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Vol. 116, No. 9/September 2001 0361-4387/01/0009-0049$05.00/0—© 2001 Allured Publishing Corp. Allured’s Cosmetics & Toiletries® magazine/49
While a chemical or physical sunscreen a safe, efficacious and pleasant product. Generally, higher SPF
active must stay on the stratum corneum values protect better because SPF is a measure of sunscreen’s
to be effective, a biological sunscreen efficacy. As shown in Figure 1, a SPF 2 sunscreen will block
active would have to reach the viable 50% of the sunburn response.
tissues to be effective. The role of very high SPF values (SPF > 30) may be unclear
A chemical sunscreen active is believed to the consumer. An SPF 25 blocks 96% of the sunburn response,
to protect the viable tissues by absorbing while an SPF 50 only blocks 2% more, or 98% of the total sun-
the UV radiation and transforming it into burn response. Very high SPF products are more expensive,
less damaging radiation such as heat or may be more irritating to the consumer’s skin and eyes and
light. Chemical sunscreen actives might may offer little extra protection for the average consumer. Very
also generate free radicals in response to sun-sensitive individuals may benefit from the extra protection,
UV radiation. Regardless of the mecha- however, suggesting that a market niche exists.
nism, chemical sunscreen actives should In the recent Final Monograph on sunscreens, the US Food
absorb the UV radiation before it can and Drug Administration (FDA) established the upper limit for
reach the viable tissues. For this to occur, SPF at 30+.2 Any product offering a SPF greater than 30 can only
the sunscreen active must maintain a high exhibit 30+ on the label unless FDA approval is obtained.
concentration in the stratum corneum for SPF test: The SPF test approved by the FDA in its Final
several hours. Monograph defines the only method to determine the SPF of a
sunscreen.2 The procedure is simply to determine the Minimal
SPF Testing Erythema Dose (MED) on at least 20 but not more than 25 quali-
SPF is not well understood by the fied subjects. The MED is that amount of ultraviolet radiation
public, or even within the sunscreen required to produce the first perceptible redness reaction with
profession. SPF is a ratio of the ability clearly defined borders at 22 to 24 hours after irradiation.
of a person to burn with the sunscreen To determine the MED, a series of 5 exposures of increasing
relative to his ability to burn without energy is administered to the subject’s unprotected skin. Each
the sunscreen. Thus, if a person burns exposure is 25% greater than the previous exposure. At 22 to
in 10 minutes without the sunscreen, 24 hours after exposure, a trained grader other than the person
but does not burn until 150 minutes who conducted the irradiation or who applied the sunscreen
with the sunscreen, then the SPF of the evaluates the redness of each exposure site. The MED on
sunscreen is 150/10 = 15. Consequently, unprotected skin, or MEDUS, is used to calculate the radiation
the better a sunscreen protects the user’s exposures for the sunscreen-protected site.
skin against sunburn, the higher the SPF. To determine the MED in the presence of the sunscreen,
The goal of the formulator is to develop MEDPS, the first step is to apply the sunscreen to the subject’s
the highest SPF possible using the least skin, usually the back. After a wait of at least 15 minutes for
amount of sunscreen actives, because the sunscreen to dry, the treated area is exposed to seven
the sunscreen actives are expensive and geometrically increasing doses of radiation. The geometric
may be irritating. progression is dependent on the predicted SPF of the sun-
Requirements for higher SPF increase
the difficulty for the formulator to generate
SPF PCD
30+ high
Figure 1. SPF efficacy versus UV absorbance 12-30 moderate
2-12 minimal
50/Allured’s Cosmetics & Toiletries® magazine www.TheCosmeticSite.com Vol. 116, No. 9/September 2001
screen, as shown in Table 1, where X One controversy in water-resistant sunscreens is whether
is the product of the expected SPF and water resistant is the same as sweat resistant. In essence, the
the subject’s MED. debate is whether water coming from outside the skin acts
The MEDPS is the lowest dose of radia- identically to water coming from inside the skin in disrupting
tion that produces the first perceptible red- sunscreen efficacy. In the 1993 Tentative Final Monograph,3
ness reaction with clearly defined borders the FDA ruled that because the water-resistant test was more
of the exposure site at 22 to 24 hours after stringent than the sweat-resistant test, any product that passed
exposure. The SPF value is the ratio of the the water-resistant or very-water-resistant test could also make
energy required to produce the MEDPS to the claim of sweat resistant.
that required to produce the MEDUS. Based Recommended approach for testing: The target for the
on its SPF, the sunscreen is placed in one novice sunscreen formulator is to develop a sunscreen that will
of three product category designations, or meet the customer’s SPF requirements. General principles to
PCD, as shown in Table 2. Any product meet those requirements will be discussed later. After a few years
with a SPF below 2 should not be labeled of formulating sunscreens to meet SPF values, the experienced
as a sunscreen drug product.2 sunscreen formulator can then begin to formulate sunscreens
Water-resistant or very-water- with improved cosmetic properties. The experienced formulator
resistant test: To determine the water remembers that SPF formulations must meet the requirements
resistance of a sunscreen formulation, of the tests first and meet consumer requirements second.
you must first subject the skin with the Methods exist for clinical testing labs to obtain high SPF
sunscreen test material to repeated ex- values and stay within the FDA testing guidelines. For example,
posures to fresh water. Fresh water in COLIPA has greater defined values for the emission spectrum of
an indoor pool, whirlpool, or Jacuzzia solar simulators than the FDA’s Final Monograph. When testing
is maintained at 23° to 32°C for the test. a sunscreen for the US market, the solar simulator must only
The sunscreen is applied to the skin and emit between 290 nm and 400 nm with a spectrum similar to
allowed to dry. sunlight at sea level from the sun at a zenith angle of 10°. A
The subject enters the water and en- solar simulator can have an increased amount of UVB that then
gages in moderate activity for 20 minutes. generates a higher SPF relative to the COLIPA-certified solar
The subject exits the water to rest for 20 simulator. Using solar simulators with higher amounts of UVB
minutes, being careful to avoid rubbing off relative to UVA will increase the SPF of sunscreen products
the sunscreen. For a water-resistant claim, containing UVB sunscreen actives.
the 20 minutes in the fresh water while UVA protection testing: Currently, there is no FDA-accepted
engaging in moderate activity is repeated method to test for UVA protection. Developing an accepted
once more, for a total of 40 minutes in method is difficult because of the inability to easily detect
the water. For a very water-resistant claim, any acute changes in skin resulting from non-erythemal UVA
the 20 minutes in the fresh water while radiation (340-400 nm). Sunburn satisfies the requirements for
engaging in moderate activity is repeated UVB radiation and for erythemal UVA radiation. However, for
three more times, for a total of 80 minutes non-erythemal UVA radiation, no easy method exists to detect
in the water. Each 20-minute segment in changes. It seems that we may be attempting to provide pro-
the water is followed by a 20-minute rest tection from UV radiation that causes only minimal changes in
period out of the water. skin biochemistry.
Following the water immersion pro-
cedure, the sunscreen sites are allowed
Sunscreen Actives
to air dry. Then the SPF of the sunscreen The FDA has published a Final Monograph which details
is determined in a manner identical to the sunscreen actives that can be used in OTC sunscreens in
that described above under SPF test. the US.2 This Final Monograph incorporates the two additional
The SPF of the sunscreen determined actives that were added after the Tentative Final Monograph
after 40 total minutes of water expo- was published.4,5 A list of these sunscreen actives appears in
sure is the SPF placed on the label of Table 3 with additional pertinent information. Many suppliers of
a water-resistant sunscreen. The SPF of these sunscreen actives can be found in different source books,
the sunscreen determined after 80 total such as the International Cosmetic Ingredient Dictionary and
minutes of water exposure is the SPF Handbook.6 To obtain additional information, you need only
placed on the label of a very water- ask one or more of the suppliers.
resistant sunscreen. The Final Monograph includes only maximum concentrations
of sunscreen actives when used alone and in combination with
a
Jacuzzi is a registered trademark of Jacuzzi other sunscreen actives. The sunscreen active concentrations
Inc., Walnut Creek, CA. allowed by the Final Monograph are shown in Table 3.
52/Allured’s Cosmetics & Toiletries® magazine www.TheCosmeticSite.com Vol. 116, No. 9/September 2001
Sunscreens are safe and effective Titanium dioxide and zinc oxide are two new important
for the prevention of sunburn as de- sunscreen actives for the formulator. Each of these metal oxides
termined by the SPF test. Ultraviolet displays absorbing properties throughout much of the UVB
radiation triggers many biological and UVA spectrum. These actives can impart high SPF values
events, including acute, delayed and at relatively low concentrations, provide for broad-spectrum
chronic skin effects in addition to protection, and are relatively inexpensive. The difficulty in
sunburn. Animal and human studies formulating with titanium dioxide or zinc oxide is creating a
indicated that sunscreens prevent these product with acceptable consumer qualities. Recent research
biological events. The risk of allergic by Kobo Products and by Sunsmart has advanced the formu-
contact dermatitis or of photoallergic lation possibilities of these two sunscreen actives.
contact dermatitis due to sunscreen
actives is low. 7 Gasparro, Mitchnick Sunscreen Active Solvents
and Nash published a thorough review Once the formulator has decided which sunscreen active(s)
on sunscreen safety in 1998.8 to use in the formulation, the next step is to choose a solvent or
To formulate a high SPF sunscreen, solvents to solubilize those sunscreen actives. The solvents allow
one must first block much of the UVB, so the sunscreen actives to emulsify and may have additional effects
in selecting sunscreen actives, you must on the orientation of the sunscreen actives after the actives are
first choose a UVB blocking active. For applied to the skin. Some of these solvents, such as butyloctyl
many years, Padimate O was the UVB salicylate,b may actually stabilize some sunscreen actives against
sunscreen active of choice because it photodegradation.9-11 Rassat and colleagues published a list of
was very effective, inexpensive and rela- solvents for the newest sunscreen active, avobenzone.12
tively easy to formulate. Recently, octyl For the inexperienced sunscreen formulator, benzoate esters
methoxycinnamate has become more are perhaps the best starting point. Formulations using C12-15
popular with experienced formulators alkyl benzoates are shown in Formulas 2 and 8. A common sol-
owing to concern about increased photo- vent for the sunscreen active avobenzone is butyloctyl salicylate.
sensitization with Padimate O relative to Some selected sunscreen solvents are shown in Table 4.
octyl methoxycinnamate and to increased The more experienced formulator can examine the use of
stinging with Padimate O. Although the unique co-solvent systems such as the combinations of the
former concern appears to be unfounded,7
the public now looks for sunscreens that b
Butyloctyl salicylate is marketed as HallBrite BHB, which is a trademark
are “PABA free.” owned by The C.P. Hall Company, Chicago, IL.
54/Allured’s Cosmetics & Toiletries® magazine www.TheCosmeticSite.com Vol. 116, No. 9/September 2001
alkyl benzoates with isopropanol. Suppliers are now making Agents Imparting Water Resistance
new sunscreen solvent blends available, such as hexyldecyl
Agents imparting water resistance
benzoate with butyloctyl benzoate and C12-15 alkyl benzoate,
are materials that protect the sunscreen
stearyl ether benzoate and dipropylene glycol dibenzoate.
active from being removed easily with
The subject of sunscreen solvents is a very active area of
water. This is an important characteristic
research within the R&D programs of raw material suppliers
for sunscreens that will be used at the
as well as of sunscreen formulators. Much useful information
beach or swimming pools, or during
on the issue of solvency should be available from experienced
times of high physical activity. Under
sun-care formulators during the next several years.
these conditions, the sunscreen should
Inorganic Sunscreen Active Dispersions be able to avoid any loss of efficacy from
the aqueous environment. Sweating or
Inorganic sunscreen actives, titanium dioxide and zinc oxide,
swimming will cause a loss of activity
present formulation difficulties unlike those of organic sunscreen
from a sunscreen product without water
actives. Inorganic sunscreen actives must have a small particle
resistance. With these agents, the sun-
size to avoid the “whitening” effect, a particle size large enough
screen actives are not lost to an aqueous
to absorb UV radiation,13 and proper wetting and dispersion to
environment.
avoid agglomeration. The optimum particle size for titanium
The first waterproof sunscreen was
dioxide seems to be about 15-20 nm, while that for zinc oxide
developed by Johnson & Johnson in 1977.
appears to be slightly larger, 15-35 nm. These sizes are best for
Coppertone quickly followed with a water-
avoiding the “whitening effect” while maintaining strong UVB
resistant product using a polyanhydride
and UVA absorption.
resin, PA-18, as the agent imparting water
Proper wetting and dispersion of the inorganic sunscreen
resistance. PA-18 has several characteris-
will prevent agglomeration and precipitation in the formula.
tics that make it ideal for imparting water
Some advances have been made by treating or coating the
resistance in sunscreens. First, it imparts
particles to improve dispersion and stability. For example,
water resistance to the sunscreen; it’s
Schlossman patented the treatment of titanium dioxide with
effective. Second, it is very inexpensive.
isopropyl titanium triisostearate.14 This treated material has
Third, it is safe topically as evidenced by
greater dispersability and minimizes aggregation.
years of successful use. Unfortunately,
PA-18 is under patent until 2002.15
Several other agents can be used to
Table 4. Selected solvents for organic sunscreen actives impart water resistance to sunscreen
formulations. These are generally based
Alkyl salicylate Isostearyl benzoate on film forming characteristics or on
Butyloctyl salicylate Isotridecyl isononanoate hydrophobic barrier characteristics. A
C12-15 Alkyl benzoate Isotridecyl isononanoate listing of selected water-resistant agents
C12-15 Triethoxy alkyl benzoate Methyl gluceth-20 benzoate
appears in Table 5.
Cocoglycerides Octyldodecyl benzoate
Dipropylene glycol benzoate Poloxamer 105 benzoate
One important note for the formulator
Isocetyl salicylate Poloxamer 182 dibenzoate using a film former is to use the lowest
Isodecyl isononanoate PPG-15 stearyl ether benzoate possible concentration of emulsifier. The
Isodecyl salicylate Tridecyl salicylate emulsification system dries on the skin
Isononyl isononanoate
with the waterproofing agents. If too
much emulsifier exists, then the addition
of water can cause the waterproofing
agent to re-emulsify and wash off. This
Table 5. Selected agents imparting water resistance would allow the sunscreen active to wash
off as well.
Film formers Sunscreen actives cause irritation to
PVP hexadecene copolymer the eyes. When a waterproof sunscreen
PVP eicosene copolymer enters the eye, the waterproofing agents
Tricontanyl PVP
adhere to the mucus membrane of the
Acrylates/C10-30 alkyl acrylate crosspolymer
eye. This holds the sunscreen actives
Acrylates/t-octylpropenamide copolymer
in place, causing severe and prolonged
Hydrophobic barrier formers
irritation. Therefore, this author suggests
Cetyl dimethicone
Maleated soybean oil
that waterproof sunscreen products never
be tested for eye irritation. Alternatively,
Vol. 116, No. 9/September 2001 www.TheCosmeticSite.com Allured’s Cosmetics & Toiletries® magazine/55
the product without the waterproofing
agents in the formula might be tested in Formula 1. Sunscreen Lotion (SPF 30) (ISP Van Dyk)
an eye-stinging assay. A Water (aqua) 50.40% wt
Xanthan gum 1.00
Emulsifiers for Sunscreen Products B Glyceryl stearate (and) laureth-23 6.00
sunscreen product will spread over the Acrylates/C10-30 alkyl acrylates crosspolymer 0.30
skin into the eyes of the user. Sport type C Water (aqua) qs
sunscreen products are designed to hold Disodium EDTA 0.10
the sunscreen actives in place so they Carbomer 0.20
do not spread. These formulations are D Butylene glycol 2.00
designed for customers with an active Preservative qs
lifestyle. The first product of this class Panthenol and propylene glycol 0.50
was marketed by Coppertone under the Hydroxypropyl methylcellulose 0.20
name Coppertone Sport. Since its creation, E Triethanolamine 0.50
several similar “sport” type formulations 100.00
have been developed.
Procedure: Mix A until dissolved. Add B to A and heat to 50-55°C. Mix C.
Because the majority of raw material Add D to C and heat to 50-55°C. With vortex stirring, add AB to CD and
costs for a sunscreen are for the sunscreen stir for 30 min. Cool while stirring. Adjust viscosity with disodium EDTA.
actives, the formulator must develop
56/Allured’s Cosmetics & Toiletries® magazine www.TheCosmeticSite.com Vol. 116, No. 9/September 2001
products with high SPF values and low
concentrations of sunscreen actives. Re- Formula 3. Waterproof Sunscreen Formula (SPF 14)
cently, several companies have developed (Kobo Products)
materials referred to as SPF boosters or
A Cetyl dimethicone 3.00% wt
enhancers. These raw materials attempt to
Cyclomethicone 7.50
increase the SPF of a formulation without
increasing sunscreen actives. These SPF Isononyl isononanoate 6.00
58/Allured’s Cosmetics & Toiletries® magazine Vol. 116, No. 9/September 2001
References
Formula 4. SPF 15 Lip Balm (Protameen Chemicals) Address correspondence to Michael Caswell, Ph.D. c/o Editor, Cosmetics &
Toiletries magazine, 362 South Schmale Road, Carol Stream, IL 60188-2787
USA.
A Isostearyl linoleate 10.00% wt
Caprylic/capric triglyceride 60.20 1. M Caswell, The theory of sunscreens and tanning, Chap 3 in vol 2 of The
Chemistry and Manufacture of Cosmetics, ML Schlossman, ed, 3rd edn,
Octyl methoxycinnamate 7.00
Carol Stream, IL: Allured Publishing (2000)
Benzophenone-3 3.00 2. Fed Reg 64(98) 27666-27693 (May 21, 1999)
Propylparaben 0.10 3. Fed Reg 58(90) 28194-28302 (May 12, 1993)
C30-40 alkyl methicone 4.00 4. Fed Reg 61(180) 48645-48655 (Sep 16, 1996)
5. Fed Reg 63(204) 56584-56589 (Oct 22, 1998)
Ozokerite wax, white 5.00
6. International Cosmetic Ingredient Dictionary and Handbook, 7th ed, JA
Petrolatum 10.00 Wenninger and GN McEwen, Jr, eds, Washington, DC: Cosmetic, Toiletry,
B Fragrance (parfum) 0.70 and Fragrance Association (1997)
100.00 7. S Schauder and H Ippen, Contact and photocontact sensitivity to
sunscreens. Review of a 15-year experience and of the literature, Cont
Procedure: Heat A to 80°C, mixing until uniform. Cool to 65°C. Add B. Pour
Derm 37 221-232 (1997)
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efficacy, Photochem Photobiol 68(3) 243-256 (1998)
9. US Pat 5,788,954, Hydrating skincare and sunscreen composition
containing dibenzoylmethane derivative, eg, Parsol 1789, and C12,
C16, C18 branched chain hydroxy-benzoate and/or C12, C16 branched
chain benzoate stabilizers/solubilizers, CA Bonda and SP Hopper (Aug 4,
Formula 5. Sunscreen Spray 1998)
10. US Pat 5,783,173, Stable sunscreen composition containing
dibenzoylmethane derivative, eg, Parsol 1789, and C12, C16, and C18
A C12-15 alkyl benzoate 10.00% wt branched chain hydroxybenzoate and/or C12, C16 branched chain
Octyl methoxycinnamate 7.50 benzoate stabilizers, CA Bonda and SP Hopper (Jul 21, 1998)
Octyl salicylate 4.00 11. US Pat 5,849,273, Skin care and sunscreen composition containing
B Isododecane 73.50 dibenzoylmethane derivative, eg, Parsol 1789, and C12, C16, and C18
branched chain hydroxybenzoate and/or C12, C16 branched chain
Isohexadecane 5.00
benzoate stabilizers/solubilizers, CA Bonda and SP Hopper (Dec 15,
C Fragrance (parfum) qs 1998)
100.00 12. F Rassat, H Gonzenbach and GH Pittet, Use of sunscreens and vitamins
in the daily-use cosmetic, DCI 12 16-30 (1997)
Procedure: Mix A. Add B and continue mixing. Add C.
13. R Sayre et al, Physician sunscreens, J Soc Cos Chem 41 103-109
(1990)
14. US Pat 4,877,604, Method of incorporating
cosmetic pigments and bases into products
containing oil and water phases, ML
Schlossman (Oct 31, 1989)
15. US Pat 4,522,807, Substantive topical
compositions, C Kaplan (Jun 11, 1985)
16. GH Dahms, Choosing emollients and
emulsifiers for sunscreen products, Cosmet
Toil 109(11) 45-52 (1994)
17. J Guth, G Martino, D Patel and J Pasapane,
Versatility in sun protection, Cosmet Toil
105(12) 87-90 (1990)
60/Allured’s Cosmetics & Toiletries® magazine www.TheCosmeticSite.com Vol. 116, No. 9/September 2001