U.S. patent number 3,912,808 [Application Number 05/267,664] was granted by the patent office on 1975-10-14 for hair waving and straightening process and composition containing water-soluble amino and quaternary ammonium polymers.
This patent grant is currently assigned to The Gillette Company. Invention is credited to Phillip E. Sokol.
United States Patent |
3,912,808 |
Sokol |
October 14, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Hair waving and straightening process and composition containing
water-soluble amino and quaternary ammonium polymers
Abstract
A composition and process for waving or straightening hair by
applying to it an aqueous solution of (1) a reducing agent capable
of reducing the disulfide linkages in hair keratin and (2) a water
soluble secondary or tertiary amine polymer or a polymer of
diallylamine or a quaternary polymer of diallyldialkylammonium
salts.
Inventors: |
Sokol; Phillip E. (Chicago,
IL) |
Assignee: |
The Gillette Company (Boston,
MA)
|
Family
ID: |
26685800 |
Appl.
No.: |
05/267,664 |
Filed: |
June 29, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
14205 |
Feb 25, 1970 |
|
|
|
|
Current U.S.
Class: |
424/70.2; 8/405;
8/426; 424/DIG.2; 424/62; 8/127.51; 8/406; 424/DIG.1;
424/70.17 |
Current CPC
Class: |
A61Q
5/06 (20130101); A61Q 5/12 (20130101); A61Q
5/10 (20130101); A61Q 5/02 (20130101); A61Q
19/10 (20130101); A61K 8/817 (20130101); A61Q
9/02 (20130101); A61Q 5/04 (20130101); C07D
211/14 (20130101); Y10S 424/01 (20130101); Y10S
424/02 (20130101); A61K 2800/5426 (20130101) |
Current International
Class: |
A61K
8/72 (20060101); A61K 8/81 (20060101); C07D
211/14 (20060101); C07D 211/00 (20060101); A61Q
5/02 (20060101); A61Q 19/10 (20060101); A61Q
5/04 (20060101); A61Q 9/02 (20060101); A61Q
5/10 (20060101); A61Q 5/06 (20060101); A61Q
5/12 (20060101); A61K 007/09 () |
Field of
Search: |
;424/47,71,72,78,DIG.1,DIG.2 ;260/8.3N,88.3,89.7N ;8/127.51 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Meyers; Albert T.
Assistant Examiner: Clarke; Vera C.
Parent Case Text
This application is a continuation-in-part of application Ser. No.
14,205 filed Feb. 25, 1970, now abandoned.
Claims
What is claimed is:
1. A composition for waving or straightening hair containing an
aqueous solution of (1) a reducing agent capable of reducing the
disulfide linkages in hair keratin and of (2) a water soluble
polymer having a molecular weight from 20,000 to 3,000,000 and
having a molecular chain containing units selected from the group
consisting of ##EQU4## wherein R is hydrogen or methyl; R' is
hydrogen, alkyl having one to 22 carbon atoms, lower hydroxyalkyl
having from one to five carbon atoms, or lower alkyl containing a
terminal amido group; and A and B are independently alkyl having
from one to 22 carbon atoms, lower hydroxyalkyl, or lower alkyl
containing terminal amido, or wherein A and B taken together with N
are piperidinyl or morpholinyl, the amount of said reducing agent
being from 0.5 to 10% by weight of the total aqueous composition
and the amount of said polymer being from 0.05% to 40% by weight of
the total aqueous composition.
2. The composition as claimed in claim 1 in which the polymer is
polydiallyldiethylammonium chloride.
3. The composition as claimed in claim 1 in which A and B are both
methyl.
4. The composition as claimed in claim 1 in which A and B are both
ethyl.
5. The composition as claimed in claim 1 in which the polymer
contains in addition up to 95% by weight of the total of units
selected from the group consisting of ##EQU5##
6. The composition as claimed in claim 5 in which A and B are both
methyl groups.
7. A process of waving or straightening hair which comprises
applying thereto an effective amount of a composition containing an
aqueous solution of (1) a reducing agent capable of reducing the
disulfide linkages in hair keratin and of (2) a water soluble
polymer having a molecular weight from 20,000 to 3,000,000 and
having a molecular chain containing units selected from the group
consisting of ##EQU6## wherein R is hydrogen or methyl; R' is
hydrogen, alkyl having one to 22 carbon atoms, lower hydroxyalkyl
having from one to five carbon atoms, or lower alkyl containing a
terminal amido group; and A and B are independently alkyl having
from one to 22 carbon atoms, lower hydroxyalkyl, or lower alkyl
containing terminal amido, or wherein A and B taken together with N
are piperidinyl or morpholinyl, the amount of said reducing agent
being from 0.5 to 10% by weight of the total aqueous composition
and the amount of said polymer being from 0.05% to 40% by weight of
the total aqueous composition.
Description
This invention relates to hair treating compositions for bleaching,
waving or straightening, or coloring or dyeing hair and more
specifically to such compositions containing high molecular weight
water soluble polymers having a multiplicity of amino or of
quaternary salt groups.
Modern day living results in exposure of individuals to increasing
amounts of sunlight, chlorine water, harsh detergents and chemical
specialty products. Because of this, hair treating products must be
capable of leaving the hair with luster and softness while
overcoming natural or induced harshness and dryness. This is in
addition to a product's primary purpose whether it be to impart or
maintain a hair style or to alter the natural color of the hair.
There is, in each case, the corollary requirement that the hair be
left with an improved appearance and feel. In those types of
products where the hair is subjected to chemical reaction, it is
important that the cosmetic be capable of restoring the hair as
nearly as possible to its original state in relation to the feel of
the hair, and frequently by its ease of combing.
There have been in the past several means of achieving this end.
One of the simplest means of doing so has been to dissolve a
conditioning material in a suitable solvent or vehicle. In some
cosmetic forms, after application, the evaporation of solvent
deposits the conditioning material. This method has been useful in
the deposition of natural gums, certain of the synthetic polymers,
and a few protein derivatives. A shortcoming of such systems, when
aqueous, is that any such material that can be dissolved in water
is equally subject to subsequent removal by simple washing. Water
insoluble materials deposited on hair from organic solvent, while
more resistant to water removal, require that the hair be subjected
to the reaction of organic solvent materials capable themselves of
extracting natural constituents of hair. Non-aqueous oleaginous
mixtures have sometimes been used to deposit coatings of
conditioning materials on hair. The standard hot oil treatment for
hair and some hair grooms are representative. Such oil coatings,
however, whether of mineral, animal or vegetable origin, are
generally too greasy to satisfy modern tastes. Application of
conditioning materials to hair from emulsion systems is often
practiced enabling many materials to be used which would otherwise
be difficult to apply. As in the previously indicated case of
application from aqueous solvent systems, the deposited film is
generally easily removable by simple water washing, the original
emulsifying materials present in the composition also remaining
behind to reduce the binding potential of the conditioning material
to hair.
One of the more interesting and most widely used means for
overcoming a harsh feeling in human hair is by the deposition of
cationic materials which are absorbed by the protein structure of
the substrate. Especially useful have been the cationic fatty
quaternary compounds having fatty chain lengths of approximately
eight to 18 carbon atoms. These materials which form the basis of
many of the conditioning hair rinse products found on the market,
though substantive to skin and hair, cannot withstand, to any
substantial extent, the action of most detergent materials used for
personal cleansing. While these materials are an improvement over
the older modes of conditioning described above, they can soften
the hair excessively leaving it unmanageable and with a lack of
body. It has not generally been found helpful to simply reduce the
concentration of the quaternary material since to do so would
reduce the combing benefits and/or conditioning properties imparted
by such products to the hair. Furthermore, because many of the most
widely used products for treating hair contain anionic surfactants
and because cationic materials are usually inactivated by reaction
with anionic surfactants, it is customary to employ cationic
materials only as a separate composition such as a post shampoo
rinse separately applied. There has been disclosed another means of
depositing conditioning materials on hair. U.S. Pat. No. 3,313,734
and Canadian Pat. No. 762,893 describe cosmetic compositions
containing certain polymers having cationic sites. The compositions
yield a fine precipitate of the polymer components upon dilution
with water. This precipitate adheres to the surface of the hair
shaft, thereby altering surface properties of the hair fibers. This
effect, as described in the above patents, is limited however to
shampoo compositions and produces in many instances an undesirably
heavy deposit of material which leaves the hair feeling coated and
unclean.
It has now been discovered that the surface characteristics of hair
can be modified and its condition improved by applying thereto a
composition containing certain water soluble polymers containing
secondary and tertiary amino or quaternary ammonium groups. These
polymers are incorporated in the hair treating composition itself
instead of being used in the form of separate solutions separately
applied. The hair treating composition in each case includes in
addition to water and the water-soluble polymer (as defined below)
a coloring agent, i.e., a hair dye or hair dye precursor; or a hair
waving or straightening agent such as a reducing agent capable of
breaking the disulfide linkages in hair keratin; or a peroxide such
as hydrogen peroxide in the case of hair bleaching compositions or
neutralizing compositions (for use in conjunction with waving or
straightening compositions). Also present in the case of the hair
coloring and hair bleaching compositions are a surface active agent
such as a soap or detergent and sufficient water miscible aliphatic
hydroxylated solvent (or a mixture of such solvent with a
water-soluble salt inert to the ingredients and to hair) to
maintain the composition homogeneous, i.e., in a single phase.
The polymers are equally effective when an anionic surface active
agent such as soap, etc. is present as when only cationic,
nonionic, or ampholytic agents are present despite the fact that
ionic interaction would be expected to lead to the formation of an
inactive and insoluble catan wax. The polymer can be used
effectively in amounts ranging upwardly from 0.05% by weight of the
total composition. There is no critical upper limit to the amount
of polymer which may be present, and amounts as great as 40% by
weight of the composition or even more may be used, particularly
when application of the composition to the hair is followed by a
water rinse. If the composition is supplied in such concentrated
form, however, it is generally desirable to dilute it with water to
a polymer content of 0.5 to 15% by weight before use. The
compositions in which the polymers may be effectively employed may
vary widely in acid or base content, having a pH, when in water,
from 1.5 to 11.5. The polymers are effective to alter the surface
characteristics of the hair and maintain the desired conditioned
effect even though the application of the composition is followed,
intentionally or unintentionally, by a water rinse. Indeed, the
conditioning effect produced by incorporating these polymers in a
hair treating composition is remarkably durable, persisting in many
cases through several successive rinses and even through successive
washings with a conventional detergent or shampoo composition. This
is true even in the case of hair coloring and hair bleaching
compositions which contain soap or detergent which in itself would
be expected to remove the polymer even if no shampoo were
subsequently used.
In the hair coloring compositions of the present invention the
coloring agents may be any of the known acidic, basic, or disperse
dyes or oxidation dye intermediates; they may be present in any
effective amount ranging from 0.03 to 10% by weight of the total
composition, depending on the type of dye and the desired color
result, as is well known to those skilled in the art. When the
coloring agent is an oxidative dye intermediate, it is usually
desirable to mix with the composition before applying it to the
hair an oxidizing agent such as hydrogen peroxide, sodium peroxide,
urea hydrogen peroxide or the like, in accordance with conventional
practice, in an amount effective to develop the desired color.
The hair bleaching compositions contain in aqueous solution an
oxidizing agent such as hydrogen peroxide or urea hydrogen peroxide
together with conventional stabilizers such as phenacetin and/or
sodium stannate together, if desired, with a suitable conventional
buffer to maintain the pH at the desired level of 2.5 to 6.5. The
amount of oxidizing agent, in accordance with conventional
practice, may be from 0.5 to 20% by weight of the total
composition.
The hair waving and straightening compositions of the present
invention contain aqueous solutions of reducing agents capable of
reducing the disulfide linkages in hair keratin, of which many are
well known such as water soluble mercaptans e.g. sodium or ammonium
thioglycolate, magnesium thioglycolate, thioglycerol, sodium or
potassium borohydride, sodium or ammonium sulfite, etc. The amount
of such reducing agent, as is well known, may be from 0.5 to 10% by
weight of the total composition. A variety of conventional
additives for such compositions may also be present.
The neutralizer compositions of the present invention, which are
used for applying to the waved or straightened hair to restore the
disulfide linkages in the hair keratin, contain in aqueous solution
any of the oxidizing agents conventionally employed for this
purpose, such as hydrogen peroxide, urea hydrogen peroxide, sodium
carbonate peroxide, sodium or potassium bromate, sodium perborate,
or sodium hypochlorite; the neutralizer compositions used with
sulfite waving or straightening composition may contain simply
sodium sesquicarbonate instead of an oxidizing agent.
The surface active agent present as an essential ingredient of the
hair coloring or hair bleaching composition may be a soap, i.e., an
alkali metal, ammonium or amine salt of a long chain aliphatic
acid, particularly a fatty acid, such as the sodium, potassium,
lithium or ammonium salts or the salts of such amines as mono-,
di-, or tri-ethanolamine, 2-amino-1-butanol,
2-amino-2-methyl-1-propanol, diethylamine, mono- and
diisopropanolamine, polyglycolamine, N-ethylmorpholine with such
acids as capric, undecylic, lauric, myristic, palmitic, stearic,
oleic, linoleic, ricinoleic, dimer or trimer acids produced by
polymerization of C.sub.18 fatty acids, hydrogenerated rosin acids,
lanolin acids, phenylstearic acid, coconut fatty acids, tallow
fatty acids, or castor fatty acids including hydroxyricinoleic acid
and the like. The surface active agent may also be an anionic
material such as sodium di-(2-ethylhexyl) phosphate, dioctyl sodium
sulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl
sulfate, or disodium ethoxylated alcohol half ester of
sulfosuccinic acid. Cationic surface active agents can also be
used, such as stearyldimethylbenzylammonium chloride, stearic
aminoamide, dimethyldialkylammonium chlorides in which each alkyl
group has from eight to 18 carbon atoms, polyethoxylated quaternary
ammonium salts, amidoamine oxide derivative of lauric acid, or
cetylpyridinium chloride. Among nonionic surface active agents
which can be used are various condensates of alkylene oxides, e.g.
ethylene oxide or propylene oxide with other molecules, each
condensate molecule containing from five to 500 alkylene oxide
units, such as octylphenoxypolyethoxyethanol, condensates of
ethylene oxide with hydrophobic bases formed by condensing
propylene oxide with propylene glycol, mono- and diglycerides of
long chain fatty acids, sorbitan esters of long chain fatty acids,
polyoxyethylene sorbitan monolaurate, monopalmitate or
monostearate, polyoxyethylene lauryl ether, polyoxyethylene stearyl
ether, lauric diethanolamide, dimethyloctadecylamine oxide,
nonylphenylpolyethylene glycol ether, ethylene oxide condensates
with long chain fatty amides, acetylated lanolin alcohols, or
coconut fatty acid alkanolamides. Amphoteric surface active agents
useful in the compositions of the present invention include
imidazoline derivatives made by condensing polyamines with long
chain fatty acids including lauric, capric, oleic and stearic sold
under the trade name Miranol in the form of various salts such as
the potassium, sodium, mono-, di-, or triethanolamine or
isopropanolamine salts, N-coco-beta-aminopropionic acid or its
sodium salt, disodium N-lauryl-beta-iminodipropionate,
N-lauryl/myristyl-beta-aminopropionic acid, or a complex
polyalkylamido imidazolinium sulfate sold under the trade name
Soromine CAZ-75. Any of these surface active agents may be present
as an optional ingredient in the hair waving or straightening
compositions or neutralizing compositions of the present invention.
The surface active agents can be used in amounts from 0.1 to 50% by
weight of the total composition, preferably from 0.3 to 25% by
weight.
When a surface active agent is present in any of the compositions,
there must also be present sufficient water miscible hydroxylated
organic primarily aliphatic solvent, or a mixture of such solvent
with inert water-soluble salt, to solubilize all of the
ingredients. Among suitable solvents are ethanol, isopropanol,
benzyl alcohol, hexylene glycol, hexanol, 2-methylpentanol,
2-ethylbutanol, diethylene glycol, tetraethylene glycol, propylene
glycol, 1,5-pentanediol, polyethylene glycol, glycol ethers such as
2-ethoxyethanol, 2-phenoxyethanol, monoethylether of diethylene
glycol, monobutyl ether of diethylene glycol, monobutyl ether of
diethylene glycol, monobutyl ether of 1,2-propanediol, monomethyl
ether of dipropylene glycol, or 1-butoxyethoxy-2-propanol. The
minimum amount of such solvent needed to ensure homogeneity will
vary depending upon the identity and quantity of other ingredients
present but in general may range from 1 to 90% by weight of the
total composition.
The water soluble salts which can be used in conjunction with the
hydroxyl-containing solvent to increase its effectiveness include
those which are chemically inert to the remaining ingredients of
the composition as well as to the hair such as the sodium,
potassium, lithium, ammonium or lower alkanolamine chlorides,
bromides, sulfates, or acetates. They can be used in amounts from
0.01 to 15% by weight of the total composition, preferably from
0.05 to 5% by weight.
The polymers useful in the present invention are high molecular
weight water-soluble amino and quaternary ammonium homopolymers and
copolymers having as constituents of the chain or backbone of the
polymer molecule (apart from end groups which terminate each such
chain and which have no important effect upon the properties and
characteristics of the polymer) units of the following formulas:
##EQU1## where R is hydrogen or methyl; R' is hydrogen, or an alkyl
group having one to 22 carbon atoms, or a lower hydroxyalkyl group
having from one to five carbon atoms, or a lower alkyl group
containing a terminal amido group such as beta-propionamido; and
wherein A and B are independently (i.e., either both the same or
different) alkyl groups having one to 22 carbon atoms, lower
hydroxyalkyl groups having from one to five carbon atoms, and lower
alkyl groups containing terminal amido groups such as
beta-propionamido; and wherein A and B together with N are
piperidinyl or morpholinyl groups. Salts of Polymer I such as the
hydrochloride, hydrobromide or sulfate are the full equivalent of
Polymer I. In the case of both the polymer of Formula I and the
polymer of Formula II the preferred homopolymers and copolymers are
those in which R is hydrogen; and in the case of the polymer of
Formula II the preferred homopolymers and copolymers are those in
which A and B are independently lower alkyl groups having from 1 to
5 carbon atoms or in which A and B form together with nitrogen atom
a piperidinium or a morpholinium group. These linear homopolymers
and copolymers have a molecular weight from about 20,000 to
3,000,000. In the case of homopolymers, all of the units in the
polymer chain are identical, while in the case of copolymers, the
units, while having the structure defined above, are not all
identical to each other and in addition, may contain the structures
of acrylamide or diacetone acrylamide as described below. Any of a
wide variety of nontoxic or cosmetically acceptable anions, organic
as well as inorganic, may be present in the polymer and associated
with the quaternary ammonium cationic groups, among which are, for
example, acetate, borate, bromide, chloride, citrate, tartrate,
bisulfate, bisulfite, sulfate, phosphate, and succinate. The
homopolymers and copolymers of Formulaa I can be prepared as
described in Butler et al U.S. Pat. No. 2,926,161 by polymerizing
the appropriate diallylamine or amine salt. The homopolymers and
copolymers of Formula II can be made by polymerizing
diallyldialkylammonium chloride or bromide or other appropriate
diallyl monomeric ammonium salts using a free radical generating
polymerization catalyst such as a peroxide, then using an anion
exchange column technique for exchanging the anion, if desired, and
are described in U.S. Pat. Nos. 3,288,770 and 3,412,019. If a
polymer of a chloride is dissolved in an aqueous solution or in a
cosmetic base containing salts of any other anions, of course, the
resulting solution contains both anions, each being associated to
some extent with the quaternary ammonium groups of the polymer.
Other monomers which can be copolymerized with diallylamine or with
the desired diallylammonium salt to form copolymers containing
units of Formula I or II include acrylamide and diacetone
acrylamide. The polymer units derived from acrylamide have the
structure ##EQU2## while those derived from diacetone acrylamide
have the structure ##EQU3## The amount of these acrylamide-type
monomers incorporated in the copolymer may vary from 5% to 95% by
weight of the total monomers; The copolymers can be made by
subjecting the mixture of monomers to the same polymerization
conditions as used in making the homopolymers. It generally makes
no difference, so far as the present invention is concerned,
whether the polymer or copolymer containing a particular desired
anion or combination of anions is prepared in pure form before
being mixed with the hair treating composition or whether the
desired anions are introduced into the composition in the form of
other salts. It is usually most convenient to employ the least
expensive salt of the polymer which is readily available,
regardless of the anion which it contains, and add the desired
anions in the form of other less expensive salts. Hair treating
compositions, as is well known, contain any of a wide variety of
non-toxic anions, numerous examples of which are given herein.
Particularly preferred is a polymer of a diallyldimethylammonium
salt, that is, a polymer having repeating units of the formula
given above where A and B are both methyl groups, all of the units
being identical.
The following specific examples are intended to illustrate more
fully the nature of the present invention without acting as a
limitation upon its scope.
EXAMPLE 1
A conventional hair straightening lotion base was prepared having
the following compositions:
Ingredient Weight Percent ______________________________________
Ammonium bisulfite 10.0 Urea 15.0 Isopropanol 4.0
Hydroxyethylcellulose 1.0 Ammonium hydroxide to pH 7.1 Water to
100.0 ______________________________________
To one portion of the lotion was added 0.5% by weight of a polymer
of diallyldimethylammonium chloride in the form of a 40% by weight
aqueous solution having a viscosity of about 12,500 centipoises.
Samples of the lotion with and without the added polymer were then
employed to treat separate heads of hair under identical
conditions, viz. application to clean hair and allowing to stand 20
minutes covered with a turban, application of additional lotion and
allowing to stand for another 20 minute period covered with a
turban, rinsing with water, applying a neutralizer a 4.5% aqueous
solution of sodium sesquicarbonate dihydrate, and finally rinsing
with water. It was found that the hair treated with the
polymer-containing lotion was soft, lustrous and easy to comb both
wet and dry as contrasted to the harsh feeling, difficult-to-comb
hair resulting from the other lotion. The difference was still
apparent after 4 weeks and several intervening shampoos. When as
little as 0.05% of the polymer or as much as 2.0% were used, the
results were very similar.
It has been found that the presence of relatively large quantities
of inorganic salts commonly employed in cosmetic bases, such as
sodium carbonate, sodium sulfate, sodium phosphate, or sodium
tripolyphosphate has little or no effect upon the conditioning
properties of a 10% by weight aqueous solution of a polymer of
diallyl dimethyl ammonium chloride which has, in the form of a 40%
by weight aqueous solution, a viscosity of 5,000cps. higher
molecular weight polymer of the same species which exhibited a
viscosity of 130,000 cps. in 40% aqueous solution.
EXAMPLE 2
Results similar to those obtained in Example 1 were obtained by
dissolving 2% by weight of the same polymer in the neutralizer
solution instead of mixing polymer with the straightening
lotion.
EXAMPLE 3
A hair waving lotion base was prepared having the following
composition:
Ingredient Weight Percent ______________________________________
Ammonium thioglycolate 7.8 Diisopropanolamine 6.7
Polyoxyethylene(25)oxypropylene(5) monostearate 0.5 Perfume 0.125
Water to 100.0 ______________________________________
To one portion of the lotion was added 0.5% by weight of the
polymer used in Example 1. Samples of the lotion with and without
the added polymer were then employed to treat separate heads of
hair under identical conditions, viz. application of the lotion to
hair previously shampooed, winding of the hair on curlers,
application of additional lotion to the hair and allowing to stand
for 15 minutes, rinsing with water and allowing to stand covered
with a turban for 30 minutes. A neutralizer consisting of an
aqueous solution containing 1.2% hydrogen peroxide and 0.05% of
stearyl dimethyl benzyl ammonium chloride was then applied to the
hair on the curlers, the hair was removed from the curlers and the
neutralizer again applied. The hair waved with the lotion
containing the polymer was soft, lustrous, and easy to comb both
wet and dry in contrast to the hair waved with the other lotion
which was harsh, difficult to comb, and readily tangled. The marked
difference in conditioning or surface characteristics of the hair
persisted even after both heads had been subjected to six
successive shampoos.
Similar results were obtained by dissolving the polymer in the
neutralizer instead of in the lotion, as in Example 2.
EXAMPLE 4
A hair bleaching base composition containing the polymer of Example
1 was prepared by mixing 1 volume of composition A and 2 volumes of
solution B with 10 volumes of 6% aqueous hydrogen peroxide
solution, as follows:
Composition A Ingredient Weight Percent
______________________________________ Ammonium Persulfate 80.0
Sodium Silicate 15.0 Sodium Lauryl Sulfate 5.0 100.0 Solution B
Ingredient Weight Percent ______________________________________
Oleic acid 35.0 Ammonium hydroxide (29%) 11.0 Isopropanol 15.0
Polymer of Example 1 4.0 Octylphenoxypolyethoxy(9-10) 15.0 ethanol
Water 20.0 100.0 ______________________________________
The composition was applied to hair and allowed to stand for
periods of time from 30 to 90 minutes depending upon the extent of
bleaching desired. After rinsing and shampooing the hair displayed
the same superior condition as was observed in the hair of the
preceding examples, in contrast to the undesirable condition of
hair bleached with a similar composition omitting the polymer.
EXAMPLE 5
A hair dyeing base composition containing the polymer of Example 1
was prepared by mixing 6% aqueous hydrogen peroxide with an equal
volume of the following solution:
Ingredient Weight Percent ______________________________________
Oleic acid 20.0 Ammonium hydroxide (29%) 7.6
Octylphenoxypolyethoxy(9-10) ethanol 20.0 Isopropanol 18.0 Polymer
of Example 1 5.0 Ethylenediaminetetraacetic acid 0.05 Sodium
Sulfite 0.05 p-Phenylenediamine 0.1 Resorcinol 0.02 Water to 100.0
______________________________________
The composition was applied to the hair, allowed to stand about 20
minutes, rinsed with water and shampooed. The condition of the hair
was markedly superior to that of hair treated with the same
composition omitting the polymer, the differences being similar to
those of the preceding examples.
EXAMPLE 6
An oxidative hair dyeing base composition containing our polymer
was prepared by mixing 6% aqueous hydrogen peroxide with an equal
volume of the following solution:
Ingredient Weight Percent ______________________________________
Oleic acid 20.0 Ammonium hydroxide (29%) 7.6
Octylphenoxypolyethoxy(9-10) ethanol 20.0 Isopropanol 18.0 Polymer
of Example 1 5.0 Ethylenediaminetetraacetic acid 0.05 Sodium
sulfite 0.05 p-Phenylenediamine 0.1 Resorcinol 0.02 Water to 100.0
______________________________________
The composition was applied to the hair, allowed to stand about 20
minutes at room temperature, rinsed with water and shampooed. The
hair was dyed a light ash blonde color. In order to ascertain the
presence of the conditioning effect, the following test is
performed. Tresses are prepared using hair that has been bleached
and waved. This type of hair is difficult to comb either wet or dry
and represents a realistic standard for the evaluation of
conditioning treatments. An untreated tress is marked as a control
and is evaluated both for wet and dry combing properties. A number
of tresses from the same hair lot (to eliminate variations from lot
to lot) are then subjected to the hair treating composition to be
tested. The evaluations are made by a panel of cosmetic scientists
or beauty operators. The tresses are combed and ranked on a 1 to 5
scale, where 1 is the poorest and 5 is the best. The change in
rating from the control value is an indication of the effectiveness
of the conditioning treatment. Persistence of high ratings after a
series of shampoos indicates the continued existence of
conditioning on the tress. The ratings reported in the following
examples are based on the above scale and are for wet combings
unless specified otherwise. The condition of the hair treated with
the composition of this Example 6 was markedly superior (rating 4)
compared to that of hair treated with the same composition omitting
the polymer (rating 2).
EXAMPLE 7
An aerosol oxidative hair dyeing composition was prepared to be
used in a two compartment aerosol container described in U.S. Pat.
No. 3,241,722:
Ingredient Weight Percent ______________________________________
Oleic acid 8.7 Monoethanolamine 5.0
Octylphenoxypolyethoxy(9-10)ethanol 6.0 Isopropanol 25.0
Ethylenediaminetetraacetic acid 0.05 Sodium Sulfite 0.05 Polymer of
Example 1 1.0 Sodium Chloride 1.0 p-Phenylenediamine 0.1 Resorcinol
0.05 Water to 100.0 ______________________________________
To 93 grams of the above composition was added 9.3 grams of 50/50
blend of propellants dichlorodifluoromethane and
dichlorotetrafluoroethane. About 27 grams of a 16% aqueous hydrogen
peroxide solution was placed in the inner compartment while the
other composition together with the propellant mixture was placed
in the outer compartment. Tresses dyed for 20 minutes at room
temperature with this composition were a medium ash blonde. The
condition of the tresses was excellent and persisted through at
least four shampoos.
EXAMPLE 8
An aerosol oxidative hair dyeing composition was prepared and
employed in the two compartment container described in U.S. Pat.
No. 3,241,722. To 93 grams of the composition described below was
added 9.3 grams of a 50/50 blend of propellants as described in
Example 7 and placed in the outer portion of the container.
______________________________________ Ingredient Weight Percent
______________________________________ Oleic acid 8.7
Monoethanolamine 6.7 Isopropanol 20.4
Octylphenoxypolyethoxy(9-10)ethanol 0.4 Polymer of Example 1 0.5
p-Phenylenediamine 0.5 Resorcinol 0.3 2,4-diaminoanisole 0.05
p-aminophenol 0.3 Water - q.s. 100.0
______________________________________
27 grams of 6.15% aqueous hydrogen peroxide was placed in the inner
container. The above creamy composition was applied to blonde hair
tresses, allowed to remain for 20 minutes at room temperature and
rinsed. The tresses were dyed a dark ash brown. Conditioning was
evaluated after shampooing and rated as 4.0.
EXAMPLE 9
An oxidative hair toning composition was prepared according to the
following recipe and mixed with an equal weight of 6% aqueous
hydrogen peroxide.
______________________________________ Ingredient Weight Percent
______________________________________ Triethanolamine 7.0
Isopropanol 16.0 Polymer of Example 1 2.0 Polyoxyethylene(2)oleyl
ether 18.0 Polyoxyethylene(10)oleyl ether 2.0
Ethylenoxide(12)condensate of a C-18 fatty amine 10.0 Sodium Oleate
5.0 p-Phenylenediamine 0.25 Resorcinol 0.05 Water to 100.0
______________________________________
After 20 minutes contact at room temperature with blonde hair
followed by rinsing and shampooing, the tress was toned a medium
ash blonde. A combing evaluation rated the hair 3.5. A control
without the polymer was rated 2.2. After two weeks, the original
tress was again shampooed and evaluated and was rated at 3.2.
EXAMPLE 10
An aerosol oxidative hair dyeing composition was prepared and
employed in the two compartment container described in U.S. Pat.
No. 3,241,722. To 93 grams of the composition described below was
added 9.5 grams of a 50/50 mixture of propellants as described in
Example 7; the mix was placed in the outer portion of the
container. 27 grams of aqueous hydrogen peroxide (6%) was placed in
the inner container.
______________________________________ Ingredient Weight Percent
______________________________________ Oleic Acid 17.4
Octylphenoxypolyethoxy(9-10)ethanol 2.0 Isopropanol 15.0
Monoethanolamine 6.9 Polymer of Example 1 0.6 p-Phenylenediamine
0.06 Resorcinol 0.06 Water q.s. to 100.0
______________________________________
Blonde hair tresses were treated with the creamy composition
discharged from the container, being left in contact with it at
room temperature for 25 minutes, rinsed and shampooed. The hair was
dyed to a light ash blonde. The tresses were combed and rated 4.5.
A similar composition without the polymer produced a rating of 2.0
on similarly treated tresses.
EXAMPLE 11
A permanent hair color was prepared using oxidation dye
intermediates without hydrogen peroxide:
Ingredient Weight Percent ______________________________________
Polydiallyldiethylammonium Chloride 3.0 Hexylene Glycol 10.0 Sodium
Chloride 1.0 Sodium Coco-N-methyltauride 5.0 p-Phenylenediamine 3.0
p-Aminophenol 1.0 Resorcinol 0.5 Water q.s. to 100.0
______________________________________
The two phase product was shaken before use and applied to blonde
tresses for 15 minutes. The hair was rinsed and found to be dyed an
ashen light brown. After two shampoos the combing rating was still
4.5.
EXAMPLE 12
A disperse dye composition for dyeing human hair was prepared and
evaluated on blonde bleached/waved tresses.
______________________________________ Ingredient Weight Percent
______________________________________ Polyoxyethylene(23)lauryl
ether 5.00 Lauric diethanolamide 5.00 C. I. Disperse Black, C. I.
No. 11365 1.00 Polydiallyldimethylammonium chloride (viscosity 500
cps.) 20.00 Isopropanol 25.00 Perfume 0.10 Water q.s. to 100.0
______________________________________
After 30 minutes contact with the composition, the hair was dyed a
golden blonde. After two shampoos, the combing rating of the hair
was still 4.0.
EXAMPLE 13
The following disperse dye composition for dyeing human hair was
prepared and evaluated on blonde bleached/waved tresses.
______________________________________ Ingredient Weight Percent
______________________________________ Polydiallyldimethylammonium
chloride (viscosity 128000 cps.) 20.00 Sodium Chloride 1.00 Benzyl
Alcohol 4.00 C. I. Disperse Black 1, C. I. No. 11365 1.00 Sodium
lauroylsarcosinate 13.17 Perfume 0.1 Water q.s. to 100.00
______________________________________
The composition was applied and worked up to a lather on tresses
and allowed to stand for 30 minutes. Water was applied and worked
up to a lather again and rinsed. The hair was dyed a golden blonde
and after two shampoos, had a wet rating of 4.0.
EXAMPLE 14
A basic dye hair toning composition was prepared and evaluated on
bleached-waved hair.
______________________________________ Ingredient Weight Percent
______________________________________
Stearyldimethylbenzylammonium chloride 1.8 Polymer of Example 1 4.5
Methylene Blue 0.045 Hexylene Glycol 25.00 Polyethyleneoxide, M.W.
100,000 0.45 Perfume 0.1 Water q.s. to 100.0
______________________________________
Bleached-waved hair was treated for 30 minutes, water-rinsed, and
shampooed. The hair was toned a pleasant pale green, actually blue
on a yellow substrate, and after two shampoos was rated 3.25.
EXAMPLE 15
A hair lightener composition was prepared having the following
composition. Lighteners usually produce roughened hair and
conditioning in these systems is particularly advantageous.
______________________________________ Ingredient Weight Percent
______________________________________ Oleic Acid 20.00
2-Amino-2-methyl-1-propanol 9.31 Polymer of Example 1 5.00 Ethanol
10.00 Perfume 0.20 Water q.s. to 100.0
______________________________________
To one part by weight of the above composition was added two parts
of aqueous 6% hydrogen peroxide and the mixture was applied to
brown hair for 30 minutes. The hair was water-rinsed and found to
be lightened about one shade and was readily combed. Using the same
composition on bleached-waved hair, the conditioning was found to
be 4.5 to 5.0 after two shampoos.
EXAMPLE 16
The same composition was prepared as in Example 15 except that
instead of mixing in two parts of the hydrogen peroxide solution
there was mixed in 0.5% by weight of C.I. Basic Brown 2 (C.I. No.
21030). The composition was applied to white hair for 30 minutes,
rinsed and shampooed. The hair was colored a light auburn.
Bleached-waved hair to which the same composition was applied had a
combing rating of 5.0 after two shampoos.
EXAMPLE 17
The following conditioning acid dye composition was prepared and
evaluated on white hair.
______________________________________ Ingredient Weight Percent
______________________________________ Miranol C2M Conc* 8.00
Polymer of Example 1 5.00 F.D. & C Blue No. 2, C.I. No. 73015
0.50 Benzyl alcohol 4.50 Perfume 0.10 Water q.s. to 100.0
______________________________________ CH.sub.2 *.angle. NCH.sub.2
CH.sub.2 CH.sub.2 OCH.sub.2 --COONa .parallel..vertline. CH.sub.11
H.sub.23 CN.angle. .vertline. OHCH.sub.2 COONa
The composition was applied to white hair for 30 minutes after
which a lather was worked up. After rinsing, the hair was found to
be toned a pale blue. The color was only semi-permanent and much
was removed after two shampoos. Evaluation of the composition on
bleached-waved hair after two shampooings showed a rating of 4.5 to
5.0.
EXAMPLE 18
The following aerosol basic-dye hair conditioning composition was
prepared and evaluated on white hair for color and condition.
______________________________________ Ingredient Weight Percent
______________________________________ Polydipropyldiallylammonium
chloride 4.0 Ethanol 85.9 Condensate of 10% ethylene oxide and 90%
propylene oxide with propylene glycol (M.W. about 1100) 10.0
Methylene Blue 0.10 ______________________________________
Ninety parts by weight of the above composition are packaged with
10 parts of propellant mixture consisting of
trichloromonofluoromethane 45%, dichlorodifluoromethane 45% and
isobutane 10%, in an aerosol container. The container was shaken
prior to use and the composition was applied to damp hair and left
for 30 minutes then water-rinsed and shampooed. The hair was dyed a
light blue. After two shampoos, the condition of the hair was still
rated 3.0.
EXAMPLES 19-21
The following compositions (Table I) were prepared with four
different polymers, the compositions being suitable for use as hair
dyes by the addition of the conventional desired dye. The
compositions, each containing a different polymer, were then mixed
with an aqueous 16% hydrogen peroxide solution in the proportion of
3.5 parts by weight of the composition to 1.0 part of peroxide
solution, and the mixture left in contact with hair tresses, one
virgin hair which had never been bleached or chemically waved, the
other bleached and waved hair, for 20 minutes at room temperature,
then rinsed.
Each hair tress was then rated for condition with the results set
forth in Table II. In this case the hair tresses were rated both
while wet (WC) and after drying (DC) as well as being rated again
after one shampoo and rinse (1S) and after three (3S).
Table I ______________________________________ Percent Ingredient
by Weight ______________________________________ Oleic acid 8.7
Monoethanolamine 5.0 Triton X-100 (Octylphenoxypolyethoxy)
(9-10)ethanol) 1.0 Triton X-35 (Octylphenoxypolyethoxy
(3-4)ethanol) 5.0 Isopropanol 25.0 EDTA 0.05 Sodium sulfite 0.05
Polymer 1.0 Water q.s. ______________________________________
Table II
__________________________________________________________________________
Hair Condition Virgin Bleached/Waved Polymer WC DC WC(1S) WC(3S) WC
DC WC(1S) WC(3S)
__________________________________________________________________________
Polymer of Example 1 4.5 3.5 4.5 4.0 4.3 4.0 4.0 3.0
Polydipropyldiallyl- ammonium chloride 4.0 3.0 3.5 3.5 2.8 4.0 2.5
2.5 Polydiallylpiperidinium chloride 4.5 3.0 4.5 3.5 4.3 4.0 3.5
2.5 Polydiallylamine 4.5 3.0 4.5 4.0 4.3 3.5 4.0 3.0 hydrochloride
None 3.5 3.0 3.5 3.5 2.5 4.0 2.5 2.5
__________________________________________________________________________
EXAMPLES 22-32
Hair bleaching compositions were prepared by mixing with one part
by weight of a 16% aqueous hydrogen peroxide solution 3.5 parts of
each of several compositions having the following recipe, the
polymer in each case being different as listed in Table III.
______________________________________ Recipe Weight Ingredient
Percent ______________________________________ Oleic acid 9.0
Monoethanolamine 5.1 Octylphenoxypolyethoxy (9-10) ethanol 1.0
Octylphenoxypolyethoxy (3-4) ethanol 5.0 Isopropanol 15-37 Cationic
polymer 1.0 Water q.s. to 100.0
______________________________________
Table III ______________________________________
Polydimethyldiallylammonium chloride Polydiallylamine hydrochloride
Polydipropyldiallylammonium chloride Polydiallylpiperidinium
chloride Copolymer (50:50) of dimethyldiallylammonium chloride and
acrylamide Copolymer (75:25) of dimethyldiallylammonium chloride
and acrylamide Copolymer (27:63) of dimethyldiallylammonium
chloride and acrylamide Copolymer (13:87) of
dimethyldiallylammonium chloride and acrylamide Copolymer (7:93) of
dimethyldiallylammonium chloride and acrylamide Copolymer (90:10)
of dimethyldiallylammonium chloride and diacetone acrylamide
Copolymer (95:5) of dimethyldiallylammonium chloride and diacetone
acrylamide ______________________________________
The compositions were evaluated by applying them to tresses of both
virgin and bleached/waved hair and allowing them to stand for 20
minutes. After rinsing and shampooing, the tresses displayed the
same superior condition as observed in the other examples in
contrast to the undesirable condition of tresses treated with
similar compositions omitting the polymer.
Also useful in the present invention in addition to the polymers
and copolymers specifically described above are various other
polymers and copolymers described in U.S. Pat. Nos. 3,288,770 and
3,412,019; particularly effective are a homopolymer of
methyl-beta-propionamidodiallylammonium chloride as well as a
copolymer made from 75:25 by weight mixture of
dimethyldiallylammonium chloride and of
methyldodecyldiallylammonium chloride and a copolymer made from a
50:50 by weight mixture of these monomers. These polymers and
copolymers can be substituted in the foregoing examples with only
slight differences in degree of effectiveness of the resultant
cosmetic composition.
* * * * *