Perawatan Wajah

16
Factors Affecting Cosmetics

Adhesion to Facial Skin
Zhi Li and Hy Si Bui*
L’Oreal Research and Innovation, Clark, NJ, USA
Abstract
Long-wear make-up formulations have gained traction as consumers continue to
seek products that help them maintain their good look all day. Waterproof, matte
finish, smudge-proof, sweat-proof and natural look are the benefits that under-
score demands for a long-wear make-up formulation. However, the adhesion of
face make-up products to the skin is a complex interfacial phenomenon due to the
involvement of many ingredients in the formulation interacting with skin surface,
as well as the diversity and intricacy of human skin.
Using a silicone-based long-wear liquid foundation as a study model, this chap-
ter discusses the key factors that influence the adhesion of this type of products to
skin. Fundamental understanding of these factors should help long-wear formu-
lation development based on rational design and understanding of components
interactions, develop novel long-wear formulation approaches, and properly eval-
uate emerging new technologies.
Keywords: Face, skin, foundation, make-up, silicone resin, silicone film-former,

long-wear, non-transfer
16.1 Introduction
More than half of color cosmetic products users seek out long-wear prod-
ucts. Make-up that does not last has long been a common complaint among
women. Since the early 1990s, the product category of long-lasting facial
make-ups has grown from just for a few niche lines to cover mainstream
*Corresponding author: hy.bui@rd.loreal.com
K.L. Mittal and H.S. Bui (eds.) Surface Science and Adhesion in Cosmetics, (543–584) © 2021
Scrivener Publishing LLC
543
544 Surface Science and Adhesion in Cosmetics
mass-market offerings and many premier brands. With the selfie craze, high
definition cameras and multimedia displays, consumers nowadays want to
look flawless on social media and in person throughout the day. As a result,
beauty industry has been investing a considerable amount of resources for
technical breakthroughs in this frontier. Recent formulation advances have
transformed the perception of these products from drying/tacky and paint-
like sensory and appearance to that of regular make-up [1].
Commonly applied to facial skin, a foundation is intended to even
out skin tone, provide smooth texture, and hide imperfections such as
pores and fine lines [2]. It may also moisturize the skin and/or minimize
the oily appearance as well as provide protection against the effects of
UVA, heat, pollution and other environmental factors [3]. In addition,
the consumers also expect pleasant sensory experience associated with
the foundation application, including a lightweight feel, good spreadabil-
ity on skin, and a smooth/silky skin feel [3]. Driven by consumer needs,
over the past decades, liquid foundation in emulsion-form has been gain-
ing traction. Since the early 1990s, significant technology development
has been made in silicone-based long-wear liquid foundations, notably
Revlon’s Colorstay foundation launched in 1995 [4]. Such liquid founda-
tions are water-in-silicone (W/Si) or water-in-oil (W/O) emulsions, slip-
pery and spread smoothly without caking or streaking, and dispersing
pigments evenly across skin. After application, volatile liquids in the for-
mulations are able to quickly evaporate, and pigments get anchored to the
skin by silicone film-formers, together with other nonvolatile ingredients
[5]. For the last two decades, a great effort from cosmetic scientists has
been made to improve the long-lasting and non-transfer characteristics
of silicone-based liquid foundation without sacrificing consumer sensory
experience.
16.2 Factors Affecting Adhesion to Skin: Skin

Substrate Properties
To better understand long-wear liquid foundation adhesion to facial skin,
a quick overview of skin structure is provided below. Human skin is com-
prised of three distinct layers: the subcutaneous layer, dermis, and epi-
dermis [6]. As illustrated in Figure 16.1, the epidermis is the outermost
multilayered structure, of which the stratum corneum (SC) is the exter-
nal layer. For a long-wear liquid foundation, the product will spread and
adhere to the external layer SC surface as a protective coating for facial skin.
Factors Affecting Cosmetics Adhesion to Facial Skin 545
Hair shaft
Sweat pore
Epidermis Epidermal ridge

Dermal papilla
Papillary
layer Arrector pili muscle
Sebaceous (oil) gland
Dermis Sweat gland duct
Reticular
Merocrine sweat gland
layer
Vein
Artery
Subcutaneous
layer
Adipose connective tissue
Hair Sensory Areolar Sensory
follicle receptors connective nerve fiber
tissue
Figure 16.1 Structure of human skin.
16.2.1 Skin Types

Human facial skin is commonly classified into four types: oily, dry, nor-
mal, and combination skins [7]. These various skin types have a significant
influence on the adhesion property of the cosmetic products and the sen-
sorial feel throughout the wear. For example, through blending with the
foundation and affecting skin’s surface free energy (SFE), sebum negatively
impacts foundation’s wear [5]. Consumers with oily skin will perceive less
wear and better comfort from the product, while the normal skin and dry
skin consumers may perceive better wear but experience an uncomfortable
feel. Therefore, the marketed foundation products have been tailored to
specific skin types for consumers.
16.2.2 Surface Free Energy of Skin

Generally, the skin surface is hydrophobic and has low critical surface ten-
sion and low surface free energy (SFE) as compared to typical cosmetic
products which are mostly Oil-in-Water (O/W) emulsions [5]. The SFE
of the skin is very important as it affects the wetting, spreading and adhe-
sion of a cosmetic product on skin [8]. It is understood that to completely
wet the skin, the liquid should have surface tension no higher than the
critical surface tension of bare skin. Therefore, the surfactant system is
very important, not only to stabilize the O/W emulsion but also to reduce
surface tension of the final product for better wetting and spreading on
skin.The recorded skin SFE ranges from 38.5 - 46 mJ/m², depending on
location, type, and surface residuals [9–12]. For example, the SFE of oily
skin can be reduced by cleansing with soap and water [13]. The value of
the surface free energy of the forehead can be reduced from 42.5 mJ/m² to
34.5 mJ/m² after cleansing with soap [11]. Table 16.1 summarizes the SFE
of volar forearm and forehead.
In the case of a silicone-based long-wear liquid foundation, the sur-
face tension of the W/O emulsion is lower than the skin SFE, as the exter-
nal phase is either silicone fluid or hydrocarbon oil with surface tension
around 18 mN/m (silicone D5) or 24.8 mN/m (isododecane). Therefore,
the wetting and spreading of the W/O foundation on skin will be less of an
issue for the product sticking/adhering to the facial surface.
16.2.3 Skin Young’s Modulus

Human skin can be considered as a multilayer composite tissue with highly
non-homogeneous, nonlinear elastic, anisotropic, viscoelastic material
properties similar to those of soft elastomers [5]. Depending on the mea-
surement, anatomical site, skin hydration level, age, the theoretical model
applied, and the probe size, the Young’s modulus of human skin (in vivo)
was reported to be from 1.09 x103 Pa to 8.5x105 Pa as shown in Table 16.2.
Notably, Luboz et al. measured elastic properties of facial skin and reported
the Young’s modulus of the overall facial area to be 3.4 x104 Pa, twice of the
Table 16.1 Summary of skin surface free energy values on volar

forearm and forehead, before and after cleansing.
Surface free energy Surface free energy
mJ/m2 mJ/m2
(before washing ) (after washing) Location Reference
38.5 32.4 Forearm [10]
44.8 (20 oC) 36 Forearm [12]
42.8 (35 oC) 34.7
42-46 34.5 Forehead [11]
Table 16.2 Young’s modulus determined in vivo using various methods for
different skin regions and ages.
Young’s Modulus
Method (MPa) Age Test region Reference
Suction 0.12-0.25 20-30 Forehead & [17]
abdomen
Indentation 0.00109 Forearm [18]
0.0045-0.008 30 Arm [15]
0.0062-0.0021 55 -70 Arm [16]
0.007 -0.033 Arm and face [19]
Torsion 0.42 -0.85 30- 89 Dorsal forearm [20]
Light Aspiration 0.031 Cheek [14]
0.0349 Cheekbone
0.0173 Forehead
0.0337 Lower lips
forehead value [14]. Also, it was found that the Young’s modulus is higher for
older people and overall elasticity decreases with age [15, 16].
With this in mind, for a long-wear foundation, the film formed on the
skin should be soft and flexible without high internal stress and tension,
should remain continuous, and should not crack with repeated facial
movements. Since the skin has a low Young’s modulus in the range of 103
-105 Pa, the desired Young’s modulus of the film should not exceed 105 Pa
in order to provide a comfortable feel. Depending on the chemical nature
and use of other additional ingredients, most silicone film-formers and
elastomers possess Young’s modulus in the range 104 -106 Pa; therefore,
they are good candidate materials for use in long-wear face products.
16.2.4 Skin Surface Roughness

The topography and morphology of skin surface are important in the
application of cosmetic products. The roughness of the human skin was
reported to vary significantly, depending on anatomical location and age
[14, 19–21]. The skin surface roughness on human face such as forehead,
cheek and nose was observed to be different as shown in Table 16.3. Aging
Table 16.3 Mean skin surface texture parameter Sa (in

micrometers) for 3 age groups and 4 anatomical sites [22].
Age Cheek Nose Forehead Hand
20-39 yr old 23.09 16.2 18.8 23.9
40-59 yr old 20.63 33.84 20.05 34.3
≥ 60 yr old 28.65 26.13 21.08 46.5
also increased skin surface roughness, for example, about 2 µm difference

for forehead but around 24 µm difference for the hand, measured on peo-
ple from 20 years old to over 60 years [14, 22].
16.2.5 Wetting and Spreading of Sebum and Sweat

on Human Skin
The outer layer of the human skin, the stratum corneum (SC), is comprised
of mostly sebum and dead skin cells. The function of sebum is to hydrate
and protect the skin from the environment. Sebum is a mixture of lipids
comprised of the following substances: Triglycerides, Free fatty acids, Wax
esters, Squalene, Cholesterol and Cholesterol ester [21]. Typically, the
greatest amount of sebum will be found on the forehead, nose and chin
also known as the “T-zone” area of the face. The surface tension of sebum
is 24.9 mN/m (between 26.5oC and 31oC) which is lower than the skin sur-
face free energy, ranging from 38.5 - 46 mJ/m² [9–12]. Thus sebum is easy
to spread on the skin.
Sweat consists of 99% water and 1% mineral, lactate and urea. Its pH is
between 4.5 and 7.0 [23]. The metal ions in the sweat are sodium, potas-
sium, calcium, and magnesium cations. The sweat is acidic and has a pH
between 4 and 6.8 depending on the degree of sweating [23]. The surface
tension of sweat as it accumulates on the skin surface was reported to be
about 70 mN/m [24]. In a separate study, the surface tension of thermally
stimulated sweat on 22 subjects was reported to be 54 mN/m for the apo-
crine sweat and 60 mN/m for the eccrine sweat from the skin surface of
the back and the abdomen [25]. If the sweat is contaminated, its surface
tension could be lower.
Both sebum and sweat have very strong impacts on the adhesion of
foundation to the skin. The sebum and sweat can delaminate or plasticize
make-up films. This may result in a sticky feel and increased migration of
the product into the texture of the skin. It could also impact the color of the
product on the skin, causing it to “shift” and appear deeper in color. Due
to delamination, when in contact with other substrates (such as clothing),
foundation’s incidence of color transfer also increases. To minimize the
wetting and spreading of sweat and sebum on the foundation products, it
is necessary to use materials that can either absorb these liquids or reduce
the surface free energy of the products.
16.3 Factors Affecting Adhesion to Skin: Formulation

Components
To illustrate factors affecting cosmetics adhesion to facial skin, we focus on
the long-wear foundation product category. Aiming to understand today’s
state-of-the-art long-wear foundations, we surveyed 149 foundation/
illuminator/concealer products in the US market with long-lasting claims,
launched between January 2018 and June 2019 [26]. As shown in Figure 16.2,
water-in-silicone emulsion, first developed over two decades ago, remains the
leading formulation type for long-wear foundations in the market.
We further dissected recent water-in-silicone-based liquid foundations
by closely analyzing their ingredient labels. Six recently launched long-wear
liquid foundations were analyzed and key ingredients of each are summa-
rized in Table 16.4. In Table 16.5, an exemplary formulation disclosed by
Revlon in patent literature is listed [27].
Anhydrous Stick/Balm O/W or Hydrogel

2.7% 1.3%
W/O Fluid (non-Silicone)
6.0%
Anhydrous Oil/Serum
7.4%
Powder
14.8%
W/O Fluid (Silicone)

67.8%
Figure 16.2 A survey of formulation types of 149 recently launched foundations in the
US market with long-wear claims.
Table 16.4 Ingredient analysis of several long-wear liquid foundations launched in 2018.
Givenchy Teint Smashbox Studio NYX Can’t Stop Dior Diorskin Maybelline Superstay
Couture Everwear Flawless 24 Hr Kat Von D Lock-It Won’t Stop Forever 24H Full Coverage
Volatile Fluids Water, Methyl Water, Dimethicone, Water, Water, Dimethicone, Cyclopentasiloxane, Cyclopentasiloxane,
Trimethicone, Dimethicone, Isododecane Isododecane; Water Alcohol, Water,
Isododecane, Methyl Isohexadecane Isododecane,
Alcohol, Trimethicone, Dimethicone,
Dimethicone
Primary Acrylates/ Trimethyl Trimethyl Acrylates/ Trimethyl Polypropyl

Film-formers dimethicone siloxysilicate/ siloxysilicate Polytrimethyl siloxysilicate silsesquioxane
Copolymer dimethiconol siloxymethacrylate
Crosspolymer Copolymer
(Continued)
Table 16.4 Ingredient analysis of several long-wear liquid foundations launched in 2018. (Continued)
Primary PEG-9 Polydimethyl Lauryl PEG-9 PEG/PPG-18/18 PEG-10 Dimethicone; PEG-9 PEG-10 Dimethicone;
Emulsifiers siloxyethyl Polydimethyl Dimethicone; Bis-PEG/PPG- Polydimethyl Dimethicone/
Dimethicone siloxyethyl Sorbitan 14/14 Dimethicone siloxyethyl polyglycerin-3
Dimethicone, Sesquioleate Dimethicone Crosspolymer
PEG-10
Dimethicone
Selected Fillers, Diphenyl Disteardimonium Aluminum Starch Nylon-12, Silica, Disteardimonium C30-45
Emollients, Dimethicone/ Hectorite, Octenylsuccinate; Synthetic Hectorite; Vinyl Alkyldimethylsilyl
and Rheology vinyl Diphenyl Polysilicone-11 Silica; Fluorphlogopite; Dimethicone/ Polypropyl
Modifiers Dimethicone/ Phenyl Dimethicone Isononyl methicone silsesquioxane;
silsesquioxane Trimethicone, Silylate; Isononanoate Silsesquioxane Disteardimonium
Crosspolymer, Neopentyl Polysilicone-11; Crosspolymer; Hectorite; Silica;
Diisostearyl Glycol Phenyl Glyceryl Undecyl Nylon-12
Malate, Diheptanoate Trimethicone; Dimethicone
Disteardimonium Isononyl
Hectorite Isononanoate
Pigment Surface Amino Acid (Sodium Alkylsilane Silicone (Methicone) Alkylsilane Amino Acid Amino Acid
Treatment Myristoyl (Triethoxy (Triethoxy (Sodium (Disodium Stearoyl
Chemistry Glutamate) caprylylsilane) caprylylsilane) Myristoyl Glutamate)
Glutamate)
Table 16.5 An exemplary long-wear liquid foundation formulation disclosed in

patent literature [27].
Ingredient wt% Function
Water 30.5 Volatile Fluids
Cyclopentasiloxane 26.7
Isododecane 2.25
Ethanol 3
Trimethylsiloxysilicate/ 7.5 Film-former
Dimethiconol Crosspolymer
PEG/PPG 18/18 Dimethicone 2 Emulsifiers
Cetyl PEG/PPG-10/1 Dimethicone 0.25
Sorbitan sesquioleate 0.05
Titanium dioxide/Methicone 8 Methicone treated pigments
Red iron oxide/Methicone 0.98
Yellow iron oxide/Methicone 1.13
Black iron oxide/Methicone 0.17
Mica/methicone 1.21
Silk powder 0.1 Fillers/Rheology modifiers
Boron nitride 3.51
Nylon-12 2
Tribehenin 1.5 Emollients/Rheology modifiers
Polyisobutene 1
Dimethicone 1
Glyceryl rosinate 1.25 Emollient/emulsifier
Sodium chloride 1 Emulsion stabilizer/anti-freezer
Butylene glycol 4.5 Humectant/anti-freezer
Propyl paraben 0.1 Preservatives
Methyl paraben 0.2
Tetrasodium EDTA 0.01
Bisabolol 0.05 Fragrance
As illustrated in both Table 16.4 and Table 16.5, a typical water-in-

silicone long-wear liquid foundation contains a significant quantity of
volatile carrier fluids (water and volatile silicones/isoparaffins). The
emulsions of water in the carrier fluids are stabilized mainly by using
polymeric silicone emulsifiers. Silicone-based film-formers and pig-
ments (mostly surface-treated) are dispersed in the external phase (sili-
cone phase), together with fillers, rheology modifiers, and emollients. To
understand factors relevant to the adhesion of the long-wear foundations
to the skin and the wear performance, we will first discuss each type of
ingredients in detail.
16.3.1 Volatile Fluids

Constituting over 60 wt% of a typical long-wear liquid foundation, volatile
fluids serve as the major components of both water and silicone phases,
and as carriers for other formulation components. Water makes up 30-40
wt% of a typical water-in-silicone liquid foundation, while the aqueous
phase in total makes up 40-50% of the formulation. The nature of volatile
fluids in silicone phase strongly influences emulsion’s physical character-
istics (e.g. rheology and surface tension) and stability, as well as product’s
user experience (e.g. product spreadability, duration of finger rubbing,
finger feel). Key physical and chemical characteristics of common volatile
fluids in liquid foundations are summarized in Table 16.6.
Shown in Figure 16.3 is a simple demonstration of the impact of volatile
solvents on formulation performance. Solutions with 20% MQ resin and
1% Red 7 pigment were cast as 100 µm films and dried on a glass surface.
When isododecane was used as the carrier fluid, significant de-wetting was
observed. While drying, isododecane solution’s contact area with the glass
surface was shrinking. Eventually, pigment concentrated in only very small
areas. Compared to isododecane, cyclopentasiloxane (D5) has a lower
surface tension and a higher viscosity. As shown in Figure 16.3, when D5
was used as carrier fluid, minimal dewetting was observed throughout D5
evaporation. Solution’s contact line with the glass surface barely moved,
and a more homogeneous MQ/Red 7 film was formed.
Historically, due to its relatively low cost, balanced volatility, low heat
of vaporization, and low surface tension, cyclomethicones, esp. cyclopen-
tasiloxane (D5), have been widely used as the main volatile fluid in the
silicone phase. From manufacturing safety standpoint, D5 is also preferred
due to its relatively higher flash point (77°C), compared to other volatile
fluids (isoparaffins, trisiloxane, etc.) [29]. Together with silicone emulsi-
fier, fillers, and rheology modifiers, D5 creates liquid foundations with
Table 16.6 Key physical parameters of volatile fluids commonly used in liquid foundations [28–30].
Surface tension Heat of vaporization
INCI name Density (g/cm3) (mN/m) Viscosity (cSt) Boiling point (oC) (J/g)
Water 1 72.8 0.89 100 2257
Ethanol 0.79 22.1 1.1 78 846
Cyclopentasiloxane 0.95 18 3.9 210 163
Dimethicone 0.85 18 1.5 192 ---
Methyl Trimethicone 0.85 16.8 1.5 191 ---
Isododecane 0.75 24.8 1.4 170 - 200 272
Isohexadecane 0.79 23.2 5.2 210 - 250 ---

20% MQ in Dry
Isododecane
(w/ 1% pigment)
20% MQ in D5 Dry
(w/ 1% pigment)
Figure 16.3 Pigmented solutions (20 wt% MQ resin, 1 wt% Red 7 pigment, and 79
wt% volatile solvent) cast and dried on glass surfaces. Top: isododecane used as solvent;
Bottom: cyclopentasiloxane used as solvent.
good ‘spreadability’ and a luxurious, comfortable feel on skin [29]. D5 is

also associated with minimal percutaneous absorption, but rather evapo-
rates quickly with minimal cooling sensation on skin, leaving the skin dry,
smooth and silky [31]. In addition, compared with most volatile isoparaf-
fins and linear siloxanes, D5 has a higher viscosity and a density closer to
the internal phase density of a typical W/Si emulsion. These two unique
properties help enhance W/Si emulsion stability, as understood by Stokes
Law of emulsion stability.
However, concerning D5’s environmental impact, the European Union
introduced in early 2018 restrictions on D5 use in cosmetic products that
are intended to be washed off before evaporation [32]. D5 concentrations
above 0.1% in wash-off products were determined to have a risk of accu-
mulating in the water supply. Although the current restriction does not
apply to liquid foundation (which is not regarded as a wash-off cosmetic
product), efforts have been made to replace D5 [26].
Non-volatile fluids are also used in the external phase for feel adjust-
ment and/or pigment dispersion. It is believed that excessive non-volatile
fluids in the external phase may negatively impact long-wear performance,
as these fluids may plasticize polymer film-formers and loosen pigments
on skin [5, 33]. Thus, less than 5 wt% of non-volatile fluids is commonly
used in typical long-wear liquid foundations. A summary of commonly
used cosmetic fluids is given in Table 16.7.
Table 16.7 Commonly used cosmetic fluids in long-wear foundations.

Type INCI name Volatility Structure
Silicones Cyclopentasiloxane Volatile H3C CH3
Si
O
H3C O CH3
Si Si
H3C O O CH3
Si O Si
H3C CH3
CH3 CH3
Trisiloxane Volatile CH3 CH3 CH3

CH3 Si O Si O Si CH3
CH3 CH3 CH3
Dimethicone Volatile CH3 CH3 CH3

CH3 Si O ( Si O )2Si CH3
CH3 CH3 CH3
Dimethicone Semi-volatile CH3 CH3 CH3

CH3 Si O ( Si O )3Si CH3
CH3 CH3 CH3
Dimethicone Non-volatile CH3 CH3 CH3

CH3 Si O ( Si O )nSi CH3
CH3 CH3 CH3 n > 3
Methyl Trimethicone Volatile Si(CH3)3

O
(CH3)3Si O Si O Si(CH3)3
CH3
Phenyl Trimethicone Non-volatile Si(CH3)3

O
(CH3)3Si O Si O Si(CH3)3
Trimethylsiloxyphenyl Non-volatile Si(CH3)3

O CH3
Dimethicone (CH3)3Si O ( Si O)( Si O ) Si(CH3)3
n m
CH3
Esters Caprylic/Capric Non-volatile O
Triglyceride CH2O C(CH2)xCH3

O
HCO C(CH2)xCH3
CH2O C(CH2)xCH3
Isononyl Isononanoate Non-volatile O

(iso-C9H17) C O (C9H19-iso)
(Continued)
Table 16.7 Commonly used cosmetic fluids in long-wear foundations. (Continued)

Type INCI name Volatility Structure
Pentaerythrityl Non-volatile O
Tetraisostearate O CH2O CR O
RC OCH2 C CH2O CR
CH2O CR
Diisostearyl Malate Non-volatile O O
C18H37O CCHCH2C OC18H37
OH
Alcohol Octyldodecanol Non-volatile CH3(CH2)9CHCH2OH
CH3(CH2)7
Isoparaffins Isohexadecane Non-volatile e.g. iso-C16H34 mixtures
Isododecane Volatile e.g.

iso-C12H26 mixtures
Polymer Hydrogenated Non-volatile CH3

Polyisobutene CH2C
CH3
x
16.3.2 Treated Pigments

Pigments are the essential components of foundation for creating natural
skin tones, and pigments adhesion to facial skin ultimately determines a
foundation’s wear performance. Various foundation shades are obtained
by adjusting respective ratios among the pigments, as Titanium Oxide
(TiO2), Zinc Oxide, Kaolin come in white and Iron Oxide particles come in
a variety of colors from yellow to red and black. Ultramarines, chromium,
chromium hydroxide may also be used for dark skin tones. A liquid foun-
dation’s coverage on skin is impacted by its pigment loading, ranging from
less than 5 wt% pigment content for a typical light-coverage to 15 wt% or
more pigments for full-coverages.
Dispersed in the external phase (silicone/oil), pigments used in long-

wear liquid foundations are mainly chemically treated pigments with a
lipophilic coating on particle surface. Surface treatment agents commonly
used are silicones, silanes, amino acids, lecithin, metal soaps, natural wax/
esters, polyacrylates, polyethylene, etc. Compared to untreated ones, sur-
face treated pigments, in general, have much better pigment dispersion in
silicone/oil phase, more enhanced pigment loading in the formulation, and
easier manufacturing. Table 16.8 highlights several popular surface treat-
ment chemistries relevant to long-wear liquid foundations.
16.3.2.1 Silicone Surface Treatment

Silicone surface treatment provides long-wear and water-proofing prop-
erties and the best dispersion and compatibility with both volatile silicone
fluids and silicone film-formers. Two types of silicone surface treatment
chemistries are commonly used. Methicone (polymethylhydrogensilox-
ane) treatment involves uniform silicone coating via reacting methicone’s
SiH groups with OH groups on the surface. This coupling reaction is effi-
cient and can result in very hydrophobic pigments that cannot be dis-
persed in common solvents other than fluids with high silicone content.
Methicone treatment is commonly associated with dry & powdery sen-
sation in the formulation. One downside of methicone surface treatment
is the safety concern of potential H2 gas generation from unreacted SiH
groups. Dimethicone surface treatment involves grafting dimethicone
(with terminal functionality) on pigment via forming siloxane bonding
between dimethicone chain ends and OH groups on pigment surface
[34, 35]. While the related coupling reaction may be less efficient than
methicone treatment, dimethicone treated pigments and fillers may have
good slip and a more lubricious feel than methicone treated ones. Silicone-
treated pigments are available from Miyoshi (SI and SA products lines) and
several other suppliers.
16.3.2.2 Amino Acid Surface Treatment

Amino acid surface treated pigments were introduced by Miyoshi in 1979,
and have been well adopted in liquid make-up formulations. This treatment
involves reacting alkyl modified amino acids (most commonly Disodium
Stearoyl Glutamate and Sodium Myristoyl Glutamate) with pigment sur-
face OH groups in the presence of aluminum hydroxide [36]. It is believed
that the small amount of residual COOH groups renders the treated pig-
ments weakly acidic, thus are more compatible with skin pH (commonly
Table 16.8 Commonly used pigment surface treatment chemistries.

INCI Name Pigment Surface Treatment Chemistry
Methicone CH3 CH3 CH3 CH3 CH3 CH3
CH3-Si-O-Si-O-
( )nSi-CH3 CH3-Si-O-Si-O-
( )nSi-CH3
CH3 H CH3 CH3 CH3
+ OH O O
- H2 O
HO OH
Dimethicone CH3 CH3 CH3

CH3-Si-O-( Si-O-Si-OH
)n CH3 CH3 CH3
CH3 CH3 CH3 CH3-Si-O-Si-O-Si-O-
( )n
+ OH - H2O O CH3 CH3
Disodium Stearoyl Glutamate C H COO-

C2H4COO- H 2 4
(and) Aluminum H C17H35CON–C-COO
Hydroxide C17H35CON–C-COO- Al
+ OH + Al(OH)3 O
- H2O
Triethoxycaprylylsilane C2 H
5 -O
C2H5-O-Si-C8H17 C8H17 C8H17
O Si )n
C 2H 5- + ( Si O
- CH3CH2OH O
OH O O
HO OH
Isopropyl Titanium CH3 O O

Triisostearate O-C-C17H35
CH3-CHO-Ti-(O-C-C17H35)3 O O
+ C17H35-C-O Ti O-C-C H
OH O 17 35
- (CH3)2CHOH
between 4.7 and 5.75). It is also believed that the chemical structural
similarity between alkyl amino acid and stratum corneum lipids results
in improved pigment adhesion to skin. Amino acid treated pigments are
known for enhancing formulations’ creamy sensory and moisture percep-
tion. In addition, “natural” product claims were made by some manufac-
turers based on the fact that amino acids surface treatment chemical agents
can be derived from vegetable sources. Amino acid treated pigments are
available from Miyoshi (e.g. NAI product line), KOBO (ASG product line)
and several other suppliers.
16.3.2.3 Silane Surface Treatment

Silane surface treatment involves the condensation reaction of silanols
(from silane hydrolysis) with pigment surface OH groups. Subsequent
curing results in stable chemical anchoring to pigment surface. Residual
silanes may be found in the silane-treated pigments, and may lead to some
odor. The level of residual silanes is an indication of treatment quality
and surface coating stability. Triethoxycaprylylsilane is a commonly used
alkylsilane. Pigments treated with triethoxycaprylylsilane tend to be more
hydrophobic than methicone treated pigments, but are dispersed more
easily in common cosmetic oils, and have lower oil absorption. Alkylsilane
treatment may also help achieve higher pigment loading in the formula-
tion. Compared to silicone treated ones, triethoxycaprylylsilane treated
pigments show better compatibilities with mineral oils, esters and other
non-silicone fluids.
Perfluorosilane treated pigments can also be found in long-wear color
cosmetic products. Perfluorohexylethyltriethoxysilane, as an example, can
make pigment both hydrophobic and lipophobic. KOBO studied contact
angles of water and oil on substrates of titanium dioxide treated with dif-
ferent chemistries [37]. As shown in Figure 16.4, water and oil beaded well
Contact Angle (water) Contact Angle (oil)
Non-treated
TiO2
Silicone-treated
TiO2
Fluorosilane-treated
TiO2
Figure 16.4 Images of water and oil droplets on substrates of titanium dioxide. The top
images are related to untreated TiO2; the middle images are related to silicone-treated
TiO2; the bottom images are related to fluorosilane-treated TiO2 [37].
on fluorosilane treated TiO2 and displayed large contact angles (all > 90 o).
KOBO claimed both sweat resistance and improved sebum resistance for
these fluorosilane-treated pigments. On the other hand, formulation and
manufacturing of the make-up products containing fluorinated pigment
could be difficult, because of low miscibility of fluorinated pigments with
common oils. Silane treated pigments are available from KOBO (11S prod-
uct line), Sensient (AS product line), Daito Kasei (FHS product line) and
several other suppliers.
16.3.2.4 Organo-titanate Surface Treatment

Organo-titanate surface treatment uses alkyl alkoxy titanates as surface
modification agents. Isopropyl titanium triisostearate (ITT), for example,
is reactive to many pigments and forms a uniform coating of fatty ester
groups. Like alkylsilane treated ones, the alkyl-titanate treated pigments
can be easily wetted by and dispersed in common oils (like esters, mineral
oils) or petrolatum. Oil absorption is substantially reduced and loading
of the pigments in the formulation can thus be increased [38]. Organo-
titanate treated pigments are available from KOBO (ITT product line),
Daito (ITT product line) and several other suppliers.
16.3.2.5 Hybrid Surface Treatment Chemistries

Hybrid treatment chemistries have been developed by using more than one
surface treatment agent [39]. This is to take advantage of the interesting
properties of each surface treatment chemistry, while reducing the impact
of their down sides. For instance, silicone treated pigments are exception-
ally hydrophobic and readily disperse in silicone fluids, but poorly in esters
and oils. Conversely, while organo-titanate treated pigments are known for
their compatibility with a wide range of cosmetic fluids, organo-titanate
treated pigments are not as hydrophobic as silicone treated pigments. To
encompass the positive attributes of both coating chemistries, KOBO devel-
oped a hybrid pigment surface treatment known as TTB treatment [40,
41]. ITT (an organo-titanate) and branched dimethicone with triethox-
ysilane groups (Triethoxysilylethyl polydimethylsiloxyethyl dimethicone)
are used together to coat pigments. As a result, a crosspolymer coating
is formed at the surface of pigments, making them “super-dispersible” in
esters, silicones and hydrocarbons [40].
16.3.2.6 Surface Treatment Chemistry Affects Formulation

Performance
The nature of treatment chemistry influences a pigment-containing for-
mulation’s physical properties, adhesion to skin, and water/sweat/sebum
resistances. As a simple illustration, Daito compared different surface
treatments (methicone, alkylsilane, acrylsilicone co-polymer, and alkyl-
titanate) on TiO2 particle surface [42]. Figure 16.5 compares the viscosi-
ties of dispersions of untreated TiO2 and surface treated TiO2. Untreated
TiO2 cannot be well dispersed in either D5 or squalane as uniform paste,
and show dispersion viscosities out of scale of the particular measure-
ment. At the same pigment loading, all four types of treated TiO2 can
be dispersed in both D5 and squalane. Among the surface treated ones,
methicone treatment resulted in the lowest viscosity in D5 and the high-
est viscosity in squalane. This is because methicone has similar siloxane
molecular structure as D5 but is very distinct from squalane. On the
other hand, alkyltitanate (isopropyl titanium triisostearate) treated tita-
nium dioxide showed lower viscosity in squalane and higher viscosity
in D5.
Note that the performance of a particular treatment chemistry may be
formulation dependent, and the compatibility of treated pigments with
other formulation components (carrier fluid, film-former, etc.) is worthy of
investigation. Shown in Figure 16.6 is a simple illustration, where water con-
tact angles on iron oxide pigments were measured. Pigments were treated
with 3 different chemistries, dispersed in Dimethicone 2 cSt fluid, and
cast on glass substrate. FHS (Perfluorooctyltriethoxysilane) surface treat-
ment is typically associated with lower surface free energy, so higher water
200
Out of scale Out of scale
Viscosity (Pa.s)
100
0
Untreated Methicone Alkylsilane Silicone ITT Untreated Methicone Alkylsilane Silicone ITT
Acrylate Acrylate
Figure 16.5 Viscosity of dispersions of untreated and treated titanium dioxides.

Left: pigment dispersed in D5. Right: pigment dispersed in squalene [42].
TTB : 143° FHS : 119° NAI : 74°
to straighten
Figure 16.6 Water contact angles (top images) and micrographs (bottom images) of
treated pigment film on glass. Dimethicone 2 cSt fluid was used as carrier fluid for
pigment dispersion and film casting.
contact angle than that of TTB (a hybrid treatment using both Isopropyl
Titanium Triisostearate and Triethoxysilylethyl Polydimethylsiloxyethyl
Dimethicone). However, as shown in the top images of Figure 16.6, pig-
ments with TTB treatment showed much higher water contact angle than
those with FHS treatment or NAI treatment (Disodium stearoyl glutamate
(and) Aluminium hydroxide). Optical microscope images further revealed
that the TTB treated pigment film was much more homogeneous than FHS
and NAI treated pigment films. Considerable aggregates were seen for FHS
and NAI treated pigment films. The observation that TTB treated pigment
film has the highest water contact angle was explained by the difference in
dispersability of each treated pigment in 2 cSt silicone fluid: TTB treated
pigments have the best compatibility with 2 cSt silicone fluids and form the
most uniform coating on glass. For FHS and NAI treated pigment films,
the less compatibility between pigment and carrier fluid resulted in pig-
ment aggregates and lower coverage on glass, thus reducing the water con-
tact angles.
16.3.3 Film-Formers
Virtually, every facial make-up with long-wear claim contains at least one
organic or silicone “film-former,” such as polyvinylpyrrolidone (PVP)-
type copolymers, acrylate-type copolymers, polyethylene, silicone MQ
resin, silicone resin waxes, and silicone acrylates [1, 3]. Today’s prevailing
technology in long-lasting liquid foundation is based on using silicone
“film-formers,” examples of which are listed in Table 16.9 and discussed
below [5].
Table 16.9 Commonly used silicone film-formers in color cosmetics.

Commercial
Film-formers INCI name examples
MQ and MQ Trimethylsiloxysilicate TMS-803 (Powder
Hybrids from Wacker);
SR-1000 (Powder
from Momentive);
MQ-1600 (Flake
from Dow);
Silsoft 74 Fluid
(isododecane
dispersion from
Momentive); RSN-
0749 (D5 dispersion
from Dow)
Trimethylsiloxysilicate/ FC-5002 (Dow)
Dimethiconol Crosspolymer
Vinyldimethyl/ BELSIL RG 90
Trimethylsiloxysilicate Stearyl (Wacker)
Dimethicone Crosspolymer
Dimethicone/ Belsil REG 102
Vinyltrimethylsiloxysilicate (Wacker)
Crosspolymer
Polymethylsilsesquioxane/ MQI-T50 (Grant)
Trimethylsiloxysilicate
Silicone Acrylates/ FA 4002 ID (Dow); FA
Acrylates Polytrimethylsiloxymethacrylate 4001 (Dow)
Copolymer
Acrylates/Dimethicone Copolymer KP-545 (Shin Etsu)
Acrylates/Stearyl Acrylate/ KP-561 (Shin Etsu)
Dimethicone Methacrylate
Copolymer
Isobutylmethacrylate/Bis- BMAS (Grant)
Hydroxypropyl Dimethicone
Acrylate Copolymer
(Continued)
Table 16.9 Commonly used silicone film-formers in color cosmetics. (Continued)

Commercial
Film-formers INCI name examples
Butyl Acrylate/Hydroxypropyl BAS-NC (Grant)
Dimethicone Acrylate
Copolymer
T-Resin Polymethysilsesquloxane PMS MK (Wacker);
SilForm Flexible
(Momentive)
Polypropylsilsesquioxane 670 Fluid (Dow); 680
ID (Dow)
Polyphenylsilsesquioxane SPR 45 VP (Wacker)
Silicone/ Nylon 611/Dimethicone Dowsil 2-8179 (Dow)
Organic Copolymer
Hybrids
Trimethylsiloxysilylcarbamoyl TSPL-30-D5 (Shin
Pullulan Etsu)
Bis-Carboxydecyl Dimethicone INX fluid (Momentive)
Water Based Bis-Ethylhydroxycyclohexyl HyFlex emulsion
Methacrylate/Butyl Acrylate (Momentive)
Crosspolymer
Acrylates/ FA 4103 (Dow)
Polytrimethylsiloxymethacrylate
Copolymer
(and) Laureth-1 Phosphate
16.3.3.1 MQ Silicone Resins

Among silicone film-formers, silicone MQ resin is the most commonly
used. With an INCI name of trimethylsiloxysilicate and historically also
known as trimethylated silica, MQ resin is a methyl capped quadrafunc-
tional silicone resin with some residual silanol functional groups, see Figure
16.7. M stands for the methyl capping units (Me3SiO), while Q stands for
the units (SiO4/2) of the three-dimensional core. Commercial MQ resins
are polydisperse compositions of polyhedral structures of different sizes
and shapes [5, 43]. MQ resin is supplied as a pure component (as flake
or powder) or in a solvent such as cyclopentasiloxane or isododecane.
Examples of commercially available MQ resins are Momentive SR 1000
OH
Si
CH3
O
Si
O
CH3 Si
O
CH3 Si Si
O
O 3
CH
O
O
Si
O
Si O Si Si 3
Si CH
O
HO
O
O
O
OO Si
Si O Si Si H3
OH O C
O O O Si O Si
Si O Si O OO
O
Si O Si Si
O CH3
O O O Si
Si O Si CH3 CH3
O O
CH3 Si O Si
Si
CH3 CH3 O OO
Si O Si Si
O O O OH
Si O Si
Figure 16.7 Structure illustration of an MQ resin.
(powder), Wacker TMS 805 (powder), Dow MQ-1600 (flake), Momentive

SILSOFT 74 (75% MQ in isododecane), and Dow 749 Fluid (50% in cyclo-
pentasiloxane). These MQ resins typically have number-average molecular
weight Mn around 10,000 Da with the glass transition temperature (Tg)
from 200 °C to 370 °C depending on the M/Q ratio. The M/Q ratio is typ-
ically in the range 0.6–1.2:1 [44]. In addition to molecular weight and the
M to Q ratio, MQ resin’s properties also depend on the particular manufac-
turing process for making it. For example, MQ resins prepared by hydro-
lytic condensation of sodium silicate, followed by capping reaction using
trimethylchlorosilanes, are likely to have relatively higher silanol contents,
while MQ resins prepared by co-condensation of hexamethyldisiloxane
with tetraethoxysilane (TEOS) or ethyl polysilicate have relatively lower
silanol contents [43, 45].
As a tackifier for non-cured silicone and a structure enforcing agent for
cured silicone, MQ resin is used in a wide range of industrial applications,
e.g., pressure-sensitive adhesives, hot-melts adhesives, and long-wear sur-
face coatings [44]. It is understood that the performance of silicone MQ
resin as adhesive and structure enforcement agent in industrial applica-
tions is based not on MQ resin itself, but largely on the combined use of
MQ resin and poly(dimethylsiloxane) (PDMS), MQ resin’s great miscibil-
ity with PDMS, and its ability to tune PDMS viscoelastic profile. The use of
MQ resins in cosmetics was first documented by Shiseido. Subsequently,
for the last three decades, MQ resins have been used in many color cos-
metic products, such as in long-wear lipsticks (anhydrous) and founda-
tions (water-in-oil emulsion) [4, 46–48]. Examples of these long-wear
liquid foundations containing MQ resins are: Dior (Teint Ideal Mat 1994),
Revlon (Colorstay 1995), Clarins (Ultra Mat 1996), Estee Lauder (Double
Wear 1997), Kanebo (Essence in Liquid 2001), and Beiersdorf (Skin Like
2003). These foundation formulations are developed for specific skin types
(normal/dry skin and oily skin) and they promise exceptional coverage,
24-hour transfer-resistant wear, and a smooth finish [5].
16.3.3.2 T-Propyl Silicone Resin

While MQ resin provides wear and non-transfer benefits by holding pig-
ments and fillers in place, it can also cause a dry and sticky feel to the skin.
To resolve this problem without sacrificing performance, T-Propyl resin
(INCI name Polypropylsilsesquioxane), a more flexible silicone resin, was
utilized in the long-wear foundation products, like Maybelline SuperStay
24 HRS Foundation [5, 49].
A T-resin (also known as silsesquioxane) is an organosilicon compound
with the chemical formula [RSiO3/2]n (R = H, alkyl, aryl, phenyl or alkoxyl).
T stands for the building block units (SiO3/2). T-Propyl resin, [propyl-SiO3/2]n,
is formed by the hydrolysis and condensation of propyltrichlorosilane
and is believed to have a ladder-like structure or loose network structure,
Figure 16.8 [50]. The commercial T-Propyl resin dispersed in silicone or
in hydrocarbon solvent can be obtained from Dow Chemical under trade
name Dowsil 670 Fluid (~50% in D5) or Dowsil 680 ID (~75% isododec-
ane). These T-Propyl resins have Mw in the range of 10,000–20,000 and
softening temperature of 16 °C. With Tg/softening temperature much
lower than those of typical MQ resins, the T-Propyl resin is sticky at room
R R R R R R
R HO Si
O Si O O Si O Si OH
HO Si O R R HO Si Si HO O R
R
HO Si Si O Si O O O O O
R Si O Si
R O OH O R HO O
O O Si O O
HO Si Si O Si Si
O
Si O Si O O Si OH Si O Si O R
O R OH Si O R O Si
O R R Si O
HO Si R O R R R
R R R
O Si
R HO O Si R
OH
(a) (b) (c)
Figure 16.8 T-Propyl silsequioxane resin with loose cage structures such as in (a) or (c)
or a ladder-like structure (b).
temperature and ready to form a very flexible and sticky film upon drying.
Therefore, T-Propyl resin can act as liquid binder for pigments and fillers
in the formulation to give good adhesion to skin [5].
16.3.3.3 Silicone Acrylates

Another type of silicone film-forming polymers used in the long-wear
make-up is silicone acrylate, a hybrid of acrylate polymer and silicone.
Current silicone acrylates in the market have several chemical configura-
tions, such as an acrylate polymer backbone with linear silicone or dendritic
silicone grafted along the backbone, see Figure 16.9. Typically, these silicone
acrylate copolymers can be dispersed well in many solvents like isododecane
and cyclopentasiloxane. The glass transition temperature (Tg) of these sili-
cone acrylates depends on the ratio of acrylate to silicone components, the
copolymer molecular weight, and the type/ratio of acrylate monomer.
One type of the commonly used silicone acrylate film-former in long-wear
liquid foundation is an acrylic copolymer with linear siloxane (dimethylpoly-
siloxane) grafted along the acrylate backbone. This type of copolymer can be
obtained from Shin Etsu under the trade name KP-545 (30% solid in D5) or
KP-550(40% solid in isododecane). The glass transition Tg of this copolymer
(acrylate/dimethicone) is about 23 °C [51]. Another type of silicone acrylate is
a copolymer of the dendritic Polytrimethylsiloxymethacrylate grafted on the
acrylate backbone polymer. One commercial example of this type is Dowsil FA
4002 (INCI name: Acrylates/Polytrimethylsiloxymethacrylate Copolymer)
from Dow [52]. This copolymer is a brittle solid at room temperature upon
drying and has a glass transition Tg of ~75 °C based on Differential Scanning
Calorimetry (DSC) study [33]. For both types of silicone acrylates, the films
formed can be rigid and may need to be plasticized. For example, to improve
Acrylate backbone O
Acryl O
O Si
Si O
O
O Si Si
Si O Si Si O Si O Si O
O
R O O
Si
Si Si
Siloxane
Si O Si O Si
O
Si
Figure 16.9 Illustration of two types of silicone acrylates. Left: acrylate polymer backbone
grafted with linear silicone. Right: acrylate polymer backbone grafted with dendritic silicone.
the flexibility, the T-Propyl resin (a silsesquioxane) can be used to plasticize

silicone acrylates for balanced adhesion and tack [49, 53].
It was hypothesized that upon drying on the substrate, silicone acrylates
begin to phase- separate as the solvent evaporates. As a result, the copoly-
mers will adapt a configuration such that acrylate segments can anchor to
the skin and the silicone segments migrate to the surface [54]. With this
arrangement, silicone acrylate can deliver good adhesion to the skin with
a silicone texture on the film surface [5, 54]. Silicone acrylates are known
to provide various benefits for liquid foundations including water/sweat/
sebum resistances, smooth texture/feel and comfortable wear on skin. The
first long-wear foundation product using a silicone acrylate copolymer was
from Kobayashi Kose [55]. Silicone acrylate ingredient was noted in other
foundations such as from Clarins, Avon and Dior. L’Oreal also adopted the
dentritic silicone acrylate in their long-wear foundations L’Oreal Infallible
and Lancome Teint Idole Ultra 24 HR.
16.3.3.4 MQ/Dimethicone Hybrids

A number of MQ/dimethicone hybrid materials are used in long-wear
make-up as adhesive for pigments anchoring to the skin. Marketed under the
tradename of “Bio-PSA”, trimethylsiloxysilicate/dimethiconol crosspoly-
mer is a type of pressure-sensitive silicone adhesive originally developed
for pharmaceutical applications, e.g., medical adhesives and transder-
mal drug delivery systems [56]. Trimethylsiloxysilicate/dimethiconol
crosspolymer can be produced through a condensation reaction of a sila-
nol endblocked poly(dimethylsiloxane) (i.e., dimethiconol) with a silicate
resin (MQ resin), see Figure 16.10. Trimethylsiloxysilicate/dimethiconol
crosspolymer can form tacky and flexible adhesive upon drying. Like these
non-covalent blends of MQ resin and PDMS, the dimethiconol impacts
the wetting and spreading properties of the adhesive, while the resin acts
as a structure reinforcing agent and tackifier. The formation of covalent
bonds between MQ resin and dimethiconol further enhances the cohesion
of this hybrid material while its ability to adhere to low free energy sur-
faces is maintained. MQ resin to dimethiconol ratio is the major factor for
obtaining the optimum balance of tack, adhesion and cohesion [56]. One
commercial example of trimethylsiloxysilicate/dimethiconol crosspolymer
is Dowsil FC-5002 IDD Resin Gum (40% resin in isododecane). Liquid
foundations using trimethylsiloxysilicate/dimethiconol include Smashbox
Studio Skin Flawless 24 HR and Clinique Even Better.
OH
HO HO OH
+NH3
Silanol Endblocked PDMS Heat
–H2O HO
Polycondensation
Soluble Silicate Resin
OH
O O
HO OH
O
Adhesive Condensate OH
+ Polydimethylsiloxane (PDMS) Plasticizer
Heat
PDMS PDMS
OH
O O
HO OH
PDMS O PDMS
OH
PDMS
Figure 16.10 Chemistry of preparing trimethylsiloxysilicate/dimethiconol

crosspolymer [56].
16.3.4 Emulsifiers
16.3.4.1 Silicone Emulsifiers
Used as the primary emulsifier (approximately 2-3 wt%) for creating
water-in-silicone liquid foundation, silicone emulsifiers are a series of
amphiphilic polymers containing both silicone and water-soluble groups
with varying and controllable levels of solubility in oil, water and sili-
cone. Known as an excellent wetting agent, silicone emulsifier also helps
formulations’ spreading on skin [57]. Widely used and historically also
known as silicone copolyol, silicone polyether is a general term used for
a group of silicone emusifiers made from dimethicone and polyethers
(polyoxyethylene and/or polyoxypropylene). The most common sili-
cone polyether is PEG/PPG-18/18 Dimethicone, commercially available
from Dow as DOWSIL 5225C (~10% in cyclopentasiloxane) and sev-
eral other suppliers. PEG/PPG-18/18 Dimethicone was first introduced
into personal care market as the emulsifier for antiperspirant clear gel
(water-in-silicone) in the early 1980s. High aqueous phase content (~80
wt%) and cold processing can be achieved with only ~1 wt% PEG/PPG-
18/18 Dimethicone active. Like most silicone polyethers, commercial
PEG/PPG-18/18 Dimethicone may also contain small amounts of poly-

ethers (less soluble in silicone phase) that may act as a co-emulsifier
and contribute to the raw material’s performance [58]. PEG/PPG-18/18
Dimethicone has been used by major liquid foundation brands like Estee
Lauder Double Wear, REVLON Colorstay, and Covergirl Outlast Stay.
Examples of other silicone polyethers used in long-wear liquid founda-
tion products are PEG-9 polydimethylsiloxyethyl dimethicone (KF 6028
from Shin Etsu,) and PEG-10 Dimethicone from several silicone suppli-
ers, see Figure 16.11.
Conventional silicone polyethers are known to have difficulty in emul-
sifying low to medium polarity oils (e.g. fatty acid esters of short- and
long-chain alcohols, triglycerides, and organic sunscreen actives). To
address this issue, alkyl modified silicone polyethers were developed.
One example of alkyl modified silicone polyether is Cetyl PEG/PPG-
10/1 Dimethicone, a copolymer of Cetyl Dimethicone and an alkox-
ylated derivative of Dimethicone containing an average of 10 moles of
CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3

CH3 Si O ( Si O ) ( Si O )n Si CH3 CH3 Si O ( Si O ) ( Si O )n Si CH3
m m
CH3 CH3 (CH2)3 CH3 CH3 CH3 (CH2)3 CH3
CH3 O O
H(OCH2CH2)10
H(OCHCH2)18 (OCH2CH2)18
Me Me Me Me Me
CH3 CH3 CH3 Si Si Si Si Si Me
Me O O O O
Me Me Me
x
(CH3)3Si SiO SiO SiO Si(CH3)3
CH3 (CH3)3 (CH2)2 O

x
O Si(CH3)2 1
O
(CH2CH2O)9H O
10
y HO
Si(CH3)3
z
y z
Figure 16.11 Chemical structures of four silicone emulsifiers. Top Left: PEG/
PPG-18/18 Dimethicone; Top Right: PEG-10 Dimethicone; Bottom Left: PEG-9
Polydimethylsiloxyethyl Dimethicone; Bottom Right: Cetyl PEG/PPG-10/1
Dimethicone.
ethylene oxide and 1 mole of propylene oxide, see Figure 16.11. Examples
of recently launched liquid foundations containing this silicone emulsi-
fier are Bobbi Brown Skin Long-Wear Weightless Foundation, e.l.f. 16HR
Camo Concealer, and IT Cosmetics Bye Bye - Full-Coverage Foundation.
Cetyl PEG/PPG-10/1 Dimethicone is commercially available from
Evonik as EM 90 and several other suppliers.
16.3.4.2 Non-Silicone Emulsifiers

Co-emulsifiers, like Polyglyceryl-4 Isostearate, Polyglyceryl-3 Diisostearate,
and Laureth-7, are also commonly used in W/Si liquid foundations to
enhance emulsion stability. In addition, electrolytes (e.g. sodium citrate,
magnesium sulfate, sodium chloride) and glycols (e.g. butylene glycol,
poly(ethylene glycol)) are used to help W/Si emulsions stability by reduc-
ing the emulsion droplet size, increasing viscosity, and enhancing freeze-
thaw stability.
16.3.5 Fillers
Fillers are defined as inert ingredients that add bulk and texture to a cos-
metic product. Fillers used in long-wear liquid foundations adjust formula-
tion’s sensorial & physical properties by affecting viscosity, tribology, color
deposition and blendability on the skin, and skin feel. Some fillers are able
to create “soft-focus” optical effect, i.e., scattering light to diminish the look
of skin imperfections and fine lines, while letting enough light through so
that skin still looks natural. In addition, two important functions of fillers
used in long-wear liquid foundation are to reduce formulation tack and to
enhance sebum resistance.
Tackiness during and after application on the skin is a common con-
sumer dissatisfaction of long-wear liquid foundation. Current silicone
film-formers essentially function as elastomeric based adhesives that cre-
ate bonding with both skin and pigments. The same bonding may also be
formed between the formulation and the finger during foundation appli-
cation as volatile fluids evaporate. Fillers and rheology modifiers can be
used to modify tacky skin feel (typically by reducing tackiness) to balance
adhesion and tack. By changing physical characteristics of a liquid founda-
tion such as modulus and glass transition, fillers would also influence the
adhesion of the product to the skin [5].
Sebum is recognized as a major cause for make-up deterioration over
time. Secreted from human sebaceous glands, sebum is mainly made of
triglyceride oils, fatty acids, wax, and squalene. Sebum may lead not only
to a make-up’s uneven coverage on facial skin, but also to excessive plas-
ticization of cosmetic films, wetting of pigments, and weakened make-up
adhesion to the skin. This can result in oily appearance, make-up shade
change, and easier transfer. To control sebum and sweat, oil absorbent fill-
ers such as silica and nylon are commonly used in long-wear foundation to
mitigate the proliferation of sebum and sweat excreted on the skin. These
fillers aid in preventing plasticization of the film, thereby resisting wear
and transfer [5].
Typical fillers and rheology modifiers used in long-wear liq-
uid foundations include Nylon 12, Boron nitride, silica, Tribehenin,
Disteardimonium Hectorite, Dimethicone Crosspolymer, and kaolin.
Table 16.10 is a summary of common fillers used in long-wear founda-
tions. For examples, Nylon 12 is commonly used in long-wear make-up
products due to its ability to absorb oils and sebum to give long-lasting
effect for foundation, and the optical effect to blur the wrinkles on the
skin. In addition, the spherical shape and particle size range of Nylon
12 (5 - 20 µm) can contribute to the sensory such as velvety feeling due
to friction coefficient reduction during spreading the product on skin.
Another common filler, Boron Nitride, contributes to different sensory
and optical effects, as well as to adhesion to skin to maintain the wear of
foundation. For example, the Softouch* CC6058 Boron Nitride Powder
from Momentive with a flat, graphitic, hexagonal crystal structure,
delivers a matte look with superb “soft-focus” properties, see Figure
16.12.
16.4 Factors Affecting Adhesion to Skin:

Combination of Film-Formers and Emulsifiers
As shown previously, the formulation of a typical long-wear liquid founda-
tion is very complex, in many cases containing over 20 ingredients. After
skin application, volatile solvents in a liquid foundation evaporate, leav-
ing a pigmented film with most non-volatile components. Intuitively, wear
performance on skin should be controlled by the way pigments interact
with skin, in the presence of resin/film-formers and many other nonvola-
tile components (emulsifiers, fillers, rheology modifiers, etc). Nevertheless,
research to date on the lasting of long-wear make-up on skin disclosed in
the public domain has been focusing on understanding behaviors of indi-
vidual film-former or pigment.
Table 16.10 Examples of fillers commonly used in long-wear liquid foundations

and their commercial sources.
INCI name Description Commercial sources
Nylon-12 Microporous polyamide-12 Evonik (Tegolon®),
fine particles. It is believed Arkema
the lipophilic surface has (Orgasol®)
good compatibility with
the stratum corneum for
long-wear benefits. It also
enhances smoothness feel
and has “soft-focus” and
sebum control benefits
Talc A type of magnesium Imerys, Nippon
phyllosilicate (natural platelet Talc, Mondana
structure) naturally extracted
from regions like China,
Brazil, and EU. Talc is known
for its lubricity, nice touch,
oil absorption capability,
anti-caking property, and its
ability to create “soft-focus”
optical effect. Asbestos fibers
and heavy metal impurities
are of concern.
Disteardimonium Disteardimonium cations Elementis (Bentone
Hectorite replace some of the sodium Gel®)
cations of hectorite surfaces
(octahedral magnesium/
lithium silicate sheets).
Excellent thickener &
suspending agent
Boron Nitride Crystalline B-N platelets Saint-Gobain (TRÈS
(graphite-like lamellar crystal BN®), Merck
structure) with low coefficient KGaA,
of friction. Improves texture, Momentive
slip, color deposition, (SOFTTOUCH®)
spreadability and adhesion. It
may also create “soft-focus”
effect with luminosity.
(Continued)
Table 16.10 Examples of fillers commonly used in long-wear liquid foundations

and their commercial sources. (Continued)
INCI name Description Commercial sources
Synthetic Fluorine substituted phlogopite BASF, Merck,
Fluorophlogopite (a type of magnesium mica) Sudarshan
with properties similar to
natural mica, but known for
cleaner mass tone and lower
heavy metals content.
Kaolin A type of magnesium Kamin, Imerys,
phyllosilicate from regions Burgess Pigments,
like USA, Brazil, and EU BASF
Silicone Also known as silicone Dow, Shin Etsu,
Crosspolymer elastomer, this is a type of Momentive,
crosslinked dimethicone Grant
typically supplied in the
form of swollen gel or dried
powder. It provides unique
sensory properties (non-
greasy and light silky skin
feel, tack reduction) and
“soft-focus” benefits
Figure 16.12 SEM images showing filler morphology. Left: Nylon-12 particles from
Toray with a mean particle size of 5 µm; Right: Softouch* CC6058 Boron Nitride from
Momentive with a mean particle size of 11 µm.
For instance, MQ resin, by itself, is ineffective for anchoring pigments

on skin. Many current transfer-resistant cosmetics adopt the combination
usage of MQ resin and non-volatile silicone oil [4]. The formulation wear
performance is derived not only from the physical and chemical properties
of the MQ resin, but also the non-volatile oil and its ratio to MQ resin [59].
Nevertheless, despite all the commercial adoption and technology, other
than a vague concept of “MQ + plasticizer,” fundamental understanding
and systematic studies of how different formulation components interact
and collectively contribute to pigments adhesion to skin have not well dis-
cussed in the literature.
Here, in the context of silicone-based long-wear liquid foundation, we
will discuss a few initial steps we have taken towards understanding inter-
actions among nonvolatile components and their impacts on wear per-
formance. Particularly, we will discuss properties of binary blends of two
indispensable nonvolatile components in a long-wear liquid foundation:
silicone film-formers and silicone emulsifiers.
16.4.1 Combination of MQ Resin and Silicone Emulsifier

With silicone MQ resin being the prevailing film-former used in long-
wear liquid foundations, the combined usage of silicone emulsifier and
MQ resin is common. We investigated the interactions between silicone
emulsifier and MQ resin by first mixing solutions of silicone emulsifier and
MQ resin blends in volatile carrier fluids. Films of MQ/silicone polyether
binary blends can be formed after casting mixed solutions on the surface
and evaporating the solvent. For most of the MQ/silicone polyether blends
we studied, the films formed are optically transparent, suggesting good
miscibility between MQ resin and silicone polyether [59]. AFM study
(data not shown) also showed film roughness to be typically below 5 nm.
Tackiness of films was assessed by a texture analyzer and was found to
be highly dependent on MQ resin content [59]. Figure 16.13 shows tack
force (peak value) required for texture analyzer probe to disengage from
the film surface after contact. A higher tack force typically correlates to
a tackier film. For binary blends of MQ resin and PEG/PPG-18/18 with
lower fraction of MQ resin, the tack steadily increases with the increase
of MQ resin content, before reaching maximum with MQ resin at 50 wt%
in the binary mixture. Further increasing the MQ resin content greater
than 50 wt% leads to significant decrease in film tackiness. This behavior
can be explained by the contribution of MQ resin to the rigidity or elastic
modulus which reduces the adhesion force when high amount of MQ resin
is present in the film. At low MQ/emulsifier ratio up to 1:1, MQ resin is
800
700
Tack Force (gram)
600
500
400
300
200
100
0
3:7 4:6 5:5 6:4 7:3 8:2
MQ to Silicone Polyether Ratio (wt)
Figure 16.13 Film tackiness of MQ resin and PEG/PPG-18/18 dimethicone (Silicone

Polyether) blends studied by texture analyzer at different MQ to silicone polyether ratios [59].
well dispersed and plasticized by the low Tg emulsifier and has low modu-
lus. Increase in MQ/emulsifier ratio up to 1:1, the tack gets maximum and
adhesion related to the tack is optimized.
The ratio of MQ resin to silicone polyether (SPE) also controls both film
surface free energy and flexibility. Shown in Figure 16.14 are sebum and
water contact angles on MQ and PEG/PPG-18/18 Dimethicone films at
different MQ to SPE ratios. Both contact angles are highly dependent on
MQ/SPE ratio. At MQ/SPE ratio lower than 4:6, the water contact angles
of the films are higher than 110°. Increasing the MQ resin content in the
blend above 50 wt% (i.e., MQ/SPE ratio over 1:1), the water contact angles
drop below 110° and are constant up to 80 wt% MQ resin. This behavior
could be explained by the effect of surface roughness or the polarity of the
130
Sebum Water
110
Contact Angle (°)
90
70
50
30
3:7 4:6 5:5 6:4 7:3 8:2
MQ to Silicone Polyether Ratio (wt)
Figure 16.14 Sebum and water contact angles on MQ resin and PEG/PPG-18/18
dimethicone (Silicone Polyether) films at different MQ to silicone polyether ratios [59].
MQ exposed on the film surface. Similarly to the behavior of water contact

angle on MQ/emulsifier ratio, the sebum contact angles on the films are in
the range of 50° when MQ resin is less than 60 wt% and are reduced to 35°
and become constant when MQ is 60 wt% and above.
Film flexibility was studied by first creating films of polymer blends on
a rubber band [59]. It was observed that the films with high amount of
MQ resin (MQ to PEG/PPG-18/18 dimethicone ratio above 7 to 3) were
not flexible and cracked under elongation. In addition, the rub-off test was
conducted on the films with or without artificial sebum to test the adhesion
of pigments to the collagen substrate. The results showed high color trans-
fer and poor adhesion when the wt ratio of MQ resin to silicone emulsifier
was less than 6 to 4. With higher amount of MQ resin (i.e. higher ratio
of MQ/silicone emulsifier), the non-transfer of color was achieved even
with 100 rubbing cycles in the case without exposing to sebum. However,
minimum color transfer was observed after 50 rubbing cycles with sebum
when MQ resin was loaded at 75 wt% in the film. Therefore, with low MQ
resin amount, sebum can plasticize the films, softening polymer blends
and weakening films anchoring to the surface. By increasing MQ resin to
a sufficient amount, the film can have a good sebum resistance and sustain
mechanical stress [59].
Li et al. further demonstrated the impact of different types of emulsi-
fiers on the adhesion to skin using W/Si emulsion containing MQ resins.
Depending on the type of emulsifier, the sebum resistance and rub-off
resistance performances were observed to be varied. These results indi-
cated that the MQ/emulsifier ratio and the chemical nature of the emulsi-
fier are important factors influencing the long-wear foundation in terms of
balancing the tack, adhesion, flexibility and sebum resistance under rub-
bing [59].
16.4.2 Combination of Silicone Acrylate and Silicone

Emulsifier
As previously discussed, silicone acrylate is a type of silicone film-former
used in long-wear liquid foundations. Particularly, L’Oreal adopted the
dendritic silicone acrylate in their long-wear foundations L’Oreal Infallible
and Lancome Teint Idole Ultra 24 HR. For these water-in-silicone for-
mulations, after skin application and volatile solvents evaporation, the
dendritic silicone acrylate and silicone emulsifier remain the main poly-
meric components on the facial skin. To understand the interactions
between the two, blends of silicone acrylate (SiAc) and silicone poly-
ether (SPE) at various ratios were prepared by mixing and evaporating
the volatile solvent. The particular silicone acrylate used was Acrylates/
Polytrimethylsiloxymethacrylate Copolymer (Dowsil FA 4002 from Dow).
Silicone acrylate (SiAc) and PEG/PPG-19/19 Dimethicone (a silicone
polyether) are blended at 7:3 ratio forming an optically transparent plastic
material, suggesting compatibility between the two materials. Differential
Scanning Calorimetry (DSC) measurement showed that the Tg of the neat
SiAc is reduced from 72 °C to 43 °C when blending it with SPE at 7/3 ratio.
The result indicates that silicone polyether may function as an effective
“plasticizer” for the relatively rigid silicone acrylate [33].
The combination of silicone acrylate with silicone polyether was fur-
ther investigated by blending the same Acrylates/Polytrimethylsiloxyme
thacrylate Copolymer with a different emulsifier (Bis-Isobutyl PEG/
PPG-10/7 Dimethicone Copolymer) at different ratios [33]. In this polymer
blend system, film hardness was studied by the pendulum film hardness test,
where a higher count is correlated to a harder film. Film tackiness was mea-
sured by a texture analyzer. Figure 16.15 suggests a correlation between
higher fraction of silicone polyether in the blends and the mechanical
property of the film. Within the ratio range studied, the film becomes tack-
ier with increasing the fraction of silicone polyether, Figure 16.15b.
Cracking and flexibility of color cosmetic films containing silicone
acrylate/silicone polyether blends were further investigated. For a formu-
lation using silicone acrylate as the sole polymeric component, dried film
exhibited visible cracks (data not shown). On the other hand, the formu-
lation with a combination of silicone acrylate and Bis-Isobuty PEG/PPG-
10/7 Dimethicone Copolymer at 7:3 wt ratio yielded a dry film exhibiting
no observable cracks (data not shown). Stretching test was conducted and
Film Hardness Film Tack

Pendulum Hardness Count
70 90
60
Tack (gram force)
50 60
Harder Higher
40
Tack
30
30
20
10
0 0
10:0 9:1 8:2 7:3 6:4 5:5 10:0 9:1 8:2 7:3 6:4 5:5 4:6
SiAc to SPE Ratio SiAc to SPE Ratio
(a) (b)
Figure 16.15 Film hardness and tack. a): Pendulum film hardness measurement on
blends of silicone acrylate (SiAc) and silicone polyether (SPE) at different ratios. b): Film
maximum tack force measured by texture analyzer [33].
it was found that films with an adequate fraction of silicone polyether did
not crack under the test conditions, suggesting a more flexible film than
films based on lower fractions of silicone polyether [33].
In conclusion, the silicone polyether can be used as an effective plasti-
cizer for silicone acrylate and its content in the blend with silicone poly-
ether will impact the adhesion and flexibility of the final film on skin.
16.5 Summary and Prospects

To meet customers’ higher expectation, innovations in developing long-
lasting, non-transfer cosmetics with excellent sensory perception and easy
removability will continue for the foreseeable future. While experts in the
field have skillfully manipulated the existing commercially available mate-
rials to meet many of the above attributes in designing their products, the
interactions among components and contributions of each to pigments
adhesion to facial skin is not well understood.
From a materials science perspective, ideally, a cosmetic film formed
from the non-volatile components would need to be flexible and breath-
able for comfort. For lasting property the cosmetic film needs to promote
adhesion between pigment and skin, as well as be sebum/sweat resis-
tant. Hence, it is important to study the interactions among non-volatile
components, especially polymeric non-volatiles, in a given formulation.
Therefore, understanding and application of fundamental polymer phys-
ics principles will continue at the frontier of long-wear color cosmetic
development.
Beyond materials science, long-wear color cosmetics development is
also impacted by changing consumer & media perceptions and regula-
tions. For instance, we are experiencing growing consumer demand for
“clean” & “natural” products. While silicone-based technologies have
dominated the long-wear liquid foundation development for over twenty
years due to their excellent sensory and wear characteristics, silicones
are synthetic and strongly associated with “non-natural” perceptions.
Further limitation of silicone usage is also expected due to growing regu-
latory scrutiny and non-governmental organizations’ objection. In addi-
tion, in the past several years, there have been growing concerns about
“microplastics” as persistent toxic pollutants in the environment (esp.
in oceans). Many cosmetic companies are taking actions to voluntarily
phase out usage of “microplastic” ingredients (e.g., silicone crosspoly-
mers, Nylon-12 micro-particles) in their products. While great efforts
have been made to replace “microplastic” fillers and silicone-based
ingredients (film-formers, elastomers, and emulsifiers) in long-wear cos-

metic products with non-plastic or non-silicone materials such as natural
or biodegradable particles or polymers, achieving the same performance
(esp. long-lasting and sensorial feel) is still a great challenge in cosmetic
research and development.
Acknowledgements
The authors would like to thank Hubert Lam and Yun Shao (KOBO) for
pigments and fillers discussion, Dr. Ronni Weinkauf, Mohamed Kanji and
L’Oreal Research & Innovation Department for supporting this work.
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16

Factors Affecting Cosmetics

L’Oreal Research and Innovation, Clark, NJ, USA

Keywords: Face, skin, foundation, make-up, silicone resin, silicone film-former,

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

16.2 Factors Affecting Adhesion to Skin: Skin

Epidermis Epidermal ridge

Figure 16.1 Structure of human skin.

16.2.1 Skin Types

16.2.2 Surface Free Energy of Skin

16.2.3 Skin Young’s Modulus

Table 16.1 Summary of skin surface free energy values on volar

16.2.4 Skin Surface Roughness

Table 16.3 Mean skin surface texture parameter Sa (in

also increased skin surface roughness, for example, about 2 µm difference

16.2.5 Wetting and Spreading of Sebum and Sweat

16.3 Factors Affecting Adhesion to Skin: Formulation

Anhydrous Stick/Balm O/W or Hydrogel

W/O Fluid (Silicone)

Primary Acrylates/ Trimethyl­ Trimethyl­ Acrylates/ Trimethyl­ Polypropyl­

Table 16.5 An exemplary long-wear liquid foundation formulation disclosed in

As illustrated in both Table 16.4 and Table 16.5, a typical water-in-­

16.3.1 Volatile Fluids

Isohexadecane 0.79 23.2 5.2 210 - 250 ---

good ‘spreadability’ and a luxurious, comfortable feel on skin [29]. D5 is

Table 16.7 Commonly used cosmetic fluids in long-wear foundations.

Trisiloxane Volatile CH3 CH3 CH3

Dimethicone Volatile CH3 CH3 CH3

Dimethicone Semi-volatile CH3 CH3 CH3

Dimethicone Non-volatile CH3 CH3 CH3

Methyl Trimethicone Volatile Si(CH3)3

Phenyl Trimethicone Non-volatile Si(CH3)3

Trimethylsiloxyphenyl Non-volatile Si(CH3)3

Esters Caprylic/Capric Non-volatile O

Triglyceride CH2O C(CH2)xCH3

Isononyl Isononanoate Non-volatile O

Table 16.7 Commonly used cosmetic fluids in long-wear foundations. (Continued)

Diisostearyl Malate Non-volatile O O

C18H37O CCHCH2C OC18H37

Alcohol Octyldodecanol Non-volatile CH3(CH2)9CHCH2OH

Isoparaffins Isohexadecane Non-volatile e.g. iso-C16H34 mixtures

Isododecane Volatile e.g.

Polymer Hydrogenated Non-volatile CH3

16.3.2 Treated Pigments

Dispersed in the external phase (silicone/oil), pigments used in long-

16.3.2.1 Silicone Surface Treatment

16.3.2.2 Amino Acid Surface Treatment

Table 16.8 Commonly used pigment surface treatment chemistries.

Dimethicone CH3 CH3 CH3

Disodium Stearoyl Glutamate C H COO-

Isopropyl Titanium CH3 O O

16.3.2.3 Silane Surface Treatment

Contact Angle (water) Contact Angle (oil)

16.3.2.4 Organo-titanate Surface Treatment

16.3.2.5 Hybrid Surface Treatment Chemistries

16.3.2.6 Surface Treatment Chemistry Affects Formulation

Figure 16.5 Viscosity of dispersions of untreated and treated titanium dioxides.

TTB : 143° FHS : 119° NAI : 74°

Table 16.9 Commonly used silicone film-formers in color cosmetics.

Table 16.9 Commonly used silicone film-formers in color cosmetics. (Continued)

16.3.3.1 MQ Silicone Resins

Figure 16.7 Structure illustration of an MQ resin.

(powder), Wacker TMS 805 (powder), Dow MQ-1600 (flake), Momentive

Primary Acrylates/ Trimethyl Trimethyl Acrylates/ Trimethyl Polypropyl

As illustrated in both Table 16.4 and Table 16.5, a typical water-in-