Journal of Analytical Sciences, Methods and Instrumentation, 2012, 2, 87-91 Published Online June 2012 ( 87
Comparison between Pigment Printing Systems with
Acrylate and Butadiene Based Binders
Mansoor Iqbal, Javaid Mughal, Munazza Sohail, Arsheen Moiz, Kamran Ahmed, Khalil Ahmed*
Applied Chemistry Research Centre, PCSIR Laboratories Complex, Karachi, Pakistan.
Email: *
Received December 25th, 2011; revised January 16th, 2012; accepted January 31st, 2012
Pigment printing was carried out on lab scale by simple screen-printing techniques. By the application of acrylate and
butadiene based binder, the crocking fastness, formaldehyde release and PVC migration of fabric printed with Imparon
red KB pigment was evaluated. The effect of curing time on K/S values was also investigated. It has been found that
butadiene based binder shows good performance in terms of crocking fastness, formaldehyde release and PVC migra-
tion. It has also been observed that by increasing the binder concentration, the release of formaldehyde decreased and
by increasing the curing time, the K/S values of printed fabric were decreased.
Keywords: Printing; Pigment; Binder; Acrylate; Butadiene
1. Introduction
Cotton is one of the most important fibers in the textile
industry and its coloration could be achieved with either
dyes, by dyeing or printing in aqueous solution, or with
pigment by using a print paste. Printing of cellulosic fi-
bers are considered to account for more than 70% of all
printed substrates and pigment printing is a major
method [1]. The use of pigments for printing of textile
products has dramatically increased over the last 50 years.
Pigments are now used to produce printed products for a
number of end uses including apparels, home furnishing,
crafts and nonwoven articles of the over 18 billion liners
yards of printed fabric produced worldwide each years,
about 50% of this yardage is pigment printed. In the
united state alone, currently about 80% of all printing is
done with pigment [2]. There are of course limitations to
balance against the substantial advantages of pigment
printing. The printer should be fully aware of these, since
the use of pigments in applications where dyes are re-
quired can bring about a negative attitude to pigments,
even in suitable applications [3]. In pigment printing,
insoluble pigments, which have no affinity for fibers, are
fixed on to the fibers with binding agents or binders [4].
Depending upon the properties required in the binding
film (softness, elasticity, plasticity, solvent stability),
binders can be tailor-made by choosing suitable base
product. It is necessary to copolymerize different mono-
mers. Typically, unsaturated monomers are used, such as
vinyl chloride, dichloroethene, acrylic acid, acrylonitrile,
acrylic acid esters & ethers. The binder used in the pig-
ment printing process is usually based on styrene-buta-
diene, styrene acrylate or vinyl acetate—acrylate co-
polymer [5]. Binders are the mechanism used to keep the
color on the fabric wh en using pigments for printing tex-
tiles. The choice of binders will always depend upon the
final fastness requirements as well as the cost require-
ments of the process. Choosing a binder for pigment col-
oration is a complex but critical step in developing a rec-
ipe which will meet very specific requirements. The
place to start to determine which final fabric properties
are important as various end use applications may require
a different polymer to achieve the desired results [6].
Almost all the binders used in textile pigment printing
are the addition polymerization products. They are actu-
ally copolymer type; the structure may be represented as
Figure 1 [7].
The binder film in pigment print is a three-di mension al
structure, the third dimension is rather less important
than the other two. The binder is a film-forming sub-
stance made up of long chain macromolecules, which
when applied to the textile together with the pigment,
produces a three-dimensionally network. The links are
Figure 1. General structure of acrylate copolymer.
*Corresponding author.
Copyright © 2012 SciRes. JASMI
Comparison between Pigment Printing Systems with Acrylate and Butadiene Based Binders
formed during some suitable fixing process, which usu-
ally consists of dry heat and change in pH value, bringing
about either self-crosslinking or reaction with other suit-
able crosslinking agents [8]. Elasticity and improved
adhesion of the film to the substrate is achieved by
crosslinking. The crosslinking reaction must produce
covalent bonds, which are insensitive to hydrolyzing
agents (washing liquor, perspiration, industrial atmos-
phere). The reaction should be activated in dry hot air by
curing process [9]. While the prints are being dried, a
film is formed from the dispersed binder. Its formation
takes place in two stages: flocculation (or coagulation)
and coalescence. During the first stage of film formation,
water and surfactants are removed from the binder by
absorption and evaporation. The dispersed solids coagu-
late to form a gel-like layer of very tightly packed ‘balls’,
which have only poor solidity and adhesive properties. If
the mechanically more stable, more redispersible, disper-
sion binders are used, these coagulated particles can be
brought back to th eir original form by rubbing them with
water. During the second phase, the gel particles flow
together to form a continuous film.
The lowest temperature at which a film can be formed
depends upon chemical constitution, but for pigment
printing it is usually around 5˚C. The speed at which the
film is formed depends upon the range of particle size
[10]. The reaction between the binders and the cellulosic
substrate may be represented as follows in equ a tion:
Binder-CH-ORHO-CelluloseBinder-CH-O-Cellulose + ROH
where R is CH3 or H.
Cross linking increases the crocking, washing and dry
cleaning fastness properties, but detrimentally affects the
handle of the fabric. When the binder molecule have no
self-crosslinking groups, an additional cross linking agent
such as urea formaldehyde or melamine formaldehyde
condensate, methylolated urethane compounds etc, hav-
ing at least two reactive groups per molecule are added in
the binder system [11].
The present research work demonstrates the comparisons
between pigment printing systems with acrylate and buta-
diene based binders. The influence on the crocking fast-
ness, PVC migration, formaldehyde release and K/S values
of the printed cotton fab ric has also been investigated.
2. Experimental
2.1. Material
An optical brightener free, 100% cotton woven fabric
having construction 25 ends/cm2, 21 picks/cm2 and an
area density of 142 gm/m2 was used for pigment prin ting
purpose. The fabric was desized enzymatically, scoured
and bleached by an exhaust method.
2.2. Chemical & Colorants
Commercial pigment Imparon KB of BASF was used as
a colorant in the printing process. Two different binder,
binder ET (polyacrylate based) and halazarine binder
FRS (butadiene based) of BASF were used. Leutexol HP
was also supplied by BASF and used as a thickener.
Printofix WB liquid (melamine based) used as a fixative.
All other chemicals ammonia, urea, polyvinyl chloride,
TiO2 were purchased from Merck chemicals Pakistan
2.3. Equipments
Printing was carried out by laboratory hand screen-print-
ing. Samples were cured on curing machine of Rapid.
Crocking fastness evaluated on AATCC Crock meter
(CM-5 SDL Atlas), Fastness rating was evaluated on
color matching cabinet of Verified by comparing with
grey-scale. The viscosity of the thickener paste was de-
termined by Brookfield viscometer (DV-E model) with
spindle number 6.The relative color strength of the prints,
expressed as K/S values L, a, b, c CIE lab of the printed
samples were determined by reflectance measurements
using Data color intern ational spectrophotometer SF600.
2.4. Print Paste Preparation
The print paste was prepared in soft water with heavy
string by adding 15 g/kg acrylate and butadiene based
binder separately, 12 - 14 g/kg thickener, 6 g/kg ammo-
nia to attain a pH 8 - 9 and 0.7% - 0.8% w/w fixative
were also added. Each print paste was prepared with 5%
Imparon KB pigment and 95% stock paste. The viscosity
of the final print paste was 28000 cp s as determined with
Brookfield viscometer.
2.4.1. Prin t Method
The printed fabric dried at 120˚C for 2 min and cured at
155˚C for 5 minutes.
2.4.2. Fastness Testi ng
The fastness properties were determined according to the
international standards of textile testing. The specific
tests used were ISO-105-X10, BS1006:1990 (Assessment
of migration of textile color into polyv inyl chloride coat-
ing), ENISO-14184-1:1998 (Formaldehyde release),
AATCC-08 (color fastness to crocking) [12-14].
3. Results & Discussion
The pigment printing was performed with 5% Imparon
red KB pigment in the laboratory with simple screen
Copyright © 2012 SciRes. JASMI
Comparison between Pigment Printing Systems with Acrylate and Butadiene Based Binders 89
printing method. The effect of two different binders,
acrylate based and butadiene based on crocking, PVC
migration and formaldehyde release were investigated.
3.1. Effect of Binder Concentration on K/S
As the binder concentration increases, the K/S values of
both printed fabric treated with acrylate and butadiene
based binder increases however the K/S values recorded
for fabric treated with butadiene was higher than the fab-
ric treated with acrylate based binder (Figure 2). The
maximum values of K/S, 13.46, attained at a butadiene
concentration of 15 g/l. Pigment particles are molecular
aggregates which does not contain any groups capable of
reacting with fibers or substrate. The size and lack of
functionality required that pigment could be bonded to
the fibers by the use of binder, which is a high molecular
weight film forming material. The binder is the only
linkage between pigment and the fabric and therefore
plays crucial part in determining the co lor strength of the
finished fabric.
3.2. Effect of Curing Time on K/S Values
The K/S values decreases with increase in curing time of
the printed fabric treated with both butadiene and acry-
late based binder. The maximum K/S values, 13.72 have
been recorded after 2 minutes for butadiene based binder
(Figure 3). The curing time slightly affects K/S values;
the binder which encloses the pigment molecules, forms
a film under curing conditions. The improved adhesion of
the film to the substrate could be achieved by crosslink-
ing. The reaction should be activated in dry ho t air.
3.3. Effect of Binder Concentration on
Formaldehyde Release
The formaldehyde release decreased for both type of
K/S 1: Butadiene binder; K/S 2: A crylate binder.
Figure 2. Binder concentration v/s KS value.
binders with increase in binder concentration. Butadiene
showed minimum values of formaldehyde content i-e
0.87 ppm at a concentration ratio of 15 g/l. It may be due
to the interaction of the formaldehyde molecules with the
binders and also the butadiene based binders have more
reactive sites as compared to the acrylate based binder
and probability of crosslinking with formaldehyde mole-
cule will be more in case of butadiene based binder as
compared to the acrylate based binder (Figure 4).
3.4. Effect of Binder Concentration on Crocking
As the butadiene concentration increases the wet and dry
crocking fastness for both butadiene and acrylate based
binder also increases. At a binder concentration of 15%
the butadiene binder shows optimum results of crocking
i.e. 5 both for wet and dry crocking (Table 1).
Binder 1: Butadiene binder; Binder 2: Acrylate binder.
Figure 3. Curing time v/s KS value.
Binder 1: Butadiene binder; Binder 2: Acrylate binder.
Figure 4. Binder concentration v/s formaldehyde content.
Copyright © 2012 SciRes. JASMI
Comparison between Pigment Printing Systems with Acrylate and Butadiene Based Binders
Factors that affect crocking are the elasticity of the
binder in conjunction with the pigment film placement on
the fabric and the quantity of the binder in the mixture.
Also important is the adh esion of the pigment to the fab-
ric with uniformity of the pigment within the color ma-
trix. Factors which affect wet crocking are the toughness
of the binder film as well as the water resistance of the
binder. Butadiene improves the crock fastness and also
softened the hand of the fabric. Butadiene is unique in
the fact that it contains two reactive double bond, one
polymerized there remain one unsaturated double bond.
Thus double bonds give butadiene its elastic properties
which make it soft and provide good dimensional recov-
ery. Acrylates are thermoplastic polymers which mean
they do not have good dimensional recovery. This results
in reduced abrasion resistance. All acrylates binders re-
quire copolymerization with functional monomers to
achieve acceptable fastness properties.
3.5. Effect of Binder Concentration on PVC
Tables 2 and 3 show the Effect of Binder Concentration
on PVC migration. At a concentration of binder i.e. 13%
the K/S indicates that PVC migration decreases after 6
minutes. It is found to be minimum for both types of
binder. The minimum values of PVC migration could be
achieved for butadiene after 6 minutes at K/S values of
0.32. It may be due to the cross linking properties of
formaldehyde which resist the PVC migration.
3.6. Binder Toxicity
A very large number of workers in the plastics and textile
industry are exposed to acrylic and butadiene based
polymers. The widespread use of these polymers in in-
dustry and in certain laboratories raises questions perti-
nent to their toxicological properties and their short- and
long-term health effects on persons exposed to them.
Butadiene is listed as a po tential carcinogen by the In-
ternational Agency for Research on Cancer (IARC),
among others. It has been shown to cause cancer in labo-
ratory. Butadiene Epidemiology studies have linked em-
ployment in two different chemical operations each with
a Different type of cancer. The factors causing these ex-
cess cancers have not been determined because the
workers were also exposed to other chemicals. Butadiene
has caused birth defects and also injury to reproductive
organs [15].
Generally, the systemic toxic effects of the lower mo-
lecular weight acrylic based polymers are manifested by
an immediate increase in respiration followed by a de-
crease in 15 - 40 min. A prompt fall in blood pressure
also occurs, followed by recovery within 4 - 5 min. As
the person approaches to death, respiration becomes
Table 1. Colorfastness to crocking (AATCC-08).
Butadiene Acrylate
% of Binder Dry Wet Dry Wet
10% 4 3 3 - 4 2
11% 4 3 - 4 3 - 4 2 - 3
12% 4 4 4 2 - 3
13% 4 - 5 4 4 - 5 3
14% 4 - 5 4 - 5 4 - 5 3 - 4
15% 5 5 4 - 5 3 - 4
Table 2. Effect of PVC migration with butadiene binder.
Binder Concentration/
Curing time L a b C K/S
13% for 4 min 89.23 5.23 0.82 1.680.78
13% for 5 min 91.23 4.03 0.68 1.420.34
13% for 6 min 91.27 4.12 0.65 1.270.32
Table 3. Effect of PVC migration with Acrylate Binder.
Binder Concentration/
Curing time L a b c K/S
13% for 4 min 88.47 6.50 1.06 2.080.86
13% for 5 min 89.80 5.43 0.88 1.630.67
13% for 6 min 90.05 5.23 0.72 1.340.48
labored and irregular, lacrimation may occur, defecation
and urination increase, and finally reflex activity ceases
and the person die in coma [16].
4. Conclusions
The present studies have been made to evaluate the
crocking fastness properties, PVC migration and formal-
dehyde release of pigment printed fabric by the use of
acrylate based binder and butadiene based binder. By the
above investigation the following conclusions have been
Butadiene showed good results of PVC migration,
crocking fastness and formaldehyde release as compared
to the acryalate based binder. Butadiene showed minimum
value of formaldehyde content of 0.87 ppm at a concen-
tration of 15%. The K/S values of butadiene binder found
to be maximum after 2 minutes i.e. 13.72, at a binder
concentration of 15%; the butadiene showed optimum
results of crocking i.e. 5 both for wet and dry rubbing.
An increase in the binder concentration will results in
lowering the formaldehyde release for both type of bind-
ers, however this release is minimum in case of butadi-
ene binder. It has also been observed that as the curing
time increased the value of K/S decreased for both type
Copyright © 2012 SciRes. JASMI
Comparison between Pigment Printing Systems with Acrylate and Butadiene Based Binders
Copyright © 2012 SciRes. JASMI
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