Note: Descriptions are shown in the official language in which they were submitted.
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PERSONAL CARE COMPOSITIONS COMPRISING AN ADHESIVE COPOLYMER
TECHNICAL FIELD
The present invention relates to personal care compositions, especially to
hair
spray compositions having improved removeability from hair as defined by hair
stiffness
and flaking values. These compositions comprise an adhesive copolymer and a
solvent
for the copolymer selected from the group consisting of water, ethanol, n-
propanol,
isopropanol, acetone, propylene glycol, and mixtures thereof. The copolymer
component, when dried, exhibits a cohesive strength of greater than about 0.5
kgf/mm2,
a total energy absorption per unit volume of greater than about 0.55
kgfmm/mm3, and an
impact strength of greater than about 7000 ergs.
BACKC'~ROUND OF THE INVENTION
Personal care products play an important role in the life of most consumers.
Personal care products cover a wide variety of products and forms and include
shampoos, soaps, hair sprays, lotions, creams, antiperspirants, anti-acne
products, nail
enamels, lipsticks, foundations, mascaras, and sunscreens. Consumers are
constantly
seeking personal care products that provide the desired benefit sought and
represent a
good value.
Many personal care products use contain various resins, gums, and adhesive
polymers. The polymers are used for a variety of purposes including
thickening, feel
properties, film-forming ability, active deposition, active penetration, hair
holding, etc.
Consequently there is constantly a search for developing polymers having
improved
properties for use in personal care products.
It has surprisingly been found in the present invention that adhesive
copolymers
having certain physical parameters are highly useful. These copolymers are
used in
combination with a solvent for the copolymer selected from the group
consisting of
water, ethanol, n-propanol, isopropanol, and mixtures thereof. The copolymer
solvent
mixtures, when dried, have a cohesive strength of greater than about 0.5
kgf/mm2, a total
energy absorption per unit volume of greater than about 0.55 kgfmm/mm3, and an
impact strength of greater than about 7000 ergs. Without being limited by
theory, it is
believed that these physical characteristics of the dried hair spray
composition account
for the benefits observed.
It has also been found that the preferred hair spray compositions of the
present
invention have an improved removeability from hair during shampooing, wherein
the
removeability is defined in terms of hair stiffness and hair flaking values
ranging from 0
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to about 3.5 (0 to 4 scale) These hair stiffness and flaking values are
indirect measures
of hair spray removeability. Each of these values are determined in accordance
with the
methodology defined herein.
It is therefore an object of this invention to provide personal care
compositions
comprising an adhesive copolymer and a solvent for the copolymer selected from
the
group consisting of water, ethanol, n-propanol, isopropanol, acetone,
propylene glycol,
and mixtures thereof.
It is another object of this invention to provide methods for treating skin or
hair
using these compositions.
It is another object of this invention to provide methods for styling and
holding
hair.
These and other objects will become readily apparent from the detailed
description which follows.
SUMMARY OF THE INVENTION
The present invention relates to personal care compositions comprising:
(a) an adhesive copolymer having a weight average molecular weight from about
10,000 to about 5,000,000, and
(b) a solvent for said copolymer selected from the group consisting of water,
ethanol, n-propanol, isopropanol, acetone, propylene glycol, and mixtures
thereof,
wherein said composition, when dried, has a cohesive strength of greater than
about 0.5
kgf/rnm2, a total energy absorption per unit volume of greater than about 0.55
kgfmm/mm3, and an impact strength of greater than about 7000 ergs. The
compositions
are preferably hair spray compositions having improved removeability, wherein
removeability is defined by a hair stiffness value of from 0 to about 3.5 and
a hair flaking
value of from 0 to 3.5 (0 to 4 scale)
In further embodiments, the present invention relates to a method for treating
the
skin or hair by applying to the skin or hair an effective amount of a
composition
comprising,
a copolymer component comprising:
(a) an adhesive copolymer having a weight average molecular weight from about
10,000 to about 5,000,000, and
(b) a solvent for said copolymer selected from the group consisting of water,
ethanol, n-propanol, isopropanol, and mixtures thereof,
wherein said composition, when dried, has a cohesive strength of greater than
about 0.5
kgf/mm2, a total energy absorption per unit volume of greater than about 0.55
kgf/mm2,
and an impact strength of greater than about 7000 ergs. These methods are
preferably
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directed to the hair spray compositions of the present invention having the
removcability
values (hair stiffness values and hair flaking values) as defined herein.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 illustrates an overhead view of a dumbbell-shaped planar dried hair
spray
film sample useful for measuring the physical properties such as the cohesive
strength
and total energy absorption per unit volume as described herein.
Fig. 2 illustrates a cross-sectional view, showing the thickness of the
dumbbell-
shaped dried film illustrated in Fig. 1.
DETAILED DESCRIPTION OF THE INVENTION
The essential components of the present invention are described below. Also
included is a nonexclusive description of various optional and preferred
components
useful in embodiments of the present invention.
The present invention can comprise, consist of, or consist essentially of any
of
the required or optional ingredients and/or limitations described herein.
All percentages and ratios are calculated on a weight basis unless otherwise
indicated. All percentages are calculated based upon the total composition
unless
otherwise indicated.
All molecular weights are weight average molecular weights and are given in
units of grams per mole.
All ingredient levels are in reference to the active level of that ingredient,
and are
exclusive of solvents, by-products, or other impurities that may be present in
commercially available sources, unless otherwise indicated.
All measurements made are at ambient room temperature, which is approximately
73°F, unless otherwise designated.
All documents referred to herein, including all patents, patent applications,
and
printed publications, are hereby incorporated by reference in their entirety
in this
disclosure.
The term "suitable for application to human hair" as used herein, means that
the
compositions or components thereof so described are suitable for use in
contact with
human hair and the scalp and skin without undue toxicity, incompatibility,
instability,
allergic response, and the like.
The term kgf is a standard physical term denoting a kilogram of force
subjected to
gravitational acceleration, i.e. 9.82 m/s2.
Adhesive Copol
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The compositions of the present invention comprise from about 0.1% to about
30%, preferably from about 0.5% to about 20%, and more preferably from about
0.5% to
about 10%, by weight of the composition, of an adhesive copolymer.
By "adhesive" is meant that when applied as a solution to a surface and dried,
e.g., the hair or skin, the copolymer forms films or welds. Such a film or
weld will have
adhesive and cohesive strength, as is understood by those skilled in the art.
The copolymers, or salts thereof, of the present invention are soluble or
dispersible
in a solvent selected from the group consisting of water, ethanol, n-propanol,
isopropanol, and mixtures thereof, at a concentration of at least about 0.1
mg/mI,
preferably at least about 0.5 mg/ml, and more preferably at least about 1
mg/ml, at about
73°F.
The copolymers of the present invention have a weight average molecular
weight,
in grams/mole, of at least about 10,000. There is no upper limit for molecular
weight
except that which limits applicability of the invention for practical reasons,
such as
viscosity, processing, aesthetic characteristics, spreadability, formulation
compatibility,
etc. The weight average molecular weight is generally less than about
5,000,000, more
generally less than about 2,500,000, and typically less than about 1,500,000.
Preferably,
the weight average molecular weight is from about 10,000 to about 5,000,000,
more
preferably from about 20,000 to about 1,000,000, even more preferably from
about
30,000 to about 500,000, and most preferably from about 50,000 to about
300,000.
A wide variety of adhesive copolymers are useful in the present invention,
provided the physical parameters of the dried hair spray film and the
solubility or
dispersibility requirements and the molecular weight requirements of the
copolymer are
met.
Adhesive Conolymers
The adhesive copolymers of the present invention are formed from the random
copolymerization of vinyl monomer units and macromonomer units containing a
polymeric portion and a vinyl moiety copolymerizable with vinyl monomer units.
Upon
completion of polymerization, the polymeric portion of the macromonomer units
can
form side chains of the copolymer. The vinyl monomer units and the vinyl
moiety
portion of the macromonomer units form the backbone. The vinyl monomer and the
macromonomer can be selected form a wide variety of structures as long as the
copolymer has the required properties described herein.
As will be clear to one skilled in the art, and especially from the Examples,
the
copolymer may have one or more side chains grafted to the backbone. In
addition, the
compositions of the present invention can include, in addition to the
copolymer, low
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levels of the corresponding copolymers having no side chains grafted to the
backbone.
As known in the art, synthetic graft copolymerization processes may produce a
mixture
of polymer molecules containing none, one, or more than one side chains
covalently
bonded to and pendant from the polymeric backbone. From kno-wledge of the
amount
and number average molecular weight of side chains in a polymer sample, and
the
number average molecular weight of the polymer sample, it is possible to
calculate the
average number of side chains per polymer backbone.
The grafted copolymers should satisfy the following two criteria:
(2) the polymeric side chain portion is covalently bonded to the backbone
portion; and
(3) the number average molecular weight of the polymeric side chain portion is
from about 1000 to about 50,000.
The copolymers of the present invention are prepared by the polymerization
combination of vinyl monomers and macromonomers. The copolymers can be
synthesized by free radical polymerization of the monomers and macromonomers.
The
general principles of free radical polymerization methods are well understood.
See, for
example, Odian, "Principles of Polymerization", 3rd edition, John Wiley &
Sons, 1991,
pp. 198-334. The desired vinyl monomers and macromonomers are all placed in a
reactor, along with a sufficient amount of a mutual solvent so that when the
reaction is
complete the viscosity of the reaction is reasonable. Undesired terminators,
especially
oxygen, are removed as needed. This is done by evacuation or by purging with
an inert
gas, such as argon or nitrogen. The initiator is introduced and the reaction
brought to the
temperature needed for initiation to occur, assuming thermal initiators are
used.
Alternatively, redox or radiation initiation can be used. The polymerization
is allowed to
proceed as long as needed for a high level of conversion to be achieved,
typically from a
few hours to a few days. The solvent is then removed, usually by evaporation
or by
precipitating the copolymer by addition of a nonsolvent. The copolymer can be
further
purified, as desired.
As an alternative to a batch reaction, the copolymer can be made by a semi-
continuous or continuous process. In the semi-continuous process, two or more
additions of monomers or macromonomers are made during the polymerization
reaction.
This is advantageous when the copolymer is made of several monomers which
react
during the polymerization at different rates. The proportions of monomers
added to the
reaction at the separate points of addition can be adjusted by one of ordinary
skill in the
art such that the polymers of the final product have a more uniform structure.
In other
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words, the polymers of the final product will have a more consistent monomer
content
distribution for each of the monomer types charged to the reaction.
Examples of related copolymers and how they are made are described in detail
in
U.S. Patent 4,693,935, Mazurek, issued September 15, 1987, U.S. Patent
4,728,571,
Clemens et al., issued March 1, 1988, both of which are incorporated herein by
reference.
Additional grafted polymers are also disclosed in EPO Application 90307528.1,
published as EPO Application 0 408 311 A2 on January 11, 1991, Hayama, et al.,
U.S.
Patent 5,061,481, issued October 29, 1991, Suzuki et al., U.S. Patent
5,106,609, Bolich
et al., issued April 21, 1992, U.S. Patent 5,100,658, Bolich et al., issued
March 31, 1992,
U.S. Patent 5,100,657, Ansher-Jackson, et al., issued March 31, 1992, U.S.
Patent
5,104,646, Bolich et al., issued April 14, 1992, U.S. Serial No. 07/758,319,
Bolich et al,
filed August 27, 1991, and U.S. Serial No. 07/758,320, Torgerson et al., filed
August 27,
1991, all of which are incorporated by reference herein in their entirety.
The copolymers are prepared by the polymerization combination of vinyl
monomers and macromonomers. The copolymer composition is characterized by the
amount of each monomer charged to the polymerization reaction vessel, or
alternatively
used in a continuous or semi-continuous process.
By appropriate selection and combination of the particular vinyl monomer units
and macromonomer units, and by the choice of specific relative ratios of the
units well
within the ability of one of ordinary skill in the art, the copolymers can be
optimized for
various physical properties and for compatibility with other ingredients
commonly used
in hair care applications.
Alternatively, the copolymers of the present invention can correspond to block
type structures which can be described by the formulas A-B, A-B-A, and -(A-B)n-
wherein n is an integer of 2 or greater. A-B represents a diblock structure, A-
B-A
represents a triblock structure, and -(A-B)n represents a multiblock
structure. The
monomer units used to prepare these block copolymers are as described under
the
heading below.
Vinyl Monomer Units
The copolymers of the present invention comprise from about 50% to about 98%,
preferably from about 60% to about 95%, and more preferably from about 70% to
about
90% by weight of the vinyl monomer units. For the block copolymer, the vinyl
monomer units can comprise 100%.
The vinyl monomer unit is selected from copolymerizable monomers, preferably
ethylenically unsaturated monomers. Either a single type of vinyl monomer unit
or
combinations of two or more vinyl monomer units can be utilized. The vinyl
monomers
.~ __._~.____~_- _.__ T
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are selected to meet the requirements of the copolymer. By "copolymerizable",
as used
herein, is meant that the vinyl monomer can be reacted with or polymerized
with the
polysiloxane macromonomers in a polymerization reaction using one or more
conventional synthetic techniques, such as ionic, emulsion, dispersion,
Ziegler-Natta,
free radical, group transfer or step growth polymerization. In the present
invention,.
monomers and macromonomers that are copolymerizable using conventional free
radical
initiated techniques are preferred. The term "ethyleneically unsaturated" is
used herein to
mean a material that contains at least one polymerizable carbon-carbon double
bond,
which can be mono-, di-, tri- or tetra-substituted.
The monomer units can be derived from hydrophilic monomers (typically polar
monomers), or mixtures of such hydrophilic monomers with hydrophobic monomers
(typically low polarity monomers), provided that the solubility
characteristics of the
overall copolymer is achieved. As used herein, "hydrophilic monomers" means
monomers which form homopolymers which are substantially water soluble;
"hydrophobic monomers" means monomers which form substantially water insoluble
homopolymers.
Nonlimiting classes of monomers useful herein include monomers selected from
the group consisting of unsaturated alcohols, unsaturated monocarboxylic
acids,
unsaturated dicarboxylic acids, unsaturated anhydrides, alcohol esters of
unsaturated
monocarboxylic acids, alcohol esters of unsaturated dicarboxylic acids,
alcohol esters of
unsaturated anhydrides, alkoxylated esters of unsaturated monocarboxylic
acids,
alkoxylated esters of unsaturated dicarboxylic acids, alkoxylated esters of
unsaturated
anhydrides, aminoalkyl esters of unsaturated monocarboxylic acids, aminoalkyl
esters of
unsaturated dicarboxylic acids, aminoalkyl esters of unsaturated anhydrides,
amides of
unsaturated monocarboxylic acids, amides of unsaturated dicarboxylic acids,
amides of
unsaturated anhydrides, salts of unsaturated alcohols, salts of unsaturated
monocarboxylic acids, salts of unsaturated dicarboxylic acids, unsaturated
hydrocarbons,
unsaturated heterocycles, and mixtures thereof.
Representative examples of such monomers include acrylic acid, methacrylic
acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized
dimethylaminoethyl methacrylate, methacrylamide, N-t-butyl acrylamide, malefic
acid,
malefic anhydride and its half esters, crotonic acid, itaconic acid,
acrylamide, acrylate
alcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride, vinyl
pyrrolidone, vinyl ethers (such as methyl vinyl ether), maleimides, vinyl
pyridine, vinyl
imidazole, other polar vinyl heterocyclics, styrene sulfonate, allyl alcohol,
vinyl alcohol
(such as that produced by the hydrolysis of vinyl acetate after
polymerization), vinyl
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caprolactam, methacrylic acid esters of C 1-C 1 g alcohols, such as methanol,
ethanol,
methoxy ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-
pentanol, 2-
pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-
butanol, 1-
methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, t-butanol(2-
methyl-2-
propanol), cyclohexanol, neodecanol, 2-ethyl-1-butanol, 3-heptanol, benzyT
alcohol, 2-
octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3;5,5-
tri
methyl-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol, 1-octa decanol, and
the like,
the alcohols having from about 1-18 carbon atoms with the number of carbon
atoms
preferably being from about 1-12; dicyclopentenyl acrylate; 4-biphenyl
acrylate;
pentachlorophenyl acrylate; 3,5-dimethyladamantyl acrylate; 3,5-
dimethyladamentyl
methacrylate; 4-methoxycarbonylphenyl methacrylate; trimethylsilyl
methacrylate;
styrene; alkyl substituted styrenes including alpha-methylstyrene and t-
butylstyrene;
vinyl esters, including vinyl acetate, vinyl neononanoate, vinyl pivalate and
vinyl
propionate; vinyl chloride; vinylidene chloride; vinyl toluene; alkyl vinyl
ethers,
including isobutyl vinyl ether and s-butyl vinyl ether; butadiene;
cyclohexadiene;
bicycloheptadiene; 2,3-dicarboxylmethyl-1,6-hexadiene; ethylene; propylene;
indene;
norbornylene; (3-pinene; a-pinene; salts of acids and amines listed above, and
combinations thereof. The quaternized monomers can be quaternized either
before or
after the copolymerization with other monomers of the graft copolymer.
Preferred monomers include acrylic acid, methacrylic acid, N,N-dimethyl
acrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl
methacrylate, vinyl pyrrolidone, acrylic or methacrylic acid esters of C 1-C 1
g alcohols,
styrene, alpha-methylstyrene, t-butylstyrene, vinyl acetate, vinyl propionate,
2-
methoxyethyl acrylate, 2-ethoxyethyl acrylate, n-butyl methacrylate, isobutyl
methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl
methacrylate, methyl
methacrylate, salts of any acids and amines listed above, and mixtures
thereof.
Macromonomer Units
The copolymers of the present invention comprise from about 2% to about 50%,
preferably from about 5% to about 40%, and more preferably from about 10% to
about
30%, by weight of the copolymer of macromonomer units.
The macromonomer units are copolymerizable with the vinyl monomers, said
macromonomers preferably having a vinyl moiety. Either a single type of
macromonomer unit or combinations or two or more macromonomer units can be
utilized herein. The macromonomers are selected to meet the requirements of
the
copolymer. By "copolymerizable", as used herein, is meant that the
macromonomers can
~.~-_~ _ _____ ___ __ .
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be reacted with or polymerized with the vinyl monomers in a polymerization
reaction
using one or more conventional synthetic techniques, as described above.
The macromonomers that are useful herein contain a polymeric portion and a
copolymerizable moiety which is preferably an ethylenically unsaturated
moiety.
Typically, the preferred macromonomers are those that are endcapped with the
vinyl.
moiety. By "endcapped" as used herein is meant that the vinyl moiety is at or
'near a
terminal position of the macromonomer.
The macromonomers can be synthesized utilizing a variety of standard synthetic
procedures familiar to the polymer chemist of ordinary skill in the art.
Furthermore,
these macromonomers can be synthesized starting from commercially available
polymers. Typically, the weight average molecular weight of the macromonomer
is from
about 1000 to about 50,000.
Preferred macromonomers are polyalkylene macromonomers. Polyalkylene
macromonomers are exemplified by the general formula:
~I~n'~WJm-E
wherein I is an optionally present initiator (i.e. n = 0 or 1), W is a monomer
unit, E is an
endcapping group, and m is an integer from about 10 to about 2000.
I is an optionally present chemical initiator moiety. Without being limited by
theory, I can be derived from a chemical initiator or solvent used in the
synthesis of the
macromonomer. Nonlimiting exmaples of such initiators from which I can be
derived
include hydrogen ion, hydrogen radical, hydride ion, hydroxide ion, hydroxyl
radical,
peroxide radical, peroxide anion, C 1-C20 carbocations, C 1-C20 carbanions, C
1-C20
carbon radicals, C1-C20 aliphatic and aromatic alkoxy anions, ammonium ion,
and
substituted ammonium ions (e.g., C 1-C20 alkyl and C 1-C20 alkoxy
substituted), and
mixtures thereof. I can be derived from any useful solvent, nonlimiting
examples of
which include water, methanol, ethanol, propanol, isopropanol, acetone,
hexane,
dichloromethane, chloroform, benzene, toluene, and mixtures thereof.
W is selected from one or more monomer units. Nonlimiting classes of such
monomers include C 1-C 18 acrylate esters, C 1-C 18 methacrylate esters, C2-
C30 straight
and branched chain alkenes, styrenes, C1-C30 vinyl ethers, C4-C30 straight and
branched chain dimes, and mixtures thereof.
Nonlimiting examples of W groups include those selected from the group
consisting of t-butyl acrylate, acrylic acid, methacrylic acid, n-propyl
methacrylate, iso-
butyl acrylate, n-butyl acrylate, dodecyl acrylate, ethyl acrylate, 2-
ethybutyl acrylate, n-
heptyl acrylate, n-hexylacrylate, iso-butyl acrylate, iso-decyl acrylate, iso-
propyl
acrylate, 3-methylbutyl acrylate, 2-methylpentyl acrylate, nonyl acrylate,
octyl acrylate,
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1-propyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, n-dodecyl
methacrylate, n-octadecyl methacrylate, n-decyl methacrylate, n-pentyl
methacrylate,
isobutylene, isoprene, 1,2-butadiene, 1,3-butadiene, S-methyl-1-hexene, 6-
methyl-1-
heptene, 4,4-dimethyl-1-pentene, iso-butyl vinyl ether, stryene, 2-methyl
styrene, 3-
methylstyrene, 4-methyl styrene, 2-t-butyl styrene, 3-t-butyl styrene, 4-t-
butyl styrene,.
and mixtures thereof. A mixture of W units can be used herein. Additionally;
these
macromonomers can comrpise polymers derived from the polymerization of
acrylates,
methacrylates, and other ethylenic moieties. The polymers derived from these W
units
can be selected for have either high (>25°C) or low Tg (< 25°C)
values. The term Tg
means glass transition temperature, which is familiar to one of ordinary skill
in polymer
science.
E is a copolymerizable moiety or "endcapping" group. Preferably E is an
ethyleneicaily unsaturated moiety. More preferred is when E is selected from
the group
consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 2-
vinylbenzyl, 3-
vinylbenzyl, 4-vinylbenzyl, 2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl, I-
butenyl,
I-propenyl, isobutenyl, cyclohexenyl, cyclopentenyl, and mixtures thereof.
Even more
preferred is when E is selected from the group consisting of vinyl, allyl,
acryloyl,
methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-
vinylbenzoyl,
I-butenyl, I-propenyl, isobutenyl, and mixtures thereof. Most preferred is
when E is
selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl,
ethacryloyl, 3-
vinylbenzyl, 4-vinylbenzyl, and mixtures thereof.
Nonlimiting examples of macromonomer units useful herein include those
selected from the group consisting of acryloyl, methacryloyl, or 3-, or 4-
vinylbenzyl
endcapped polymers of poly(n-butyl acrylate), poly(dodecyl acrylate), poly(2-
ethylhexyl
acrylate), poly(2-ethylbutyl acrylate), poly(n-ethyl acrylate), poly(n-heptyl
acrylate),
poly(n-hexyl acrylate), poly(iso-butyl acrylate), poly(iso-decyl acrylate,
poly(iso-propyl
acrylate), poly(3-methylbutyl acrylate), poly(2-methylpentyl acrylate),
poly(nonyl
acrylate), poly(octyl acrylate), poly(propyl acrylate), poly (2-ethylhexyl
methacrylate),
poly(tridecyl methacrylate), poly (hexyl methacrylate), poly(decyl
methaerylate),
poly(octyl methacrylate), poly(octadecyl methacrylate), poly(dodecyl
methacrylate),
poly(n-pentyl methacrylate), poly(isobutylene), poly(isoprene), hydrogenated
poly(1,2-
butadiene), hydrogenated poly(I,4-butadiene), hydrogenated poly(isoprene),
poly(1,2-
butadiene), poly(1-butene}, poly(5-methyl-I-hexene), poly(6-methyl-I-heptene),
poly(4,4-dimethyl-1-pentene), poly(iso-butyl vinyl ether), poly[4-t-butyl
vinyl benzene-
co-2-ethylhexyl acrylate], poly[2-ethylhexyl acrylate-co-octyl acrylamide),
poly[2-ethyl
~_ _. _.._ _. .__ __.. .. . . t
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vinyl benzene-co-octyl_methacrylate)], poly(n-propyl methacrylate-co-
methacrylic acid),
and mixtures thereof.
Neutralized Copolymers
As is known in the art, polymers which have acidic functionalities, such as
carboxyl groups, are usually used in at least partially neutralized form to
promote
solubility/dispersibility of the polymer. In addition, use of the neutralized
form aids in
the ability of the dried compositions to be removed from the hair or skin.
When
neutralized, it is preferred that from about 10% to 100%, more preferably from
about
20% to about 90%, and even more preferably from about 40% to about 85%, of the
acidic monomers of the copolymer be neutralized.
Any conventionally used base, including organic or inorganic (metallic or
other)
bases, can be used for neutralization of the polymers. Metallic bases are
particularly
useful in the present compositions. Hydroxides, where the canon is ammonium,
an
alkali metal or an alkaline earth metal, are suitable neutralizers for use in
the present
compositions. Preferred neutralizing agents for use in compositions of the
present
invention are potassium hydroxide and sodium hydroxide. Examples of other
suitable
neutralizing agents which may be included in the compositions of the present
invention
include amines, especially amino alcohols such as 2-amino-2-methyl-1,3-
propanediol
(AMPD), 2-amino-2-ethyl-1,3-propanediol (AEPD), 2-mino-2-methyl-1-propanol
(AMP), 2-amino-1-butanol (AB), monoethanolamine (MEA), diethanolamine (DEA),
triethanolamine (TEA), monoisopropanolamine (MIPA), diisopropanolamine (DIPA),
triisopropanolamine (TIPA) and dimethyl stearamine (DMS). Particularly useful
neutralizing agents are mixtures of amines and metallic bases.
Polymers having basic functionalities, e.g., amino groups, are preferably at
least
partially neutralized with an acid, e.g., hydrochloric acid.
Neutralization can be accomplished by techniques well known in the art, and
before or after polymerization of the monomers comprising the graft copolymer.
Solubility of the copolymer, as described above, should be determined after
neutralization, if any, as well as after addition of other ingredients that
may be included
in the copolymer/solvent systems.
Preferred Polymers Of The Present Invention
Nonlimiting examples of preferred polymers of the present invention include
those selected from the group consisting of poly[(t-butylacrylate-co-n-
butylacrylate-co-
acrylic acid)-graft- poly(t--butylacrylate-co-acrylic acid)-graft-
[poly(isobutylene)],
poly(4-t-butylstyrene-co-methacrylic acid)-graft-[(poly(isobutylene)], poly[(t-
butylstyrene-co-methacrylic acid)]-graft-[poly(2-ethylhexyl methacrylate))],
poly[(t-
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butylacrylate-co-2-methoxyethyl acrylate-co-methacrylic acid)]-graft[poly(n-
propyl
methacrylate-co-methacrylic acid)], poly[(t-butylacrylate-co-2-methoxyethyl
acrylate-co-
methacrylic acid)]-graft-poly(n-propyl methacrylate-co-acrylic acid)], poly[(t-
butylacrylate-co-2-methoxyethyl acrylate-co-methacrylic acid)]-graft-
[poly(styrene-co-
methacrylic acid)], and mixtures thereof.
Nonlimiting examples of preferred polymers of the present invention include
those
selected from the group consisting of poly[(t-butylacrylate-co-2-methoxyethyl
acrylate-
co-methacrylic acid)]-graft-poly(n-propyl methacrylate-co-methacrylic acid).
More specific examples of copolymers of the present invention include the
following, where the composition is given as weight percentage of each monomer
used
in the polymerization reaction (i.e. the weight percentage of the monomers and
macromonomers charged).
poly~t-butylacrylate-co-2-methoxyethylacrylate-co-acrylic acid, rg aft-(poly(n-
proQyl
methacrylate-co-methacrylic acid)1 having a weight average molecular weight of
about
150,000, comprising about 22% t-butylacrylate, 42% 2-methoxyethylacrylate, 18%
acrylic acid, 18% poly(n-propylmethacrylate-co-methacrylic acid) macromonomer
with
a weight average molecular weight of about 6000.
poly[(t-butylacrylate-co-2-methoxyethyl acrylate-co-acrylic acids rg aft-
jpoly,isobutylene~j having a weight average molecular weight of about 200,000,
comprising about 40% t-butylacrylate, 20% n-butylacrylate, 20% acrylic acid,
with a
molecular weight of about 10,000, and 20% poly(isobutylene) macromonomer with
a
molecular weight of about 4,000..
Solvent
The compositions of the present invention comprise from about 70% to about
99.9%, preferably from about 75% to about 98%, and more preferably from about
85%
to about 98%, by weight of the composition, of a solvent for the copolymer.
The solvent
is selected from the group consisting of water, ethanol, n-propanol,
isopropanol, and
mixtures thereof.
Where water and alcohol mixtures are used, for instance, water-ethanol or
water-
isopropanol-ethanol, the water content of the compositions is generally in the
range of
from about 0.5% to about 99%, preferably from about 5% to about 50%, by weight
of
the total composition. In such mixtures, the alcohol solvents are generally
present in the
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range of from 0.5% to about 99%, preferably from about 50% to about 95%, by
weight
of the total composition.
In yet another aspect of this invention are provided hair spray compositions
which contain reduced levels of volatile organic compounds such as solvents.
As used
herein, "volatile organic compounds" or "VOCs" are those organic compounds
that
contain less than 12 carbon atoms or have a vapor pressure greater than about
0.1 mm of
mercury. A reduced volatile organic compound hair spray composition of the
present
invention contains no more than 80% volatile organic compounds.
Properties Of The Dried Copolymer Component
The copolymer component of the personal care compositions of the present
invention, when dried, have specific physical properties as defined by the
cohesive
strength and total energy absorption per unit area. The dried copolymer
components also
exhibit specific impact strength properties, and when used in the preferred
hairspray
embodiments of the present invention have an improved removeability as defined
in
terms of hair stiffness and flaking values.
Cohesive Strengt~kgf/mm2)
Cohesion is the strength of the bonds formed within a sample, e.g., a dried
hair
copolymer solvent composition. The cohesive strength, which is designated as
kgf/mm2
(kilograms of force per square millimeter) is the maximum unit stress a
material will
withstand when being subjected to displacement in tension. Stress is the ratio
of
measured load (kg X f) to the original cross-sectional area (mm2) of the
sample.
The cohesive strength of the dried copolymer components of the current
invention
are determined using the following method. This method is based on ASTM
Designation: D 638-91, Standard Test Method for Tensile Properties of
Plastics,
Published January 1992, herein incorporated by reference in its entirety. The
following
test method to measure cohesive strength is similar to the ASTM standard,
however,
several modifications are made to better represent the tensile properties of
the dried
films. The measurements are made at about 73°F and about 50% relative
humidity. The
test method, described herein specifically uses a modified dumbbell shape with
a
thickness equal to about 0.4 mm., and uses an Instron Model Mini-55 (available
from
Instron Corporation, Canton, MA) as the testing machine for applying the force
to the
polymer film samples.
A dried film sample is prepared by drying an amount of the hair spray
composition
(i.e., the silicone-containing adhesive copolymer and solvent selected from
the group
consisting of water, ethanol, n-propanol, isopropanol, and mixtures thereof,
and any
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additional optional components) in a flat-bottomed aluminum mold coated with
PFA
(perfluoroalkoxy) Teflon. The copolymer film is dried at about 73°F and
about 50%
relative humidity until film has attained a "constant weight". By "constant
weight" is
meant that there is less than a 1 % weight fluctuation in the sample over a
period of 24
hours. The drying film should be kept in an area protected from air currents,
which could
result in non-uniform drying and formation of air bubbles. The copolymer film
is cut
into a dumbbell shape for testing . The sample should be substantially free of
defects,
i.e. cracks, chips, tears, etc. Figures 1 and 2 illustrate the planar dumbbell
shaped film to
be used in the tensile testing described herein for the cohesive strength and
the total
energy absorption per unit volume. Figure 1 illustrates an overhead view of
the
dumbbell shaped sample. Figure 2 illustrates a cross section through the
dumbbell
shaped sample. The width of the narrow section, 1, of the dumbbell is about 3
mm ( 1 = 3
mm). The length of the narrow, 3 mm., section of the dumbbell, 3, is about 13
mm. (3 =
13 mm.). The gauge length of the narrow section, 2, is the initial film length
used in the
determination of the strain of the sample. The gauge length is equal to or
less than the
length of the narrow section, preferably equal to the length of the narrow
section (i.e., 2 =
3}. The width of the ends of the dumbbell, 4, are about 10 mm. (4 = 10 mm.).
The
distance between end sections of the film, 5, is about 28 mm. (5 = 28 mm.).
The overall
length of the film, 6, is about 64 mm. (6 = 64 mm.). The length of the wide
ends of the
film is about I8 mm. ( (6-5)I2 = 18 mm.). The transition sections between the
wide ends
and the narrow section of the film are about 6.5 mm. in length (i.e. (5-3)/2 =
6.5 mm.).
Also the end portions of the narrow, center portion should be smoothly curved
to avoid
any stress points in the sample. The curve of the transition section, should
have a radius,
7, of from about 0.5 in. to about 5 inches, and should join tangentially to
the narrow
section. The film is formed to a thickness, 8, of 0.4 mm. {8 = 0.4 mm.). The
dumbbell
shaped samples are further equilibrated to a "constant weight". By "constant
weight" is
meant that over a selected 4 day period, there is no more than 0.2% average
weight gain
or loss, relative to the dumbbell's measured weight 4 days previous and no
more than ~
0.2% weight drift should be observed between two consecutive measurements in
the four
day period of time. The dumbbell should be tested within a 7 day period of
reaching this
constant weight.
The samples are tested on a calibrated Instron Model Mini-55 tensile tester.
Before
mounting the sample into the Instron, the length, 3, width, 1, and thickness,
8, of the
narrow section of the dumbbell shaped sample are measured to the nearest
micron with a
calibrated micrometer. The dimensional measurements are required by the
Instron for
force per unit area calculations. The wide ends of the dumbbell samples are
clamped into
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the Instron and pulled at a crosshead rate of 5 mm. per minute. The Instron
tester
measures the overall forces (e.g., kgf) applied to the film. These forces are
spread over
the cross sectional area of the narrow section of the film. The cohesive
strength of the
copolymer is the maximum unit force measured by the Instron divided by the
cross
sectional area of the narrow portion of the film
The dried copolymer component of the compositions of the present invention
have
a cohesive strength of greater than about 0.5 kgf/mm2, preferably greater than
about 0.6
kgf/mm2, and more preferably greater than about 0.7 kgf/mm2.
Total Ener~y_Absomtion Per Unit Volume (e.g.=k~fmm/mm3)
The total energy absorption per unit volume, which is designated as kgfmm/mm3
(kilograms of force millimeters per millimeter cubed), is the ratio of the
total energy
required to reach the autobreak point (in kgf X mm) to the original volume of
the sample
(mm3). The total energy required to reach the break point is calculated using
standard
techniques by determining the area under a load versus displacement curve for
the
sample. The total energy absorption per unit volume is also known as
"toughness" by
those skilled in the art of polymer science and materials testing.
The measurements are made at about 73°F and about 50% relative
humidity.
The dried copolymer component of the compositions of the present invention
have
a total energy absorption per unit volume of greater than about 0.55
kgfmm/mm3,
preferably greater than about 0.75 kgfmm/mm3, more preferably greater than
about 1.10
kgfmm/mm3, more preferably greater than about 1.60 kgfmm/mm3, and most
preferably
greater than about 2.15 kgfmmlmm3.
Impact Strength
Impact strength is the mean-failure energy (mass X gravity X height) required
to
produce sample failure, e.g., in a dried hair spray composition. The sample
failure is
characterized by a crack or split created by the impact of the falling weight
that can be
seen by the naked eye under normal laboratory lighting conditions.
The impact strength of the dried copolymer components of the compositions of
the
current invention are determined using the following method. This method is
based on
ASTM Designation: D 5420-93, Standard Test Method for Impact Resistance of
Flat,
Rigid Plastic Specimen by Means of a Striker Impacted by a Falling Weight
(Gardner
Im act , Published 1995, herein incorporated by reference in its entirety,
however,
several modifications are made to better represent the impact properties of
the dried film.
The measurements are made at about 73°F and about 50% relative
humidity.
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16
The test method, described herein specifically uses rectangular shaped samples
with
a thickness equal to about 0.4 mm, and uses a GCA/Precision Scientific
Penetrometer
modified to drop a blunt faced probe to a distance of 70 mm and equipped with
a
Precision Scientific solenoid controller for GCA Penetrometer, a blunt faced
cylindrical
probe with a surface area of 8 mm2 (OK M&T Corp. - part# WSU30), and a ruler
which
measures in 1 mm increments.
The samples are prepared using the film drying method described above in the
cohesive strength measurements. The copolymer film is cut into the rectangular
shape,
e.g. 10 mm X 20 mm. The thickness of the sample is 0.4 mm. The film thickness
of
various test samples should be maintained within ~15% of 0.4 mm.
The following measurement process is used. Turn on the solenoid operated probe
release controller. The controller should begin to cycle on and off as
indicated by a red
light. Be sure the probe face is flush with the impact surface so that the
sharp edge of the
probe does not strike the film. Place a film sample on the Impact Tester over
the target
area. Direct the metric ruler gently on the film sample. Direct the lightening
source
across the surface of the sample such that the light source is in the same
plane as the
surface of the film. Small fractures in the film will reflect light and be
easily detected.
Move the probe up to desired drop distance. A suggested distance progression
is: 1 mm,
3 mm, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, and further 5 mm increments up to 70
mm. (70 mm is the upper limit of the instrument). Turn on the instrument
switch, to
drop the probe onto the sample. The first step in the measurement of impact
energy is to
find the range of probe height necessary to fracture the film. Start at 1 mm
for the first
step. Continue to move up according to the suggested distance progression
until a
fracture is observed. When a fracture is observed make a note of it and move
to a new
sample. The second step in determining impact energy is to set a new sample
and start
drop at an observed fracture point in the range procedure. Set a new film
sample and
move the probe to the next lowest setting. If the film fractures, record
result and repeat
previous step. If the film does not fracture, set a new sample and move to the
next
distance. Continue to set new samples and increase the drop distance until the
film
fractures. Continue the procedure until 5 fractures are observed. Calculate
the amount
of work energy, i.e. the fracture strength using the following formula:
W=mxgxh,where
W = amount of work energy in ergs,
m = mass of probe (59.53 g) (The probe is removable and can be replaced with
one
of different mass or impact surface area).
g = gravitational constant (980.665 cm/sec2),
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h = average distance probe travels to impact (cm).
The dried hair spray compositions of the present invention have an impact
strength
of greater than about 7000 ergs, preferably greater than about 20,000 ergs,
and more
preferably greater than about 50,000 ergs.
Hair Sprat/ Removeability
The adhesive copolymers herein have improved removeability when used in the
preferred hairspray embodiments of the present invention. In this context,
removcability
means that the adhesive copolymers are more easily removed from the hair or
other
applied surface during shampooing.
For purposes of defining the preferred hair spray compositions of the present
invention, removeability is determined indirectly by evaluating hair stiffness
and the
appearance of observable white flakes after treating the hair in accordance
with the
removeability methodology described hereinafter. It has been found that the
removeability of a hair spray formulation after shampooing correlates with the
resulting
stiffness/softness of the hair and the appearance/nonappearance of white
flakes on the
hair after a series of shampooing cycles. The hair spray compositions of the
present
invention have high removeability e.g., reduced stiffness and reduced white
flaking. The
term "removeability" as used herein therefore refers to hair stiffness values
(0-4 scale)
and white flaking values (0-4 scale) as measured in accordance with the
methodology
described hereinafter.
For purposes of the defining the preferred hair spray compositions of the
present
invention, the removeability of the hair spray compositions is defined as a
combination
of hair stiffness values and hair flaking values, wherein the hair spray
compositions
provide hair flaking values ranging from 0 to about 3.5, preferably from 0 to
about 2.5,
more preferably from 0 to about 2.0, and hair stiffness values ranging from 0
to about
3.5, preferably from 0 to about 2.5, more preferably from 0 to about 2Ø
Methodology: Hairspray Removeability
Removeability of the hairspray composition of the present invention, as
indirectly
evaluated in terms of hair stiffness and the appearance of white flakes, is
determined in
accordance with the following methodology. The methodology simulates multiple
application and multi-cycle application of hairspray compositions so as to
indirectly
determine how readily and effectively such hairspray compositions are removed
from
hair.
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The methodology described herein provides a means of evaluating hair switches
blindly treated with hairspray embodiments of the present invention. The
method by
which each hair switch is treated with the hairspray embodiments, and the
method by
which each treated hair switch is then evaluated for removeability are
described in detail
below.
Two trained panelists each evaluate identically treated hair switches or sets
of
hair switches for stiffness and the appearance of white flakes. The panelists
then
individually assign each of the treated hair switches with a numerical score
(0 to 4 scale)
for hair stiffness and a numerical score for flaking (0 to 4 scale). The order
in which the
hair switches are treated with different hair spray embodiments is randomized
and
conducted round robin. Two identical sets of switches are prepared as
described below
for each panelist so that each has a fresh set of switches to evaluate. Before
evaluating
the blindly treated hair switches, each panelist also evaluates (not blinded)
an untreated
hair switch as a zero reference for hair stiffness and flaking. Each panelist
also
evaluates a control treated hair switch as a flaking reference (score 4.0) and
another
control treated hair switch as a hair stiffness reference (score 4.0). The
hair stiffness
values as defined herein are determined by averaging the hair stiffness scores
provided
by the two panelist. Likewise, the hair flaking values as defined herein are
determined
by averaging the hair flaking scores provided by the two panelists.
The hair switches are treated with either an aerosol or non-aerosol hair spray
embodiment of the present invention in accordance with the following steps.
The hair
stiffness reference and the flaking reference are also prepared in accordance
with the
following steps, except that each is treated with the corresponding hair spray
formulations as described hereinafter in Tables 2 and 3.
1 ) Vertically suspend a clean hair switch ( 10 inch European virgin brown
hair, 20
gram) from its bound end and comb (black rubber comb, 5 inches by 1 inch, 1/2
fine tooth) through the switch to remove any tangles.
2) If necessary, use a static gun to eliminate any static build-up on the
switch.
3) For non-aerosol products, spray the switch from a distance of 4 inches
while
applying ten pumps of the product to the switch and while moving the atomized
spray pattern in a fluid up-and-down motion to cover the entire switch, or for
aerosol products, spray each switch from a distance of 6 inches while applying
the aerosol stream to the switch for a period of 3 seconds and while moving
the
aerosol stream in a fluid up-and-down motion to cover the entire switch.
4) Repeat step 3 on the opposite side of the switch.
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5) After spraying the opposite side of the switch, hang the treated switch
from its
bound end to allow it to dry for one hour at ambient temperature, pressure and
humidity.
6) Comb the dried switch using a black rubber comb (5 inches x 1 inch, 1/2
inch fine
tooth) by combing away from the bound end of the switch but by initially
starting toward the unbound end taking smaller strokes and then gradually
taking
larger strokes until the comb passes through the entire unbound length of the
treated switch.
7) Repeat steps 1 through 6.
8) Wet the treated hair switch with water (+I S-20 grain hardness,
38°C, 1 gal/min.
water pressure).
9) Apply 1 ml of shampoo ( Table 1: methodology shampoo) along the length of
the
front of the wet hair switch and apply another 1 ml of the shampoo along the
length of the reverse side of the wet hair switch.
10) Gently milk the switch from top to bottom (hand over hand between thumb
and
fingers) for 15 seconds at 1 stroke per second.
11 ) Rinse the hair switch with water (38°C, +I S-20 grain hardness, 1
gal/min. water
pressure) for 15 seconds. Gently squeeze the hair between the first and second
fingers, drawing the fingers down the switch after 5 seconds, 10 seconds, and
after final rinse.
12) Hang the treated switch and allow it to dry for two hours at 60°C
in a hot box.
13) Remove the dried switches from the hot box.
I 4) Comb the dried switch using a black rubber comb (5 inches x 1 inch, 1 /2
inch fine
tooth) by combing away from the bound end of the switch but by initially
starting toward the unbound end taking smaller strokes and then gradually
taking
larger strokes until the comb passes through the entire unbound length of the
treated switch.
15) Repeat steps 1-14.
16) Repeat steps 1-13.
17) A panelist then evaluates the treated switch by feeling it between their
first and
second fingers of their dominant hand and between their thumb and other
fingers
for stiffness and resistance to bending, and then assigns to the treated
switch a
hair stiffness score (0 to 4 scale). The value of the assigned score is
relative to
the hair stiffness reference score (4) and the untreated reference score (0).
18) The panelist then combs the evaluated switch in accordance with the
procedure
set forth in Step 14 above, and then visually evaluates the combed switch for
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white flakes, coating, and white haze and assings it a hair flaking score (0
to 4
scale). The value of the assigned score is relative to the hair flaking
reference
score (4) and the untreated reference score (0).
Table 1: Methodology Shampoo
Ingredient List Percent CompositionPercent
As Added Composition
Chemical
Content
Sodium Laureth Sulfate40.0000 10.0000
Water - USP Purified 30.3000 30.3000
Sodium Lauryl Sulfate29.1000 8.0025
Cocamide DEA .5000 .4000
Kathon CG .1000 .0015
Citric Acid Solution ** adj. from
(50% 0 - 1%
active) (note:
water level qs.
to
100%)
Table 2: High Flaking Control
Raw Materials Percent Percent
CompositionComposition
As Added Chemical Content
Octylacrylamide/Acrylates/Butylaminoethyl4.50 4.50
Methacrylate Copolymer (National
Starch lot
AF-6713 )
Water - USP Purified 15.50 15.50
Ethanol (SDA 40) 80.00 80.00
Table 3: High Stiffness Control
Raw Materials Percent Percent
CompositionComposition
As Added Chemical Content
Octylacrylamide/Acrylates/Butylaminoethyl6.00 6.00
Methacrylate Copolymer (National
Starch lot
AF-6713)
Aminomethylpropanol, 95% 1.04 0.99
Water - USP Purified 15.50 15.50
Diisobutyl Adipate 0.20 0.20
SUBSTITUTE SHEET (RULE 26)
__ _ _ _
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21
Ethanol (SDA 40) ( 80.00 I 80.00
Each of the formulations described in Tables 1-3 are prepared by conventional
formulation and mixing techniques.
Optional Ingredients
The compositions of the present invention can also comprise a wide variety of
optional ingredients that are suitable for application to human hair.
The compositions hereof can optionally contain a plasticizer for the
copolymer.
Any plasticizer suitable for use in hair care products or for topical
application to the skin
or hair can be used. A wide variety of plasticizers are known in the art.
These include
glycerin, diisobutyl adipate, butyl stearate, propylene glycol, tri-C2-Cg
alkyl citrates,
including triethyl citrate and tri-propyl, -butyl, -pentyl, etc., analogs of
triethyl citrate.
Triethyl citrate is preferred.
Plasticizers are typically used at levels of from about 0.01 % to about 10%,
by
weight of the composition, preferably from about 0.05% to about 3%, more
preferably
from about 0.05% to about 1 %. Preferably, the weight ratio of graft copolymer
to the
plasticizer is from about 1:1 to about 40:1, preferably from about 2:1 to
about 30:1,
more preferably from about 3:1 to about 25:1.
Optionally, the compositions of the present invention can contain an effective
amount of a non-surface active ionic strength modifier system for reducing the
viscosity
of the hair spray composition. When used, the ionic strength modifiers will be
present in
the present compositions at a level of at least about 0.01 %, by weight of the
composition.
The upper limit is dependent upon the maximum amount of the ionic strength
modifiers
that can be present in the particular compositions hereof such that the hair
setting resin
remains solubilized or dispersed. As will be understood by those skilled in
the art, as the
ionic strength of the composition is increased, the resin will eventually fall
out of
solution, or otherwise no longer remain solubilized or dispersed in the
hydrophilic liquid
carrier. The upper limit of the ionic strength modifier system level will vary
depending
upon the particular ionic strength modifiers, liquid vehicle, resin, and other
ingredients
present in the composition. Thus, for example, the maximum amount of the ionic
strength modifiers that can be used will tend to be lower for compositions
with liquid
vehicles containing less water, compared to compositions with more water.
Generally,
the compositions will comprise about 4%, by weight, or less of the ionic
strength
modifiers, more generally about 2% or less, and typically about 1 % or less.
Preferably,
the compositions hereof will comprise from about 0.01% to about 0.5%, more
preferably
from about 0.01 % to about 0.1 %, of the ionic strength modifier system.
SUBSTITUTE SHEET (RULE 26)
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The ionic strength modifier system comprises a mixture of monomeric cations
and anions. The ions of the ionic strength modifier system hereof are non-
surface active,
i.e. they do not significantly reduce surface tension. For purposes hereof,
non-surface
active shall mean the ions, which at a 0.5% aqueous solution concentration,
reduce
surface tension by no more than 5.0 dynes/cm2. Generally, the ions of the
ionic strength
modifier system hereof will be characterized by having, at maximum, four or
less carbon
atoms per charge, preferably two or less carbon atoms, in any aliphatic chain
or straight
or branched chain organic heterochain.
The ionic strength modifier system comprises monomeric ions of the type which
are products of acid-base reactions. Thus, basic and acidic ions OH- and H+ do
not
constitute part of the ionic strength modifier system hereof, although they
may be
present in the composition. The ions hereof are incorporated into the
composition in a
form such that they can exist in the composition as free ions, i.e., in
dissociated form. It
is not necessary that all of the ions added exist in the composition as free
ions, but must
be at least partially soluble or dissociated in the composition. The ionic
strength
modifiers can be incorporated into the hair styling compositions, for example,
by
addition of soluble salts, or by addition of mixtures of acids and bases, or
by a
combination thereof. It is a necessary aspect of the invention that both
anions and
cations of the ionic strength modifier system be included in the composition.
Suitable cations for use include, for example, alkali metals, such as lithium,
sodium, and potassium, and alkaline-earth metals, such as magnesium, calcium,
and
strontium. Preferred of the divalent canons is magnesium. Preferred monovalent
metal
ions are lithium, sodium, and potassium, particularly sodium and potassium.
Suitable
means of addition to the compositions hereof include, for example, addition as
bases,
e.g., hydroxides, sodium hydroxide and potassium hydroxide, and such as salts
that are
soluble in the liquid carrier, e.g. salts of monomeric anions such as those
described
below.
Other suitable cations include organic ions, such as quaternary ammonium ions
and cationic amines, such as ammonium mono-, di-, and triethanolamines,
triethylamine,
morpholine, aminomethylpropanol (AMP), aminoethylpropanediol, etc. Ammonium
and the amines are preferably provided in the forms of salts, such as
hydrochloride salts.
Monomeric anions that can be used include halogen ions, such as chloride,
fluoride, bromide, and iodide, particularly chloride, sulfate, ethyl sulfate,
methyl sulfate,
cyclohexyl sulfamate, thiosulfate, toluene sulfonate, xylene sulfonate,
citrate, nitrate,
bicarbonate, adipate, succinate, saccharinate, benzoate, lactate, borate,
isethionate,
tartrate, and other monomeric anions that can exist in dissociated form in the
hair styling
_ _? _ _.~_...._._._ __
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23
composition. The anions can be added to the compositions hereof, for example,
in the
form of acids or salts which are at least partially soluble in the liquid
vehicle, e.g.,
sodium or potassium salts of acetate, citrate, nitrate, chloride, sulfate,
etc. Preferably,
such salts are entirely soluble in the vehicle.
The use of ionic strength modifiers are especially useful in reduced volatile
organic solvent compositions.
The present compositions can also contain various hydrophobic volatile
solvents
such as cyclomethicone and volatile hydrocarbons such as isododecane and
isohexadecane.
The present compositions can contain a wide variety of other optional
ingredients, including among them any of the types of ingredients known in the
art for
use in hair care compositions, especially hair setting compositions such as
especially hair
spray compositions and hair setting tonics. Generally, such other adjuvants
collectively
can comprise from about 0.05% to about 5% by weight and preferably from about
0.1%
to about 3%, by weight. Such conventional optional adjuvants are well known to
those
skilled in the art and include, but are not limited to, surfactants (which may
be anionic,
cationic, amphoteric, or zwitterionic and which include fluorinated
surfactants and
silicone copolyols), propellants, hair conditioning agents (e.g., silicone
fluids, fatty
esters, fatty alcohols, long chain hydrocarbons, cationic surfactants, etc.);
emollients;
lubricants and penetrants such as various lanolin compounds; protein
hydrolysates and
other protein derivatives; ethylene adducts and polyoxyethylene cholesterol;
dyes, tints,
bleaches, reducing agents and other colorants; pH adjusting agents;
sunscreens;
preservatives; thickening agents (e.g. polymeric thickeners, such as xanthan
gum); and
perfume.
Personal Care Products
The compositions of the present invention can be formulated as a wide variety
of
personal care products. Such products can include shampoos, soaps, hairsprays,
lotions,
creams, antiperspirants, anti-acne products, nail enamels, lipsticks,
foundations,
mascaras, and sunscreens.
In preferred embodiments, the compositions of the present invention are
formulated as hair spray compositions. These hairspray compositions preferably
have
removeability values as defined hereinbefore, and may be dispensed as sprayed
or
atomized products from containers which are pump spray dispensers or aerosol
canisters.
Such containers are well known to those skilled in the art and are
commercially available
from a variety of manufacturers, including American National Can Corp. and
Continental Can Corp.
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When the hair spray compositions are to be dispensed from a pressurized
aerosol
container, a propellant which consists of one or more of the conventionally-
known
aerosol propellants can be used to propel the compositions. A suitable
propellant for use
can be generally any liquifiable gas conventionally used for aerosol
containers. Suitable
propellants for use are volatile hydrocarbon propellants which can include
liquified
lower hydrocarbons of 3 to 4 carbon atoms such as propane, butane and
isobutane.
Other suitable propellants are hydrofluorocarbons such as 1,2-difluoroethane
(Hydrofluorocarbon 152A) supplied as Dymel 152A by DuPont. Other examples of
propellants are dimethylether, nitrogen, carbon dioxide, nitrous oxide, and
atmospheric
gas. The hydrocarbons, particularly isobutane, used singly or admixed with
other
hydrocarbons are preferred.
The aerosol propellant may be mixed with the present hair spray compositions
and the amount of propellant to be mixed is governed by normal factors well
known in
the aerosol art. Generally, for liquifiable propellants, the level of
propellant is from
about 10% to about 60% by weight of the total composition, preferably from
about I S%
to about 50% by weight of the total composition.
Alternatively, pressurized aerosol dispensers can be used where the propellant
is
separated from contact with the hair spray composition such as a two
compartment can
of the type sold under the tradename SEPRO from American National Can Corp.
Other suitable aerosol dispensers are those characterized by the propellant
being
compressed air which can be filled into the dispenser by means of a pump or
equivalent
device prior to use. Such dispensers are described in U.S. Patents 4,077,441,
March 7,
1978, Olofsson and 4,850,577, July 25, 1989, TerStege, both incorporated by
reference
herein, and in U.S. Serial No. 07/839,648, Gosselin et al., filed February 21,
1992, also
incorporated by reference herein. Compressed air aerosol containers suitable
for use are
also currently marketed by The Procter & Gamble Company under their tradename
VIDAL SASSOON AIRSPRAY~ hair sprays.
Conventional nonaerosol pump spray dispensers, i.e., atomizers, can also be
used.
Other hair styling compositions include tonics and lotions, which are
typically
dispensed in a conventional bottle or tube, and applied directly to the hair
or first
dispensed to the hand and then to the hair.
Method of Makine
The compositions of the present invention, including the preferred hairspray
embodiments, can be made using conventional formulation and mixing techniques.
The
adhesive copolymer and the solvent are mixed to provide a homogeneous mixture.
Any
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other ingredients are then added and mixed to yield the final composition. If
the polymer
is neutralized, the neutralizer is preferably added prior to addition of other
ingredients.
For hair spray products, the composition is packaged in conventional
mechanical pump
spray devices, or alternatively, in the case of aerosol sprays products, the
composition is
packaged in conventional aerosol canisters along with an appropriate
propellant system.
Method of Use
The compositions of the present invention, including the preferred hairspray
embodiments of the present invention, are used in conventional ways to provide
the
benefits of the present invention. These products can be applied to the skin
or hair.
Typical amounts of products can range from about 0.1 mg/cm2 to about 25 mg/cm2
of
skin or hair, although a wider range can be used depending upon the exact
product
application. For hair care products, the methods generally involve application
of an
effective amount of the product to dry, slightly damp, or wet hair before
and/or after the
hair is dried and arranged to a desired style. Application of the product is
normally
effected by spraying or atomizing the product using an appropriate device,
e.g. a
mechanical pump spray, a pressurized aerosol container, or other appropriate
means.
The composition is then dried or allowed to dry. By "effective amount" is
meant an
amount sufficient to provide the hair hold and style benefits desired. In
general, from
about O.Sg to about 30g of product is applied to the hair, depending upon the
particular
product formulation, dispenser type, length of hair, and type of hair style.
The following Experimentals and Examples further illustrate embodiments
within the scope of the present invention. They are given solely for the
purposes of
illustration and are not to be construed as limitations of the present
invention as many
variations of the invention are possible without departing from its spirit and
scope.
Examples
The following examples further describe and demonstrate embodiments within the
scope of the present invention. The examples are given solely for the purpose
of
illustration and are not to be construed as limitations of the present
invention, as many
variations thereof are possible without departing from the spirit and scope of
the
invention. Ingredients are identified by chemical or CTFA name.
Examples 1-4: Syntheses of macromonomers and copolymers.
Example 1
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Synthesis of Vinylphenyl-terminated Poly(n-Propel methacrylate-co-Methacr'rlic
Acid)
Macromonomer
Into a round-bottomed-flask fitted with magnetic stirring and under slight
argon pressure
(8 psi), is added tetrahydrofuran (1L), trimethylsilylmethacrylate (1008,
0.632 mole), and
n-propylmethacrylate (100g, 0.780 mole). The solution is cooled to -80C then
initiated
with diphenylhexyllithium (0.0275 moles) for chain propagation via anionic
polymerization mechanism. After continuous stirring for 0.5 h, vinylbenzoyl
chloride
(8.33 mL, 0.05 mole) is charged to the solution and continued stirring for 0.5
h. The
solution is then warmed to ambient temperature and H20 (lOmL) is added and
stirred for
0.25 hours to deprotect the acid groups. The macromonomer, which has a weight
average molecular weight of about 6000, is obtained by precipitating the
resulting
solution in hexanes, collecting precipitate, and drying under vacuum.
Example 2
Synthesis of Poly(t-butylacrylate-co-2-methoxvethylacrvlate-co-acrylic acid)-
~raft-
f poly(Propyl methacrylate-co-Methacrylic Acid)) Copo~mer
To a round-bottomed-flask equipped with a reflux condenser, temperature
control, mechanical stirring mechanism, and under slight argon pressure
{8psi), is added
acetone (O.SL), t-butylacrylate (24g), 2-methoxyethylacrylate (38g), acrylic
acid (19g),
and vinylphenyl-terminated (n-propylmethacrylate-co-methacrylic acid)
macromonomer
( 19g) (from Example 1 ). Solution is stirred until all components are
dissolved, then
heated to 60C. Azobisisobutyronitrile (0.7g) is charged to the system. After
lOh,
solution is cooled and precipitated in water to yield silicone modified graft
copolymer.
Example 3
Synthesis of Acrylo,~rl Encapped Polyisobutylene Macromonomer
Prepare a solution of 100 grams (0.024 mol) hydroxyl endcapped polyisobutylene
polymer (PIB-OH) having a weight average molecular weight of 4,172 g/mol by
conventional living carbocationic polymerization of isobutylene (for example,
as
described in G. Kaszas, Poly. Bull., 20, 413 ( 1989). Add a two fold mole
excess (4.84 g,
0.048 mol) triethylamine to the solution. Add this solution dropwise to a
solution of
acryloyl chloride (4.35 g, 0.048 mol) in dry methylene chloride {100 g) at 0
oC. Stir for
about 12 hours at room temperature, filter the mixture and evaporate the
excess
triethylamine and methylene chloride to obtain acryloyl endcapped
polyisobutylene
macromonomer.
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27
Example 4
Synthesis of Polyf(t-butylacrylate-co-2-methoxyethyl acrylate-co-acrylic acid)-
~raft-
[pol (isobutylene)i
Place 22 parts acrylic acid, 44 parts t-butyl acrylate, 22 parts n-
butylacrylate, 12
parts polyisobutylene macromonomer (4172 MW) (from Example S) in a flask. Add
sufficient tetrahydrofuran as the reaction solvent to produce a final monomer
concentration of about 20%. Purge the vessel with an inert atmosphere,
preferably
nitrogen or argon. Add initiator, (2,2'-azobisisobutyronitrile) to a level
appropriate for
the desired molecular weight. Typically this is in the range of 0.5% to I.0%
by weight
relative to the amount of monomer. Heat to 60°C and maintain this
temperature for 48
hours while agitating. Terminate the reaction by cooling to room temperature.
The
polymer is purified by drying off the reaction solvent in an oven.
Alternatively, acetone
can be used in place of tetrahydrofuran, in which case the polymer is
precipitated by
adding water and the precipitated polymer is collected and dried.
Examales 5-12
The following examples
represent nonaerosol hairspray
compositions of the
present invention.
Example No.
Component (wt%) 5 6 7 8 9 10 11 12
Copolymer 4 4.00 5.00 6.00 4.00 --- --- --- ---
Copolymer 2 --- --- --- --- 3.00 3.50 2.50 4.00
Isododecanel 1.00 --- --- --- --- 1.0 2.0 ---
Diisobutyl adipate 0.40 0.90 0.55 --- --- --- 0.40
---
Sodium 0.96 1.20 1.44 --- --- 1.20 --- 1.35
hydroxide2
Potassium -- -- -- 1.21 1.00 -- 0.70 --
hydroxide3
Perfume 0.10 0.10 0.10 0.10 0.10 0.15 0.10 0.15
Water QS10 QS10 QS10 QS10 QS10 QS10 QS10 QS10
0 0 0 0 0 0 0 0
Sodium Benzoate -- -- -- -- 0.10 0.10 -- 0.10
Ethanol4 76.54 71.95 81.5671.25 79.40 69.26 78.0055.00
I PERMETHYL 99A, from Presperse,
Inc.,
South
Plainfleld,
NJ,
USA.
2 Sodium hydroxide is 30%
active.
3 Potassium hydroxide is
45% active.
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4 SDA 40 ( 100% ethanol).
Examples I3-18
The following examples represent aerosol hairspray compositions of the present
lnventlon.
Example No.
Component (wt%) 13 14 15 16 17 18
Copolymer 2 5.00 4.00 3.50 --- --- ---
Copolymer 4 --- --- --- 4.00 3.00 4.00
Isododecanel 0.50 --- --- -- -- 0.50
Triethyl citrate2 -- -- 0.21 -- -- --
Diisobutyl adipate 0.70 0.45-- 0.40 0.25 0.35
Propylene glycol -- -- 0.30 -- --- ---
Sodium hydroxide3 1.00 -- -- -- 1.0 ---
Potassium -- 0.94 1.20 1.04 --- 1.20
hydroxide4
Perfume 0.10 0.10 0.10 0.10 0.10 0.10
Water QS100 QS100 QS100 QS100 QS100 QS100
Sodium Benzoate 0.10 0.10 -- 0.10 0.20 --
Ethanol5 56.69 57.42 72.0 50.0 30.00 54.5
Propellant - -- -- 7.02 15.00 10.00 --
I sobutane
Propellant - n-butane 10.00 -- -- -- --
---
Propellant - 10.00 --- -- 15.00 15.00 --
Dimethyl ether6
Propellant - -- 25 15.98 -- -- 32.32
Hydrofluorocarbon
152a7
1 PERMETHYL 99A, from Presperse,c., South Plainfield, NJ, USA.
In
2 CITROFLEX-2, from Morflex,
Inc., Greensboro, NC, USA.
3 Sodium hydroxide is 30%
active.
4 Potassium hydroxide is
45% active.
SDA 40 (100% ethanol).
6 DYMEL - A, from Dupont.
~ DYMEL-152a, from Dupont.
The compositions are prepareds described above, by first mixing
a the polymer
with the ethanol, neutralizing
the polymer with sodium
or potassium hydroxide,
then
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29
adding sequentially (as applicable) with mixing, isododecane, plasticizer,
perfume, and
water. If sodium benzoate is used, it is added after water addition. Most
preferably a
premix of water and sodium benzoate is made and then added after the main
water
addition. Propellants for aerosol compositions are charged to conventional
aerosol
containers after the remainder of the prepared composition has been added.
The hair spray embodiments of the present invention described in Examples 5-18
have high removeability from hair, and when evaluated by the removeability
methodology described herein, provide a hair stiffness value of less than 2.0
and a hair
flaking value of less than 2Ø
While particular embodiments of the subject invention have been described, it
will be obvious to those skilled in the art that various changes and
modifications to the
subject invention can be made without departing from the spirit and scope of
the
invention. It is intended to cover, in the appended claims, all such
modifications that are
within the scope of the subject invention.
EXAMPLE 19
The following is a hair conditioner composition representative of the present
mvenhon.
Ingredients Wei hg t
Water Q.S. to 100%
Perfume 0.10
Stearalkonium Chloride 0.87
Methylchloroisothiazolinone Methylisothiazolinone 0.03
Sodium Hydroxide Solution (30% by weight) 0.70
Polymer 2 3.00
Ethanol 20.0
This product is prepared by dispersing the copolymer 3 in ethanol then adding
the
remaining ingredients and stirring for about 30 minutes.
EXAMPLE 20
The following is a hair styling gel composition representative of the present
invention.
Ingredients Wei hg t
Copolymer 4 2.50
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Water QS 100%
Carbomer 940 0.50
Sodium Hydroxide Solution (30% by weight) 0.80
Panthenol 0.05
Polysorbate 80 0.20
Perfume 0.20
This product is prepared by dispersing the copolymer # 4 and carbomer 940 in
water and adding the sodium hydroxide. The mixture is stirred for
approximately one
half hour and the remaining components are added.
EXAMPLE 21
The following is a spray-on gel hair composition representative of the present
Invention.
Ingredients Weight
Water Q.S. to 100
Ethanol 15.00
Panthenol U.OS
Potassium Hydroxide Solution (45% by weight) 0.50
Perfume 0.20
Copolymer # 2 2.00
This product is prepared by dissolving the copolymer # 2 ethanol and then
adding
the water and potassium hydroxide solution to facilitate the incorporation of
the
copolymer into the solvent. The mixture is stirred for one half hour and the
other
components are mixed in.
EXAMPLE 22
The following is a hair styling mousse composition representative of the
present
Invention.
Ingredients Weight
Water Q.S. to 100
Lauramine Oxide 0.20
Panthenol 0.05
Perfume 0.05
Copolymer #4 3.00
Sodium Hydroxide Solution (30% 1.00
by weight)
Isobutane 7.00
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This product is prepared by dissolving the copolymer #2 in water and adding
the
sodium hydroxide solution with mixing for one half hour. The other components
(except
isobutane) are added and mixed for an additional 10 minutes. Aluminum aerosol
cans
are then filled with 93 parts of this batch, affixed with a valve whcih is
crimped into
position, and lastly pressure filled with 7 parts Isobutane. This composition
is useful for
application to the hair to provide conditioning, styling and hold.
EXAMPLE 23
Sunscreen Composition
Ingredients Weight
Water QS 100
Carbomer 1342 1 ~ 0.16
Octyi Methoxycinnamate 0.50
Dimethicone copolyol 0.10
Tocopheryl Acetate 0.10
Sodium Hydroxide (30% sol. 1.50
by weight)
Ethanol 40.00
Copolymer #4 4.00
~1~ Available as Carbopol~ 1342 from B.F. Goodrich.
The water, ethanol, sodium hydroxide solution and polymer 4 are mixed for one
half hour. The remaining ingredients are added and mixed for an additional
half hour.
EXAMPLE 24
The following is an anti-acne composition representative of the present
invention.
Ingredients Wei hg t
Copolymer # 2 2.00
Water Q.S. to 100
Ethanol (SDA 40) 40.00
Carbomer 940 0.75
Sodium Hydroxide Solution (30% by weight) 0.90
Salicylic Acid 2.00
This product is prepared by mixing the water, ethanol, copolymer 2, and
carbomer together for about 10 minutes. The remaining ingredients are added
and the
mixture is stirred for an additional 30 minutes. This composition is useful
for application
to the skin to provide improved water resistance and is useful in the
treatment of acne.
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EXAMPLE 25
The following is a nail polish clear coat composition representative of the
present
invention.
Ingredients Wei hg t
Copolymer # 4 15.00
Ethanol 42.00
Acetone 40.00
NaOH soln., 30% 3.00
This product is prepared by mixing all the ingredients until dispersed.
EXAMPLE 26
The following is a facial wrinkle remover composition representative of the
present Invention.
Ingredients Weight
Copolymer # 4 6.00
NaOH soln., 30% 2.10
DRO water q.s.
This product is prepared by mixing all the ingredients until dispersed.
EXAMPLE 27
The following is a styling lotion composition representative of the present
mventlon.
Ingredients Wei hg t
Copolymer # 2 4.00
Natrosol 250HH 1 0.50
NaOH soln., 30% 1.35
Kathon CG 0.03
Ethanol 8.00
DRO water q.s.
1 Natrosol 250HH-Hydroxyethylcellulose offered by Aqualon.
The copolymer is first dissolved in the ethanol and then added to a premix
composed of the remaining ingredients and mixed until well dispersed.
EXAMPLE 28
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33
The following is an aftershave splash composition representative of the
present
invention.
Ingredients Weight
Copolymer # 2 2.00
NaOH soln., 30% 0.60
Ethanol 50.00
Perfume 0.20
Menthol 0.20
DRO water q.s.
This product is preparedall the ingredients until
by mixing dispersed.
