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 S u n s c r e en s ;
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

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

Reference Pigment Avobenzone remaining Primary particle

Avobenzone and Untreated Pigments Type after irradiation size (PPS) in nm
Avobenzone None 100 % -
100 R1 Rutile TiO2 < 1% 200
Z1 R1
A1 R2 Rutile TiO2 < 1% 200
80

A1 Anatase TiO2 < 1% 300

60 AVO A2 Anatase TiO2 < 1% 300
40 Z1 Zinc Oxide < 1% 35

20
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
0 tr an sm ittan ce of Av oben zon e after irr adiation .
250 300 350 400
Wavelength (nm)
450 500
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
Reference Pigment Treatment Avobenzone remaining
Avobenzone With Treated Anatase Titanium Dioxide Type Type after irradiation
A1-SL Anatase TiO2 Silane 19%
100 A1-MS A1-MS Anatase TiO2 Methicone < 1%
A2-DS A2-SL Anatase TiO2 Silane < 1%
80
A2-MS Anatase TiO2 Methicone < 1%
A1-SL
60 A2-DS Anatase TiO2 Dimethicone < 1%

40 Avobenzone With Treated Rutile Titanium Dioxide

AVO
20

100 R1-SL
0
R1-DS
250 300 350 400 450 500
80
Wavelength (nm)

60

Reference Pigment Treatment Avobenzone remaining 40 R1-MS

Type Type after irradiation
AVO
R1-SL Rutile TiO2 Silane < 1% 20

R2-SL Rutile TiO2 Silane < 1%

0
R1-MS Rutile TiO2 Methicone 38% 250 300 350 400 450 500
Wavelength (nm)
R1-DS Rutile TiO2 Dimethicone < 1%

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
Avobenzone With Other treatments on Titanium Dioxide Pigment Treatment remaining P.P.S.
Reference Type Type after irradiation (nm)

100 R5-SA R3-SC Rutile TiO2 Silica 76% 90

C9-15 Fluoro-
R4-PF Rutile TiO2 Alcoholphosphate 28% 300
80

R4-PF R5-SA Rutile TiO2 Stearic Acid and 3% 15

60 Aluminum Hydroxide

40 R3-SC
Other treatm en ts were also ev aluated. Th e silica treated
20 AVO titan ium dioxide ( R3-SC ) g av e th e best s tability .
0
250 300 350 400 450 500
Wavelengt h (nm)

3. Influence of Treated Zinc Oxides and Iron Oxides on the Stability of Avobenzone
Reference Pigment Avobenzone remaining Primary particle
Avobenzone With Zinc Oxide Type after irradiation size (PPS) in nm
Z2-SC Silica 49 % 25
100
Z3-MS
Z1-SC Silica 18 % 35
Z4-SL
80 Z3-MS Methicone < 1% 25
Z4-SL Silane 3% 120
Z1-SC
60

40
Treated zin c oxides were ev aluated. Av oben zon e is
Z2-SC m ore stable with the presence of Silica treated Zn O.
20 AVO

0
250 300 350 400 450 500
Wavelength (nm)

Po ster A vo benz one - SSC N Y2001

 Reference Treatment Avobenzone remaining
Type after irradiation Avobenzone with Iron Oxides
RED-SL Silane 97 %
YEL-SL Silane < 1% 100
YEL-SL
BLK-SL Silane < 1% BLK-SL
80

60
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 40
RED-SL
determ in e if these pigm en ts would im pair th e activ ity of
20
Av obenzone. Red iron oxide was found to hav e a negligible AVO
effect on th e stability of Av obenzon e, while yellow an d 0

black iron oxides, on the con tr ary, lead to a com plete 250 300 350 400
Wavelen gth ( nm)
450 500

degradation of Av obenzone.

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 Trade name Reference code Trade name
A1 CTFA328 R3-SC MAX LIGHT TS-04
A1-SL BTD-11S2 R4-PF PF-5 TIO2 CR-50
A1-MS BTD-MS2 R5-SA TTO-51-C
A2 TiO2 FF PHARMA Z1 ZNO-350
A2-MS TIO2 FFP-MS2 Z1-SC ZNO-350 SIO2(5)
A2-DS TIO2 FFP-DS4 Z2-SC MAX LIGHT ZS-032
R1 Tronox CR-837 Z3-MS ZNO XZ-MS4
R1-SL RBTD-11S2 Z4-SL A120-ZNO-11S3
R1-MS RBTD-MS2 BLK-SL BBO-11S2
R1-DS RBTD-DS4 RED-SL BRO-11S2
R2 CR-834 YEL-SL BYO-11S2
R2-SL RBTD-834-11S2

Poster A vobenzon e - SSCN Y2001