uv protection by ciba sept 03 -...

Home & Personal CareCiba Spezialitätenchemie Grenzach

1

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.


2

Ø UV Absorbers overview

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

Ø UV Protection by Ciba§ TINOSORB® M§ TINOSORB® S§ Registration status§ Market Products with Ciba®UV Absorber


3

Protection at the beach around 1900


4

Objective: Tanning without Sunburn, 1930

First transparent sun protection creams Fr

omTa

venr

ath

Sim

one,

200

0


5

Skin cancer as headline, Germany 1993

Dangerous sun: How to save our skin

Warnings from:• „Sun Allergy“• Photodermatosis• Sunburn• Skin-aging• Skin cancer

From

Tave

nrat

hS

imon

e, 2

000


6

UV exposure of the skin

Spectrum of the Sun

Stratosphere

Ozone layer

Surface of the earth

Horny layer of the skin

Epidermis

Dermis

Hypodermis

Wavelength nm 200 290 320 400 800

UV-C Visible light InfraredUV-B UV-A

UV-B: 70% reflected by Stratum

CorneumUV-A:

30% penetrates into Dermis


7

Penetration of Sun Light

0

10

20

30

40

50

60

70

80

90

100250 300 350 400 450

Wavelength / nmP

enet

rati

on

Dep

th /

µm

UVB UVA

SC

22001200

1200800

550600

90400

60350

6300

1,5280

Penetration Depth [µm]

Wavelength [nm]


8

Effects of UV Radiation on Human Skin

ØMain risk of UVB 290-320 nm

§ Sunburn

§ Skin cancer

ØMain risk of UVA 320-400 nm

§ Accelerated photoageing

§ Damage of blood vessels and connective tissues

§ Contribution to sunburn

§ Contribution to skin cancer


9

Requirements of UV AbsorbersØ Efficacy

Molecules have to provide an efficient absorption of UV radiation (UVB and/or UVA)

Ø Ease of FormulatingMolecules have to be compatible with most ingredients used in formulations

Ø SafetyMolecules have to be safe, i.e. avoid of adverse effects


10

Most frequently used cosmetic UV Absorbers


11

UV-Filter consumption in Western Europe

Kline 2002

PSA

OT

EHMC

OCT

BMBM

MBCEHS

BP3

BP4

Other

TiO2

ZnO

20%18%

13%

14%

4%

Value: Total € 97.3mio

BMBM

MBC

EHS

BP3

PSA

OT

BP4

Other

OCT

EHMC

TiO2ZnO

Volume: Total 4840 t

41%

11%9%

14%3%


12

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

UV-B:EthylHexyl MethoxyCinnamate (EHMC)

UV-A:Butyl MethoxyDibenzoylMethane (BMBM)

O

O

O

OCH3

O OM

olar

Ext

ictio

n

Mol

ar E

xtic

tion

Wavelength (nm) Wavelength (nm)

The ideal combination?


13

0,20

0,40

0,60

0,80

1,00

0 1 2 3 4 % BMBM

+ 5% OCR

+ 5% OCR and5% EHMC

dashed lines: irradiation with 10 MED

BMBM

Photostability of BMBM and EHMC

UVA

/UVB

-Rat

io

BMBM/EHMC combinations are not photostable


14

New UVA- and Broad-Spectrum UV Filters, 2003

üüXXTINOSORB SBEMTS 81

üüXNEOHELIOPAN APDPDTS 80

üüXXTINOSORB MMBBTS 79

noüXXMEXORYL XLDTSS 73

noüXMEXORYL SXTDSAS 71

Freely available

Approved

(Europe)UVAUVBTradenameINCI#


15



Ø UV Protection by Ciba– TINOSORB® M– TINOSORB® S– Registration status– Market Products with Ciba®UV Absorber


16

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


17

In vivo: UVA-PF (PPD)

Ø Persistant Pigment Darkening = PPDØ Principle:

§ Measurement of UVA-induced pigmentation 2 hours after irradiation when the pigmentation has stabilized.

Ø Conditions: § UVA-dose about 15 J/cm² § 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


18

In vitro: Australian Standard

0

2 0

4 0

6 0

8 0

1 0 0

2 9 0 3 1 0 3 3 0 3 5 0 3 7 0 3 9 0 400

Australian Standard

Tra

nsm

issi

on (

%)

λ (nm)

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


19

In vitro: UVA/UVB-ratio

0

100

200

300

400

500

600

700

290 310 330 350 370 390

Wavelength / nm

E (1

%,1

cm)

Principle: Ratio of the average of extinction E in the UVA- and the UVB-range, spectrum measured on special substrates

UV-B UV-A

UVA-UVB ratio of around 1 = broad band filter systemUVA-UVB ratio of < 0.5 = UVB absorberUVA-UVB ratio of > 1 = UVA absorber


20

Star-rating

ØUV-A / UV-B ratio§ 0.2 – 0.4 =

§ 0.4 – 0.6 =

§ 0.6 – 0.8 =

§ > 0.8 =


21

In vitro: Critical Wavelength

0

100

200

300

400

500

600

700

290 310 330 350 370 390

Wavelength / nm

E (

1%,1

cm)

Principle: λc 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

The higher the λc = The better the UVA protection

λc


22

Photostable UVA ProtectionØ Traditional combination of BMBM (Parsol 1789) and EHMC

are effective, but not photostable.

Ø Stabilization with OCR is effective for BMBM alone, but not in combination with EHMC

Ø TINOSORBM and TINOSORBS are the only broad spectrum and photostable UV Absorbers available on the market


23



Ø UV Protection by Ciba– TINOSORB® M

o Propertieso Performanceso Formulating with TINOSORB® M

§ TINOSORB® S§ Registration status§ Market Products with Ciba®UV Absorber


24

TINOSORB®M

Organic Micropigment with Broad-Spectrum UVA/UVB Performance and

High Inherent Photostability


25

Chemical Properties

Active Ingredient of TINOSORB®M:

INCI name: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol(abbr.: MBBT)

Melting point: 195 °CSolubility in H2O: < 10-8 g/lMolecular mass: 658.86 g/mol

OH OH

NN

N

N

N

N

UV absorbance E1%,1cm


26

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 TINOSORB®M

(Particle Size Range: 70 nm - 400 nm

= 0,07µm - 0,40µm)


27

Composition of TINOSORB®M

MBBT particles 50.0%Surfactant (Decyl Glucoside) 7.5%Thickener (Xanthan gum) 0.2%Propylene glycol 0.4%Water ad 100%

pH 10.5 – 11.5

No preservation necessary because of alkaline pH


28

Importance of small particle sizes

The smaller the particle size, the higher the molar extinction of TINOSORB®M Particles

0

10000

20000

30000

40000

280 300 320 340 360 380 400 420

Wavelength / nm

Mo

lar

Ext

inct

ion

/ l/(

mo

l·cm

)

d(0.5) = 0.16 µm

d(0.5) = 0.21 µm

d(0.5) = 0.34 µm

d(0.5) = 0.78 µm

d(0.5) = 4.37 µm


29

Importance of small particle sizes

Qualitative Explanation of the Increase of in vitro SPF with Smaller ParticlesThe UV-attenuating coverage by the sunscreen film is more efficientwith smaller particles. Average thickness of film: 20 µm; 10% particles =20% TINOSORB®MAssumption: two layers of particles for an efficient coverage

particle size d (µm)

1052,51,25

Max. coverage

10%20%40%80%


30

pH Stability of TINOSORB®M

→ TINOSORB ®M dispersion in water

2,5 3 6 8 11 13

pH value

Stable formulations in a broad pH range possible


31

Concentration / SPF correlation

0

2

4

6

8

10

12

14

16SP

F ca

lc.

5 10 20

% TINOSORB M

Ø6,6% TINOSORB M are required to fulfill Australian standardØTINOSORB M is recommended up to 20% in cosmetic formulations


32

Synergistic effect of TINOSORB®M and EHMC

0

5

10

15

20

25

30

35

40

8% TINOSORB M 5% EHMC 5% EHMC + 8%TINOSORB M

5% EHMC +20%TINOSORB M

SPF

in-v

ivo


33

TINOSORB®M and TiO28% TINOSORB M

0,0000

0,2000

0,4000

0,6000

0,8000

1,0000

1,2000

290 310 330 350 370 390

Wavelength / nm

Ext

inct

ion

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

3.5% TiO2

0,0000

0,2000

0,4000

0,6000

0,8000

1,0000

1,2000

290 310 330 350 370 390

Wavelength / nm

Ext

inct

ion

Combination

0,0000

0,2000

0,4000

0,6000

0,8000

1,0000

1,2000

290 310 330 350 370 390

Wavelength / nm

Ext

inct

ion


34

Comparison of UVA Performance

3240.08>20%Ethylhexyl Triazone

3480,29>10%Octocrylene

3370.21>10%Ethylhexyl Methoxycinnamate

3640.5> 10%Benzophenone-3

3480.299%TiO2

3831.223%BMBM (Parsol 1789)

3760.818%ZnO (Nanox)

3880.986.6%TINOSORB®M

Critical Wavelength(nm)

UVA/UVB RatioAustralian Standard

UV-Absorber


35

Synergistic effect of TINOSORB®M with EHMC

0

2

4

6

8

10

12

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

UV

A-P

F

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


36

0

20

40

60

80

100

0 5 10 20UV-Dose in MED

% r

eco

very

of

UV

-Filt

ers

TINOSORB M EHMC BMBM MBC

Photostability in vitro

Max MED in Central EuropeMinimal Erythemal Dose


37

0

20

40

60

80

100

0 10

UV-Dose in MED

Rec

ove

ry o

f EH

MC

in%

Stabilization of EHMC by TINOSORB®M

EHM

C a

lone

2.4

%

EHM

C &

TIN

OSO

RB M

10%


38

Formulation Guideline with TINOSORB®MØ Optimized way of incorporation

§ After emulsification, during the cooling phase (~60°C), pour TINOSORB®M into the emulsion under gentle stirring.§ Additional homogenization should be avoided.

Ø Alternative way of incorporation

§ Incorporation of TINOSORB®M 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


39



Ø UV Protection by Ciba– TINOSORB® M– TINOSORB® S

o Propertieso Performanceso Formulating with TINOSORB® S

§ Registration status§ Market Products with Ciba®UV Absorber


40

TINOSORB®S

The most efficient Broad-Spectrum UV-Absorber


41

Chemical Properties

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

Melting point: 80 °CSolubility: Oil solubleMolecular mass: 627,8 g/molSolubility in H2O: 10-7 g/l

N N

N

OHO

OO

H

OCH3

0

100

200

300

400

500

600

700

800

290

300

310

320

330

340

350

360

370

380

390

400

Wavelength / nm

E (

1%, 1

cm)

UV-spectrum of TINOSORB®S


42

Inherent Photostability by Photo-Tautomerism

N

N

N

O

R1

R2

R3

R4

R5

N

N

N

O

R1

R2

R3

R4

R5

H

H

h ν


43

UV-A Protection with TINOSORB®S

0

2

4

6

8

10

12

1416

18

Placebo 1% 2% 4%

Placebo TINOSORB S plus 5% EHMC

% TINOSORB S

PFA

(PP

D m

eth

od)

PFA (Japan)

PA +

PA ++

PA +++


44

Comparison of UVA Performance

3640.5> 10%Benzophenone-3

3480,29>20%Octocrylene

3370.21>20%Ethylhexyl Methoxycinnamate

3240.08>20%Ethylhexyl Triazone

3480.299%TiO2

3831.223%BMBM (Parsol 1789)

3760.818%ZnO (Nanox)

3880.986.6%TINOSORB®M

3700.732%TINOSORB®S

Critical Wavelength (nm)UVA/UVB RatioAustralian

StandardUV-Absorber


45

Synergistic effect of TINOSORB®S with EHMC

13579

11131517

1 2 3% UVA Filter (BMBM or TINOSORB S)

UV

A-P

F

BMBM BMBM & 5% EHMC & 5% OCRTINOSORB S TINOSORB S & 5% EHMC


46

TINOSORB®S and Ethylhexyl Triazone

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

4% EHT

-0,2000

0,0000

0,2000

0,4000

0,6000

0,8000

1,0000

1,2000

1,4000

1,6000

290 310 330 350 370 390

Wavelength / nm

Ext

inct

ion

3% TINOSORB S

0,0000

0,2000

0,4000

0,6000

0,8000

1,0000

1,2000

1,4000

1,6000

290 310 330 350 370 390

Wavelength / nm

Ext

inct

ion

Combination

0,0000

0,2000

0,4000

0,6000

0,8000

1,0000

1,2000

1,4000

1,6000

290 310 330 350 370 390

Wavelength / nm

Ext

inct

ion

SPFcalc . 6SPF

calc . 7

SPFcalc. 20


47

0

20

40

60

80

100

0 5 10 20UV-Dose in MED

% r

eco

very

of

UV

-Filt

ers

TINOSORB S EHMC BMBM MBC

Photostability in vitro

Max MED in Central EuropeMinimal Erythemal Dose


48

20

40

60

80

100

0 10

UV-Dose in MED

Stabilization of BMBM by TINOSORB®S

BMBM

alo

ne

BM

BM

& 3

%TI

NO

SORB

S

Reco

very

of

BM

BM

in %


49

Formulation Guideline with TINOSORB®SØ Solubilize TINOSORB®S by adding it directly to the oil phase

and heat up to 80°C.

Ø For cold process : solubilize TINOSORB®S 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/O´s stability – Reasonable limit of use in W/O : < 3%


50

Solubility of TINOSORB®S

Ø Very good solubility (15-20%)§ UV Absorbers, Pyrrolidones

Ø Good solubility (8-15%)§ Fatty Acids Esters, Benzoic Acid Esters

Ø Low solubility (2-5%)§ Triacylglycerides, vegetables oils

Ø Very Low solubility (<1%)§ Alcohol, silicones and hydrocarbon derivates


51

Solubility of TINOSORB®S• Fatty Acid Esters

Isodecyl Salicylate (Dermol IDSA) 18%Diethylhexyl Succinate (Crodamol OSU) 10%Dicaprylyl Carbonate ( Cetiol CC) 9%Propylene Glycol Dicaprylate/Dicaprate (Crodamol PC) 7%Isopropyl Myristate ( Tegosoft M) 6%

• Benzoic Acid EstersC12-C15 Alkyl Benzoate (Tegosoft TN) 13%Isostearyl Benzoate (Finsol SB)

8%

• TriacylglyceridesCaprylic/Capric Triglyceride (Miglyol 812) 5%

• PyrrolidonesCaprylyl Pyrrolidone (Sulfadone LP100) 20%

• UV AbsorbersEthylhexyl Methoxycinnamate (TINOSORB OMC) 17%Ethylhexyl Salicylate (Eusolex OS) 20%


52

TINOSORB®M & TINOSORB®Sthe ideal couple


53

Characteristics of TINOSORB®M & TINOSORB®S

0.731.0UV-A/UV-B ratio

373nm388nmCritical Wavelength

Higher absorbanceCovers long UVABroad-spectrumPerformance

OilWaterEmulsion Phase

PowderParticles dispersionPhysical state

TINOSORB® STINOSORB® M


54

Synergy between TINOSORB®M & TINOSORB®S

02468

1012141618

TINOSORB S 0% TINOSORB S 2%

0% 5% 10% 15%TINOSORB®M conc.


55

Summary

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

Ø 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


56



Ø UV Protection by Ciba

§ TINOSORB® M

§ TINOSORB® S

§ Registration status§Market Products with Ciba®UV Absorber


57

Registration Status


58

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

TINOSORB®M & TINOSORB®S


59

TINOSORB®M & TINOSORB®SRegistrationØ No registration of the raw material required. Sunscreen products have to

be registered by Ministry of Health.§ Colombia§ Chile§ Ecuador§ Peru§ Korea

Ø Ongoing registration work:§ USA§ Japan§ Mexico§ Canada

Ø Sunscreen products are free to be placed on the market as long as no therapeutic claims are made:§ Honkong§ Singapore


60



Ø UV Protection by Ciba

§ TINOSORB® M

§ TINOSORB® S

§ Registration status§Market Products with Ciba®UV Absorber


61

French Market

Ø All Pharmacy Brands (except L‘Oréal Brands) use TINOSORB MØ All Pharmacy Brands use Ciba TechnologyØ About 20 Brands on Market incorporate TINOSORB M and/or

TINOSORB S


62

German Market

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


63

Swiss Market

Ø Highest per capita spendings on sunscreenØ Three out of the top four Sun Care Brands use TINOSORB (Nivea

Sun, Daylong, Ambre Solaire, Sunlook) Ø All PizBuin products contain TINOSORB M and TINOSORB SØ Private Label sunscreen with TINOSORB M launched 2003


64

Other MarketsESPØNo 1 Brand Nivea uses TINOSORB SØPharmacy brands ISDIN (A. Puig) and E.Carreras (Novartis)

incorporate TINOSORB M

GBRØTwo strong Mass Market brands use TINOSORB (Nivea, PizBuin)ØIncorporation of TINOSORB M in some Private Label products

(Superdrugs‘s Solait, M&S, Tesco)

ITAØMarket Leader Nivea incorporates TINOSORB SØLocal Brands (Collistar, Bottega Verde, Biovitamin C, Bio Nike) use

TINOSORB M in some of their formulations


65

Ingredient Branding (official)

Daylong, Switzerland

Co-Branding

No more suntan, India

RoC Minesol, Europe


66

Ingredient Branding (inofficial)

Bergasol, France

Ella Baché, France

Lutsine, France

Shandiz, Iran

Polysianes, France


67

Ciba® Sunscreen Simulator


68

Ciba® Sunscreen Simulator

uv protection by ciba sept 03 -...

Documents