U.S. patent application number 09/391560 was filed with the patent office on 2001-06-14 for method for inhibiting corrosion in an aqueous aerosol or foam hair styling composition.
Invention is credited to CHANG, CHING-JEN, KEENAN, ANDREA CLAUDETTE, SCHWARTZ, CURTIS.
Application Number | 20010003581 09/391560 |
Document ID | / |
Family ID | 22277154 |
Filed Date | 2001-06-14 |
United States Patent
Application |
20010003581 |
Kind Code |
A1 |
CHANG, CHING-JEN ; et
al. |
June 14, 2001 |
METHOD FOR INHIBITING CORROSION IN AN AQUEOUS AEROSOL OR FOAM HAIR
STYLING COMPOSITION
Abstract
A method for improving the corrosion resistance of aerosol or
foam hair spray formulations in metal containers is disclosed. In
particular, the present invention involves the use of phosphate
ester emulsifiers in the preparation of the emulsion polymer hair
fixative resins to provide corrosion resistance of the hair styling
composition in metal containers without negatively affecting the
performance of the hair styling product itself. Use of the selected
emulsifiers is particularly useful in non-corrosive aqueous hair
styling compositions containing low (80% or less) volatile organic
compound (VOC) concentrations.
Inventors: |
CHANG, CHING-JEN; (AMBLER,
PA) ; KEENAN, ANDREA CLAUDETTE; (PLYMOUTH MEETING,
PA) ; SCHWARTZ, CURTIS; (AMBLER, PA) |
Correspondence
Address: |
THOMAS J HOWELL
ROHM AND HAAS COMPANY
100 INDEPENDENCE MALL WEST
PHILADELPHIA
PA
191062399
|
Family ID: |
22277154 |
Appl. No.: |
09/391560 |
Filed: |
September 8, 1999 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60099898 |
Sep 11, 1998 |
|
|
|
Current U.S.
Class: |
424/47 ; 424/45;
424/70.1 |
Current CPC
Class: |
Y10S 514/945 20130101;
A61K 8/046 20130101; A61K 8/8152 20130101; A61Q 5/06 20130101; Y10S
514/938 20130101; A61K 8/556 20130101; A61K 2800/526 20130101 |
Class at
Publication: |
424/47 ; 424/45;
424/70.1 |
International
Class: |
A61K 009/12 |
Claims
We claim:
1. An aqueous aerosol or foam hair styling composition comprising:
(a) from 1 to 15 weight percent of at least one acrylic hair
fixative resin, based on total weight of the aqueous aerosol or
foam hair styling composition, wherein the acrylic hair fixative
resin is a polymer comprising as polymerized units from 2 to 100
weight percent of at least one (C.sub.1-C.sub.12)alkyl
(meth)acrylate, based on total weight of the acrylic hair fixative
resin; and (b) from 10 to 70 weight percent of at least one
propellant, based on total weight of the aqueous hair styling
composition; wherein the hair fixative resin is an emulsion polymer
prepared in the presence of a phosphate ester emulsifier.
2. The composition of claim 1 further comprising at least one
neutralizer.
3. The composition of claim 2 wherein the neutralizer is selected
from one or more of 2-amino-2-methyl-1,3-propanediol,
2-amino-2-methyl-1-propanol,
N,N-dimethyl-2-amino-2-methyl-1-propanol, potassium hydroxide,
triethanolamine and triisopropanolamine.
4. The composition of claim 1 further comprising volatile organic
compounds in a concentration up to 98 weight percent, based on
total weight of the aqueous hair styling composition.
5. The composition of claim 4 wherein the volatile organic
compounds are selected from one or more of ethanol, isopropanol,
n-propanol, dimethoxymethane, dimethylether and C.sub.1-C.sub.12
straight or branched chain hydrocarbons.
6. The composition of claim 4 wherein the volatile organic
compounds concentration is 80 weight percent or less.
7. The composition of claim 1 wherein the hair fixative resin
further comprises as polymerized units from 2 to 70 weight percent
of least one hydroxyalkyl (meth)acrylate.
8. The composition of claim 1 wherein the hair fixative resin
further comprises as polymerized units from 2 to 50 weight percent
from of at least one C.sub.3-C.sub.8 monoethylenically unsaturated
monocarboxylic acid monomer.
9. The composition of claim 1 wherein the hair fixative resin
further comprises as polymerized units from 1 to 25 weight percent
of at least one C.sub.4-C.sub.8 monoethylenically unsaturated
dicarboxylic acid monomer.
10. The composition of claim 1 wherein the composition has a pH
from 6 to 9.5.
11. The composition of claim 1 wherein the hair fixative resin
comprises as polymerized units (i) from 5 to 95 weight percent of
at least one (C.sub.1-C.sub.12)alkyl (meth)acrylate, (ii) from 2 to
70 weight percent of least one hydroxyalkyl (meth)acrylate and
(iii) from 2 to 50 weight percent from of at least one
C.sub.3-C.sub.8 monoethylenically unsaturated monocarboxylic acid
monomer.
12. The composition of claim 11 wherein: (a) the
(C.sub.1-C.sub.12)alkyl (meth)acrylate is from 2 to 67 weight
percent of at least one (C.sub.2-C.sub.5)alkyl acrylate and from 5
to 71 weight percent of methyl methacrylate; (b) the hydroxyalkyl
(meth)acrylate is from 2 to 26 weight percent of hydroxyethyl
methacrylate; and (c) the C.sub.3-C.sub.8 monoethylenically
unsaturated monocarboxylic acid monomer is from 2 to 30 weight
percent of methacrylic acid.
13. The composition of claim 12 wherein the hair fixative resin
further comprises as polymerized units from 1 to 25 weight percent
of at least one C.sub.4-C.sub.8 monoethylenically unsaturated
dicarboxylic acid monomer.
14. The composition of claim 1 wherein the propellant is selected
from one or more of dimethyl ether, 1,1-difluoroethane, n-butane
and isobutane.
15. The composition of claim 1 wherein the phosphate ester
emulsifier is selected from one or more long-chain
alkyloxypoly(alkyleneoxide), long-chain
alkylaryloxypoly(alkyleneoxide), long-chain alkyl and long-chain
alkylaryl mono- and di-esters of phosphoric acid, and corresponding
salts.
16. The composition of claim 15 wherein the phosphate ester
emulsifier is selected from one or more
(C.sub.8-C.sub.18)alkylaryloxypoly(alkyleneoxid- e) and
(C.sub.10-C.sub.18)alkyloxypoly(alkyleneoxide) mono- and di-esters
of phosphoric acid, and corresponding salts.
17. The composition of claim 1 wherein the phosphate ester
emulsifier is present in an amount from 0.5 to 5 weight percent,
based on total weight of polymer.
18. The composition of claim 1 wherein the hair fixative resin is
prepared substantially in the absence of sulfate or sulfonate type
emulsifiers.
19. An improved method for inhibiting corrosion in an aqueous
aerosol or foam hair styling composition comprising (a) from 1 to
15 weight percent of an acrylic hair fixative resin, based on total
weight of the aqueous hair styling composition, selected from one
or more polymers comprising as polymerized units from 2 to 100
weight percent of at least one (C.sub.1-C.sub.12)alkyl
(meth)acrylate, based on weight of the hair fixative resin; and (b)
from 10 to 70 weight percent of at least one propellant, based on
total weight of the aqueous hair styling composition; wherein the
improvement comprises preparing the acrylic hair fixative resin by
emulsion polymerization in the presence of a phosphate ester
emulsifier.
20. The method of claim 19 wherein the hair fixative resin
comprises as polymerized units: (i) from 5 to 95 weight percent of
at least one (C.sub.1-C.sub.12)alkyl (meth)acrylate, (ii) from 2 to
70 weight percent of least one hydroxyalkyl (meth)acrylate, and
(iii) from 2 to 50 weight percent from of at least one
C.sub.3-C.sub.8 monoethylenically unsaturated monocarboxylic acid
monomer, based on total weight of the acrylic hair fixative resin.
Description
BACKGROUND
[0001] The present invention relates to aerosol or foam hair
styling compositions delivered from metal containers and a method
of inhibiting corrosion of the metal container holding the hair
styling composition. More particularly, the present invention
relates to a method of inhibiting corrosion to tin plate or
aluminum aerosol cans caused by the hair spray composition without
compromising performance of the hair spray product or without the
expense of special can liners. In a preferred embodiment, the
present invention also relates to non-corrosive aqueous hair
styling compositions containing low (80 weight percent or less)
volatile organic compound (VOC) concentrations.
[0002] Hair styling products, such as hair sprays, styling gels,
spray gels and mousses are used on hair to hold the hair in place.
The hair styling products, when applied, form a thin film or weld
of resin on the hair, most efficiently in the seam between adjacent
hair fibers or at a point where the fibers cross one another, and,
as a result, hold the hair in a particular shape or
configuration.
[0003] Hair styling products can be applied to the hair in several
ways. One of the most desirable ways is to formulate the hair
fixative resin under pressure in a system containing solvent and
propellant. The resin is delivered to hair as a fine mist where the
propellant is used to drive the product out of its container onto
the hair. Typically, the container is a tin plated metal or
aluminum can. Preventing the hair spray formulation from corroding
the metal container during storage is a key parameter in
formulating an aerosol hair spray suitable for the trade.
[0004] Legislation in New York, California and other states
mandates that the amount of VOC formulated into hair styling
products that are sprayed, such as aerosol and pump hair sprays,
must not exceed 80 weight percent (%) in the product. By June 1999,
the amount of VOC in hair styling products that are sprayed must be
reduced to 55% in California. Other states have enacted similar
legislation mandating the reduction of VOC in hair styling products
that are sprayed. Present hair styling products in the United
States that are sprayed typically have VOC levels of 80% or less.
Such VOC include, for example, ethanol, dimethyl ether and
hydrocarbons; the most likely replacement for VOC is water.
[0005] The introduction of water into the hair styling product
accelerates corrosion kinetics (rate of corrosion). Corrosion is
also accelerated by presence of certain additives, and reduced in
the presence of other additives, called corrosion inhibitors (Spray
Technology & Marketing, C. M. Rocafort, December, 1995). The
presence of certain additives, such as those required to prepare a
hair fixative resin (for example, emulsifiers, surfactants, chain
transfer agents, initiators and redox agents) may accelerate
corrosion to an extent that it cannot be inhibited even with a high
concentration of corrosion inhibitors in the formulation or by
increasing the pH. These additives, being part of the polymer
processing package, cannot be removed or replaced without
negatively affecting the ability to prepare the polymer.
[0006] The problem addressed by the present invention is to reduce
the tendency of hair fixative resin formulations to corrode metal
containers in aerosol formulations, particularly low-VOC
formulations, without negatively affecting the performance of the
hair styling product or its cost effectiveness, and without
affecting the ability to prepare the hair fixative resin polymer in
high yield with low residual monomer and in a form easily used by
the hair styling composition formulator.
[0007] U.S. Pat. No. 4,196,190 discloses acrylic hair fixative
resins containing 10-30% of an alkyl acrylate, 41-60% of methyl
methacrylate, 5-20% of hydroxyethyl methacrylate and 10-30% of
methacrylic acid. Although disclosing that water can be used in a
hair styling composition containing the acrylic hair fixative
resins, this reference does not disclose or suggest methods for
overcoming the problems associated with hair styling compositions
regarding corrosion. U.S. Pat. No. 5,658,558, although disclosing
how to improve the performance of acrylic resins in low-VOC
systems, also does not disclose how to overcome corrosion
problems.
[0008] The use of phosphate esters as emulsifiers to prepare
acrylic emulsion polymers is disclosed in "Phosphate Esters as
Primary Anionic Emulsifiers for Acrylic Latex Synthesis" by N.
Shachat and Y. Z. Li, at Water-Borne & Higher Solids and Powder
Coatings Symposium, New Orleans, La. (USA), February 24-26, 1993.
GB Patent No. 2,203,156 discloses corrosion resistant compositions
for metal surfaces coated with acrylic resin and organic
phosphate/phosphite mixtures. Neither of these references discloses
how to overcome the problems associated with aerosol hair styling
compositions regarding corrosion.
[0009] The present invention seeks to overcome deficiencies of the
prior art hair fixative resin technology by using hair fixative
resins prepared by emulsion polymerization using selected
emulsifiers as processing aids to minimize corrosion in the hair
styling formulation while retaining other beneficial hair fixative
properties.
STATEMENT OF INVENTION
[0010] One embodiment of the present invention provides an aqueous
aerosol or foam hair styling composition comprising (a) from 1 to
15 weight percent of at least one acrylic hair fixative resin,
based on total weight of the aqueous aerosol or foam hair styling
composition, wherein the acrylic hair fixative resin is a polymer
comprising as polymerized units from 2 to 100 weight percent of at
least one (C.sub.1-C.sub.12)alkyl (meth)acrylate, based on total
weight of the acrylic hair fixative resin; and (b) from 10 to 70
weight percent of at least one propellant, based on total weight of
the aqueous hair styling composition; wherein the hair fixative
resin is an emulsion polymer prepared in the presence of a
phosphate ester emulsifier.
[0011] In another embodiment, the present invention provides the
aforementioned aqueous aerosol or foam hair styling composition
further comprising volatile organic compounds in a concentration up
to 98 weight percent, based on total weight of the aqueous hair
styling composition.
[0012] In a further embodiment, the present invention provides an
improved method for inhibiting corrosion in an aqueous aerosol or
foam hair styling composition as described as above, wherein the
improvement comprises preparing the acrylic hair fixative resin by
emulsion polymerization in the presence of a phosphate ester
emulsifier.
DETAILED DESCRIPTION
[0013] The method of the present invention is useful for improving
the corrosion resistance of aerosol or foam hair styling
formulations when the hair styling formulation is provided in metal
containers, such as aerosol cans. We have found that the use of
certain selected emulsifiers, that is, phosphate esters, in the
preparation of the emulsion polymer hair fixative resins
surprisingly improves the corrosion resistance of the hair styling
composition in metal containers without negatively affecting the
performance of the hair styling product itself.
[0014] By an "aqueous hair styling composition" we mean a hair
spray or mousse (aerosol or foam) that is used on hair to hold the
hair in a particular shape or configuration. Preferably, the hair
styling composition in the present invention is a hair spray.
[0015] As used herein, all percentages referred to will be
expressed in weight percent (%) unless specified otherwise.
[0016] The aqueous hair styling compositions typically will contain
at least 2% and up to 98% water, more typically, from 25 to 70%
water, based on the total weight of the aqueous hair styling
composition. By "low-VOC" we mean the hair styling composition
contains 80% or less volatile organic compounds, that is, typically
10% or more of water. Preferably, the hair styling composition
contains less than 70%, and more preferably 55% or less, VOC.
Optionally, the hair styling composition may contain no VOC.
[0017] The term "(meth)acrylate" means methacrylate or acrylate.
The term "(meth)acrylic acid" means methacrylic acid or acrylic
acid. As used herein, the term "unsaturated dicarboxylic acid
monomer" refers to monoethylenically unsaturated dicarboxylic acids
containing 4 to 8, preferably from 4 to 6, carbon atoms per
molecule and anhydrides of the corresponding dicarboxylic acids.
Dicarboxylic acid monomers include, for example, maleic acid,
maleic anhydride, fumaric acid, .alpha.-methylene glutaric acid,
itaconic acid, itaconic anhydride, citraconic acid, mesaconic acid,
cyclohexenedicarboxylic acid, and water-soluble salts thereof.
[0018] When the word "soluble" is used to further describe a
compound, such as for example the "soluble hair fixative resins,"
we mean herein that the compound described is soluble in the hair
styling composition. When the word "insoluble" is used to further
describe a compound, such as for example the "insoluble hair
fixative resins," we mean herein that the compound described is
insoluble in the hairstyling composition.
[0019] As used herein, VOC are compounds containing at least one
carbon atom and are typically used as solvents or propellants in
hair styling compositions. VOC include, for example,
C.sub.1-C.sub.12 straight or branched chain alcohols such as
methanol, ethanol, propanol, isopropanol and butanol;
C.sub.1-C.sub.12 straight or branched chain hydrocarbons such as
methane, ethane, propane, isopropane, isobutane, pentane,
isopentane and butane; or ethers such as dimethyl ether and
dimethoxymethane. Preferred VOC are selected from one or more of
ethanol, isopropanol, n-propanol, dimethoxymethane, dimethylether
and C.sub.1-C.sub.12 straight or branched chain hydrocarbons.
[0020] Soluble hair fixative resins that are useful in the present
invention are soluble in the hair styling composition "as is" or
upon neutralization of some or all of any acid groups contained in
the soluble hair fixative resins. The soluble hair fixative resins,
when sprayed, preferably have viscosities less than
30.times.10.sup.-3 pascal.cndot.seconds (Pa.cndot.sec) (or 30
centipoise), and more preferably less than 25.times. 10.sup.-3
Pa.cndot.sec, in an aerosol concentrate.
[0021] In general, polymers useful as hair fixative resins in
practicing the present invention may be any acrylic emulsion
polymer containing as polymerized units from 2 to 100%, preferably
from 5 to 95%, more preferably from 45 to 90%, of at least one
(C.sub.1-C.sub.12)alkyl (meth)acrylate, based on total weight of
the acrylic hair fixative resin. Preferably, the
(C.sub.1-C.sub.12)alkyl (meth)acrylate comprises substantially
(C.sub.1-C.sub.10)alkyl (meth)acrylates, and more preferably
(C.sub.1-C.sub.8)alkyl (meth)acrylates.
[0022] Optionally, the polymer may contain, as polymerized units,
from 2 to 70%, and preferably from 2 to 26%, of at least one
hydroxyalkyl (meth)acrylate. The alkyl group of the hydroxyalkyl
(meth)acrylate is preferably a (C.sub.1-C.sub.5)alkyl group. For
example, the hydroxyalkyl (meth)acrylate is preferably selected
from one or more of hydroxyethyl (meth)acrylate, hydroxypropyl
(meth)acrylate, hydroxybutyl (meth)acrylate and hydroxypentyl
(meth)acrylate. More preferably the hydroxyalkyl (meth)acrylate is
selected from one or more of hydroxyethyl methacrylate and
hydroxypropyl acrylate.
[0023] Optionally, the polymer may contain, as polymerized units,
from 2 to 50% of at least one C.sub.3-C.sub.8 monoethylenically
unsaturated monocarboxylic acid monomer. The C.sub.3-C.sub.8
monoethylenically unsaturated monocarboxylic acid monomer is
preferably selected from one or more of acrylic acid, methacrylic
acid and crotonic acid. More preferably, the C.sub.3-C.sub.8
monoethylenically unsaturated monocarboxylic acid is methacrylic
acid.
[0024] Optionally, the polymer may contain, as polymerized units,
from 1 to 25% of at least one C.sub.4-C.sub.8 monoethylenically
unsaturated dicarboxylic acid monomer. The C.sub.4-C.sub.8
monoethylenically unsaturated dicarboxylic acid monomer is
preferably selected from one or more of itaconic acid, maleic acid
and the corresponding anhydrides. Preferably, the C.sub.4-C.sub.8
monoethylenically unsaturated dicarboxylic acid monomer is itaconic
acid.
[0025] Optionally, the polymer may also contain, as polymerized
units, additional vinyl monomers, such as for example, vinyl
acetate, vinyl neodecanoate, vinylpyrrolidone, octylacrylamide and
t-butylaminoethyl methacrylate.
[0026] Preferably, the hair fixative resin comprises as polymerized
units (i) from 5 to 95%, and more preferably from 45 to 90%, of at
least one (C.sub.1-C.sub.12)alkyl (meth)acrylate, (ii) from 2 to
70%, and more preferably from 2 to 26%, of at least one
hydroxyalkyl (meth)acrylate and (iii) from 2 to 50%, more
preferably from 2 to 30%, and most preferably from 12 to 26%, of at
least one C.sub.3-C.sub.8 monoethylenically unsaturated
monocarboxylic acid monomer. More preferably the hair fixative
resin further comprises as polymerized units from 1 to 25% of at
least one C.sub.4-C.sub.8 monoethylenically unsaturated
dicarboxylic acid monomer. Most preferably the C.sub.4-C.sub.8
monoethylenically unsaturated dicarboxylic acid monomer is from 2
to 10% of itaconic acid.
[0027] Preferably, the (C.sub.1-C.sub.12)alkyl (meth)acrylate is
selected from one or more (C.sub.1-C.sub.5)alkyl (meth)acrylates
such as, for example, methyl (meth)acrylate, ethyl (meth)acrylate,
propyl (meth)acrylate, butyl (meth)acrylate and pentyl
(meth)acrylate.
[0028] More preferably the (C.sub.1-C.sub.12)alkyl (meth)acrylate
component comprises at least one (C.sub.1-C.sub.3)alkyl
methacrylate and at least one (C.sub.2-C.sub.5)alkyl acrylate. Most
preferably the (C.sub.1-C.sub.12)alkyl (meth)acrylate component
comprises methyl methacrylate and butyl acrylate. The amount of the
at least one (C.sub.1-C.sub.3)alkyl methacrylate in the hair
fixative resin is preferably from 5 to 71%, more preferably from 41
to 60%, based on the total monomers used to form the hair fixative
resin. The amount of (C.sub.2-C.sub.5)alkyl acrylate is preferably
from 2 to 67% and more preferably from 10 to 30%, based on the
total monomer used to form the acrylic hair fixative resin.
Preferably, the (C.sub.1-C.sub.12)alkyl (meth)acrylate is from 2 to
67 weight percent of at least one (C.sub.2-C.sub.5)alkyl acrylate
and from 5 to 71 weight percent of methyl methacrylate.
[0029] The proportions of the monomers comprising the acrylic hair
fixative resin are selected to provide for an optimum
hydrophilic/hydrophobic balance. This optimum balance provides,
especially in a low-VOC hair styling composition, curl retention
under humid conditions, moisture resistance, shampoo removability,
feel or stiffness, and desirable aesthetics to the hair, such as
minimal flaking of the hair fixative resin.
[0030] The acrylic hair fixative resins are preferably added to the
hair styling composition to provide a total concentration of from 1
to 15%, more preferably from 4 to 7%, of the acrylic hair fixative
resins, based on the total weight of the hair styling
composition.
[0031] The acrylic hair fixative resins may be prepared by
conventional emulsion polymerization methods well known to those
skilled in the art. Preferably, the acrylic hair fixative resins
are made by a continuous in-line emulsification process. U.S. Pat.
Nos. 3,245,932, 3,453,245 and 4,196,190 may be consulted for
further general and specific details on suitable emulsion
polymerization methods. For the purposes of the present invention,
emulsifiers used to prepare the hair fixative resins comprise one
or more phosphate ester emulsifiers. Preferably, the phosphate
ester emulsifier is selected from one or more long-chain
alkyloxypoly(alkyleneoxide), long-chain
alkylaryloxypoly(alkyleneoxide), long-chain alkyl and long-chain
alkylaryl mono- and di-esters of phosphoric acid, such as
(C.sub.8-C.sub.18)alkylaryloxypoly(alkyleneoxide- ),
(C.sub.10-C.sub.18)alkyloxypoly(alkylene-oxide),
(C.sub.10-C.sub.18)alkyl, and (C.sub.8-C.sub.18)alkylaryl mono- and
di-esters of phosphoric acid. More preferably, the phosphate ester
emulsifier is one or more
(C.sub.8-C.sub.18)alkylaryloxypoly(alkyleneoxid- e) and
(C.sub.10-C.sub.18)alkyloxypoly(alkylene-oxide) mono- and di-esters
of phosphoric acid, and corresponding salts (such as, for example,
sodium and ammonium salts).
[0032] Preferably the poly(alkyleneoxide) moieties of the phosphate
ester are based on one or more of ethylene oxide and propylene
oxide; the average number of alkylene oxide units per group is
typically from 2 to 100, preferably from 3 to 50, more preferably
from 4 to 20, and most preferably from 6 to 10. The long-chain
alkyl and long-chain alkylaryl groups are typically selected from
one or more (C.sub.8-C.sub.18)alkylary- l and
(C.sub.10-C.sub.18)alkyl groups; preferred long-chain alkyl and
long-chain alkylaryl groups include, for example, nonylphenyl,
t-octylphenyl, lauryl, tridecyl and stearyl.
[0033] Suitable acrylic hair fixative resins for use in the hair
styling compositions include, for example, those described in U.S.
Pat. No. 4,196,190, that is, polymers containing 10-30% of an alkyl
acrylate, 41-60% of methyl methacrylate, 5-20% of hydroxyethyl
methacrylate and 10-30% of methacrylic acid. The acrylic hair
fixative resin may be soluble or insoluble in the hair styling
composition.
[0034] When the acrylic hair fixative resins contain acidic groups,
such as carboxylic acid groups, these may be neutralized by
conventional techniques with at least one base to promote
solubility of the resins in the hair styling composition. The
acrylic hair fixative resins are preferably neutralized with at
least one neutralizer.
[0035] Bases that will neutralize the soluble hair fixative resins
may be selected from one or more amines, alkali or alkaline earth
metal hydroxides, and ammonium hydroxide. Suitable amine
neutralizers include, for example, 2-amino-2-methyl-
1,3-propanediol, 2-amino-2 -methyl-1-propanol,
N,N-dimethyl-2-amino-2-methyl-1-propanol, mono-isopropanolamine,
triisopropanolamine, ethanolamine, triethanolamine and morpholine.
Suitable alkali or alkaline earth metal hydroxides include, for
example, sodium hydroxide and potassium hydroxide. Preferably, the
neutralizer is selected from one or more of
2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol,
N,N-dimethyl-2-amino-2-methyl-1-propanol, potassium hydroxide,
triethanolamine and triisopropanolamine.
[0036] The amount of neutralizer added to the hair styling
composition is that amount needed to provide solubility of the
soluble hair fixative resins in the hair styling composition.
Typically from 5 to 100%, preferably from 10 to 100%, more
preferably from 50 to 100%, and most preferably from 75 to 100%,
based on molar equivalents, of the acid groups in the hair fixative
resins are neutralized.
[0037] The aqueous hair resin composition that suspends or
dissolves the acrylic hair fixative resin before being added to the
hair styling composition is preferably an aqueous emulsion that was
obtained from the process that produced the acrylic hair fixative
resins. The aqueous emulsion, hereinafter called the "acrylic hair
resin emulsion," is typically unneutralized and has a pH from 1.5
to 4.5; optionally the emulsion may be partially neutralized. The
acrylic hair resin emulsion preferably contains from 30 to 60% of
the acrylic hair fixative resins, greater than 30% water, based on
total weight of the emulsion; and 0.05 to 5%, preferably from 0.1
to 2%, and more preferably from 0.3 to 1%, of one or more phosphate
ester emulsifiers, based on total weight of the hair fixative
polymer. Preferably, the acrylic hair resin emulsion is prepared
substantially in the absence of sulfate or sulfonate type
emulsifiers (such as sodium lauryl sulfate, sodium tridecylether
sulfate, diester sulfosuccinates, and alkyl or aryl polyether
sulfonates), that is, less than 0.05%, more preferably less than
0.01%, and most preferably zero %, based on total weight of the
hair fixative polymer.
[0038] In addition to the soluble hair fixative resins, the
insoluble hair fixative resins and water, the hair styling
composition may also contain surfactants, solvents, propellants,
and other preservatives.
[0039] One or more surfactants may be added to the hair styling
composition, typically to reduce the surface tension of the
composition. When surfactants are present in the hair styling
composition, they are preferably present at a concentration of from
0.001 to 1%, based on the total weight of the composition. The
surfactants that may be used in the hair styling composition
include, for example, anionic, cationic, nonionic and amphoteric
surfactants. For example, suitable surfactants include PPG 28
Buteth 35, PEG 75 lanolin, perfluoropolymethyl isopropyl ether,
octoxynol-9, PEG-25 hydrogenated castor oil, polyethylene
terephthalate, polyethylene glycol 25 glyceryl trioleate, oleth-3
phosphate, PPG-5-ceteth-10 phosphate, PEG-20 methyl glucose ether,
glycereth-7-triacetate and n-alkyl substituted lactam (such as
n-octyl pyrrolidone).
[0040] One or more plasticizers may be added to the hair styling
composition of the present invention. When plasticizers are present
in the hair styling composition, they are preferably present at a
concentration of from 0.001 to 1%, based on the total weight of the
composition. The plasticizers that may be used in the hair styling
composition include, for example, dimethicone copolyol,
dimethicone, phenyltrimethicones, trialkylcitrates, and others that
are known and typically used in the art.
[0041] One or more solvents may be added to the hair styling
composition of the present invention. When solvents are added to
the hair styling composition they preferably comprise up to 70%,
more preferably up to 55%, of the total hair styling composition,
based on the total weight of the hair styling composition. Suitable
solvents include, for example, C.sub.2-C.sub.6 organic alcohols
(such as ethanol, isopropanol, n-propanol) and acetone.
[0042] In a low-VOC hair styling composition using an aerosol
spray, one or more propellants are used. Preferably the propellants
are used at a total concentration of from 10 to 70%, more
preferably from 30 to 60%, based on the total weight of the hair
styling composition. Suitable propellants include, for example,
n-butane, isobutane, dimethyl ether, 1,1-difluoroethane,
chlorodifluoroethane, chlorodifluoromethane and other
chlorofluorocarbons. Preferred propellants are selected from one or
more of dimethyl ether, 1,1-difluoroethane, n-butane and isobutane.
These propellants are commercially available from a variety of
manufacturers.
[0043] Preservatives that may be used in the hair styling
composition include, for example, one or more of isothiazolones,
iodopropynylbutyl carbamate, benzyl alcohol, imidazolidinylurea and
alkyl parabens. A preferred antimicrobial agent is
iodopropynylbutylcarbamate (commercially available from Lonza Inc.,
Fairlawn, N.J.) The preservatives preferably comprise from 0.001 to
1% active ingredient in the hair fixative resin emulsion.
[0044] Other additives, such as those commonly used by those
skilled in the art, may be added to the hair styling composition.
The other additives used in the hair styling composition will
depend upon the type of hair styling composition desired. Other
additives include, for example, one or more of fragrances;
moisturizers (such as hydrolyzed silk protein and hydrolyzed wheat
protein); detangling aids such as panthenol; conditioning agents
(U.S. Pat. No. 5,164,177 may be consulted for further general and
specific details on suitable conditioning agents); emulsifiers;
antistatic aids; extracts; proteins; vitamins; dyes; tints;
colorants; UV protectors; and corrosion inhibitors. The other
additives typically comprise from 0.005 to 5%, and more preferably
from 0.01 to 1%, of the hair styling composition.
[0045] Additional other additives, as well as additional
surfactants, solvents, other preservatives, and thickeners, that
may be suitable in the hair styling composition may be found in the
International Cosmetic Ingredients Dictionary, 5th Edition, 1993,
published by the Cosmetics Toiletries Fragrances Association
(CFTA), Washington D.C.
[0046] Examples 1-4A describe polymer preparations representative
of hair fixative resin polymers of the present invention, including
comparative compositions. All ratios, parts and percentages are
expressed by weight unless otherwise specified, and all reagents
used are of good commercial quality unless otherwise specified.
Abbreviations for monomers, emulsifiers and other materials
described in the Examples are presented in Table 1. Hair fixative
resin monomeric unit composition/emulsifier data are summarized in
Table 2.
1TABLE 1 BA = Butyl Acrylate IBOA = Isobornyl Acrylate IBOMA =
Isobornyl Methacrylate MMA = Methyl Methacrylate HEMA =
Hydroxyethyl Methacrylate MAA = Methacrylic Acid IA = Itaconic Acid
DDM = Dodecyl Mercaptan SLS = Sodium Lauryl Sulfate PPE-1 =
Tridecyloxypoly(ethylen- eoxide).sub.6 Phosphate (55/45)
Mono/Diester PPE-2 = Tridecyloxypoly(ethyleneoxide).sub.10
Phosphate (60/40) Mono/Diester PPE-3 =
t-Octylphenoxypoly(ethyleneoxide).sub.7.5 Phosphate Monoester
[0047]
2TABLE 2 Polymer ID # Hair Fixative Resin Composition 1 25 BA/47
MMA/10 HEMA/13 MAA/5 IA with PPE-1 1A-comp 25 BA/47 MMA/10 HEMA/13
MAA/5 IA with SLS 1B 25 BA/47 MMA/10 HEMA/13 MAA/5 IA with PPE-2 1C
25 BA/47 MMA/10 HEMA/13 MAA/5 IA with PPE-3 2-comp 25 BA/47 MMA/10
HEMA/18 MAA with SLS* 2A 25 BA/47 MMA/10 HEMA/18 MAA with PPE-1*
3-comp 18 BA/7 IBOA/47 MMA/10 HEMA/18 MAA with SLS 3A 18 BA/7
IBOA/47 MMA/10 HEMA/18 MAA with PPE-1 4-comp 21 BA/4 IBOMA/47
MMA/10 HEMA/13 MAA/5 IA with SLS 4A 21 BA/4 IBOMA/47 MMA/10 HEMA/13
MAA/5 IA with PPE-1 *0.3% (based on total monomer) additional PPE-1
added before corrosion testing
[0048] The corrosion performance data reported in Table 3 are based
on visual ratings for 3 different "cans" (for the same polymer
composition) by 3 different observers; this corresponds to 9
observations for each corrosion rating of a particular
polymer/emulsifier composition; the average corrosion rating value
and standard deviations are given. Example 5 describes the
corrosion test method used to evaluate the different hair fixative
resin compositions. Visual corrosion ratings were based on the
following scale:
3 No corrosion = 0 Slight corrosion = 1 Moderate corrosion = 3
Severe corrosion = 5
[0049] Comparisons of corrosion data for different hair fixative
resin formulations are only valid when the pH values of the
compositions are similar, that is, within .+-.0.5 pH units,
preferably within .+-.0.2 pH units or less. As the pH decreases
below about 8, the overall degree of corrosion is greater and
differences between the polymer/phosphate-ester emulsifier
compositions versus the polymer/sulfate-emulsifier compositions are
magnified. As the pH approaches 9, the overall degree of corrosion
generally decreases; however, there is still a significant
observable difference between polymer compositions prepared with
phosphate-ester emulsifiers versus those prepared with sulfate
emulsifiers. For example, the difference in corrosiveness
(.DELTA.C) between SLS and phosphate ester prepared emulsion
polymers ranges from +0.4 up to +4 for Polymer Compositions 1, 2
and 3 (Table 3).
[0050] Aerosol hair styling compositions may have pH values from 5
to 10, preferably from 6 to 9.5, and more preferably from 7 to 8.5.
Although corrosion is generally less of a problem in aerosol
containers for compositions having pH values above 8.5 (depending
on the hair fixative resin composition), the higher pH values may
detract from the overall hair fixative resin properties due to
plasticization of the hair fixative resin. This may lead to poorer
high humidity curl retention, lower stiffness and increased
tackiness of the resin film on the hair. Residues from the hair
fixative resin formulation (such as sulfate and sulfonate
emulsifiers) may promote corrosion regardless of the pH. It is,
therefore, advantageous to be able to formulate aerosol hair
styling compositions at a pH that allows solubility or
dispersibility in the hair styling formulation and good shampoo
removability without overneutralizing (that is, increasing the pH)
the hair fixative resin in the hair styling composition. Use of
hair fixative resins prepared according to the method required by
the present invention allows for improved corrosion resistance over
a wide pH range without compromising hair styling performance of
the hair fixative resin and also allows the hair styling
composition formulator to use lower levels of conventional
corrosion inhibitors, further lessening the likelihood of
negatively affecting hair fixative resin performance.
[0051] Hair styling performance properties (such as curl retention,
stiffness, drying time, tackiness and film clarity) of hair
fixative resins based on Polymer Compositions 1-4 are unaffected by
the emulsifier used to prepare the polymer.
4 TABLE 3 Polymer Corrosion Standard Composition Rating Deviation
pH .DELTA.C** 1 0.2 0.3 8.7 +1.2 1A-comp 1.4 0.6 8.7 -- 1B 0.2 0.1
8.8 +1.2 1C 0.4 0.25 8.9 +1.0 2-comp 4.3 0.85 7.3 -- 2A 2.2 0.9 7.2
+2.1 2-comp 4.0* 0.0 6.4 -- 2A 0.0* 0.0 6.5 +4.0 3-comp 0.7 0.8 8.8
-- 3A 0.3 0.2 8.4 +0.4 4A 1.2 0.3 8.8 -- 4-comp 0.8 0.9 8.8 --
*based on average of 6 observations, others on 9 observations
**difference in corrosion rating between SLS polymer and phosphate
ester polymer
EXAMPLE 1
[0052] To a three liter, four-neck round bottom flask equipped with
overhead stirrer, condenser, nitrogen adapter and a thermocouple
was added 43.5 grams (g) itaconic acid (IA) powder, 255.0 g
deionized water and 8.5 g of 25% (in water) mixed phosphate ester
emulsifier as ammonium salt (55/45 weight ratio mixture of
mono-tridecyloxypoly(ethyleneoxide) and
di-tridecyloxypoly(ethyleneoxide) esters of phosphoric acid having
an average of 6 ethyleneoxide units per group [PPE-1 in Table 1];
available as Rhodafac RS-610A from Rhne-Poulenc; Rhodafac is a
trademark of Rhne-Poulenc Inc.). With the nitrogen turned on, the
reactor and contents were heated to 83.degree. C. and an initiator
solution of 2.2 g ammonium persulfate and 17.5 g deionized water
was added with stirring. After the initiator solution was charged,
50 g of monomer emulsion, from a monomer emulsion containing 388 g
deionized water, 12.75 g mixed phosphate ester emulsifier, 408.9 g
methylmethacrylate (MMA), 217.5 g butylacrylate (BA), 87 g
hydroxyethylmethacrylate (HEMA), 113.1 g methacrylic acid (MAA) and
11.0 g n-dodecyl mercaptan (DDM), was charged to the reactor. The
remaining monomer emulsion feed was then fed over 120 minutes while
maintaining a temperature of 83.degree. C. A cofeed initiator
solution containing 0.73 g ammonium persulfate and 79.0 g deionized
water was gradually added simultaneously with the monomer emulsion
feed over 120 minutes.
[0053] After the monomer emulsion and initiator feeds were
complete, the reaction mixture was "chased" with a ferrous sulfate,
t-butyl hydroperoxide, ammonium persulfate and d-isoascorbic acid
combination to reduce residual monomer levels. The reaction mixture
was then cooled to room temperature and filtered. The composition
of the resulting polymer was 47 MMA/25 BA/10 HEMA/13 MAA/5 IA. The
amount of PPE-1 emulsifier was 0.6%, based on total monomer
weight.
EXAMPLE 1A
(Comparative)
[0054] An emulsion polymer composition was again prepared according
to the procedure in Example 1 except for the surfactant employed
and its total amount based on monomer. Sodium lauryl sulfate (28%
aqueous solution) was charged at 8.5 g as part of initial reactor
charge and 4.25 g as part of the monomer emulsion.
EXAMPLES 1B-4A
[0055] Additional emulsion polymer compositions (1B, 1C,
2-comparative, 2A, 3-comparative, 3A, 4-comparative and 4A) were
prepared similarly to Examples 1 or 1A and are summarized in Table
2 for monomeric unit composition and emulsifier used.
EXAMPLE 5
Corrosion Test Method
[0056] Screening tests for corrosion of aqueous based aerosol cans
were based on the DuPont Closed Cell Galvanic test (described in
Spray Technology & Marketing, M. E. Boulden, April 1993); this
test provides a good prediction of long term corrosion stability.
The galvanic corrosion evaluations were conducted for 96 hours at
ambient temperature using tin plate cans containing 65 to 70 parts
dimethyl ether propellant and 30 to 35 parts concentrate. The
concentrate was composed of sufficient hair fixative resin solids
to provide 5% total solids in the resulting hair styling
composition, based on combined weight of concentrate and
propellant. The numerical corrosion rating was an overall visual
assessment of the entire interior of the can, for example, joints,
base, walls, seams and dome.
* * * * *