Clear hair spray formulations containing a linear sulfopolyester

A clear hair spray formulation which exhibits less than 30 NTU's and contains a linear sulfopolyester and a water-soluble polymer wherein the formulation is in water or a water/alcohol mixture. The sulfopolyester has a glass transition temperature of 40.degree. C. to 60.degree. C. and contains repeat units from the reaction product of a dicarboxylic acid, a diol and a difunctional sulfomonomer. The difunctional sulfomonomer is present in an amount from 18.5 to 22.5 mole percent based on 100 mole percent dicarboxylic acid and 100 mole percent diol. The hair spray formulation may optionally contain a propellant.

FIELD OF THE INVENTION 
This invention relates to hair spray formulations based on (1) a 
sulfonate-containing, water-dispersible or water-dissipatible, linear 
polyester having a glass transition temperature of 40.degree. C. to 
60.degree. C., In addition, the formulations contain water or a 
water/alcohol mixture as the liquid vehicle and optionally a propellant. 
The diol component of the sulfopolyester contains 10 to 30 mole percent 
1,4-cyclohexanedimethanol. The sulfopolyester contains 18.5 to 22.5 mole 
percent sulfomonomer, and the sulfopolyester has a glass transition 
temperature (Tg) of 40.degree. C. to 60.degree. C. The hair spray 
formulations may be applied in pump or aerosol form. 
BACKGROUND OF THE INVENTION 
The use of water-dispersible linear sulfopolyesters in hair spray 
formulations has been disclosed in U.S. Pat. Nos. 4,300,580 and 5,158,762. 
U.S. Pat. No. 4,300,580, issued Nov. 17, 1981, and assigned to Eastman 
Kodak Company, discloses hair grooming formulations containing a 
sulfopolyester comprising a dicarboxylic acid, a diol wherein at least 20 
mole percent is a poly(ethylene glycol), and 8 to 45 mole percent of a 
dicarboxylic acid sulfomonomer. U.S. Pat. No. 5,158,762, issued Oct. 27, 
1992, and assigned to ISP Investments Inc., discloses hair spray 
compositions containing a blend of two polymers. One of the polymers is a 
sulfopolyeser comprising a dicarboxylic acid, a diol wherein at least 40 
mole percent is 1,4-cyclohexanedimethanol, and 16 to 25 mole percent of a 
sulfomonomer. U.S. Pat. No. 5,158,762 states that useful sulfopolyesters 
are AQ 38 and AQ 55 which are available from Eastman Chemical Company. It 
is interesting to note that while the patent discloses a range of 
sulfomonomer of 16 to 25 mole percent, AQ 38 has 11 mole percent 
sulfomonomer. Moreover, AQ 38 has 22 mole percent of 
1,4-cyclohexanedimethanol which is below the 40 mole percent requirement 
set forth in U.S. Pat. No. 5,158,762. In contrast, neither AQ 38 nor AQ 55 
are operable in the present invention. The other polymer in U.S. Pat. No. 
5,158,762 is a water soluble polymer which includes polyvinyl pyrrolidone 
(PVP) and polyvinyl acetate. 
Such hair grooming compositions generally perform effectively in providing 
most of the properties considered desirable for hair preparation, 
including fine spray patterns, prolonged curl retention under humid 
conditions, good holding power and resistance to build-up. However, these 
and other hair spray formulations available in the art are generally 
cloudy and contain precipitate that clogs the exit ports of aerosol cans 
or pump containers. 
The present inventors have unexpectedly discovered four critical ranges 
that are necessary to produce clear hair spray compositions. The diol 
component of the sulfopolyester must contain 10 to 30 mole percent 
1,4-cyclohexanedimethanol; the sulfopolyester must contain 18.5 to 22.5 
mole percent sulfomonomer; the sulfopolyester must have a glass transition 
temperature (Tg) of 40.degree. C. to 60.degree. C.; and the sulfopolyester 
must have an inherent viscosity (I.V.) of 0.2 to 0.6 dl/g. The clear hair 
spray compositions of the present invention exhibit less than 30 NTU's 
which is a measure of turbidity. In the cosmetic field greater than 30 
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 
hair spray formulation. 
It is another object of the invention to provide a 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 hair spray formulation 
having excellent storage stability and which does not clog the exit port 
of an aerosol or pump container. 
These and other objects are accomplished herein by a clear hair spray 
composition comprising: 
(1) a sulfopolyester having a Tg of 40.degree. C. to 60.degree. C. 
consisting essentially of repeat units from 
(a) a dicarboxylic acid selected from the group consisting of aromatic 
dicarboxylic acids, saturated aliphatic dicarboxylic acids, cycloaliphatic 
dicarboxylic acids, and combinations thereof; 
(b) a diol provided 10 to 30 mole percent of the diol is 
1,4-cyclohexanedimethanol; and 
(c) a difunctional sulfomonomer containing at least one sulfonate group 
attached to an aromatic nucleus wherein the functional groups are hydroxy, 
carboxy or amino, provided the difunctional sulfomonomer is present in an 
amount from 18.5 to 22.5 mole percent based on 100 mole percent 
dicarboxylic acid and 100 mole percent diol, provided that the hair spray 
composition contains 1 to 20 weight percent of the sulfopolyester; and 
(2) a liquid vehicle selected from the group consisting of water and a 
water/alcohol mixture. 
DESCRIPTION OF THE INVENTION 
The hair sprays of this invention contain a sulfopolyester, component (1), 
in an amount of about 1 to about 20 weight percent, preferably less than 
10 weight percent, based on the total weight of the hair spray 
formulation. The sulfopolyesters have an inherent viscosity (I.V.) of 0.2 
to 0.6 dl/g as 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. The sulfopolyester has a glass transition temperature 
of 40.degree. C. to 60.degree. C. and contains repeat units from a 
dicarboxylic acid, a diol and a difunctional sulfomonomer. 
Dicarboxylic acids useful in the present invention include aromatic 
dicarboxylic acids preferably having 8 to 14 carbon atoms, saturated 
aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, and 
cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms. 
Specific examples of dicarboxylic acids are: terephthalic acid, phthalic 
acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 
cyclohexanedicarboxylic acid, cyclohexanediacetic acid, 
diphenyl-4,4-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, 
azelaic acid, sebacic acid, and the like. The sulfopolyester may be 
prepared from two or more of the above dicarboxylic acids. 
It should be understood that use of the corresponding acid anhydrides, 
esters, and acid chlorides of these acids is included in the term 
"dicarboxylic acid". 
The diol component of the polyester contains 10 to 30 mole percent of 
1,4-cyclohexanedimethanol. In addition to 1,4-cyclohexanedimethanol, 
suitable diols include cycloaliphatic diols preferably having 6 to 20 
carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms. 
Examples of such diols to be used with 1,4-cyclohexanedimethanol are: 
ethylene glycol, diethylene glycol, triethylene glycol, propane-1,3-diol, 
butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 
3-methylpentanediol-(2,4), 2-methylpentanediol, (1,4), 
2,2,4-trimethylpentane-diol-(1,3), 2-ethylhexanediol, (1,3), 
2,2-diethylpropane-diol, (1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy), 
benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy, 1,1,3,3, 
tetramethyl, cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl), propane, and 
2,2-bis-(4, hydroxypropoxyphenyl)-propane. The polyester may be prepared 
from two or more of the above diols. 
The difunctional sulfomonomer component of the polyester may be a 
dicarboxylic acid or an ester thereof containing a sulfonate group 
(--SO.sub.3.sup.--), a diol containing a sulfonate group, or a hydroxy 
acid containing a sulfonate group. The cation of the sulfonate salt may be 
Na+, Li+, K+, NH.sub.4 +, and substituted ammonium. The term "substituted 
ammonium" refers to ammonium substituted with an alkyl or hydroxy alkyl 
radical having 1 to 4 carbon atoms. The difunctional sulfomonomer contains 
at least one sulfonate group attached to an aromatic nucleus wherein the 
functional groups are hydroxy, carboxy or amino. 
Advantageous difunctional sulfomonomer components are those wherein the 
sulfonate salt group is attached to an aromatic acid nucleus such as 
benzene, naphthalene, diphenyl, oxydiphenyl, sulfonyldiphenyl or 
methylenediphenyl nucleus. Preferred results are obtained through the use 
of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, 
4-sulfonaphthalene-2,7- dicarboxylic acid, and their esters. The 
sulfomonomer is present in an amount from 18.5 to 22.5 mole percent, based 
on 100 mole percent dicarboxylic acid and 100 mole percent diol. 
It is important to note that all four of the critical ranges must be 
satisfied in order to attain a clear hair spray composition. The diol 
component of the sulfopolyester must contain 10 to 30 mole percent 
1,4-cyclohexanedimethanol; the sulfopolyester must contain 18.5 to 22.5 
mole percent sulfomonomer; the sulfopolyester must have a glass transition 
temperature of 40.degree. C. to 60.degree. C.; and the sulfopolyester must 
have an inherent viscosity of 0.2 to 0.6 dl/g. The hair sprays of the 
present invention exhibit less than 30 NTU's which is a measure of the 
turbidity of a mixture. In the cosmetic field greater than 30 NTU's is 
characteristic of a cloudy mixture that is visible to the eye. 
Component (2) of the hair spray is a liquid vehicle. The liquid vehicle of 
the formulations 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). The alcohol should have two to four carbon atoms. Specific 
alcohols include ethanol, isopropanol, and t-butanol. 
The liquid vehicle in aerosol hair sprays is preferably water. However, a 
water/alcohol mixture may be employed as long as the alcohol is present in 
an amount less than about 55 weight percent. In such aerosol hair spray 
formulations where an alcohol/water mixture is employed, preferably 35 to 
45 weight percent of the mixture is alcohol. In pump formulations, the 
liquid vehicle is preferably a water/alcohol mixture wherein the alcohol 
is present in an amount less than about 55 weight percent to satisfy 
current environmental standards. The preferred alcohol is ethanol. In a 
pump hair spray formulation containing only a sulfopolyester, component 
(1) and a liquid vehicle, component (2), the liquid vehicle will be 
present in an amount of about 80 to about 99 weight percent of the hair 
spray. However, if additional ingredients are used in the hair spray 
formulation, the amount of the liquid vehicle will be proportionally 
reduced. For example, in the case of an aerosol hair spray containing a 
water soluble polymer and a propellant, the liquid vehicle is preferably 
present in an amount of 55 to 70 weight percent, based on the total 
formulation. 
The hair spray compositions may optionally contain a water-soluble polymer, 
component (3), which is prepared from monomers having one or more of the 
following structures: 
##STR1## 
In the above formulas, R.sup.1 is a C.sub.1 -C.sub.5 aliphatic group, 
preferably a C.sub.1 -C.sub.3 alkyl group, or is of the structure 
##STR2## 
R.sup.8 and R.sup.9 are, independently, a C.sub.1 -C.sub.5 alkyl group. 
R.sup.2 is a C.sub.1 -C.sub.10 aliphatic group, preferably a C.sub.1 
-C.sub.3 alkyl group. R.sup.3 is a C.sub.1 -C.sub.16 aliphatic group, 
preferably a C.sub.8 alkyl group, R.sup.4 is H or a C.sub.1 -C.sub.8 
aliphatic group, preferably H or a C.sub.8 group. R.sup.5 is a C.sub.1 
-C.sub.8 aliphatic group, preferably C.sub.9 alkyl group, R.sup.6 is 
hydrogen or methyl, and R.sup.7 is hydrogen or an alkyl group having 1 to 
4 carbon atoms. 
Accordingly, suitable water soluble polymers include polyvinyl pyrrolidone 
(PVP), polyvinyl caprolactam, polyvinyl acetate (VA), polyacrylates and 
methacrylates, and copolymers and terpolymers of such monomers, such as 
VP/VA, VA/crotonic acid/vinyl neodecanoate, VA/crotonic acid, or 
octylacrylamide/acrylates/butyl aminoethyl methacrylate, VA, mono-n-butyl 
maleate and isobornyl acrylate; and VP/VC/dimethylaminoethyl methacrylate. 
A preferred vinyl polymer or copolymer contains at least 50 mole percent of 
the residues of n-vinyl lactam monomer such as N-vinylpyrrolidinone. A 
preferred terpolymer is derived from the polymerization of vinyl 
caprolactam, vinylpyrrolidone and an ammonium derivative monomer having 
from 6-12 carbon atoms selected from dialkyl dialkenyl ammonium halide and 
a dialkylamino alkyl acrylate or methacrylate. 
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 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 
generally present in an amount of about 1 to about 7 weight percent, based 
on the total weight of the hair spray formulation. 
For aerosol hair spray formulations, a propellant, component (4), is 
necessary. The propellant is selected from the group consisting of a 
C.sub.1 -C.sub.4 aliphatic hydrocarbons and dimethyl ether. The aliphatic 
hydrocarbons may be branched or straight chain and include methane, 
ethane, propane, n-butane, isobutane, or mixtures thereof. A preferred 
aliphatic hydrocarbon propellant is a mixture containing about 83 percent 
isobutane and about 17 percent propane. The propellant is present in an 
amount of about 3 to about 40 weight percent of the total 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 30 to 
about 40 weight percent, preferably, 30 to 35 weight percent, is employed. 
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. 
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% solids), 
and is used as a fixative. 
GLYDANT (CTFA Adopted Name: DMDM Hydantoin) available from Lonza, Inc. is 
1-(hydroxymethyl)-5,5-dimethyl hydantoin, and is used as a antimicrobial. 
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. 
EXAMPLES I-X 
(1) Preparation of water-dispersible sulfopolyesters. 
A round bottom flask equipped with ground-glass head, an agitator shaft, 
nitrogen inlet and a side arm was charged with isophthalic acid, 
5-sodiosulfoisophthalic acid (SIP), diethylene glycol (DEG), and 
1,4-cyclohexanedimethanol (CHDM), in the mole percents as set forth in 
Table I. In each Example, titanium isopropoxide (50 ppm of titanium), and 
sodium acetate (10% of the mole% of SIP), were added. 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. The sulfopolyesters were extruded and 
pelletized. The mole percent of the components for each of the 
sulfopolyesters, glass transition temperatures and inherent viscosities 
are listed in Table I. 
(2) Preparation of aerosol hair spray formulations using the 
sulfopolyesters of Examples I-VIII. 
Ten grams of each of the sulfopolyesters prepared in Examples I-VIII, were 
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. The mixtures 
were vacuum filtered through a course center glass filter. 
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 I. 
(3) Preparation of pump hair spray formulations using the sulfopolyesters 
of Examples I-X. 
Ten grams of each of the sulfopolyesters prepared in Examples I-X, were 
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. The mixtures 
were vacuum filtered through a course center glass filter. 
1-(hydroxymethyl)-5,5-dimethyl hydantoin, 0.2 grams was added. 
To 25 grams of each of the mixtures was added 25 grams of SDA 40C. The 
mixtures were poured into a glass cuvette which was placed in the 
Turbidimeter. The mole percent of the components of the sulfopolyesters 
and turbidity results are listed in Table I. 
TABLE I 
______________________________________ 
Exam- Diol SIP IV Tg Turbidity (NTU's) 
ple (Mole %) (Mole %) (dl/g) 
(.degree.C.) 
Aerosol 
Pump 
______________________________________ 
I CHDM 24.2 15.6 0.29 39 41.5 30.5 
DEG 75.8 
II CHDM 21.5 19.4 0.33 41 16.5 12.7 
DEG 78.5 
III CHDM 21.9 20.2 0.33 42 18.9 10.8 
DEG 78.1 
IV CHDM 23.0 22.0 0.33 47 15.7 6.4 
DEG 77.0 
V CHDM 20.7 22.6 0.19 37 30.8 25.1 
DEG 79.3 
VI CHDM 21.5 11.0 0.36 38 64.6 50.4 
DEG 78.5 
VII CHDM 46.0 18.0 0.33 55 36.1 60.0 
DEG 54.0 
VIII CHDM 20.6 20.1 0.29 43 -- 12.8 
DEG 79.4 
IX CHDM 36.8 19.8 0.18 44 -- 52.3 
DEG 63.2 
X CHDM 34.0 20.6 0.28 47 -- 38.0 
DEG 66.0 
______________________________________ 
KEY TO ABBREVIATIONS: 
CHDM = 1,4cyclohexane dimethanol 
DEG = diethylene glycol 
SIP = 5sodiosulfoisophthalate 
The data in Table I indicates that aerosol and pump hair sprays prepared 
using the critical ranges of the present invention (Examples II-VIII) 
exhibit less than 30 NTU's which is a measure of the turbidity of a 
mixture as compared to hair sprays wherein one or more critical limitation 
is not satisfied. It is important to note that in the cosmetic field 
greater than 30 NTU's is characteristic of a cloudy mixture that is 
visible to the eye. 
EXAMPLES XI-XVII 
(1) Preparation of aerosol hair spray formulations using the 
sulfopolyesters prepared in Examples I-VII. 
Ten grams of each of the sulfopolyesters prepared in Examples I-VII, were 
dispersed in 85 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 5 grams of a 
water soluble vinyl copolymer 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 course center glass 
filter. 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 mole percent of the components of the 
sulfopolyesters and turbidity results are listed in Table II. 
(2) Preparation of pump hair spray formulations using the sulfopolyesters 
prepared in Examples I-VII. 
Ten grams of each of the sulfopolyesters prepared in Examples I-VII, were 
dispersed in 85 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 5 grams of a 
water soluble vinyl copolymer 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 course center glass 
filter. 1-(hydroxymethyl)-5,5-dimethyl hydantoin, 0.2 grams was added. 
To 25 grams of each of the mixtures was added 25 grams of SDA 40C. The 
mixtures were poured into a glass cuvette which was placed in the 
Turbidimeter. The mole percent of the components of the sulfopolyesters 
and turbidity results are listed in Table II. 
TABLE II 
______________________________________ 
Ex- SIP PVP/ Turbidity 
am- Diol (Mole IV Tg VA (NTU's) 
ple (Mole %) %) (dl/g) 
(.degree.C.) 
(Wt. %) 
Aerosol 
Pump 
______________________________________ 
XI CHDM 24.2 15.6 0.29 39 5 41.0 35.8 
DEG 75.8 
XII CHDM 21.5 19.4 0.33 41 5 17.7 11.2 
DEG 78.5 
XIII CHDM 21.9 20.2 0.33 42 5 19.8 15.0 
DEG 78.1 
XIV CHDM 23.0 22.0 0.33 47 5 15.9 8.9 
DEG 77.0 
XV CHDM 20.7 22.6 0.19 37 5 27.8 12.4 
DEG 79.3 
XVI CHDM 21.5 11.0 0.36 38 5 63.0 54.8 
DEG 78.5 
XVII CHDM 46.0 18.0 0.33 55 5 33.8 19.2 
DEG 54.0 
______________________________________ 
KEY TO ABBREVIATIONS: 
CHDM = 1,4cyclohexane dimethanol 
DEG = diethylene glycol 
SIP = 5sodiosulfoisophthalate 
The data in Table II indicates that aerosol and pump hair sprays prepared 
with a water soluble polymer and using the critical ranges of the present 
invention (Examples XII-XV) exhibit less than 30 NTU's which is a measure 
of the turbidity of a mixture as compared to hair sprays wherein one or 
more critical limitation is not satisfied. It is important to note that in 
the cosmetic field greater than 30 NTU's is characteristic of a cloudy 
mixture that is visible to the eye. 
EXAMPLE XVIII 
(1) Preparation of a water-dispersible sulfopolyester. 
A round bottom flask equipped with ground-glass head, an agitator shaft, 
nitrogen inlet and a side arm was charged with 78.2 moles of isophthalic 
acid, 21.8 moles of 5-sodiosulfoisophthalic acid, 83.5 moles of diethylene 
glycol, and 16.5 moles of 1,4-cyclohexanedimethanol. Titanium isopropoxide 
(50 ppm of titanium), and sodium acetate (10% of the mole % of SIP), were 
added. 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. The 
sulfopolyester was extruded and pelletized. The glass transition 
temperature and I.V. were determined to be 42.degree. C. and 0.28 dl/g 
respectively. 
(2) Preparation of an aerosol hair spray formulation. 
The sulfopolyester prepared above, 7.14 grams, was dispersed in 52.15 grams 
of distilled water by heating and stirring until a temperature of 
75.degree. C. to 85.degree. C. was reached. After cooling to 40.degree. C. 
any water lost during heating was replaced and 5.71 grams of a water 
soluble vinyl copolymer consisting of 70 mole percent of 
N-vinyl-2-pyrrolidinone and 30 mole percent of vinyl acetate (50% solids) 
was added. The mixture was vacuum filtered through a course center glass 
filter. 1-(hydroxymethyl)-5,5-dimethyl hydantoin, 0.2 grams was added. 
To 65 grams of the mixtures was added 42 milliliters of dimethyl ether. The 
mixture was sprayed into a glass cuvette which was placed in the 
Turbidimeter. Turbidity was measured after aging at 45C. for 19 months in 
an oven. The turbidity was 30.7 NTU's. Thus, the aerosol formulation 
showed good clarity and storage stability. 
EXAMPLE XIX 
(1) Preparation of a water-dispersible sulfopolyester. 
A round bottom flask equipped with ground-glass head, an agitator shaft, 
nitrogen inlet and a side arm was charged with 73.1 moles of isophthalic 
acid, 16.9 moles of 5-sodiosulfoisophthalic acid, 81.2 moles of diethylene 
glycol, and 18.8 moles of 1,4-cyclohexanedimethanol. Titanium isopropoxide 
(50 ppm of titanium), and sodium acetate (10% of the mole % of SIP), were 
added. 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. The 
sulfopolyester was extruded and pelletized. The glass transition 
temperature and I.V. were determined to be 39.degree. C. and 0.36 dl/g 
respectively. 
(2) Preparation of an aerosol hair spray formulation. 
The sulfopolyester prepared above, 7.14 grams, was dispersed in 52.15 grams 
of distilled water by heating and stirring until a temperature of 
75.degree. C. to 85.degree. C. was reached. After cooling to 40.degree. C. 
any water lost during heating was replaced and 5.71 grams of a water 
soluble vinyl copolymer consisting of 70 mole percent of 
N-vinyl-2-pyrrolidinone and 30 mole percent of vinyl acetate (50% solids) 
was added. The mixture was vacuum filtered through a course center glass 
filter. 1-(hydroxymethyl)-5,5-dimethyl hydantoin, 0.2 grams was added. 
To 65 grams of the mixtures was added 42 milliliters of dimethyl ether. The 
mixture was sprayed into a glass cuvette which was placed in the 
Turbidimeter. Turbidity was measured after aging at 45.degree. C. for 19 
months in an oven. The turbidity was 53 NTU's. Thus, the aerosol 
formulation showed good clarity and storage stability. 
EXAMPLE XX 
Aerosol hair spray formulations were prepared using the sulfopolyesters of 
Examples IV and VI. The sulfopolyester in Example IV contained 23 mole % 
CHDM, 22.0 mole % SIP, Tg of 47.degree. C., and an I.V. of 0.33. The 
sulfopolyester in Example VI contained 21.5 mole % CHDM, 11.0 mole % SIP, 
Tg of 38.degree. C., and an I.V. of 0.36. Preparation of the aerosol hair 
sprays is described in Examples I-X. 
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 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 aerosol hair spray prepared from the sulfopolyester of Example IV and 
the aerosol hair spray prepared from the sulfopolyester of Example VI were 
sprayed on a tress for ten seconds. 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) 
Ex. 0 10 20 30 40 50 60 
______________________________________ 
IV 100 100 98.1 96.5 96.5 95.2 95.2 
VI 100 91.4 88.9 84.3 84.3 84.3 84.3 
______________________________________ 
The test results in Table III indicate that aerosol hair sprays prepared 
using the critical ranges of the present invention (Example IV) clearly 
are superior in maintaining curl retention as compared to aerosol hair 
sprays that fall outside the critical ranges. 
EXAMPLE XXI 
Pump hair spray formulations were prepared using the sulfopolyesters of 
Examples IV and VI as described above. The pump hair sprays were sprayed 
onto tresses as prepared in Example XX. 
Each of the pump hair sprays were applied to the tresses by pumping ten 
times. 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 
IV. 
TABLE IV 
______________________________________ 
Curl Retention Evaluation of Pump Hair Sprays 
Time (minutes) 
Ex. 0 10 20 30 40 50 60 
______________________________________ 
IV 100 96.3 96.3 93.5 93.5 93.5 93.5 
VI 100 98.1 96.2 90.4 88.5 88.5 88.5 
______________________________________ 
The test results in Table IV indicate that pump hair sprays prepared using 
the critical ranges (Example IV) of the present invention clearly are 
superior in maintaining curl retention as compared to pump hair sprays 
that fall outside the critical ranges. 
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.