Application and Dispersion

of
Nano Pigments for Color Cosmetics

Yun Shao, Ph.D.

Kobo Products, Inc.

New Jersey, USA
Outline

1. Introduction of nano pigments

2. Comparison of color strength

3. Dispersion and color development of nano pigments

4. UV protection by nano pigments

5. Color development of organic lakes

6. Conclusions
1. Introduction

Common Iron oxides

Color General Formula Shape Size (m)

Red Fe2O3 Spheroid 0. 2 ~ 0.5
Yellow Fe2O3 . H2O Acicular 0.1 ~ 0.25 x 0.6 ~ 0.8
Black FeO . Fe2O3 Spheroid 0. 2 ~ 0.5
Tan ZnO . Fe2O3; MgO . Fe2O3 Acicular 0.2 ~ 0.3 x 1 ~ 1.5
Brown Blend of R,Y and B Mixed 0.2 – 0.5
1. Introduction

Common Iron oxides

Color General Formula Shape Size (m)

Red Fe2O3 Spheroid 0. 2 ~ 0.5
Yellow Fe2O3 . H2O Acicular 0.1 ~ 0.25 x 0.6 ~ 0.8
Black FeO . Fe2O3 Spheroid 0. 2 ~ 0.5
Tan ZnO . Fe2O3; MgO . Fe2O3 Acicular 0.2 ~ 0.3 x 1 ~ 1.5
Brown Blend of R,Y and B Mixed 0.2 – 0.5

Pigmentary Titanium Dioxide

Structure: Rutile or Anatase

Formula: TiO2
Size: 0.15 - 0.25 m
Generation of color
1. TiO2

White light White light

Scattering
Refractive Index:
2.76 (R), 2.52 (A) Higher opacity

• White color (or opacity) is generated by scattering light.

• Maximum scattering occurs when the particle size is around 0.2 m.
When size gets smaller, it will loose opacity and get transparent
Generation of color
2. Iron Oxides
White light White light
Red Red

Scattering
Absorption
Color Stronger & Deeper
R.I.: 2.90 (R), 2.26 (Y), 2.42 (B)

• Color is generated by both Scattering and Absorption

• Absorption will increases as the size decreases
• Maximum scattering occurs when size is around 0.2 m
Drawbacks of pigmentary grades

1. High refractive index leads to strong scattering and high opacity

which results in a dull appearance

2. Large particle size often generates unpleasant skin feel

3. Size reduction can improve skin feel and absorption, but increase
the opacity in most cases.

4. Primary particle size now comes into play

Transparent pigments
Transparent pigments

1. Transparent oxides

Particle size: 100 nm in length, 10 - 20 nm in width

Application: automotive paints
wood finishes
artist colours
industrial coatings
some plastic applications
cosmetics
Transparent pigments

1. Transparent oxides

Particle size: 100 nm in length, 10 - 20 nm in width

Application: automotive paints
wood finishes
artist colours
industrial coatings
some plastic applications
cosmetics

2. Transparent TiO2

Particle size: 10 - 60 nm, larger size for some grades

Application: mainly for use as sunscreens
Common nano iron oxides

Primary particle Mean Particle

Product Supplier
size (m) Size (m)
Trans-oxide Red Cookson Matthey 0.02 x 0.1 54.9
Tarox TRR -100 Sakai 0.02 x 0.1 72.5
Ferroxide Red Rockwood 0.08 – 0.1 ---

Trans-oxide Yellow Cookson Matthey 0.02 x 0.1 56.9

Tarox TRY-100 Sakai 0.02 x 0.1 72.7

Trans-oxide Black Cookson Matthey ~ 0.01 ---

Black NF Kobo 0.2 2.1

Ferroxide Orange Rockwood 0.07 ----

Primary Particle Aggregate Agglomerate

New Grade of nano iron oxide

SEM Pictures of Iron Oxides (from Titan Kogyo)

Conventional
FRO-3-LP Pigmentary Oxide
Transparent Oxide
Particle shape Spherical Acicular Irregular
Particle size (nm) 30 20 x 100 700
Oil Absorption
14 48 12
(cc/100g)
Specific Surface
37 120 3
Area (m2/g)
Less aggregation and easy to disperse
Nano TiO2 for color cosmetics

KQ-1 from ISK

Crystal form Rutile

TiO2 (%) 95-99

Surface Treatment Al(OH)3

Specific Surface Area
23-27
(m2/g)
Particle size (nm) 60

100nm
- High UV-A protection
- Low oxidation/photocatalytic activity
- Moderate opacity (to be discussed)
Nano TiO2 for color cosmetics

ST-490 from Titan Kogyo

Crystal form Rutile

TiO2 (%) 94

Surface Treatment Al(OH)3

Specific Surface Area
130
(m2/g)
Particle size (nm) 150

- UV-A protection
- Fan shape
- Easy to disperse
2. Comparison of color strength
Color Analysis (CIE Lab) of Tint Strength
(std: C33-128 Cosmetic Russet; C33-8073 Cosmetic Yellow)
2. Comparison of color strength
Color Analysis (CIE Lab) of Tint Strength
(std: C33-128 Cosmetic Russet; C33-8073 Cosmetic Yellow)

15 Red
Yellow
10

0
ΔL Δa Δb ΔC ΔH ΔE
-5

-10

-15

Color Strength vs. Std

Trans Red 49.0%
Trans Yellow 83.5%
2. Comparison of color strength
Color Analysis (CIE Lab) of Tint Strength
(std: C33-128 Cosmetic Russet; C33-8073 Cosmetic Yellow)

15 Red 15

Yellow Red
10 10 Yellow

5
5
0
ΔL Δa Δb ΔC ΔH ΔE 0
-5 ΔL Δa Δb ΔC ΔH ΔE

-5
-10

-15 -10

Color Strength vs. Std Color Strength vs. Std

Trans Red 49.0% TRR-100 56.9%
Trans Yellow 83.5% TRY-100 84.6%
Iron oxide dispersion (CMKP75R) -effect of size
1. 75% ITT treated red iron oxide in cyclomethicone
2. Dispersant : KP-575
Color Analysis (CIE Lab) of Masstone

Premix 1 2 3
35
30
25
20
15
10
5
0
L a b

19 0.54 0.53 0.51 m No effect of additional grinding

can be observed
Premix 1st 2nd 3rd
CMKP75R Dispersion : Masstone
Dried Drawdown
40

Premix 1 2 3
30

20

10

0
L a b

More grinding makes color

19 0.54 0.53 0.51 m • Darker

• Bluer
Premix 1st 2nd 3rd
CMKP75R : Tint strength comparison
Iron oxide : TiO2 = 15 :85
Color Analysis of Tint Strength

Premix 1st 2nd

60

40

20

0
L a b

Premix 1st 2nd 3rd • Similar to dried masstone

• More grinding results in

higher color strength
Silane treated TiO2 dispersion : Effect of Size
Dispersant: Abil EM 97
Solids: 70% Color and Size Analysis

99 L Size 0.8

98 0.6

Size ( m m)
97 0.4

96 0.2

95 0
Premix 1st 2nd

• More grinding results in

slightly lower brightness
• Crowding effect
Premix 1st 2nd
Tint strength comparison : silane treated TiO2
TiO2 : Black iron oxide = 85 :15 L
53

51

49

47

45
Premix 1st 2nd

a b
0

-2
-4
-6
-8
Premix 1st 2nd Premix 1st 2nd
-10

More grinding Higher opacity(Opposite to masstone)

Bluer Color
3. Dispersion of the pigment and color development

• General mechanism : • Formulation Considerations :

› Shear force › Primary particle size
› Impact action › Surface treatment
› Carrier
› Dispersant
Surface Treatment -- Pre-Wetting of the Pigment
Untreated Treated
15nm TiO2 : 45% *
A B Treatment : Methicone (B & D)
w/o dispersant

Vehicle : Cyclopentasiloxane
Dispersant : 10 % KF-6017 (C & D)

* note : in mix A, only 33% TiO2

was used (maximum amount
possible)

Chunky paste Viscous slurry

C D
w/ dispersant

Easy handling
Better dispersion

Chunky paste Fluid

Common surface treatments
Surface Compatible
Chemical
property vehicle
Metal Soap (AHSA)
Ester
Isopropyl Titanium Lipophilic
Oil
Triisostearate
Methicone
Organic Silicones
Dimethicone Hydrophobic
coating Ester
Triethoxy Caprylylsilane
Lipophobic and
C9-15 Fluoroalcohol phosphate Silicones
Hydrophobic
Water
Simethicone Amphoteric Oil
Silicones
Triethanolamine
Hydrophilic Water
Polyol
Silica
Inorganic Alumina
Hydrophilic Water
coating Zirconium oxide
Sodium hexametaphosphate
Effect of size on surface treatment and dispersibility

Nano pigment:
• Small primary particle size, large surface area
• High surface energy for more severe aggregation and reactivity

Surface treatment: Needs more coating

Dispersion: Low pigment load and hard to grind

% of Solids% in
Pigment Surface Area
Coating DC 5225C
C33-218 Cosmetic Russet < 10 m2/g 1 –2 70
Trans-oxide Red ~ 80 m2/g 10 30
Nano iron oxide in C12-15 alkyl benzoate

Iron Red Iron Yellow

TN45TOR T N70R TN45TOY TN55Y
Raw Pigment Transoxide Pigmentary Transoxide Pigmentary
Surface treatment TCS ITT TCS ITT
Solids,% 45 70 45 70
Viscosity, cPs 178,400 247,000 210,000 85,000
Dispersion size (nm) 112 290 102 350

TCS: triethoxy carprylylsilane; ITT: isopropyl titanium dioxide

TN45TOR TN70R TN45TOY TN55Y

Nano iron oxides in ester ---tint strength

Color Analysis (CIE Lab) of Tint Strength

20 TN45TOR
TN45TOY
15

10

TN45TOR TN70R 0
ΔL Δa Δb ΔC ΔH ΔE
-5

-10

Color Strength vs. Std

Trans Red 69.3%
Trans Yellow 120.2%

TN45TOY TN55Y

TN45TOY TN55Y
Dispersion of 100 nm TiO2

Dispersion in
Isononyl Isononanoate Color Analysis of Tint Strength

0
ΔL Δa Δb ΔC ΔH ΔE
-2

-4

-6
INH65K9 IN80C TiO2 : Iron black = 85 : 15

PPS Surface PS
Dispersion % Result: Less opaque, bluer
(nm) treatment (nm)
INH65K9 100 ITT/w s 190 65
IN80C 170 ITT 263 80
Dispersion of 60 nm TiO2

Dispersion in
Cyclomethicone Color Analysis of Tint Strength

8
6

4
2
0

-2 ΔL Δa Δb ΔC ΔH ΔE

-4
-6
CM3K50KQM CM3FA70STC
-8 TiO2 : Iron black = 85 : 15
PPS Surface PS
Dispersion %
(nm) treatment (nm)
CM3K50KQM 60 MS 185 50 Result: much less opaque and more bluer

CM3FA70STC 170 MS 280 70

4. UV Protection from nano pigments

UV/Vis transmittance curves of nano iron oxides

100
Nano Yellow
UV Visible Nano red
80
Pig. yellow
Pig. red
60
T%

40

20
0.001%

0
280 320 360 400 440 480 520 560 600 640 680
Wavelength (nm)
UV/Vis transmittance curves - TiO2 Dispersions

PPS:
100
60 nm
UV Visible
80
100 nm
60 180 nm
T%

40

20

0
280 320 360 400 440 480 520 560 600 640 680
Wavelength (nm)
5. Color development of organic lakes

Red 6 lake in synthetic wax

(SW30R6B) Formula

Raw Pigment Red 6 Ba Lake

Surface treatment ITT
Solids,% 30
Dispersion size (nm) 386

* Size of powder: 3 - 6 microns.

Premix Milled

Gloss and feel are much improved as particle size gets

milled down.
 Color development of lakes - Dispersion vs. Powder

Color property --
Red 6 Ba lake dispersion vs. powder

Masstone Tint Stre ngth

8
8
6 6

4 4

2 2

0
0
DL* Da* Db* DC DH DE
DL* Da* Db* DC DH DE -2
-2
-4

Color strength is greatly increased when the particle size

is reduced to submicron
Conclusions:
 Conclusions:

1. Nano pigments have their unique properties and require

more considerations in:
• Surface treatment
• Color development
 Conclusions:

1. Nano pigments have their unique properties and require

more considerations in:
• Surface treatment
• Color development

2. Nano pigments can provide more UVA protection and help

boost SPF.
 Conclusions:

1. Nano pigments have their unique properties and require

more considerations in:
• Surface treatment
• Color development

2. Nano pigments can provide more UVA protection and help

boost SPF.
3. Milling organic lakes is important for their color development.
 Conclusions:

1. Nano pigments have their unique properties and require

more considerations in:
• Surface treatment
• Color development

2. Nano pigments can provide more UVA protection and help

boost SPF.
3. Milling organic lakes is important for their color development.

4. Although nano pigments have been available on marketplace

for many years, use in cosmetics still needs to be explored.