoniacal buffer); this reaction takes 30 minutes at 30.degree. C. 
Analysis of the hair indicates a reduction rate of 20-30% (ratio of 
cysteine content after reduction compared to the cystine content before 
reduction). 
Example 5b 
Method of reacting the polymer with the reduced hair 
After reduction, the hair is immersed in a polymer solution whose pH has 
been adjusted to 9 (buffer consisting of 50 g of NH.sub.4 Cl, 900 ml of 
water, NH.sub.4 OH d=0.92 to adjust pH to 9, water ad 1 l.) and which is 
maintained at 30.degree. C. for 30 minutes; alternatively, the hair is 
first reduced and rinsed in a pH 9 buffer solution, impregnated in the 
polymer solution and maintained at 30.degree. C. for a further 30 minutes. 
In both cases, the hair is subsequently rinsed and dried. In this example, 
after setting on rollers, the hair can be dried under a hood. 
Example 5c 
Determination of the chemical change to the hair after reacting with the 
polymer 
General method: 
After the polymer treatment, the hair undergoes acid hydrolysis inside 
sealed tubes at 110.degree. C.; the percentage of aminoacids on the 
hydrolysate is determined with a Technicon TSM auto-analyser. The cysteine 
which is reacted with the haloacetamide or the haloacetate group is 
transformed to S-carboxymethylcysteine according to the following scheme: 
##STR8## 
where X represents the halogen and P.sub.1 and P.sub.2 the remaining 
polymer. 
Example 6 
Examples of reduced hair treatment by polyhaloacetylated polymers 
Example 6a 
The polymer employed in Example 3c is dissolved in a 30:70 mixture of a pH 
9 buffer and ethanol. Stoichiometric proportions of the cysteine present 
on the hair after reduction and the chloroacetamido polymer groups are 
employed. 10 ml of 0.9% polymer solution is prepared for the treatment of 
300 mg of hair. 
Depending on the rate of hair reduction, the reaction yield varies from 27 
to 56%. 
Example 6b 
The polymer employed in Example 3b is reacted under the same conditions as 
in the previous example, except that in this case a 1.8% polymer solution 
is prepared in the ammoniacal buffer at pH 9. Reaction yields of 36-68% 
were obtained during various tests. 
Example 6c 
The polymer employed in Example 3d is reacted under the same conditions as 
in Example 5b. Reaction yields with the cysteine in the hair of 55-59% 
were obtained. 
Example 6d 
The polymer employed in Example 4 was dissolved to a concentration of 4.4% 
in a 33:66 pH 9 ammoniacal buffer:ethanol solution and reacted with the 
reduced hair (0.058 mole of cysteine per 100 g of hair). After 30 minutes 
of reaction at 30.degree. C., a reaction yield of 43% was obtained. 
Example 6e 
The polymer employed in Example 3g was dissolved to a 2.45% in the the pH 9 
ammoniacal buffer and reacted cysteine on the one hand and with the 
reduced hair on the other hand; after 30 minutes at 30.degree. C., 
reaction yields of 98% and 65% respectively were obtained. 
Example 6f 
The polymer employed in Example 3h was dissolved in a 70:30 mixture of the 
pH ammoniacal buffer and ethanol and then reacted for 10 and 30 minutes 
with stoichiometric proportions of cysteine. Reaction yields of 89% and 
98% respectively were obtained. 
Example 6g 
Example 6b was repeated except that in this case, the treatment was applied 
to a whole head of hair by impregnation. In this case, the rate of hair 
reduction by 0.3M thioglycol acid at pH 9 was 5% (6.10.sup.-3 moles of 
cysteine present per 100 g of hair). After reacting with the polymer 
employed in example 3b, a sample of hair was taken and hydrolyzed. The 
S-carboxymethyl cysteine determination indicated a yield of 25-30% in this 
case. 
Example 6h 
The previous example was repeated except that the rate of reduction was 
raised to 12.5%. 
After reacting with the polymer employed in example 3b, a reaction yield of 
9% was obtained. 
Example 6i 
The polymer employed in this example was dissolved in the ammoniacal buffer 
at pH 9 and then reacted with reduced hair, whereby equimolecular 
quantities of the reactant groups were employed. After 30 minutes at 
30.degree. C., a reaction yield of 44% was obtained. 
Example 6j 
The polymer employed in this example was dissolved in the ammoniacal buffer 
at pH 9 and reacted with the reduced hair, whereby equimolecular 
quantities of the reactant groups were employed. After 30 minutes at 
30.degree. C., a reaction yield of 51% was obtained. 
Conclusion 
Generally speaking, after treatment of reduced hair by polyhaloactylated 
polymers according to the means proposed in the present invention, an 
enhancement of the cosmetic properties of the hair is observed. The 
following properties, in particular, display improvement: 
Curl retention curls after winding around rollers; Easier disentanglement 
(the hair is easier to comb out) Furthermore, it is observed that hair 
treated according to this means possesses improved softness as well 
Example 7 
Some typical formulations 
The following formulations can be used for the implementation of the means 
according to the present invention: 
Lotions 
______________________________________ 
Polymer according to Example 3c 
.90 g 
Ethanol 70.00 g 
Fragrance .05 g 
Liquid ammonia ad pH 9 
Water ad 100.00 g 
______________________________________ 
In this example, the polymer according to example 3c may be substituted by 
the same quantity of the polymer according to example 3a. 
Example 7b 
______________________________________ 
Polymer according to Example 3b 
1.80 g 
Ethanol 70.00 g 
Fragrance .02 g 
Liquid ammonia ad pH 9 
Water ad 100.00 g 
______________________________________ 
In this example, the polymer according to example 3b may be substituted by 
the same quantity of the polymer according to example 3d. 
Example 7c 
______________________________________ 
Polymer according to Example 4 
4.40 g 
Ethanol 66.00 g 
Fragrance .04 g 
Liquid ammonia ad pH 9 
Water ad 100.00 g 
______________________________________ 
Example 7d 
______________________________________ 
Polymer according to Example 3g 
2.45 g 
Fragrance .05 g 
Liquid ammonia ad pH 9 
Water ad 100.00 g 
______________________________________ 
Example 7e 
______________________________________ 
Polymer according to Example 3h 
1.00 g 
Ethanol 33.0 g 
Fragrance .02 g 
Liquid ammonia ad pH 9 
Water ad 100.00 g 
______________________________________ 
Gels 
Example 7f 
______________________________________ 
Polymer according to Example 3i 
5.00 g 
Hydroxymethylcellulose marketed 
by Hercules Inc., as "Natrosol HHR 250" 
3.00 g 
Fragrance .03 g 
Liquid ammonia ad pH 9 
Water ad 100.00 g 
______________________________________ 
This gel is colorless and clear and has a viscosity of 2800 cP as measured 
with a Dragge Mobile spindle III apparatus. 
Example 7g 
______________________________________ 
Polymer according to Example 3i 
3.00 g 
Polyoxyethylenated nonylphenol (containing 
9 moles of ethylene oxide) sold by 
GAF Inc., as "Antarox CO 630" 
5.00 g 
Fragrance .03 g 
Liquid ammonia ad pH 9 
Distilled Water ad 100.00 g 
______________________________________ 
85 g of this solution are packaged with 15% of an F114/F12 propellant 
mixture in proportions of 43:57 sold as "Freons" by the Du Pont de Nemours 
Corp. 
These lotions, gels and aerosol foams are applied to hair which has first 
been chemically reduced, and which may or may not have been permanently 
deformed by mechanical means, for about 30 minutes at a temperature of 
about 30.degree. C. 
After removal of the mechanical means of deformation, where appropriate, 
followed by rinsing and drying, the hair is found to be soft to the touch 
and can be easily combed or brushed out. 
Solution 
Example 7h 
______________________________________ 
Polymer according to example 3k 
4 g 
Propylene glycol 15 g 
______________________________________ 
For use, this solution in propylene glycol is mixed with 80 ml of water 
whose pH has been raised to 9 by the addition of ammonia. This solution is 
applied to hair which has first been chemically reduced and subject to 
mechanical deformation by means such as rollers. After 30 minutes the 
rollers are removed and the hair is rinsed. The resulting curls are soft 
and easily combed. 
Powder 
Example 7i 
4 g of the polymer according to example 3k are packaged in the form of a 
powder. For use, the powder is dissolved in 96 g of water whose pH has 
been raised to 9 by the addition of ammonia. This solution is applied hair 
which has first been chemically reduced but not to mechanical deformation. 
After allowing the solution to act on the hair for about 30 minutes, the 
hair is rinsed in plain water. The hair is soft to the touch and can be 
easily combed out.