Note: Descriptions are shown in the official language in which they were submitted.
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CP-09~9
~lPROVED ilAIR SPRAY C0~1~'0SITION
I. Description:
field of the Invention:
Th~is application relates to hair spray compositions ha~ing im-
proved holding ability and feel ~hen sprayed onto the hair.
Background of the Invention:
Among the most important requirements of hair spray compositions
are to have good holding ability for curl retention, without giving a
harsh, brittle feeling to the hair and they should be able to hold the
curl e~en under humid conditions. Furthermore, the hair spray should
be water soluble so that it can be wastled out of the hair at the time
it is shampooed. Other requirements for hair sprays include a lack of
stickiness, good combing characteristics and a lack of powdering or
flaking.
The most commollly employed polymer ingredient of hair sprays is a
copolymer of methyl ~inyl ether with maleic acid or maleic anhydride
(sold by GAF Corporation under the trade name Gantrez*ES-225) which
has the CTFA designation Ethyl ester of PVM/MA copolymer. (CTFA des-
ignations refer to the CTFA Cosmetic Ingredient Dictionary published
by The Cosmetic, Toiletry and Fragrance Ass~ciation in 1982). These
polymers are not water soluble.
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~ ater solu~ility is a (iesired feature of hair sprays. The resin
is rendered water soluble by being partially neutralized by reacting
the free carboxylic groups of the polymer with a base, such as ammo-
nia, dimethylamine, diethylamine, diethanolamine, triethanolamine,
* trade mark.
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triisopropanolamine, 2-methyl,2-amino-1-propanol, and the ~ike. ~lost
commercial hair sprays "Jhether dispensed ~rom pressurized aerosol
containers or from Inanual pump dispensers, are o~ the aforementioned
type whicll cont~in Ethyl ester o~ PVM/MA copolymer. Typical composi-
tions of tllis kind are described, for example, in U.S. Patents Nos.
3,922,3~41 and 4,164,562.
Whereas, the alcoholic solutions of the copolymer are considered
stable and have relatively good shelf life, the solutions of the par-
tially neutralized copolymer tend to darken upon standing at room tem-
perature within a few months and faster at elevated temperatures. The
rate of the discoloration of the initially clear solution of the par-
tially neutralized resin, and the intensity of the discoloration de-
pends on the particular base that is employed for neutralization.
Although the discoloration can be su~stantially reduced by the use of
different neutralizing bases, the requirement of good curl-holding
ability o-f the ultimate product often compels the use of certain neu-
trali2ing base compounds which result in a more pronounced darkening
effect than can be obtained with some other bases. Lack of discolor-
ation of the hair spray solution is a special requirenlent of sprays
that are to be sold in transparent or translucent containers.
There are a number of patents showing attempts at mixing various
resins with each other for hair spray compositions. Most commonly
these deal with resin combinations including the aforementioned Ethyl
ester of PVM/MA copolymer (e.g. U.~r Patent No. 3,83~,637), and with
combination of polyvinylpyrrolidone with other resins (e.g. U.S. Pat-
ents hos. 3,0`/3,79~; 3,914,qO3; 3,928,558; aJld 4,007,005).
-A problem frequently encountered in attempting to mix resins with
each other is the lack of the stability of the mixture due to the in-
compatability of the resins that are to be mixed, resulting in phase
separation. Another requirement is that the various resin ingredients
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of the mixture should be soluble in the same solvent. Furthermore,
the properties of the resins that are to be mixed should complement
each other in some beneficial fashion.
Detailed Descri~tion of the Inv ntion
We have discovered that two different, specific resin combina-
tions provide d complete range of advantageous properties eminently
satisfying the desirable features that are outlined above. Both of
these specific resin combinations are based on the discovery that when
each of two resins with a yood curl-holding ability but each having a
stiff feel on the hair, are each combined with a modifying resin to
make the feel acceptable, the quality of the curl-holding aDilities of
the resulting mixture of resins is, surprisingly, essentially equival-
ent to the curl-holding ability of the component having a good curl-
holding ability in itself. This is so even if the modifying resin in
itself has in-ferior curl-holding characteristics. The stiff holding
resin is either an octylacrylamide/acrylic acid/ methylmethacrylate
copolymer (sold by The National Starch Co. under the trade designation
Resin 2~-4961, and is referred to hereinafter as "Resin 2~-4961") and/
or an octylacrylamide/acrylates/butyaminoethyl methacrylate copolymer'
wherein the acrylates include two or more monomers consisting of'acryl-
ic acid, methacrylic acid or any of their simple esters, such as methyl
methacr~late and hydroxypropyl methacrylate'(sold by The National
Starch Co.), having the CTFA name Ampholner in combination with d mod-
ifying resin. The latter is an ac~ylate/acrylamide copolymer (sold by
Ciba-Geigy Corporation under the trade name Ultrahold-~) having the
CTFA nan~e Acnylate/ac~ylall~ide copolymer. A-combination of dt least
one of the aforementioned stiff-holding resins with the Acrylate/
acrylamide copolymer modifying resin is the principal ingredient of
the hair spray compositions of the present invention.
* trade mark.
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Thus the essential ingredients of the compositions of the present
invention comprise at least one of Resin ~8-496`1 and Amphonner, in com-
-bination with Ultrahold-8, disolved in a preferably alcohol solvent.
The free carboxylic groups of the polymers are at least partially neu-
tralized to make the resin conlbination sufficiently soluble to be able
to be rfnloved from the hair by shampooing. The composition containing
the combined resins is stable and does not separate and, depending on
the nature of the particular perfume that is employed, the color of
the resin composition is stable and resists discoloration upon stor-
age, without any additional preservatives.
By means of the present invention it is possible to reduce the
amollnt of resin solids to obtain equivalent or better curl-holding
ability with hair spray formulations of the prior art. This results
in d lower r~sin build-up on hair between shampoos, lessened sticki-
ness, faster drying and lower costs. The solids content of the resin
is generally between about 1'~ and 10% by weight of the hair spray com-
position, suitably between about 1.2% and about 4.8% by weight.
The good curl-holding resin component comprises a major part of
the two resins that are present in the compositions of the present
invention (Resin 28-4961 or Amphomer or a mixture of both~ whereas the
modifying resin component (Acrylate/acrylamide copolymer) comprises a
smaller`part. These major and smaller parts can be suitably present
~ in a weight ratio of about 60-95:40 5. Suitably the weight ratio can
be about 70-85:30-1~. -
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Both the optimulll solids concenlration of the resin conlpollent of
the composition and the weight ratio of the two kinds of resins to
ea~h other can be conveniently determined by routine experimentation,
as will be described later. The form of dispensing, such as by pump
spray or through aerosol application, may require slight modifications
of composition formulations as is well known in the art.
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A further, optional ingredient of hair spray compositions accord-
ing to the present invention is a plasticizer which assists in the
improvement of the combability of the sprayed hair and eliminates
snarling of the hair by assisting its detangling. A number of ~nown
plasticizers can be employed. For example, a polymer of dimethylsil-
oxane w~ith polyoxyethylene and/or polyoxypropylene side chains having
the CTFA name Dimethicone copolyol (such as is sold by Mazer Chemi-
cals, Inc. under the trade name tlasil 1066, and by General Electric
Co. under the trade name GE Silicone 1066)~ or a mixture ùf ethanol-
amides of lauric acid having the CTfA name Lauralnide DEA (such dS is
sold by Mona Industries, Inc. under the trade name Monamid 716), can
be conveniently employed for this purpose. Some other plasticizers
have been found not to perform as well as those indicated above. Such
other plasticizers include mink oil, persimmon oil and the diester of
d 2-ethylhexyl alcohol and sebacic acid known under the CTFA name Oi-
octyl sebacate.
The concentrdtion of the plasticizer can be suitably between
about 0.02% and about 1% by weight based on the composition. More
suitably, in tl~e case of tl~e Dimethicone polyol the concentration is
between about 0.02% and about 0.06%, and in the case of the Lauramide
DEA bet~een about 0.03% and about 1% by weight. The identity of suit-
able plasticizers and their optimum concentrations can be determined
by rout~ne experimentation in a manner known ~ se.
Curl-holding ability can be tel~ted and compared, for example, by
spraying curled hair tresses with the test composition and others with
a control composition and tl~en placillg the tresses into a cabinet un~
der controlled temperature and humidity and observing the rate of e-
longation (i.e. rate of curl release) of the curled tress. Such a
technique is described, for example, in an article by Micchelli and
Koehler in the Journal of the Society of Cosmetic Chemists, Vol. 19,
l968, pp. 863-880.
* trade mark.
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Ease of combability can be determined by spraying a curled tress
of hair and, after drying the spray, pulling a comb throuyh the hair
and determining -either subjectively or instrumentally- the ease by
which the comb is pulled tllrQugll the hair. A suitable instrumental
test is described in an article by Garcia and Dia2 in the Journal of
the Soc,iety of Cosmetic Chemists, Vol. 27, 1976, pp. 379-398.
The composition may contain other, conventional ingredients, such
as a perfume and the like. The bulk of the cornposition is an organic
solvent, such as an alcohol, suitably an aljpilatic alcohol, such as
ethanol, isopropanol or mixtures of such alcohols. Generally no wate~
is added, except for the water content of any of the ingredients that
are available in aqueous solutions, dispersions or emulsions.
In the mdnufacture of the compositions of the present invcntion
sufficient amount of a neutralizer, such as of suitably bet~een about
0.2% and about 0.7% (solids basis) of aminomethylpropanol, is employed
to neutralize most, such as about 90%, of the free carboxylic groups
-to estabish the water solubility of the resin in a manner known ~ se.
Hair swatches of equal weight, having a fully extended length L,
were prepared by curling in an equal manner over a mandrel, then
spraying the curled swatches so that each received an equal amount of
hair spray. After the spray dried, the swatches were l~ung from a clip
and their lengthes (LO) were measured. The swatches were then ex-
posed in a chamber to 90% relativellhumidity at 25C. Curl length
(Lt) "readings were taken after lt?, 1, 2, 3, 4, 5 and 24 hour inter-
vals ~rom the start of the cxperiment. Curl.rctention in X was cal-
culated by the formula:
L-Lt
% Curl Retention = . 100
L ~o
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In applying a statistical analysis to the results including com-
bined measurement results and their standard devidtions ~s a function
of the number of tresses that were tested it was obser~/ed that a lo~-
er resin concentration of the samples according the present invention
combining Resin 28-4961 and Acrylate/acrylalnide copolymer in an 80:20
weight ratio at a concentration of about 4.4% the tresses started to
exceed the curl-holding ability of the control (a conlnercial hair
spray containing 4.75% Gantrez ES-225 resin) in a statistically sig-
nificant m~nner after about four ho~rs exposure. As the resin concen-
tration of the samples was increased to 4.7%t the samples according to
the present invention showed a statistically significant improvement
over tresses treated with the prior art composition after less than
two hours exposure.
In the case of a composition containing 4.5% by weight of a com-
bination of Resin 28-4961 and Acrylate/acrylamide copolymer in an
~0:20 weight ratio the average curl retention percentage was 60% after
24 hoursg compared to 40% of the cornmercial spray ~hich contained
4.75% by weight Gantrez ES-225 resin. The results were essentially
similar when the solids content of the test composition was increased
to 4.7% resin solids. Similar results are obtained by substituting
Amphomer for part or all of the Resin 28-4961 content.
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