Stability Study of Avobenzone with Inorganic Sunscreens

Uyen Ngu yen and David Schlossman Kobo Products, Inc. - 690 Montrose Av enue - South Plainfield, NJ 07080
I ntroduction T itan iu m diox ide an d z in c oxide are pr efer able UV A / U V B s un screen s becaus e of th eir efficien cy a n d low ir r itat ion . In or der to i n cr eas e th e p r otection in th e UV A r an g e, in m a n y coun t r ies, Av oben z on e h as been u sed in com bin ation with titan ium dioxide an d / or zin c oxide. How ev er , in t h e U S A c om b in a t i o n s o f Av o b en z o n e a n d p h y s i ca l s u n s cr e en s a r e n ot p e r m i t te d. Av oben z on e h as been r epor ted to be un s table w h en con tain ed in for m ulation s w ith p h y s ical s un s cr een s. S urf ace coatin g of th e p igm en t h as s om etim es been sh ow n to in cr ease its s tability Objective In th is study com bin ation s of Av oben zon e an d in or gan ic pigm en ts w er e ir r adiated in order to determ in e th e in fluen ce of th e pigm en ts an d th eir s urface tr eatm en ts on stability of Av oben z on e. Sam ple P repara tion 0. 04% A v oben z on e w as d is pe r se d w it h 4. 0% i n or g an ic p ig m en t in E t h an ol. Each s am ple w as ir radiated ( Spectr olin e UV lam ps - XX-15NB) for on e w eek, th en cen tr ifug ed to s ep ar ate th e solution from th e in or gan ic pigm en t. All s am ples w er e dil uted to 0. 001% w / w Av ob en z on e base d on its in it ially added am ou n t. Tr an s m ittan ce an d abs or ban ce w ere m eas ur ed us in g UV / V is spectroph otom eter ( U-3010 from Hitach i) . Avobenzone
O O C4H9 OCH3

R eferences D e v e l o p m e n t o f T h i n - l a y e r S i l i ca - co a t e d Z i n c O x i d e a n d S u p e r i o r N. Ish ii, K. W ada, M. Takam a, K. Ogawa, K. J oich i an d K. Oh n o Proceed ing XXI IFSCC Internation al Cong ress 2000, Berl in, p. 519 P h otocataly tic Activ ity of T itan ium Dioxide an d Zin c Oxide; M. Kobay ash i an d W . Kalriess Co sm etics & Toiletries, v ol. 112, n o 6, p. 83

S u n s c r e en s ;

1. Influ ence of U ntreated P hysical Sunscreens on the Stability of A vobenzone

Reference Avobenzone
100

Avobenzone and Untreated Pigments

Pigment Type None Rutile TiO2 Rutile TiO2 Anatase TiO2 Anatase TiO2 Zinc Oxide

Avobenzone remaining Primary particle after irradiation size (PPS) in nm 100 % < 1% < 1% < 1% < 1% < 1% 200 200 300 300 35

Z1
80

A1

R1

R1 R2 A1 AVO

60

A2 Z1

40

20

0 250 300 350 400 450 500 Wavelength (nm)

N o s ig n i f ica n t ch a n g e w as ob s e r v ed i n t h e tr an sm ittan ce of Av oben zon e after irr adiation . U n t r e at e d t it a n iu m dio x ide a n d z in c ox i de deg raded Av oben zon e.

Poster A vobenzo ne - SSC N Y2001

2. Influence of Treated Titanium Dioxides on the Stability of Avobenzone

Avobenzone With Treated Anatase Titanium Dioxide Reference A1-SL
100

Pigment Type Anatase TiO2 Anatase TiO2 Anatase TiO2 Anatase TiO2 Anatase TiO2

Treatment Type Silane Methicone Silane Methicone Dimethicone

Avobenzone remaining after irradiation 19% < 1% < 1% < 1% < 1%

A1-MS A2-DS

A1-MS A2-SL A2-MS A2-DS AVO

80

60

A1-SL

40

Avobenzone With Treated Rutile Titanium Dioxide

20 100 0 250 300 350 400 450 500 Wavelength (nm) 80

R1-SL R1-DS

60

Reference R1-SL R2-SL R1-MS R1-DS

Pigment Type Rutile TiO2 Rutile TiO2 Rutile TiO2 Rutile TiO2

Treatment Type Silane Silane Methicone Dimethicone

Avobenzone remaining after irradiation < 1% < 1% 38% < 1%

40

R1-MS AVO

20

0 250 300 350 400 450 500 Wavelength (nm)

Com parisons of anatase and rutile pigm ents after treatm en t with m eth icone, dim ethicone, and octyltriethoxy silane were m ade. Silane treatm ent: an atase A1-SL gav e a better stability . Methicon e treatm en t: rutile R1-MS gav e a better stability. An atase A2 h ad poor stability with all treatm ents.
Avobenzone With Other treatments on Titanium Dioxide
100

Reference R3-SC R4-PF

Pigment Type Rutile TiO2 Rutile TiO2 Rutile TiO2

Treatment Type Silica C9-15 FluoroAlcoholphosphate Stearic Acid and Aluminum Hydroxide

Avobenzone remaining after irradiation 76% 28% 3%

P.P.S. (nm) 90 300 15

R5-SA

80

R4-PF
60

R5-SA

40

R3-SC AVO
250 300 350 400 450 500

20

Other treatm en ts were also ev aluated. Th e silica treated titan ium dioxide ( R3-SC ) g av e th e best s tability .

0 Wav elengt h (nm)

3. Influence of Treated Zinc Oxides and Iron Oxides on the Stability of Avobenzone
Avobenzone With Zinc Oxide
100

Reference Z2-SC Z1-SC

Pigment Type Silica Silica Methicone Silane

Avobenzone remaining after irradiation 49 % 18 % < 1% 3%

Primary particle size (PPS) in nm 25 35 25 120

Z3-MS Z4-SL

80

Z3-MS Z4-SL

60

Z1-SC

40

Z2-SC
20

AVO

Treated zin c oxides were ev aluated. Av oben zon e is m ore stable with the presence of Silica treated Zn O.

0 250 300 350 400 450 500 Wavelength (nm)

Po ster A vo benz one - SSC N Y2001

Reference RED-SL YEL-SL BLK-SL

Treatment Type Silane Silane Silane

Avobenzone remaining after irradiation 97 % < 1% < 1%

80 100

Avobenzone with Iron Oxides

YEL-SL BLK-SL

Av oben zone m ay also be form ulated in m ake-up products. W e ev aluated sev eral grades of Iron Oxides, in order to determ in e if these pigm en ts would im pair th e activ ity of Av obenzone. Red iron oxide was found to hav e a negligible effect on th e stability of Av obenzon e, while yellow an d black iron oxides, on the con tr ary, lead to a com plete degradation of Av obenzone.

60

40

RED-SL

20

AVO
0 250 300 350 400 450 500 Wavelen gth ( nm)

Conclusion In the course of th is study, we h av e sh own th at Av oben zone, wh en com bined with uncoated ph ysical sunscreens, retains little activ ity following irradiation . W e also dem onstrated th at th e surface treatm en t of pigm ents could lim it this degradation, an d in th e best case of silica treated Titan ium diox ide R3-SC, 76 p er cen t of th e activ ity was retain ed. Additional m easurem ents are needed to better un derstand the UV properties of com bination s of Av obenzone and inorgan ic pigm ents. W ork is in progress in our laboratories to determ in e the influence of the following param eters : Pigm ent type and m orphology ; Extent and type of surface treatm en t; Particle size of th e pigm ent. The results will n eed to be correlated with approv ed m eth ods for testin g sun screens form ulations.

Acknowledgment The a uth ors want to th ank Dr. Yun Sh ao for h is tech nica l contribution and Dr. Pascal Delrieu for h is technical contribution and his art work on this poster. Referen ce Codes an d Trade Nam es of Pigm en ts used in th is study : Reference code A1 A1-SL A1-MS A2 A2-MS A2-DS R1 R1-SL R1-MS R1-DS R2 R2-SL Trade name CTFA328 BTD-11S2 BTD-MS2 TiO2 FF PHARMA TIO2 FFP-MS2 TIO2 FFP-DS4 Tronox CR-837 RBTD-11S2 RBTD-MS2 RBTD-DS4 CR-834 RBTD-834-11S2 Reference code R3-SC R4-PF R5-SA Z1 Z1-SC Z2-SC Z3-MS Z4-SL BLK-SL RED-SL YEL-SL Trade name MAX LIGHT TS-04 PF-5 TIO2 CR-50 TTO-51-C ZNO-350 ZNO-350 SIO2(5) MAX LIGHT ZS-032 ZNO XZ-MS4 A120-ZNO-11S3 BBO-11S2 BRO-11S2 BYO-11S2

Poster A vobenzon e - SSCN Y2001