Silicone dispersants - Kobo Products Inc.

Silicone Dispersants 

and Physical Sunscreen Dispersions 

Recent Developments 

David Schlossman & Yun Shao, Ph.D. 

Kobo Products, Inc. 

The European Sunfilters 

Conference - Paris 

October 14-15, 2003 

www.koboproducts.com

Outline 

• Silicone dispersants 

– Silicone Polyether Copolymers 

– Silicone/Acrylate Copolymers 

• Physical sunscreen dispersions 

– Common elements influencing size reduction 

– Comparisons among silicone dispersants and 

also with a non-silicone dispersant 

• Formulations 

• Conclusions 


Silicone Dispersants 

• Functions 

– enhance the wetting of each pigment particle 

– stabilize dispersed particles 

treated 

pigment 

treated 

pigment 

silicone 

dispersant 

treated 

pigment 

treated 

pigment 


Popular Silicone Polyether Copolymers 

Product INCI name % Active HLB Supplier 

DC 5225C 

formulation aid 

SF1528 

Cyclopentasiloxane (and) 

PEG/PPG-18/18 Dimethicone 

Cyclopentasiloxane (and) 

PEG/PPG-20/15 Dimethicone 

10 1.7 Dow Corning 

10 2-3 GE Silicones 

Abil EM 90 Cetyl PEG/PPG-10/1 Dimethicone 100 4-6 Goldschmidt 

Abil EM 97 

Bis-PEG/PPG-14/14 Dimethicone 

(And) Cyclopentasiloxane 

85 4-6 Goldschmidt 

KF-6107 PEG-10 Dimethicone 100 4.5 Shin-Etsu 

The hydrophilicity or organophilicity of the copolymer 

are typically adjusted by varying the silicone content, 

side chains and EO/PO ratios. 


Popular Silicone Polyether Copolymers 

CH 3 CH 3 CH 3 

CH 3 

CH 3 Si O Si O Si O Si CH 3 

CH 3 

(CH 2 ) 3 

CH 3 CH 3 

m 

n 

O 

PE 

DC 5225C, SF1528 

KF-6017 

CH 3 

Si 

CH 3 

CH 3 

CH 3 

O Si O Si O Si O 

CH 3 

PE Si O Si 

R 

(CH 2 ) 3 

CH 3 

O 

PE 

CH 3 

m 

n 

CH 3 

Si CH 3 

CH 3 

Abil ® EM 90 

CH 3 

CH 3 CH 3 

O Si PE 

CH 3 CH 3 CH m 3 

Abil ® EM 97 

PE = (CH 2 ) 3 -O-(C 2 H 4 O) x -(C 3 H 6 O) y -H 

R = Alkyl -(CH 2 ) x -CH 3 


Acrylic / Silicone Copolymers 

Product INCI name % Active Supplier 

KP-575 

Cyclopentasiloxane (And) Acrylates/ 

Ethylhexyl Acrylate/ Dimethicone 

Methacrylate Copolymer 

30 Shin-Etsu 

CH 2 

=C(CH 3 

)COO(CH 2 

) 3 

- Silicone 

+ CH 2 

=CHCOO - Alkyl + CH 2 

=CHCOOH 

Silicone 

Alkyl 

COOH 

Acryl Polymer 

COOH 


Physical Sunscreen Dispersions 

• Common elements influencing dispersion 

particle size : 

– grinding parameters (sheer force and collision 

of particles) 

– dispersion formula (composition) : 

• micronized pigment 

• surface treatment 

• vehicle (silicone, hydrocarbon, ester) 

• dispersant 


Effect of Surface Treatment & Dispersant 

Untreated 

Treated 

w/o dispersant 

A 

B 

15nm TiO 2 

: 45% * 

Treatment : Methicone (B & D) 

Vehicle : Cyclopentasiloxane 

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

* note : in mix A, only 33% TiO 2 

was used (maximum amount 

possible) 

w/ dispersant 

Chunky paste 

C 

Viscous slurry 

D 

Chunky paste 

Fluid 


Dispersion Formulations (Composition) 

• Micronized TiO 2 

or ZnO pigment 

– primary particle sizes of 10 to 200 nm / indicative 

of UVA/B ratio and visible light scattering 

• Surface treatment (inorganic and organic) 

– provides physical and chemical stability 

– modifies pigment surface to hydrophobic 

and/or lipophilic 

– pre-wets the pigment surface, enhances flow 

characteristics and stability in the vehicle 

– decreases the adsorption of the dispersant 

– improves tactile properties 


Organic Surface Treatments for Pigments 

• Hydrophobic treatments 

– Methicone, Dimethicone 

• Lipophilic treatments 

– Isopropyl Titanium Triisostearate (ITT) 

• Hydrophobic / Lipophilic treatments 

– Triethoxy Caprylyl Silane 

– Aluminum Hydroxide and Stearic Acid (AHSA) 

– ITT / TCS Crosspolymer (INCI name pending) 

– ITT / Methicone Crosspolymer (INCI name pending) 


Chemical Structures of 

Crosspolymer Treated Pigments 

ITT/TCS Crosspolymer: R = C 8 

H 17 

ITT/Methicone Copolymer: R = CH 3 

ITT/FOTS Crosspolymer: R =C 8 

F 17 

Provisional US patent application 

No. 60/472,527 


Dispersions with 15nm TiO 2 

Influence of Silicone Dispersants 

Formulas 

Ingredient DC40TS CMKP45TS CM3K50S4 CEM35TS 

15nm TiO 2 (AHSA) 40% 45% 50% 35% 

DC3225C 60% --- --- --- 

KP-575 --- 10% --- --- 

KF-6017 --- --- 10% --- 

EM-97 --- --- --- 3% 

Test Results 

Ingredient DC40TS CMKP45TS CM3K50S4 CEM35TS 

Viscosity (cPs) 100,000 126,000 159,000 624,000 

Particle size (nm) 148 159 143 290 

Index of aggregation 9.9 10.6 9.5 19.3 

TiO 2 (%) 33 37 41 33 


UV/Vis Transmittance of 15nm TiO 2 Dispersions 

Particle 

size 

Ext. ratio 

308/360 

Ext. ratio 

308/524 

l max. 

(nm) 

DC40TS 148 3.6 26.0 290 

CMKP45TS 159 2.5 12.7 295 

CM3K50S4 143 3.4 27.2 289 

CEM35TS 290 1.4 4.7 311 

DC40TS CMKP45TS CM3K50S4 CEM35TS 

100 

80 

60 

40 

DC40TS 

CMKP45TS 

CEM35TS 

20 

CM3K50S4 

TiO 2 : 0.001% 

0 

280 320 360 400 440 480 

Wavelength (nm) 



Influence of Silicone Dispersants 

Formulas 

Ingredient CM3K25VM CMKP25VM CME730VM 

SIV-MS7 (alumina and 

methicone) 

25% 25% 30% 

KF-6017 12% --- --- 

KP-575 --- 12% --- 

Abil EM 97 --- --- 10% 

Cyclopentasiloxane 63% 63% 60% 

Test Results 

Ingredient CM3K25VM CMKP25VM CME730VM 

Viscosity (cPs) < 100 19 100,000 

Particle size (nm) 110 104 238 

Index of aggregation 11.0 10.4 23.8 

TiO 2 (%) 20 20 24 



Particle 

size 

Ext. ratio 

308/360 

Ext. ratio 

308/524 

l max. 

(nm) 

CM3K25VM 110 7.9 93.0 278 

CMKP25VM 104 8.0 164.8 < 280 

CME730VM 238 2.0 9.1 302 

CM3K25VM CMKP25VM CME730VM 

100 

80 

CM3K25VM 

CMKP25VM 

60 

40 

CME730VM 

20 

TiO 2 : 0.001% 

0 

280 320 360 400 440 480 



Dispersions with 20-35 nm TiO 2 

Influence of Silicone Dispersant 

Formulas 

Ingredient CM3K60TM CMKP60M262 

35 nm TiO2 

(methicone) 

20 nm TiO2 (alumina and 

dimethicone) 

Test Results 

60% --- 

--- 60% 

Cyclopentasiloxane 30% 28% 

KF-6017 10% --- 

KP-575 --- 12% 

Ingredient CM3K60TM CMKP60M262 

Viscosity (cPs) 102,000 12,000 

Particle size (nm) 179 143 

Index of aggregation 5.1 7.2 

TiO2 (%) 56 53 


UV/Vis Transmittance of 20-35nm TiO 2 Dispersions 

Particle 

size 

Ext. ratio 

308/360 

Ext. ratio 

308/524 

l max. 

(nm) 

CM3K60TM 179 1.5 6.7 318 

CMKP60M262 143 1.9 9.0 299 

100 

CM3K60TM 

CMKP60M262 

80 

60 

40 

CM3K60TM 

20 

CMKP60M262 

TiO 2 : 0.001% 

0 

280 320 360 400 440 480 



Dispersions with ZnO 

Influence of Silicone Dispersant 

Formulas 

Ingredient CM3K50XZ4 CMKP50XZ4 CM3K40HP1 

20 - 30 nm ZnO 

(methicone) 

Z-Cote HP-1 (

UV/Vis Transmittance of ZnO Dispersions 

Particle 

size 

Ext. ratio 

308/360 

Ext. ratio 

308/524 

l max. 

(nm) 

CM3K50XZ4 145 1.1 37.0 358 

CMKP50X4 147 1.0 32.5 359 

CM3K40HP1 250 0.9 7.8 371 

CM3K50XZ4 CMKP50XZ4 CM3K40HP1 

100 

80 

CMKP50XZ4 

60 

40 

20 

CM3K50XZ4 

CM3K40HP1 

ZnO TiO 2 : : 0.005% 0.001% 

0 

280 320 360 400 440 480 




Influence of the Dispersion Formula 

Formulas 

Ingredient CM3K25VM TNP40VTTS TNP55VTTS 

10nm TiO2 (methicone) 25% --- --- 

10nm TiO2 (ITT/TCS) --- 40% 55% 

KF-6017 12% --- --- 

Cyclopentasiloxane 63% --- --- 

C12-15 Alkyl benzoate --- 57% 42% 

Polyhydroxy stearic 

acid 

--- 3% 3% 

Test Results 

Ingredient CM3K25VM TNP40VTTS TNP55VTTS 

Viscosity (cPs) 100 150 10,000 


TiO2 (%) 19.5 32.0 44.0 



Particle 

size 

Ext. ratio 

308/360 

Ext. ratio 

308/524 

l max. 

(nm) 

CM3K25VM 110 7.9 93.0 278 

TNP40VTTS 100 6.9 74.0 274 

TNP55VTTS 100 6.9 74.0 274 

CM3K25VM TNP40VTTS TNP55VTTS 

100 

80 

CM3K25VM 

60 

40 

TNP40VTTS 

TNP55VTTS 

(superimposed) 

20 

TiO 2 : 0.001% 

0 

280 320 360 400 440 480 



Dispersions with 14 nm TiO 2 

Influence of Dispersants & Vehicles 

Formulas 

Ingredient PM9P60M170 PM9P50M170 TNP50M170 CM3K40M170 

14nm TiO2 (alumina 

and dimethicone) 

60% 50% 50% 40% 

Isododecane 37% 47% --- --- 

C12-15 Alkyl benzoate --- --- 47% --- 

Cyclopentasiloxane --- --- --- 46% 

Polyhydroxy stearic 

acid 

3% 3% 3% --- 

KF-6017 --- --- --- 14% 

Test Results 

PM9P60M170 PM9P50M170 TNP50M170 CM3K40M170 

Viscosity (cPs) 180 20 600 275 

Particle size (nm) 172 110 165 165 

Index of aggregation 12.3 7.9 11.8 11.8 

TiO 2 (%) 46.5 38.8 31.0 38.8 


UV/Vis Transmittance of 14 nm TiO 2 Dispersions 

Particle 

size 

Ext. ratio 

308/360 

Ext. ratio 

308/524 

l max. 

(nm) 

PM9P60M170 172 3.3 12.3 281 

PM9P50M170 110 5.4 55.0 277 

TNP50M170 165 2.9 10.3 274 

CM3K40M170 165 4.2 31.2 280 

PM9P60M170 PM9P50M170 TNP50M170 CM3K40M170 

100 

80 

PM9P50M170 

CM3K40M170 

60 

40 

PM9P60M170 

TNP50M170 

20 

TiO 2 : 0.001% 

0 

280 320 360 400 440 480 



Dispersions with 20-30 nm ZnO 

Influence of Dispersants & Vehicles 

Formulas 

Ingredient TNP50ZSI TNP50ZCLS CMKP50XZ4 

20-30 nm ZnO 

(methicone) 

20-30 nm ZnO 

(Triethoxycapryl Silane) 

Test Results 

--- --- 50% 

50% 50% --- 

C12-15 Alkyl Benzoate 47% 47% --- 

Poyhydroxystearic acid 3% 3% --- 

Cyclopentasiloxane --- --- 40% 

KP-575 --- --- 10% 

TNP50ZSI TNP50ZCLS CMKP50XZ4 

Viscosity (cPs) 100 60 100 


Index of aggregation 5.2 4.4 5.9 

ZnO (%) 47.0 47.0 47.0 


UV/Vis transmittance of ZnO Dispersions 

Particle 

size 

Ext. ratio 

308/360 

Ext. ratio 

308/524 

l max. 

(nm) 

TNP50ZSI 130 1.1 29.0 358 

TNP50ZCLS 110 1.0 35.0 360 

CMKP50XZ4 147 1.0 32.5 359 

TNP50ZSI TNP50ZCLS CMKP50XZ4 

100 

80 

TNP50ZCLS 

TNP50ZSI 

60 

CMKP50XZ4 

40 

20 

ZnO TiO 2 

: : 0.005% 0.001% 

0 

280 320 360 400 440 480 



Sunscreen Formulations 

Formulation type Dispersion % Active SPF 

SPF per 

% active 

Sunscreen spray TNP50ZCLS 8.9% 15 1.7 

Water-in-silicone emulsion CM3K25VM 11.7% 40 3.4 

Water-in-silicone foundation CMKP60M262 13.0% 44 3.4 

Water-in-oil emulsion TNP50ZSI 14.1% 25 1.8 

Water-in-oil emulsion TNP40VTTS 9.3% 24 2.6 

Water-in-oil emulsion 

(w/ octylmethoxycinnamate) 

TNP40VTTS 3.1% 50 


Extinction ratios 

Pigment 

TiO 2 

ZnO 

Primary particle size 

Ratio (1) 

Ratio (2) Maximum 

305/360 305/524 absorption @ 

10 nm 7.0 - 8.0 70 - 90 275 nm 

15 nm (High Speed TM Disp) 4.5 - 5.5 50 - 55 280 - 290 nm 

15 nm (High Solids ® Disp) 3.4 - 3.9 11 - 16 290 - 305 nm 

20 nm 2.0 9 300 nm 

35 nm 1.5 - 2.0 7 - 17 315 nm 

150 nm 1.1 2.6 318 nm 

20 nm 1.0 - 1.1 30 - 37 360 nm 

60-100 nm 1.1 6.3 371 nm 

120 nm 0.9 2.9 375 nm 

(1) 305/360 ratio : indication of UVB/UVA ratio 

(2) 305/524 ratio : indication of transparency 


Conclusions (1) 

• Among the silicone dispersants studied, acrylic 

silicone copolymers provide the best wetting and 

stabilizing in cyclopentasiloxane. 

• Titanium dioxide dispersions with particle sizes 

of 100 nm and viscosity of 100 cPs can be 

produced with silicone and non-silicone 

dispersants (and to date higher pigment solids 

may be obtained with non-silicone dispersants) 


Conclusions (2) 

• The degree of dispersion can be controlled by the 

dispersion formula besides the milling. 

• The surface treatment is paramount to 

maintaining dispersion stability. 

• Additional studies on the influence of smaller 

particle size and more fluid dispersions on UV 

attenuation and spreading in formulations are 

required. 


Acknowledgements 

• Scott Holzapfel, Joe Sprovkin and Pascal Delrieu 

for their support by making the formulations and 

aid with the presentation. 

This presentation is available for download and view on 

our web site (www.koboproducts.com). 

Formulations described here are fully listed in the 

downloadable version. 



SPF 15 spray formula with TNP50ZCLS 

Phase Ingredient Trade Name/Vendor % 

A Deionized water --- 69.8 

Butylene Glycol --- 3.0 

Phenoxyethanol (And) Methylparaben (And) Propylparaben 

(And) Ethylparaben (And) Butylparaben (And) Isobutylparaben 

Phenonip 1.0 

B C14-22 Alcohols (And) C12-20 Alkyl Glucoside Montanov L 4.5 

Zinc Oxide (And) C12-15 Alkyl Benzoate (And) 

Polyhydroxystearic Acid (And) Triethoxy Caprylylsilane 

TNP50ZCLS 19.0 

Squalane Phytolane LS 1.0 

Tridecyl Stearate Liponate TDS 1.0 

Tocopheryl Acetate --- 0.2 

C 

Acrylamides Copolymer (And) Mineral Oil (And) C13-14 

Isoparaffin (And) Polysorbate 85 

Sepigel 501 0.5 


SPF 40 water-in-silicone with CM3K25VM 



Sodium Chloride --- 0.5 

B 

Cetyl Dimethicone Copolyol &(And) Polyglyceryl- 4 - 

Isostearatehexyl Laurate 

Abil WE -09 5.0 

Rosemary oleoresin --- 0.2 

Cyclopentasiloxane & Titanium Dioxide & Alumina & (And) 

Dimethicone Copolyol & Methicone 

CM3K25VM 60.0 

C PEG-150/Smdi Copolymer Aculyn 44 2.0 

Diazolidinyl Urea Germall Plus 0.2 


SPF 44 liquid foundation with CMKP60M262 


A Cyclopentasiloxane (And) PEG/Ppg-20/15 Dimethicone SF1528/GE 12.5 

Cyclopentasiloxane Dimethicone/Vinyldimethicone 

Crosspolymer 

SFE839/GE 1.25 

Cyclopentasiloxane SF1202 17 

Bis-Phenylpropyl Dimethicone SF1555 1 

Polymethylsilsesquioxane Tospearl 2000 5 

Cyclomethicone Trimethylsiloxysilicate SS4230 4 

Phenoxyethanol (And) Methylparaben (And) Propylparaben 

(And) Ethylparaben (And) Butylparaben (And) Isobutylparaben 

Phenonip 1 

B 

Titanium Dioxide (And) Cyclopentasiloxane (And) 

Acrylates/Ethylhexyl Acrylate/Dimethicone Methylacrylate 

Copolymer (And) Alumina (And) Silica (And) Methicone 

Yellow Iron Oxide, Decamethyl Cyclopentasiloxane,Dimethicone 

Copolyol, Triethoxy Caprylylsilane 

Red Iron Oxide, Decamethyl Cyclopentasiloxane,Dimethicone 


Black Iron Oxide, Decamethyl Cyclopentasiloxane,Dimethicone 


CMKP60M262 25 

FA50YSI 6 

FA55RSI 1 

FA60BSI 0.4 

C Water QS 

Butylene Glycol Butylene Glycol 12.5 

Polysorbate 20 RITAbate 20/RITA 0.5 

Sodium Chloride Sodium Chloride 1 

Glycerin Glycerin 2 

D Ethanol SD 39C 5 


SPF 25 W/O emulsion with TNP50ZSI 


A Deionized water --- 40 

Xathan Gum --- 0.15 

Magnesium sulphate --- 2 

Propylene Glycol --- 3 

B 

C12-15 Alkyl Benzoate (And) Zinc Oxide (And) 

Polyhydroxystearate (And) Triethoxy Caprylylsilane 

TNP50ZSI 30 

Isostearyl Neopentanoate Ceraphyl 375 (ISP) 16.95 

Glyceryl Dilaurate Emulsynth GDL (ISP) 1 

PEG-30 Dipolyhydroxystearate Arlacel P135 (ICI) 3 

C Polyethylene CL-2080 2.5 

Polyethylene Liposatin PE35 (Lipo) 1 

Diazolidinyl urea & Iodopropynyl Carbamate & Propylene Glycol Liquid Germall Plus (ISP) 0.4 


SPF 24 W/O emulsion with TNP40VTTS 



Xathan Gum --- 0.15 

Magnesium sulphate --- 2 

B 

C12-15 Alkyl Benzoate (And) Titanium Dioxide (And) Alumina 

(And) Polyhydroxystearate (And) ITT / TCS Crosspolymer 

TNP40VTTS 30 

Isostearyl Neopentanoate Ceraphyl 375 (ISP) 15.85 

Rosemary Oleoresin HQ 3401 (Hilltech) 0.1 

Glyceryl Dilaurate Emulsynth GDL (ISP) 1 

PEG-30 Dipolyhydroxystearate Arlacel P135 (ICI) 3 

C16-18 Tryglycerides Cegesoft GPO (Cognis) 0.5 

C Polyethylene CL-2080 2 

Polyethylene Liposatin PE35 (Lipo) 1 

Oat flour Oat flour (Textron) 0.5 

Beta glucan Dragro betaglucan (Symrise) 1 

Diazolidinyl urea & Iodopropynyl Carbamate & Propylene Glycol Liquid Germall Plus (ISP) 0.4 

Soybean(glycine soja)protein & oxido-reductase Preregen (Centerchem) 3 


SPF 50 W/O emulsion with TNP40VTTS 


A Deionized Water --- 52.4 

Sodium Chloride --- 0.5 

Propylene Glycol --- 3.0 

Allantoin --- 0.2 

Methyl Paraben --- 0.2 

B 

C12-15 Alkyl Benzoate (And) Titanium Dioxide (And) Alumina 

(And) Polyhydroxystearate (And) Isopropyl Titanium 

TNP40VTTS 10.0 

Triisostearate (And) Triethoxy Caprylylsilane 

Microcrystaline Wax (Strahl & Pitsch) 0.5 

Wax Abil Wax 9801 (Goldsmidt) 1.0 

Octyl stearate Cetiol 868 (Cognis) 4.0 

Shea Butter (Cognis) 1.0 

PEG-30 dipolyhydroxystearate Arlacel P135 (ICI) 2.5 

Polyglyceryl-4 Isostearate (And) Cetyl Dimethicone Copolyol 

(And) Hexyl Laurate 

Abil WE 09 (Cognis) 2.5 

Cyclomethicone DC 345 (Dow Corning) 1.0 

Propyl Paraben --- 0.1 

Cetearyl Alcohol (And) Cetearyl Phosphate Crodafos CES (Croda) 1.0 

Octyl Methoxy Cinnamate (BASF) 8.5 

Octocrylene (BASF) 10.0 

Rosemary Extract 

Romary Oleoresin HQ 3401 

(Hilltech) 

Benzophenone-3 (BASF) 1.5 

0.2

Silicone dispersants - Kobo Products Inc.

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