U.S. patent application number 09/897199 was filed with the patent office on 2002-01-10 for hair styling gels.
This patent application is currently assigned to Helene Curtis, Inc.. Invention is credited to Bhatt, Darshna, Galleguillos, Ramiro, Rizvi, Riaz.
Application Number | 20020004035 09/897199 |
Document ID | / |
Family ID | 24882001 |
Filed Date | 2002-01-10 |
United States Patent
Application |
20020004035 |
Kind Code |
A1 |
Bhatt, Darshna ; et
al. |
January 10, 2002 |
Hair styling gels
Abstract
Hair styling gels containing a carboxylated polyurethane resin,
a viscosity enhancer, and an optional second hair fixative resin,
in an aqueous carrier, are disclosed. The styling gel compositions
impart excellent hair styling, conditioning, and hair set retention
properties to treated hair.
Inventors: |
Bhatt, Darshna; (Schaumburg,
IL) ; Rizvi, Riaz; (Glendale Heights, IL) ;
Galleguillos, Ramiro; (Glendale Heights, IL) |
Correspondence
Address: |
UNILEVER
PATENT DEPARTMENT
45 RIVER ROAD
EDGEWATER
NJ
07020
US
|
Assignee: |
Helene Curtis, Inc.
|
Family ID: |
24882001 |
Appl. No.: |
09/897199 |
Filed: |
July 2, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09897199 |
Jul 2, 2001 |
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09596997 |
Jun 20, 2000 |
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6274129 |
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09596997 |
Jun 20, 2000 |
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08717429 |
Sep 20, 1996 |
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6132704 |
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Current U.S.
Class: |
424/70.1 |
Current CPC
Class: |
A61K 8/8176 20130101;
A61K 8/87 20130101; A61K 8/8158 20130101; A61Q 5/06 20130101; A61K
2800/594 20130101; Y10S 424/02 20130101; A61Q 5/12 20130101; A61K
8/731 20130101; A61K 8/8147 20130101 |
Class at
Publication: |
424/70.1 |
International
Class: |
A61K 007/06 |
Claims
What is claimed is:
1. A hair styling gel composition comprising: (a) about 0.25% to
about 6% by weight of a carboxylated polyurethane resin; (b) about
0.01% to about 3% by weight of a viscosity enhancer; and (c) about
15% to about 99.5% by weight of a carrier comprising water, wherein
the carboxylated polyurethane resin has a weight average molecular
weight of about 15,000 to about 300,000.
2. The composition of claim 1 further comprising 0% to about 6% by
weight of a second hair fixative resin.
3. The composition of claim 2 wherein a weight ratio of the second
hair fixative resin to the carboxylated polyurethane resin is 0 to
about 1.
4. The composition of claim 1 wherein the composition is free of a
neutralizing agent for the carboxylated polyurethane resin.
5. The composition of claim 1 having a viscosity of about 10,000 to
about 100,000 centipoise.
6. The composition of claim 1 wherein the carboxylated polyurethane
resin has a weight average molecular weight of about 30,000 to
about 200,000.
7. The composition of claim 1 wherein the carboxylated polyurethane
resin has a weight average molecular weight of about 40,000 to
about 190,000.
8. The composition of claim 1 wherein the carboxylated polyurethane
resin has an acid value of at least 7 mg KOH/g resin.
9. The composition of claim 1 wherein the carboxylated polyurethane
resin has a melting point of about 40.degree. C. to about
120.degree. C.
10. The hair styling gel of claim 1 wherein the carboxylated
polyurethane resin comprises a reaction product of a mixture
comprising: (i) about 10% to about 90% by weight of the mixture of
a polyoxyalkylene diol having a number average molecular weight of
about 200 to about 20,000; (ii) about 0.01% to about 20% by weight
of the mixture of an alkylene glycol; (iii) about 3% to about 80%
by weight of the mixture of an organic diisocyanate; (iv) about
0.1% to about 8% by weight of the mixture of a
2,2-di(hydroxymethyl)alkanoic acid; and (v) about 0.01% to about
0.45% by weight of the mixture of water, wherein a ratio of
isocyanate groups to hydroxyl groups is about 0.5 to about 1.
11. The composition of claim 10 wherein the polyoxyalkylene diol
comprises a blend of two or more polyoxyalkylene diols.
12. The composition of claim 10 wherein the polyoxyalkylene diol is
selected from the group consisting of a polyoxyethylene diol having
a number average molecular weight of about 200 to about 20,000, a
polyoxypropylene diol having a number average molecular weight of
about 200 to about 2,500, a polyoxytetramethylene diol having a
number average molecular weight of about 200 to about 4,000, a
block copolymer of ethylene oxide and propylene oxide having a
number average molecular weight of about 1,000 to about 9,000, and
mixtures thereof.
13. The composition of claim 10 wherein the polyoxyalkylene diol
comprises a polyoxyethylene diol having a number average molecular
weight of about 6000 to about 10,000.
14. The composition of claim 13 wherein the polyoxyalkylene diol
further comprises a polyoxypropylene glycol having a number average
molecular weight of about 200 to about 2,500, a block copolymer of
ethylene oxide and propylene oxide having a number average
molecular weight of about 1,000 to about 5,000, a polyoxyethylene
diol having a number average molecular weight of about 400 to about
5000, a polyoxytetramethylene diol having a number average
molecular weight of about 200 to about 4,000, or a mixture
thereof.
15. The composition of claim 14 wherein the water is present in an
amount of about 0.03% to about 0.4%.
16. The composition of claim 10 wherein the alkylene glycol is
selected from the group consisting of ethylene glycol, propylene
glycol, 2-ethyl-1,3-hexanediol, tripropylene glycol, triethylene
glycol, 2,4-pentanediol, 1, 4-butanediol, 2-methyl-1,
3-propanediol, cyclohexanediol, cyclohexanedimethanol, glycerol,
hexylene glycol, 2-methyl-1,3-pentadediol, dipropylene glycol,
diethylene glycol, and mixtures thereof.
17. The composition of claim 10 wherein the organic diisocyanate is
an aliphatic diisocyanate.
18. The composition of claim 17 wherein the aliphatic diisocyanate
is selected from the group consisting of methylene
bis(cyclohexyl-4-isocyana- te), trimethylhexamethylene
diisocyanate, isophorone diisocyanate,
tetramethylene-1,4-diisocyanate, hexamethylene diisocyanate,
trimethylene diisocyanate, cyclohexane-1,2-diisocyanate,
decamethylene-1,10-diisocyana- te, cyclohexane-1,4-diisocyanate,
and mixtures thereof.
19. The composition of claim 10 wherein the 2,2-di(hydroxymethyl)
alkanoic acid comprises dimethylolpropionic acid.
20. The composition of claim 1 wherein the
2,2-di(hydroxymethyl)alkanoic acid is present in an amount of about
0.3% to about 7% by weight.
21. The composition of claim 10 wherein the water is present in an
amount of about 0.03% to about 0.4% by weight.
22. The composition of claim 10 wherein the water is present in an
amount of about 0.05% to about 0.35%.
23. The composition of claim 10 wherein the water is present in an
amount of about 0.03% to about 0.4%, by weight, and the ratio of
isocyanate groups to hydroxyl groups is about 0.6 to about
0.98.
24. The composition of claim 10 wherein the water is present in an
amount of about 0.05% to about 0.35% by weight, and the ratio of
isocyanate groups to hydroxyl groups is about 0.65 to about
0.98.
25. The composition of claim 10 wherein the ratio of isocyanate
groups to hydroxyl groups is about 0.65 to about 0.85.
26. The composition of claim 1 wherein carboxyl groups of the
carboxylated polyurethane resin comprise carboxylic acid groups,
ester groups having an alkyl group having one to three carbon
atoms, or a mixture thereof.
27. The composition of claim 1 wherein the carboxylated
polyurethane resin comprises a PVP/polycarbamyl polyglycol
ester.
28. The composition of claim 1 wherein the carrier comprises water
and 0% to about 20%, by weight of the composition, of a lower
alcohol.
29. The composition of claim 1 wherein the carrier is free of a
lower alcohol.
30. The composition of claim 2 wherein the second hair fixative
resin is cationic resin.
31. The composition of claim 2 wherein the second hair fixative
resin is an anionic resin.
32. The composition of claim 2 wherein the second hair fixative
resin is a nonionic resin.
33. The composition of claim 2 wherein the second hair fixative
resin has a glass transition temperature of about 100.degree. C. or
greater.
34. The composition of claim 2 wherein the second hair fixative
resin is selected from the group consisting of an acrylamide
copolymer, acrylamide/sodium acrylate copolymer, acrylate/ammonium
methacrylate copolymer, an acrylate copolymer, an acrylic/acrylate
copolymer, adipic acid/dimethylaminohydroxypropyl
diethylenetriamine copolymer, adipic acid/epoxypropyl
diethylenetriamine copolymer, allyl stearate/VA copolymer,
aminoethylacrylate phosphate/acrylate copolymer, an ammonium
acrylate copolymer, an ammonium vinyl acetate/acrylate copolymer,
an AMP acrylate/diacetoneacrylamide copolymer, an AMPD
acrylate/diacetoneacrylam- ide copolymer, butyl ester of
ethylene/maleic anhydride copolymer, butyl ester of PVM/MA
copolymer, calcium/sodium PVM/MA copolymer, corn
starch/acrylamide/sodium acrylate copolymer, diethylene
glycolamine/epichlorohydrin/piperazine copolymer, dodecanedioic
acid/cetearyl alcohol/glycol copolymer, ethyl ester of PVM/MA
copolymer, isopropyl ester of PVM/MA copolymer, karaya gum, a
methacryloyl ethyl betaine/methacrylate copolymer, an
octylacrylamide/acrylate/butylaminoeth- yl methacrylate copolymer,
an octylacrylamide/acrylate copolymer, phthalic
anhydride/glycerin/glycidyl decanoate copolymer, a
phthalic/trimellitic/glycol copolymer, polyacrylamide,
polyacrylamidomethylpropane sulfonic acid, polybutylene
terephthalate, polyethylacrylate, polyethylene, polyquaternium-1,
polyquaternium-2, polyquaternium-4, polyquaternium-5,
polyquaternium-6, polyquaternium-7, polyquaternium-8,
polyquaternium-9, polyquaternium-10, polyquaternium-11,
polyquaternium-12, polyquaternium-13, polyquaternium-14,
polyquaternium-15, polyvinyl acetate, polyvinyl butyral, polyvinyl
imidazolinium acetate, polyvinyl methyl ether, PVM/MA copolymer,
PVP, PVP/dimethylaminoethylmethacrylate copolymer, PVP/eicosene
copolymer, PVP/ethyl methacrylate/methacrylic acid copolymer,
PVP/hexadecene copolymer, PVP/VA copolymer, PVP/vinyl
acetate/itaconic acid copolymer, shellac, sodium acrylate/vinyl
alcohol copolymer, sodium carrageenan, starch diethylaminoethyl
ether, stearylvinyl ether/maleic anhydride copolymer, sucrose
benzoate/sucrose acetate isobutyrate/butyl benzyl phthalate
copolymer, sucrose benzoate/sucrose acetate isobutyrate/butyl
benzyl phthalate/methyl methacrylate copolymer, sucrose
benzoate/sucrose acetate isobutyrate copolymer, a vinyl
acetate/crotonate copolymer, vinyl acetate/crotonic acid copolymer,
vinyl acetate/crotonic acid/methacryloxybenzophenone-1 copolymer,
vinyl acetate/crotonic acid/vinyl neodecanoate copolymer, and
mixtures thereof.
35. The composition of claim 2 wherein the second hair fixative
resin comprises a butyl ester of a copolymer of vinyl methyl ether
and maleic anhydride, an
octylacrylamide/acrylate/butylaminoethylmethacrylate copolymer, or
a mixture thereof.
36. The composition of claim 2 comprising about 1% to about 3% of
the carboxylated polyurethane resin, about 1% to about 3% of the
second hair fixative resin, 0% to about 10% ethanol, and about 80%
to about 98% water, wherein a weight ratio of second hair fixative
resin to carboxylated polyurethane resin is one or less.
37. A method of treating hair to fix the hair in a desired
hairstyle comprising: (a) wetting the hair; (b) applying a hair
styling gel composition to the hair, said hair styling gel
composition comprising (i) about 0.25% to about 6% by weight of a
carboxylated polyurethane resin; (ii) about 0.01% to about 3% by
weight of a viscosity enhancer; and (iii) about 15% to about 99.5%
by weight water, wherein the carboxylated polyurethane resin has a
weight average molecular weight of about 15,000 to about 300,000;
and (c) then drying the hair while styling the hair into the
desired hairstyle.
38. The method of claim 37 wherein the hair styling gel composition
further comprises 0% to about 6% by weight of a second hair
fixative resin.
Description
FIELD OF INVENTION
[0001] The present invention is directed to hair styling gels that
are applied to the hair to shape, style, and condition the hair.
The gels have excellent hair styling, detangling, and style
retention properties, and are washable from treated hair. In
particular, the present invention relates to hair styling gels
comprising a carboxylated polyurethane resin, an optional second
hair fixative resin, a viscosity enhancer, and a carrier comprising
water.
BACKGROUND OF THE INVENTION
[0002] Normal hair can be so fine, limp, and lacking in body that
the hair does not hold a hair set well. Furthermore, hair can lose
body and be weakened as a result of being subjected to chemically
active hair treatments, such as permanent waves and tints.
Additionally, hair can be weakened even further by other
contributing factors, such as bleaching by the sun or chlorinated
swimming pool water.
[0003] The condition and appearance of hair can be improved by
applying a composition that conditions the hair and helps maintain
the hair in a predetermined configuration, or hairstyle. Hair
setting and conditioning can be achieved by applying such a
composition to wet hair, fixing the hair by drying, then combing to
give finishing touches and provide the desired hairstyle.
Similarly, after applying the composition to the hair, the wet hair
can be set by using any of a variety of rollers or curlers to
mechanically fix the hair in a predetermined configuration before
drying. In either case, the wet hair is dried, either by ambient
air drying, electric drying, or hot air, i.e., blow, drying, to set
the hair.
[0004] The inherent problem encountered in hair setting is the
natural tendency of hair to return to its natural shape. For
example, set hair returns to its natural shape almost immediately
if moistened. Likewise, high humidity conditions accelerate the
tendency of hair to return to its natural shape. Therefore,
intensive efforts have been directed toward providing a hair set
with sufficient holding power to maintain the desired hairstyle
until at least the next shampoo, and, accordingly, giving the hair
set a degree of permanency.
[0005] As indicated by the natural tendency of hair to return to
its natural shape, hair is an elastic structure. As a result, the
slight deformations in hair structure resulting from setting the
hair are completely reversible. However, the rate of return of hair
to its natural shape is dependent upon the method used to deform,
or set, the hair. Hair sets performed with wet strands of hair
being rolled tightly, either in curls around the finger or on
curlers, followed by drying the hair and unrolling the curlers
after drying, corresponds to the release of the hair from a
deformation-causing load. The deformation, or set, obtained can
last for several days, but the hair set is not retained if the hair
is wetted.
[0006] Investigators have sought to delay the combined action of
natural forces and moisture that cause hair to return to its
original state by applying compositions containing naturally
occurring or synthetic polymers that assist the hair in retaining
the desired hairstyle configuration. When applied to hair from
aqueous or aqueous/alcoholic solutions, gels, or mousses, the
polymers form a film on the hair, after drying, to help maintain
the hair in the desired hair set configuration. The polymeric film
promotes cohesion and gives stability to the hair set, and also
acts as a moisture barrier. The principal objective of a hair
styling composition, therefore, is to cover the styled hair with an
invisible polymeric film that gives the styled hair a degree of
rigidity, protects the hairstyle against wind and humidity, retains
the hairstyle, and imparts a good feel and conditioning to the
styled hair.
[0007] One type of hair styling composition is a hair spray
product. Hair spray products are applied to wet and/or dry hair and
contain a polymer, or polymer mixture, that remains fixed on the
previously styled hair and effects the hair in various ways. For
example, a "mechanical" effect is exerted on each individual hair.
The film-forming polymers are used to provide a flexible sheath of
polymeric film on the shaped hair after drying, and, therefore, for
mechanical reasons, retard the return of each individual hair to
its natural shape. In addition, the polymeric film provides an
overall stiffening of the hair. The hair behaves as if the
individual hair strands are welded together, and the final
hairstyle has better cohesion, therefore, resisting the natural
forces that return the hair to its natural shape. Finally, the
polymeric film protects the hair from humidity. The ability of the
polymeric film to attract and absorb water preferably is minimal,
such that the polymeric film retards moisture uptake by hair and
retards the return of the hair to its natural state.
[0008] Hair styling gels are another type of hair styling
composition. Hair styling gels are applied to wet or damp hair
prior to configuring the hair in a predetermined configuration.
Hair styling gels are applied by rubbing the gel onto the hair
manually. The treated hair then is dried and set in a desired
configuration, such as with a blow dryer.
[0009] The general principles of hair styling and setting are
thoroughly discussed by C. Zviak, in The Science of Hair Care,
Marcel Dekker, pp. 149-181 (1986). Zviak reviews both the polymers
used in hair styling products and the formulation principles used
to produce a hair styling composition that provides such beneficial
hair set properties as improved hairstyle retention, easy
application and combing, quick drying and nonstickiness, good hair
body and bounce, increased hair volume and gloss, and
hydrophobicity. It is evident that in the formulation of any
end-use hair styling product, some of these benefits must be
sacrificed to some degree to achieve a competing benefit.
Therefore, the formulation of hair styling compositions has proved
difficult.
[0010] To overcome some of the inherent disadvantages of the
polymers used to set and style hair, and to minimize the drawbacks
of a particular polymer used in the formulation, hair styling
compositions are available in diversified forms. For example, hair
styling compositions are available as plasticizing lotions,
plasticizing gels, aerosol foams, all-purpose lotions, hair sprays,
holding lotions, conditioners, and shampoos.
[0011] Nonionic, cationic, and anionic polymers have been used in
hair styling compositions, with the anionic polymers providing the
best hair set results. However, anionic polymers also have
disadvantages, such as high water solubility, and, therefore, low
hydrophobicity; and low substantivity on hair fibers, therefore,
generating a crust and flaking due to easy elimination from the
hair by combing and brushing. As a result, investigators have
continued to search for compounds and compositions that provide the
benefits of improved durability and feel of the hair set, while
conditioning the hair.
[0012] The use of resins, or polymers, in hair styling compositions
is well known, as summarized in Grollier et al. U.S. Pat. No.
4,445,521. The resins typically used in hair styling compositions
are linear vinyl (e.g., an alkyl vinyl ether) or acrylic (e.g., an
alkyl acrylate) polymers prepared by copolymerizing two or more
monomers in a free radical polymerization reaction. The vinyl and
acrylic-based resins often are used in relatively high
concentrations in a hair styling composition to fix the hair in a
particular configuration and to provide good hair set retention.
However, at high concentrations, the vinyl and acrylic-based resins
exhibit disadvantages that adversely affect the hair, such poor
combing, poor feel, and excessive stiffness, crust, and
flaking.
[0013] The vinyl and acrylic-based hair fixative resins
conventionally used in hair styling compositions were designed for
use in anhydrous alcoholic hair spray compositions. The resins,
therefore, had excellent compatibility with, and solubility in,
alcohols (e.g., ethanol) used in pump spray compositions and
hydrocarbons used as propellants in aerosol compositions. However,
due to environmental and toxicological concerns, government
regulations require a decrease in the amount of organic solvents
used in hair setting and related compositions. Therefore, the
alcohols and the hydrocarbon gases traditionally present in hair
setting compositions, and especially hair sprays, are being
replaced with water and water-soluble solvents, like dimethyl
ether, that pose less harm to the environment. In addition, the
traditional hair sprays are being replaced by hair styling gels and
mousses.
[0014] The solvent changes required by government regulation made
the traditional vinyl and acrylic-based resins unsuitable in
aqueous hair setting compositions. The presence of water in hair
spray compositions increased the viscosity of the composition,
thereby making spraying difficult to impossible when traditional
resins are used. The relatively high viscosity of the hair spray
compositions, therefore, required a reduction in the resin
concentration of the composition, which, in turn, results in
insufficient hair set retention. The presence of water also
increases the tackiness of the resin on the hair, thereby
prolonging the drying time of the hair spray on the hair. Water
also reduces the hair-wetting ability of the compositions,
resulting in beading and flaking of the resin from the hair. In the
case of aerosol hair spray products, the combination of water,
resin, and propellant gas results in poor delivery and foaming of
the composition, large aerosol particle size, and beading of the
resin. Similar disadvantages were observed when a traditional hair
fixative resin was used in an aqueous hair styling gel.
[0015] The disadvantages attributed to traditional vinyl and
acrylic resins led investigators to search for new hair fixative
resins that overcome the disadvantages associated with the vinyl
and acrylic resins. As set forth in European Patent Application 0
619 111, one class of resins is the polyurethanes. However, the
hair fixative compositions disclosed in EP 0 619 111 require a base
to neutralize, and solubilize, the polyurethane resin. It would be
desirable to provide an aqueous hair styling gel that overcomes the
disadvantages associated with traditional vinyl and acrylic resins,
that imparts good hair style and a natural feel to the hair, that
retains the hair set, and that conditions the hair.
SUMMARY OF THE INVENTION
[0016] The present invention is directed to hair styling gels
containing (a) a hydrophilic, carboxylated polyurethane resin, (b)
an optional second hair fixative resin, (c) a viscosity enhancer,
and (d) a carrier comprising water. The optional second hair
fixative resin is a traditional hair setting resin, such as a vinyl
or acrylic resin. The optional second hair fixative resin can be an
anionic, cationic, or nonionic resin because each class of resin is
compatible with the carboxylated polyurethane resin.
[0017] The hair styling gels impart good hair set retention and a
soft, natural feel to treated hair, and provide superior hairstyle
retention at high relative humidity. The hair styling gels also
detangle hair and condition the hair. Such results are unexpected
because traditional hair setting resins are hydrophobic. In
contrast, the carboxylated polyurethane resins are hydrophilic, yet
provide a soft, natural feel to the hair, and the hair is not
tacky.
[0018] In particular, the present invention is directed to hair
styling gels comprising: (a) about 0.25% to about 6%, by total
weight of the composition, of a carboxylated polyurethane resin,
(b) 0% to about 6%, by total weight of the total composition, of an
optional second hair fixative resin, (c) about 0.01% to about 3%,
by total weight of the composition, of a viscosity enhancer, (d) 0%
to about 20%, by total weight of the composition, of an alcohol,
like ethanol, and (e) water. The hair styling gels have a pH of
about 6 to about 10, and a viscosity of about 10,000 to about
100,000 cps (centipoise). In a preferred embodiment, the weight
ratio of the second hair fixative resin to the carboxylated
polyurethane resin is 0 to about 1.
[0019] The polyurethane resins used in the hair styling gels, also
termed a polycarbamyl polyglycols, have pendant carboxyl groups and
are hydrophilic. The carboxyl groups can be a carboxylic acid group
(i.e., CO.sub.2H), an ester group (i.e., CO.sub.2R, wherein R is an
alkyl group containing one to three carbon atoms), or a mixture
thereof. The polyurethane resin also can be a copolymer of
polyvinylpyrrolidone and a polyurethane, termed a PVP/polycarbamyl
polyglycol ester.
[0020] The polyurethane resins have good tear strength, excellent
washability, good adhesion, and are soluble in water and polar
solvents, thereby making them useful in aqueous hair styling
compositions. In addition, the polyurethane resins, alone and in
combination with the optional second hair fixative resin, form
clear, i.e., transparent, compositions in neutral to slightly basic
aqueous solvents. The carboxylated polyurethane resins form
flexible, elastic films that give treated hair a natural feel,
while retaining the desired hairstyle.
[0021] The hair styling gels can be designed to impart a natural
feel, a conditioned feel, or a stiff feel to treated hair by
incorporating an optional second hair fixative resin in the gel,
and by a judicious selection of the second hair fixative resin and
of the amount of the second hair fixative resin in the hair styling
gel. The hair styling gels provide a soft polymeric film on the
hair after application because of the associative nature of the
carboxylated polyurethane resin. The optional second hair fixative
resin is included in the hair styling gel to impart a desired
degree of stiffness to treated hair. The hair styling gels,
therefore, impart superior hair set retention, good conditioning
properties, and can be designed to impart any desired feel to
treated hair.
[0022] In accordance with another important aspect of the present
invention, the hair styling gels exhibit improved washability from
the hair when the carboxylated polyurethane resin has an acid value
of at least about 7 mg KOH/g (milligrams potassium hydroxide per
gram of resin), and preferably about 7 to about 50 mg KOH/g of
resin. The carboxylated polyurethane resins do not require
neutralization with a base to provide a useful hair styling
gel.
[0023] In accordance with one embodiment of the present invention,
the carboxylated polyurethane resin is a copolymer of
polyvinylpyrrolidone and a polyurethane. In another embodiment, the
carboxylated polyurethane resin used in the hair styling gel is
produced by reacting: (a) a diol component comprising a
polyoxyalkylene diol; (b) an alkylene glycol; (c) a diisocyanate;
(d) water in an amount of about 0.01% to about 0.45% by weight of
the mixture; and (e) a 2,2-di(hydroxymethyl)alkanoic acid,
preferably 2,2-di-(hydroxymethyl)propionic acid, wherein the ratio
of NCO (isocyanate) groups to OH (hydroxyl) groups in the water,
diol, and glycol, i.e., the R-value, is about 0.5 to about 1.
[0024] The hydrophilic, carboxylated polyurethane resin contains
polyoxyalkylene units, i.e., soft segments, and/or alkylene units,
i.e., hard segments, connected by urethane linkages. Preferably,
the carboxylated polyurethane resin contains soft and hard
segments. Also incorporated into the polymer chain is a small
amount of diol having a pendant carboxyl group. The polymer chain
further contains urea linkages resulting from a reaction between
water and isocyanate groups, which modify the hair styling
properties of the polyurethane.
[0025] Polyoxyethylene soft segments of the polyurethane resin
impart hydrophilicity to the polyurethane. Soft segments derived
from polyoxypropylene and polyoxytetramethylene diols provide a
softer, but less hydrophilic, polyurethane. Hydrophilic
polyurethane resins having improved strength and superior adhesive
properties can be formed by using combinations of polyoxyalkylene
diols.
[0026] In another embodiment of the present invention, the
carboxylated polyurethane resins used in the hair spray composition
are produced from (a) a major portion of polyoxyethylene diol
having a number average molecular weight (Mn) of 6000 to 10,000;
(b) an alkylene glycol, preferably diethylene glycol,
cyclohexanedimethanol, or dipropylene glycol; (c) a diisocyanate;
(d) water in the amount of about 0.01% to about 0.45% by weight;
and (e) a 2,2-di-(hydroxymethyl)alkanoic acid, wherein the ratio of
NCO to OH in the water, diol, and glycol mixture (i.e., the
R-value) is about 0.6 to about 0.98. These polyurethane resins are
soluble in dilute (neutral to basic) aqueous solutions, and exhibit
good sprayability, superior feel, low flaking, desirable crust, and
good set retention when applied to hair. The polyurethane resins
are hydrophilic, and provide a soft feel in a hydrated state. In a
particular embodiment of a polyurethane resin produced with a major
portion of polyoxyethylene diol, water is added in the amount of
about 0.04% to about 0.25% by weight, and the ratio of NCO to OH of
the water, diol and glycol mixture (i.e., the R-value) is about 0.6
to about 0.98 to provide a carboxylated polyurethane resin having
improved adhesiveness to the hair and improved slip, i.e., good
combing properties.
[0027] Another aspect of the present invention is to provide a hair
styling gel that provides good hair set retention at high relative
humidity, imparts a soft, natural, nontacky feel to the hair, and
conditions and detangles the hair. Accordingly, a hydrophilic
polyurethane resin incorporated into a present hair spray
composition has a weight average molecular weight of about
(M.sub.w) of about 15,000 to about 300,000, preferably 30,000 to
about 200,000, and to achieve the full advantage of the present
invention about 40,000 to about 190,000. The polyurethane resins
also have a polydispersibility index (PDI) of about 1 to about 4,
and preferably about 1 to about 3. Preferred polyurethane resins
have an R-value of about 0.65 to about 0.98.
[0028] In accordance with another important aspect of the present
invention, the carboxylated polyurethane resin modifies the
properties of the optional second hair setting resin to provide a
clear, i.e., transparent, hair styling gel that can be easily
applied to the hair to give the hair a natural through a stiff
feel, as desired, while conditioning the hair and imparting good
set retention without excessive crust formation or flaking.
DETAILED DESCRIPTION OF THE INVENTION
[0029] The present hair styling gels contain a carboxylated
polyurethane resin, an optional second hair setting resin, and a
viscosity enhancer in an aqueous carrier. The polyurethane resins
are soluble in water and in a broad range of water/alcohol
mixtures, and help solubilize the second hair fixative resin to
provide a clear composition. The carboxylated polyurethane resins
also possess thermal properties that allow styling of the hair with
curling irons and blow dryers. The present hair styling gels,
therefore, overcome problems and disadvantages associated with
compositions which contain only a traditional acrylic or
vinyl-based hair fixative resin, and provide improved hair styling,
hair set retention, hair feel and conditioning, and
washability.
[0030] In particular, the present hair styling gels comprise about
0.25% to about 6%, and preferably about 0.5% to about 5%, by total
weight, of a carboxylated polyurethane resin. To achieve the full
advantage of the present invention, the styling gel comprises about
1% to about 4%, by total weight of the composition, of a
carboxylated polyurethane resin.
[0031] The polyurethane resins are linear, hydroxyl-terminated
copolymers having pendant carboxyl groups. The carboxyl group can
be a carboxylic acid group or an ester group, wherein the alkyl
moiety of the ester group contains one to three carbon atoms. The
hydrophilic polyurethane resins typically are ethoxylated and/or
propoxylated at least at one terminal end. The carboxylated
polyurethane resin also can be a copolymer of polyvinylpyrrolidone
and a polyurethane, having a CTFA designation PVP/polycarbamyl
polyglycol ester. In accordance with an important feature of the
present invention, the polyurethane resins can be solubilized in
water, or in a hydroalcoholic solution, in the absence of a
base.
[0032] The carboxylated polyurethane resins are soft and flexible,
and have a melting point of about 40.degree. C. to about
120.degree. C., and preferably about 60.degree. C. to about
100.degree. C. To achieve the full advantage of the present
invention, the polyurethane resins have a melting point of about
70.degree. C. to about 90.degree. C.
[0033] The carboxylated polyurethane resins provide treated hair
with a conditioned, soft, nontacky, natural feel, while maintaining
good style retention. The polyurethane resins also exhibit good wet
combing and detangling properties, and are washable from the
hair.
[0034] One useful polyurethane resin incorporated into a present
hair styling gel comprises a reaction product of a diol component,
an alkylene glycol, a diisocyanate, water, and a
2,2-di-(hydroxymethyl)alkanoic acid. Alternatively, an amine, such
as diglycolamine, can be substituted for at least a portion of the
water in the reaction mixture. Aqueous solutions of the
carboxylated polyurethane resins impart a soft feel, good set
retention, reduced flaking and crust, and improved hair setting and
conditioning properties to treated hair.
[0035] The hydrophilic polyurethanes are prepared using an
aliphatic diisocyanate, an aromatic diisocyanate, or a mixture
thereof. An aliphatic diisocyanate is preferred. Typically, the
diisocyanate is interacted with a low molecular weight glycol or
triol, such as ethylene glycol, diethylene glycol, propylene
glycol, glycerol, hexylene glycol, cyclohexanediol,
cyclohexanedimethanol, 1,4-butanediol, tripropylene glycol,
triethylene glycol, dipropylene glycol, or mixtures thereof,
wherein the glycol or triol has at least two hydroxyl groups and a
molecular weight up to about 200, to provide a polyurethane. The
diisocyanate also can be reacted with a polymeric
dihydroxy-terminated oligomer, e.g., a polyoxyalkylene glycol
having a molecular weight of about 200 to 20,000 to provide a
hydrophilic polyurethane. Exemplary oligomers include, but are not
limited to, polypropylene glycols, polyethylene glycols, ethylene
glycol-propylene glycol copolymers, polybutylene glycols, and
mixtures thereof. Preferably, a diisocyanate is interacted both
with a low molecular weight diol or triol and with an oligomer to
provide a hydrophilic polyurethane.
[0036] Exemplary, but nonlimiting, diisocyanates include
trimethylhexamethylene diisocyanate, isophorone diisocyanate,
decamethylene-1,10-diisocyanate, cyclohexane-1,2-diisocyanate,
methylene bis(cyclohexyl-4-isocyanate), toluene-1,4-diisocyanate,
toluene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate,
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, m-phenylene
diisocyanate, p-phenylene diisocyanate, chlorophenylene
diisocyanate, hexamethylene-1,6-diisocyanate,
tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate,
naphthalene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate,
4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl
diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate,
3,3,'-dichlorophenyl-4,4'-diisocyanate,
2,2',5,5'-tetrachlorodiphenyl-4,4'-diisocyanate,
trimethylhexamethylene diisocyanate, m-xylene diisocyanate, and
mixtures thereof.
[0037] The polyurethane resin contains pendant carboxyl groups to
improve the water solubility or dispersibility of the polyurethane
resin. Preferably, the number of carboxyl groups is sufficient to
give the polyurethane resin an acid value of at least about 7, and
preferably about 7 to about 50, mg KOH/g resin. Examples of useful
carboxylated polyurethanes are disclosed in Gould et al. U.S. Pat.
No. 5,000,955, incorporated herein by reference. Other useful
hydrophilic polyurethanes are disclosed in U.S. Pat. Nos.
3,822,238; 4,156,066; 4,156,067; 4,255,550; and 4,743,673, also
incorporated herein by reference.
[0038] In one embodiment, the polyurethane resin comprises the
reaction product of: a diol component comprising a polyoxyalkylene
diol, preferably a polyoxyethylene diol having a number average
molecular weight (M.sub.n) of about 200 to about 20,000, a
polyoxypropylene diol having an M.sub.n of about 200 to about 2500,
a block copolymer of ethylene oxide and propylene oxide having an
M.sub.n of about 1,000 to about 9,000, or a polyoxytetramethylene
diol having an M.sub.n of about 200 to about 4,000; about 0.01% to
about 10% by weight of a low molecular weight alkylene glycol
selected from the group consisting of ethylene glycol, propylene
glycol, 2-ethyl-1,3-hexanediol, tripropylene glycol, triethylene
glycol, 2,4-pentanediol, 2-methyl-1,3-propanediol,
2-methyl-1,3-pentanediol, cyclohexanediol, cyclohexanedimethanol,
dipropylene glycol, diethylene glycol, and mixtures thereof; an
organic diisocyanate; a 2,2-di-(hydroxymethyl)alkanoic acid; and
water in an amount of about 0.01% to about 0.45% by weight of the
reaction mixture, wherein the NCO/OH ratio (i.e., the R-value) is
about 0.5 to about 1, and preferably about 0.6 to about 0.98. To
achieve the full advantage of the present invention, the R-value is
about 0.65 to about 0.98.
[0039] An amine can be used in the reaction mixture for at least a
portion of the water. The amine can be added to the reaction
mixture in an amount of about 0.01% to about 0.8% by weight amine,
preferably about 0.02% to about 0.5% amine to about 0.01% to about
0.2% water in the reaction mixture. Amines that can be used in the
reaction are ethylenediamine, propylenediamine, monoethanolamine,
diglycolamine, and JEFFAMINE D1-230, D-400, D-2000, D-4000,
ED-0600, ED-900, or ED-2001. The hydroxylamines and the JEFFAMINE
products are manufactured by Texaco Chemical Company. Preferably,
the amine is a hydroxylamine, and most preferably the amine is
monoethanolamine and/or diglycolamine.
[0040] The polyoxyethylene diols are available from Union Carbide
Corporation under the trademark CARBOWAX, such as CARBOWAX.RTM.
1450 and CARBOWAX.RTM. 8000 wherein the number represents number
average molecular weight. The polyoxypropylene diols (PPG) are
available from various sources, such as the PPG series of ARCO
NIAX.RTM. PPG 1025, PPG 425, PPG 725, PPG 1225, and PPG 2025, and
as R2134 (2200) and R2135 (4400), wherein the number represents
number average molecular weight. Triols are also available from
ARCO as NIAX.RTM. Polyols 11-34, LG-650, LG-56, LG-168, LHT-28,
LHT-240. The polyoxytetramethylene diols are available from E.I.
DuPont de Nemours as TERATHANE 600, 1000, 1400, 2000, and 2900.
Polyetherpolycarbonate is available from BASF under the tradename
polytetrahydrofuran 1000 CD and 2000 CD.
[0041] A block polyoxyalkylene polymer also can be used in the
reaction. For example, a propylene oxide terminated block of
ethylene glycol manufactured by BASF under the tradename PLURONIC R
and a ethylene oxide terminated block of propylene glycol
manufactured by BASF under the tradename of PLURONIC can be used
for the polyoxyalkylene in the reaction. Examples of the block
copolymers of the sequential addition of ethylene oxide and
propylene oxide to ethylene diamine are made by BASF under the
tradename of PLURONIC, such as PLURONIC F68, F64, F127, L35, L92,
L82, 17R2, and 25R2.
[0042] Preferably, the polyoxyalkylene diol used in forming the
hydrophilic polyurethane resin is polyoxyethylene diol. The blends
of polyoxyalkylene diols contain at least about 10% polyoxyethylene
diol, preferably, at least 20% polyoxyethylene diol, and most
preferably, at least 25% polyoxyethylene diol, by weight.
[0043] The amount of polyoxyalkylene diol having a molecular weight
of 400 to 20,000 in the polyurethane resin can vary from about 10%
to about 90%, preferably about 30% to about 90%, and most
preferably about 40% to about 90%, by weight, and the number
average molecular weight (M.sub.n) of the polyoxyalkylene diol can
vary from about 200 to about 20,000, preferably from about 800 to
about 15,000, and more preferably from about 1000 to about
12,000.
[0044] The alkylene glycols can be purchased from numerous sources.
For example, propylene glycol can be purchased from Aldrich
Chemical Company as 1,2-propanediol. The amount of the alkylene
glycol (hard segment) component in the polyurethane resin can be
about 0.01% to about 20%, preferably about 0.05% to about 15%, more
preferably about 0.1% to about 12%, still more preferably about
0.5% to about 10%, and most preferably about 1% to about 8%, by
weight of the reaction mixture.
[0045] The diisocyanate in the reaction mixture can be an aliphatic
diisocyanate, an aromatic diisocyanate, or a mixture thereof. The
aliphatic diisocyanates are preferred. An especially preferred
diisocyanate is methylene bis(cyclohexyl-4-isocyanate). other
examples of diisocyanates are trimethyl hexamethylene diisocyanate
and isophorone diisocyanate. Representative examples of the
preferred aliphatic diisocyanates include, but are not limited to
tetramethylene diisocyanate, hexamethylene diisocyanate,
trimethylene diisocyanate, trimethylhexamethylene diisocyanate,
cyclohexane-1,2-diisocyanate, and cyclohexane-1,4-diisocyanate.
Examples of aromatic diisocyanates are 2,4-toluene diisocyanate and
2,6-toluene diisocyanate. Also suitable are the isocyanate
equivalents which form urethane linkages, exemplified by nitrile
carbonates, such as adiponitrile carbonate of U.S. Pat. No.
4,810,543, incorporated herein by reference. The amount of
diisocyanate varies from about 3% to about 80%, preferably from
about 4% to about 70%, more preferably from about 5% to about 60%,
still more preferably from about 6% to about 55%, and most
preferably from about 6.5% to about 50%, by weight. The
polyurethane resins are prepared by reacting the polyoxyalkene
diols with the diisocyanates.
[0046] The amount of water in the reaction mixture is about 0.03%
to about 0.40%, and more preferably about 0.05% to about 0.35%, by
weight, of the reaction mixture.
[0047] The amount of 2,2-di-(hydroxymethyl) alkanoic acid in the
reaction mixture is about 0.1% to about 8%, preferably about 0.3%
to about 7%, and most preferably about 0.5% to about 6%, by weight.
Preferably the 2,2-di-(hydroxymethyl)alkanoic acid is
dimethylolpropionic acid. The final reaction product has an acid
value of at least about 0.2, preferably at least about 0.5, and
most preferably at least about 1.
[0048] The ratio of NCO to OH groups from the diol, alkylene
glycol, amines and water (i.e., the R-value) in the reaction
mixture is about 0.5 to about 1, preferably about 0.6 to about
0.98, and most preferably from about 0.65 to about 0.98. The weight
average molecular weight (M.sub.w) of the carboxylated polyurethane
resin is about 15,000 to about 300,000, preferably about 30,000 to
about 200,000, and most preferably about 40,000 to about 190,000.
The sum of all ingredients, including the diols, glycols, water,
and diisocyanate in the reaction mixture total 100% by weight.
[0049] In another embodiment, the hydrophilic polyurethane resin
comprises a reaction product of: (a) a diol having a major portion
of a polyoxyethylene diol having an M.sub.n of 6,000 to 10,000, and
a minor portion of a polyoxypropylene diol having an M.sub.n of
about 1,000 to about 3,500 or a polyoxyethylene diol having an
M.sub.n of about 600 to about 2000; (b) an alkylene glycol; (c) a
diisocyanate; (d) water in an amount of about 0.01% to about 0.45%
by weight of the reaction mixture; and (e) a
2,2-di(hydroxymethyl)alkanoic acid, and an equivalent mole weight
ratio of NCO to OH of the water, diol and glycol of about 0.6 to
about 0.98. Preferably, at least 45% of the polyoxyethylene glycol
of M.sub.n about 8000, more preferably at least about 55%, still
more preferably at least about 65%, and most preferably at least
75%, by weight, is used in the total reaction mixture. The amount
of the lower molecular weight polyoxyethylene diol having an
M.sub.n of about 600 to about 2,000 is about 1% to about 15%, and
preferably from about 2% to about 10%, by weight of the reaction
mixture. Preferably, the alkylene glycol is diethylene glycol,
cyclohexanedimethanol, dipropylene glycol, or a mixture
thereof.
[0050] The 2,2-di-(hydroxymethyl)alkanoic acid preferably is
dimethylolpropionic acid. The amount of dimethylolpropionic acid is
about 0.1% to about 8%, preferably about 0.3% to about 7%, and most
preferably about 0.5% to about 6% by weight of the reaction
mixture. The final product has an acid value of at least about 7 mg
KOH/g resin. To achieve the full advantage of the invention, the
polyurethane resin has an acid value of about 7 to about 50 mg
KOH/g resin. The sum of all ingredients, including the diols,
glycols, water, and diisocyanate in the reaction mixture totals
100% by weight.
[0051] Alternatively, an amine can be used in place of a portion of
the water in the reaction mixture. An amount of about 0.15% to
about 0.6% amine, based on diglycolamine, is used with about 0.06%
to about 0.5% of water, more preferably about 0.1% to about 0.4% of
water, and most preferably of about 0.15% to about 0.3% of
water.
[0052] The preferred diol is a polyoxyethylene diol, preferably a
polyoxyethylene diol of M.sub.n about 6000 to about 10,000,
alternatively with about 1% to about 10% of a polyoxyethylene diol
of M.sub.n about 600 to about 2,000. The preferred water level is
about 0.03% to about 0.4%, and most preferably about 0.05% to about
0.35%, by weight.
[0053] The carboxylated polyurethane resins of this embodiment are
especially useful in hair setting compositions because the
polyurethane resins are soluble in ethanol/water mixtures, and in
dilute neutral to basic aqueous solutions. The polyurethane resins
also impart improved feel and conditioning to treated hair, low
flaking and crust, and improved set retention. These and other
advantageous properties are observed when the carboxylated
polyurethane resins are admixed with an optional second hair
fixative resin, e.g., increased water solubility of the second hair
fixative resin, improved feel of treated hair, and reduced crust
and flaking.
[0054] For hair setting compositions, the hydrophilicity of the
polyurethane resin is an unexpected important property in
combination with other desirable properties, such as washability.
Conventional hair fixative resins are hydrophobic materials that
impart a stiff feel to treated hair. The polyurethane resins are
hydrophilic materials that give hair a soft, natural feel, yet are
adhesive to the hair and impart excellent hair set retention. A
combination of a conventional hair fixative resin and a
polyurethane resin retains the desirable properties of each resin,
and allows a desired degree of stiffness to be imparted to the
hair. It also has been found that the hair styling properties of
the polyurethane resin can be effected by small changes in the
amount of water, the ratio of NCO/OH, and the amount of the
di(hydroxymethyl)alkano- ic acid in the reaction mixture.
[0055] The weight average molecular weight of the carboxylated
polyurethane resins can be adjusted by modifying the amount of
water in the reaction mixture within a predetermined range. The
above-described polyurethane resins having an M.sub.w of about
30,000 to about 75,000, and preferably about 35,000 to about
50,000; and a kinematic viscosity at 3 wt. % in 55/42 ethanol/water
(by weight) of about 4 to about 40 centistokes (cs), are formed
using about 0.1% to about 0.3% by weight water in the reaction
mixture, an NCO/OH ratio (i.e., R-value) of about 0.75 to about
0.95, and about 0.5% to about 2.7% by weight of the reaction
mixture of dimethylolpropionic acid.
[0056] A polyurethane resin having an Mw of about 55,000 to about
300,000 can be formed using about 0.3% to about 0.45% by weight
water, a preferred NCO/OH ratio of about 0.75 to about 0.98, and
about 0.5% to about 2.7% by weight dimethylolpropionic acid.
[0057] Polyurethane resins prepared using about 0.08% to about
0.45% by weight water in the reaction mixture, and an NCO/OH ratio
of about 0.55 to about 0.95, preferably from about 0.6 to about
0.7, have a set retention at 30 minutes of about 80% to about 90%.
An amount of water of about 0.15% to about 0.45% by weight in the
reaction mixture and an NCO/OH ratio of about 0.6 to about 0.92,
preferably from about 0.7 to about 0.9, can be used to provide
polyurethane resins having a set retention of about 85% to about
98% at 30 minutes.
[0058] Alternatively, small amounts of diglycolamine can be
substituted for the water in the reaction mixture, e.g., about
0.02% to about 1%, preferably from about 0.03% to about 0.75%, more
preferably from about 0.04% to about 0.5%, and most preferably from
0.05% to about 0.4% by weight diglycolamine can be used in the
reaction mixture.
[0059] The alkylene glycol used in this embodiment can be, for
example, ethylene glycol, diethylene glycol, propylene glycol,
dipropylene glycol, cyclohexanediol, 1,4-butanediol,
cyclohexanedimethanol, tripropylene glycol, or triethylene glycol;
preferably diethylene glycol, cyclohexanedimethanol, or dipropylene
glycol; and most preferably diethylene glycol. The amount of the
alkylene glycol (hard segments) in the reaction mixture is about
0.01% to about 20%, preferably about 0.05% to about 15%, more
preferably about 0.1% to about 12%, still more preferably about
0.5% to about 10%, and most preferably about 1% to about 5%, by
weight.
[0060] In each embodiment, the polyurethane-forming reaction is
catalyzed by known catalysts. Tin-containing catalysts, such as tin
salts or organotin esters, for example, stannous octoate and
dibutyltin dilaurate, or tertiary amines, such as triethylene
diamine and N,N,N',N'-tetramethyl-1,3-butane diamine, are
preferred. The catalyst is used in an amount effective to catalyze
the reaction, i.e., about 0.001 to 1 weight percent of the total
weight of the reactive components. Reaction temperature is about
40.degree. C. to about 120.degree. C.
[0061] In the previous embodiments, the carboxylated polyurethane
resin contained carboxylic acid groups. However, carboxylated
polyurethane resins wherein carboxylic acid groups are converted to
ester groups with an alcohol having one to three carbon atoms also
can be utilized as the carboxylated polyurethane resin.
[0062] Other useful carboxylated polyurethane resins are
PVP/polycarbamyl polyglycol esters, which are copolymers of
polyvinylpyrrolidone and polyurethane. These carboxylated
polyurethane resins are available commercially from Phoenix
Chemical, Inc., Somerville, NJ, as PECOGEL A-12, PECOGEL H-12,
PECOGEL H-115, and PECOGEL H-1220.
[0063] In addition to the carboxylated polyurethane resin, the hair
styling gel contains 0% to about 6%, and preferably about 0.25% to
about 5%, by weight of an optional second hair fixative resin. To
achieve the full advantage of the present invention, the hair
styling gel contains about 0.5% to about 4%, by weight of the
composition of the second hair fixative resin. Preferably, the
weight ratio of optional second hair fixative resin to carboxylated
polyurethane resin in the composition is about one or less, i.e., 0
to about 1. The second hair fixative resin can be a nonionic,
cationic, or anionic resin, because the carboxylated polyurethane
resin is compatible with each class of resins. It also is
envisioned that the optional second hair fixative resin is a
mixture of two or more hair fixative resins in a total amount of 0%
to about 6% by weight of the composition.
[0064] The second hair fixative resin preferably is a hydrophobic
compound that retards the tendency of hair to absorb water. The
second hair fixative resin also is a hard, brittle compound having
a glass transition temperature of about 100.degree. C. or greater,
e.g., up to 200.degree. C., and preferably about 110.degree. C. or
greater. An important feature of the second hair fixative resin is
to reduce flaking attributed to the carboxylated polyurethane
resins, and to impart to the hair the properties typically
associated with the second hair fixative resin, e.g.,
stiffness.
[0065] In particular, the optional second hair fixative resin can
impart a desired and predetermined degree of stiffness to the hair.
In contrast, the carboxylated polyurethane resin provides an
elastic, flexible film on the hair, which gives the hair a soft,
natural feel. However, consumers often equate a good hair setting
composition with a degree of hair stiffness. The present hair
styling gels, therefore, impart the desired stiffness to the hair,
while further providing the benefits attributed to the polyurethane
resin, such as conditioning, good style retention, and good hair
feel.
[0066] Nonlimiting examples of second hair fixative resins useful
in the present hair spray compositions can be found in Grollier et
al. U.S. Pat. No. 4,445,521, incorporated herein by reference.
Specific second hair fixative resins include, but are not limited
to, acrylamide copolymers, acrylamide/sodium acrylate copolymer,
acrylate/ammonium methacrylate copolymer, acrylate copolymers,
acrylic/acrylate copolymers, adipic acid/dimethylaminohydroxypropyl
diethylenetriamine copolymer, adipic acid/epoxypropyl
diethylenetriamine copolymer, allyl stearate/VA copolymer,
aminoethylacrylate phosphate/acrylate copolymer, ammonium acrylate
copolymers, ammonium vinyl acetate/acrylate copolymers, AMP
acrylate/diacetoneacrylamide copolymers, AMPD
acrylate/diacetoneacrylamid- e copolymers, butyl ester of
ethylene/maleic anhydride copolymer, butyl ester of PVM/MA
copolymer, calcium/sodium PVM/MA copolymer, corn
starch/acrylamide/sodium acrylate copolymer, diethylene
glycolamine/epichlorohydrin/piperazine copolymer, dodecanedioic
acid/cetearyl alcohol/glycol copolymer, ethyl ester of PVM/MA
copolymer, isopropyl ester of PVM/MA copolymer, karaya gum,
methacryloyl ethyl betaine/methacrylate copolymers,
octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers,
octylacrylamide/acrylate copolymers, phthalic
anhydride/glycerin/glycidyl decanoate copolymer,
phthalic/trimellitic/gly- col copolymers, polyacrylamide,
polyacrylamidomethylpropane sulfonic acid, polybutylene
terephthalate, polyethylacrylate, polyethylene, polyquaternium-1,
polyquaternium-2, polyquaternium-4, polyquaternium-5,
polyquaternium-6, polyquaternium-7, polyquaternium-8,
polyquaternium-9, polyquaternium-10, polyquaternium-11,
polyquaternium-12, polyquaternium-13, polyquaternium-14,
polyquaternium-15, polyvinyl acetate, polyvinyl butyral, polyvinyl
imidazolinium acetate, polyvinyl methyl ether, PVM/MA copolymer,
PVP, PVP/dimethylaminoethylmethacrylate copolymer, PVP/eicosene
copolymer, PVP/ethyl methacrylate/methacrylic acid copolymer,
PVP/hexadecene copolymer, PVP/VA copolymer, PVP/vinyl
acetate/itaconic acid copolymer, shellac, sodium acrylate/vinyl
alcohol copolymer, sodium carrageenan, starch diethylaminoethyl
ether, stearylvinyl ether/maleic anhydride copolymer, sucrose
benzoate/sucrose acetate isobutyrate/butyl benzyl phthalate
copolymer, sucrose benzoate/sucrose acetate isobutyrate/butyl
benzyl phthalate/methyl methacrylate copolymer, sucrose
benzoate/sucrose acetate isobutyrate copolymer, vinyl
acetate/crotonate copolymers, vinyl acetate/crotonic acid
copolymer, vinyl acetate/crotonic acid/methacryloxybenzophenone-1
copolymer, vinyl acetate/crotonic acid/vinyl neodecanoate
copolymer, and. mixtures thereof.
[0067] In addition to the carboxylated polyurethane resin and the
optional second hair fixative resin, the hair styling gel contains
about 0.01% to about 3%, and preferably about 0.1% to about 2%, by
weight of the composition, of a viscosity enhancer. To achieve the
full advantage of the present invention, the hair styling gel
contains about 0.2% to about 1.5%, by weight, of a viscosity
enhancer. The viscosity enhancer can be a gelling agent, a
thickener, or any other compound capable of providing a flowable
semi-solid composition having a viscosity of about 10,000 to about
100,000 cps.
[0068] The viscosity of a present hair styling gel comprising a
carboxylated polyurethane resin and an optional second hair
fixative resin in water is about 10,000 to about 100,000, and
preferably about 20,000 to about 1000,000, cps. The achieve the
full advantage of the present invention, the hair styling gel has a
viscosity of about 30,000 to about 90,000 cps (as measured on a
Brookfield Viscometer with a #6 spindle at 5 rpm).
[0069] The identity of the viscosity enhancer, therefore, is not
limited, as long as the viscosity enhancer is compatible with the
carboxylated polyurethane resin, and, if present, the second hair
fixative resin, and does not adversely affect the stability or
efficacy of the hair styling gel. Nonlimiting examples of viscosity
enhancers include, but are not limited to, acacia,
acrylate/steareth-20 methacrylate copolymer, agar, algin, alginic
acid, ammonium acrylate copolymers, ammonium alginate, amylopectin,
attapulgite, bentonite, C.sub.9-15 alcohols, calcium alginate,
calcium carrageenan, capramide DEA, carbomers, carboxymethyl
hydroxyethylcellulose, carboxymethyl hydroxypropyl guar,
carrageenan, cellulose, cellulose gum, cocamide DEA, cocamide MEA,
cocamide MIPA, cocoyl sarcosinamide DEA, corn starch, damar,
dextrin, dibenzylidene sorbitol, ethylene dihydrogenated
tallowamide, ethylene dioleamide, ethylene distearamide, gelatin,
guar gum, guar hydroxypropyltrimonium chloride, hectorite,
hyaluronic acid, magnesium silicates, methoxy PEG-22/dodecyl glycol
copolymer, methylcellulose, microcrystalline cellulose,
montmorillonite, myristamide DEA, myristamide MEA, myristamide
MIPA, oat flour, oleamide DEA, oleamide MEA, oleamide MIPA,
palmamide DEA, palmamide MEA, palmamide MIPA, palmitamide DEA,
palmitamide MEA, palm kernelamide DEA, palm kernelamide MEA, palm
kernelamide MIPA, peanutamide MEA, peanutamide MIPA, pectin,
PEG-2M, PEG-5M, PEG-7M, PEG-9M, PEG-14M, PEG-20M, PEG-23M, PEG-45M,
PEG-90M, PEG-115M, polyacrylic acid, polyvinyl alcohol, potassium
alginate, potassium aluminum polyacrylate, potassium carrageenan,
potato starch, propylene glycol alginate, ricinoleamide DEA,
ricinoleamide MEA, ricinoleamide MIPA, sodium acrylate/vinyl
alcohol copolymer, sodium carboxymethyl dextran, sodium
carrageenan, sodium cellulose sulfate, sodium lauroyl sarcosinate,
sodium myristoyl sarcosinate, sodium oleate, sodium palmitate,
sodium polymethacrylate, sodium polystyrene sulfonate, sodium
silicoaluminate, sodium stearate, sodium sulfate, sodium tallowate,
soyamide DEA, stearalkonium bentonite, stearalkonium hectorite,
stearamide DEA, stearamide MEA, stearamide MIPA, tallamide DEA,
tallowamide DEA, tallowamide MEA, TEA-hydrochloride, tragacanth
gum, tromethamine magnesium aluminum silicate, undecylenamide DEA,
undecylenamide MEA, wheat flour, wheat starch, xanthan gum,
hydrated silica, hydroxybutyl methylcellulose,
hydroxyethylcellulose, hydroxyethyl ethylcellulose, hydroxyethyl
stearamide-MIPA, hydroxypropylcellulose, hydroxypropyl guar,
hydroxypropyl methylcellulose, hydroxystearamide MEA, isostearamide
DEA, isostearamide MEA, isostearamide MIPA, karaya gum, kelp,
lanolinamide DEA, lauramide DEA, lauramide MEA, lauramide MIPA,
lecithinamide DEA, linoleamide DEA, linoleamide MEA, linoleamide
MIPA, locust bean gum, magnesium aluminum silicate, and mixtures
thereof.
[0070] The hair styling gel also can contain 0% to about 20%, by
total weight of the composition, of a lower alcohol, i.e., an
alcohol having one to seven carbon atoms. Preferably, the
composition contains 0% to about 15%, by weight, of a lower
alcohol. In order to reduce the adverse environmental affects
attributed to volatile organic compounds, the amount of alcohol is
maintained at as low a level as possible without adversely
affecting the esthetics or efficacy of the hair styling gel. To
achieve the full advantage of the present invention, the
composition is free of a lower alcohol.
[0071] The alcohol typically used in the hair spray composition is
ethanol, although isopropyl alcohol also can be incorporated into
the composition. The carboxylated polyurethane resins are readily
solubilized in water and in a wide range of hydroalcoholic
solutions, without the addition of a basic neutralizer, thereby
permitting a decrease in the amount of alcohol present in the hair
styling gel.
[0072] The hair styling gel also contains water as the predominant
carrier. The amount of. water is maximized in order to minimize the
amount of VOC in the composition and to maximize composition
viscosity. Because the carboxylated polyurethane resins are
hydrophilic, it is not necessary to include a base in the water to
neutralize and solubilize the polyurethane resin. The carboxylated
polyurethane resin also assists in solubilizing the optional second
hair fixative resin.
[0073] Other optional ingredients also can be incorporated into the
hair styling gel. The identity of the optional ingredients is not
limited as long as the optional ingredients do not adversely affect
the esthetics or efficacy of the hair styling gel. Such optional
ingredients are well known to those skilled in the art, e.g.,
emulsifiers such as anionic or nonionic surf actants; preservatives
such as benzyl alcohol, methyl paraben, propyl paraben, or
imidazolidinylurea; cationic conditioners such as cetyl trimethyl
ammonium chloride, stearyl dimethyl benzyl ammonium chloride, and
di(partially hydrogenated tallow) dimethyl ammonium chloride;
coloring agents such as any of the FD&C or D&C dyes;
perfume oils; and chelating agents such as
ethylenediaminetetraacetic acid. These optional ingredients
generally are included individually at a level of 0% to about 5%,
by weight of the total composition.
[0074] The aqueous formulations of the present invention also can
contain conventional hair care adjuvants in amounts which generally
range from 0% to about 2% by weight, and preferably 0% to about 1%
by weight. Among the additives which can be used are plasticizers
such as glycols, phthalate esters, and glycerine, silicones,
emollients, lubricants, and penetrants such as various lanolin
compounds, protein hydrolysates and other protein derivatives,
ethylene adducts and polyoxyethylene cholesterol.
[0075] The hair styling gels of the present invention are prepared
by simply admixing and dissolving the polyurethane resin and the
optional second hair fixative resin in an aqueous or hydroalcoholic
carrier, with heating if necessary. Then, an aqueous solution of
the viscosity enhancer and any optional ingredients is admixed with
the aqueous solution of the hair setting resins to provide a
homogeneous hair styling gel.
EXAMPLE A
Preparation of a Carboxylated Polyurethane Resin A
[0076] A polyoxyethylene diol having an M.sub.n of 8000 was heated
under vacuum to 0.048% of water, then 744 parts of the dried diol
was added to 21 parts diethylene glycol, 4.3 parts
dimethylolpropionic acid, and 0.37 parts water. The resulting
mixture was heated, with stirring, until a homogenous melt was
obtained. Then, 88 parts methylene bis-cyclohexyl-4-4'-diisocyanate
was added to the mixture. The NCO/OH ratio was about 0.98. When the
temperature reached about 65.degree. C., 2.25 ml of dibutyl tin
dilaurate was added to the mixture, and the mass exothermed. The
mass then was heated to 100.degree. C., and held at 100.degree. C.
for about one hour to complete polyurethane formation. The
polyurethane resin had a weight average molecular weight (M.sub.w)
of 141,000. At 5% concentration, the polyurethane resin dissolved
in 55/45 ethanol water to give a solution having a viscosity of 180
cps. At a concentration of 3%, in 60/40 propylene glycol/water, the
solution had a viscosity of 5300 cps. A gel containing 19% of the
polyurethane resin in 20/80 propylene glycol/water was tough,
exceptionally clear and adhered to glass. The viscosity of the gel
was reduced by raising the pH to about 7.0.
EXAMPLE B Preparation of Polyurethane Resin B
[0077] A polyoxyethylene diol having an M.sub.n of 8000 was heated
under vacuum to 0.037% of water, then 744 parts of the dried diol
was added to 21 parts diethylene glycol, 18.6 parts
dimethylolpropionic acid, and 0.23 parts water. The resulting
mixture was heated, with stirring, until a homogenous melt was
obtained. Then, 115 parts methylene
bis-cyclohexyl-4,4'-diisocyanate was added to the mixture. The
NCO/OH ratio was about 0.98. When the temperature reached about
65.degree. C., 2.25 ml dibutyl tin dilaurate was added to the
mixture, and the mass exothermed. The mass then was heated to
100.degree. C., and held at 100.degree. C. for about one hour to
complete polyurethane formation. The polyurethane resin had an
M.sub.w of 63,000. At 5% concentration, the polyurethane resin
dissolved in 55/45 ethanol water to give a solution having a
viscosity of 1680 cps, and a reduced viscosity of 225 cps upon the
addition of 2 ml ammonia to 180 grams of the solution. At a
concentration of 3%, in 60/40 propylene glycol/water, the solution
had a viscosity of 144 cps. A gel containing 19% of polymer in
20/80 propylene glycol/water was tough, exceptionally clear, and
adhered to glass, displaying improved adhesive properties compared
to gels made using a polyurethane without the alkanoic acid.
EXAMPLE C
Preparation of A Carboxylated Polyurethane Resin C
[0078] Polyoxyethylene diol having an M.sub.n of 8000 was heated
under vacuum to 0.060% of water, and 736 parts of the dried diol
was added to 21 parts of diethylene glycol, 18 parts of
dimethylolpropionic acid, and 0.96 part of water. The mixture was
heated with stirring until a homogeneous melt was obtained. Then,
114 parts of methylene bis-cyclohexyl-4-4'-diisocyanate were added.
The NCO/OH ratio was 0.85. When the temperature reached about
63.degree. C., 1.85 ml of dibutyltin dilaurate was added, and the
mass was allowed to exotherm. The mass was heated at 100.degree. C.
for about one hour to complete formation of the polyurethane resin.
The polyurethane resin dissolved in slightly basic 55/45
ethanol/water solution (wt/wt) at a concentration of 5 wt. % was
clear and had a viscosity of 14 cps. The polyurethane resin had an
Mw of 40,000 and was used in a hair styling aid to give a superior
soft feel, excellent set retention, low crust, and low flaking
properties to treated hair. The hair styling aid imparted a crust
rating of 4.9, a feel of 6.7, a flaking rating of 7, a set
retention of 97% at 30 minutes, and a set retention of 95% at 60
minutes to treated hair.
EXAMPLE D Preparation of Polyurethane Resin D
[0079] Polyoxyethylene diol having an M.sub.n of 8000 was heated
under vacuum to 0.215% of water, and 736 parts of the dried diol
was added to 21 parts of diethylene glycol, 59 parts of
dimethylolpropionic acid, and 1.81 parts of water. The mixture was
heated with stirring until a homogeneous melt was obtained. Then,
168 parts of methylene bis-cyclohexyl-4-4'-diisocyanate were added.
The NCO/OH ratio was 0.65. When the temperature reached about
70.degree. C., 1.85 ml of dibutyltin dilaurate was added, and the
mass was allowed to exotherm. The mass was heated at 100.degree. C.
for about one hour to complete formation of the polyurethane resin.
The polyurethane resin had an M.sub.w of 15,000 and dissolved in
slightly basic 55/45 ethanol/water (wt/wt) solution at a
concentration of 5 wt. % was clear and had a viscosity of 10 cps.
The polyurethane resin had a kinematic viscosity of 4.60 cps in
55/42/3 ethanol/water/polymer solution by weight. The polyurethane
resin was used in a hair styling aid to impart superior soft feel,
excellent set retention, low crust, and low flaking properties to
treated hair. The hair styling aid imparted a crust rating of 4.5,
a feel of 4.5, a flaking rating of 1.8, and a set retention of 85%
at 30 minutes to treated hair.
[0080] An important property of a hair styling gel is the ability
to wash the hair setting resin from the hair, and thereby avoid
polymer build-up on the hair. In accordance with an important
feature of the present invention, the carboxylated polyurethane
resin used in the hair styling gel can be removed from the hair by
simply shampooing the hair. The unexpected washability of the hair
spray composition is attributed to the hydrophilic nature of the
polyurethane resin, and especially to the acid value of the
carboxylated polyurethane resin. When the acid value of the
hydrophilic polyurethane resin is at least about 7 mg KOH/g of
resin, the polyurethane resin can be rinsed from the hair during
shampooing without the need to neutralize the resin with an organic
base.
[0081] The acid value is an indication of the number pendant
carboxylic acid groups on the polyurethane resin backbone. Although
noncarboxylated polyurethane resins are hydrophilic, they are
difficult to wash from the hair in a short time. Washability is
enhanced by incorporating pendant carboxylic acid groups onto the
polyurethane backbone.
[0082] The effect of acid value is illustrated in Table 1, wherein
it is shown that washability is independent of M.sub.w or R-value,
but varies with acid value. In effect, carboxylated polyurethane
resins having an acid value of about 7 mg KOH/g resin or greater,
i.e., about 7 to about 50 mg KOH/g resin, had improved washability
over resins having an acid value less than 7 mg KOH/g resin.
1TABLE 1 PROPERTIES OF POLYURETHANE RESINS (R-VALUE = 0.73 TO 0.98)
Poly- urethane Acid Molecular Wash- Resin R-value Water Value.sup.1
Weight.sup.2 PDI.sup.3 ability.sup.4 1 0.98 low 0.42 174,000 2.00
no 2.sup.5 0.98 low 2.28 141,000 2.00 no 3 0.84 low 8.01 28,000
2.00 yes 4.sup.6 0.98 low 8.28 63,000 2.00 yes 5 0.98 medium 0.50
188,000 2.20 no 6 0.85 medium 2.47 64,000 1.90 no 7 0.88 medium
7.87 30,000 1.60 yes 8 0.90 medium 7.70 43,000 1.80 yes 9 0.90
medium 8.04 39,000 1.70 yes 10 0.94 medium 7.78 39,000 1.80 yes 11
0.90 high 7.70 46,000 1.90 yes .sup.1The acid value was measured by
titrating a solution of the resin with potassium hydroxide, the
acid value is expressed in milligrams of KOH per gram of
polyurethane; .sup.2The molecular weight is the weight average
molecular weight (Mw) measured by size exclusion chromatography
using polyethylene glycol calibration standards; .sup.3PDI is an
abbreviation for "polydispersity index," i.e., the ratio [Weight
average molecular weight]/[Number average molecular weight], which
measures the relative spread in the molecular weight of the
polyurethane resin; .sup.4The washability of the resin was
determined by applying 3 wt. % solution of polyurethane resin onto
clean, 2 gram, 6-inch long hair tresses, allowing the hair to dry,
then washing the hair tresses with shampoo and warm water for about
3 minutes; .sup.5Polyurethane Resin A; and .sup.6Polyurethane Resin
B.
[0083] To demonstrate the hair styling gels of the present
invention, several styling gels were prepared. Each composition
contained 0.5% to 2% by weight of a carboxylated polyurethane
resin. The compositions of Examples 1-6 in Table 2 contained a
polyurethane resin having an M.sub.w of about 40,000 and a nonionic
viscosity enhancer. The compositions of Examples-7-13 in Table 3
contained a carboxylated polyurethane resin having an M.sub.w of
about 15,000 and an anionic viscosity enhancer.
[0084] Each composition was prepared by dissolving the carboxylated
polyurethane resin and the second hair fixative resin in a mixture
of water and ethanol at 60.degree. C. After cooling to room
temperature, an aqueous solution of the viscosity enhancer was
added to the resin solution, with mixing, until a homogeneous hair
styling gel was provided.
2TABLE 2 Example 1 2 3 4 5 6 D.I. Water 38.10.sup.7 37.85 38.25
37.75 38.05 38.05 Ethanol 10.00 10.00 10.00 10.00 10.00 10.00
Polyurethane 0.75 0.75 0.75 0.75 0.75 0.50 Resin C.sup.8 D.I. Water
50.00 50.00 50.00 50.00 50.00 50.00 METHOCEL 0.75 1.00 40-100.sup.9
VERSENE 0.40 0.40 100.sup.10 NATROSOL 1.00 1.50 1.00 1.00
250.sup.11 Citric Acid 0.20 0.20 (50%) PVP K-120.sup.12 0.25 Total
100.00 100.00 100.00 100.00 100.00 100.00 Gel clear clear clear
clear clear clear Appearance Viscosity viscous viscous viscous
elastic, elastic, elastic, fluid fluid fluid viscous viscous fluid
fluid fluid .sup.7percent by weight of the composition; .sup.8a
carboxylated polyurethane resin having a molecular weight of about
40,000, as set forth in Example C; .sup.9METHOCEL 40-100 is a
poly(hydroxypropyl methylcellulose) available commercially from Dow
Chemical Co., Midland, MI; .sup.10VERSENE-100 is tetrasodium EDTA,
an ion chelating agent available commercially from Dow Chemical
Co.; .sup.11NATROSOL-250 is a hydroxyethyl cellulose polymer
available commercially from Aqualon Co., Wilmington, DE; and
.sup.12pvp K-120 is polyvinylpyrrolidone with K-value = 120, as
defined in "Kollidon" by Wolker Buhler, BASF, Ludwigshafen, Ch. 2,
2nd edition (1993).
[0085]
3TABLE 3 Example 7 8 9 10 11 12 13 D.I. Water 25.00.sup.7 25.00
50.00 50.00 50.00 50.00 50.00 Ethanol 5.00 5.00 Polyurethane Resin
D.sup.13 2.00 2.00 2.00 2.00 2.00 2.00 2.00 D.I. Water 66.60 66.50
46.50 46.495 46.49 46.47 46.45 Carbopol, Ultrez.sup.14 0.40 0.50
0.50 0.50 0.50 0.50 0.50 TEA (50%).sup.15 1.00 1.00 1.00 1.00 1.00
1.00 1.00 Polyacrylamide 0.005 0.01 0.025 0.05 Total 100.00 100.00
100.00 100.00 100.00 100.00 Gel Appearance sl. hazy sl. hazy sl.
hazy sl. hazy sl. hazy sl. hazy sl. hazy Viscosity viscous viscous
viscous viscous viscous viscous viscous Tactile Property stringy
stringy stringy stringy .sup.13a carboxylated polyurethane resin
having an M.sub.w of about 15,000, as set forth in Example D;
.sup.14a polyacrylic acid available from B. F. Goodrich Co.,
Cleveland, O; and .sup.15triethanolamine, 50% in water.
[0086] Examples 1-13 in Tables 2 and 3 show that hair styling gels
containing a carboxylated polyurethane resin and a viscosity
enhancer, and having a low VoC (e.g., 10% by weight or less), can
be prepared. Tables 2 and 3 further show that a hair styling gel
containing a low molecular weight polyurethane resin (e.g., about
15,000) or a high molecular weight polyurethane resin (e.g., about
40,000) can be prepared.
[0087] The hair styling gels also impart good hold and hair set
retention to treated hair. For example, a hair styling gel
containing a carboxylated polyurethane resin having an M.sub.w of
about 30,000 or greater provided equal or better set retention at
70% relative humidity than a control hair spray product containing
the resin AMPHOMER. AMPHOMER is an acrylic copolymer resin and is
widely used in commercial aerosol and pump hair spray products.
Hair setting products containing AMPHOMER, therefore, were used as
a control for comparison to hair setting compositions containing a
polyurethane resin.
[0088] In tests designed to test the ability of a present hair
styling gel to hold a hair set, hair styling gels containing 3
parts by weight carboxylated polyurethane resin and 0.5 parts by
weight of a viscosity enhancer dissolved in a mixture of 10 parts
by weight ethanol and 86.5 parts by weight water were prepared. The
compositions were used in a test to determine the ability of the
hair styling gel to maintain a hair set at 25.degree. C. and 70%
relative humidity over a 24-hour period.
[0089] The set retention test measures the ability of a hair
styling gel to hold or retain a hairstyle for an extended time at a
particular relative humidity. Set retention was measured by
applying 0.5 cc (cubic centimeters) of the hair styling gel to a
one gram hair tress, and testing six tresses per composition. The
sprayed tresses were allowed to dry overnight, at 30% relative
humidity (i.e., RH), in a zigzag shape. The tresses were hung
inside a humidity chamber at 25.degree. C. and a predetermined
relative humidity (e.g., 70% RH). The relaxed length was recorded
of the tresses and set retention was calculated using the equation:
1 % Set Retention = L - L t L - L o .times. 100 ,
[0090] wherein L is the length of the fully extended tress, L.sub.o
is the length of treated hair before relaxation, L.sub.t is the
length after of exposure for a time, t. Six tresses were tested per
hair styling gel composition and the data was statistically
analyzed and compared at the 95% confidence level. In all the
experiments, AMPHOMER was used as the resin in a control hair
setting product.
[0091] Hair set retention was measured at a low relative humidity
(i.e., 70% RH) at 25.degree. C. Table 4 summarizes hair set
retention tests from hair styling gels incorporating carboxylated
polyurethane resins of different M.sub.w. The hair set retention
results were compared to the results provided by a control hair
styling gel containing AMPHOMER. The comparative tests show that
hair styling gels containing a carboxylated polyurethane resin
having an Mw of about 30,000 or greater, e.g., about 30,000 to
about 200,000, exhibited comparable or improved hair set retention
over AMPHOMER. The hair set retention provided by the carboxylated
polyurethane resins, therefore, is considered to be excellent
because AMPHOMER is used in successful commercial hair setting
compositions.
4TABLE 4 HAIR SET RETENTION OF POLYURETHANE RESINS 25.degree. C.,
70% Relative Humidity Poly- Molecular % Set % Set % Set % Set
urethane Weight Retention, Retention, Retention, Retention, Resin
(M.sub.W) 30 min. 1 hour 2 hours 24 hours 5 188,000 95.7 93.5 92.2
89.7 1 174,000 94.6 91.1 90.5 87.4 2.sup.5 141,000 95.0 90.8 90.0
84.7 6 64,000 90.2 83.5 81.3 75.4 4.sup.6 63,000 91.5 86.7 83.6
81.3 11 46,000 90.0 86.3 83.5 76.2 8 43,000 88.1 83.2 79.8 67.71 9
39,000 92.3 86.1 78.9 69.86 10 39,000 88.3 82.94 78.22 67.80 7
30,000 81.63 66.5 59.4 50.0 3 28,000 77.9 71.23 68.38 60.05 AMPHO-
not 84.6 76.1 71.8 63.1 MER.sup.16 available .sup.16AMPHOMER is a
commercial hair fixative resin available from National Starch and
Chemical Corp., Bridgewater, NJ and is an
octylacrylamide/acrylates/butylaminoethylmethacrylatecopolymer.
[0092] The following is another example of a hair styling gel of
the present invention that was easily and uniformly applied to the
hair, and exhibited good hair styling and hair set retention
properties. The hair styling gel contains a hydrophilic copolymer
of a polyurethane and polyvinylpyrrolidone. The hair styling gel is
free of alcohol, and contains water as the sole component of the
carrier.
5 Ingredients % wt. Deionized water 92.437 Carbomer.sup.17 0.403
Ammonium hydroxide 0.480 PECOGEL H-12.sup.18 6.680 .sup.17CARBOPOL
940, a polyacrylic acid available commercially from B. F. Goodrich
Co., Brecksville, O; and 18PECOGEL H-12, a 12% by wt. copolymer of
polyurethane and polyvinylpyrrolidone, distributed by Phoenix
Chemicals Inc., Somerville, NJ.
[0093] Accordingly, a preferred hair styling gel contains a
carboxylated polyurethane resin having a weight average molecular
weight of about 30,000 to about 200,000. At a molecular weight
below about 30,000, the carboxylated polyurethane resin has a
reduced ability to hold the hair in a predetermined configuration
for a sufficient time to meet consumer demands, unless a second
optional hair fixative resin is present in the hair styling gel. If
the molecular weight is greater than about 200,000, the hair
styling gel can impart a tacky feeling to the hair. An optional
second hair fixative resin also can be added to the hair styling
gel to impart a desired degree of stiffness to treated hair.
[0094] A hair styling gel also possesses properties in addition to
set retention in order to meet consumer demands. In particular, the
present, consumer-acceptable hair styling gels impart a good feel
to the hair and avoid excessive flaking and crust. Hair styling
gels that provide natural, or reduced, crusts are desired. Hair
crust is tested subjectively in this test wherein a group of
trained judges evaluate hair tresses treated with a hair styling
gel. The hair flaking test measures the amount of flakes or dust
that form on the hair after combing hair that has been treated with
the composition and dried. The present hair styling gels imparted a
consumer acceptable feel to treated hair, and the crust and flaking
was within acceptable limits.
[0095] Many modifications and variations of the invention as
hereinbefore set forth can be made without departing from the
spirit and scope thereof, and, therefore, only such limitations
should be imposed as are indicated by the appended claims.
* * * * *