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Патент USA US3099613

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3,099,6t37
r.
0 " 1C€
United States Patent
Patented July 30, 1963
2
1
mands considerable manipulative skill from a woman
who is waving her own hair.
3,099,603
The volatility and susceptibility to oxidation of the ac
tive ingredients in many of the conventional hair waving
lotions make the ordinary methods of commercial pack
TWO PHASE FAST BREAKING FOAM PRES“
SURIZED HAIR ‘WAVING CQMPQSI'I‘ION
Robert D. Banker, Cincinnati, and Preston W. Grounds
and Robert A. Cody, Spring?eld Township, Hamilton
County, Ohio, assignors to The Procter & Gamble Com
pany, Cincinnati, Qhio, a ‘corporation of Ohio
No Drawing. Filed June 13, 1960, Ser. No. 35,393
17 Claims. (til. 167--87.1)
aging inappropriate for a container of lotion which can
be used and stored repeatedly without loss of activity.
A type of packaging then, which will enable alternate
use and storage should enjoy widespread consumer accept
10
This invention relates to compositions packaged in
pressurized containers for the cold permanent waving of
hair. The two liquid phase composition contains a vapor
ance for touch-up Waves as well as for periodic full Wav
mg.
Pressurized containers or aerosol packages are well
known and have been widely employed for packaging
many products for household purposes. In spite of its
pressure depressant and is dispensed in the form of a fast
recognized advantages in other areas, this packaging tech
15
breaking foam.
nique has not yet found widespread commercial usage in
Cold permanent waving of hair is accomplished by con
the ?eld of cold permanent waving, not because of tech
tacting the hair with some chemical composition which
nical packaging difficulties, but because of the inherent
will soften and plasticize it at room temperature. Ac
demands of the cold waving technique. Even with the
cording to the present understanding in the art, such chem~
conventional
hair Waving procedures described hereinbe
ical compositions reduce the keratin structure of the hair, 20 fore, it is di?icult to achieve the requisite uniform satura
thereby breaking disul?de linkages. While the hair
tion of the hair with lotion. The outside of a wound tress
tresses are mechanically held in a new con?guration, the
may receive a heavy concentration of the lotion, while
disul?de linkages are restored by oxidation to ?x the
the portion of the hair inside a wound curl may receive
tresses in the new con?guration.
a much smaller amount. As a result, portions of the hair
25
In a conventional home waving procedure, the hair is
may be damaged by the too high concentration, and other
?rst shampooed. After rinsing and removal of excess
parts of the hair may not be redced at all because they
water, the individual hair tresses are saturated with re
are not contacted by sufficient lotion to break the
ducing lotion before being wound on a curler or mandrel.
disulphide bonds. The usual aerosol methods which
The individual hair tresses, after having been Wound on
might be used to dispense hair waving lotion as a foam
30
the mandrel, are again saturated with reducing lotion.
or mist are by their very nature less able to meet the de
After a suitable period of time, the reducing lotion is re
mands of cold hair waving than is the conventional tech
moved from the hair with a water rinse; and the reduced
nique. On the one hand, a foam vacts as a physical im
hair, while still wound on the mandrel, is ?xed by applica
pedimeut to the penetration \of the reducing agent into the
tion of a chemical or by air oxidation. In the pin curl
hair. On the other hand, a mist is unsatisfactory because
procedure, a few tresses saturated with lotion are formed 35 of the wide diffusion of the hair waving lotion; most lo~
on curlers as described, ‘and the remainder are wound
tions are, to some individuals, unpleasant in odor and
around a ?nger without prior saturation with lotion. The
they may stain clothing.
latter curls, held by bobby pins, ‘are then, along with those
The dispensing of products such as shaving cream and
on curlers, saturated with lotion. These curls are sub 40 toothpaste as foams from pressurized containers is shown
sequently treated in the same way as those held on curlers.
in Spitzer et al., in US. Patent 2,655,480. ‘The contents
In most commonly employed home waving procedures,
of the package exist in the form of an emulsion and are
the waving lotion is manually applied to the hair in the
discharged as ‘a stable foam.
initial saturation step and again in the resaturation step
A ?rst group of objects of this invention is: (l) to pro
after the hair has been wound on mandrels.
A cotton 45
pad or sponge which is repeatedly saturated by being
dipped into the lotion is used as an applicator. The dis
advantages inherent in such a procedure are readily appar
ent. The independent saturation of each individual hair
tress, performed before and after winding on the mandrel,
is both tedious and time consuming. Most modern hair
waving lotions have an alkalinity above pH 9 and may be
have as irritants when repeatedly brought into direct con
tact with the skin of sensitive individuals. The com
vide compositions packed in pressurized containers which
make possible an improved method for waving hair, and
(2) to provide packaged compositions which can be used
for more than one wave without deterioration between
uses. The improved method eliminates manual applica—
tion of waving lotion to the hair, thereby reducing the pos
sibility of skin irritation which may result from the con
tact of highly alkaline waving lotion with the hands; and
the improved method eliminates run-o? of excess lotion
the hair.
monly employed methods for applying waving lotion pro 55 from
These objects are achieved by a composition which is
vide opportunity for prolonged and repeated contact of
discharged as a f=ast~breaking foam, i.e., as an unstable
this alkaline solution with the hands as the subject satu
foam which substantially completely breaks or collapses
rates the applicator and then applies the applicator to the
to a liquid promptly after discharge. This fast-breaking
hair. Furthermore, if not carefully applied, the run-off
property permits the composition to be applied with the
of lotion on the scalp and down the hands and wrists may 60 ‘ease of a foam; and it achieves the requisite penetrability
of a liquid. The limitations of both foam and liquid are
Recently, attempts have been made to eliminate some
eliminated vat the ‘same time. The application of the
of the opportunities for the lotion to contact the hands by
lotion as an unstable foam prevents run-off (and yet per
‘applying the lotion directly from a plastic squeeze bottle.
mits the lotion to return fairly rapidly to a fluid state
A comb-tip may be, used in the initial saturation step.
which will be ‘absorbed by the hair tress. The foam col
This method does not eliminate the dripping of excess
lapses at about the same rate at which the ?uid pene
lotion from the tresses and requires the user to transfer
tnates the hair tress.
the lotion solution from the glass package in which it is
In order to achieve a fast-breaking foam the composi
supplied to the plastic bottle. A further development has
tion of the product must be correct. A most important
be discomforting.
been to provide a catch tray which can be held under a
wound curl to catch the excess lotion as it runs off. The
catch tray cannot be used in the initial saturation and de
requirement is that at the time of application propellant
be ?nely dispersed throughout the composition. A true
3,099,603
3
4
solution, that is, a molecular dispersion, is ideal in degree
of dispersion and stability. However, propellants in gen
permanent waving composition having the advantages
which result from discharge as a fast-breaking foam with
eral are not very soluble in aqueous solutions, particularly
out the necessity of adding an alcoholic solvent or ex
cessive amounts of an emulsi?er and (2) to provide a
those containing keratin-reducing agents. It is therefore
di?icult to dissolve enough of the usual propellants to
give a satisfactory product or else it is necessary to add
considerable quantities of a mutual solvent for the pro
pressurized cold permanent waving composition preferably
having a reduced vapor pressure which makes possible a
larger charge of propellant which performs satisfactorily,
pellant in the aqueous liquid. For example, alcohol is
effective; but it possesses the disadvantage of being in?am
mable if used in excess.
has less tendency for leakage and permits lower pressure
It is, of course, more expensive 10
than water. A satisfactorily ?ne dispersion of propellant
in product can be achieved by an emulsion. However,
it is difficult to formulate emulsions which are per
manently stable. The presence of an emulsifying agent
packaging.
This second group of objects is accomplished by pro
viding a cold permanent waving composition, which exists
in the package in two liquid phases, and in which a
speci?ed propellant is used, preferably in combination
which can be deleterious to the hair wave results or 15 with a vapor pressure depressant as hereinafter more
fully described. The keratin-reducing agent is pre
which might react with the active hair waving agent is
dominantly in an aqueous phase; and the second phase is
usually required. Most surface active agents or emulsi
predominantly propellant and, when included, vapor pres
?ers in concentrations above a few percent cause in
sure depressant. However, (all constituents are partitioned
combination with the keratin-reducing agent a decrease of
mildness of the waiving lotion. The use of two liquid 20 between the two phases as would be expected from
physical-chemical principles. Part of the propellant and
phase compositions in pressurized packages is well known.
other volatile constituents are in the vapor space of the
For example, Eaton in U.S. Patent 2,728,495 shows an
package.
aqueous liquid phase ?oating on top of the propellant
In brief this invention is a cold hair waving composi.
liquid phase. His composition was not discharged as
a foam. ‘If the compositional Variables were properly 25 tion packaged in a pressurized container and comprising
a keratin reducing agent in aqueous solution, a speci?ed
adjusted, such a two phase system might discharge as a
propellant,
a surface active agent, and preferably a
foam for a few seconds after violent agitation; but it
vapor pressure depressant. In the package, the composi
would not continue to discharge as a foam for long be
tion is in the form of two liquid phases and a vapor phase.
cause of the rapidity with which the propellant phase
The composition is discharged as an unstable foam which
separates from the lighter aqueous phase.
30
If the essential requirement of having propellant ?nely
substantially completely collapses to a liquid promptly
after discharge.
dispersed in the product (at the time of discharge is satis
The objects of this invention can be accomplished by
?ed by using a propellant with su?icient solubility, dis
using, as the speci?ed propellant, difluoroethane or mono
advantages relating to the pressure prevailing in the
package may be encountered which are preferably avoided. 35 chlorodi?uoroethane. When di?uoroethane is used, it is
preferably used either with enough vapor pressure de
In may cases in which propellants which are highly soluble
pressant to provide a package pressure depressed to a
(are used, only a small quantity of propellant ordinarily
desirable range, as hereinafter described, ‘or with enough
can be put in the package containing an aqueous phase
vapor
pressure depressant not only to provide a desirable
at pressures usually considered safe. Under ideal condi
pressure
but to adjust the densities of the two liquid phases
tions, such a package containing a small amount of highly 40
of the composition to substantially the same value, also as
soluble propellant may prove entirely satisfactory, but
hereinafter described. In the latter case, wherein the den
if there is slow leakage or if propellant is accidentally
sities
of the two liquid phases are balanced, monochloro
discharged from the pacleage without product, then the
di?uoroeth'ane also can be used as the speci?ed propellant.
quantity of the propellant will be insufficient to properly
discharge the product from the package in the form of 45 When the densities of the two liquid phases are balanced,
they become readily mixable ‘and the aforementioned
a su?icient amount :of fast breaking foam. It is ordi
requirement for a ?ne dispersal of propellant in the prod
narily preferable not to add more propellant to over
uct is easily obtained by preparatory mixing. When
come these disadvantages because the pressure in the
monochlorodi?uoroethane
is used as the speci?ed propel
package would be higher than is usually desired. The
accuracy required to package a su?icient amount of the 50 lant without a vapor pressure depressant (for example,
when it is not necessary to avoid high pressures, e.g., by
usualhighly soluble propellants, without exceeding pres
use
of strong containers or absence of high temperatures)
sures which are ordinarily ‘observed, assuming that none
?ne dispersal of propellant is easily obtained by prepara
would be lost by leakage or accidental discharge, would
tory mixing. When vapor pressure depressants are used
be so great that commercially feasible production would
with monochlorcdi?uoroethane, however, balancing of the
A mutual solvent can be added to increase 55 liquid
phase densities is necessary to provide a satisfactory
product. However, when di?uoroethane is used as the
as has been mentioned before, there are disadvantages
propellant, mixing is not necessary whether or not vapor
inherent in the addition of such solvent. High pressures
pressure ‘depressants are used. The necessity for prepara
be di?icult.
the solubility of the propellant in the aqueous phase; but,
in the package are ordinarily undesirable, particularly
with conventional containers, since they may lead to ex
cessive leakage of propellant from the package and limit
the type of package that can be employed under accepted
safety conditions.
tory mixing, while it is a relatively easy and minor step,
requires extra instruction for the user, and if the user
forgets to perform the mixing step, the results may not be
as expected. However, even though preparatory mixing is
not necessary when difluoroethane is used as the propel
If the pressure problem could be solved or ignored,
lant in the compositions of this invention to obtain good
such as by use of very strong containers or when high 65
results therefrom, it is not intended that the product should
storage temperatures are not encountered, merely using
not be mixed. Users often shake pressurized products
a su?icient quantity of a propellant that has high solubility
in the aqueous phase does not necessarily result in a
by habit and shaking may ‘be desirable to distribute more
evenly any perfume present in the composition.
stable hair waving product having desirable fast breaking
Low molecular weight water-soluble mercaptans con
foaming characteristics. For example, it has been found 70
taining another functional group, such as carboxyl, hy
that if the propellant is too» soluble in the aqueous phase,
no foam, fast breaking or otherwise, is formed.
Other
highly soluble propellants have prohibitive vapor pressures
droxyl, or amide, in addition to the mercaptan group, are
suitable keratin-reducing agents for the" waving lotions
of this invention. The mercapto-alkanoic acids described
A second group of objects is: (l) to provide a cold 75 in U.S. Patent 2,736,323 are preferred keratin-reducing
substances because of their effectiveness and because they
or are hydrolytically unstable.
3,099,603
5
6
foam, with or without preparatory mixing, the propellant
are not skin sensitizers. Among these, thioglycolic acid
used in the compositions of this invention should have a
solubility in water at 70° F. greater than about 0.05
weight percent. However, no foam, fast breaking or
desirable to have the pH of the waving lotion above 7 to
is formed if the propellant used has a solu
obtain rapid and effective action and to have the pH Cl otherwise,
bility
too
great,
i.e., greater than about 0.40 weight per
below 10 to avoid damaging the hair. A particularly de
cent at 70° F. The importance of the correct propellant
sirable range is from pH 8.5 to pH 9.5. Within this range,
solubility on foam breaking time is shown by comparing
a pH of about 9.3 is especially suitable. Any suitable
the
four compositions in the following table:
alkali may be used to adjust the pH; but it is preferred to
is especially preferred in the practice of this invention, and
rnercapto-propionic acid is almost equally suitable. It is
Comp.
Comp.
Comp.
Comp.
A
B
C
D
Ingredient:
Monoethanolammonium thioglycolate, percent ________ -_
Monoethanolammonium dithiodiglycolate, percent.
Monoethanolamine, ca, percent ________________ _.
Polyoxyethylene lauryl ether with an average of 23
groups per lauryl group, percent ____________________________ ._
Perfume, percent
_
SiOz (added as sodium silicate-having an slot; Nazdratio of
2.5:1), pereent____
Isopropyl myristate, percent _________________________________ __
Dioetyl phthalate, percent. _ _
Water to make 100% ___________________________ __
Total weight, ems
__I
Total volume, fl. oz ________________________________________ ..
Propellant (extra):
Monoohlorodi?uoroethane, gms--_
_
Dichlorodifluoromethane, gins ________________________________ _.
Di?uoroethane, ems
Tri?uoromonochloroethane, gnis-_
use a weak base as a major portion of the alkali, thereby
providing desirable buffering capacity. Suitable weak
.
It was not practical to compare compositions A, B, C,
30 and D on a completely parallel basis because of marked
differences in propellant characteristics. In each compo
bases have disassociation constants of less than 10*8 and
sition the waving lotion formulation was the same. Each
preferably less than 10*”, they include ammonia, mono
composition was packaged in a pressurized container
?tted with valves to control the discharge of the product
anolamine and glycerylamine are further examples of 35 and with foam nozzles.
ethanolamine, diethanolarnine, tris(hydroxymethyl)-amin0
methane and 3-amino-2-methyl~l,3-propanediol. Trieth
bases which may be used.
In determining the foam breaking time, each of the
four compositions was subjected to prepartory mixing to
Monoethanolamine is an es
pecially preferred weak base. When the pH of the lotion
disperse the propellant in the aqueous phase although
is adjusted to the preferred range with a weak base, there
such mixing was not necessary for compositions B and
will usually be present free base in excess of that required
to form the salt of the rnercapto-alkanoic acid. Examples 40 D because of the relatively high solubility of their pro
pellants. On discharge from the container, compositions
of strong bases which may be used in minor proportions
A,
B and C formed a sufficient amount of foam, but
in conjunction with weak bases in this invention are so
the foam breaking times of only compositions B and C
dium hydroxide, lithium hydroxide, potassium hydroxide,
were satisfactory. Composition D, containing a highly
and strong organic bases such as tetramethylammonium
soluble propellant, formed no foam at all, even though
hydroxide. Mixtures of weak bases can be employed, and
it contained as much propellant as composition C and a
greater amount of propellant than A or B. The compo
it is often advantageous to do so. Soluble carbonates and
bicarbonates, such as ammonium salts, can be added for
sitions had foam breaking times as follows, determined
their pH stabilizing effect. Use of a thioglycolate salt in
preparing the lotion is, of course, equivalent to preparing
it in situ from thioglycolic acid and the appropriate base.
The keratin-reducing agent is incorporated into the
as described immediately below:
lotion at a level equivalent to from 1 to about 10 weight
percent, based on the total composition, of thioglycolic
acid. (All percentages used herein are by weight.) The
preferred compositions contain keratin-reducing agent at
a level equivalent to from about 3% to about 6% thio
glycolic acid.
A propellant is required to force the hair waving com
position from the pressurized container. While any liq
1
A. 180 seconds
B. 17 seconds
‘C. 37 seconds
D.
55
0 seconds (no foam)
The foam breaking time test consists of the steps of
exactly ?lling a cylinder cup 1/2 inch high and 1%‘;
inches in diameter with foam from a container of the
pressurized waving composition and measuring the time
taken for the foam to collapse completelyr to a liquid.
The range of desirable foam breaking times, according to
ue?able 'gas having the proper vapor pressure and water 60 this test, is 1045 seconds. This range is substantially
solubility can be considered, certain ?uorinated and chlo
rinated hydrocarbons have advantageous properties for
use in this invention. The selection of the propellant is
very important to obtain the desired product character
equivalent to a range of about 2 to about 10 seconds for
the foam to break and soak into a curl when the com
position is applied to the hair.
Thus, as regards foam breaking time, only di?uoro
istics. An important factor in selection of the propellant 65 ethane
and monochlorodi?uoroethane each when used as
is its solubility in water. Following is a table of the
the
sole
propellant provide a deirable product. However,
approximate solubility of a number of propellants in
when
monochlorodifluoroethane
is used as the sole pro
water at 70° F. and at one atmosphere in weight percent:
pellant, preparatory mixing of the composition is necessary
Propellant:
Solubility 70 to obtain satisfactory results. When a vapor pressure
depressant is used with monochlorodi?uoroethane, the
Dichlorodi?uoromethane ________________ __ 0.01
depressant should also be used to balance the densities
Monochlorodifluoroethane _______________ __ 0.13
of the two liquid phases of the composition whereby the
Di?uoroethane _________________________ __ 0.32
two phases are made readily mixable. (The densities
Tri?uoromonochloroethane ______________ __ 0.44
It was found that in order to provide a fast breaking 75 of the liquid phases of composition C are so balanced.)
7
3,099,603
When di?uoroethane is used as the sole propellant, no
preparatory mixing is necessary to produce the desired
amount of fast breaking foam. When, without pre‘~
paratory shaking, compositions B, C and D were dis
charged from their containers, only composition B (con
taining di?uoroethane) produced foam even though it
contained a lesser amount of propellant than composition
‘C (wherein the propellant had a lower solubility than
8
ing foam. Not more than about 20% should be used in
order to avoid too high pressures in the container. When
‘di?uoroethane is used as the propellant the preferred
amount is in the range of 2.5% to 15%.
A vapor pressure depressant is preferably added to the
compositions of this invention to lower the total vapor
pressure of the composition and can be used to balance
the density of the liquid propellant phase with that of the
aqueous phase (i.e., make these two phases substantially
di?uoroethane) or composition D (wherein the propellant
had a greater solubility than di?uoroethane).
A ‘further advantageous characteristic that di?uoro 10 equal in density). The latter function is not necessary,
ethane has and which is not possessed by the other pro
pellants listed above is that it is less dense than the aqueous
lotion phase and ?oats thereon. This has the advantage
however, when di?uoroethane is used as the propellant,
although it may be done. A vapor pressure depressant
suitable for use in this invention must have the following
characteristics.
that in a can with the dip-tube leading to the bottom 15
(1) It must be relatively soluble in the propellant and
—-so that the contents can all be exhausted while the can
relatively insoluble in the aqueous phase;
is in an upright position—there is no danger of acci
(2) It must be stable at the alkaline pH suitable for
dentally discharging the propellant without product.
waving hair;
Another advantage of di?uoroethane is its high degree of
(3) It must be safe as to toxicity and irritation;
hydrolytic stability in the cold waving compositions of 20
(4)
It must be free of undesirable odor and color;
this invention. Its stability is slightly better than that
(5) It must not react with the active ingredients of the
of monochlorodi?uoroethane.
waving composition; and
Monochlorodi?uoromethane has solubility character
istics similar to those of di?uoroethane and will pro
(6) It must serve its functions of lowering vapor pres
not provide foam, fast-breaking or otherwise; it is also
than about 135 p.s.i.g. ‘at 130° F., and, when adjusting
density, which balances the density of the aqueous and
propellant phases. Such a pressure is su?icient to expel
sure and, when appropriate, adjusting density.
vide a fast-breaking foam but has a vapor pressure so
‘high (125 p.s.i.g. at 70° P. and 320 p.s.i.g. at 130° F.) 25 The vapor pressure depressant may consist of a single
compound or it may be a mixture of compounds. The
that it cannot be safely used as the sole propellant even
exact amount to be used is the amount Which gives the
with vapor pressure depressants. Dichloromono?uoro
desired vapor pressure, i.e., a composition vapor pressure
methane has solubility characteristics similar to those of
not greater than about 90 p.s.i.g. at 70° F . and not greater
tri?uoromonochloroethane, i.e., it is so soluble that it will
hydrolytically unstable, particularly in alkaline systems.
Other commonly employed chloro?uoro hydrocarbon
propellants, such as trichloromono?uoromethane have
the waving lotion in the form of a satisfactory amount of
solubilities which are too low for use in this invention.
fast breaking foam Without exceeding the conditions which
It was found that desired propellant solubility char
acteristics cannot be obtained by blending two or more
are preferably observed for safety reasons. It is usually
not necessary to depress the vapor pressure of di?uoro
ethane below about 40 p.s.i.g. at 70° F. A vapor pres
propellants having high and low solubilities, e.g., tri
?uoromonochloroethane and dichlorodi?uoromethane, in
an effort to arrive at a compromise solubility in the de
sure below about 90 p.s.i.g. at 70° F. can be obtained
However, a vapor
40 Without a vapor pressure depressant.
pressure depressant is preferably used in the composition
sired range. Apparently the foam breaking character
istics imparted to the composition by the propellant are
not additive and are determined by the least soluble pro
to ensure that the vapor pressure of the composition does
not exceed 135 p.s.i.g. at 130° F. This latter condition
pellant. However, propellants other than the speci?ed
is desirably observed for safety reasons because tempera
di?uoroethane or di?uoromonochloroethane propellants
tures of up to 130° F. or more may be encountered in
can be blended with the speci?ed propellants so long as
foam volume and stability are not adversely affected.
storage or transit and about 135 p.s.i.g. is the maximum
safe pressure for conventional metal containers. The
above discussion of preferred vapor pressures is partic
For example, although monochlorodi?uoromethane has
ularly applicable to the usual metal pressurized containers.
the desired product characteristics, i.e., fast breaking foam,
a vapor pressure too high to be satisfactorily used as the 50 Lower pressures are preferably observed when using glass
pressurized containers.
sole propellant, it may be used in minor amounts with
The quantity of vapor pressure depressant depends upon
di?uoroethane or monochlorodi?uoroethane at safe pres~
upon the identity of the depressant and propellant and
sures; it may be desirable to use it to raise the density
upon the quantity of propellant; it can constitute from
of the propellant mixture or to increase its vapor pres
sure. Tri?uoromonochloroethane, although it is too s0lu~
ble, as noted above, to provide satisfactory foam char
acteristics, can be used with di?uoroethane or di?uoro
monochloroethane in minor amounts both as a vapor pres
sure depressant and as an additional propellant.
When di?uoroethane and monochlorodi?uoroethane
55 about 1% to about 20% by weight of the total composi
tion. Less has insufficient effect on the pressure, if it is
desired to depress the pressure, and more may leave an
undesirable oily feel on the hair. The preferred amount
vapor pressure depressant, when used, is about 1% to
60 of
10%.
While there are methods available for determining den
sities of liquid under pressure, a convenient way of ascer
ture, the product will usually perform in accordance with
taining the amount of vapor pressure depressant required
the characteristics of monochlorodi?uoroethane because
of its lower solubility and will require preparatory mix 65 when adjusting the densities of the propellant and aqueous
phases, is to slowly add the compound to the otherwise
ing. Mixing is not necessary if the monochlorodi?uoro
complete system until the propellant phase changes its
ethane is present ‘in relatively minor amounts.
position, i.e., if it was ?oating, add until it sinks, or if the
The level at which propellant is employed depends upon
aqueous phase was ?oating, add until it sinks. By per
the propellant chosen, the other ingredients of the com
position and the desired pressure in the package. Desir 70 forming this test carefully the quantity of vapor pressure
depressant required to balance the density of the phases
ably, from about 2 Weight percent to about 20 weight
can be determined. Preferably the densities will be ad
percent propellant, either di?uoroethane or monochloro
justed so that the propellant phase just ?oats. This had
di?uoroethane is employed. Not less than about 2% is
the advantage that in a can with the dip-tube leading to
necessary to expel the product in the form of a fast break
are used in the compositions of this invention in admix
75 the bottom-so that the contents can all be exhausted
3,099,603
9
10
sure depressant is decreased, it is discovered that the pro_
while the can is in an upright position-th-ere is no danger
pellant phase ?oats when ‘the ?nal composition. is G and
that the densities of the aqueous and propellant phases
are substantially equal.
of accidentally discharging propellant Without product.
Compounds suitable for vapor pressure depressants are
organic aromatic and aliphatic carboxylic esters and halo
genated propellants having a high solubility in Water and
Percent
a relatively low vapor pressure. The ester vapor pressure
Ingredient
depressants should have a minimum molecular Weight of
about 190 because of the low volatility requirement; ade
Comp.E Comp. F Comp. G
quate vapor pressure depressant effect sets a maximum
molecular weight for the esters of about 600. The halo 10 Monoethanolammonium thiglycolate__ _
Monoethanolammonium dithiodiglyco
genated propellants should have a solubility in water
late _________________________________ __
Monoethanolamine, ca ____ __
greater than about .05 Weight percent as 70° F. and have
8. 0
8. 0
8. 0
3. 2
2. 3
3. 2
2. 3
3. 2
2. 3
1. 0
1. 0
1. 0
Polyoxyethylene lauryl ether with an
average of 23 oxyethylene groups per
a vapor pressure appreciably lower than the speci?ed
propellant when used. Desirable compounds ‘for use as
lauryl group ________________________ __
vapor pressure depressants include the following:
(1) Dialkyl phthalates where each alkyl radical con
Perfume _________ __
1. 0
1. 0
1. 0
Dioctyl phthalate... __
Isopropyl myristate- _
4. 6
0. 0
0. 0
4. 6
3. 0
1. 7
tains from 2 to 12 carbon atoms; examples are dipropyl
Water ________________________________ __
Monoehlorodifluoroethane
phthalate, dihexyl phthalate, ethylbntyl phthalate, and di
dodecyl phthalate;
(2) Dialkyl glutarates, adipates and pimelates where
20
each alkyl radical contains from 2 to 12 carbon atoms;
examples are dioctyl glutarate, didecyl glutarate, ethyl—
octyl adipate, dihexyl pirnelate, and diethyl pimelate;
(3) Alkyl laurates, myristates and palmitates where
each alkyl radical contains from 3 to 8 carbon atoms; ex
amples ‘are octyl laurate, hexyl laurate, propyl myristate,
7. 0
7. 0
Bal.
Bal.
The importance of having the densities of the aqueous
and propellant phases substantially equal is shown vby the
length of time after shaking that products, with varying
ratios of isopropyl myristate to dioctyl phthalate, will give
a satisfactory thick dry foam. The above compositions
and others, differing only in the ratio of ispropyl myristate
to dioctyl phthalate, were made up and tested.
iso-butyl myristate, hexyl palmitate, and pentylpalmitate.
(4) Tri?uoromonochloroethane.
Percent
Percent
Location of
"l‘ime,l
isopropyl dioctyl propellant minutes
myristate phthalate
phase
Phosphate esters such as tricresyl phosphate have satisfac
tory physical properties but may have undesirable physio
logical properties.
4. 6
2. 1
1. 7
1. 5
0. 0
Examples of especially preferred compounds for use as‘
vapor pressure depressants include: the dialkyl phthalates,
ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,
decyl, and iso-decyl; iso-propyl myristate and palmitate;
butyl myristate and palmitate; dioctyl adipate, and tri?uo
romonochloroethane.
7. 0
Bal.
0. 0
2. 5
3. 0
3. 2
4. 6
Comp.
4
20
25
40
8
F
H
G
I
E
1 Time required for phase separation resulting in poor qual
ity foam.
To make clear the manner of choosing a satisfactory
Among the several compositions, composition G is the
combination of propellant and vapor pressure depressant 40 choice for commercial use. The densities of phases are
when adjusting the densities of the propellant and aqueous
almost exactly balanced in I but the exact control of pro
phases, an illustration is given herewith. ‘It is desired to
portions required to insure that the propellant ?oats is
have a product which can be packed in a plastic covered
not economical in commercial production. At 1.3% iso
glass container so monochlorodi?uoroethane is chosen as
propyl myristate and 3.4% dioctyl phthalate the propel
a propellant. However, its vapor pressure will not ‘be 45 lant phase sinks.
less than about 29 p.s.i.g. at 70° F.; and since all inert
Difluoroethane can be employed if the composition is
gasses can not be purged from the package, the pressure
to be packed in a metal can and a higher pressure is de
in the package will be still higher. A pressure less than
sired. This propellant has a higher vapor pressure than
25 p.s.i.g. at 70° F. is preferred for glass packaging for
monochlorodi?uoroethane and its density is about 0.911
safety reasons. An aqueous phase of the desired compo
g. per cc. Dibutyl phthalate, having a density of 1.04 g.
per cc., is slowly added to an aqueous. composition like
sition has a density of ‘about 1.03 ‘g. per cc. and the pro
pellant has a density of ‘about 1.12 g. per cc. (both at
70° F.); and, therefore, the propellant sinks to the bot
tom of the container.
Addition of dioctyl phthalate to give the ?nal composi
tion E, shown below, lowers the vapor pressure sui?ciently
(to about 25 p.s.i.g.); but, as its density is 0.982, it does
not lower the density of the propellent, into which it dis.
solves, sufficiently to- cause it to float.
on shaking and will remain dispersed without further
The two phases 60 shaking for about 20 minutes.
differ substantially in density' ‘and remain di?iculty dis
persible in each other, and when dispersed promptly sepa
rate into two phases.
that of E, but with di?uoroethane propellant, until the
?oating propellant phase just sinks. ‘It is then known
that the correct quantity of dibutyl phthalate is just a little
less than that employed and this is con?rmed by making
a solution of composition K. The propellant phase floats
and the density of the propellant phase is almost equal to
that of the liquid phase. The two phases readily disperse
'
Addition of isopropyl rnyr-istate to ‘give the composi
tion F, lowers the vapor pressure satisfactorily (to 22 65
p.s.i.g. ‘at 70° F.). Having a low density of 0.85 g. per
cc. and dissolving in the propellant, isopropyl myristate
causes the propellant phase to float. However, because
of a relatively high density differential the two liquid
phases are still di?icult to mix and separate promptly 70
when mixed.
Keeping the same total amount of vapor pressure de
pressant which gave the desired pressure and watching the
Ingredients:
Percent comp. K
Monoethanolammonium thioglycolate ______ __
8.0
Monoethanolammonium dithiodiglycolate___.__ 3.2
Monoethanolamine, ca ___________________ __
2.3
Polyoxyethylene lauryl ether with an average
of 23 oxyethylene groups per lauryl group-..
1.0
Perfume ______________________________ __
1.0
Dibutyl phthalate _______________________ __
8.7
Di?uoroethane
4.3
Water
_
_
________________________ __.
_
_____
_ _ . __
Bal.
In summary, when adjusting the density of the propellant
and aqueous phases, the vapor pressure depressant to go
?oating behavior of the propellant phase as the ratio of
dioctyl phthalate to isopropyl myristate in the vapor pres 75 with a particular propellant is composed of an ester or
3,099,603
11
esters in amount to give the desired lowering of vapor
pressure.
The vapor pressure depressant is selected ac
cording to the relative density of the esters and the propel
lant to make the density of the propellant phase substan
tially equal to the density of the aqueous phase. Densities
of propellants and esters are found in the printed litera
ture.
-
A surface active agent is included in the compositions
of this invention. Its presence enables the achievement
12
ing soap is rinsed from the hair with hard Water, soap
curd may form and be left as a dulling ?lm on the hair.
Synthetic detergents are generally free of this disadvan
tage. Water soluble nonionic synthetic organic deter
gents are suitable for use in this invention; they include
compounds produced by the condensation of alkylene
oxide groups (hydrophilic in nature) with an organic hy—
drophobic compound which may be aliphatic or alkyl aro
matic in nature. Examples of such detergents are: the
of a stiff “dry'” fast breaking foam. “Fast breaking” is 10
polyalkylene glycol esters, ethers, and thioethers of the
types,
seconds, ‘and preferably in ‘about 2 to about 10 seconds,
after discharge onto the hair. If too much surface active
agent is employed the foam tends to break too slowly;
intended to mean a foam which breaks in less than 40
enough must be used to achieve desirably thick foam. 15
Suitable surface active agents are found among the anionic
wherein vR represents long chain alkyl radicals having
detergents and among nonionic detergents. In the ‘case
from about 8 to about 18 carbon atoms and n is an integer
of anionic detergents, it is preferred that the cation of
from about 4 to about 30; the polyethylene oxide conden
the detergent be one which confers high solubility on the
sates of alkyl phenols, e.g., the condensation products of
detergent; with this limitation, the cations of the alkaliz
alkyl phenols having about 6 to 12 carbon atoms in the
ing agents listed hereinbefore may be used. The choice 20 alkyl group, in either straight chain or branched chain
of a surface active agent is not critical, most of those
con?guration, with ethylene oxide in amounts equal to 10
commonly employed in shampoos and other personal
to 25 moles of ethylene oxide per mole of alkyl phenol;
products ‘being satisfactory.
compounds formed by condensing ethylene oxide with a
Examples of anionic synthetic detergents suitable for
hydrophobic base formed by the condensation of propyl
the practice of this invention are the detergents of the sul 25 ene oxide with propylene glycol; the condensation prod
fonated and sulfated types such as the alkyl (Ca-C18)
uct of ethylene oxide with the product resulting from the
sulfates, the alkyl (CFCIB) polyethenoxy (1-10 units of
reaction of propylene oxide and ethylene diamine. Com
-—C2H4O—) ether sulfates, the alkyl (Cg-C18) aromatic
pounds with ether linkages are preferred because of their
sulfonates, the mono- or di-alkyl (C8~C18) esters of sulfo 30 resistance to hydrolysis in alkaline solutions. More spe
succinic acid, sulfonated or sulfated amides of higher fatty
ci?c examples of some suitable non-ionic detergents are:
acids, sulfuric acid esters of polyhydric alcohols incom
the reaction products of t-octylphenol with an average of
pletely esteri?ed with higher fatty acids, higher fatty acid
from 9 to 30 moles of ethylene oxide per mole, and the
esters of low molecular weight alkylol sulfonic acids,
water—soluble waxy reaction products of lauryl alcohol
etc., usally in the form of their sodium, potassium, am 35 and ethylene oxide having a titer of about 35° C. or higher
monium, or lalkanolammonium salts. Some of the par
and of oleyl alcohol and ethyleneoxide having a titer of
ticular detergents of this category are sodium octyl sulfate,
about 29° C. or higher.
sodium nonyl sulfate, sodium decyl sulfate, mono-ethanol
The quantity of surface active agent employed is from
ammonium dodecyl sulfate, ammonium tetradecyl sulfate,
about 0.05% to about 2%. The surface active agent
monoethanolammonium pentadecyl sulfate, monoethanol
serves the primary purpose of contributing tothe produc
ammonium hexadecyl sulfate, monoethanolammonium
tion of a foam having the desired characteristics; it also
octadecyl sulfate, monoethanolammonium oleyl sulfate,
aids in solubilizing or emulsifying the perfume and con
sodium salts of dioctyl sulfosuccinate, sodium octyl ben
tributing to the solubilization of the propellant. In such
zene sulfonate, sodium nonyl benzene sulfonate, sodium
proportions the surface active agent does not have the
dodecyl benzene sulfonate, sodium tetradecyl benzene sul
disadvantages mentioned in connection with emulsi?ers
fonate, ammonium pentadecyl benzene sulfonate, am
hereinbefore, i.e., a decrease of mildness of the Waving
monium triisopropyl benzene sulfonate, sodium salts of
lotion, possible interaction with the Waving agent and a
the oleic acid ester of isethionic acid, sodium salt of the
tendency for poor waving results.
lauric acid amide of taurine, triethanol-ammonium coco
Various minor ingredients can be included in the com
nut oil monoglyceride monosulfate, monoethanolam
positions of this invention and are generally desirable for
monium tallow diglyceride monosulfate.
the purposes of making the product more pleasant to use
Mixtures of various of the anionic synthetic detergents
and leaving the hair in a particularly good condition. It
also come within the scope of the general class de?nition
above. For example, the commercially available deter
is generally desirable to include a soluble salt of the disul
?de of the keratin-reducing agent, especially the disul
gents are generally not pure compounds but are mixtures 55
?de of thioglycolic acid, at a level, based on the total com
of homologous compounds. Thus, sodium alkyl benzene
sulfonate wherein the alkyl group contains 12 to 18 car
bon atoms, a mixture of triethanolammonium alkyl sul
fates consisting mostly of triethanolammonium lauryl sul
position, equivalent to from about 0.5% to 5% of dithio
diglycolic acid. The soluble salts ‘which can be used in
clude those formed from the bases listed as suitable for
making the pH adjustment. These additives protect the
fate, and a mixture of monoethanolammonium polyethen 60 hair
from over-treatment and leave it in a particularly
oxy ether sulfates wherein the alkyl group contains from
good
condition as is disclosed in US. Patents 2,719,814
12 to 18 carbon atoms and there are from 1 to 6 units of
and 2,719,815. A perfume will be added in the preferred
—-C2‘H4O— per molecule, are well known detergents. As
compositions of this invention.
a further example of commercially important mixtures,
The compositions of this invention must be packaged in
alkanolammonium salts of coconut sulfate and coconut 65
suitable pressure-tight containers. For pressures lower
polyethenoxy ether sulfate are among the detergents which
than about 25 p.s.i.g. at 70° F., glass bottles, which are
are highly suitable for use in this invention.
The coco
nut alkyl radical is derived from the middle distillation
cut and typically will ‘contain the following appropriate
percentages
of
various
chain lengths:
Cur-66%, C14——-23% and C16—9%.
coated on the outside with plastic and metal cans are suit
able. Metal cans are preferably employed for higher
pressures. A metal which is not appreciably corroded by
Clo-2%, 70 the product should be chosen and/ or a corrosion inhibitor
Water soluble soaps of fatty acids, such as sodium, po
tassium, ammonium or triethanol amine salts of tallow
or coconut oil fatty acid, may be used, but the synthetic
detergents are preferred. When waving lotion contain
should be added to the formulation.
Aluminum cans are
preferred because of their lightness, economy and resist
ance to corrosion.
When aluminum cans are used, it is
particularly desirable to include in the waving lotion, as a
corrosion inhibitor, from about .001% to about 0.1%
3,099,603
13
ment can be from pH 8.5 to pH 9.5 in this example with
out losing its advantages.
SiOZ, as Water soluble sodium silicate. Water soluble
sodium silicates having a weight ratio of SiO2:Na2O in
the range of about 5 :1 to about 1:1 are quite satisfactory.
Example 11
The valves, with which the pressurized containers are
?tted to control their opening and discharge of product, C71
The following composition was prepared and packed
‘are those commercially employed for other aerosol prod
in a pressurized aluminum can ?tted with a valve to con
ucts. Nozzles for discharge of the product are not criti
trol the discharge of the product and a foam nozzle.
cal except that it is preferred to use a foam type nozzle.
This type of nozzle provides opportunity for an appreci
Ingredients:
able pressure drop while the product is still con?ned with 10
Monoethanlolammonium
Percent
thioglycolate ______ __ 7.6
Monoethanolammonium ditthiodiglycolat-eun 3.05
in the nozzle. This pressure drop within the enclosed
channel causes foam to be generated Within the nozzle.
Foam nozzles are commercially available and have been
repeatedly described in the literature. For example, the
US. Patent 2,655,480 of Spitzer et a1. shows a typical 15
foam nozzle. For additional convenience a comb-type
applicator which discharges the foam from its “teeth”
Tri?uotronronoclrloroethane ______________ __ 1.09
Di?uoroethane _________________________ __ 3.26
over the Width of the tress can be used on the nozzle.
SiOz (added as sodium silicate having an
Monoethanolamine (to adust pH to 9.3)_____ 2.1
Polyoxyethylene lauryl ‘ether with an average of
23 oxyethylene groups per lauryl group_____ ‘0.95
Perfume ______________________________ __ 0.95
In the following, speci?c examples are set forth as illus
SiO2:Na2O ratio of 2.5:1) _____________ __ 0.01
trative of the invention and of certain of the relationships 20
important in its practice. Compositions are expressed
Water ________________________________ __ Bal.
The vapor pressure of this composition was 60 p.s.i.g.
at 70° F. and 100- p.s.i.g. at 130° F. The composition
discharged ‘from the foam nozzle as a thick, dry foam
which collapsed on the hair in ‘about 5 seconds. There
was no need for preparatory mixing. The propellant
phase was lower in density than the aqueous phase and
in weight percent.
Example I
The following composition was prepared and intro
duced into pressurized ‘aluminum cans ?tted with valves
to control the discharge of the product and with foam
?oated thereon. The composition proved effective in
waving hair and left the hair in good condition.
nozzles.
Ingredients:
The nonionic detergent in this composition can be re
placed by any one of the following detergents at the level
indicated while retaining the advantages of this invention:
Percent
Monoethanolammonium thioglycolate ______ __ 7.6
Monoethanollammonium dithiodiglycolate____ 3.05
tn'ethanolamine lauryl polyethenoxy other sulfate in which
M'onoethanolamine (to adust pH to 9.3) ____ __ 2.1
the average number of ethenoxy groups per molecule is
Isopropyl myristate _____________________ __ 4.78
Di?uoroethane
about 3—-0.5%; triethanolamine lauryl sulfate-0.5%;
alkylaryl polyether alcohol (the reaction product of t
________________________ __ 4.35
Polyoxyethvlene lauryl ether with an average of
23 oxyethylene groups per lauryl group____ 0.95
octylphenol with an average of 9—10 moles of ethylene
oXide)-—0.05 % .
Perfume ______________________________ __ 0.95
SiO-Z (added as sodium silicate having an
Example III
40
siozzNazO ratio of 2.5:1) _____________ __ 0.01
The following composition was prepared and intro
Water ________________________________ __ Bal.
duced into pressurized plastic-covered glass bottles ?tted
The nronoethauolammonium thioglycolate in this com
with valves to control the discharge of the product and
with foam nozzles.
position is equivalent to about 4.5% thioglycolic acid.
Monoethanolammonium dithiodiglycolate, perfume and
Ingredients:
sodium silicate while having a desirable effect on the prod
uct, ‘are not essential to the success ‘of the present inven
Percent
Monoethanolammonium thioglycolate ______ __ 7.7
tion.
This composition gave a pressure of 60 p.s.i.g. at 70° 50
F. and 11S p.s.i.g. at 130° F. Iand discharged from the
container in the form of a thick, dry, fast-breaking foam.
Monoethanolammonium tdithiodiglyoolate_____ 3.1
Monoethanolamine (to adjust pH to 9.3)_____ 2.1
There was no necessity for preparatory mixing.
Monochlorodi?uoroethane _______________ __ 7:0
The
time required for substantially complete collapse of the
foam ‘on the hair was about 5 seconds.
The propellant 55
?oated on the aqueous phase. When used in waving
hair, it gave results fully as good as leading commercial
Sodium silicate having an SiO2:Na2O ratio of
2.5 :1 _______________________________ __ 0.03
easy to apply neatly without run~o? of excess lotion.
The following vapor pressure depressants were subti 00
tuted for the isopropyl myristate in the composition of
Example I in substantially equal amounts with substan
The level of monoethanolarnrnonium thioglycolate can
be increased to the equivalent of 7% thiogiycolic acid to
Polyoxyethylene lauryl ether with ‘an average of
23 oxyethylene groups per lauryl group____ 0.93
Perfume ______________________________ __ 0.93
waving preparations; and it had the advantage of being
tially equal results: diethyl phthalate, dibutyl phthalate,
dihexyl phthalate, dioctyl phthalate, didecyl phthalate, iso
propyl palmitate, butyl myristate, dioctyl glutarate, di
hexyl pimelate and dioctyl adipate.
Isopropyl myristate _____________________ __ 1.7
Dioctyl phthalate _______________________ __ 3.0
Water ________________________________ __ Bal.
The monoethanolammonium thioglycolate in this com
position is equivalent to about 4.6% thioglycolic acid.
Monoethanolammonium dithiodiglycolate, perfume and
65
sodium silicate, While having a ‘desirable effect on the
product, are not essential to the success of the present
invention.
This composition gave a pressure of 23 p.s.i.g. at room
temperature ‘and discharged from the container in the
form of a thick, dry, fast-breaking foam. The time re
give a very curly wave While retaining the advantages of
quired for substantially complete collapse of the foam
this invention; or it ‘can be reduced to the equivalent of 70 in the cup test was about 35 seconds. The two phases
3% thioglycolic acid to give a very loose and casual wave
stayed sufficiently well mixed after shaking‘ so that foam
while retaining the advantages of this invention. Am
of the desired properties was obtained for about 25
monia, tr-is(hydr.oxymethyl)aminomethane, 2-amino-2
minutes. On separation the propellant ?oated on the
methyl-1,3-propaned-iol and diethanolamine can replace
75 aqueous phase. When used in waving hair, it gave re
monoethanolamine, in whole or in part, and pH adjust
8,099,603
15
10
suits fully as good as leading commercial waving prepara
The foam breaks to a liquid in about 30 seconds in the
tions; and it had the advantage of being easy to apply
cup test.
This composition waved hair effectively and left the
hair in good condition. It combined the performance
of a conventional Waving lotion With the conveniences
neatly without run-off of excess lotion.
The level of monoethanolammonium thioglycolate can
be increased to the equivalent of 7% thioglycolic acid
to give a very curly wave while retaining the advan
tages of this invention; or it can be reduced to the equiv
inherent in the compositions of this invention.
Example VI
alent of 3% thioglycolic acid to give a very loose and
casual wave While retaining the advantages of this in
10
vention. Ammonia, tris(hydroxymethyl)amino-methane,
can replace monoethanolamine, in whole or in part, and
pH adjustment can be from pH 8.5 to pH 9.5 in this
aqueous phase.
Ingredients:
example without losing its advantages.
Percent
15
Monoethanolam-monium thioglycolate ____ __ 7.7
Example IV
Monoethanolammonium dithiodiglycolate ____ 3.1
iMonoethanolarnine (to adjust pH to 9.3) ____ 2.1
The following composition was prepared and packed
in a pressurized aluminum can ?tted with a valve to con
20
trol the discharge of the product and a foam nozzle.
Ingredients:
The following composition was prepared and packaged
in a plastic covered glass bottle ?tted with a valve and
a foam nozzle. The propellant phase ?oated on the
2-amino-2-methyl - 1,3 - propanediol and diethanolamine
Diootyl adipate ________________________ __ 3.9‘
Dioctyl phthalate ______________________ __ 0.97
Monochlorodi?uoroethane _______________ __ 7.0
Polyoxyethylene lauryl ether with an average
of 23 oxyethylene groups per lauryl group 0.93
Percent
Monoethanolammonium t‘hioglycolate ____ __ 7.7
‘Perfume ______________________________ __ 0.93
Monoethanolammonium dithiodiglycolate ____ 3.1
Sodium silicate having an SiO2:Na2O ratio of
Monoethanolamine (to adjust pH to 9.3) ____ 2.1
2.5 :1 _______________________________ __ 0.03
Water ________________________________ __ Bal.
Dibutyl phthalate ______________________ __ 8.7
Di?uoroethane _________________________ __ 4.4
The pressure in the package was 25 p.s.i.g. at 70° F.
(It would have been greater than 29 p.s.i.g. Without the
vapor pressure depressant.) On actuating the valve, the
Polyoxyethylene lauryl ether with an average
of 23 oxyethylene groups per lauryl group 0.93
Perfume ______________________________ __ 0.93
‘Sodium silicate having an SiO2:Na2O ratio of
0.03
Bal. 35
The vapor pressure of this composition was about 43
p.s.i.g. at room temperature. The composition dis
charged from the foam nozzle as a thick, dry foam
which collapsed in the cup test in about 20 seconds.
2.5 :1 _______________________________ __
Water ________________________________ __
product was dispensed as a thick dry foam which broke
to a liquid in the cup test in about 30 seconds. The
two liquid phases comprising the product were readily
mixed by shaking and remained su?’iciently well mixed
to give a good foam for about 20 minutes.
This composition is well adapted for waving hair and
possesses the advantages inherent in the fast-breaking
foam of this invention.
The propellant phase was slightly lower in density than
Example VII
the aqueous phase, but after agitation they remained
sufficiently dispersed in each other for at least 15 min
The ‘following composition was prepared and packaged
utes. The composition proved effective in waving hair
in a plastic covered glass ‘bottle ?tted with a valve and
and left the hair in good condition.
a foam nozzle.
The nonionic detergent in this composition can be 45
Ingredients:
Percent
replaced by any one of the following detergents at the
Monoethanolammonium thioglycolate ____ __ 7.7
level indicated while retaining the advantages of this
invention: triethanolamine lauryl polyethenoxy ether
Monoethanolammonium dithiodiglycolate ____ 3.1
sulfate in which the average number of ethenoxy groups 50
per molecule is about 3——O.5%; triethanolamine lauryl
Isopropyl myristate _____________ __‘ _____ __ 4.8
sulfate—0.5%; alkylaryl polyether alcohol (the reaction
Tri?uoromonochloroeth'ane ______________ __ 3.5
Monochlorodi?uoroethane ______________ __ 3.5
product of t-octylphenol with an average of 9—10 moles
of ethylene oxide)~0.05%.
Example V
55
packed in a pressurized plastic covered glass bottle ?tted
with a valve to control the discharge of product and 60
The composition was that of Example
The amount of water was de
Perfume ______________________________ __ 0.93
2.5:l1 _______________________________ __ 0.03
Water ________________________________ __ Ba].
The propellant phase ?oated ion the aqueous phase.
The pressure in the package was 18 p.s.i.g. at 70° F.
After shaking, the product was discharged as a thick dry
foam which broke to a liquid in the cup test in about 30
III except that: the level of dioctyl phthalate was raised
to 8.10%; the level of isopropyl myristate was raised
to 4.60%; and the level of monochlorodi?uoroethane
was raised to 18.6%.
Polyoxyethylene lauryl ether with an average
of 23 oxyethylene groups per lauryl group‘ 0.93
Sodium silicate having an SiO2:Na2O ratio of
A composition as described below was prepared and
a foam nozzle.
Monoethanolamine (to adjust pH to 9.3) ____ 2.1
65
creased correspondingly. This composition without the
seconds. The two liquid phases comprising the product
were readily mixed by shaking and remained su?iciently
well mixed to give a good foam for about 20 minutes.
vapor pressure depressants would exert a pressure of
This formula is Well adapted for waving hair with the
greater than 29 p.s.i.g., depending on the thoroughness
advantages of manipulation inherent in the fast-breaking
of purging.
foam of the invention.
The composition with the vapor pressure
depressant exerted a vapor pressure of 22 p.s.i.g. at 70
room temperature. The propellant phase ?oated on the
Example VIII
aqueous phase and was readily dispersible by shaking.
The following compositions were prepared and pack
The phases stayed su?iciently dispersed to give a good
dry thick foam for periods up to about one-half hour. 75 aged each in an aluminum can ?tted with a valve and a
foam nozzle.
3,099,603
L
M
18
position a pH of from 8.5 to 9.5; as a propellant, not less
than about 2.5% and not more than about 15% di?uoro
ethane; as a vapor pressure depressant, from about 1% to
N
about 20% of an organic compound selected from the
group consisting of: dialkyl phthalates, glutanates, adi
Ingredients:
Monoethanolamine thioglycolate, per
cent ________________________________ _.
Monoethanolamine dithiodiglycolate,
percent ______________________ __
-___
7. 7
7. 7
7.7
3.1
3.1
3.1
Monoethanolamine, percent __________ __
2.1
Monochlorodi?uoroethane, percent____.
7.0
Difluoroethane, percent _________________________ ._
2.1
2.1
3. 5 ______ __
3. 5
7. 0
Polyoxyethylene lauryl ether with an
average of 23 oxyethylene groups per
lauryl group, percent ______ ._
Perfume, percen ___________ _.
__
0.93
0. 93
0. 93
0. 93
0. 93
0. 93
0.03
Bal.
0. 03
Bal.
0. 03
Bel.
pates, and pimelates wherein the alkyl group contains 2 to
12 carbon atoms, alkyl laurates, myristates, and palmitates
wherein the alkyl radical contains from 3 to 8 carbon
atoms, and tri?uoromonoehlonoethane, said organic com
10 pound being present at a level such that the vapor pressure
of the composition is not ‘greater than about 135 p.s.i.g.
at 130° F.; {from about 0.05% to about 2% of a surface
active agent selected ‘from the [group consisting of non
Sodium silicate having an SlOgZNEzO
ratio of 2.51, percent ________________ __
Water to make 100% __________________ __
Characteristics:
Composition vapor pressure at 70° F.,
p.s.i.g ______________________________ ..
30
54
62
seconds ___________________________ ._
35
30
18
Foaming breaking speed (cup test), in
Preparatory mixing re
ionic and anionic surface active agents; and the balance
15 substantially water.
3. The composition of claim 2 wherein the vapor pres
sure depressant is isopropyl my-ristate.
4. A pressure tight aluminum container which contains
ired to obtain
Yes
Yes
No
Propellant layer location ______________ _- Bottom
thick dry foam _____________________ __
Top
Top
the composition of claim 2, said composition containing
20 addition-ally, as a corrosion inhibitor, from about .001%
These formulas ‘are well adapted ior waving hair with
the advantages of manipulation inherent in the fast-break
to about 0.1% SiOz added as water soluble sodium silicate.
5. A two liquid phase pressurized hair waving composi
tion adapted for discharge from its container as a team,
which collapses to a liquid promptly after discharge con
of this example can be safely employed without a vapor
pressure depressant; however, when doing so it would be 25 sisting ‘essentially of: from about 3% to about 6% of
ing foam of this invention. The pmessurized compositions
thioglycolic acid, an alkalizing agent, a substantial part of
desirable to avoid unusually high temperatures unless con
tainers somewhat stronger than the ordinary containers
which is a base selected from the group consisting of am
are used.
methyl) aminomethane, 2-armino-2~methyl - 1,3 - propane
In the case of compositions L and M (containing mono
monia, monoethanolarnine, diet-hanolamine, tris(hydroxy
diol and mixtures thereof imparting to the composition a
ohlorodi?uonoethane) the dispersion of rthe propellant in 30 pH
of about 9.3; as a propellant, not Hess than about 2.5%
the aqueous phase persisted and ‘gave good, past-breaking
foam for about 20 minutes.
However, if a vapor pressure
depressant had been used, it would have been necessary
to balance the densities of the liquid phases to obtain such
persistance of dispersion and ioarn.
This application is a continuation-in-part of copending
application Serial No. 839,282, ?led September 11, 1959,
now abandoned.
and not more than about 15% di?uoroethane; as a vapor
pressure depressant from about 1% to about 10% of an
organic compound selected from the ‘group consisting of:
dialkyl phthalates, glutarates, ladipates, and pimelates
wherein the alkyl group contains 2 to 12 carbon atoms,
alkyl laurates, myristates and palmitates wherein the alkyl
radical contains from 3 to 8 carbon atoms, and mixture
thereof, ‘said organic compound being present at a level
So far as the waving ingredients of the
this invention are concerned, they are conventional and ‘40 such that the vapor pressure of the composition is not
greater than about 135 psig. :at 130° F.; and from about
compositions of A _
no claim is made to them per se.
»
0.05% to about 2% of a surface active agent selected
from the group consisting of nonionic and anionic surface
1. A two liquid phase pressurized hair waving composi
active agents; and the balance substantially ‘water.
tion adapted ‘for discharge from its container as a foam,
6. The composition of claim 5 wherein the vapor pres
which collapses to a liquid promptly after discharge, con 45
What is claimed is:
sisting essentially of: from about 1% to about 10% of a
low ‘molecular weight mercapto-alk-anoic acid, an alk-aiiz
ing agent a substantial part of which is a base with a dis~
sure depressant is isopropylmyristate.
7. A pressure tight aluminum container which contains
the composition of claim 5, said composition containing
additionally, as a corrosion inhibitor, from about .001%
sociation constant less than 10*5 imparting to the composi
tion a pH above about 7 but below 10; from about 2% to 50 to about 0.1% SiOz added as water soluble sodium silicate.
8. A two liquid phase pressurized hair waving composi
ab out 20% of a propellant selected from the group con
tion
adapted for discharge from its container as a foam,
sisting of difluoroethane and monochl-orodi?uoroethane;
which
collapses to a liquid promptly after discharge,
as a vapor pressure depressant inom about 1% to about
20% of an onganic compound selected from the ‘group
consisting of: dialkyl p-hthalates, glutanates, ‘adipates and
pimelates ‘wherein the \alkyl group contains 2 to 12 carbon
atoms, alkyl laurates, myristates, and palmitates wherein
the alkyl radical contains from 3 to 8 carbon atoms, and
mixtures thereof, said organic compound being present at
consisting essentially of: from about 1% to about 10%
of a low molecular weight mercapto-alkanoic acid, an
alkalizing agent a substantial part of which is a base with
a dissociation constant less than 10*5 imparting to the
composition a pH of from 8.5 to 9.5; as a propellant,
from about 2% to about 20% of di?uoroethane; as a vapor
a level such that the vapor pressure of the composition is 60 pressure depressant and density balancer, from about 1%
to about 20% of organic esters selected from the group
less than about 135 =p.s.i.g. at 130° lF., and, when mono
consisting of: dialkyl phthalates, glutarates, adipates, and
chlorodiiiuoroethane is the propellant, such that the den
sity of the propellant phase is substantially equal to the
density of the aqueous phase, the two liquid phases thereby
pimelates wherein the alkyl group contains 2 to 12 car
sisting of nonionic and anionic surface active agents; and
the balance substantially water.
2. A two liquid phase pressurized hair waving composi
according to their density relative to the propellant and
being present at a level such that the density of the propel
lant phase is substantially equal to the density of the
low molecular weight mercapto-alkanoic acid, an alkaliz
nonionic and anionic surface active agents; and the bal
bon atoms, alkyl laurates, myristates, and palmitates
being made readily mixab-le; from about 0.05% to about 65 wherein the alkyl radical contains ‘from 3 to 8 carbon
atoms, and mixtures thereof, said esters being selected
2% of a surface active agent selected ‘from the ‘group con
aqueous phase, the two liquid phases thereby being made
tion adapted for discharge from its container as a foam, 70
readily mixable; ‘from about 0.05% to about 2% of a
which collapses to a liquid promptly a?ter discharge, con
surface active agent selected from the group consisting of
sisting essentially oi: from ‘about 1% to about 10% of a
ance substantially water.
ing agent a substantial part of which is a base with a dis
9. The composition of claim 8 wherein the vapor pres
75
sociation constant less than 10-5 imparting to the com
19
3,099,603
sure depressant and density balancer is' dibutyl phthalate.
the density of the propellant phase is substantially equal
10. A two- liquid phase pressurized hair waving com
position adapted' for discharge from its container as a
to the density of the aqueous phase, the two liquid phases
thereby being made readily mixable; and from about
foam, which collapses to a liquidrpromptly after discharge,
0.05 % to about 2% of a surface active ‘agent selected from
consisting essentially of : from-about 1% to about-10% of
a low molecular weight mercapto-alkanoic acid, an alkaliz
the group consisting of nonionic and anionic surface active
agents; and the balance substantially water.
14. A two liquid phase pressurized hair waving com
position adapted for discharge from its container as a
ing agent a substantial part of which is a- base with a dis
sociation constant less than 10*5 imparting to; the com~
position a pH of ‘from 8.5 to 9.5; as a propellant, from
about 2% to about 20% monochlorodi?uoroethane; as 10 foam, which collapses to a liquid promptly after discharge,
consisting esesntially of: from about 1% to about 10%
a vapor pressure depressant and density balancer, from
of a low molecular weight mercapto-alkanoic acid, an
about 1% to about 20% of organic esters selected from
alkalizing agent a substantial part of which is a base with
a disass'oc'iation constant less than 10—5 imparting to the
‘composition a pH above about‘7v but below 10; from about
2% to about 20% of a propellant selected from the group
the group consisting of: dialkyl phlthalates, glutarates,
adipates, and pimelates wherein the alkyl group contains
2 to 12 carbon atoms, alkyl laurates, myristates and palmi
tates wherein the alkyl radical contains from 3 to 8 car~
consisting of di?uoroethane and monochlorocli?uoroeth
bon atoms, and mixtures thereof, said esters. being selected
ane; fioin about 0.05% to about 2% of a surface active
according to their density relative to the propellant and
being present at a level such ‘that the density of the pro
pellant phase is substantially equal to the density of the
agent selected from the group consisting of nonionic and
anionic surface active agents; and the balance substan~
tially water.
15. The composition of claim 14 which contains, as
a vapor pressure depressant, about 1% to about 20% tri
?uoromonocliloroethane and su?ic-ient in amount that the
aqueous phase, the two liquid phases thereby being made
readily mixable; from about 0.05% lto'about 2% of a
surface active agent selected from the group consisting of
nonionic and anionic surface active agents; and the bal
vapor pressure of the composition is not greater than
ance substantially water.
25 about 135 p.s.i.g. at 130° 1F.
11. The composition of claim 10 wherein the vapor
16. A two liquid phase pressurized hair waving com
pressure depressant and density balancer is a mixture of
position adapted ‘for discharge from‘ its container as a
isopropyl myristate and dioctyl phthalate.
foam, which collapses to a liquid promptly after discharge,
consisting essentially of: from about 3% to about 6% of
its container as a 30
thioglycolic acid, an alkalizing agent, a substantial part of
foam, which collapses to a liquid promptly after discharge,
which is a base selected from the group consisting of
consisting essentially of: from'abou't 3% to about‘ 6% of
ammonia, monoethanolamine, diethanolamine, tris(hy
thioglycolic acid, an alkalizing agen -a substantial part
droxymethyl) aminomethane, 2-amino-2-methyl-1,3-pro
of which is a base selected fromthegroup consisting of
12. A two liquid phase ‘pressurized hair- waving com
vposition adapted [for discharge from
ammonia,‘ monoetlranolamiine, diethanolamine, tris(h'y
droxymethyDaminomethane, 2 - amino-2-methyl-L3-pr'o
35
panediol and mixtures thereof imparting to-the composi
tion a pH of about 9.3; as a propellant, from about‘2%
to about 20% of di?uoroethane;-as a vaporE pressure de
pressant ‘and density balancer, from about‘ 1% to about
20% of dibutyl phthalate, said dibutyl phthalate being
present at a level such that the density of- the propellant
phase is substantially equal to the-density of the aqueous
panediol‘and mixtures thereof imparting to the composi
tion a pH in the range of 8.5 to 9.5; from about 2% to
about 20%‘. of aprope'llant selected from the group con
sisting of- di?uoroethane and monochlorodi?uoroethane;
from about 0.05 % to about 2% of a surface active agent
selected'from-the group consisting of nonionic and anionic
surface'active- agents; and ‘the balance substantially water.
17. The composition of claim 16, which contains as
a vapor presure depressant, about 1% to about'20% tri
?uoromonochloroethane and suf?cient in amount that'the
pressure ‘of the composition is not greater than ‘about
mixable; and from about 0.05% ‘to about 2% of‘ a‘ surface 45 vapor
1'35v p.s.i.g.' at'130‘° F.
active agent selected from the group consisting-of non
ionic and anionic ‘surfaceractive agents; and-the balance
References Cited in the ?le of this patent
phase, the two liquid phases thereby being made readily
substantially water.
I
UNITED STATES PATENTS
13. Av two liquid. phase pressurized hair waving‘ com
position adapted for discharge"v from itscontaliner as a 50 2,719,129
Richardson __________ __ Sept. 27, 1955
foam, which ‘collapses to a liquid promptly after discharge,
OTHER REFERENCES
consistingessentially of: from about3% to about~6% of
thioglycolic acid, an-alkalizing agent a substantial part'of
‘ Downing‘ et al, Soap and Sanitary Chemicals, 29:1,
which is a base selected from the" group consisting? of am
monlia, monoethanolamine, diethanolamine, tris(hydroxy- . 55
methyDaminomethane, 2-amino-2-m'ethyli1,3-propanedi'ol
September1953, pp". 142, 143, 145, 147, 149,’ 153, 155,
177,‘and-178.
_
Reed, J; 8.’, Cosmetic Chemists, 7:2, March 1956, pp.
and mixtures thereof imparting to the composition‘ av pH
of about 9.3;
a propellant, from about 2%“ to about
137-149:
20% monochlorodi?uoroethane;
Pub_., Inc, New-York‘ (1957), pp. 610, 611, and 836.
as- a vapor pressure de"
_
Sagarin, Cosmetics, Science, and Technology, Intersci.
pressant and density balancer, from- about 1% to about 60 'Callans 'et at, Soap and Chemical Specialties, January
10% of a. mixture of isopropyl m-yni'state‘ and dioctyl
1957, 3351, PP. 68-9, 71, 73, and 75.
vphthalate, said'mixture beingépresen-tat-a level such that
Armstrong, Soap and Chem. Spec, January 1959, 35:1,
pp. 91, 95, and 97.
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