J. Soc. Cosmet. Chem.

, 38, 209-221 (July/August 1987)

The effect of solvents on the ultraviolet absorbance

of sunscreens
LOUISE E. AGRAPIDIS-PALOYMPIS and ROBERT A. NASH,

St.John's University, Jamaica, NY 11439, and

NADIM A. SHAATH,* Research & Development Laboratory, Felton Worldwide Inc., Brooklyn, NY 11237.
Received March 25, 1987.
Synopsis

Theefficacy ofsunscreens isoften influenced bythesolvents in which they aredissolved. In thisregard, the ultraviolet (UV) absorption spectra of 13 UVA andUVB sunscreen chemicals weredetermined in 12 solvents ofvarying polarity and cosmetic interest. Changes in both thewavelength ofmaximum absorbance (K max) andmolar absorptivity () were observed formany of thesunscreen-solvent systems studied. Observed hypsochromic and bathochromic shifts in Kmax fora number ofsunscreen chemicals were related to theirstructure andpolarity. Polar solvents shifted theK maxof polar sunscreens to shorter wavelengths (hypsochromic) andshifted less polar sunscreens to longer wavelengths (bathochromic). Ortho-substituted sunscreen chemicals, such assalicylates andanthranilates experienced a minimum or no UV absorbance
shift.

With theexception of PABA,most sunscreens showed increased absorbance in bothpolar andnon-polar

solvents and decreased absorbance in semi-polar solvents, suchas hexylene glycoland C2-C5 alcohols
benzoate.

Theresults of thisstudy should aidthecosmetic chemist in selecting appropriate solvents andvehicles for
sunscreen chemicals.

INTRODUCTION

In 1960,Riegelman andPenna (1) were thefirstto observe marked changes in theUV absorbance of p-aminobenzoic acid(PABA)andseveral less important UV absorbers in five different solvents (water,alcohol USP, polyethylene glycol400, isopropyl palmirate, andmineraloil). The authors concluded that a sunscreen's effectiveness couldbe influenced by the solvent in whichit is dissolved. Twelve years later,Groves, using a thin-filmspectrophotometer, confirmed the previous findings for a smallnumber of sunscreen chemicals in polyethylene glycol400, isopropyl palmitate, andmineraloil (2). Shifts in the spectral absorbance of PABAin water andisopropyl alcohol werealso reported by Cumpelik (3). Morerecently, Klein andDoshihaveshown that the UV absorbance of several important sunscreen chemicals, aloneand in combination with
* Address all correspondence to: Dr. NadimA. Shaath, Technical Director, Felton Worldwide, Inc., 599
Johnson Ave., Brooklyn,New York, 11237-USA.
209

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eachother, will change considerably when they are dissolved in selected liquid emollients (4).

The present study(5) was undertaken to determine the influence of 12 cosmetic and relatedsolvents of varyingpolarityon the UV absorption characteristics of 13 sunscreen chemicals in orderto aid the cosmetic chemist in achieving a betterunderstanding of the interactions that arepossible between UV absorbers andliquid components usedin
sunscreen formulations.

EXPERIMENTAL
MATERIALS

Thirteen sunscreen chemicalswhich are widely used in cosmeticformulationswere

tested.The list included five UVA (320 to 360 nm) absorbers (i.e., menthylanthranilate, oxybenzone, dioxybenzone, sulisobenzone, and butylmethoxy dibenzoylmethane) andeight UVB (290 to 320 nm) absorbers (i.e., PABA, ethyl dihydroxypropyl PABA, octylcyano diphenylacrylate, octyl methoxycinnamate, octyl salicylate, homomenthyl salicylate, octyl dimethyl PABA, and triethanolamine salicylate). All of the sunscreens tested,with the exception of butylmethoxy dibenzoylmethane, havebeenassigned Category 1: safeandeffective status by the FDA over-the-counter reviewpanel(6).
Twelve solvents werealsoselected for study, based uponeither their usage in cosmetic formulation or theirpolarity,andarelistedin TableI in decreasing orderof polarityin accordance with Vaughan's solubilityparameter assignments (7).
Chromatographic analysiswas performedon all sunscreens and solvents used in the studyin orderto confirmtheir purity. Our assays showed that the materials usedwere well within the purity specified by the supplier (i.e., not lessthan 98%).
METHODOLOGY

Solutionsfor UV spectralanalysiswere accurately preparedusing sunscreen-solvent

Table I

Solvents and Their Corresponding SolubilityParameters Listedin Decreasing Orderof Polarity

Solubilityparameter
Solvent at 25C

Ethanol 70%-water

30%
10%

16.0

Propylene glycol
Ethanol 90%-water
Ethanol

14.0
13.9
12.8

Hexyleneglycol Methyl carbitol

12.3 10.7

Ethoxyethanol Isopropyl myristate

Isopropylpalmitate

10.6 8.0
7.8

C2-C5 alcohols benzoate

Hexane Mineral oil

7.6
7.3 7.0

SOLVENTS

AND

SUNSCREEN

ABSORBANCE

211

combinations wherethe solubilityof the sunscreen waspossible in the solventat room temperature. A 50 mg _+ 1 mg sample of eachsunscreen wasweighedaccurately into a 100-ml volumetricflaskandthen dilutedto the mark with solvent.The resultingstock solution wasthen diluted 1:100 to yield a final sunscreen concentration of 5 mg/L.
UV absorbance curves of each final dilution were obtained with the aid of a Perkin-

ElmerLambda 4B UV/VIS spectrophotometer. A background correction wasperformed using 1-cm quartz cellsfilled with blank solvent.The UV absorbance curvewasthen recorded by scanning wavelengths between 200 and400 nm, using a sample of the final dilution in the 1-cmquartzcell. The wavelength of maximumabsorbance ( max) and the corresponding absorbance valuewere determined and displayed by the microprocessor unit of the spectrophotometer.
The spectrophotometer's wavelength accuracy is _+ 0.3 nm and its absorbance accuracy
is -+0.005 A when measured at 1,000 absorbanceunit (A). A holmium chloride

standard cell was usedto calibrate the spectrophotometer and its microprocessor unit. Our resultswere within the specifications established for the standardcell and the spectrophotometer.

The molar absorptivity ()wascalculated for eachtest solutionat the wavelengths of maximumabsorbance ( max)in the ultraviolet regions (UVA, UVB, andUVC). However, only the valuesin the UVA and UVB regions are reportedin this paper(8).

RESULTS

The ultravioletabsorption spectral properties (X max and values)of 13 sunscreen chemicals in variouspolar, semi-polar,and non-polarsolvents were obtained. These data are summarizedin TablesII-IV as three separate groupsof compounds. Sunscreens where the max is shiftedtowardsshorterwavelengths (hypsochromic or blue
Table II

UV Spectral Data of Sunscreen Chemicals Showing Hypsochromic Shiftsin the . max

PABA

Dioxybenzone
max

Sulisobenzone
. max

Oxybenzone
. max

Solvent

}, max

Ethanol 70%-water 30%

266

13,600

326

9,400

324

8,600

321

9,300

Propylene glycol
Ethanol90%-water 10% Ethanol

272
271 272

14,500
13,800 13,100

326
326 327

9,100
9,400 9,300

324
325 326

7,500
8,900 8,400

322
324 325

8,400
9,500 9,400

Hexylene glycol Methyl carbitol Ethoxyethanol Isopropyl myristate Isopropyl palmirate C2-C5alcohols benzoate
Hexane

268 291 293 ins. ins. ins.

ins.

13,400 18,300 18,900 ins. ins. ins.

ins.

329 324 325 352 351 352

351

7,600 8,900 9,600 10,600 10,200 9,900

13,100

331 333 334 ins. ins. ins.

ins.

7,000 5,600 8,500 ins. ins. ins.

ins.

327 323 327 328 327 328

328

8,200 8,400 9,000 9,000 9,000 8,300

8,800

Mineral oil

ins.

ins.

352

11,400

ins.

ins.

329

7,800

Wavelengthshift from non-polarto polar solvent

Ah max = -27nm

Ah max = -26nm

Ah max = -10nm

Ah max = -8nm

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Table III

UV Spectral Data of Sunscreen Chemicals Showing Little or No Shiftin the X max

Triethanolamine salicylate
Solvent X max E

Octyl salicylate
}x max E

Homomenthyl salicylate
max e

Menthyl anthranilate
max e

Ethanol 70%-water 30%

298

2,800

308

4,900

306

4,800

336

5,600

Propylene glycol
Ethanol 90%-water Ethanol 10%

298
297 298

2,100
3,000 2,900

307
305 307

4,800
4,000 4,200

307
305 306

3,700
4,300 4,600

335
337 338

4,800
5,000 5,000

Hexylene glycol Methylcarbitol Ethoxyethanol Isopropyl myristate Isopropyl palmitate C12-C5 alcohols benzoate
Hexane Mineral oil

298 301 301 ins. ins. ins.

ins. ins.

2,200 3,100 3,000 ins. ins. ins.

ins. ins.

306 309 310 309 308 309

310 310

3,900 4,000 4,000 4,200 4,600 3,900

4,100 4,200

306 307 307 308 307 308

308 308

2,300 4,800 4,700 5,100 5,000 4,900

5,100 4,500

339 338 339 338 337 337

334 334

4,800 5,700 5,600 4,600 4,700 6,200

5,400 6,000

Wavelength shiftfrom
non-polarto polar
solvent

A. max =
-- 3 nm

A. max ----- 2 nm

A. max ----- 2 nm

A. max =
q-2 nm

shift) in goingfrom non-polar to polarsolvents are listed in Table II. Sunscreens that experienced little or no shift in their }t max in the varioussolvents testedare listed in Table III. Sunscreens, where the }t max was shifted towardslonger wavelengths (bathochromic or red shift), are listed in Table IV. Experimental valuescouldnot be obtained in thoseinstances wherethe sunscreen wasnot soluble in the particular solvent selected for studyand are soindicated in eachtable.

The change in thewavelength of maximum absorbance (A }t max)fromtheleast polar

solvent(i.e., mineral oil) to the mostpolarsolvent(i.e., ethanol70%-water 30%) for each sunscreen is listed at the bottom of eachtable (II-IV). Where a sunscreen was

insoluble in eithera particular polaror non-polar solvent, the A }t maxwascalculated

betweenthe leastpolar solventand the mostpolar solventin which the sunscreen was
soluble.

In addition,selected UV absorption spectra of several of the moreimportantsunscreen chemicals in eachcategory (hypsochromic, bathochromic, and minimum or no shift), illustratingthe magnitudeof the shift in the }t max in both polarand non-polar solvents, are alsopresented in Figures1-5.

DISCUSSION
CHANGES IN WAVELENGTH OF MAXIMUM ABSORBANCE

In orderfor the cosmetic chemistto estimate the effectformulationcomponents haveon the UV characteristics of a particular sunscreen chemical, the polarityof the sunscreen

andthe polarityof the components in thepreparation should be determined. The rela-

SOLVENTS AND SUNSCREEN ABSORBANCE

213

O-IC'-IC'-IC'-IC'-IC'-IC'-IC'-IC'-IC'-I

_.[_

II

0000

+ II

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rO 72?
t
Absorbance
units

'%,.,

,
\ /'
/

//

x,,
I"
!,

100% ETHYL ALCOHOL

\
588,8

,,

/'

Wavelepgth (rim}
!

-6.?62

/
Absorbance

ETHOXY

ETHANOL

units

Wavelength(rim) Figure 1. UV absorption spectra of PABAshowing a hypsochromic shiftin the . maxin theUVB region (290 to 320 nm) from a less polarsolvent (ethoxyethanol) to a morepolarsolvent (ethanol).

tive lipophilicity,a measure of a compound's relativepolarity,hasbeendetermined by calculating the log of the partitioncoefficient between octanol, a modellipid, andwater (log P) for 15 sunscreen chemicals. Thesedata are listed in decreasing orderof polarity (i.e., increasing log P values) in Table V. The log P values werecalculated from the
structural formula of each sunscreen in accordance with Rekker's method of deter-

SOLVENTS

AND

SUNSCREEN

ABSORBANCE

215

100%

ETttY

ALCOItOI,

Absorbance
units

-8.881

38g.8

488 g

Wavelength

8.72

units

28e.

38e.e

488 e

Wavelength(nm)

Figure2. UV absorption spectra of dioxybenzone showing a hypsochromic shiftin thek maxin theUVA
region(320 to 360 nm) from a non-polar solvent (hexane) to a polarsolvent (ethanol).

mining hydrophobic fragmental constants (9). All of the sunscreen chemicals included in this paperare listedin Table V with the exception of sulisobenzone. Nevertheless, because of solubility (Table II) and structuralconsiderations, sulisobenzone is consideredto behighlypolar.The datareported in TableV indicate that therearetwo groups

of sunscreens: onethat is morepolar(i.e., log P values between -0.02 to 2.84) and the otherthat is considered to be less polar(i.e., log P values between 4.53 and6.08). The main ingredient in the cosmetic preparation that usually will cause the k max to
shift is the solventor vehicle.If the solventis very volatile and evaporates when the

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JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

100%
Absorbance units

ETHYL

ALCOHOL

--

Wvelength (nm)
I I

!
!
!

i i

I
I

!
I

Absorbancr units

8.88

Wavelength (nm)

Figure 3. UV absorption spectra of octylsalicylate showing no apparent shiftin the X maxin the UVB
region(290 to 320 nm) from a non-polarsolvent(hexane) to a polar solvent(ethanol).

sunscreen formulationis placeduponthe skin, then other lessvolatileingredients in high concentration will affectthe UV characteristics of the sunscreen chemical. If the sunscreen is polar(i.e., PABA, dioxybenzone, sulisobenzone, and oxybenzone), then interactions with polar solvents will cause the UV absorbance spectra to shift towards shorter wavelengths (TableII andFigure1). Thus PABA becomes less effective asthe polarityof the solvent increases and k max shiftsfrom the UVB regionto the UVC region.In the case of the threebenzophenones tested, a hypsochromic shiftoccurs
within the UVA region.

SOLVENTS

AND

SUNSCREEN

ABSORBANCE

217

100%

ETHYL

ALCOIIOL

0 425

Absorbance
units

/
/'
/

Wavelength (nm),
I

-8.415
ALonoe

HEXANE

units

.0.005
Wavelength (nm) Figure 4. UV absorption spectra of octyl p-methoxy cinnamate showing a bathochromic shift in the max in the UVB region(290 to 320 nm) from a non-polar solvent(hexane) to a polarsolvent(ethanol).

On the other hand, if the sunscreen is lesspolar (i.e., octyl dimethyl PABA, octyl cyanodiphenylacrylate, octyl p-methoxycinnamate, butyl methoxydibenzoylmethane, and ethyl dihydroxypropyl PABA), then interactions with polar solvents will shift the UV absorbance spectra to longer wavelengths (TableIV; Figures 4 and5). In the case of octyl dimethylPABA, it still remains within the UVB regionregardless of the polarity
of the solvent in which it dissolves.However, as the solvent becomeseither more or less

polar, k max is displaced from 308 nm, the wavelength of optimumprotection for a UVB absorber. In the case of octyl p-methoxycinnamate, formulatingwith non-polar solvents should be avoided since suchsolvents will shiftthe k max awayfrom 308 nm.

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JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

100% ETHYL ALCOHOL

,/'\,\
Absorbance
units

800

',--.--'"-"-",-,. "

. ,./' II "

,,

Wveleth (nm)l
I

I
I
I

I
I

HEINE

Absorbance
units

'
/,.'I
,

,
1

O
Waveleith (nm)

Figure 5. UV absorption spectra of octyldimethylPABAshowing a bathochromic shiftin the h maxin the UVB region(290 to 320 nm) froma non-polar solvent (hexane) to a polarsolvent (ethanol).

Triethanolaminesalicylate,octyl salicylate,homomenthylsalicylate,and menthyl anthranilate showed only minor variations in h max in both polarand non-polar solvents(Table III and Figure 3). The minimum shift of the h max is due to the orthosubstituted configuration of salicylates andanthranilates. The lonepair of electrons are involvedin the six-membered cyclicarrangement and, asa result, are not available for interaction with polarsolvents (Figure 6). Hence,ortho-substituted compounds tendto exhibit moderate to low max shiftsin polar solvents. Althoughoxybenzone and dioxybenzone bothmayforma six-membered cyclical arrangement, similar to the salicy-

latesandanthranilates, theyexhibitadded polarity dueto the additional hydroxy and

methoxygroups.

A more in-depthexplanation for the shiftsand changes observed in the max that occurwhen sunscreen chemicals aredissolved in bothpolarand non-polar solvents has beenprovided in separate reports by Shaath (10, 11).

SOLVENTS

AND

SUNSCREEN

ABSORBANCE

219

Table
Between Octanol

V
and Water

RelativeLipophilicity of Sunscreen Chemicals Based Upon Their CalculatedPartition Coefficients

CTFA

name

Other names

Log P @25c

Glyceryl PABA Benzophenone-4

PABA

1,2,3-Propanetriol, 1-(4-aminobenzoate)
Sulisobenzone

- 0.02
- 1.51

Benzophenone-8
Cinoxate

Benzophenone-3 Ethyl dihydroxypropyl PABA Amyl dimethyl PABA Butylmethoxy dibenzoylmethane Menthyl anthranilate Octyl salicylate
Homosalate

Octyl methoxycinnamate Octocrylene Octyl dimethyl PABA

p-Amino benzoic acid Dioxybenzone Ethoxyethylmethoxy cinnamate Oxybenzone Ethyl-4-bis(2-hydroxypropyl-aminobenzoate) Amyl dimethylPABA Butylmethoxy dibenzoylmethane Menthyl-O-aminobenzoate 2-Ethylhexylsalicylate Homomenthylsalicylate Ethylhexyl-p-methoxy cinnamate Octyl cyanodiphenylacrylate 2-Ethylhexyl-p-dimethyl aminobenzoate

0.74 2.15 2.55 2.63 2.84 4.53 4.86 5.05 5.30 5.61 5.65 5.69 6.08

CHANGES

IN MOLAR

ABSORPTIVITY

In additionto shiftsin X max, both increases and decreases in the molar absorptivities ()of sunscreen chemicals were alsoobserved in the varioustest solvents.

In general, andwith the exception of PABA, the restof theUVA andUVB sunscreens selected for studyshowed increased values at X max in both polar(ethanol-water systems) andnon-polar (hexane andmineral oil) solvents. In contrast, there were significant decreasesin values at max when the sunscreenchemicals were dissolved in

semi-polar solvents such ashexylene glycol andC2-C5alcohols benzoate. These data

(takenfrom Data TablesII-IV) havebeensummarized in TablesVI andVII.

Reduction in molarabsorptivity varied between 12%and55% forhexylene glycol and between 7% and28% forC2-C5 alcohols benzoate. In addition, employing a spectrophotometric technique suggested byVogelman etal. (12),overall reduction in thearea

I 0 -- Menthyl

I 0 -- Octyl

(a)
ylate.

(b)

Figure 6. Steric configuration ofortho-substituted molecules, (a)menthyl anthranilate and(b)octyl salic-

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JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Table VI

Sunscreens andSolvent Systems That Showed Changes in MolarAbsorptivity

Approximate

Solvent exhibiting
increased
Sunscreen

Solvent exhibiting
decreased

reduction in
molar

molar absorptivity
Hexane

molarabsorptivity
Hexyleneglycol Methyl carbitol Isopropylpalmitate Isopropylmyristate Hexyleneglycol C12-C15 alcohols benzoate
Mineral oil

absorptivity
40% 37% 25% 25% 24% 24%
18%

UVA Absorbers

Dioxybenzone
Sulisobenzone

Menthyl anthranilate

Ethanol 90%-water Ethanol 70%-water Ethanol 90%-water

10% 30% 10%

Butylmethoxydibenzoylmethane

Oxybenzone

Ethanol 90%-water

10%

underthe absorbance-vs-wavelength curveof 32% to 35% wasobserved for oxyben-

zone,dioxybenzone, andoctylcyanodiphenylacrylate, andthere wasa 75% reduction

for triethanolamine salicylate in goingfrompolarto non-polar solvents. Klein hasrecentlyreported(4, 13) almostcomplete suppression of UV absorbance

spectra of octyldimethyl PABA,octyl p-methoxycinnamate, andbenzophenones alone

and in combinationwith eachother in two branched-chain liquid fatty esters (i.e.,

isostearyl neopentanoate and isopropyl linoleate). Klein'sfindingfor octyldimethyl

PABA in isostearyl neopentanoate hasbeenconfirmed in our laboratory.

The principal characteristics of a UV absorption bandareits position (k max)andits intensity or molar absorptivity ().In thecase of thelatter,values at k maxofmost of the sunscreen chemicals testedwere greatest in polarand non-polar solvents and reduced in hexylene glycol andC2-C5alcohols benzoate. Drastic reductions in value

Table

VII

Sunscreens and Solvent Systems That Showed Changes in Molar Absorptivity

Solvent exhibiting
increased
Sunscreen

Solventexhibiting
decreased

Approximate reduction in
molar

molarabsorptivity Ethoxyethanol Ethanol 90%-water 30%

Ethanol 70%-water Ethanol 70%-water 30% 30%

molar absorptivity Ethanol Hexyleneglycol

Hexyleneglycol C12-C 15alcohols benzoate

absorptivity 33% 23%

21% 25%
29% 20%
55% 28%

UVB Absorbers
PABA

Ethyl dihydroxypropyl
PABA

Octyl dimethyl PABA Octyl p-methoxy

cinnamate

TEA salicylate Octyl salicylate Homomenthylsalicylate Octyl-2-cyanodiphenylacrylate

Methyl carbitol
Ethanol 70%-water 30% Hexane Isopropylmyristate Hexane
Ethanol

Hexylene glycol
Hexyleneglycol Hexyleneglycol
benzoate C12-C15 alcohols

SOLVENTS

AND

SUNSCREEN

ABSORBANCE

221

in suchsemi-polar solvents would requireincreasing the concentration of requiredsunscreen for maximumprotection or, in the case of branched-chain liquid fatty esters, replacement with a moreappropriate solvent.

In conclusion, the wavelength of maximum absorbance (h.max)in the UVA and UVB regions of the spectrum andthe resultant molarabsorptivity (E)of a sunscreen chemical oftenwill be affected by the solvent in which it is dissolved. The changes observed in these two important parameters appear to be strongly influenced by the polarityand chemicalstructureof both the sunscreen and the solvent.The resultsof the present
study of the interactionbetweensunscreens and solvents providepracticalinformation that cosmetic chemists may find usefulin formulatingsunscreen preparations.

REFERENCES

(1) S. Riegelmanand R. P. Penna,Effectof vehiclecomponents on the absorption characteristics of sunscreen compounds, J. Soc. Cosmet. Chem. 11, 280-291 (1960). (2) G. A. Groves, Factors influencing the formulation of sunscreens, Amer.Cosm. Perf., 87, 54-58 (July
1972).

(3) B. M. Cumpelik, Sunscreens at skin application levels:Direct spectrophotometric evaluation, J. Soc. Cosmet. Chem., 31, 361-366 (1980). (4) K. Klein and I. Doshi, Sunscreen/solvent interactions:An in-vitro evaluation, 14th International IFSCC Congress, September 16-19, 1986, Barcelona, Spain. (5) For a moredetailedexplanation of the experimental procedure andresults, referto: L. E. AgrapidisPaloympis, TheInfluence ofSolvent ontheUV Absorbance ofSunscreens, M.S. Thesis, St. John's University
(1987).

(6) Department of Health, Educationand Welfare, US FDA, Sunscreen drug productsfor over-thecounter humanuse,Fed.Reg.,43(166), 36206-38269 (1978). (7) C. Vaughan, Using solubility parameters in cosmeticformulations, J. Soc.Cosmet. Chem.36,
319-333 (1985).

(8) Spectrometry nomenclature, Anal. Chem. 56, 125 (1984). (9) R. F. Rekker, The Hydrophobic Fragment Constant (Elsevier ScientificPublishing Company,New
York), 1977.

(10) N. A. Shaath,The chemistry of sunscreens, Cosmetics and Toiletries, 101, 55 (March 1986).

(11) N. A. Shaath, On theTheory of Ultraviolet Absorption of Sunscreen Chemicals, Annual Meeting ofthe Society Cosmetic Chemists, New York, December 1986,J. Soc.Cosmet. Chem., 82, 193-207 (May/
June 1987).

(12) J. Vogelman,E. Nieves,J. Brind, R. Nash, and N. Orentreich,A spectrophotometric methodfor determining relative SPFvalues of sunscreen preparations, J. Applied Cosmetol., 1, 1-11 (1985). (13) K. Klein, Van Dyk Division,Mallinckrodt,Inc., Belleville,NJ 07109, privatecommunication.