Sunflower wax as a New Natural Cosmetic Raw Material: Purification
and Application in Lipsticks
A Maru*, U Pattamatta
and VB Patravale
Loknete
ABSTRACT
Sunflower
Wax is a component of the hull of sunflower (Helianthus annus) oil seeds. The wax is
essentially composed of extensively saturated esters of long chain fatty acids
(C20-C22) and fatty alcohols (C22-C29).
Due to its low economical value, it is often considered as industrial waste.
Thus, the focus of the work was to purify the wax and explore its use in
cosmetic product, lipstick. The replacement of beeswax with sunflower wax did
not alter the properties of the lipstick, thereby providing an economical
alternative to beeswax.
1. INTRODUCTION:
Lipstick
is one of the decorative cosmetic products that command a unique market.
Advanced technology has been used to manufacture modern lipsticks with vast functionality. In the last quarter of
twentieth century, cosmetic industries exist with technology of their own.
Every year, users were introduced with various new cosmetics products of the
latest trend. The quality of lipstick
is directly linked to the basic material used in the formulation. Varying the
ratio of the ingredient used determines the final product characteristic.1
In this work, a new natural wax, Sunflower
Wax has been explored to formulate lipstick with desired attributes.
The Sunflower Wax is obtained from the hull of sunflower (Helianthus
annus) oilseed which also gives the highest oil
yield. Because of its high B vitamin and protein content, and also its balance
amino acid composition, the sunflower oil cake can be favorably compared to the
best oil cakes (soya, peanut). 2 As with the other oilseeds, the
production of the oil liberates an enormous quantity of the low density hull as
byproduct. Due to limited use, hull often accounts for major waste, making its
utilization an important industrial problem. 2
In the early
seventies, tremendous work has been done by Cancalon to provide detailed chemical composition of the hull wax.
(table1-2) These waxes are mainly
located in the hull of sunflower seeds with concentrations up to 3% depending
on the hybrid and origin of the seed. 3-6 Thus, the work involved
purification of the sunflower wax, characterization of the pure wax and
evaluation its application in lipsticks.
2. EXPERIMENTAL:
2.1.
Materials
Sunflower wax was generous gift sample from Maru Industries,
2.2
Purification of sunflower wax
Sunflower wax was purified by treating the wax with
different solvents such as acetone, hexane and petroleum ether. The wax was
shredded using a shredder and a mixture of 10 gm shredded wax alongwith 20 ml of the solvent was taken in a conical flask
with stopper. The mixture was shaken for one hour and the resultant white
crystalline wax was filtered out. Oil was recovered by distilling out acetone.
2.3.
Characterization of the purified sunflower wax
2.3.1.
Melting point
Melting point of the sunflower wax was determined by the
drop point method. The wax was applied to the thermometer bulb and inserted
2.3.2. Specific
gravity
A
graduated measuring cylinder was filled with a mixture of equal volumes of
water and alcohol. The specific gravity of this mixture was determined using
specific gravity bottle. To the measuring cylinder, 20 g if the wax was added
and the increase in the volume of the liquid was noted.
2.3.3 Hardness
The
hardness was found out by using the penetrometer. A
load of 100g was taken and the depth to which the needle penetrated through the
sample was noted.
2.3.4. Saponification value
2.269
gm of wax was taken in conical flask containing 30 ml absolute alcohol. 25 ml
of approximately 1N alcoholic KOH was gently added into the flask with constant
stirring. The contents of the flask were refluxed for at least one hour with
occasional shaking.When the mixture started boiling,
the the excess of KOH was titrated with 0.1 N HCl using a mixture of phenolphthalein and 1 ml of methylene blue as an indicator. Mixtures of indicators so
that the end point were sharply distinguished
from a brownish purple to clear pale
or dark green colour. The saponification
value was found out by the following formula
Saponification value = (Vb – Vw
x 56.104 x NHCl) / W
Where,
W= weight of sample taken, Vb, Vw are respectively number of millimeters of
normal HCl using in the blank and actual analysis.
2.3.5. Acid Value
4
gm of wax was warmed with 50 ml of carefully neutralized alcohol in a 250 ml
flask. A few drops of phenolphthalein was added to the mixture and titrated
with vigorous shaking against 0.1 N alcoholic KOH until a semi pink color
appeared.
Acid Value = (Vw
x 56.104 x NKOH)/ W
2.3.6. Ester Value
The
ester value was determined by deducting the acid value from the saponification value.
2.3.7. Iodine Number
0.5
g of wax was dissolved in 10 ml of CCl4 in a dry I2
flask. 20 ml of previously moistened with dilute KI, ICl
solution was added and the stoppered mixture was
allowed to stand in the dark at 15οC to 25 οC
for 30 minutes. 15 ml of dilute KI solution was carefully introduced in the mixture and then diluted
with 100ml water. The solution was titrated with 0.1 M sodium thisulphate using starch mucilage as an indicator. Iodine
value was calculated using the following equation;
Iodine value =1.269 Vx N/w
Where,
V= difference in ml between the titrations; w= Weight in gms
of the substance taken.
2.3.8. Unsaponifiable matter
For the unsaponifiable matter, the alcohol was distilled off from the saponified sample and the residue was taken up in 200cc of water and placed in a 500 cc separator; ether (200cc) was added, and the whole was shaken gently. The aqueous layer was twice extracted with ether.
2.4. Formulation of
Lipsticks
The
colour lake, bromo acid and
titanium dioxide were thoroughly mixed. A mixture of castor oil, isopropyl myristate, lanolin and preservative were added to the
staining dye mixture and heated on a water bath with continuous stirring. Waxes
were melted in another beaker and this was mixed with colour
dispersion and then stirred slowly. This mass was removed from the water bath,
perfume was added and then it was poured into lubricating molds. The lipstick
was allowed to set in the molds.
2.5. Evaluation of
Lipsticks:
2.5.1. Softening point
Lipstick
was placed with protruded salve in the flat bottom tube. Thermometer was fixed
through a cork in such a way that the bulb of the thermometer just touched the
lipstick salve. The arrangement was inserted into a 1 litre
beaker filled with water to a level one centimeter above the upper tip of the
lipstick salve. Slowly water bath was heated while stirring so that temperature
rises at a rate not exceeding 2 οC/ min. When the
temperature reached about 45 οC, the
temperature was raised at the rate of 1 οC/ min. The
temperature, the salve starts bending
and losing its shape was recorded as the softening point.
2.5.2. Bending load
test
Lipstick
container was firmly fixed with protruded salve into a screw type of chuck so
that the assembly was perfectly horizontal. Burette was adjusted just above the
lipstick salve. Marking was made at a distance of 1.5 cm from the base of the
salve where the lipstick salve sits in salve holder. The aluminum container was
weighed along with hook and suspended. On this 1.5 cm mark, water was released
form the burette into the aluminum container till the slave breaks. Burette
reading was added with the mass of the suspended container gives the breaking
load of the lipstick.
2.5.3. Pay off test
The
apparatus consists of constant speed electric motor of power 180 watts attached
to gear arrangement, which pulls the strip of paper from a roller onto another
roller fixed on platform through a support. A slot arrangement having a
cylindrical tube of 4 cm length and 1.7 cm diameter is also fixed on the
platform. The top portion (approx 1 cm) of the lipstick salve was chopped off
using a sharp blade. Remaining portion of the salve was rubbed on a piece of
paper and there by the end portion was made perfectly flat. Constant speed
motor was run and the time required for pulling out 100 cm of the paper length
was determined. The lipstick was inserted in the slot arrangement so that the
flattened slave portion rests on the surface of the paper strip. A load of 50g
was placed on the top of the lipstick. Constant speed motor was started and
with the help of stopwatch 100 cm length of paper was allowed to run. Lipstick
after rub off was weighed. The length and breadth of the lien drawn on the
paper strip was measured.
Pay-Off (g/cm2) = (M1-M2)/
Lx B
Where,
M1 = Mass of the lipstick before the test
M2
= Mass of the lipstick after the test
L
= Length in cm of the line drawn on paper strip
B=
Breadth in cm of the line drawn on paper strip
Table1:
Wax Fatty acid Composition2
|
Fatty
Acids |
Percent
a |
|
Myristic |
1.94 |
|
Pentadecanoic |
0.4 |
|
Palmitic |
6.8 |
|
Heptadecanoic |
0.2 |
|
Iso-stearic |
0.35 |
|
Stearic |
5.6 |
|
Oleic |
4.72 |
|
Nonadecylic |
3.07 |
|
Linoleic |
0.78 |
|
lso-arachidic |
1.3 |
|
Araehidic |
46.5 |
|
lso-medullic |
0.9 |
|
Medullic |
0.7 |
|
Behenic |
16.3 |
|
Tricosanoic |
0.53 |
|
Lignoceric |
4.5 |
|
Pentacosanoic |
0.23 |
|
Montanic |
2.2 |
a Unknown
peaks account for the difference
between the total and 100%.
Table2:
Wax Fatty Alcohol Composition2
|
Fatty
Alcohol |
Percent
a |
|
Dodecanol |
0.16 |
|
Tridecanoic |
0.24 |
|
Tetradecanol |
traces |
|
Pentadecanol |
traces |
|
Hexadecanol |
0.2 |
|
Heptadecanol |
0.17 |
|
Octadecanol |
3.0 |
|
Oleilol |
O.15 |
|
Nonadecan el |
0.17 |
|
Eicosanol |
2 |
|
Heneicosanol |
0.15 |
|
Docosanol |
12 |
|
Tricosanol |
0.4 |
|
Tetraeosanol |
34.6 |
|
Pentacosanol |
3.45 |
|
Hexacosanol |
14.35 |
|
Octacosanoi |
6.65 |
|
Nonaeosanol |
5.75 |
|
Triacontanol |
2.17 |
a Unknown
peaks account for the difference
between the total and 100%.
Table3:
Characterization values of refined Sunflower wax
|
Parameters |
Results |
|
Colour |
White |
|
Melting Point |
78 οC |
|
Specific gravity |
0.8445 |
|
Softening point |
75 οC
-76 οC |
|
Hardness |
18 |
|
Saponification Value |
75.3666 |
|
Acid Value |
5.213 |
|
Ester Value |
.70.152 |
|
Iodine Value |
0.748 |
|
Unsaponifiable matter |
45 |
2.5.4. Test for Heavy
Metals
The
colour produced with hydrogen sulphide
solution was matched against that obtained with standard lead solution. 1.6g of
lead nitrate was dissolved in water and the solution was made up to 100 ml. 10
ml of solution was pipetted out and diluted to 1000
ml with water (0.01mg of lead/ml).
1g
of the material was dissolved in 3 ml of dil. HCl
with slight warming. This was diluted to 50 ml with water. The solution was
filtered, 25 ml of filterate
was transferred into a Nessler cylinder, 2ml of
dilute acetic acid, 1 ml of standard lead solution was added and volume made upto 25 ml. 10 ml of hydrogen sulphide
solution was added to each Nessler cylinder volume
was made upto 50 ml
with water. It was then allowed to stand for 10 minutes and the colour produced in both the Nessler
cylinders was compared.
Table4:
Composition of Lipstick formulations
|
Ingredients |
Standard
formulation (10g) |
Developed
formulation (10g) |
|
Carnauba wax |
0.3 g |
0.3 g |
|
Candellia wax |
0.1 g |
0.1 g |
|
Ozokerite wax |
0.3 g |
0.3 g |
|
Beeswax |
0.7 g |
--- |
|
Sunflower wax |
--- |
0.7 g |
|
Lanolin |
1 g |
1 g |
|
Castor Oil |
6.5 g |
6.5 g |
|
Isopropyl myristate |
0.5 g |
0.5 g |
|
Colour |
0.5 g |
0.5 g |
|
Perfume |
q.s. |
q.s. |
|
Preservative |
0.1 g |
0.1 g |
Table5:
Characterization values of standard and developed lipsticks
|
Test |
Standard
formulation |
Developed
formulation |
|
Melting Point |
60 οC |
61 οC |
|
Softening Poitn |
58 οC |
60 οC |
|
Pay- Off test |
3.8 x 10-4
g/cm2 |
3.5 x 10-4
g/cm2 |
|
Penetrometer Test |
0.6 cm |
0.55 cm |
|
Breaking Load test |
395 |
410 |
|
Particl Size |
4.1 microns |
4.9 microns |
|
Test for heavy
metals |
Colour produced
in the developed formulation was comparable to standard. |
|
|
Test for arsenic |
||
2.5.5. Test for
Arsenic
2g
of the sample was weighed in a flask of 500 ml capacity. 15 ml of concentrated sulphuric acid was added followed by 4 ml of concentrated
nitric acid and cautiously heated. Dropwise addition
of Nitric acid was done to hasten the rate of oxidation of the sample. The
completion of oxidation was indicated by clear and faint yellow solution; at
this stage 20 ml of water was added and boiled to fuming. The stain of the
sample and standard (0.004g of arsenic dioxide) was compared.
2.5.6. Penetrometer test
Lipstick
was melted to 70 οC and molded in stainless steel tube. It was alloed to
set for 24 hrs. After setting the lipstick rod was removed form the cast and
cooled to 25 οC. The molded lipstick
rod was placed horizontally on the penetrometer
platform. The penetrometer need le was adjusted so
that it just sits on the surface of the molded lipstick rod. The needle
attachment was released and the penetrating reading was recorded. Penetration
on several points on the surface of the lipstick was determined and the average
of all such determinations was reported in micrometer.
2.5.7. Particle size
of undispersed pigments
A
small portion of the lipstick paste was applied on glass slide. The slide was
observed under the microscope using a specially calibrated eye piece. The
particle size of the largest pigment particle was determined.
3. RESULTS AND
DISCUSSIONS
3.1. Purification of
sunflower wax
Sunflower
wax was purified by removing the oil using different solvents like acetone,
hexane and petroleum ether. Since the sunflower oil seed contain highest amount
of linoleate which tend to produce large quantities
of volatiles, especially pentane and hexanol. Thus,
at lower temperature, the removal of oil from the wax was found to be
difficult.
When
petroleum ether was used as a solvent, the wax obtained was not pure white and
crystalline, this could be attributed to incomplete removal of the oil. Hence,
it had to be retreated with the solvent to facilitated complete removal of the
oil. Purification of was using hexane was found to be unfeasible due to partial
solubility of wax in the solvent and poor removal of solvent at lower
temperatures. While acetone proved to be the better solvent for removal of oil,
using acetone it was possible to obtain white and crystalline wax.
3.2. Characterization
of wax:
Chemical
constants such as acid, ester , hydroxyl and iodine numbers are determined to
identify, differentiate or classify the
waxes. The saponifcation number is a direct
evaluation of the total amount of esters and free aids, if any, in a wax which
is free from polyesters and resins. It approaches the constant number for a
particular kind of wax. The acid value expresses the free fatty acid and is more
of a variable then the saponifcation number. The unsaponifiable matter, is an important determination in the
identification of a wax or in the study of its composition. It includes not
only the unsaponifiable portion of wax such as the
combined alcohols, split off from the ethers or esters as a result of saponification, but also hydrocarbons and free alcohols and
ketones, if any.
The
chemical constants assist greatly in determining the chemical compositions of
the wax once the individual constituents are recognized by the molecular
weight, melting point and other determinations. The chemical constants for
refined sunflower wax have been reported in Table 3.
3.3. Formulation and
evaluation of lipsticks
Melting point and hardness of the wax mainly
decide their application in many formulations. The requirements of a good
lipsticks are that it must be non injurious, easily spreadable without being
excessively greasy; its colour must be reasonably
permanent; it must not sweat, crumble or crack. In addition to these qualities,
its color must be absolutely uniform, unchanged and free from mottling. It will
be seen from the foregoing statements that the consistency of the stick is to
determined by the melting point of the waxes.
When
sunflower wax was substituted for carnuba wax, the
lipstick formed was very soft and was not rigid. So the entire evaluations
tests were not carried out for this formulation. Sunflower wax was substituted
for both ozokerite wax and beeswax. In this case, the
lipstick had shown better results, but the lipstick was not hard in comparison
with the standard. While formulation where only beeswax was substituted by
sunflower wax, the lipstick was quite hard and comparable to standard as shown
in table 5.
4. CONCLUSIONS
The
demand for waxes is increasing day by day in various fields of the industry.
Since
5. REFERENCES:
1.
Awang Bono,
et.al., Effect of various formulation
on viscosity and melting point of natural ingredient based lipstick, Studies
in Surface Science and Catalysis, Vol 159: 693-696 (2006)
2.
Paul Cancalon, Chemical Composition of Sunflower Seed Hulls, J. Am.
Oil Chem. Soc.,
Vol. 48 (10): 629—632 (1971).
3.
Morrison, W.H., III, Variation in the Wax
Content of Sunflower Seeds with Location and Hybrids, J. Am. Oil Chem.
Soc.60:1013–1015 (1983).
4.
Ramos Ayerbe,
et.al., A Study on the Recovery of Byproducts from the Dewaxing
of Sunflower Oils of National Production, Grasas
Aceites 36:1–4 (1985).
5.
Mariani, C.,
et.al, Minor Components of Vegetable Oils: Non-glyceridic
Esters, Riv. Ital. Sostanze Grasse 66:397–401 (1989).
6.
Amalia A. Carelli,
et.al,Wax Composition of Sunflower Seed Oils, J. Am. Oil Chem. Soc., Vol. 79
(8): 763-768 (2002).
Received on
10.06.2009
Accepted on
18.06.2009
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Publication all right reserved
Research
Journal . of Pharmaceutical Dosage Forms and Technology. 1(1): July.-Aug. 2009, 45-48