Process and composition for setting the hair

A composition and process for setting hair comprises impregnating the hair with a composition containing in solution in a cosmetic vehicle at least one water-soluble polymer containing at least 5% of units having a primary amide function, a crosslinking agent and an acid catalyst. The hair is then placed on hair-setting rollers and dried by means of an external heat source. The hair rollers are then removed.

The present invention relates to a new process for treating hair and more 
particularly to a process for setting the hair as well as to a 
hair-setting composition. 
Hair setting lotions or compositions essentially comprise an aqueous or 
hydroalcoholic solution of a resin, which is applied to the hair. After 
application of the composition, the hair, placed on rollers, is dried. 
Thereafter, the rollers are removed. 
Resins generally used in these compositions can be natural resins or, more 
currently, synthetic polymers whose properties must result in a good 
holding of the hair set, that is to say, have a slight or weak absorption 
of humidity so as not to render the hair sticky, or to provoke the 
formation of resin flakes. The resin at the same time should impart to the 
hair a shiny appearance and facilitate its combing or disentanglement. 
Various polymers or resins have already been proposed for use in such hair 
setting compositions and on the whole these known polymers provide 
satisfactory results. 
However, it has now been observed that a particularly perceptible 
improvement of the hair setting properties, principally, a better hold 
between successive shampoos can be obtained by using certain types of 
polymers and by crosslinking these polymers on the hair. 
Such crosslinking improves the various sought-after properties and 
especially a long lasting hold or set, ease of combing the hair, an 
absence of resin or polymer powdering when the hair is brushed or combed 
as well as hair liveliness and shininess. 
The present invention thus relates to a new process for setting the hair 
which achieves these desirable objectives, the said process comprising 
impregnating the hair with a composition containing, in solution in an 
appropriate cosmetic vehicle, at least one water-soluble polymer 
containing at least 5%, and preferably 10-100%, of units having a primary 
amide function, a crosslinking agent and an acid catalyst, placing the 
hair on hair setting rollers, drying the hair by contacting it with an 
external heat source and removing the said hair setting rollers. 
Representative preferred water-soluble polymers capable of being used in 
the process according to the present invention, include the following 
polymers: 
(1) a copolymer having the formula 
##STR1## 
wherein: R.sub.1 and R.sub.2 represent hydrogen or methyl with the 
proviso that R.sub.1 and R.sub.2 cannot simultaneously represent methyl, 
R.sub.3 represents a member selected from the group consisting of 
(i) --CO--Z--(CH.sub.2).sub.y --R.sub.5, wherein Z represents --NH-- or 
--O--, y is 2 or 3 and R.sub.5 is 
##STR2## 
wherein R.sub.6 is alkyl having 1-4 carbon atoms and X represents Cl, Br, 
I or OSO.sub.3 CH.sub.3, 
(ii) --CO--Z--(CH.sub.2).sub.t --CH.sub.3, wherein Z has the meaning given 
above and t is a whole number ranging from 0 to 17 inclusive, 
(iii) --CN, 
(iv) --COOH, 
(v) --CH.dbd.O, 
(vi) 
##STR3## 
and (vii) --C.sub.6 H.sub.5, 
R.sub.4 represents hydrogen or methyl when R.sub.3 represents (i) to (iv), 
or R.sub.4 represents only hydrogen when R.sub.3 represents (v) to (vii), 
the (a) unit representing from 5 to 100% of the total units in the polymer 
and preferably from 8 to 70% and 
the (b) unit representing from 95 to 0% of the total units in the polymer 
and preferably from 30 to 82%, the units (a)+(b) being equal to 100%. 
Representative monomers capable of providing units I(a) include acrylamide, 
methacrylamide and crotonamide. 
Representative monomers capable of providing units I(b) include 
2-N,N-dimethylamino ethyl methacrylate, butyl methacrylate, octyl 
methacrylate, dodecyl methacrylate and octadecyl methacrylate as well as 
the corresponding acrylates, methacrylamides and acrylamides, 
acrylonitrile, acrylic acid, methacrylic acid, acrolein, 
N-vinylpyrrolidone and styrene. 
Copolymers of this type can be bi-, tri-, tetra- or higher copolymers. 
Representative copolymers of formula (I) which can be used in accordance 
with the present invention include, in particular, those described in 
French Pat. No. 71/03017; 
(2) a cyclopolymer having the formula 
##STR4## 
wherein: R.sub.1 and R.sub.2 have the same meaning as given above in the 
definition of the polymer of formula (I), 
R.sub.7 and R.sub.8 each independently represent alkyl having 1-12 carbon 
atoms or hydroxyalkyl having 2-3 carbon atoms, 
A represents Cl, Br, I or OSO.sub.3 CH.sub.3, 
the (b') unit represents 95-5% of the total units in the polymer and 
preferably 92-30%, 
the units (a') and (b') being equal to 100 percent. 
The cyclopolymers of this type are more particularly described in French 
Pat. No. 73.23970; and 
(3) polymers of poly-.beta.-alanine type resulting from the anionic 
polymerization of crotonamide, acrylamide or methacrylamide, these 
polymers having the formula 
##STR5## 
wherein R and R' represent hydrogen or methyl, 
R" represents hydrogen or a branching of the formula: 
##STR6## 
the percentage of terminal primary amide units (b) being between 5 and 35 
percent relative to the total of the amide units of the polymer. 
The preparation of these poly-.beta.-alanine type polymers is described in 
U.S. Pat. Nos. 2,749,331 and 4,082,730. 
Polymers other than those mentioned above can also be used in the 
compositions according to the present invention. Representative ones of 
these other polymers include, in particular, those described in French 
Pat. Nos. 76.30886, 77.10220, 77.15088 and 78.27074. These other polymers 
have a structure which corresponds to the preceding definition, that is to 
say, polymers containing at least 5% of units having a primary amide 
function. 
Generally, the polymers used in the process according to the present 
invention have a molecular weight ranging between 500 and about 200,000, 
preferably between 2,000 and 100,000 (the molecular weight being 
determined by the light diffusion method). 
Although the impregnation of the hair can be carried out in several stages, 
for example, by application in a first stage of a solution containing the 
polymer and the crosslinking agent and the application in a second stage 
of a solution of the acid catalyst, it is preferable, so as to obtain a 
good impregnation and a satisfactory result, to prepare the impregnation 
composition at the time of use, that is to say, by admixing in a cosmetic 
carrier the polymer, the crosslinking agent and the acid catalyst. 
The cosmetic carrier is, preferbly, water or a hydroalcoholic solution of a 
lower aliphatic alcohol, such as ethanol or isopropanol. 
The impregnation composition, although soluble at ambient temperature, 
should be applied to the hair as soon as the acid catalyst has been 
introduced into the admixture so as to avoid any significant premature 
onset of the crosslinking reaction. 
Representative crosslinking agents usefully employed in the present 
invention include glyoxal, glutaraldehyde and formaldehyde, as well as 
compounds capable of liberating formaldehyde such as dimethylolurea or 
thiourea, dimethylol ethylene urea or thioeurea and trimethylolmelamine. 
The acid catalyst is preferably an organic or mineral acid such as 
hydrochloric acid, oxalic acid and the like, the catalyst being present in 
the hair setting composition, in an amount sufficient so as to impart to 
the final impregnation composition a pH between 1 and 2. Optionally there 
can be employed with the organic or mineral acid a mineral salt such as 
potassium chloride. 
After impregnation of the hair using a sufficient amount of the composition 
of the present invention, which amount can be a function of the amount of 
the hair being impregnated, although that amount is generally between 
about 5 and 100 cc, the hair is then wound or rolled on hair setting 
rollers having a diameter which can vary between about 10 and 50 mm. 
Once this operation is completed, the hair is then dried at a temperature 
of about 40.degree. to 65.degree. C. for a period of time ranging from 
about 15 to 90 minutes, this drying operation having the effect of 
initiating and completing the crosslinking reaction of the polymer. 
After drying the hair, the rollers are then removed and the hair is given a 
final combing. 
Tests measuring the holding power of the curls or waves obtained by the 
hair setting process of the present invention in an atmosphere of 
controlled humidity and temperature, have shown that the curls exhibit 
better retention than those obtained with conventional hair setting 
compositions. 
The present invention also relates to a composition for use in the process 
of the present invention, this composition being packaged in several parts 
which are to be mixed at the moment of use. The final composition, after 
admixture of the various parts, contains in an aqueous or hydroalcoholic 
solution the above defined polymer in an amount ranging from 0.1 to 5 
weight percent, the aforementioned crosslinking agent in an amount between 
4 and 30 percent by weight relative to the weight of the polymer in said 
composition and the said acid catalyst in an amount sufficient to provide 
a pH between 1 and 2. 
According to the first embodiment, the composition of the present invention 
is provided in the form of a two-part package. 
In accordance with one variation of this first embodiment, the first part 
comprises an aqueous or hydroalcoholic solution of the polymer and the 
crosslinking agent, and the second part comprises the acid catalyst. 
The pH of the first part of the composition is generally between 5-8, 
preferably close to neutral. 
In accordance with a second variation of this first embodiment, the first 
part comprises an aqueous or hydroalcoholic solution of the polymer at an 
acid pH (pH between 1 and 2), and the second part comprises an aqueous or 
hydroalcoholic solution of the crosslinking agent also at an acid pH 
(again generally about 1-2). 
According to a second embodiment of the invention, the composition is 
provided in the form of a three-part package, the first part comprising an 
aqueous or hydroalcoholic solution of the polymer, the second part 
comprising an aqueous or hydroalcoholic solution of the crosslinking agent 
and the third part comprising an aqueous solution of the acid catalyst. 
The polymer solutions can also contain other conventional hair setting 
lotion adjuvants. Among these adjuvants are, in particular, perfumes, 
coloring agents, preservatives, softening agents and the like.

The following non-limiting examples illustrate the present invention. 
EXAMPLE 1 
(a) 2-part package 
A hair setting composition is packaged in the following two-parts which are 
to be mixed at the moment of use. 
______________________________________ 
1st Part 
Poly-.beta.-alanine (having 17% of primary 
1 g 
amide terminal units) 
Glutaraldehyde 0.1 g 
Perfume 0.05 g 
Water, sufficient amount for the 
100 g 
pH of this solution is 6 
2nd Part 
2.1 cc of 1 N HCl solution 
______________________________________ 
(b) Hair setting process 
At the moment of use the said second part is introduced with stirring into 
the first part. The pH of the resulting composition is 2. 
As soon as the mixture has been effected the composition is applied to the 
hair after which the hair is rolled up on hair curlers having a diameter 
of 15 mm. 
After drying the hair under a hood at a temperature of 60.degree. C. for 
about 30 minutes, the rollers are removed and the hair is combed. 
The resulting curls have a long lasting hold, the hair combs easily and is 
soft to the touch. 
EXAMPLES 2-6 
(a) 2-part package 
EXAMPLE 2 
______________________________________ 
1st Part 
0.2 N KCl solution 25 ml 
0.2 N HCl solution 67 ml 
Poly-.beta.-alanine (having 17% primary 
1 g 
amide terminal units) 
2nd Part 
0.2 N KCl solution 25 ml 
0.2 N HCl solution 67 ml 
Glutaraldehyde 0.07 g 
______________________________________ 
EXAMPLE 3 
______________________________________ 
1st Part 
0.2 N KCl solution 25 ml 
0.2 N HCl solution 67 ml 
Poly-.beta.-alanine (having 30% primary 
9 g 
amide terminal units) 
2nd Part 
0.2 N KCl solution 25 ml 
0.2 N HCl solution 67 ml 
Glutaraldehyde 0.36 g 
______________________________________ 
EXAMPLE 4 
______________________________________ 
1st Part 
0.2 N KCl solution 25 ml 
0.2 N HCl solution 67 ml 
Poly-.beta.-alanine (having 17% primary 
0.4 g 
amide terminal units) 
2nd Part 
0.2 N KCl solution 25 ml 
0.2 N HCl solution 67 ml 
Glutaraldehyde 0.12 g 
______________________________________ 
EXAMPLE 5 
______________________________________ 
1st Part 
0.2 N KCl solution 27 ml 
0.2 N HCl solution 73 ml 
Poly-.beta.-alanine (having 17% primary 
1 g 
amide terminal units) 
2nd Part 
0.2 N KCl solution 27 ml 
0.2 N HCl solution 73 ml 
Glutaraldehyde 0.07 g 
______________________________________ 
EXAMPLE 6 
______________________________________ 
1st Part 
0.2 N KCl solution 100 ml 
0.2 N HCl solution 26 ml 
Poly-.beta.-alanine (having 17% primary 
0.8 g 
amide terminal units) 
2nd Part 
0.2 N KCl solution 100 ml 
0.2 N HCl solution 26 ml 
Glutaraldehyde 0.08 g 
______________________________________ 
(b) Hair setting process. 
At the moment of use the two parts in each of Examples 2-6 above are mixed 
together, and the resulting compositions are applied to the hair. 
The hair is then rolled up on hair setting rollers having a diameter of 
about 15 mm. The hair is dried under a hood at 60.degree. C. for about 45 
minutes. 
The resulting curls have a long lasting hold, the hair combs easily and is 
soft to the touch. 
EXAMPLE 7 
(a) 2-part package 
A hair setting composition is packaged in the following two parts which are 
mixed at the moment of use. 
______________________________________ 
1st Part 
Copolymer of 5% acrylamide/ 
1.5 g 
95% N,N--dimethyl,N,N-- 
diallylammonium chloride 
(French patent No. 73.23970) 
Glutaraldehyde 0.15 g 
Perfume 0.08 g 
Water, sufficient amount for 
100 g 
2nd Part 
2.1 cc of 1 N HCl solution 
______________________________________ 
(b) Hair setting process 
At the moment of use the second part, above, is introduced with stirring 
into the first part. 
The resulting mixture is then applied to the hair after which the hair is 
rolled upon rollers having a diameter of 15 mm. 
The hair is then dried under a hood at about 50.degree. C. for 20 minutes 
and the rollers are removed. The resulting curls have an excellent hold, 
principally in a humid atmosphere. 
EXAMPLE 8 
(a) 2-part package 
A hair setting composition is packaged in the following two parts which are 
mixed at the moment of use. 
______________________________________ 
1st Part 
Copolymer of 68% N--vinylpyrrolidone/ 
1 g 
8% acrylamide/8% acrylic acid/ 
8% 2-N,N--dimethylamino ethyl methacrylate/ 
8% 2-N,N--dimethylamino ethyl methacrylate 
quaternized with dimethyl sulfate 
(French patent No. 71.03017) 
Glutaraldehyde 0.1 g 
Perfume 0.07 g 
Water, sufficient amount for 
100 g 
2nd Part 
2.1 cc of HCl solution 
______________________________________ 
(b) Hair setting process 
At the moment of use the second part is admixed with the first part with 
stirring. 
After having effected this admixture the composition is then applied to the 
hair which is then rolled up on rollers. 
After drying the hair under a hood the rollers are removed and the hair is 
given a final combing. 
The resulting curls have an excellent hold and the hair is shiny and soft 
to the touch.