Hair spray composition having 80% or less VOC and advantageous physical and performance characteristics

A hair spray composition of 80% or less VOC includes a fixative which is the half-ester of a copolymer of maleic anhydride and methyl vinyl ether having advantageous physical and performance properties even at low fixative levels. The copolymer is made by polymerizing the monomers at a selected temperature in the presence of a predetermined amount of a polymerization initiator whose decomposition fragments are soluble in hydroalcoholic solutions containing high levels of water. The composition is clear and without precipitate formation, has a low weight average molecular weight and a narrow molecular weight distribution or polydispersity, affording a low solution viscosity. The composition also forms a spray pattern of small particle size, providing clear, hard fixative films with superior adhesion to the hair of the user, an advantageous high humidity curl retention (hold), and low tack and dry times, in both pump and aerosol products.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to hair spray compositions, and, more particularly, 
to 80% or less VOC hair spray compositions which have advantageous 
physical and performance characteristics. 
2. Description of the Prior Art 
Copolymers of maleic anhydride and methyl vinyl ether, in the form of the 
C.sub.1 -C.sub.5 alkyl half-ester, e.g. the ethyl half-ester, have been 
used extensively as the film-forming resin or fixative in hair spray 
compositions. Generally such ester copolymers have been prepared by 
polymerization of the monomers benzene or acetone solution in the presence 
of a free radical polymerization initiator followed by esterification. See 
Brit. Pats. 863,379; 1,233,468 and 712,220; Ger. Pat. 540,101; and U.S. 
Pat. Nos. 2,047,398; 4,908,413; 4,939,198; 5,139,034 and 5,223,567. 
In general, free radical initiators used in such polymerization processes 
at elevated temperatures have included alkyl peresters, dialkyl peroxides, 
perketals, peroxydicarbonates, hydroperoxides, azo compounds and 
carbon-carbon labile compounds. Copolymerization also has been carried out 
at relatively low temperatures, e.g. room temperature, using a redox 
catalyst, such as, a combination of a redox catalyst and ascorbic acid, 
or, of a peroxydicarbonate and benzoin. It has been possible also to 
employ the polymerization initiator conjointly with a suitable 
accelerator, for example, an amine derived from a cyclic or phenyl 
structure, the amine being used by itself or together with an organic 
compound of a transition metal. Copolymerization also has been carried out 
with a mixture of different polymerization initiators having different 
decomposition temperatures. 
The following compounds have been employed as initiators in free radical 
initiated polymerizations: 
acetyl cyclohexanesulfonyl peroxide, 
diacetyl peroxydicarbonate, 
dicyclohexyl peroxydicarbonate, 
di-2-ethylhexyl peroxydicarbonate, 
tert-butyl per[oxy]-neodecanoate, 
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); 
tert-butylperoxy pivalate, 
dioctanoyl peroxide, 
dilauroyl peroxide, 
2,2'-azobis-(2,4-dimethylvaleronitrile), 
tert-butylazo-2-cyanobutane; 
dibenzoyl peroxide, 
tert-butylper[oxy]-2-ethylhexanoate, 
tert-butylper[oxy]maleate, 
2,2-azobis(isobutyronitrile); 
bis(tert-butylperoxy) cyclohexane, 
tert-butylperoxyisopropyl carbonate, 
tertbutylper[oxy]acetate; 
2,2-bis(tert-butylperoxy)butane, 
dicumyl peroxide, 
di-tert-amyl peroxide, 
di-tert-butyl peroxide, 
pinane hydroperoxide, 
cumene hydroperoxide, and tert-butyl hydroperoxide. 
Ethyl half-esters of copolymers of maleic anhydride and methyl vinyl ether 
(Gantrez.RTM. ES-225), may be prepared in acetone according to the free 
radical polymerization process described by Zamora et al., in U.S. Pat. 
No. 5,223,567, using decanoyl peroxide as the polymerization initiator. 
Such copolymers are supplied by International Specialty Products, Inc. as 
a 50% solids solution in ethanol. 
Recent governmental legislation, however, has required that hair spray 
compositions contain only 80% or less volatile organic compounds (VOCs). 
Accordingly, it has been necessary for formulators of such hair spray 
products to substitute water for much of the ethanol solvent presently 
used to dissolve the hair fixative resin. However, an increase in the 
water content creates some significant problems, including: 
A decrease in resin solubility 
An increase in solution viscosity 
An increase in spray particle size causing a poorer spray pattern 
An increase in dry and tack times 
A decrease in high humidity curl resistance (hold) 
In aerosol formulations, the presence of water creates two additional 
problems: 
Can corrosion 
Solvent-propellant incompatibility. 
Specifically, in a low VOC formulation, and particularly in a 55% VOC 
composition, which contains a very high water content, Gantrez.RTM. ES-225 
forms only hazy compositions and has a high solution viscosity. These 
appearance properties are unacceptable commercially because of the cloudy 
appearance of the product and formation of a precipitate with time. In 
addition, such high viscosity formulations are difficult to spray 
adequately into spray patterns of fine particles. Accordingly, 
Gantrez.RTM. ES-225 has not been considered as a suitable fixative 
candidate for a 55% VOC hair spray product. 
Goertz et al., in U.S. Pat. No. 4,908,413, described the preparation of 
ethyl half-ester copolymers of maleic anhydride and excess methyl vinyl 
ether by thermal polymerization of precharged monomers in acetone, 
followed by a second phase free radical polymerization. Esterification was 
carried out in ethanol in the presence of an esterification catalyst such 
as p-toluenesulfonic acid. However, the alcoholic solutions of such 
copolymers were considered as being only "equivalent in their physical 
properties and performance characteristics to the corresponding ones 
obtained by previous processes". 
For these and other reasons, there has been an extensive ongoing research 
and development effort in both the chemical and cosmetic industries to 
find new polymers, and/or mixtures of polymers, which would provide 
acceptable 80% and 55% VOC hair spray compositions for the consumer. 
Accordingly, it is an object of this invention to provide an 80% or less 
VOC hair spray composition, particularly a 55% VOC composition, which 
exhibits excellent performance properties, even at a low fixative solids 
level, and a clear fixative solution, without precipitate formation, and 
which has a low solution viscosity, a low copolymer weight average 
molecular weight and a narrow molecular weight distribution (MWD), and 
also which forms a spray pattern of small particle size, providing clear, 
hard fixative films with superior adhesion to the hair of the user, and 
which provides an effective high humidity curl retention (hold), as well 
as low tack and dry times, in both pump and aerosol hair spray products. 
These and other objects and features of the invention will be made apparent 
from the following more detailed description of the invention. 
SUMMARY OF THE INVENTION 
What is described herein is a hair spray composition containing 80% or less 
VOC comprising, by weight, 
(a) about 0.5-12% of the ethyl or butyl half-ester copolymer of maleic 
anhydride and methyl vinyl ether, which is made by copolymerizing the 
monomers in a solvent at a predetermined temperature, in the presence of a 
selected amount of a polymerization initiator whose decomposition 
fragments in the solution are soluble in a 55% VOC hydroalcoholic 
composition, followed by esterification, preferably in the absence of an 
esterification catalyst, and wherein the copolymer solution is crystal 
clear, has a low weight average molecular weight of about 30,000 to about 
120,000, preferably 50,000 to 100,000, and most preferably 60,000 to 
80,000, a narrow polydispersity or molecular weight distribution (MWD) of 
less than about 2.5, preferably 1.8 to 2.2, and a solution specific 
viscosity of about 0.25 to 0.39, preferably 0.28 to 0.35, 
(i) optionally neutralized in an amount up to about 25 mole %, 
(b) 0-80% ethanol, 
(c) 19-99% water, and 
(d) 0-35% propellant. 
The hair spray composition of the invention is crystal clear in appearance, 
has a Brookfield viscosity of less than 30 cps, preferably less than 20 
cps, as a 5% solids solution, and forms clear, hard films having an 
effective high humidity curl retention (hold) of greater than 90%, a tack 
time of below 30 seconds, a dry time of below 45 seconds, and forms spray 
particles in pump systems having a size of less than 100 .mu.m, and, in 
aerosol systems, of less than 80 .mu.m. 
DETAILED DESCRIPTION OF THE INVENTION 
What has been discovered herein is that manufacture of alkyl half-esters of 
maleic anhydride and methyl or butyl vinyl ether according to Zamora, 
using decanoyl peroxide as the polymerization initiator, resulted in 
formation of initiator decomposition fragments which remained in the 
copolymer solution and were insoluble in water. Accordingly, it is these 
initiator decomposition fragments which caused hydroalcoholic solutions, 
and water-containing hair spray compositions, which have 80% or less VOC, 
particularly 55% or less VOC, containing such commercial copolymer 
solutions, to appear hazy and cloudy, and even to form a precipitate in 
time upon standing. In contrast, it has been found that the half-ester 
copolymer itself is readily soluble in 80% VOC or 55% VOC compositions. 
Such solutions appear crystal clear. 
Accordingly, in this invention, water-compatible copolymers and solutions 
therefrom are made using polymerization initiators whose decomposition 
fragments are compatible in 80% or 55% VOC hydroalcoholic solutions and 
compositions. Suitable initiators include azobis compounds having a 
solubility of 0.5 g initiator/100 g water. These compounds can be present 
during polymerization in an amount of about 0.05% to about 10% by weight 
of the monomers used, preferably about 1 to about 5%. 
Representative azo initiators for use herein thus include: 
1,1'-azobis (1-cyclohexanecarbonitrile); 
2,2'-azobis (N,N'-dimethyleneisobutyramidine) dihydrochloride; 
2,2'-azobis(2-amidinopropane) dihydrochloride; 
2,2'azobis(N,N'-dimethyleneisobutyramidine); 
4,4'-azobis(4-cyanopentanoic acid); 
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} 
; 
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide}; 
2,2'-azobis[2-methyl-N-(2-hydroxyethyl) propionamide; and 
2,2'-azobis(isobutyramide) dihydrate. 
Other azo initiators which have a solubility in water lower than 0.5 g/100 
g water but their decomposition products are suitably soluble in 
hydroalcoholic solutions also may be used. Such azo initiators include: 
2,2'-azobisobutyronitrile; 
2,2'-azobis-(2,4-dimethylvaleronitrile); 
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); 
1,1'-azobis-(1-cyclohexanecarbonitrile); and 
dimethyl-2,2'-azobis-(isobutyrate). 
Copolymers made using suitable azo initiators, and their solutions and hair 
spray compositions, have advantageous physical and performance properties 
as compared to copolymer solutions and hair spray compositions prepared by 
either the Zamora or Goertz processes. 
In particular, the copolymers of this invention have a low weight average 
molecular weight and narrow polydispersity or molecular weight 
distribution, which provides hair spray compositions having a desirable 
low viscosity suitable for forming advantageous spray particles of small 
size, in both pump and aerosol systems. With these copolymer solutions and 
compositions, the consumer can experience an exceptional holding power on 
the hair, while affording acceptable tack and dry times. 
In this invention, the weight average molecular weight and polydispersity 
of the copolymer may be controlled by using a predetermined amount of the 
azo initiator during polymerization, and by selection of a suitable 
polymerization temperature. For example, for a selected low weight average 
molecular weight of about 50,000 to 80,000, and a polydispersity of about 
1.8 to 2.2, a suitable amount of an azo initiator having a 10-hour 
half-life of about 60.degree. to 70.degree. C. is about 1 to about 5% by 
weight of the maleic anhydride monomer present during polymerization, and 
the polymerization temperature is about 60.degree. to about 90.degree. C. 
Furthermore, the advantageous physical and performance properties of the 
half-ester copolymer of the invention in hair spray compositions also is 
enhanced herein by carrying out the polymerization step by free radical 
polymerization only, which reduces the weight average molecular weight of 
the copolymer. Preferably, esterification is carried out in the absence of 
an esterification catalyst. Such acid catalysts remain in the resultant 
ester copolymer solution and produce a hazy film when cast from 
hydroalcoholic solutions of high water content. Furthermore, the presence 
of an esterification catalyst will produce significant amounts of the 
diester copolymer, which is undesirable because it is less water 
compatible than the half-ester copolymer. The diester also has a reduced 
Tg so that its fixative film is softer than the half-ester copolymer of 
this invention. 
If desired, the half-ester copolymer solution herein may be neutralized up 
to about 25 mole % with a suitable neutralizing agent, such as 
triisopropanol amine (TIPA), 3-aminopropanol (AMP-95), NH.sub.4 OH or 
NaOH, and the like. In general, a higher degree of neutralization will be 
used in a hair spray composition containing a higher water content. 
The invention will now be described in detail by reference to the following 
examples.

EXAMPLE 1 (INVENTION) 
Preparation of the Ethyl Ester of a Maleic Anhydride-Methyl Vinyl Ether 
Copolymer in Ethanol 
(a) Copolymerization 
A pressurized reactor vessel was precharged with 7819 lbs of acetone and 
maintained at 70.degree.-80.degree. C. with agitation under a nitrogen 
atmosphere. Then separate streams of 5225 lbs of molten maleic anhydride 
(MA), 3713 lbs of liquid methyl vinyl ether (MVE) and a solution of 209 
lbs. of 4,4'-azobis(4-cyanopentanoic acid) in 1033 lbs of acetone, (4% by 
weight based on MA) were introduced separately and continuously into the 
precharged reactor. 
The MA addition rate was 15.47 lb/min; the MVE addition rate was 21.77 
lb/min; and the initiator solution addition rate was 5.18 lb/min. The 
period of addition was 6 hours. The product was clear and odorless, 
viscous, 50% solids acetone solution of the maleic anhydride-methyl vinyl 
ether copolymer having a specific viscosity of about 0.3 and less. 
Residual monomers, acetone and maleic acid were substantially absent from 
the solution. 
(b) Esterification and (c) Solvent Exchange 
The copolymer solution (in acetone) then was esterified and solvent 
exchanged with ethanol by injecting vaporized ethanol at 
85.degree.-95.degree. C. continuously through spargers below the surface 
of the solution over an 8 hour period while simultaneously distilling 
acetone overhead at atmospheric pressure at the boiling point of the 
solution (approximately 60.degree. C.). The product was a crystal clear, 
odorless ethanol solution of the ethyl half-ester of the copolymer, at a 
50% solids level, with less than 0.2% acetone therein, and substantially 
no residual monomers or maleic acid, at a specific viscosity of about 0.4 
or less. 
COMATIVE EXAMPLES 
EXAMPLE 2 (ZAMORA) 
Zamora, U.S. Pat. No. 5,233,367, Example 1 (which used decanoyl peroxide as 
the polymerization initiator) was repeated to provide the ethyl half-ester 
copolymer of maleic anhydride and methyl vinyl ether as a 50% solution in 
ethanol. A hair spray composition was prepared at 55% VOC using this 
copolymer solution, and its properties were determined in comparative 
testing with similar hair spray compositions containing the copolymer 
solution of the invention. 
EXAMPLE 3 (GOERTZ) 
Goertz, U.S. Pat. No. 4,908,413, Example 1 (which used 
2,2'-azobis-(2,4-dimethylvaleronitrile as polymerization initiator and 
p-toluenesulfonic acid as the esterification catalyst) was repeated to 
provide an ester copolymer of maleic anhydride and methyl vinyl ether as a 
50% solution in ethanol. Then a hair spray composition was prepared at 55% 
VOC using this copolymer solution, and its properties were determined in 
comparative testing with the composition of this invention. 
INVENTION COMPOSITIONS 
Several pump and aerosol compositions containing the invention were 
prepared, and are shown in Table 1 below. 
TABLE 1 
______________________________________ 
55% VOC Hair Spray Compositions of Invention 
Pump* 
% by Wt. 
Components (A) (B) 
______________________________________ 
Copolymer of Ex. 1 4.0 4.0 
(as 100% solids) 
AMP-95 -- 0.18 
TIPA 0.38 -- 
Ethanol (total) 55.0 55.0 
Water 40.62 40.82 
pH 5.40 5.55 
*Seaquist Euromist II (160 mcl output) with 0.018" .times. 0.010" 
deep actuator. 
Aerosol** 
(A') (B') 
______________________________________ 
Copolymer of Ex. 1 5.0 5.0 
(as 100% solids) 
AMP-95 0.23 0.23 
Ethanol (total) 20.0 20.0 
Water 39.17 8.92 
Corrosion Inhibitors 
Liquid phase (MEA-Borate and 
0.40 0.40 
MIPA-Borate Menacore .RTM. BE) 
Vapor phase (NH.sub.4 OH) 
0.20 0.20 
Propellant 
DME (Dimethyl ether) 
35.00 -- 
HFC-152A (duPont) -- 30.00 
______________________________________ 
(A) (B) 
______________________________________ 
**Seaquist ST-74 Valve 
**Seaquist ST-74 Valve 
0.018 .times. CAP .times. 0.015 
0.013 .times. 0.062 Std .times. No 
VT .times. 0.050 ID VT .times. 0.122 ID 
Actuator: ST-150 Misty 
Actuator: ST-200 Misty 
Orifice: 0.023" Orifice: 0.018" 
pH (of concentrate, 6.5 6.6 
without propellant) 
______________________________________ 
In high solids hair spray formulations, e.g. at 10-12% solids, a suitable 
spray is made by using suitable atomizer equipment, as follows: 
For aerosols: a Seaquist ST-74 valve system having a 0.010" stem/cap 
body/0.010" VT/0.030"ID; Actuator: ST-150 Misty, 0.020" orifice. 
Spray rate: 0.25"-0.28" 
Pattern: 3 1/2-4" 
PROPERTIES OF COPOLYMERS OF INVENTION 
Table 2 summarizes the weight average molecular weights, polydispersity and 
specific viscosities for the various examples. As can be seen from Table 
2, the invention possesses the lowest weight average molecular weight and 
specific viscosity values, namely, 63,900 and 0.28, respectively, as 
compared to the other examples. The invention example also possesses the 
narrowest polydispersity of 2.0. 
TABLE 2 
______________________________________ 
PHYSICAL PROPERTIES OF COPOLYMERS OF 
INVENTION AND COMATIVE COPOLYMERS 
Weight Average 
Polydisper- 
Molecular Wt,* 
sity, Specific 
Copolymer M.sub.w M.sub.w /M.sub.n 
Viscosity** 
______________________________________ 
Invention 63,900 2.0 0.28 
(Example 1 herein) 
Zamora 82,700 3.2 0.35 
(Example 2 herein) 
Goertz 160,000 3.2 0.99 
(Example 3 herein) 
______________________________________ 
*based on polystyrene calibration curve 
**1 wt. % solution of copolymer in ethanol 
Table 3 presents the user performance characteristics of 55% VOC pump hair 
spray compositions containing (A) Gantrez.RTM. ES-225 copolymer, in 
ethanol, with copolymers prepared according to (B) Zamora or (C) Goertz, 
compared to (D) the Invention. As shown therein, the low weight average 
molecular weight and narrow polydispersity of the invention copolymers 
provides performance attributes in the respective formulations which are 
superior to those containing Gantrez.RTM. ES-225, or the Zamora or Goertz 
copolymer solutions. The low specific viscosity of formulations utilizing 
the invention copolymer solution also reduces tack and dry times of the 
system, and provides a very desirable spray pattern. 
TABLE 3 
__________________________________________________________________________ 
COMISON OF USER PERFORMANCE OF 
55% VOC PUMP HAIR SPRAY COMPOSITIONS 
(A) (B) (C) (D) 
Gantrez .RTM. ES-225 
Zamora Goertz Invention* 
(100% VOC) 
(55% VOC) 
(55% VOC) 
(55% VOC) 
__________________________________________________________________________ 
% Active 5.5% 4.0% 4.0% 4.0% 
(polymer solids) 
Film Hardness 
3H-4H 6H 9H 5H 
(70F/50% RH) 
9H = Very Hard 
1B = Very Soft 
Film Clarity 
Clear Sl. Hazy 
Sl. Hazy 
Clear 
(70F/50% RH) 
HHCR (Hold) 
95.35% 98.03% 96.06 98.52% 
(80F/90% RH) 
@ 90 minutes 
HHCR 92.61% 96.03% 94.60% 96.15% 
(80F/90% RH) 
@ 4 hrs 
Duration of Tack 
18 secs 42 secs 
36 secs 
23 secs 
Dry Time 39 secs 54 secs 
65 secs 
44 secs 
__________________________________________________________________________ 
COMISON OF USER PERFORMANCE OF VARIOUS 
55% VOC PUMP HAIR SPRAY COMPOSITIONS 
(A) (B) (C) (D) 
Gantrez .RTM. ES-225 
Zamora Goertz Invention 
(100% VOC) 
(55% VOC) 
(55% VOC) 
(55% VOC) 
__________________________________________________________________________ 
Stiffness 6 7.6 8.0 8 
10 = Very very Stiff 
1 = Very very Soft 
Non-Flaking 
9 9.2 7.2 8.6 
10 = No Flaking 
1 = Heavily Coated 
Ease of Combing 
6.8 6.6 8.6 6.2 
10 = No Drag 
1 = Very heavy drag 
Removability 
Acceptable 
Acceptable 
Acceptable 
Acceptable 
Particle Size 
80 microns 
105 microns 
143 microns 
83 microns 
D[v, 0.5] 
Spray Pattern @ 6" 
2.5-3" 3 1/2-4 
3 1/2" 3.5" 
Spray Character 
Fine spray 
Coarse spray 
Coarse spray 
Very fine spray 
Initial Curl Droop 
6% 28% 10% 7% 
(70F/50% RH) 
@ 10 minutes 
__________________________________________________________________________ 
*Copolymer is 10% neutralized 
PUMP: Seaquist Euromist II (160 mcl output) with 0.018" .times. 0.010" 
deep actuator 
More particulary, as shown in Table 3 above, the invention compositions (D) 
provide crystal clear hair spray compositions, with a hold of &gt;90%, a tack 
time of &lt;30 seconds, a dry time of &lt;45 seconds, and a pump particle size 
of &lt;100 .mu.m, as fine particles. In contrast, Zamora's hair spray 
compositions (B) are hazy, provide less than 90% hold, a tack time of 
greater than 40 seconds, a dry time of greater than 60 seconds, and only 
coarse spray particles of greater than 100 .mu.m in size. Hair spray 
compositions prepared using the Goertz copolymer solution (C) also have a 
slight haze, an extended tack time of 36 seconds, a very long dry time of 
65 seconds, and a particle size of 143 .mu.m, and coarse in appearance. 
Accordingly, the copolymer solutions of the invention, and 55% VOC hair 
spray compositions made therefrom, exhibit physical and performance 
characteristics which are commercially acceptable, whereas both 
Gantrez.RTM. ES-225, and the Zamora and Goertz copolymer solutions and 
compositions, provide much poorer and less acceptable products. 
From Table 3, also, it is seen that the invention provides a desirable low 
initial curl droop in 55% VOC formulations of 7%, which is comparable to 
anhydrous systems, while formulations utilizing the Zamora and Goertz 
copolymers give an initial curl droop of 28% and 10%, respectively. 
As discussed, the initiator residues of decanoyl peroxide are responsible 
for the unacceptable haze/precipitate in formulations utilizing the Zamora 
copolymer which contain a high percentage of water. These initiator 
residues, e.g. ethyl decanoate, also appear to plasticize the copolymer 
and may contribute to the observed extended tack and dry times, soft films 
and the high initial curl droop for hair spray compositions containing 
such copolymer solutions. 
A similar study for aerosol compositions is given in Table 4 below. The 
results parallel those for pump systems. 
TABLE 4 
__________________________________________________________________________ 
COMATIVE AEROSOL HAIR SPRAY COMPOSITIONS 
(B) (B') 
Invention Invention 
(A) Copolymer Copolymer 
Gantrez .RTM. ES-225 
35% DME 30% 152a 
(100% VOC, 
(55% VOC, (55% VOC, 
4% Active) 
5% Active) 5% Active) 
__________________________________________________________________________ 
Film Hardness 
9H 9H 9H 
(70F/50% RH) 
9H = Very Hard 
1B = Very Soft 
Film Clarity 
Clear Clear Clear 
(70F/50% RH) 
HHCR, % 100 98.81 100 
(80F/90% RH) 
@ 90 minutes 
HHCR, % 84.39 89.32 98.75 
(80F/90% RH) 
@ 4 hrs 8.4 7.2 
Duration of Tack, sec. 
49.8 13.0 20.8 
Dry Time 65.6 22.0 33.2 
Stiffness 8.4 7.2 8.2 
10 = Very very Stiff 
1 = Very very Soft 
Non-Flaking 
8.8 8.8 8.4 
10 = No Flaking 
1 = Heavily Coated 
Ease of Combing 
6.8 8.0 6.4 
10 = No Drag 
1 = Very heavy drag 
Removability 
Acceptable 
Acceptable Acceptable 
Particle size 
97 microns 
38 microns 69 microns 
D[v, 0.5] 
Spray Pattern, @ 6" 
4" 4" 4.5" 
Spray Character 
Very fine spray 
Fine spray Fine spray 
Spray Rate 0.54 0.60 0.90 
(grams/sec) 
Valve/Actuator Seaquist ST-74 
Seaquist ST-71 
0.018 .times. Capillary .times. 
0.013 .times. 0.062 Std .times. 
0.015 VT .times. 0.050 
NO VT .times. 0.122 
ID ST-150 Misty 
ID ST-200 Misty 
0.023" 0.018" 
__________________________________________________________________________ 
The invention copolymer solutions may be used at VOC levels up to 80% VOC, 
as described in Table 5 below. 
TABLE 5 
______________________________________ 
70% VOC AND 80% VOC INVENTION COMPOSITIONS 
at 70% VOC at 80% VOC 
______________________________________ 
Film Clarity 2 3 
Hard Film 9H 9H 
Acceptable pH 4.3 4.55 
Long Term HHCR-90 min 
100.00 100.00 
Long Term HHCR-4 hr 
98.21 99.43 
Drying (Dry Time) 
46.4 46.0 
Tack (Duration) 32.8 33.0 
Stiffness 6.8 6.0 
Comb 7.6 8.0 
Hair 9.2 8.8 
Shine 9.2 9.6 
Combability 7.6 7.4 
Curl Snap 8.4 7.0 
Manageability 6.2 3.4 
Static 3.2 3.6 
Particle Size D[v,0.5] 
83.30 microns 
86.13 microns 
Spray Pattern 4- 1/2" 4- 1/2" 
Sprayability fine spray fine spray 
w/spots w/spots 
Rate (g/sec) 0.13 0.13 
______________________________________ 
In summary, the low solution viscosities of hair spray compositions 
containing the copolymer solution of the invention improves the spray 
characteristics of the hair spray formulation resulting in excellent 
particle size and leading to improved tack and dry times. Such 
formulations, even at low solution viscosities, also show excellent hair 
hold under normal usage levels. The narrow polydispersity of the invention 
copolymers also maximizes the use of an optimized average molecular weight 
for an enhanced hold property while minimizing the amount of low molecular 
weight fractions, which might plasticize the film and reduce hold. The 
substantial absence of high molecular weight fractions in the copolymer of 
the invention also is advantageous because such fractions produces 
undesirable viscosity fluxes and negatively affect spray aesthetics. In 
addition, the low viscosity of high solids formulations of the copolymer 
solutions herein provides a stiffer hold characteristic for the user. 
APPENDIX 
The following test protocols were used herein; other property and 
performance characteristics were obtained by standardized test procedures. 
1. SOLUBILITY 
To determine whether copolymers and polymer solutions were soluble in 80% 
VOC or lower ethanol/water solutions, the following procedure was used. 
PROCEDURE: 
1. Prepare an 80% VOC or lower VOC hair spray formulation with the "test" 
copolymer. 
2. Neutralize the copolymer as necessary with a base. 
3. Visually examine the finished prototype and rate the test solution as 
follows: 
RATING: 
Clear--Polymer completely soluble. 
Hazy--Polymer dissolved; but solution is hazy in appearance. 
Insol/PPT--Polymer is not soluble; and precipitates out of solution. 
2. HIGH HUMIDITY CURL RETENTION 
The curl retention properties of styling or finishing products containing 
resins are measured at 80.+-.2 F/90.+-.2% RH over a specified period. The 
change in percentage curl retention versus time is plotted to illustrate 
differences among various formulations. 
EQUIPMENT 
Duco Cement 
8" European Brown Hair 
Scissors 
Nylon Comb 
Plexiglass cut to 1" squares 
2 7/8".times. 5/8" blue curler and metal clips or 5/8" 
Plexiglass mandral, and retention boards with 1/4" markings 
Environmental Chamber (with precision of .+-.2% RH and 80.+-.2 F) Shampoo 
______________________________________ 
PROCEDURE: 
A. Preparation of Hair Swatches 
______________________________________ 
1. Separate hair into swatches, 2 grams in weight. 
2. Glue the root ends onto a 1" plexiglass square. 
Allow glue to dry completely. 
3. Comb tresses to remove excess hair. 
4. Cut each hair swatch to measure 6.5" in length 
from the bottom of the plexiglass square to the 
end of the tress. Be sure that the length of 
all of the tresses used is the same length. 
Your initial length is referred to as Lo. 
5. Wash hair swatches in 10% shampoo solution 
(reviving, lite or EFA shampoos are acceptable; 
but make sure the same shampoo is used for all 
testing). 
6. Rinse tresses thoroughly with warm tap water. 
7. Comb through to untangle hair tresses. 
______________________________________ 
______________________________________ 
B. Preparation and Exposure of Test Samples 
______________________________________ 
8. Squeeze out excess water by running tress 
between your thumb and index finger. 
NOTE: Tresses must be prepared one day 
prior to testing and cannot be used 
if in rollers longer than 24 hours 
9. Check chamber for conditions (80 + 2 F/90 + 2% 
RH). Adjust as necessary and allow chamber to 
equibrate prior to preparing tresses for 
testing. 
* Check (Section C) below for application of 
products prior to curling hair 
10. Curl hair in a coil configuration by rolling it 
on a diagonal onto a 5/8" curler. Secure hair 
on curler with a metal clip. 
11. Dry hair in the curler at room temperature 
overnight on a horizontal surface, or suspend 
from hooks under bonnet dryer for one (1) hour, 
except for gel and mousse. Curls treated with 
gel or mousse must be dried in oven set at 
100.degree. C. for one (1) hour and then dried at room 
temperature overnight on a horizontal surface. 
12. The next day, carefully remove clip and slide 
the curler out of the hair. 
13. Suspend the curled tress from the plexiglass 
end and apply a controlled amount of product as 
discussed below. 
14. Lay the treated curls on a horizontal surface 
and allow to air dry for 1/2 hour except as 
stated below for gels and mousse. 
15. Suspend the dry treated curls in a random 
fashion from graduated, plexiglass retention 
boards. 
16. Recheck chamber for conditions prior to placing 
boards in chamber. 
17. Take initial readings of the curl heights prior 
to placing boards in the chamber. These 
readings are referred to as Li. 
18. Place boards in chamber and close door. Do not 
open chamber until testing is completed. 
19. Record curl heights at specific time intervals. 
These readings are referred to as Lt. 
______________________________________ 
Time intervals are 15, 30 minutes, 1, 1 1/2, 2, 3, 4, 6 hours or longer if 
required. 
NOTE: For Spritz, gel and mousse record data only up to 4 hours. For 
screening purposes, 90 minutes may be used; for decision making purposes 
four (4) hours is preferred. 
______________________________________ 
C. Application of Products 
Product Amount to Apply 
______________________________________ 
Aerosol Hair Spray 
Two (2) second burst evenly 
applied to both front and back 
of curled tress at a distance of 
8". 
Pump Hair Sprays 
Two (2) sprays delivered 
uniformly to both front and back 
of curled tress at a distance of 
8". 
Spritz Type Products 
Two (2) sprays delivered 
uniformly to both front and back 
of curled tress at a distance of 
8". 
Gels 0.50 grams of product is applied 
to wet hair, and combined 
through to evenly distribute. 
Hair is then rolled onto curler 
as specified and dried in a 
100.degree. C. oven for one (1) hour, 
then overnight at room 
temperature on a flat surface. 
Mousse 0.50 grams of product is applied 
to wet hair, and combed through 
to evenly distribute. Hair is 
then rolled onto curler as 
specified and dried in a 100.degree. C. 
over for one (1) hour, then 
overnight at room temperature on 
a flat surface. 
______________________________________ 
D. Calculations 
1. Calculate percent curl retention as follows: 
##EQU1## 
Where: Lo=length of fully extended hair 
Li=lengths of hair before exposure (initial) 
Lt=length of hair after exposure 
2. Use Lotus 123 program for data entry and graph generation. 
E. References 
The Aerosol Handbook, Montfort A. Johnson, "High Humidity Curl Retention 
Testing", p. 432. 
3. DRYING TIME AND STICKINESS/TACKINESS OF HAIRSPRAYS 
(Trained Panel Method) 
As solvent evaporates from freshly applied hairspray, the formulation 
experiences a period of time during which it is sticky to the touch. This 
effect is due to the plasticizing action of the solvent and is influenced 
by a number of factors. Among these are heaviness of the spray, 
temperature, air movement, intrinsic tendency of a formulation toward 
stickiness and its propensity for solvent retention. In this test, the 
first three factors are controlled while stickiness and total drying time 
of a formulation are determined. 
EQUIPMENT: 
31/2 gram hair swatches (virgin brown European hair) cut to 61/2 length. 
Lab Timer or Stopwatch. 
Pump or Aerosol prototype to test. 
PROCEDURE: (3 to 5 replicates are normally run). 
1. Suspend hair swatch vertically from tress board. 
2. Apply a controlled amount of product to hair tress from an 8" distance. 
For pumps apply two (2) spray depressions to front of tress. For aerosols 
apply a two (2) second burst to front of tress. 
3. Start timer and have participant evaluate tresses. 
4. Feel the entire length of tress with hands and indicate when hair (a) 
starts being sticky/tacky, (b) stops being sticky/tacky and (c) is 
completely dry. 
5.Total drying time and duration of the sticky period can therefore be 
determined for the test and control samples. 
NOTE To minimize right-handed bias, alternate hands when evaluating 
samples. 
REPORT: 
An average of 3-5 evaluations per sample. 
4. INITIAL CURL DROOP 
Measure the amount of curl droop of hair after being sprayed to simulate 
the real world experience of a consumer when they spray their hair and the 
actual loss of "hold" of the hairstyle that takes place before it dries. 
EQUIPMENT/MATERIALS: 
1. Hair tress (length: 6.5 weight: 2 gram) rolled in a spiral. 
2. Bobby pins. 
3. Stopwatch or timer. 
4. Rollers--5/8" outer diameter. 
5. Tress board with 1/4" delineated lines. 
PREATION OF HAIR: 
1. All the hair is thoroughly washed and while still wet, rolled in a 
spiral curl diagonally on a 5/8" roller, and secured with bobby pins at 
each end. 
Note; the spirals should not overlap each other, but be covering the entire 
curler. 
2. The tresses are dried overnight, or placed in a 45.degree. C. oven for 
one (1) hour, or placed under a salon hair dryer for one (1 ) hour. 
3. Before spraying the hair the rollers are carefully removed, trying to 
maintain the curl as tight as possible. 
4. The tress is then sprayed with the product and the curl droop is 
measured every minute for ten (10) minutes. 
5. Application is determined using the following chart; 
______________________________________ 
Hair Spray Amount of Product 
Type Distance from Curl 
Applied 
______________________________________ 
Pump 8" 4 depressions - front only 
Aerosol 8" 4 seconds - front only 
______________________________________ 
6. The conditions, ideally, should be 70.degree. F. and 50% relative 
humidity. Six (6) swatches are tested for each variable and the data 
compared statistically using the following formula, and worksheet; 
##EQU2## 
lo=original length, fully extended hair li=initial length curled, before 
drying 
lf=final length curl, after drying 
While the invention has been described with particular reference to certain 
embodiments thereof, it will be understood that changes and modifications 
may be made which are within the skill of the art. Accordingly, it is 
intended to be bound only by the following claims, in which: