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Journal of Cleaner Production 43 (2013) 20e26

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Journal of Cleaner Production


journal homepage: www.elsevier.com/locate/jclepro

Vanillin, a potential carrier for low temperature dyeing of polyester


fabrics
V. Pasquet a, b, A. Perwuelz a, b, N. Behary a, b, *, J. Isaad a, b
a
b

ENSAIT-GEMTEX: ENSAIT, GEMTEX, Roubaix, France


Univ Lille Nord de France, USTL, F-59655 Villeneuve dAscq Cedex, France

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 10 April 2012
Received in revised form
10 December 2012
Accepted 12 December 2012
Available online 11 January 2013

The potential use of vanillin for the chemical substitution of toxic carriers used in low temperature
dyeing of polyester fabrics, was assessed. Both para and ortho-vanillin were used to compare the dyeing
of a woven polyester fabric with two different blue disperse dyes: a high molecular weight anthraquinone dye D79 and a low molecular weight azoic dye D56. When 1 g of vanillin was used for dyeing with 3%
of disperse dye, the dye uptakes increased for both vanillins, but were higher with ortho-vanillin
especially in the case of the low molecular weight dye. The impact of different dyeing parameters
such as pH, o-vanillin concentration and use of ethanol co-solvent, on the dye uptake was also studied.
Highest dye uptake was reached with 2 g of ortho-vanillin at pH 7, without use of the co-solvent.
Dye uptakes were compared to those of traditional carriers such as phenylphenol, dichlorobenzene,
benzoic acid, and a commercial Levegal DTE carrier. With 2 g of vanillin, K/S of dyed fabric reached 16,
which is equivalent to that obtained with 1 g of the commercial carrier. The study conrms that vanillin
can be used as a chemical substitute to traditional carriers and leads to good wash and rub fastness
properties.
At present, few literature data are available to compare toxicity of all carriers and apply the principle of
substitution. A toxicity analysis carried out using USEtox model showed that both para and ortho
vanillins used in agro-food industries are not recognized as toxic for human health, unlike most traditional carriers. Ortho-vanillin has however high ecotoxicity.
2013 Elsevier Ltd. All rights reserved.

Keywords:
Chemical substitution
Dyeing
Polyester
Carrier
Vanillin

1. Introduction
Environmental issues are being increasingly taken into account
in textile dyeing and nishing industries because of strict legislations and a growing ecological concern. Main environmental impacts of textile dyeing & nishing industries involve high water
consumption, high energy use and also input of a wide range of
chemicals (dyes, surfactants, carriers, etc.). Some of these chemicals
are hazardous for both human health and environment. In the last
few years, researchers working in the eld of wet textile processing
are trying to implement natural and safer molecules, in line with
the principles of a more eco-friendly chemistry (Szente et al., 1998;
Vankar et al., 2006; Montoneri et al., 2008). Meanwhile, the Substitution Principle based on hazard assessments appear to justify
the use of safer chemical alternatives (Thorpe and Rossi, 2007;

* Corresponding author. Ecole Nationale Suprieure des Arts et Industrie Textiles


(ENSAIT), Laboratoire de Gnie et Matriaux Textiles (GEMTEX), 2, alle Louise et
Victor Champier, BP 30329, 59056 Roubaix Cedex 01, France. Tel.: 33 3 20 25 75
64; fax: 33 3 20 24 84 06.
E-mail address: nmassika.behary@ensait.fr (N. Behary).
0959-6526/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jclepro.2012.12.032

Ozturk et al., 2009; Lavoie et al., 2010; Hansonn et al., 2011). The
purpose of our study was to assess the feasibility of substituting
toxic molecules called carriers used for dyeing of polyester fabrics
by vanillin which is an agro-sourced product.
In 2009, global production of polyester bres reached 31.9
million tonnes; about 45% of worldwide ber production (Oerlikon,
2010). Polyester (polyethylene terephtalate (PET)) bers have
a growing importance, and are mainly used in clothing, geotextile
and automotive industries. PET has excellent tensile strength and
chemical resistance. However as PET is hydrophobic and has no
chemically active groups, its dyeing in aqueous conditions is quite
difcult. Dyeing is achieved with disperse dyes having good diffusivity and solubility in PET ber. Moreover, the highly crystalline
structure of PET ber slows down the rate of dye diffusion into the
ber (Trotman, 1970; Cegarra and Puente, 1967; Carrion, 1995).
Dyeing of polyester fabrics can be achieved using three different
methods depending on the quantity of fabrics to be dyed (Dupont,
2002; Dewez, 2008). Thermosol process used for continuous
dyeing of thousands of meters of polyester fabrics, is
carried by impregnation of the PET fabric in the dye bath
followed by squeezing of excess dye bath and then a prior drying

V. Pasquet et al. / Journal of Cleaner Production 43 (2013) 20e26

(at 100e140  C) before dye xation (at 200e225  C during 12e


25 s). This technique is however restricted to disperse dyes that
can sublimate and penetrate inside the PET ber in gaseous state.
Thus, only a limited amount of color shades can be obtained.
When special shades are needed, dyeing of polyester fabrics
with disperse dyes is achieved using exhaustion method (deep
dyeing). The fabric to be dyed is immerged in the dye bath for
longer period (about 1 h) under high temperature and pressure,
under agitation, with or without addition of a carrier to allow dye
diffusion inside the polyester ber. Exhaustion method is used for
dyeing of smaller quantities of polyester fabrics or for dyeing of
polyester textiles in the form of bers, yarns or knitted fabrics. Two
exhaust dyeing methods are used: 1 - Dyeing under atmospheric
conditions (below 100  C) with the aid of carriers and 2 - Dyeing
under high-temperature and pressure conditions (125e135  C). The
last method is the most commonly applied but it requires high
energy consumption because of high temperature conditions.
Carriers are used for dyeing of PET bers in order to improve
adsorption and accelerate diffusion of disperse dyes into the ber at
low temperature and pressure conditions. Nevertheless, most of
carriers are toxic for humans and aquatic organisms (Murray and
Mortimer, 1971a; Shenai, 1998; Tavanaie, 2010). During dyeing
and rinsing, a large amount of carriers is released into wastewater,
but part remains entrapped in the ber (Vigo, 1994; Park, 2004) and
is likely to be emitted into air during drying, thermoxation and
later use (eg. ironing).
Chemical carriers include: phenolics, chlorinated aromatics,
aromatic hydrocarbons and ethers (Vigo, 1994). Some carriers are
said hydrophobic and some are hydrophilic, and their mode of
action differ accordingly. Hydrophobic carriers are more effective
than hydrophilic ones (Burkinshaw, 1995). In textile industry, hydrophobic carriers such as dichloro and trichloro-benzene are
already substituted by hydrophilic carriers such as benzoic acid
(Vigo, 1994).
1.1. Action of carriers
During the rst stage of dyeing, adsorption of carriers on PET
ber takes place in a manner which is similar to that of disperse
dyes. Interactions between PET ber and carrier involve primarily
dispersive forces acting between aromatic parts of the carrier and
the PET polymer (Murray and Mortimer, 1971b; Ingamells and
Yabani, 1977; Burkinshaw, 1995).
As the carrier molecules are smaller in size than the dye molecules, they diffuse more rapidly into the amorphous regions of ber
after their adsorption onto PET ber. There is then a swelling of PET
ber and creation of spaces between PET macromolecular chains.
Amorphous regions then become more easily accessible to the dye
molecules. This swelling phenomenon causes a plasticization of
PET and therefore a reduction of glass transition temperature Tg
(Murray and Mortimer, 1971a; Vigo, 1994; Burkinshaw, 1995). The
carrier has thus the effect of accelerating dye diffusion inside PET
ber.
Hydrophilic carriers have a different mode of action: they act
as powerful dispersing agent, increasing solubility of the disperse
dye in water, (Burkinshaw, 1995; Arcoria, 1989), but their increased
solubility in water decreases their diffusion inside the PET ber.
Carriers such as phenols have aromatic group which contributes to
their adsorption on the ber (Balmforth et al., 1966).
1.2. Vanillin
Molecular structure of vanillin is similar to that of traditional
carriers, which confers to all of them a solubility parameter close to

21

that of PET. Hence it would be interesting to study the possible use


of vanillin to substitute traditional toxic carriers.
Naturally occurring vanillin in pods is very expensive and was
for a long time replaced by petrochemical vanillin for its use in agrifood and perfumery. There is now a great concern for its production
using biotechnological solution: Rhodia markets biosynthetic
vanillin prepared by the action of microorganisms on ferulic acid
extracted from rice bran and today lots of research is being undertaken to synthesize vanillin from agro-resources such as lignin
(McShan, 2005). Moreover, vanillin is antioxidant (Tai et al., 2011)
antimicrobial and anti-mutagenic effects (Walton et al., 2003).
In this article, the feasibility of substituting traditional carriers
by 2 different types of vanillins: para and ortho-vanillin (see
Fig. 1(a) and (b)) was assessed. PET fabric was dyed in atmospheric
conditions using two different disperse dyes having differing molecular weight. The toxicity risks related to the use of vanillin
compared to the existing carrier molecules were also analyzed
using literature data.
2. Experimental
2.1. Dyeing methods
A 100% PET plain woven fabric, ready-to-dye (supplied by Subrenat) density 167 g/cm2 was used.
The samples, weighing 3 g, were dyed in 200 ml beakers (Labomat
machine) with two dyes, disperse dye blue D56 (M 349.14 g mol1)
and disperse dye blue D79 (M 639.41 g mol1), see Fig. 2(a) and (b).
For each dyeing the liquor volume was set to 150 ml. The amount of
dye used was 3% o.w.f. at a liquor ratio of 50:1. Dyeing was carried out
at 90  C for 1 h at different pH values (3, 5, 7, 9, 11). pH was adjusted
using aqueous hydrochloric acid and potassium hydroxide. Then,
dyed samples were reduction cleared using soda and sodium
hydrosulte for 30 min at 50  C, to remove all physi-sorbed dye
molecules on PET fabric surface. At the end, dyed samples were
washed twice at 30  C for 10 min in distilled water and dried at room
temperature.
Dyeing was carried out using vanillin as carrier and results were
compared to those of 5 traditional carriers (pure products), and to
a commercial carrier Levegal DTE supplied by Bayer.
The chemical formula of the 5 chemical carriers used, are shown
in Fig. 3.
2.2. Measurements and analysis
Reectance of the cleaned dyed samples was measured with
a spectraash SF-650 spectrophotometer. Relative color strengths
K/Smax (at l 640 nm) were then determined using the Kubelkae
Munk equation

K=S

1  R2 1  R2

2R
2R0

O
OH

O CH 3
OH

(a) Para-Vanillin

O CH3

(b) Ortho-vanillin

Fig. 1. Chemical formula of the two vanillins used: (a) Para-Vanillin, (b) Orthovanillin.

22

V. Pasquet et al. / Journal of Cleaner Production 43 (2013) 20e26

Fig. 2. Chemical formula of dyes used in this study: (a) Anthraquinone disperse dye
D56, (b) Azoic Disperse dye D79.

where R is the decimal fraction of reectance of dyed fabric (at


l 640 nm), R0 is the decimal fraction of reectance of undyed
fabric, K is the absorption coefcient, and S is the scattering
coefcient.
Dye concentrations inside PET ber was quantied by colorimetric analysis after dye extraction with dimethylformamide
(DMF) using a Kumagawa extractor. Calibration curves (of absorbance v/s dye concentration) using pure dye solutions were used to
determine the dye concentration inside PET ber.
Dyed samples were tested according to ISO standard methods.
Specic tests used were ISO 105-C10 for color fastness to washing
and ISO 105-X12 test for color fastness to rubbing.
For the fastness to washing, a specimen of dyed polyester fabric
was washed at 50  C for 45 min. Color degradation was evaluated
by comparison with a non-washed specimen. Color difference was
measured to assess the wash color fastness: 1 e poor, 2 e fair, 3 e
moderate, 4 e good, 5 e excellent.
For dry rubbing test, dyed polyester fabric was placed on the
base of a crockmeter, a white squared cotton testing fabric was
allowed to slide on the dyed polyester fabric back and forth twenty
times. The staining on white cotton sample was assessed on a grey
scale: 1 e poor, 2 e fair, 3 e moderate, 4 e good, 5 e excellent. For
wet rubbing test, white cotton samples were thoroughly damped
with distilled water before performing the test.

Fig. 4. K/Smax values of PET fabric dyed with 2 different disperse dyes
(D56 349.14 g mol1 and D79 639.41 g mol) in presence of 1 g of the 3 different
carriers (p-vanillin, o-vanillin and Levegal DTE) at 90  C and pH 7 for 1 h, with LR 1/50.

The smaller disperse dye molecule D56 yields a higher K/Smax


value compared to the larger disperse dye D79. Several studies have
shown that disperse dye uptake by PET fabrics depends on the size
of dye molecules (Lee and Kim, 1998; Dhouib et al., 2006). Both ovanillin and p-vanillin increase the K/Smax values but o-vanillin
yields a higher color strength value. However, the highest K/Smax
value is obtained with the commercial carrier Levegal DTE. Thus,
with the smaller dye D56, K/Smax value increases from 1 to 4 with
p-vanillin, reaching K/Smax 8 with o-vanillin, and K/Smax 16
with the commercial conventional carrier.
Moreover, Table 1 shows that with the larger dye D79, wash
fastness is not very good (3.5) especially when o-vanillin or the
commercial carrier is used.

3. Results
3.1. Effect of the blue dye molecule size
Fig. 4 shows the color strength expressed in terms of K/Smax (at

l 640 nm) of polyester fabrics dyed separately with two disperse

dyes: D56 and D79, in presence of o-vanillin, p-vanillin and the


commercial carrier Levegal DTE.

3.2. Inuence of pH
Fig. 5 shows the variation of K/Smax values as a function of pH for
dyeing with disperse dye D56, with 1 g of each vanillin carrier. At
low pH values (pH 2e7), K/Smax does not vary signicantly but at
basic pH values (9e11), K/Smax values decrease sharply for both
vanillins. We used Marvin software to identify species charge
distribution according to pH values. The pKa of p-vanillin is
around 7.4 and that of o-vanillin is around 9. For pH values
higher than the pKa values, predominant species are anionic
forms of p-vanillin and o-vanillin because alcohol groups lose
a hydrogen ion. As far as the disperse dye D56 is concerned, it
acquires an anionic form for pH > 9.8. At basic pH, it has already
been shown that PET was negatively charged (Ran et al., 2011). At
high pH values, electrostatic repulsion between negatively charged

Table 1
Fastness properties of dyed polyester fabrics with 3% dye owf.
Washing

Fig. 3. Chemical formula of chemical traditional carriers used in the study: (a) phenylphenol, (b) para and ortho-dichlorobenzene, (c) benzoic acid, (d) biphenyl.

No carrier
1 g p-vanillin
1 g o-vanillin
1 g commercial carrier
(Levegal DTE)

Dry rubbing

Wet rubbing

D56

D79

D56

D79

D56

D79

4.5
4.5
4.5
3.5

4
4
3.5
3.5

5
5
4.5
4.5

4.5
4.5
4.5
3.5

4.5
4.5
4.5
4

4
4
4
4.5

V. Pasquet et al. / Journal of Cleaner Production 43 (2013) 20e26

23

9
8
7

o-vanillin

K/Smax

p-vanillin

5
4
3
2
1
0
0

10

12

pH
Fig. 5. K/Smax values of PET fabric dyed with D56, (at 90  C, 1 h, LR 1/50, 1 g of p-vanillin
or 1 g of o-vanillin) at different pH values.

PET, and negatively charged dye and vanillins, would make dye
adsorption more difcult and would thus decrease the dye uptake.
Dye fastnesses were almost the same (Table 2) whatever the pH
used. However, to reduce the input of chemical additives in dye
bath, all dyeings in the following parts were carried out at pH 7,
where dye uptake was maximal.
Also, the impact of vanillin on dye uptake being higher for the
smaller disperse dye D56, only this dye was retained for the following part of the study.

Fig. 6. K/Smax values of PET fabric dyed at 90  C during 1 h at pH 7, with a LR 1/50, and
3% owf of disperse dye D56) with different amounts of o-vanillin at two different
concentrations of ethanol.

The presence of ethanol did not inuence the wash and rub
fastness values which were similar to those obtained without
ethanol (values not shown here).
3.4. Comparison of vanillin with other chemical traditional carriers

3.3. Inuence of vanillin concentration and presence of ethanol


solvent on dye uptake
The dashed curve in Fig. 6 shows that increasing the concentration of o-vanillin leads to a higher dye uptake (K/Smax values).
Burkinshaw (Burkinshaw, 1995) showed that the amount of carrier
increased the amount of dye inside the ber to a certain value. Here,
we can see that as the concentration of vanillin increases from 0 to
2 g, the K/Smax value increased proportionally. 2 g of vanillin was
the optimum quantity necessary for optimum dyeing, with K/Smax
value reaching 16. Beyond 2 g, there is no further signicant
increase in dye uptake, and unlevel dyeing took place.
A recent study (Ferrero et al., 2011) showed the benets of using
ethanol as co-solvent for dyeing bers such as polyester. Indeed,
disperse dyes and vanillin are not (or little) water soluble. Thus, the
inuence of ethanol when dyeing with vanillin as carrier was
studied. K/Smax values were recorded for dyeing with different
concentrations of vanillin carrier without and with 1 ml/l or 2 ml/l
of ethanol. Fig. 6 shows that for quantities of vanillin 1 g, very
little increase in K/Smax values was measured with 5 ml/l of ethanol
only (DK/S w 1). Indeed, Arcoria et al. (1985) showed that ethanol
has an effect on the dyeing of PET with disperse dyes, but the effect
is highly dependent on the structure of dye.

Table 2
Fastness properties of PET fabric dyed with D56, (90  C, 1 h, LR 1/50, 1 g of p-vanillin
or 1 g of o-vanillin) at different pH, with 3% dye owf.
Washing

pH
pH
pH
pH
pH

3
5
7
9
11

Dry rubbing

Wet rubbing

p-vanillin

o-vanillin

p-vanillin

p-vanillin

o-vanillin

p-vanillin

4.5
5
4.5
4.5
5

5
4.5
4.5
4.5
4

4.5
4.5
5
5
5

5
4.5
4.5
4.5
4.5

4.5
4.5
4.5
4
5

5
4.5
4.5
4.5
4.5

After studying the inuence of several parameters on the dyeing


of PET with vanillin, dye uptake in presence of vanillin was compared to 5 other chemical carriers.
Fig. 7 shows the measured K/Smax values of fabrics dyed in
presence of 1 g of carrier and 3% of dye D56.
Indeed, compared to the 5 conventional carriers, o-vanillin
yields a K/Smax value which is similar to that of benzoic acid. The
other 4 conventional carriers yield very high K/Smax values which
are 5e6 times higher than that obtained with o-vanillin. P-vanillin
yields the smallest K/Smax. However when fastness (Table 3) results
are compared, the wash fastness of polyester fabrics dyed using any
of the two vanillins is better than that using chemical carriers such
as the two dichlorobenzenes or the commercial Levegal DTE.
The K/Smax values of the dyed fabrics were then compared to the
% of dye from the dye bath which penetrates inside PET ber. Dye
extraction method described in part 2 was used to quantify the
amount of dye inside the PET ber. Fig. 8 shows that without any
carrier, only 7.5% of the dye from the dye bath solution penetrates
the PET ber. With the chemical carriers, dye penetration inside the
ber is highly increased especially with p-dichlorobenzene, where
63.8% of dye in dye bath penetrates the PET ber. Only 13.8% and
18.3% of the dye penetrates the ber with the p-vanillin and ovanillin respectively, but with o-vanillin, dye penetration inside PET
ber is slightly higher than that with benzoic acid. Indeed when all
K/Smax values are plotted against the % of dye inside the PET ber,
a linear regression curve appears (see Fig. 7), indicating that the
K/Smax values are proportional to the concentrations of dye inside
the ber, and this is true for all carriers studied here. This would
mean that the kinetics of dye penetration inside the PET ber is
similar for all carriers used in this study. This result also conrms
that the small size dye D56 diffuses uniformly inside the PET ber
whatever is the nature of the carrier used.
To better understand the differences in dye uptakes with the
different carriers, the K/Smax values were compared to the Hoy

24

V. Pasquet et al. / Journal of Cleaner Production 43 (2013) 20e26

Fig. 7. K/Smax values of PET dyed fabric plotted against the % of dye from dye bath which penetrates inside PET ber.

solubility parameter and to the solubility limit in water, of each


carrier. As specied in literature, carrier molecules which are
smaller in size than dye molecules, diffuse more rapidly into the
amorphous regions of PET causing a swelling of PET and creation of
spaces between PET macromolecular chains facilitating thus, the
access to dye molecules. Penetration of carrier molecules in PET
will depend on the solubility of the carrier in the PET (Tavanaie,
2010). Indeed, several studies have shown (Slark and OKane,
1997) correlation between good absorption of a molecule by
a polymer and proximity of the solubility parameter. Using group
contribution method for each chemical group, the Hoy solubility
parameter of the two vanillins and of polyethylene terephtalate
were calculated, and compared to that of the other carriers. Table 4
shows that though the Hoy solubility parameter of all carriers is
close to that of PET, there is no real correlation between the carrier
Hoy parameter and K/Smax of dyed fabrics.
The measured K/Smax values were also compared to the solubility limit of each carrier in water (see Fig. 8). The higher is the
solubility limit in water, the lower is the K/Smax value of the PET
dyed fabric The values of the solubility limit in water of the two
vanillins are even higher than that of the hydrophilic carrierbenzoic acid. The very low dye uptake with p-vanillin would thus
be explained by its very high solubility in water. However, though
the solubility limit in water of the o-vanillin is higher than that of
benzoic acid, the dye uptake (K/Smax values) in presence of
o-vanillin is slightly higher than that with the benzoic acid.
3.5. Summary on the potential use of vanillin as a carrier for dyeing
PET fabric

Fig. 8. K/Smax values of PET fabric dyed (at 90  C, 1 h, pH 7, LR 1/50) with 3% of disperse
dye D56 and 1 g of carrier, compared to the solubility limit in water, of each carrier.

vanillins are similar to that of PET, their diffusion inside the PET
ber would be reduced due to their increased afnity with respect
to water molecules in the dye bath. Our study showed that the color
yield (K/Smax value) is higher with ortho-vanillin than with paravanillin. With 1 g of o-vanillin, dye uptake is slightly higher than
that with 1 g of hydrophilic benzoic acid carrier (K/Smax 7.5), and
with 2 g of o-vanillin, dye uptake value is doubled (K/Smax
value 16), which is a value obtained with 1 g of commercial
Levegal carrier.

All the study carried here showed that when compared to


chemical carriers, both vanillins seem to allow a uniform distribution of the small dye D56 in the ber, just as the other chemical
carriers. However, though the Hoy solubility parameters of the two

4. Toxicity assessment

Table 3
Fastness properties of fabrics dyed using 1 g of different carriers, with 3% dye D56
owf.

Table 4
Solubility parameters of different carriers used.

p-vanillin
o-vanillin
Benzoic acid
Biphenyl
Phenylphenol
p-dichlorobenzene
o-dichlorobenzene
Levegal DTE

Washing

Dry rubbing

Wet rubbing

4.5
4.5
4.5
4.5
4
3.5
3.5
3.5

5
4.5
4.5
5
4.5
4
4
4.5

4.5
4.5
4.5
4
4
4
4
4

A further study, based on literature data was conducted to


compare toxicity of these molecules to show the interest of using

Solubility parameter
(Hoy) en Cal1/2 cm3/2
p-vanillin
o-vanillin
Benzoic acid
p-dichlorobenzene
o-dichlorobenzene
Biphenyl
Phenyl-phenol
PET

9.9
10.17
10.87
9.31
9.31
9.24
12.12
11.18

V. Pasquet et al. / Journal of Cleaner Production 43 (2013) 20e26

25

Table 5
Different parameters of toxicity for the different carrier molecules.

p-vanillin
o-vanillin
Benzoic acid
p-dichloro-benzene
o-dichloro-benzene
Biphenyl
Phenyl-phenol
a
b
c
d

Acute toxicityb,d

Cancerogenicityc

Neuro-toxicityb

Developmental or
reproductive harma,b

Endocrine
disruptora,b

Ecotoxicitya,d

Slight
Slight to moderate
Slight
Slight
Slight
Slight
High

Not listed
Not listed
Not listed
2B
3
3
2Be3

No
No
No
No
No
No
No

?
?
?
?
?
?
Yes

?
?
?
?
?
Suspected
Suspected

Not acutely toxic


?
Not acutely toxic
Moderate
Slight to moderate
Moderate
Moderate to high

Hazardous Substances Data Bank (HSDB).


Pesticide Action Network (PAN).
International Agency for Research on Cancer (IARC).
Material Safety Data Sheets (MSDS).

Table 6
Characterization factors of ecotoxicity and human health calculated by USEtox model.

p-vanillin
o-vanillin
Benzoic acid
Phenylphenol
Biphenyl
o-dichlorobenzene
p-dichlorobenzene

Freshwater ecotoxicological characterization factor in


CTUe [PAF m3 day/kg emitted]

Human health characterization factor in


CTUh [cases/kg emitted]

Emission to

Emission to

Water

Air

Soil

Water

Air

Soil

528
5050
49
8300
1730
613
1030

31
242
5.30
163
12
3
4.1

108
969
3.62
13.4
2.3
22
34

n/a
n/a
1.43$108
9.03$10.8
2.32$108
1.52$108
9.19$108

n/a
n/a
7.82$109
8.10$1010
1.45$109
1.13$108
6.88$108

n/a
n/a
5.77$108
3.55$108
5.52$108
2.65$108
1.74$107

The characterisation factor for aquatic ecotoxicity (ecotoxicity potential) is expressed in comparative toxic units (CTUe) and provides an estimate of the potentially affected
fraction of species (PAF) integrated over time and volume per unit mass of a chemical emitted (PAF m3 day kg1).

vanillin as a carrier. We attempted to apply principles of chemical


substitution advocated in literature (Hansonn et al., 2011) to justify
the use of vanillin. The toxicity risks involved at different stages
(dyeing and nal use) in the life cycle of PET textile product dyed
using a carrier, were considered. Carriers can come in direct contact
with human being when inhaled by workers or when they are in
direct contact with the users skin. They can also be released in
water or in air, causing water or air pollution and inducing thus,
some ecotoxicity. So, parameters such as human toxicity and ecotoxicity have to be taken into account when assessing the toxicity
risks of two vanillins.
Toxicity risks of the two vanillins were compared to those of
traditional carriers. The following toxicity risks were considered:
acute toxicity, carcinogenic potential, toxicity on reproduction
or development of a species, neurotoxicology, and endocrine
disruption.
Several reports give information on safety data of molecules
used in our study. There is however still a lack of data for all toxicities considered here (Hansonn et al., 2011). Thus data on the
following toxicities are still missing: toxicity on reproductive system or development of a species and endocrine disruption (see
Table 5). Moreover, the different toxicity risk parameters are not
necessarily related to each other, and each of them yields to different conclusions. For example, although ortho-vanillin is not listed as a potentially cancerigenous molecule when compared to
dichlorobenzene, it has nevertheless, a higher acute toxicity.
Finally, the USEtox model was used to carry out a comparative
study on the different molecules used as carrier. Indeed, USEtox
model is an environmental model for characterization of human
health and ecotoxic impacts in comparative assessment and for
ranking of chemicals according to their inherent hazard characteristics (Ralph et al., 2008). It has been developed by a team of
researchers and has already been applied to several thousands of
chemicals. In particular, emissions to air and water are considered.
Table 6 shows that it is not proved that the two vanillins are toxic

for human health. Moreover, Lirdprapamongkol et al. (2009) conrmed the antimutagenic properties of the two vanillins. However
safety data sheet from suppliers does point out that o-vanillin may
cause eye irritation, skin inammation and respiratory irritation
when inhaled. Ecotoxicity in terms of emissions to air, of p-vanillin
is higher than that of benzoic acid, while o-vanillin has the highest
ecotoxicity.
In spite of its high ecotoxicity, o-vanillin seems to be a promising
carrier molecule to improve disperse dye uptake by PET bres. In
addition, both vanillins present antibacterial and antifungal characteristics and would probably impart these properties to the
polyester fabric, too.
5. Conclusion
Conventional carriers having high toxicity are gradually being
replaced by other processes, which are not always environmentallyfriendly. This study was carried out to study the potential use of an
agro-sourced vanillin molecule for substituting carriers used for
polyester fabric dyeing process. Increased disperse dye uptake is
observed when o-vanillin or p-vanillin is used, but for small size
disperse dye only. Our experiments showed that both vanillins seem
to allow a uniform distribution of the small disperse dye in the ber,
just as other chemical carriers. Our study showed that in the dyeing
conditions used (3% of dye solution), the color yield (K/Smax value) is
higher with o-vanillin than with p-vanillin. With 1 g of o-vanillin,
color yield is slightly higher than that with 1 g of hydrophilic benzoic
acid carrier (K/Smax 7.5), and with 2 g of o-vanillin, dye uptake
value is doubled (K/Smax value 16), which is a value obtained
with 1 g of commercial Levegal carrier. Moreover dyeing with
vanillin can be carried at neutral pH without addition of other
chemicals to adjust pH.
The study conrms that vanillin may substitute traditional carriers used in the dyeing of polyester with disperse dyes of small
sizes.

26

V. Pasquet et al. / Journal of Cleaner Production 43 (2013) 20e26

USEtox model shows that both vanillins do not present any


proved human toxicity, however o-vanillin which gives the highest
dye uptake has a high fresh water ecotoxicity.
These results highlight the perspective of studying other agrosourced products as substitutes for chemicals used in textile
processing.
However, in the framework of a life cycle assessment, several
toxicity data are missing. Environmental and toxicity risks of using
carriers are mainly due to their inhalation, their cytotoxicity and
ecotoxicity. The quantity of vanillin present or which may be
released (during use) at the fabric surface or emitted in air or water
should be evaluated for similar dye uptake values.
Acknowledgments
This work was realized within the framework of ACVTEX project
which is nanced by Europe (Interreg and FEDER), Conseil Rgional
du Nord e Pas-de-Calais, ADEME, DIRECCTE and Rgion Wallone.
The authors also would like to thank Christian Catel for his kind
help.
References
Arcoria, A., Longo, M.L., Parisi, G., 1985. Effects of the phenol on the dyeing of
polyester bre with some disperse azo-dyes. Dyes and Pigments 6, 155e161.
Arcoria, A., 1989. Carrier dyeing of polyester bre with some disperse azo dyes. Dyes
and Pigments 11, 269e276.
Balmforth, D., Bowers, C.A., Bullington, J.W., Guion, T.H., Roberts, T.S., 1966. Equilibrium studies on the dyeing of polyester bre with disperse dyes in the
presence of carriers. Journal of the Society of Dyers and Colourists 82, 405e409.
Burkinshaw, S.M., 1995. Chemical Principles of Synthetic Fibre Dyeing. Blackie
Academica & Professionnal, London.
Carrion, F.J., 1995. Dyeing polyester at low temperatures: kinetics of dyeing with
disperse dyes. Textile Research Journal 65, 362e368.
Cegarra, J., Puente, P., 1967. Considerations on the kinetics of the dyeing process of
polyester bers with disperse dyes. Textile Research Journal 37, 343e350.
Dewez, S., 2008. Utilisation des micro-ondes dans lennoblissement textile. PhD
thesis, University of Lille.
Dhouib, S., Lallam, A., Sakli, F., 2006. Study of dyeing behavior of polyester bers
with disperse dyes. Textile Research Journal 76, 271e280.
Dupont, G., 2002. La teinture. Editions de lIndustrie Textile, Paris.
Ferrero, F., Periolatto, M., Rovero, G., Giansett, M., 2011. Alcohol-assisted dyeing
processes: a chemical substitution study. Journal of Cleaner Production 19,
1377e1384.
Hansonn, S.O., Molander, L., Ruden, C., 2011. The substitution principle. Regulatory
Toxicology and Pharmacology 59, 454e460.
Ingamells, W., Yabani, A., 1977. The swelling and plasticization of poly (ethylene
terephthalate) during carrier dyeing. Journal of the Society of Dyers and Colourists 93, 417e423.
Lavoie, T.E., Heine, G.L., Holder, H., Rossi, S.M., Lee II, E.R., Connor, A.E., Vrabel, A.M.,
Diore, M.D., Davies, L.C., 2010. Chemical alternatives assessment: enabling

substitution to safer chemicals. Environmental Science and Technology 44,


9244e9249.
Lee, W.J., Kim, J.P., 1998. Effect of particle size of disperse dyes on their dyeing
properties. Journal of the Korean Fiber Society 35, 100e104.
Lirdprapamongkol, K., Kramb, J.P., Suthiphongchai, T., Surarit, R., Srisomsap, C.,
Dannhardt, G., Svasti, J., 2009. Vanillin suppresses metastatic potential of human cancer cells through PI3K inhibition and decreases angiogenesis in vivo.
Journal of Agricultural and Food Chemistry 57, 3055e3063.
McShan, D., 2005. Heuristic search for metabolic engineering: de novo synthesis of
vanillin. Computers & Chemical Engineering 29, 499e507.
Montoneri, E., Boffa, V., Savarino, P., Tambone, F., Adani, F., Micheletti, L., Gianotti, C.,
Chiono, R., 2008. Use of biosurfactants from urban wastes compost in textile
dyeing and soil remediation. Waste Management 29, 383e389.
Murray, A., Mortimer, K., 1971a. Dye auxiliaries in the application of disperse dyes to
man-made bres. Journal of the Society of Dyers and Colourists 87, 173e181.
Murray, A., Mortimer, K., 1971b. Carrier dyeing. Review of Progress in Coloration and
Related Topics 2, 67e72.
Oerlikon, 2010. The Fiber Year 2009/10 A World Survey on Textile and Nonwovens
Industry, Management.
Ozturk, E., Yetis, U., Dilek, F.B., Demirer, G.N., 2009. A chemical substitution study for
a wet processing textile mill in Turkey. Journal of Clean Production 17, 239e247.
Park, K.H., 2004. Contribution la modlisation, lidentication et la simulation
dun procd de teinture des microbres de polyester. PhD thesis, University of
Lille.
Ralph, K., Rosenbaum, R.K., Till M Bachmann, T.M., Gold, L.S., Huijbregts, M.A.J.,
Jolliet, O., Juraske, R., Koehler, A., Larsen, R.F., MacLeod, M., Margni, M.,
McKone, T.E., Payet, J., Schuhmacher, M., Van de Meent, D., Hauschild, M.Z.,
2008. USEtox e the UNEP-SETAC toxicity model: recommended characterisation factors for human toxicity and freshwater ecotoxicity in life cycle impact
assessment. International Journal of Life Cycle Assessment 13, 532e546.
Ran, J., Bnistant, G., Campagne, C., Prichaud, A., Chai, F., Blanchemain, N.,
Perwuelz, A., 2011. Characterization of nonwoven poly (ethylene terephtalate)
devices functionalized with cationic polymer. Journal of Applied Polymer
Science.
Shenai, V.A., 1998. Toxicity of polyester dyeing carriers. Textile Dyer and Printer 31,
11e16.
Slark, A.T., OKane, J., 1997. Solute diffusion in relation to the glass transition temperature of solute-polymer blends. European Polymer Journal 33, 1369e1376.
Szente, L., Mikuni, K., Hashimoto, H., Szejtli, J., 1998. Stabilization and solubilization
of lipophilic natural colorants with cyclodextrins. Journal of Inclusion Phenomena and Macrocyclic Chemistry 32, 81e89.
Tai, A., Sawano, T., Yazama, F., Ito, H., 2011. Evaluation of antioxidant activity of
vanillin by using multiple antioxidant assays. Biochimica et Biophysica Acta
(BBA) e General Subjects 1810, 170e177.
Tavanaie, 2010. Polypropylene/poly (butylene terephthalate) melt spun alloy bers
dyeable with carrier-free exhaust dyeing as an environmentally friendlier
process. Journal of Cleaner Production 18, 1866e1871.
Thorpe, B., Rossi, M., 2007. Require safer substitutes and solutions: making the
substitution principle the cornerstone of sustainable chemical policies. New
Solutions 17, 177e192.
Trotman, E.R., 1970. Dyeing and Chemical Technology of Textile Fibres, pp. 521e531.
Vankar, P.S., Shanker, R., Verma, A., 2006. Enzymatic natural dyeing of cotton
and silk fabrics without metal mordants. Journal of Cleaner Production 15,
1441e1450.
Vigo, T.L., 1994. Textile Processing and Properties: Preparation, Dyeing, Finishing,
and Performance. Elsevier Science Publishers B.V., Amsterdam.
Walton, N.J., Mayer, M.J., Narbad, A., 2003. Vanilin. Phytochemistry 63, 505e515.