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Pigment Surface Treatments

Kobo Products, Inc.South Plainfield, NJ 07080, USA

1. Common surface treatments and their properties

2. Hybrid treatment

3. Hydrophilic treatment

4. Conclusions

Outline

• Modifies pigment surface to hydrophobic

and/or lipophilic

• Improve the skin feel

• Improve the chemical stability of metal oxides

• Improves pigment wetting and size reduction during dispersion process

• Improved dispersion stability and formula stability

1. Surface Treatment

Pigment

OH

OH

OH

OHHOHO

HO

HOHO

Common and Popular Surface Treatment

for Color Cosmetics

Si O Si O Si CH3H3C

CH3

CH3

CH3

H

CH3

CH3

OO

HH OO

HO Si O

CH3 Si(CH3)3Si O

CH3

OH

(H3C)3Si

OO

O Si O

CH3

Si(CH3)3

Si O

CH3

O

(H3C)3SiO

HOH

O

- H2

More heat

- H2

Pigment

n - H2

PigmentHeat

Pigment

CH3

Properties:

• Very Hydrophobic• Chemically bonded and stable at pH of 3 - 9• Very popular in silicone based formulas.• Not easy for o/w or w/o formula

• Hydrogen potential -processing hazard

Methicone

Code MS

Si O Si O Si OO

CH3

CH3

CH3

CH3

CH3

CH3

OO

HH

HH

OO

SiSi

H3C

H3CCH3

CH3

O Si O

CH3

CH3

n

Pigment

n- H2O

Pigment

Properties:

• Easy to disperse in cyclomethicone• Have good slip and a more lubricious feel than methicone• No Hydrogen potential

• Hydrophobicity can be low when the reactive sites are limited.

Dimethicone

Code DS

OH

O Ti O C C17H35

O

CH3 CH

CH3

OTi

C17H35OCO OCOC17H35

OCOC17H35

pigment surface---hydrophlic

pigment surface---hydrophobic lipophilic

3

- (CH3)2CHOH

Organo Titanate

Isopropyl Titanium Triisostearate

Properties:

• Lipophilic and easy to disperse in oil, ester, hydrocarbon and silicone• Easy to grind so color can be consistent• Have excellent affinity to the skin• Suitable for cream-to-powder formula and pressed powder

• Not stable to acid

Code ITT

Kobo patent on ITT treated pigments and powders : # 4877604

Dispersion of 40% TiO2

ITT treated Untreated

Organo Titanate (II)

Metal Soap -- Magnesium Myristate

Properties:

• Creamy feel: Increased adhesion to skin and wear• Better pressability. Suitable for powders• Hydrophobic / Lipophilic

Soluble salt of Fatty Acid+

Metal salt

Fatty Acid+

Metal hydroxide

Metal soap

PigmentDeposition

Code MM

Triethoxycaprylylsilane

HO Si CnH2n+1

OH

OH

C2H5O Si CnH2n+1

OC2H5

OC2H5

O

H

H

OH OH OHOH- H2O

Si O

CnH2n+1

O

Hydrophobic

Si

- 3 C2H5OH

CnH2n+1

Opigment

OO

pigment

xHO Si CnH2n+1

OH

OH

Properties:

• Excellent hydrophobicity• Zero Hydrogen Potential, no Si-H bonds• More compatible with ester and oil

• Stable at pH = 3

(code 11S2)

Fluorinated compounds

M

O

M

O

P

OCnF2n+1CH2CH2OO

HH

Pigment Surface

Properties:• Hydrophobic • Lipophobic• Good for long wear

• Hard to wet and grind; color consistency can be an issue

Natural look

With PF treated pigments,light is scattered

With conventional (lipophilic)pigments, light is reflected

Skin OilLipophilic PigmentSkin Surface

Skin OilPF Treated PigmentSkin Surface

C9-15 Perfluoroalcohol Phosphates ( code PF)

Lecithin

Non-hydrogenated : code CL

Hydrogenated : code PC

Properties:

• Nature ingredient• Highly moisturizing• Very creamy texture and good for powder• Hydrogenated lecithin provide fair hydrophobicity, but is much less odorous and more heat stable.

Hydrophilic coating

Polyether Alkoxysilane Treatment

OC2H5

Si PEG-8

OC2H5

C2H5O

OH OH OH OH

O O O O

Si O Si

PEG-8 PEG-8

x

+

Hydrophilic treatment - Structure

PEG-8 Methyl Ether Triethoxysilane - Code SW

PEG-8 Triethoxysilane Treatment in H2O

non-treated treated

non-treated treated

non-treated treated

Immediately after mixing

After 30 seconds

After 10 minutes

Mixed 2 grs of TiO2 CR-837 in 50 ml H2O

Viscosity of metal oxide pigments premixes at 65% solids.Iron Oxide Black C33-5198TiO2 CR-837

200,000

300,000

400,000

0Untreated 1% silane

cPs

100,000

2% silane

48,400 cPs18,500 cPs

100,000

150,000

200,000

0Untreated 1% silane

50,000

2% silane

4,500 cPs 4,600 cPs

cPs


15 nm Hydrophilic TiO2

Non treated

TreatedViscosity of premix at 42% solids

500,000

1,000,000

0Untreated 5% treatment

cPs

250,000

750,000

2,800

850,000


New Hybrid Treatment

1. Modify surface energy

* US Provisional patent application No. 60/472,527

AlkoxysilaneMethiconeDimethicone

Crosslinked coating on pigment{

Design of Superdispersible Surface Treatment

Isopropyl titanium triisostearate

(ITT)+

• Captures advantages of both coatings in one single treatment. • A broader range of materials can be coated.• Allow better color retention for pigments and particle size control.

Metal Soap / ITT TTS Crosspolymer

TTS coated pigment floats almost indefinitely at pH 2

Stability of TTS Treatment Toward Acid

0.5

1.0

2.0

0

1.5

pH1 2 3 4

Over7 days

ITTMagnesium Myristate

10

20

0

30

Control NeutralWashing

Washingat pH 2

40

Hydrophobicity by Floating Test

73% in Cyclopentasiloxane75% in Mineral Oil

Viscosity of Iron Oxide Dispersions

cPs

500,000

1,000,000

1,500,000

0Untreated I T T SilaneITT/TCS

Crosspolymer

Too thickto measure

500,000

1,000,000

1,500,000


Crosspolymer

cPs

Too thickto measure

ITT/TCS (TTS) Crosspolymer Treatment

* Dispersant: 1.5 %of polyhydroxystearic acid

Viscosity of 75% Rutile TiO2 Dispersions

Out of scale

100,000

200,000

0Untreated MS ITT ITT/TCS

Crosspolymer

cPs

50,000

150,000

Silane

TTS Crosspolymer in C12-15 Alkyl Benzoate

Viscosity of 75% Anatase TiO2 Dispersions

TTM & TTDM Crosspolymer Treatments

* w/ 2.5% of PEG/PPG-20/15 dimethicone ** w/ 1.5% of polyhydroxystearic acid

Isododecane*cyclomethicone*C12-15 AlkylBenzoate**cP

s

0

100,000

200,000

300,000

400,000

ITT MS TPDM TTM TTDM

800,000

en t

2. PF + Silane = FOTS Hybrid -- Improved compatibility

PF treatment

HYBRIDTREATMENT

Silanetreatment

F3C CF2 CH2 CH2 P OH( )n m

O

3-m

PF

FOTS - Improved dispersibility- Retained lipohobicity- Popular in Japan

Silane

e n t

P F t re a t m e n t

H Y B R ID

T R E A T M E N T

F3

C C F2

C H2

C H2

P O H( )n m

O

3- m

ITT

FITT - More lipophlic and easy to formulate


3. PF + ITT = FITT Hybrid -- Improved compatibility

NT: No treatmentMS: MethiconeNNS: Methoxy Amodimethicone/Silsesquioxane Copolymer(And) Triethoxy Caprylylsilane

(WO 03/043567 A3, May 30, 2003)

4. Treatment of Organic Lakes

FD&C Blue 1 Aluminum Lake

NT MS NSS

FD&C Red 40 Aluminum Lake

NT MS NSS

2% in water, Standing over 4 days

0.125%

0.0%Red 40 Al Lake Blue 1 Al Lake

< 0.01%0.02% 0.02%

0.08%

11.1%15.3%

0.25%

Bleeding of 2% aqueous suspensions by spectrophotometry

Non-tr eated : after 1 day @ r oom tem per atu r e

NSS-tr eated : af ter 30 days @ r oom temper atur e

NSS-tr eated : af ter 30 days @ 50°C

Treatment of Organic Lakes


pH2 pH3 pH11 pH12mineral acid organic acid organic base mineral base

Effect of pH on the stability in water (2% lake in water; 1 day test)

Effect of pH on the stability in water


Methicone NSStreatment treatment

Effect of surfactants on the stability in Water

(2% lake in 2% SDS aqueous solution; 7 days test)

Conclusions

• The use of hybrid or composite materials to treat pigments can

enhance their chemical stability and wetting by multimedia.

• Organo titanates and dimethicone crosspolymer treatment was

found to be super dispersible in hydrocarbon, cyclomethicone

and ester.

• Hybrid compounds offer more benefits and will be the future for

pigment surface modification.

Coating Pros Cons

Methicone Hydrophobic H2 potential Disperses poorly in esters

DimethiconeNice feel

No H2 potentialNot as stable at low pH

Disperses poorly in esters

Alkoxysilane No H2 potential Hydrophobic

Reacts too slowly Dispersibility in esters is fair

ITT / Metal soap Lipophilic Easy to react with pigments

Not very hydrophobic, especially at low pH

Perfluorinated compounds Repel both water and oil Difficult to wet

Polysaccharide Natural product No chemical bonding

Synthetic surfactant Highly dispersible No chemical bonding

Hydrophobic

Hydrophilic

Common Treatments & Their Drawbacks

www.koboproducts.com

Novel Surface Treatment For Hydrophobicizing Pigments

Frank Mazzella, David Schlossman, and Yun Shao, Ph.D.Kobo Products, Inc.

PCITX - New YorkSeptember 28-30, 2004


Overview

• What is needed to make a good surface treatment ?

• Common used substrates.

• Common Treatments.

• Specialty Treatments.

• Summary.


• Improve performance :– Make the product Hydrophobic.– Make the product Lipophobic.– Improve the products ability to disperse in various

media.– Change the oil absorption of the product.

• Improve wear, adhesion, or other desirable attribute.

Surface Treatments : Why ?


• The surface has free hydroxyl groups or available surface moisture.– This allows the treatment to react and attach.

• Surface area to mass is low.– The smaller the particle the more treatment

required due to the larger surface area available.

• The substrate is compatible with the process.

Requirements for Good Surface Treatment


• Examples of good surface to coat :– Most metal oxides such as iron oxide and titanium

dioxide.– Starch.

• Examples of Hard to Coat surfaces :– Organic Pigments and Lakes– Polymers– Minerals such as Mica

Requirements for Good Surface Treatment


Coating Pros Cons





AlkoxysilaneNo H2 potential

HydrophobicReacts too slowly

Dispersibility in esters is fair

ITT / Metal soapLipophilic

Easy to react with pigmentsNot very hydrophobic,

especially at low pHPerfluorinated compounds Repel both water and oil Difficult to wet



Hydrophobic

Hydrophilic

Popular Hydrophobic Organic Treatments


• Crosspolymer treatments (TTS, TTB & TTM) : promote the wetting of pigments in multimedia.

• Branched Alkyl Silane treatment (BAS) : enhance wetting in non-polar media.

• Aminosilane / Silane Treatment for Hard to Treat Surfaces (HTT) : super hydrophobic; prevents bleed.

Treatments Studied


Crosspolymer Treatments


Crosspolymer Treatments - Structure

ITT/TCS Crosspolymer: R = C8H17

ITT/Methicone Copolymer: R = CH3

C17H35OCO

C17H35OCO OCOC17H35Ti

O

O

O

O O OO

Si

R RRSi

Si

OCOC17H35Ti

OCOC17H35

O

Kobo codes : TTS = ITT / Silane ( R = Caprylyl)TTM = ITT / Methicone ( R = Methyl)TTB = ITT / Dimethicone (R = Branched Dimethicone)


Crosspolymer Treatments - Structure

INCI Names :

• TTS : Isopropyl Titanium Triisostearate/ Triethoxycaprylylsilane Crosspolymer

• TTM : Isopropyl Titanium Triisostearate / Methicone Crosspolymer

• TTB : Isopropyl Titanium Triisostearate / Dimethicone Crosspolymer

US patent # No. 60,472,527


2 gr. of Treated Pigment in 50 mL WaterShaken 10 times - Picture taken after 10 minutes

Hydrophobicity of Crosspolymer vs Its Components


FormulasIngredient CM3K25VM TNP40VTTS

10nm TiO2 (methicone) 25% ---10nm TiO2 (ITT/TCS) --- 40%KF-6017 12% ---Cyclopentasiloxane 63% ---

C12-15 Alkyl benzoate --- 57%

Polyhydroxy stearic acid --- 3%

Test ResultsIngredient CM3K25VM TNP40VTTS

Viscosity (cPs) 100 150

Particle size (nm) 110 100

TiO2 (%) 19.5 32.0

Ext. ratio 308/360 7.9 6.9

Ext. ratio 308/524 93 74

λ max. (nm) 278 274

Dispersions with 10 nm TiO2


Branched Alkyl Silane Treatment


• Very low Hydrogen potential.

• Better affinity in many organic non polar systems

• More hydrophobic than the straight chained alkyl Silanes.

Branched Alkyl Silane


Branched Alkyl Silane - Structure

Schematic Representation of the Branched Alkyl Silane used to Coat


Comparison of Methicone vs BAS treatments

60 nm TiO2 Dispersions in Silicone

40% - Methicone Treated 50% - BAS Treated


Comparison of Methicone vs BAS treatments

Initial Viscosity

5 Days 10 Days 15 Days 20 Days 25 Days 30 Days

CM3F40KQM 1st pass sample

7,320 82,400 32,000 42,800 16,080 14,000

CM3F40KQM 2nd pass sample

14,120 63,200 30,240 90,000 16,800 15,600

CM3F50KQBAS Lot A

312 170 140 150 152 134

CM3F50KQBAS Lot B

311 253 256 282 245 236


Branched Alkyl Silane - Summary

Benefits of the Branched Alkyl Silane in a Dispersion :

• Higher pigment levels in the dispersion with,

• Lower viscosity dispersion (pourable)

• Very good dispersion stability

• No gelling, or settling

• No vehicle separation


Treatment for Hard to Treat Surfaces


• A process for treating and coating materials that traditionally do not coat well. (Patent # WO 03/043567).

• These include such materials as :- Organic pigments and lakes (example Red 7 Ca Lake) - Mineral Silicates such as Mica and Sericite- Porous Silicates.

Hard to Treat Surfaces


• Treatment type :- Amino Silane or Amino Alkoxy Silane treatment

• Advantages to this treatment type:- No residual Silane reactions.- Surfaces that could not be effectively treated to make them hydrophobic can now be treated.

Hard to Treat Surfaces


Stability of Organic Lakes in Water

FD&C Blue 1 Aluminum Lake FD&C Red 40 Aluminum Lake

NT MS HTT NT MS HTT

NT : non-treated lake - after 1 day @ room temperature

MS : methicone-treated lake - after 7 day @ room temperature

HTT : Hard to treat treatment on lake - after 30 day @ room temperature


Stability of Organic Lakes in Water

Comparison of percent bleed between HTT-treated and non-treated lakes in 2% aqueous suspensions. Measurements by spectrophotometry, results expressed in percent of the original lake content.

Non-treated -1 day @ room temp

HTT-treated -30 day @ room temp

HTT-treated -30 day @ 50°C


Effect of pH on Stability in Water


pH 2 Mineral Acid

pH 3 Organic Acid

pH 11 Organic Base

pH 12 Mineral Base

1 Day test : 2% Lake in water


Effect of Surfactant on Stability in Water


Methicone treatedin 2% SLS

HTT treatedin 2% SLS

7 Days test : 2% lake in water


Stability on Mineral Surface

Methicone treatedSericite

HTT treatedSericite

1 Day test : 2% Sericite in water


• Much improved hydrophobic properties.

• Outperforms Methicone with no Hydrogen potential.

• Coat very well to mineral surfaces that normally don’t coat well.

• Prevent water bleed at various pHs and in salts.

Hard to Treat Surfaces - Summary


• Surface treatments can be made and modified to achieve a specific performance criteria :

» Improved Dispersability

» Improved Hydrophobicity.

» Reduce or eliminate synerisis

» Increase or Reduce Gloss

Summary


I wish to thank the following for their efforts in making this presentation possible :

Shirley Wang, Eric Smith, David Cornelio, Scott Holzapfel, Uyen Nguyen, and Pascal Delrieu.

Acknowledgements


Super Dispersible Pigment Treatment

for Applications in Multimedia

Yun Shao, Ph.D. & David SchlossmanKobo Products, Inc.

23rd IFSCC - OrlandoOctober 27, 2004


Outline

1. Common surface treatments and their properties

2. Design and formation of superdisperible surface treatment

3. Evaluation of stability of surface treatment

4. Evaluation of dispersibility

5. Conclusions


• Modifies pigment surface to hydrophobic

and/or lipophilic

• Improve the skin feel

• Improve the chemical stability of metal oxides

• Improves pigment wetting and size reduction during dispersion process

• Improved dispersion stability and formula stability

1. Surface Treatment

Pigment

OH

OH

OH

OHHOHO

HO

HOHO


Coating Pros Cons





Alkoxysilane No H2 potential Hydrophobic

Reacts too slowly Dispersibility in esters is fair

ITT / Metal soap Lipophilic Easy to react with pigments

Not very hydrophobic, especially at low pH

Perfluorinated compounds Repel both water and oil Difficult to wet



Hydrophobic

Hydrophilic

Popular Treatments & Their Drawbacks


Large θPoor wetting Small θ

Good wetting

Wetting

Young-Dupre Equation

γ: interfacial tensionθ: Contact angle

Penetration

The driving force for the capillary action

Force = 2 πrγ LV cosθr = radius of the crack opening

γSV = γSL + γLV cosθ

Wetting & Penetration


• Surface tension is a result of difference in surface energy

• Liquid of lower surface energy can wet surface of higher energy and show a smaller contact angle

• Smaller contact angle generates a higher driving force for penetration

Theory :

Wetting & Penetration

Practice:

• Increase the surface energy of coating without loss of hydrophobicity


Surface Energy of Common Coatings & Liquids

Coatings Surface Energy (dyne/cm2)Perfluorinated compounds 18 – 20

Dimethicone 20 –24Methicone -

Alkoxysilane -Wax (polyethylene) 30 - 31

Metal Soap/Organic Titanate 30 - 35

Liquids Surface Energy (dyne/cm2)Water 72.8

Castor oil 39Olive oil 35.8

Liquid petrolatum 33.1Capric caprylic triglyceride 30

Mineral oil 30 - 35Dimethicone 20 –24

Perfluorinated liquid 16 – 20Cyclomethicone 17.8 ( @25°C)

(All measured @ 20 oC)


Anchoring Through Ionic or Acidic/Basic Groups.

Anchoring ThroughHydrogen-Bonding Groups.

++

++

+

++

++

+

H

H

H

O

OH

Anchoring Through Solvent-Insoluble Polymer Blocks.

solubleinsoluble

Act of Dispersants

OO

Result: reduced inter-particulate attraction for aggregation


Chunky paste

Chunky paste

Viscous slurry

Fluid

w/o

dis

pers

ant

w/ d

i spe

r san

t

A B

C D

15nm TiO2 : 45% *Treatment : Methicone (B & D)Vehicle : CyclopentasiloxaneDispersant : 10 % KF-6017 (C & D)

* note : in mix A, only 33% TiO2was used (maximum amount possible)

Untreated Treated

Easy handlingBetter dispersion

Pigment Dispersion Examples


1. Modify surface energy

2. Minimize the interaction among particulates

Coating + Dispersant as secondary coating

* US Provisional patent application No. 60/472,527

AlkoxysilaneMethiconeDimethicone

Crosslinked coating on pigment{

Design of Superdispersible Surface Treatment


(ITT)+


Chemical Reactions During Surface Treatment

O

CH3

HO

CH3

OPigment

C17H35OCO-Ti-O - Pigment

C8H17- Si (OC2H5)3 C8H17-Si-(OH)3 + HO - Pigment (C8H17-Si-O3)x - Pigment

- C3H7OH

- C2H5OH -H2O

(C17H35OCO)3-Ti-OC3H7 + HO - Pigment

Si + HO - Pigment-H2

x Six

OC2H5 OC2H5 OC2H5 OH OH OH O O Opigment

-C2H5OH -H2O

ITT

Triethoxy caprylylsilane (TCS)

Methicone (MS)

Triethoxysilylethyl polydimethylsiloxyethyl dimethicone (TPDM)


ITT/TCS Crosspolymer: R = C8H17

ITT/Methicone Copolymer: R = CH3

C17H35OCO

C17H35OCO OCOC17H35Ti

O

O

O

O O OO

Si

R RRSi

Si

OCOC17H35Ti

OCOC17H35

O

R = C8H15, ITT/TCS (TTS)

R = CH3, ITT/Methicone (TTM)

R = [ Si(CH3)2O]x, ITT/TPDM (TTDM)

Crosspolymer Treatment - Structure

Crosslinked, 3-dimensionalweb-like structure


2 g of Treated Pigment in 50 mL WaterShaken 10 times - Picture taken after 10 minutes

Hydrophobicity of treated 10 nm TiO2

Catalytic Effect of Titanate on Silicone Reactions

7% 7% 3.5% of each


Hydrophobicity ofVarious Surface Treatments

Contact angle ofVarious Surface Treatments

Hydrophobicity of Crosspolymer Treatment

120

100

140

160

10

0

40

60

20

30

50


Metal Soap / ITT TTS Crosspolymer

TTS coated pigment floats almost indefinitely at pH 2

Stability of TTS Treatment Toward Acid

0.5

1.0

2.0

0

1.5

pH1 2 3 4

Over7 days

ITTMagnesium Myristate

10

20

0

30

Control NeutralWashing

Washingat pH 2

40

Hydrophobicity by Floating Test



Viscosity of Iron Oxide Dispersions

cPs

500,000

1,000,000

1,500,000


Crosspolymer

Too thickto measure

500,000

1,000,000

1,500,000


Crosspolymer

cPs

Too thickto measure

ITT/TCS (TTS) Crosspolymer Treatment


* Dispersant: 1.5 %of polyhydroxystearic acid

Viscosity of 75% Rutile TiO2 Dispersions

Out of scale

100,000

200,000


Crosspolymer

cPs

50,000

150,000

Silane

TTS Crosspolymer in C12-15 Alkyl Benzoate


Viscosity of 75% Anatase TiO2 Dispersions

TTM & TTDM Crosspolymer Treatments

* w/ 2.5% of PEG/PPG-20/15 dimethicone ** w/ 1.5% of polyhydroxystearic acid

Isododecane*cyclomethicone*C12-15 AlkylBenzoate**cP

s

0

100,000

200,000

300,000

400,000

ITT MS TPDM TTM TTDM

800,000


• INCI: Acrylates/Ethylhexyl Acrylate/Dimethicone Methylacrylate Copolymer

• Designed for dispersing pigment primarily in cyclomethicones

Use of Dispersant as Auxiliary Coating

Alkyl

Acrylic Polymer

Silicone

COOHCOOH


Effect of Acrylate/Silicone Copolymer on Dispersibility

0

50,000

100,000

150,000

200,000

250,000

300,000

350,000

MS TCS TTM

( 2.5% of PEG/PPG-20/15 Dimethicone)Viscosity of 75% TiO2 Dispersion

in Isododecane in Cyclopentasiloxane

cPs

cPs

3% of Acrylate/Silicone Copolymer 0 %

0

10,000

20,000

30,000

40,000

50,000

MS TCS TTM

59,000


0

200,000

400,000

600,000

800,000

1,000,000

MS TCS TTM

Viscosity of 75% TiO2 Dispersion(With 1.5% of polyhydroxystearic acid)

In C12-15 Alkyl Benzoate

cPs

Effect of Acrylate/Silicone Copolymer on Dispersibility

3% of Acrylate/Silicone Copolymer 0 %


Conclusions

• The use of hybrid or composite materials to treat pigments can

enhance their chemical stability and wetting by multimedia.

• Organo titanates and dimethicone crosspolymer treatment was

found to be super dispersible in hydrocarbon, cyclomethicone

and ester.

• When used as auxiliary coating, proper dispersant can greatly

improve the dispersibility of treated pigments. Acrylate /

Silicone copolymer was found to be very effective for

dispersing pigments in hydrocarbon and cyclomethicone.

• Hybrid compounds offer more benefits and will be the future for

pigment surface modification.


• Shirley Wang• Eric Smith• Scott Hozalpfel

• Pascal Delrieu, Ph.D.

Acknowledgements

www.koboproducts.comChulalongkorn University Seminar, Thailand

June 25, 2004

Surface Treatment and Dispersions of Inorganic

UV Filters

David Schlossman and Yun Shao, Ph.D.,

Kobo Products, Inc.


June 25, 2004

Absorption : 420 nm (TiO2 rutile) / 390 nm (TiO2 anatase)380 nm (ZnO)

Scattering :

Merit : Inert and safe when coated; Antimicrobial (ZnO)

Drawback : Whitening

Inorganic UV Filters: TiO2 and ZnO

UV VisibleLarge particles :- less efficient against UV- whitening

Small particles :- Highly efficient against UV- transparent


June 25, 2004

Extinction Ratios

280 320 360 400 440 4800

0.2

0.4

0.6

0.8

1.0

Wavelength (nm)

1.2

520

308 360 524

308 nm : max erythemal effectiveness360 nm : Mid of UVA524 nm : Blue end of visible light

Ext. 308Ext. 524

UVB attenuationTransparency

Ext. 308Ext. 360 UVA and UVB ratio


June 25, 2004

Rutile Type

Titanium Dioxide Particles (TEM)

15 nm coated 35 nm uncoated 180 nm pigmentary


June 25, 2004

Zinc Oxide Particles (TEM)

ZnO (20 nm) ZnO (60 nm)


June 25, 2004

Manufacturer Trade name Internet addressDegussa P-25 www.degussa.com

Ishihara Sangyo Kaisha, Ltd. TTO www.iijnet.or.jp/itc-fmp/Kemira Pigments Oy UV Titan www.kemira.com/pigments

Rhodia Mirasun www.rhodia.comSachtleben Hombitec www.sachtleben.de/h/e/hom/0000e.html

Showa Denka Maxlight www.sdk.co.jp/chemicals/index.htmlTayca Corporation MT Series www.tayca.co.jp/english/file/04/04_02.html

Titan Kogyo STT www.titankogyo.co.jpUniquema Solaveil, Tioveil www.uniquema.com/pc

Manufacturers of Titanium Dioxide


June 25, 2004

General Properties of Micronized Titanium Dioxide

Supplier Grade TiO2 (%) Crystal Form

Primary Particle Size (Surface Area - BET)

Surface Treatment

Degussa P-25 99.5 < Anatase 21 nm (50 + 15 m2/g) None

EMD Eusolex T-2000 76-82 Anatase 10-15 nmAlumina,

DimethiconeISK TTO S-4 82 < Rutile 15 nm AHSAISK TTO S-3 82 < Rutile 15 nm AluminaISK TTO V-3 82 < Rutile 10 nm Alumina

Kemira UV Titan M170 75 < Rutile 14 nm Alumina, Methicone

Kemira UV Titan M262 85 < Rutile 20 nm Alumina, Dimethicone

Sachtleben Hombitec L5 75-85 Anatase (80-160 m2/g) Silica, SiliconeShowa Denka Maxlight TS-04 64 35 nm Silica

Tayca MT-100T 80 < Rutile 15 nm AS / AHTayca MT-500B 96 < Rutile 35 nm AluminaTayca MT-100Z 73 < Rutile 15 nm AS / AH

Titan Kogyo STT 65C-S 96.5 Anatase (64 m2/g) None


June 25, 2004

Manufacturer Trade name Internet addressAdvanced Nano Technologies Zinclear www.ant-powders.com/zinclear.htm

BASF Z-Cote www.basf.comElementis Specialties Nanox www.elementis-specialties.com

Zinc Corporation of America USP-1 www.zinccorp.comNanophase NanoGuard www.nanophase.com

Sakai Finex www.sakai-chem.co.jpShowa Denka Maxlight ZS www.sdk.co.jp/chemicals/index.html

Sumitomo Cement ZnO series www.socnb.com/index_e.htmlTayca Corporation MZ Series www.tayca.co.jp/english/file/04/07_03.html

Haarmann and Reimer ZnO Neutral www.symrise.com

Manufacturers of Zinc Oxide


June 25, 2004

General Properties of Micronized Zinc Oxide

Supplier Grade ZnO (%) Primary Particle Size (Surface Area - BET)

Surface Treatment

ANT Zinclear --- 25 nm Stearic acid

BASF Z-Cote 98 < 200 nm None

Elementis Nanox 200 > 99 60 nm (17 m2/g) NoneFinexSF-20

Showa Denka ZS-032 80 31 nm Silica

Sumitomo Cement

ZnO-350 >99 35 nm None

Tayca MZ-700 >99 10-20 nm NoneTayca MZ-500 >99 20-30 nm NoneTayca MZ-300 >99 30-40 nm None

Sakai >99 60 nm (20 m2/g) None


June 25, 2004

• Difficult to disperse (wet + stabilize) in media (re-agglomeration of particles is common)

• Visible whitening on skin is unpopular in most markets

• Must be physically and chemically stable to avoid decomposition of other ingredients in the formula and to have a stable formulation.

• Obtaining a broad spectrum protection + high SPF

• Rub in quickly (good spreadability)

Technical Challenges (1/2)


June 25, 2004

• Hydrophilic

• Surface active

• Regulatory :

• Titanium dioxide (globally approved, except in combination with avobenzone in the USA)

• Zinc oxide (not approved in Europe, may not be combined with avobenzone in the USA)

• Must meet USP requirements in the USA for purity• Patents which limit use of actives, or place restrictions on

particle size, dispersants, emulsifiers, dispersions, etc

Technical Challenges (2/2)


June 25, 2004

Large θPoor wetting

Small θGood wetting

Young-Dupre EquationγSV = γSL + γLV cosθ γ: interfacial tension

The wetting agent should reduce the liquid-solid surface tension and the liquid-vapor tension.

Wetting


June 25, 2004

• General mechanism :

› Shear force

› Impact action

• General processor :

› High shear mixer

› Mills

› Homogenizer

Mechanical Breakdown


June 25, 2004

• Steric stabilization

› by adsorbing polymeric materials

• Electrostatic stabilization

› by adsorbing charge additive

Steric Interactions Coulombic Interactions

Stabilization of Particulates


June 25, 2004

Attractive Forces Between Particulates

• Smaller particles can be stabilized with thinner polymer layers• Overcrowded dispersion tends to aggregate

Influence of Particle Size & Distance on Stability


June 25, 2004

Stokes’ LawThe relationship between the free falling velocity of a spherical particle in a Newtonian fluid and the particle diameter.

V = (2gr²)(d1-d2)/9µwhere: V = velocity of fall

µ = viscosity of medium ( higher is better)r = radius of particle (smaller is better)

g = acceleration of gravity dl, d2 = density of particle and medium

Sedimentation of Particulates


June 25, 2004

Comparison of in-vitro SPF

W/O Sun Lotion O/W Sun Lotion

0

5

10

15

20

25

30

TiO2@ 2.5%

TiO2@ 5%

TiO2@ 8%

0

5

10

15

20

25

30

TiO2@ 5%

TiO2@ 8%

TiO2 powderTiO2 dispersion

TiO2 powderTiO2 dispersion

Benefits of using Dispersions over Particulates

Study made by Tri-K (USA) for MT-100T


June 25, 2004

Factors Influencing the DispersionPigment

Packing Density

Particle Shape

Surface Character

Percent Solids

Medium

Chemical Composition (Treatments, Carrier, Dispersant)

Concentrations

Viscosity

Polarity

Process Conditions

Dispersing Machine

Temperature

Viscosity

Energy Input

Particulate Dispersion


June 25, 2004

Influence of Percent Solids (1/2)Attenuation TiO2 in Isononyl Isononanoate

PPS (nm)

Product Name

Surface Treatment

PS (nm)

% Solids

15 IN60TS AHSA w/s 132 60

15 IN40TS AHSA w/s 160 4060% 40%


June 25, 2004

280 320 360 400 440 4800

20

40

60

80

100

Wavelength (nm)

TiO2 : 0.001%

IN40TS

IN60TS

Influence of Percent Solids (2/2)


June 25, 2004

• Provides physical and chemical stability

• Modifies pigment surface to hydrophobic and/or lipophilic

• Pre-wets the pigment surface (lower oil absorption)

• Decreases the adsorption of the dispersant

• Improves Pigment Wetting and Size Reduction

• Improved flow and dispersion stability by minimizing the re-aggregation

Influence of Surface Treatment


June 25, 2004

Formulation tip: Only coated TiO2 and ZnO should be used.

CH3CHO + H2O + 2h+ CH3COOH + 2H +

CH3COOH + H2O + 8h+ 2 CO2 + 8H +

TiO2 + UV irradiation e- + h + ( hole +)Oxidation ofAcetaldhyde

Rate Constant of The First Order Reaction PPS (nm)

Size (nm) Treatment Rate Treatment Rate

TiO2 410 None 4.76 2% Methicone < 0.01

TiO2 30 - 50 Alumina 0.13 3% Lecithin 0.033

ZnO 15 - 35 None 1.83 3% Methicone < 0.01

M. Kobayashi and W. Kalriess, Cosm & Toil., Vol. 112, No. 6, p83, 1997

Influence of Surface Treatment on Physical Stability


June 25, 2004

• Alumina

• Silica

• Aluminum Hydroxide

• Zirconia (popular in Japan)

Inorganic Surface Treatments for Pigments


June 25, 2004

Coating Pros Cons





AlkoxysilaneNo H2 potential

HydrophobicReacts too slowly

Dispersibility in esters is fair

ITT / Metal soapLipophilic

Easy to react with pigmentsNot very hydrophobic,

especially at low pHPerfluorinated compounds Repel both water and oil Difficult to wet



Hydrophobic

Hydrophilic

Popular Treatments and Their Drawbacks


June 25, 2004

Chunky paste

Chunky paste

Viscous slurry

Fluid

w/o

dis

pers

ant

w/ d

i spe

r san

t

A B

C D

15nm TiO2 : 45% *Treatment : Methicone (B & D)Vehicle : CyclopentasiloxaneDispersant : 10 % KF-6017 (C & D)

* note : in mix A, only 33% TiO2was used (maximum amount possible)

Untreated Treated

Easy handlingBetter dispersion

Surface Treatment : Pre-Wetting of the Pigment


June 25, 2004

11S2 : R = CaprylylSW : R = Polyethylene Oxide

Silane treatments Crosspolymer treatments

TTB : R = Branched DimethiconeTTS : R = CaprylylTTM : R = Methyl

New Silane Surface Treatments


June 25, 2004

* US Provisional patent application No. 60,472,527

Results :• Hydrophobicity comparable to silane and methicone treatments

• Stable over a pH range of 2 - 9

ITT +

AlkoxysilanePerfluoro AlkoxysilaneMethiconeDimethicone

Crosslinked coating on pigment

pigments{Titanate reacts and catalyzes silicone compounds

Crosspolymer Treatments


June 25, 2004

Hydrophobicity of TTS treatment

2 gr. of Treated Pigment in 50 mL WaterShaken 10 times - Picture taken after 10 minutes


June 25, 2004


Viscosity of Iron Oxides premix

cPs

500,000

1,000,000

1,500,000


Crosspolymer

Too thickto measure

500,000

1,000,000

1,500,000


Crosspolymer

cPs

Too thickto measure

ITT/TCS Crosspolymer Treatment


June 25, 2004

Viscosity of TiO2 CR-837 premix at 75% solids

* Dispersant: 1.5 % Polyhydroxystearic acid

Out of scale

100,000

200,000


Crosspolymer

cPs

50,000

150,000

Silane

ITT/TCS Crosspolymer in C12-15 Alkyl Benzoate


June 25, 2004

Treatment of TiO2 CR-837

• ITT / Methicone Crosspolymer treatments are hydrophobic with lower hydrogen potential

• Hydrogen potential reduction is even more significant on micronized TiO2

Methicone ITT/ Methicone Hydrophobicity

A 2 -- Good

B 1 -- Poor

C -- 2 Good

10

20

30

0Methiconetreatment

ITT / Methiconetreatment

A

C

ITT/Methicone Crosspolymer : H2 Potential


June 25, 2004

15 nm Hydrophilic TiO2

Non treated

TreatedViscosity of premix at 42% solids

500,000

1,000,000

0Untreated 5% treatment

cPs

250,000

750,000

2,800

850,000



June 25, 2004

INCI name : Dimethicone Kobo code : BS

=

O O O

Si O

CH3

CH3

x(

O-Et O-Et O-Etpigment

• Branched structure increases dispersion stability• No Hydrogen potential

Branched Dimethicone Treatment : Structure


June 25, 2004

MS : MethiconeBS : DimethiconeSilane : Triethoxy

CaprylsilaneITT : Isopropyl

Titanium Triisostearate

TTM : ITT/Methicone Crosspolymer

TTS : ITT/TCS Crosspolymer

* Dispersant : 2.5% PEG/PPG-20/15 Dimethicone from SF1528

600,000

1,200,000

0Untreated

cPs

MS

300,000

900,000

BSSilane ITT TTM TTS


Dimethicone Treatment in Cyclopentasiloxane


June 25, 2004

* Dispersant : 2.5% of Bis-PEG/PPG 14/14 Dimethicone (Abil EM 97)

MS : MethiconeBS : DimethiconeSilane : Triethoxy

CaprylsilaneITT : Isopropyl

Titanium Triisostearate

TTM : ITT/Methicone Crosspolymer

TTS : ITT/TCS Crosspolymer

300,000

600,000

0Untreated MS

cPs

150,000

450,000

BSSilane ITT TTM TTS


Dimethicone Treatment in Cyclopentasiloxane


June 25, 2004

Primary Particle Size (PPS) 15nm 35nm 100nm 200nm

TiO2 Dispersions In Isononyl Isononanoate

PPS (nm)

Product Name

Surface Treatment

PS (nm)

% Solids

15 INH60TS AHSA w/s 125 60

35 INH70T ITT w/s 154 70

100 INH65K9 ITT w/s 251 65

200 IN80C ITT 263 80

Influence of Primary Particle Size (1/3)


June 25, 2004

0

20

40

60

80

100

280 320 360 400 440 480wavelenght (nm)

INH65K9

IN80C

INH60TS

INH70T

absorption scattering

TiO2: 0.001%

Influence of Primary Particle Size (2/3)UV/Visible Transmittance curves


June 25, 2004

Influence of Primary Particle Size (3/3)10nm TiO2 make transparent dispersions for all skin types

1 2 3

Black

1 2 3

Asian

1 2 3

Caucasian

1 = 1 0nm T iO2 D isper sion2 = 1 5nm T iO2 D isper sion3 = Comm er cial ly A v ai lable

D isper sion


June 25, 2004

Test Results

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%

Formulas

Ingredient CM3K25VM CMKP25VM CME730VMViscosity (cPs) < 100 19 100,000

Particle size (nm) 110 104 238

Index of aggregation 11.0 10.4 23.8

TiO2 (%) 20 20 24

Dispersions with 10 nm TiO2Influence of Silicone Dispersants


June 25, 2004

280 320 360 400 440 4800

20

40

60

80

100

Wavelength (nm)

TiO2 : 0.001%

CM3K25VMCMKP25VM

CME730VM

CM3K25VM CMKP25VM CME730VM

Particle size

Ext. ratio 308/360

Ext. ratio 308/524

λ max. (nm)

CM3K25VM 110 7.9 93.0 278

CMKP25VM 104 8.0 164.8 < 280

CME730VM 238 2.0 9.1 302

UV/Vis Transmittance of 10 nm TiO2 Dispersions


June 25, 2004

Test Results

Ingredient CM3K60TM CMKP60M26235 nm TiO2 (methicone) 60% ---

20 nm TiO2 (alumina and dimethicone) --- 60%

Cyclopentasiloxane 30% 28%KF-6017 10% ---KP-575 --- 12%

Formulas

Ingredient CM3K60TM CMKP60M262

Viscosity (cPs) 102,000 12,000

Particle size (nm) 179 143

Index of aggregation 5.1 7.2

TiO2 (%) 56 53

Dispersions with 20-35 nm TiO2Influence of Silicone Dispersants


June 25, 2004

280 320 360 400 440 4800

20

40

60

80

100

Wavelength (nm)

CMKP60M262

CM3K60TM

TiO2 : 0.001%

CM3K60TM CMKP60M262

Particle size

Ext. ratio 308/360

Ext. ratio 308/524

λ max. (nm)

CM3K60TM 179 1.5 6.7 318

CMKP60M262 143 1.9 9.0 299

UV/Vis Transmittance of 20-35 nm TiO2 Dispersions


June 25, 2004

Test Results

Ingredient CM3K50XZ4 CMKP50XZ4 CM3K40HP1

20 - 30 nm ZnO (methicone) 50% 50% ---

Z-Cote HP-1 (<200nm, dimethicone) --- --- 40%

Cyclopentasiloxane 40% 40% 50%

KF-6017 10% --- 10%

KP-575 --- 10% ---

Formulas

Ingredient CM3K50XZ4 CMKP50XZ4 CM3K40HP1

Viscosity (cPs) 200 75 1,500



ZnO (%) 48 48 38

Dispersions with ZnOInfluence of Silicone Dispersants


June 25, 2004

CM3K50XZ4 CMKP50XZ4 CM3K40HP1

Particle size

Ext. ratio 308/360

Ext. ratio 308/524

λ max. (nm)

CM3K50XZ4 145 1.1 37.0 358

CMKP50X4 147 1.0 32.5 359

CM3K40HP1 250 0.9 7.8 371

UV/Vis Transmittance of ZnO Dispersions

280 320 360 400 440 4800

20

40

60

80

100

Wavelength (nm)

TiO2 : 0.001%

CM3K40HP1CM3K50XZ4

CMKP50XZ4

ZnO : 0.005%


June 25, 2004

FormulasIngredient 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 ResultsIngredient CM3K25VM TNP40VTTS TNP55VTTS

Viscosity (cPs) 100 150 10,000


TiO2 (%) 19.5 32.0 44.0

Dispersions with 10 nm TiO2Influence of the Dispersion Formula


June 25, 2004

280 320 360 400 440 4800

20

40

60

80

100

Wavelength (nm)

TNP40VTTSTNP55VTTS

(superimposed)

TiO2 : 0.001%

CM3K25VM

CM3K25VM TNP40VTTS TNP55VTTS

Particle size

Ext. ratio 308/360

Ext. ratio 308/524

λ max. (nm)

CM3K25VM 110 7.9 93.0 278

TNP40VTTS 100 6.9 74.0 274

TNP55VTTS 100 6.9 74.0 274



June 25, 2004

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 ResultsPM9P60M170 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

TiO2 (%) 46.5 38.8 31.0 38.8

Dispersions with 14 nm TiO2Influence of Dispersants & Vehicles


June 25, 2004

280 320 360 400 440 4800

20

40

60

80

100

Wavelength (nm)

PM9P60M170TNP50M170

TiO2 : 0.001%

PM9P50M170CM3K40M170

PM9P60M170 PM9P50M170 TNP50M170 CM3K40M170

Particle size

Ext. ratio 308/360

Ext. ratio 308/524

λ 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



June 25, 2004

Formulas

Test Results

Ingredient TNP50ZSI TNP50ZCLS CMKP50XZ420-30 nm ZnO (methicone) --- --- 50%

20-30 nm ZnO (Triethoxycapryl Silane) 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



ZnO (%) 47.0 47.0 47.0

Dispersions with 20-30 nm ZnO Influence of Dispersants & Vehicles


June 25, 2004

280 320 360 400 440 4800

20

40

60

80

100

Wavelength (nm)

TiO2 : 0.001%

TNP50ZCLSTNP50ZSI

CMKP50XZ4

ZnO : 0.005%

TNP50ZSI TNP50ZCLS CMKP50XZ4

Particle size

Ext. ratio 308/360

Ext. ratio 308/524

λ max. (nm)

TNP50ZSI 130 1.1 29.0 358

TNP50ZCLS 110 1.0 35.0 360

CMKP50XZ4 147 1.0 32.5 359

UV/Vis Transmittance of ZnO Dispersions


June 25, 2004

Pigment Primary particle size Ratio (1)

305/360Ratio (2)

305/524Maximum

absorption @10 nm 7.0 - 8.0 70 - 90 275 nm15 nm (High SpeedTM Disp) 4.5 - 5.5 50 - 55 280 - 290 nm15 nm (High Solids® Disp) 3.4 - 3.9 11 - 16 290 - 305 nm20 nm 2.0 9 300 nm35 nm 1.5 - 2.0 7 - 17 315 nm150 nm 1.1 2.6 318 nm20 nm 1.0 - 1.1 30 - 37 360 nm60-100 nm 1.1 6.3 371 nm120 nm 0.9 2.9 375 nm

TiO2

ZnO

(1) 305/360 ratio : indication of UVB/UVA ratio(2) 305/524 ratio : indication of transparency

Extinction ratios


June 25, 2004

In-Vivo vs. In-Vitro SPF Test Results

IMS CPTS

3103/2 (o/w) TiO2 10.49 125.3 50 40.4 24.7

2504/2 (w/o) TiO2 10.49 132.1 37.5 73.4 59.3

TiO2 6.24 132.1

TiO2 4.23 194.5

3103/4 (o/w) TiO2 10.29 154.1 28.4 65.2 50.2

3103/3 (o/w) ZnO 14.97 228.2 16 11.5 16.2

2577/1(w/o) ZnO 14.97 228.2 14 22.3 22.3

In-vivo SPF

In-vitro SPF

2550/2 (w/o) 30.5 45.1 42.2

Formula Active Active (%)

P. S. (nm)


June 25, 2004

In-vivo vs. in-vitro PFA Test Results

IMS CPTS

2577/1(w/o) ZnO 14.97 228.2 7.50 0.71 0.72

3103/3 (o/w) ZnO 14.97 228.2 7.50 0.74 0.70

3120/2 (w/o) ZnO 14.97 263 4.73 ----- 0.83

3103/4 (o/w) TiO2 10.29 154.1 6.75 0.64 0.69

3103/2 (o/w) TiO2 10.49 125.3 4.50 0.45 0.55

2504/2 (w/o) TiO2 10.49 132.1 3.05 0.47 0.61

TiO2 6.24 132.1

TiO2 4.23 194.52550/2 (w/o) 3.05 0.56 0.6

In-vivo PFA

Uva/UVB ratioFormula Active Active

(%)P. S. (nm)


June 25, 2004

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

TNP50ZCLS

TNP50HPI

TNP55T7

TNP50ZSI

1.2

19.7%Water-in-oil emulsion

Water-in-silicone emulsion 19.3% 24

Sunscreen Formulations


June 25, 2004

Fundamental to meeting the technical challenges required for the successful use of inorganic particulates to attenuate UV light :

Summary

• Proper surface treatment and dispersion

• Understanding the influence of particle size on UV attenuation


June 25, 2004

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 Fitoderm 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 15 Spray Formula with TNP50ZCLSKSL-083A


June 25, 2004



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

Rosmarinus Officinalis (Rosemary) Extract 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 24 W/O Emulsion with TNP40VTTSKSL-084


June 25, 2004


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 25 W/O with TNP50ZSIKSL-043


June 25, 2004



Sodium Chloride --- 0.5

BCetyl Dimethicone Copolyol &(And) Polyglyceryl- 4 - Isostearatehexyl Laurate Abil WE -09 5.0

Rosmarinus Officinalis (Rosemary) Extract --- 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 40 Water-in-silicone with CM3K25VMKSL-067


June 25, 2004

Phase Ingredient Trade Name/Vendor %A Cyclopentasiloxane (And) PEG/PPG-20/15 Dimethicone SF1528/GE 7.83

Cyclopentasiloxane Dimethicone/Vinyldimethicone Crosspolymer

SFE839/GE 0.78

Cyclopentasiloxane SF1202 10.64Bis-Phenylpropyl Dimethicone SF1555 0.63Polymethylsilsesquioxane Tospearl 2000 3.13Cyclomethicone Trimethylsiloxysilicate SS4230 2.50Phenoxyethanol (And) Methylparaben (And) Propylparaben (And) Ethylparaben (And) Butylparaben (And) Isobutylparaben Phenonip 1.00

BTitanium Dioxide (And) Cyclopentasiloxane (And) Acrylates/Ethylhexyl Acrylate/Dimethicone Methylacrylate Copolymer (And) Alumina (And) Silica (And) Methicone

CMKP60M262 25.00

Yellow Iron Oxide (And) Decamethyl Cyclopentasiloxane (And) Dimethicone Copolyol (And) Triethoxy Caprylylsilane

FA50YSI 6.00

Red Iron Oxide (And) Decamethyl Cyclopentasiloxane (And) Dimethicone Copolyol (And) Triethoxy Caprylylsilane

FA55RSI 1.00

Black Iron Oxide (And) Decamethyl Cyclopentasiloxane (And) Dimethicone Copolyol (And) Triethoxy Caprylylsilane

FA60BSI 0.40

C Water 26.07Butylene Glycol Butylene Glycol 7.83Polysorbate 20 RITAbate 20/RITA 0.31Sodium Chloride Sodium Chloride 0.63Glycerin Glycerin 1.25

D Ethanol SD 39C 5.00

SPF 44 Foundation Make-Up with CMKP60M262

KLF-016


June 25, 2004

Phase Ingredient Trade Name/Vendor %A Deionized Water --- 52.39

Sodium Chloride --- 0.50Propylene Glycol --- 3.00Allantoin --- 0.20Methyl Paraben --- 0.15

BC12-15 Alkyl Benzoate (And) Titanium Dioxide (And) Alumina (And) Polyhydroxystearate (And) Isopropyl Titanium Triisostearate (And) Triethoxy Caprylylsilane

TNP40VTTS 10.00

Microcrystaline Wax SP 94 (Strahl & Pitsch) 0.50Wax Abil Wax 9801 (Goldsmidt) 1.00Octyl stearate Cetiol 868 (Cognis) 4.00Shea Butter Cetiol SB 45 (Cognis) 1.00PEG-30 dipolyhydroxystearate Arlacel P135 (ICI) 2.50Polyglyceryl-4 Isostearate (And) Cetyl Dimethicone Copolyol (And) Hexyl Laurate Abil WE 09 (Cognis) 2.50

Cyclopentasiloxane DC 345 (Dow Corning) 1.00Propylparaben --- 0.06Cetearyl Alcohol (And) Cetearyl Phosphate Crodafos CES (Croda) 1.00Octyl Methoxy Cinnamate Uvinul MC 80 (BASF) 8.50Octocrylene Uvinal N 539 T (BASF) 10.00

Rosmarinus Officinalis (Rosemary) ExtractRomary Oleoresin HQ 3401

(Hilltech) 0.20

Benzophenone-3 (BASF) 1.50

SPF 50 W/O Emulsion with TNP40VTTSKSL-086


June 25, 2004


Sodium Chloride --- 0.50PEG-150/Smdi Copolymer Acculyn 44 4.00Paragon MEPB McIntyre 0.60

B Zinc Oxide (And) C12-15 Alkyl Benzoate (And) Polyhydroxystearic Acid (And) Triethoxy Caprylylsilane

TNP50ZCLS 30.00

C12-15 Alkyl Benzoate (And) Zinc Oxide (And) Dimethicone TNP50HPI 10.00

Polyglyceryl-4 Isostearate (And) Cetyl Dimethicone Copolyol (And) Hexyl Laurate Abil WE 09 (Cognis) 2.00

Cyclomethicone SF1204 (G.E.) 5.00Methyl Glucose Sesquistearate Tegocare PS (Degussa) 0.60Cetyl Dimethicone Abil Wax 9801 (Degussa) 2.00Jojoba Esters Floraesters 15 (Floratec) 2.00

SPF 24 Waterproof SunscreenKSL-092


June 25, 2004


Sodium Chloride --- 0.56Allantoin Sutton 0.20

B C12-15 Alkyl Benzoate (And) Titanium Dioxide (And) Alumina (And) Polyhydroxystearic Acid (And) Methicone

TNP55T7 29.00

C12-15 Alkyl Benzoate (And) Zinc Oxide (And) Polyhydroxystearic Acid (And) Triethoxy Caprylylsilane

TNP50ZSI 10.00

Polyglyceryl-4 Isostearate (And) Cetyl Dimethicone Copolyol (And) Hexyl Abil WE 09 (Cognis) 2.50Cyclomethicone SF1204 (G.E.) 5.00Methylparaben NIPA 0.15Propylparaben NIPA 0.06Shea Butter Cognis 1.00PEG-30 Dipolyhydroxystearate Arlacel P135 (Uniqema) 2.50Argan Oil Centerchem 1.00Rosemarinus Officinalis (Rosemary) Extract HQ 3401 (Hilltech) 0.20Butyloctyl Salicylate Hallbrite BHB (Hall Co.) 3.00Ascorbyl Palmitate Acatris 0.30Mica (And) Silica Micronasphere M (EMD) 0.30Mica (And) Iron Oxide (And) Titanium Dioxide Colorona Oriental Beige 0.05Bismuth Oxichloride Biron Fines (EMD) 0.50Octyl Carbonate Cetiol CC (Cognis) 3.00Jojoba Esters Floraesters 15 (Floratec) 3.00

C Urethane / C1-12 Alkyl PEG Copolymer Acculyn 44 (Rohm & Haas) 3.00Water (And) Triticum Vulgare (Wheat) Extract (And) Saccharomyces Cerivisiae Extract (And) Sodium Hyaluronate Iricalmin (Centerchem) 3.00

W/O High SPF Suncare emulsionKSL-098

Part II

Analysis of Commercial Products

Co d e Pro d u c t SPF % TiO2

R2 0 Re v lo n A g e D e fy in g A ll D ay Lif tin g 2 0 8 .6 %

+3 .2 5 Zn O

R1 5 Re v lo n Co lo rs tay Lite Mak e -u p 1 5 5 .2 %

Oil Oil o f Olay 1 5 4 .0 %

HR He le n a Ru bin s te in Sp e c tac u lar Mak e -u p

1 0 3 .1 %

N N e u tro g e n a Oil Fre e 2 0 2 .4 %

R20 R15 Oil HR N

Comparison of Marketed Foundations (I)

0.019%of formulas in CHCl3

Code TiO2

R20 15 – 35 nm

R15 15 nm

Oil 15 nm + Organic

HR Pigmentary + Organic

N 35 nm + Organic

Same Formula Concentration

Comparison of Marketed Foundations (II)

0.001% TiO2 in CHCl3

Code TiO2

R20 15 – 35 nm

R15 15 nm

Oil 15 nm TiO2 + Organic

HR Pigmentary TiO2 + Organic

N Pigmentary TiO2 + Organic

Same TiO2 Concentration

Comparison of Marketed Foundations (III)

Comparison of Marketed Foundations (IV)

Co d e Pro d u c t A v e ra g e SPF

Crit ic a l Wa v e le n g th

A v e ra g e UV A Ra tio

R2 0 Re v lo n A g e D e f y in g A ll D a y Lif t in g 8 6 .6 4 3 8 5 n m 0 .8 0

R1 5 Re v lo n Co lo rs ta y Lite Ma k e -u p 9 0 .1 0 3 8 4 n m 0 .7 2

O il O il o f O la y 1 9 4 .5 1 3 8 8 n m 0 .9 3

H R H e le n a Ru b in s te in Sp e c ta c u la r Ma k e -u p

7 7 .7 1 3 8 7 n m 0 .8 8

N N e u tro g e n a O il Fre e 8 7 .3 8 3 8 6 n m 0 .8 2

In vitro SPF Testing

• Presence of pigments in color cosmetic generate much scatteringwhich tends to give artificially high SPF.

Part III

Selection of Inorganic Sunscreens for Color Cosmetics

UV TiO2 in Lipsticks

• Shade is deep and intense.

• Sunscreens to be very transparent

• Organic • Transparent TiO2 or ZnO dispersions

* Eyeshadow -- same caution

TNP40VTTS 100 nmTNP40VM 100 nmIN60S4 130 nmCM3K25VM 110 nm

Lipsticks : Addition of TiO2

Dark Shade

Pink Shade

With 2.4% TiO2

With 2.4% TiO2

Without

Without

Color Changes

Delta L : -0.4 (Darker)Delta a : 1.3 (Redder)Delta b : -0.5 (Bluer)

Delta L : 0.4 (Whiter)Delta a : -0.5 (Greener)Delta b : 0.9 (Yellower)

Dispersion: CM3K35VM(PS 110 nm, PPS 10 nm)

Makeup or foundation -- Color Dispersions

Product Treatm ent PS (nm ) % Solids

WE70 U ITT 3 2 8 7 0 %

WE5 5 Y ITT 3 1 7 5 5 %

WE7 0 R ITT 2 2 7 7 0 %

WE7 0 B ITT 1 ,0 6 5 7 0 %

WE70U WE55Y WE70R WE70B

UV Curves of Inorganic Color Dispersions

0.001% in CHCl3

• Pigments can provide UVA and weak UVB protection• Smaller size give better protection

UV TiO2 in Makeup or foundation

Dark shades:• Very transparent TiO2• 10 or 15 nm TiO2 dispersion

Dispersion in esters:

TNP40VTTS: 100 nmTNP40VM: 100 nmIN60S4: 130 nm

Dispersion in D5:

CM3K25VM: 110 nmCM3K40T4: 120 nm

Medium to light shades:• UV TiO2 can be little opaque • 20 - 35 nm TiO2 dispersion• More UVA protection

UV TiO2 in Makeup or foundation

Dispersion in esters:

TNP40G8: 150 nmINH70T: 154 nmKQ-1 dispersionsL 180 nm

Dispersion in D5:

CMKP50M262: 160 nmKQ-1 dispersions: 180 nm

UV TiO2 in Pressed powder

Dark shades:• Replace part of Pigmentary TiO2 withlarger size TiO2 ( 25 - 60 nm)

KQ-I4: 60 nmKQ-MS4: 60 nmUV-Titan M262: 20 nm (claimed but opaque)

All shades:

• Use small size TiO2 (10 or 15 nm)• Jet pulverize to get more UV performance

SIV-MS7, SIV-TTS7 10 nmTTO-MS4 15 nm

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