Egypt Regulation UV Portfolio 130510

Global Norms, Standards and Test Methods in UV Protection

Global Norms & Standards / SPF

SPF Range

Proposed Monograph SPF 50+ Max.

Claims

In-vivo SPF = Claimed SPF

Relevant Test Method

In-vivo SPF FDA Method

2

Max. SPF 50+

Max. SPF 30+

In-vivo SPF In-vivo SPF = Claimed = Claimed SPF SPF

Max. SPF 50+

Max. SPF 50+

Categories: low, medium, high & very high protection SPF claim specified: 6, 10, 15, 20, 25, 30, 50 and 50+

In-vivo SPF ISO24444 Method

Max. SPF 99

Categories like EU but individual SPF claim possible Colipa and ISO method

Erythemal Effectiveness of Sunlight

EA( ), SI( ) / arbitrary units

UVB

UVA

308nm

1

Erythemal Action Spectrum Standard Sun Spectrum Erythemal Effectiveness 0 290

310

330

350

 / nm 3

Technical Service SunCare E-EMV/GU

370

390

SPF measurement in vivo  SPF represents mainly a protection in the UVB range UVAII contributes to 20 % to SPF

    E  I SPF   E   I   T    400

290 400 290

Biological response = sunburn = max at 308nm (UVB)

T = Sunscreen Transmittance at  E = Spectral irradiance of UV source at  I = Erythemal action spectrum at  Technical Service SunCare E-EMV/GU

4

SPF measurement in vivo Principle: Measurement of the UV induced erythema 20 ± 4h after irradiation Conditions:  Xenon lamp solar simulator with Cosmetic Europe Standard UV spectrum

 Application: 2 mg/cm²  Choice of an adequate panel of human volunteers  10 to 20 subjects max., skin types I, II and III

(screening only on 5 volunteers)

5


Impact of Application Amount on SPF

60

SPF (calc.)

50 40 30 20 10 0

In-vivo SPF measurement

=35g / Application =

2mg/cm2

Reality

1.5mg/cm2

1mg/cm2

0.5mg/cm2

Linear correlation between SPF and film thickness 6

Technical Service SunCare E-EMV/DU

SPF measurement in vivo Principle: Measurement of the UV induced erythema 20 ± 4h after irradiation Conditions:  Xenon lamp solar simulator with COLIPA Standard UV spectrum

 Application: 2 mg/cm²  Choice of an adequate panel of human volunteers  10 to 20 subjects max., skin types I, II and III

(screening only on 5 volunteers)

7


The different skin types

Self Protection Time / Minutes

80 70

>70

60 50 40 30

Skin types for in-vivo SPF testing

20 10

<10

10-15

15-30

30-60

20-45

0

Type 1

8

Type 2

Type 3

Type 4

Type 5

Type 6

data based on the conditions of a clear day in early July at noon time, 32° latitude North (T.B. Fitzpatrick, Archives of Dermatology, 124, 1988, p.869)

BASF Personal Care

SPF measurement in vivo Determination: UV exposure in defined MED steps

Pretest: Determination of Minimal Erythemal Dose = MED

MED: quantity of UV radiation required to produce the first perceptible, unambiguous redness reaction with clearly defined borders

SPF = MED p / MED up P = Protected aera

Up = Unprotected aera

9


SPF 50 protects five times better than SPF10

10

http://www.youtube.com/watch?v=8cc8qRr7oMQ

SPF measurement in vivo Limitations:  Reproducibility from institute to institute  Reproducibility from day to day  SPF (US) not the same as SPF (EU) not the same as SPF (Asia)  Ethics  Price  Does not represent protection over the whole UV (Sunburn protection = UVB mainly)  Application rate (2 mg/cm²) not used by consumers 0.5-1 mg/cm² is the amount used => less protection as indicated !

11


SPF measurement in vitro  Principle:

In vitro SPF calculated from the spectral transmittance of UV light from 290 to 400nm Measurement through a sunscreen film on a rough surface (PMMA plates).


12

SPF measurement in vitro  Equipment: Labsphere UV Transmittance analyzer UV-2000S


13

SPF measurement in vitro  BASF Conditions:  Application: 1.2 mg/cm² on sandblasted PMMA plates (Helioscience)  4 plates with 11 measurements on each plate  Blank with glycerin


15

SPF measurement in vitro  Limitations:  Different methods – no harmonized method

 Equipment and application techniques not harmonized  Strong influence of individual application technique  Photostability is not taken into account by most of the methods  Influence of product rheology Conclusion: In vitro SPF suitable for comparison and evaluation of similar formulations. Determination of absolute SPF level difficult


16

Global Norms & Standards / UVA-PF UVA protection

Claims

Test Method

Max. UVA needed 17

Critical Wavelength

UVA-PF

UVA-PF

UVA-PF

CW >370 = Broad spectrum SPF>15 → decreases risk of skin cancer

PA+ PA++ PA+++

PA+ PA++ PA+++ PA++++ (01.2013)

UVA-PF/SPF ≥ 1/3 / CW >370

CW / FDA final rule 2011

PPD invivo ISO 24442

PPD invivo ISO 24442

>8

>8

>16

UVA/ UVB ratio

UVA-PF

UVA-PF/SPF ≥ 1/3 / CW >370 ULTRA

UVA-PF invitro ISO24443 (PPD ISO 24442 EU only)

>20

UVA/UVB ratio (incl. Photostability)

>30

UVA-PF invitro ISO24443 or PPD ISO 24442

>33

UVA Test Methods  In vivo method  UVA – PF (PPD)  In vivo / in vitro method  UVA-PF ”in vitro” / SPF label (EC recommendation – Cosmetic Europe Method)

 In vitro methods  UVA/UVB ratio


18

In vivo: UVA-PF (PPD) acc. to JCIA Measurement Persistent Pigment Darkening = PPD

    E  I UVA  PF   E   I  T    400

320 400

320

= Biological Action Spectrum Where : T = Sunscreen Transmittance at E = Spectral irradiatance of UV source at  I = Biological action spectrum at

= Persitent Pigment Darkening




19

In vivo: UVA-PF (PPD) Conditions:  Xenon lamp, spectrum: 320 to 400 nm  10 volunteers of skin types II, III and IV

 The Minimal Pigmenting Dose (MPD) corresponds to the minimal UVA dose producing a minimal darkening effect 2 hours after exposure to 6 increasing doses of UVA.

UVA PF = MDPp / MPD up The MPD for the protected area (MPDp) is then compared with the MPD for the unprotected area (MPDup). 20


The different skin types

Self Protection Time / Minutes

80 70

>70

60 50

Test subjects for in-vivo UVA-PF

40 30

30-60

20 10 0

<10

Type 1

10-15

Type 2

15-30

Type 3

20-45

Type 4

Type 5

Type 6

data based on the conditions of a clear day in early July at noon time, 32° latitude North (T.B. Fitzpatrick, Archives of Dermatology, 124, 1988, p.869) 21


In vivo: UVA-PF (PPD) PPD is the standard method in Japan for UVA assessment Japan Cosmetic Industry Association adopted a classification scheme rather than numerical values for expressing UVA protection

UVA-PF

<2

No protection Classification against UVA Claims

4-8

8 – 16

>16*

PA +

PA ++

PA +++

PA ++++

Protection Considerable High Greatest No claims against Protection protection protection UVA

* From 13 January 2013 22

2-4


In vivo: UVA-PF (PPD) Benefit:

 Takes photostability into account  PPD is the skin‘s response to UVA (connected to skin damage via free radicals)

Limitation:

 Difficulty to standardize

23


In-vitro UVA-PF (Cosmetic EU Guideline 2011)  Principle:

 In vitro transmission measurement ( measurement in vitro SPF (solar spectrum – erythema action spectrum)  Mathematical adjustment of the transmission spectrum such that the in vitro SPF equals the labeled in vivo SPF, by applying a constant c as exponent for the transmissions 1,2

Absorbance

1 0,8 0,6

14 13 12

0,4

In-vitro measured absorption spectrum

0,2

11

Calculated SPF

Adapted Spectrum would reach claimed SPF

10

0

290

300

310

320

330

340

350 360 370 380 390 400 Technical Service SunCare E-EMV/GU

24

In-vitro UVA-PF (Cosmetic EU Guideline 2011)  Calculation of the UVA-PF in vitro between 320 and 400 nm using the adjusted transmission curve (together with the PPD action spectrum and the spectrum of the UVA lamp)  Irradiation linked to UVA-PF static  D = 1,2 J/cm² X UVA-PF static  In vitro transmission measurement after irradiation  calculation of the UVA-PF in vitro after irradiation using the same coefficient c  Calculation of the Colipa ratio :

SPF label / UVA-PF in vitro a.i.

< 3


25

In-vitro UVA-PF (Cosmetic EU Guideline 2011) 

Conditions:



Blank: Glycerin



Application: –

1.3 mg/cm² on moulded HD6 plates (2011 revision)



3 plates with 4 measurements on each plate



Irradiation dose is UVA-PF dependent (UVA-PF X 1.2J/cm²)



Critical wavelength is measured after irradiation



If Lc >370nm AND

Cosmetic EU ratio method 2011

UVA-PF / SPF ≥ 1/3


26

In-vitro UVA-PF - EC recommendation Benefits  Expression of the UVA protection in relation to the SPF

 Photostability is taken into account

27


In vitro: BOOTS STAR RATING UVA/UVB-ratio (2011 revision)

 Conditions:

 In vitro transmission measurement

Blank with Glycerin Quartz or PMMA plates (2 – 4µm) Application amount: 1 mg/cm²  Irradiation dose: 17,5 J/cm² (3MED)


28


Ratio of the average absorption in the UVA- (320-400 nm) to that in the UVB-(290-320 nm) range of the absorption spectrum of a product Before and after 17.5J/cm² 700 600

E (1%,1cm)

500 400 300 200

UV-A

UV-B

100 0 290

310

330

350

370

390

Wavelength / nm Technical Service SunCare E-EMV/GU

29


Allocation of star ratings from  to  stars

UVA/UVB RATIO after irradiation

0.0 - 0.56 0.57 - 0.75 0.76 - 0.85 0.86 -…

0.0 to 0.59 No Rating No Rating No Rating No Rating

INITIAL UVA/UVB RATIO 0.6 to 0.79 0.8 to 0.89 No Rating No Rating

  

  

0.9 and over No Rating

  



ratio of zero :

No UVA absorbance



ratio of < 0,5

UVB absorber



ratio of 1,0 :

Equal UVA and UVB absorbance (broad spectrum filter system)



ratio of > 1,0

UVA absorber Technical Service SunCare E-EMV/GU

30

Overview Sun Care Portfolio 2013 Global Technical Service Sun Care E-EMC/DU

UV Filter Performance Overview

35

Why a new UV filter? 320 - 340nm

1600

UVB

UVAII

UVAI

E (1,1)

1200

800

400

0 290 295 300 305 310 315 320 325 330 335 340 345 350 355 360 365 370 375 380 385 390 395 400

Wavelenght [nm] UVB absorber

UVA absorber

Current lack of performance in UVA II 36

E-EMC/DU Technical Service SunCare

Why a new UV filter? 320 - 340nm

1600

UVB

UVAII

UVAI

E (1,1)

1200

800

400

0 290 295 300 305 310 315 320 325 330 335 340 345 350 355 360 365 370 375 380 385 390 395 400 Wavelenght [nm] UVB absorber

Tinosorb A2B (Active)

UVA absorber

High performance of Tinosorb® A2B in UVA II 37


Tinosorb® A2B - Product data Form

Aqueous dispersion ~50% active ingredient

Structure

N

N N

INCI

Tris-Biphenyl Triazine (nano) (Abbr: TBPT)

Emax. (1,1)

1100

 max

315 nm

Concentration maximum

20% (=10% TBPT)

Molecular mass

537.22 g/mol

Melting Point

261°C

38


Tinosorb®A2B - Particle Size and Efficacy  Absorbance spectrum dependent on the particle size  Optimal performance achieved with a particle size of around 100nm  Same effect observed for organic as well as inorganic particulate UV filters

40

Tinosorb® A2B – Boosting effect with soluble UV filters Performance by: Absorption, Reflection & Scattering

UV Light Other non particulate filters

Tinosorb® A2B

Skin 42

Tinosorb® A2B - Total UV Absorbance Comparison to other UVB Filters 600

Area = Total absorbance Area- 400 nm from 290

500

400

300

200

100

0 HMS

EHS

BMP

OCR (Uvinul N539T)

TiO2

B3

PBSA

EHMC (Uvinul MC 80)

IMC

DBT

EHT TBPT (Uvinul T (Tinosorb 150) A2B-active)

Tinosorb® A2B (TBPT)  most efficient contributor to SPF 44

INTERN - Tinosorb®A2B Challenge Session

Tinosorb® A2B - Contribution to SPF Comparison to EHMC, EHT and PBSA 14 12

SPF

10

TBPT in vivo

8

TBPT 6

EHMC 4

PBSA EHT

2 0

0

2

4

In silico data calculated on BASF Sunscreen Simulator (www.basf.com/sunscreen-simulator)

6

8

10

12

Concentration %

By incorporating Tinosorb® A2B  higher SPF with lower UV filter concentration  more formulation flexibility 45

Tinosorb® A2B - Photostability Comparison to other UVB Filters

Determined by HPLC method

Tinosorb® A2B is photostable 46

INTERN - E-EMV/GU - BASF confidential

Tinosorb® A2B Incorporation Instructions Emulsifiers

Recommended incorporation process  Generally, possible with all incorporation methods

O/W

 Recommended incorporation:

Non ionic

After emulsification (predilution into water), below 50°C, under stirring – final high shear homogenization possible

Anionic

Cationic

 Possible with all incorporation methods with tested emulsifiers – final high shear homogenization possible

 Incompatibility with cationic emulsifiers whatever the incorporation process is  Cationics with low charge might work

W/O emulsifiers 47

 After emulsification (with predilution into water), below 50°C, under stirring – final high shear homogenization possible


Tinosorb® A2B Performance in a Sunscreen Formulation 2,5

320 - 340nm

SPF 30

Absorbance

2

1,5

SPF 20 1

Base Base + 4% Tinosorb®A2B

0,5

0 290

310

330

350

370

390

Wavelength (nm)

High contribution of Tinosorb® A2B to UVB & UVA II performance 48

INTERN - E-EMV/GU - BASF confidential

Tinosorb® A2B – performance in a photostable UVA base – SPF 30 UVA-PF in vitro / Addition of UVB filter

SPF in vivo SPF claimed 30

Base (UV09071-1-1)

17.2

>1/3

+ 3% PBSA (UV09071-1-4)

28.8

< 1/3

25.1

< 1/3

+ 3% TiO2 active ingr. (UV09071-1-6)

+ 3% EHMC (UV09071-1-3)

Base: 3% Uvinul®T150 1% Tinosorb®S

28.2

< 1/3

4% Uvinul®A Plus + 3% DBT (UV12103-1-1)

37.2

< 1/3

43.0

> 1/3

+ 6% Tinosorb®A2B (3% active) (UV12103-1-4)

By incorporating Tinosorb®A2B  significant increase of SPF without unbalancing the absorbance in the UVA The filter combination above is for research purpose only. The combination of Uvinul® A Plus and Tinosorb® A2B is blocked by the patent rights of EP2196189 and the equivalent patent rights thereof in many countries.

49


Tinosorb® A2B – performance in a photostabilized UVA base – SPF 30 Addition of UVB filter

UVA-PF in vitro / SPF in vivo SPF claimed 30

Base

20.3 +/- 4.4

>1/3

+ 3% EHMC

28.7 +/- 3.5

< 1/3

+ 3% PBSA

33.4 +/- 3.8

< 1/3

+ 3% EHT

39.4 +/- 5.7

< 1/3

+ 3% DBT

27,0 +/- 6.1

<1/3

+ 3% TiO2

28.3 +/- 7.5

> 1/3 10.1

+ 6% Tinosorb® A2B (3% active)

36.9 +/- 3.7

> 1/3 13.5

Base: 6.0% OCR 2.0% BMDBM 1.0% Tinosorb® S

4.5% Tinosorb® M

By incorporating Tinosorb® A2B  significant increase of SPF without unbalancing the absorbance in the UVA  fills the gap 50


in-cosmetics 2013

Photostable UVA Protection 15

20

30

50

UV12063-1-3

UV12063-2-2

UV12063-3-3

UV12063-4-6

Uvinul®MC80

5.0

5.0

7.5

7.5

Tinosorb®A2B

1.5

3.0

4.0

8.0

UVA

Uvinul®A Plus

2.0

3.0

5.0

5.0

B-S

Tinosorb®M

---

---

---

5.0

Colipa

5.1 > 1/3

7.1 > 1/3

10.4 > 1/3

16.8 > 1/3

PA claim cal.

PA++

PA++

P+++

PA ++++

SPF cal.

16.3

21.6

32.7

52.4

Claimed SPF UVB

UVA-PF in vitro a.i.

a.i.- after irradiation The filter combination above is for research purpose only. The combination of Uvinul® A Plus and Tinosorb® A2B is blocked by the patent rights of EP2196189 and the equivalent patent rights thereof in many countries. 51


Light Feeling Sun Care Cream SPF 50 GEUV12063-4-6

The filter combination above is for research purpose only. The combination of Uvinul® A Plus and Tinosorb® A2B is blocked by the patent rights of EP2196189 and the equivalent patent rights thereof in many countries.

52


Highest Performance •

For high SPFs with high UVA protection high amount of crystalline UV filters are required

•

Solubility limitations of crystalline UV filters require high amounts of emollients

•

High emollient loads leads to heavy formulations and are difficult to stabilize

 Particulate UV filters for the water phase can help to reduce the load of emollients

53


High Performance Sun Screens with „Dry Touch“ Appearance 50

50

50

10.0%

10.0%

10.0%

---

4.0%

4.0%

DBT

4.5%

---

---

UVA

BMDBM

5.0%

3.0%

3.0%

B-S

Tinosorb® S

3.5%

2.0%

1.0%

---

---

1.0%

Total Filter concentration

23%

19%

19%

UVA-PF calc.

17.1

18.9

19.6

UVA-PF / SPF

>1/3

>1/3

>1/3

SPF calc.

49.7

52.0

50.8

Required Cetiol® AB Equivalents

23%

10%

7%

Claimed SPF UVB

Uvinul® N539T (OCR) Tinosorb® A2B (active)

Tinosorb® M (active)

Identical performance, reduced oil phase by the use of particulated UV filters 54

Tinosorb® A2B - Summary Benefits of Tinosorb® A2B  Unique absorbance spectrum  By addition of Tinosorb® A2B, the SPF is increased and the absorbance spectrum is kept balanced to still meet the required UVA protection  Its introduction to the water phase offers more flexibility for the formulator  Thanks to its particulate form, Tinosorb® A2B offers a boosting effect of other dissolved UV filters  Compatible with all commonly used UV filters

 Compatible with commonly used cosmetic raw materials including Ethanol Fill the GAP with Tinosorb® A2B 55


Tinosorb® M Profile INCI name:

Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (nano) (MBBT)

US FDA Drug name:

Bisoctrizole

Appearance:

Dispersion of microfine, organic particles

CAS Number:

103597-45-1

Dispersion:

Tinosorb® M 46.0 - 55.0 % 6.0 - 10.0 % 0.2 - 0.6 % 0.1 - 0.5 % ad 100 % pH value 11

UV Spectrum Tinosorb M

MBBT particles Decyl Glucoside Propylene Glycol Xanthan Gum Water

Melting point:

195 ℃

Type:

Water dispersion

Molecular mass:

658.86 g/mol

Solubility in H2O:

< 10-8 g/l

Approved use conc.: 20% Tinosorb® M (10 % active) EU, JP, Asia US pending 56

Size of Common of UV Filters UV Filter Categories

Molecular Weight

PBSA, EHMC

< 300 Da

< 1 nm

EHT, BEMT

> 500 Da

> 1 nm

6000Da

3 nm

>3’000’000 Da

20-500 nm

Polisilicone-15 (Polymer)

MBBT, TBPT Microfine organic particles, partially “Nano”

Size Molecule / Particle Diameter

(= smallest particles)

Which UV Filters will penetrate into the skin most? For UV Filters Nano is BIG ! 57

BASF Personal Care

20 nm

®M ® T Tinosorb Uvinul

150

Benefits Tinosorb® M, a broad-spectrum UV filter available for the water phase  Microfine organic particles in water increases flexibility regarding the oil phase

 Synergy effect with oil soluble UV filters  Absolutely photostable  The only UV-filter with significant absorbance close to visible light  High contribution to UVA-PF due to strong absorbance in long UVAI  The only completely white UVA filter  Positive impact formulation color

58

Tinosorb® M Triple Action

Tinosorb M provides absorption, reflection and scattering = Triple Action 59

Tinosorb® M

SPF in vivo (International Method)

Combined with EHMC - Synergy Effect

8% Tinosorb® M

Benefit:

5% EHMC

5% EHMC + 8% Tinosorb® M

Synergistic effect with EHMC improves the SPF

5% EHMC + 16% Tinosorb® M

Tinosorb® M Combination with oil soluble UV filters Tinosorb® M: dispersion of the filter in the water phase (O/W)

Oil droplets (black) protection by oil soluble UV filter

By combination of Tinosorb® M and oil soluble UV filter protection in both emulsion phases = boosting effect 07.03.2012

62

Tinosorb® M Stabilization of EHMC

EHMC 2.4%

- 27%

3.4% EHMC & 10% Tinosorb® M

- 8%

Tinosorb® M provides efficient stabilization of EHMC 07.03.2012

63

Tinosorb® M Impact of Filter Composition on Formulation Color

Filter composition

UVA-PF (Colipa)

Gel cream

Gel cream

(UV09100-1-3)

(UV09100-1-4)

7% Uvinul® MC80 5% Uvinul® A Plus 1% Tinosorb® S

5% Uvinul® MC80 2% Uvinul® A Plus 1% Tinosorb® S 4% Tinosorb® M

21.5

21.3

Impact on emulsion color

Identical UVA performance, difference in formulation colour 07.03.2012

65

Tinosorb® M Modification of Skin Sensory Reduction of skin stickiness

Stickiness

more

less

71

Tinosorb® M Formulation Tips  Add Tinosorb® M to the final formulation at low temperature at efficient stirring (or even homogenization)

 Combine Tinosorb® M with oil soluble UV filters in order to achieve synergy effect

 Compensate potential stickiness by the use of light emollients or sensory enhancers

 Check stability carefully in case cationic emulsifiers are used

77

Tinosorb® S Profile INCI-Name:

Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (BEMT)

US FDA Drug Name (USP): Bemotrizinol Appearance:

Slightly yellow powder

CAS Number:

187393 – 00 – 6

Melting point:

80°C

Type:

Oil soluble

Molecular mass:

627.8 g/mol

Solubility in H2O:

10-7 g/l

Approved use conc.:

10% (EU), 10% (Asia), 3% (JP) US pending

UV Spectrum Tinosorb S

78

®S ® Tinosorb Uvinul

T 150

Benefits Tinosorb® S, the only and most efficient oil soluble broadspectrum UV filter  High contribution to SPF  High UVA-PF already at low concentration  Best fit with all approaches in Sun Care  Outstanding photostability  Efficient stabilizer for photoinstable UV filters

79

Tinosorb® S Inherent Photostability by Photo-Tautomerism R1

R4

O N H

N

R2

N R5

R3

h R1

tc

=10-12

sec

R4

N

N

O H

R2

N 07.03.2012

R5

R3

80

Tinosorb® S Contribution to UVA-PF

UVA-PF (PPD method)

 Formulation Base 10 9 8 7 6 5 4 3 2 1 0

 Addition of Tinosorb S

7% EHMC 1.5% ZnO 3.0% TiO2

Base

+ 1%

+ 2% % Tinosorb® S

+ 3%

Tinosorb® S provides good UVA-PF at low concentration 81

Tinosorb® S Contribution to SPF

SPF in-vivo

(International Method)

 34 32

 Addition of Tinosorb S

Formulation Base 7.0% EHMC 1.5% ZnO 3.0% TiO2

30 28 26 24 22 20 18 Base

+ 1%

+ 2%

%

Tinosorb®

+ 3%

S

Tinosorb®S provides good SPF at low concentration 82

Tinosorb® S Stabilization of EHMC

3.4% EHMC & 2% Tinosorb® S

- 42%

EHMC 3.4%

- 19%

Tinosorb® S provides efficient stabilization of EHMC 84

Tinosorb® S Solubility in selected Cosmetic Oils

Cosmetic Oils

86

Tinosorb® S Microscopic Evaluation of Crystals

Magnification, x 125

BEMT: Needle form crystals 88

Tinosorb® S Formulation Tips  Choose polar emollients with best solubility for Tinosorb® S such as e.g. Ethylhexyl Methoxycinnamate (Uvinul® MC80), Ethylhexyl Salicylate (Neoheliopan Type OS), Dicaprylyl Carbonate (Cetiol® CC), C12-15 Alkyl Benzoate (Cetiol® AB), Dibutyl Adipate (Cetiol® B)

 The oil phase might be adapted in order to solubilize Tinosorb® S and other oil soluble filters completely.

 Dissolve Tinosorb® S completely in the oil phase

 Check potential crystallization (microscopy) at low storage temperatures

94

Limitations in Sun Care Formulations  Formulations with high SPF need high load of filter concentration  Most filters are either oils or need to be dissolved in polar emollients  The oil phase has to be adapted depending on the oil soluble filters in quantity as well as in quality  High oil phases reduce the flexibility to modify sensory of formulations  Use of filter mainly in one formulation phase often achieve lower performance than expected

Tinosorb® S Aqua = more formulation flexibility 96

Tinosorb® S Aqua Profile INCI-Name:

Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (and) Polymethyl Methacrylate

US FDA Drug Name (USP): Bemotrizinol UV Spectrum Appearance:

Slight yellow liquid dispersion

CAS Number:

187393–00–6/ 9011–14-7/ 1335-72-4/ 124-68-5

Dispersion:

Tinosorb® S Aqua 18.0 - 22.0 % 17.0 - 21.0 % 1.0 - 2.0 % 0.4 - 0.8 % ad 100 pH value 8-11

Tinosorb® S Aqua

Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Polymethylmethacrylate Sodium Laureth Sulfate Amino Methyl Propanol

Type:

Water dispersion

Molecular mass:

627.8 g/mol

Solubility in H2O:

10-7 g/l

Approved use conc.:

50% EU, Asia (10% acitve) 15% JP (3% active) US pending 98

Tinosorb® S Aqua Benefits



Based on highly efficient Tinosorb® S technology



Increased formulation flexibility - Addition before or after emulsification, short term exposure to higher temperatures possible - Prevention of overload of the oil phase = more flexibility to adapt the oil phase



Improved efficacy due to more homogeneous filter distribution - Water resistance of formulations is not negatively impacted and could even be improved

99

Tinosorb® S Aqua Formulation Flexibility Plus Point Lotion SPF50+ (GEUV09102-4-18)

Uvinul® T150 PBSA T-Lite® SF-S Uvinul® A Plus Tinosorb® S

Filter composition

3.5% 4.0% 4.5% 9.0% 3.5%

Filter concentration

24.5%

Water Resistant Sun Matrix SPF50+ (GEUV10080-4-1) 3.0% 3.0% 8.0% 2.0% 10%

Uvinul® T150 PBSA Uvinul® A Plus Tinosorb® S Tinosorb® S Aqua

18.0% Replacement of TiO2 = transparency

Filter Cost

100%

~85%

Emollient Concentration needed

30%

20%

Performance

SPF (in vivo) UVA-PF

53 / 73 22.2

SPF (in vivo) 59.6 / 68.4 UVA-PF (in vitro) 23.7 WR (2*20min) 63.9%

Increased formulation flexibility, reduced filter concentration, lower oil phase, enhanced transparency, reduced filter cost

106

Tinosorb® S Aqua Manufacturing Process in O/W Tinosorb® S Aqua

Before emulsification

75°C

Macroscopic evaluation

Homogeneous

Tinosorb® S Aqua

Tinosorb® S Aqua

Emulsion

Emulsion

75°C

Homogeneous

30°C

Homogeneous

Microscopic evaluation X125 under cross polarized light – After 3 months

Independent from manufacturing process homogeneous distribution of Tinosorb® S Aqua is achieved.

Uvinul® A Plus Profile INCI-Name:

Diethylamino Hydroxybenzoyl Hexyl Benzoate (DHHB)

US FDA Drug Name (USP):

--

Appearance:

CAS Number:

White to light salmon granular UV Spectrum 302776-68-7

Melting point:

54°C

Type:

Oil and alcohol soluble

Molecular mass:

397.5 g/mol

Approved use conc.:

10% EU, Asia, JP

Uvinul® A Plus

113 113

Uvinul® A Plus Benefits Uvinul® A Plus, the only photostable UVA filter on the market

   

Absolute photostable UVA protection

High formulation flexibility due to excellent solubility Good compatibility with other UV filters and cosmetic ingredients Excellent performance in radical protection

114

Uvinul® A Plus and BMDBM  Uvinul® A Plus can easily replace BMDBM in formulations  Comparable absorption curve  Better solubility

1200

 Perfect photostability

1000

DHHB

BMDBM

BMDBM after 12MED irradiation

E (1,1)

800

600

400

200

390

370

350

330

310

290

0

Wavelength (nm) 07.03.2012

116

Uvinul® A Plus Contribution to SPF and UVA-PF

Base: 10% EHMC

addition of Uvinul A Plus

Uvinul® A Plus Solubility in various cosmetic oils compared to BMDBM 45

Solubility of in Selected Cosmetic Oils (%) at 25°C

40

Uvinul® A Plus

35

Solubility %

30

BMDBM

25 20 15 10 5 0

Cosmetic Oils

Uvinul® A Plus has superior solubility in selected cosmetic oils than BMDBM 07.03.2012

124

Uvinul® A Plus Influence of emulsifier on emulsion color  Summary

L*: 92.0 a*: -7.3 b*: 17.5

L*: 93.1 a*: -5,8 b*: 15.0

5.0% Eumulgade® PL 68/50 1.0% Eumulgin® Prisma

3.5% Cremophor® A6 1.5% Cremophor® A25

5/10/2013

1.5% Eumulgin® Prisma

L*: 89.3 a*: -10.0 b*: 26.8

L*: 93.6 a*: -7.0 b*: 17,2 magnification x 400

L*: 94.4 a*: -7.0 b*: 16.1

3.5% Eumulgin® BA 25 1.5% Lameform® TGI

2.0% Tinovis ADE Technical Service SunCare E-EMC/DU

Spectrometer Lambda 650; CIELab; D65 / 10 o 131

Uvinul® A Plus Formulation Tips  It is possible to use Uvinul® A Plus in a wide spectrum of polar oils due to its excellent solubility in a wide range of emollients

 Good solubility also in Ethanol

 Check cristallization at low temperatures

153

BASF Portfolio Zinc Oxide

Trade Name

INCI

Product description

Z-COTE®

Zinc Oxide

Water and Oil dispersible (amphiphilic character)

Z-COTE® HP1

Zinc Oxide (and) Triethoxycaprylylsilane

Oil / Silicone phase dispersible

154

BASF Personal Care

Z-COTE® HP1 Description Chemical name

Hydrophobic Zinc Oxide

INCI-name

Zinc Oxide (and) Triethoxycaprylylsilane

CAS-numbers

1314-13-2, 63148-62-9

Structural formula

ZnO

Molar mass

81.37 g/mol (for ZnO)

Appearance

white powder

Odor

none

Purity

99%

Particles size

mean is 140nm (laser scattering particles size distribution analyser)

20% < 100nm

155

BASF Personal Care

Z-COTE® HP1 Approval Situation



EU:

 Positive SCCS opinion on ZnO (nano form)  SCCS (Scientific Committee on Consumer Safety), Opinion on ZnO (nano form), 18 September 2012



USA:

 ZnO is approved in the Cat.I of the FDA Final Monograph for Sunscreen Drug product for  



OTC Human Use. Upper limit = 25% Not allowed in combination with BMDBM

Japan

 Not considered as UV absorbers  Use without limitation (except eyeliner, lip, oral & bath preparation) 156

BASF Personal Care

Z-COTE® HP1 Formulation Tips

Choose appropriate dispersant aids: Uvinul® MC80 / Uvinul ® N539T Cetiol ® B / Cetiol ® AB

Disperse the ZnO under homogenizer (high energy needed)

Disperse each powder separatly

157

BASF Personal Care

Add 0.05% PBSA to avoid pH shift

If pH adjustement is necessary use Citric Acid only when emulsion is finish

Anionic surfactant (low levels 0.2% Lanette® E) helps to stabilise emulsion

Z-COTE® HP1 Formulation Tips

Disperse ZnO in appropriate hot

Homogenizer ZnO

75°C - 80°C

158

BASF Personal Care

(75-80°C) oil phase under high speed homogenizer

Add rest of hot oil phase Prepare formulation Adjust pH with Citric Acid

Uvinul® T 150 Profile INCI-Name:

Ethylhexyl Triazone (EHT)


Ethylhexyl Triazone

UV Spectrum

Appearance:

White powder

CAS Number:

88122-99-0

Melting point:

128-132°C

Type:

Oil Soluble

Molecular mass:

823 g/mol

Approved use conc.:

5% EU, JP, Asia US pending

Uvinul T150

159

Uvinul® T 150 Benefits Uvinul® T 150, the most powerful and photo stable UVB filter  Highest efficient UVB filter in the market  Excellent compatibility with all UV filters  Excellent photo stability  Odor free (PC12/118) and colorless  Combine with broad-spectrum filters and/or UVA filters in order to achieve better performance also in respect of SPF

160

Uvinul® T 150 Solubility in Selected Cosmetic Oils Uvinul® T 150 Solubility in Selected Cosmetic Oils (%) 25°C

*Beware of patent restrictions

18

16 14

Solubility %

12 10

8 6

4 2 0

*

*

*

Cosmetic Oils

164

Uvinul® T 150 Formulation Tips

 Choose emollients with best solubility for Uvinul® T 150 like Ethylhexyl Methoxycinnamate (Uvinul® MC 80), Dibutyl Adipate (Cetiol® B)

 Dissolve Uvinul® T 150 completely in the oil phase (at elevated temperature)

 Check potential crystallization (microscopy) at low storage temperatures

 The formulation itself (emulsifiers, stabilizers and thickeners) has a positive impact (less re-crystallization of Uvinul ® T 150)

169

Uvinul® MC 80 Profile INCI-Name:

Ethylhexyl Methoxycinnamate (EHMC)


Octinoxate

Appearance:

Colourless liquid UV Spectrum

CAS Number:

5466 – 77 - 3

Type:

Oil soluble

Molecular mass:

290 g/mol

Approved use conc.:

10.0% EU, JP 7.5% KR, US 20.0% JP

Uvinul MC 80

170

Uvinul® MC 80 Formulation Tips  Avoid combination with BMDBM due to photo degradation O

O

O O

EHMC O

h·

+

O O

O

OH OH

O

O

Increased photoinstability because of 2+2-heterophotocycloaddition of BMDBM and EHMC

BMDBM

 Stabilize Uvinul® MC 80 by the use of stabilizers like Tinosorb® S  Use Uvinul® MC 80 as excellent solubilizer for oil soluble UV filters

172

Uvinul® MC 80 Impact of photostability in formulations Filter composition (%) 10% Uvinul® MC80 (EHMC) 5% BMDBM

7% Uvinul® MC80 (EHMC) 3% Uvinul® A Plus (DHHB) 1% Tinosorb® S (BEMT)

7% Uvinul® MC80 (EHMC) 4% Tinosorb® M (MBBT)

Lack of photostability result in changed performance during use and high filter concentration needed 07.03.2012

173

Uvinul® N 539 T Profile INCI-Name:

Octocrylene


Octocrylene

Appearance:

Clear yellow viscous liquid

CAS Number:

6197 – 30 - 4

Type:

Oil soluble

Molecular mass:

361 g/mol

Approved use conc.:

10% EU, US, JP, Asia

UV Spectrum Uvinul 539 T

174

Uvinul® N 539 T Benefit Uvinul® N 539 T – wide UVB absorbance band and efficient photo stabilization

 High photo stability

 Efficient stabilizer for photo instable filters

 Contribution to UVAII absorbance of the final product

175

Uvinul® N 539 T Formulation Tips  Easy to use  Due to the low spreading behaviour high spreading emollients are recommended for a better sensory

176

Best Emollients for Sun Care Overview Remarks

Hair

Color

Body

Face

Applications

Deodorant

Wax

High

Medium

Refractive Viscosity index ** mPas at 20 oC at 20 oC

Antiperspirant

Spreading Polarity Value mm2/10 min

Spreading

Sun

INCI Name

Slow

Tradename

Propylheptyl Caprylate

·

1900

medium

1.444

5

· ·* · · · · ·

The Happy Emollient Multidimensional Softness

Dicaprylyl Carbonate

·

1600

medium

1.436

7

·

· · · · ·

The Benchmark for dry emollients

Cetiol® RLF

Caprylyl–Caprylate/Caprate

·

1400

medium

1.436

5

·

· · · · ·

The emollient for sensitive skin

Cetiol® C 5

Coco-Caprylate

·

1300

medium

1.437

5

· ·* · · · · ·

High spreading emollient The silicon alternative

Cetiol® B

Dibutyl Adipate

·

1000

high

1.435

6

·

· · ·

·

Very good solubility properties for crystalline UV filter

· · ·

·

Commonly used emollient in Sun care

Cetiol® Sensoft

Cetiol® CC

Cetiol® AB

Myritol® 331

C12-15 Alkylbenzoate

·

700

high

1.485

30

·

Cocoglycerides

·

750

high

1.455

45

·

* Anhydrous formulations only 177

BASF Personal Care

· · ·

Medium spreading emollient with good solubility properties for crystalline UV filter

Best Emulsifiers for Sun Care Overview Sprayable Emulsion

++

+

++

+

++

++

++

Flexible emulsifier for different applications and ingredients

Eumulgin® SG

++

++

+

++

+

++

++

++

Strong emulsifier especially for high amount of electrolytes

Eumulgin® VL 75

++

+

++

++

+

++

++

Liquid emulsifier for sprayable applications

Emulgade® PL 68/50

++

++

++

++

+

Mild emulsifier with good sensoric

++

++

++

Flexible W/O emulsifier

++

++

+

W/O emulsifier for liquid emulsions

++

Dehymuls® LE

++

++

184

BASF Personal Care

++

Remarks

Sun Care

W/O ++

+

Body Care

Fluid Emulsion

++

Dehymuls® PGPH

Application Face Care

Gel Cream

Texture Creamy Emulsion

Eumulgin® Prisma

P.I.T.

Technology O/W

Emulsifier

Skin Care Leave-On Polymers Guide Contains EO/PO

Ethanol Compatibility

Salt Tolerance

Sensory Profile

Thickening

Emulsion Stabilization

Body Care

Face Care

Sun Care

>88

P

Anionic

0.2 – 1

6 – 12

No

++

+

++

++

++







Cosmedia® Triple C

Polyquaternium-37 (and) Dicaprylyl Carbonate (and) Lauryl Glucoside

~50

L

Cationic

0.5 – 3

3 – 11

No

+++

+

+++

+

++







Cosmedia® Ultragel 300

Polyquaternium-37

> 92

P

Cationic

0.5 – 1.5

3 – 11

No

+++

+

+++

++

+







Luvigel® EM

Caprylic/Capric Triglycerides (and) Sodium Acrylates Copolymer

~25

L

Anionic

0.5 – 3

6–9

Yes

+

o

+

++

++







Luvigel® STAR AT

Polyurethane-39

~20

L

Non-Ionic

0.5 – 5

2 – 12

Yes

++

+++

++

+

o







Tinovis®

Sodium Acrylates Copolymer (and) Hydrogenated Polydecene (and) PPG-1 Trideceth-6

~55

L

Anionic

0.5 – 1.5

5 – 12

Yes

++

+

+

++

++







Carbomer

>97

P

Anionic

0.1 – 1.0

4 – 12

No

+++

++

o

+++

++









>97

P

Anionic

0.1 – 1.0

3 – 10

No

++

+++

+

+

++









ADE

Rheocare® C Plus Rheocare® XG

Physical form:

191

Xanthan Gum

P = Powder L = Liquid

Performance:

o Low



+ Good ++ Very Good

AP/Deo

pH application range

Sodium Polyacrylate

INCI Name

Self Tanning

Recommended dosage as is in %

Cosmedia® SP

Trade Name

Clear Gels

Type

Application

Physical form

Performance

Active Polymer %

Product Information

Remarks

Improve cushion

High transparency





Associative thickener, Tolerant to H2O2





High transparency, improves peaking

+++ Excellent

Importance of Efficient UVA Protection

Factors Influencing Skin Aging  Intrinsic (genetic, life-age related) factors - they can‘t be influenced

 Extrinsic (environmental) factors can contribute to a much higher extent to the visible signs of aging than intrinsic factors – but they can be influenced !

UV LIGHT

NUTRITION

LIFESTYLE POLLUTION

208

UV light damages Erythema

Contribution to skin cancer

Skin aging

Skin pigmentation

Imunosuppression

20

Action spectrum of ROS formation in human 1,0

Arb. Units

0,8 0,6 0,4 0,2 0,0

290

315

340

365

WL (nm)

Gary Haliday, ESP Conference 2011 (ESP = European Society of Photobiology)

390

Correlation of UVA-PFsim and RSFexp

UVA-PF (sim)

20

n = 17

15

r = 0.932

10

slope = 0.51 5

0 0

10

20

30

40

RSF (exp)

Correlation of UVA-PF and RSF Confirmed 211

UVA Protection for Daily Sun Care Options



UVA protection

Minimal UVA Protection



Optimal UVA Protection «Spectral Homeostasis»

Same requirements for UVA protection as in SunCare  EC recommendation for UVA protection (Sept. 2006) Attenuation in intensity but without altering the quality of the natural spectrum of sunlight reaching the skin

Criterion

UVA-PF / SPF ≥ 1/3

Very well balanced absorbance homoeostasis 1,2

0,9 Extinction

Options

0,6

0,3

Before Irradiation (adjusted) After Irradiation (adjusted)

0,0 290

310

330

350

370

390

 / nm



Radical Protection (anti-ageing claims)

212

Small amounts of photostable UVA filters reduce free radical formation and long term UVA damage significantly

For Day Care without SPF claim

An in vivo study on Asian volunteers Testpanel:

22 Volunteers of Asian origin

(14 females and 8 males, between 28 and 42 years old, mother and father originating either from Thailand or the Philippines).

Irradiation regime:

3x / week, 12 weeks with <1 MED

On volunteers back; Irradiation by Solar Light Simulator (SSR) for 12 weeks, i.e. 3x / week, 12 weeks with <1MED (dose monthly adjusted; effective dose UV-A 320 - 400 nm 24 -26 J/cm2, UV-B 280 - 320 0,04 - 0,06 J/cm2) 30 min after cream application.

Control:

unprotected, irradiated skin area

Test Products We tested 3 day creams with increasing amounts of Tinosorb®M, i.e. of UV-A protection 2% EHMC 1% Tinosorb M (SPFcalc 5.3)

2% EHMC 2% Tinosorb M (SPFcalc 6)

2% EHMC 4% Tinosorb M (SPFcalc 7)

Tinosorb M is an organic particulate broad-spectrum filter and such ideal for combination with cosmetic actives used in day care cosmetics.

Further ingredients: Aqua (up to 100%) ; Caprylic/Capric Triglyceride (5%) ; C12-15Alkyl Benzoate (5%), Cetearyl Isononanoate (5%); Glyceryl Stearate (3%); Glycerin (3%); Potassium Cetyl Phosphate (2%); Cetyl Alcohol (1%); Cetyl Stearate (1%); Phenoxyethanol/ Parabenes (1%); Steareth-10 Allyl Ether/Acrylates Copolymer (0.5%). Ethylhexyl Methoxycinnamate (2%) ; Tinosorb®M (1 – 4%)

UV Transmission of the test products 2% EHMC 1% Tinosorb®M (SPFcalc 5.3)

2% EHMC 2% Tinosorb®M (SPFcalc 6)

2% EHMC 4% Tinosorb®M (SPFcalc 7)

100%

100%

100%

0%

0%

0%

60% of UVA I is absorbed



High absorption of UVA light is achieved with low concentrations of Tinosorb M

Test Results Start

1st month 2nd month 3rd month 100%

2% EHMC/ 1% Tinosorb® M SPFcalc. 5.3

60% UV-AI is absorbed

2% EHMC/ 2% TIinosorb® M SPFcalc. 6 2% EHMC/ 4% Tinosorb® M SPFcalc. 7

UV Transmission

0% 100%

70% UV-AI is absorbed 0% 100%

80% UV-AI is absorbed 0%

100%

irradiated (<1 MED) No protection 290

320 340

0% 400 nm

The better UV-A protection, the more effective the cream

Conclusion  90% of UV induced free radicals are generated by UVA light  Free radicals in viable skin are a main factor of accelerated skin aging  UVA light is a main trigger for melanin synthesis and skin tanning

 Efficient UVA protection provides an “anti aging” effect and is most efficient in tanning prevention which is the first step for efficient skin lightening.

5/10/2013

217

DISCLAIMER This document, or any answers or information provided herein by BASF, does not constitute a legally binding obligation of BASF. While the descriptions, designs, data and information contained herein are presented in good faith and believed to be accurate, they are provided for your guidance only. Because many factors may affect processing or application/use, we recommend that you make tests to determine the suitability of a product for your particular purpose prior to use. It does not relieve our customers of the obligation to perform a full inspection of the products upon delivery or any other obligation. The claims and supporting data provided in this publication have not been evaluated for compliance with any jurisdiction’s regulatory requirements and the results reported may not be generally true under other conditions or in other matrices. Users must evaluate what claims and information are appropriate and comply with a jurisdiction’s regulatory requirements. NO WARRANTIES OF ANY KIND, EITHER EXPRESS OR IMPLIED, INCLUDING WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE, ARE MADE REGARDING PRODUCTS DESCRIBED OR DESIGNS, DATA OR INFORMATION SET FORTH, OR THAT THE PRODUCTS, DESIGNS, DATA, OR INFORMATION MAY BE USED WITHOUT INFRINGING THE INTELLECTUAL PROPERTY RIGHTS OF OTHERS. IN NO CASE SHALL THE DESCRIPTIONS, INFORMATION, DATA, OR DESIGNS PROVIDED BE CONSIDERED A PART OF OUR TERM SAND CONDITIONS OF SALE.

218

BASF Personal Care

219

BASF Personal Care

Egypt Regulation UV Portfolio 130510

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