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Influence of Titanium Dioxide Dispersions on Water Resistance of Sun Care Products

Presentation at In-Cosmetics 13-15 April 2010

Horst Westenfelder, Dr. Thomas Satzinger

In-Cosmetics 13-15 April 2010

CONTENT OF PRESENTATION 1 COLIPA Guideline for Evaluating Sun Products on 1 COLIPA Guideline for Evaluating Sun Products on Water Resistance Water Resistance 2 Factors Influencing Water Resistance 2 Factors Influencing Water Resistance
Emulsifiers Emulsifiers Polymers Polymers Formulation Requirements Formulation Requirements Influence of UV Filters Influence of UV Filters

3 Influence of Different Particulate UV-Filters on 3 Influence of Different Particulate UV-Filters on Water Resistance Water Resistance
In-vitro Test System to Analyze Water Resistance In-vitro Test System to Analyze Water Resistance Test Results Test Results

In-Cosmetics 13-15 April 2010

CONTENT OF PRESENTATION 1 COLIPA Guideline for Evaluating Sun Products on 1 COLIPA Guideline for Evaluating Sun Products on Water Resistance Water Resistance 2 Factors Influencing on Water Resistance 2 Factors Influencing on Water Resistance
Emulsifiers Emulsifiers Polymers Polymers Formulation Requirements Formulation Requirements Influence of UV Filters Influence of UV Filters

3 Influence of Different Particulate UV-Filters on 3 Influence of Different Particulate UV-Filters on Water Resistance Water Resistance
In-vitro Test System to Analyze Water Resistance In-vitro Test System to Analyze Water Resistance Test Results Test Results

In-Cosmetics 13-15 April 2010

COLIPA Guidelines to Test Water Resistance

of product has to be applied and the SPF has to be tested according the standard way of SPF testing. 2mg/cm2 3

10 to 12 persons are required to run a full study The people are immersed for 20 minutes after that step they have to leave the bath and allow to dry for 15 minutes The use of towels is not recommended air drying is preferred After 15 to 30 minutes of drying time the volunteers have to do a second run of 20 minutes of immersion Drying step of 15 minutes without using towels After that the SPF has to be tested again according the COLIPA standard Calculation of the SPF the next day

In-Cosmetics 13-15 April 2010

COLIPA Guidelines to Test VERY Water-Resistance

4 2mg/cm2 of product has to be applied and the SPF has to be tested according the standard way of SPF testing. 10 to 12 people are required to run a full study Same procedure as for water-resistant but 2 more immersion steps of 20 minutes are required After that step the SPF has to be tested again according the COLIPA standard Calculation of the SPF the next day

In-Cosmetics 13-15 April 2010

CONTENT OF PRESENTATION 1 COLIPA Guideline for Evaluating Sun Products on 1 COLIPA Guideline for Evaluating Sun Products on Water Resistance Water Resistance 2 Factors Influencing on Water Resistance 2 Factors Influencing on Water Resistance
Emulsifiers Emulsifiers Polymers Polymers Formulation Requirements Formulation Requirements Influence of UV Filters Influence of UV Filters

3 Influence of Different Particulate UV-Filters on 3 Influence of Different Particulate UV-Filters on Water Resistance Water Resistance
In-vitro Test System to Analyze Water Resistance In-vitro Test System to Analyze Water Resistance Test Results Test Results

In-Cosmetics 13-15 April 2010

GNPD Research of Sunscreen Product Launches since 2005

AMPHISOL is the Emulsifier of choice for all kind of Sun Care Products
4.101 Glyceryl Stearate Citrate Glycerine Stearate Cetyl Peg AMPHISOL 1.379 823 297 Hypoallergenic 9% 41% 25% 25% In-Cosmetics 13-15 April 2010 43% UV Protection 12% 23% 70% 23% Water Resistant 0% 15% 15% 53% Waterproof 17% 15% 15% 4.500 4.000 3.500 3.000 2.500 2.000 1.500 1.000 500 0

Influence of Emulsifiers on Water Resistance

Emulsifiers have a tremendous influence on SPF performance and water resistance Reason for that is AMPHISOL K can not be easily washed off after the volatile part of the formulation is evaporated This leads in many cases to a water resistant formulation AMPHISOL K can be combined with polymers to improve the water-resistance or to achieve the claim very water-resistant 7

In-Cosmetics 13-15 April 2010

Local Trends and how they Influence the Composition of Cosmetic Formulations
Silicones are very useful to improve water resistance, however due to upcoming regional safety discussions silicones are becoming under pressure Silicone issue started in Canada and is spreading now to France and Germany Only volatile Silicone oils are seen as critical, but this becom es a big influence for using Silicones in general Silicone Emulsifiers (W/Si) could be helpful for water resistant formulations but the use is becoming impossible for some companies 8

In-Cosmetics 13-15 April 2010

Local Trends and how they Influence the Composition of Cosmetic Formulations
9 Light formulations are very important Water/Oil formulation could be very useful to formulate waterresistant and even very water-resistant products Consumer expectations are different, many companies are forced by their customers to formulate very light and easy to absorb products AMPHISOL K can be an emulsifier of choice because all levels of oil loading are possible

In-Cosmetics 13-15 April 2010

Influence of UV filters
The use of water soluble UV filters is always critical in water resistant formulations and have to be chosen carefully Most of the relevant UV filters are oil soluble But there is a certain number of water soluble filters available and used: q Benzophenone 4 q PEG-25 PABA q Phenylbenzimidazole sulphonic acid PARSOL HS q Disodium phenyl dibenzimidazole tetrasulfonate q Methylene bis-benzotriazolyl tetranethylbutylphenol dispersion To achieve water resistance it is crucial that the SPF is not mainly coming from the water-soluble UV-filter part of the formulation but it is still useful to have some of these filters in the formulation.
In-Cosmetics 13-15 April 2010

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PARSOL SLX High Protection Water Resistant Efficacy Data Water Resistance
DSM 6B with a PARSOL HS content of 2% - provides waterresistance according to the COLIPA method (Spa)
60
Water Resistance
55,9 48,0 42,4

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50 40 30 20 10 0

UV Filter Combination PARSOL SLX (Polysilicone-15) PARSOL HS (Phenylbenzimidazole Sulfonic Acid) PARSOL 340 (Octocrylene) PARSOL 1789 (Butyl Methoxydibenzoylmethane) In-Cosmetics 13-15 April 2010

DSM 6

DSM 6A

DSM 6B

3.0 % 4.0 % 3.6 % 4.0 %

3.0 % 3.0 % 6.0 % 4.0 %

3.0 % 2.0 % 8.0 % 4.0 %

PARSOL SLX High Protection Water Resistant Efficacy Data - Summary

UV Filter Combination PARSOL SLX (Polysilicone-15) PARSOL HS (Phenylbenzimidazole Sulfonic Acid) PARSOL 340 (Octocrylene) PARSOL 1789 (Butyl Methoxydibenzoylmethane) Results In vivo SPF SPF 95% Cl In vivo SPF (wet) after 40 min SPA pool Water Resistance (%) WRR 90% Conf. Interval In-Cosmetics 13-15 April 2010 DSM 6 DSM 6A DSM 6B

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3.0 % 4.0 % 3.6 % 4.0 %

3.0 % 3.0 % 6.0 % 4.0 %

3.0 % 2.0 % 8.0 % 4.0 %

35.4 29 - 42 14.5 42.4 % 36 - 49 %

37.6 31 - 44 18.7 48.0 % 42 - 54 %

35.8 28 - 44 20.2 55.9 % 47 -64 %

CONTENT OF PRESENTATION 1 COLIPA Guideline for Evaluating Sun Products on 1 COLIPA Guideline for Evaluating Sun Products on Water Resistance Water Resistance 2 Factors Influencing on Water Resistance 2 Factors Influencing on Water Resistance
Emulsifiers Emulsifiers Polymers Polymers Formulation Requirements Formulation Requirements Influence of UV Filters Influence of UV Filters

3 Influence of Different Particulate UV-Filters on 3 Influence of Different Particulate UV-Filters on Water Resistance Water Resistance
In-vitro Test System to Analyze Water Resistance In-vitro Test System to Analyze Water Resistance Test Results Test Results

In-Cosmetics 13-15 April 2010

Influence of Technical Ingredients on Water Resistance for example TiO2 / TiO2 Dispersions
14 Water resistance is a very sensitive test and is influenced by many factors In an in vitro study we have analyzed the influence of technical ingredients (Emulsifiers) We compared PARSOL TX versus PARSOL TX50 AB and also some other dispersions of particulate organic and inorganic UV Filters We analyzed the SPF performance and compared the water resistance in vitro by using our test system

In-Cosmetics 13-15 April 2010

In vitro Set Up to Test Water Resistance

15 To test water-resistance in vivo is very expensive We were looking to find an in vitro system which gives us an indication of the water resistance As starting point we have tested the in vitro SPF by using our MUT system Apply 0.7mg/cm2 on PMMA plates Immersion took place in 2L beakers at 29C at moderate stirring Water quality was tap water SPF test with MUT Two times 20 minutes of immersions by slightly moving the tap water

In-Cosmetics 13-15 April 2010

In vitro Set Up to Test Water Resistance

1. Application of product 2. Homogenous distribution of the product

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3. Water bath 29C tap water (Water is moved 29 (Water carefully) carefully

In-Cosmetics 13-15 April 2010

Test Formulations for Water Resistance in vitro study

PARSOL TX50 AB PARSOL TX Competitor 1 Competitor 2 Competitor 3

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AMPHISOL K Lanette Cetiol C Finsolv TN Dermofeel BGC BHT Phenonip

PARSOL 1789/ PARSOL 340, PARSOL 5000 PARSOL TX50 AB PARSOL TX

2.00 2.00 4.00 8.00 5.00 0.05 0.80 4.00/ 8.00/ 4.00 10.00

2.00 2.00 4.00 8.00 8.00 0.05 0.80 4.00/ 8.00/ 4.00

2.00 2.00 4.00 8.00 8.00 0.05 0.80 4.00/ 8.00/ 4.00

2.00 2.00 4.00 8.00 8.00 0.05 0.80 4.00/ 8.00/ 4.00

2.00 2.00 4.00 8.00 5.00 0.05 0.80 4.00/ 8.00/ 4.00

5.00 10.00 5.00 11.10 0.4/ ad 100 0.4/ ad 100 0.4/ ad 100 0.4/ ad 100 0.4/ ad 100

MBTP Dispersion (50% active) Titanium Dioxide (TMCS)

Titanium Dioxide (and) Diethylhexyl Carbonate (and) Polyglyceryl-6 Polyhydroxystearate (45% active)

Pemulen/ Keltrol/ EDTA/ Wasser

In-Cosmetics 13-15 April 2010

In vitro Water Resistance of Sunscreens containing different Pigment Qualities

Quality of coating and optimized emulsifier system have a tremendous influence on water resistance and SPF
73,2
Titanium Dioxide (and) Diethylhexyl Carbonate (and) Polyglyceryl-6 Polyhydroxystearate (45% active) Titanium Dioxide, C12-15 Alkyl Benzoate, Polyglyceryl-2-Dipolyhydroxystearate, Silica, Dimethicone

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80 70 60 50 40 30 20 10 0
Competitor 3 Competitor 2 Competitor 1

76,2
Titanium Dioxide, Silica, Dimethicone

79,2

53,2

52,0

Titanium Dioxide (TMCS)

MBTP Dispersion (50% active)

PARSOL TX

PARSOL TX50 AB

In-Cosmetics 13-15 April 2010

Test Results for Water Resistance in vitro study

Quality of coating and the composition of the formulation has a strong influence on performance
PARSOL TX50 AB PARSOL TX Competitor 1 Competitor 2 Competitor 3

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In vitro SPF initial In vitro SPF after 20 min water immersion In vitro SPF after 40 min water immersion Water resistance (%) after 40 min water immersion

46.10

48.50

48.10

43.10

38.30

41.00

42.10

26.10

28.40

30.00

36.70

37.20

25.50

23.40

28.30

79.16

76.21

52.02

53.21

73.19

In-Cosmetics 13-15 April 2010

Conclusions
Emulsifiers have a tremendous influence on SPF performance and water resistance AMPHISOL is the Emulsifier of choice for all kind of Sun Care Products Silicones are very useful to improve water resistance, however due to upcoming regional safety discussions under pressure The use of water soluble UV filters is always critical in water resistant formulations and have to be chosen carefully In vitro water resistant tests are useful to give an indication of formulation performance Quality of coating and optimized emulsifier system have a tremendous influence on water resistance and SPF PARSOL TX50 AB fulfills all requirements to formulate water resistant formulations
In-Cosmetics 13-15 April 2010

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Thank You!

Thomas Satzinger Marc Hentsch 21 Jrgen Vollhardt Christine Mendrok-Edinger Anne Janssen Karina Radomsky

offer a full range of innovative high-performance UVA and UVB filters We and technical support to meet your sunscreen formulation requirements, while guaranteeing the highest standards in quality, safety, reliability and compliance.

In-Cosmetics 13-15 April 2010