U.S. patent number 3,678,157 [Application Number 04/770,074] was granted by the patent office on 1972-07-18 for hair treatment compositions containing polycondensable compounds.
This patent grant is currently assigned to Societe anonyme dite: L'Oreal. Invention is credited to Jean-Louis Abegg, Henri Philippe De Beaulieu, Guiliana Ghilardi, Gregoire Kalopissis.
United States Patent |
3,678,157 |
Kalopissis , et al. |
July 18, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
HAIR TREATMENT COMPOSITIONS CONTAINING POLYCONDENSABLE
COMPOUNDS
Abstract
A composition for treating hair containing a cosmetically
effective amount of a polycondensable compound having the formula:
##SPC1## In which: Y is selected from the group consisting of H,
hydrocarbon chains comprising one to 30 carbon atoms, groups
consisting of cosmetic constituents which have --S--S, --SH,
--COOH, basic quaternary ammonium, and fatty chain groups, X is
selected from the group consisting of O, S and NH, R.sub.1 and
R.sub.2 are selected from the group consisting of lower alkyl and
together may form a heterocyclic group, comprising nitrogen and/or
oxygen atoms, R.sub.3 is selected from the group consisting of H,
alkyl, and the two R.sub.3 groups may form a heterocyclic group,
comprising nitrogen and/or oxygen atoms.
Inventors: |
Kalopissis; Gregoire (Paris,
FR), Abegg; Jean-Louis (Le Perreux, FR),
Ghilardi; Guiliana (Paris, FR), De Beaulieu; Henri
Philippe (Paris, FR) |
Assignee: |
Societe anonyme dite: L'Oreal
(N/A)
|
Family
ID: |
25087389 |
Appl.
No.: |
04/770,074 |
Filed: |
October 23, 1968 |
Current U.S.
Class: |
424/70.51;
8/127.51; 424/DIG.1; 544/85; 544/139; 544/159; 544/168; 424/70.2;
8/127.6; 424/47; 544/86; 544/158; 544/160; 544/162; 546/332 |
Current CPC
Class: |
A61Q
5/06 (20130101); A61K 8/49 (20130101); A61Q
5/04 (20130101); C07D 295/13 (20130101); A61K
8/416 (20130101); Y10S 424/01 (20130101) |
Current International
Class: |
C07D
295/00 (20060101); C07D 295/13 (20060101); A61k
007/10 () |
Field of
Search: |
;260/246,247.1,247.2,247.2A,553R ;424/70,71,72
;8/116.2,116.3,127.51,127.6 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Meyers; Albert T.
Assistant Examiner: Clarke; Vera C.
Claims
What is claimed is:
1. A composition for treating human hair comprising a solution in a
solvent selected from the group consisting of water and
hydroalcoholic solutions of 0.5 to 12 percent by weight of a
polycondensable compound selected from the group consisting of
morpholinomethylurea quaternized with methyl iodide and
methoxymethylureidomethyl pyridinium chloride.
2. A composition according to claim 1 which also contains an acid
catalyst selected from the group consisting of acetic acid, lactic
acid, phosphoric acid, monosodium phosphate and monopotassium
phosphate.
3. A composition for treating human hair comprising a solution in a
solvent selected from the group consisting of water and
hydroalcoholic solutions, of 0.5-12 percent by weight of a
polycondensable compound selected from the group consisting of
(N-carbamyl-N'-morpholinomethylcarbamyl)-cystamine;
N,n'-(morpholinomethylcarbamyl)cystamine;
N-(morpholinomethylcarbamyl)cysteamine;
N-(morpholinomethylcarbamyl)glycine;
(diethyl-methyl-morpholinomethyl-ureidoethyl) ammonium iodide;
(dimethyl-copra-morpholinomethyl-ureidoethyl) ammonium
chloride;
[N-(morpholinomethyl)ethylurea-diethyl-ethylurea]ammonium
chloride;
methyl-propylurea N-(morpholinomethyl)propylurea amine;
methyl di-[N-(morpholinomethyl)propylurea] amine;
(N-dimethyl-ethylurea-N'-dimethyl-morpholinomethylureidoethyl)cystamine
dichloride;
N-dodecyl-N'-(morpholinomethyl)urea; and
N-octadecyl-N'-(morpholinomethyl)urea.
4. The composition according to claim 3 which also contains an acid
catalyst selected from the group consisting of acetic acid, lactic
acid, phosphoric acid, monosodium phosphate and monopotassium
phosphate.
Description
SPECIFICATION
This invention relates to a cosmetic composition for improving the
condition of human hair and imparting thereto properties which are
advantageous when the hair is to be subsequently subjected to a
cosmetic treatment.
It is known that the hair is more or less degraded by the action of
atmospheric agents such as the sun and sea water, and by chemical
treatments to which it is subjected, for example, during permanent
waving and bleaching.
The effects of such degradation may be to a large extent eliminated
by using the compositions according to the present invention.
It has already been proposed that the strength and elasticity of
the hair be increased by treating it with compounds which may be
polymerized inside the keratinic fiber, and at the same time become
attached to the reactive groups of the keratin.
Among the compounds heretofore suggested for this purpose are
dimethylolurea and dimethylolthiourea, which have, however, the
disadvantage of causing the release of a substantial quantity of
free formol, the presence of which in contact with the scalp cannot
be tolerated.
It has also been suggested that compounds which are more stable
than dimethylolurea and dimethylolthiourea, that is to say,
compounds which release much less free formol be used for this
purpose.
However, these compounds have in common the characteristic of
comprising hydroxymethyl groups which prevent them from being
completely stable. Moreover, these products are difficult to
prepare in a very pure state, from which it follows that the
process of preparing them do not lead to rigorously reproducible
results.
On the other hand, a great many of these compounds are difficult to
dissolve in the aqueous solvents generally used in the cosmetic
field.
In order to at least partially eliminate these disadvantages, it
has been suggested that one might use, instead of the hydroxymethyl
derivatives themselves, particular derivatives of these compounds
obtained in a known manner by condensing them with secondary amines
in accordance with the Mannich reaction.
The compounds produced in accordance with this reaction are more
soluble, more stable, and easier to prepare than the corresponding
hydroxymethyl compounds and are thus appreciably more satisfactory
when used for the cosmetic purpose of strengthening the hair.
On the other hand, this method of treating the keratin of the hair
also seeks to introduce into the hair reactive groups having a
particular cosmetic value, at the same time that it strengthens the
hair.
Specifically, cosmetic compounds having disulfide bonds have been
chemically attached to the hair. This supplement to the S--S bonds
improves the behavior of the hair and affects the action of the
fiber with respect to the chemical reactants customarily used in
the cosmetic field, such as reducing solutions containing
mercaptans or sulfites, or oxidizing agents containing hydrogen
peroxide, for example.
In like manner cosmetic compounds having carboxylic groups have
been attached inside the hair. These additional acid groups greatly
increase the affinity of the fiber for basic dyes.
On the other hand, basic groups, or even fatty chains, have been
introduced into the hair in order to increase the affinity of the
hair for acid dyes, or improve the sheen and "feel" of the hair
over a substantial period of time.
It has now been discovered that these different purposes may be
served by using compounds having in their molecule both a function
capable of causing polycondensation and a second function serving
the other cosmetic purposes outlined above. In this manner, when
this type of product is polycondensed in a conventional manner
inside the keratin, the result is to simultaneously achieve both
the desired cosmetic effect and improved properties with respect to
their mechano-elastic behavior.
It is the object of the present invention to provide a composition
for treating or modifying the keratin of the hair essentially
characterized by the fact that it comprises a cosmetically
effective amount of a polycondensable compound having the formula:
##SPC2##
in which:
Y is selected from the group consisting of H, hydrocarbon chains
comprising one to 30 carbon atoms, groups consisting of cosmetic
constituents which have --S--S--, --SH, --COOH, basic quaternary
ammonium, and fatty chain groups,
X represents oxygen, sulfur, or --NH,
R.sub.1 and R.sub.2 represent lower alkyl groups and may form part
of a heterocyclic ring,
R.sub.3 represents a hydrogen atom or an alkyl radical, and the two
R.sub.3 groups may be connected together to form a heterocyclic
ring comprising nitrogen and/or oxygen atoms.
In one particular embodiment of the invention, the composition for
treating or modifying the keratin of the hair comprises at least
one polycondensable compound corresponding to the formula:
##SPC3##
in which:
X represents oxygen, sulfur, or --NH,
R.sub.1 and R.sub.2 represent lower alkyl groups and may form parts
of a heterocyclic ring, comprising nitrogen and/or oxygen
atoms,
R.sub.3 represents hydrogen, or an alkyl radical, and the two
R.sub.3 groups may be connected together to form a heterocyclic
ring, comprising nitrogen and/or oxygen atoms,
R.sub.4 represents hydrogen, an alkyl radical, or a radical
corresponding to the formula: ##SPC4##
in which:
X, R.sub.1 R.sub.2 R.sub.3 and Y have the significances set forth
in formulas I and II,
R.sub.5 represents an alkyl radical or a radical having a function
or chemical bond imparting a cationic property to the nitrogen
and,
A.sup.- represents an anion of the halide or sulfate type.
Among the polycondensable compounds of this type which may be used
in the composition according to the invention are:
morpholinomethylurea quaternized with methyl iodide having the
formula: ##SPC5##
In a preferred embodiment of the invention the group according to
the above formula I is attached to a group having a chemical
function which is especially reactive with respect to conventional
cosmetic reagents, which group is hereinafter referred to as the
"cosmetic constituent" and corresponds to group R.sub.4 in formula
II.
Among the cosmetic constituents suitable for use in carrying out
the present invention are those groups having a disulfide function,
a thiol function, a carboxylic acid function, a basic or quaternary
ammonium function, or a fatty chain.
Among the cosmetic constituents which may be used in compositions
according to the invention are:
(N-carbamyl-N'-morpholinomethylcarbamyl)cystamine, having the
formula: ##SPC6##
In a preferred embodiment of the invention the cosmetic
compositions are in the form of aqueous or hydroalcoholic solutions
containing 0.5 to 12 percent by weight and preferably 2 to 4
percent by weight of at least one polycondensable compound such as
has been hereinbefore described. These cosmetic compositions may
have a pH of 1.5 to 10.
The cosmetic compositions according to the invention may also
contain an acid catalyst which may be either a mineral or an
organic acid, such as phosphoric acid, acetic acid, etc, or an acid
reaction salt such as monosodium and monopotassium phosphate
capable of promoting the polycondensation of these compounds with
the keratinic fiber when heated.
The cosmetic compositions according to the invention may also
contain nitrogenous compounds of the urea family and in particular
ureins, which may have cosmetic constituents of the type defined
above attached to their nitrogen atoms.
Such ureins can correspond to the following formula
in which
X is selected from the group consisting of O, S, NH,
n = 1 or 2
Y is a chemical group which has cosmetic properties selected from
the group consisting of disulfide, carboxylic acid, tertiary amine,
quaternary amine, fatty chain and --SH groups.
The composition may also take the form of a gel, cream, or aerosol.
It may also contain any conventional cosmetic additives, such as
surface-active agents, penetrating agents, perfumes, resins,
etc.
In accordance with the invention, the cosmetic composition may be
packaged in two phases destined to be mixed at the moment of use on
the hair, one phase being solid and containing the polycondensable
compounds and the other phase being aqueous or hydroalcoholic and
containing the acid catalyst and any conventional cosmetic
additives.
In particular, the solid or aqueous phase of the cosmetic
composition packaged in this manner may also contain a salt of
sulfurous acid, such as sodium metabisulfite.
A further object of the present invention is to provide a new
process for treating hair characterized by the fact that the hair
is impregnated with the above composition, and dried by the
application of heat, possibly after having been rinsed.
In a first method of carrying out this process, the cosmetic
composition does not itself contain the acid catalyst necessary to
cause polycondensation of the polycondensable compounds in the
keratinic fiber, and this acid catalyst is instead applied directly
to the hair either before or after applying the composition
according to the invention.
In another method of carrying out this process, a cosmetic
composition which does contain the acid catalyst is applied
directly to the hair, which is then dried as previously
described.
The treatment according to the invention makes it possible to
substantially strengthen the keratinic fiber of the hair by forming
a polycondensate inside the hair which also becomes attached to the
reactive groups of the keratin. In this manner it makes it possible
to obtain sets of excellent quality when the hair is treated while
wound up on setting rollers.
On the other hand, when the polycondensable compounds also comprise
cosmetic constituents, the treatment according to the invention
also makes it possible to carry out subsequent cosmetic treatments,
such as bleaching, dyeing, permanent waving, etc., under greatly
improved conditions.
It is a further object of the present invention to provide, as a
new article of manufacture, compounds corresponding to the formula:
##SPC7##
in which
X, R.sub.1, R.sub.2, R.sub.3 are as defined above, and
R.sub.4 represents a cosmetic constituent as hereinbefore
defined.
The present invention comprises, in particular, the following new
compounds:
N-(carbamyl-N'-morpholinomethylcarbamyl)cystamine,
N,N'-(morpholinomethylcarbamyl)cystamine,
N-morpholinomethylcarbamyl)cysteamine,
N-(morpholinomethylcarbamyl)glycine,
(diethyl-methyl-morpholinomethyl-urei doethyl) ammonium iodide,
(dimethyl-copra-morpholinomethyl-ureidoethyl) ammonium chloride,
[N-(morpholinomethyl) ethylurea-diethyl-ethylurea]ammonium
chloride, methyldi-[N-(morpholinomethyl)propylurea]amine,
methyldi-[N-(morpholinomethyl) propylurea]amine, and
(N-dimethyl-ethylurea-N'-dimethyl-morpholinomethyl ureidoethyl)
cystamine dichloride, the formulas for which compounds have been
given above.
It is also an object of the present invention to provide a process
for preparing the above-described new compounds, which process is
characterized by the fact that, in a first step, a urein is
prepared which contains the cosmetic constituent defined above by
reacting a cyanate or an alkaline thiocyanate with a primary amino
hydrochloride so that the nitrogen of the amine becomes attached to
the cosmetic constituent.
In a second step, a reaction of the "Mannich" type such as
described in "Organic Reactions" vol. 1, ch. 10, p. 303 and Houban
Weyl XIV/2, pp. 342-354 is carried out by reacting the urein which
has thus been formed with a secondary amine in the presence of
formol, the reaction being carried out in aqueous solution, either
at room temperature or at a temperature of about 50.degree. to
60.degree. C.
In an alternative process according to the present invention a
tertiary amine is quaternized with a halogeno-ethylurea, so that
the nitrogen of the amine becomes attached to a cosmetic
constituent.
In a second step in this alternative process the urein compound
obtained in the first step is reacted with a secondary amine in the
presence of formol, as hereinbefore described.
In order that the invention may be better understood, several
examples will now be described, purely by way of illustration.
EXAMPLES OF PREPARATION
1. preparation of dimorpholinomethylthiourea
1 mol of thiourea is dissolved in two mols of formol in an aqueous
30 percent solution, at a temperature of
40.degree.-50.degree.C.
This is cooled below 20.degree.C and 2 mols of morpholine are added
slowly while keeping the temperature between 15.degree. and
20.degree.C. This is then cooled to -10.degree.C until the
dimorpholinomethylthiourea crystallizes out. (This takes at least
24 hours.)
The result is a white crystalline solid which melts at
130.degree.C. The yield of the reaction is 90 percent.
2. Preparation of (N-carbamyl-N'-morpholinomethylcarbamyl)
cystamine ##SPC8##
1 mol of N,N'-dicarbamyl-cystamine, 1 mol of formol in an aqueous
30 percent solution, 1 mol of morpholine and 500 cc of distilled
water are mixed while stirring.
The resulting reaction is exothermic but it is nevertheless
necessary to heat the mixture to 50.degree.-55.degree.C to dissolve
the reagents. The mixture is then permitted to revert to the
ambient temperature and cooled to -15.degree.C. The reaction
product solidifies, and is dried under vacuum on P.sub.2
O.sub.5.
It is a white crystalline product. The yield of the reaction is
better than 90 percent.
Total amines 3.0 meq/g Theoretical 2.96 meq/g
Tertiary amines 2.7 meq/g Theoretical 2.96 meq/g
3. Preparation N,N'-(morpholinomethylcarbamyl)cystamine.
##SPC9##
1 mol of N, N'-dicarbamyl cystamine, 2 mols of formol in an aqueous
30 percent solution, 2 mols of morpholine and 500 cc of distilled
water are mixed together while stirring.
These are heated at about 55.degree.-60.degree.C until they are
completely dissolved. After cooling, the mixture is evaporated
under vacuum at a temperature below 40.degree.C. The residue is a
white crystalline product. The yield of the reaction is greater
than 90 percent.
Tertiary amines 4.0 meq/g Theoretical - 4.6 meq/g
4. Preparation of (dimethyl-copra-morpholino-methylureidoethyl)
ammonium chloride. ##SPC10##
1 mol of (dimethyl-copra-ureidoethyl) ammonium chloride, prepared
by quaternization of dimethyl-copra with chloroethylurea, is
dissolved in distilled water. 1 mol of formol in an aqueous 30
percent solution is then added. Morpholine is then added slowly,
while stirring. The reaction is exothermic. The temperature is kept
near 50.degree.C. When the temperature falls, the reaction mixture
is evaporated until dry. This is redissolved by heating it in 2,400
cc of ethanol, and the mixture is then again evaporated until dry.
The resulting product is a yellow oil, which after mixing with
ether and vacuum drying, forms a translucent light-colored paste.
The yield of the reaction is 87 percent.
5. Preparation of C.sup.2 . ##SPC11##
1 mol of N-methyl-dipropylurea, 2 mols of formol in an aqueous 30
percent solution, and 2 mols of morpholine are mixed while
stirring, and then heated for 30 minutes at 50.degree.C. The
reaction mixture is evaporated until dry, and after washing several
times with ether and vacuum drying on P.sub.2 O.sub.5 , the result
is a white crystalline product.
The yield of the reaction is 82.5 %.
Total amines 6.57 meq/g Theoretical 7.0 meq/g
Tertiary amines 6.32 meq/g Theoretical 7.0 meq/g
EXAMPLES OF APPLICATION
Example i:
a head of hair is first bleached with a conventional oxidizing
composition, rinsed, and dried. The hair is then impregnated with
the following solution:
monomorpholinomethylthiourea 2 g polyvinylpyrrolidone/vinyl acetate
copolymer 0.4 g acetic acid, q.s.p. pH=2.8 water, q.s.p. 100 cc
A head of hair is then set and dried under a hood for 30 to 40
minutes at a temperature of about 45.degree.-50.degree.C. The hair
is markedly hardened and is easily arranged. The tips of the hair
appear to be in good condition. The set is springy, and lasts
well.
Example ii:
a solution having the following composition is applied to natural
hair which has first been washed and dried:
1,4 -bis(carbamidomethyl)piperazine 4 g water 100 cc
The hair is then wound up on setting rollers and carefully
impregnated with a 2 percent lactic acid solution. The hair is left
to dry under a hood at about 45.degree.C and a set of excellent
quality results.
Example iii:
hair which has been strongly bleached is impregnated with a
solution obtained by mixing, at the moment of use, a powder
containing:
monomorpholinomethylurea 6 g urea 1 g
with 100 cc of a phosphoric acid solution diluted to a pH of
2.5.
The hair is dried while keeping the temperature between 40.degree.
and 45.degree.C for about 30 minutes.
Hair which has thus been treated is permanently waved in a
conventional manner. The results of this permanent are excellent,
whereas it is usually impossible to give a satisfactory permanent
wave immediately after bleaching.
Example iv:
the following composition is applied to hair which has just been
bleached in a conventional manner.
(dimethyl-copra-morpholinomethyl-ureido- ethyl ammonium chloride 1
g N-methyl di-[N-(morpholinomethyl)propylurea]amine 1 g acetic
acid, q.s.p. pH = 2.5 water 100 cc
The hair is then set in a conventional manner and excellent results
are obtained with respect to resilience and holding power, as well
as the condition, feel and sheen of the treated hair.
Example v:
a solution having the following composition is applied to hair
which is to be strongly bleached.
N,N'-(morpholinomethylcarbamyl) cystamine 4 g phosphoric acid
q.s.p. pH = 2.5 water q.s.p. 100 cc
The hair is then dried under a hood for about 30 minutes at a
temperature of about 45.degree.C.
The hair is then bleached with a conventional oxidizing agent. The
quality of hair which has been thus bleached after being first
treated in accordance with the invention is excellent, under both
humid and dry conditions.
Example vi:
the first step of a conventional permanent wave is carried out
using the following composition:
N-(morpholinomethylcarbamyl)cystamine 1.3 g
N,N'-(morpholinomethylcarbamyl)cystamine 4 g monoethanolamine,
q.s.p. pH = 9.5 water q.s.p. 100 cc.
The hair is impregnated with this solution, wound up on rollers of
the usual diameter, and again saturated with this solution. It is
then left for 15 minutes under a plastic cap at room temperature.
The hair is then rinsed, after which an aqueous solution of
hydrogen peroxide at 6 volumes is applied. This solution has been
brought to a pH of 1.5 by adding phosphoric acid.
The hair is then put under a hood and dried in a conventional
manner. The result is a set of excellent quality, which lasts well,
with the hair shiny with a very soft "feel."
Example vii:
natural hair, or hair which has first been bleached is permanently
waved, using the following self-neutralizing composition:
thioglycolic acid 2 g (N-carbamyl-N'-morpholinomethyl-
carbamyl)cystamine 7 g ammonia q.s.p. pH = 9.5 water q.s.p. 100
cc
and then keeping the hair wound up on rollers of small diameter,
under a cap, for about 15 minutes.
The hair is then rinsed with a 2 percent lactic acid solution and
set in conventional manner.
The result is a permanent which imparts excellent cosmetic
properties to the hair, improving its sheen and giving it an
agreeable feel.
The hair is springy and the wave lasts well when exposed to the
weather.
* * * * *