Note: Descriptions are shown in the official language in which they were submitted.
-
~7;~507
~ his invention relates to hairsprays and in particular to
an aerosol hairspray composition in whicb a hairspray resin is
dissolved in a liquid vehicle comprising a ~nixture of an
; organic solvent and a propellant liquid, which composition is
S packaged within a container fitted with a discharge spray valve
comprising a mechanical break-up actuator. When the actuator
ol~ the valve is operated the composition is discharged in
aerosol form through the outlet or terminal orifice in the
actuator, by the pressure within the container. Many marketed
aerosol hairsprays are of the above type at the presen-t time.
When a composition is discharged as an aerosol from a
pressurised pack, some of the aerosol particles may be inhaled
by the user or by other persons in the vicinity. The
proportion of the product discharged which is capable of
; 15 reaching and being deposited in the lung and is called herein
the "respirable fraction" of the product. Industry is
concerned that the user should not be exposed unnecessarily to
respirable particles (see the article "Health related hazards
of aerosols" by J.J. Sciarra published in Aerosol Age, Dece~ber
; 20 1977, page 4~).
- ~his invention is concerned with providing an improved
aerosol hairspray package.
; According to the present invcntion there is provided a
package for containing and dispensing a hairspray resin,
including in combination a con-tainer having a spray valve
provided with a mechanical hreak-up actuator for dispensing a
liquid in aerosol ~orm and a composition within the container
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~la 7Z5~7
comprising a solution of a hairspray resin in a liquid vehicle
comprising a mixture of an organic solvent and a liquefied
propellant, wherein
(A) the viscosity of the composition is 0.80 to .4.00
centistokes, preferably 0.85 to 2.00 centistokes,
at 25C;
(B) the pressure within the container is from 20 to 42
psig at 25C; and
(C) the mechanical break-up actuator is such -that ~/D1D2has a value up to 0.80 Such as from 0.15 to 0.80 (eg
0.50 to 0.-~0) wbere Z is the sum of the cross-
sectional areas of the s~irl channels of the actu~tor;
D1 is the diameter of the spray (terminal) orifice of
the actuator; and D2 is the diameter of the swirl
chamber of the actuator. ~.
Preferred features of the package of the invention are
(D) the diameter of the housing orifice (also known as
the body orifi.ce or tail piece orifice) o~ the valve
or, in the case where the dip tube of the valve is
fitted within the housing orifice, the internal
diameter of the dip tube is at least 25 x 10 3 ins,
eg 25 to 150 x 10 3 ins; and
(E) the valve does no-t have a vapour phase tap.
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Preferably both of the lat-ter features (D) and (E~ are
part of the package of the invention.
For a discussion of the construction of aerosol valves
reference is made to chapter 6 of "Principles of Aerosol
Technology~ by Paul A. Sanders (1970). ~ typical mechanical
- break_up actuator is described in British Patent Specification
No.799~68 (The Risdon Manufacturing Company) the drawings of
which illustrate a spray valve having four s~irl channels 58
leading to a s~irl chamber 52 from ~YhiGh liquid emerges through
the spray orifice 68. Commercially available mechanical
; break-up actuators usually have two, three or four swirl
channels and in some forms the channels taper towards the
swirl chamber. The value of Z for an actuator with tapering
swirl channels is the sum of the mean values of the cross-
: --. 15 sectional areas of the channels.
The hairspray resin is preferably included in the
composition in an amount of from ~.1 to 7.5% by weight.
The hairspray resin may be any of those known to be
suitable for holding the hair in a desired style. Amongst
2~ those that have found ~Yide commercial application are polyvinyl-
pyrrolidone; copolymers of from 92.5 to 87.5% vinyl acetate
and from 7.5 to 12.5% crotonic acid as described in US Patent
No.2~996j~71, eg National Starch Resyn 28-1310; terpolymers
of from 7 to 89% vinyl acetate9 6 to 13% crotonic acid and from
2S 5 to 80% of a vinyl ester of an alpha-branched saturated
aliphatic monocarboxylic acid having a minimum of five carbon
atoms in the carboxylic moiety, said acid having the formula
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~1~7ZSO7
R3C(R1)(R2)COOH where R1 and R2 are alkyl radicals and~R3 is
selected from hydrogen, a].kyl7 alkaryl, aralkyl and aryl
radicals, such terpolymers being described in British
t~ 3l~J0~9~ 4~ ~ 7~
Specification ~o.1,169,862 and US~ pplication Scrial No.~5,~3~,
and similar terpolymers being described in US Yatent No.3,5~9~629,
a commercially available terpolymer of -this type being that sold
under the name National Starch Resyn 2~-2930; copolymers of
from 20 to 60~o of N-vinyl pyrrolidone and from ~0 to 8~C/o of
vinyl acetate such as those described in US Patent ~o.39171,784,
- 10 and which copolymers are commercially available under the
designations Luviskol 37E and Luviskol 28I; copolymers of
maleic anhydride (1 mole) and an olefin (1 mole) containing 2
.. .. . .... . . . . ....
to 4 carbon atoms9 particularly ethylene, said copolymer having
a ~olecular weight of about 25,000 to 70,00~, preferably being
esterified to the exten-t of 50 to 70% with a saturated aliphatic
alcohol containing from 1 to 4 carbon atoms~ such as are
described in US Patent No.29957,838; amphoteric acrylic resins
as described in ~S Patent No.3972692~8 and available commercially
. under the trade name Amphomer;. and copolymers of methyl vinyl
ether and maleic anhydride (rnolar ratio about 1:1) and such
; copolymers esterified with a saturated aliphatic alcohol
containing from 1 to 4 carbon atoms9 an example thereof being the
resin available commercially under the trade name Gantrez ES ~35.
~owever, those skilled in the art will appreciate that other
resins are suitable for use in hairsprays, see for example the
section entitled "~air Lacquers or ~air Sprays", commencing on
. page 35Z of Volume 2 of "Cosmetics Science and Technology"
: edited by M.S. Balsam and Edward Sagarin (1972~.
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~7Z507
Those copolymers T~hich contain acidic group~ and are water-
insoluble are usually used in their neutralised water-soluble
formO Suitable neutralising agents which may be included in
the hairspray composi-tion are amines, especially aminoalcohols,
preferably 2-amino-2-methyl-1,3-propanediol and 2-amino-2-methyl-
1-propanol. Other suitable neutralising agents are also given
in US Patent No.2,996,471.
Organic solvents for the hairspray resin which are commonly
used in formulating hairspray compositions are ethanol9
isopropanol~ methylene chloride, methoxyethanol and 2-ethoxy-
ethanol, and mixtures thereof with water.
The propellant gases used in formulating aerosol hairsprays
are well known to those skilled in the art. The propellant is
usually a halogenated hydrocarbon~ the fluorochlorohydrocarbons
i5 of the C1 and C~ alkanes being the most ~ell known, or a
liquefiable hydrocarbon. Commonly used propellants are
trichlorofluoromethane (propellant 11), dichlorodifluoromethane
(propellant 12), butane and propane9 and mixtures thereof.
Other suitable propellants are referred to in US Patents Nos.
20 39026,2509 39145,147 and 299579838, and more general:ly in the
section entitled "Propellants" commencing on page 443 of
Volume 2 of "Cosme-tics Science and Technology" referred to
previously.
The hairspray colnpositions of this invention may contain
2~ adjuvants conventionally used in compositions of this type ~or
example plasticisers, perfume.s9 dyestuffs and anti-seborrhoeic
agents. Suitable anti-seborrhoeic agents are described in
- 6 _ /
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British Specifications Nos .1 9 296,102 and 1,305,358.
Polydimethylsiloxane-polyoxyalkylene copolymers as described
in British Specification No.1,42~,002 may also be included.
The respirable fraction of the particles produced by an
5 aerosol pack was determined in the following experiments using
an IIexhlet elutriator (Brit. J. industr. Med.~ 19549 119 28~)
which separates particles according -to their falling ~elocities
in the air. The aerosol is drawn at a controlled hori~ontal
veloci-ty through a parallel plate elutriator; the vertical
spacing of the plates is such that particles settling on them
during the transit of the aerosol through the elutriator
correspond to those which would separate aerodynamically in the
upper respiratory tract of man. Thlls the particles passing
through the elutriator and collected on a filter represent
those which would penetrate to the human lungs. The upper
aerodynamic si~e limit for respirable particles collected in the
Hexhlet is about 7 microns.
,' The procedure was as follows. A filter, dried and
weighed, was loaded into the Hexhlet sampler and the
pressurised pack to be tes-ted was weighed. The ,-~acuum was
adjusted so that the gauge on the Hexblet showed about 300 mm Hg.
~fter thorough shaking the aerosol was sprayed in-to a cabi~et
fitted to the front of the Hexhlet sampler, each spray was of
2 second duration, the sprays being repeated with shaking every
2~ second for a total of 20 sprays. Sampling was continued
'-~ for 5 minutes after the last spray. The pack was re-weighed ',
- -to gi,ve the weigbt of product di,scharged. The weight collected
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; is expressed in milligrams per 1~ g of product discharged.
This weight is a measure of the respirable material irl an
aerosol cloud. In order to be able to compare respirable
fractions obtained from products containing different amounts of
resin9 it is necessary to allow for the evaporation of the
solvents from the droplets in the aQrosol cloud during sampling9
and this is effected by dividing the respirable fraction
(mg/100 g) by the percentage weight of the resin in the productg
the quotient being referred to herein as the Corrected
Respirable Fraction.
The measurement of respirable fraction was carried out at
a relative humidity of 50% and a temperature of 20C.
Experiment,s will now be described illustrating the effect
of the above parameters on the corrected respirable fraction of
an aerosol spray~ Measurements of viscosity and pressure were
~--carried out at 25C unless stated otherwise. In all cases~ -
prior to ~illing with propellant all aerosol cans were purged
of air: Percentages are by weight.
The effect of can pressure, formulation viscosity and
mechanical break-up actuator on the corrected respirable
fraction is illustrated in Table I.
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TA~I,E I
___
__ ___ ______ _
Can Pressure Formulation Value of Z_ Corrected
(psig) Visco~ity for D D2 Respirable
(centistokes) Actuator 1 Fraction
___ ____ _ _ __________ ____
S 3z I _ _0.8Z _ _ L _.6 _ _ 10 _
~ _ ~ 1.7 ~ 0'7
0.82 0.66 24
0.75 33
~0 - - 1-.~ -- L o 66 - = -i
The compositions employed in the experiments summarised in
~able I had a product to propellant ratio of 40:60. The
product consisted of a solution of National Starch Resyn 28-1310
(a copolymer of vinyl acetate (90%) and crotonic acid (1~)) in
ethanol. The lower viscosity composition contained 0.8% resin
and the higber viscosity one 3~0 resin. The products also
co~tained 10% based on the weight o e the resin of amino methyl
propanol as a neutralising agent. In each case a blend of
Propellants 11 and 12 were used, -the ratios being 70:30 and 50:50
in the case O:e the lower and higher pressure compositions,
respectively.
~ 9
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In these experiments the same valve was llsed. The
housi,ng orifice of the valve had a diameter of 80 x 10 3 ins.
The effect of formulation viscosity on tlle corrected
respirable fraction is also shown by the data given in Table II
; 5 below. In this case the can pressure (46 psig) was constant
and the same valve and actuator were used, the latter having a
,; /D1D2 value of O.i8 The housing orifice of the valve had a
' diameter of 80 x 10 ins.
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'' TABLE II --
,
- 10 ~nount of Resin Fornnulation Viscosity Corrected Respirable
~ (%) (centistokes) Fraction
:' _ _ ._ __ _ __
' 0.2 ~.2~ ~00
O .5 ~. 25 265
1.0 0.3~ 200
' 1.8 ~.~5 17
~' 3.0 ~.8~ 75
`................. 4.0 1.35 30
_ _ __ _
: In the experiments whose results are reported in Ta'ble II,
the resin employed was National St,arch Resyn 28-2930 (a
terpolymer O-r vinyl acetate (75%)7 crotonic acid (10%) and a
vinyl ester of a 'branched chain fatty acid (i5%) ) . Amino
methyl propanol in an amount oi' 10% 'based on the weight of the
resin as a neutralising agent was also present. The
25 formulations had the following composition:
,, - 1 0 - / - -
~97%~07
Prodllct
Res:in as speci.riecl in Table II
NeutYal:i9illg agent10% Of resin
Ethanol to 15
Propellan-t
l':ropellant 11 51
Propellant 12 34
Ttle e.f'.t'ect o:t' variation in the value of the ratio Z/D1D2
:ror the actllator of the valve is also shown by the data giver
1l:) in Tabl,e III. ,
TABLE III
2 Corre _ed Respirable Fraction
, 0.36 1~
0.66 28
0.75 38
().~5 ~6
:l.10 52
The data in Table III were obtained employing a hairspray
having the following composition:
2 0 o/o
National Starch Resyn 28-1310 2.0
Amino methyl propanol 0.2
¢thanol 37.8
l'ropellants 1l/12 (ti5:35) 60.0
: -- 11 -/ ., .
~ ~7;~51~7
This composition had a v-iscosity of 0.9~ centistokes and
the pressure within the aerosol container was 36 psig. The
housing orifice ol the valve had a diameter of 80 x 10 3 ins.
The results of experiments showing the effect of the
diameter of the housing orifice on the corrected respirable
fraction are summarised in Table nr.
TABLE IV
.
_____ ___ __ ________ .....
~ousing Orifîce Corrected Respirable
(thousandths of an inch) Fraction
__ _ . _ ___ _____
: 1~) 13 52
18 41
27
` 80 22
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In the experiments on which t~e results of Table IV are --
based there was used a Formulation containin~ 2yo of National
Starch Resyn 28-1310. The remainder of the composition
consisted of amino methyl propanol (0.2%) ~ ethanol (37.8%) and
a 65:35 blend (60%) o-F propellants 11 and 12. The composition
had a viscosity of 0.94 centistokes and the pressure within the
aerosol con-tainer was 36 psig. T~le same actuator was used
throughout -this experiment and it had a /DlD2 value of 0. 43.
In all the above experiments the valve employed had no
vapour phase tap. Use of a vapour phase tap leads to an
increase in the respirable fraction. This can be seen from
the following Table V ~hich gives values for the corrected
respirable fractions for two pairs of packages the individual
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packages of each pair differing only in that -the spray valve
of one had a vapour phase tap whereas the other did not.
For the second pair a spray valve with a larger housing orifice
was employed.
TAB LE
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. =
Housing Orifice Housing Orifice
D i ame-t e r o f D i amet er o f
25 x 10-3 ins ~0 x 1[)~3 ins
___ __ _ . ~ ___
10 No vapour phase tap 136 64
~apour phase tap of 204 ~3
L 13 x 10-3 ins L _
The formulation of the aerosol composition was as follows:
0~
National Starch Resyn 28-2930 1.10
Amino methyl propanol O . li
Ethanol i3 . 79
Propellant 11 - 51. 00
Propellant 12 34 . 00
This composition had a viscosity ol' 0.32 centis-tokes and
the pressure within the aerosol container was 46 psig. Tbe
value of the ratio Z/D1D2 for the mechanical break-up actuator
was 0.43.
The following Examples illustrata the use of hydrocarbon
25 propellants.
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Composi-tion Example 1 E~ample 2
National Starch Resyn 28-2930 2.30 2.30
A~ino metbyl propanol0.23 0.23
Sucrose octaacetate 0.10 0.08
Perfume 0.20 0.20
Water 10-.`00
Methylene chloride - 25.00
Hydrocarbon propellant16.00 18.00
Industrial methylated spiritto 1~0.00 to 100.00
.
- 10 Viscosity of composition1.51 1.10
(centis-tokes)
Pressure within the aerosol 36 25
container (psig)
Actuator Z/DlD2 ratio0.36 0.36
Diameter of ~ousing orifice 80 80-
(x 10-3 in)
Gorrected respirable fraction 8 10
The spray valves employed had no vapour phase tap.
The hydrocarbon propellant was Calor Aerosol Propellant
- 20 Grade 30~ a commercial hydrocarbon blend consisting mainly of
- a mixture of propane and butanes having a vapour pressure of
about 30 psig at 21C.
In all the aerosol products referred to above the aerosol
valve was provided with a so-called standard dip tube, ie the
dip -tube was fitted over the end of the valve tail piece. Tbe
- dip tubes employed had an internal dian~eter in -the range from
~ 80 to 120 x 10- ins. However, it is possible to employ so-
~6~7Z507
called capillary dip tubes which fit within the housin~ ori~ice.
In this case it is required that the internal diameter of the
dip tube is at least 25 x 10 3 ins. Increasing the diameter of
` the capillary dip tube acts to reduce the va~ue of the corrected
respirable ~raction. Capillary dip tubes usually have an
internal diameter up to about 60 x 10 3 ins.
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