Adhesion Aspect in Mascara

17
Adhesion Aspect in
Semi-Permanent Mascara
Christopher Pang and Hy Si Bui*
L’Oreal Research and Innovation, Clark, NJ, U.S.A.
Abstract
The current mascara on the market is typically comprised of an emulsion of water
and waxes to provide excellent volume, length, and other attributes to enhance the
look of the human eye. Other attribute that is sought in mascara is long lasting or
long wear. In this chapter, we will review the trend of using long-wear mascara
that lasts from 1 day to 2 days, and semi-permanent mascara that lasts from 3 days
up to 30 days. Such products typically contain silicone film-formers, hydrocarbon
resins or oxidative dyes from hair color to achieve long lasting effect without re-
application. However, the removability of such products from eyelashes is a chal-
lenge for consumers. This chapter will review and discuss the factors influencing
the adhesion of mascara to eyelashes such as mascara composition, its rheology
and mechanical properties for long lasting performance. Finally, the removability
of the long-wear mascara from the eyelashes is also discussed.
Keywords: Semi-permanent mascara, long-wear mascara, waterproof,

smudgeproof, eyelash, removability
17.1 Introduction
17.1.1 History of Mascara - Invention of the Mascara
“Eyes are the window to the soul”. This phrase has been used by
Shakespeare, the Bible (Matthew 6:22), and also Cicero (106-43 B.C.)
where he said “Ut imago est animi voltus sic indices oculi”, which means
“the face is a picture of the mind as the eyes are its interpreter”.
*Corresponding author: hy.bui@rd.loreal.com
K.L. Mittal and H.S. Bui (eds.) Surface Science and Adhesion in Cosmetics, (585–634) © 2021
Scrivener Publishing LLC
585
586 Surface Science and Adhesion in Cosmetics
People have always wanted to make their eyes and eyelashes more beau-
tiful. This dates back to early civilizations, such as the Assyrian, where they
had simply used dust of ground precious stones to decorate their eyes. As
shown in Figure 17.1, modern day mascara has evolved considerably since
the start from Ancient Egyptians (3400-30 B.C). They created the simple
mascara formulation, using kohl, water, crocodile droppings, and honey,
and applicator using bone and ivory. Kohl was a black substance used to
make typical eyeliner, which was made up of powdered antimony, burnt
almonds, black copper oxide and brown ochre [1]. Egyptians first lined
their eyes with kohl and then used the mascara to deepen their eyelashes.
Slowly the use of mascara revolved around medicine and religion to ward
off any evil spirit or death practices, while its functionality would be to
protect their eyes from dust and microorganisms [2].
Cosmetic products began to gain popularity in different regions of
the world. Similarly to Egypt, Greece and Rome (750 BC – 400 AD) also
adopted the ritual of using cosmetics for fashion and religious ceremonies
[3]. In Victorian Era (1837 – 1901), cosmetics appealed to women of mid
and high social classes where they took the time and effort to try different
cosmetic recipes in their own dressing rooms [4]. The most important part
of their makeup was mascara because it was able to transform their eye-
lashes to appear darker and longer.
17.1.2 Birth of the First Mascara

In 1872, petroleum jelly was patented [5], and later a French chemist
named Eugene Rimmel combined it with black charcoal dust to create
the first innovative, commercial, and packaged mascara in Europe called
3500BC –
30BC 1837–1901 1940 1975
Eye makeup Eye makeup Mascara Latex used in
used in in Victorian product in a mascara
Egypt Era tube container formulation
750 BC – 400 AD 1915 1960 2019

Eye makeup First Helena Modern
used in marketed Rubenstein mascara
Rome mascara mascara -
product in packaged in
square box brush/wiper
system
Figure 17.1 Timeline of the evolution of mascara from Ancient Egypt (3500 BC) to
modern day mascara.
Adhesion Aspect in Semi-Permanent Mascara 587
“rimmel” [6]. During the same time frame, a Chicago chemist, Tom Lyle
Williams, invented the first modern eye cosmetic made for everyday use
called Maybelline Cake Mascara, named after his older sister, Maybel [7].
During the time of 1920 – 1950, different types of packagings of mascara
were introduced but all of them resembled the same concept of a cake in
a pot accompanied by an external brush. In 1957, the mascara market was
revolutionized when Helena Rubinstein introduced an “automatic” mas-
cara called Mascara-matic because the mascara formulation was picked up
automatically by the brush applicator [8]. It was a creamy mascara in a dra-
matically new applicator invented in 1962 by Joss Ira, Philip M. Lederberg,
and Silson Victor and it became the modern mascara packaging we see
today [9]. See Figure 17.1 for the evolution of mascara.
17.2 Structure of Eyelash and Eye Lid: An Overview

There are not many studies about human eyelash structure that can be found
in literature, compared to the study of human hair. It is well known that the
primary role of eyelashes is to protect and maintain the well-being of the
eye surface and eyelid margin. The various functions of the eyelashes are:
1. Act as dust catcher to protect the eye from dust falling from
above [10]
2. Act as sensor which, upon contact with foreign object, trig-
ger the eyelid to close to protect the eye [11]
3. Draw attention to enable communication of expression [12]
4. Act as a shield for the eye from sunlight [13]
5. Provide optimum aerodynamics around the eye area to
decrease evaporation of the tear film at the ocular surface
and also to decrease the particle deposition on the lashes.
This is also to prevent drying of the eyes [14]
It was reported that the lower and upper eyelids contained different amounts
of eyelashes. The lower lid consists of three to four rows of eyelashes that
total up to 70-75 and the upper lid consists of five to six rows of eyelashes
that total up to 90 – 160 [15, 16]. The growth rate of eyelash is 50 – 140 µm
daily and the length ranges from 6 to 12 mm and never exceeds 12 mm for
the upper eyelid, regardless of ethnicity. The lower eyelid ranges 6 – 8 mm
[18]. The eyelash follicle growth rate is quite variable, with an average rate
of 0.12 +/- 0.05 mm daily. The thickness of the lash, amount of lashes, and
lift/curl degree in lashes would differ between ethnicities but the length and
Table 17.1 The differences between Asian (Korean), Japanese and

Caucasian(women) eyelashes.
Growth
Rate
Thickness Length Density Curvature (mm/
(µm) (mm) (# lashes) (°) day)
Caucasian 61 + 21.4 7.1 + 1.8 170 57.2 + 9.8 0.12
[16] – 0.15
Asian [16] 71.7 + 22.4 7.0 + 1.9 140 35.1 + 16 0.13
- 0.16
Japanese 7.47+ 71.8 +13
[17] 0.68
growth rate can be similar, such as between Asian and Caucasian (Table 17.1)
[16]. The difference in the length and curvature of eyelashes between Asians
(Korean) and Japanese in references [16, 17] are due to the way these were
measured. However, such physical differences between ethnicities would
influence the mascara performance when the same product is used.
Similarly to the structure of hair, eyelashes also have a bulb, root, and
shaft. The bulb and root are located underneath the skin where these are in
contact with the derma papillae and the glands. The shaft is located outside
of the skin layer. The lash structure consists of three parts. The innermost
structure is called the medulla and it contains loose cells. Surrounding it
is the second layer, the cortex, which provides the medulla with strength,
stability and also contains melanin to provide pigmentation to the lashes.
The outermost layer, the cuticle, is the impermeable cell layer which serves
as the protection for the internal structures [18].
Since the knowledge of hair structure is well established, we can com-
pare the hair and eyelash structures. It is observed that there are three
major differences between hair and eyelashes: eyelash follicles lack arrector
pili muscles, which regulate the hair’s response to cold or intense emotions,
such as goose bumps [19], eyelash has a shorter life cycle (9 – 11 months)
compared to hair (2-7 years) [15], and eyelash is the last hair to become
grey, thus it is the darkest hair in the body [19, 20].
Based on the eyelash properties, the key parameters that can have influ-
ence on the performance of mascara on eyelashes are:
1. Thickness or density of eyelash

2. Length of eyelash
3. Curvature of eyelash
4. Modulus or rigidity of eyelash
5. Blinking rate of eyelash
When applying a curling mascara formulation, the curvature and the

thickness of the eyelash are two aspects influencing the curl of eyelash.
The thickness of the eyelash provides the rigidity where it differs not only
among ethnicities, but also from different sections of the eyelash. The
thickness of the eyelash decreases from the root to the tip of the eyelash.
Thus when applying a curling mascara, it would be easier to curl the thin-
ner eyelash type and also the tip section due to its thinness. The curvature
of the eyelash appears to be less curled with Asian eyelashes compared with
Caucasian eyelashes. Hence to achieve equivalent curl for both ethnicities,
Asian eyelashes would require formulation of higher rigidity to overcome
the thickness and straightness of the eyelashes to maintain the curl. The
length of eyelash does not vary much with ethnic group as seen for Asian
and Caucasian.
Blinking plays a role in the durability of mascara deposited on eyelash as
it creates friction between the top and bottom eyelashes. Average blinking
rate is 15 - 20 blinks per minute [21]. When blinking occurs, the mascara
at the top eyelash would rub against the bottom eyelash, or the mascara
film on the bottom eyelash if mascara was applied, and this friction would
cause flaking of the mascara film. Asian eyelashes tend to be more straight
and downward which would touch the bottom eyelashes more frequently,
so more flaking is noticeable.
17.3 Types of Mascaras

Mascara formulation is generally comprised of water, oil, waxes, film-
formers, thickeners, and pigments as shown in Figure 17.2. These mascara
compositions have been used for many years to increase the thickness, length
and overall appearance of human eyelashes. The mascara can be formulated
as washable, waterproof and smudgeproof. The term washable mascara
refers to compositions that may be removed with water and/or soap. These
formulations are typically emulsions (waxes in water) as creams, gels or
cakes. Waterproof mascara, which requires the use of an oil based make-up
remover product, generally comes in the form of dispersion of waxes in
an organic solvent. Unlike waterproof mascara, another type of mascara is
called smudgeproof or smudge-resistant mascara which can deliver both
length and volume benefits but easy to remove with warm water.
Washable Mascara
1%–5%
5%–15% 12%–19%
Waxes
Pigment
4%–10% Water
4%–10% Film-Former
Surfactant
Thickener
35%–55%
Smudgeproof Mascara
5%–10%
8%–15%
Waxes
Pigment
Water
Film-Former
Surfactant
30%–50% Thickener
20%–35%
Waterproof Mascara
5%–8%
5%–12% Waxes
19%–25% Pigment
Water
Isododecane
Film-Former
Others
3%–7%
30%–50%
0%–7%
Fiugre 17.2 Mascara compositions.

By varying the mascara components such as amount of wax, amount or

type of film-former, emulsification system and emulsion type, the mascara
can perform from washable to waterproof or smudgeproof, while the other
mascara benefits such as volume, length and curl can be varied.
These types of mascaras require re-application maybe every 4 hours or
6 hours, which can be time consuming and inconvenient for most con-
sumers. In 2018, census was done on 720 female mascara users on the
attributes they sought in mascara and it showed that the long-wearing,
smudgeproof, and waterproof were among the top 5 attributes after the
volume and lengthening as shown (Figure 17.3 – Mintel) [22]. Therefore,
long-wear mascara is being increasingly sought after by consumers who
want to look beautiful throughout the day or week, after rigorous work-
out routine, challenging weather conditions, or busy work schedule with-
out putting much effort into their makeup routine. However, one of the
problems with long-wear mascara is that making the composition with
excellent adhesion to the eyelashes would also create adhesion among the
eyelashes. Some clumping is inevitable, but if too many individual eye-
lashes stick together and appear as large clumps, the consumer does not
get the desired look. Alternatively, two-step mascaras were developed [23],
where the topcoat protected the basecoat mascara. These are typically not
intended for wear beyond the normal 8-12 hours per day. These two-step
mascaras are typically removed at night with soap and water.
Currently, consumer products have been launched in the market that
claim multiday benefits (Figure 17.4). For products promising wear for
1-5 days, they act more as either eyelash stains, which provide an eyelash
darkening benefit but fail to provide fullness and length, or water-proof
type “long-wear” mascaras that do not maintain the initial look over
multiple days. Furthermore, the eyelash stain products tend to degrade
rapidly after the first day of wear. Another long lasting type for home
use eye make-up which aims to last at least 1 week or more is the semi-
permanent mascara. Semi-permanent mascara provides full mascara
benefits of long, dark beautiful eyelashes for at least 5 days or more and
is viewed as time saver as it does not require daily application or the fre-
quent touch-ups of conventional mascara. Such products utilize differ-
ent long lasting ingredients from hair coloring dyes, film-forming latex
polymers, silicone resin, and hydrocarbon resin to maintain the color
of the mascara on the eyelashes for at least 5 days and provide the end
makeup look that will be discussed in the following sections. As seen in
Figure 17.4, the removability of long-wear mascara is a challenge when
mascara lasts longer than 1 day.
“Which of the following are important to you when selecting mascara?”
Volumizing 63%
Lengthening 53%
Long-wearing 51%
Smudgeproof 47%
Waterproof 45%
Type of brush/applicator 37%
Sweatproof 27%
Curling 23%
For sensitive eyes 21%
Conditioning ingredients 18%
Contains eyelash-growth serum 14%
None of the above 2%
Figure 17.3 Ranking of the mascara attributes which were preferred by consumers (from
Mintel) [22].
MAPPING OF PRODUCTS CLAIMING AT LEAST 24HR WEAR

Convenient to
apply & remove CONVENTIONAL MASCARA
Extreme Wear Products
5+ days
Avon Color Super

Extend Infinitize Cil Tint
Acrylates/Ethylhexyl MQ/PSPA
Acrylate Copolymer Launch 2014
LashStain 4 Day
Cover Girl
Lash Ink
MQ
TAKE HOME PROFESSIONAL
Lash-Blast 24 Hour Max Factor Lash
Finity 3 day Mascara
Launch June 2014 KIT USE
Rosinate+ Waxes
Rosinate
Launch June 2013 REACTIVE
CHEMISTRY
Revlon Colorstay
Overtime Colorstay Overtime
MQ+waxes Lash Tint
Polysiloxane - 6
Launch June 2002 Tarte 4 day
MQ/Rosinate
Godefroy 28 Day Permanent
Launch June 2008
Mascara Nova lash
Pyrogallol - Silver Nitrate cyanoacrylate
Launch August 2012 ester
Kose Fasio Curl Lock
Mascara 24 Hr
MQ-Rosinate + waxes
HIGH LEVEL OF
FILM-FORMERS Color sport 30 Day
Xtreme lashes
Mascara
Synthetic polyester-
Hydrogen
cyanoacrylate
Peroxide
medical grade
1 2 3 4 5 10
Launch 2011
30
Long Wear (days)
Figure 17.4 Mapping the needs of long-wear mascara.

17.4 Components in Mascara Formulations

Shown below are the typical ingredients in various types of mascaras:
washable, waterproof, smudgeproof and one-day wear. The mascara for-
mulations contain:
• Volatile fluid: water or isododecane

• Surfactant systems: to stabilize O/W emulsion or Wax/W
emulsion.
• Film-formers: water soluble polymers or oil soluble poly-
mers as binders for pigments and wax.
• Waxes: contribute to volume/curl or thickening.
• Thickener/Gellants: polymers or gelling agents
• Pigments: black iron oxide or carbon black.
• Preservatives
• Tables 17.2 - 17.4 below are examples of 3 types of mascara
formulations: washable mascara, waterproof mascara, and
smudgeproof mascara.
Table 17.2 shows the key ingredients that are often used in the washable
mascara formulations. The washable mascara is a wax-in-water emul-
sion and it can contribute volume and length or curl benefits due to
high amount of wax dispersion in the formulation. The composition of
the washable mascara consists of water, surfactant, film-formers, waxes,
pigments, and others. Representative washable mascara products in 2019
are: Maybelline New York Snapscara Washable Mascara, L’Oréal Paris
Voluminous Lash Paradise Mascara, Milk Makeup Kush High Volume
Mascara, Wander Beauty Mile High Club Mascara, and Pat McGrath Labs
FetishEyes Mascara.
As shown in Table 17.3, waterproof mascara formulations are either
water-in-oil or anhydrous formulations. Representative waterproof mas-
cara products are Voluminous Waterproof Mascara by L’Oreal Paris,
Inimitable Waterproof Mascara by Chanel, In Extreme Dimension
Waterproof Mascara by M.A.C., Hypnose Water proof Mascara by
Lancôme, and Better Than Sex Waterproof Mascara by Too Faced. The typ-
ical composition of a waterproof mascara consists of isododecane, waxes,
oil soluble film formers, surfactants for W/O emulsion, oil thickener, pig-
ment, and others with their ranges of concentrations as shown in Table
17.3. Waterproof mascaras consist of isododecane as the main solvent
because it is a universal volatile solvent for many polymers in cosmetics.
Table 17.2 Typical ingredients in a commercial washable mascara.

Ingredients Function Amount (wt%)
Water Volatile solvent ~35 - 55
Cera alba/beeswax Waxes/ ~10 - 20
Synthetic beeswax film-formers
Carnauba wax
Paraffin wax
Palmitic acid, Surfactants/ ~5 -15
stearic or isostearic acid emulsifiers
Oleic acid
Potassium cetyl phosphate,
Ceteareth 20,
Steareth 20/21
PEG 200 glyceryl stearate
Vinylpyrrolidone/Eicosene copolymer Polymers/ ~4 – 10
(oil soluble) film-formers
Vinylpyrrolidone/Hexadecane
copolymer (oil soluble)
Polyvinylpyrrolidone (water soluble)
Ethyl acrylate/methyl methacrylate
Styrene/acrylate/ammonium
methacrylate copolymer
Thickener ~1 - 5
Pigments ~4 - 10
After isododecane has evaporated, it leaves the mascara deposit as a

hydrophobic film on the eyelashes which is waterproof. Therefore, the
waterproof mascara can last from 6 hours to 8 hours and the removal of
mascara requires an oil based make-up remover product.
Table 17.4 shows the key ingredients in a smudgeproof or smudge
resistant mascara. Typical smudgeproof mascara formulation consists of
water, water-based film-formers, waxes, surfactants, thickeners, pigments,
and others [24–26]. This formulation is very similar to washable mas-
cara formulation where it uses the same acrylate copolymers as the film-
formers except the levels used are higher to ensure that the formulation is
resistant to sebum. The amount of waxes used is less in order to achieve
good wear and without flaking because high amount of waxes would
interfere with the film formation of the latex. Since the amount of waxes
Table 17.3 Typical ingredients in a commercial waterproof mascara.

Isododecane Volatile solvent ~30 – 50
Cera alba/beeswax Waxes/ ~15 - 25
Copernicia Cerifera Cera/Carnauba Wax film-formers
Synthetic beeswax
Paraffin wax
Oryza Sativa Cera/Rice Bran Wax
Vinylpyrrolidone /Eicosene Polymers/ ~5 – 12
Allyl stearate/Vinylacetate copolymer film-formers
Glyceryl hydrogenated rosinate
Vinylacetate/Vinyl butyl benzoate/
crotonate copolymer
Thickener ~5- 8
Pigments ~3 - 7
Table 17.4 Typical ingredients in a smudgeproof mascara [24–26].

Cera alba/beeswax/ Waxes/film-formers ~8 - 15
Synthetic Carnauba wax
Sorbitan stearate Surfactants/ ~5 - 10
Stearic or isostearic acid emulsifiers
Steareth 20
Steareth 21
Polyvinylpyrrolidone (water soluble) Polymers/ ~30 - 50
Polyurethane-35 film-formers
Acrylate/Ethyl hexyl acrylate
Styrene/acrylates/ammonium
methacrylate copolymer
Thickener ~0.5 - 1
Pigments ~4 – 8
used for emulsification is lower, this requires the usage of thickeners to

increase the viscosity of the formulation. Typical viscosity enhancers used
in smudgeproof formulation are xanthan gum, cellulose, pullulan, ben-
tonite, and other vinylpyrrolidone copolymers such as vinylpyrrolidone/
vinylacetate and polyvinylpyrrolidone. All these mascaras will last for one
day but might require re-application during the middle of the day. The
smudgeproof mascara is water resistant, and it can deliver both length and
volume benefits but is easy to remove with warm water.
17.5 Long-Wear Mascaras

As we discussed above, one way of making a mascara composition which is
both waterproof and long-wear is to make it anhydrous. Thus, the compo-
sition will typically comprise volatile solvents and film-forming polymers.
This type of composition, however, is not washable with water. In this sec-
tion, we will overview the new trend of mascara that can be waterproof,
smudgeproof and long-wear and can last from 24 hr to weeks (extreme-
wear) as shown in Figure 17.4 and Tables 17.5-17.6.
17.5.1 One-Day Wear Mascara

The trend of using long-wear mascara that lasts from 24 hr up to 48 hr
has increased from the fact that many cosmetic companies recently have
launched such products: Covergirl Lashblast Mascara 24 hrs, Revlon
Colorstay Overtime 24 hrs, Neutrogena Lash tint, etc. These products
contain either silicone resin MQ, or acrylate polymer dispersion (latex) or
Pentaerythritol Hydrogenated Rosinate as film-formers for long lasting, up
to 24 hour, wear benefit.
17.5.2 Semi-Permanent Mascara (3 - 5-Day Wear)

Most mascaras that last for more than 2 day-wear can be consid-
ered as extreme-wear or semi-permanent such as Lancôme Lash Tint,
Max Factor Lashfinity Mascara, Tarte 4 Day Stay Lash Stain, Wunder2
Wunderextensions Stain 72 HRS Mascara, and Hard Candy Lash Ink 4
Day Lash Stain. These products also contain the same film-formers such as
silicone resin MQ, or Pentaerythritol Hydrogenated Rosinate as in 1 day-
wear mascara. The difference is that the film-former concentrations can
be much higher to form more cohesive films and the formulations do not
Table 17.5 Typical commercial long-wear mascara products from 1 day to 4 days wear.
WUNDER2
WUNDER
Revlon Colorstay EXTENSIONS
Overtime COVERGIRL Lash MAXFACTOR
Lengthening Lashblast Neutrogena Extension LANCOME Cil Lashfinity 3 TARTE 4 day lash HARD CANDY
Mascara 24 hr Lash Tint Stain 72 Tint day Mascara stain LASH INK Avon Everlast
Lastingness 1 day 1 day 1 day 3 days 3 days 3 days 4 days 4 days 18 hrs – 1 day
Volatile Isododecane, Aqua Petroleum Water, SDA Aqua/ Water, Isododecane Isododecane Isododecane, Water, Isododecane
Fluids ((Water) Eau) Distillates Alcohol Alcohol Denat., Alcohol, Aqua Isododecane
40-2, Isododecane
Primary Film Trimethyl Pentaerythrityl Acrylates Trimethyl Trimethyl Pentaerythrityl Trimethyl Trimethyl Acrylates
Former siloxysilicate Hydro Copolymer siloxysilicate siloxysilicate Hydro siloxysilicate, siloxysilicate Copolymer
genated Pentaerythrityl genated Pentaerythrityl
Rosinate, Hydrogenated Rosinate Hydrogenated
Rosinate, Rosinate
Architecture Emulsion Anhydrous Emulsion Anhydrous Anhydrous Anhydrous Anhydrous Anhydrous Emulsion
Table 17.6 Long-wear mascara products with 4-week wear or longer.

Godefroy 1000 hour eyelash kit
Duration 4 weeks (28 days) 6 weeks

Composition Cream colorant: Pyrogallol 3% Hydrogen Peroxide
Cream: 2-Chloro-p-
Gel activator: silver nitrate, Phenylenediamine
ammonia
contain wax. It is observed that both MQ resin and ester rosin are used in
Tarte 4 Day Stay Lash Stain.
17.5.3 Micropigmentation/Lash Tinting (30-Day Wear

or Longer)
For multiple week lasting mascara, the only ingredients that can achieve
such performance is from hair dye. Many of these products have two parts:
oxidizer and a colorant cream. Godefroy 28 Day Mascara Permanent
Eyelash Tint uses pyrogallol, an oxygen-sensitive compound, as the main
colorant that gets oxidized. Such ingredient was first used in photography
where using silver nitrate would create a grayish color [27]. Other products
typically use hydrogen peroxide with other oxidative dyes to generate last-
ing color on eyelashes.
17.6 Evaluation Methods for Long-Wear Mascara

17.6.1 In Vitro Evaluation
There is no publication in the literature for evaluating the long-wear and
extreme-wear mascaras systematically. Only Dempsey and coworkers have
described the waterproof mascara and the methodology of rubbing and color
transfer for evaluating the performance of semi-permanent mascara formu-
lations [28, 29]. Most of the evaluation methods were developed to evaluate a
certain aspect of wear for mascara formulations and are only found in patent
literature [29–41]. To evaluate systematically the performance of long-wear

mascara or semi-permanent mascara, the following scientific evaluation
techniques can be applied and are summarized in Table 17.7.
The rheology measurements are commonly used to characterize the
mascara formulation performance with mascara applicator, mascara for-
mulation texture and the formulation stability. Some rheological methods
such as oscillation strain at fixed frequency in the linear viscoelastic regime
is used to obtain the texture and stability of the mascara bulk. The flow
experiments such as viscosity as a function of shear rate give information
on shear-thinning behavior which is important for the application with
mascara brush/applicator. Time-dependent viscosity or thixotropic behav-
ior indicates the length of time where consumers are able to keep applying
the mascara formulation on their eyelashes prior to its drying. Also, thixo-
tropic behavior will allow to understand the complex structure recovering
under shear.
A long-wear mascara should have good resistance to sweat, sebum, and
water to ensure there is no smudging throughout the daily wear. Artificial
sebum [42] composition is used as a way to mimic the fatty acid secretion
from skin. There are a few test methodologies where artificial sebum was
used as the stimulus on the different mascara formulations to test their
resistance to human sebum and sweat.
Contact angle measurement was utilized to evaluate the wetting, spread-
ing and resistance of water and sebum to the long-wear foundation [43],
so this technique can also be applied to mascara films deposited on glass
substrate. Mascara composition is first applied on a substrate and a drop
of artificial sebum or water is placed over the dried mascara film. The ini-
tial and final contact angles of sebum or water, after a duration of time,
are measured and compared. For the mascara with low sebum resistance,
sebum would slowly spread over the dried mascara film and decrease the
contact angle (CA) over time. A semi-permanent mascara would not have
a decrease in the sebum CA with time. For a waterproof mascara, the water
CA should be greater than 90°.
In an extreme case, mascara was first applied on keratinous substrate
and allowed to completely dry. Then the eyelashes are submerged in the
artificial sebum solution for at least 1 hour or longer (12 hr – 24 hr) and the
eyelashes are rubbed on a blotter paper to assess the level of color transfer to
the paper (Figure 17.5a, b). A semi-permanent mascara would have strong
resistance against the artificial sebum and not reveal any color transfer to
the blotter paper. Similarly to sebum test, the water resistance of the mas-
cara is tested in the same way, in which the false eyelash coated with mas-
cara is either placed under running water (cold/warm) or submerged in
Table 17.7 Summary of test methodologies for long-wear and semi-permanent

mascaras.
Test method Property evaluated
Rheology measurement Viscoelastic property and flow behavior of
mascara.
Stability of mascara formulation
Contact angle measurement Wetting and spreading of sebum, sweat, and
water on mascara films deposited on glass
Resistance of mascara film to sebum and
water
Surface free energy of mascara deposit
Immersion in test liquid Resistance of mascara film to sebum, water,
(24 hours or longer) and soap.
Color transfer
Colormetry (lightness (L*), Color transfer of mascara before and after
chroma (a*), and hue (b*)) exposure to sebum and water
Wear resistance of mascara film after rubbing
Tape test Adhesion of mascara film
Mechanical rubbing test Flaking of mascara
Stretching test Integrity and cohesiveness of mascara deposit
Brushing Integrity and cohesiveness of mascara deposit
Dynamic Mechanical Young’s modulus, elastic modulus and glass
Analysis (DMA) transition temperature (Tg)
Instron tensile testing Young’s modulus and flexibility/durability of
mascara
DSC Thermal property of mascara film: glass
transition temperature (Tg) and melting
temperature (Tm)
SEM/ cryo-SEM Mascara deposition on false eyelash
Atomic Force Microscopy Deposit of mascara on false eyelash
(AFM) Nano-mechanical and adhesion property of
mascara
water for 24 hr. After being submerged in water, the samples were rubbed
on a blotter paper to assess the color transfer level. Water-resistant mascara
would have no color transfer to the blotter paper (Figure 17.5b).
Another water and soap resistance test methodology was developed by
placing a drop of water and surfactant mixture over a dried mascara film.
The drop was rubbed by a paper towel and the color transfer to the paper
towel was assessed [28, 29]. There should be no color transfer to the paper
towel to claim water resistance.
In another methodology, artificial sebum was mixed with the long-wear
cosmetic formulation and the interaction between the sebum and the cos-
metic composition mimicked the behavior of cosmetic absorbing sebum
throughout the day. When the combination gels up the sebum, the makeup
composition can be considered to have maintained the wear because the
sebum is solidified.
Scientists from Dermapro tried to correlate the in vitro and in vivo eval-
uations on 20 female subjects for the waterproof eyeliners [33]. In vitro,
20 sets of false eyelashes were used to evaluate the waterproof property of
mascaras. For evaluating water-resistant property, the areas on which eye-
liners and mascaras were applied, depending on the substrate used, were
immersed in water and allowed to dry in ambient environment for over 20
min (not artificial drying by a drier), L* value of the eyeliners applied on
the forearm before and after the immersion, and intensity analysis values
of mascaras applied on the false eyelashes were used to calculate the mean
percentage waterproof removal (%WPR). A product was hypothesized to
be water resistant if the value for the mean %WPR was ≤50%. The eyeliners
were not waterproof if their mean %WPR was >50%, whereas the eyelin-
ers were waterproof if their mean %WPR was <50%. For mascaras, the
(a) (b)
Figure 17.5 (a) Mascara coated on false eyelash immersed in artificial sebum (left)
and water (right) (b) After immersion, the mascara was rubbed on color transfer paper
andintensity of the color on the paper indicates the level of transfer.
mean %WPR was <50% after 1- to 2 - h after immersion in water for both
non-waterproof and waterproof products. After 3 - 4 h, the mean %WPR
for the non-waterproof mascaras was >50%, rendering them not water-
proof, whereas the mean %WPR for the waterproof mascaras was <50%,
making them waterproof.
Mascara with long-wear properties would need to withstand mechan-
ical rubbing throughout the day. Many companies have developed differ-
ent methods for assessing the mechanical strength of the mascara film on
eyelashes. For flaking and mechanical robustness, various equipment, such
as dynamic mechanical analyzer (DMA) and Instron, are used to con-
duct stretch tests on the mascara to simulate rubbing of the eyes and to
ensure the mascara is able to resist rubbing. Then, the mascara film can
be observed through SEM to ensure the mascara deposits smoothly and
uniformly on the eyelashes, providing good lasting wear.
For example, a semi-permanent mascara film was cast on a substrate
and allowed to dry. After it dried, a napkin was placed on top of it and
a constant weight of 2kg force was applied on the napkin and rubbed.
The film was then subjected to a color reading and the least amount of
color change would indicate least transfer and most resistance to water [28,
29]. Figure 17.6 shows the rub test results for water resistance from various
mascaras using this test method [29].
Stretch test determines the durability and flexibility of the mascara
film and likelihood of flaking for the duration of wear from rubbing of
Rub Test Results

0.00
–2.00
–4.00
Cover Girl Lash Exact
Cover Girl Lash Exact Waterproof
–6.00
Delta L
Maybelline Define-A-Lash
Maybelline Define-A-Lash Water proof
Maybelline XXL Pro 24HR Bold
–8.00 Semi-permanent Mascara Prototype
Tarte 4 day Stay Lash Stain
–10.00
–12.00
–14.00
Figure 17.6 Rub test results for various mascaras [29].

eyelashes. Mascara film was cast on an elastic substrate and allowed to dry.
Once dried, the elastic substrate was stretched at a constant rate to see if
the mascara film would crack or flake off. Semi-permanent mascara film
would not flake off the elastic substrate upon stretching the substrate.
Scanning Electron Microscopy (SEM) is a good technique to observe the
deposition of the mascara on the eyelashes to ensure the film is smooth and
homogeneous to provide good lasting wear. Mascara was first applied on
keratinous substrate and then the sample was treated accordingly for view-
ing in the SEM. Shown in Figure 17.7 is an example of a semi-permanent
mascara, Tarte 4-day lash tint film, on keratinous substrate.
Dynamic Mechanical Analysis (DMA) measures the modulus of the
dried mascara film under different temperature and humidity conditions.
Under high humidity conditions, the modulus of the semi-permanent
mascara film should not be affected due to its high water resistance and
also prevents water vapor from plasticizing it. Similarly, Instron can mea-
sure the ductility and the Young’s modulus of the dried mascara film as it
stretches.
Atomic Force Microscopy (AFM) has been used to study the hair struc-
ture and products deposited on hair fiber. Thus AFM might also give infor-
mation on surface roughness, nano-mechanical and adhesion properties
of mascara deposited on a single false eyelash.
17.6.2 In Vivo Evaluation by Expert Panels or Consumers

After numerous prototypes had been assessed through all the in vitro test
evaluations, the best mascara candidate was subjected to in vivo testing by
2013/05/07 16:16 L x500 200 um
Figure 17.7 SEM image of semi-permanent mascara deposited on the false eyelash.
DAY 5 WEAR
DAY 3 WEAR
INITIAL APPLICATION
BARE EYELASH
Figure 17.8 In-vivo evaluation of a semi-permanent mascara prototype.
consumers or expert panels [28–30]. Figure 17.8 shows the lastingness of

the 5-day wear mascara prototype from consumers. Each picture was taken
to indicate the presence of the mascara on the eyelashes during each day to
indicate the lastingness on consumers during their normal lifestyle.
17.7 Factors Affecting Adhesion of Mascara

to an Eyelash
For a mascara to last more than one-day wear, it should possess the follow-
ing attributes:
a. High resistance to water (hot and cold) and soap under

showering and during daily face cleansing [28].
b. High resistance to sweat and sebum under hot and humid
condition.
c. High abrasion resistance to rubbing, changing clothes and
contacting with pillow during daily activities and at sleep
[28].
To meet such requirements, the mascara performance is dependent on

many factors such as mascara composition, rheology of mascara formula-
tion, surface property of mascara deposit after drying and its mechanical
property during daily life activities.
17.7.1 Factors Affecting Adhesion of Mascara to Eyelash:

Mascara Composition
The mascara formulations for 3- and 4-day wear as semi-permanent
mascaras contain these main ingredients: 1) film-formers, 2) volatile
solvent, 3) pigments and fillers, and 4) rheology modifiers. For the best
performance, the semi-permanent mascara formulations do not con-
tain wax.
17.7.1.1 Film-Formers
Table 17.5 shows the ingredients of some commercial one-day wear and
semi-permanent mascara products. Three types of film-formers are used
in the formulations: silicone resins, rosin ester, and acrylate latex. These
resins or film-formers act as a binder for pigments and fillers to provide
both adhesion and cohesion properties for the mascara.
17.7.1.1.1 Trimethylsiloxysilicate Resins

Trimethylsiloxysilicate resins (also known as MQ resins as in Figure 17.9)
have been used in long-wear and non-transfer cosmetic applications to
provide lipsticks or foundations exceptional wear and adhesion due to
their low surface free energy (SFE) [44]. The interaction of MQ resin with
solvents, pigments and fillers gives good adhesion to the skin. The flexi-
bility of the resulting film depends on non-volatile solvent, the emulsifier,
and solids content. This resulting film formed on the skin has very good
oil, sweat and sebum resistance with high water contact angles in the range
100° -112°.
Besides providing the long lasting of color in make-up products, MQ
resins are also used for long lasting effect in hair repair or hair color. For
example, the MQ resins in the emulsion with SFE matching the SFE of hair
can spread and wet the hair well, forming a durable coating on hair fiber
under shampooing and washing conditions. The plasticized MQ resin can
repair the split ends of the hair [45].
By combining MQ resins with a film-forming amino silicone polymer,
a thickener, and color pigments in a solvent, a durable and dry thin film
can form on hair fiber. The hair treated with such composition shows an
enhancement in pigment adhesion and color remains against shampooing
and washing. It was believed that a combination of amino silicone polymer
and MQ resin provides an excellent film via a dehydration mechanism [46].
Therefore, MQ resins can be employed in mascara formulations to
deliver the long- lasting benefits such as no-transfer and lasting of color
CH3
CH3 Si O Si
CH3 Si
O O O
O
Si O Si Si
Si O Si CH3
CH3 O O O
O O O Si
CH3 O
Si Si
Si O Si Si O O
O
O O O Si O Si CH3
Si
Si O Si O O O
CH3 CH3
O
Si O Si Si
O CH3
O O O Si
Si O Si CH3
CH3
O O
CH3 Si O Si
Si
O O O
CH3 CH3
Si O Si Si
O O O
Si O Si
Figure 17.9 Structure of MQ resin.
under washing or bathing condition with sweat/ sebum resistance or under

mechanical stress for longer than 1 day. In addition, the mascara formu-
lated with MQ resin can be considered as waterproof, smudge-resistant,
and long-lasting mascara. From these properties, blending of MQ resin
with silicone gum was also used in the topcoat formulation [29] for the
semi-permanent mascara (Table 17.8).
Furthermore, the use of cross-linked silicone film-former with a sili-
cone gum in a mascara composition can deliver a long lasting color with
reduced smudging and exhibiting an enhancement in color [39]. The cross-
linked silicone film-formers used in such formulations are dimethicone
silylate and trimethylsiloxysilicate (MQ). Similarly, cross-linked silicone
film-former from trisiloxane and dimethicone silylate with clay mixture
delivered a mascara lasting more than one-day wear with minimum flak-
ing and exhibiting glossy look. The mascara formulation demonstrated
that its color still remained on the eyelashes after 3 days compared to the
commercial mascara product containing acrylate latex which was claimed
to last for 3 days [40].
Table 17.8 Example of mascara composition containing MQ resin as a topcoat

for semipermanent mascara from patent US 10,034,829 [29].
Supplier/
Raw Material Description Trade Name Function %Wt/Wt
Isododecane Presperse/ Volatile Solvent 49.995%
Permthyl 99A
Trimethylsiloxysilicate Momentive/ Film Former 38.025%
MQ Resin
Dimethicone Momentive/ Film Former 10.980%
SE-30 Gum
1,2 Hexanediol, Caprylyl Symrise/ Preservative 1.000%
Glycol Symdiol 68
Total 100%
As a result, MQ resins are widely utilized in the 1 day-wear mascara such

as RevlonColorStay Overtime and in semi-permanent mascara formula-
tions such as Tarte 4 Day Stay Lash Stain, Hard Candy Lash Ink, Wunder2
WunderExtensional Lash, and Lancôme Cil Tint.
17.7.1.1.2 Rosin Esters

Rosins are used in other industries such as food, cosmetics, and pharma-
ceuticals, functioning as film-formers, adhesion promoters, and emul-
sifiers [47–49]. The esterification of rosin containing carboxylic acid
groups with different alcohols form rosin esters with various molecular
weights and softening points. For example, glycerol and pentaerythritol
react with rosin acid forming glyceryl rosinate and pentaerythritol ros-
inate (Figure 17.10 a–b). The cohesion and adhesion of pentaerythritol
rosinate are higher than glyceryl rosinate, therefore pentaerythritol ros-
inate is commonly used as tackifier in pressure-sensitive adhesives. In
addition, the critical surface tension of pentaerythritol rosinate is lower
than most polymers, about 32 mN/m, which is another factor for it being
a tackifier [50].
The available rosin esters for cosmetic formulations are hydrogenated
rosin ester derived from gum rosin with high oxidative stability. These
hydrogenated rosin esters can be soluble in many cosmetic oils and are
compatible with waxes. The hydrogenated glyceryl rosin and pentaeryth-
ritol rosin esters derived from highly stabilized gum rosin can be obtained
H H
H
O H H
O H O O
O O
H O O
O H
H
(a) (b)
Figure 17.10 Structures of rosin derivatives (a) Pentaerythrityl rosinate and (b) Glyceryl
rosinate.
from Eastman as Foral™ 85-E CG and Foral™105-E CG hydrogenated

rosins. The hydrogenated glyceryl rosin Foral™ 85-E CG has a softening
point of 85°C, and a high refractive index of 1.502 while hydrogenated
pentaerythritol rosin ester Foral™105-E CG has higher softening point
and refractive index 101°C and 1.512, respectively [51].
Rosin esters are used as film-formers for long-wear cosmetic formu-
lations because of their hydrophobicity, flexibility, cohesion, adhesion
and shine/gloss properties [52, 53]. With low critical surface tension
and high water contact angle of 76° [50], pentaerythritol rosin ester
can easily wet and adhere to keratin substrate and has good water
resistance. Therefore, it is a good candidate as film-former for using in
semi-permanent mascara formulation. The semi-permanent mascara
MaxFactor Lashfinity with 3-day wear contains rosin ester as film-for-
mer in the mascara composition. The rosin film-formers in their mas-
cara compositions were selected from the group consisting of tall oil
glycerides, pentaerythrityl rosinate, glyceryl rosinate, and the hydro-
genated versions and mixtures [28, 29]. To achieve an extreme-wear,
up to 3-day wear, the mascara composition contains high amount of
rosin film-former with no wax or with a low wax content less than 3%,
based on the volume concentration of solids in relation to the critical
pigment volume concentration (CPVC) [54]. Example of a semi-
permanent mascara formulation is shown in Table 17.9 [29]. The formu-
lation containing rosin esters could also be used as topcoat for various
types of basecoat mascaras to improve the volume, color intensity and
lastingness [31]. However, the pentaerythrityl hydrogenated rosinate
can be sensitive to sebum, so the mascara containing this film-former
can have good waterproof property but might not be smudgeproof. The
Table 17.9 Mascara composition containing rosin

ester for semi-permanent mascara [29].
Semi-Permanent Mascara Composition
Material Wt%
Isododecane 45.5
1,2 Hexanediol and Caprylyl Glycol 1
Benzyl Alcohol 0.65
Tall Oil Glycerides 13.5
Pentaerythrityl Hydrogenated Rosinate 13.5
Black Iron Oxide (Jet Milled) 10
Disteardimonium Hectorite QS
pentaerythrityl hydrogenated rosinate is also found in other long-wear

mascaras such as Wunder2 Wunderextensions Stain 72 HRS Mascara,
and Tarte 4 Day Stay Lash Stain as shown in Table 17.5.
17.7.1.1.3 Latex
A long-wear mascara, (which is typically waterproof mascara) due to its
anhydrous composition, provides high water resistance. In 1975, water-
based mascara was developed and specifically latex was first mentioned
in 1994. Latex is a term used for spherical polymer particles dispersed
in water usually by means of emulsion polymerization. Latex is used as
the film-former due to its long lasting property, low viscosity, low VOC,
easy to formulate, and easy removability. In mascara formulation, latex
provides long-lasting benefit, smooth application, lasting lift, lengthen-
ing, and thicker look. The film formed itself might be chemically and
mechanically resistant but there are many factors that can affect the
film formation. Such factors can be influenced by surfactants, plasticiz-
ers, temperature, humidity, pigments, and particle shape. Usually, such
materials will weaken the film properties and making it less resistant to
water or to mechanical forces. The ambient room conditions will affect
the minimum film forming temperature (MFFT), which is defined as
the lowest temperature at which latex particles will uniformly coalesce
on a substrate and form a clear and homogeneous film. Film cast below
this temperature would yield a non-uniform film which is opaque and
powdery [55]. Films formed at lower temperature (near 25°C) would

tend to be softer and more flexible while films formed at higher tempera-
ture (50°C < T) tend to be more rigid and brittle. The film formation tem-
perature can be influenced by a plasticizer where its role is to decrease
the film formation temperature. Pigments act as defects embedded in the
film where they modify the mechanical properties but do not affect the
MFFT [55–57].
Because of these properties, latex has been used in many mascara prod-
ucts such as washable mascara or smudgeproof mascara with a low solids
content. For achieving long lasting or semi-permanent mascara, the latex
has to be formulated with high solids content in order to form a continu-
ous film covering the eyelash as shown in Figure 17.11.
To achieve the desired mechanical properties and good adhesion to eye-
lash, high Tg and low Tg latices can be blended at various ratios to form
hybrid films as reported for polyurethane and styrene/acrylate copolymer
latex blend [25] (Figure 17.12).
The combination of acrylate copolymers having relatively low and high
Tgs provides mascara composition which helps to improve rheological,
texture and wear properties. The soft and hard latexes contribute to the
balance of both cohesion and adhesion properties of the latex film, there-
fore the hybrid latex in mascara formulation provides individual eyelash a
flexible film with little flaking [26].
Plasticizer/Coalescent
Water
Latex
Drying
Eyelash
Water-Based Film Formation
Figure 17.11 Latex as a coating for eyelash.
Hybrid Latex Film Formation Process
Soft, Flexible Matrix (PU, Low Tg) Hard Filler Embedded (Acrylic, High Tg)
Figure 17.12 Hybrid latex system using a blend of polyurethane (PU) and acrylic for
long-wear mascara.
However, the lastingness of mascaras from these formulations cannot

extend to more than 2 days because the latex particle concentration used
in these formulations was lower than 30% solids. With latex concentration
greater than 30%, the blending of 2 amorphous latexes of styrene acrylate
copolymer (low and high Tgs) and acrylate copolymer (low Tg) in a ratio
of 1 to 1, gave the best viscoelasticity for application as well as the best
smudge resistance compared to either one-day wear mascara (Covergirl 24
HRS LastBlast) or semi-permanent mascara (Tarte 4-day wear mascaras)
(Figure 17.13).
Another example is the blending of semi-crystalline and amorphous
latexes in mascara composition such as an olefin/acrylate grafted polymer
and a styrene/acrylate copolymer (Figure 17.14a) to deliver a long-wear
mascara with good water and sebum resistances [35].
The resulted film will have less crystals and more flexibility because an
amorphous copolymer disrupts the crystallinity of a semi-crystalline copo-
lymer. In addition, the semicrystalline polymer latex with a low Tg acts as
Artificial sebum resistance Water resistance after

after 24 hr 24 hr
Latex blend
Tarte
CoverGirl
Lash Blast 24 hr
Figure 17.13 Comparison of sebum and water resistance for long-wear mascaras
containing latex blend of amorphous and semi-crystalline polymers in current
commercial products.
a plasticizer for the high Tg amorphous latex, resulting in a film having an

intermediate Tg for the blend depending on their ratios in the composition.
Another way to achieve an extreme long-lasting mascara using citric
acid to plasticize the high Tg latex is described [36]. The inventors found
that the use of a polycarboxylic acid such as citric acid (Figure 17.14c)
with a latex film-forming polymer not only enhances the viscosity of the
composition and assists in the suspension of pigments in the composition,
but also increases the adhesion of the latex film to eyelashes, resulting in a
mascara having extremely long wear. The in vivo test results showed that
the lastingness of the mascara composition containing styrene/acrylate
copolymers improved from 2-day wear to 5-day wear in the presence of
3% citric acid.
Other material found to improve the mechanical properties of styrene/
acrylate copolymer latex film was hyperbranched polymer (Figure 17.14b)
containing polyacid with high acid functional groups (acid value = 80)
[37]. The hyperbranched polyacid is a semi-crystalline polymer having a
melting point of 60°C and a low Tg of -5°C. With the incorporation of
hyperbranched polyacid, the glass transition temperature Tg of the styrene/
acrylate copolymer latex film was reduced from 20°C to less than 5°C. As
a result, the film formed is softer and more flexible than without hyper-
branched polymer and it has less chance for flaking off the eyelashes when
the eyelashes are bent. Therefore, the final film property is improved with
high resistance to mechanical stress and adhesion to eyelashes is increased.
As a result, the mascara is extremely long-wear, lasting up to 5 days after
application without flaking. Figure 17.15 shows the SEM images of a single
hair fiber coated with the latex film and another hair fiber coated with the
blend of latex and hyperbranched polyacid film. After drying, both hair
fibers were tied as a knot and visually the film could be seen coated on the
R R
X
R
CH3
CH2 CH CH2 CH R O OH
OH O
x y R
HO O O OH
OH
R X
R
Styrene Acrylate C30 Olelin/Undercylenic acid

Citric Acid
copolymer hyperbranched copolymer
(a) (b) (c)
Figure 17.14 (a) Styrene/ Acrylate copolymer, (b) hyperbranched copolymer of C30
Olefin/Undecylenic acid, and (c) Citric Acid.
Joncryl770001 2013/11/04 19:16 L x100 1 mm Mascara0003 2013/09/25 10:17 L x100 1 mm
Latex without polyacid Latex with polyacid
Figure 17.15 SEM images of latex film coated on hair substrate without and with polyacid.
hair fiber along with any cracks or defects on the film, caused by tying the
knot, which indicates film flexibility.
17.7.1.2 Critical Pigment Volume Concentration (CPVC)

The paint industry has identified that continuous film formation is influ-
enced by volume concentration of solids. The critical pigment volume con-
centration (CPVC) is the transition point where the amount of solids in the
polymer solution is maximum to provide a continuous film [54, 58].
For a semi-permanent mascara, the formulation contains high amount
of film-formers, and no wax or low amount of wax. Thus such mascara
formulation should form a continuous film on the eyelash with pigment
volume concentration below the CPVC. Figure 17.16 shows SEM images
of mascara deposits from CoverGirl Lash Exact waterproof, our semi-
permanent mascara prototype, latex combined with a hyperbranched
polyolefin copolymer mascara, and Tarte 4-day Lash Tint on false eye-
lashes with various roughnesses. It is observed that the prototype of semi-
permanent mascara and the latex/polyacid mascara formed continuous
and smooth films on the false eyelashes while the others have rougher sur-
faces with wax particles. The continuous films formed from our prototype
and latex/polyacid mascaras indicate that the volume concentration of sol-
ids (Latex/polymer and pigments) in the formulations are lower than the
critical pigment volume concentration (CPVC).
For a film formed below the CPVC, the film is continuous and exhibits
excellent adhesion and mechanical properties. As the solids volume con-
centration increases above the CPVC, the film begins to lose its chemi-
cal and mechanical properties [58–62]. In the mascara, the film will be
more brittle as well as its abrasion resistance and gloss will decrease. For
JML-10-16 3.0 kV 16.1 nvm x250 SE(M) 4/12/2010 200µm JML-10-16 3.0 kV 15.5 nvm x260 SE(M) 4/8/2010 200µm Mascara0003 2013/09/25 10:17 L x100 1 mm JML-10-16 3.0 kV 15.1 mm x250 SE(M) 4/13/2010 200µm
(a) (b) (c) (d)
Figure 17.16 SEM images of (a) CoverGirl Lash Exact waterproof, (b) semi-permanent
mascara prototype, (c) latex with polyacid polymer, and (d) Tarte 4-day Lash Tint.
creating the long-wear mascara, the CPVC can be increased using smaller
particles, such as hectorite (D90<10 µm) and iron oxide (D90< 1µm),
and the level of film-former has to be increased up to 30% to ensure a
continuous film formation [29, 30]. D90 is a standard indication of par-
ticle size distribution where ninety percent of the particles would be less
than the defined particle diameter.

Rheology of Mascara
The overall performance of mascara is dependent on the rheological prop-
erty of the formulation after manufacture, during the application, and the
final viscoelastic property of its deposit on the eyelash after solvent has
evaporated.
17.7.2.1 Bulk Rheology of Long-Wear Mascara Formulation

The mascara used is thick and paste-like texture and it is a viscoelastic
composition. The viscoelastic property of mascara originates from the
complex interaction among polymeric film-formers, thickeners, gellants,
surfactants, pigments and waxes in the compositions both in anhydrous
and in emulsion systems. For long-wear mascara and semi-permanent
mascara, the bulk rheology or viscoelasticity is strongly influenced by the
solids content of film-formers and gellants dispersed in a volatile solvent.
To characterize the texture of mascara formulation or bulk mascara, the
strain sweep experiment at a fixed frequency ω of 1 rad/s is performed
at room temperature to determine the linear and nonlinear viscoelastic
regimes. The viscoelastic property of the mascara can be determined in the
linear viscoelastic regime before the yield strain occurs under high defor-
mation. The complex modulus G* and phase angle δ are used as intrinsic
properties of mascara and are defined as:
G ∗ = G ′ 2 + G ′′ 2 (17.1)
G ′′
tanδ = (17.2)
G′
where G’ and G’’ are storage (elastic) and loss (viscous) moduli, respectively.
G ′′
When tanδ = < 1 or phase angle δ < 450 , the system is elastic, and
G′
G ′′
when tanδ = > 1 or phase angle δ > 450 , the system is viscous.
G′
Figure 17.17 shows a comparison of the viscoelastic properties of long-
wear (1-day wear) and semi-permanent mascaras (3- and 4-day wear).
In the linear viscoelastic regime, one-day wear mascara such as Revlon
Colorstay Overtime has high G* above 104 Pa while the semi-permanent
mascaras MaxFactor (3-day wear) and Tarte (4-day wear) have lower G* in
the order of 103 Pa due to no wax or surfactant present in the formulations.
The MaxFactor Lashfinity and Tarte 4-day lash stain have similar G* in the lin-
ear regime, but are different in terms of yield strain and response to deforma-
tion in the non-linear region. The yield strains of the 3- and 4-day mascaras are
higher than the yield strain of 1-day wear mascaras. The 1-day wear mascara
105 90
80
70
104
Complex modulus G* (Pa)
60
Phase angle δ (°)
50
103
40
30
102
20
Max Factor Lashfinity
TARTE 4 DAY LASH STAIN 10
Revlon Colorstay Overtime
101 0
10–2 10–1 100 101 102 103
Oscillation strain γˆ (%)
Figure 17.17 Complex modulus G* and δ for commercial long-wear mascaras from 1-day
wear (Revlon Colorstay) to 4-day wear (Max Factor Lashfinity and Tarte 4Day Lash Stain).
such as Revlon Colorstay is a W/O emulsion, containing waxes, surfactant so

it has thicker consistency with high G* and a low yield strain (<1%) and low δ.
For 3-day wear mascara, Lancôme Cil tint and MaxFactor both are
anhydrous and thickened by using clay, so they behave similarly under
strain deformation, except the G* of MaxFactor is one order of magnitude
higher than Lancôme as shown in Figure 17.18. The viscoelastic properties
such as complex modulus and δ of 3-day to 4-day wear mascaras are pre-
sented in Figures 17.19. It is interesting to observe that the semi-perma-
nent mascara formulations have G* less than 104 Pa with high elasticity δ
< 20°. In addition, the semipermanent mascaras have higher critical yield
strain γc > 1% compared to traditional mascaras containing waxes and high
amount of surfactants.
17.7.2.2 Flow Property of Long-Wear Mascara Formulations

Traditionally, a mascara is comprised of high amounts of volatile fluids
such as isododecane or water, film-formers, thickeners, waxes, surfactants,
and pigments. Therefore, mascara formulation is a complex fluid, exhibit-
ing a yield stress followed by shear-thinning and thixotropic behaviors. In
order to have good adhesion of the mascara formulation on the brush when
it is removed from the tube and provide good application on eyelashes, the
mascara needs to have a good shear-thinning property. Thus, the viscosity
104 90
Max Factor Lashfinity
Lancome Cil Tint
80
70
Complex modulus G* (Pa)
103
Phase angle δ (°)
60
50
40
102
30
20
101 10
10–2 10–1 100 101 102 103
Oscillation strain γˆ (%)
Figure 17.18 Complex modulus G* and δ for semi-permanent mascaras (3-day wear).
2500
2000
MAXFACTOR
TARTE
1500
G* (Pa)
HARD
1000 CANDY
500
LANCOME
0
13 13.5 14 14.5 15 15.5 16
δ (°)
Figure 17.19 Complex modulus G* and δ for semi-permanent mascaras (3 & 4-day
wear).
at high shear rates around 100 (1/s) to 1000 (1/s) dictates the good flow
characteristic of mascara during applying on the eyelash. Normally, it is
observed that consumers apply mascara with 5 strokes or 10 strokes, some-
times 20 strokes or higher, for example 30 strokes per eye, depending on
their eyelash type or their desired thickness for the look. Therefore, the
mascara should have low viscosity during multiple applications in order to
build thickness or volume and not be dried out during application. So the
mascara composition should have a good thixotropic behavior, at which
viscosity should build up slowly but not too slowly during applying mas-
cara to eyelash.
Figure 17.20 shows the shear flow viscosity of the 3 different types of
long-wear mascaras measured at shear rates from 0.01(1/s) -1000 (1/s) in
3 minutes. The shear viscosity of the 4-day wear mascara is lowest while
the shear viscosities of 1-day and 3-day wear mascaras are higher and show
similar behavior under deformation. However, the thixotropy of these
mascaras behaves differently as shown in Figure 17.21a-b. The thixotropic
behavior is described by the hysteresis loop area between the forward
curve of the stress when increasing shear rate and the backward curve of
the stress when reducing shear rate (Figure 17.21a). Therefore, the thixo-
tropic area value is the degree of destruction of the mascara formulation
after it has been shear-thinned.
The 1-day wear has the largest thixotropic loop (area), which means
the mascara formulation is of thick consistency due to high amounts of
waxes, surfactants, and other aggregates which are thinned out under
shear and require longer time to recover. For the 3-day and 4-day wear
mascaras, they have a smaller thixotropic loop due to lower amounts of
105
revlon 24 hr max factor 3 day tarte - 4 day stain
104
103
Viscosity η (Pa.s)
102
101
100
10–1
10–2 10–1 100 101 102 103
.
Shear rate γ (1/s)
Figure 17.20 Shear viscosity of long-wear and semi-permanent mascaras.
104 104
Flow ramp - 1
Revlon Colorstay Overtime Flow ramp - 2 Tarte 4 day lash stain
103 103
Stress σ (Pa)
Stress σ (Pa)
102 102
Flow ramp - 1
Flow ramp - 2
101 101
10–2 10–1 100 101 102 103 10–2 10–1 100 101 102 103
. .
Shear rate γ (1/s) Shear rate γ (1/s)
(a)
7.E+05
6.E+05
Thixotropic Area (Pa/s)
5.E+05
4.E+05
3.E+05
2.E+05
1.E+05
0.E+00
Revlon Maxfactor Lancome Hard Tarte
ColorStay 3 day Cil Candy 4 day
Overtime wear Tint lash ink lash stain
Mascara products
(b)
Figure 17.21 (a) Thixotropic area (loop) of long-wear (Revlon Colorstay) and semi-
permanent (Tarte 4day) mascaras. (a) (filled square: forward step, unfilled square:
backward step) (b) Thixotropic behavior of long-wear and semi-permanent mascaras.
waxes, surfactants, and other aggregates as seen in Figure 17.21b. The

differences in thixotropic behavior are due to the contribution of gel-
lants and waxes in the formulations such as Benton gel (hectorite clay).
The 1-day wear mascara contains a lot of waxes that are disrupted under
shear with slowly recoverable structures, resulting in a large thixotropic
loop. On the other hand, the 3-day and 4-day wear mascaras contain clay
as thickener such that their structures recover faster than wax structure,
resulting in a smaller thixotropic loop as shown in Figure 17.21a–b.

Surface Property of Mascara Deposit
17.7.3.1 Spreading and Wetting of Long-Wear Mascara on Eyelash
The first consideration for achieving a long-wear mascara is the deposi-
tion of mascara product evenly on eyelash. The spreading and wetting of
mascara on eyelash are found to depend on its viscosity and surface ten-
sion. Since mascara contains a lot of surfactants and emulsifiers, its surface
tension is less than 40 mN/m, which is close to the surface free energy of
hair fiber. As shown above, the low-shear viscosities of long-wear mascara
products are in the range of 102 Pa.s to 104 Pa.s with a good shear-thinning
under application with an applicator or brush. Therefore, mascara can wet
and spread on the eyelash and form a film deposit after solvents have evap-
orated. The thickness of the deposit on the eyelash will depend on the vis-
cosity and surface tension of mascara, and the structure of the applicator.
This is an important subject for a systematic study in the future, especially
for a low viscosity semi-permanent mascara.
17.7.3.2 Deposition of Mascara on Eyelash

The deposition of mascara on the eyelash depends on the rheology of for-
mulation combined with the applicator as mentioned above. The amount
of mascara acquired by the brush and the application methodology such as
the number of strokes to apply on eyelash will dictate the amount depos-
ited onto eyelash. For example, mascaras that claim to provide high volume
on eyelashes contain high amounts of soft waxes with a solid-like behavior
which causes clumping and uneven deposit on eyelash. On the other hand,
the long-wear mascara which contains less wax amount or no wax with a
liquid-like behavior will bridge the eyelashes together through capillary
effect, similar to hair spray.
1 day wear 3 day wear 4 day wear

Revlon Lash tint Lash ink
Avon Maxfactor 3 Day tarte
Figure 17.22 Images of commercial long-wear mascaras from 1-day wear to 4-day wear
deposited on false eyelashes.
Therefore, the viscoelastic property of mascara formulation and the

brush design are important factors for an even deposit on eyelash without
clumping. Examples of the different mascara films deposited on false eye-
lashes are shown in Figure 17.22.
17.7.3.3 Internal Stress

During application of mascara on an eyelash, volatile solvents evaporate and
solids concentration increases and finally forms a solid film on eyelashes
and the thickness of the mascara formulation deposited will decrease. The
internal stress develops as the mascara dries from its creamy texture to a
solid film on the eyelash substrate. High internal stress in mascara film can
cause curling, flaking, and decrease of adhesion to eyelash substrate.
When mascara formulation is applied on the surface of eyelash, the curl-
ing will occur if the modulus of the mascara is higher than the modulus of
eyelash substrate. Flaking or cracking depends on the thickness, mechan-
ical toughness, Tg and elastic property of mascara film. If the adhesion at
the interface between mascara and eyelash substrate is weak, then internal
stress can delaminate the film.
Other factors such as temperature, humidity and water exposure can
affect the internal stress in mascara as observed for coatings [63–68]. As
a result, the daily activities will influence the internal stress of the deposit
film on eyelash and impact the wear performance of mascara.
The final stress in the mascara deposit will depend on the initial solution
concentration and final thickness of the deposit as reported for polyure-
thane and nitrocellulose lacquers. For mascara coated on eyelash with a
curvature and variation of thickness from root to tip, the deposit is not uni-
form. Therefore, the internal stress can be varied from the tip coated with
a thinner film to the root or in the middle of eyelash with a thicker film.
Croll [63, 64] discussed that the internal stress in a coating increases with
thickness until it reaches the critical stress which is higher than the inter-
facial adhesion force and the coating delaminates. For a thermoplastic, the
internal stress was observed to be independent of film thickness and con-
centration due to the depression of Tg in the presence of residual solvents.
The internal stress in the final mascara film can be either compressive or
tensile stress or both. The tensile stress is developed when the film con-
tracts during film formation (crosslinking or coalescence) or temperature
changes from hot to cold. The compressive stress occurs when the film
expands under high humidity and high temperature. These conditions will
change the glass transition temperature Tg and modulus of the mascara
film. Therefore, the tensile stress can have more impact on the adhesion of
mascara than the compressive stress at which the mascara has low modu-
lus and is more flexible under humidity or at elevated temperature.
17.7.3.4 Sebum/Sweat/Water Resistance

A semi-permanent mascara has to be durable under hot/cold water, sweat
and sebum under humid conditions. Therefore, the selection of film-formers
as binders in mascara formulation as well as their amounts will influence the
water, sweat and sebum resistant properties. To test the sebum resistance of
current 1-day and semi-permanent mascara products, we applied 30 strokes
of mascara on false eyelashes and let it dry for 2 hours, then submerged the
eyelashes into the artificial sebum solution and let it soak for 1 hour. The eye-
lashes were rubbed on paper 10 times so the transfer of color from mascara
to paper after exposing to sebum was observed. During immersion in sebum
solution, some of the mascara films delaminated from the eyelash and fell
into the bottom of the sebum solution in small pieces as seen in Figure 17.23.
The results of color transfer to paper show that Revlon, MaxFactor and Tarte
are not smudgeproof but Lancôme and Hard Candy Lash Ink have smudge
resistance. Even with the use of the same film-former MQ, the sebum resis-
tance performances of Revlon, Lancôme and Hard Candy are different. The
Lancôme Cil Tint has higher smudge resistance than Hard Candy Lash Ink
because Cil Tint contains MQ resin associated with a thermoplastic elasto-
mer. The Revlon is not smudge resistant because the formulation contains
Products Revlon Lancôme Cil Maxfactor Tarte 4 Day Hard Candy

ColorStay Tint Lashfinity 3 day Lash Stain Lash INK
Overtime Mascara
Film-former MQ MQ Rosinate (MQ+Rosinate) MQ
Lasting (day) 1 3 3 4 4
Flake Test
Smudge Test
Figure 17.23 Sebum transfer test on blotting paper from 5 commercial mascaras after
immersing in artificial sebum for 12 hours.
Oil H 2O
Figure 17.24 No color transfer was observed from latex mascara after immersing in oil
and water for 1 week.
high amount of waxes. Max Factor and Tarte have similar smudge resis-
tance because both of them contain hydrogenated rosinates which are also
sensitive to sebum. However, our prototype of semi-permanent mascara
containing latex was exposed to oil and water for one week and no transfer
of color was observed (Figure 17.24).

Mechanical Property of Mascara Deposit
In order for mascara to be long lasting, more than one day, the final film
deposited on the eyelash should be continuous and cover the whole eye-
lash from root to tip. As mascara dries, the solvent evaporates and a solid
film is formed which has a measurable film elastic modulus. Therefore, the
amount of the binder/polymers or resin should be high and the volume of
filler, pigments and wax should be less than the critical pigment volume
concentration (CPVC) as discussed for semi-permanent mascaras [29]. To

prevent flaking issue, the mascara deposit film should be flexible and the
Young’s modulus should be low because the internal stress is proportional
to Young’s modulus and strain. The best system for a long-wear mascara
should have polymers concentration greater than 20%, be plasticized and
contain less solid particles.
For the mascaras with PCV greater than CPVC which contain a large
amount of solid particles (waxes, pigments, fillers …) and a low amount
of polymers (4 to 14%), the resulting films will be hard and brittle. In this
case, the mascara deposit will have high Young’s modulus and will easily
flake during the day.
To modulate the mechanical property of the latex film for hair styling
formulations, Tan and coworkers blended soft and hard latexes at various
ratios [69]. At a constant stress of 10 MPa, the response strain (%) varies
from low to high, corresponding to high Young’s modulus to low Young’s
modulus respectively depending to the ratio of soft and hard latexes in
the blend. In this case, the Young’s modulus of hybrid latex films varies
from 0.1 MPa to 1000 MPa which can be applied to different hair styles.
Thus, the same principle can be applied to mascara formulation containing
latexes to modulate the mechanical property of mascara film.
To reduce the flaking issue from mascara formulation, polyacid was used
to plasticize the latex film [26]. Figure 17.25 shows the effect of polyacid
concentration on the elastic modulus E’ of mascara containing latex. With
10000
1000
Storage Modulus (MPa)
+
100
10 Mascara with 3% polyacid

Mascara with 1% polyacid
polyacid
0% polyacid .001
Mascara with 5% polyacid
0.7% citric acid
1
–40 –20 0 20 40 60
Temperature (°C) Universal V4.7A TA Instruments
Figure 17.25 Effect of polyacid on the storage (elastic) modulus E’ of the mascara.
an increase of polyacid from 1% to 5%, the best performances of mascara

in terms of adhesion and wear without flaking are found for 3% polyacid
with E’ around 200 MPa at 25°C. The results could be explained by the
relation between adhesion and elastic modulus of eyelash substrate and
mascara coating film. The plasticized mascara film has low elastic modulus
and should have good adhesion to a low surface free energy (SFE) and low
modulus eyelash substrate. The result obtained was similar to a study on
adhesives on various SFE substrates from Gordon and Fakley [70]. They
observed that for an effective adhesion, a high modulus adhesive should be
used when the substrate has a high elastic modulus. The ‘‘best’’ bonding to
low SFE substrate is obtained with the lower modulus adhesive, while the
higher modulus systems show no particular advantage. As SFE of substrate
increases, the higher modulus adhesives exhibit an improved performance
over the lower modulus adhesives.
17.8 Removability of Mascara

Make-up removal formulations come in many forms from oil, lotion,
cream to gel. To facilitate the removal of long-wear and transfer-resistant
make-up products containing silicone resins and film-formers, volatile oils
such as isododecane, isohexadecane and cyclopentadimethicone are com-
monly used.
However, the removability of long-wear mascara and semi-permanent
mascara becomes more challenging because it cannot be easily washed
off by such oils when a high amount of oil soluble film-formers or high
amount of latex are used in the formulations (Figure 17.26).
To facilitate the removability of mascara, most efforts have focused on
the development of the mascara formulations with a good long lasting effect
and easy removability. For example, Estee Lauder disclosed a patent for a
waterproof and smudge-resistant mascara/eye shadow containing both
acrylate/VA copolymer and acrylate copolymer that are flexible and resis-
tant to water below 43°C, and can be easily removed by warm water [71].
Easy to remove Difficult to remove
Washable Smudgeproof Waterproof Semi-Permanent
Figure 17.26 Dependence of removability on the mascara type.

Mary Kay developed a water-proof mascara with the benefit of increas-

ing the length of the eyelash and ease of removability. The polymeric
film-formers used in the mascara composition are PPG-17/IPDI/DMPA
copolymer and acrylates/ethylhexyl acrylate copolymer, and the natural
film-former is Acacia senegal gum (Arabic gum) [72]. Shiseido described
the mascara composition containing an aqueous emulsion of methyl
methacrylate and ethyl acrylate/butyl acrylate copolymer to achieve the
water resistance and smudge resistance with good removability [73]. Avon
used film-forming, pH- dependent copolymers such as methacrylic acid -
methyl methacrylate (ratio 1:1 or 1:2) (Figure 17.27) in the mascara formu-
lation to increase wear time, while allowing for removal of products with
soap and water by modulating the pH to dissolve or disperse the polymers
[74, 75]. L’Oreal developed a long-wear mascara with low wax content
which could be easily removed by make-up remover [76]. By using sucrose
fatty acid ester such as sucrose tristearate in the formulation, the mascara
composition delivered a high color intensity with good sebum and water
resistance to color transfer, less flaking under rubbing, and easy wash off
by make-up remover.
For cleansing make-up products, the biphase make-up remover can be
used to remove the long-wear mascara. The biphase composition has two
distinct immiscible phases, an aqueous phase and an oily phase being sep-
arated by a single interface. When using biphase composition, initial agita-
tion is required to form an extemporaneous emulsion but when it is left to
stand, the two phases rapidly separate and regain their initial state [77–80].
L’Oréal prepared the biphase with cyclo-siloxane, that efficiently dissolves
silicone MQ resin. The bicontinuous phase has oil- and water-continuous
microstructures, showing affinity for both aqueous and oily substances.
This bicontinuous phase was expected to remove the semi-permanent mas-
cara containing MQ resins. However, the use of biphase remover to take off
the long-wear and semipermanent mascara is still difficult, requiring a lot
of rubbing (5 times) as shown (Figure 17.28). The biphase remover works
effectively for Lancôme Cil Tint, Tarte 4-day lash tint and Avon while Hard
CH3
CH3
H3CO O
m HO O n
Figure 17.27 Structure of acrylate copolymer of methacrylic acid/methyl methacrylate.

1st rub
2nd rub
3rd rub
4th rub
5th rub
Hard Candy MaxFactor Revlon Avon Tarte 4 Day Lancome

Lash INK 3 Day Colorstay Cil Tint
2 1 2 5 4 4
Figure 17.28 The removability of long-wear and semi-permanent mascaras by Biphase

Remover where the degree of mascara removal is ranked from 1 (difficult) to 5 (easy).
Candy is mostly removed from 1st rubbing with a thin mascara deposit left
at the 5th rub. However, MaxFactor and Revlon products are difficult to
remove with this remover.
Bernard and coworkers [81] developed a composition that could remove
the long-wear make-up products from skin and eyelash. The make-up
remover composition contains a low-viscosity, low-volatility silicone oil
with viscosity in the range 5 cSt to 100 cSt. The low viscosity silicone oil is
prepared in the biphase, or in the water-in-oil emulsion, or in the oil-wax
dispersion. Their data showed that the composition could remove the
water-proof mascara and the long-wear foundation easily and it had less
oily or greasy feel compared to the silicone oil alone.
Another way to remove long-wear mascara containing high solids con-
tent of latex, beeswax dispersion with various particle sizes was incorporated
into the formulation [82]. Three different particle sizes of wax dispersions
with diameters of 10, 20 and 80 µm (Figure 17.29) were incorporated into
latex mascara formulations to impart removability of mascara with warm
water. In order to incorporate high amount of wax dispersion, only 17%
10 µm 20 µm 80 µm
Figure 17.29 Optical Microscopy images of beeswax dispersions with various particle sizes.
solid latex in the formulation was used to study the effect on mascara remov-
ability as functions of wax concentration and particle size. Figure 17.30
shows that the removability of mascara with warm water (60°C - 70°C) was
improved with increasing concentration of wax particles of 10 and 20 µm,
but decreased with increasing particle size. The largest wax dispersion of 80
µm had no effect on the mascara removability. The decreasing removabil-
ity of mascara by using large wax particle dispersion was due to reduction
of particle surface area and the particle packing density as seen in Figure
17.30. It was surprising to find out that an addition of wax particles did not
affect the sebum and water resistance. From the result, the best mascara
formulation should contain 10 µm wax particles with at least 10% solids to
have the most effective removability with warm water.
17% Latex 0% wax

5
17% Latex 5% wax
4.5 17% Latex 10% wax
4
Removal
3.5 1 = Hard to remove
2 = Slightly removed
Removability
3 3 = Moderately removed
4 = Mostly removed
2.5 5 = Completely removed
1.5
0.5
0
10 20 80
Particle size of wax (µm)
Figure 17.30 Mascara removability with warm water decreases with increasing wax
particle size.
17.9 Summary and Prospects

Through many centuries, mascara has slowly evolved to meet consumer
demands for different countries and ethnicities. Mascara had begun with
a simple formulation of colorant and paste for eyelash beautification. In
the last century, mascara has not changed its main purpose for beautifying
eyelashes but what has changed is the demand of lastingness on the eye-
lashes from consumers. With the emerging market for semi-permanent
and permanent make-up, there have been many formulations developed to
achieve such goal. Typical washable mascara has the weakest water resis-
tance among the categories of mascaras because its formulation contains
surfactants, water soluble polymers, etc. Waterproof mascara was created
to provide long-lasting, all day, benefit since the formulation was not sus-
ceptible to water so the lastingness was better than conventional washable
mascaras. However, a waterproof mascara contains high levels of waxes
and oil soluble ingredients that make the formulation susceptible to sebum
smudging throughout the day. The promising technologies that address the
water and sebum resistance property for enhancing conventional mascara
to provide longer wear than one day are silicone resins, hydrocarbon resin,
and latex, while micropigmentation/tinting are unconventional method-
ologies adapted from hair dye. With each technology, there are different
drawbacks, such as removability, volume, and length. Silicone resins and
hydrocarbon resins create a film which is waterproof and sebum resistant
at low levels of waxes. These products will lack the desired volume on the
eyelashes and sebum resistance will decrease over time since the formula-
tion is oil based. Latex is polymer dispersed in water but will coalesce to
provide a waterproof and sebumproof film at high solids content to ensure
the film formed is continuous and cohesive. However, at a high latex con-
centration with minimal pigment content, the film can be extremely diffi-
cult to remove.
The key factors affecting the adhesion of mascara to eyelashes are also
discussed through mascara composition, rheology of mascara, and surface
and mechanical properties of mascara deposit film. In the mascara com-
position, the type of film-former, film-former concentration together with
pigment volume concentration play an important role for good adhesion
to eyelash, influencing internal stress and durability of the mascara coating
during daily activities. However, the removal of such long-lasting mascara
is still a technical challenge, and the quest for a “smart” mascara with a
long-lasting benefit and ease of removability will continue in the near future.
Acknowledgments
The authors would like to thank Ronni Weinkauf, Mohamed Kanji and
L’Oréal Research and Innovation Department for supporting this work.
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17

L’Oreal Research and Innovation, Clark, NJ, U.S.A.

Keywords: Semi-permanent mascara, long-wear mascara, waterproof,

*Corresponding author: hy.bui@rd.loreal.com

17.1.2 Birth of the First Mascara

750 BC – 400 AD 1915 1960 2019

17.2 Structure of Eyelash and Eye Lid: An Overview

Table 17.1 The differences between Asian (Korean), Japanese and

1. Thickness or density of eyelash

When applying a curling mascara formulation, the curvature and the

17.3 Types of Mascaras

Fiugre 17.2 Mascara compositions.

By varying the mascara components such as amount of wax, amount or

“Which of the following are important to you when selecting mascara?”

MAPPING OF PRODUCTS CLAIMING AT LEAST 24HR WEAR

Avon Color Super

Figure 17.4 Mapping the needs of long-wear mascara.

17.4 Components in Mascara Formulations

• Volatile fluid: water or isododecane

Table 17.2 Typical ingredients in a commercial washable mascara.

After isododecane has evaporated, it leaves the mascara deposit as a

Table 17.3 Typical ingredients in a commercial waterproof mascara.

Table 17.4 Typical ingredients in a smudgeproof mascara [24–26].

used for emulsification is lower, this requires the usage of thickeners to

17.5 Long-Wear Mascaras

17.5.1 One-Day Wear Mascara

17.5.2 Semi-Permanent Mascara (3 - 5-Day Wear)

Table 17.6 Long-wear mascara products with 4-week wear or longer.

Duration 4 weeks (28 days) 6 weeks

17.5.3 Micropigmentation/Lash Tinting (30-Day Wear

17.6 Evaluation Methods for Long-Wear Mascara

literature [29–41]. To evaluate systematically the performance of long-wear

Table 17.7 Summary of test methodologies for long-wear and semi-permanent

Rub Test Results

Figure 17.6 Rub test results for various mascaras [29].

17.6.2 In Vivo Evaluation by Expert Panels or Consumers

2013/05/07 16:16 L x500 200 um

Figure 17.8 In-vivo evaluation of a semi-permanent mascara prototype.

consumers or expert panels [28–30]. Figure 17.8 shows the lastingness of

17.7 Factors Affecting Adhesion of Mascara

a. High resistance to water (hot and cold) and soap under

To meet such requirements, the mascara performance is dependent on

17.7.1 Factors Affecting Adhesion of Mascara to Eyelash:

17.7.1.1.1 Trimethylsiloxysilicate Resins

Figure 17.9 Structure of MQ resin.

under washing or bathing condition with sweat/ sebum resistance or under

Table 17.8 Example of mascara composition containing MQ resin as a topcoat

As a result, MQ resins are widely utilized in the 1 day-wear mascara such

17.7.1.1.2 Rosin Esters

from Eastman as Foral™ 85-E CG and Foral™105-E CG hydrogenated

Table 17.9 Mascara composition containing rosin

pentaerythrityl hydrogenated rosinate is also found in other long-wear

powdery [55]. Films formed at lower temperature (near 25°C) would

Figure 17.11 Latex as a coating for eyelash.

Hybrid Latex Film Formation Process

However, the lastingness of mascaras from these formulations cannot

Artificial sebum resistance Water resistance after

a plasticizer for the high Tg amorphous latex, resulting in a film having an

Styrene Acrylate C30 Olelin/Undercylenic acid

Joncryl770001 2013/11/04 19:16 L x100 1 mm Mascara0003 2013/09/25 10:17 L x100 1 mm

Latex without polyacid Latex with polyacid

17.7.1.2 Critical Pigment Volume Concentration (CPVC)

(a) (b) (c) (d)

17.7.2 Factors Affecting Adhesion of Mascara to Eyelash: