Formulating High SPF Sun Care Products With A - External Factor ...

Reprint 

from 

7-2005 

International Journal 

for Applied Science 

■ Personal Care ■ Detergents ■ Specialities 

K. Berg-Schultz, Ch. Mendrok, F. Sit, R. Jermann: 

Formulating High SPF Sun Care Products 

with a Liquid-Mineral UV Filter

SUN CARE 

LIQUID-MINERAL UV FILTER 

K. Berg-Schultz, Ch. Mendrok, F. Sit, R. Jermann* 

Formulating High SPF Sun Care Products 

with a Liquid-Mineral UV Filter 

Keywords: Sun Care, Polysilicone UV Filter, High SPF Formulation, Enhanced Sensorial Profile 

� Introduction 

Abstract 

The novel architecture of the 

new UVB filter, PARSOL ® SLX 

(INCI: Polysilicone-15) combines 

the desirable attributes of 

both polydimethylsiloxane and organic 

UV filters. It exploits the 

film-forming characteristics of 

polydimethylsiloxanes on human 

skin, ensuring an optimal distribution 

of the attached UV absorbers 

when applied as a sun cream. 

This results in remarkably high 

performance sun care products 

which are suitable for all skin 

types but especially for sensitive 

skin due to its minimal skin penetration. 

Formulated products containing 

Polysilicone-15 also convey 

appealing sensorial aspects 

while remaining easy to use and 

handle. 

Due to the increased awareness of consumers 

that excessive sun exposure can 

lead to damages such as premature skin 

aging, sunburn, immune suppression, and 

different types of skin cancer (1,2) the 

consumption of sun care products has 

steadily increased in the last decades. Simultaneously, 

the sun protection factor 

(SPF) of products found in the marketplace 

increased significantly. Whereas, 

10 years ago an SPF of 4 to 20 was the 

common practice, today usual sun care 

products exhibit SPF’s of 20 up to SPF’s 

of 50+. 

For formulators the preparation of a 

sunscreen having a SPF of 40 or more is 

still a challenging task and needs a lot of 

experience and skills, especially as it is 

well known that an increase of the UVfilter 

concentration does not steadily 

lead to a higher SPF. Thus, in order to 

achieve a high SPF different UV-filters 

have to be combined (Fig. 1) (3). Nevertheless, 

not all UV-filter combinations 

lead to expected higher SPF’s and often 

several trials of different combinations 

are necessary (4). 

In a sun care product with a high SPF, the 

UV-filters represent an important proportion 

of the total formulation and 

SPF 

filter 1+2+3 

filter 1+2 

Fig. 1 Synergistic effect of UV filter 

combinations in cosmetic formulations 

therefore contribute significantly to the 

sensory profile of the product. However, 

high levels of traditional organic sun filters 

can lead to aesthetically unpleasing 

effects with regard to greasiness and 

tackiness of the formulation. On the other 

hand inorganic UV-filters such as minerals 

and pigments have an undesirable 

residual whitening effect on the skin 

which makes the skin look pale (Fig. 2). 

Fig. 2 Whitening effect on the skin 

As the consumers dislike such features 

the choice and combination of UV-filters 

used in sunscreen formulations is crucial. 

Additionally, photo-stability, safety aspects, 

easy handling in production, product 

stability and costs have to be taken 

into account in the development of a 

sunscreen product. For this reason, the 

cosmetic industry desires UV-filters which 

provide effective protection against UV 

radiation reflected by a remarkable SPF 

performance, which are easy to formulate 

and have a pleasant skin feel. 

2 SÖFW-Journal | 131 | 7-2005 

filter 1 

UV-filter concentration

� Polysilicone-15 – 

a liquid mineral UV-filter 

Polysilicone-15 is the first commercial 

example of a completely new generation 

of UV filters which were specifically designed 

to meet the needs of the cosmetic 

industry. Unlike conventional monomeric 

UV filters, this innovative UV filter constitutes 

a hybrid of silicone technology 

and classic organic UV-filter chemistry. A 

closer look at the structure of the molecule 

reveals, that the mineral silica in 

form of a polysiloxane chain serves as 

polymeric backbone for the chromophore 

units (Fig. 3). 

This combination leads to a unique polymeric 

UV filter which besides being liquid 

at all temperatures has excellent cosmetic 

properties and minimizes the risk 

of skin penetration due to its high molecular 

weight of about 6000g/mol. Although 

the polymeric backbone represents 

more than 70% of the molecular 

mass and does not contribute to the UV 

absorption as reflected by a low UV specific 

extinction (E 1%, 1cm), Polysilicone- 

15 delivers in vivo SPF performance comparable 

with industry standards, such as 

Ethylhexyl Methoxycinnamate (EHMC) 

(Fig. 4). This, at first sight, surprising result, 

can be explained by looking into 

the behavior of different UV-filters on 

the skin. 

� In vivo performance of 

Polysilicone-15 versus EHMC 

How can it be, that a molecule, which has 

less than 30% of its molecular weight 

contributing to sun protection, obtains 

the same SPF performance as the benchmark 

molecule EHMC? An explanation of 

this question needs some insight into the 

behavior of sun-filters in general and of 

their behavior on the skin. 

Numerous attempts have been made to 

understand how sunscreen preparations 

protect against UV radiation (5-9). Up to 

now the measurements of the sun protection 

factor (SPF) of emulsions containing 

traditional UV absorbers clearly 

indicated that the efficacy depends on 

the absorption characteristics of each single 

UV filter substance. However, it is also 

well accepted that the Lambert Beer’s Law 

is not obeyed at high concentrations 

SUN CARE 


Fig. 3 Structure of Polysilicone-15 

Fig. 4 In vivo SPF comparison of Polysilicone-15 and EHMC 

(>0.01M) as present in sunscreen formulation 

due to electrostatic interactions 

between molecules in close proximity. At 

high UV absorber concentrations, as commonly 

found in sunscreen formulations, 

this leads to a drop of the UV absorption 

properties and consequently to a loss of 

the theoretical protection abilities. Additionally, 

the degree of UV absorption 

achieved by the UV filters within a sunscreen 

formulation depends on the irregularities 

in the geometry of the sunscreen 

film after application on the skin 

(5, 8-12). Reason for the uneven distribution 

of UV-filters on the skin are manifold 

and can be caused besides the rough- 

ness of the skin due to wrinkles, cracks, 

hair and gland shafts, by aggregation of 

the aromatic UV filter molecules due to 

π-π interactions (13,14) or agglomeration 

of nanopigments as well as by microcrystallisation 

of an ingredient on the 

skin (15). 

Various models have been proposed in 

order to predict the in vivo SPF which are 

based on the Lambert Beer’s Law and 

which take the film irregularities into account. 

In 1983 O’Neill (12) proposed a 

simple model of irregular film, a step film 

geometry, which satisfactorily account 

for the discrepancy between measured in 

vivo data and simple spectroscopic data. 

SÖFW-Journal | 131 | 7-2005 3

SUN CARE 


This purely mathematical model shows 

that the transmission properties of a homogenous 

film decreases significantly 

with increasing film irregularities represented 

by the step film parameters f and 

g and can be calculated as the sum of the 

transmissions through the two fractions 

of the film (Fig. 5). 

Herzog et al. (10,11) refined this simple 

model by correlation of calculated data 

with measured in vivo SPF data and 

hereby defining the parameters f and g 

to be g = 0.269 and f = 0.935. These values 

reflect a considerable roughness of a 

sunscreen film as visualized in Fig. 6. 

Using these parameters they have a 

calibrated tool at their hands, called ‘the 

sunscreen simulator’ (16). This tool allows 

a good prediction of in vivo SPF’s 

for a given roughness of the film and 

in dependency of the UV-filter concentration 

(Table 1, B1-B3). However, this 

method fails in the prediction of the in vivo 

performance for formulations containing 

Polysilicone-15 (Table 1, A1-A3). 

This result is not surprising as Polysilicone-15 

has a comparable low UV specific 

extinction. Nevertheless, there are 

other effects compensating the low UV 

specific extinction which can be explained 

using the same mathematical 

model based on the step film theory. Traditional 

organic UV-filters as well as inorganic 

or organic pigments are concentrated 

on the skin surface after application 

and evaporation of the water phase. 

During this concentration process, traditional 

organic UV-filters tend to aggregate 

(13) as well as pigments tend to agglomerate. 

Due to these reasons, it is difficult 

to distribute the UV-filters evenly 

over the inherently rough skin surface. 

The model proposed by Herzog (16) using 

formulation containing traditional 

UV filters takes these effects into account 

through the choice of the parameters 

f and g. However, this model does 

not consider effects which lead to a more 

even distribution of the UV-light absorbing 

units on the skin which would 

consecutively be reflected in higher values 

for g and lower values for f. 

Through the unique structure of Polysilicone-15 

the aggregation of the chromophoric 

systems is significantly reduced. 

This is the case as the chromophore units 

are hold apart by the dimethylsiloxy- 

Fig. 5 The step film model as introduced by O´Neill (12) 

Fig. 6 The calibrated step film model by Herzog et al (10,11,16) reflecting 

in vivo conditions 

INCI A1 B1 A2 B2 A3 B3 

Polysilicone-15 

Ethylhexyl 

PARSOL® SLX 5 3 3 

Methoxycinnamate 

Butyl Methoxy- 

PARSOL® MCX 5 3 3 

dibenzoymethane 

Phenylbenzimidazol 

PARSOL® 1789 2 2 2.5 2.5 

Sulfonic Acid 

4-Methylbenzylidene 

PARSOL® HS 2 2 2 2 

Campher PARSOL® 5000 3 3 4 4 

Titanium dioxide Uvinul® TiO2 4 4 

Calculated in vivo SPF according to (16) 4 7 14 20 33 44 

Measured in vivo SPF* 10 11 20 21 44 41 

*International Sun Protection Factor (SPF) Test Method, COLIPA, February 2003 

Table 1 The ‘sunscreen simulator’ 

4 SÖFW-Journal | 131 | 7-2005

uilding blocks leading to a defined distance 

between the chromophores. The 

average ratio of the dimethylsiloxy-units 

to the chromophore carrying silicone 

units is about 15 to 1 at an average chain 

length of 64 (Fig. 3). Thus, every chromophore 

unit in Polysilicone-15 contributes 

more effectively to the sun protection 

activity. Furthermore, due to a 

low surface activity which is generally 

found in silicone oils as e.g. described for 

polydimethylsiloxanes in (17,18), Polysilicone-15 

has due to its molecular structure 

excellent spreading and film forming 

abilities. Therefore, polysilicone-15 

is able to smoothen the roughness of 

the film leading to a significantly increased 

protection despite the low UV 

specific extinction. For these reasons, 

Polysilicone-15 at equal concentrations 

compared to EHMC gives similar in vivo 

SPF’s. 

� Polysilicone-15 in combination 

with other UV-filters 

As explained in the beginning, UV-filters 

are normally combined to reach a cost 

effective SPF. The Tables 2 and 3 shows 

the advantages but also limits of Polysili 

cone-15 in combination with other UVfilters. 

All formulations used are basic oil 

in water emulsions and contain the UVAfilter 

Butyl Methoxydibenzoyl Methane 

(BMDBM). An exemplary O/W formulation 

is shown in Table 4. 

Replacement of EHMC by 

Polysilicone-15 

For sun care products, where safety is 

very important and it is desirable to replace 

EHMC by another UVB-filter, Polysilicone-15 

is a potent and safe alternative. 

Table 1 shows the in vivo SPF comparison 

of formulations containing either 

3% EHMC or 3% Polysilicone-15. It 

has been shown, that similar in vivo SPFs 

can be obtained. 

Synergistic effect of Polysilicone-15 

with other UV-filters 

Combinations of Polysilicone-15 with existing 

UV-filters show synergistic effects 

on the in vivo SPF as can be seen in Table 2. 

SUN CARE 


INCI A B C D 

Polysilicone-15 PARSOL® SLX 3 3 

Butyl Methoxydibenzoymethane PARSOL® 1789 2.5 2.5 4 4 

Phenylbenzimidazol Sulfonic Acid PARSOL® HS 2 2 4 4 

4-Methylbenzylidene Campher PARSOL® 5000 4 4 

Titanium dioxide Uvinul® TiO2 3 3 

Measured in vivo SPF* 18 30 38 53 


Table 2 High SPF formulation with polysilicone-15 

INCI A1 B1 

Polysilicone-15 PARSOL® SLX 3 3 

Ethylhexyl Methoxydibenzoymethane PARSOL® MCX 3 

Butyl Methoxydibenzoymethane PARSOL® 1789 2.5 2.5 

Phenylbenzimidazol Sulfonic Acid PARSOL® HS 2 2 

4-Methylbenzylidene Campher PARSOL® 5000 4 4 

Measured in vivo SPF* 30 25 


Table 3 Unfavorable interaction between polysilicone-15 and EHMC 

INCI A B 

Phase A Polysilicone-15 PARSOL® SLX 0 3 

4-Methylbenylidene Camphor PARSOL® 5000 4 4 

Butyl Methoxydibenzoylmethane PARSOL® 1789 2.5 2.5 

Octocrylene PARSOL® 340 2 2 

Hydrogenated Coco-Glycerides 3 3 

Cetearyl Alcohol 2 2 

Caprylic/Capric Triglyceride 21 21 

BHT 0.05 0.05 

preservative qs. qs. 

Potassium Cetyl Phosphate AMPHISOL® K 2 2 

Phase B Aqua qs. qs. 

Titanium Dioxide 6 3 

Butylene Glycol 

Acrylates/C10-30 Alkyl Acrylate 

5 5 

Crosspolymer 0.3 0.3 

Disodium EDTA 0.1 0.1 

Phase C Aqua qs. qs. 

Phenylbenzimidazole Sulfonic Acid PARSOL® HS 2 2 

Tromethamine 2 2 

Table 4 Standard O/W emulsion 

SÖFW-Journal | 131 | 7-2005 5

SUN CARE 


The inclusion of 3% Polysilicone-15 raises 

the SPF from 18 to 30 (A and B) and 

from 38 to 53 (C and D). This data are in 

line with many other experiments where 

it was found, that Polysilicone-15 exerts 

synergistic effects when combined with 

4-Methylbenzylidene Camphor (MBC), 

Phenylbenzimidazol Sulfonic Acid (PBSA) 

(19), Titanium Dioxide (TiO2). A possible explanation for these synergistic 

effects can be found 

1. In the film forming properties of Polysilicone-15 

2. Reduction of the aggregation of the 

traditional UV-filters 

3. Reduction of the agglomeration of 

pigments 

and thus supporting a better distribution 

of traditional UV-filters on the skin surface 

(Fig. 7). 

Thus, Polysilicone-15 can be used to exploit 

more efficiently the UV-absorbing 

potential of the traditional UV-filters. 

Low performance of Polysilicone-15 

in combination with EHMC 

Table 3 shows the unexpectedly low in 

vivo SPF results if EHMC is combined 

with Polysilicone-15. If EHMC is added 

to a standard sun care formulation with 

SPF 30 containing 3.0% Polysilicone-15 

the in vivo SPF decreased to 25. This initially 

surprising result can be caused by 

significant π-π interactions of the aromatic 

chromophoric systems (14). This interactions 

result from the similar structural 

features of the benzalmalonate chromophore 

and the EHMC chromophore 

leading to a energetically favored aggregation. 

As is known and has been discussed 

above, these interactions reduce 

the sun protection activity. Thus, it is not 

recommended to combine Polysilicone- 

15 with EHMC. 

� Further unique characteristics 

of Polysilicone-15 

With the structure of Polysilicone-15 given, 

some unique characteristics are implied 

which can not be found with other 

UV-filters, and which give additional 

benefits for the products and the consumers. 

Improved Sensorial Profile 

Having a polysiloxane backbone in the 

molecule, Polysilicone-15 exerts a silicone-like 

feeling when applied on the 

skin, especially compared to traditional 

mineral UV-filters. This new technology 

UV-filter shows specific advantages in 

the sensorial profile and the reduced 

residual whitening of the skin. To prove 

this advantages two similar sun care formulations 

were created (composition see 

Table 4). Formulation A contained 6% 

TiO 2 . In formulation B 3% of the TiO 2 was 

replaced by 3% Polysilicone-15. Both 

formulation achieved a comparable SPF 

of 27 (A), respectively 28 (B). The replacement 

of TiO 2 by Polysilicone-15 had 

a considerable influence on the sensorial 

profile. The two formulations were analyzed 

at an external test institute where 

12 trained panellists quantified the sen- 

sorial profile of both formulations. Fig. 8 

shows the parameters where the most 

important differences were measured. It 

can be seen that the speed of absorption, 

the coolness, the melting and the ease of 

spreading were almost all significantly 

better for the formulation containing 

Polysilicone-15. The whitening during and 

after spreading was significantly reduced 

when 3% TiO 2 was replaced by 3% Polysilicone-15. 

The formulation containing 

Polysilicone-15 exerts the same protection 

of the skin as TiO 2 , but provides a 

formulation with a much better sensorial 

profile. 

Increased consumer protection 

The same two formulations as described 

above were used for the following consumer 

test at an external test institute: 

Fig. 7 Synergistic effect of Polysilicone-15 in combination with other UV-filter 

Fig. 8 Sensorial test: Comparison of application characteristics of a sun care 

formulation with and without 3% Polysilicone-15 

score 

14 

6 SÖFW-Journal | 131 | 7-2005

15 female volunteers in the age of 19- 

52 years applied during two weeks under 

normal conditions twice daily each 

of the two formulations on either arm. 

At the end of the application period, the 

remaining product was collected and 

the amount of product used was measured. 

This consumer test showed that in 

the average the volunteers used 29% 

more of the formulation, which contained 

Polysilicone-15. This means that 

the consumer is much better protected 

because the amount of sun filter on the 

skin is almost 30% higher if Polysilicone- 

15 is included in the sun care product 

(Fig. 9). 

Photo-stabilisation of BMDBM 

To achieve broadspectrum UV protection, 

Polysilicone-15 and Butyl Methoxydibenzoyl 

Methane are perfect partners. 

BMDBM was the first globally approved 

UVA filter and has been on the market in 

Europe for more than 15 years. However, 

BMDBM needs to be photo-stabilised 

as the molecule itself tends to photodegrade 

upon irradiation. 

Even though every UV-filter, purely by its 

UV-light absorbing properties, stabilizes 

BMDBM to a certain extent, an efficient 

stabilisation can only be achieved by the 

addition of a suitable triplet quencher. 

BMDBM has a triplet energy of 59,5 kcal/ 

mol (20) and hence a suitable quencher 

for BMDBM should have a triplet energy 

in the order of 55-60 kcal/mol. Although 

many organic molecules fulfill this requirement, 

not all have a regulatory status 

allowing their use in cosmetic preparations, 

nor do they have a photostability 

per se sufficient for this purpose. Next 

to 4-Methylbenzylidene Champhor and 

Octocrylene, two well established photostabiliser 

for BMDBM (21,22), Polysilicone-15 

with a triplet energy of 57.9 kJ/ 

mol acts as efficient photostabilisator 

for BMDBM. The chromophoric unit, responsible 

for the triplet quenching properties 

of the Polysilicone-15 has the possibility 

to dissipate the accepted energy 

via an E/Z isomerization. Fig. 10 shows 

the behavior of BMDBM at different concentrations 

of Polysilicone-15. Note that 

the stabilizing effect is not a question of 

a defined ratio as would be expected if 

it were a filter effect. 

SUN CARE 


Outstanding safety profile 

The architecture of Polysilicone-15 ensures 

that the molecule stays on the surface 

of the skin to absorb the harmful 

UVB radiation. Skin penetration studies 

performed under the European SCCNFP 

guidelines and GLP conditions showed 

maximum retention on the skin surface 

(23). Polysilicone-15 alone or in combination 

with other macromolecular sun 

filters (pigments or minerals) form a perfect 

shield against UVB radiation for day 

care products, for sensitive or damaged 

skin, or for products intended for baby 

and children care. 

∆ 

Easy to use 

Being a liquid-mineral UV-filter enables 

Polysilicone-15 to be easily formulated 

into almost any cosmetic product without 

the risk of crystallisation. Furthermore, 

the molecule is stable even at harsh 

conditions up to pH 9. Table 5 shows the 

main properties of Polysilicone-15 which 

are relevant for the formulator when 

handling the product. 

The broad stability and usability of Polysilicone-15 

enables the formulator to 

utilize it in various product forms for different 

applications, such as high SPF sun 

protection products, sun protection and 

Fig. 9 Consumer test: Comparison of amount of product applied between a sun care 

formulations with and without 3% Polysilicone-15 

Fig. 10 Stabilization of BMDBM by Polysilicone-15 in a cosmetic emulsion 

SÖFW-Journal | 131 | 7-2005 7

SUN CARE 


PARSOL® SLX: 

• liquid at all temperature 

• stable in the pH range of 4 - 9 

• stable up to 80°C for 6 hours without any loss on activity 

• compatible with a wide range of organic and inorganic UV filters, common 

emollients and emulsifiers 

• can be formulated into O/W-, W/O- and Si/W-emulsions as well as in translucent 

gels, shampoos or sprays 

• no undesirable effects such as odour, discoloration, etc. 

• approved in Europe at a maximum use concentration of 10% as well as in 

People’s Republic of China, Taiwan, Latin America and selected Asian countries 

Table 5 PARSOL® SLX – robust and easy to use 

daily protection for sensitive and damaged 

skin, baby and children care products 

with safe sun protection or as »technical 

UV-filter« in specific decorative cosmetics 

(e.g. pressed powders). Additionally, Polysilicone-15 

has been shown to have excellent 

hair protecting properties against 

UV radiation as described in (24-26). 

� Conclusion 

Polysilicone-15 (PARSOL® SLX) represents 

a new generation of UV filters coined 

»Liquid-Mineral UV Filter« by DSM Nutritional 

Products, providing optimal distribution 

of the chromophores on the 

skin. It is an ideal complementary UVfilter, 

enhancing SPF values when used 

with other UV-filters in high SPF formulations. 

Polysilicone-15 has excellent skin feel 

and positively influences the sensorial 

characteristics of a sun care product. It 

also enhances the amount of sunscreen 

applied on the skin and provides thus a 

better protection against UV-irradiation 

for the end consumers. 

Because Polysilicone-15 remains on the 

skin surface, it has an outstanding safety 

profile. It is easy to formulate and suitable 

for a broad range of high SPF and 

photo-stable sun care products. 

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Author’s addresses: 

* Katja Berg-Schultz, Christine Mendrok, 

Fintan Sit, Roland Jermann 

DSM Nutritional Products Ltd. 

PO Box 3255 

4002 Basel 

Switzerland 

Correspondence: 

Email: roland.jermann@dsm.com 

8 SÖFW-Journal | 131 | 7-2005 

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