Note: Descriptions are shown in the official language in which they were submitted.
5~7
HAIR WAVING OR STRAIGHTENING PROCESS
THAT SII~ULTANEOllSLY CONDITIONS HAIR AND HAIR
WAVING COMPOSITION THEREFOR
This invention relates to compositions for waving or straighten-
ing hair, and especially human hair, and to processes for effecting
the same. More p~rticularly, it concerns compositions and methods of
the aforesaid character which leaves the hair in a conditioned or
improved manner.
Hair waving or strai~hteniny (also often referred to as "perman-
ent" treatment) usually involves the application of an agent for redu-
cing or cleaving the disulfide linkages of keratin in hair (herein-
after referred to as "reducing agent", and compositions containing a
reducing agent hereinafter referred to as "reducing" or "waving" ''co
position" or "lotion"J~ thereby to permit hair to be shaped without
any internal elasticity or other resistance, and the subsequent appli-
cation of a neutralizing agent which reestablishes the keratin link-
ages and sets the hair in its new, desired shape. The neutralizing
agent is generally an oxidizing solution, such as an aqueous solution
of llydroyen peroxide and the like~
Distinguished from the waving and straightening of hair by a
reducin~ lotion, is the so-called relaxing of hair wherein a strong
alkali, usually in the form of a pas-te or cream is employed~ The
mechanism of the action of the alkali is different from the mechanism
of action of the reducing agent in conventional permanent waving and
straightening. While in the latter case the disulfide linkages of
keratin are cleaved and remain cleaved until restored by the neutral~
izer, in the caustic alkaline treatment the disulfide linkages of
keratin are converted to monosulfide bonds and the following "neutral-
ization" with an acid is merely the conventional neutralization of -the
residual base with an acid. Hence the terms "~aving" and "straighten-
ing", as used herein, do not contemplate the relaxation of hair by
strong bases.
Waving or straightening of hair with reducing agents such as mer-
captans, sulfites or phospines is almost invariably accompanied by
deterioration of tactile properties of hair~ increased tangling and
difficult combing. This is true for all types of hair and particular~
ly bothersome for hair which9 prior to waving, had been exposed to
bleachingg coloring or prolonged weathering. The conventional way to
ameliorate this situation is to treat the waved hair with conditioning
ayents such as alkyl-dimethyl benzyl halides, emulsions of mineral
ila lanolin, etc. Conditioning agents of this type are usually in-
corporated in the neutralizing step of the waving or the straightening
process. While these conditioning compounds improve the feel of hair
and allow for easier comDing, their beneficial effects are only tran-
sitory and are entirely lost ~hen the hair is shampooed.
U.S. patent No. 3,912,808 to Sokol discloses a process for waving
or straightening hair which involves a waving lotion containing a
reducing agent and a polydimethyldiallylammonium chloride, a cationic
polymer. The teaching of this patent is employed in a commercial
product which was tested and compared in connnection with this appli-
cation. Polydimethyldiallylammonium chloride is not being used in
accordance with the present invention~
U.S. patent No. 4,175~572 to Hsiung et al. relates to a caustic
alkaline hair relaxer and not to waving or straightening, which, among
others, also contains polydimethyldiallylammonium chloride. The poly-
mer can be applied also separately from the alkaline relaxer, before
or after its application. It is stated that an acidic shampoo is
employed after relaxing and conditioning to remove the excess alkaline
solution. The last shampoo step or its composition i5 not specified
further and it is stated not to be a part of the conditioning pro-
cess. In that sense it can be equated to the commercial product based
on the above-mentioned U.~. patent No. 3~912,808 in which a cationic
surfactant is employed in the neutrali~ing composition. In contrast,
in addition to not employing polydimethyldiallylammonillm chloride, the
present invention requires the presence specifically of an anionic
surfactant to form the conditioning precipitate in the presence of
hair. Furthermore, the present invention is not useful in connection
with strong alkali relaxer ccmpositions.
It has now been found that durable conditioning of hair can be
obtained in a hair waving or a hair straightening process that is
superior in its effects to conventional techniques and persists
through repeated shampooing which comprises treating said nair with an
;
aqueous waving composition containing an effective amount of reducing
ayent and the cationic polymer Clairquat-l,
defined in more detail
below, and then treating said hair with an aqueous neutralizing
composition containing an oxidi7ing agent and an anionio surfactantO
As a result o~ the sPquen~e of the initial reducing in the waving (or
straightening) and subsequent neutralizing steps and a unique
combination of ingredients, a conditioning complex, stable to repeated
snampooings, is formed in ~he hair.
It is accordingly an object of this invèntion to provide a pro-
cess for waving or straightening nair ~hich leaves tne hair in a con-
ditioned fashion which resists repeated shampooings.
It is also an object of the present invention to provide composi-
tions which are useful in carrying out the aforesaid process.
Other and more detailed o~jects of this invention will be appar-
ent from the following description and claimsO
In the following description and the claims, wherever possible~
reference is made to chemicals by their CTFA names as contained in the
Cosmetic Ingr~dient Dictionary of The Cosmetic, Toiletry and Fragrance
Association, Inc.
The cationic polymers that are useful for the purpose of the pre~
sent invention are from a few speci~io types. Molecular weights are
given on a weight average basisO A somewhat less preferred type is
polyquaternium-l, a polymeric quaternized dimethylbutenylammonilJm
chloride terminated with quaternized ethanolamine groups~ sold by Onyx
Chemicals Co. under the name Onamer M (hereinaft2r referred to as
"Onamer"), and said to have the formula:
_ ..
-CH2CH2 Cl CH3 Cl / C 2CH20H
2CH 7 N ~ CH2-CH = C~l-C~2 N - GH2 -CH = CH~CH - N ~ CH2CH2H
OH-CH2CH2 CH3 n CH2CH20H
* L rademarks
l~L9~85'7
wnere n is a cardinal number which is proportional to molecular
weignt and the molecular weight is between 800 and 5,000 suitably
between 1,000 and 3~500.
Proceeding to the more preferred cationic polymers9 another type
that can be employed in the present invention are polymers and
copolymers of quaternized polyvinylamine prepared in a manner known
se. These are believed to be constituted from repeating units of
the moiety:
CH2 - CH ~ ~__
R - 1~+ - R l
R3 X n
wnere ~1~ R2 and R3 are either the same or different radicals
and represent alkyl group having between 1 and 20 carbon atoms, and
X is a cosmetically acceptable anion such as halide (e.~O icdide
or chloride) sulfate or carboxylate and n is a cardinal number that
is p,roportional to molecular weight. The molecular weight is
suitaDly between 3,000 and 150,000. This polymer is reFerred to
hereinafter a "QPVAMINE". 8y way of example, mention can be made of
trimethyl polyvinyl ammonium sulfate which is believed to be
constituted of repeating units of
_
H2 ~ CH _ CH2 ~ ICH--
CH3-~+-CH3 CH3 - ~ -CH3
CH3 CH3
S04 L ~
having an average molecular weight of about 50,000.
Another type of useful cationic material is a polymer of quater-
nized poly-4-vinylpyridine which is prepared in a manner known
se. This can be described by the general ~ormula:
i~, !i
- 4
'7
_ CH2 ~ CH _ ~
~ X~
~ ~ n
where R is an alkyl radical having between 1 and 20 carbon atoms and
X is a cosmetically acceptable anion such as a halide, sulfate or
carboxyla-te. This a~so will have a molecular weight in the range of
from about 5,000 to aDGUt 50090~0~ This polymer is referred to
hereinafter as "QPVP".
As an example of the cationic polymer of this type, the follow-
ing can be mentioned:
rD
..r. r ~1
N
L CH3 ~ , n
polyvinyl methyl pyridinium iodide, e~g. having an average molecular
~eight of about 50,C00.
Another cationic polymer which was found to produce excellent
results in accord~nce with the present invention is poly (methacryl-
arnidopropyltrimethylammonium chloride) which is made by polymerizing
in a manner known ~ se the corresponding monomer sold by Texaco
Chemicals under the name MAPTAC. This po~mer is said to be cons-ti-
tuted of repea~ing units of the moiety.
~ .
CH3
-- C H2 11 .
T CONHCH2CH2CH2N = CH3 ¦
- 5 -
~ 7
.
where n is a number which is proportional to moleçular weight. The
molecular weight is advantageously between 5,000 and 500,000. This
polymer is ~ereafter referred to as Clairquat-l".
As mentioned abov ~ the particular cationic polymers described
are contained in the reducing lotion employed in the process. The
quantity of cationic polymer that will be present in the reducing
lotion can vary somewhat depending on the results that are desired.
Ordinarily, this will constitute between about 0.2~ to about 10~ by
weigh~ based on the total weight of the reducing lotion with the
optimal range bein~ Detween about l~o to about 5~ by weight ~hereof.
No structural or known physico-chemical features of cationic
po1ymers can be used to predict whether a cationic polymer can be
used in accordance with the present invention. Accordingly it was
found that a number of cationic polymers9 when suDstituted for those
~isclosed and claimed herein, will produce inadequate durable con-
ditioning of hairO Some of these cationic polymers that were found
to work insufficiently9 are:
quaternized poly-2-vinylpyridine
adipic acid/epoxypropyl diethylenetriamine copolymer (sold by
Hercules Chemical Co. under the name Uelsett*e 101);
adipic acid/dimethylaminohydroxypropyldiethylenetriamine copoly-
mer (sold by Sandoz, Inc. under the name Cartaretic F-4`);
poly (N-(3 dimethylamino)propyl)-~ (3-(ethyleneoxyethylene di-
methylamino)propyl) urea dichloride (sold under tne name Mirapol A15
oy Miranol Chelnical Co., Inc.~;
quaternium-23~ a quaternary ammonium polymer formed by the reac-
tion of dimethyl sulfate and a copolymer of vinyl pyrrolidone and
dimethylaminoethylmethacrylate (sold by GAF Corporation under the
narne Gafquat 755N );
quaternium-199 a polymer of hydroxyethyl cellulose r acted with
epichlorohydrin and then quaternized with trirnethylamine (sold by
Union Carbide Corp. under the name Polymer JR-40~);
a quaternary ammonium derivative of a hydrolyzed collagen pro-
tein (sold by Croda, Inc. under the name of Crotein Q),
quaternium-39~ a copolymer of acrylamide and beta-methacryloxy
ethyl trimethyl ammonium methosulfate (sold by Hercules Chemical Co.
under the name Reten 205 M~;
* Trademarks
- 6 --
9~5~
aminoethylacrylate phosphate/acrylate copolymer (sold by
National Starch CoO under the name Catrex~: and
quaternium-41 which isla copolymer of dimethyldiallylammonium
chloride with acrylamide (sold by Merck & CO., Inc. under the name
Merquat-~55).
In addition to the cationic polymer, the waving or reducing
lotion emp10yed in this invention can also contain vther convention-
al ingredients com~only employed in such waving lotion. ThuS, the
vehicle for the lotion is an aqueous vehicle which has incorporated
therein one or more reducing agents. A variety of reducing agents
are known in the prior art which are useful in waving or straighten-
ing hair. By way of example, we can mention thioglycollic acid,
cysteine? thiolactic acid, sodium-, potassium-, and ammonium sul-
fites and bisulfites, tris(hydroxyethyl phosphine). Although the
present invention can be employed with all waving and straightening
compositions, in the preferred form of this invention ~he reducing
agents that will be employed are thioglyco11ic acid and alkali metal
salts e.g. sodium salts of sulfurous acids (e.g. sulfites and bisul-
fites).
The quantity of reducing agent contained in the waving lotion
will also vary somewhat depending on the agent selected and the
results desired. Usually9 however, the waving lotion will contain
from about O.SX to about 20~ by weight of reducing agent based on
the total weight of the waving lotion. Optimal results are obtained
when the reducing agent comprises from about 2X to about 10% by
weight based on the total ~eight of the lotion. Tne term "effective
amount"9 as used throughout the specification and the claims with
respect to any ingredient of the composition, means an amount
effective to achieve the intended purpose~ Generally there is no
criticality in any given range of concentration and the invention
does not reside in any particular concentration, but rather in the
components themselves. The amount that is most effective can be
determined by routine experimentation~
In addition, the waving lotion can also contain fragrances,
alkalizing agents and other conventional waving lotion ingredients~
Most often the lotion has a p~ in the range of from about ~ to abou~
10.
* Trademarks
-- 7 --
~9~5~
The second essential component o~ the present conditioning sys-
tem are amphoteric or anionic detergents which will constitute part
of the neutraliziny lotion. There are a nurnber of amphoteric deter-
gents that are suitable for use in th~ present invention. However,
two classes of deteryents have Deen found to be especially effec-
tive. The firs~ class can be defined by the formula:
CH2COONa
2 _ C ~ CH2CH2CH2C
Il ~
N CH2
\ ~
CH2
in which R is a long ohain fatty radical containing from 10 to 18
carbon atoms. A typi~al exarnple of suoh a compound or compounds is
the case in which R represents coconut fatty radicals. A material
of this character is known as amphoteric-2 and is sold under the
trade name Miranol C2MSF~
A second variety o~ arnphoteric detergents that is particularly
effective for the purposes of the present invention can be defined
by the formula:
R _ NH _ CH~ CH2 _ ~OOH
wherein R is a long chain fatty alkyl group having from 10 to 18
carbon atoms. In an exarnple of such a detergent the R in the for~
mula is a mixture of lauryl and myristyl fatty alkyl groups. This
material is known ~s lauraminopropionic acid and is sold under the
trade name Deriphat 170C.
,j . .
Not all amphoteric surfactants werP found to be suitable. None
oP a number of betaines worked in accordance with the present inven-
tionO Since betaines are zwitterionic compoundsg it could be ex~
p~cted that some zwitterionic surfaetants ~ay not work as well"
although we found 7witterionic surfactants that are acceptable. As
used throughOUt the specification and the clai~ns, the term "ampho-
* Trademarks
teric surfactant product" denotes that the amphoteric surfactantwill work in accordance with the invention. Whe-ther any amphoteric
surfactant is an amphoteric surfactant product can be simply and
routinely determined by adding an aqueous solution of the surfactant
to an alkaline pH solution of one of the claimed cationic polymers
and if a precipitate is -formed; then the amphoteric surfactant is an
ampohteric surfactant product. Since amphoteric sur~actants become
anionic above their pKa value, the term "anionic sur~actant" as used
throughout the speci~ication and the claims~ encompasses both anionic
surfactants and amphoteric surfactant products.
All anionic detergents that were tested llave been found useful
in this invention; thus, salts of alkyl sulfonates, alkyl sulfates,
sulfonated and sulfated alkyl ethers as well as long chain carDoxyl-
ic acids (where the ch 2 in length is at least ClG) exhibit forma-
tion of conditioning complexes. By way of specifically illustrating
the anionic detergents that are useful herein, the following may be
mentioned: sodium lauryl sulfate, sodium lauryl ether sulfate, TEA
lauryl sulfate, sodium stearate, etc.
The quantity of amphoteric or anionic detergent which will be
contained in the neutralizing lotion of this invention will vary
somewhat again depending on the economics and the results sought.
However, usually this will be in the range of from about 0.2 to
about 50~0 by weight and ideally, in the range of from about 0.5~ to
about 20i~ by weight based on the total weight of the neutralizing
lotion.
The neutralizing lotion can also contain other ingredients
usually employed in such neutralizing lotions that are utilized in
hair waving or hair straightening procedures~ Again, the vehicle
will or~inarily be an aqueous vehicle which will contain an oxidiz-
ing agent that will serve to "neutralize" the action of the reducing
agent contained in the waving lotion after the latter has been ap
plied to the head. A number of oxidizing agents are known to those
skilled in this art which will accomplish this purpose. These
include hydrogen peroxide, sodiumand potassiumbromates, sodium per-
borate, etc.
_ g _
The quantity of oxidizing agent tha~ will be contained in the
neutralizing lotion can also vary somewhat; again, depending on the
agent selected and the results desired. For the most part, this
will comprise between about 0~2~ to about 20~o by weight of the neu~
trali~ing lotion based on the total weight of said neutralizing
lotion. In a preferred form oF the invention, the oxidizing agent
will constitute about 1~ to about 10~ by weight based on the total
weight of the neutralizing lotion.
In addition to the above, among the other ingredients that can
be contained in the neutralizing lotion. Mention can be made of
such materials as organic and inorganic acids (e.g. phosphoric,
citric acid, etc.). The pH of the neutralizing lotion will usually
be in the range of from about 2 to about 10, except when an ampho-
teric surfactant is employed in which case the pH would be more on
the basic side~
The term "anionic surfactant"~ as used throughout the specifica-
tion and the clailns, includes arnphoteric surfactant products when
the pH of the neutralizing composition is above the pKa value of the
amphoteric surfactant product~ since at such basic pH levels the
ampho-teric has anionic character.
Conveniently the compositions of the present invention can be
sold in a package containing two containers, one containing the wav-
ing lotion including at least one of the enumerated cationic poly-
rners and the reducing agent, and the other bottle containing the
reducing solution which contains the reducing agent and the anionic
surFactant.
The following specific examples are intended to illustrate more
fully the nature of the present invention without limiting its scope.
EXAMPLE 1
Waving Lotion - A hair waving lotion was prepared having the
fo1lowing composition:
-- 10 --
a~onium thioglycollate 7.0
monoethanolamine 3.5
fragrance 0.1
Clairquat-l 3.0
water to 100.0
Neutralizing Lotion This was prepared having the following
composition:
By Wt._
amonium lauryl sulfate 3.~
hydrogen peroxide 1.4
phosphoric acid 0.1
water to 100.0
In addition to the above samples, both the waving lotion and the
neutralizer have also been prepared without the cationic polymer and
the anionic detergent respectively.
Four sets of intact caucasian hair tresses were treated under
identical conclitions of time and temperature followed by rinsing and
neutralization. The tresses were wound on 1/2 inch rods and two of
them saturated with the waving lotion containing the polymer while
the other two were saturated with the waving lotion without that
cationic polymer. All tresses were then wrapped in Saran Wrap and
placed for 20 minutes in an over kept at 35C. After this time, the
waving lotion was rinsed off and the tresses, while still on rods,
were treated for 5 minutes with the neutralizing solutionsO The
neutralizing solution containing ammonium laur~yl sulfate was applied
to two waved tresses (one waved with and one without the polymer)
while the other two were exposed to the neutralizer in which there
was no ammonium lauryl sulfate present.
It was found that only in the case of the waved hair tress where
the waving solution employed contained the polymer and where the
neutralizer contained the anionic detergent~ was it soft9 lustrous
and conditioned. The effect was found to be durable by being resis-
tant to at l~ast four shampoos.
t~7
In Example 2 below, the embodiments of the invention are direct-
ly compared with the products available now on the market. In one
of the products (Product Ij a cdtionic polymer i.e. a high molecular
weight polydimethyldiallyammonium chloride is presen~ in the WdYin9
solution and a cationic conditioner is used in the neutralizing
step, the product being sold under the trade name Toni Lightwave and
made in accordance with U.S. patent No. 37912.808. The other
product, Product II7 contains no polymer in the waving lotion but
claims that a conditioner is present in the neutralizing solution.
EXAMPLE 2
Waving Lotion - A hair waving lotion was prepared having the
following composition:
Bx Wt.
al~onium sulfite 3.0
sodium sulfite 2.0
onamer 5.0
cysteine HCl o.~
water to 100.0
Neutralizing Lotion -- This was prepared having the following
composition:
By Wt._
so~ium bromate 6.0
amonium laureth sulfate 6.0
preservative 0.1
fragrance Ool
water to 100.0
The procedures utilized for each product are briefly described
as follows:
Product I Procedure:
Clean (shampooed), damp tresses are wound on rods, using end
papers. The activator and sta~ilizer of Product I are poured into
the shaping lotion, After shaking well for 30 seconds~ the lotion
* Trademark
-- 12 --
'7
is applied to the pre-wrapped tresses until the hair is well s~tur~
ated. The tresses are then placed in a 35 oven fo~ 35 minutes.
Tresses are rinsed under tap water for 2 minutes. After the rinse,
hair is removed from the rods and treated with Product I conditioner
(optional step), working it well into the hair. After 1 minute9 the
hair is thoroughly rinsed.
Product II Procedure-
Waving lotion applied to clean (shampooed), damp tresses, and
wound on rods, using end papers. Hair resaturated with lotion,
wrapped in plastic wrap and placed in 35 oven for 1 hour. Tress
then rinsed under tap ~ater for 3 minutes. Excess water blotted
with paper towel and tress saturated with neutralizer. After 10
minutes at 3~, tress removed from rod9 neutralizer worked through
the hair, and hair then rinsed thoroughly. Hair combed and hung to
air dry.
Procedure for Present Invention:
. _
The procedure was as that descri~ed above in connection with
Proouct II up to after the water rinse but for 2 minutes after 1
hour treatment. After rinse, hair was removed from rod and treated
with 1 cc. of the broma$e neu-tralizer, the latter was worked into a
la-ther and left on hair for 5 minutes9 followed by thorough rinsing.
Each of the above procedures was per-Formed on six tresses of
both virgin and three-times dyed tresses.
The waved tresses were evaluated -For wet and dry combability
utilizing the technique for these measurements as described by
Garcia and Diaz (J. Soc. Cosmet. Chem. 27, 379, 1976). The test
essentially involves passing of hair tress through a comb attached
to a strain gauge which in turn is connected to a recording device.
Work is expended to accomplish the passage of the hair tress through
the comb, and this work, read off the integrator9 is the objective
measure of combing ease/difficulty~ The greater the values, the
harder it is to comb the hair and thus the less conditioned the hair
is, The data for both virgin and dyed hair tresses are given in
Table I.
- 13 -
TA~LE I
Wet and Dry Combability of Waved Hair
Work of Combing (gcm)
Virgin Hair Dyed Hair
Product Wet Dry Wet _ Dr~
Control 337 277 2567 3606
(no waving)
Product I 363 225 1979 2392
Product II 682 273 3060 1392
Present Invention 142 217 260 361
There was no significant change in conditioning ranking of these
products after as many as six repeated applications.
Although -the invention has been described with reference to
specific forms thereof9 it will be understood that many changes and
modifications rnay be made without departing from the spirit of this
invention.
- 14 -
