Methods of conditioning hair which utilize polymeric N-vinyl formamide

The present invention relates to hair conditioning compositions which utilize as a hair conditioning additive a water-soluble polymer in amounts effective to impart hair conditioning properties to the hair conditioning composition, wherein the polymer contains the residue of N-vinyl formamide and the residue of at least one vinyl polymerizable moiety which contains an amine selected from the group consisting of secondary, tertiary and quaternary amines. The conditioning composition also includes one or more ingredients such as conditioning agents, emulsifiers, viscosity modifiers, gelling agents, opacifiers, stabilizers, preservatives, sequestering agents, chellating agents, pearling agents, clarifying agents, fragrances, colorants, and propellants; and water. The invention also relates to methods of conditioning hair.

FIELD OF THE INVENTION 
This invention relates to hair conditioning compositions which utilize as a 
hair conditioning additive polymers containing the residue of vinyl 
polymerizable moieties which contain a secondary, tertiary or quaternary 
amine and to methods of conditioning hair. 
BACKGROUND OF THE INVENTION 
Hair conditioning agents are functional additives used in hair care 
products such as lotions, shampoos, creme rinses, mousses and setting gels 
to improve the tactile and physical properties of hair. Such properties 
include, for example, substantivity of the conditioning agent on the hair 
without excessive build-up and enhancement of hair manageability, i.e., 
wet combability, dry combability, neutralization of static charge 
generated by combing and ease of styling. Other properties include 
lubrication of the hair to reduce friction between hair and comb and to 
minimize tangling. The additive should also soften the hair and impart 
gloss to dull hair and smooth the feel of the hair by filling in gaps or 
flattening cuticle scales. It is also advantageous for the hair 
conditioner to improve set retention of the hair. 
Cationic quaternary ammonium compounds, both mono- and di-functional, low 
molecular weight quaternary ammonium salts and certain high molecular 
weight polymers, are employed as conditioning additives in hair care 
products such as shampoos, conditioners, creme rinses, mousses, sprays and 
setting gels to impart wet and dry combability, improve feel, enhance curl 
retention and impart antistatic properties to hair. The Cosmetics, 
Toiletries and Fragrances Association (CTFA) has established a designation 
index for compounds employed in cosmetic and toiletry products. Two low 
molecular weight quaternary ammonium compounds that are commonly used in 
haircare products because of their low cost are 
stearylbenzyldimethylammonium chloride (CTFA designation--stearalkonium 
chloride) and cetyltrimethylammonium chloride (CTFA 
designation--cetrimonium chloride). 
The high molecular weight, cationic quaternary ammonium polymers 
(polyquats) are being used increasingly in hair care products because of 
their reported advantages over the simple quaternary ammonium salts in 
enhancing wet combability, mending split ends and improving appearance. 
Commonly used polyquats include: UCARE.TM. Polymer JR (CTFA 
designation--Polyquaternium 10) from Union Carbide, a quaternized 
cellulose; Gafquat.TM. (CTFA designation--Polyquaternium 11) from 
International Specialty Products, a quaternized copolymer of 
vinylpyrrolidone and dimethylaminoethylmethacrylate; and Merquat.TM.550 
(Polyquaternium 7) from Calgon, a homopolymer of dimethyldiallylammonium 
chloride. 
These quaternary ammonium conditioning additives have in common the 
quaternary ammonium functional group: 
##STR1## 
where R.sub.1 through R.sub.4 may be various substituted or unsubstituted 
alkyl or aryl substituents, or in the case of the polyquats, represent 
alkylene or arylene segments of a polymer chain. Associated with the 
positively charged quaternary ammonium nitrogen atom is a negatively 
charged counterion. This anion, X.sup.- may be a halide, hydroxide, 
methylsulfate or similar negatively charged group. 
While it is known that copolymers of vinylpyrrolidone and quaternary 
ammonium compounds are used as hair conditioning additives in hair 
conditioning compositions, it is desirable to develop new polymers which 
can be used as a hair conditioning additive. 
SUMMARY OF THE INVENTION 
The present invention relates to hair conditioning compositions which 
utilize as a hair conditioning additive a water-soluble polymer in amounts 
effective to impart hair conditioning properties to the hair conditioning 
composition, wherein the polymer comprises the residue of N-vinyl 
formamide and the residue of at least one vinyl polymerizable moiety which 
contains an amine selected from the group consisting of secondary, 
tertiary and quaternary amines. The conditioning composition also includes 
one or more ingredients selected from the group consisting of conditioning 
agents, emulsifiers, viscosity modifiers, gelling agents, opacifiers, 
stabilizers, preservatives, sequestering agents, chelating agents, 
pearling agents, clarifying agents, fragrances, colorants, and 
propellants; and water. The hair conditioning polymers may further include 
the residue of at least one vinyl monomer, as that term is defined herein. 
The invention is also directed to methods of conditioning hair which 
comprise applying to the hair an amount of the conditioning composition of 
the present invention which is effective to condition the hair.

DETAILED DESCRIPTION OF THE INVENTION 
N-vinyl formamide (NVF) is available from Air Products and Chemicals, Inc., 
Allentown, Pa., under the trade name Vinamer.TM. EF. Processes for 
preparing N-vinyl formamide are disclosed in U.S. Pat. No. 4,578,515, 
4,906,777, 4,942,259 and 5,037,927. In the present invention, NVF is not 
hydrolyzed prior to preparation of the hair conditioning polymer. 
The vinyl polymerizable moiety contains at least one amine group selected 
from the group consisting of secondary, tertiary and quaternary amines. 
The term "vinyl polymerizable moiety", as used herein, is meant to include 
those moieties that will copolymerize with NVF, other than "vinyl 
monomers", as that term is defined herein. Particularly preferred vinyl 
polymerizable moleties are the quaternary amine-containing moleties. 
Suitable moleties containing a quaternary amine include, for example, 
methacrylatoethyltrimethyl ammonium sulfate (MAETAS), 
methacrylamidopropyltrimethyl ammonium chloride (MAPTAC) and dimethyl 
diallyl ammonium chloride (DMDAAC). Preferred quaternary amine-containing 
moleties are MAPTAC and DMDAAC. 
The secondary and tertiary amines may be nonionic or cationic, although 
cationic amines are preferred. In certain embodiments, nonionic secondary 
and tertiary amines, such as t-butyl aminoethyl methacrylate (t-BAEM), 
dimethylaminoethyl methacrylate (DMAEMA) and dimethylaminopropyl 
methacrylamide (DMAPMA) are converted to cationic amines. One method for 
such conversion is to neutralize the secondary or tertiary amines with an 
appropriate acid to form an ammonium salt. Alternatively, the secondary or 
tertiary amines may be reacted with quaternizing agents to form quaternary 
amines. Such quaternizing agents include, for example, alkyl halides such 
as methyl chloride, or dialkyl sulfates such as dimethyl sulfate. One 
skilled in the art will recognize that there may be other routes to 
convert the nonionic secondary and tertiary amines to cationic amines. 
Suitable moleties containing a nonionic tertiary amine include, for 
example, DMAEMA and DMAPMA. Suitable moleties containing a nonionic 
secondary amine include, for example, t-BAEM. 
In certain embodiments, the polymer may be a copolymer comprising the 
residue of N-vinyl formamide and the residue of the vinyl polymerizable 
moiety. Preferably, the copolymer comprises from about 50 to about 95 
weight percent of the residue of NVF and from about 5 to about 50 weight 
percent of the residue of the vinyl polymerizable moiety. More preferably, 
the copolymer comprises from about 60 to about 90 weight percent of the 
residue of NVF and from about 30 to about 10 weight percent of the residue 
of the vinyl polymerizable moiety. Most preferably, the copolymer 
comprises from about 75 to about 85 weight percent of the residue of NVF 
and from about 25 to about 15 weight percent of the residue of the vinyl 
polymerizable moiety. 
In other embodiments, the polymer may further comprise the residue of at 
least one vinyl monomer(s). The term "vinyl monomer", as used herein, 
refers to vinyl monomers which are copolymerizable with NVF and which do 
not contain secondary, tertiary or quaternary amines. Suitable vinyl 
monomers include, (a) styrene and derivatives thereof, (b) C.sub.1 
-C.sub.18 alkyl esters of acrylic acid, (c) C.sub.1 -C.sub.18 alkyl esters 
of methacrylic acid, (d) vinyl esters of the formula CH.sub.2 =CH-OCOR 
where R is C.sub.1 -C.sub.18, (e) alkyl substituted acrylamides and 
methacrylamides of the formula CH.sub.2 =CR-CONR.sub.1 R.sub.2 where R is 
H or CH.sub.3 ; R.sub.1 is H or C.sub.1 -C.sub.12 and R.sub.2 is C.sub.1 
-C.sub.18, (f) monoesters and diesters of fumaric, itaconic and maleic 
acids, (g) vinyl ethers such as methyl vinyl ether, isobutyl vinyl ether 
and the like, (h) hydroxy functional acrylates and methacrylates such as 
hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate 
and hydroxypropyl methacrylate, (i) acrylamide, (j) non-alkyl substituted 
acrylamides such as diacetone acrylamide, and (k)cyclic amides such as 
vinylpyrrolidone and vinylcaprolactam. 
The hair conditioning compositions of the present invention comprise an 
amount of the hair conditioning polymer which is effective to impart hair 
conditioning properties to the hair conditioning compositions. Typically, 
the hair conditioning compositions comprise from about 0.1 to about 15 
weight percent of the polymer, preferably from about 0.25 to about 10 
weight percent of the polymer, based on the total weight of the hair 
conditioning composition. 
In one embodiment, the hair conditioning composition is a conditioning 
lotion. In addition to the inventive conditioning polymer, the lotion may 
further comprise other conditioning agents, such as cationic surfactants, 
fatty acid salts, hydrolyzed proteins such as collagen, keratin and amino 
acids, and oily materials such as lanolin, fatty alcohols, waxes and 
botanical oils. The lotion may also further comprise other ingredients 
such as emulsifiers, viscosity modifiers, opacifiers, pearlizers, 
stabilizers, preservatives, fragrances and colorants. In certain 
embodiments, the lotion may be applied via a spray delivery system. 
In other embodiments, the hair conditioning composition is a conditioning 
shampoo. The shampoos generally comprise primary surfactants for cleansing 
and foam, secondary surfactants for cleansing, foam boosting and 
conditioning and additional additives for special performance, stability, 
fragrance and color. More specifically, these aqueous-based systems may 
contain surfactants, conditioning agents such as cationic or amphoteric 
surfactants, oily materials, proteins, botanicals, synthetic resins and 
silicone polymers, in addition to other additives such as sequestering or 
chelating agents, viscosity modifiers, opacifying, pearling or clarifying 
agents, stabilizers, fragrances, colorants and preservatives. 
The hair conditioning composition also may comprise a gelling agent in 
amounts effective to form a conditioning gel. Preferably, the conditioning 
gel comprises from about 0.05 to about 3 weight percent of the gelling 
agent, more preferably from about 0.1 to about 1.0 weight percent of the 
gelling agent, based on the total weight of the conditioning gel. Examples 
of such gelling agents include synthetic polymers such as the 
acrylic-based Carbopol.RTM. series of thickeners available from B. F. 
Goodrich, Cleveland, Ohio and associative thickeners such as Aculyn.TM., 
available from Rohm & Haas, Philadelphia, Pa. Other exemplary gelling 
agents include, cellulosic thickeners, such as derivatized hydroxyethyl 
cellulose and methyl cellulose, starch-based thickeners, such as 
acetylated starch, and naturally occurring gums, such as agar, algin, gum 
arabic, guar gum and xanthan gum. 
In yet other embodiments, the hair conditioning composition may be in the 
form of mousse or spray. The mousse or spray may contain, in addition to 
the ingredients mentioned herein above, propellants such as ethers, 
compressed gases, halogenated hydrocarbons and hydrocarbons. Exemplary 
propellants are dimethyl ether, propane, butane, 1,1-difluoroethane, and 
mixtures thereof. 
The hair conditioning compositions may include organic solvents to modify 
certain properties of the hair conditioning compositions, such as 
viscosity, solubility or drying. Typical solvents include, for example, 
ethanol, isopropanol, acetone, dimethoxymethane and methyl ethyl ketone. 
When used, the amounts of organic solvents preferably are minimized. More 
preferably, the compositions will be free of organic solvents. 
The hair conditioning compositions will contain from about 0.5 to about 20 
weight percent of one or more ingredients selected from the group 
consisting of conditioning agents, emulsifiers, viscosity modifiers, 
gelling agents, opacifiers, stabilizers, preservatives, sequestering 
agents, chelating agents, pearling agents, clarifying agents, fragrances, 
colorants, and propellants. Preferably, the composition will comprise from 
about 1 to about 10 weight percent of the one or more ingredients. 
The invention is also directed to methods of conditioning hair which 
comprise applying to the hair an amount of the conditioning composition of 
the present invention which is effective to condition the hair. By 
conditioning the hair, it is meant that the hair conditioning composition 
will impart at least one conditioning property to the hair, or improve at 
least one hair conditioning property of the hair, as those properties are 
discussed herein. 
The following examples are indicative of preferred hair conditioning 
compositions and hair conditioning polymers utilized therein. They are not 
intended and should not be construed to limit the scope of the claims 
appended hereto. All percentages noted herein are weight percent unless 
noted otherwise. 
Polymer Preparation by Solution Polymerization 
The polymers were prepared in 4-neck, 2-L flasks equipped with a stirring 
shaft powered by a mechanical stirrer, 2 addition funnels, water bath, 
thermometer and reflux condenser. In the flask were introduced the initial 
charge of 18 g of NVF, 4.5 g of a 53.0% aqueous solution of MAPTAC, 53.5 g 
of a 70:30 ethanol/water mixture (wt %), 10 g of water, and 1.12 g of 
t-butyl peroctoate. The mixture was brought to reflux to allow formation 
of a solvent atmosphere blanket about the reagents. After 15 min of 
reflux, a monomer slow-add of the following composition was regularly and 
continuously added over a period of 4 hours, the refluxing conditions 
being maintained: 142 g NVF, 35.5 g of a 53.0% aqueous solution of MAPTAC 
and 235 g of water. Two hours after the beginning of the above addition, a 
mixture of 26.5 g of a 70:30 ethanol/water mixture (wt%) and 0.2 g of 
t-butyl peroctoate was regularly and continuously added over a period of 2 
hours. When the above slow-adds had been introduced a post-scavenging 
slow-add composed of 37 g of a 70:30 EtOH/water mixture (wt%) and 0.66 g 
of t-butyl peroctoate was added regularly and continuously over a period 
of 3 hours, refluxing conditions being maintained. This was followed by a 
hold period of 5 hours during which reflux was also maintained. After 
cooling, the setup was modified by the incorporation of a Dean-Stark trap. 
The organic solvent was distilled off, steam being introduced above the 
reaction mixture when the vapor temperature had reached 90.degree. C. When 
the reflux temperature had reached 100.degree. C., steam was injected 
subsurface and the operation maintained for 15 min. 
The final aqueous solution appeared clear and was diluted to 19.4% solids 
content. The polymer was designated Polymer B (NVF 88/MAPTAC 12). The 
final polymer had a inherent viscosity of 1.27 dl/g.sup.-1. Inherent 
viscosity (I.V.) was determined on 1 wt % polymer in 1N KCl aqueous 
solutions. GPC analysis was performed at 80.degree. C. in 0.03N NaNO.sub.3 
DMSO solutions. Dextrans were used as standards. GPC analysis gave the 
following data: 
EQU Mn=6.3.times.10.sup.4 ; Mw=3.9.times.10.sup.5 ; Ip (polydispersity, i.e., 
Mw/Mn)=6.3. 
The following copolymers were prepared using the above procedure, the 
amount of monomer used being calculated to meet the formulated final 
composition: 
Polymer A: NVF 80/MAPTAC 20 
Polymer C: NVF 80/DMDAAC 20 
Procedures for Evaluation of Conditioning Compositions 
Polymers A-C were evaluated against a control as a hair-conditioning 
additive with respect to the following properties: wet combability, dry 
combability, gloss, presence of static flyaway, flakiness and feel. 
Details of the test are described below. 
The polymers were evaluated as 2% active aqueous solutions and compared to 
a control consisting of water. Virgin dark brown hair was obtained from 
DeMeo Brothers, 129 W. 28th Street, New York, N.Y. 10001. A separate 5.25 
gram hair swatch, 10" in length, was used for each polymer or water 
treatment. 
Swatches were saturated with tepid water. Excess water was removed by 
squeezing the wet swatch between the thumb and index finger. Five drops of 
the test solution were dropped along the length of the swatch and were 
worked into the swatch using 10 (ten) downward strokes. The swatch samples 
were grouped as pairs (polymer-treated versus water-treated). A total of 
eight pairs of samples were evaluated. Performance was evaluated by a 
trained panel of four members, who compared the coded, inventive polymers 
to a control of only water. Each member on the panel rated two pairs of 
samples (polymer vs. water) as being inferior/superior (-/+) one to the 
other, or as no statistical difference (NS). Eight pairs in all were 
tested for each polymer. Each swatch was evaluated as follows: 
1. Wet combability--The swatch was gently combed several times and rated 
for ease of comb-out. 
After drying for one hour at 120.degree. F., the following properties were 
evaluated: 
2. Gloss--The swatch was visually rated for gloss and sheen. 
3. Stiffness--The swatch was handled by the panelist and rated for 
stiffness versus softness according to the resistance felt when attempting 
to bend the hair swatch. 
4. Dry Combability--The swatch was gently combed several times and rated 
for ease of comb-out. 
5. Flakiness--The swatch was visually examined for flaking following 
combing. 
6. Static flyaway--The swatch was vigorously combed and then rated for the 
extent of static flyaway exhibited. 
7. Feel--The swatch was evaluated for tactile properties by the panelist. 
Data acquired from these methods are qualitative and not quantitative, and 
therefore subjective. However, panelists who participated in these blind 
studies have been trained in the analysis of hair swatches for these 
properties. Additionally, the subjective evaluations are statistically 
analyzed to identify differences at the 90% confidence level. Results of 
the evaluation are found in Table 1. 
TABLE 1 
______________________________________ 
Property Polymer A Polymer B Polymer C 
______________________________________ 
Wet Combability 
+ NS + 
Gloss + + NS 
Stiffness + + + 
Dry Combability 
- - - 
Flakiness - - - 
Static Flyaway 
- - NS 
Feel NS NS NS 
______________________________________ 
As the results indicate, NVF/MAPTAC Polymers A and B exhibit hair 
conditioning properties, such as improved hair gloss and stiffness, while 
Polymer A exhibited improved wet combability. Additionally, although not 
statistically different (NS) under the test criteria, a majority of the 
samples utilizing Polymer B were found to improve wet combability. The 
NVF/DMDAAC Polymer C was found to improve wet combability and stiffness. 
Additionally, although not statistically different under the test 
criteria, a majority of the panelists found Polymer C to improve static 
flyaway and the feel of the hair. As indicated herein, additional vinyl 
monomers may be used in combination with the NVF monomer and the vinyl 
polymerizable moiety to modify or improve certain hair conditioning 
properties of the of the conditioning compositions. 
The following are hair conditioning formulations in which the inventive 
hair conditioning polymers may be used. As one skilled in the art will 
recognize, once armed with the present specification, the formulations are 
not inclusive of all conditioning formulations anticipated by the present 
invention. Additionally, each class of conditioner represented by the 
formulations may include other ingredients such as those discussed herein 
above. Parts by weight of the conditioning polymer are on a dry weight 
basis. 
Hair Conditioning Formulations 
______________________________________ 
Conditioning Lotion: 
Ingredient Parts by weight 
______________________________________ 
Conditioning Polymer 
1.00 
Carbopol .RTM. 940 thickener 
0.15 
Triethanolamine 0.15 
Deionized Water 98.70 
100.00 
______________________________________ 
Procedure: The Carbopol.RTM. 940 thickener is dispersed in water with good 
agitation. The conditioning polymer is added to the water and mixed until 
dissolved. While mixing, triethanolamine is added. Mixing is continued 
until a homogeneous mixture is produced. 
______________________________________ 
Conditioning Shampoo 
Ingredient Parts by weight 
______________________________________ 
Conditioning Polymer 
1.80 
TEA Lauryl Sulfate 25.00 
Cocamide DEA 5.00 
Dowicil .RTM. 200 preservative 
0.10 
Deionized Water 68.10 
100.00 
______________________________________ 
Procedure: The conditioning polymer is dissolved in 20 parts water. In a 
separate container, the remaining water is heated to 70.degree. C. TEA 
Lauryl Sulfate and Cocamide DEA are then added to the heated water. The 
polymer solution from step 1 is added to the heated water. The mixture is 
cooled to 40.degree. C. and the preservative is added. The mixture is 
cooled to room temperature. Dowicil.RTM. 200 is available from The Dow 
Chemical Company, Midland, Mich. 
______________________________________ 
Conditioning Gel 
Ingredient Parts by weight 
______________________________________ 
Conditioning Polymer 
3.00 
Triethanolamine (TEA) 
0.60 
Deionized Water 47.85 
Carbopol .RTM. 940 thickener 
0.60 
Dowicil .RTM. 200 preservative 
0.10 
Deionized Water 47.85 
100.00 
______________________________________ 
The polymer and TEA are mixed in D.I. water until homogenous. In a separate 
vessel, the Dowicil.RTM. 200 preservative and Carbopol.RTM. 940 thickener 
are combined with D.I. water and mixed until the thickener goes into 
solution. Parts A and B are then combined and mixed gently until a clear 
viscous gel is formed. 
______________________________________ 
Conditioning Mousse 
Ingredient Parts by Weight 
______________________________________ 
Conditioning Polymer 2.50 
Tergitol .RTM. NP15 surfactant 
0.50 
Brij .RTM. 97 surfactant 
0.30 
Dowicil .RTM. 200 preservative 
0.10 
Propellant (20:80/Propane:butane) 
10.00 
Water 86.60 
100.00 
______________________________________ 
Procedure: The conditioning polymer is dissolved in water with adequate 
agitation. The surfactants and preservative are added and the solution is 
mixed until homogenous. The product is filtered and filled into a 
container. The container is then charged with the propellant. 
Tergitol.RTM. NP15 surfactant is available from Union Carbide Chemical and 
Plastics Company, Danbury, Connecticut. Brij.RTM. 97 surfactant is 
available from ICI Specialty Chemicals, Wilmington, Del. 
In addition to the subjective, stiffness evaluation performed by the 
trained panel, Polymer A was formulated into the above conditioning mousse 
formulation and compared to three comparative polymers, each of which also 
was formulated into the above mousse formulation. Comparative Polymers D 
and E are quaternary ammonium polymers formed by the reaction of diethyl 
sulfate and a copolymer of vinyl pyrrolidone and dimethyl 
aminoethylmethacrylate. Comparative Polymer F is a polyvinylpyrrolidone 
homopolymer. Each of the formulated mousses were tested on three dampened 
4.5 inch Brown Virgin Italian hair swatches. To each swatch was applied 
0.2 g of the respective mousse. The mousse was worked into the swatch and 
each swatch dried in an oven at 110.degree. F. for two hours. The swatches 
were placed in a constant temperature and humidity chamber at 50% relative 
humidity and 23.degree. C. and allowed to remain therein overnight. The 
stiffness of the swatches were measured using an appropriate device for 
measuring stiffness. The results were statistically analyzed and reported 
at the 95% confidence level. The mousse formulated with Polymer A had a 
stiffness value 24% greater than that of a mousse formulated with 
Comparative Polymers D and F and 32% greater than a mousse formulated with 
Comparative Polymer E. The improved stiffness is particularly important to 
conditioning gel, mousse and spray embodiments of the present invention.