Note: Descriptions are shown in the official language in which they were submitted.
foe
~UATEPllARY NITROGEN CONTINUITY
POLYVINYL ALCOHOL PYRES FOR USE III SKIN
CONDITION lug, COSMETIC AND PHA~IACEUTICAL FEALTIES
The present invention is directed to skin conditioning
5 polymers which when applied to skin form thin films which aid in
reducing moisture loss. The invention relates on general to film
forming polyvinyl alcohol polymer derivatives end specifically to
those having certain cat ionic qua ternary nitrogen containing
pendant groups. Of particular interest are polymers having a
10 polyvinyl alcohol backbone or base chain with pendant substituent
qua ternary ammonium groups attached through oxygen linkages to the
chain and spaced at random along the base chain. As a result of
the presence of these qua ternary amm~nium groups in the polymer,
thin film coatings on animal skin penetrate the outer layers of
15 the skin to provide sufficient adhesive properties while remaining
sufficiently elastomeric to avoid discomfort after drying. While
the thin films act as a partially impenetrable barrier to prevent
loss of moisture by evaporation they also behave as moisture
retainers through the possible formation of hydrates at the
20 qua ternary anl~onium sites and by inclusion of water molecules
through hydrogen bonding on the hydrophilic polymer matrix. In
general the compositions are made by treating readily available
polyvinyl alcohol polymers with hydroxy reactive compounds
containing quaternized anonym groups linked thereto.
It is an object of the invention to provide for a
quarter nary nitrogen containing polyvinyl alcohol polymer base
chain (having a number average molecular weight of at least 2,00Q
and preferably up to about 200,000 and higher when unmodified) and
a random distribution of a multiplicity of oxy-linked pendant
30 groups having the general formula:
:: :
-R-N+RlR2R3A
::
,
`,
, .: . Jo
.
.
~36~39
--2--
wherein
R is alkaline, substituted alkaline preferably
hydroxyalkylene, or acylene of formula weight- ranging
from 14 to about 3,000,
Al, R2, R3 are alkyd or arylalkyl radicals having 1-20
carbon atoms which may be the same or difîerer.t,
' A is an anion,
such that the total nitrogen content in the resin polymer ranges
from 0.012-7.0% by weight. Another object is to provide for a
10 preferred process for the synthesis of such compositions. It is
still another object to provide for aqueous solutions containing
0.1-307~ by weight of these polymers which are useful in skin
conditioning lotions, ointments, cosmetic and pharmaceutical
formulations for application to hair, skin and nails. Another
15 object is to provide for a film forming polymer which also
performs as a dispersant for particulate in such formulations.
R in the above formula may be selected from alkyd groups
such as ethylene, ethylene, propylene, battalion, pentylene,
hexylene, ethylhexylene, dodecylene, tetradecylene, hexadecylene,
20 octadecylene, and substituted alkyd groups such as hydroxy-
propylene, hydroxybutylene, acutely, propionyl, bitterly, octal
decanoyl, and octadecenoyl and their equivalents.
Al, R2, and Pi may be selected from the alkyd groups
such as methyl, ethyl, propel, bottle, ponytail, Huxley, octal, decal,
25 dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl,
phonology and bouncily and their equivalents.
may be selected from a large number of anions such as
chloride, bromide, iodide hydroxide lower alkylsulfate (1-6
carbon atoms), tetrafluoroborate, nitrate and per chlorate to name
30~s~few.
The qua ternary nitrogen containing polyvinyl alcohol
I; polymer compositions of the invention may be represented by a
typical polymer segment having the following idealized structural
formula
::
:
- -
:
'
~2~63~
-3-
2 1R2R3A Jo CH2CHOH-)m(CH2CHORN+RlR2R3A-)] -
where n = 20-3000, and
m = 0-600, and
' R, Al, R2, R3, and A- are the same as described above.
' Illustrative of the types of numerous pendant qu~ternary
groups linked by oxygen as randomly distributed units in the
polyvinyl alcohol base chain may be given as follows:
(l) -CH2CH(OH)CH2N (C~3)3
( 2 [SHEA (C~3)3Cl ]O)nCH2CH(OH)CH2N+(C~3)3Cl-
n = 1-20
(3) -(COUCH (CH2CH3)3Br
4) -CH2CH(OH)C~2ll (CH3)2(CH2P )
( ) CH2CH2~l (cH3)(cH2c~3)(cH2ph)cH3so4
where Pi = phenol.
While the above structures serve to illustrate the types
15 of pendant qua ternary ammonium groups which can be added to the
polyvinyl alcohol base chain it is apparent to one skilled in the
art that many other arrangements of similar chemical structure can
be easily incorporated. It has been found that each of the above
types of groups used alone or in combination with one or more of
Thea others as a substituent on the polyvinyl alcohol base chain
yields the desired combination of products having useful moisture
barrier properties especially whorl the nitrogen content of the
final product ranges from 0.01%-7% and preferably .01-3~ by
White Depending on the type of radical attached to the nitrogen.
2~5 of~the~quaternary group the effective range of the nitrogen
content could be even more specific It has been found for
'
~L236~
example what when the Al, I R3, in the above general formulas
are all methyl radicals the effective nitrogen content may range
from 0.1-3~ by weight.
While many techniques have been employed in the art to
add 'substituent qua ternary groups to vary polymer charge four
preferred methods for attaching the substituent groups to
polyvinyl alcohol im701ve the reaction of the hydroxy groups Or
polyvinyl alcohol with an epoxy (oxirane) group or a halohydrin
group in aqueous solution, or a low molecular weight alkyd alcohol
10 ester of the sllbstituent in a bipolar aprotic solution or an acid
halide in either a bipolar aprotic solvent or a two phase
system in the presence of base catalyst or acid catalyst when
appropriate.
While a number of methods may be utilized for the
15 preparation of the PEA derivatives described in this invention,
the use of non-aqueous solvents such as dim ethyl formamide or
similar polar materials is possible, but generally these solvents
must be thoroughly removed from the final product. The use Or
aqueous solvents or mixed aqueous systems is preferable but, in
20 this case, yields must be optimized because of competitive
reactions of the qua ternary ammonium compound with water as well
as PEA hydroxyls in the presence of catalyst. Improved yields can
be obtained by increasing the PEA concentration in water, adding
the oxirane compound as a concentrate and reducing to a minimum
25 the amount of base used to catalyze the addition reaction. Salt
formed during the reaction is preferentially removed from the
final product, since it may have a deleterious effect on the skin
moisture barrier properties and its formulation. It has also been
found that the pi of the derivatized PEA may affect the skin
30 moisture barrier properties as well as the substantivity to skin..
It is generally desirable to work in a pi range between 2-10
preferably from 5-9.
The product can be obtained in a dry form by
precipitation, filtering, drying and grinding. The precipitation
35 is accomplished by adding the reaction mixture to a nonsolvent
such as acetone, methanol, ethanol and the like. The product also
finds use in the form of the aqueous solution or suspension which
:,...
:
,
~236~39
--5--
can preferably be obtained by dwelling the reaction mass to free
it from salts and low molecular weight unrequited intermediates.
To obtain a better understanding of the preparative techniques
found to be most satis~aetory attention is dray to the following
5 generalized and specific preparations which are intended to
illustrate but not limit the invention and wherein all proportions
mentioned are based on weight unless otherwise specified.
General Preparation I
A flask equipped with a water cooled condenser,
lo mechanical stirrer and thermometer is charged with polyvinyl
alcohol and distilled water. The polyvinyl alcohol (POW) which is
generally a commercially available product prepared by hydrolysis
of polyvinyl acetate may have from 0 to 25% residual acetate
groups, preferably from 2 to 15% and the number average molecular
15 weight may range from 2,000 to 200,000 and higher and preferably
from 25,000 to 150,000. In addition, and for the purpose of this
invention, a polyvinyl alcohol base chain may include up to I by
weight of another comonomer such as vinyl pyrolid~ne, acrylic and
methacrylic acids and esters thereof. The aqueous slurry is
20 heated to 80-90C and held for 1 hour or until the polyvinyl
alcohol is completely dispersed or salivated. A catalytic amount
of aqueous base such as alkali hydroxide such as sodium or
potassium hydroxide is then added and the solution cooled to
40-90C. At this point 2,3-epoxypropyltrialkylammonium halide,
25 either in aqueous solution or crystalline form, may be added
incrementally or all at once. This reagent is typically used in
0.003-l.0 mow ratio preferably from 0.10-0.3 mow per mow of
hydroxyl group on the polyvinyl alcohol base chain. The entire
solution is then stirred for an additional period typically 4
30 hours at 60C after which the solid product may be recovered.
Recovery is accomplished by one of two general
techniques. The solution can be poured into a polymer non-solvent
to precipitate solid product from aqueous solution. Alternatively
I,
3L236~
the solution may be dialyzed through a simpers membrane and the
purified aqueous polymer used as obtained or precipitated out.
The precipitation is preferably accomplished either if.
acetone or in methanol affording yields up to I or better by
weight after drying. Depending on reaction conditions the
precipitated products have a nitrogen content in the range of
0.01-7~.
In the purification by dialysis the reaction mixture is
freed from all species below a certain molecular weight. Two
lo methods may be used one a static and one dynamic. In the static
method the reaction mixture is placed inside a commercial
semi-porous dialysis tube and the tubes are submerged in distilled
water typically for periods of I to 48 hours. The contents of
the tubes are then recovered and the product may be used as is.
15 In the dynamic system a pressure pump is used to Jove water iron.
the reaction mixture through a simpers membrane. The water
carries out any inorganic and lo- molecular weight organic. The
resulting concentrated product stream is then collected.
General Preparation II
A flask equipped as described in General Preparation 1
is charged with polyvinyl alcohol and distilled water. The
aqueous slurry is heated to 80-90C and held for one hour or until
the polymer is completely salivated. A catalytic amount of aqueous
alkaline hydroxide such as sodium or potassium hydroxide is added
25 and the pot cooled to 60-65C. At this point, (chlorohydroxy-
propyl)trimeth~lammonium halide, either in aqueous solution or
crystalline form, is added either incrementally or all at once.
This reagent is typically used in Lowe mole ratio preferably
from OWE mole per mole of hydroxyl group on the polyvinyl
30 alcohol base chain. The entire solution is then stirred at 40-
~90C for an additional period, typically four hours. The product
; is then recovered by one of the methods described in GeneralPr~eparatioD I.
::
.
36639
--7--
General Preparation III
In preparing qua ternary ammonium groups linked to the
polyvinyl alcohol base chain through ester linkages it is
preferred to prepare thrill using a transesterification technique.
In a typical reaction a four-neck one liter round bottom flask
equipped with a thermometer, mechanical stirrer, water cooled
condenser and a nitrogen sparser is charged with polyvinyl alcohol
as described in the above General Preparation I, dim ethyl-
formamide, a trialkylalkoxycarbonyl ammonîum halide, and a small
10 amount of a transition metal salt as catalyst as manganese acetate
for example. The entire dispersion is then heated to a
temperature of Luke for 2 to 24 hours preferably 3 to 6
hours. Nitrogen is used as a carrier gas to remove the alcohol
formed during the esterification reaction. The solution is then
15 cooled to ambient temperature and poured into a polymer nonsolvent
such as for example methanol, ethanol or acetone. The resulting
precipitate is collected by filtration, washed, shredded
mechanically and dried under vacuum to afford a nearly white
product with a desired nitrogen content.
Jo ..
20 General Preparation IV
A flask equipped as described in General Preparation I
is charged with polyvinyl alcohol and distilled water. The
aqueous slurry is heated to 80-90C and held for one hour or until
the polymer is completely dispersed or salivated. A catalytic
25 amount of an acid such as sulfuric acid or aluminum hydrosilicate
or any proton acid or Lewis acid is added and the pot cooled to
40-90C. At this point 2,3-epoxypropyltrialkyla~r~onium halide may
be added incrementally or all at once. This reagent is typically
used in 0.003-1.0 mole ratio preferably from 0.1-0.3 mow per mow of
30 hydroxyl group on the polyvinyl alcohol base chain. The entire
solution lo then stirred for an additional period typically 4
::
~L23~t';39
hours at 60C aster itch thy solid product may be recovered by
one of the methods described in General Preparation I.
The following examples and preparations serve to
illustrate but not limit the invention. All proportions used
5 Rafferty parts by weight unless otherwise specified.
r
Preparation A
(Chlorohydroxypropyl)trimethylammonium chloride
A one-liter flask equipped with dropping funnel,
mechanical stirrer, thermometer a condenser was charged with
10 epichlorohydrin (95 grams, 1.0~ molt and placed in an isothermal
bath at 18C. Aqueous trimethylamine (238.7 grams, 25% by weight,
1.01 molt was then added drops over a 3 hour period maintaining
the temperature below 25CC when the addition was complete the
solution was allowed to stir overnight at ambient temperature.
Example 1
RN RlR2R3A = -CH2-CH(OH)CH2N(CH3)3Cl
A flask equipped as described in General Preparation I
was charged with 44 grams polyvinyl alcohol (commercially
available) having a molecular weight of 126,000 (98~ hydrolyzed -
20 2% acetate) and 400 milliliters of distilled water. The resulting slurry was heated to 85C and held for 1 hour. The polymer
dissolved completely to afford a pale yellow transparent solution.
Potassium hydroxide (3.0 gram, 0.11 molt in water (30 milliliters)
was then added and the solution cooled to 60C. Aqueous (sheller-
25~hydroxypropyljtrimethylammdnium chloride (78 milliliters of 4~7~ boutiques solution prepared according to Preparation A), was
then added all at once and the entire solution was heated to 6Q-
65C~for 4 additional hours. The warm solution was poured with
::: :` : :
:
~;~36639
g
stirring into acetone (2.0 liters) and allowed to stand. 63.5
grams OX colorless solid precipitate was collected by filtration
shredded mechanically and dried under vacuum.. The nitrogen
content of the product was 2.15% by weight wherein the value for
(m) -in the above general formula segment is approximately 21.
Preparation B
Crystalline 2,3-epoxypropyltrimethylammonium chloride
A one-liter flask equipped with gas sparser, Messianic
stirrer, thermometer and an aqueous acid trap was charged with
10 epichlorohydrin (55.2 grams, 6.0 molt and placed in an isothermal
bath at 19C. Tri~ethylamine gas (119.5 grams, 2.0 molt was then
sparred into the epichlorohydrin over a period of 3 hours. The
temperature was mairltained below 23C. The solution was stirred
for an additional 30 minutes and the precipitate collected by
15 filtration. The crystalline product was washed with diethylether
and vacuum dried to afford 262.2 grams of 2,3-epoxypropyltri-
methylammonium chloride.
Example 2
-Rl~+RlR2R3A - -(H2cH(oH)cH2N(cH3)3cl
The procedure of Example 1 was repeated exactly except
that pure crystalline 2,3-epoxypropyltrimethylammonium chloride
(15.2 grams, 0.10 molt was added in place of the aqueous solution.
The mixture was then stirred for an additional 5.5 hours at 60C
Jo and recovered from acetone as described. The nitrogen content of
5~the~fina~1 product was 1.12% by weight wherein the value for (m) is
approximately 28.
: :
,,~., : :
Jo :
::
:' ' ` ' ` '''
` ~%36~39
-10 -
example 3
-RN+RlR2R3A = -CH2cH(O~)CH2N(cH3)3cl
' The procedure of Example was reproduced except that
the amount of aqueous 2,3-epoxypropyltrimethyla~monium chloride
5 was 56.2 milliliters of 48% solution and the warm aqueous polymer
was recovered by precipitation in methanol (2.0 liters). The
solid collected was shredded mechanically dried under vacuum and
ruled to a fine powder. The yield was 49.9 grams and the
nitrogen content was 0.22% by weight wherein the value for (I) in
lo the general formula segment is approximately 282.
Example 4
-RN+RlR2R3A = -CH2CH(OH)CH2N(CH3)3Cl
The procedure of Example 3 was reproduced with the
exception that the aqueous reaction mixture was cooled to ambient
15 temperature and placed in a commercially available dialysis tube.
The simpers membrane in the dialysis tube retains all
molecules with molecular weights greater than 8,000. The tubs
were placed in water (4 liters) and allowed to stand. The bath
water was changed ever 6-8 hours over a 36 hour period. The tubes
20 were then recovered and the aqueous polymer solution inside was
tested for moisture barrier properties.
Example 5
RN RlR2R3A = -C~2cH(OH)c~2~(cH3)3cl
The procedure of Example 3 was reproduced with the
I; 25 exception that recover was accomplished by precipitation from
acetone lo liters). The scale was slightly reduced to 38.0
grams polyvinyl alcohol and 49 mill lens of 48% aqueous epoxide
:: : : : :
:
: ,
I: : :
: : '
:
:
,,
63~
solution. The yield was 63.5 trams and the nitrogen content was
2.63% by weight wherein the flu for em) in the general formula
segment is approximately 15.
Preparation C
Preparation of 2,3-epoxypropyltr nethylammonium bromide
A flask equipped with a sparser, mechanical stirrer,
thermometer and efficiency condenser was charged with acetone (500
milliliters) at ambient temperature. Trimethylamine (58 grams,
0.98 molt was charged into the solution. The pot was cooled to
10 10C and epibromohydrin (137 grams, 1.0 molt was added drops
over a l hour period. The resultant cloudy solution was allowed
to slowly rise to ambient temperature and stand for 60 hours.
Precipitate was collected by filtration washed with acetone (60
milliliters) and dried yielding a colorless crystalline product
15 tl79.4 grams, 94~).
sample 6
RlR2P~3A -c~2cH(oH)cH2N(cH3)3Br
A flask equipped as described m General Preparation I
was charged with polyvinyl alcohol (44.0 groans), (98% hydrolyzed,
20 number average molecular weight equals 125,000) and 500
milliliters water. The slurry was warmed to 70C and potassium
hydroxide (3.0 grams) was added. The pot was stirred an
additional 30 minutes and 2,3-epoxypropyltrimethylammonium bromide
(49~.0 grams, 0.25 Poles) was added through a powder funnel. This
solution stirred for 16 hours at 80C. The solution was then
poured into acetone (1500 milliliters) and the precipitate was
collectedly filtration, shredded, washed and dried. The pale
brown solid powder which resulted had a nitrogen content of 2.10%
..,
:
;
.
. . . .
~3~639
-12-
by weight wherein the value for (m) in the general formula segment
is approximately 19.
Example 7
-
RlR2R3A = -CH2CH(O~)CH2N+(CH3)3Cl
A flask equipped as described in General Preparation I
woes charged with polyvinyl alcohol (44~0 grams), (100% hydrolyzed,
number average molecular weight equals 86,000), 200 milliliters
distilled water and 3 grams potassium hydroxide. The pot was
heated to 60C an aqueous (chlorohydroxypropyl)trimethylammoniu~
lo chloride (320 milliliters, 48% aqueous solution as prepared in
Preparation A) was added. Heating was continued for an additional
24 hours and recovery was accomplished by precipitation, from
acetone. After collection joshing and drying the nitrogen content
was 0.72% wherein the value for (m) in the general formula segment
lo is approximately 80.
Example 8
RlR2R3A = -cH2cH(oH~cH2N+(cH3)3cl
A flask equipped as described in General Preparation 1
was charged with polyvinyl alcohol t88.0 grams), (98.5~
20 hydrolyzed, having a molecular weight of 25,000) and 800
milliliters of water. The reaction was carried out exactly as
d~escr~ibed~in~Example 2 using crystalline I;
2,3-epoxypropyltrimethylammonium chloride (79.6 grams). Recovery
was accomplished by precipitation yin acetone. The nitrogen
continuity was 1~.01% by weight wherein the value for (m) in the
general formula segment is approximately 84.
:
:,
39
-13-
Example 9
-RN+RlR2R3A = -Cohesion (SHEA 2
A flask equipped as described in general Preparation TO
was charged with polyvinyl alcohol (44.0 grams), (100% hydrolyzed,
molecular weight 86,000), 500 milliliters dimethylformamide, 5.5
grams manganese acetate, and benzyldimethylethoxycarbonylmethyl
ammonium chloride (51.0 grams, 0.25 mole). A nitrogen stream was
passed through the solution as was heated to 125C and held for 6
hours. The resulting solution was poured into acetone (1500
10 milliliters) while hot. The precipitate was collected by
filtration, shredded mechanically, washed again with polymer nor.-
; solvent and dried. The product was found to have a chloride content of 4.10~ by weight and a calculated nitrogen content of
1.62% wherein the value for (m) in the general formula segment is
15 approximately 28.
Example _
1~`2~`3' -COHESION (CH3)2(CH2Ph)Cl
The process of Example 9 was repeated with polyvinyl
alcohol (98% hydrolyzed having molecular weight of ]26,000). The
20 chloride content of the product was 4.41% by weight and the
calculated nitrogen content was 1.72% wherein the value for (m) in
the general formula segment is approximately 25.
Example 11
ROY -C~2CH(OH)CH2N (Shekel
25~ Polyvinyl alcohol (44.0 g, MY = 12~,000, 98% hydrolyzed)
was~stirred`in water (400 ml) and warmed to 85-90CC. The solution
was cooled to 80C and aqueous potassium hydroxide (5.6 g in 30 ml
: "' '' '' :
, , .........
~236~39
-14-
HO) was added. This solution was cooled over 30 minutes to 60$C
and I chloro-2-hydroxypropyl)trimethyla~monium chloride (18.8 g,
0.10 molt was added all at once. The pi at this time was 7.3.
The product was recovered by dialysis through a semi-porous
5 membrane as previously described. The nitrogen content was 0.15
which corresponds Jo idealized formula with m = 415.
-
Example I
-RN+RlR2R3A = -CH2CH(OH)CH2~ (Shekel
Polyvinyl alcohol (22.0 g), Jo = 126,000, 98~
lo hydrolyzed) was stirred in water (210 ml) and warmed to 85C over
45 minutes. Potassium hydroxide (1.5 g in 10 ml HO) was then
added and the solution cooled to 60C. Crystalline 2,3-epoxy-
propyltrimethylammonium chloride (75.8 g, 0.50 molt was added and
the entire solution held at 60C for 4 hours. The product was
15 then recovered by precipitation from acetone, filtration and
drying to afford 102 trams of white powder. The nitrogen content
was 5.96% or 88~ of theoretical, and wherein (m) has a value of
approximately 2Ø
Example 13
RlR2R3A -cH2cH(oH)cH2N~(cH3)
Polyvinyl alcohol (44.0 g), (MET = 126,000, 98%
hydrolyzed wag stirred in water (400 ml) and warmed to 85C over
~30 minutes. The solution was cooled to 80C and Potassium
hydroxide g in 20 ml HO) was added. The entire solution way
;~25 cooled to 60C over 45 minutes and~2,3-epoxypropyltrimethyl- -
ammonium~chlor~ide (37.9 g in 100 ml HO) was added drops over
~30 minutes. The solution was stirred at 60C for 3 additional
hours and the product recovered by precipitation from acetone.
The reaction afforded 50.4 grays of white solid with a nitrogen
, , : - ' ''
:
I..
~236~3~
-15-
content of 2.92~ or 71% of theoretical, and wherein (m) has a
value of approximately 13.
Moisture Barrier Test On per
While the modified polyvinyl alcohol polymers of the
invention are best tested for retentivity, substantivity and
moisture barrier film forming properties on living animal spin an
indication of their effectiveness as a moisture barrier eon be
obtained by testing on filter paper. In the test results listed
in the following Table 1 a 2.5 inch circle of number 1 Whitman
10 filter p&per was treated with aqueous solutions containing from
5-10/o by weight of the modified polymer as described if. the
examples to obtain a polymer film deposit amounting to about 0.1
gram when dried at room temperature. The test is carried out by
taking about 2 grams of aqueous solution of the modified polymer
15 and dropping it over a water wet circle of filter paper from one
side. The saturated paper is permitted to dry overnight at room
temperature and weighed. Depending on the concentration of
solution the procedure may be repeated until the weight pickup is
about 0.1 gram so that each filter paper is treated with
20 substantially an equal amount of polymer. The dry paper is sealed
over the opening of a test cell containing 100 grams of water arid
permitted to stand or 1~0 hours in a constant humidity and
typewriter room at 70F at 40% relative humidity. The weight of
water passing through the paper under these conditions is measured
25 by weighing the amount of water remaining in the test cell. Each
test employs a control cell containing the identical paper having
no polymer treatment. Considering the weight loss through
untreated paper as lC0 thy test results which are listed as
percentage reduction in evaporation of water are calculated from
Thea water remaining in the cell. The paper test results provide a
rough indication of effectiveness as a moisture barrier for
further testing on animal skin.
I: I: :: : :
:: : : :
:::: : : : ::
:: :
.
~3~639
-16-
Table 1
6 Reduction
Example in Evaporation
Control (unmodified PEA 40-50
' l 55
2 36
3 61
c 4 58
33
6 59
7 46
9 40
51
: 15 In-vitro tests on animal skins having 1, 3 and 5 weight
percent of the modified polyvinyl alcohol polymers of this
: invention indicate comparable results with regard to water vapor
transmission on Neonatal Rat Stratum Corneum as shown in the
results listed in Table 2.
Table 2
Water Vapor Transmission
I polymer solution on neonatal
rat stratum corneum)
Sample : % Reduction
25 Control 66.7
Example 1 55.6
Example 7 77.8
example 55.6
I: The effect of polymer coatings having 5% modified POW
Jo polymers on the elasticity of pi skin is shown in Table 3.
Table :3
Elasticity of pigskin treated:
with 5% polymer solution.
Elasticity
:35~ Control
Expel 1~:8.~8'2.0
Example .11.4i2.0
Example l.6~0.8
,: : . :
- -
. :
2 3 6 3 9
-17-
Compares skin elasticity (petroleum jelly produces maximum
elasticity - approximately 28 units)
The use of unmodified polyvinyl alcohol polymer- in film
forming ointment bases and barrier creams for use in protecting
the skin against the action of Paternal irritants has met with
only limited success (JOB. Ward and G. J. Spurned, "American
Perfumer and Cosmetics" Volume 79, pages 53-55 (1964)). Film
forming creams are difficult to produce with polyvinyl alcohol
because they are either very difficult to formulate because of
10 their poor mixing characteristics or whey form poor fullers.
Lotions and creams made with polyvinyl alcohol in general lack
elegance, that is, the in-vitro films made from ointments and
lotions containing about 15% polyvinyl alcohol are either slow
drying, become greasy and tacky and eventually leave a film which
15 is hard and leathery. Furthermore, Good PEA moisture barrier
films usually are very hard to remove from the skin because whey
are difficult to remove with soap and water.
The problems associated with employing unmodified PEA in
film forming bases are substantially overcome by the compositions
20 of this invention in that they are easily dispersible in water are
compatible with typical lotion formulations, and when applied to
the surface of the skin, they dry quickly to form an elastic,
smooth pellicle which retains its integrity over long periods of
time and is easily removed with soap and water. Tests for
25 pharmaceutical elegance is accomplished by applying typical
moisture barrier lotion formulas to the back of the hand and
making observations with respect to ease of application, feel on
the skin, time of drying, durability of the film, ease of removal
and a host of subjective factors. In most instances, the
30 formulations evaluated do not adversely effect the film forming
characteristics of the modified polyvinyl alcohol compositions of
this invention. The aqueous moisture barrier compositions of the
invention generally have a lotion consistency and may be in the
form of oil-in-water or water-in-oil emulsions with the former
35 being preferred because of their more pleasing cosmetic
'
.
6 6 3
-18-
properties. The lotions are preferably Audi by first preparing
the oil phase then preparing the water phase and thereafter adding
the water phase to the oil phase. Usually the aqueous phase to
heated to a temperature of about 70 to about 80~C and then added
sly with stirring to the oil phase which is heated to about the
same temperature.
The oil phase components may contain a variety of
materials including emulsifiers, emollients, oils, waxes,
perfumes, lanolin, polyalkylenes, strolls and the like.
Water phase components may contain many different
materials josh include humectants, modified POW moisture barrier
components of the invention, proteins and polypeptides,
preservatives, alkaline agents, thickening agents, perfuses,
stabilizers and antiseptics.
The lotions and ointments of the invention contain as an
essential ingredient from n. 1-15~ by weight and preferably from
.5-5% by weight of the above described modified polyvinyl alcohol
polymers of the invention. They may be added as aqueous
dispersions containing 0,1-30~ by weight of modified PEA or as dry
20 powder.
The lotions may contain an emulsifier in an amount of
from about 0.05 to about I and preferably from about 0,25 to
about 5% to emulsify the oil components. Typical emulsifiers are
selected from the group consisting of polyethoxylated fatty acids
25 having less than about 30 mows of ethylene oxide per mow of fatty
acid, ethyoxylated esters, unethoxylated sugar esters, polyoxy-
ethylene fatty ether phosphates, fatty acid asides, phospholipids,
polypropoxylated fatty ethers, acyllactates, polyethoxylated polyp
oxypropylene glycols, polypropoxylated polyoxyethylene glycols,
30 polyoxyethylene, polyoxypropylene ethylene dominoes, soaps and
mixtures thereof.
Examples of such emulsifiers include polyoxyethylene (~)
Stewart, myristyl ethics (3) myristate, myristyl ethics (3)
palpitate, methyl glucose sesquistearate, sucrose distrait,
35 sucrose laureate, certain monolaurate, polyoxyethylene (3) oilily
:: :
~2~S3~
-19-
ether phosphate, polyoxyethylene (10) oilily ether phosphate,
Laurie diethenyl aside, Starkey monthly aside, lecithin,
lanolin alcohol propoxylates, sodium stearoyl-2-lactate r calcium
stearoyl-2-lactate, and the Pluoronics~ offered by BASS Wyandotte
Soars such as alkaline metal or triethanolamine salts of long
chain; fatty acids which include sodium Stewart, triethanolamine
stout and similar salts of lanolin fatty acids. A preferred
emulsifier is polyoxyethylene ( 1) stroll ether.
The lotion formulations may contain an emollient
10 material in an amount ranging from 0.2 to 25% and more often 1 to
8% by weight. One function of the emollient is to ensure that the
modified polyvinyl alcohol polymer is classified sufficiently to
allow it to be in a film-like state on the surface of the skin..
Typical emollients are selected from the group consisting of fatty
15 alcohols, esters having fewer than about 24 carbon atoms (for
example, isopropylpalmitate), branch chain esters having greater
than about 24 total carbon atoms (for example, cetearyl octonate),
skyline, liquid or solid paraffins, mixtures of fatty acids and
skyline, mixtures ox fatty acids and liquid or solid paraffins
20 and mixtures thereof. Typical alcohols and fatty acids which are
useful include those having from 12 to 22 carbon atoms such as
Seattle alcohol, myristyl alcohol, stroll alcohol, Starkey acid and
palmitic acid. Paraffins include, for example, mineral oil,
petrolatum and paraffin wax.
The lotions and ointments are particularly stable and
effective when adjusted to a pi of I
The following formulations will serve to demonstrate but
not limit the formulations containing the modified polyvinyl
alcohol film forming moisture barrier polymer of the invention.
30 Typical lotions contain 0.1-5.0% of the above described modified
PEA polymers, 2-5% of a fatty alcohol, and 2-5% emulsifier in an
aqueous emulsion.
':..
,
foe
-20 -
Exhume
A portion of the aqueous solution- prepared according to
Example 4 containing 0.5 grams of modified PEA polymer was dilute
with water and added to an aqueous solution containing 2.4 grays
5 Seattle alcohol, 1.6 grams stroll alcohol and 3.0 grams of
polyethylene (21) stroll ether (Baja 721 surfactant by ICY
Americas Inc.). Additional water was added to bring the water
concentration to 92.5%. After stirring for about five minutes at
75C the emulsion to per lied to cool to room temperature and
stored. The lotion Was tested subjectively for cosmetic elegance
lo by applying the product to the back of the hand and arm. It was
determined to have smooth, silky feel, drying time of less thaw 15
minutes and a film durability in excess of two days. Residual
films and lotions are easily removed from the skin with soap and
water.
As mentioned above the polymers of the invention had
advantageous cosmetic properties that permit them to be used in
preparing cosmetic formulations either as ready to use
compositions or concentrates which have to be diluted before use.
Therefore, the cosmetic formula may contain the modified polyvinyl
20 alcohol polymers in concentrations ranging from 0.01-15% by
weight. The solution of these polymers are particularly useful
when they are applied to hflir, either alone or with other active
substances during a treatment such as shampooing, dyeing, setting,
blow drying, permanent waving, etc. They may improve notably the
I quality of the hair. Zen employed in hair treatment they
facilitate untangling of wet hair and do not remain on dry hair as
a sticky residue. In some instances they are expected to give dry
hair additional life, a soft feel, a glossy appearance and
resistance to tangling.
pair treating formulations containing dilute aqueous,
alcohol or dilute alcohol solutions of the modified polyvinyl
alcohol polymer can be cr,lployed. Furthermore, they may be
employed as creams, lotions, gels or as aerosol sprays. Thyme
~3~i~3~
-21
be used in combination with perfumes, dyes, preserving agents,
sequestering agents, thickening agents, emulsifying agents, etc.
Example B
A typical hair rinse formulation containing 5 grams of
5 the modified polymer of Example 8, 7 grams Swahili alcohol, 3 grams
of a linear polyoxyethylenated C10-Cl8 fatty alcohol, 2 grams of a
cozen derivative, 0.5 grams tetradecyltri~,ethyla~monium chloride
and 82.5 grams of water and a minor amount of hair dye can be used
to treat hair having improved looks and anti-static properties.
Example C
A typical oxidation hair dye solution containing a 2.5
gram of the modified polymer of Example 9, 10 trams bouncily
alcohol, 20 grams oleic acid, 3 grams polyoxyethylene (30), Leo
Seattle alcohol, 7 grams Olin diethanolamide, 7.5 grams 2 octyldo-
15 decanol, 2.5 grams triethanolamine Laurie sulfate, 10 grams ethanol, 18 milliliters aqueous ammonium, 1 gram n,n-bis(2-
hydroxy-ethanol)parapherlylenediamine, 0.4 grams resorcin, 0.15
grams m-aminophenol, .4 grams alphanaphthol, 0.1 grams hydra-
quinine, 0 24 grams ethylene Damon tetracetic acid, 1 milliliter
20 sodium bisulfite, and water sufficient to make 100 grams is a
typical ammo a oil composition for use as an oxidation hair dye
when 130 grams of the solution is mixed with 30 grams of hydrogen
peroxide bleach. After hair is treated with the material and
allowed to stand for 30-40 minutes and thereafter rerinsed the
us hair is expected to untangle easily and Dave a spiky touch.
The modified polyvinyl alcohol compositions ox the
invention may be explored to improve the elegance and stability of
personal care products such as liquid and bar soaps, shaving
creams, bath products, antiperspirants, sunscreens, cleansing
30 creams and as a suspending agents for insoluble pigments and
pharmaceutical active. Improvement is generally realized when
so
~66;~9
-22-
from 0.5-5~ by weight of the compositions of this invention are
employed in conventional formulations as hereinafter exemplified.
-
- Roll-On Antiperspirant
e
:5 Ingredient % WOW
Example 3 4.0
polyoxyethylene (21) stearylether 0.76
polyoxyehtylene (2) stearylether 3.24
water (deionized) 34.76
: 10 Dozily 200~, Dow Chemical 0.
: Al Or tetrachlorohydrex-Gly,
: Russell 36G, Rehems 57.14
: Example E
Aerosol Shave Cream
Ingredient % W/W
Example 3 5.0
Seattle alcohol 4.3
polyoxyethylene (21) stearylether 2.2
sorbic acid .17
20 water 74.9
: : fragrance .08
: water 13.35
:
Example F
Oil-in-Water sun are en Lotion
us ln~redien~ W/W :
monorail : :18.~ :
c~tyl:alcohol 5.0 :
Aurelius emulsifier 2.5
Tween:60~:emulsifier:: : : 7.5
30 Amy para~-dimethylaminobenzoic acid 1~.2
Employ 2 0 Jo
rreser-ative~ us
,,,,.~ ,. .. . .
. ,
: ; Jo .: ' '
.
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-23-
Example G
Water-in-Oil Pigmented Makeup
- Ingredient W/W %
Mineral Oil 10
5 Beeswax 1.5
Cevesin wax 1.0
Arlacel 186P emulsifier 3.2
Sorb sorbitol 28.8
Two and other pigments 20.0
10 water 33.5
Example 6 2.C
Example H
Calamine Lotion
Calamine 80 gyms
Zinc Oxide 80 gyms
glycerine 20 mls
bentonite magma 250 mls
calcium hydroxide 950 mls
(concentrated aqueous sol.)
Example 1 50 gyms
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