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UV Protection by Ciba

Ciba Specialty Chemicals Holding Inc.; All rights reserved. The information given in the documentation is based on the present state of our knowledge. It shows without liability on our part the uses to which our products can be put.

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UV Absorbers overview UV-A Test Methods (in vivo / in vitro) UV Protection by Ciba TINOSORB M TINOSORB S Registration status Market Products with CibaUV Absorber

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Protection at the beach around 1900

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Objective: Tanning without Sunburn, 1930

First transparent sun protection creams


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From Tavenrath Simone, 2000

Skin cancer as headline, Germany 1993


Dangerous sun: How to save our skin
Warnings from: Sun Allergy Photodermatosis Sunburn Skin-aging Skin cancer

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From Tavenrath Simone, 2000

UV exposure of the skin


Spectrum of the Sun Stratosphere Ozone layer UV-C UV-B UV-A Visible light Infrared

Surface of the earth Horny layer of the skin Epidermis Dermis Hypodermis Wavelength nm 200 290 320

UV-B: 70% reflected by Stratum Corneum UV-A: 30% penetrates into Dermis

400

800

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Penetration of Sun Light


Wavelength [nm] 280 300 350 400 600 800 1200 Penetration Depth [m] 1,5
Penetration Depth / m
0 10 20 30 40 50 60 70 80 90 100 250

SC

6 60 90 550 1200 2200

UVB

UVA

300

350 Wavelength / nm

400

450

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Effects of UV Radiation on Human Skin


Main risk of UVB 290-320 nm
Sunburn Skin cancer

Main risk of UVA 320-400 nm


Accelerated photoageing Damage of blood vessels and connective tissues Contribution to sunburn Contribution to skin cancer

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Requirements of UV Absorbers
Efficacy Molecules have to provide an efficient absorption of UV radiation (UVB and/or UVA) Ease of Formulating Molecules have to be compatible with most ingredients used in formulations Safety Molecules have to be safe, i.e. avoid of adverse effects

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Most frequently used cosmetic UV Absorbers

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UV-Filter consumption in Western Europe


ZnO TiO2 Other BP4 OT PSA BP3 EHS MBC BMBM OCT
BP4 ZnO EHMC

EHMC

TiO2

14% 3%

18% 20% 41%


Other

13% 4% 14%

OCT

9%

11%

OT PSA BP3 MBC EHS

BMBM

Volume: Total 4840 t

Value: Total 97.3mio


Kline 2002

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Two most frequently used absorbers for UV-B and UV-A


O O O

OCH 3

UV-B:
EthylHexyl MethoxyCinnamate (EHMC)

UV-A:
Butyl MethoxyDibenzoylMethane (BMBM)

Molar Extiction

Wavelength (nm)

Molar Extiction

Wavelength (nm)

The ideal combination?


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Photostability of BMBM and EHMC


BMBM
+ 5% OCR + 5% OCR and 5% EHMC

1,00 0,80 0,60 0,40 0,20 0 1 2 3

UVA/UVB-Ratio

dashed lines: irradiation with 10 MED


4 % BMBM

BMBM/EHMC combinations are not photostable


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New UVA- and Broad-Spectrum UV Filters, 2003


#
S 71 S 73 S 79 S 80 S 81

INCI
TDSA DTS MBBT DPDT BEMT

Tradename MEXORYL SX MEXORYL XL TINOSORB M


NEOHELIOPAN AP

UVB

UVA

Approved

(Europe) X X X X X X X X

Freely available no no

TINOSORB S

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UV Absorbers overview UV-A Test Methods (in vivo / in vitro) UV Protection by Ciba TINOSORB M TINOSORB S Registration status Market Products with CibaUV Absorber

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UV-A Test Methods (in-vivo / in-vitro)

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In vivo: UVA-PF (PPD)


Persistant Pigment Darkening = PPD Principle:
Measurement of UVA-induced pigmentation 2 hours after irradiation when the pigmentation has stabilized.

Conditions:
UVA-dose about 15 J/cm 10 volunteers of skin types 2,3 and 4 The Minimal Pigmenting Dose (MPD) corresponds to the minimal UVA dose producing the first perceptible pigmentation 2 hours after exposure to 6 increasing doses of UVA. Protected area is then compared with unprotected area. UVA PF = MDPp / MPD np

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In vitro: Australian Standard


Principle: Measurement of the UVA-transmission of the formulation at d=0.0008cm between 320 and 360nm

Definition: Transmission < 10% at any wavelength in this range


100

80

Transmission (%)

60

40

Australian Standard
20

0 290 310 330 350 370 390

400

(nm)
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In vitro: UVA/UVB-ratio
Principle: Ratio of the average of extinction E in the UVA- and the UVBrange, spectrum measured on special substrates
700 600 500

UV-B

UV-A

E (1%,1cm)

400 300 200 100 0 290

310

330

350

370

390

Wavelength / nm

UVA-UVB ratio of around 1 = broad band filter system UVA-UVB ratio of < 0.5 = UVB absorber UVA-UVB ratio of > 1 = UVA absorber
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Star-rating
UV-A / UV-B ratio
0.2 0.4 0.4 0.6 0.6 0.8 > 0.8 = = = =

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In vitro: Critical Wavelength


Principle: c is the upper limit of the spectrum from 290nm on, within which 90% of the area under the extinction curve of the whole range between 290 and 400nm is covered
700 600 500
E (1%,1cm)

400 300 200 100 0 290 310 330 350 370 390 Wavelength / nm

The higher the c = The better the UVA protection


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Photostable UVA Protection


Traditional combination of BMBM (Parsol 1789) and EHMC are effective, but not photostable. Stabilization with OCR is effective for BMBM alone, but not in combination with EHMC TINOSORBM and TINOSORBS are the only broad spectrum and photostable UV Absorbers available on the market

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UV Absorbers overview UV-A Test Methods (in vivo / in vitro) UV Protection by Ciba TINOSORB M
o Properties o Performances o Formulating with TINOSORB M

TINOSORB S Registration status Market Products with CibaUV Absorber


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TINOSORBM
Organic Micropigment with Broad-Spectrum UVA/UVB Performance and High Inherent Photostability

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Chemical Properties
Active Ingredient of TINOSORB M: INCI name: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (abbr.: MBBT)
N OH OH N N N

Melting point: 195 C Solubility in H 2O: < 10-8 g/l Molecular mass: 658.86 g/mol
UV absorbance E1%,1cm

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Physical Properties
The micronization is performed with a ball milling process ending up with an aqueous dispersion of microfine MBBT particles (d0.5<200nm):

Atomic Force Microscopic Image of TINOSORBM


(Particle Size Range: 70 nm - 400 nm = 0,07m - 0,40m)

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Composition of TINOSORBM
MBBT particles Surfactant (Decyl Glucoside) Thickener (Xanthan gum) Propylene glycol Water pH 10.5 11.5 No preservation necessary because of alkaline pH 50.0% 7.5% 0.2% 0.4% ad 100%

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Importance of small particle sizes


The smaller the particle size, the higher the molar extinction of TINOSORBM Particles
40000

Molar Extinction / l/(molcm)

30000 d(0.5) = 0.16 m d(0.5) = 0.21 m 20000 d(0.5) = 0.34 m d(0.5) = 0.78 m d(0.5) = 4.37 m 10000

0 280

300

320

340

360

380

400

420

Wavelength / nm
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Importance of small particle sizes


Qualitative Explanation of the Increase of in vitro SPF with Smaller Particles The UV-attenuating coverage by the sunscreen film is more efficient with smaller particles. Average thickness of film: 20 m; 10% particles =20% TINOSORBM Assumption: two layers of particles for an efficient coverage

particle size d (m) 10 5 2,5 1,25


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Max. coverage 10% 20% 40% 80%

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pH Stability of TINOSORBM
TINOSORB M dispersion in water

2,5

6
pH value

11

13

Stable formulations in a broad pH range possible


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Concentration / SPF correlation


16 14 12 SPF calc. 10 8 6 4 2 0 5 10 % TINOSORB M 6,6% TINOSORB M are required to fulfill Australian standard TINOSORB M is recommended up to 20% in cosmetic formulations
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Synergistic effect of TINOSORBM and EHMC


40 35 30 25 20 15 10 5 0
8% TINOSORB M 5% EHMC 5% EHMC + 8% TINOSORB M 5% EHMC + 20%TINOSORB M

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SPF in-vivo

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TINOSORBM and TiO2


3.5% TiO2 1,2000 1,0000
1,2000 1,0000 8% TINOSORB M

Extinction

Extinction

0,8000 0,6000 0,4000 0,2000 0,0000 290

0,8000 0,6000 0,4000 0,2000 0,0000

310

330

350

370

390

290

310

330

350

370

390

Wavelength / nm

Wavelength / nm

Combination 1,2000

SPF calc. = 12 Crit. Wavelength = 385 UVA/UVB ratio: 0.8 Australian Standard Fulfilled Star Rating:

1,0000 Extinction 0,8000 0,6000 0,4000 0,2000 0,0000 290

310

330

350

370

390

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Wavelength / nm

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Comparison of UVA Performance


UV-Absorber
TINOSORBM ZnO (Nanox) BMBM (Parsol 1789) TiO2 Benzophenone-3 Ethylhexyl Triazone Ethylhexyl Methoxycinnamate Octocrylene

Australian Standard
6.6% 8% 3% 9% > 10% >20% >10% >10%

UVA/UVB Ratio Critical Wavelength


(nm)
388 376 383 348 364 324 337 348 0.98 0.81 1.22 0.29 0.5 0.08 0.21 0,29

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Synergistic effect of TINOSORBM with EHMC


ZnO TINOSORB M ZnO & 5% EHMC TINOSORB M & 5% EHMC

12 10

UVA-PF

8 6 4 2 0 4 8 16 % UVA Filter (ZnO or TINOSORB M)

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Photostability in vitro
TINOSORB M
% recovery of UV-Filters

EHMC

BMBM

MBC

100 80 60 40 20 0 0 UV-Dose in MED


Minimal Erythemal Dose

10
Max MED in Central Europe

20

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Stabilization of EHMC by TINOSORBM

Recovery of EHMC in%

100
EHMC alone 2.4%

80 60 40 20 0

0 UV-Dose in MED
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EHMC & TINOSORB M 10%

10

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Formulation Guideline with TINOSORBM


Optimized way of incorporation
After emulsification, during the cooling phase (~60C), pour TINOSORBM into the emulsion under gentle stirring. Additional homogenization should be avoided.

Alternative way of incorporation


Incorporation of TINOSORBM into the water phase under continuous stirring prior to the emulsification at 75/80 C Incorporation into the oil phase has to be avoided Exposition time at high temperatures should be as short as possible

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UV Absorbers overview UV-A Test Methods (in vivo / in vitro) UV Protection by Ciba TINOSORB M TINOSORB S
o Properties o Performances o Formulating with TINOSORB S

Registration status Market Products with CibaUV Absorber


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S TINOSORB
The most efficient Broad-Spectrum UV-Absorber

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Chemical Properties
INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (abbr.: BEMT)
OCH3

Melting point: Solubility: Molecular mass: Solubility in H2O:

80 C Oil soluble 627,8 g/mol 10-7 g/l


UV-spectrum of TINOSORBS
800 700 E (1%, 1cm) 600 500 400 300 200 100 0
29 0 30 0 31 0 32 0 33 0 34 0 35 0 36 0 37 0 38 0

HO

N N

OH

39 0

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Wavelength / nm

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40 0

Inherent Photostability by Photo-Tautomerism


R1 O R4 N N R5 R3 N

H
R2

h
R1 O R4 N N R5 R3 NH R2

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UV-A Protection with TINOSORBS


Placebo
18
PFA (PPD method)

TINOSORB S

plus 5% EHMC
PFA (Japan)

16 14 12 10 8 6 4 2 0 Placebo 1% 2%
% TINOSORB S

PA +++

PA ++ PA +

4%

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Comparison of UVA Performance


UV-Absorber
TINOSORBS TINOSORBM ZnO (Nanox) BMBM (Parsol 1789) TiO2 Benzophenone-3 Ethylhexyl Triazone Ethylhexyl Methoxycinnamate Octocrylene

Australian Standard
2% 6.6% 8% 3% 9% > 10% >20% >20% >20%

UVA/UVB Ratio
0.73 0.98 0.81 1.22 0.29 0.5 0.08 0.21 0,29

Critical Wavelength (nm)


370 388 376 383 348 364 324 337 348

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Synergistic effect of TINOSORBS with EHMC


BMBM TINOSORB S BMBM & 5% EHMC & 5% OCR TINOSORB S & 5% EHMC

17 15 13 11 9 7 5 3 1

UVA-PF

% UVA Filter (BMBM or TINOSORB S)

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TINOSORBS and Ethylhexyl Triazone


F SP
Extinction 1,6000 l ca 1,4000 1,2000 1,0000 0,8000 0,6000 0,4000 0,2000 0,0000 -0,2000290 310 330 350 370 390 Extinction

7 c.

4% EHT 1,6000 1,4000 1,2000 1,0000 0,8000 0,6000 0,4000 0,2000 0,0000 290

3% TINOSORB S

SP Fc

alc .

310

330

350

370

390

Wavelength / nm

Wavelength / nm

Combination 1,6000

SPF calc. = 20 Crit. Wavelength = 371 UVA/UVB ratio: 0.48 Australian Standard Fulfilled Star Rating:

1,4000 1,2000 Extinction 1,0000 0,8000 0,6000 0,4000 0,2000 0,0000 290 310 330

SPFcalc. 20

350

370

390

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Wavelength / nm

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Photostability in vitro
TINOSORB S
% recovery of UV-Filters

EHMC

BMBM

MBC

100 80 60 40 20 0 0 UV-Dose in MED


Minimal Erythemal Dose

10
Max MED in Central Europe

20

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Stabilization of BMBM by TINOSORBS

100 80 60 40 20
BMBM alone
BMBM & 3%TINOSORB S Recovery of BMBM in %

0 UV-Dose in MED
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10

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Formulation Guideline with TINOSORBS


Solubilize TINOSORBS by adding it directly to the oil phase and heat up to 80C. For cold process : solubilize TINOSORBS in the most polar oil Emulsification at room temperature
O/W Emulsions
Need of sufficient polar oils for solubilization Reasonable limit of use in O/W : < 5%

W/O Emulsions
Need of sufficient polar oils for solubilization Use of minimal quantity of non-polar oils for W/Os stability Reasonable limit of use in W/O : < 3%

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Solubility of TINOSORBS
Very good solubility (15-20%) UV Absorbers, Pyrrolidones Good solubility (8-15%) Fatty Acids Esters, Benzoic Acid Esters Low solubility (2-5%) Triacylglycerides, vegetables oils Very Low solubility (<1%) Alcohol, silicones and hydrocarbon derivates

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Solubility of TINOSORBS
Fatty Acid Esters Isodecyl Salicylate (Dermol IDSA) Diethylhexyl Succinate (Crodamol OSU) Dicaprylyl Carbonate ( Cetiol CC) Propylene Glycol Dicaprylate/Dicaprate (Crodamol PC) Isopropyl Myristate ( Tegosoft M) Benzoic Acid Esters C12-C15 Alkyl Benzoate (Tegosoft TN) Isostearyl Benzoate (Finsol SB) Triacylglycerides Caprylic/Capric Triglyceride (Miglyol 812) Pyrrolidones Caprylyl Pyrrolidone (Sulfadone LP100) UV Absorbers Ethylhexyl Methoxycinnamate (TINOSORB OMC) Ethylhexyl Salicylate (Eusolex OS)
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18% 10% 9% 7% 6% 13% 8% 5% 20% 17% 20%

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TINOSORBM & TINOSORBS the ideal couple

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Characteristics of TINOSORBM & TINOSORBS


TINOSORB M Physical state Emulsion Phase Broad-spectrum Performance Critical Wavelength UV-A/UV-B ratio Particles dispersion Water Covers long UVA 388nm 1.0 TINOSORB S Powder Oil Higher absorbance 373nm 0.73

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Synergy between TINOSORBM & TINOSORBS


TINOSORBM conc.
18 16 14 12 10 8 6 4 2 0 0% 5% 10% 15%

TINOSORB S 0%

TINOSORB S 2%

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Summary
TINOSORB M
unique micronized organic particles broad band absorption wide coverage of UVA range Excellent photostability Synergy with most UV-B absorber

TINOSORB S
the first cosmetic UV-filter based on innovative HPT technology superior full spectrum protection oil solubility = formulation flexibility high efficacy at low concentrations = ideal for day care Photostable Synergy with most UV-B absorber

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UV Absorbers overview UV-A Test Methods (in vivo / in vitro) UV Protection by Ciba
TINOSORB M TINOSORB S Registration status Market Products with CibaUV Absorber

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Registration Status

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TINOSORBM & TINOSORBS


Registration
Approved as UV filter in: Europe in a concentration of use up to 10% active (=20% TINOSORB M)
(European cosmetics directive 76/768/EEC)

Switzerland Brazil Paraguay Argentina Bolivia Uruguay French Guyana South Africa China Australia (only TINOSORB M) Taiwan

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TINOSORBM & TINOSORBS


Registration
No registration of the raw material required. Sunscreen products have to be registered by Ministry of Health. Colombia Chile Ecuador Peru Korea Ongoing registration work: USA Japan Mexico Canada Sunscreen products are free to be placed on the market as long as no therapeutic claims are made: Honkong Singapore
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UV Absorbers overview UV-A Test Methods (in vivo / in vitro) UV Protection by Ciba
TINOSORB M TINOSORB S Registration status Market Products with CibaUV Absorber

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French Market
All Pharmacy Brands (except LOral Brands) use TINOSORB M All Pharmacy Brands use Ciba Technology About 20 Brands on Market incorporate TINOSORB M and/or TINOSORB S

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German Market
BDF is most important purchaser of TINOSORB S (e.g. Nivea) Premium Brand Marbert incorporates TINOSORB First Private Label products on market with TINOSORB M

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Swiss Market
Highest per capita spendings on sunscreen Three out of the top four Sun Care Brands use TINOSORB (Nivea Sun, Daylong, Ambre Solaire, Sunlook) All PizBuin products contain TINOSORB M and TINOSORB S Private Label sunscreen with TINOSORB M launched 2003

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Other Markets
ESP
No 1 Brand Nivea uses TINOSORB S Pharmacy brands ISDIN (A. Puig) and E.Carreras (Novartis) incorporate TINOSORB M

GBR
Two strong Mass Market brands use TINOSORB (Nivea, PizBuin) Incorporation of TINOSORB M in some Private Label products (Superdrugss Solait, M&S, Tesco)

ITA
Market Leader Nivea incorporates TINOSORB S Local Brands (Collistar, Bottega Verde, Biovitamin C, Bio Nike) use TINOSORB M in some of their formulations

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Ingredient Branding (official)

RoC Minesol, Europe

Co-Branding

Daylong, Switzerland No more suntan, India


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Ingredient Branding (inofficial)

Bergasol, France Ella Bach, France

Lutsine, France

Polysianes, France Shandiz, Iran

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Ciba Sunscreen Simulator

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Ciba Sunscreen Simulator

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