International Journal of Cosmetic Science, 2002, 24, 117^122

UV protection of artificially coloured hair using a

leave-on formulation
Ph. Maillan
Cosmetic Research, RocheVitamins Ltd, Basel, Switzerland

Received12 October 2001, Accepted 27 November 2001

Keywords: articial hair colour protection, ethylhexyl methoxycinnamate, hair weathering, polysiloxane UV-B
lter

Synopsis
The present article describes the use of a polymeric
organosiloxane sunscreen (SLX), to protect the articial colour of human hair upon simulated solar radiation. The cosmetic vehicle used to treat the coloured
hair is a leave-on formula. It has been found that the
semi-permanent and permanent colours can both
be degraded when exposed to simulated sunlight.
The ecacy of SLX to protect the articial colours
was compared to ethylhexyl methoxycinnamate
(EHMC), the most often used UV lter in marketed
sun sprays. SLX (1^5%) was more eective than
EHMC (1^5%) to protect the articially coloured hair,
especially by protecting the lightness of the hair.
Resume
Le present article decrit lutilisation dun ecran solaire
de type organosiloxane polymerique (SLX), pour proteger la coloration articielle des cheveux humains
face a' un rayonnement solaire simule. Le vecteur
cosmetique utilise pour traiter les cheveux colores
est une formule sans rincage. On observe que les colorations permanentes et semi-permanentes sont
toutes deux susceptibles detre degradees lorsquelles
sont exposees a' la lumie're solaire simulee. Lecacite
de la SLX pour proteger les colorations articielles
a ete comparee au methoxycinnamate dethylhexyle

Correspondence: Ph. Maillan, Cosmetic Research, Roche

Vitamins Ltd, CH-4070, Basel, Switzerland. E-mail:
philippe.maillan@roche.com
This work was presented at the SCS Meeting in Chepstow
Hair care ^ Beyond the fringe March 2001.

2002 Blackwell Science Ltd

(EHMC), le ltre anti-UV le plus couramment utilise

dans les sprays solaires commercialises. LaSLX (1a'
5 %) est plus ecace que le EHMC (1a' 5 %) pour proteger les cheveux colores articiellement, en particulier pour la protection de leclat de la chevelure.
Introduction
The fact that solar radiation can aect the appearance of hair is becoming more and more conscious
to the mind of cosmetic consumers. In response to
this, cosmetic products are tending to be more than
just a concept in trying to protect the hair from those
photo-induced changes. Contrary to the skin, the
hair will not send a message of pain owing to the
overexposure telling that a change is occurring. The
message is more likely to come after cumulating solar
radiation over several weeks. The hair will noticeably
be less manageable, weaker, more brittle and will
have developed more split ends [1]. This loss in manageability will also be accelerated through the frequent wash-and-dry cycle, typical during the
summer activities.
The natural colour of the hair will also be aected
and this change will be most visible for naturally
blonde and light-brown hair [2].The resulting bleaching is often unevenly distributed especially for long
hair and can be considered as unattractive. The
change in manageability will also be more perceptible for long hair, as the hair will show poor combability and more split ends [3], something which is
undesirable. Hair damage resulting from weathering
can be evaluated using numerous techniques, such
as tensile testing [4^6], analysis of proteins, melanin
and lipids [7^10] and image analysis (i.e. scanning

117

UV protection of articially coloured hair using a leave-on formulation

electron microscopy) [11]. Experiments to assess the

colour stability of natural or dyed hair upon weathering can be made using colour measurements (i.e.
with a L
a
b Colormeter) [6, 12]. This type of analysis
is relatively quickly and easily carried out.
In the present paper, we veried that the hair colour resulting from a cosmetic treatment (articial
colour) is also sensitive to sun exposure. Changing
the colour of the hair has gained popularity and
is no longer an exclusive hair-salon activity. Most
colouring products are nowadays formulated to
guarantee user-friendliness at home. The younger
population enjoys using semi-permanent dyes,
whereas the older one is more dedicated to permanent hair colour changes. The permanent hair-colour change activity is bound to grow as the
population is getting older and also because hair
appearance is a growing concern for the male population. As a consequence, there is a need to have cosmetic products that will protect the articial or
natural colour of the hair during the summer holidays and to a lesser extent all year long. Yet, a few
questions arise: are all lters equal in terms of hair
colour protection? Is there a UV lter really capable
of protecting the colour of the hair in a cosmetically
acceptable way?

Achieving real colour protection

Most products on the market today, which contain a
UV lter for hair care are formulated with ethylhexyl
methoxycinnamate (EHMC). These products are
mostly leave-ons like gels or sprays. We believe that
real colour protection will be achieved best using a
leave-on formula, much better than with a formula
which has to be rinsed o the hair. EHMC is an economically attractive lter and easy to formulate. We
have found sun sprays on the market containing as
much as 8% EHMC. Colour protection should also be
achieved in a cosmetically acceptable way, which
means that the ideal lter should be liquid (will not
re-crystallize after the spray has dried), photostable
and safe for the scalp and skin.
The latest UV lter developed and registered which
meets these needs is presented in Fig. 1. This polymeric lter has as a polysiloxane backbone to which
UV-B absorbing chromophores are attached. This
new generation UV-B lter (referred to as SLX) possesses a unique safety prole, essentially owing to
the large size of the molecule.
The specications listed in Table I and the UV
absorption curve in Fig. 2 indicate that SLX is a UV-B

118

Ph. Maillan

Figure 1 Structure of the polysiloxane UV-B lter (SLX).

Table I Specications of SLX

Specifications
Appearance
Specific extinction E (1%, 1 cm)
lmax
Specific gravity

Clear, pale yellow, liquid

160190
310314 nm in ethanol
1.0151.045

lter. Owing to its silicone backbone, SLX also oers

conditioning and good spreadability over the hair
bre.

Goals of the study

We performed a study to clarify two points:
 The colour of articially coloured hair can be
degraded when exposed to simulated solar radiation.
 How does SLX perform in comparison to ethylhexyl methoxycinnamate, the most widely used lter for Hair Sun Sprays, in terms of colour
protection?
Materials and methods
Cosmetic ingredients: the polysiloxane lter SLX (trade
name: Parsol SLX) and ethylhexyl methoxycinnamate (trade name: Parsol MCX) were obtained from
Roche Vitamins (Basel, Switzerland). Cyclomethi-

2002 International Journal of Cosmetic Science, 24, 117^122

UV protection of articially coloured hair using a leave-on formulation

Ph. Maillan

Figure 2 UV absorption of SLX in

ethanol.

cone (trade name: DC 245 Fluid), dimethicone (trade

name: DC 200 Fluid 350 cSt) and hexamethyldisiloxane (trade name: DC 200 Fluid 0.65 cSt) were
obtained from Dow Corning (Brussels, Belgium).
Ethanol was obtained from Merck (Darmstadt,
Germany).
Hair: we used bleached blond hair swatches from
Fischbar & Muller, Laupheim, Germany. The
swatches are at, weigh 1 g, and are 10 cm long.
We washed all hair swatches with a commercial
shampoo prior to dyeing.
Dyeing the hair: we carried a rst trial with a semipermanent dye from Warner & Jenkinson (A rianor
type). This dye was used as a 0.5% solution in water
to dye the hair. A second trial was carried out using
a permanent colour by dyeing the hair with a commercial dyeing kit from Garnier. In both cases,30 hair
tresses were simultaneously dyed and allowed to dry
in ambient conditions.
Semi-permanent dyeing: the hair swatches were
immersed for 10 min in the dye solution and then
rinsed under running water until no more colour
could be rinsed out.
Permanent dyeing: the hair swatches were treated
as follows: The colouring cream was obtained by following the instructions given in the kit except that
the conditioning oil was not added.The hair swatches
were coloured (25 min) and rinsed under running
water until no more colour could be rinsed out. The
hair swatches were then washed with a neutralizing
shampoo.
Treating the hair with the spray: the coloured tress
was immersed in 20 g of the spray in a glass cylinder
and the cylinder was shaken for 1 min. The tresses
were then removed, suspended for 2 min, combed 10
times from root to end in a downward motion to
remove the excess solution, and allowed to dry in
ambient conditions.
Irradiating the coloured hair: we used a solar simulator (Heraeus Suntest CPS) to irradiate the coloured

2002 International Journal of Cosmetic Science, 24, 117^122

hair tresses. The tresses were disposed on a cardboard plate and aluminium foil was used to create
windows. The tresses were irradiated on one side
under the following conditions:
 Irradiance (300^400 nm) 6.5 mW cm2;
 Irradiation time140 h;
 Temperature 45 8C; and
 Relative humidity 15%.
These conditions are comparable to conditions
described elsewhere in the literature [11].
Measuring colour changes on the tress: we used a Colormeter (Minolta CR-300) to measure the colour of
the tress using the CIE L
a
b measuring system. The
parameters listed below can be used to quantify virtually any colour: L: lightness (high L-values for high
lightness) a: the red/green nuance axis (a: red colours, a: green colours) b: the yellow/blue nuance
axis (b: yellow colours, b: blue colours) Initial
values were obtained when the hair had been
coloured and treated with the leave-on formula.
These values are described as L0, a0, b0: Final values
were obtained after the hair had been irradiated.
These values are described as L, a, b. We decided to
look separately at the change in lightness and the
chromatic change which occurred owing to the irradiation.
The change in lightness (DL), the chromatic
change (DC) and in some cases the dierence in the
yellow nuance (Db) were calculated using the following formulas:

L L  L0

C a  a0 2 b  b0 2
1=2

b b  b0

Results
We dened a perimeter (middle of the tress) in
which we repeatedly measured the colour of the

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UV protection of articially coloured hair using a leave-on formulation

Ph. Maillan
Table II Leave-on formulas

EHMC (%)
SLX (%)
Ethanol (%)
Cyclomethicone (%)
Dimethicone (%)

Placebo

EHMC 1%

EHMC 5%

SLX 5%

30
65
5
100

30
65
4
100

30
65

100

5
30
65

100

tress (6^10 times) to obtain mean values for the L, a

and b parameters. The uncertainty of the results
are calculated on the 95% probability that each
mean values of L, a, b are contained in the condence interval (CI) (P 95%, n 6^10, Students
distribution).

Semi-permanent colour protection

Spray formulation: the leave-on formula used to treat
the hair tresses before irradiation are given in
Table II.This type of formula could be used for a shine
spray.
The placebo hair tress showed a signicant degradation in colour and lightness after the irradiation
as shown in Fig. 3. In the same conditions, the tress
treated with EHMC showed no protection compared
to placebo, in protecting the lightness or the colour
of the semi-permanent hair dye. These observations
are also supported by L
a
b measurements shown in
Fig. 4. A signicant yellowing was even observed
when using 5% EHMC as shown by the Db-value.
SLX signicantly protected the lightness of the hair
compared to placebo and to a lesser extent also protected the colour of the hair. No yellowing of the tress
was observed.

Permanent colour protection

Spray formulation: the leave-on formula used to
treat the hair tresses before irradiation are given in
Table III. This type of formula could be used for a
shine spray.

The placebo hair tress showed a signicant degradation in colour and lightness after the irradiation
as shown in Fig. 5. These observations are also supported by L
a
b measurements shown in Fig. 6.
EHMC showed some potential compared to placebo
in protecting the lightness and the colour of this permanent hair dye. In this case, no signicant yellowing was observed with EHMC. However, SLX was
here superior to EHMC in protecting the lightness of
the hair whereas the colour protection was comparable to the one obtained with EHMC.
Discussion
We only tested two colours (one semi-permanent
and one permanent) and evaluated the colour protection by comparing two UV-B lters. The combination
of SLX with a UV-A lter would make sense to optimize the colour protection upon simulated solar
radiation.
The semi-permanent colour was only tested with
5% SLX whereas the permanent colour was tested
with 1% SLX. Further work is presently carried out
to get results for both types of colour with dierent
SLX concentrations. The inuence of humidity was
not looked at, and we expect that irradiation at higher
humidity could accelerate colour degradation. The
hair was not washed between the colour measurements.
It was also of interest to determine the amount of
sun lter deposited on the hair when treating the
tresses with the leave-on. This quantity was determined by sonicating the hair tresses in an appropriTable III Leave-on formulae

EHMC (%)
SLX (%)
Ethanol (%)
Hexamethyldisiloxane (%)

120

Placebo

EHMC 1%

EHMC 5%

SLX 1%

72
28
100

71
28
100

67
28
100

1
71
28
100

2002 International Journal of Cosmetic Science, 24, 117^122

UV protection of articially coloured hair using a leave-on formulation

Ph. Maillan

Figure 3 Hair tresses coloured with

a semipermanent colour. Results after
irradiation.

Figure 4 L
a
b changes after irradiation (semipermanent

colour: Arianor Sienna Brown).

Figure 6 L
a
b changes after irradiation (permanent colour kit from Garnier: dark blue).

Figure 5 Hair tresses coloured with

a permanent colour. Results after irradiation.

2002 International Journal of Cosmetic Science, 24, 117^122

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UV protection of articially coloured hair using a leave-on formulation

Table IV Sunscreen deposition on the hair tress

Percentage of
UV-filter used in the
leave-on formula

Amount of filter deposited

(mg g1 of hair)

1
5

3.54.0
17.620.5

ate solvent followed by HPLC analysis. The amount of

lter on the hair (expressed in mg g1) is given in
Table IV. This deposition would correspond to applying 0.4 g of a protective leave-on to1 g of hair.
The conditions to which the hair tresses were
exposed are quite harsh. In fact, the irradiance of 6.5
mW cm2 roughlycorresponds to the irradiance which
is found in Miami, Florida (noon, summer season, clear
sky). This means that the dose cumulated over144 h in
the sun simulator would approximately correspond to
4 weeks of exposure in Florida (6 h day1, centred
around noon, summertime, clear sky).
We are aware that the conditions used in the present study dier from the real-life conditions. On the
other hand, our experimental protocol enabled us to
clearly evaluate and compare the potential of the
two lters in terms of colour protection. Some of the
remarks above are considered for further experiments in this eld.
Conclusion
In the described conditions, it has been found that the
polysiloxane lter SLX is superior to EHMC in protecting the colour and especially the lightness of the
articially coloured hair upon simulated solar irradiation. SLX being a liquid, is also easy to formulate
and oers superior spreadability over the hair bre
owing to its silicone backbone as well as inherent

122

Ph. Maillan

conditioning. All these advantages make SLX an

ideal candidate for its use in protecting the hair
against UV-induced photodamages.
References
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Cosm.Toil.107,95^102 (1992).
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2002 International Journal of Cosmetic Science, 24, 117^122