U.S. patent number 3,800,033 [Application Number 05/313,077] was granted by the patent office on 1974-03-26 for hair control compositions and method of use.
This patent grant is currently assigned to Lever Brothers Company. Invention is credited to Richard Edwin Flawn, Malcolm Richard Nearn, Peter John Petter.
United States Patent |
3,800,033 |
Flawn , et al. |
March 26, 1974 |
HAIR CONTROL COMPOSITIONS AND METHOD OF USE
Abstract
A hair control preparation, particularly an aerosol hairspray,
comprises a solution of a film-forming resin and a normally solid
plasticiser for the resin which gradually volatilises from the
resin after the hair control preparation has been applied to the
hair, the weight ratio of resin to volatile plasticiser being from
1:2 to 20:1.
Inventors: |
Flawn; Richard Edwin
(Shepperton, EN), Nearn; Malcolm Richard (Camberley,
EN), Petter; Peter John (Maidenhead, EN) |
Assignee: |
Lever Brothers Company (New
York, NY)
|
Family
ID: |
10478007 |
Appl.
No.: |
05/313,077 |
Filed: |
December 7, 1972 |
Foreign Application Priority Data
|
|
|
|
|
Dec 8, 1971 [GB] |
|
|
56968/71 |
|
Current U.S.
Class: |
424/47;
424/DIG.2; 424/DIG.1; 424/70.11 |
Current CPC
Class: |
A61K
8/046 (20130101); A61K 8/8182 (20130101); A61K
8/42 (20130101); A61Q 5/06 (20130101); A61K
8/368 (20130101); A61K 8/8147 (20130101); Y10S
424/01 (20130101); Y10S 424/02 (20130101) |
Current International
Class: |
A61k 007/10 () |
Field of
Search: |
;424/71,47 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rosen; Sam
Attorney, Agent or Firm: Kline, Jr.; Louis F.
Claims
What is claimed is:
1. A hair control preparation for imparting hold to the hair yet
enabling the hair subsequently to be easily brushed out as the hold
diminishes, said hair control preparation comprising a solution
of
i. from about 1 percent to about 10 percent by weight of a
film-forming resin having a glass transition temperature of from
about 20.degree. C to about 150.degree. C,
ii. a plasticiser for the resin which is a solid and which has a
vapour pressure at a temperature of 25.degree. C and a pressure of
760 mm Hg of from about 0.00001 mm to 2 mm Hg, and which gradually
volatilises from the resin thereby diminishing the hold property of
the preparation, after applying the preparation to the hair, and
the weight ratio of film-forming resin to volatile plasticiser
being from 1:2 to 20:1.
2. The hair control preparation as claimed in claim 1, wherein the
resin is a copolymer of vinyl pyrrolidone and vinyl acetate
containing at least 70 percent by weight of vinyl acetate.
3. The hair control preparation as claimed in claim 1, wherein the
resin is a copolymer of vinyl acetate and crotonic acid.
4. The hair control preparation as claimed in claim 2, wherein the
volatile plasticiser is propionamide.
5. The hair control preparation as claimed in claim 2, wherein the
volatile plasticiser is selected from the group consisting of
benzoic acid and salicylic acid.
6. The hair control preparation as claimed in claim 3, wherein the
volatile plasticiser is propionamide.
7. The hair control preparation as claimed in claim 1, additionally
comprising an aerosol propellant.
8. A process for treating human hair to impart hold to a desired
style and subsequently to facilitate the brush-out property of the
hair as the hold diminishes, which process includes the step of
applying to the hair a hair control preparation as claimed in claim
1.
Description
This invention relates to hair preparations, and more particularly
to hair control preparations for holding the hair in a desired
configuration. Preparations of this kind include hair setting
lotions and hairsprays, the most popular form of such product being
the aerosol hairspray or hairdressing.
These preparations act by forming a deposit of a film-forming resin
on the hair which acts to hold the hair in place and maintain it in
the desired configuration.
Users of products of this type, particularly users of hairsprays,
who use the products frequently find that the resin deposited on
the hair tends to build up despite brushing of the hair between
applications and that as a consequence the hair becomes
progressively more difficult to comb and brush out. Furthermore,
this accumulation of resin gives the hair an unnatural feel. One
can, of course, mitigate this disadvantage by applying less resin
to the hair but this, however, results in less hold being
obtained.
In the work leading up to the present invention we found that the
resins which have the better hair retaining properties are those
which are relatively flexible whereas those which are the more
easily combed or brushed out of the hair are the more brittle
resins. In other words, those resins having the lower glass
transition temperatures (Tg) have the better hold characteristics
and those of higher glass transition temperatures have the better
comb-out properties.
We have now discovered that improved hair control preparations can
be formulated by including along with resin a resin-modifying agent
which is normally solid (i.e., is solid at 20.degree. C) and which
softens the resin and improves its initial holding properties but
which over a relatively short period of time, say within 15 hours,
volatilises from the hair whereby the resin is gradually converted
into a form in which it is more easily combed out of the hair.
Accordingly the invention provides a hair control preparation
comprising a solution of a film-forming resin and a normally solid
material which plasticises the resin and which gradually
volatilises from the resin after applying the preparation to the
hair, the weight ratio of resin to volatile plasticiser being from
1:2 to 20:1.
An advantage of the invention is that by the use of the volatile
plasticiser one can improve the initial holding properties of the
resin (matching that obtainable with a comparable or even greater
amount of a softer resin) and produce a resin deposit which
develops over a period of time an improved ease of removal as the
plasticiser volatilises from the hair. From another aspect, the use
of a volatile plasticiser in accordance with the invention permits
one to improve the initial hold properties of a hair preparation
without increasing the amount of the resin in the preparation: an
increase in the amount of the resin would result in more resin
being applied to the hair with the consequence that the hair would
be more difficult to comb out.
The film-forming resins used in preparations in accordance with the
invention desirably have glass transition temperatures (Tg) of at
least 20.degree. C. The use of the Tg is a common way of
characterising resins and is described for example by Burrell, H in
"Official Digest," 34, 131 (1962). It can be determined by the
technique known as Differential Thermal Analysis (see, for example,
the method of Keavney, JJ and Eberlin, EC in J.Appl.Polymer Sci., 3
47 (1960). A high Tg is an indication of the brittleness of a
resin. In accordance with our finding that the more brittle the
resin the more easily it is combed out of the hair, the preferred
resins used in hair compositions of this invention are those having
a Tg of at least 35.degree. C and usually no more than 150.degree.
C.
The volatile plasticisers used in preparations in accordance with
the invention desirably have a vapour pressure at a temperature of
25.degree. and at a pressure of 760 mm Hg of from 0.00001 mm to 2
mm Hg. The preferred plasticisers have a vapour pressure of from
0.0001 mm to 0.1 mm Hg.
Suitable combinations of resin and volatile plasticiser that
illustrate the invention are listed below together with relevant
glass transition temperature and vapour pressure data.
______________________________________ Compatible Volatile Resin
Plasticisers ______________________________________ LUVISKOL VA 28I
propionamide (a copolymer containing benzoic acid 20% vinyl
pyrrolidone and salicylic acid 80% vinyl acetate having menthol a
Tg value of 42.degree.C and thymol supplied as a 50%
methyl-2-naphthylketone solution in isopropanol) LUVISKOL VA 37E
propionamide (a copolymer containing benzoic acid 30% vinyl
pyrrolidone and salicylic acid 70% vinyl acetate having
hexachloroethane a Tg value of 65.degree.C and benzophenone
supplied as a 50% solution in ethanol A copolymer containing
propionamide about 43% methacrylic acetamide acid and about 57%
hexachloroethane methyl acrylate having benzophenone a Tg value of
95.degree.C ______________________________________
We have also found that propionamide is also a suitable volatile
plasticiser for use with the following resins:
______________________________________ Tg Value* Resin .degree.C
______________________________________ Bina 405, an acrylic ester
amide copolymer containing carboxyl groups 90 National Starch Resyn
28-1310, a copolymer of vinyl acetate and crotonic acid 47
Aristoflex C, a copolymer of vinyl acetate and crotonic acid 48 VEM
640 - M48, a vinyl terpolymer containing ester, acrylic and
carboxyl groups (supplied as a 48% solution in ethanol) 35 Gantrez
ES 225, a copolymer of methyl vinyl ether and monoethyl ester of
maleic acid (supplied as a 50% solution in ethanol) 90 Gantrez ES
335-I, a copolymer of methyl vinyl ether and monoisopropyl ester of
maleic acid (supplied as a 50% solution in isopropanol) 35 Gantrez
ES 435, a copolymer of methyl vinyl ether and monobutyl ester of
maleic acid (supplied as a 50% solution in isopropanol) 96
______________________________________ (* as determined by the
Keavney et al. method)
The vapour pressures at a temperature of 25.degree. C and at a
pressure of 760 mm Hg of the volatile plasticisers referred to
above are as follows:
______________________________________ Vapour Pressure Volatile
Plasticiser (mm Hg) ______________________________________
Propionamide 1.2 .times. 10.sup.-.sup.2 Benzoic acid 6.5 .times.
10.sup.-.sup.4 Salicylic acid 1.4 .times. 10.sup.-.sup.4 Menthol
5.0 .times. 10.sup.-.sup.2 * Thymol 1.6 .times. 10.sup.-.sup.2
Methyl-2-naphthylketone 4.0 .times. 10.sup.-.sup.4 *
Hexachloroethane 6.3 .times. 10.sup.-.sup.1 Benzophenone 2.0
.times. 10.sup.-.sup.3 * Acetamide 1.8 .times. 10.sup.-.sup.2
______________________________________ * estimated values
It is to be understood that the invention is not limited solely to
the resin/volatile plasticiser combinations specifically referred
to above. Some experimentation may be necessary in order to select
other suitable combinations of resin and normally solid volatile
plasticiser for use in the present invention. A plasticiser for one
resin is not necessarily suitable for plasticising another resin.
For instance, benzophenone, when used with resins obtained by
copolymerising vinyl pyrrolidone with no more than an equal amount
of vinyl acetate (and with certain other water-soluble resins) is
reported in British Patent Specification No. 868,879 to result in a
stiffening of the resin (i.e., the opposite of a plasticising
effect).
The film-forming resin and the volatile plasticiser are both
present in the hair preparation as a solution in a mutually
suitable solvent. As an example, the solvent can be a volatile
organic solvent such as an alcohol, especially ethanol, isopropanol
or 2-methoxyethanol: methylene chloride is also a suitable volatile
organic solvent.
The weight ratio of film-forming resin to volatile plasticiser in
the hair preparation according to the invention is from 1:2 to
20:1. By appropriate choice of the ratio of resin to plasticiser
and of the content of resin in the solution, it is possible to
obtain hair preparations which differ widely in their
properties.
At low resin:plasticiser ratios, the difference between the degree
of hold exerted by the hair preparation initially and that exerted
when the majority of the plasticiser has volatilised is quite
marked, whereas at high resin:plasticiser ratios the difference
between the initial hold and the hold at a later time is less
marked.
The preferred weight ratio of film-forming resin to volatile
plasticiser is from 1:1 to 10:1.
The amount of resin present in the solution will depend on the
degree of hold the product is intended to produce and will usually
be from 1 to 10 percent by weight of the solution.
The hair preparation is preferably in the form of an aerosol
hairspray. In this case the solvent, especially one of those
previously exemplified, the film-forming resin and the volatile
plasticiser will be present in an aerosol dispenser together with a
suitable aerosol propellant, usually a liquefied normally gaseous
substance. Commonly used propellants are trichlorofluoromethane
(propellant 11) and dichlorodifluoromethane (propellant 12) but
others may be employed. Suitable propellants and propellant
mixtures for use with hairsprays are well known to those in the
art.
Aerosol hairspray preparations in accordance with the invention
will comprise concentrate and propellant in the usual ratios,
generally from about 2:1 to 1:5 with the concentrate having
typically the following composition:
% by weight ______________________________________ Resin 1 to 10
Volatile plasticiser 0.05 to 10 Perfume 0.3 to 1 Solvent balance to
100
In aerosol hairsprays, the amount by weight of resin based on the
total weight of hairspray is usually from 0.5 to 4.0 percent.
In further embodiments of the hair control preparation of the
invention other than those based on an aerosol formulation, the
preparation may simply be in the form of a solution of the resin
and plasticiser in the solvent, for example in the weight
proportions as set out for the above concentrate. In other product
forms, particularly for hair setting lotions, an aqueous alcoholic
solvent can be used. In certain other cases it might also be
possible to use water as the solvent, although the presence of a
volatile organic solvent is preferred to give a quick drying
product. Other conventional ingredients can be incorporated, if
desired, for example a denaturant for ethanol.
In accordance with a further aspect of the invention, a process is
provided for treating human hair to impart hold to a desired style
and subsequently to facilitate the brush out property of the hair
as the hold diminishes by applying to the hair a hair control
preparation of the type defined herein .
Examples of hair control preparations in accordance with the
invention will now be described. Percentages are by weight.
EXAMPLE 1
A hairspray of lotion was prepared having the following
composition:
% ______________________________________ Luviskol VA 37E (50%
solution in ethanol) 6.0 Propionamide 0.6 Perfume 0.5 Denaturant
0.2 Industrial methylated spirit to 100.0
EXAMPLE 2
An aerosol hairspray was prepared having the following
composition:
% ______________________________________ Luviskol VA 37E (50%
solution in ethanol) 4.00 Propionamide 0.40 Perfume 0.20 Denaturant
(sucrose octaacetate) 0.05 Industrial methylated spirit 35.35
Propellant 11 39.00 Propellant 12 to 100.00
EXAMPLE 3
An aerosol hairspray was prepared having the following
composition:
% ______________________________________ Luviskol VA 37E (50%
solution in ethanol) 4.0 Benzoic acid 0.4 Perfume 0.2 Denaturant
0.1 Industrial methylated spirit 35.3 Propellant 11 39.0 Propellant
12 to 100.0
EXAMPLE 4
An aerosol hairspray was prepared having the following
composition:
% ______________________________________ Luviskol VA 28I (50%
solution in isopropanol) 3.2 Propionamide 1.0 Perfume 0.2
Denaturant 0.1 Industrial methylated spirit 35.5 Propellant 11 39.0
Propellant 12 to 100.0
EXAMPLE 5
An aerosol hairspray was prepared having the following
composition:
% ______________________________________ National Starch Resyn
28-1310 1.50 2-amino-2-methyl-1-propanol 0.14 Propionamide 0.75
Perfume 0.20 Denaturant 0.10 Industrial methylated spirit 37.31
Propellant 11 39.00 Propellant 12 to 100.00
2-amino-2-methyl-1-propanol is present as a neutralising agent for
the resin.
EXAMPLE 6
An aerosol hairspray was prepared having the following
composition:
% ______________________________________ Bina 405 1.20 Propionamide
0.24 Perfume 0.20 Denaturant 0.10 Industrial methylated spirit
38.26 Propellant 11 39.00 Propellant 12 to 100.00
EXAMPLE 7
An aerosol hairspray was prepared having the following
composition:
% ______________________________________ National Starch Resyn
28-1310 2.00 2-amino-2-methyl-1-propanol 0.19 Propionamide 0.40
Perfume 0.20 2-methoxyethanol 6.00 Methylene chloride 36.21
Propellant 11 27.50 Propellant 12 to 100.00
The following Tests illustrate in vitro and in vivo experiments
where hair control preparations according to the invention were
applied to hair and certain properties of the hair were evaluated
over a period of a few hours as the plasticiser volatilised from
the resin. In two experiments, control data where a plasticiser was
omitted from the hair preparation is also provided for
comparison.
TEST 1
The following experiment showed the variation with time of the
resistance to combing of hair switches when sprayed with an aerosol
hairspray of the following composition:
% ______________________________________ Copolymer * 2.0
Plasticiser 0.4 Industrial methylated spirit 37.6 Propellant 11
39.0 Propellant 12 to 100.0 * Containing about 43% of methacrylic
acid and about 57% of methyl acrylate
20 switches of 28 cms length, prepared from untreated Italian hair
fitted with clips at each end were sprayed with the above aerosol
hairspray for a predetermined time so that the same amount of resin
was sprayed onto each switch. After various intervals of time four
of the switches were taken and each switch drawn through a comb
five times and an average combining resistance value determined for
the switches. In this experiment, the comb used was one which had a
strain gauge transducer cemented onto the back of it and the
varying resistance produced by varying strains on the gauge as the
hair travelled through the comb was processed electronically.
During the determination of the combing resistance value, the hair
switches were in a cabinet maintained at a temperature of
23.degree. C and a relative humidity of 35 percent.
The combing resistance values given below have been corrected to
allow for any variation in resistance to combing of the untreated
switches, so that the values given are a measure, in empirical
units, of the increase in work required to comb the hair due to the
applied hairspray.
The above test procedure was carried out on a number of
compositions containing different plasticisers and the results are
given in Table I.
We have found that the hold of the hair as judged by users
correlates well with the combing resistance.
TABLE I
__________________________________________________________________________
Time of Measurement Combing Resistance value
__________________________________________________________________________
of Combing Resistance Plasticiser
__________________________________________________________________________
Benzophenone Hexachloroethane Acetamide Propionamide
__________________________________________________________________________
1 hour after spraying 195 195 225 130 2 hours after spraying 180
175 150 110 3 hours after spraying 170 145 120 95 4 hours after
spraying 160 130 110 85 5 hours after spraying 155 125 105 80
__________________________________________________________________________
TEST 2
A similar test was carried out with an aerosol hairspray of the
following composition and the results are given in Table II.
% ______________________________________ Luviskol 37E (50% solution
in ethanol) 4.0 Plasticiser 0.4 Perfume 0.2 Industrial methylated
spirit 35.4 Propellant 11 39.0 Propellant 12 to 100.0
TABLE II
__________________________________________________________________________
Time of Measurment Combing Resistance Value
__________________________________________________________________________
of Combing Resistance Plasticiser
__________________________________________________________________________
Propionamide Hexachloroethane Benzoic Acid Salicylic Acid
__________________________________________________________________________
1 hour after spraying 170 180 114 256 2 hours after spraying 166
155 110 200 3 hours after spraying 164 130 107 145 5 hours after
spraying 160 82 92 132 8 hours after spraying 92 85 54 120
__________________________________________________________________________
TEST 3
A further test, similar to those described above, was performed to
demonstrate the effect on combing resistance at two hourly
intervals after spraying of variation in the resin:plasticiser
ratio. The test products used had the following
% ______________________________________ Copolymer used in Test 1
Propionamide 2.4 Industrial methylated spirit 37.6 Propellant 11
39.0 Propellant 12 to 100.0
The results are given in Table III.
TABLE III ______________________________________ Combing Resistance
Value Resin:Plasticiser after (wt. ratio) 2 hours 4 hours 6 hours
______________________________________ 5:1 106 84 51 2:1 176 95 85
1:2 140 129 58 ______________________________________
For a comparative product containing 2.4 percent of the resin and
no plasticiser, the combing resistance value was constant with time
at 88 units.
TEST 4
Two experimental hairsprays, one containing 2.4 percent of Luviskol
VA 37E solution (product A), the other containing 2.4 percent of
Luviskol VA 37E solution together with 0.24 percent of propionamide
(product B), were compared with a commercial hairspray containing
2.25 percent of National Starch Resyn 28-1310 (product C) in a user
panel test involving 80 women. All the women used each of the three
products for a two week period, at the end of which they completed
a questionnaire on the performance of the hairspray.
Comparison of the results for products A and C showed the
preferences as set out in Table IVa.
TABLE IVa ______________________________________ Product Level of
Statistical Preferred Significance
______________________________________ Holding power C 1 in 50 Lack
of stiffness A 1 in 10 Ease of brushing A 1 in 20 Stickiness after
brushing A 1 in 20 ______________________________________
A similar comparison of the results for products B and C showed the
preferences as set out in Table IVb.
TABLE IVb ______________________________________ Product Level of
Statistical Preferred Significance
______________________________________ Holding power B = C -- Lack
of stiffness B 1 in 100 Ease of brushing B 1 in 20 Stickiness after
brushing B 1 in 10 ______________________________________
Thus the addition of propionamide to a lightly holding resin
allowed the superior hold of the control (product C) to be matched
while retaining the superior ease of brushing and feel after
brushing of the lighter holding resin (in product B).
TEST 5
The following experiment was performed to investigate the loss by
volatilisation of propionamide from a film of Luviskol VA 37E resin
plasticised with this volatile material.
Five switches of hair of 25 cms length prepared from untreated
Italian hair and fitted with clips at the root ends, were sprayed
with the aerosol hairspray used in Test 2 and containing
propionamide as the plasticiser. After various time intervals the
switches were combed out and the resin flakes were collected in
specimen tubes. Each sample was analysed for the presence of
propionamide by gas/liquid chromatography. The results are given in
Table V.
TABLE V ______________________________________ Time of Analysis %
by weight of propionamide after spraying present in resin sample
______________________________________ 30 mins 14.9 50 mins 6.7 100
mins 4.1 150 mins 2.3 20 hours 0.5
______________________________________
* * * * *