Clear aerosol hair spray formulations containing a linear sulfopolyester in a hydroalcoholic liquid vehicle

This invention relates to an aerosol hair spray formulation containing 0.5 to 15 weight percent of a water-dispersible or water-dissipatible, linear sulfopolyester having a Tg of 40.degree. C. to 50.degree. C. and an inherent viscosity of 0.24 to 0.60 dl/g which contains repeat units from 20 to 26 mole percent dimethyl-5-sodiosulfoisophthalate and 74 to 80 mole percent isophthalic acid, based on 100 mole percent dicarboxylic acid; 10 to 30 mole percent 1,4-cyclohexanedimethanol and 70 to 90 mole percent diethylene glycol, based on 100 mole percent diol; and up to 60 weight percent of an alcohol. The aerosol hair spray formulations are clear, have improved dry time and curl retention, and exhibit less than 20 NTU's, which is a measure of turbidity, even at high concentrations of alcohol.

FIELD OF THE INVENTION 
This invention relates to an aerosol hair spray formulation containing 0.5 
to 15 weight percent of a water-dispersible or water-dissipatible, linear 
sulfopolyester having a Tg of 40.degree. C. to 50.degree. C. and an 
inherent viscosity of 0.24 to 0.60 dl/g which contains repeat units from 
20 to 26 mole percent dimethyl-5-sodiosulfoisophthalate and 74 to 80 mole 
percent isophthalic acid, based on 100 mole percent dicarboxylic acid; 10 
to 30 mole percent 1,4-cyclohexanedimethanol and 70 to 90 mole percent 
diethylene glycol, based on 100 mole percent diol; and up to 60 weight 
percent of an alcohol. The aerosol hair spray formulations are clear, have 
improved dry time and curl retention, and exhibit less than 20 NTU's, 
which is a measure of turbidity, even at high concentrations of alcohol. 
BACKGROUND OF THE INVENTION 
Hair sprays provide human hair with a particular shape or configuration and 
function by applying a thin film of a resin or gum onto the hair to adhere 
adjacent hairs together so that they retain the particular shape or 
configuration at the time of application. 
U.S. Pat. No. 5,164,177 discloses a hair spray formulation containing 2-40% 
of a linear polymer including at least one vinyl or acrylate monomer, a 
water-soluble electrolyte, 30-90% water, and 0-30% alcohol. The 
water-soluble electrolyte is added to lower the viscosity of the 
composition to achieve a higher percentage of polymer in the composition. 
Such formulations, however, have poor humidity resistance, hold and curl 
retention. 
U.S. Pat. No. 4,300,580 discloses hair spray formulations containing a 
water-dispersible or water-dissipatible linear sulfo-polyester fixative in 
a water/alcohol mixture. The diol component of the sulfopolyester contains 
at least 20 mole percent 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. For example, prolonged 
washing is required to completely remove the water-dispersible, linear 
polyester fixative to obtain hair with no tacky or sticky feel. U.S. Pat. 
No. 4,300,580 suggests adding other substances such as poly(alkylene 
ether) to increase the hardness and reduce the tackiness of the 
formulations. However, when such formulations containing a combination of 
the poly(alkylene glycol) and sulfopolyester are applied to hair and 
allowed to dry, the fixative causes a matting of the hair. Such matting 
hinders combing, brushing and styling of hair. 
U.S. Pat. No. 5,266,303 discloses hair spray formulations containing a 
water-dispersible sulfopolyester having a glass transition temperature of 
36.degree. C. to 40.degree. C., a water-soluble polyvinyl lactam polymer, 
and water. The performance characteristics of such formulations are good. 
However, the drying time is too long, and the addition of alcohol, which 
would improve dry time, causes the formulations to become cloudy. Thus, 
the use of alcohol is not an option for improving the dry time of such 
formulations. 
U.S. Pat. No. 5,158,762, discloses hair spray compositions containing a 
blend of a sulfopolyester and a water-soluble polymer in water. The 
sulfopolyester contains at least 40 mole percent 
1,4-cyclohexanedimethanol. The performance characteristics of such 
formulations are good, however, the drying time is too long, and the 
addition of alcohol, which would improve dry time, causes the formulations 
to become cloudy. Thus, the use of alcohol is not an option for improving 
the dry time of such formulations. 
U.S. Pat. No. 5,266,308, discloses aqueous hair spray compositions which 
contain a sulfopolyester, a water-soluble polymeric resin and a 
homopolymer of polyvinylpyrrolidone. The performance characteristics of 
such formulations are good, however, the drying time is too long, and the 
addition of alcohol, which would improve dry time, causes the formulations 
to become cloudy. Thus, the use of alcohol is not an option for improving 
the dry time of such formulations. 
In contrast, the present inventors have unexpectedly determined that 
aerosol hair spray formulations which are clear and provide properties 
considered desirable for hair preparation such as fine spray patterns, 
fast drying times, prolonged curl retention under humid conditions, good 
holding power and resistance to build-up may be prepared with as much as 
60 weight percent alcohol to facilitate rapid drying on the hair. The hair 
spray formulations of the present invention are clear and exhibit less 
than 20 NTU's which is a measure of turbidity. In the cosmetic field 
greater than 20 NTU's is characteristic of a cloudy mixture that is 
visible to the eye. 
SUMMARY OF THE INVENTION 
Accordingly, it is one object of the present invention to provide a clear 
aerosol hair spray formulation. 
It is another object of the invention to provide a aerosol hair spray 
formulation which is not tacky, has a fast drying rate, acceptable body, 
consistency and exhibits improved curl retention. 
Another object of the invention is to provide a aerosol hair spray 
formulation which is clear and has excellent storage stability and which 
does not clog the exit port of a aerosol container. 
These and other objects are accomplished herein by an aerosol hair spray 
formulation having improved dry time and curl retention and exhibiting 
less than 20 NTU's as a measure of clarity which comprises: 
(1) a sulfopolyester having a Tg of 40.degree. C. to 50.degree. C. and an 
inherent viscosity of 0.24 to 0.60 dl/g which consists essentially of 
repeat units from 
(a) a dicarboxylic acid component consisting essentially of 20 to 26 mole 
percent dimethyl-5-sodiosulfoisophthalate and 74 to 80 mole percent 
isophthalic acid, based on 100 mole percent dicarboxylic acid; 
(b) a diol component consisting essentially of 10 to 30 mole percent 
1,4-cyclohexanedimethanol and 70 to 90 mole percent diethylene glycol, 
based on 100 mole percent diol; 
(2) a water/alcohol liquid vehicle; and 
(3) 3 to 60 weight percent based on the weight of components (1), (2), and 
(3) of a propellant selected from the group consisting of a C.sub.1 
-C.sub.4 aliphatic hydrocarbon, dimethyl ether, and mixtures thereof, 
provided the sulfopolyester, component (1), is present in an amount of 0.5 
to 15 weight percent, based on the total weight of the aerosol hair spray 
formulation.

DESCRIPTION OF THE INVENTION 
The aerosol hair sprays of the present invention exhibit less than 20 NTU's 
which is a measure of the turbidity of a mixture. In the cosmetic field 
greater than 20 NTU's is characteristic of a cloudy mixture that is 
visible to the eye. The clear aerosol hair spray formulations of this 
invention contain a sulfopolyester, component (1), in an amount of 0.5 to 
15 weight percent, preferably 3 to 10 weight percent, and more preferably 
5 to 8 weight percent, based on the total weight of the aerosol hair spray 
formulation. 
The sulfopolyester, component (1), has a glass transition temperature of 
40.degree. C. to 50.degree. C. and contains repeat units from a 
dicarboxylic acid, a diol and a difunctional sulfomonomer. The 
dicarboxylic acid component of the sulfopolyester contains 20 to 26 mole 
percent of dimethyl-5-sodiosulfoisophthalate and 74 to 80 mole percent 
isophthalic acid, based on 100 mole percent dicarboxylic acid. The diol 
component of the sulfopolyester contains 10 to 30 mole percent 
1,4-cyclohexanedimethanol and 70 to 90 mole percent diethylene glycol, 
based on 100 mole percent diol. The sulfopolyester has an inherent 
viscosity (I.V.) of 0.24 to 0.60 dl/g. 
Component (2) of the aerosol hair spray is a liquid vehicle. The liquid 
vehicle may be water or a water/alcohol mixture. Distilled or deionized 
water are the preferred sources of water since tap water generally 
contains ions which may precipitate the sulfopolyester, component (1). If 
a water/alcohol mixture is used, the amount of volatile organic components 
which include the alcohol and propellant cannot exceed 60% of the aerosol 
hair spray formulation. Therefore, at least 40% of the formulation is 
water and the remaining 60% is alcohol and propellant. Preferably a 
water/alcohol mixture is used wherein the alcohol is present in an amount 
of 20 to 30 weight percent based on the weight of the aerosol hair spray 
formulation. The alcohol provides faster drying of the formulation on hair 
as compared to formulations prepared with only water as the liquid 
vehicle. The alcohol is an aliphatic straight or branched chain monohydric 
alcohol having 2 to 4 carbon atoms. Isopropanol and ethanol are the 
preferred alcohols. 
The aerosol hair spray formulations of the present invention require a 
propellant, component (3). The propellant can be any liquefiable gas 
conventionally used for aerosol containers. Examples of materials that are 
suitable for use as propellants are trichlorofluoromethane, 
dichlorodifluoromethane, dichlorotetrafluoroethane, 
monochlorodifluoromethane, trichlorotrifluoroethane, dimethyl ether, 
methane, ethane, propane, n-butane and isobutane, used singly, or admixed. 
Water-soluble gases such as dimethyl ether, carbon dioxide, and/or nitrous 
oxide also can be used to obtain aerosols having reduced flammability. 
Other insoluble, compressed gases such as nitrogen, helium and 
fully-fluorinated oxetanes and oxepanes also are useful to deliver the 
formulations from aerosol containers. Other means of delivery of the 
above-described aqueous styling aid formulations include, aerosol 
sprayers, all forms of bag-in-can devices, in situ carbon dioxide 
(CO.sub.2) generator systems, compressors, and the like. 
Preferably, the propellant is either a C.sub.1 -C.sub.4 aliphatic 
hydrocarbon or dimethyl ether. A preferred aliphatic hydrocarbon 
propellant is a mixture containing about 83 percent isobutane and about 17 
percent 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% to about 60%, preferably from 5% to 45%, 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 weight percent, preferably 4 to 7 weight percent, is employed. In 
the case where dimethyl ether is used as the propellant, generally, about 
20 to about 40 weight percent, preferably, 30 to 35 weight percent, is 
employed. If a propellant such as dimethyl ether utilizes a vapor pressure 
suppressant (e.g., trichloroethane or dichloromethane), for weight 
percentage calculations, the amount of suppressant is included as part of 
the propellant. 
The aerosol hair spray formulations may optionally contain a water-soluble 
polymer or resin, component (4). The water-soluble polymer must be soluble 
or dispersible in liquid vehicle, component (2). The term "water-soluble" 
refers to any material that has solubility of at least 1 gram per 100 
grams of water, i.e. 1%, preferably a solubility of at least 5% by weight. 
Conversely, the term "water-insoluble" refers to substances that are 
insoluble at a level of less than 1 gram per 100 grams of water, i.e., 
less than 1% by weight. Solubility or dispersibility is determined at 
ambient conditions (e.g., a temperature of about 25.degree. C. and 
atmospheric pressure). 
Water-soluble polymers useful in the formulations of the present invention 
are homopolymers or copolymers that can be rendered dispersible or soluble 
in aqueous or water/alcohol mixtures. The water-soluble polymer is a 
synthetic, linear, homopolymer or random copolymer including at least one, 
and preferably two or more, vinyl or acrylate monomers of the following 
group: 
##STR1## 
In the above formulas, R is a C.sub.1 to C.sub.10 alkyl and R' is a C.sub.1 
to C.sub.10 alkylene. Preferred monomers for use in the water-soluble 
polymers are acrylic acid, vinyl pyrrolidone, vinyl acetate, crotonic 
acid, methacrylic acid or a combination thereof. Examples of preferred 
copolymers are the mono ethyl, isopropyl or n-butyl esters of poly(methyl 
vinyl ether/maleic acid); poly(vinyl pyrrolidone/vinyl acetate, poly(vinyl 
pyrrolidone/ethyl methacrylate/methacrylic acid), poly(ethyl 
acrylate/acrylic acid/N-t-butyl acrylamide), and poly(vinyl 
acetate/crotonic acid). 
Other suitable classes of polymers include anionic, nonionic, amphoteric 
and cationic polymers. Specific polymers include polyvinylpyrrolidone 
(PVP), copolymers of PVP and methylmethacrylate, copolymers of PVP and 
vinyl acetate (VA), polyvinyl alcohol (PVA), copolymers of PVA and 
crotonic acid, copolymers of PVA and maleic anhydride, hydroxypropyl 
cellulose, hydroxypropyl guar gum, sodium polystyrene sulfonate, 
PVP/ethylmethacrylate/methacrylic acid terpolymer and 
octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers, and 
mixtures. A preferred vinyl polymer or copolymer contains at least 50 mole 
percent of the residues of n-vinyl lactam monomer such as 
N-vinylpyrrolidinone. 
With certain of the acidic water-soluble polymers, it may be necessary to 
neutralize some acidic groups to promote solubility/dispersibility, e.g., 
PVA/crotonic acid. Neutralization and increased solubilization are 
accomplished with one or more inorganic bases such as sodium hydroxide, 
potassium hydroxide, ammonium hydroxide and/or ammonium carbonate. Among 
stable organic bases are the water soluble bases such as monoethanolamine 
(MEA), diethanolamine (DEA), triethanolamine (TEA), 
2-methyl-2-amino-1-propanol (AMP), monoamino glycols, and the like, which 
help solubilize the polymer in water solutions. The level of 
neutralization required for solubilization varies for each polymer. All of 
the above-described acidic polymers become soluble in water and 
hydroalcoholic solutions at 100% neutralization, and all described levels 
of water/alcohol/propellant solutions. The pH of these solutions usually 
ranges from 9 to 12. The lowest neutralization level needed to render the 
polymer water soluble or dispersible depends on the kind of polymer, and 
the amount of alcohol, water and propellant. For instance, for poly(methyl 
vinyl ether/maleic acid) in water the lowest neutralization level is about 
40% with sodium hydroxide and AMP; for poly(ethyl acrylate/acrylic 
acid/N-t-butyl acrylamide) the lowest neutralization level is about 75% 
with AMP and 65% with sodium hydroxide. At these neutralization levels, 
the pH of the solutions range from about 5 to about 7. A slightly acidic 
or neutral pH such as this is preferred, however, the pH of the 
formulations of the present invention can vary from about 4 to about 9. 
Saponification of the ester linkages may occur under alkaline conditions. 
The water-soluble polymers may be prepared according to known procedures 
wherein, for example, a N-vinyl lactam is polymerized, optionally in the 
presence of one or more other vinyl monomers such as those described 
above. The N-vinylpyrrolidinone/vinyl acetate copolymers supplied by BASF 
under the trademark LUVISKOL VA are typical of the water-soluble polymers 
which may be used in the aerosol hair spray formulations of the present 
invention. The preferred water-soluble polymers comprise homopolymers of 
N-vinyl-2-pyrrolidinone and copolymers of N-vinyl-2-pyrrolidinone and up 
to 50 mole percent vinyl acetate having weight average molecular weights 
in the range of about 1000 to 100,000. The water-soluble polymers are used 
at a level of from about 0.5% to about 10% by weight, generally about 1% 
to about 5% by weight, and preferably from 2% to 4% by weight of the total 
formulation. The weight average molecular weight of the water-soluble 
polymers is not critical but is generally in the range from about 1,000 to 
2,000,000. 
The aerosol formulations also can contain a variety of other nonessential, 
optional components suitable for rendering such formulations more 
acceptable. Such conventional optional ingredients are well known to those 
skilled in the art, e.g., other emulsifiers such as anionics (e.g., sodium 
alkyl sulfate); preservatives such as benzyl alcohol, methyl paraben, 
propyl paraben and imidazolidinylurea; cationic emulsifiers/conditioners 
such as cetyl trimethyl ammonium chloride, stearyl-dimethyl benzyl 
ammonium chloride, and di(partially-hydrogenated tallow) dimethylammonium 
chloride; thickeners and viscosity modifiers such as diethanolamide of a 
long chain fatty acid, fatty alcohols (i.e., cetearyl alcohol), sodium 
chloride, sodium sulfate, and ethyl alcohol; pH adjusting agents such as 
citric acid, succinic acid, sodium hydroxide and triethanolamine; coloring 
agents such as any of the FD&C or D&C dyes; hair oxidizing (bleaching) 
agents such as hydrogen peroxide, perborate salts and persulfate salts; 
hair reducing agents such as thioglycolates; perfume oils; chelating 
agents such as ethylenediaminetetraacetic acid; and among many other 
agents, polymer plasticizing agents such as glycerin and propylene glycol. 
These optional materials are generally used individually at a level of 
from about 0.001% to about 19%, preferably from 0.01% to 5% by weight of 
the total formulation. It is important to note that the use of cationic 
emulsifiers in amounts of greater than 1% may precipitate the 
sulfopolyester, component (1). 
The aerosol hair-spray formulation of the present invention may also 
include from about 0.01% to 10%, preferably, 0.1% to 2% by weight of a 
non-volatile silicone compound or other conditioning agent(s), preferably 
a water-insoluble, emulsifiable conditioning agent. The preferred 
non-volatile silicone compound is a polydimethylsiloxane compound, such as 
a mixture of a low molecular weight polydimethylsiloxane fluid and a 
higher molecular weight polydimethylsiloxane gum. The non-volatile 
polydimethylsiloxane compound is added to the formulation of the present 
invention in an amount sufficient to provide improved combing and improved 
feel (softness) to the hair after shampooing. 
Another particularly suitable conditioning agent that can be included in 
the formulation of the present invention is a volatile hydrocarbon, such 
as a hydrocarbon including from about 10 to about 30 carbon atoms, that 
has sufficient volatility to slowly volatilize from the hair after 
application of the aerosol hair spray formulation. The volatile 
hydrocarbons provide essentially the same benefits as the silicone 
conditioning agents. 
The preferred volatile hydrocarbon compound is an aliphatic hydrocarbon 
including 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), wherein n ranges from 2 to 5, 
##STR2## 
Examples of volatile hydrocarbons useful in the aerosol hair spray 
formulation of the present invention are the commercially-available 
compounds PERMETHYL 99A and PERMETHYL 101A, corresponding to compounds of 
general structure (I) wherein n is 2 and 3, respectively, available from 
Permethyl Corporation, Frazer, Pa. A volatile hydrocarbon compound is 
useful in the formulation of the present invention either alone, in 
combination with another volatile hydrocarbon, or in combination with a 
volatile silicone. 
Examples of other suitable water-insoluble conditioning agents that can be 
incorporated into the hair spray formulations of the present invention 
include the following: polysiloxane polyether copolymers; polysiloxane 
polydimethyl dimethylammonium acetate copolymers; acetylated lanolin 
alcohols; lauryl dimethylamine oxide; a lanolin-derived extract of sterol 
on sterol esters; lanolin alcohol concentrate; an isopropyl ester of 
lanolin fatty acids; sulfur rich amino acid concentrates; isopropyl ester 
of lanolin fatty acids; oleyl alcohol; stearyl alcohol; stearamidopropyl 
dimethyl myristyl acetate; a polyol fatty acid; a fatty amido amine; guar 
hydroxypropyltrimonium chloride; cetyl/stearyl alcohol; keratin protein 
derivatives; isostearamidopropyl dimethylamine; stearamidopropyl 
dimethylamine; an aminofunctional silicone; isopropyl ester of lanolic 
acids, ethoxylated (30) castor Oil; acetylated lanolin alcohol, fatty 
alcohol fraction of lanolin, a mineral oil and lanolin alcohol mixture; 
high molecular weight esters of lanolin; 
vinylpyrrolidone/dimethylaminoethylmethacrylate 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; 
stearamidopropyl dimethylamine lactate, ethylene glycol monostearate and 
propylene glycol mixture; stearamidopropyl dimethylamine lactate; 
acetamide MEA; lactamide MEA; stearamide MEA; behenalkonium chloride; 
behenyl trimethyl ammonium methosulfate and cetearyl alcohol mixture; 
cetearyl alcohol; tallow imidazolinum methoxulfate, stearyl trimonium 
methosulfate; mixed ethoxylated and propoxylated long chain alcohols; 
stearamidopropyl dimethylamine lactate, polonitomine oxide; oleamine 
oxide, stearamide oxide; soya ethyldimonium 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 aminal 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; hydrid 
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 MEA sulfosuccinate; disodium oleamide PEG-2 
sulfosuccinate; disodium oleamide MEA sulfosuccinate; disodium ricinoleyl 
MEA sulfosuccinate; disodium wheat germamido MEA sulfosuccinate; disodium 
wheat germamido PEG-2 sulfosuccinate; stearamido amine; stearamido 
morpholine; isostearamido amine; isostearamido morpholine; polyethylene 
glycol (400) mono and distearates; synthetic calcium silicate; isostearic 
alkanolamide; ethyl esters of hydrolyzed animal protein; blend of cetyl 
and stearyl alcohols with ethoxylated cetyl or stearyl alcohols; amido 
amines; polyamido amines; propoxylated (1-20 moles) lanolin alcohols; 
isostearamide DEA; and hydrolyzed collagen protein. Water-insoluble 
cationic conditioning agents in amounts of less than about 1% may also be 
used. The use of water-insoluble cationic conditioning agents in amounts 
of greater than 1% may precipitate the sulfopolyester, component (1). 
The aqueous formulations of the present invention also can contain the 
conventional hair spray adjuvants in amounts which generally range from 
about 0.01 to 2% by weight and preferably 0.1% to 1% by weight. Among the 
additives which can be used are plasticizers such as glycols, phthalate 
esters and glycerine; silicones; emollients; lubricants and penetrants 
such as various lanolin compounds; protein hydrolysates and other protein 
derivatives; ethylene adducts and polyoxyethylene cholesterol; dyes, tints 
and other colorants; and perfumes. 
Other conventional additives such as preservatives, fragrances, antifoaming 
agents, hair conditioners, plasticizers, etc. may be added in such 
quantities as desired, up to about 5.0% by weight of the total 
formulation. Although the film-forming formulations described herein are 
particularly useful as aerosol hair sprays for the grooming of hair, it is 
possible that the formulations, with or without modification, may be used 
in other types of personal care products. 
Suitable plasticizers include: Dimethicone Copolyol (Dow Corning 190) at 
0.01-0.02%, PEG-6 Capric/Caprylic Glyceride (Softigen 767) at 0.5-2.0%,. 
Diacetin at 1.0-2.0, Lauramide DEA (Monamid. 716) at 0.1-1.0%, Phenyl 
Trimethicone (Abil AV 20-1000) at 0.1-0.2%, propylene glycol at 1.0-5.0%, 
dipropylene glycol at 1.0-5.0%. 
The materials and testing procedures used for the results shown herein are 
as follows: 
DYMEL A (CTFA Adopted Name: Dimethyl Ether) available from DuPont, is a 
dimethyl ether and is used as a propellant. 
LUVISKOL VA 73W PVP/VA (CTFA Adopted Name: PVP/VA Copolymer), available 
from BASF, is a water-soluble vinyl copolymer of 70 mole percent of 
N-vinyl-2-pyrrolidinone and 30 mole percent of vinyl acetate (50% solid). 
SDA-40C is ethanol that has been diluted with ethyl acetate, and is 
available from Eastman Chemical Company. 
Glass transition temperature was determined using a differential scanning 
calorimeter (DSC). 
Inherent viscosity (I.V.) was measured at 23.degree. C. using 0.50 grams of 
polymer per 100 ml of a solvent consisting of 60% by weight phenol and 40% 
by weight tetrachloroethane. 
Turbidity was measured in NTU's using a model DRT-100B Turbidimeter. 
The invention will be further illustrated by a consideration of the 
following examples, which are intended to be exemplary of the invention. 
All parts and percentages in the examples are on a weight basis unless 
otherwise stated. 
EXAMPLE I 
Preparation of Water-dispersible Sulfopolyesters A-E 
A round bottom flask equipped with ground-glass head, an agitator shaft, 
nitrogen inlet and a side arm was charged with isophthalic acid, 
dimethyl-5-sodiosulfoisophthalate (SIP), diethylene glycol (DEG), and 
1,4-cyclohexanedimethanol (CHDM), in the mole percents as set forth below. 
For comparison purposes, Table I summarizes critical values for each 
sulfopolyester. A catalyst was added and the flask was immersed in a 
Belmont bath at 200.degree. C. for one hour under a nitrogen sweep. The 
temperature of the bath was increased to 230.degree. C. for one hour. The 
temperature of the bath was increased to 280.degree. C. and the flask was 
heated for 45 minutes under reduced pressure of 0.5 to 0.1 mm of Hg. The 
flask was allowed to cool to room temperature and the copolyester was 
removed from the flask. Each sulfopolyester was extruded and pelletized. 
More specifically, the composition of each sulfopolyester was as follows: 
Sulfopolyester A was prepared with 20.2 mole percent 
dimethyl-5-sodiosulfoisophthalate and 79.8 mole percent isophthalic acid, 
and 21.9 mole percent 1,4-cyclohexanedimethanol and 78.1 mole percent 
diethylene glycol, based on 100 mole percent dicarboxylic acid and 100 
mole percent diol. Sulfopolyester A has a Tg of 42.degree. C. and an I.V. 
of 0.33 dl/g. 
Sulfopolyester B was prepared with 22.0 mole percent 
dimethyl-5-sodiosulfoisophthalate and 78.0 mole percent isophthalic acid, 
and 23.0 mole percent 1,4-cyclohexanedimethanol and 77.0 mole percent 
diethylene glycol, based on 100 mole percent dicarboxylic acid and 100 
mole percent diol. Sulfopolyester B has a Tg of 47.degree. C. and an I.V. 
of 0.33 dl/g. 
Sulfopolyester C was prepared with 15.6 mole percent 
dimethyl-5-sodiosulfoisophthalate and 84.4 mole percent isophthalic acid, 
and 24.2 mole percent 1,4-cyclohexanedimethanol and 75.8 mole percent 
diethylene glycol, based on 100 mole percent dicarboxylic acid and 100 
mole percent diol. Sulfopolyester C has a Tg of 39.degree. C and an I.V. 
of 0.29 dl/g. 
Sulfopolyester D was prepared with 11.0 mole percent 
dimethyl-5-sodiosulfoisophthalate and 89.0 mole percent isophthalic acid, 
and 22.0 mole percent 1,4-cyclohexanedimethanol and 78.0 mole percent 
diethylene glycol, based on 100 mole percent dicarboxylic acid and 100 
mole percent diol. Sulfopolyester D has a Tg of 38.degree. C. and an I.V. 
of 0.36 dl/g. 
Sulfopolyester E was prepared with 18.0 mole percent 
dimethyl-5-sodiosulfoisophthalate and 82.0 mole percent isophthalic acid, 
and 46.0 mole percent 1,4-cyclohexanedimethanol and 54.0 mole percent 
diethylene glycol, based on 100 mole percent dicarboxylic acid and 100 
mole percent diol. Sulfopolyester E has a Tg of 55.degree. C. and an I.V. 
of 0.33 dl/g. 
TABLE I 
______________________________________ 
Summary of Sulfopolyester Compositions: 
Sulfopolyester 
SIP CHDM I.V. Tg 
______________________________________ 
A 20.2 21.9 0.33 42.degree. C. 
B 22.0 23.0 0.33 47.degree. C. 
C 15.6 24.2 0.29 39.degree. C. 
D 11.0 22.0 0.36 38.degree. C. 
E 18.0 46.0 0.33 55.degree. C. 
______________________________________ 
EXAMPLE II 
Preparation of Aerosol Hair Spray Formulations Using the Sulfopolyesters of 
Example I 
In some examples, ten grams of the sulfopolyester was dispersed in 54.3 
grams of distilled water by heating and stirring until a temperature of 
75.degree. to 85.degree. C. was reached. After cooling to 40.degree. C. 
any water lost during heating was replaced and in some cases a 
water-soluble polymer consisting of 70 mole percent of 
N-vinyl-2-pyrrolidinone and 30 mole percent of vinyl acetate (50% solids) 
was added. Ethanol, 35.7 grams as SDA 40C, was added. The mixtures were 
vacuum filtered through a coarse center glass filter. A preservative, 
1-(hydroxymethyl)-5,5-dimethyl hydantoin, 0.2 grams, was added. 
In some examples, ten grams of the sulfopolyester was dispersed in 90 grams 
of distilled water by heating and stirring until a temperature of 
75.degree. to 85.degree. C. was reached. After cooling to 40.degree. C. 
any water lost during heating was replaced and in some cases a 
water-soluble polymer consisting of 70 mole percent of 
N-vinyl-2-pyrrolidinone and 30 mole percent of vinyl acetate (50% solids) 
was added. The mixtures were vacuum filtered through a coarse center glass 
filter. A preservative, 1-(hydroxymethyl)-5,5-dimethyl hydantoin, 0.2 
grams, was added. 
To 65 grams of each of the mixtures was added 42 milliliters of dimethyl 
ether. The mixtures were sprayed into a glass cuvette which was placed in 
the Turbidimeter. The turbidity results are listed in Table II. 
TABLE II 
______________________________________ 
Turbidity Results (NTU's) 
Using Sulfopolyesters (A-E) 
Example A B C D E 
______________________________________ 
7% Sulfopoly 
18.9 15.7 41.5 64.6 36.1 
0% EtOH 
30% DME 
5% Sulfopoly 
19.8 15.9 41.0 63.0 33.8 
2% PVP/VA 
0% EtOH 
30% DME 
7% Sulfopoly 
14.0 14.0 325 301 981 
25% EtOH 
30% DME 
5% Sulfopoly 
2% PVP/VA 
25% EtOH 
30% DME 13.0 13.0 238 205 1290 
______________________________________ 
The results in Table II clearly indicate that aerosol hair sprays prepared 
with Sulfopolyesters A and B, which meet the criteria of the present 
invention, result in clear hair sprays even at 55% volatile organic 
solvent. The hair sprays prepared with Sulfopolyesters A and B exhibit 
significantly less than 20 NTU's which is a measure of turbidity. Greater 
than 20 NTU's is characteristic of a cloudy mixture. Moreover, the 
presence of a water-soluble polymer in the formulations of the present 
invention does not deleteriously effect the clarity of the aerosol hair 
spray formulations. In contrast, the addition of alcohol to hair spray 
formulations prepared with Sulfopolyesters C, D, or E result in extremely 
cloudy hair spray formulations with as little as 30% volatile organic 
solvent. 
EXAMPLE III 
Curl Retention Evaluation of Aerosol Hair Sprays 
The aerosol hair spray prepared from Sulfopolyesters B and D of Example II 
and LUVISKOL VA 73W PVP/VA were sprayed on a tress for ten seconds. 
Testing was done on natural brown, European virgin hair tresses in which 
about two grams of hair, root end, were glued to a 2" by 2" plastic tab. 
The tresses were cut so that the length of hair hanging below the tabs was 
six inches. Prior to applying the aerosol hair spray, the tresses had been 
washed with a nonconditioning shampoo, placed in ethanol bath for 15 
minutes, rinsed with deionized water, wrapped around a one inch diameter 
curler while wet, and placed in an oven at 45.degree. C. to dry. The 
tresses were removed from the oven and allowed to cool to room 
temperature. 
The tresses were hung in a humidity chamber at 25.degree. C. and 80% 
relative humidity. The curl loss or droop was determined over a one hour 
period in ten minute intervals. The test results are listed in Table III. 
TABLE III 
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Curl Retention Evaluation of Aerosol Hair Sprays 
Time (minutes) 
Polymer 0 10 20 30 40 50 60 
______________________________________ 
Sulfo 100 100 98.1 96.5 96.5 95.2 95.2 
poly B 
Sulfo 100 91.4 88.9 84.3 84.3 84.3 84.3 
poly D 
PVP/VA 100 79.8 74.3 70.4 67.2 67.2 67.2 
______________________________________ 
The test results in Table III indicate that aerosol hair sprays prepared 
using the critical ranges of the present invention clearly are superior in 
maintaining curl retention as compared to aerosol hair sprays that fall 
outside the critical ranges. In addition, the data indicates that the use 
of water-soluble PVP/VA polymers without the sulfopolyesters of the 
present invention result in poor curl retention and poor humidity 
resistance. 
Many variations will suggest themselves to those skilled in this art in 
light of the above detailed description. All such obvious modifications 
are within the full intended scope of the appended claims.