Note: Descriptions are shown in the official language in which they were submitted.
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P-0981
NEUTRALIZING COMPOSITION AND METHOD
~--76 FOR HAIR WAVING AND STRAIGHTENING
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to a novel oxidant containing
-neutralizing composition for use in conjunction with hair
waving and straightening treatments and to a process for
conditioning hair which has been subjected to such treatments.
More particularly, the present invention relates to a
I neutralizing composition containing an oxidant and an amino-
functional polymeric silicone additive for imparting durable
conditioning benefits to hair which has been treatetl with a
reducing agent to reduce the Courtney bonds in the hcLir
as well as to the hair treating process using such opposition
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It Discussion of the Prior-Art
Hair waving and hair straightening processes almost
invariably include two sequential steps. In the first step,
the hair is softened or relaxed with a reducing lotion which
allows the hair to be molded to a desired shape. In the second,
I a neutralizer is applied to the softened hair to harden and
stabilize the newly imparted configuration.
The principal active ingredient of conventional neutralizers
is an oxidizing agent, of which hydrogen peroxide is currently
the most popular. The function of the oxidant is two-fold:
(i) to remove any residual excess of the reducing agent
used in the softening step of the process; and
(ii) to rebuild the disulfide cross-links in hair and,
thus, to stabilize the new fiber shape and restore its strength
and elasticity.
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However, as presently practiced, not all of the disulfide _
bonds cleaved in the softening stage of the waving or
straightening process can be rebuilt, and an increase
in the fiber porosity and deterioration in tactile properties
of hair are frequent side effects of such processes. In
many cases, the neutralizing compositions contain conditioning
agents such as qua ternary alkylammonium compounds, to assure
smooth texture, easy combing and control of fly-away. However
the conditioning effects obtained through such additives,
IO although beneficial, are transient and are lost after a
single shampooing.
An early example of a permanent "cold" hair waving
process using mercaptan reducing agents is disclosed by
Schwartz in US. Patent 2,540,494. Schwartz teaches that
. the oxidizing agents in the neutralizing or setting
solution used to restore the disulfide bonds can consist
of any ox the typical oxidizing compounds which are non-
harmful when applied to hair on the human head and are
non-toxic and exemplifies such oxidizing agents with salts
I of oxidizing acids, e.g. bromates and idiots ox sodium
and potassium; hydrogen peroxide and its salts, such as
ammonium-sulfate_p.eroxide~ urea peroxide and pyrophosphate
peroxides, carbonate peroxides and perorates of sodium
and potassium, as well as metal salt peroxides, salts of
~Z5 per sulfuric acid and organic peroxides and substituted
peroxides. ---It--is--also known from-Schwarz thatch setting
"neutralizing" solution can include at -least one acidifying
reagent which may be provided by an acidic oxidizing agent
such as potassium bromate or potassium idiot, or any acid
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capable of establishing a pi range in the neutralizing
solution of from 2 to 4. This patent lists as exemplary _
acids moo- or poly-carboxylic organic acids such as
Masonic, succinic, malefic, acetic, prop ionic, butyric and
crotonic; organic acids with hydroxy groups, e.g. lactic,
citric, tartaric, mafia and glycollic; inorganic acids
such as sulfuric, hydrochloric and phosphoric; and acid
salts including potassium or sodium, acid tart rate, citrate,
or phthalate. It is further taught that a buffering salt
can be employed to stabilize the phi for example, sodium
acetate and acetic acid at a 2:1 ratio to provide a pi of
about 3.
It is also known in the art to use various types of
silicon containing polymers such as polysiloxanes for condo-
toning hair in permanent waving processes. For instance,
Stein Bach en at in US. Patent 3,248,~96 disclose various
epoxy ~organosiloxanes to provide an elastic coating to
protect hair which has been subjected Jo a sequential
reducing treatment and oxidizing treatment from penetration
by water without making the hairs stick to each other. In
this case, the epoxy :organosiloxanes are applied after
the neutralization step with hydrogen peroxide oxidizing
agent.
Showier, et at in US. Patent 3,687,606, which is
I described as an improvement of the aforementioned Steinbeck,
et at patent, explains that the epoxy organosiloxanes
function by having the epoxy groups react with the substance
of the hair while the organcpolysiloxane moiety imparts
water repellency. However, the prior compounds are noted to
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have the disadvantages of presenting an oily gloss to the
hair and not being water soluble. Accordingly, Showier, _
et at provide epoxy sullenness as treating agents which are
applied before the neutralizing treatment with the peroxide
oxidizing agent but after the reducing treatment with, for
example, a thioglycollic acid reducing agent.
In US. Patent 2,~44,94~ to Charles methylsilyl Marquette-
acetates are used as permanent wave treating agents for single
step use. These compounds dissociate into a Marquette reducing
agent while generating polymers of silanols to protect the hair
and facilitate combing. This patent does not talk about any
subsequent treatment such as fixing by peroxides and it is
not clear whether any such treatment would be required.
Other hot and cold waving and straightening hair treating
compositions, which may or may not be used in conjunction with
reducing and/or oxidizing agent, in which various types of
selection polymers are used to fur protective film coatings
on individual hairs are described in, for example, US.
Patents 2,643,375, ~,750,947, 2~782,796, 2,7~7,274, and
I 2,840,087. US. Patent 3,143,476 to Grant discloses a cold
wave neutralizing composition and process in which sodium
and potassium bromates are used as the neutralizing agents
in the presence~o~-~erruus,~~fer^ic and copper ions which
junction as catalysts to increase the reaction rate of
I the neutralizing agents.
There swill remains a need fox neutralizing compositions
for use in-a cold permanent waving or straightening hair
treating process which provides durable conditioning benefits,
i.e. stable to repeated shampooings. There is additionally
guy
a need in the art for such neutralizing compositions which
can be applied to either waved or straightened hair which
significantly reduces drying time and which bring about a
drastic decrease in the hair fiber porosity resulting from
excessive destruction of the hair bonds while bringing
about such additional beneficial results as smooth texture,
easy combing and control of fly-away and which also reduces
drying time.
SUMMERY OF THE INVENTION
It is an object of an aspect of the present inane-
lion to provide a neutralizing composition for hair waving
and straightening which provides durable conditioning
benefits, namely stability to repeated shampooings.
It is an object of an aspect of the invention to
provide a composition capable of neutralizing excess
reducing agent and to rebuild the disulfide cross-links
in hair resulting from a hair softening step which allows
the hair to be dried in a reduced amount of time and
which imparts improved texture, comb ability and reduced
fly to the so-treated pair.
It its an object ox an aspect of toe present invent
lion to provide a process for simultaneously neutralizing
and conditioning hair on a human head which has been
I subjected to exposure to a Courtney redwing agent such as
thioglycollic acid
These and other objects of the present invention
which will become apparent from the hollowing detailed
description of preferred embodiments are accomplished by
a neutralizing and.condltioning composition four hair in
the form ox an Allis solution of an oxidizing agent and
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emulsified in the aqueous composition an amino-functional
silicone polymer conditioning agent. The amino-functional
silicone polymer is selected from the class of silicone
polymers having amino functional group sand in particular,
the silicone polymers include repeating structural units
of the formula (It:
I Silo -R (I)
C~3
NH
(R31
NH2
wherein R represents a hydrogen atom or trim ethyl-
sill,
lo Al represents.hydroxyl or methyl
R2 represents an alkyd group of from l to 6 carbon
atoms 7
R3 represents an alkyd group of from l to 4 carbon
atoms,
x is a positive number of at least I,
y is a positive number of at least 2,
and the sum ox x and y is such that the silicone polymer
has a molecular weight of from about 5,000 to about Lowe,
the composition having a pi in the range of from about 2.0
to 5.0
The present invention also provides a process for
neutralizing and conditioning keratinic fibers such as
human hair which has been subjected to a reducing treatment
to reduce the disulfid~ bonds in the keratinic fibers by
applying to the reduced fibers an aqueous solution of an
oxidizing agent and emulsified in the solution an amino
functional silicone polymer conditioning agent which
includes the repeating structural units ox the Formula (I).
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3 ~2~3~5
DETAILED DISCUSSION OF THE INVF,NTIOM
_ AND PREFERRED EMBODIMENTS_ .
The composition and process of the present invention
are generally applicable to any of the conventional reducing
agents and reducing compositions as well as to any of the
conventional active neutralizing agents. The reducing agents
and reducing agent compositions which are gerlerally based
on ~hioglycollic acid or thioglycollic acid salts are well-
known in the art and do not, per so, form any part of the
lo present invention. In addition to the thioglycollic acid
class of reducing agents other hair treating agents for
imparting capability to hair, such as, for example, the
"hair waving mercaptans" (see US. Patent 2,540,494); alkali
relaxer co~Fositions, sulfite based systems, and the like can
also be effectively neutralized by the neutralizing and
conditioning composition of this invention.
In neutralizing and conditioning compositions of this
invention, hydrogen peroxide is the preferred n~utral~zin~/oxidizing
agent. However, other neutralizing agents including inorganic
pa and organic peroxides and peroxide salts, perorates, bromates
and the like, can also be used. In addition, neutralization
can also be provided in the case of the alkali reducer compost-
.. . .
toils by acidic neutralizing agents, including clowned other
inorganic mineral acids in appropriate dilute concentrations.
US The amount of oxidizing agent can be within the ranges normally
utilized for neutralizer compositions and will depend, for
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example, upon the type of oxidizing agent, the amount employed
and the type of the reducing agent, etc. enroll, the
amount of the oxidizing agent, will range from about 0.5% to
I about 10% by weight preferably from about 1% to about 4% bar
weight.
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¦ . For optimum results, the neutralizing and conditioning
¦ compositions of the invention should have an acidic pi in the _
¦ range of about 2 to 5, preferably about 2.5 to 4.5. Any Go
l the acids conventionally used in hair neutralizing and oxidizing
¦ compositions such as those disclosed in the aforementioned
Cheerios Patent 2,540,494 can be used in the present invention.
It is most preferred, however, to use a buffered acidified
solution so that, for example, the generally present high natural
alkalinity of hair will not substantially increase the pi of
IO the invention compositions. Although optional, the use of the
buffer is also preferred so that the amount of damage to the hair
from harsh waving chemicals will be minimized. Any acid and
buffer system capable of maintaining a pi in the desired pi
range of 2 to 5 can be used in the composition of this invention.
Especially good results have been obtained using phosphoric acid
as top acidifying agent and a citric acid/citrate ion buffer
: siesta. however, other acids and buffer systems can also be
used so long as the pi can be maintained in the range of 2 to 5.
Preferably, the buffering agent is provided separately from eye
I remaining ingredients of the composition to avoid breaking the
silicone emulsion in the, e.g. peroxide, neutralizing agent upon .
standing on the shelf for a prolonged time due to the high acid
capacity generated my toe buffer,~and-is-combin~d with the-other- .
ingredients just prior to use.
The oxidizing agent, e.g. hydrogen peroxide, is the main
active ingredient of the composition and functions to remove any
residual excess of the reducing agent or alkali used in the -
¦ softening step of the waving or straightening process wile
additionally restoring the Courtney disulfide bonds cleaved in the
previous reducing step.
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¦ The other critical component of the compositions of this
. I invention is the silicone polymer conditioning agent. These
¦ are amino-functional silicone polymers which can be represented
. ¦ by the following formula (I):
So - --O } -O R (I)
i NH
NH2
wherein R represents a hydrogen atom or trimethylsilyl,
Al represents hydroxyl or methyl,
R2 represents a diva lent alkyd group of from 1 to 6 carbon
atoms, preferably 2 to 4 carbon atoms, which may be straight or
lo branched;
R3 represents a diva lent alkyd group of from 1 to 4 carbon
atoms, preferably 2 to 3 carbon atoms, which may be straight or
branched;
. x is a positive number of at least 4; and
y is a positive number of at least I.
One such suitable amino-functional silicone polymer has
top common name amodimethicone which is a cat ionic polymer of
the formula (1) wherein R is hydrogen, Al is -SHEA, R2 is
SHEA and I is ~GH~2. Amodimethicone is commercially availably
in the form of its aqueous emulsion from Dow Corning under the
designations Dow Corning 929 Emulsion and Silicone 929 Cat ionic
Emulsion.
The amount of the silicone polymer- is generally in the
range of from about 0.1 to 10% by weight, preferably from about
1 to 2% by weight of the composition. At amounts below about
."~,,~,.
~293~
¦ 0.1%, the conditioning benefits are insufficient while at amounts
above about 10%, no additional benefits are observed and stable
emulsions are more difficult to prepare.
l Any emulsifying agents which can maintain a stable Emil-
soon and which are compatible with the remaining ingredients can
be used in the neutralizing and conditioning compositions of
this invention. Preferably cat ionic type emulsifying agents
will be used with the cat ionic silicone polymers RHO and
non ionic type emulsifying agents will be used with the non ionic
silicone polymers (R= trimethylsilyl). Generally, these amino-
functional silicone polymers are commercially available in the
form of emulsions and can be used as such in the compositions
of this invention without separate addition of an emulsifying
agent. For instance, Dow Corning Emulsion 929, which is an
emulsion of the cat ionic silicone polymer, amodimethicone,
includes a mixture of a cat ionic emulsifier (tallow trimonium
chloride) and a non ionic emulsifier Jan ethoxylated phenol).
The Dow Corning Emulsion X2-7224, which, according to its
manufacturer, is an emulsion containing about 35% by weight of
a non ionic silicone polymer of formula I in which R is in-
methylsilyl, Al is methyl, I is isobutyl ~CH2CHCH2~ and
SHEA
R3 is ethyl ~C~2CH I, includes-a-mixture of non ionic emuls liens,
namely about 3% by weight of an ethoxylated alcohol (Briton X405,
a product of Room and Hays) and about 3X by weight of an ethics-
fated phenol ~Tergitol TMN-6, a product of Union Carbide).
Generally, any of the conventional emulsifying agents
typically used in hair treating compositions can be used in the
compositions ox this invention. Representative non ionic
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¦ emulsifiers include, for example, polyethoxylated or Polyp
¦ glycerolated alcohols, alkylphenols or fatty acids having a .
¦ linear chain of 8 to 18 carbon atoms, and generally 2 to 3q moles
l of ethylene oxide, ethylene oxide/propylene oxide copolymers,
¦ fatty alcohols, condensates of ethylene or propylene oxide with
fatty alcohols, polyethoxylated fatty asides, polyethoxylated
fatty amine, ethanolamides, glycol esters of fatty acids,
sorbitol esters of fatty acids and succors esters of fatty
acids.
I . Representative cat ionic emulsifiers include, for example,
qua ternary ammonium, morpholinIum, and purred em compounds.
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The amount of the emulsifying agent or agents is not
particularly critical so long as the silicone polymer is main- _
twined in the emulsified state aster blending with the oxidizing
agent and other components of the compositions. enroll,
amounts of thy emulsifier or emulsifiers in the range of from
about 2 to about 20%, preferably from about 8 to about
18 %, by weight of the silicone polymer are satisfactory.
The silicone polymer, if it is not provided in an emulsi-
fled state, is preferably emulsified with one or more emulsifying
I agents before being mixed with the aqueous acidic solution of
the oxidizing agent. The mixing of the emulsifying agents)
with the silicone polymer, if necessary, and the blending of
the emulsified silicone polymer with the aqueous acidic
solution of the oxidizing agent can be simply performed by
It mixing the ingredients in any conventional mixing or blending
apparatus at room temperature or at slightly elevated tempera-
Tory Of course, mixing speeds, shear rate, etc., should not
be such as to cause breaking of the emulsion.
Other conventional additives, such as, for example,
ZOO perfumes and other fragrances, thickening agents, surface
active agents, other conditioning agents, germicides, beater .
iocides, and the like, can be added to the compositions in
amounts which-do~-not`interfere with the activity of the oxidizing
agent or silicone polymer and which do not interfere with the
2-5 stability of the emulsion.
The buffering agent can be added to the composition sat
any time, however, it issue lye preferred to package the buffering
agent separately from the other components of the compositions
with instructions to the user to mix the two packages just
pa prior to use.
. . . .. . . . .. . .
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¦ Although not wishing to be bound by any particular theory
¦ as to the mechanism by which the silicone polymers exhibit
¦ their beneficial properties, it is presumed that the silicone
¦ polymers form a stable, adherent, mechanically strong, and
l abrasion resistant film on the individual hairs which eases
¦ comba~ility and facilitates drying ox the hair. The latter
phenomenon may be due to the low surface tension properties
of the silicone polymers which results in formation of thin
water films which can be more easily evaporated from the
treated hair.
As previously described, the neutralizing and conditioning
compositions of this invention can be used with substantially
any hair treating composition which accomplishes its waving
or straightening function by reduction of the keratinic
desulfide bonds. The following is representative of a typical
relaxer composition:
Concentration
Ingredient Lowe hi %)
Petrolatum 24.00
Mineral Oil 16.00
Polawax (non ionic 8.00
emulsifying wax)
Solulan 25 ~ethoxylated 3.00
lanolin alcohol)
Propylene glycol 2.50
Sodium hydroxide 1~75
Seattle alcohol 1.25
Fragrance 0.50
Water us to 100.00
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A conventional thioglycolate waving composition is provided
by the following lotion formulation:
Concentration
Ingredient (Weight%)
Ammonium thioglycolate 5.1
Monoethanolamine 2.5
Brim 35 (polyoxyethylene 1.2
laurel ether)
Fragrance 1.0
Pacifier 1.0
Water us to 100.0
The invention will now be described by way of the
following illustrative but non-limitative examples in which
all "parts" and percentages are on a weight basis unless
otherwise noted.
EXAMPLE I
Three brown Caucasian hair tresses, 2 g each, are wound
on 1/2 inch rods and are saturated with a conventional
thioglycolate lotion (0.6 M ammonium thioglycolate, pi 9.2).
After 20 minutes, the waving lotion is rinsed off and the
tresses, while still on the rods, are treated in the
following manner:
Tress #1 is saturated for 5 min. with 1.2% HOWE
adjusted to pi with phosphoric acid;
Tress #2 is saturated for 5 min. with 1.2% HOWE
containing 1.5% amodimethicone adjusted to pi 4 with
phosphoric acid;
Tress #3 is saturated for 5 min. with 1.2% HOWE
containing 1.5% amodimethicone adjusted to pi 3 with
phosphoric acid and buffered with citric acid (0.25 M).
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After 5 minutes, the rods are removed, the peroxide solutions
are worked into loose hair coils, left for an additional 3 _
minutes and rinsed off under running tap water. The tresses
are then wet combed using a strain gauge comb and the work of
combing is recorded. The following results are obtained:
Tress # Work of Comb go (grow)
1 795
2 137
3 132
Aster combing, the tresses are reimmersed in water, removed
and freely hung to dry. Their weights are reworded immediately
after removal from water and after drying. me water contents
of tresses as calculated from the difference in dry end wet
weights are as follows:
Tress Kit Water pickup 'glue of hair)
Jo 1 2.5
2 1.5
3 1.6
The amount of water held by the hair after centrifuging (liquid
retention of porosity index) is also measured, yielding the
following results:
tress # Jo Liquid Retention (OWE)
1 42.5
2 41.3
Z5 3 it
Finally, the tresses are shampooed twice and their wet combing
is redetermined. the values of combing work are as follows:
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Tress T~Jork of Combing (Ram)
1 764 _
2 1~0
3 133
EXAMPLE II
In order to demonstrate the faster rate of hair drying
at the completion of the waving (or straightening) Procedure,
the following experiment us carried out.
A group of four hair tresses (intact ~eMeo brown hair,
It 2 g per tress) is waved for lo minutes at 35C using a con-
~entional waving lotion. The hair is then rinsed and two
tresses are neutralized with a conventional neutralizer (2.0%
H202) while the other two are neutralized with a combination
of H202 (2.G%~ and amodimethicone I In Roth cases, the
neutralization is carried out for 10 minutes, after which time
the tresses are rinsed and each of them is attached to a stress
gauge allowing for accurate weight determination. The weighing
is continuously monitored for a period of 45 minutes. The data
of Table I show the weight changes (mean average of 2) at
I selected time interval. The lower the water content of hair .
the faster it dries.
TABLE I
__ _
Water content of hair 'g Hug of hair)
following neutralization
I Neutralization
= - I 0 1 15( l I D 45
.51 1 lo I US I .84 '74 Lo 1 I
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I EXAMPLE III
I
¦ A composition according to the invention is prepared by
¦ adding two thickening agents (Igepol C0 430 and Ige~ol (C0 630)
l and an additional emulsifying agent, Seattle alcohol:
S Component Lotte
Hydrogen peroxide 2.0
Seattle Alcohol 0.2
Igepol C0 430 4.0
Igepol C0 630 4.0
Phosphoric Acid 0.03
Dow Corning Emulsion 92~ ~.00
Water 85.77
A stable thickened composition is obtained.
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