Filtri Solari: Tipologie chimico-fisiche, Funzionalità, compatibilità ed incompatibilità

SICC Seminario Tecnico

26 e 27 febbraio 2015

Carmina Casas

(carmina.casas@dsm.com)

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)

200 230 260 290 320 350 380 410

UV- vacuum short wave

UVC

medium wave UVB

long wave UVA

visible light

radio waves

cosmic radiation

gamma radiation

X-ray radiation

visible light

infrared radiation

micro waves

UV radiation

wave length in nm

The spectrum of solar light at the Earth's surface

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-ultraviolet

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

200 220 240 260 280 300 320 340 360 380 400

Wavelength (nm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

ENERGY SKIN

PENETRATION

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

The spectrum of solar light at the Earth's surface

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

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, sunburn

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)

Sun Effects

UV Radiations

Photoaging

Solar elastosis:

breakage induced by

chronic UV exposure,

the breakdown of

collagen, elastin

accumulation

structure and loss of

deep wrinkles cause dermal network

Solar lentigines or age

spots: irregular brown

pigmented spots

formed by UV exposure

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

DAY TIME

EXPOSITION TIME

TRANSMISSION

REFLEXION

1. Intensity of the light

2. Skin Phototypes

Skin

Type Classification Behavior Hair & eyes

I very light, also "Nordic" Always burns, never

tans

Tends to have freckles, red or

blond hair, blue or green eyes.

II light, or light-skinned European Usually burns,

sometimes tans

Tends to have light hair,

blue/green or brown eyes.

III

light intermediate, or dark-

skinned European or "average

Caucasian"

May burn, usually

tans

Tends to have brown hair and

eyes.

IV dark intermediate, also

"Mediterranean" or "Olive"

Sometimes burns,

often tans.

Tends to have dark brown eyes

and hair.

V dark or "Brown" type

Moderate

constitutional

pigmentation Brown

Often has dark brown eyes and

hair.

VI very dark or "Black" type Marked constitutional

pigmentation Black Black-brown eyes and hair.

Fitzpatrick (1975)

Skin Phototypes and the reaction to the sun

(M.A. PATHAK - 1983) MED= MINIMAL ERYTHEMA DOSE

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

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

SPF = Sun Protection Factor (only against UVB)

The Sun Protection Factor (SPF) - 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. Benzophenones

5. Antranylates

6. Dybenzoylmethanes

7. Camphor Derivatives

8. Organic particulates

9. Others

1. PABA derivatives and p-aminobenzoates

UVB

C = O

N

OR

H

H

Organic UV Filters

2-ethylhexyl dimethyl PABA (Padimate O)

2. Salicylates

UVB

R

O

H

C

OR’

O

Benzyl salicylate

Ethylhexyl salicylate

Homomenthyl salicylate

Trietanolamine salicylate

Potassium salicylate

Amyl salicylate

p-isopropylphenyl salicylate

4-isopropylbenzyl salicylate

Organic UV Filters

3. Cinnamates

UVB

17 cinnamates, the most common ones: Ethylhexyl-p-methoxycinnamate (λmax: 310 nm) Isoamyl-p-methoxycinnamate Dietanolamine-p-methoxycinnamate

OR

C = O Ö CH = CH -

CH3 Ö CH3 Ö CH3 Ö CH3

Organic UV Filters

Ethylhexyl-p-methoxycinnamate

4. Benzophenones

UVB-UVA

C

=

O

O

H

RÖ

Dioxybenzone (8)

Oxybenzone (3)

Sulisobenzone (4)

Mexenone (10)

Organic UV Filters

5. Antranilates (orto amino benzoates)

UVA (λ max 336 nm)

N N

C

H

O

O

H

C10H19

Menthyl Antranilate

Organic UV Filters

6. Dibenzoylmethanes

UVA

C

=

O O

H

R1

C

=

O

R2

Organic UV Filters

Butyl Methoxydibenzoylmethane (Avobenzone) 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. Octocrylene 2. Polysilicone-15 (Parsol®SLX) 3. Methylbenzylidene camphor 4. Bemotrizinol (Tinosorb® S) 5. Bisoctrizole (Tinosorb® M) 6. Butyloctyl Salicylate (HallBrite® BHB) 7. Hexadecyl Benzoate 8. Butyloctyl Benzoate 9. Undecylcrylene dimethicone (HallBrite® PSF) 10.Ecamsule (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

4. Incompatible with TiO2 Al3+ coated

7. Camphor Derivatives

UVB

Organic UV Filters

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 sunscreens

• Improves sunscreen 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

36

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

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

N

H

O

O

N

H

O

O

N H

O

N

N

N

N H

UVB

Ethyl Hexyl Triazone (Uvinul® T150, EHT)

UVB (λmax: 314 nm)

N

N

N

N H

N H

N H

O

O

O

O

O

O

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

UVA

O O

O

O H

N

Uvinul® A Plus B: Ethylhexyl methoxycinnamate & Diethylamino Hydroxybenzoyl Hexyl Benzoate

Disodium Phenyl Dibenzimidazole Tetrasulfonate (Neo Heliopan® AP, DPDT)

UVA-WS

N

H

N

N

H

N

S O

3

H

S O

3

N a

S O

3

N a

H O

3

S

Terephthalilydene Dicamphor sulfonic acid (Mexoryl® SX)

UVA-WS λmax: 338 nm

O

O

S O 3

N a N a O

3 S

Drometrizole Trisiloxane (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)

N

N

N

O H

O H

O O

O C H 3

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

0

200

400

600

800

1000

1200

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

nm

E1

/1

BEMT

MBBT

DHHB

DPDT

Avobenzone

Benzophenone-3

BEMT: Tinosorb S MBBT: Tinosorb M DHHB: Uvinul A+ DPDT: Neoheliopan AP

*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

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%

Octyl Salicylate 5% 5% 10%§§

Octocrylene 10% 10% 10%

Avobenzone 5% 3% 10%§§§

Inorganic UV Filters

1. Titanium dioxide

2. Zinc Oxide

Rutile

Coating 1

Coating 2

TiO2 Formulation Compatibility

with ascorbyl palmitate

Test protocol

10% TiO2 and 10% ascoryl palmitate are added in diisobutyl sebacate

Optical evaluation (after 60 min)

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

• • • • • • • •

•UVB •UVA

High SPF contribution: Performance impact by crystal size

“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 non-coated reference

•Rutile is more compact and has a higher light and thermal stability

• 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

TiO2- Aluminium free

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

Formulation

Example 1

Formulation

Example 2

Formulation

Example 3

SPF Performance

+ 3 % TiO2 •Base Formulation

•Base Formulation

•Base Formulation

Test protocol

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

25% SPF boost

43% SPF boost

30% SPF boost

High SPF contribution: TiO2 with organic UV filters

+ 3% TiO2

+ 3% TiO2

ANY QUESTION??

Thank you for your attention

Referencias: Europe – Cosmetic Legislation

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

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=46523 • 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&published=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 – Efficacy

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 –Claims

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&numTexte=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

Referencias: Europe

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

CROSSPOLYMER

0.10

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

210

SILICA 3.00

Preservative q.s.

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

61