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Cosmetic Pigment Coatings

Article · February 2020

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 COLUMN: Science for Formulators

Evaluating coated pigmented products role in determining success in product

development. Dispersion is one most
important processes in utilizing pigments
KEYWORDS: Pigments, coated pigments, oil soluble wetting agents, to create color cosmetics”.
pigment dispersions, coating stability, emulsions, Soxhlet extractor,
stability screening. Figure 1 shows a schematic of the
complicated multi-stepped dispersion
process. pigment dispersion (4).

As seen in the image, the process starts

TONY O’LENICK
Nascent Technologies Corporation, Lawrenceville Ga, United States with solid pigments being introduced into
a liquid solvent. The solvent coats the
pigment’s surface. For a pigment to be
wetted by a liquid, the surface tension of

ABSTRACT
the liquid must be lower than the surface
In the personal care market, the color cosmetic segment is perhaps the most technically
energy of the pigment. This interaction
challenging class of products a formulator faces. This class of products generally includes
between pigment and liquid is described
several types of oils, silicones, wetting agents, film formers and pigments. The emulsion is
below by the Young equation. A liquid
generally invert (water in oil) and the consumer expectations are high. Since invert
emulsions are very complicated and difficult, the formulator needs an approach to look at with a low surface tension typically
potential approaches to address emulsion instability. Additionally, the aesthetics include wets pigments better than one with a
cushion, play time and feel of the invert emulsion, but also the feel of the final film after higher surface tension. The next step
evaporation of a suitable solvent. Pigments are critical components that need to be properly in the process is the deagglomeration
wetted out for proper aesthetics of formulation out of the bottle, after evaporation of the stage. This involves grinding or breaking
volatile solvent and to deliver acceptable the proper color and color stability on the skin. up the pigments into smaller particles.
This article will suggest some screening techniques for pigmented emulsions. This typically requires a lot of energy
and precision to ensure the broken-
down particles are uniform in size. After
DISPERSIONS a stable dispersion is critical. This can be the particles are broken down into the
achieved by selecting oil combinations desired size, they must be stabilized or
Cosmetic dispersions typically contain that intrinsically wets the pigment, or that suspended in the dispersing media. This
a solid pigment(s). Typically, these contains an oil soluble wetting agent. is where wetting agents are of paramount
solid pigments are inorganic particles. Wetting agents serve to wet out the importance. The wetting agents must wet
Particle size of 3 – 5 mm is necessary particles to allow a stable homogeneous the surface of the particle, otherwise the
for optimum color development. Some dispersion (2). particles with flocculate back together
examples of these inorganic particles due to Brownian motion.
are: titanium dioxide (TiO2), zinc oxide
(ZnO) and iron oxide (Fe2O3). These FORMULATOR TIP A major factor that needs to be
particles are insoluble in the formulation. considered is the compatibility of the
Therefore, a uniform dispersion of these Dispersions, like emulsions, are inherently pigment coating with the oil phase
particles must be achieved in order to unstable. It is critical for a formulator to not only at the time the formulation is
have a successful cosmetic product. The select not only the correct pigment for the prepared, but over the useful life of the
dispersion of these pigments becomes a application, but they must also consider formulation. Problems that can be
critical part of the formulation. Creating the coating (if any) on the pigment to encountered by a pigment coating that is
this dispersion is tricky, pigments cannot have the correct compatibility with not compatible with the coating are (1)
be simply stirred into the solvent (1). To the formulation. If there isn’t a coated color shift; (2) unpredictable formulation
make it easier for the pigments to be pigment available, the formulator should stability and (3) stability issues especially
incorporated into the solvent, a number consider a utilizing a wetting agent. invert pigmented emulsions.
of pigment treatments are available
commercially. These “treatments” are
typically a surface modification of the PREPARATIONS OF THE DISPERSION WHY TREAT PIGMENT
pigment, which makes the pigment
easily dispersed into a media. There are Kelly Dobos points out (3): There are four reasons to treat pigments,
two ways of treating the surface of a “The incorporation of color in cosmetic all are related to product stability and
particle: covalently bonding an organic and personal care products is part art compatibility of the phases in the
moiety onto the surface, or physically and part science. What seems like a emulsion. They are:
coating the particle’s surface with a simple and fun exercise in pigment 1. Make pigment more hydrophobic;
surfactant. These surface treatments blending is reliant on a complex set of 2. Make pigment more compatible with
allow the solvent to wet the pigment decisions. Factors such as the regulatory oil phase;
allowing the pigment to be suspended in environment, cost, and stability as well 3. Make pigment less likely to
the media. The selection an oil phase that as physical and chemical properties agglomerate;
efficiently wets the pigment and provides of each colorant all play an essential 4. Make emulsion more stable.

26 HPC Today vol. 15(2) 2020

 COLUMN: Science for Formulators

EXAMPLE 1

A pigment is coated with oleic acid in a

ribbon blender. The result is an organo-
modified pigment on which the oleic
acid is roughly uniform. There is no
reaction. The oleic acid stays on the
pigment simply by wetting it out and
Figure 1. Cartoon showing the complicated, multi-step process of pigment wetting and dispersions.
making it hydrophobic.

TYPES OF COATED PIGMENTS water soluble or dispersible materials, The oleic acid coated pigment is placed
like PEG 8 dimethicone and other in an invert emulsion along with an
Reacted Pigment Coatings- surface active silicones. emulsifier, an oil, water and other
The products of this class of coatings additives, including thickener. Under
are the reaction of pigments making While differences between the classes normal conditions the emulsifier and pH
a new covalent bond between the exist, both classes of coatings can be of the formulation would form a soap
pigment and the coating. These treated used to produce satisfactory dispersions and remove the oleic acid coating. The
pigments are based upon reactive but must be tested in formulation for acid would end up in the oil phase, that
coating materials, including silicones, stability. All formulations need to be is the phase in which it is most stable.
silanes and free radical products, specifically treated for stability regardless The formulation now has an uncoated
that are bonded to the pigment by a of the type of coating. Pigments that pigment and oleic soap present.
chemical process. Hong et al. reported are the result of a reactive coating can
the preparation of Polystyrene-grafted decrease stability if the reacted coating If the formulation is thickened and
ZnO nanoparticles by utilization of the is incompatible with the oil phase (i.e. a the emulsion has stability would be
chemical reaction of methoxysilane silicone coating on the pigment dispersed observed over a longer period of time
modified polystyrene and the hydroxyl in a mineral oil in which it is incompatible). as predicted by Stokes law. All this does
end group of zinc oxide. Likewise, a chemisorbed coating can is delay the whole process of emulsion
be problematic if it is easily removed by instability!
Depending upon the specific formulation the emulsifies chosen. The choice of
and the type of pigment being coated, the improper coating, or wetting agent, What does the formulator see? Firstly
reactive pigment coatings include for a pigment which results in pigment a “bad emulsion” secondly color shift,
(1) perfluorooctyltriethoxy silane incompatibility in the oil results in the since what was originally a coated
(oleophobic and hydrophobic) 7 (2) formation of that has been called a “bad pigment is now a naked pigment,
carpyltriethoxysilane (8, 9) (oleophobic); emulsion”. The bad emulsion shows not Additionally, since the emulsion
and (3) methicone treatments (silanic only an unstable emulsion, but often a instability is accelerated by higher
hydrogen containing polymers) color shift from what is expected. temperature the instability is said
Oleophobic). These coatings are applied to lack of predictability. What is
to the pigment and heated. When reacted the approach for a formulator with
the ethoxysilanes release ethanol. FORMULATOR TIP emulsion instability? Change emulsifier
and potentially change process for
The selection of the proper coated emulsification. This approach will
NON-REACTIVE COATING pigment for use in a formulation can simply not work, since small changes
be one of the best experiences that a the “HLB” of the emulsifier will not
Chemisorbed Pigment Coatings – The formulator could ever enjoy, selecting overcome the addition of the fatty acid
products of this class of coatings made by the wrong coated pigment for use in a soap.
the interactions of pigments and coatings formulation can well be one of the worst
based upon solubility and hydrophobicity. formulation experiences.
They are coating by physical bonding an EXAMPLE 2
oil to a pigment making it hydrophobic.
Typically, these materials are surfactants PIGMENT EVALUATION Consider a pigment that has not been
or oligomeric spices. reacted properly in the coating process.
Pigment having the incorrect coating Assume the pigment is only partially
This series of pigment coatings include for the formulation can exhibit many reacted. The emulsion formulation will
(1) dimethicone; (2) cetyl dimethicone; problems including a formulation with have reacted and not reacted coating
(3) crosslinked cetyl dimethicone (4) (1) color shift (2) unpredictable results and the unreacted coating may cause
oleic acid, (5) polyhydroxystearic acid; and (3) emulsion stability issues instability in the formulation.
and (6) Jojoba Oil and many others. especially pigmented emulsions (W/
The selection of the proper coating will Si). Therefore, it is suggested that the This formulation problem is one that
depend upon the pigment chosen and pigment being used in a formulation introduces a random (batch to batch)
the formulation in which it is used. be evaluated for the presence of and lack of performance and is worse in
Finally, pigments can be coated with permanence of the coating. many ways since it is unpredictable

vol. 15(2) 2020 HPC Today 27

 COLUMN: Science for Formulators

batch to batch, driving production and upon product the final product’s quality, treated (coated) or dispersed in oils
QC people crazy! is time well spent. It is always easier to to provide formulation stability and
fix a problem in a lab batch than it is in effective formulation effectiveness.
the plant!
SOXHLET EXTRACTOR The problem with pigment is that they
need to remain stable in the formula
A Soxhlet extractor (10), shown in Figure This test will allow for the establishment and apply properly to the skin. If water
2 is a type of laboratory glass ware of a specification for % coating removed and an emulsifier are used in the
invented in 1879 by Franz von Soxhlet. (gravimetric analysis) and allow for an formulation the system is generally
It can be used to extract coating from FTIR identification of groups present in more complicated. The emulsifier can
a coated pigment and is recommended the removed coating. interfere with the pigment, destabilizing
for incoming quality control of coated the formulation, a problem that only
pigments. The amount extracted and gets worse over time.
the type of coating is determined using EMULSION STABILITY TESTING
this method. Once the stability of the The evaluation of the stability of the
formulation is determined, the raw The testing of the stability of the formulation with and without pigment
material pigment used to make it should coating with emulsifiers is also very can help pinpoint any potential problem
be tested for lot to lot consistency. important. This will allow the formulator and establish a corrective formulation
to make sure the coating remains on program.
the pigment. There are two suggested
TEST METHODOLOGY approaches.
This test simply is one in which a REFERENCES
A known weight of formulation with and without coated
the coated pigment pigment is prepared. Both subjected 1 Studies in Interface Science, Volume
is placed inside a to emulsion stability testing. If both 20, 2005, 97 – 171.
“thimble” made from emulsions are unstable, the pigment 2. Tego Journal, 4th edition; 2012. 79 – 89.
filter paper, which is probably ok, but if the pigment 3. h t t p s : / / w w w. c o a t i n g - a d d i t i v e s .
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Soxhlet extractor. pigment product does not split, look to downloads/an%20efficient%20
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4. Mueller, Brodo. Understanding
containing a solvent
Additives. European Coating Literature,
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Vincentx Network GmbH & Co.:
Figure 2. solvent is heated, Hannover Germany.
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hot solvent vapor pigmented formulation and the same Ding, J.; Polym. Adv. Technol, 2007
travels up to the condenser, where it formulation free of pigment. Often the 6. Dobos, K. Color in Cosmetics, the
cools and drips down onto the test pigmented version of the formulation Importance of Dispersion, Society of
material. The chamber containing the splits in all formulations, while the Cosmetic Chemists, 2019. https://
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solvent until, when it is almost full the not split. This is a very good indication of-dispersion/
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solvent and extracted coating drips that the coting on the pigment is the
topics/biochemistry-genetics-and-
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11. U.S. Patent 5,486,631 Mitchnick et al,
CONCLUSIONS Silicone polymers for the treatment of
FORMULATOR TIP Zinc Oxide Jan 23, 1996.
Pigments are ubiquitous ingredients in 12. O’Lenick, Anthony Silicones for
Time spent evaluation the raw color cosmetics. They are commonly Personal Care 2nd Edition Allured.
materials, process steps and their effect solid materials that need to be either

28 HPC Today vol. 15(2) 2020

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