Practical tools for boosting sunscreen efficacy - Kobo · PDF filePractical tools for boosting...
Transcript of Practical tools for boosting sunscreen efficacy - Kobo · PDF filePractical tools for boosting...
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Practical tools for boosting
sunscreen efficacy
Yun Shao, Pascal Delrieu, Ed Bartholomey and David Schlossman
Kobo Products, Inc.
Sunscreen Symposium 2015
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High SPF Sunscreen Trend
High SPF (50+) has become more desirable with increased consumer awareness of the risks of
harmful UV exposure. Market share of SPF 50+ products has experienced global growth.
Sunscreen boosters have become popular for efficacy enhancement and added skin benefits.
High SPF Sunscreen Products
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Organic sunscreens Photostabilizer Anti-oxidants and bioactives
Banana Boat Ultra Defense Clear
Continuous SPF 110 UltraMist
Sunscreen Spray
Diethylhexyl
Syringylidenemalonate
Diethylhexyl Syringylidenemalonate, Aloe Barbadensis Leaf
Extract, Retinyl Palmitate, Ascorbic Acid, Tocopheryl Acetate
Coppertone Sport Sunscreen Lotion
SPF 75+
Diethylhexyl
Syringylidenemalonate
Diethylhexyl Syringylidenemalonate,Tocopherol (Vitamin E),
Retinyl Palmitate (Vitamin A), Sodium Ascorbyl Phosphate
Neutrogena Sport Face Lotion
SPF 70+
Diethylhexyl 2,6-
Naphthalate
Bisabolol, Artemia Extract, Saccharomyces/Zinc Ferment,
Saccharomyces/Magnesium Ferment, Saccharomyces/Calcium
Ferment, Saccharomyces/Sodium Ferment, BHT, Dipotassium
Glycyrrhizate
Neutrogena Pure & Free Baby
Sunblock Lotion, SPF 60+ Butyloctyl Salicylate
Ascorbic Acid (Vitamin C), Retinyl Palmitate, Tocopheryl
Acetate, Bisobolol, Pantothenic Acid, Avena Sativa (Oat)
Kernel Extract, Dipoassium Glycyrrhizate (Licorice Root)
High SPF Sunscreens – Ingredient Analysis
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High SPF Sunscreen – Ingredient Analysis
Inorganic sunscreens Photostabilizer Anti-oxidants and bioactives
Replenix Ultra Sheer Physical
Sunscreen Spray SPF 50 ---
Ascorbic Acid, Ascorbyl Palmitate, Biotin, Camellia Sinensis (Green
Tea) Polyphenols, Emblica Officinalis Fruit Extract, Retinyl
Palmitate, Resveratrol, Tocopheryl Acetate, Ubiquinone
skinCeuticals Physical Fusion UV
Defense SPF 50 Butyloctyl Salicylate Tocopherol, Artemia Extract
DermaQuest SunArmor SPF 50 ---
Tocopheryl Acetate, Ectoin, Palmitoyl Oligopeptide, Palmitoyl
Tetrapeptide-7, Vitis Vinifera (Grape) Fruit Cell Extract,
Polygonum Aviculare Extract, Tocopherol, Ascorbic Acid, Ascorbyl
Palmitate
Dr Dennis Gross Sheer Mineral Sun
Spray SPF 50+ ---
Ascorbic Acid, Ascorbyl Palmitate, Biotin, Camellia Sinesis Leaf
Extract, Resveratrol, Tocopheryl Acetate, Ubiquinone
iS Clinical Eclipse SPF50+ Sunscreen --- Tocopherol, Tocopheryl Acetate
AVEENO® Natural Protection Lotion
Sunscreen with Broad Spectrum SPF
50
--- Bisabolol, Dipotassium Glycyrrhizate, Avena Sativa(Oat) Kernel
Extract
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Transmittance Curves of Inorganic Sunscreens
320 360 400 440 nm 0
20
40
60
80
100
%T
• Antioxidants/bioactives do not affect the
UV attenuation of inorganic UV filters
• No effect on critical wavelength
• But they do greatly boost SPF to SPF50+
Sunscreen
product
Actives on label Est SPF based
on active% TiO2% ZnO%
Replenix NA 13.75 < 30
Dr. Dennis Gross NA 12 < 25
SkinCeutical 6 5 < 20
Eclipse 5.2 1.1 < 20
T% curves match the patterns of those
of TiO2, ZnO or their combo
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Outline
I. Test and analysis the boosting effect of
Antioxidants and bioactive compounds
Organic sunscreen photostabilizers
Film formers / Light scattering particles
II. High SPF/PFA formulation strategy
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Antioxidant &
bioactive compounds
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Patents and Other Literature
• Claims that antioxidants can protect against free-radicals & cellular damage have become
widely accepted by consumers
• Projected demand for antioxidant-fortified products is increasing by about 8.5%-10.0% annually
(Cosmeceuticals, US Industry Study with Forecasts for 2012 & 2017, The Freedonia Group)
1. Antioxidants in sunscreens for Improved ROS protection
KM Hanson, C&T, Vo. 126, No. Oct. 2011
0.5% vitamin E and 0.9% diethylhexyl syringylidene malonate (DESM)
-- prevent ROS formation
-- Effect levels off at high SPF (70)
2. T Meyer et al. US 20090189090 A1, Jul 30, 2009
Method to test the composition for ability to inhibit both UV induced lipid peroxidation on skin
and ROS formation in the epidermis.
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Patents and Other Literature
H Murad, US 5,804,168, Sept 8, 1998
- pharmaceutical compositions and methods for protecting and treating sun damaged skin
• mixture of botanical extracts to boost SPF of TiO2 Sunscreen up to ~ 10%
Olga Dueva, US 8465729 B2, June 18, 2013
- Sunscreen compositions with SPF enhancer (carotenoid )
• 16 Wt. % sunscreen agents and about 0.011% lutein
• SPF 29.65 was boosted to 31.5
JD Rigal, US 5618521 A, April 8, 1997
-Photoprotective/cosmetic compositions comprising antioxidants and filamentous bacterial extracts
… (i) at least one antioxidant and (ii) at least one extract of at least one nonphotosynthetic and
nonfructifying filamentous bacteria.
E Shim US 20080102045 A1, May 1, 2008
-Topical preparations containing antioxidant extracts of broccoli, green tea, and red tea … for the
protection of photocarcinogenesis
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Discoloration of TiO2 by Antioxidants
Primary size: 10 nm 15 nm 60 nm TiO2
Composition:
TiO2 - coated with alumina and silicone 1.0 g
Ascorbyl palmitate (as example) 0.01g
Ester 6.5 g
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Objective of Study
• Create an antioxidant ‘cocktail’ with the purpose of
meeting aesthetic requirements, low odor, light color, etc.
substantially boosting SPF of sunscreen compositions
compatible with inorganic UV filters
• Provide a practical guidance of use level and estimated boosting
effect
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Compatibility with Nano TiO2
0 10 20 30 40
TNP50T7 - CONTROL
IBR-CLC
Argan Oil
Stay C 50 (Sodium Ascorbyl …
dl-alpha-Tocopheryl Acetate
IBR-AAC
Magnesium Ascorbyl Palmitate
IBR-TCLC in Jojoba Oil
Merlot Polyphenols
Ethyl Ascorbic Acid
Combray
dl-alpha-Tocopherol (USP)
Vitamin A Palmitate (1.7 MIU/g)
Covi-Ox T70C
White Tea Herbasol Extract …
FSG33 (Feruloyl Soy Glycerides)
Green Tea Herbasol Extract …
Green Tea Liposomes
Rosemary Oleoresin
White Tea Liposomes
Ascorbic Acid Fine Powder
Aquarox 10-302057
Ascorbyl Pamitate
• TNP50T7 – 50% Disp of 15 nm TiO2
w/alumina+methicone coating
• 5% addition to TNP50T7
• 5 days at RT
Discoloration (DE)
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Antioxidants Selected for SPF Boosting
Two stable compounds are selected:
> Argan oil: produced from the kernels of the Argan tree; Contains antioxidants
such as tocopherols, phenols, carotenes….
> Tocopheryl acetate: a very potent anti-oxidant
A Booster Blend ATB was created with:
Argan oil – major component
VE acetate – minor component
Bisabolol – minor component, a natural anti-irritant, anti-inflammatory agent
Stable with 15 nm TiO2 for over 2 years (DE < 1.5)
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Base W/O Formula for Testing Pt Percent INCI Name
1
18.53 C12-15 Alkyl Benzoate (And) Titanium Dioxide (And) Alumina (And)
Polyhydroxystearic Acid (And) Methicone
10.00 Cyclopentasiloxane
10.00 C12-15 Alkyl Benzoate (+ Boosters to tested)
3.00 Caprylyl Methicone
3.00 Polyglyceryl-4 Isostearate (And) Cetyl PEG/PPG-10/1 Dimethicone (And)
Hexyl Laurate
1.00 Trihydroxystearin
1.00 Glyceryl Stearate
1.00 Dimethicone
2
46.97 Water
1.00 Propylene Glycol (And) Diazolidinyl Urea (And) Methylparaben (And)
Propylparaben
1.00 Sodium Chloride
1.00 PEG-150/Decyl Alcohol/SMDI Copolymer
0.50 Polysorbate 20
3 2.00 Silica
TiO2: added as dispersion
TiO2%: 7
QS : C12-15 alkyl Benzoate
Control: Base formula with no
booster. Same through
this work
UV Protection testing:
Lab: AMA Laboratory
SPF/CW: FDA method
PFA: JCIA PPD method
Panel: 3 persons
Skin type II and III
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Boosting Efficacy vs. Use Level
(Booster Blend ATB%)
22.5 27.5
32.0 36.5
32.1
38.5
0
10
20
30
40
0 1 2 3 4 5
SPF
Boosting effect is significant (up to 60%)
Boosting plateaus in the range of ~ 3 – 5%
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Contribution of Components
Each component is extracted
from 3% of Booster blend ATB
Both anti-oxidant and anti-
inflammatory agent boost SPF
Contribution from each
component is fairly balanced out
at the ratio in Blend ATB 0
10
20
30
Control ARGAN OIL BISABOLOL VE Acetate
SPF
SPF Boost 22% 27% 17%
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Boosting effect of each components is largely cumulative in this formulation
Component ratio ensures optimal synergy
Cumulative Boosting Effect
SPF
0
10
20
30
40
Control ARGAN OIL BISABOLOL VE Acetate 3% ATB
SPF Boost 22% 27% 17% 62%
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Booster Blend ATB - Efficacy vs. TiO2%
TiO2% 7 12
ATB 3.0 4.2 5 6.5
SPF 36.5 32.1 38.5 52.3
SPF/TiO2% 5.21 4.58 5.50 4.35
At high TiO2 use level, boosting effect may be neutralized due to
less additive impact on skin cells
There is possibly a range for maximum boosting efficiency, which
corresponds to the finding in Hanson’s work
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Boosting Inorganic Sunscreens
F11A F11C
% TiO2 6.0 6.0
% ZnO 4.6 4.6
% ATB - 5.0
SPF 31.40 44.93
% Boost - 43.1%
Booster blend ATB boosts the SPF of combined inorganic sunscreens
Booster blend ATB provides boosting in UVA as effective as in UVB
F12 F12A
% TiO2 4.8 4.8
% ZnO 3.4 3.4
% ATB - 3.6
PFA 7.49 10.09
% Boost - 34.7%
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SPF Boost to Organic Sunscreens
F13 F13V
% Avobenzone 3.0 3.0
% Homosalate 15.0 15.0
% Octisalate 5.0 5.0
% Oxybenzone 3.0 3.0
% ATB - 5.0
SPF 40.9 54.8
% Boost - 34.0%
SPF boosting effect is still significant.
Boosting effect to high SPF (50+) formulas seems to be lower than that for low
SPF (30+) formulas.
No effect on critical wavelength was observed.
F15A F15B
TiO2 (230 nm)
ZnO (265nm)
Ocinoxate
% ATB - 5.0
SPF 44.0 57.5
% Boost - 30.0%
CW (nm) 373.7 373.8
3.60%
11.85%
7.50%
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Organic Sunscreen
Photostabilizers
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Organic Sunscreen Photostabilizers
• Butyloctyl salicylate (BOS)
> Stabilize Avobenzone
> Boost SPF effectively
> Helpful for SPF 30+ formulas
> lmax: 306 nm (UVB)
• Ethylhexyl Methoxycrylene-(EHMC)
> Stabilize Avobenzone
> Boosts PFA very effectively
> Helpful for PA+++ or higher
> lmax : 340 nm (UVA)
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Boosting Effect of Butyloctyl Salicylate
• Control: base formula with 7% TiO2
• BOS was added in the form of TiO2 Dispersion
• SPF unit/BOS%: estimate to be 1.6
40%
0
10
20
30
Control Control + BOS (5%)
22.5
31.5
SPF
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PFA Boosting effect of Ethylhexyl Methoxycrylene
PFA boosting is significant
The phtotostabilizer shows a great synergy with ZnO, and
expectedly TiO2 due to their scattering nature
Effective SPF boosting is also expected because of enhanced PFA
Formula F16 F17 F16H F17A
ZnO Primary size (nm) ~25 ~260
ZnO% 15% 15% 15% 15%
EMHC
(as part of ZnO Disp) -- 5.85 --- 2.86
PFA 7.5 11.7 5.52 10.8
% boost -- 56 --- 96
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Film Formers &
Light Scattering Particles
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N Herman, WO 2013036878 A1, Mar 14, 2013
-Polyamide compositions for personal care
• Disclose a hydrophobic polyamide made from a dimerized fatty acid and polyamine
• SPF increase: 160% in an SPF 30 & > 250% in an SPF 50+ formulation
Literature - Film Former
JR Strobridge, US 4917883, April 17, 1990, - O/W emulsion sunscreen composition
-… 0.5 and about 20 weight percent of a copolymer of ethylene and vinyl acetate together with a second
polymeric film forming agent which increases the substantivity of the film forming composition
TA Meyer, WO 2010129215 A2, Nov.11, 2010
-Enhanced efficiency of sunscreen compositions
-Compositions comprising UV blocking agents, a film forming polymer containing acid groups and a
neutralizing agent…
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Film Formers Tested
Acrylates Copolymer (ACP)
- High MW,
- Water dispersible latex
- Film forming - irreversible
CH2 C CH2 CH
CH3
COOCH3 COOC2H5
x y
Hydrogenated Polycyclopentadiene
(HPCD)
- Low MW
- Oil soluble
- Adhesion promoter
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SPF Boosting Effect of Film Former
0
10
20
30
40
Control ACP (2% active) HPCD (2%)
SPF
Both water dispersible and oil soluble film former helps boost SPF
The use level needs to be controlled to maintain good skin feel
SPF Boost 22% 53%
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H Xing US 20120107253 A1, May 3, 2012
-sunscreen formulations using natural oceanic clay (aka marine glacial clay)
• Sunscreen formulations use the Natural Oceanic Clay when combined with sunscreen actives
such as zinc oxide, can provide significant enhancement in absorbance of UVA, UVB, and
UVC… ( clay size: 80 – 200 mesh; Boosting by in-vitro testing: 50 – 236% )
Sunsphere™ PGL from Dow, -- Technical Brochure Sept. 2003
• Hollow styrene/acrylic copolymer spheres (~250 nm) for enhancing UV protection
• 5% Sunsphere (~1.25% active) boosts SPF up to 70%
Literature – Light Scattering Agents
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Formulation Strategy for High UV Protection
Antioxidants
Anti-inflammatory Sunscreen actives
Film formers
Light scattering
agents
Organic sunscreen
stabilizer
Zone
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Part Percent INCI Name 1 45.70 Water
2 5.00 Niacinamide
1.00 Polysorbate 20
0.20 Methylparaben
3 4.00 Glycerin
0.20 Xanthan Gum
4 9.80 Zinc Oxide (And) Ethylhexyl Methoxycrylene (And) C12-15 Alkyl Benzoate (And)
Polyhydroxystearic Acid (And) Hydrogen Dimethicone
9.50 C12-15 Alkyl Benzoate
8.65 Butyloctyl Salicylate (And) Titanium Dioxide (And) Alumina (And) Silica (And) Stearic
Acid (And) Polyhydroxystearic Acid
5.00 Argania Spinosa Kernel Oil (And) Tocopheryl Acetate (And) Bisabolol
2.45 PEG-100 Stearate
1.00 Glyceryl Stearate
0.40 Shea Butter
0.10 Propylparaben
5 3.00 Silica
1.00 Polyacrylamide (And) C13-14 Isoparaffin (And) Laureth-7
6 3.00 Acrylates Copolymer (And) Water
High UV Protection Testing Formula (O/W)
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Ingredient INCI %
Sunscreen actives TiO2 (40 nm) 3.54
ZnO (265 nm) 7.15
Antioxidant/ Anti-inflammatory Booster blend ATB 5.00
UV absorber/Stabilizer Ethylhexyl Methoxycrylene 1.37
Butyloctyl salicyalte 4.48
Film former Acrylates copolymer 1.5
Index Value Estimated value
without boosters
SPF 66 15 - 20
PFA 21 5
CW (nm) 380 380
Summary of Formula and Testing Scores
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Antioxidants and bioactive compounds have great ability to boost the UV protection of
sunscreen formulas against both UVA and UVB. The boost effect can be cumulative.
However, their chemical compatibility with inorganic UV filters needs to be tested.
Certain organic sunscreen photostabilizers can also boost effectively SPF or PFA
depending on the absorption peak. They have good synergy with inorganic UV filters.
Both water dispersible and oil soluble film formers were tested to be effective.
SPF/PFA boosters of different mechanisms, when used in proper combination, can boost
protection multifold. This also helps to reduce the use of actives and improve the skin
feel and asethetics of sunscreen formulations.
Summary
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Fred Ortiz
Kobo Application Lab
Acknowledgment