Académique Documents
Professionnel Documents
Culture Documents
17
ARC Handbooks of Cancer Prevention, Volume 5: Sunscreens
UVB absorbers
Cinnamates
- Ciroxate 104-23-9 S-29 Y Y Y
DEA methoxycinrmmale 56265-46-4 S-24 Y
- DOsopropyl methyl cinnamate 32580-71-5 S-23 Y
- Elhylbexyl methoxyc nnamate 5466-77-3 S-28 Y Y Y Y
- Ethyl methoxycinnamate 99880-64-5 - Y
- D yceryl ethyihexanoate dimethoxyc nnamate - Y
- Isoamy -para-methoxycirnamale 71617-10-2 S-27 Y
- Isopropyl-para-methoxycinnamate and - Y
dilsopropylcinnamale mixture
Salicylates
- Dipropylena glycol salicylate 7491-14-7 - Y Y
Ethylene glyccl salicylate 87-28-5 - Y
- Ethylhexyl salicylate 118-605 S-13 Y Y Y Y
- Homosa ate 118-56-9 S-12 Y Y Y Y
- Isopropylbenzyl salicylate 94134-93-7 S-16 Y
Methyl salicylate 119-36-8 - Y
- Phenyl salicylate 118-55-8 S-14 Y
- TEA salicylate 2174-16-5 S-9 Y Y
Camphor derivatives
- 3-Berizylidene camphor 15087-24-8 S-61 Y
- Benzylidene camphor sultonic acid 56039-58-8 S-59 Y
Camphor benzalkcnium methosulfate 52793-97-2 8-57 Y
- 4-Methylbenzylidene camphor 38102-62-4 S-60 Y Y
- Polyacrylamidomethyl benzylidene camphor 113783-61-2 3-72 Y
Miscellaneous
- Diethyhexylbutamido triazcne 154702-15-5 S-78 Y
- Digalloyl trioleate 17048-39-4 S-55 Y
- Ethylliexyl triazone 88122-99-0 8-69 Y Y
- 5-Methyl-2-pheriylbenzoxazole 7420-86-2 S-47 Y
- Octocrylerie 5197-30-4 S-32 Y Y
Chemical and physical characteristics
UVA absorbers
Benzophenones
- Renzoplienone-1 131-56-6 S-33 Y
- Benzophenone-2 131-55-5 S-34 Y Y
- Benzophenone-3 131-57-7 S-38 Y Y Y Y
- Benzophenone-4 4065-45-6 S-40 Y Y Y Y
- Benzophenone-5 6628-37-1 S-40 Y Y
- Benzophlenone-6 131-54-4 S-35 Y
- Benzophenone-8 131-53-3 - Y Y
- Benzopherione-9 78656-36-5 S-36 Y
- Benzophenone-10 1541-17-4 S-39 Y
Camphor derivative
-
Terephthalylidene dicamphor sulfonic acid 90457-82-2 S-71 Y Y
Dibenzoylmethane
-Butyl methoxydiberzoylmethane 70356-09-1 S-66 Y Y Y Y
Anthranhlate
- Menthyl anlhranhlate 134-09-8 - Y Y
Miscellaneous
Bisymidazylate (proposed INCI name) 180898-37-7 S-80 Y
Miscellaneous
- Anisotriazine (proposed INCI name) 187393-00-6 S-81 Y
- Dromeirizole trisiloxane 155633-54-8 S-73 Y
- Methylene-bis-benzotriazolyl 103597-45-1-P S-79 Y
tetramethylbutylphenol
INCI, International Nomenclature of Cosmetic Ingredients; CAS, Chemical Abstracts Service; COLIPA, European Cosmetic, Toiletry and Perfumery
Association; EU, European Union
e From European Commission (2000)
From Ministry of Health and Welfare (1999)
C
From Food and Drug Administration (1999)
d' The chemical UVR absorbers approved by the FDA (USA) and European Commission (EU) would be acceptable in Australia (Commonwealth
19
IARC Handbooks of Cancer Prevention, Volume 5: Sunscreens
R- =r-
-=- ' -C- ,
11 O
O
Cinnamate derivatives para-Aminobenzoate derivatives
Salicylate derivatives
/ O
Figure 14 The seven major groups of organic chemical sunscreen filters currently used in sunscreens
Benzophenones are dibenzoyl- tron delocalization and a shift in the max- Biological pigments
methane derivatives that belong to the imum absorption. Anthranilates, like sali- Melanin is the only natural pigment con-
aromatic ketone category. They resonate cylates, are stable and safe and have no sidered to be a sunscreen ingredient. it
easily, thus requiring a low quantum of significant solvent effects in cosmetic for- absorbs UVR and might provide both
energy; they therefore have a longer mulations. practical protection and the tanned'
wavelength for electron transition. Dibenzoylmethanes are substituted appearance desired by some people, but it
The main drawbacks to use of benzo- diketones with a ketoenol tautomerism is not available commercially (Chedekel &
phenones as UVR filters are concern which confers the characteristics of UVA Zeise, 1997).
about their safety, as aromatic ketones filters (enol form). The keto form is
are more difficult to detoxify than esters, responsible for high photoisomerization, Vehicles and formulations
and their solid state, which impairs their resulting in a significant loss of protective pH and various solvents can profoundly
solubilization in cosmetic formulations. power. These compounds have excep- influence the effectiveness of a
When high SPFS (20-30) are required, tionally high molar extinction coefficients sunscreen chemical because of shifts in
benzophenone-3 is usually used in but low photostability. absorption characteristics (Shaath,
combinations with solubilizers. Of the miscellaneous compounds, 1997b). In addition, the final formulation
Camphor derivatives are bicyclic phenylbenzimidazole sulfonic acid is a strongly influences the suspension,
compounds with high extinction coeffi- water-soluble sunscreen with effective distribution, stability and retention of the
cients. With only one exception, they are dose-response relationships with SPFs. sunscreen on the skin (Klein, 1997).
solid. They are approved for use in It has limited use in the USA.
Europe but not in the USA. Ti02 became more popular after the Additional ingredients
Anthranilates, such as menthyl introduction of micronized grades, but At various times and under various cir-
anthranilate, are ortho-disubstituted this product is still difficult to formulate. cumstances, products containing sun-
aminobenzoates. This allows easy elec- ZnO is used largely as a UVA absorber. screening agents have also contained a
20
Chemical and physcal characteristics
wide variety of other ingredients, because of real or perceived cutaneous analyses are also performed (Klein,
including urocanic acid, antioxidants, reactions, including irritation and contact 1992; Shaath etal., 1997b).
stabilizers, vitamins, hormones, animal sensitization (Funk et al., 1997).
and plant extracts and preservatives. One such ester (ethylhexyl dimethyl New chemical absorbers
Whether and how these ingredients PABA) is reported to induce phototoxicity Several patents have been assigned for
interact with the sunscreen chemical and photo mutagenicity in budding yeast modifications of chemical UVR
during use is not well documented. cells (Knowland et al., 1993). Gulston absorbers, including benzophenones,
Topically applied psoralens are and Knowland (1999) reported enhance- derivatives of dibenzoyi methane, feru lic
known to enhance the induction of ment of DNA damage in human acid amides, polyvalent metal salts of
melanogenesis in skin exposed to UVR. keratinocytes in vitro by a SPF-1 5 PABA, para-dimethyl PABA and 4-
For this reason, some sunscreen formu- sunscreen formulation, and they attrib- methoxycin namic acid (Shaath, 1997a).
lations were marketed with bergamot oil uted the effect to ethylhexyl dimethyl Other derivatives (indoline derivatives,
containing 5-methoxypsoralen. Since PABA. chalcone derivatives, benzylidene cam-
psoralens are known to enhance photo- Martincigh et al. (1997) catalogued phor) appear to be useful as chemical
carcinogenesis (see IARC, 1987), they the reported photochemical and absorbers.
are no longer permitted in sunscreen for- photophysical characteristics of sun- Natural and biosynthesized raw
mulations in Europe or the USA (Autier screens, related compounds and their materials have also been described in
etal., 1995, 1997a). photoproducts. They also reviewed the patents and articles, including DL -c -toco-
evidence for photodimerization of DNA pherol, thiamine or thiamine esters and
Stability, photostability and by sunscreens in vitro. They speculated genetically produced melanin incorpo-
reactivity that these events presage mutagenesis rated in a polymer-based delivery system.
Analysis and quality control measures in vitro and, by extension, in vivo. They Several forms (microparticles and
indicate that sunscreens stored under acknowledged that if such events occur ultrafine powder) of the inorganic
standard conditions meet or exceed the only in the stratum corneum during use chemical absorbers Ti02 and ZnO and
requirements for stability (Shaath, 1997c). of sunscreens, little damage would be other metal oxides have been shown to
Ideally, sunscreen molecules should caused to viable cells. be superior to those available on the
absorb UV photons and then dissipate market. In addition, plastics, resin emul-
the excess energy through such Analysis, verification and quality sions and particles have been studied for
processes as radiative decay (fluores- control use as reflectors to block UVR
cence and phosphorescence), self- Analytical techniques of particular use in
quenching or internal conversion sunscreen chemistry have been reviewed Other properties of sunscreen
and vibrational relaxation (heat). In short, (Shaath etal., 1997a). The quality control ingredients
they should undergo little or no photo- procedures first involve physical and Sunlight generates active oxygen
chemistry. The following examples show chemical analysis (Shaath, 1997o). The intermediates, including free radicals, in
that not all sunscreens meet this ideal. physical analysis includes tests for cells and tissues (Tyrrell, 1994), and
Butyl methoxydibenzoylmethane was odour, colour, physical appearance, these may damage cellular defence
introduced in 1978 in Europe as a melting-point, refractive index, specific pathways. The free-radical scavenging
sunscreen ingredient that absorbed gravity, optical rotation, solubility, antioxidant properties of the active
principally in the UVA region. The first moisture, viscosity, pH and flash-point. components of sunscreens have not
formulation containing this ingredient The chemical analysis involves determi- been investigated systematically. They
that was marketed in the USA lost a nation of saponification value, acid will be relevant when sunscreens
significant amount of its effectiveness value, functional groups and metal penetrate the cells and tissues in which
during use, reportedly because of content. Chromatographic and spectro- active damaging intermediates are
photoreactions (Sayre & Dowdy, 1999). scopic (UVR spectrum, infrared generated.
The use of several esters of PABA spectrum, nuclear magnetic resonance
has been reduced or discontinued spectroscopy, mass spectrometry)
21