A Diester to Protect Hair from

Color Fade and Sun Damage

Timothy Gao, PhD, Jung-Mei Tien, Abhijit Bidaye, Scott Cardinali and Jena Kinney
Croda Inc., Edison, N.J., USA
L
ike skin, hair is susceptible to
damage from exposure to the sun.
This damage affects its aesthetics and
mechanical and physical properties,
resulting in dull, flat hair. Research
indicates that both UVA and UVB
radiation are responsible for this dam-
age. Hoting,
1
for example, studied hair
tresses dyed red by exposing them to
UVA and UVB radiation, finding that
the tresses underwent more fading
after UVA irradiation. Artificial hair
color based on pyrazole intermediates
also has shown significant fading after
shampoo washing and UV exposure.
2
Hoting thus concluded that expo-
sure to UVA radiation resulted in a
significant and perceivable change
in the dyed red hair color. Accord-
ing to his research, the red pigment
introduced into the hair fiber by the
dyeing process acts as a photoreceptor,
absorbing photons and photochemi-
cally degrading after UVA and visible
light irradiation.
The effects of UVB radiation on
hair also can be severe, resulting in
the breakdown of disulfide bonds
both inside the hair fiber and on the
surface of the cuticle.
3
Such disrup-
tions to the disulfide linkages of the
hair fiber can have a major impact on
hairs mechanical properties, resulting
in the loss of tensile strength and an
increase in porosity and irregularities
on the hair surface.
To protect hair from UV damage,
UV filters deposited on the hair
surface absorb incident UV light.
KEY WORDS: diester, colorfade, tryptophan degradation, hair ber
integrity, broad-spectrum UV lter
ABSTRACT: A new broad-spectrum UV lter to protect hair from
color fading and integrity damage, quaternium-
95 (and) propanediol, has been developed for
rinse-off formulations. Shampoos and conditioners
containing this material protected dyed hair against
surface tryptophan degradation and tensile strength
reduction.
As noted, since both UVA and UVB
radiation cause severe and perceiv-
able damage, broad-spectrum UV
absorbers provide the best protection
from fading and sun damage. In
addition to broad spectrum cover-
age, deposition and absorption onto
the hair surface are crucial factors to
consider when designing materials
for rinse-off systems.
In the present article, the authors
introduce a quaternized diester
a

designed to provide broad-spectrum
protection to hair in rinse-of systems.
An absorption spectrum of the diester
solution (20.0 mg/L active in SDA-40),
shown in Figure 1, ranges from the
UVB region (280320 nm) to the UVA
region (320400 nm). Te absorption
peak, located at 310 nm, falls within the
UVA region, thus researchers concluded
the material should provide effica-
cious color protection for dyed hair.
Additional studies (data not shown)
examined the materials stability afer
fve days of UV exposure, showing no
change in absorbance or net weight for
the diester.
Thus, further studies were war-
ranted to examine its ability to protect
hair fbers from cuticle damage and
reduced tensile strength resulting
from degradation of tryptophan and
proteins on the hair surface and inside
Articial hair color based
on pyrazole intermediates
has shown signicant
fading after shampoo
washing and UV exposure.
a
ChromAveil (INCI: Quaternium-95 (and)
Propanediol) is a product of Croda Inc.
b
Te Atlas Ci300+ Xenon Weather-Ometer is
a product of Atlas Material Testing Solutions,
International Hair Importers
1796.indd 1 7/2/09 3:11:42 PM
the hair fber. Te ability of the diester
to protect hair from colorfade in the
presence of UV radiation also was
examined.
Materials and Methods
Various protocols were used to
evaluate the diesters ability to protect
hair fibers from UV damage. Bleached
European brown hair tresses were
dyed with either a commercially
available medium brown hair color
or medium auburn color for 30 min
following the instructions provided
in color kits. For testing of UVB
damage, virgin dark brown hair
was used. Some tresses were treated
with control and diester-containing
shampoos and conditioners (see
Formulas 1 and 2). A subset of treated
tresses were then irradiated
b
for
3 hr on each side, totaling 6 hr-
equivalent to one day of UV exposure
4
-
with UV radiation (200400 nm) at
50 W/m
1
using a quartz inner filter
and type s borosilicate outer filter. At
the start of the study and at intervals
equivalent to every five days of UV
exposure-e.g., after every 30 hrs-
tresses were treated again with control
and diester-containing shampoos and
conditioners. Irradiated tresses were
exposed to the total equivalent of 15
days of UV exposure. Test conditions
were maintained at 40C and 65%
relative humidity.
Different types of tresses were
compared, including those that were
dyed and not exposed to treatment
or UV exposure; dyed and treated
with the control shampoos and
conditioners and exposed to UV; and
dyed and treated with shampoos and
conditioners containing the diester
and exposed to UV. Comparative
col or l oss was determined both
objectively and subjectively. The
total color loss (E) was calculated
by assessing the changes in L*, a*,
b* readings on the treated tresses
using a spectrocolorimeter
c
. The
equation used to calculate the total
color loss was:
E = [(L)
2
+ (a)
2
+ (b)
2
]
1/2
Figure 1. Absorption spectrum of the diester solution
c
LabScan XE Spectrocolorimeter is a product of
HunterLab.
d
Spex FluoroLog-3 is a instrument manufactured
by Horiba Jobin Yvon.
e
Miniature Tensile Tester (MTT) 670 is a product
of Dia-Stron Ltd.
Formula 1. Shampoo test formulations
Ingredient Control Diester Shampoo
Sodium laureth sulfate 35.00% w/w 35.00% w/w
Cocamidopropyl betaine 10.00 10.00
Quaternium-95 (and) propanediol, 75%
active (ChromaVeil, Croda) --- 2.00
PEG-150 pentaerythrityl tetrastearate
(and) PEG-6 caprylic/capric glycerides
(and) water (aqua) --- 2.80
Water (aqua) 55.00 50.20
100.00 100.00
Table 2. Conditioner test formulations
Ingredient Control Diester
Conditioner Conditioner
Quaternium-91 (and) cetrimonium
methosulfate (and) cetearyl alcohol 2.14% w/w 2.14% w/w
Cetearyl alcohol 3.86 3.86
Quaternium-95 (and) Propanediol, 75% active
(ChromaVeil, Croda) --- 2.00
Phenoxyethanol (and) methylparaben
(and) ethylparaben (and) butylparaben
(and) propylparaben (and)
isobutylparaben (Phenonip, Clariant) 1.00 1.00
Water (aqua) 93.00 91.00
100.00 100.00
UVB can break down
disulde bonds inside
the hair ber and on the
surface of the cuticle.
1796.indd 2 7/2/09 3:11:43 PM
using a spectrofluorometer
d
. The
excitation wavelength was set at
295 nm and the tryptophan emis-
sion intensity was measured at
340 nm. Te emission intensity was
assumed to be directly proportional to
the surface tryptophan concentration.
Using surface tryptophan intensities
of the hair sample before UV exposure
as the baseline, the tryptophan protec-
tion factors of hair samples treated
with diester shampoo or the control
shampoo afer UV exposure can be
calculated using the equation:
F (Tr) = [I
f
/ I
o
] X 100%
In this equation, F(Tr) is the trypto-
phan protection factor, calculated as a
percentage; I
f
is the surface tryptophan
fuorescence intensity of the hair sample
afer UV exposure; and I
o
is the surface
tryptophan fuorescence intensity of the
same hair sample before UV exposure.
UVB rays not only decompose the sur-
face tryptophan but also penetrate the hair
cuticle and cause damage inside the cor-
tex. Tis damage afects hairs mechanical
properties and can be measured in terms
of its tensile strength (stress-to-break).
Using a tensile tester
e
, the tensile strength
of single fbers from the treated tresses was
measured before and afer UV exposure.
To test the ability of the diester
to protect hair fibers in rinse-off
systems, a shampoo and conditioner
were formulated with and without
the diester (see Formulas 1 and 2).
UV Protection with Diester
UVA protection in shampoo:
Auburn-colored tresses were treated
with the control and diester shampoo
and exposed to 15 equivalent days
of UV exposure (see Figure 2). The
treated tresses were visually compared
Te changes in hair color indexes
were calculated using the respective val-
ues afer the shampoo and conditioner
treatments and before UV exposure;
and after the equivalent of 15 days
of UV exposure. The results of the
instrumental evaluations were con-
firmed via subjective testing. The
swatches were photographed and com-
pared to dyed but untreated swatches,
which represent the initial dye color, to
allow for visual comparisons. Panelists
were also asked to rate the color protec-
tion efects in simple comparisons of the
control and the diester swatches to the
Figure 2. Effects of the diester vs. control shampoo on medium auburn hair
untreated control.
To determine the amount of damage
on the hair fber due to the UVB irradia-
tion, several parameters of the hair fber
were measured. As noted, UV exposure
to hair can break down the disulfde
bonds in the hair fber. Tryptophan
is a key amino acid found on the hair
surface and it decomposes under UVB
irradiation.
2

Surface tryptophan degradation
is thus an indicator of damage to
the disulfide bonds and it can be
quantifed through comparative fuo-
rescence intensities of hair tresses
The addition of the
diester into the shampoo
improved the protection
against degradation of
amino acids in the hair
ber.
Figure 3. Total color changes of medium auburn-colored hair treated with different
shampoos after 15 days of UV exposure
1796.indd 3 7/2/09 3:11:49 PM
to one another and to a dyed tress that
was not exposed to UV irradiation
(Figure 2a). The tresses treated with
the control shampoo (Figure 2b-c)
lost a significant amount of color
while the hair tresses washed with
the shampoo containing the diester
(Figure 2d-e) showed less color fade.
The total color loss (E) of the
tresses treated with the shampoos
was also assessed after 15 days of UV
exposure. Tresses that demonstrated
better color protection had a smaller
E. The quantitative color loss data
confirms what the visual assessment
illustratesthat the shampoo con-
taining the diester had a significantly
smaller E, and the diester-treated
tress maintained more color. The
diester thus demonstrates col or
Figure 5. Total color change of medium brown-colored hair treated with different
shampoos after 15 days of UV exposure
Figure 4. Effects of the diester vs. control shampoo on medium
brown hair
Tryptophan is a key
amino acid found
on the hair surface,
and it decomposes
under UVB irradiation.
Figure 6. Effects of the diester vs. control conditioner for
medium auburn color
protection with a E of 10.5, com-
pared to the control shampoo with
a E of 12.4, a difference of almost
2 units (see Figure 3).
To confirm the correlation between
visual inspection of images, color
index measurement and consumer
perception, 17 panelists selected
the tresses they thought had the
most and least change in color after
tresses were exposed to 15 days
of UV. Subjective evaluation results
indicated that 100% of the panelists
perceived that the diester shampoo
gave superior color protection on the
medium auburn treated hair (data
not shown).
A similar study was performed with
the shampoos on hair dyed with medium
brown color. Te tresses shown in Figure
4 were treated with the control and
diester shampoo. Hair tresses washed
with the diester shampoo (Figure 4e-f)
showed less colorfade than the control
shampoo (Figure 4c-d). Te lef two
tresses were dyed and not exposed to UV
(Figure 4a-b), to serve as a reference.
Figure 5 shows the quantitative E
total color changes of hair tresses col-
ored medium brown that were treated
with both shampoos and exposed to
15 days of UV exposure. Hair tresses
treated with the diester shampoo
showed less total color change, almost
3 units, than the control shampoo, indi-
cating the diester shampoo provided
better color protection.
Again, the panel evaluation dem-
onstrated a strong correlation between
the visual results and the instrumental
results. On medium brown hair, 94.1%
of panelists chose the tresses treated
with the diester shampoo as having
retained the most color.
UVA protection from a conditioner:
Another set of auburn-colored
tresses was treated with a rinse-off
conditioner containing the diester
1796.indd 4 7/2/09 3:11:59 PM
(Formula 2) and the same conditioner
without the UV flter to serve as a control.
Figure 6 shows that hair tresses washed
with the diester conditioner (Figure 6d-e)
showed less colorfade on auburn-colored
hair than the control conditioner (Figure
6b-c). Te lef tress was dyed but not
exposed to UV radiation (Figure 6a) to
serve as a reference.
Although not as definitive as the
shampoo studies, 64.7% of the panelists
preferred the diester conditioner on
auburn-colored hair.
UVB protection from a shampoo: To
assess for surface tryptophan damage, the
surface fuorescence intensities of virgin
brown tresses treated with either the
control or diester shampoo were deter-
mined afer 15 equivalent days of UV
irradiation (see Figure 7) and compared
to the fuorescence intensities of the hair
before UV exposure.
The shampoo containing the diester
showed 97.48% tryptophan protec-
tion after the 15 equivalent days of
exposure, while the control shampoo
showed 91.42% tryptophan protec-
tion. The addition of the diester to
the shampoo improved the protection
against degradation of amino acids
in the hair fiber. The tryptophan
degradation testing was not performed
on the conditioner series; however,
researchers anticipate similar results
would be seen.
Testing UVB Protection
with Tensile Strength
Fibers showing a decrease in stress-
to-break forces afer UV exposure have
undergone a loss in mechanical strength
primarily due to the breaking of disulfde
bonds inside the hair cortex. A com-
parison of the tensile strength of virgin
brown hair treated with the diester sham-
poo was made to hair similarly treated
Diester delivered from the
conditioner also provided
protection against the
damage to ber integrity.
Figure 7. Change in tryptophan intensity after UV exposure and treatment with diester
shampoo
Figure 8. Change in tensile strength after UV exposure and treatment with shampoos
Figure 9. Change in tensile strength after UV exposure and treatment with
conditioners
With Croda products, you can reverse the damage from styling,
perming, straightening or coloring as well as protect your
tresses from further insult. Leave your bad hair days behind
and always look like you just left the salon...

Softer, more manageable hair
CRODAZOSOFT

SCQ,
CRODAZOSOFT

DBQ,
INCROQUAT

BEHENYL TMS-50
Strong, healthy tresses KERAVIS

Moisture management CROPEPTIDE

W
Brilliant shine CRODAMOL

STS
Smooth surface with a no frizz nish
CRODABOND

CSA, LUSTREPLEX

Replenishment of essential lipids

INCROQUAT

18-MEA-40,
INCROQUAT

BEHENYL 18-MEA
For samples, data and other hair enhancing ideas
contect your Croda rep or visit crodausa.com
with Croda
Innovation you can build on

Every day is a great hair day

North America email:marketing@crodausa.com www.crodausa.com
Latin America email:marketing@croda.com.br www.croda.com/br
Europe, Middle East & Africa email:pc-europe@croda.com www.croda.com/europe
Asia Pacic email:sales@croda.com.sg www.croda.com/asia
Croda.5p_GCI_CondR.indd 1 7/1/09 4:19 PM
1796.indd 5 7/2/09 3:12:01 PM
with the control rinse-of product. Note
that disulfde bonds inside the cortex
have been broken in the tresses treated
with the control shampoo, while
tresses treated with the diester have no
disulfde bond breakage (see Figure 8).
Te diester shampoo protected the hair
from UVB damage and preserved the
hairs natural strength.
Using the same methodology, virgin
brown hair tresses were treated with
the control and diester conditioner,
respectively, for tensile strength mea-
surements. Te diester conditioner also
provided protection against damage to
the fber (see Figure 9).
Conclusions
While protection of hair from the
sun is not a new concept, technology
continues to improve to ofer consum-
ers better protection as part of their
daily regimen. As shown, the diester
is substantive to the hair and ofers
broad-spectrum protection in rinse-of
systems. Although the diester has not
yet been tested in leave-in systems, the
authors expect the diester to provide
good hair protection.
The addition of the diester in
wash-off systems provides protec-
tion against UVA-induced colorfade
as well as protection from UVB-
induced disulfide bond breakage that
manifests as a loss of hair strength.
The diester also protects from the
degradation of amino acids on the
hair surface. This broad-spectrum
protect i on gives consumers t he
freedom to enjoy the sun without
the concern for hair damage. In
addition, it offers protection for arti-
ficial hair color and fiber integrity.
Acknowledgments: Te authors would like
to acknowledge Marni Dexter, Sety Britton
and Abel Pereira for their hard work and
contributions to this project.

References:
Send e-mails to t.gao@crodausa.com
1. E Hoting, Sunlight-induced modications in
bleached, permed, or dyed human hair, J Soc
Cosmet Chem, 48 7991 (Mar/Apr 1997)
2. B Locke and J Jachowicz, Fading of articial
hair color and its prevention by photolters,
J Cosmet Sci, 56 407425 (2005)
3. T Gao and A Bedell, UV damage on natural
gray hair and its photoprotection, J Soc Cos-
met Chem, 52 103118 (Mar/Apr 2001)
4. M Jeanmougin and J Civatte, Dosimetrtrie du
rayonnement UV solaire, Ann Dermatol Ven-
erol, 114 671676 (1987)
Reprinted from May 2009 Cosmetics & Toiletries magazine, Vol. 124, No. 5, p. 70-78. www.cosmeticsandtoiletries.com.
Cosmetics & Toiletries magazine. All rights reserved. Foster Printing Service: 866-879-9144, www.marketingreprints.com.
With Croda products, you can reverse the damage from styling,
perming, straightening or coloring as well as protect your
tresses from further insult. Leave your bad hair days behind
and always look like you just left the salon...

Softer, more manageable hair
CRODAZOSOFT

SCQ,
CRODAZOSOFT

DBQ,
INCROQUAT

BEHENYL TMS-50
Strong, healthy tresses KERAVIS

Moisture management CROPEPTIDE

W
Brilliant shine CRODAMOL

STS
Smooth surface with a no frizz nish
CRODABOND

CSA, LUSTREPLEX

Replenishment of essential lipids

INCROQUAT

18-MEA-40,
INCROQUAT

BEHENYL 18-MEA
For samples, data and other hair enhancing ideas
contect your Croda rep or visit crodausa.com
with Croda
Innovation you can build on

Every day is a great hair day

North America email:marketing@crodausa.com www.crodausa.com
Latin America email:marketing@croda.com.br www.croda.com/br
Europe, Middle East & Africa email:pc-europe@croda.com www.croda.com/europe
Asia Pacic email:sales@croda.com.sg www.croda.com/asia
Croda.5p_GCI_CondR.indd 1 7/1/09 4:19 PM
1796.indd 6 7/2/09 3:12:02 PM