U.S. patent number 3,876,760 [Application Number 05/270,409] was granted by the patent office on 1975-04-08 for hair dressing compositions containing a hair substantive quaternary resin.
This patent grant is currently assigned to Bristol-Myers Company. Invention is credited to Taras Durbak, Fred Hubner, Ara Nersesian.
United States Patent |
3,876,760 |
Nersesian , et al. |
April 8, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Hair dressing compositions containing a hair substantive quaternary
resin
Abstract
A hair dressing composition comprising a hair substantive
quaternary resin to impart hair-holding properties to hair when
supplied, and a grooming agent; the grooming agent preferably being
incompatible with the quaternary resin.
Inventors: |
Nersesian; Ara (Livingston,
NJ), Hubner; Fred (Edison, NJ), Durbak; Taras
(Irvington, NJ) |
Assignee: |
Bristol-Myers Company (New
York, NY)
|
Family
ID: |
26954280 |
Appl.
No.: |
05/270,409 |
Filed: |
July 10, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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868892 |
Oct 23, 1969 |
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Current U.S.
Class: |
424/70.13;
424/DIG.1; 424/DIG.4; 424/DIG.2; 424/47; 514/941 |
Current CPC
Class: |
A61K
8/39 (20130101); A61Q 5/06 (20130101); A61K
8/731 (20130101); Y10S 424/04 (20130101); Y10S
514/941 (20130101); A61K 2800/5426 (20130101); Y10S
424/02 (20130101); Y10S 424/01 (20130101) |
Current International
Class: |
A61K
8/72 (20060101); A61K 8/73 (20060101); A61k
007/06 () |
Field of
Search: |
;424/70,71,78 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Goldberg; Jerome D.
Assistant Examiner: Clarke; Vera C.
Attorney, Agent or Firm: Holtzman; Irving Mugford; David J.
Mentis; George A.
Parent Case Text
This application is a continuation of Application Ser. No. 868,892
filed Oct. 23, 1969, now abandoned.
Claims
What is claimed is:
1. A hair dressing composition comprising a hair-fixative
quaternary cellulose ether resin having a high affinity for hair
and a hair grooming agent dissolved in an aqueous alkyl alcoholic
solvent in which the alkyl alcohol has from 2 to 6 carbons
wherein:
a. said resin is present in the range of from about 0.1 to 7.0
percent by weight based on the total weight of the composition;
b. said hair grooming agent is present in the range of from about 1
to 60 percent by weight based on the total weight of the
composition;
c. the ratio of said resin to said hair grooming agent being
present in the ratio of about 1 part of resin to 10 to 30 parts of
grooming agent;
said resin being 2-hydroxypropyltrimethyl ammonium chloride ether
of hydroxyethyl cellulose having a viscosity in 2 percent aqueous
solution from about 50 to 1000 cps at 25.degree.C and being of the
formula: ##SPC17##
wherein:
n = a number from 1 to 5;
x = is a number from 50 to 20,000;
A is hydrogen or ##SPC18##
said hair grooming agent being of the formula: ##SPC19##
in which n.sup.2 has an average value of 25.
2. A hair dressing composition comprising a hair-fixative
quaternary cellulose ether resin having a high affinity for hair
and a hair grooming agent dissolved in an aqueous alkyl alcoholic
solvent in which the alkyl alcohol has from 2 to 6 carbons
wherein:
a. said resin is present in the range of from about 0.1 to 7.0
percent by weight based on the total weight of the composition;
b. said hair grooming agent is present in the range of from about 1
to 60 percent by weight based on the total weight of the
composition;
c. the ratio of said resin to said hair grooming agent being
present in the ratio of about 1 part of resin to 10 to 30 parts of
grooming agent wherein:
said resin is of the formula: ##SPC20##
wherein:
Y indicates the degree of polymerization and is a number from 50 to
20,000;
R.sub.4, r.sub.5 or R.sub.6 is a radical of the formula:
##SPC21##
in which:
a is a whole number 2 or 3;
b is a whole number 2 or 3;
c is a whole number 1 to 4;
m is a number from 0 to 10;
n is a whole number from 0 to 3;
p is a whole number from 0 to 10;
q is zero or 1;
R.sub.7 is H or COOMe group in which Me is H, Na, K or NH.sub.4
;
X is a salt forming anion;
v is a number equal to the valence of X;
R.sub.1, r.sub.2 and R.sub.3 are alkyl, aryl, aralkyl, alkaryl,
cycloalkyl, alkoxyalkyl or alkoxyaryl in which the alkyl moieties
have up to 6 carbon atoms; the aryl moieties having up to 12 carbon
atoms and the cycloalkyl moieties having 5 to 6 carbon atoms and
wherein two or three of the radicals R.sub.1, R.sub.2 and R.sub.3
may constitute a nitrogen heterocyclic nucleus having 5 to 6 atoms
in the nucleus, one atom of which may also be oxygen;
and wherein the resin defined by the formula I above contains the
quaternary group: ##SPC22##
in the average of about 0.1 to 3 quaternary groups per
anhydroglucose unit;
said hair grooming agent being a quaternary compound of the
formula: ##SPC23##
wherein R.sub.11 and R.sub.12 are alkyl radicals having 1 to 6
carbon atoms; R.sub.13 is an aliphatic hydrocarbon group having 1
to 6 carbon atoms; R.sub.15 is hydrogen or alkyl having 1 to 6
carbons, n is a whole number from 6 to 40, .beta. is H, carboxy
acyl having 2 to 36 carbons or hydrocarbon having 1 to 36 carbons,
.phi. is a salt forming anion selected from the group consisting of
chloride, bromide, iodide, hydroxy, sulfate, methosulfate,
ethosulfate, nitrate, phosphate, acetate, formate, carbonate, 1 to
4 C sulfonate and methyl chloroacetate; and v is a number equal to
the valence of .phi..
3. A composition according to claim 2 wherein the hair-fixative
quaternary cellulose ether resin is of the formula: ##SPC24##
wherein:
n = a number from 1 to 5;
x = a number from 50 to 20,000;
A is selected from the group consisting of: ##SPC25##
in which R.sub.8, R.sub.9 and R.sub.10 are the same or different
and are lower alkyl having from 1 to 6 carbon atoms; B is hydrogen
or lower alkyl having from 1 to 6 carbon atoms; and X is a salt
forming anion selected from the group consisting of chloride,
bromide, iodide, sulfate, methylsulfate, nitrate, sulfonate,
phosphate and acetate; at least one A being one of said quaternary
groups; and v equals the valence of X.
4. A hair dressing composition comprising a hair-fixative
quaternary cellulose ether resin having a high affinity for hair
and a hair grooming agent dissolved in an aqueous alkyl alcoholic
solvent in which the alkyl alcohol has from 2 to 6 carbons
wherein:
a. said resin is present in the range of from about 0.1 to 7.0
percent by weight based on the total weight of the composition;
b. said hair grooming agent is present in the range of from about 1
to 60 percent by weight based on the total weight of the
composition;
c. the ratio of said resin to said grooming agent being present in
the ratio of about 1 part of resin to 10 to 30 parts of grooming
agent wherein
said resin is of the formula: ##SPC26##
wherein:
Y indicates the degree of polymerization and is a number from 50 to
20,000;
R.sub.4, r.sub.5 or R.sub.6 is a radical of the formula:
##SPC27##
in which:
a is a whole number 2 or 3;
b is a whole number 2 or 3;
c is a whole number 1 to 4;
m is a number from 0 to 10;
n is a whole number from 0 to 3;
p is a whole number from 0 to 10;
q is zero or 1;
R.sub.7 is H or COOMe group in which Me is H, Na, K or NH.sub.4
;
X is a salt forming anion;
v is a number equal to the valence of X;
R.sub.1, r.sub.2 and R.sub.3 are alkyl, aryl, aralkyl, alkaryl,
cycloalkyl, alkoxyalkyl or alkoxyaryl in which the alkyl moieties
have up to 6 carbon atoms; the aryl moieties having up to 12 carbon
atoms and the cycloalkyl moieties having 5 to 6 carbon atoms and
wherein two or three of the radicals R.sub.1, R.sub.2 and R.sub.3
may constitute a nitrogen heterocyclic nucleus having 5 to 6 atoms
in the nucleus, one atom of which may also be oxygen;
wherein the resin defined by the formula I above contains the
quaternary group: ##SPC28##
in the average of about 0.1 to 3 quaternary groups per
anhydroglucose unit;
and wherein said hair grooming agent is a lower alkoxy
polyoxyalkylene glycol which has an average molecular weight
greater than about 900 and not greater than about 4000, the lowr
alkoxy ranging in carbon atom content from 1 to about 6.
5. A hair dressing composition comprising a hair-fixative
quaternary cellulose ether resin having a high affinity for hair
and a hair grooming agent dissolved in an aqueous alkyl alcoholic
solvent in which the alkyl alcohol has from 2 to 6 carbons
wherein:
a. said resin is present in the range of from about 0.1 to 7.0
percent by weight based on the total weight of the composition;
b. said hair grooming agent is present in the range of from about 1
to 60 percent by weight based on the total weight of the
composition;
c. the ratio of said resin to said hair grooming agent being
present in the ratio of about 1 part of resin to 10 to 30 parts of
grooming agent wherein
said resin is of the formula: ##SPC29##
wherein:
Y indicates the degree of polymerization and is a number from 50 to
20,000;
R.sub.4, r.sub.5 or R.sub.6 is a radical of the formula:
##SPC30##
in which:
a is a whole number 2 or 3;
b is a whole number 2 or 3;
c is a whole number 1 to 4;
m is a number from 0 to 10;
n is a whole number from 0 to 3;
p is a whole number from 0 to 10;
q is zero or 1;
R.sub.7 is H or COOMe group in which Me is H, Na, K or NH.sub.4
;
X is a salt forming anion;
v is a number equal to the valence of X;
R.sub.1, r.sub.2 and R.sub.3 are alkyl, aryl, aralkyl, alkaryl,
cycloalkyl, alkoxyalkyl or alkoxyaryl in which the alkyl moieties
have up to 6 carbon atoms; the aryl moieties having up to 12 carbon
atoms and the cycloalkyl moieties having 5 to 6 carbon atoms and
wherein two or three of the radicals R.sub.1, R.sub.2 and R.sub.3
may constitute a nitrogen heterocyclic nucleus having 5 to 6 atoms
in the nucleus, one atom of which may also be oxygen;
wherein the resin defined by the formula I above contains the
quaternary group: ##SPC31##
in the average of about 0.1 to 3 quaternary groups per
anhydroglucose unit;
and wherein said hair grooming agent is a polyoxypropylene triol
having a M. W. of about 700.
6. A hair dressing composition comprising a hair-fixative
quaternary cellulose ether resin having a high affinity for hair
and a hair grooming agent dissolved in an aqueous alkyl alcoholic
solvent in which the alkyl alcohol has from 2 to 6 carbons
wherein:
a. said resin is present in the range of from about 0.1 to 7.0
percent by weight based on the total weight of the composition;
b. said grooming agent is present in the range of from about 1 to
60 percent by weight based on the total weight of the
composition;
c. the ratio of said resin to said hair grooming agent being
present in the ratio of about 1 part of resin to 10 to 30 parts of
grooming agent wherein:
said resin is of the formula: ##SPC32##
wherein:
Y indicates the degree of polymerization and is a number from 50 to
20,000;
R.sub.4, r.sub.5 or R.sub.6 is a radical of the formula:
##SPC33##
in which:
a is a whole number 2 or 3;
b is a whole number 2 or 3;
c is a whole number 1 to 4;
m is a number from 0 to 10;
n is a whole number from 0 to 3;
p is a whole number from 0 to 10;
q is zero or 1;
R.sub.7 is H or COOMe group in which Me is H, Na, K or NH.sub.4
;
X is a salt forming anion;
v is a number equal to the valence of X;
R.sub.1, r.sub.2 and R.sub.3 are alkyl, aryl, aralkyl, alkaryl,
cycloalkyl, alkoxyalkyl or alkoxyaryl in which the alkyl moieties
have up to 6 carbon atoms; the aryl moieties having up to 12 carbon
atoms and the cycloalkyl moieties having 5 to 6 carbon atoms and
wherein two or three of the radicals R.sub.1, R.sub.2 and R.sub.3
may constitute a nitrogen heterocyclic nucleus having 5 to 6 atoms
in the nucleus, one atom of which may also be oxygen;
wherein the resin defined by the formula I above contains the
quaternary group: ##SPC34##
in the average of about 0.1 to 3 quaternary groups per
anhydroglucose unit;
and wherein said hair grooming agent is a higher alcohol.
7. A hair dressing composition comprising a hair-fixative
quaternary cellulose ether resin having a high affinity for hair
and a hair grooming agent dissolved in an aqueous alkyl alcoholic
solvent in which the alkyl alcohol has from 2 to 6 carbons
wherein:
a. said resin is present in the range of from about 0.1 to 7.0
percent by weight based on the total weight of the composition;
b. said hair grooming agent is present in the range of from about 1
to 60 percent by weight based on the total weight of the
composition;
c. the ratio of said resin to said hair grooming agent being
present in the ratio of about 1 part of resin to 10 to 30 parts of
grooming agent wherein
said resin is of the formula: ##SPC35##
wherein:
Y indicates the degree of polymerization and is a number from 50 to
20,000;
R.sub.4, r.sub.5 or R.sub.6 is a radical of the formula:
##SPC36##
in which:
a is a whole number 2 or 3;
b is a whole number 2 or 3;
c is a whole number 1 to 4;
m is a number from 0 to 10;
n is a whole number from 0 to 3;
p is a whole number from 0 to 10;
q is zero or 1;
R.sub.7 is H or COOMe group in which Me is H, Na, K or NH.sub.4
;
X is a salt forming anion;
v is a number equal to the valence of X;
R.sub.1, r.sub.2 and R.sub.3 are alkyl, aryl, aralkyl, alkaryl,
cycloalkyl, alkoxyalkyl or alkoxyaryl in which the alkyl moieties
have up to 6 carbon atoms; the aryl moieties having up to 12 carbon
atoms and the cycloalkyl moieties having 5 to 6 carbon atoms and
wherein two or three of the radicals R.sub.1, R.sub.2 and R.sub.3
may constitute a nitrogen heterocyclic nucleus having 5 to 6 atoms
in the nucleus, one atom of which may also be oxygen;
wherein the resin defined by the formula I above contains the
quaternary group: ##SPC37##
in the average of about 0.1 to 3 quaternary groups per
anhydroglucose unit;
and wherein said hair grooming agent is a fatty acid ester.
Description
This invention relates to hair dressing compositions. More
particularly, it concerns hair dressing compositions designed to be
applied to hair to maintain hair in place, and at the same time to
impart thereto certain desirable grooming characteristics, such as
lubricity (without greasiness), soft feel, shine, anti-static
properties, etc. The properties of these compositions which serve
to maintain hair in place is herein referred to as their holding or
fixative properties. On the other hand, those properties which give
the hair lubricity, soft feel, shine, anti-static properties, etc.,
are herein described collectively as the grooming and conditioning
properties.
Hair dressing compositions of the prior art have, in general,
suffered from at least two distinct disadvantages. In those
compositions containing a hair fixative (which usually was a film
forming resin) dissolved or dispersed in a solvent system, when
they were applied to the hair and allowed to dry, tended to cement
fibers of hair together giving the hair an overall boardiness. On
the other hand, those prior art compositions which leave out the
hair fixative and contain only the hair grooming and conditioning
agents, as defined above, do not have adequate hair holding
properties.
It has now been found that these disadvantages can be avoided by
formulating a hair dressing composition comprising, in combination,
a hair substantive quaternary resin and a hair grooming agent. The
quaternary resin is characterized by its great affinity for hair,
which is preferably greater than that which the grooming agent has
for hair. The grooming agent is preferably one which is
incompatible with the resin and which separates therefrom on the
evaporation of a solvent in which they are both dissolved.
Although applicants do not want to be bound by any theory of
operation, it is believed that the excellent results obtained with
the instant composition are due in large part to the
incompatibility of the resin and grooming agent, and their
different affinities for hair. When, for example, the compositions
are applied in the form of solutions containing the quaternary
resin and grooming agent; on the evaporation of the solvent, the
quaternary resin, having a greater affinity for hair, coats the
same and imparts thereto its fixative properties. The grooming
agent, being incompatible with the quaternary resin and having less
affinity for hair, separates therefrom. The results appear to be
that substantially each hair fiber is provided with a first coat of
hair fixative quaternary resin and an over-coat of grooming and
conditioning agent. The holding properties of the fixative resin
are imparted to the hair fibers. At the same time, they are
maintained substantially as uncemented discrete fibers by virtue of
the lubricating properties of the over-coat of grooming and
conditioning agents. Furthermore, the over-coat of grooming and
conditioning agents imparts its other desirable characteristics to
the hair, e.g. soft feel, shine, anti-static properties, natural
appearance, etc.
It is accordingly an object of the present invention to provide a
hair dressing composition capable of simultaneously holding hair in
place, and imparting thereto grooming and conditioning
characteristics.
It is a further object of the present invention to provide a
composition of the aforesaid type which comprises a hair
substantive quaternary resin in combination with a hair grooming
agent which is incompatible with said hair substantive quaternary
resin.
Other and more detailed objects of the present invention will be
apparent from the following description and claims.
The compositions of the present invention may take a wide variety
of physical forms. Thus, they may take the form of liquids, gels,
creams, sticks, pastes, aerosol sprays, etc. As liquids, they may
be simple solutions in a variety of solvent systems, such as water,
aqueous alcohol, or other organic solvents and mixtures thereof. It
may also take the form of an oil-in-water or a water-in-oil
emulsion. In the preferred form of this invention, the composition
assumes the form of solutions of the active ingredients in an
aqueous solvent and particularly, an aqueous alcoholic solvent
system. The alcohol is preferably a lower (C.sub.2 to C.sub.6)
alkyl alcohol e.g., ethyl, propyl, isopropyl or butyl alcohol.
A variety of hair substantive quaternary resins known in the prior
art are suitable for the purposes of the present invention. One
representative class is described in French Patent 1,492,597, which
is incorporated herein by way of reference.
These compounds are quaternized cellulose ethers which can be
prepared by first etherifying cellulose or alkali cellulose to
prepare the ether, e.g., methyl cellulose, hydroxyethyl cellulose,
hydroxypropyl cellulose, hydroxypropyl-methyl cellulose,
carboxymethyl cellulose or its salts. These may then be quaternized
by reacting the respective ethers or mixtures thereof with the
halohydrin quaternary salt. ##SPC1##
or the epoxy quaternary salts; ##SPC2##
in which Z above is a halogen, e.g. Cl, Br or I;
R.sub.1, R.sub.2 and R.sub.3 have the values ascribed to them
below;
Q is the anion of a strong mineral acid; and
t is a whole number equal to the valence of Q.
The resulting compounds may be described generally by the formula:
##SPC3##
wherein:
Y indicates the degree of polymerization and is a number from 50 to
20,000; R.sub.4, R.sub.5 or R.sub.6 is a radical of the general
formula: ##SPC4##
in which:
a is a whole number 2 or 3;
b is a whole number 2 or 3;
c is a whole number 1 to 4;
m is a number from 0 to 10;
n is a whole number 0 to 3;
p is a whole number from 0 to 10;
q is zero or 1;
R.sub.7 is H or COOMe group in which Me is H, Na, K or NH.sub.4
;
X is an anion, e.g. Cl.sup.-, Br.sup.-, I.sup.-, sulfate,
methylsulfate, sulfonate, nitrate, phosphate, acetate, etc.;
v is a number equal to the valance of X;
R.sub.1, R.sub.2 and R.sub.3 are organic radicals (e.g. alkyl,
aryl, etc.) any two or three of which may also constitute together
a heterocyclic nitrogen radical. In the general polymer defined in
Formula III above, the quaternary group ##SPC5##
is present on the average of about 0.1 to 3 quaternary groups per
anhydroglucose unit.
R.sub.1, R.sub.2 and R.sub.3 above may be, by way of example,
alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxyalkyl or
alkoxyaryl. These radicals will usually contain up to 12 carbon
atoms. When they are aryl moieties, they are usually hydrocarbon
moieties. When they are alkyl moieties they are usually lower
alkyl, e.g. 1 to 6 carbon atoms (methyl, ethyl, propyl, butyl,
t-butyl, amyl, hexyl, etc.). In the case when they are cycloalkyl,
they usually have 5 to 6 carbon atoms in the cycloalkyl ring.
As noted above, any two or three of R.sub.1, R.sub.2 or R.sub.3 may
constitute together a heterocyclic nitrogen radical. These will
usually contain 5 to 6 atoms in the heterocyclic nucleus and may
contain oxygen as well as nitrogen in the heterocyclic ring. By way
of illustration, the following may be mentioned: pyridine,
.alpha.-methylpyridine; 3,5-dimethylpyridine;
2,4,6-trimethylpyridine; N-methylpiperidine, N-ethylpiperidine;
N-methylmorpholine or N-ethylmorpholine.
Within the broader class of quaternized cellulose ethers described
above, there is a preferred group of materials which are
particularly suitable for the purposes of the present invention.
These may be described by the formula: ##SPC6##
wherein:
n = a number from 1 to 5;
x = a number from 50 to 20,000 and preferably
from 200 to 5000;
A is sellected from the group consisting of: ##SPC7##
in which R.sub.8, R.sub.9 and R.sub.10 are the same or different
and are lower alkyl having from 1 to 6 carbon atoms; B is hydrogen
or lower alkyl having from 1 to 6 carbon atoms; and X is an anion
such as Cl.sup.-, Br.sup.-, I.sup.-, sulfate, methylsulfate,
nitrate, sulfonate, phosphate, acetate, etc; at least one A in said
Formula V being one of said quaternary groups; v is a number equal
to the valence of X.
One group of hair fixative quaternary resins of special interest in
the present invention are Union Carbide's JR-1 Resins. These are
advantageous in that they impart holding properties without
excessive stiffness; they are effective at low concentrations
(0.1%); they form a substantive, elastic film on hair, thus
powdering or flaking does not result; they demonstrate good
resistance to high humidity conditions; they are soluble in water
and can tolerate large concentrations of alcohol (75%); they form a
clear film, thus do not dull the hair, and they are compatible with
quaternary grooming and germicidal agents.
JR-1 Resins may be described as 2-hydroxypropyl trimethyl ammonium
chloride ethers of hydroxyethyl cellulose. The molecular weights of
the resins are in the range 200,000 to 2,000,000. The structural
formula of the resins can be represented as follows: ##SPC8##
where R.sub.10 is H or ##SPC9##
n is 1 to 5 and z is a whole number that represents the degree of
polymerization. There are currently two viscosity grades of JR-1
Resins available. One of them is the low viscosity grade JR-1L
Resin which has at 25.degree.C a viscosity of (2% aqueous solution)
from about 50 to 1000 cps. The other grade is a high viscosity
grade (JR-1H Resin) which has a viscosity of (2% aqueous solution)
above 1000 cps.
The quantity of quaternary resin that may be incorporated in the
compositions of the present invention may vary considerably. In
general, however, it will constitute about 0.1 to 7 percent by
weight of the total composition.
A second essential component of the instant compositions is the
grooming agent. A wide variety of grooming agents are known in the
prior art which may be used for the present purposes. Since the
compositions will ordinarily comprise an aqueous base, it is
advantageous that these grooming agents be soluble in aqueous
solvent systems such as water or aqueous alcohol. By way of
illustrating the grooming agents which can be employed in the
composition, the following are mentioned which may be used either
alone or in combination:
1. Alkoxy polyoxyalkylene glycols such as butoxy polyoxypropylene
glycols (Ucon LB series); butoxy polyoxyethylene-polyoxypropylene
glycols (Ucon 50HB and 75H series); methoxy polyoxyethylene glycols
(Carbowaxes 350, 550, etc.). The preparation of compounds of the
"Ucon" series is described in U.S. Pat. No. 2,425,845 to Toussaint
et al. A preferred class of materials is also described in U.S.
Pat. No. 3,061,519. The latter are described as water soluble lower
alkoxy polyoxyalkylene glycols or polyoxyalkylene diols in which
the oxyalkylene is a mixture of oxyethylene and oxypropylene in a
ratio of about 3:1 to about 1:3 and which have an average molecular
weight greater than about 900 and not greater than about 4000.
Lower alkoxy is intended to include alkoxy radicals ranging in
carbon atom content from 1 to about 6.
2. Polyoxyalkylene glycols such as polyoxypropylene glycols;
polyoxyethylene glycols (Carbowaxes 400, 600, 1000, etc.);
polyoxypropylene-polyoxyethylene glycols (Wyandotte's Polyol
WL-360, Pluronics, etc.).
3. Alkoxy polyoxyalkylene glycol esters (Ucon oleate) and
polyoxyalkylene glycol esters (PPG 2000 monooleate).
4. Glycerol and trimethylolpropane based triols such as
polyoxypropylene triols (Emcol CD-18) and
polyoxypropylene-polyoxyethylene triols.
5. Polyoxyalkylene ethers such as polyoxyethylene ethers (Volpos,
Brijs) and polyoxypropylene ethers (Procetyl).
6. Diesters of dicarboxylic acids such as diisopropyl adipate,
diisopropyl sebacate, etc.
7. Lanolin and its derivatives such as polyoxyalkylene lanolin
ethers (Polychols) and acetylated ethoxylated ester-ethers (Solulan
98).
8. Protein derivatives such as collagen derived hydrolysates
(Polypeptide LSN, Wilson's WSP X-250); cassein derived hydrolysates
(Cascoloids) and protein hydrolysate esters (Promois).
9. Fatty alcohol ethers and fatty acid esters.
10. Higher alcohols (hexadecyl), oleyl, lauryl, cetyl, etc.).
11. Cationic or quaternary compounds, e.g. substituted amine
oxides, substituted ammonium halides and substituted
imidazolines.
A particularly useful class of grooming agents for the purposes of
the present invention are the cationic quaternary ammonium
compounds: ##SPC10##
wherein R.sub.11 and R.sub.12 are alkyl radicals; R.sub.13 is an
aliphatic hydrocarbon group; R.sub.14 is a polyoxyalkylene radical
and .phi. is an anion; and v is a number equal to the valence of
.phi. .
In formula VI above, R.sub.11 and R.sub.12 can vary in the number
of carbon atoms contained in the alkyl chain. Ordinarily these will
be lower alkyl chains containing from 1 to 6 and particularly 1 to
2 carbon atoms. Similarly, R.sub.13 can vary in chain length but
will usually be an alkyl or alkenyl group having 1 to 6 carbon
atoms.
R.sub.14 of formula VI above may be a polyoxyalkylene radical
preferably containing at least 18 carbon atoms and derived from an
.alpha.-epoxide containing at least 3 carbon atoms, e.g., propylene
oxide. More specifically, it may be described by the formula:
##SPC11##
wherein R.sub.15 is hydrogen or alkyl radical containing 1 to 6
carbon atoms; and n is a whole number from 6 to 40 and .beta. is H,
acyl radical of a carboxy acid having 2 to 36 carbon atoms or a
hydrocarbon radical having 1 to 36 carbon atoms.
When .beta. is an acyl radical, it may be derived from any of a
number of acids. These include such acids as acetic, lauric, oleic,
stearic, palmitic, lanolin fatty acids, etc. When .beta. is a
hydrocarbon radical, the compound is an ether. This ether likewise
may be derived from a variety of alcohols such as ethyl, lauryl,
oleyl, stearyl and lanolin alcohols.
The esters are prepared in the following manner: To a refluxing
solution of the acid chloride in anhydrous ethyl ether, the
tertiary amine (e.g. ##SPC12##
is slowly added. A 10 percent excess of the acid chloride is
employed. The acid chloride is added over a period of 75 minutes
and the mixture is maintained at reflux for an additional 2 hours.
The reaction mixture is cooled to room temperature and 2N HCl is
added. Water is added to the reaction mixture which is then
extracted with anhydrous ethyl ether. The acid aqueous residue
which contains the tertiary amine ester as the HCl salt is now made
basic with concentrated ammonia whereby the free amine ester comes
out of solution. This product is extracted with ether and the ether
is then driven off leaving the tertiary amine ester. This is then
quaternized with methyl chloride by heating a mixture of the amine
ester with excess methyl chloride (100% excess) in a sealed tube at
60.degree.C for 18 hours. The tube is then opened and the solvent
and excess methyl chloride is evaporated.
The corresponding ethers may be prepared by reacting the tertiary
amine alcohol (e.g. ##SPC13##
with a fatty alcohol, e.g. lauryl alcohol, ethyl alcohol or stearyl
alcohol in the presence of a small quantity of a catalyst (e.g.
p-toluene sulfonic acid). Excess HCl is added and the reaction mass
is extracted with ethyl ether. The aqueous acidic residue is made
basic with concentrated ammonia and reextracted with ether. The
ether is then evaporated and the amine ether is quaternized with
methyl chloride in a fashion similar to that described above for
the preparation of the quaternized amine ester.
The radical .phi. of formula VI can be any negative or salt-forming
radical as, for instance, halide such as chloride, bromide and
iodide; hydroxy; sulfate, alkyl sulfate (methosulfate or
ethosulfate); nitrate; phosphate; acetate; formate; carbonate;
lower alkyl (1 to 4 carbon atoms) sulfonates; and the like. Of
particular interest are those of the cation-active surface active
agents in which the anion is chloride, bromide, methyl
chloroacetate, methosulfate, and ethosulfate.
Cationic surface active quaternary ammonium grooming compounds that
are useful for the purpose of the present invention and the manner
of preparing the same are described in U.S. Pat. Nos. 3,123,640;
3,123,641 and 3,141,904 which are incorporated herein by way of
reference. Of special interest are compounds described by the
formula: ##SPC14##
in which n has an average value of about 8, 25 and 40 respectively
and whose apparent molecular weights are 600, 1600 and 2500
respectively.
A number of the cationic surface active quaternary ammonium
compounds mentioned above are available commercially. By way of
example, mention may be made of products sold under the trade
designations EMCOL CC-9, EMCOL CC-36 and EMCOL CC-42.
The quantity of grooming agent incorporated in the present
composition also will obviously vary with the intended purpose. In
general, however, this will constitute between 1.0 to 60 percent by
weight of the total composition.
Optimum results are obtainable by maintaining the grooming agent at
a higher level than the quaternary resin in the composition. The
preferred ratio is 1 part of quaternary resin to 10 to 30 parts of
grooming agent.
It is sometimes advantageous to modify the properties of the
aforesaid composition by including therein one or more auxiliary
resins. A number of resins are known in the prior art which could
serve as auxiliary resins. In this connection, mention may be made
of the following:
AUXILIARY RESINS
1. Polyvinyl pyrrolidone (PVP) and its derivatives such as
alkylated polyvinylpyrrolidone (Ganex) polyvinylpyrrolidone-vinyl
acetate copolymers (PVP/VA), etc.
2. Hydroxyalkyl cellulose derivatives such as hydroxyethyl
cellulose (Cellosize, Natrosol); hydroxypropyl cellulose (Klucel);
hydroxymethylhydroxypropyl cellulose (Methocel), etc.
3. Polyvinyl alcohols (Elvanol).
4. Polyoxyethylene resins (Polvox).
The above list is given by illustration only and does not enumerate
all possible auxilliary resins.
The quantity of auxiliary resins that may be employed can also vary
considerably. In general, it may constitute between 0 to about 3
percent by weight of the total composition.
In addition to the aforesaid ingredients, if desired, other
conventional ingredients commonly found in hair grooming
preparations may be included in the present composition. These
include such agents such as slip agents, plasticizers, germicides,
fragrance, colors, solvents and other vehicles, etc. By way of
illustration, the following may be mentioned:
1. Plasticizers which are compatible with the resin may be
incorporated to control the hardness and elasticity of the resin
film are as follows: glycerol, glycols (propylene, dipropylene,
polyoxyethylene, etc.), phthalic acid esters, quaternary compounds
(stearyl dimethyl benzyl ammonium chloride, etc.) and others as
used in the art.
2. Germicides and preservatives such as quaternary nitrogen
compounds (benzethonium chloride, cetyl pyridinum chloride, etc.);
p-hydroxy benzoate esters (Parabens), chlorinated phenols (e.g.
hexachlorophene) etc.
3. Thickening agents such as carboxyvinyl polymer (Carbopol).
4. Rubefacients such as methyl nicotinate, capsicum tincture,
dipropylene glycol salicylate, etc.
5. Keratolytic agents such as salicylic acid, resorcinol, sulfur,
etc.
6. Antidandruff agents such as Zinc Omadine (i.e., zinc pyrithione
C.sub.10 H.sub.8 N.sub.2 O.sub.2 S.sub.2 Zn), selenium sulfide,
biphenamine hydrochloride, etc.
7. Hair coloring agents.
8. Fragrances.
9. Color.
The preferred form of this invention comprises an aqueous alcoholic
solution of quaternary resin and grooming agent. Table I below sets
the general range of ingredients and the preferred concentrations
in this aspect of the invention.
TABLE I ______________________________________ PERCENT BY WEIGHT
INGREDIENTS GENERAL RANGE PREFERRED CONCENTRATION
______________________________________ Quaternary Resin 0.1 - 7.0
0.3 Ethyl alcohol 0.0 - 75.0 50.0 Water 25.0 - 98.0 44.7 Grooming
agents 1.0 - 60.0 5.0 Auxilliary agents q.s. q.s.
______________________________________
The following Examples are further illustrative of the present
invention. It is to be understood, however, that the invention is
not limited thereto. In these Examples when the following terms
appear, they have the meaning described below:
1. JR-1L Resin: For description see specification above;
2. Emcol CC-9; Emcol CC-36 and Emcol CC-42- ##SPC15##
Emcol CC-9; n in above formula has an average value of 8; average
M. W. = 600;
Emcol CC-36; n in above formula has an average value of 25; average
M. W. = 1600;
Emcol CC-42; n in above formula has an average value of 40; average
M. W. = 2500;
3. Grooming Agent No. 2000: Butoxypolyoxyethyleneoxypropylene
glycol having an M. W. of 2650 and a viscosity of 2000 Saybolt
Universal seconds at 100.degree.F; the oxyethylene and oxypropylene
are in equal parts;
4. Grooming Agent No. 450: Polyoxyethyleneoxypropylene diol having
a M. W. of 990 and a viscosity of 450 Saybolt Universal seconds at
100.degree.F; the ratio of oxyethylene to oxypropylene is 3:1;
5. Triol 700 : polyoxypropylene triol having an average M. W. of
about 700 (reaction product of glycerine and propylene oxide);
6. Emcol CC-9 Laurate, Emcol CC-9 Stearate: ##SPC16##
Emcol CC-9 Laurate, n in the formula above has an average value of
about 8 and R is lauroyl, i.e.
CH.sub.3 (CH.sub.2).sub.10 CO--;
Emcol CC-9 -- Stearate; n in the formula above has an average value
of about 8 and R is stearyl.
7. Freon 12 -- Dichlorodifluoromethane;
8. Carbowax 400 -- Polyoxyethyleneglycol M. W. 400;
9. Polyoxyethylene glycol (400) Monooleate -- The monooleate of
polyoxyethylene glycol having an M. W. of 400;
10. Ucon 50 HB 660 -- Butoxypolyoxyethylenepolyoxypropylene glycol
having a polyoxyethylene to polyoxypropylene ratio of 1:1 and a
viscosity of 660 Saybolt Universal seconds at 100.degree.F; M. W.
about 2000;
11. Ucon LB 1715 -- Butoxypolyoxypropyleneglycol having a viscosity
of 1715 Saybolt Universal seconds at 100.degree.F; M. W. about
2000;
12. Methocel 60 HG 4000; hydroxypropyl methylcellulose ether having
28 to 30 percent by weight of methoxy substituents and 7 to 12
percent by weight of hydroxypropyl substituents; the degree of
substitution with methoxy and hydroxypropyl substituents is from
1.68 to 1.82 and from 0.17 to 0.3 respectively; viscosity 3500-5600
cps. (2% aqueous solution at 20.degree.C). (See U.S. Pat. No.
3,427,382).
13. Carbopol 940: (purified form of Carbopol 934) water soluble
polymer of acrylic acid cross linked with 1 percent of a polyallyl
ether of sucrose having an average of about 5.8 allyl groups for
each molecule of sucrose (See U.S. Pat. No. 3,133,865).
14. P.V.P.: See THE MERCK INDEX, eighth edition, page 849-850.
15. Stepans Polypeptide AAS-20% Active: This is an alcohol soluble
base hydrolyzed collagen protein derivative. (See "Protein, Some
New Derivatives" by Richard Riso -- Proceedings of the Toilet Goods
Association No. 42, pages 36-39, December, 1964.
EXAMPLE I ______________________________________ INGREDIENT PERCENT
BY WEIGHT ______________________________________ JR-1L Resin 0.30
Emcol CC-36 4.00 Diisopropyl adipate 1.00 Dipropylene glycol 0.70
Benzethonium chloride 0.10 *Perfume 0.40 *Color (.1% aqueous
solution) 0.37 Ethyl alcohol (95% aq.) 50.00 Water 43.13 100.00
______________________________________ *The perfume and color may
be omitted from this composition if desired, i which event they are
replaced by an equal quantity of water.
EXAMPLE IA TO IE
The composition similar to that of Example I is prepared excepting
that for the JR Resin of Example I an equal quantity of the product
of Example I of French Patent No. 1,492,597 is utilized as the
quaternary resin. In a similar fashion, a series of compositions
are prepared similar to that of Example I above excepting that each
contains an equal quantity of the material prepared by the Examples
of 2, 5, 7, 9 and 12 of French Patent No. 1,492,597 in place of the
JR-1L Resin of Example I as the quaternary resin.
The following Examples 2 through 19 are given in tabular form. They
illustrate other aqueous or aqueous alcoholic systems in which the
quaternary resin and the grooming agents are dissolved in the
solvent system.
TABLE 2
__________________________________________________________________________
PERCENT BY WEIGHT INGREDIENT EX. EX. EX. EX. EX. EX. EX. EX. EX.
EX. EX. EX. EX. EX. EX. EX. EX. EX. 2 3 4 5 6 7 8 9 10 11 12 13 14
15 16 17 18 19
__________________________________________________________________________
PRODUCT OF EX. 1 French Patent 0.1 0.5 1.0 2.0 0.3 0.3 0.3 0.3 2.85
0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 1,492,597 WATER 44.9 44.5 44.0
43.0 44.7 47.7 39.7 94.7 92.15 44.7 74.7 49.7 29.7 29.7 24.7 44.7
44.7 44.7 ETHYL ALCOHOL (95%) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 --
-- 30.0 -- -- 65.0 60.0 60.0 50.0 50.0 50.0 PRODUCT OF EX. 1 U.S.
Patent 5.0 5.0 5.0 5.0 5.0 2.0 10.0 -- -- -- -- -- -- -- -- 2.5 2.5
2.5 3,123,641 GROOMING AGENT No. 2000 -- -- -- -- -- -- -- 5.0 5.0
25.0 25.0 50.0 -- -- -- 2.5 -- -- GROOMING AGENT No. 450 -- -- --
-- -- -- -- -- -- -- -- -- 5.0 10.0 15.0 -- 2.5 -- TRIOL-700 -- --
-- -- -- -- -- -- -- -- -- -- -- -- -- -- -- 2.5
__________________________________________________________________________
The following examples further illustrate aqueous alcoholic systems
in which the active ingredients are present in solution. In these
examples different quaternary grooming agents are employed:
INGREDIENT PERCENT BY WEIGHT ______________________________________
EXAMPLE 20 21 22 ______________________________________ JR-1L Resin
0.3 0.3 0.3 Emcol CC-9 5.0 -- -- Emcol CC-36 -- 5.0 -- Emcol CC-42
-- -- 5.0 Ethyl Alcohol 50.0 50.0 50.0 Water 44.7 44.7 44.7
Perfume, Color, etc. q.s. q.s. q.s.
______________________________________
The following examples also illustrate the use of certain
quaternary grooming agents in combination with the quaternary
resin.
______________________________________ INGREDIENT PERCENT BY WEIGHT
______________________________________ EXAMPLE
______________________________________ 23 24 Emcol CC-9 Laurate
15.0 -- Emcol CC-9 Stearate -- 5.0 JR-1L Resin 1.0 0.3 Ethyl
Alcohol 40.0 50.0 Water 44.0 44.7 Perfume, Color, etc. q.s. q.s.
______________________________________
The following example illustrates the use of a substituted amine
oxide-type grooming agent.
______________________________________ INGREDIENT PERCENT BY WEIGHT
______________________________________ EXAMPLE 25 Lauryl amine
oxide 5.0 JR-1L Resin 0.3 Ethyl alcohol 50.0 Water 44.7 Perfume,
color, etc. q.s. ______________________________________
The following examples illustrate the use of auxilliary resins in
combination with the quaternary resin in accordance with the
present invention.
______________________________________ INGREDIENT PERCENT BY WEIGHT
______________________________________ EXAMPLE 26 27 JR-1L Resin
0.5 0.5 Methocel 60 HG 4000 -- 0.5 PVP 0.5 -- Emcol CC-36 5.0 5.0
Ethyl alcohol 50.0 30.0 Water 44.0 64.0 Perfume, color, etc. q.s.
q.s. ______________________________________
The following example illustrates the present invention in which it
takes the form of a gel.
______________________________________ INGREDIENT PERCENT BY WEIGHT
______________________________________ EXAMPLE 28 Carbopol 940 1.0
JR-1L Resin 0.5 Triethanolamine 1.5 Emcol CC-36 5.0 Water 62.0
Ethyl alcohol 30.0 Perfume, color, etc. q.s.
______________________________________
The following examples illustrate the present invention in the form
of an aerosol spray.
______________________________________ INGREDIENT PERCENT BY WEIGHT
______________________________________ EXAMPLE 29 30 JR-1L Resin
0.3 0.3 Emcol CC-36 4.0 4.0 Water 25.7 30.7 Ethyl alcohol 30.0 30.0
Freon 12 40.0 -- Isobutane -- 35.0 Perfume, color, etc. q.s. q.s.
______________________________________
The following examples are a miscellaneous group of examples
illustrating a variety of aspects of the present invention.
______________________________________ INGREDIENT PERCENT BY WEIGHT
______________________________________ EXAMPLE 31 32 33 34 35 JR-1L
Resin 0.3 0.3 0.3 0.3 0.3 Ethyl alcohol 50.0 65.0 50.0 50.0 65.0
Water 44.7 29.7 44.7 39.7 29.7 Polyoxyethylene glycol (Carbo- wax
400) 5.0 -- -- -- -- Polyoxyethylene glycol 400 monooleate -- 5.0
-- 5.0 -- Acetylated, ethoxylated ester-ether of lanolin alcohols
(Solulan 97) -- -- 5.0 -- -- *Collagen protein hydrolysate
(Stepan's Poly- peptide AAS-20% active) -- -- -- 5.0 -- Lauryl
lactate -- -- -- -- 5.0 Perfume, color, etc. q.s. q.s. q.s. q.s.
q.s. INGREDIENT PERCENT BY WEIGHT
______________________________________ EXAMPLE 36 37 38 JR-1L Resin
0.1 0.3 2.0 Ethyl alcohol 50.0 50.0 50.0 Water 44.9 46.2 43.0 Emcol
CC-36 5.0 3.0 5.0 Collagen protein hydrolysate (Stephan's
Polypeptide LSN) -- 0.5 -- Perfume, color, etc. q.s. q.s. q.s.
INGREDIENT PERCENT BY WEIGHT ______________________________________
EXAMPLE 39 40 41 JR-1L Resin 2.85 0.3 0.3 Ethyl alcohol -- 30.0 --
Water 92.15 44.7 74.7 Butoxy polyoxyethylene- polyoxypropylene
glycol (Ucon 50HB660) 5.00 25.0 25.0 Perfume, color, etc. q.s. q.s.
q.s. INGREDIENT PERCENT BY WEIGHT
______________________________________ EXAMPLE 42 43 44 JR-1L Resin
0.3 0.3 0.3 Ethyl alcohol 60.0 50.0 50.0 Water 29.7 44.7 44.7
Butoxy polyoxypropylene glycol (Ucon LB1715) 10.0 -- 2.5 Emcol
CC-36 -- 2.5 2.5 Butoxy polyoxyethylene- polyoxypropylene glycol
(Ucon 50 HB 660) -- 2.5 -- Perfume, color, etc. q.s. q.s. q.s.
INGREDIENT PERCENT BY WEIGHT ______________________________________
EXAMPLE 45 46 47 JR-1L Resin 0.3 0.3 0.3 Emcol CC-36 5.0 5.0 5.0
Hexachlorophene 0.5 -- -- Salicylic acid -- 1.0 -- Benzethonium
chloride -- 0.3 -- Biphenamine hydrochloride -- -- 1.0 Ethyl
alcohol 50.0 50.0 50.0 Water 44.2 43.4 43.7 Perfume, color, etc.
q.s. q.s. q.s. ______________________________________ *Polypeptide
LSN (Average M.W. 900 - 1500) may be used in place of Stepan's
Polypeptide AAS.
The following examples further illustrate cream and lotion
formulations within the scope of the present invention.
INGREDIENT PERCENT BY WEIGHT ______________________________________
EXAMPLE 48 49 50 51 JR-1L Resin 0.5 0.5 0.5 0.5 Emcol CC-36 5.0 --
-- 5.0 Isopropyl myristate 2.0 -- -- -- Glyceryl monostearate 7.0
4.0 2.0 2.0 Lanolin -- 1.0 -- -- N-(lauryl colaminoformyl-
methyl)pyridinium chloride -- 0.5 -- -- Glycerine -- 2.0 -- --
Mineral Oil (55-65Vis) -- 2.0 5.0 3.0 Cetyl alcohol -- 1.0 -- --
Carbopol 940 -- -- 1.0 1.0 Triethanolamine -- -- 1.0 1.0
Ethoxylated (15 mol. ethylene oxide) coconut oil amine (Ethomeen
C/25 Armour) -- -- 1.0 1.0 Water 85.5 89.0 89.5 86.5 Perfume,
color, preservative q.s. q.s. q.s. q.s.
______________________________________
* * * * *