doi: 10.1111/j.1478-4408.2010.00245.

Polymer- and wax-based monoconcentrate

predispersed pigments in the colouring of
Coloration
plastics
Technology
Suresh P Deshmukh,a Mahindra B Parmar,b Ashok C Raoa and
Varinder Wadhwaa,*
a
Institute of Chemical Technology, Mumbai, India
Email: varinder_wadhwa@yahoo.co.in
b
Polyblend Color Concentrate, Mumbai, India
Society of Dyers and Colourists

Received: 8 September 2009; Accepted: 19 March 2010

Over the past few decades, masterbatch production has been increasing year by year. Pigments are
used primarily in masterbatches because of their ability to impart colour or opacity to a matrix. The
effectiveness of pigments depends not only on their intrinsic ability to absorb or scatter light, but also,
importantly, on the dispersiblity and distribution of the pigments that can be achieved in plastics.
Nowadays, stringent environmental as well as excellent quality controls are making inevitable the use of
non-dusty monoconcentrated predispersed pigments for the production of masterbatches for the
colouring of plastics. Commercially, for the most part, two types of monoconcentrated predispersed
pigments are being used for the colouring of thermoplastic masterbatches. These are polymer- and
wax-based predispersed pigments. This study has been undertaken to provide a comparison of the
colouring properties of polymer- and wax-based monoconcentrated predispersed pigments. Four
commercially used organic pigments have been selected. Both types of monoconcentrate predispersed
pigments have been developed on a co-rotating twin-screw compounding extruder with a length ⁄ diameter
ratio of 44. A detailed analysis on the comparison of the colouring properties is presented. Results
indicate that good colour properties are achieved when operating conditions are optimised.

Introduction good formulation and conservation practices by

As in the survey conducted by Applied Market
Information Ltd (Bristol, UK), published in 2006,
European masterbatch production has been increasing at
4% per annum and now exceeds 900 000 tonnes per year
[1]. The consumption of pigments in masterbatches is
much more than that of performance additives, which are
widely used in the special applications for improving the
properties of plastics [2]. In the world of plastics
colouring, there are two major categories of colourants,
pigments and dyes. Pigment is defined as a distinct
particulate material that remains essentially unchanged
during the processing and life cycle of the plastics
product. In contrast, a dye is a colorant that becomes
soluble in the polymeric system. This does not imply that
the dye is soluble only in the polymer itself. Dyes can also
be soluble in components of the polymer system.
Pigments are a major component in the colouring of
plastics, used primarily for their ability to impart colour or
opacity to a matrix. Effectiveness in this use depends not
only on an intrinsic ability to absorb or scatter light, but
also, importantly, on the dispersiblity and distribution of
pigments achieved in plastics. Dispersiblity is the
separation of pigment particles and clusters, called
agglomerates and aggregates, into their individual
particles, with complete coating of the surface of the
individual particles with a polymer; whereas distribution
refers to the uniformity of the colour in the particle.
Predispersed pigments for manufacturing masterbatches
Colourants come in many forms and particle sizes, with a
wide range of melting point and thermal stability
characteristics. The average price of a colourant is,
however, often far higher than that of additives, requiring
compounders to control cost. For manufacturing coloured
thermoplastic masterbatches, there are three main
categories of pigments used: (i) normal powder pigments;
(ii) polymer-based monoconcentrate predispersed
pigments; and (iii) wax-based monoconcentrate
predispersed pigments. Predispersed pigments are already
dispersed in a carrier resin, such as polymer or wax, and
have many advantages over normal powder pigments.
The handling of the dry powder pigments creates
housekeeping problems. When the dry powder pigments
are blended in high-intensity blenders, pigments fly off
everywhere around the blenders. Well-packed blenders
reduce the dusty environment to some extent during the
blending, but a 100% dust-free environment is not
possible when using dry powder pigments. Moreover,
when a blender needs to be changed from one colour to
another, it needs thorough cleaning. Each and every part
of the blender needs to be cleaned thoroughly to avoid
contamination from the previous pigments. Therefore,
almost all parts of the blender are dismantled and
cleaned separately; in effect, each and every screw and
bolt of the blender needs to be clean. In this way, overall
cleaning time continues to increase. In the case of
predispersed pigments, the cleaning time is far less
compared with that for dry powder pigments. The
manual weighing of the powdered raw material
constituents for the masterbatch formulation represents a
significant potential for personnel exposure to dust
emissions. Based on routine monitoring results, exposure
levels experienced by personnel directly performing
weighing activities may range from a low of 0.35 mg ⁄ m3
to a high of 6.55 mg ⁄ m3 (total dust). Mixing vessels are
sealed and thus no emissions are generated during the

ª 2010 The Authors. Journal compilation ª 2010 Society of Dyers and Colourists, Color. Technol., 126, 189–193 189
Deshmukh et al. Polymer- and wax-based monoconcentrate predispersed pigments

actual mixing process. However, manual loading of the

dry powder formulation into the mixer, and unloading of
the mixed formulation into a hopper when mixing is
completed, represent the greatest risk for generating dust
emissions. Because predispersed pigments are free
flowing and dust free, dust emissions are significantly
reduced. Moreover, the positive environmental properties
of the predispersed pigments also offer advantages by
giving a better-quality product, i.e. they give a better
dispersion quality to the finished product, thus providing
superior colour properties than the dry powder pigments.
Experimental
Materials
Linear low-density polyethylene (LLDPE) resins used in
this study are butane-based copolymers of 50 MFI
obtained from Reliance Industries (India). The wax used
was low molecular weight polyethylene wax from BASF
(India). Four commercial organic pigments, which are
difficult to disperse, were selected for comparison of
colouring properties: three organic pigment
phthalocyanines, CI Pigment Green 7 (1), CI Pigment
Blue 15:1 (2) and CI Pigment Blue 15.3 (3) (obtained from
Heubach Pigments, India), and a dioxazine, CI Pigment
Violet 23 (4) (obtained from Clariant, India). An organic
pigment is normally recognised as a synthetic product,
based upon a backbone of carbon, hydrogen and nitrogen
and, as such, these organic-derived colourants will
produce very little ash if heated above the point of its
decomposition.
Cl Cl
Cl Cl
Cl
N
Cl
N N
N Cu N
N N
N
Cl(3-4) 1 Cl(3-4)
Cl
H5C2 N O N
N O N C2H5
Cl
4
Copper phthalocyanine green
Copper Phthalocyanine Green is the commercial name for
CI Pigment Green 7 (PG7). It is a green pigment with a
blue hue, made by introducing 15 chlorine atoms into
each copper phthalocyanine molecule. This green
pigment exhibits outstanding fastness properties to
solvents, heat, light and outdoor exposure.
Copper phthalocyanine blue
The most important and most widely used blue
throughout all applications of the pigment-consuming
marketplace is Copper Phthalocyanine Blue. This pigment
offers brightness, cleanliness, strength and economy, with
excellent fastness properties. It is available in two major
commercial forms, the stablilised alpha form CI Pigment
Blue 15:1 (PB15:1) and the beta crystal form CI Pigment
Blue 15:3 (PB15:3). The alpha crystal is a clean shade
of blue with a red hue and the beta crystal is a clean blue
shade with a green hue. The CI Pigment Blue 15:1 used
in this study is in a modified form to render the pigment
‘non-crystallising’. This is the most commonly used
phthalocyanine blue in the plastics industry because of
the high tint strength and exceptional heat stability
offered by this clean, red-shaded colourant. CI Pigment
Cl
Blue 15:3 represents the most stable crystal, green-
shaded, beta copper phthalocyanine and offers excellent
Cl
light fastness and useful heat stability.
Dioxazine violet
Dioxazine Violet is used in most plastic applications and
is prepared by the reaction of chloranil with 2 mol of
aminoethyl carbazole. The pigment is used at very low
levels to produce ‘brighter whites’ by imparting a bluer
hue to the undertone of the white.

N Pigment formulations
N N Based on these four commercial pigments 1–4, two types
N Cu N of monoconcentrate predispersed pigment have been
N N developed based on carrier resin composition: the first is
designated as MCP, primarily polymer-based predispersed
N pigments; and the other is designated as MCW, primarily
2 wax-based pigments. In the polymer-based MCP
formulations, 40 parts by weight of pigment were
dispersed; in each polymer-based designation, 20 parts by
wax and 40 parts by linear low-density polyethylene of
N
50 MFI were used; in wax-based predispersed pigments,
N N 50 parts by weight of each pigment and wax were
N Cu N dispersed (Tables 1 and 2).
N N
Processing of monoconcentrate predispersed pigments
N The monoconcentrated predispersed pigments were
3 processed by the following basic scientific principles: (i)

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 Deshmukh et al. Polymer- and wax-based monoconcentrate predispersed pigments

Table 1 Monoconcentrate polymer-based predispersed pigment co-rotating twin-screw extruder was used for an
formulations experimental run. This twin-screw extruder is made by
Cooperion Kaya (China) and has a segmented screw
Formulation Conc. element. The twin-screw extruder has a screw diameter of
designation Ingredient (% wt ⁄ wt)
65 mm and a length ⁄ diameter ratio of 44. The materials
were weighed using the formulations given in Tables 1
MCP G7 LLDPE 40
and 2. The materials were pre-blended in a high-speed,
Wax 20
CI Pigment Green 7 40 intensity mixer for 3–4 min. Mixing conditions and
MCP Blue 15:1 LLDPE 40 charge sizes were optimised for each product. The pre-
Wax 20 blended material from the high-intensity mixer was then
CI Pigment Blue 15:1 40
metered into a hopper of twin-screw compounding
MCP Blue 15:3 LLDPE 40
Wax 20 extruders. A proprietary screw profile was employed.
CI Pigment Blue 15:3 40 Barrel temperatures, screw speed and throughput rates
MCP Violet 23 LLDPE 40 were optimised for individual formulations.
Wax 20
CI Pigment Violet 23 40
Sample preparation and analysis
All monoconcentrated predispersed pigments samples
were injected into a single-screw injection-moulding
Table 2 Monoconcentrate wax-based predispersed pigment
machine in accordance with the formulation and
formulations 2 · 3 cm high-finish injection-moulded chips were
produced. The base polymer used for testing was 35-MFI
Formulation Conc. polypropylene (PP). Chromatic characteristics were
designation Ingredient (% wt ⁄ wt) determined using a GretagMacbeth (USA) spectro-
photometer (Color-Eye 2180) with D65 illumination and
MCW G7 CI Pigment Green 7 50 reflections were included using a 10 standard observer.
Wax 50 All CIElab colour values (DL*, Da*, Db*) and colour
MCW Blue 15:1 CI Pigment Blue 15:1 50
difference (DE and DH) results were determined as an
Wax 50
MCW Blue 15:3 CI Pigment Blue 15:3 50 average of five readings using standard algorithms
Wax 50 incorporated in the GretagMacbeth spectrophotometer
MCW Violet 23 CI Pigment Violet 23 50 software.
Wax 50
All prepared predispersed pigments were also assessed
for dispersibility. Dispersion was tested by calculating the
filter pressure value under standard conditions, following
dispersive mixing, i.e. reducing agglomerates to their fines the test method outlined in the standard BS EN 13900-5:
form; and (ii) distributive mixing, i.e. achieving a high Pigments and extenders. Methods of dispersion and
degree of homogeneity throughout the polymeric matrix. assessment of dispersibility in plastics. Determination by
Five primary compounding processes are used in the filter pressure value test. This is also known as the
industry following the outlined principles including: pressure-rising test method. The test mixture, consisting
single-screw extrusion; twin-screw extrusion; continuous of a colour concentrate and a basic test polymer, is
mixer; batch mixers; and kneaders. In their various forms, passed through an extruder fitted with a melt pump and
they all attempt to melt, mix, devolatise and pressurise screen pack with breaker plate. In front of the screen
the polymer melt, while simultaneously optimising pack is a melt pressure transducer. The pressure
pigment dispersion, throughput rate and product difference between the start pressure and the maximum
consistency. pressure has been used to calculate the filter pressure
The selection of a specific processing technology is value (FPV). The filter pressure value equipment is a
highly dependent on the nature of the materials being single-screw type with a length ⁄ diameter ratio of 30 and a
processed. Intermeshing twin-screw technologies are diameter of 25 mm. An electronic controller with a screw
preferred for difficult-to-disperse organic pigment systems speed ⁄ pressure feedback loop has been provided to
[3]. The modular nature of the twin-screw extruder maintain the pressure at a constant of 50 bar. This is to
allows a high level of selectivity when it comes to the make sure that the melt pump is completely filled and
location of mixing elements and the placement of vacuum also ensure homogeneity of the melt. To calculate the
or atmospheric venting ports and the supplementary FPV values, 6.25% of colourant and a 20-lm mesh was
downstream feeder. In the late 1970s and early 1980s, a used.
number of alternate compounding technologies were
developed in an attempt to more effectively integrate all Polypropylene formulations for testing
(or most) of the critical compounding functions in a For the MCP and MCW preparations, two formulations of
single device. Devices such as the Instamelt rotary each were prepared using varying levels of the
extrusion system [4] and the Parrel diskpack [5,6] predispersed pigment (PDP) for the development of the
achieved significant technical success but were largely injection-moulded chips, as outlined in Table 3. This
commercial failures. implied that PG7-F1 was used in the moulding chips,
To achieve the required excellent dispersion and which were prepared by adding 2.5% of polymer-based
distribution of monoconcentrate pigments, an intermeshing predispersed CI Pigment Green 7 in 35-MFI

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Deshmukh et al. Polymer- and wax-based monoconcentrate predispersed pigments

Table 3 Percentage of predispersed pigments used in Table 6 Spectrophotometric colour analysis results for injection-
polypropylene for development of injection-moulded chips moulded chips of predispersed CI Pigments Blue 15.3

Moulded chip % of PDP Carrier resin Designation DL* Da* Db* DE DH

designation used (wt ⁄ wt) of PDP
MCP(B15:3)F1 )0.382 0.026 0.780 0.869 0.363
MCP(PDP)-F1 2.5 LLDPE vs
MCP(PDP)-F2 2.0 LLDPE MCW(B15:3)F1
MCW(PDP)-F1 2.0 Wax MCP(B15.:3)F2 )0.011 )0.555 1.200 1.322 0.017
MCW(PDP)-F2 1.6 Wax vs
MCW(B15:3)F2
MCP(B15:3)F1 )0.777 0.433 )0.620 1.084 0.123
vs
polypropylene. Similarly, all others samples have been MCP(B15:3)F2
developed and analysed for comparison of colour MCW(B15.:3)F1 )0.501 0.245 )0.440 0.710 0.028
vs
properties.
MCW(B15:3)F2

Results and Discussion

The CIELab colour values and colour ⁄ hue differences for
the predispersed pigment samples investigated in this Table 7 Spectrophotometric colour analysis results for injection-
study are shown in Tables 4–7. The observed colour values moulded chips of predispersed CI Pigment Violet 23
(DL*, Da*, Db*) are consistent across various comparisons,
as shown in the tables. No significant colour shifts were Designation DL* Da* Db* DE DH
observed in the samples tested. The colour difference (DE)
and hue difference (DH) values are shown to be less than MCP(V23)F1 0.601 0.350 )0.240 0.736 )0.345
1.5 for all sample comparisons. Thus, overall consistent vs
colour properties have been observed. MCW(V23)F1
MCP(V23)F2 0.073 0.019 0.280 0.290 0.243
As pigments could be affected by the relative pH of the vs
carrier resins (alkalinity or acidity), a shift in colour MCW(V23)F2
MCP(V23)F1 0.388 0.273 )0.040 0.476 )0.173
vs
Table 4 Spectrophotometric colour analysis results for injection- MCP(V23)F2
moulded chips of the predispersed CI Pigment Green 7 MCW(V23)F1 0.083 1.827 1.140 2.155 )0.168
vs
MCW(V23)F2
Designation DL* Da* Db* DE DH

MCP(G7)-F1 )0.274 )0.215 0.060 0.354 )0.146

vs could take place. As the colour values are shown to be
MCW(G7)-F1 consistent throughout, the comparisons imply that carrier
MCP(G7)-F2 0.299 )1.140 0.200 1.195 )0.614
vs resins are well suited for organic pigments. If the shear
MCW(G7)-F2 energy input is too high, the product colour could be
MCP(G7)-F1 0.117 0.319 0.180 )0.385 )0.023 damaged or degradation could take place. If the shear
vs energy input is too low, the product dispersion could be
MCP(G7)-F2
MCW(G7)-F1 0.383 )1.321 0.480 1.457 )0.941 too poor to yield good colour properties. As, in our case,
vs all comparisons gave consistent results for colour values
MCW(G7)-F2 and no significant colour shift was observed, it is implied
that the shear energy input was well optimised for each
individual product.
The polymer- and wax-based monoconcentrate
Table 5 Spectrophotometric colour analysis results for injection-
moulded chips of the predispersed CI Pigment Blue 15:1
predispersed pigments were also compared for different
percentages of levels of colour addition. It was observed
that, for polymer-based monoconcentrate, when the
Designation DL* Da* Db* DE DH
addition of monoconcentrate was decreased from 2.5 to
2% wt ⁄ wt, there was no significant change in colour.
MCP(B15:1)F1 0.383 )0.282 0.520 0.705 )0.011
vs Similarly, for wax-based monoconcentrate predispersed
MCW(B15.1)F1 pigments, when the addition of monoconcentrate
MCP(B15:1)F2 )0.130 )0.142 )0.280 0.340 )0.254 predispersed pigment was decreased from 2 to 1.6%
vs
wt ⁄ wt, no significant change in the colour properties was
MCW(B15:1)F2
MCP(B15:1)F1 0.428 0.133 )0.340 0.642 )0.040 observed.
vs
MCP(B15:1)F2 Filter pressure value analysis
MCW(B15:1)F1 0.409 )0.731 )0.800 1.158 )1.00
The FPVs obtained for the polymer- and wax-based
vs
MCW(B15:1)F2 predispersed pigments are given in Tables 8 and 9,
respectively. The FPVs for polymer-based phthalocyanine

192 ª 2010 The Authors. Journal compilation ª 2010 Society of Dyers and Colourists, Color. Technol., 126, 189–193
 Deshmukh et al. Polymer- and wax-based monoconcentrate predispersed pigments

Table 8 Filter pressure values for polymer-based predispersed The FPV signifies the performance of predispersed
pigments pigments. For fibre applications where high dispersion is
essential for a trouble-free process, an FPV of <2 is
Structure no. PDP F1 (polymer based) FPV (bar ⁄ gm) recommended. A value any higher than this often leads to
problems during processing; for example, such as
1 CI Pigment Green 7 0.48 plugging of pigment, fibre breakage, etc. As polymer-
2 CI Pigment B15.1 0.72
based monoconcentrate predispersed pigments have a
3 CI Pigment B15.3 0.64
4 CI Pigment V23 1.12 value of <2, they are recommended to be used for fibre
applications; in addition, they could also be used for film
and injection-moulding applications. Wax-based
predispersed pigments have FPVs >2 and so are not
Table 9 Filter pressure values for wax-based predispersed recommended for fibre applications.
pigments

Structure no. PDP F1 (wax based)
1 Pigment Green 7
2 Pigment B15.1
3 Pigment B15.3
4 Pigment V23
predispersed pigments are in the range of 0.48–
0.72 bar ⁄ gm and for dioxazine CI Pigment Violet 23 they
have a value of 1.12 bar ⁄ gm. For the wax-based
predispersed pigments, it was observed that the FPVs are
in the range of 1.76–4.16 bar ⁄ gm, with the exception of
CI Pigment Violet 23 which, at 14.32 bar ⁄ gm, is very
high. This could be attributed to the fact that pigments,
being of different chemical types with different surface
characterstics, vary in the rate at which they wet out in a
given system. Also, the bond energies between the
primary particles in the pigment aggregate and
agglomerate vary in strength, which also controls the
wetting of the system.
Conclusions
FPV (bar ⁄ gm)
The results of this study clearly indicate that both
polymer- and wax-based monoconcentrate predispersed
1.76
3.20 pigments exhibit similar colour properties. The CIELab
4.16 colour values (DL*, Da*, Db*) and colour difference (DE
5.68 and DH) values are consistent for both types of
monoconcentrate predispersed pigments. Polymer-based
predispersed pigments have better dispersion as
compared with wax-based predispersed pigments.
References
1. Focus on Pigments, Vol. 2006, Issue 4 (Oxford: Elsevier,
2006).
2. R A Charvat, Coloring of Plastics: Fundamentals, 2nd Edn
(Hoboken: Wiley Interscience, 2004).
3. E L Canedo and N L Valsamis, International Polymer
Processing (New York: Hanser Publishers, 1994) 225.
4. G J Hahn and R N Rutledge, US4501543 (Cosden
Technology; 1995).
5. Z Tadmor, P Hold and L Valsamis, 37th SPE ANTEC
Technical Papers, New Orleans, USA (1979) 193.
6. P Hold, Z Tadmor and L Valsamis, 37th SPE ANTEC
Technical Papers, New Orleans, USA (1979) 205.

ª 2010 The Authors. Journal compilation ª 2010 Society of Dyers and Colourists, Color. Technol., 126, 189–193 193