Filtri Solari: Tipologie chimico-fisiche, Funzionalità,

compatibilità ed incompatibilità

SICC Seminario Tecnico 26 e 27 febbraio 2015 Carmina Casas ([email protected]) The Sun

 The Sun is the star at the center of the Solar System.  Sunlight is by far the most important source of energy for life on Earth.  Directly and indirectly, all living things depend on the sun.  But how this energy reaches the planet? by nuclear fusion

(converts hydrogen into helium)

E = hc/(λ)

E = Energy (Jules)

h = Planck constant (~6.626 × 10-34J·s)

c = speed of light in vacuum (~3x108m/s)

λ = wavelength (m) The spectrum of solar light at the Earth's surface

cosmic gamma X-ray UV visible infrared micro radio radiation radiation radiation radiation light radiation waves waves

medium short wave long wave visible UV- vacuum wave UVC UVA light UVB

200 230 260 290 320 350 380 410 wave length in nm The spectrum of solar light at the Earth's surface

The spectrum of solar light at the Earth's surface is mostly spread across the visible and near-infrared ranges with a small part in the near- The spectrum of solar light at the Earth's surface

Radiation λ (nm) %

UV-B 290-320 0.1

UV-A 320-400 4.9

Visible 400-760 39

Infra-red 760-3000 56

The spectrum of solar light at the Earth's surface

UV-C UV-B UV-A(II) UV-A(I)

1

0.9 0.8 0.7 0.6

0.5 ENERGY SKIN 0.4 PENETRATION 0.3

0.2

0.1

0 200 220 240 260 280 300 320 340 360 380 400 Wavelength (nm) Ozone layer depletion

 Ozone can be destroyed by a number of free radical catalysts  Steady decline of about 4% per decade  The effects of the depletion: increases the surface UV radiation affecting the human health  A reduction by 10% the density of the ozone layer may produce in the world:

• 300 000 new skin cancers (carcinomas) • 4 500 new melanoma cancers • 2 millions new ocular cataracts Sun Effects

POSITIVE:  Stimulates physical and mental health  Production of the VITAMIN D3: essential for the absorption of calcium in the bones  Treatment of metabolic diseases  Atopic Dermatitis, Psoriasis

NEGATIVE:

 Solar erythema,  Photo-sensitivity: photo-immunosuppression (solar herpes), photo-toxicity, photo-allergenicity, photo-dermatitis (lupus)  Pigmentary diseases: spots, melasma (pregnancy) or vitiligo  Skin aging Accelerator : deep wrinkles and loss of density and skin elasticity  Photo-carcinogenesis (skin cancer) UV Radiations

Photoaging

Solar lentigines or age spots: irregular brown pigmented spots formed by UV exposure

Solar elastosis: breakage induced by chronic UV exposure, the breakdown of collagen, elastin accumulation structure and loss of deep wrinkles cause dermal network Photoaging

Photoaging

L’Oréal publication

New England Journal of Medicine

Do you know your ABCDEs?

A: ASYMMETRY

B: BORDER

C: COLOR

D: DIAMETER

E: EVOLVING

•http://www.skincancer.org/es-ES/Los-ABCDEs-del-Melanoma Main Factors influencing the sunburn

LATITUDE HEIGHT

SEASONALITY

1. Intensity of the light DAY TIME

EXPOSITION TIME

TRANSMISSION REFLEXION

2. Skin Phototypes Fitzpatrick (1975)

Skin Classification Behavior Hair & eyes Type

Always burns, never Tends to have freckles, red or I very light, also "Nordic" tans blond hair, blue or green eyes.

Usually burns, Tends to have light hair, II light, or light-skinned European sometimes tans blue/green or brown eyes.

light intermediate, or dark- May burn, usually Tends to have brown hair and III skinned European or "average tans eyes. Caucasian"

dark intermediate, also Sometimes burns, Tends to have dark brown eyes IV "Mediterranean" or "Olive" often tans. and hair.

Moderate Often has dark brown eyes and V dark or "Brown" type constitutional hair. pigmentation Brown Marked constitutional VI very dark or "Black" type Black-brown eyes and hair. pigmentation Black Skin Phototypes and the reaction to the sun

MED/UV-B, minutes PHOTOTYPE MED/UV-B, mJ/cm2 (*)

I 15-30 8

II 25-35 18

III 30-50 28

IV 45-60 42

V 60-100 60

VI 100-200

(*) at 40ºN, summer time (M.A. PATHAK - 1983) MED= MINIMAL ERYTHEMA DOSE The Sun Protection Factor (SPF) - UVB

SPF = Sun Protection Factor (only against UVB)

(MED = Minimal Erythema Dose) UV Filter Classification

‣ Organic chemical compounds that absorb UV light

‣ Organic particles that mostly absorb UV light

but also may reflect and scatter a fraction of light

‣ Inorganic particles that reflect, scatter and absorb UV light Organic UV Filters

Classification: 1. PABA and p-aminobenzoates 2. Salicylates 3. Cinnamates 4.

5. Antranylates 6. Dybenzoylmethanes 7. Camphor Derivatives 8. Organic particulates 9. Others Organic UV Filters

1. PABA derivatives and p-aminobenzoates UVB

OR

C = O

H N

H

2-ethylhexyl dimethyl PABA () Organic UV Filters

2. Salicylates Benzyl salicylate UVB Ethylhexyl salicylate Homomenthyl salicylate OR’ Trietanolamine salicylate

Potassium salicylate C

O Amyl salicylate

p-isopropylphenyl salicylate

4-isopropylbenzyl salicylate

H

O R Organic UV Filters

3. Cinnamates

UVB

C = O CH3 Ö CH = CH -

OR

17 cinnamates, the most common ones:

Ethylhexyl-p-methoxycinnamate (λmax: 310 nm) Isoamyl-p-methoxycinnamate Dietanolamine-p-methoxycinnamate

Ethylhexyl-p-methoxycinnamate

Organic UV Filters

4. Benzophenones (8) UVB-UVA (3) (4) H Mexenone (10)

O

O =

C

RÖ Organic UV Filters

5. Antranilates (orto amino benzoates) UVA (λ max 336 nm)

H

N H

O

C

O C10H19

Menthyl Antranilate Organic UV Filters

6. Dibenzoylmethanes UVA

H

O O

O

= =

C

C

R1 R2

Butyl Methoxydibenzoylmethane () λmax : 357nm Butyl Methoxydibenzoylmethane

Enol Keto

max 357nm max 260nm ENERGY RELEASE PATHWAYS

Kochevar,I.E., Basic Principles of Photomedicine and Photochemistry Butyl Methoxydibenzoylmethane : photoestabilization

1. 2. Polysilicone-15 (Parsol®SLX) 3. Methylbenzylidene camphor 4. (Tinosorb® S) 5. (Tinosorb® M) 6. Butyloctyl Salicylate (HallBrite® BHB) 7. Hexadecyl Benzoate

8. Butyloctyl Benzoate 9. Undecylcrylene dimethicone (HallBrite® PSF) 10. (Mexoryl® SX) 11.Diethylhexyl Naphthalate (Corapan® TQ) 12.Diethylhexyl Syringylidene Malonate (Oxynex® ST) 13.Etc. Butyl Methoxydibenzoylmethane: other warnings

1. Solubility is key: octocrylene, ethylhexyl and homomenthyl salicylates, … to avoid crystal formation

2. Incompatible with metal ions: recommended the use EDTA

3. Avoid formaldehyde and donors: have a look at the preservative systems

3+ 4. Incompatible with TiO2 Al coated

Organic UV Filters

7. Camphor Derivatives UVB

4-Methylbenzylidene camphor (Enzacamena) λmax : 302nm

Other UV Filters

Phenylbenzimidazole Sulfonic Acid (PBSA)

UVB-WS λmax : 304nm

Polysilicone –15 (Parsol® SLX)

UVB

• Dry touch silicone backbone • Liquid – no crystallization possible in formulation • Ideal for light and silky texture • Improves distribution and thus boosts SPF • Acts with water soluble PBSA in a synergistic way for highest UVB protection ® PARSOL SLX, proven synergy with PBSA to boost the SPF

In vivo SPFs measured twice according to international SPF method (COLIPA)

36 or Diethyl Hexyl ButamidoTriazone (Uvasorb® HEB, DHBT)

UVB

N H

O

N H

N N

H

N

N

N

H

O

O

O O Ethyl Hexyl Triazone (Uvinul® T150, EHT)

UVB (λmax: 314 nm)

O

O

N H

N N

H

N N N

H

O O

O O

Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul® A Plus, DHHB)

UVA

O O

O H O

N

Uvinul® A Plus B: Ethylhexyl methoxycinnamate & Diethylamino Hydroxybenzoyl Hexyl Benzoate Disodium Phenyl Dibenzimidazole Tetrasulfonate (Neo Heliopan® AP, DPDT)

UVA-WS

H O S S O H

N N

3 3

N N

H H

S O N a S O N a 3 3 Terephthalilydene Dicamphor sulfonic acid (Mexoryl® SX)

UVA-WS λmax: 338 nm

O

N a O S

3

S O N a 3

O

(Mexoryl® XL)

Benzotriazole derivative

UVB-UVA, λmax: 303 nm and 344 nm

Organic particules

Bemotrizinol o Bis-Ethylhexyloxyphenol

Methoxyphenyl Triazine (Tinosorb® S, BEMT)

UVA/UVB (λmax: 310 and 340 nm)

O C H

3

O H N N O H

N

O O

Tinosornb ® S Aqua: Benzotrizinol in Polymethylmetacrylat, dispersed in water Bisoctrizole o Methylene Bis-Benzotriazolyl

Tetramethylbutylphenol (Tinosorb® M, MBBT)

UVA/UVB-WS (λ max: 360 nm)

Absorption curves UVA range

1200 BEMT MBBT DHHB 1000 DPDT Avobenzone -3 800

600 E1/1

400

200

0 280 290 300 310 320 330 340 350 360 370 380 390 400 nm

BEMT: Tinosorb S MBBT: Tinosorb M DHHB: Uvinul A+ DPDT: Neoheliopan AP Only 8 Organic UV filters approved worldwide

INCI EU USA Japan Benzophenone-3 10% 6% 5%* Benzophenone-4 5% 10% 10%**

Ethyl-Hexyl Methoxycinnamate 10% 7,5% 10%*** Phenylbenzimidazole sulfonic acid 4% 4% 3%§

Homosalate 10% 15% 10% 5% 5% 10%§§ Octocrylene 10% 10% 10% Avobenzone 5% 3% 10%§§§

*5% in C&T, 0.02% eye lines;** 1% en C&T, 0.1% eye lines :*** 5% en C&T, 1% eye lines; § 7% en C&T,1% eye lines, §§ 1% en C&T, 0% eye lines §§§ 2% in C&T, 0.1% eye lines Inorganic UV Filters

1. 2.

Coating 1

Rutile

Coating 2 TiO2 Formulation Compatibility with ascorbyl palmitate

•Comp 1 •Comp 2 •Comp 3 •control •Copm0 •Comp 4 •Comp 5 •Comp 6

• • • • • • • •

Test protocol

. 10% TiO2 and 10% ascoryl palmitate are added in diisobutyl sebacate . Optical evaluation (after 60 min) High SPF contribution: Performance impact by crystal size

•UVB •UVA

“Nano” - Cosmetic Regulation - Europe

• Definition – Art. 2.1 (k) Regulation 1223/2009/EC ‘Nanomaterial’ means an insoluble or biopersistant and intentionally manufactured material with one or more external dimensions, or an internal structure, on the scale from 1 to 100 nm

• Labeling obligation (Art. 19.1(g)(ii)) for cosmetics containing ingredients in nano- form: i.e. in the list of ingredients, the names of such substances shall be followed by the word 'nano' in brackets. – Ex. Titanium dioxide (nano) – Applicable from 11 July 2013 on TiO2- SCCS compliant. Specifications to be fulfilled

Purity The rutile structure (>99.5% rutile TiO2 )

Crystalline structure & physical appearance as in submission (aspect ratio from ideal 1.2 up to 4.5)

Median particle size (30 to 100nm)

Volume specific surface area up to 460 m2/cm3

Coating materials stable in the final formulation and during use

Photostable in the final formulation

Photocatalytic activity (max 10%) compared to •Rutile is more compact and has a non-coated reference higher light and thermal stability

TiO2- Aluminium free

• Aluminium in cosmetic products is considered not to be safe! • Al classified as carcinogenic to humans by International Agency for Research on Cancer (IARC) • TiO2 has to be guaranteed Aluminium-free and thus very safe for cosmetic use

High SPF contribution: TiO2 with organic UV filters

+ 3 % TiO2 Formulation •Base Formulation 43% SPF boost Example 3

+ 3% TiO2 Formulation •Base Formulation 25% SPF boost Example 2

Formulation + 3% TiO2 30% SPF boost Example 1 •Base Formulation

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70

SPF Performance

Test protocol . 3% TiO2was incorporated into different emulsion systems containing different organic UV filters. In-vivo SPF was tested versus Placebo emulsion (without TiO2)

Thank you for your attention  ANY QUESTION??

Referencias: Europe – Cosmetic Legislation

EU Cosmetic Directive 76/768/EEC http://eurlex.europa.eu/LexUriServ/LexUriServ.do?uri=CONSLEG:1976 L0768:20110603:EN:PDF

EU Cosmetic Regulation No 1223/2009 (apply from July 11, 2013) http://eurlex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2009:342: 0059:0209:en:PDF

UV filters annexes & opinions (in EU Cosmetic legislation or Cosing database) • http://ec.europa.eu/consumers/cosmetics/cosing/

Referencias: Europe – Efficacy

EFFICACY • Industry Guidelines for Evaluation Water Resistance, 2005: http://www.cosmeticseurope.eu/publicationscosmetics-europe- ssociation/guidelines.html?view=item&id=18

• ISO In vivo determination of the SPF (ISO 24444:2010): http://www.iso.org/iso/iso_catalogue/catalogue_tc/catalogue_detail.htm?csnumber=465 23

• Determination of in vitro UVA protection, Colipa: http://www.cosmeticseurope.eu/publications-cosmetics- europeassociation/guidelines.html?view=item&id=33

• ISO In vivo determination of sunscreen UVA protection (ISO 24442:2011): http://www.iso.org/iso/search.htm?qt=24442%3A2011&sort=rel&type=simple&publishe d=on

• 2012, ISO 24443 Determination of in vitro UVA protection (under preparation, target : 04/2012): http://www.iso.org/iso/search.htm?qt=24443&sort=rel&type=simple&published=on

Referencias: Europe –Claims

CLAIMS • EU Commission recommandations (OJ L265, 26/9/06): http://eur- lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2006:265:0039:0043:EN:PDF

• Pictogram's to inform consumers on dangers linked to sun exposure have been created by the EU Commission: http://ec.europa.eu/health-eu/news/sun_uv_en.htm

• EU Commission Consumer information: http://ec.europa.eu/consumers/citizen/my_holidays/sunscreens_en.print.htm

Referencias: Europe

Nano • SCENIHR http://ec.europa.eu/health/scientific_committees/emerging/docs/scenihr_o_032.pdf

•REACH http://www.reach- alphelpdesk.de/de/Downloads/Kurzinfo/Kurzinfo%20Characterisierung%20Nanomaterialien %20engl.%20Fassung.pdf?__blob=publicationFile&v=2

• DG Environment http://ec.europa.eu/environment/chemicals/nanotech/

• France Decree no 2012-232 of 17.02.2012 & Order of 06.08.2012 http://www.legifrance.gouv.fr/jopdf/common/jo_pdf.jsp?numJO=0&dateJO=20120219&nu mTexte=4&pageDebut=02863&pageFin=02865

Alternatives to animal testing http://ihcp.jrc.ec.europa.eu/our_activities/alt- animaltesting/alt_test_cosmetics/ICATM%20Table%20of%20Assays%2021%20June%202012

Bare skin feel SPF 50+. Featuring VALVANCE™ Touch 210 and PARSOL® SLX for "full gliss - non stick" feel

Ingredients INCI Name % w / w

PARSOL® 1789 BUTYL METHOXYDIBENZOYLMETHANE 5.00 PARSOL® 340 OCTOCRYLENE 10.00 PARSOL® SLX POLYSILICONE-15 2.00 PARSOL® EHS ETHYLHEXYL SALICYLATE 5.00 Dermofeel® BGC BUTYLENE GLYCOL DICAPRYLATE/DICAPRATE 4.50 Finsolv TN C12-15 ALKYL BENZOATE 2.00 Dub dis DIISOPROPYL SEBACATE 3.00 Lanette O CETEARYL ALCOHOL 2.50 Lanette 22 BEHENYL ALCOHOL 1.50 AMPHISOL® K POTASSIUM CETYL PHOSPHATE 3.00

PARSOL® TX TITANIUM DIOXIDE, SILICA, DIMETHICONE 2.00

Carbopol Ultrez 21 ACRYLATES/C10-30 ALKYL ACRYLATE 0.10 CROSSPOLYMER Keltrol CG-T XANTHAN GUM 0.20

1,3-Butylenglycol BUTYLENE GLYCOL 2.00 WATER DEM. AQUA 49.85 Edeta BD DISODIUM EDTA 0.10 PARSOL® HS PHENYLBENZIMIDAZOLE SULFONIC ACID 2.00 Tris Amino Ultra PC TROMETHAMINE 1.25

VALVANCE™ Touch SILICA 3.00 210

Preservative q.s.

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