http://informahealthcare.com/phd ISSN: 1083-7450 (print), 1097-9867 (electronic) Pharm Dev Technol, Early Online: 1–4 ! 2014 Informa Healthcare USA, Inc. DOI: 10.3109/10837450.2014.965322

RESEARCH ARTICLE

BB creams and their photoprotective effect

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Ce´line Couteau, Eva Paparis, and Laurence J. M. Coiffard Faculty of Pharmacy, Universite´ de Nantes, Nantes Atlantique Universite´s, Faculty of Pharmacy, Nantes, France

Abstract

Keywords

BB creams appeared on the market quite recently. These creams, which give a perfect complexion by covering up the skin’s blemishes, have a photoprotective effect in the majority of cases. An SPF value ranging from 10 to 45 concerning the products we tested is displayed on the packaging. The 21 commercially-available BB creams were tested to assess their efficacy (determination of the SPF) and their photostability (determination of their efficacy after UV irradiation). It was shown that 70% of the products tested have an SPF determined in vitro by us which matches the SPF displayed on the product. For the remaining 30%, it can be seen that products have SPF values of between 2 and 10 times lower than those indicated on the products. It can also be noted that there is a large disparity in terms of photostability since, under the same experimental conditions, however, some products only lose 5% of their photoprotective efficacy, whereas others lose 60%.

BB cream, photostability, skin, SPF

Introduction For a number of years, a fashion has been emerging for cosmetic products other than sun products which have a Sun Protection Factor (SPF) – a universal indicator of a given product’s photoprotective nature in the UVB field. Cosmetics companies are now highlighting in their marketing argument the fact that their products have properties which protect the user against photo-aging1. We have chosen to study around twenty BB creams. BB Cream, otherwise known as Blemish Baume/Blemish Balm is a cosmetic cream which originated in Germany, and which was first used by dermatologists for its calming properties and also for hiding various problems after laser treatments such as peeling/ skin resurfacing. Since then, several Korean stars made the product popular after revealing the secret of their perfect yet natural-looking complexion. The trend then spread to Japan, the whole of south-east Asia, the United States and now Europe2. BB cream, which is an alternative to foundation, is a polyvalent cosmetic product, presented as having several properties such as moisturizing and soothing the skin, giving it an even tone, working against wrinkles and dark patches, as well as giving protection against UV rays. This is the aspect we wanted to study by determining their photoprotective efficacy with an in vitro method.

Materials and methods The commercially-available products tested are presented in Table 1. Thirty milligrams of product exactly weighed were spread on PMMA plates over the whole surface (25 cm2) using a finger cot. Polymethylmethacrylate (PMMA) plates (Roughness Value Sa ¼ 5.5) were purchased from Europlast (Aubervilliers, Address for correspondence: L. J. M. Coiffard, Universite´ de Nantes, Nantes Atlantique Universite´s, LPiC, MMS, EA2160, Faculty of Pharmacy, 9 rue Bias – Nantes, F-44000 France. Tel +33 253 484317. E-mail: [email protected]

History Received 15 April 2014 Revised 4 September 2014 Accepted 6 September 2014 Published online 30 September 2014

France). The final mass remaining on the plate after spreading is 18 mg. The SPF of the creams was measured in vitro. Three plates were prepared for each product to be tested and 9 measurements were performed on each plate3. Transmission measurements between 290 and 400 nm were carried out using two spectrophotometers equipped with an integrating sphere (UV Transmittance Analyzer UV1000S, and UV 2000 - Labsphere, North Sutton, Melbourne). The calculations for either term use the same relationship: SPF ¼

400 X 290

E S d =

400 X

E S T d

ð1Þ

290

where E is CIE erythemal spectral effectiveness, S is solar spectral irradiance and T is spectral transmittance of the sample4. Studies of stability were led using a previously-established protocol5. The PMMA plates coated with creams are placed for 2 h in a solar simulator (Suntest CPS + ) at 650 W/m2. The SPF is determined at the beginning (SPF0) and after 2 h (SPF2h). The ratio SPF2h-SPF0/SPF0  100 enables us to classify the products into two categories: photostable products which retain more than 90% of their efficacy and non-photostable products which do not retain 90% of their efficacy under the conditions of our experiment. Filters in products tested for photostability were subjected to dosing by High Performance Liquid Chromatography based on the method of Rastogi and Jensen with some modifications. Firstly, 0.1 g of each of the products which were to be analyzed was weighed. Then tetrahydrofurane or potassium hydroxide was added (0.1% w/w) in the case of phenylbenzimidazole sulfonic acid, until a total mass of approximately 10 g was obtained. The mixture was homogenized by putting it in a vortex for about 30 s until the sample was well homogenized and then put in an ultrasonic bath for 30 min. The solution was extracted using a syringe, then filtered directly in an HPLC vial. All chemicals were analytical grade and suitable for HPLC where appropriate.

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Table 1. UV combinaison in commercial products tested. Products tested (SPF labeled) 1 (30) 2 (20) 3 (30) 4 (30)

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5 (30) 6 (25) 7(35) 8 (15) 9 (20) 10 (15) 11 (20)

12 (10) 13 (20) 14 15 (30) 16 (10) 17 (25) 18 (15) 19 (20) 20 (45) 21 (20)

UV filters Octocrylene, Titanium dioxide, Bis-ethylhexyloxyphenol methoxyphenyl triazine, Methylene bisbenzotriazolyl tetramethylbutylphenol Ethylhexylmethoxycinnamate Ethylhexylmethoxycinnamate, Ethylhexylsalicylate, Benzophenone-3, Titanium dioxide Ethylhexylmethoxycinnamate (3,75%), Titanium dioxide (3,55%), Benzophenone-3 (1,00%) Homosalate, Benzophenone-3, Ethylhexylsalicylate, Octocrylene, Butylmethoxydibenzoylmethane, Titanium dioxide Titanium dioxide, Ethylhexylmethoxycinnamate, Zinc oxide (10) Ethylhexylmethoxycinnamate, Ethylhexylsalicylate, Benzophenone-3, Titanium dioxide Ethylhexylmethoxycinnamate, Bis-ethylhexyloxyphenol methoxyphenyl triazine, Diethylamino hydroxybenzoyl hexyl benzoate Ethylhexylmethoxycinnamate Ethylhexylmethoxycinnamate Octocrylene, Butylmethoxydibenzoylmethane, Terephtalydene dicamphor sulfonic acid, Drometrizole trisiloxane May contain: Titanium dioxide Zinc oxide Ethylhexylsalicylate, Octocrylene, Butylmethoxydibenzoylmethane, Phenylbenzimidazole sulfonic acid May contain: Titanium dioxide May contain: Titanium dioxide Octocrylene, Butylmethoxydibenzoylmethane Ethylhexylsalicylate, Ethylhexylmethoxycinnamate, Butylmethoxydibenzoylmethane, Octocrylene, Titanium dioxide Ethylhexylmethoxycinnamate, Octocrylene, Phenylbenzimidazole sulfonic acid May contain: titanium dioxide Titanium dioxide, Ethylhexylmethoxycinnamate Titanium dioxide, Zinc oxide Ethylhexylmethoxycinnamate, Zinc oxide, Titanium dioxide, Octocrylene, Benzophenone-3, Butylmethoxydibenzoylmethane

Separation was performed on a HPLC system (Shimadzu LC2010 CHT) equipped with quaternary pump, DAD (Photo Diode Array Detector) detector, autosampler, thermostated column oven, degasser and LC Solutions software. A X-bridge Shield RP18 column (150  4.6 mm; 3.5 mm) was used for separation. Separation was performed by following a gradient time program. The mobile phase consisted of solvent A (H3PO4 0.1% w/w) and solvent B (MeOH) with the elution profile as follows: 0–7 min, 80% B; 7–30 min, 100% B; 30–40 min, 80% B. Elution was performed at a flow rate of 1.0 mL/min. The C18 column was maintained at 30  C throughout the analysis. The detection wavelength was set at 300 nm. The injection volume was set at 10 mL. The run time was set at 40 min. The peaks were identified by comparing the retention times of the reference standards with the sample.

Results and discussion The SPF values determined by using two spectrophotometers are presented in Table 2. In 70% of cases, we observed that the values found matched the values displayed on the packaging, no matter which of the two machines was used. The percentage is equivalent to that found during previous studies on other types of products6.

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Table 2. In vitro determination of SPF for 21 bb creams tested before and after irradiation. Products tested (SPF labelled)

SPF ± DS Labsphe`re 1000S

1 2 3 4 5 6 7 8 9 10 11 12 13 15 16 17 18 19 20 21

(30) (20) (30) (30) (30) (25) (35) (15) (20) (15) (20) (10) (20) 14 (30) (10) (25) (15) (20) (45) (20)

Labsphe`re 2000

Before irradiation

After irradiation

Before irradiation

After irradiation

47 ± 6 10 ± 2 28 ± 3 29 ± 4 34 ± 3 14 ± 1 32 ± 4 33 ± 4 29 ± 4 17 ± 2 20 ± 3 5±0 23 ± 2 2±0 3±0 14 ± 2 29 ± 4 36 ± 4 32 ± 2 16 ± 3 24 ± 4

42 ± 6 9±2 18 ± 2 25 ± 2 14 ± 2 11 ± 1 21 ± 3 23 ± 3 22 ± 3 10 ± 2 16 ± 2 5±0 12 ± 2 2±0 3±0 13 ± 1 13 ± 2 29 ± 4 31 ± 3 16 ± 2 17 ± 2

64 ± 2 12 ± 2 28 ± 1 29 ± 0 38 ± 3 15 ± 1 38 ± 4 40 ± 3 31 ± 1 17 ± 1 24 ± 2 5±1 24 ± 2 3±0 4±0 15 ± 2 34 ± 2 38 ± 4 35 ± 3 16 ± 2 25 ± 1

57 ± 1 10 ± 1 18 ± 0 28 ± 3 14 ± 1 14 ± 1 24 ± 3 28 ± 0 24 ± 0 11 ± 1 16 ± 1 5±0 14 ± 1 3±0 3±0 13 ± 2 16 ± 1 29 ± 3 36 ± 3 19 ± 3 18 ± 1

These products are formulated using a mixture of organic and/or inorganic filters. However, for 6 products, the SPF value displayed on the packaging was higher than the one we found. This was the case particularly concerning products formulated with mineral filters. During a previous study, we showed the lack of efficacy of this type of filter7, which is again the case here with commercially-available products. This is all the more true in the present case, since the raw material is used in some cases here in pigmentary form as we said before. Only the products whose actual SPF values matched the values displayed on the packaging were studied for their photostability. We defined previously that a product was considered to be photostable if the SPF determined after 2 h of irradiation in a Suntest was at least 90% of its initial value5. By applying this criterion, we notice that almost all of the products studied are photolabile. The results of the dosages carried out show an large decrease in the concentration of certain filters (Table 3). Product N 19 is the only photostable product (Figure 1). This is due to the fact that it is formulated using titanium dioxide which is a very photostable filter8. We can consider that the products number 1 and number 16 are quite photostable, insofar as the SPF loss does not exceed 15% after irradiation in a Suntest. These two products contain octocrylene, a filter which is known to improve the photostability of other filters such as ethylhexylmethoxycinnamate, butyl methoxydibenzoylmethane and benzophenone-39. All the other products found to be photo-unstable are formulated with ethylhexylmethoxycinnamate, ethylhexylsalicylate and/or benzophenone-3. Salicylates turn out to be particularly photo-unstable products5. We should remind ourselves here that BB creams are cosmetic products destined for facial make-up and that, therefore, they are not designed to be reapplied throughout the course of the day. Besides BB creams are not labeled as sunscreens, their marketing argument presents them as being products which protect the user’s skin from the harmful effects of UV rays. After studying the formulation of the products tested, it can be noticed that 25% contain benzophenone-3, also known as oxybenzone. Benzophenones and particularly oxybenzone, are

BB creams and photoprotection

DOI: 10.3109/10837450.2014.965322

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Table 3. UV filters concentration before and after irradiation. UV-filters (% w/w)

Products tested

Before irradiation

After irradiation

Octocrylene Bis-ethylhexyloxyphenol methoxyphenyl triazine Methylene bis-benzotriazolyl tetramethylbutylphenol

8.44 ± 0.42 3.16 ± 0.08 1.33 ± 0.02

7.07 ± 0.33 1.72 ± 0.07 1.32 ± 0.03

Ethylhexylmethoxycinnamate Ethylhexylsalicylate Benzophenone-3

7.75 ± 0.27 4.09 ± 0.02 2.35 ± 0.29

3.25 ± 0.09 1.26 ± 0.04 2.33 ± 0.27

Ethylhexylmethoxycinnamate Benzophenone-3

3.80 ± 0.09 1.03 ± 0.04

0.75 ± 0.09 1.00 ± 0.07

Homosalate Benzophenone-3 Ethylhexylsalicylate Octocrylene Butylmethoxydibenzoylmethane

5.12 ± 0.04 3.98 ± 0.03 2.27 ± 0.01 2.09 ± 0.01 1.89 ± 0.01

3.33 ± 0.50 3.90 ± 0.02 0.85 ± 0.05 1.80 ± 0.06 0.66 ± 0.04

Ethylhexylmethoxycinnamate Ethylhexylsalicylate Benzophenone-3

7.41 ± 0.18 3.96 ± 0.05 2.25 ± 0.01

3.00 ± 0.02 1.12 ± 0.01 2.20 ± 0.05

Ethylhexylmethoxycinnamate Bis-ethylhexyloxyphenol methoxyphenyl triazine Diethylamino hydroxybenzoyl hexyl benzoate

6.58 ± 0.57 2.44 ± 0.07 2.31 ± 0.06

3.00 ± 0.02 0.85 ± 0.01 2.28 ± 0.06

Ethylhexylmethoxycinnamate

9.50 ± 0.56

4.41 ± 0.12

Ethylhexylmethoxycinnamate

4.35 ± 0.07

0.43 ± 0.01

Ethylhexylsalicylate Octocrylene Butylmethoxydibenzoylmethane Phenylbenzimidazole sulfonic acid

2.39 ± 0.01 2.22 ± 0.01 1.99 ± 0.01 1.60 ± 0.01

0.84 ± 0.05 1.92 ± 0.01 0.71 ± 0.01 1.45 ± 0.01

Octocrylene Butylmethoxydibenzoylmethane

3.03 ± 0.02 0.43 ± 0.01

2.85 ± 0.02 0.15 ± 0.01

Ethylhexylsalicylate Ethylhexylmethoxycinnamate Butylmethoxydibenzoylmethane Octocrylene

5.93 ± 0.04 3.72 ± 0.02 2.63 ± 0.02 2.60 ± 0.02

1.54 ± 0.01 1.50 ± 0.01 0.94 ± 0.01 2.30 ± 0.02

Ethylhexylmethoxycinnamate Octocrylene Phenylbenzimidazole sulfonic acid

7.74 ± 0.05 2.99 ± 0.02 2.81 ± 0.02

3.80 ± 0.02 2.50 ± 0.05 2.56 ± 0.02

Ethylhexylmethoxycinnamate

9.95 ± 0.22

4.95 ± 0.13

Ethylhexylmethoxycinnamate Octocrylene Benzophenone-3 Butylmethoxydibenzoylmethane

5.52 ± 0.25 1.93 ± 0.02 0.89 ± 0.01 1.21 ± 0.05

2.33 ± 0.15 1.85 ± 0.01 0.86 ± 0.01 0.41 ± 0.01

N 1

3

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4 5

7

8

9 10 13

16 17

18

19 21

common causes of photoallergy and are increasingly used in products other than sunscreens. Benzophenones may also produce photoallergic contact urticaria, in addition to delayed contact and photocontact dermatitis, which may complicate the clinical presentation10. Studying the list of ingredients allows us to state that 7 out of the 21 products tested contain alcohol, which is not desirable as this ingredient is a penetration enhancer. Very few products are formulated with mineral filters only: titanium dioxide and/or zinc oxide.

Few studies enable us to conclude that daily photoprotection is beneficial11. We can even reasonably think that it is not necessary for a person having no particular problems to use a photoprotective product every day of the year and at all latitudes. If we take Nantes as an example, low UV levels are seen even now, in May. The use of the BB creams is similar to a normal day moisturizer or foundation cream. BB creams must not be considered as sunscreen products. Considering the results of this research, it is highlighted that most of these products have their

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Pharm Dev Technol, Early Online: 1–4

70

Decrease of SPF (%)

60 50 40 30 20 10 0 19 16

1

4

11 18

9

8

21

3

7

10 13 17

5

Products tested

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Figure 1. Photostability of products tested.

photo-protection efficacy reduced after irradiation. The consumer must use correctly the product.

Declaration of interest The authors report no declaration of interest.

References 1. Seite S, Fourtanier A, Rougier A. Photoprotection in moisturizers and daily-care products. G Ital Dermatol Venereol 2010;145: 631–636.

2. Misery L. BB creams: a revolutionary product dating from 1860. Ann Dermatol Venereol 2014;141:74–76. 3. Couteau C, Pommier M, Paparis E, Coiffard L. Study of the efficacy of 18 sun filters authorized in the European Union tested in vitro. Pharmazie 2007a;62:449–452. 4. Sayre MR, Agin PP, Le Vee GJ, Marlowe E. A comparison of in vivo and in vitro testing of sunscreening formulas. Photochem Photobiol 1978;29:559–566. 5. Couteau C, Faure A, Fortin J, et al. Study of the photostability of 18 sunscreens in creams by measuring the SPF in vitro. J Pharm Biomed Anal 2007b;44:270–273. 6. Couteau C, Coiffard L. Les produits solaires: des proble`mes en termes d’efficacite´. Act pharm 2013;523:35–40. 7. Couteau C, Alami S, Guitton M, et al. Interest of mineral filters in sunscreen products – comparison of the efficacy of zinc oxide and titanium dioxide by in vitro method. harmazie 2008;63:58–60. 8. Hojerova´ J, Medovcı´kova´ A, Mikula M. Photoprotective efficacy and photostability of fifteen sunscreen products having the same label SPF subjected to natural sunlight. Int J Pharm 2011; 408:27–38. 9. Gaspar LR, Maia Campos PMBG. Photostability and efficacy studies of topical formulations containing UV-filters combination and vitamins A, C and E. Int J Pharm 2007;343:181–189. 10. Nedorost ST. Facial erythema as a result of benzophenone allergy. J Am Acad Dermatol 2003;49:S259–S261. 11. Seite´ S, Fourtanier AM. The benefit of daily photoprotection. J Am Acad Dermatol 2008;58:S160–S166. 12. Rastogi SC, Jensen GH. Identification of UV filters in sunscreen products by high-performance liquid chromatography–diode-array detection. J Chrom A 1998;828:311–316.