Hair care compositions

A latex composition for hair care containing a hybrid-graft copolymer of a sulfopolyester and an acid-functional polymer segment. The acid-functional polymer segment is formed from at least one acid-functional monomer, at least one ethylenically unsaturated monomer, and at least one amide-containing monomer. Such compositions exhibit superior curl retention even at high humidity.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a hybrid-graft copolymer having a sulfopolyester 
grafted with an acid-functional polymer. The hybrid-graft copolymer is 
well-suited for use in hair care formulations. The hybrid-graft copolymer 
has excellent curl retention, even at high humidity, and may be formulated 
over a wide range of volatile organic component (VOC) content. 
2. Description of the Related Art 
A hair care product must meet a variety of requirements. Performance 
requirements include, for example, exhibiting fine spray pattern, good 
film formation, good holding power, prolonged curl retention, low 
stickiness and lack of powdering or flaking, being clear, transparent and 
glossy and easy to remove upon washing the hair with soap or shampoo. In 
addition, recent environmental legislation in some states requires hair 
care products to be formulated with a low content of volatile organic 
compounds (VOC). Polymer systems addressing at least some of these 
requirements are disclosed in the following patents: 
U.S. Pat. No. 5,441,728 describes a blend of a water-soluble polymer, 
having a particular viscosity in water, with a latex of water-insoluble 
polymeric particles dispersed in water of a particular glass transition 
temperature, The latex and the water-soluble polymer interact with one 
another to provide a hair setting composition. 
U.S. Pat. No. 4,985,239 describes a hair cosmetic composition containing a 
particulate polymer having an average particle diameter of from 0.005 to 
0.2 .mu.. The particulate polymer is preferably in the form of a polymer 
latex. The particulate polymer can be blended in hair cosmetic 
compositions for shampoos, rinses, treatments, hair sprays, set lotions 
and the like. A conventional emulsion polymerization process cannot be 
used to prepare the particulate polymer. 
U.S. Pat. No. 4,300,580 describes a hair grooming composition containing a 
linear polyester derived from a dicarboxylic acid, a diol and a 
difunctional monomer containing a --SO.sub.3 M group attached to an 
aromatic nucleus which is dissipatable in water and water-alcohol 
mixtures. The diol component of the polyester contains at least 20 mol % 
of a poly(ethylene glycol). Such formulations are fast drying and have 
good hair holding properties, but possess the disadvantage of being very 
difficult to remove from the hair. 
U.S. Pat. No. 5,266,303 describes aerosol hair spray formulations based on 
a sulfonate-containing, water-dispersible or water-dissipatable linear 
polyester having a glass transition temperature of about 36.degree. C. to 
about 40.degree. C., a water-soluble polyvinyl lactam polymer, and water. 
U.S. Pat. No. 5,158,762 describes a water-based hair spray composition 
capable of providing a fine finishing mist which provides a stiff resin 
film having excellent hair holding power, with superior shine, and feel, 
and within a relatively low drying time, approaching that of alcohol-based 
systems. The composition attains its attributes by including a 
predetermined blend of at least two hair spray resins, one being a 
water-soluble resin, and the other resin being a water-dispersible 
polyester or polyester amide. 
EP Application No. 2 719 995 describes an aqueous cosmetic composition for 
hair setting based on the combination in an aqueous or low alcohol medium 
of a sulfonated polycondensation water dispersible group and a 
water-soluble copolymer containing one neutralized carboxylic acid group 
and by patterns including a cyclic ester group. The composition has 
excellent setting power and can be satisfactorily washed away with 
shampoo. 
EP Application No. 0 687 459 A1 describes capillary compositions containing 
an aqueous dispersion of polymers, such as polyesters, polyamides or 
alkyds, as film forming agents. The polymers are prepared by radical 
polymerization of a radical monomer inside and/or partially on the surface 
of the preexisting particles of the polymer. 
EP Application No. 0 705 595 A2 describes aqueous low VOC hair styling 
compositions containing at least one acrylic hair fixative resin and one 
or more plasticizing compounds selected from polycarboxylic acid esters 
and dimethiconecopolyols. Also described are low beading, low VOC hair 
styling compositions containing at least one surface tension reducing 
compound, at least one acrylic hair fixative resin, and at least one 
simethicone. Aqueous hair resin compositions containing at least one 
acrylic hair fixative resin and iodopropynyl-butylcarbamate are also 
described. An acrylic hair fixative resin contains an alkyl (meth)acrylate 
monomer, a hydroxyalkyl (meth)acrylate monomer, and a monoethylenically 
unsaturated monocarboxylic acid monomer. 
Despite such efforts, there still exists a need for a hair care polymer 
composition which is compatible with a wide range of VOC and able to form 
suitable formulations at a broad range of solvent concentrations. In 
addition, there is a need for a hair fixing composition which exhibits 
superior curl retention, even at high humidity levels. 
SUMMARY OF THE INVENTION 
The invention fulfills these needs by providing latex compositions for hair 
care containing a hybrid-graft copolymer of a sulfopolyester and an 
acid-functional polymer. Such a hybrid-graft copolymer demonstrates 
excellent curl retention, even at high humidity. 
The invention also provides hair care formulations containing a 
hybrid-graft copolymer of a sulfopolyester and an acid-functional polymer. 
Such formulations are compatible with volatile organic compounds and may 
be prepared over a wide range of volatile organic compound (VOC) 
concentrations. 
The invention further provides methods for the preparation of a 
hybrid-graft copolymer of a sulfopolyester and an acid-functional polymer. 
BRIEF DESCRIPTION OF THE DRAWINGS 
FIG. 1 depicts curl retention properties of hybrid-graft emulsion polymers 
and of commercially available materials at 72+ F. and 90% relative 
humidity (RH) as a function of time. 
FIG. 2 depicts curl retention properties of neutralized hybrid-graft 
emulsion polymers (55% VOC) and of commercially available materials (80% 
VOC) at 72.degree. F. and 90% relative humidity as a function of time.

DETAILED DESCRIPTION OF THE INVENTION 
The invention provides a latex composition containing a hybrid-graft 
copolymer. The composition is useful in hair care formulations, 
particularly in both aerosol and pump hair spray formulations. The 
hybrid-graft copolymer contains a sulfopolyester grafted with an 
acid-functional polymer segment. The term "hybrid" denotes that the graft 
copolymer may contain not only a sulfopolyester grafted with an 
acid-functional polymer segment (sulfopolyester-g-acid-functional 
polymer), but in addition may contain small amounts of free sulfopolyester 
and free acid-functional polymer. The graft yield on a polyester depends 
on the acid content of graft monomers, as discussed in S.I. Um et al, 
"Morphological Core/Shell Structure and Dispersion Stability of 
Water-Dispersible Copolyester Graft Polymerized with Acrylic Acid and 
Ethyl Acrylate," Journal of Applied Polymer Science, Vol 60, 1587-1593 
(1996). 
The hybrid-graft copolymer contains a sulfopolyester in an amount of from 
about 2 to about 90 wt % and a grafted acid-functional polymer segment in 
an amount of from about 10 to about 98 wt % based on the total dry weight 
of the hybrid-graft copolymer. A preferred hybrid-graft copolymer of the 
invention contains about 10 to about 80 wt % of the sulfopolyester and 
about 20 to about 90 wt % of the acid-functional polymer segment based on 
the total dry weight of the hybrid-graft copolymer. A more preferred 
hybrid-graft copolymer contains about 20 to about 70 wt % of the 
sulfopolyester and about 30 to about 80 wt % of the acid-functional 
polymer segment based on the total dry weight of the hybrid-graft 
copolymer. 
The hybrid-graft copolymer preferably has a weight average molecular weight 
(Mw) from about 15,000 to about 250,000, more preferably from about 20,000 
to about 200,000, as measured by gel permeation chromatography (GPC). The 
hybrid-graft copolymer preferably has a glass transition temperature (Tg) 
ranging from about 15 to about 130.degree. C., and most preferably from 
about 25 to about 55.degree. C. The sulfopolyester and acid-functional 
polymer segment of the hybrid-graft copolymer are discussed in more detail 
below. 
The Sulfopolyester 
A sulfopolyester, useful in the present invention, may be any polyester 
having sulfonate groups such as those described in U.S. Pat. Nos. 
3,734,874, 3,779,993, 4,119,680, 4,300,580, 4,973,656, 5,660,816, 
5,662,893, and 5,674,479 each of which is incorporated herein by 
reference. Preferably, the sulfopolyester exhibits a glass transition 
temperature (Tg) in the range of 15-60.degree. C. Further, the 
sulfopolyester has a preferred weight average molecular weight (Mw) of 
from about 4,000 to about 20,000, as determined by gel permeation 
chromatography (GPC). Preferably, a sulfopolyester used in the invention 
forms a hard clear film at room temperature. A preferred sulfopolyester 
is, for example, the EASTMAN AQ.RTM.-48 polyester product available from 
Eastman Chemical Company, Kingsport, Tenn. 
The sulfopolyester may be synthesized by techniques known in the art. 
Various methods to prepare a sulfopolyester are described in U.S. Pat. 
Nos. 3,734,874 and 3,779,993. In general, a preferred sulfopolyester may 
be formed by condensation polymerization of about 15 to about 26 mol % 
dimethyl-5-sodiosulfoisophthalate and about 60 to about 80 mol % 
isophthalic acid based on 100 mol % dicarboxylic acid, about 10 to about 
30 mol % of 1,4-cyclohexanedimethanol and about 70 to about 90 mol % 
diethylene glycol based on 100 mol % of diol. 
The Acid-functional Polymer Segment 
An acid-functional polymer segment, in accordance with the present 
invention, is a polymer or copolymer of ethylenically unsaturated monomers 
at least one of which contains acid functionality such as, for example, 
carboxyl or sulfonic acid groups. Partial or complete neutralization of 
the acid functionality renders the hybrid-graft copolymer dispersible or 
soluble in water or a liquid vehicle containing water, such as those used 
in hair care formulations. The acid-functional polymer segment of the 
hybrid-graft copolymer contains the following components: (1) an 
acid-functional monomer, (2) an ethylenically unsaturated monomer, and (3) 
an amide-containing monomer. Generally, the acid-functional polymer 
segment contains: about 15 to about 50 wt % of an acid-functional monomer, 
(2) about 10 to about 80 wt % of an ethylenically unsaturated monomer, and 
(3) up to about 40 wt % of an amide-containing monomer. The weight 
percentages of these monomers are based on the total weight of the polymer 
segment. These and other components of the acid-functional polymer segment 
are discussed below. 
Acid-functional Monomers 
An acid-functional monomer, in accordance with the present invention, is a 
monomer containing an acid functionality, such as a carboxylic acid group, 
a sulfonic acid group, an acid anhydride, or other group which can react 
with a base to form a salt. Suitable acid-functional monomers in 
accordance with the invention include, but are not limited to, acrylic 
acid, methacrylic acid, itaconic acid, itaconic anhydride, citraconic 
acid, maleic acid, fumaric acid, crotonic acid, maleic anhydride, 
citraconic anhydride, vinyl sulfonic acid, 2-acrylamido-2-methyl propane 
sulfonic acid, and styrene sulfonic acid. Mixtures of such acid-functional 
monomers may also be used. Of these, methacrylic acid, itaconic acid and 
acrylic acid represent preferred monomers. 
The acid-functional polymer segment may generally contain about 15 to about 
50 wt % of an acid-functional monomer based on the total weight of the 
acid-functional polymer segment. Preferably, the acid-functional monomer 
is present in an amount ranging from about 20 to about 50 wt % based on 
the total weight of the acid-functional polymer segment. A more preferred 
range is from about 25 to about 40 wt %, based on the total weight of the 
acid-functional polymer segment. The amount of the acid-functional monomer 
may be varied so that when partially or fully neutralized, the 
hybrid-graft copolymer will disperse or be soluble in water or in a 
mixture of water and at least one alcohol, ketone, or lower alkyl ester. 
Ethylenically Unsaturated Monomers 
The acid-functional polymer segment may contain an ethylenically 
unsaturated monomer in amounts ranging from about 10 to about 80 wt %, 
based on the acid-functional polymer segment. More preferably the 
ethylenically unsaturated monomers are present in about 20 to about 60 wt 
%. 
One type of ethylenically unsaturated monomers useful in the invention are 
.alpha.,.beta.-ethylenically unsaturated monomers having the general 
formula: 
EQU CH.sub.2 .dbd.C(R.sub.1)COOR.sub.2 
For monomers of this general formula, R.sub.1 is hydrogen or a C.sub.1 
-C.sub.3 alkyl group. R.sub.2 is a C.sub.1 -C.sub.20 alkyl group, phenyl, 
benzyl, hydroxy-(C.sub.1 -C.sub.4)-alkyl, C.sub.1 -C.sub.4 alkoxy-(C.sub.1 
-C.sub.4) alkyl, cyclopentyl, cyclohexyl, furyl, C.sub.1 -C.sub.4 alkyl 
furyl, tetrahydrofuryl or a C.sub.1 -C.sub.4 alkyl tetrahydrofuryl, or 
combinations of these monomers. Combinations of monomers where R.sub.1 is 
hydrogen and monomers where R.sub.1 is an alkyl group are used to modify 
the hydrophobicity and the glass transition temperature (Tg) of the film 
of the hybrid-graft copolymer. 
Examples of suitable ethylenically unsaturated monomers of the above 
formula, include, but are not limited to, methyl (meth)acrylate, ethyl 
(meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, isooctyl 
(meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl 
(meth)acrylate, phenoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, 
benzyl (meth)acrylate, furyl (meth)acrylate, methylfuryl (meth)acrylate, 
butylfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, ethoxyethyl 
(meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclopentyl (meth)acrylate, 
isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl 
(meth)acrylate and combinations or mixtures thereof. Among these, 
preferred monomers are methyl (meth)acrylate, ethyl (meth)acrylate, butyl 
(meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate 
and mixtures thereof. The term "(meth)acrylate" is used here and 
throughout the specification to denote methacrylate and acrylate monomers. 
Other ethylenically unsaturated monomers which may be used in the 
acid-functional polymer segment include styrene derivatives and vinyl 
derivatives. Examples of suitable styrene derivatives include, but are not 
limited to, styrene, a-methyl styrene, p-methyl styrene, and m-methyl 
styrene. Vinyl derivatives include, but are not limited to, vinyl esters 
such as, for example, vinyl acetate, vinyl propionate, vinyl 
2-ethylhexanoate, vinyl neononanoate, and vinyl neodecanoate. 
One or more wet adhesion promoting ethylenically unsaturated monomers may 
also be used in the acid-functional polymer segment to enhance hair 
substantivity. Examples of wet adhesion promoting monomers include 
t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, 
diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate, 
2-t-butylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, and 
N-(2-methacryloxyethyl) ethylene urea. 
Amide-containing Monomer 
An amide-containing monomer may be incorporated into the acid-functional 
polymer segment to enhance hair substantivity and/or the hair affinity of 
the hybrid-graft copolymer. Examples of such amide-containing monomers 
include, but are not limited to, vinyl pyrrolidone or N-substituted 
acrylamides. Exemplary N-substituted acrylamides are N-ethyl 
(meth)acrylamide, N-t-butyl (meth)acrylamide, N-t-octyl (meth)acrylamide, 
N-decyl (meth)acrylamide, N-dodecyl (meth)acrylamide, ethylphenyl 
(meth)acrylamide, and butylphenyl (meth)acrylamide. Mixtures of 
amide-containing monomers may also be used. The preferred amide-containing 
monomers are N-t-butyl acrylamide and N-octyl acrylamide. The 
amide-containing monomer may be present in an amount of up to about 40 wt 
%, based on the total weight of the acid-functional polymer. The preferred 
range for the amide-containing monomer is between about 4 to about 25 wt 
%, based on the total amount of the acid-functional polymer. 
Preparation of the Hybrid-graft Copolymer 
The hybrid-graft copolymer of the invention may be synthesized by emulsion 
polymerization of the monomers making up the acid-functional segment 
polymer in the presence of an aqueous dispersion of the sulfopolyester, 
each as described above. The hybrid-graft copolymer of the invention may 
be prepared using conventional emulsion polymerization techniques. For 
example, a batch process or a semi-continuous process may be used to 
prepare the hybrid-graft copolymer. A semi-continuous process is 
preferred. 
In a preferred semi-continuous process, a solution or dispersion of a 
sulfopolyester in water is prepared containing about 5 to about 40 wt % of 
a sulfopolyester based on the total weight of the solution. A mixture of 
one or more monomers to form an acid-functional polymer segment and a 
polymerization initiator may then be gradually added to the aqueous 
dispersion of the sulfopolyester. Polymerization then produces an aqueous 
hybrid-graft dispersion. It is generally desirable to have less than 100 
parts per million (ppm) of residual monomers in the final product and 
preferably less than 50 ppm residual monomer(s). The aqueous dispersion 
thus produced may be prepared with a total solids content from about 20% 
to about 60 wt %, based on the total aqueous dispersion. It is generally 
preferred, for safety reasons, not to mix the initiator with the monomers 
but to add the initiator and the monomers as separate components, although 
concurrently, to the aqueous dispersion of the sulfopolyester. 
The reaction temperature of the emulsion graft-polymerization is generally 
determined by the type of initiator. Accordingly, the reaction temperature 
may range between about 30.degree. C. to about 90.degree. C., with a 
preferred reaction temperature being between about 60.degree. and about 
85.degree. C. Typical initiators known in the art may be used to prepare 
the hybrid-graft copolymer of the present invention. Such initiators 
include, but are not limited to, peroxygen or persulfate compounds such 
as, for example, hydrogen peroxide, sodium persulfate, potassium 
persulfate or ammonium persulfate, t-butyl hydroperoxide, cumene 
hydroperoxide, lauryl peroxide, and benzoyl peroxide. A preferred amount 
of a peroxygen or persulfate initiator in accordance with the invention is 
between about 0.05 and about 1.5 wt %, based on the total weight of the 
monomers. Redox initiators may also be used. Such redox initiators 
include, but are not limited to, combinations of peroxygen compounds with 
sodium formaldehyde sulfoxylate, ascorbic acid (e.g. isoascorbic acid), 
glyoxal bisulfite, or divalent iron salts. The preferred amount of a redox 
initiator is about 0.02-1.5 wt %, based on the total weight of the monomer 
content. 
In an emulsion polymerization to prepare the hybrid-graft copolymer, an 
emulsifying agent may also be used, as known in the art. Examples of 
emulsifying agents are, but not limited to, a fatty acid, alkyl sulfate, 
alkyl sulfonate, alkylarylsulfonate, sulfated polyethoxylated alkyl 
phenol, sulfo succinate, alkali-metal alkyl phosphate, salt of abietic 
acid (hydrogenated or non-hydrogenated), and non-ionic emulsifiers, such 
as polyoxylated fatty alcohol, polyethoxylated alkyl phenol, and 
polyethoxylated fatty acid. An emulsifying agent may typically be used in 
an amount up to about 4 wt %, based on the total weight of the monomers. 
A chain transfer agent may also be employed, if desired, to regulate the 
molecular weight of the hybrid-graft copolymer. Examples of chain transfer 
agents are, but not limited to, mercaptans, such as dodecylmercaptan, 
t-butyl mercaptan, and 2-ethylhexyl-3-mercapto propionate, and haloalkyl 
compounds such as carbon tetrabromide and bromodichloromethane. 
The invention also provides a hybrid-graft copolymer having different 
acid-functional polymer segments grafted on the sulfopolyester. Such a 
hybrid-graft copolymer may, for example, contain about 5 to about 80 wt % 
of a sulfopolyester, from about 15 to about 55 wt % of a first 
acid-functional polymer segment, and about 5 to about 40 wt % of a second 
acid-functional polymer segment, based on the total hybrid-graft copolymer 
weight. The first and second acid-functional polymer segments preferably 
have different compositions and glass transition temperatures (Tg). 
A hybrid-graft copolymer having different acid-functional polymer segments 
grafted onto the sulfopolyester, according to the present invention, may 
be prepared by sequential emulsion polymerization. For example, in a 
semi-continuous process a dispersion of a sulfopolyester in water is 
prepared. Subsequently, a mixture of one or more monomers to form a first 
acid-functional polymer segment is gradually added to the reactor under 
the polymerization conditions as described above. Sequentially, another 
mixture of one or more monomers to form a second acid-functional polymer 
segment is added to the reactor. Accordingly, the polymer segments may be 
prepared from different monomer mixtures and have different glass 
transition temperatures. The term glass transition temperature (Tg) refers 
to the Tg of the polymer derived from the polymerization of the monomer 
mixture. Preferably, the Tg of a first acid-functional polymer segment is 
higher than the Tg of a second acid-functional polymer segment or other 
segments. It is further preferred that the Tg of a first acid-functional 
polymer mixture is between about 40 and about 80.degree. C., while the Tg 
of a second acid-functional polymer is between about 20 and about 
50.degree. C. 
The hybrid-graft copolymer is substantially insoluble in water or a liquid 
vehicle containing water at a low pH (below about 6.0). However, when the 
pH is adjusted to a value of from about 6.0 to about 9.5, the hybrid-graft 
copolymer exhibits substantial dissolution in aqueous media. Preferably, 
the pH ranges from about 6.5 to about 8.0. Solubilization or dispersion of 
the hybrid-graft copolymer may be accomplished by neutralizing (or 
reacting) at least some or all of the acid functionalities of the 
acid-functional polymer segment of the hybrid-graft copolymer with a 
Bronsted base. Examples of inorganic Bronsted bases include, but are not 
limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide, 
ammonium carbonate or combinations thereof. Organic bases may also be used 
and includes for example, water-soluble bases such as monoethanolamine 
(MEA), diethanolamine (DEA), triethanolamine (TEA), 
2-methyl-2-amino-1-propanol (AMP), 2-amino-2-methyl propanediol, 
N,N-dimethyl-2-amino-2-methyl-1-propanol, monoisopropanolamine, 
triisopropanolamine, morpholine, monoamine glycols, and the like. 
The degree of neutralization required for solubilization varies for each 
graft copolymer. The final pH of the solution preferably ranges from about 
6.0 to about 9.5, and more preferably from about 6.5 to about 8.0. A 
buffer may be used to maintain a desired pH. The lowest neutralization 
level needed to render the polymer water soluble or dispersible depends on 
the type of polymer, the amount of water and the amount and type of the 
VOC in the hair care formulation. 
The use of more hydrophilic monomers in the acid-functional polymer segment 
may also enhance aqueous solubility of the hybrid-graft copolymer. Thus, 
the hydrophobicity/hydrophilicity of the ethylenically unsaturated 
monomers for the acid-functional polymer segment may be adjusted so that 
the hybrid-graft copolymer may be more or less dispersible or soluble in 
water or a liquid vehicle containing water at a particular pH. 
The hybrid-graft copolymer may be isolated from the aqueous dispersion in a 
powder form by techniques known in the art. The powder material may be 
obtained by any of the conventional methods such as spray drying, 
coagulation-filtration-drying, freeze drying, and the like. The dried 
powder may be re-dispersed in water, using an alkaline base, preferably a 
volatile amine or ammonia. 
Hair Care Formulations 
In another embodiment, the invention provides a hair care formulation 
containing: (I) a hybrid-graft copolymer, according to the invention, (II) 
a liquid vehicle and (III) at least one volatile organic compound. 
Generally, a hair care formulation of the invention contains: (I) from 
about 0.5 to about 20 wt % of a hybrid-graft copolymer on a dry basis, 
according to the invention, (II) from about 80 to about 99.5 wt % of a 
liquid vehicle and (III) up to about 80 wt %, of at least one volatile 
organic compound. The weight percentages are based on the total weight of 
the hair care formulation. In a preferred embodiment, the hybrid-graft 
copolymer on a dry basis is present in an amount of from about 0.5 to 
about 15 wt %, preferably about 3 to about 10 wt %, and more preferably 
about 4 to about 8 wt %, based on the total weight of the hair care 
formulation. 
A hair care formulation of the invention may be formulated as an aerosol 
hair spray, pump hair spray, styling gel, spray-on gel, or mousse. The 
hybrid-graft copolymer of the invention has been found to be exceptionally 
useful in such formulations, particularly in aerosol hair spray 
formulations and pump hair spray formulations. Hair care formulations of 
the invention exhibit, quite unexpectedly, superior hair form retention, 
such as curl retention, even at high humidity over commercial 
sulfopolyester-containing hair fixation products. The hair care 
formulations of the invention form a glassy and clear film and may be 
easily washed out from hair by shampooing. The films produced from the 
formulation exhibit low water absorption even at high humidity, and as a 
result the hair does not stick together and the hairstyle is not lost. 
Although the film-forming formulations of this invention are particularly 
useful as hair care formulations to groom hair, it is possible that the 
formulations, with or without modification, may be used in other types of 
personal care products. 
A liquid vehicle of a hair care formulation of the invention may be water 
or an aqueous system such as a mixture of water and at least one alcohol, 
ketone, or lower alkyl ester. If a mixture of water and at least one 
alcohol, ketone, or lower alkyl ester is used, the amount of volatile 
organic components which include the alcohol and/or ketone and/or lower 
alkyl ester and, in the case of an aerosol formulation, the propellant, 
should generally not exceed about 80 wt % of the liquid vehicle, and 
preferably should not exceed about 60 wt % of the liquid vehicle of the 
hair care formulation. Therefore, at least about 20 wt % and preferably 
about 40 wt % of the liquid vehicle is water. Furthermore, if an 
alcohol/water mixture is used, the alcohol is present preferably in an 
amount of about 10 to about 30 wt % based on the weight of the hair spray 
formulation. If a ketone/water mixture is used, the ketone is present 
preferably in an amount of about 10 to about 30 wt % based on the weight 
of the hair care formulation. If an alcohol/ketone/water mixture is used, 
the alcohol is present preferably in an amount of about 5 to about 25 wt % 
and the ketone is present preferably in an amount of about 5 to about 25 
wt % based on the weight of the hair care formulation. A liquid vehicle 
containing alcohol and/or ketone provides faster drying of the formulation 
on hair as compared to formulations prepared with only water. The alcohol 
may be an aliphatic straight or branched chain having 2 to 4 carbon atoms. 
Ethanol, propanol, and isopropyl alcohol are the preferred alcohols. The 
ketone may be an aliphatic straight chain ketone having 3 to 5 carbon 
atoms. Acetone and 2-butanone are the preferred ketones. A lower alkyl 
ester may also be used in a liquid vehicle. Preferably, the lower alkyl 
ester is an acetate ester, more preferably, methyl or ethyl acetate. 
Volatile organic compounds (VOCs) represent an optional third component of 
a hair care formulation of the invention. According to the invention, a 
hair care formulation may contain zero volatile organic compounds (VOCs) 
or up to a level of about 80 wt % VOC, based on the total weight of the 
formulation. Zero-VOC clear solutions may be prepared by partially 
neutralizing a latex composition of the invention as described above. 
Solutions or formulations having zero-VOC are suitable for zero-VOC pump, 
lotion, or gel formulations. Suitable VOCs for VOC-containing formulations 
include, for example, C.sub.1 -C.sub.12 straight or branched chain 
alcohols. Preferred alcohols include, for example, methanol, ethanol, 
propanol, isopropanol, butanol and t-butanol. In addition, other preferred 
VOCs include C.sub.1 -C.sub.12 straight or branched chain hydrocarbons 
such as methane, ethane, propane, isopropane, isobutane, pentane, 
isopentane, and butane are also suitable VOCs. Further preferred VOCs 
include ethers such as dimethyl ether, diethyl ether and dimethoxy 
methane. 
A hair spray formulation of the invention may also contain conventional 
hair care adjuvants known in the art in amounts which generally range up 
to about 20%, preferably from about 0.01% to about 10% by weight based on 
the total weight of the hair care formulation. Examples of adjuvants 
include, but are not limited to, plasticizers, coalescing agents, 
silicones, emollients, emulsifiers, lubricants and penetrants such as 
various lanolin compounds, protein hydrolysates, or other protein 
derivatives, thickness and viscosity modifiers, ethylene adducts and 
polyoxyethylene cholesterol, dyes, tints and other colorants, perfumes or 
fragrances, preservatives, antifoaming agents, chelating agents, polymers 
and resins, hair conditioners, pH adjusting agents, and the like. Some of 
these conventional adjuvants are discussed below. 
A plasticizer or a coalescing agent may be added to modify the film forming 
characteristics of a hair care formulation of the invention. Examples of 
plasticizers include, but are not limited to, glycols, adipic esters, 
phthalate esters, isobutyrate esters, terephthalate esters, epoxidized 
butyl esters or fatty acids, epoxidized vegetable oils, glycerine as well 
as polymeric plasticizers. More preferred plasticizers in accordance with 
the invention are, for example, di-2-ethylhexyladipate or dioctyladipate 
(DOA), di-2-ethylhexyl phthalate or dioctyl phthalate (DOP), 
di-2-ethylhexyl terephthalate (DOTP), dicyclohexyl phthalate, diisononyl 
adipate, diisononylphthalate, n-butyl benzyl phthalate, 1,3-butylene 
glycol/adipic acid polyester, dialkyl adipate, dialkyl phthalate 
derivatives where the alkyl group is a C.sub.1 -C.sub.12 alkyl group, or 
preferably a C.sub.7, C.sub.9 or C.sub.12 alkyl group, di-n-hexylazelate, 
diphenylphthalate, tricresol phosphate, benzyl benzoate, dibutyl 
phosphate, tributyl phosphate, tributoxyethyl phosphate, triphenyl 
phosphate, butyl acetyl ricinoleate, glycerol acetyl ricinoleate, dibutyl 
phthalate, diethyl phthalate, dioctyl phthalate, dimethoxyethyl phthalate, 
diisobutyl phthalate, diamyl phthalate, dibutyl glycolate, butyl stearate, 
triethyl citrate, tributyl citrate, tributyl acetyl citrate, 
2-hexyltriethylacetyl citrate, dibutyl tartarate, camphor, epoxidized 
butyl esters of linseed oil fatty acids, epoxidized linseed oil, 
epoxidized soya oil, propylene glycol adipate, 
2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), methyl abietate, 
cumyl acetate, dibutoxyethyl adipate, di-n-hexylazalate, 
glyceryl-tri-benzerate, tri-n-butylcitrate, dioctyl fumarate, triisonyl 
trimellitate, dioctyl isophthalate, butyl oleate, chlorinated paraffin, 
tricresolphosphate and dibutyl sebacate. Other plasticizers include: 
Dimethicone copolyol (Dow Corning 190) at 0.01-0.02%, PEG-6 
capric/caprylic glyceride (SOFTIGEN 767) at 0.5-2%, DIACETIN at 1-2%, 
LAURAMIDE DEA (MONAMID 716) at 0.1-1%, Phenyl trimethicone (ABIL AV 
20-1000) at 0.1-0.2%, propylene glycol at 1-5%, and dipropylene glycol at 
1 to 5%. Examples of coalescing solvents include, but are not limited to, 
acetone, methyl acetate, di- or tri-propylene glycol methyl ethers. 
A hair care formulation of the invention may contain other polymers or 
resins typically used in hair care formulations. Such polymers or resins 
may be present in an amount of up to about 50 wt %, based on the amount of 
total polymer present, preferably, in an amount of about 0.5 to about 20 
wt %. Such polymers or resins are homopolymers or copolymers that may be 
rendered dispersible or soluble in water or in a liquid vehicle containing 
water such as, for example, alcohol/water, or alcohol/ketone/water 
mixtures. Examples of these polymers or resins include, but are not 
limited to, the mono ethyl, isopropyl, or n-butyl esters of poly(methyl 
vinyl ether/maleic acid), poly-N-vinyl pyrrolidone, poly (N-vinyl 
pyrrolidone/vinyl acetate), poly (N-vinyl pyrrolidone/ethyl (PVP), 
copolymers of PVP and methyl methacrylate, methacrylate/methacrylic acid), 
poly (ethyl acrylate/acrylic acid/N-tert-butyl acrylamide), PVP/ethyl 
methacrylate/methacrylic acid terpolymer poly (vinyl acetate/crotonic 
acid), polyvinyl alcohol (PVA), copolymers of PVA and crotonic acid, 
copolymers of PVA and maleic anhydride, hydroxypropyl cellulose, 
hydroxypropyl methylcellulose, hydroxypropyl guar gum, sodium polystyrene 
sulfonate, octylacrylamide/acrylate/butylaminoethyl methacrylate 
copolymers, and mixtures of such polymers or resins. 
A hair care formulation of the invention may also include a conditioner in 
amounts up to about 10 wt %, preferably from about 0.01 wt % to about 10 
wt %, and more preferably from about 0.1 wt % to about 5 wt %, based on 
the total weight of the hair care formulation. Typical conditioners 
include, for example, a non-volatile silicon compound or a mixture of a 
low molecular weight polydimethylsiloxane fluid and a higher molecular 
weight polydimethylsiloxane gum. The non-volatile polydimethylsiloxane 
mixture may be added to a hair care formulation of the invention in an 
amount sufficient to provide improved combing and improved feel (softness) 
to the hair after shampooing. 
Another particularly suitable conditioning agent which may be included in a 
hair care formulation of the invention is a volatile hydrocarbon, such as 
a hydrocarbon including from about 10 to about 30 carbon atoms. Preferably 
such a hydrocarbon should have sufficient volatility to slowly volatilize 
from the hair after application of the hair spray formulation. The 
volatile hydrocarbons provide essentially the same benefits as the 
silicone conditioning agents. A volatile hydrocarbon may be used in the 
formulations of the invention either alone, in combination with another 
volatile hydrocarbon or silicone. The preferred volatile hydrocarbons are 
aliphatic hydrocarbons having from about 12 to about 24 carbon atoms and 
having a boiling point in the range of from about 100.degree. C. to about 
300.degree. C. Exemplary volatile hydrocarbons are depicted in general 
structural formula (I) below, wherein n is an integer ranging from 2 to 5, 
##STR1## 
Examples of commercially-available volatile hydrocarbons useful in a hair 
spray formulation are PERMETHYL 99A and PERMETHYL 101A products, which 
correspond to compounds of general structure where n is 2 and 3, 
respectively. The products are available from Permethyl Corporation, 
Frazer, Pa. 
Water-insoluble conditioning agents may also be incorporated into a hair 
spray formulation of the invention. These agents include, for example, 
polysiloxane polyether copolymers, polysiloxane polydimethyl 
dimethylammonium acetate copolymers, acetylated lanolin alcohols, lauryl 
dimethylamine oxide, a lanolin-derived extract of sterol ester, lanolin 
alcohol concentrate, an isopropyl ester of lanolin fatty acid, sulfur rich 
amino acid concentrate, isopropyl ester of lanolin fatty acid, oleyl 
alcohol, stearyl alcohol, stearamidopropyl dimethyl myristyl acetate, a 
polyol fatty acid, a fatty amido amine, guar hydroxypropyltrimethyl 
ammonium chloride, cetyl/stearyl alcohol, keratin protein derivatives, 
isostearamidopropyl dimethylamine, stearamidopropyl dimethylamine, an 
amino functional silicone, isopropyl ester of lanolic acid, ethoxylated 
(30) castor oil, acetylated lanolin alcohol, fatty alcohol fraction of 
lanolin, a mineral oil and lanolin alcohol mixture, high molecular weight 
ester of lanolin, N-vinylpyrrolidone/dimethylaminoethyl methacrylate 
copolymer, 5 mole % ethylene oxide adduct of soya sterol, 10 mole ethylene 
oxide adduct of soya sterol, stearic acid ester of ethoxylated (20 mole) 
methyl glucoside, sodium salt of polyhydroxycarboxylic acid, hydroxylated 
lanolin, cocamidopropyl dimethylamine lactate, cocamidopropyl 
dimethylamine propionate, cocamidopropyl morpholine lactate, 
isostearamidopropyl dimethylamine lactate, isostearamidopropyl morpholine 
lactate, oleamidopropyl dimethylamine lactate, linoleamidopropyl 
dimethylamine lactate, a stearamidopropyl dimethylamine lactate, ethylene 
glycol monostearate and propylene glycol mixture, stearamidopropyl 
dimethylamine lactate, acetamide monoethanolamine, lactamide 
monoethanolamine, stearamide monoethanolamine, behenalkonium chloride, a 
behenyl trimethyl ammonium methosulfate and cetearyl alcohol mixture, 
cetearyl alcohol, tallow imidazaolinum methosulfate, mixed ethoxylated and 
propoxylated long chain alcohols, stearamidopropyl dimethylamine lactate, 
oleamine oxide, stearamide oxide, soya ethyldiammonium ethosulfate, 
ricinolamidopropyl ethyldimonium ethosulfate, 
N-(3-isostearamidopropyl)-N,N-dimethyl amino glycolate, 
N-(3-isostearamidopropyl)-N,N-dimethyl amino gluconate, hydrolyzed animal 
keratin, ethyl hydrolyzed animal keratin, stearamidoethyl diethylamine, 
cocamidopropyl dimethylamine, lauramidopropyl dimethylamine, 
oleamidopropyl dimethylamine, palmitamidopropyl dimethylamine, 
stearamidopropyl dimethylamine lactate, avocado oil, sweet almond oil, 
grape seed oil, jojoba oil, apricot kernel oil, sesame oil, safflower oil, 
wheat germ oil, cocamidoamine lactate, ricinoleamido amine lactate, 
stearamido amine lactate, stearamido morpholine lactate, isostearamido 
amine lactate, isostearamido morpholine lactate, wheat germamido 
dimethylamine lactate, wheat germamidopropyl dimethylamine oxide, disodium 
isostearamido monoethanolamine sulfo succinate, disodium oleamide PEG-2 
sulfo succinate, disodium oleamide monoethanolamine sulfo succinate, 
disodium ricinoleyl monoethanolamine sulfo succinate, disodium wheat 
germamido monoethanolamine sulfo succinate, disodium wheat germamido PEG-2 
sulfo succinate, stearamido amine, stearamido morpholine, isostearamido 
amine, isostearamido morpholine, polyethylene glycol (400 moles) and 
distearates, synthetic calcium silicate, isostearic alkanolamide, ethyl 
ester of hydrolyzed animal protein, blend of cetyl and stearyl alcohol 
with ethoxylated cetyl or stearyl alcohol, amido amines, polyamido amine, 
propoxylated (1-20 moles) lanolin alcohol, isostearamide diethanolamine, 
and hydrolyzed collagen protein. 
A hair care formulation of the invention may also contain other adjuvants 
to render such formulations more acceptable for use in hair care. For 
example, emulsifiers include, but are not limited to, cetyl trimethyl 
ammonium chloride, stearyl dimethyl benzyl ammonium chloride, 
partially-hydrogenated tallow, and dimethylammonium chloride. 
Preservatives such as benzyl alcohol, methyl paraben, propyl paraben and 
imidazolidinylurea may also be used. Thickeners and viscosity modifiers 
which may be used include, diethanolamide of a long chain fatty acid, and 
fatty alcohols (for example, cetearyl alcohol), sodium chloride, sodium 
sulfate, and ethyl alcohol. The pH of a hair care formulation may be 
adjusted using pH adjusting agents such as citric acid, succinic acid, 
sodium hydroxide, and triethanolamine. Colorants for use in hair care 
formulation are, for example, any of the Food, Drug and Cosmetics (FD&C) 
or Drug and Cosmetics (D&C) dyes. Hair oxidizing (bleaching) agents such 
as hydrogen peroxide, perborate salts, persulfate salts, and percarbonate 
salts may also be used. Hair reducing agents such as thioglycolates, 
represents another type of adjuvant. Perfume oils are also commonly found 
in hair care products and may be used here. Chelating agents, such as 
ethylenediamine tetraacetic acid (EDTA), may also be used. These adjuvants 
are generally used individually at levels of up to about 20%, preferably 
from about 0.001% to about 20%, more preferably from about 0.01% to about 
5% by weight of the total hair care formulation. 
Modes of delivery of the above-described hybrid-graft copolymer for aqueous 
styling aid formulations include, for example, aerosol sprayers, all forms 
of bag-in-can devices, in situ carbon dioxide generator systems, 
compressors, and the like. When the hair care formulation is an aerosol 
hair spray formulation, the formulation also contains a propellant. The 
propellant may be any liquefiable gas conventionally used for aerosols. 
Examples of materials that are suitable for use as propellants are, for 
example, trichlorofluoromethane, chlorodifluoromethane, 
1,1-difluoroethane, dichlorotetrafluoroethane, monochlorodifluoromethane, 
trichlorotrifluoroethane, dimethyl ether, C.sub.1 -C.sub.4 hydrocarbons 
such as methane, ethane, propane, n-butane, and isobutane, and mixtures 
thereof Water-soluble gases such as, for example, dimethyl ether, carbon 
dioxide, and/or nitrous oxide also may be used to obtain aerosols having 
reduced flammability. Other insoluble, compressed gases such as, for 
example, nitrogen, helium, and fully-fluorinated oxetanes and oxepanes 
also are useful for the aerosol delivery of formulations of the invention. 
Preferably, the propellant is either a C.sub.1 -C.sub.4 aliphatic 
hydrocarbon, 1,1-difluoroethane, or dimethyl ether. A preferred aliphatic 
hydrocarbon propellant is a mixture containing about 80 to about 85 wt % 
isobutane and about 15 to about 20 wt % propane. The amount of the 
propellant is governed by normal factors well-known in the aerosol art. 
The level of propellant is generally from about 3 wt % to about 60 wt %, 
preferably from about 5 to about 45 wt %, of the aerosol hair spray 
formulation. In the case where a C.sub.1 -C.sub.4 aliphatic hydrocarbon is 
used as the propellant, generally about 3 to about 10 wt % is employed. In 
the cases where dimethyl ether or 1,1-difluoroethane are used as the 
propellant, generally, about 20 to about 40 wt % is employed. If a 
propellant such as dimethyl ether utilizes a vapor pressure suppressant 
(for example, trichloroethane or dichloromethane), for weight percentage 
calculations, the amount of suppressant is included as part of the 
propellant. 
The following examples are given to illustrate the invention. It should be 
understood, however, that the invention is not to be limited to the 
specific conditions or details set forth in these examples. 
EXAMPLES 
Example 1 
Preparation of a hybrid-graft emulsion copolymer of a sulfopolyester 
grafted with an acid-functional polymer segment consisting of methacrylic 
acid (MAA), t-butylacrylamide (t-BAM), methyl methacrylate (MMA), and 
butyl acrylate (BA) 
Into a three-neck reaction kettle were placed a sulfopolyester (100 g, 
EASTMAN AQ.RTM.-48 polyester available from Eastman Chemical Company) and 
water (240 g). The mixture was stirred and purged with nitrogen for thirty 
minutes while being heated to 65.degree. C. Next, 1% FeSO.sub.4 --7H.sub.2 
O (0.5 g) in water (5.0 g), ethylenediaminetetraacetic acid (EDTA) (0.5 g) 
in water (5.0 g), 90% t-butyl hydroperoxide (0.1 g) in water (5.0 g), and 
isoascorbic acid (0.1 g) in water (5.0 g) were introduced into the 
reaction kettle. Next, a mixture of methacrylic acid (40 g), t-butyl 
acrylamide (20 g), butyl acrylate (30 g), methylmethacrylate (10 g) and 2 
ethylhexyl-3 mercaptopropionate (1.0 g) was charged into the reaction 
kettle along with t-butyl hydroperoxide (0.3 g) in water (50 g) and 
isoascorbic acid (0.3 g) in water (50 g) over a 60 minute period. The 
reaction was allowed to stir for an additional 90 minutes with additional 
t-butyl hydroperoxide (0.2 g) in water (5.0 g) and isoascorbic acid (0.2 
g) in water (5.0 g) to produce the desired hybrid-graft emulsion 
copolymer. 
The hybrid-graft emulsion copolymer had weight average molecular weight 
(Mw) of 78,000 and a Tg of 45.degree. C. Less than 50 ppm residual 
monomers were present. 
Example 2 
Neutralization of Hybrid-Graft Emulsion Copolymers 
Hybrid-graft emulsion copolymers A, B, C, D having the compositions shown 
in Table I were prepared in accordance with the procedure of Example 1. 
Seventy-five percent of the acid groups of each of the resulting resins 
were neutralized with 2-methyl-2-amino-propanol (AMP). The pH of each 
copolymer, after neutralization, is shown in Table I. 
TABLE I 
__________________________________________________________________________ 
Hybrid- 
Graft Eastman Methyl n-Butyl Methacrylic N-tert-Butyl Ethyl n-Butyl pH 
Polymer AQ 48 
(g) Methacrylate 
(g) Acrylate (g) 
Acid (g) Acrylamid 
e (g) Methacrylate 
(g) Methacrylate 
(g) neutralization 
__________________________________________________________________________ 
A 50 5 21 16 8 7.5 
B 50 21 16 5 8 7.7 
C 50 19 16 7 8 7.4 
D 50 16 18 9 7 7.5 
__________________________________________________________________________ 
Example 3 
Preparation of a Hybrid Graft Emulsion Copolymer of a Sulfopolyester and 
Two Acid-functional Polymer Segments by a Sequential Addition of Two 
Monomer Mixtures 
Into a three-neck reaction kettle were placed a sulfopolyester (50 g, 
EASTMAN AQ.RTM.-48 polyester available from Eastman Chemical Company), 
sodium lauryl sulfate (1.0 g), and water (240 g). The mixture was then 
stirred and purged with nitrogen for thirty minutes while being heated to 
70.degree. C. Next, 1% FeSO.sub.4 --7H.sub.2 O (0.2 g) in water (2.0 g ), 
EDTA (0.2 g) in water (2.0 g), 90% t-butyl hydroperoxide (t-BHP) (0.1 g) 
in water (3.0 g), and isoascorbic acid (0.1 g) in water (3.0 g) were 
introduced into the reaction kettle. A mixture of methacrylic acid (17.0 
g), t-butyl acrylamide (8.0 g), methyl methacrylate (17.0 g), butyl 
acrylate (8.0 g), and 2-ethylhexyl-3-mercaptopropionate (0.8 g) was then 
charged into the reaction kettle along with t-butyl hydroperoxide (0.1 g) 
in water (15 g) and isoascorbic acid (0.1 g) in water (15.0 g) over a 40 
minute period. The reaction mixture was allowed to stir an additional 30 
minutes followed by charging with a mixture of methacrylic acid (34.0 g), 
t-butyl acrylamide (16.0 g), butyl acrylate (50.0 g) and 
2-ethylhexyl-3-mercaptopropionate (1.5 g) along with 90% t-BHP (0.3 g) in 
water (15 g) and isoascorbic acid (0.3 g) in water (15.0 g) over an 80 
minute period with additional 90% t-BHP (0.1 g) in water (2.0 g) and 
isoascorbic acid (0.1 g) in water (2.0 g) to produce the desired 
hybrid-graft copolymer. 
Example 4 
Evaluation of Hair Care Formulation: 
(1) Preparation of 55% Volatile Organic Compound (VOC) aerosol: 
After 75% neutralization with AMP following the procedure of Example 2, 
each hybrid-graft emulsion copolymer of Examples 1 and 2 was aerosolized 
by the following procedure to give a 55% VOC formulation: 
Into a 124 mL vessel, equipped with valve and cup, were placed 21.0 g of a 
neutralized hybrid-graft emulsion copolymer (7.0 g solid polymer and 14 g 
water), 20.0 g of Ethanol SDA 40C (anhydrous), 23.3 g of water, and 0.7 g 
of hexamethyldisiloxane (HMS silicone). After flushing out the air with 
nitrogen, the valve and cup of the vessel are quickly crimped. A 
propellant, 35.0 g of dimethyl ether, was then added through a pressurized 
burette. 
(2) Curl Retention: 
Eight-inch Remi Blue String European brown hair, available from De Meo 
Brothers (New York), was divided into two gram swatches, secured at one 
end, and washed in 10% solution of sodium laureth-2 sulfate (25% active). 
After rinsing for one minute, the swatches were combed, trimmed to 6 inch 
lengths, and dried at 120.degree. F. 
The swatches were curled after rinsing by rolling it on a 1/2 inch OD 
Teflon mandrel, being careful to keep tension as consistent as possible. A 
plastic clip is used to secure the hair. The curled swatches were dried in 
an oven for 1 hour at 120.degree. F. After cooling at ambient temperatures 
(72.degree. F. or less and 50% relative humidity or less), the tresses 
were carefully unpinned and the curlers removed. 
The dry curls were suspended on a hook and an initial curl height reading 
(L.sub.o) was made. The curls were sprayed with a controlled amount of 
hair spray. For aerosols the curl was suspended from a slowly rotating 
shaft (20-22 rpm) and sprayed for 4 seconds from a distance of 12 inches. 
After spraying, the curls were hung an hooks and suspended in a cabinet 
maintained at 72.degree. F. and 90% relative humidity. The length of the 
curls were measured at the designated time span. 
The percentage curl-retention was calculated according with the following 
formula: 
##EQU1## 
where L=length of bunch of hair when extended (base value), L.sub.o 
=length of curl at the beginning of the test, and L.sub.t =length of curl 
after t minutes. 
FIG. 1 depicts curl retention at 72.degree. F. and 90% relative humidity 
(RH) as a function of time for a composition prepared in accordance with 
Example 1 of the present application, in comparison with three commercial 
materials. 
FIG. 2 and Table II depicts curl retention at 72.degree. F. and 90% 
relative humidity for Samples A, B, C and D in accordance with the 
invention at 55% VOC in comparison with commercial products at 80% VOC. 
TABLE II 
______________________________________ 
% Curl Retention 
Time, Min. 0 10 15 60 120 
______________________________________ 
White Rain, 80% VOC.sup.1 
100% 90 70 54 40 
Salon Selective, 80% VOC.sup.2 100% 89 81 71 62 
AC, VO5, 80% VOC.sup.3 100% 86 76 73 72 
Sample A, 55% VOC 100% 96 95 88 86 
Sample B, 55% VOC 100% 95 87 85 85 
Sample C, 55% VOC 100% 96 96 96 96 
Sample D, 55% VOC 100% 91 84 77 77 
______________________________________ 
.sup.1 Product of The Gillette Company, Boston, MA. 
.sup.2 Product of Helene Curtis, Chicago, IL. 
.sup.3 Product of AlbertoCulver Company, Melrose Park, IL. 
Numerous modifications and variations of the invention are possible in 
light of the above teachings. It is therefore to be understood that within 
the scope of the appended claims, the invention may be practiced otherwise 
than as specifically described herein.