Treating proteinaceous substrates with cationic copolymer

The treatment of proteinaceous or other substrates to render them more manageable and more stable against chemical treatment involves the use of aqueous compositions containing cationic (meth)acrylic copolymers.

BACKGROUND 
Chemical processing such as the coloring, straightening and permanent 
waving of human hair and other proteinaceous substrates can be damaging to 
those substrates. It is known in the art to protect or, in some respects, 
"stabilize" the hair, before, during or after such treatment, with a 
composition containing protective agents. 
This invention is related to that disclosed in U.S. Pat. No. 4,818,245 
which is assigned to the same company as this case. 
U.S. Pat. No. 4,371,517, to Vanlerberghe et al, describes the use of a 
combination of a cationic polymer, an anionic polymer, an alkali metal 
salt, and a non-ionic surfactant which contains carboxyl or carboxylated 
groups in compositions to be used to wash or dye hair. Copolymers 
containing tetraalkyl ammonium halide units are disclosed at column 4. 
U.S. Pat. No. 4,645,663 to Grollier et al deals with hair dyeing or 
bleaching compositions which contain copolymers having tetralklyammonium 
halide units (see column 9). 
Both of these patents refer to treatment systems in which maximum 
conditioning effectiveness requires the conjoint use of either an anionic 
polymeric component or an anionic surfactant with the cationic copolymers. 
Sokol U.S. Pat. Nos. 3,912,808 and 3,986,825 disclose similar systems of 
cationic copolymers in which surfactant is either present in the 
compositions or used in post-treatments. 
The disclosures of the above-referenced patents are hereby incorporated by 
reference. 
THE INVENTION 
The invention deals with compositions and processes for conditioning hair 
or other proteinaceous substrates. 
Applicants have discovered that the treating of hair or other proteinaceous 
substrates with compositions containing a copolymer of about 10% 
hexadecyldimethylpropyl methacrylamide ammonium bromide (HDPM) with about 
90% methylacrylamidopropyltrimethyl ammonium chloride (MAPTAC), which 
copolymers are referred to as "H-QUAT" polymers, with other chemical 
treating materials, e.g., coloring, bleaching, perming and/or shampooing 
compositions, made the hair more easily combable and manageable. 
ADVANTAGES 
The compositions of the invention have several advantages over known 
compositions and processes for treating hair and other fibrous substrates 
to render them more manageable and to stabilize them against the harsh 
side effects of chemical processing. 
One major advantage resides in the fact that compositions containing 
cationic H-QUAT polymers need not be used in conjunction with anionics in 
order to effect beneficial results. Thus, unlike other systems described 
above, the cationics can be used in one-step conditioning as the sole 
polymeric agents in the protective compositions and processes of the 
invention. 
Note that many cationic/anionic combinations result in "over conditioning" 
problems when the polymer precipitates into the hair. Such problems are 
minimized using the instant system. In fact, the "over conditioning" which 
is typical with the use of cationic/anionic complexes or combinations is 
virtually eliminated using the instant invention because no anionic 
polymer or surfactant complexes or combinations are needed for the 
operability of the invention. 
In addition, the high miscibility of these cationic polymers with aqueous 
solvents and other polar liquids make their formulation both easy and 
inexpensive. 
Furthermore, the compositions and processes of the invention produce 
improvements in the treated hair e.g. less tangling and static and better 
feel. These improvements are durable, generally lasting through several, 
e.g. 2-5, shampoos. 
These and other aspects and advantages of the invention will become more 
apparent after consideration of the following description of the 
invention. 
DESCRIPTION OF THE INVENTION 
The invention is concerned with novel polymeric compositions for treating 
proteinaceous or other fibrous substrates and to processes involving the 
use of those compositions. 
Compositions 
The compositions of the invention containing, as essential components, 
cationic polymers of a particular type and one or more carriers. 
Cationic polymers 
The cationic polymers employed herein are generally copolymers of acrylic 
and or methacrylic species. Preferably they are (meth)acrylic copolymers 
containing a significant percentage, i.e. at least 1% fatty substituted 
trialkyl ammonium halide units of formula I: 
##STR1## 
wherein R.sub.1 is H or CH.sub.3 ; A is a C.sub.1 -C.sub.5 alkylene 
linkage 
R.sub.2 is C.sub.10 -C.sub.25 alkyl, 
R.sub.3 and R.sub.4 are each independently selected from, C.sub.1-6 alkyl 
groups, and 
X is Cl, or Br. 
These units are copolymerized with units of formula II as follows: 
##STR2## 
wherein R.sub.5 is a C.sub.1-6 alkyl group, R.sub.1, A, R.sub.3, R.sub.4 
and X are as defined above for formula I. 
Preferably, the copolymer employed are those which contain from about 1 to 
about 20 mole %, preferably about 5 to about 15 mole %, most preferably 
about 10 mole % of units of formula I and about 20 to about 99 moles %, 
preferably about 85 to 95%, most preferably about 90 mole % of units of 
formula II. One particularly preferred polymer of this type is the 
"H-Quat" polymer which contains 10% hexadecyldimethylpropylmethacrylamide 
ammonium bromide (HDPM) and 90% methacrylamidopropyltrimethyl ammonium 
chloride. 
While units of formulas I and II are essential in the cationic species to 
be used, the presence of other vinyl residues is contemplated. Thus, 
useful copolymers may contain moieties derived from one or more other 
unsaturated species, such as ethylene, propylene, C.sub.1-6 
(meth)acrylates, C.sub.1-6 (meth)acrylamides, and the like. 
These polymeric component(s) may be used in combination with other 
polymers. However, no other polymers need be present. The polymeric 
components of applicants' composition are cationic polymers which requires 
no additional anionic or nonionic species for "balance". While applicants' 
copolymers are within the broad grouping of polymers disclosed in U.S. 
Pat. Nos. 4,371,517 and 4,645,663 the sole use of the specific polymers 
described above for applicants' purposes is not taught therein. 
Although anionic surfactants are not required for effect in the product, 
their use is not precluded. 
The compositions of the invention are generally applied from a liquid or 
spray formulations. Optionally, they may be formulated into gels, creams, 
or other forms. 
Diluents 
The compositions of the invention contain one or more diluents or carriers. 
Typically, the carrier employed will be aqueous, e.g. water alone, or 
water/C.sub.1-3 alcohol combinations, or C.sub.1-3 alcohols alone. 
Applicants' treatment compositions contain from about 0.05 to about 1 wt. 
%, preferably about 0.2 to about 0.5 wt. %, of one or more polymeric 
additive(s), with the remainder being one or more carrier(s) or other 
conventional additives. 
Conventional excipients or additives may be used in suitable quantities in 
the compositions of the invention. Thus, depending upon the overall 
function of the treating composition, one or more surfactants, 
plasticizers, soaps, stabilizers, fillers, thixotropic agents, colorants, 
perfumes, buffers and the like may be employed. 
When the polymeric components of the invention are used in post-shampoo 
rinses, e.g. in conditioning formulations, they will be present at 
concentration levels of about 0.05 to about 5 wt. % preferably about 1 to 
about 1.5wt. %. 
Hair Treatment 
The compositions of the invention can be applied to proteinaceous 
substrates of a variety of types. While the treatment of hair on the human 
head is highly preferred, the compositions can also be used to treat hair 
which is not on a body, e.g. in wigs, swatches, garments made of hair, 
etc. It may also be applied to non-human hair or fur, e.g., wool or dog 
hair as well as pelts o skins of other animals. 
Alternatively, the compositions can be used to treat keratin fibers such as 
hair and wool. Blends, e.g., polymer/wool, can also be present in 
substrates to be treated. 
These compositions are usually applied in any suitable liquid form such as 
sprays, lotions or creams. Thus, they can be formulate using the 
carrier(s) and/or other excipients discussed above in order to achieve 
requisite properties, e.g. viscosity, stability, handling properties, etc. 
While liquid formulations are preferred, the use of semi-solids and solids 
is contemplated. Thus, gels, mousses, creams as well as hot melt 
formulations are envisioned. 
When a liquid formulation is sprayed onto the hair it is visually used in 
the form of a solution of the polymeric component in a carrier such as 
water or mixtures of water and ethanol. 
In the preferred embodiment, the composition is applied one or more times 
via spraying from a conventional non-aerosol spray device onto the hair or 
other substrate to deposit about 0.01 to about 0.02 g. of polymer on a 
typical head of hair. The chemical treatment is then applied without 
attempting to rinse the hair. Shampooing may be done after the chemical 
treatment is used. 
While it is preferred that the compositions be applied before any chemical 
treatment, i.e., as pre-treatment compositions, they may also be used 
during, and/or after the use of conventional chemical agents.

EXAMPLES 
The following examples are given to further illustrate the present 
invention. Compositions were prepared comparing H-Quat, 
poly(methacrylamidopropyltrimethyl ammonium chloride (PMAPTAC), 
polyquaternium 10 and polyquaternium 6 as the actives and applied to hair 
previously tinted and therefore usually difficult to comb and hard to 
manage. The compositions were applied in the form of a spray. 
EXAMPLES I 
Hair Tint Composition I was mixed with 20 volume hydrogen peroxide and 
applied immediately thereafter. It was allowed to remain on hair swatches 
of 2 g. size for 30 minutes and rinsed off. Two controls were not 
pre-treated. One of these controls was post-treated with a Standard 
Conditioner Composition (Composition E) which is the usual method for 
conditioning hair. 
______________________________________ 
HAIR TINT COMPOSITION I 
PERCENT 
______________________________________ 
P-Phenylenediamine 2.20 
Resorcinol 1.10 
M-aminophenol 1.00 
Sodium Sulfite 0.10 
EDTA 0.05 
Propylene Glycol 5.00 
Isopropanol 10.00 
Nonoxynol-4 3.50 
Cetyl Alcohol 5.00 
Ammonium Hydroxide 9.00 
Ceteareth-20 3.50 
Water 59.45 
TOTAL 100.00 
______________________________________ 
The following conditioning compositions were used to pre-treat the hair 
swatches: 
______________________________________ 
Percent 
______________________________________ 
Composition A 
H-Quat 0.24 
Water 99.76 
Composition B 
POLYMAPTAC 0.24 
Water 99.76 
Composition C 
Polyquaternium 10 0.24 
Water 99.76 
Composition D 
Polyquaternium 6 0.24 
Water 99.76 
Standard Conditioner Composition 
(Composition E) 
Ceteareth-20 3.5 
Cethyl Alcohol 1.0 
Strealkonium Chloride 2.0 
Citric Acid 3.0 
Water 90.5 
100.0 
______________________________________ 
The swatches were rinsed and then evaluated for ease of wet combing before 
shampooing and after lathering with shampoo. A scale was used with the 
untreated control assigned zero and the control post treated with standard 
conditioner composition E assigned 5. 
Table I clearly illustrates the efficacy and durability of H-Quat. 
TABLE I 
______________________________________ 
Combability of tinted hair (1) immediately after treatment with 
conditioner and (2) after three latherings with shampoo*. 
Before After 3 
Composition Shampooing Latherings 
______________________________________ 
A. H-Quat 4.0 4.0 
B. POLYMAPTAC 1.5 0.0 
C. Polyquaternium 10 
0.0 0.0 
D. Polyquaternium 6 
1.5 0.0 
E. Standard Conditioner 
Composition 5.0 0.0 
Control 0.0 0.0 
______________________________________ 
*The shampoo used was condition* Shampoo from Clairol. 
EXAMPLE II 
Previously tinted hair was permed with the following composition: 
______________________________________ 
PERM COMPOSITION 
FOR TINTED HAIR PERCENT 
______________________________________ 
Ammonium Thioglycolate (60% as acid) 
12.2 
Laureth-23 1.5 
Fragrance 1.0 
EDTA 0.1 
Ammonium Hydroxide 3.5 
Water 81.7 
TOTAL 100.0 
______________________________________ 
The perm composition was neutralized with 2.0% Hydrogen Peroxide. 
Prior to perming, swatches of the size used above were treated with the 
compositions of A-D in the same manner. Two control swatches were made 
without a pre-treatment. One of the controls was post-treated with 
Standard Conditioner Composition E. The swatches were then evaluated for 
ease of wet combing after neutralization of the perm and after three 
lathers with Condition* Shampoo by Clairol. 
A combability scale was assigned with the untreated control assigned zero 
and the control post treated with Standard Conditioner Composition was 
assigned 5. Table II clearly illustrates the results. 
TABLE II 
______________________________________ 
Combability of tinted permed hair (1) immediately 
after treatment with conditioner and 
(2) after three latherings with shampoo 
Before After 3 
Composition Shampooing Latherings 
______________________________________ 
A. H-Quat (Example I) 
4.5 4.5 
B. Polympatac (Example II) 
2.5 0.0 
C. Polyquaternium 10 
0.0 0.0 
(Example III) 
D. Polyquaternium 6 3.0 1.0 
(Example IV) 
E. Standard Conditioner 
Composition 5.0 0.0 
Control 0.0 0.0 
______________________________________ 
Conditioning occurs during the chemical treatment and persists after the 
hair is washed and styled. 
EXAMPLE III 
To further illustrate the invention, the compositions A-D were applied 
prior to the application of A Standard Hair Straightening Composition. The 
straightener was left on ten minutes and then rinsed. 
______________________________________ 
STANDARD HAIR STRAIGHTENER 
PERCENT 
______________________________________ 
Water 74.25 
Propylene Glycol 2.00 
Mineral Oil 10.00 
Emulsifying Wax NF 5.00 
Laneth-15 1.00 
Cetyl Alcohol 1.00 
Ceteareth-20 3.00 
Laneth 5 and Ceteth-25 2.00 
Sodium Hydroxide 1.75 
TOTAL 100.00 
______________________________________ 
Two control swatches of the same size as those used above were made. One 
swatch was only treated with Standard Hair Straightener and the other was 
post-treated with Standard Conditioning Composition E. The swatches were 
evaluated for ease of wet combing. A scale of 0 to 5 was used with the 
control assigned 0 and the swatch post treated with Standard Conditioning 
Composition assigned 5. The results are set out in Table III. 
TABLE III 
______________________________________ 
Combability of Hair Post-Straightened after treatment 
with conditioner with combability measured, 
before and after shampooing 
Before After 3 
Composition Shampooing Latherings 
______________________________________ 
A. H-Quat 5.0 4.0 
B. POLYMAPTAC 3.5 2.0 
C. Polyquaternium 10 
1.0 0.0 
D. Polyquaternium 6 
3.5 2.0 
E. Standard Conditioner 
Composition 5.0 0.0 
Control 0.0 0.0 
______________________________________ 
The foregoing examples have illustrated the ability of H-Quat to condition 
without the necessity of complexing with an anionic surfactant and its 
improved durability by surviving various processing steps and subsequent 
shampooings. 
Reasonable variations, such as those which would occur to a skilled 
artisan, can be made herein without departing from the scope of the 
invention.