Pigment Surface Treatments

Transcription

Pigment Surface Treatments
Kobo Products, Inc.
South Plainfield, NJ 07080, USA
Outline
1. Common surface treatments and their properties
2. Hybrid treatment
3. Hydrophilic treatment
4. Conclusions
1. Surface Treatment
•
Modifies pigment surface to hydrophobic HO
and/or lipophilic
HO
HO
OH
OH
Pigment
OH
•
•
•
Improve the skin feel
•
Improved dispersion stability and formula stability
HO
HO
Improve the chemical stability of metal oxides
Improves pigment wetting and size reduction
during dispersion process
OH
Common and Popular Surface Treatment
for Color Cosmetics
Methicone
CH3
H3C
CH3
Si O Si
CH3
H
O
O Si
n
H
O
CH3
CH3
CH3
(H3C)3Si
O
- H2
CH3
H
O
Pigment
CH3
H
H
H
Si O
O
O Si
O
O
Si(CH3)3
Si(CH3)3 - H
2
- H2
O
H
Heat
O
CH3
More heat
(H3C)3Si
Si
O
CH3
O
O
CH3
Si
O
O
O
Pigment
Pigment
Code MS
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
Dimethicone
CH3
H
O
Si
O
CH3
H
CH3
Si
CH3
O
CH3
O
Si
n
CH3
O
Pigment
O
H
CH3
- H2O
H
H3C
O
Si
H3C
O
Si
O
CH3
n
O
Si CH3
CH3
Pigment
Code DS
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.
Organo Titanate
Isopropyl Titanium Triisostearate
CH3
CH3
CH O
Code ITT
O
Ti O
C
C17H35
3
C17H35OCO
Ti
H
O
pigment surface
---hydrophlic
OCOC17H35
O
OCOC17H35
- (CH3)2CHOH
pigment surface
---hydrophobic
lipophilic
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
Organo Titanate (II)
Kobo patent on ITT treated pigments and powders : # 4877604
Dispersion of 40% TiO2
ITT treated
Untreated
Metal Soap -- Magnesium Myristate
Soluble salt of Fatty Acid
+
Metal salt
Fatty Acid
+
Metal hydroxide
Metal soap
Deposition
Pigment
Code MM
Properties:
• Creamy feel: Increased adhesion to skin and wear
• Better pressability. Suitable for powders
• Hydrophobic / Lipophilic
Triethoxycaprylylsilane
OC2H5
H
O
C2H5O
H
Si
CnH2n+1
HO
OC2H5
OH
HO
OH
- 3 C2H5OH
Si
Si
(code 11S2)
CnH2n+1
OH
OH
OH
CnH2n+1
OH
OH
- H2O
O
CnH2n+1
CnH2n+1
Si
Si
O
O
O
pigment
OH
pigment
Hydrophobic
Properties:
• Excellent hydrophobicity
• Zero Hydrogen Potential, no Si-H bonds
• More compatible with ester and oil
• Stable at pH = 3
x
O
Fluorinated compounds
C9-15 Perfluoroalcohol Phosphates ( code PF)
With conventional (lipophilic)
pigments, light is reflected
O
CnF2n+1 CH2CH2O
O
P
O
M
H
H
Skin Oil
Lipophilic Pigment
Skin Surface
O
M
Pigment Surface
With PF treated pigments,
light is scattered
Properties:
Skin Oil
PF Treated Pigment
Skin Surface
•
•
•
Hydrophobic
Lipophobic
Good for long wear
•
Hard to wet and grind; color consistency can be an issue
Natural look
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
Hydrophilic treatment - Structure
OH
OC2H5
C2H5O
Si
OH
OH
OH
+
PEG-8
OC2H5
PEG-8
PEG-8
Si
Si
O
x
O
O
O
O
PEG-8 Methyl Ether Triethoxysilane - Code SW
PEG-8 Triethoxysilane Treatment in H2O
Immediately after mixing
After 30 seconds
After 10 minutes
non-treated
treated
non-treated
treated
non-treated
Mixed 2 grs of TiO2 CR-837 in 50 ml H2O
treated
Viscosity of metal oxide pigments premixes at 65% solids.
Iron Oxide Black C33-5198
TiO2 CR-837
cPs
cPs
400,000
200,000
300,000
150,000
200,000
100,000
100,000
50,000
48,400 cPs
4,500 cPs 4,600 cPs
18,500 cPs
0
0
Untreated
1% silane
2% silane
Untreated
1% silane
2% silane
15 nm Hydrophilic TiO2
cPs
1,000,000
850,000
750,000
500,000
Non treated
250,000
2,800
0
Untreated
5% treatment
Viscosity of premix at 42% solids
Treated
New Hybrid Treatment
Design of Superdispersible Surface Treatment
1. Modify surface energy
Isopropyl titanium
triisostearate +
(ITT)
{
Alkoxysilane
Methicone
Dimethicone
Crosslinked coating
on pigment
* US Provisional patent application No. 60/472,527
• 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.
Stability of TTS Treatment Toward Acid
Hydrophobicity by Floating Test
Metal Soap / ITT
TTS Crosspolymer
2.0
ITT
Magnesium Myristate
1.5
Over
7 days
1.0
40
30
20
0.5
10
0
0
1
2
3
pH
4
Control
TTS coated pigment floats almost indefinitely at pH 2
Neutral
Washing
Washing
at pH 2
ITT/TCS (TTS) Crosspolymer Treatment
Viscosity of Iron Oxide Dispersions
75% in Mineral Oil
73% in Cyclopentasiloxane
cPs
1,500,000
cPs
1,500,000
Too thick
to measure
Too thick
to measure
1,000,000
1,000,000
500,000
500,000
0
0
Untreated
ITT
ITT/TCS
Silane
Crosspolymer
Untreated
ITT
ITT/TCS
Silane
Crosspolymer
TTS Crosspolymer in C12-15 Alkyl Benzoate
Viscosity of 75% Rutile TiO2 Dispersions
cPs
200,000
Out of scale
150,000
100,000
50,000
0
Untreated
MS
ITT
ITT/TCS
Silane
Crosspolymer
* Dispersant: 1.5 %of polyhydroxystearic acid
TTM & TTDM Crosspolymer Treatments
Viscosity of 75% Anatase TiO2 Dispersions
400,000
800,000
cPs
300,000
Isododecane*
cyclomethicone*
C12-15 Alkyl
Benzoate**
200,000
100,000
0
ITT
MS
TPDM
TTM
TTDM
* w/ 2.5% of PEG/PPG-20/15 dimethicone
** w/ 1.5% of polyhydroxystearic acid
2. PF + Silane = FOTS Hybrid
-- Improved compatibility
Silane
treatment
PF treatment
en t
HYBRID
TREATMENT
F3 C
( CF2 )n CH2 CH2
m
P
OH
3-m
O
PF
FOTS - Improved dispersibility
- Retained lipohobicity
- Popular in Japan
Silane
3. PF + ITT = FITT Hybrid
-- Improved compatibility
ent
ITT
P F t re a t m e n t
H Y B R ID
TR EATM ENT
F C
3
(CF )
2
n
CH
2
CH
2
m
P
O
OH
3- m
Isopropyl titanium
triisostearate
FITT - More lipophlic and easy to formulate
4. Treatment of Organic Lakes
FD&C Blue 1 Aluminum Lake
NT
MS
FD&C Red 40 Aluminum Lake
NSS
NT
MS
NSS
2% in water, Standing over 4 days
NT: No treatment
MS: Methicone
NNS: Methoxy Amodimethicone/Silsesquioxane Copolymer
(And) Triethoxy Caprylylsilane
(WO 03/043567 A3, May 30, 2003)
Treatment of Organic Lakes
Bleeding of 2% aqueous suspensions by spectrophotometry
15.3%
11.1%
0.25%
0.125%
0.02%
< 0.01%
0.0%
Red 40 Al Lake
0.08%
0.02%
Blue 1 Al Lake
Non-tr eated : after 1 day @ r oom tem per atu r e
NSS-tr eated : af ter 30 days @ r oom tem per atur e
NSS-tr eated : af ter 30 days @ 50°C
Effect of pH on the stability in water
pH2
mineral acid
pH3
organic acid
pH11
pH12
organic base mineral base
Effect of pH on the stability in water (2% lake in water; 1 day test)
Effect of surfactants on the stability in Water
Methicone
treatment
NSS
treatment
(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.
Common Treatments & Their Drawbacks
Coating
Pros
Cons
Hydrophobic
H2 potential
Disperses poorly in esters
Nice feel
No H2 potential
Not as stable at low pH
No H2 potential
Hydrophobic
Lipophilic
Easy to react with pigments
Reacts too slowly
Dispersibility in esters is fair
Perfluorinated
compounds
Repel both water and oil
Difficult to wet
Polysaccharide
Natural product
No chemical bonding
Highly dispersible
No chemical bonding
Methicone
Dimethicone
Hydrophobic Alkoxysilane
ITT / Metal soap
Hydrophilic Synthetic
surfactant
Not very hydrophobic,
especially at low pH
Novel Surface Treatment
For Hydrophobicizing Pigments
Frank Mazzella, David Schlossman, and Yun Shao, Ph.D.
Kobo Products, Inc.
PCITX - New York
September 28-30, 2004
www.koboproducts.com
Overview
•
What is needed to make a good surface treatment ?
•
Common used substrates.
•
Common Treatments.
•
Specialty Treatments.
•
Summary.
Surface Treatments : Why ?
•
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.
Requirements for Good Surface Treatment
•
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
Popular Hydrophobic Organic Treatments
Coating
Pros
Cons
Hydrophobic
H2 potential
Nice feel
No H2 potential
No H2 potential
Hydrophobic
Lipophilic
Reacts too slowly
Perfluorinated
compounds
Difficult to wet
Polysaccharide
Natural product
No chemical bonding
Highly dispersible
No chemical bonding
Methicone
Dimethicone
ITT / Metal soap
surfactant
Treatments Studied
•
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.
Crosspolymer Treatments
Crosspolymer Treatments - Structure
C17 H35 OCO
C 17H35OCO
Ti
OCOC17H35
O
R
R
O
O
Si
Si
O
O
R
Si
OCOC17H35
O
Ti
O
OCOC17 H35
O
ITT/TCS Crosspolymer: R = C8H17
ITT/Methicone Copolymer: R = CH 3
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
Hydrophobicity of
Crosspolymer vs Its Components
2 gr. of Treated Pigment in 50 mL Water
Shaken 10 times - Picture taken after 10 minutes
Dispersions with 10 nm TiO2
Formulas
CM3K25VM
TNP40VTTS
25%
---
---
40%
KF-6017
12%
---
Cyclopentasiloxane
63%
---
C12-15 Alkyl benzoate
---
57%
Polyhydroxy stearic
acid
---
3%
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
Ingredient
10nm TiO2 (methicone)
10nm TiO2 (ITT/TCS)
Test Results
Ingredient
Branched Alkyl Silane
Treatment
Branched Alkyl Silane
•
Very low Hydrogen potential.
•
Better affinity in many organic non polar systems
•
More hydrophobic than the straight chained alkyl
Silanes.
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
150
152
134
CM3F50KQBAS
Lot B
311
253
282
245
236
140
256
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.
•
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.
Stability of Organic Lakes in Water
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
Non-treated 1 day @ room temp
HTT-treated 30 day @ room temp
HTT-treated 30 day @ 50°C
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.
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 treated
in 2% SLS
HTT treated
in 2% SLS
7 Days test : 2% lake in water
Stability on Mineral Surface
Methicone treated
Sericite
HTT treated
Sericite
1 Day test : 2% Sericite in water
Hard to Treat Surfaces - Summary
•
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.
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
Acknowledgements
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.
Super Dispersible
Pigment Treatment
for Applications in Multimedia
Yun Shao, Ph.D. & David Schlossman
Kobo Products, Inc.
23rd IFSCC - Orlando
October 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
1. Surface Treatment
•
Modifies pigment surface to hydrophobic
and/or lipophilic
HO
HO
OH
OH
HO
Pigment
•
•
•
Improve the skin feel
•
Improved dispersion stability and formula stability
OH
HO
Improve the chemical stability of metal oxidesHO
OH
Improves pigment wetting and size reduction
during dispersion process
Popular Treatments & Their Drawbacks
Coating
Pros
Cons
Hydrophobic
H2 potential
Nice feel
No H2 potential
No H2 potential
Hydrophobic
Lipophilic
Reacts too slowly
Perfluorinated
compounds
Difficult to wet
Polysaccharide
Natural product
No chemical bonding
Highly dispersible
No chemical bonding
Methicone
Dimethicone
ITT / Metal soap
surfactant
Wetting & Penetration
Large θ
Poor wetting
Small θ
Good wetting
Wetting
Penetration
Young-Dupre Equation
The driving force for the capillary action
γSV = γSL + γLV cosθ
γ: interfacial tension
θ: Contact angle
Force = 2 πrγ LV cosθ
r = radius of the crack opening
Wetting & Penetration
Theory :
•
•
Surface tension is a result of difference in surface energy
•
Smaller contact angle generates a higher driving force for
penetration
Liquid of lower surface energy can wet surface of higher
energy and show a smaller contact angle
Practice:
•
Increase the surface energy of coating without loss of
hydrophobicity
Surface Energy of Common Coatings & Liquids
Coatings
Surface Energy (dyne/cm2)
Perfluorinated compounds
Dimethicone
Methicone
Alkoxysilane
Wax (polyethylene)
Metal Soap/Organic Titanate
18 – 20
20 –24
30 - 31
30 - 35
Liquids
Surface Energy (dyne/cm2)
Water
Castor oil
Olive oil
Liquid petrolatum
Capric caprylic triglyceride
Mineral oil
Dimethicone
Perfluorinated liquid
Cyclomethicone
72.8
39
35.8
33.1
30
30 - 35
20 –24
16 – 20
17.8 ( @25°C)
(All measured @ 20 oC)
Act of Dispersants
Anchoring Through Ionic or Acidic/Basic Groups.
+
+
+
+
+
+
+
Anchoring Through
Hydrogen-Bonding Groups.
+
+
+
Anchoring Through
Solvent-Insoluble Polymer Blocks.
H
H
O
O H
soluble
insoluble
O
O
H
Result: reduced inter-particulate attraction for aggregation
Pigment Dispersion Examples
w/o dispersant
Untreated
A
Treated
B
15nm TiO2 : 45% *
Treatment : Methicone (B & D)
Vehicle :
Cyclopentasiloxane
Dispersant : 10 % KF-6017 (C & D)
* note : in mix A, only 33% TiO2
was used (maximum amount
possible)
Chunky paste
D
w/ dispersant
C
Viscous slurry
Easy handling
Better dispersion
Chunky paste
Fluid
Design of Superdispersible Surface Treatment
1. Modify surface energy
Isopropyl titanium
triisostearate +
(ITT)
{
Alkoxysilane
Methicone
Dimethicone
Crosslinked coating
on pigment
* US Provisional patent application No. 60/472,527
2. Minimize the interaction among particulates
Coating + Dispersant as secondary coating
Chemical Reactions During Surface Treatment
- C3H7OH
C17H35OCO-Ti-O - Pigment
(C17H35OCO)3-Ti-OC3H7 + HO - Pigment
ITT
- C2H5OH
-H2O
C8H17-Si-(OH)3 + HO - Pigment
C8H17- Si (OC2H5)3
(C8H17-Si-O3)x - Pigment
Triethoxy caprylylsilane (TCS)
CH3
Si
H
O
x
+ HO - Pigment
CH3
-H2
Si
O
Pigment
Methicone (MS)
-C2H5OH
OC2H5 OC2H5 OC2H5
O
x
-H2O
OH
OH
OH
O
O
O
pigment
Triethoxysilylethyl polydimethylsiloxyethyl dimethicone (TPDM)
Crosspolymer Treatment - Structure
C17 H35 OCO
C 17H35OCO
Ti
Crosslinked, 3-dimensional
web-like structure
OCOC17H35
O
R
R
O
O
Si
Si
O
O
R
Si
OCOC17H35
O
Ti
O
O
OCOC17 H35
R = C8H15, ITT/TCS (TTS)
R = CH3, ITT/Methicone (TTM)
R = [ Si(CH3)2O]x, ITT/TPDM (TTDM)
ITT/TCS Crosspolymer: R = C8H17
ITT/Methicone Copolymer: R = CH 3
Catalytic Effect of Titanate on Silicone Reactions
Hydrophobicity of treated 10 nm TiO2
7%
7%
3.5% of each
2 g of Treated Pigment in 50 mL Water
Hydrophobicity of Crosspolymer Treatment
Contact angle of
Various Surface Treatments
160
Hydrophobicity of
Various Surface Treatments
60
50
140
40
30
120
20
10
100
0
Stability of TTS Treatment Toward Acid
Hydrophobicity by Floating Test
Metal Soap / ITT
TTS Crosspolymer
2.0
ITT
Magnesium Myristate
1.5
Over
7 days
1.0
40
30
20
0.5
10
0
0
1
2
3
pH
4
Control
Neutral
Washing
Washing
at pH 2
TTS coated pigment floats almost indefinitely at pH 2
ITT/TCS (TTS) Crosspolymer Treatment
Viscosity of Iron Oxide Dispersions
75% in Mineral Oil
cPs
1,500,000
cPs
1,500,000
Too thick
to measure
Too thick
to measure
1,000,000
1,000,000
500,000
500,000
0
0
Untreated
ITT
ITT/TCS
Silane
Crosspolymer
Untreated
ITT
ITT/TCS
Silane
Crosspolymer
TTS Crosspolymer in C12-15 Alkyl Benzoate
Viscosity of 75% Rutile TiO2 Dispersions
cPs
200,000
Out of scale
150,000
100,000
50,000
0
Untreated
MS
ITT
ITT/TCS
Silane
Crosspolymer
* Dispersant: 1.5 %of polyhydroxystearic acid
TTM & TTDM Crosspolymer Treatments
Viscosity of 75% Anatase TiO2 Dispersions
400,000
800,000
cPs
300,000
Isododecane*
cyclomethicone*
C12-15 Alkyl
Benzoate**
200,000
100,000
0
ITT
MS
TPDM
TTM
TTDM
* w/ 2.5% of PEG/PPG-20/15 dimethicone
** w/ 1.5% of polyhydroxystearic acid
Use of Dispersant as Auxiliary Coating
Alkyl
Silicone
Acrylic
Polymer
COOH
COOH
• INCI: Acrylates/Ethylhexyl Acrylate/Dimethicone
Methylacrylate Copolymer
• Designed for dispersing pigment primarily in cyclomethicones
Effect of Acrylate/Silicone Copolymer on Dispersibility
Viscosity of 75% TiO2 Dispersion
( 2.5% of PEG/PPG-20/15 Dimethicone)
in Isododecane
59,000
50,000
350,000
300,000
40,000
cPs
cPs
in Cyclopentasiloxane
30,000
250,000
200,000
150,000
20,000
100,000
10,000
50,000
0
0
MS
TCS
TTM
0%
MS
TCS
TTM
3% of Acrylate/Silicone Copolymer
Effect of Acrylate/Silicone Copolymer on Dispersibility
Viscosity of 75% TiO2 Dispersion
(With 1.5% of polyhydroxystearic acid)
In C12-15 Alkyl Benzoate
1,000,000
800,000
cPs
600,000
400,000
200,000
0
MS
0%
TCS
TTM
3% of Acrylate/Silicone Copolymer
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.
Acknowledgements
• Shirley Wang
• Eric Smith
• Scott Hozalpfel
• Pascal Delrieu, Ph.D.
Surface Treatment and
Dispersions of Inorganic
UV Filters
David Schlossman and Yun Shao, Ph.D.,
Kobo Products, Inc.
Chulalongkorn University Seminar, Thailand
June 25, 2004
Inorganic UV Filters: TiO2 and ZnO
Absorption :
420 nm (TiO2 rutile) / 390 nm (TiO2 anatase)
380 nm (ZnO)
Scattering :
UV
Large particles :
- less efficient against UV
- whitening
Merit :
Visible
Small particles :
- Highly efficient against UV
- transparent
Inert and safe when coated; Antimicrobial (ZnO)
Drawback : Whitening
June 25, 2004
Extinction Ratios
1.2
308
360
524
1.0
0.8
0.6
0.4
0.2
0
280
320
360
400
440
480
520
Wavelength (nm)
Ext. 308
Ext. 524
UVB attenuation
Transparency
June 25, 2004
Ext. 308
Ext. 360
308 nm : max erythemal effectiveness
360 nm : Mid of UVA
524 nm : Blue end of visible light
UVA and UVB ratio
Titanium Dioxide Particles (TEM)
Rutile Type
15 nm coated
35 nm uncoated
June 25, 2004
180 nm pigmentary
Zinc Oxide Particles (TEM)
ZnO (20 nm)
June 25, 2004
ZnO (60 nm)
Manufacturers of Titanium Dioxide
Manufacturer
Trade name
Internet address
Degussa
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.com
Sachtleben
Hombitec
www.sachtleben.de/h/e/hom/0000e.html
Showa Denka
Maxlight
www.sdk.co.jp/chemicals/index.html
Tayca Corporation
MT Series
www.tayca.co.jp/english/file/04/04_02.html
Titan Kogyo
STT
www.titankogyo.co.jp
Uniquema
Solaveil, Tioveil
www.uniquema.com/pc
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)
EMD
Eusolex T-2000
76-82
Anatase
10-15 nm
ISK
ISK
ISK
TTO S-4
TTO S-3
TTO V-3
82 <
82 <
82 <
Rutile
Rutile
Rutile
15 nm
15 nm
10 nm
Kemira
UV Titan M170
75 <
Rutile
14 nm
Kemira
UV Titan M262
85 <
Rutile
20 nm
None
Alumina,
Dimethicone
AHSA
Alumina
Alumina
Alumina,
Methicone
Alumina,
Dimethicone
Sachtleben
Hombitec L5
Showa Denka Maxlight TS-04
Tayca
MT-100T
Tayca
MT-500B
Tayca
MT-100Z
Titan Kogyo
STT 65C-S
75-85
64
80 <
96 <
73 <
96.5
Anatase
(80-160 m2/g)
35 nm
15 nm
35 nm
15 nm
(64 m2/g)
June 25, 2004
Rutile
Rutile
Rutile
Anatase
Silica, Silicone
Silica
AS / AH
Alumina
AS / AH
None
Manufacturers of Zinc Oxide
Manufacturer
Trade name
Internet address
Advanced Nano Technologies
Zinclear
www.ant-powders.com/zinclear.htm
BASF
Z-Cote
www.basf.com
Elementis Specialties
Nanox
www.elementis-specialties.com
Zinc Corporation of America
USP-1
www.zinccorp.com
Nanophase
NanoGuard
www.nanophase.com
Sakai
Finex
www.sakai-chem.co.jp
Showa Denka
Maxlight ZS
www.sdk.co.jp/chemicals/index.html
Sumitomo Cement
ZnO series
www.socnb.com/index_e.html
Tayca Corporation
Haarmann and Reimer
MZ Series
ZnO Neutral
www.tayca.co.jp/english/file/04/07_03.html
www.symrise.com
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
Finex
SF-20
> 99
60 nm (17 m2/g)
None
>99
60 nm (20 m2/g)
None
Showa Denka
ZS-032
80
31 nm
Silica
Sumitomo
Cement
ZnO-350
>99
35 nm
None
Tayca
Tayca
Tayca
MZ-700
MZ-500
MZ-300
>99
>99
>99
10-20 nm
20-30 nm
30-40 nm
None
None
None
Sakai
June 25, 2004
Technical Challenges (1/2)
•
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)
June 25, 2004
Technical Challenges (2/2)
•
•
•
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
June 25, 2004
Wetting
Large θ
Poor wetting
Small θ
Good wetting
Young-Dupre Equation
γ = γ + γ cosθ
SV
SL
LV
γ: interfacial tension
The wetting agent should reduce the liquid-solid
surface tension and the liquid-vapor tension.
June 25, 2004
Mechanical Breakdown
•
General mechanism :
›
›
Shear force
Impact action
June 25, 2004
•
General processor :
›
›
›
High shear mixer
Mills
Homogenizer
Stabilization of Particulates
Steric Interactions
•
Steric stabilization
›
•
Coulombic Interactions
by adsorbing polymeric materials
Electrostatic stabilization
›
by adsorbing charge additive
June 25, 2004
Influence of Particle Size &
Distance on Stability
Attractive Forces Between Particulates
• Smaller particles can be stabilized with thinner polymer layers
• Overcrowded dispersion tends to aggregate
June 25, 2004
Sedimentation of Particulates
Stokes’ Law
The relationship between the free falling velocity of a
spherical particle in a Newtonian fluid and the particle
diameter.
V = (2gr²)(d1-d2)/9µ
where: 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
June 25, 2004
Benefits of using Dispersions over
Particulates
Comparison of in-vitro SPF
30
25
30
TiO2 powder
TiO2 dispersion
25
20
20
15
15
10
10
5
5
0
0
TiO2
@ 5%
TiO2
@ 8%
W/O Sun Lotion
TiO2 powder
TiO2 dispersion
TiO2
@ 2.5%
TiO2
@ 5%
TiO2
@ 8%
O/W Sun Lotion
Study made by Tri-K (USA) for MT-100T
June 25, 2004
Factors Influencing the Dispersion
Pigment
Medium
Process Conditions
Packing Density
Chemical Composition
(Treatments, Carrier,
Dispersant)
Dispersing Machine
Particle Shape
Surface Character
Percent Solids
Concentrations
Viscosity
Temperature
Viscosity
Energy Input
Polarity
Particulate Dispersion
June 25, 2004
Influence of Percent Solids (1/2)
Attenuation TiO2 in Isononyl Isononanoate
60%
40%
June 25, 2004
PPS
(nm)
Product
Name
Surface
Treatment
PS
%
(nm) Solids
15
IN60TS
AHSA w/s
132
60
15
IN40TS
AHSA w/s
160
40
Influence of Percent Solids (2/2)
100
IN60TS
80
IN40TS
60
40
20
TiO2 : 0.001%
0
280
320
360
400
440
480
Wavelength (nm)
June 25, 2004
Influence of Surface Treatment
•
•
Provides physical and chemical stability
•
Pre-wets the pigment surface (lower oil
absorption)
•
•
•
Decreases the adsorption of the dispersant
Modifies pigment surface to hydrophobic
and/or lipophilic
Improves Pigment Wetting and Size Reduction
Improved flow and dispersion stability by
minimizing the re-aggregation
June 25, 2004
Influence of Surface Treatment on
Physical Stability
Oxidation of
Acetaldhyde
TiO2 + UV irradiation
e- + h + ( hole +)
CH3CHO + H2O + 2h+
CH3COOH + 2H +
CH3COOH + H2O + 8h+
2 CO2 + 8H +
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
Formulation tip:
Only coated TiO2 and ZnO should be used.
June 25, 2004
Inorganic Surface Treatments
for Pigments
•
Alumina
•
Silica
•
Aluminum Hydroxide
•
Zirconia (popular in Japan)
June 25, 2004
Popular Treatments and Their Drawbacks
Coating
Pros
Cons
Hydrophobic
H2 potential
Nice feel
No H2 potential
No H2 potential
Hydrophobic
Lipophilic
Reacts too slowly
Perfluorinated
compounds
Difficult to wet
Polysaccharide
Natural product
No chemical bonding
Highly dispersible
No chemical bonding
Methicone
Dimethicone
ITT / Metal soap
surfactant
June 25, 2004
Surface Treatment :
Pre-Wetting of the Pigment
w/o dispersant
Untreated
A
Treated
B
15nm TiO2 : 45% *
Treatment : Methicone (B & D)
Vehicle :
Cyclopentasiloxane
Dispersant : 10 % KF-6017 (C & D)
* note : in mix A, only 33% TiO2
was used (maximum amount
possible)
Chunky paste
D
w/ dispersant
C
Viscous slurry
Chunky
paste
Fluid
Chulalongkorn
University
Seminar, Thailand
June 25, 2004
Easy handling
Better dispersion
New Silane Surface Treatments
Silane treatments
Crosspolymer treatments
11S2 : R = Caprylyl
SW : R = Polyethylene Oxide
TTB : R = Branched Dimethicone
TTS : R = Caprylyl
TTM : R = Methyl
June 25, 2004
Crosspolymer Treatments
Titanate reacts and catalyzes silicone compounds
ITT +
Alkoxysilane
Perfluoro Alkoxysilane pigments
Methicone
Dimethicone
{
Crosslinked coating
on pigment
* US Provisional patent application No. 60,472,527
Results :
• Hydrophobicity comparable to silane and methicone treatments
• Stable over a pH range of 2 - 9
June 25, 2004
Hydrophobicity of TTS treatment
2 gr. of Treated Pigment in 50 mL Water
June 25, 2004
ITT/TCS Crosspolymer Treatment
Viscosity of Iron Oxides premix
75% in Mineral Oil
cPs
1,500,000
cPs
1,500,000
Too thick
to measure
Too thick
to measure
1,000,000
1,000,000
500,000
500,000
0
0
Untreated
ITT
ITT/TCS
Silane
Crosspolymer
June 25, 2004
Untreated
ITT
ITT/TCS
Silane
Crosspolymer
ITT/TCS Crosspolymer in
C12-15 Alkyl Benzoate
Viscosity of TiO2 CR-837 premix at 75% solids
cPs
200,000
Out of scale
150,000
100,000
50,000
0
Untreated
MS
ITT
ITT/TCS
Silane
Crosspolymer
* Dispersant: 1.5 % Polyhydroxystearic acid
June 25, 2004
ITT/Methicone Crosspolymer :
H2 Potential
Treatment of TiO2 CR-837
Methicone
30
ITT/
Hydrophobicity
Methicone
A
2
--
Good
B
1
--
Poor
C
--
2
Good
20
C
10
0
• ITT / Methicone Crosspolymer
A
Methicone
treatment
ITT / Methicone
treatment
treatments are hydrophobic
with lower hydrogen potential
• Hydrogen potential reduction is even more significant on
micronized TiO2
June 25, 2004
15 nm Hydrophilic TiO2
cPs
1,000,000
850,000
750,000
500,000
Non treated
250,000
2,800
0
Untreated
5% treatment
Viscosity of premix at 42% solids
Treated
Chulalongkorn University
Seminar, Thailand
June 25, 2004
Branched Dimethicone Treatment :
Structure
pigment
O-Et
O-Et
O
O
O
O-Et
CH3
=
(
Si
O
x
CH3
INCI name : Dimethicone
•
•
Kobo code : BS
Branched structure increases dispersion stability
No Hydrogen potential
June 25, 2004
Dimethicone Treatment in
Cyclopentasiloxane
cPs
1,200,000
MS :
BS :
Silane :
900,000
ITT :
600,000
TTM :
300,000
TTS :
Methicone
Dimethicone
Triethoxy
Caprylsilane
Isopropyl
Titanium
Triisostearate
ITT/Methicone
Crosspolymer
ITT/TCS
Crosspolymer
0
Untreated
MS
Silane
BS
ITT
TTM
TTS
* Dispersant : 2.5% PEG/PPG-20/15 Dimethicone from SF1528
June 25, 2004
Dimethicone Treatment in
Cyclopentasiloxane
cPs
600,000
MS :
BS :
Silane :
450,000
ITT :
300,000
TTM :
150,000
TTS :
Methicone
Dimethicone
Triethoxy
Caprylsilane
Isopropyl
Titanium
Triisostearate
ITT/Methicone
Crosspolymer
ITT/TCS
Crosspolymer
0
Untreated
MS
Silane
BS
ITT
TTM
TTS
* Dispersant : 2.5% of Bis-PEG/PPG 14/14 Dimethicone (Abil EM 97)
June 25, 2004
Influence of Primary Particle Size (1/3)
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
Primary Particle Size (PPS)
15nm
35nm 100nm 200nm
June 25, 2004
UV/Visible Transmittance curves
absorption
scattering
100
INH60TS
80
INH70T
60
INH65K9
40
20
IN80C
TiO2: 0.001%
0
280
320
360
400
wavelenght (nm)
June 25, 2004
440
480
10nm TiO2 make transparent dispersions for all skin types
1
2
1
3
Black
1
2
3
2
3
Asian
1 = 1 0 n m T i O 2 D i sp er si on
2 = 1 5 n m T i O 2 D i sp er si on
3 = Com m er ci al l y A v ai l ab l e
D i sp er si on
Caucasian
June 25, 2004
Influence of Silicone Dispersants
Formulas
Ingredient
CM3K25VM
CMKP25VM
CME730VM
25%
25%
30%
12%
---
---
KP-575
---
12%
---
Abil EM 97
---
---
10%
63%
63%
60%
CM3K25VM
CMKP25VM
CME730VM
< 100
19
100,000
Particle size (nm)
110
104
238
Index of aggregation
11.0
10.4
23.8
20
20
24
SIV-MS7 (alumina and
methicone)
KF-6017
Cyclopentasiloxane
Test Results
Ingredient
Viscosity (cPs)
TiO2 (%)
June 25, 2004
UV/Vis Transmittance of
10 nm TiO2 Dispersions
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
CM3K25VM CMKP25VM CME730VM
100
CM3K25VM
CMKP25VM
80
60
CME730VM
40
20
TiO2 : 0.001%
0
280
320
360
400
440
480
Wavelength (nm)
June 25, 2004
Dispersions with 20-35 nm TiO2
Formulas
Ingredient
CM3K60TM
CMKP60M262
60%
---
---
60%
30%
28%
KF-6017
10%
---
KP-575
---
12%
CM3K60TM
CMKP60M262
102,000
12,000
Particle size (nm)
179
143
5.1
7.2
TiO2 (%)
56
53
35 nm TiO2
(methicone)
20 nm TiO2 (alumina and
dimethicone)
Cyclopentasiloxane
Test Results
Ingredient
Viscosity (cPs)
June 25, 2004
20-35 nm TiO2 Dispersions
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
100
CM3K60TM
CMKP60M262
80
60
CM3K60TM
40
20
CMKP60M262
0
280
320
360
400
TiO2 : 0.001%
440
480
Wavelength (nm)
June 25, 2004
Dispersions with ZnO
Formulas
CM3K50XZ4
CMKP50XZ4
CM3K40HP1
50%
50%
---
---
---
40%
Cyclopentasiloxane
40%
40%
50%
KF-6017
10%
---
10%
KP-575
---
10%
---
CM3K50XZ4
CMKP50XZ4
CM3K40HP1
Viscosity (cPs)
200
75
1,500
Particle size (nm)
145
147
250
5.8
5.9
1.3
ZnO (%)
48
48
38
Ingredient
20 - 30 nm ZnO
(methicone)
Z-Cote HP-1 (<200nm,
dimethicone)
Test Results
Ingredient
June 25, 2004
ZnO Dispersions
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
100
CM3K50XZ4 CMKP50XZ4 CM3K40HP1
CMKP50XZ4
80
60
40
CM3K50XZ4
CM3K40HP1
20
TiO2: :0.005%
0.001%
ZnO
0
280
320
360
400
440
480
Wavelength (nm)
June 25, 2004
Influence of the Dispersion Formula
Formulas
CM3K25VM
TNP40VTTS
TNP55VTTS
25%
---
---
---
40%
55%
KF-6017
12%
---
---
Cyclopentasiloxane
63%
---
---
---
57%
42%
Polyhydroxy stearic
acid
---
3%
3%
CM3K25VM
TNP40VTTS
TNP55VTTS
Viscosity (cPs)
100
150
10,000
Particle size (nm)
110
100
100
TiO2 (%)
19.5
32.0
44.0
Ingredient
10nm TiO2 (methicone)
10nm TiO2 (ITT/TCS)
Test Results
Ingredient
June 25, 2004
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
CM3K25VM TNP40VTTS TNP55VTTS
100
80
CM3K25VM
60
TNP40VTTS
TNP55VTTS
40
(superimposed)
20
TiO2 : 0.001%
0
280
320
360
400
440
480
Wavelength (nm)
June 25, 2004
Influence of Dispersants & Vehicles
Formulas
Ingredient
PM9P60M170
PM9P50M170
TNP50M170 CM3K40M170
14nm TiO2 (alumina
and dimethicone)
60%
50%
50%
40%
Isododecane
37%
47%
---
---
---
---
47%
---
Cyclopentasiloxane
Polyhydroxy stearic
acid
KF-6017
---
---
---
46%
3%
3%
3%
---
---
---
---
14%
PM9P60M170
PM9P50M170
Viscosity (cPs)
180
20
600
275
Particle size (nm)
172
110
165
165
12.3
7.9
11.8
11.8
TiO2 (%)
46.5
38.8
31.0
38.8
Test Results
June 25, 2004
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
PM9P60M170 PM9P50M170 TNP50M170
CM3K40M170
100
PM9P50M170
CM3K40M170
80
60
PM9P60M170
TNP50M170
40
20
TiO2 : 0.001%
0
280
320
360
400
440
480
Wavelength (nm)
June 25, 2004
Dispersions with 20-30 nm ZnO
Influence of Dispersants & Vehicles
Formulas
Ingredient
20-30 nm ZnO
(methicone)
20-30 nm ZnO
(Triethoxycapryl Silane)
C12-15 Alkyl Benzoate
TNP50ZSI
TNP50ZCLS CMKP50XZ4
---
---
50%
50%
50%
---
47%
47%
---
Poyhydroxystearic acid
3%
3%
---
Cyclopentasiloxane
---
---
40%
KP-575
---
---
10%
Test Results
TNP50ZSI
TNP50ZCLS CMKP50XZ4
Viscosity (cPs)
100
60
100
Particle size (nm)
130
110
147
5.2
4.4
5.9
ZnO (%)
47.0
47.0
47.0
June 25, 2004
ZnO Dispersions
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
TNP50ZSI TNP50ZCLS CMKP50XZ4
100
TNP50ZCLS
80
TNP50ZSI
60
CMKP50XZ4
40
20
ZnO
TiO2: :0.005%
0.001%
0
280
320
360
400
440
480
Wavelength (nm)
June 25, 2004
Extinction ratios
(1)
Pigment
TiO2
ZnO
Primary particle size
10 nm
15 nm (High SpeedTM Disp)
®
15 nm (High Solids Disp)
20 nm
35 nm
150 nm
20 nm
60-100 nm
120 nm
Ratio
305/360
7.0 - 8.0
4.5 - 5.5
3.4 - 3.9
2.0
1.5 - 2.0
1.1
1.0 - 1.1
1.1
0.9
(2)
Maximum
Ratio
305/524 absorption @
70 - 90
275 nm
50 - 55 280 - 290 nm
11 - 16 290 - 305 nm
9
300 nm
7 - 17
315 nm
2.6
318 nm
30 - 37
360 nm
6.3
371 nm
2.9
375 nm
(1) 305/360 ratio : indication of UVB/UVA ratio
(2) 305/524 ratio : indication of transparency
June 25, 2004
In-Vivo vs. In-Vitro SPF Test Results
Formula
Active
In-vitro SPF
Active
(%)
P. S.
(nm)
In-vivo
SPF
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
30.5
45.1
42.2
2550/2 (w/o)
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
June 25, 2004
In-vivo vs. in-vitro PFA Test Results
Formula
Active
Uva/UVB ratio
Active
(%)
P. S.
(nm)
In-vivo
PFA
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
3.05
0.56
0.6
2550/2 (w/o)
TiO2
4.23
June 25, 2004
194.5
Sunscreen Formulations
% Active
SPF
SPF per
% active
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
TNP40VTTS
9.3%
24
2.6
(w/ octylmethoxycinnamate)
TNP40VTTS
3.1%
50
19.3%
24
Formulation type
Dispersion
Sunscreen spray
Water-in-silicone emulsion
TNP50ZCLS
1.2
TNP50HPI
TNP55T7
19.7%
TNP50ZSI
June 25, 2004
Summary
Fundamental to meeting the technical challenges
required for the successful use of inorganic
particulates to attenuate UV light :
• Proper surface treatment and dispersion
• Understanding the influence of particle size on
UV attenuation
June 25, 2004
KSL-083A
SPF 15 Spray Formula with TNP50ZCLS
Phase Ingredient
A
B
C
Trade Name/Vendor
%
Deionized water
---
69.8
Butylene Glycol
---
3.0
Phenoxyethanol (And) Methylparaben (And) Propylparaben
(And) Ethylparaben (And) Butylparaben (And) Isobutylparaben
Phenonip
1.0
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
Acrylamides Copolymer (And) Mineral Oil (And) C13-14
Isoparaffin (And) Polysorbate 85
Sepigel 501
0.5
June 25, 2004
KSL-084
SPF 24 W/O Emulsion with TNP40VTTS
Phase Ingredient
A
B
C
Trade Name/Vendor
%
Deionized water
---
39.5
Xathan Gum
---
0.15
Magnesium sulphate
---
2
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)
Polyethylene
CL-2080
2
Polyethylene
Liposatin PE35 (Lipo)
1
Oat flour
Oat flour (Textron)
Beta glucan
Dragro betaglucan (Symrise)
Diazolidinyl urea & Iodopropynyl Carbamate & Propylene Glycol Liquid Germall Plus (ISP)
Soybean(glycine soja)protein & oxido-reductase
June 25, 2004
Preregen (Centerchem)
0.5
0.5
1
0.4
3
KSL-043
SPF 25 W/O with TNP50ZSI
Phase Ingredient
A
B
C
Trade Name/Vendor
%
Deionized water
---
40
Xathan Gum
---
0.15
Magnesium sulphate
---
2
Propylene Glycol
---
3
C12-15 Alkyl Benzoate (And) Zinc Oxide (And)
Polyhydroxystearate (And) Triethoxy Caprylylsilane
TNP50ZSI
30
Isostearyl Neopentanoate
Ceraphyl 375 (ISP)
Glyceryl Dilaurate
Emulsynth GDL (ISP)
1
Arlacel P135 (ICI)
3
Polyethylene
CL-2080
Polyethylene
Liposatin PE35 (Lipo)
Diazolidinyl urea & Iodopropynyl Carbamate & Propylene Glycol Liquid Germall Plus (ISP)
June 25, 2004
16.95
2.5
1
0.4
KSL-067
SPF 40 Water-in-silicone with CM3K25VM
Phase Ingredient
A
B
C
Trade Name/Vendor
%
Deionized water
---
32.1
Sodium Chloride
---
0.5
Cetyl Dimethicone Copolyol &(And) Polyglyceryl- 4 Isostearatehexyl Laurate
Abil WE -09
5.0
---
0.2
Cyclopentasiloxane & Titanium Dioxide & Alumina & (And)
Dimethicone Copolyol & Methicone
CM3K25VM
60.0
PEG-150/Smdi Copolymer
Aculyn 44
2.0
Diazolidinyl Urea
Germall Plus
0.2
June 25, 2004
SPF 44 Foundation Make-Up
KLF-016
with CMKP60M262
Phase Ingredient
A
B
C
D
Cyclopentasiloxane (And) PEG/PPG-20/15 Dimethicone
Cyclopentasiloxane Dimethicone/Vinyldimethicone
Crosspolymer
Cyclopentasiloxane
Bis-Phenylpropyl Dimethicone
Polymethylsilsesquioxane
Cyclomethicone Trimethylsiloxysilicate
Phenoxyethanol (And) Methylparaben (And) Propylparaben
(And) Ethylparaben (And) Butylparaben (And) Isobutylparaben
Trade Name/Vendor
%
SF1528/GE
7.83
SFE839/GE
0.78
SF1202
SF1555
Tospearl 2000
SS4230
10.64
0.63
3.13
2.50
Phenonip
1.00
Titanium 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)
FA55RSI
1.00
Black Iron Oxide (And) Decamethyl Cyclopentasiloxane (And)
FA60BSI
0.40
Butylene Glycol
RITAbate 20/RITA
Sodium Chloride
Glycerin
SD 39C
26.07
7.83
0.31
0.63
1.25
5.00
Water
Butylene Glycol
Polysorbate 20
Sodium Chloride
Glycerin
Ethanol
June 25, 2004
KSL-086
SPF 50 W/O Emulsion with TNP40VTTS
Phase Ingredient
A
B
Deionized Water
Sodium Chloride
Propylene Glycol
Allantoin
Methyl Paraben
C12-15 Alkyl Benzoate (And) Titanium Dioxide (And) Alumina
(And) Polyhydroxystearate (And) Isopropyl Titanium
Triisostearate (And) Triethoxy Caprylylsilane
Microcrystaline Wax
Wax
Octyl stearate
Shea Butter
PEG-30 dipolyhydroxystearate
Polyglyceryl-4 Isostearate (And) Cetyl Dimethicone Copolyol
(And) Hexyl Laurate
Cyclopentasiloxane
Propylparaben
Cetearyl Alcohol (And) Cetearyl Phosphate
Octyl Methoxy Cinnamate
Octocrylene
Benzophenone-3
June 25, 2004
Trade Name/Vendor
%
-----------
52.39
0.50
3.00
0.20
0.15
TNP40VTTS
10.00
SP 94 (Strahl & Pitsch)
Abil Wax 9801 (Goldsmidt)
Cetiol 868 (Cognis)
Cetiol SB 45 (Cognis)
Arlacel P135 (ICI)
0.50
1.00
4.00
1.00
2.50
Abil WE 09 (Cognis)
2.50
DC 345 (Dow Corning)
--Crodafos CES (Croda)
Uvinul MC 80 (BASF)
Uvinal N 539 T (BASF)
Romary Oleoresin HQ 3401
(Hilltech)
1.00
0.06
1.00
8.50
10.00
(BASF)
1.50
0.20
KSL-092
SPF 24 Waterproof Sunscreen
Phase Ingredient
A
B
Deionized Water
Sodium Chloride
PEG-150/Smdi Copolymer
Paragon MEPB
Trade Name/Vendor
%
----Acculyn 44
McIntyre
40.30
0.50
4.00
0.60
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
SF1204 (G.E.)
Tegocare PS (Degussa)
Abil Wax 9801 (Degussa)
Floraesters 15 (Floratec)
5.00
0.60
2.00
2.00
Zinc Oxide (And) C12-15 Alkyl Benzoate (And)
Polyhydroxystearic Acid (And) Triethoxy Caprylylsilane
Cyclomethicone
Methyl Glucose Sesquistearate
Cetyl Dimethicone
Jojoba Esters
June 25, 2004
KSL-098
W/O High SPF Suncare emulsion
Phase Ingredient
A
B
C
Deionized Water
Sodium Chloride
Allantoin
Trade Name/Vendor
%
----Sutton
33.68
0.56
0.20
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
Abil WE 09 (Cognis)
SF1204 (G.E.)
NIPA
NIPA
Cognis
Arlacel P135 (Uniqema)
Centerchem
HQ 3401 (Hilltech)
Hallbrite BHB (Hall Co.)
Acatris
Micronasphere M (EMD)
Colorona Oriental Beige
Biron Fines (EMD)
Cetiol CC (Cognis)
Floraesters 15 (Floratec)
Acculyn 44 (Rohm & Haas)
2.50
5.00
0.15
0.06
1.00
2.50
1.00
0.20
3.00
0.30
0.30
0.05
0.50
3.00
3.00
3.00
Iricalmin (Centerchem)
3.00
Polyglyceryl-4 Isostearate (And) Cetyl Dimethicone Copolyol (And) Hexyl
Cyclomethicone
Methylparaben
Propylparaben
Shea Butter
Argan Oil
Rosemarinus Officinalis (Rosemary) Extract
Butyloctyl Salicylate
Ascorbyl Palmitate
Mica (And) Silica
Mica (And) Iron Oxide (And) Titanium Dioxide
Bismuth Oxichloride
Octyl Carbonate
Jojoba Esters
Urethane / C1-12 Alkyl PEG Copolymer
Water (And) Triticum Vulgare (Wheat) Extract (And) Saccharomyces
Cerivisiae
ExtractSeminar,
(And) Sodium
Hyaluronate
Chulalongkorn
University
Thailand
June 25, 2004
Part II
Analysis of Commercial
Products
Comparison of Marketed Foundations (I)
R20
R15
Oil
HR
N
Co d e
Pro d u c t
SPF
% T iO 2
R2 0
Re v lo n A g e D e f y in g
A ll D ay Lif tin g
20
R1 5
Re v lo n Co lo rs tay
Lite Mak e -u p
15
5 .2 %
Oil
Oil o f Olay
15
4 .0 %
HR
He le n a Ru b in s te in
Sp e c tac u lar Mak e -u p
10
3 .1 %
N
N e u tro g e n a
Oil Fre e
20
2 .4 %
8 .6 %
+3 .2 5 Zn O
Comparison of Marketed Foundations (II)
Same Formula Concentration
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
Comparison of Marketed Foundations (III)
Same TiO2 Concentration
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
Comparison of Marketed Foundations (IV)
In vitro SPF Testing
Co d e
P ro d u c t
A v e ra g e
SP F
Cri t i c a l
Wa v e l e n g t h
A v e ra g e
U V A Ra t i o
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
385 nm
0 .8 0
R1 5
Re v lo n Co lo rs t a y
Lit e M a k e -u p
9 0 .1 0
384 nm
0 .7 2
O il
O il o f O la y
1 9 4 .5 1
388 nm
0 .9 3
HR
H e le n a Ru b in s t e in
Sp e c t a c u la r M a k e -u p
7 7 .7 1
387 nm
0 .8 8
N
N e u t ro g e n a
O il Fre e
8 7 .3 8
386 nm
0 .8 2
• Presence of pigments in color cosmetic generate much scattering
which 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
TNP40VTTS
TNP40VM
IN60S4
CM3K25VM
100 nm
100 nm
130 nm
110 nm
* Eyeshadow -- same caution
Lipsticks : Addition of TiO2
Dark Shade
Color Changes
Delta L : -0.4 (Darker)
Delta a : 1.3 (Redder)
Delta b : -0.5 (Bluer)
With 2.4% TiO2
Without
Pink Shade
Delta L : 0.4 (Whiter)
Delta a : -0.5 (Greener)
Delta b : 0.9 (Yellower)
With 2.4% TiO2
Without
Dispersion: CM3K35VM
(PS 110 nm, PPS 10 nm)
Makeup or foundation -- Color Dispersions
WE70U WE55Y WE70R
WE70B
Pro duct
Tre atm e nt
PS
(n m )
% So lids
WE7 0 U
ITT
328
70%
WE5 5 Y
ITT
317
55%
WE7 0 R
ITT
227
70%
WE7 0 B
ITT
1 ,0 6 5
70%
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:
TNP40VM:
IN60S4:
100 nm
100 nm
130 nm
Dispersion in D5:
CM3K25VM:
CM3K40T4:
110 nm
120 nm
UV TiO2 in Makeup or foundation
Medium to light shades:
• UV TiO2 can be little opaque
• 20 - 35 nm TiO2 dispersion
• More UVA protection
Dispersion in esters:
TNP40G8:
150 nm
INH70T:
154 nm
KQ-1 dispersionsL 180 nm
Dispersion in D5:
CMKP50M262: 160 nm
KQ-1 dispersions: 180 nm
UV TiO2 in Pressed powder
All shades:
• Use small size TiO2 (10 or 15 nm)
• Jet pulverize to get more UV performance
SIV-MS7, SIV-TTS7
TTO-MS4
10 nm
15 nm
Dark shades:
• Replace part of Pigmentary TiO2 with
larger size TiO2 ( 25 - 60 nm)
KQ-I4:
KQ-MS4:
UV-Titan M262:
60 nm
60 nm
20 nm (claimed but opaque)

Pigment Surface Treatments

Transcription

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