Polymer International 34 (1994) 351-361

Pigments, Dyes and Fluorescent

Brightening Agents for Plastics:
an Qverview
Robert M. Christie
Department of Textiles, The Scottish College of Textiles, Galashiels TD1 3HF, UK

(Received 20 December 1993; accepted 3 March 1994)

Abstract: Articles manufactured from plastic materials are generally enhanced

visually by the incorporation of pigments, dyes and fluorescent brightening
agents. This article provides an overview of the requirements of these colouring
materials for use in plastics and of the structures and properties of the most
important products in commercial use.

K e y words: pigment, dye, fluorescent brightening agent, plastic.

INTRO DUCT10N colouring materials. Chemically, dyes are exclusively

The main reason for incorporating a pigment, dye or
fluorescent brightening agent as an additive into a
plastic material is to modify the optical properties of the
product manufactured from the material in order to
enhance its market appeal. The most obvious role of
pigments or dyes in this respect is to impart an appro-
priate colour to the finished article. However, this need
not necessarily be their only optical function. They may
also play a decisive part either in ensuring that the
plastic material remains transparent or, in contrast, in
providing opacity depending on the desired effect in the
plastic article. Fluorescent brightening agents are
related materials which are used to enhance the degree
of ‘whiteness’ of a white product.
Pigments and dyes are distinctly different types of
colourants. A pigment is a finely divided solid which is
essentially insoluble in its polymeric application
medium. It is incorporated into the medium by a dis-
persion process. Pigments are dispersed into a polymer
in its liquid phase and after the polymer solidifies the
dispersed pigment particles are retained physically
within the solid polymer matrix. In contrast, a dye dis-
solves more or less completely in a polymeric applica-
tion medium and is usually retained as a result of an
atrnity between individual dye molecules and molecules
of the polymer. In these respects fluorescent brightening
agents more closely resemble dyes. There are other ways
in which dyes and pigments are contrasting types of
351
Polymer International 0959-8103/94/%09.000 1994 SCI. Printed in Great Britain
coloured organic compounds. Commercial pigments
include a wide range of both organic and inorganic pro-
ducts and they may be chromatic (coloured) or achro-
matic (e.g. white, black or metallic). The incorporation
of dyes into plastics has little effect on the material
other than imparting colour. In contrast, pigments may
perform functions more wide-ranging than their optical
role. Examples of the additional useful functions which
pigments may perform include reinforcement, e.g. of
rubber by carbon black pigments, and the inhibition of
polymer degradation. On occasions, the incorporation
of pigments can produce problems in plastics, such as
the warping of polyolefins as a result of uncontrolled
nucleation.
Colourants and fluorescent brightening agents may
be introduced into plastics by a variety of methods.
Direct dry colouring is a frequently used process, espe-
cially with thermoplastics, in which the powder is
incorporated into the molten polymer, often along with
other additives, using appropriate high shear dispersing
equipment. However, many manufacturers of plastic
articles find it more convenient to make use of pre-
dispersed concentrates or masterbatches of colourant in
a liquid additive such as a plasticiser or in a compatible
resin. Such concentrates are then easily incorporated by
mixing into the final polymer composition at an appro-
priate stage of the processing sequence.
The most detailed source of information on pigments,
dyes and fluorescent brightening agents is the Colour
352
Index,' a single volume of which is devoted to pigments
and solvent dyes, the two classes of colourants most fre-
quently used in plastics. The Pigment Handbook2 is a
useful reference work devoted to pigments, their charac-
terisation and application, while a recent monograph
provides an extensive review of pigments, their struc-
tures and synthetic procedure^.^ This article presents an
overview of the requirements of pigments, dyes and
fluorescent brightening agents for plastics applications
and of the structures and properties of the most impor-
tant colouring materials used commercially. A number
of texts reviewing aspects of the colouration of plastics
have appeared previ~usly.~-'A recent excellent com-
prehensive review of the colouration of plastics by
organic pigments places particular emphasis on the
need to address a range of environmental problems
posed by the use of certain inorganic pigments, notably
those containing cadmium and lead.'
1 REQUIREMENTS OF COLOURANTS AND
FLUORESCENT BRIGHTENING AGENTS
FOR PLASTICS APPLICATION
The ability to produce the desired optical effect in the
plastic product is a prime requirement for a pigment,
dye or fluorescent brightening agent. However, the
materials must in addition be capable of withstanding
the effects of the environment in which they are placed,
both in processing and in their anticipated useful life-
times. An additive will be selected for a particular appli-
cation on the basis of its technical performance with
due regard also to toxicological considerations and,
inevitably, cost.
1 . I Optical properiies
The optical properties of materials are a result of a
combination of two effects arising from the interaction
of the material with visible light: absorption and scat-
tering. An object appears coloured when it selectively
absorbs certain wavelengths of visible light. The bright-
est, most intense colours are in general provided by the
use of either dyes or organic pigments. The colours pro-
vided by inorganic pigments are as a rule weaker and
duller.
High transparency in a plastic material requires the
absence of light scattering centres either within the
structure of the polymer itself or as a result of additives
present. To produce a coloured transparent article, an
inherently transparent polymer is coloured either with
dyes which dissolve in the polymer or with organic pig-
ments. Organic pigments are generally low refractive
index materials manufactured in a fine particle size
form, much smaller than the wavelength of visible light.
This combination gives rise to minimal light scattering,
and hence organic pigments are generally highly trans-
Robert M . Christie
parent. When there is considerable light scattering the
plastic article will appear opaque. Opacity in plastics is
generally obtained by the incorporation of inorganic
pigments which are usually high refractive index
materials. Titanium dioxide, the most significant white
pigment, is especially important in this respect.
1.2 Fastness properties
The heat stability of a colourant in a plastic material
refers to its resistance towards colour change at high
plastics processing temperatures and this is clearly an
important factor for many plastics applications. Colour
changes resulting from inadequate heat stability, which
can lead to off-shades or a failure to match shades, may
well be due to thermal decomposition of the colourant.
Alternatively, they may be associated with the increas-
ing solubility of a pigment at elevated temperatures,
with pigment crystal phase changes, or with the subli-
mation of a volatile dye. In the case of thermoplastics,
heat stability is generally a critical feature in colourant
selection. The degree of heat stability required for a par-
ticular application will depend not only on the pro-
cessing temperature for the polymer in question, which
can range from 150 to 35OoC, but also on the time of
exposure. Heat stability requirements in the colouration
of thermosets will also depend on processing tem-
peratures and time, although these tend to be less severe
than is the case with thermoplastics.
The properties of lightfastness and weatherfastness
are clearly related although, on occasions, colourants
which show good resistance to fading when exposed to
light can perform less well under the combined attack of
sunlight and moisture. These properties are determined
principally by the chemical structure of the colourant
but they may also depend to an extent on its concentra-
tion in the polymer and on the nature of the polymer.
Lighter shades, especially in combination with white
pigments, tend to show poorer lightfastness than deeper
shades. Resistance towards changing colour when
exposed to acids, alkalis or other chemicals is
occasionally a feature of the selection of a colourant for
a plastics outlet, e.g. for thermosets cured in the pres-
ence of acid catalysts, for acrylic polymers incorpor-
ating peroxide curing agents, or in containers for
reactive liquids. The colouration of PVC generally
requires the use of acid-resistant pigments.
1.3 Migration resistance
There are four aspects of migration of colour from
plastic materials which may be identified. These are
contact bleed, bloom, plate-out and solvent bleed, all of
which are associated to a certain extent with solubility
of the colourant in the polymer.
Contact bleed occurs when a coloured plastic
material causes staining of a dissimilarly coloured
POLYMER INTERNATIONAL VOL. 34, NO. 4, 1994
Pigments, dyes and Puorescent brightening agents for plastics
material with which it is in contact. Colourants which
are soluble in the polymer or a plasticiser present in the
formulation are liable to give contact bleed problems as
a result of molecular diffusion. Bloom is observed when
a powdery deposit of colourant appears on the surface
of a plastic product giving rise to poor rub-fastness.
This generally results when a colourant of limited solu-
bility dissolves in the hot polymer, producing a super-
saturated solution when cooled. In time, colourant
molecules diffuse to the surface of the polymer and crys-
tallisation occurs. Plate-out refers to an accumulation of
additive on the metal surfaces of plastics processing
equipment. The reasons for plate-out are not fully
established, but it appears to be a migration phenome-
non associated with the presence in the polymer of a
number of additives of different types, e.g. pigments,
lubricants and stabilisers. Solvent bleed occurs when
colour is leached from a plastic article when immersed
in a solvent. Absence of solvent bleed is essential to
ensure, for example, that a plastic bottle does not con-
taminate its contents.
1.4 Dispersibility
It is essential that a colourant is well dispersed in a
plastic material in order to achieve an even colour dis-
tribution. In addition, control of the degree of subdivi-
sion may be important to optimise optical performance.
For example, in the case of organic pigments colour
strength increases with a reduction in particle size and a
high degree of dispersion is therefore essential. Dyes
and fluorescent brightening agents, because of their
solubility in the polymer, rarely present dispersion
problems. In contrast, pigment powders which consist
of clusters of aggregated particles must be subjected to
conditions of high shear in order to break down large
aggregates to smaller aggregates and primary particles
to the degree required to produce the optimum optical
performance. The term dispersibility refers to the ease
with which the desired degree of dispersion is achieved.
Over the years, pigment manufacturers have dramat-
ically improved the dispersibility of the products pro-
duced commercially, thus minimising the energy
requirements of the dispersion process. This is generally
achieved by a surface treatment process in which the
pigment particles are coated with surface active agents
or organic resins. The result of these treatments is a
reduced degree of particle aggregation and, in addition,
such aggregates as are formed are of lower mechanical
strength and hence easier to disrupt.
1.5 Toxicologicaland environmental considerations
Toxicological considerations must always be to the fore
in colourant selection from the point of view of hazards
presented in the workplace and exposure of the general
public to the product. These considerations are of criti-
POLYMER INTERNATIONAL VOL. 34, NO. 4, 1994
353
cal importance for applications where ingestion is a
possibility, such as plastics in contact with food and in
toys and graphic instruments. There is long-standing
legislation limiting the use of certain colourants,
notably those containing lead and cadmium, in such
applications. As a result of growing concern on the
more general impact of these pigments on the environ-
ment, extension of the legislation limiting their use
further has taken place in recent years and this process
seems set to continue into the future.
1.6 Electrical properties
Pigments which reduce the insulating properties of PVC
are, for example, unsuitable for electrical cable,
although such a defect is more often due to residual
electrolyte on the surface of the pigment than to the
pigment itself.
2 INORGANIC PIGMENT
Natural inorganic pigments derived from mineral
sources have been used as colourants since prehistoric
times and a few, notably some iron oxides, remain of
some significance today. However, they have been
largely superseded by a range of technically superior
synthetic inorganic pigments including white, black and
a variety of coloured products. Inorganic pigments are
generally well-suited to plastics applications because of
their ability to provide excellent resistance to heat, light,
weathering, migration and chemicals at relatively low
cost, and in those respects they can offer technical
advantage over many organic pigments. On the other
hand, they frequently suffer from the disadvantage of
inferior intensity and brightness of colour and organic
pigments are used in preference where good colouristic
properties are of importance. Inorganic pigments,
because of their high refractive index, are generally used
where opacity is required. The chemistry and tech-
nology of inorganic pigments have been reviewed in
detail p r e v i o ~ s l y . ~ * ~Th
* e~ -following
'~ sections sum-
marise some aspects of importance in the application of
inorganic pigments in plastics.
2.I White pigments
A wide range of insoluble white powders find extensive
use in plastics. These products may be classified as
either non-hiding white pigments, which are inexpen-
sive, low refractive index materials more commonly
referred to by the plastics industry as fillers or
extenders, or hiding white pigments which as a result of
their high refractive index are capable of providing high
opacity in plastics applications. This article concen-
trates on the hiding white pigments.
Titanium dioxide (TiO,), C I Pigment White 6, is by
354
far the most important hiding white pigment used in
plastics. It owes its dominant position to its ability to
provide a high degree of opacity and whiteness
(maximum light scattering with minimum light
absorption) and to its excellent durability and non-
toxicity.” The pigment is manufactured in two poly-
morphic forms: rutile and anatase. The rutile form with
its higher refractive index and better weathering proper-
ties is much more important commercially than the
anatase form. Reflectance curves for the two forms (Fig.
1) show that the rutile form is capable of developing
higher brightness between 420 and 700 nm. However,
the anatase form exhibits lower absorption in the blue-
violet region of the spectrum below 420nm and is fre-
quently used, often in conjunction with fluorescent
brightening agents (Section 6), when a distinct blue-
whiteness is desired. Titanium dioxide pigments
produce maximum opacity at a particle size of c.
0.25pm. However, finer particle size grades (c. 0.18pm)
which have a cleaner blue tone because of higher scat-
tering of the lower blue-violet wavelengths are generally
preferred for plastics, especially for those polymers with
an inherent yellowish colour.
As a polymer containing a white pigment degrades
on exposure to natural weathering and its surface
erodes, the release of pigment particles may produce a
white powdery deposit (‘chalking’). Titanium dioxide
pigments, as a result of their strong absorption of UV
radiation (illustrated in the reflectance curves shown in
Fig. l), provide the polymer with a degree of protection
against this degradation. The rutile form provides inher-
ently greater protection, although in a few applications,
such as in white sidewall car tyres, the controlled chalk-
ing resulting from the use of the anatase form is utilised
to advantage. Surface treatment of the pigment particles
with silica, alumina or other inorganic or organic
materials is used extensively to enhance weathering
properties, to improve dispersibility and to minimise the
irreversible yellowing which can result from the reacti-
vity of titanium dioxide towards phenolic antioxidants
used in polyalkenes, polystyrene and ABS. Another use
Lu
Y iron oxides, which provide shades ranging from yellow
f and red to brown and black. These pigments are manu-
01 ’
400 (100
WAVELENGTH lnml
Fig. 1. Reflectance spectra of rutile and anatase TiO,
Robert M . Christie
of titanium dioxide pigments is as internal delustering
agents in synthetic fibres. In spite of their lower poten-
tial opacifying power, anatase pigments offer the advan-
tage for this application of a softer texture, which
minimises the abrasion of high speed spining
equipment.
There are other white hiding pigments produced
commercially, including zinc oxide, zinc sulphide, litho-
pone (a mixture of ZnS and BaSO,) and antimony
oxide but they are of only minor importance in plastics.
2.2 Black pigments
Carbon black, C I Pigment Black 6 and 7, is by far the
most important black pigment and is the second most
important in terms of volume of all pigments used by
the plastics industry, ranking behind only titanium
dioxide. Although there is a convincing argument that
carbon black ought to be regarded chemically as an
organic pigment it is more commonly classified
amongst the inorganics. The pigments are usually classi-
fied according to their method of manufacture as
furnace, lamp, thermal or acetylene blacks.
In applications where their role is to provide a black
colour, carbon black pigments exhibit high tinctorial
strength and an outstanding range of fastness properties
at relatively low cost. However, carbon blacks can
adopt a number of other important functions when
incorporated into polymers. The pigments excel in their
ability to protect polymers against weathering as a
result of a combination of UV absorption and their
ability to function at the particle surfaces as traps for
radicals formed in photodecomposition. Carbon blacks
can also function as thermal antioxidants, particularly
in LDPE. Some grades of the pigments, which exhibit a
high degree of structure involving chain-like clusters of
particles, exhibit reinforcing characteristics which are of
considerable commercial importance, especially in
rubber applications. Properly selected grades may be
used to improve either the electrical conductivity or
insulating properties of a polymer.
2.3 Coloured inorganic pigments
The most important coloured inorganic pigments are
factured either from natural deposits or by synthetic
routes. However, the synthetic products, which offer the
advantages over their natural counterparts of higher
chemical purity and better control of physical form, are
generally preferred by the plastics industry. Red iron
oxide pigments, C I Pigment Red 101 and 102, consist
principally of anhydrous Fe,O, in its a-crystal modifi-
cation. Yellow iron oxides, C I Pigment Yellow 42 and
43, although often described as hydrated oxides, are
. more correctly formulated as the oxidehydroxide,
POLYMER INTERNATIONAL VOL. 34, NO. 4, 1994
Pigments, dyes and Juorescent brightening agents for plastics
FeO(0H). Brown iron oxides are somewhat variable in
composition, consisting principally of a non-
stoichiometric mixed oxidation state oxide
(FeO),(Fez03), (x w y). Iron oxide pigments are charac-
terised in general by excellent durability, high inherent
opacity (although fine particle size transparent grades
are also available), good UV-screening properties, low
toxicity and low cost, but rather low intensity and
brightness of colour. The yellow pigments at tem-
peratures above 175°C undergo dehydration to Fe,03
with a resulting shade change, clearly a critical limi-
tation to their use in plastics.
The only other 'simple' oxide pigment of major sig-
nificance is chromium oxide, Cr,03, C I Pigment
Green 17, a tinctorial weak dull green used in a range of
plastics applications where outstanding durability,
including thermal stability to lOOO"C, is of greater
importance than brightness of colour.
The mixed phase oxides are a group of coloured inor-
ganic pigments which were developed originally for use
in ceramics but which have subsequently found wide-
spread application in plastics particularly because of
their outstanding heat stability and weathering charac-
teristics combined with moderate colour strength and
brightness. Important commercial examples include
cobalt aluminate blue, C I Pigment Blue 28, and nickel
antimony titanium yellow, C I Pigment Yellow 53.
Structurally, these pigments may be considered to
consist of host lattices such as rutile (TiO,) and spinel
(MgAl,O,) into which are incorporated varying quan-
tities of transition metal ions giving rise to a variety of
colours which retain the excellent durability character-
istics of the host
Cadmium sulphide and sulphoselenide pigments
provide a range of colours from yellows to reds and
maroons, rather brighter and stronger than other
classes of inorganic pigments. Cadmium sulphide itself
(a-CdS) is yellow. Partial replacement of CdZ by Zn2
+ +
ions in the lattice produces progressively greener shades
of yellow, while replacement of sulphur by selenium
gives rise to the orange, red and maroon sul-
phoselenides. The use of cadmium sulphide pigments is
limited severely on the grounds of their potential tox-
icity." In the European Community there is a Directive
which restricts their use in applications where they are
not seen to be es~entia1.I~ Accordingly their use is cur-
rently based on necessity, related to their excellent tech-
nical performance and in particular heat resistance,
unmatched in their shade area by any organic pigment,
to 600°C. Their principal use tends therefore to be in
engineering polymers requiring high processing tem-
peratures such as polyamides, acetals and PTFE.
Lead chromate pigments provide a range of hues
from greenish-yellow to yellowish-red.' The mid-shade
yellows are essentially pure PbCrO, . The greener
lemon chromes are solid solutions contining PbSO, ,
while incorporation of molybdate ions into the lattice
POLYMER INTERNATIONAL VOL. 34, NO. 4, 1994
355
gives the orange and light red molybdate chromes.
These pigments, which provide bright colours with
good fastness properties, find extensive application in
paints but are used much less in plastics. Like cadmium
sulphides, their use is limited by the potential toxicity
hazards associated in this case with the presence of lead
and hexavalent chromium.
Ultramarine blue, C I Pigment Blue 29, exhibits gen-
erally good durability and especially excellent fastness
to light and heat, although rather poor resistance
towards acids. It has a complex zeolytic sodium
aluminosilicate structure containing trapped S; radical
anions which are responsible for its colour. The pigment
is widely used to provide bright clean reddish-blue
shades in plastics although it has only a fraction of the
tinctorial strength of copper phthalocyanine (Section
3.2), the most important organic blue pigment. Prussian
blue, or iron blue, C 1 Pigment Blue 27, a hydrated iron
(111) hexacyanoferrate, Fe,(Fe(CN),), .nH,O, is the
longest established of all the synthetic colouring
materials. It is a low cost blue pigment with good light
fastness but relatively poor resistance to heat and
alkalis and its use in plastics is restricted largely to
LDPE.
3 ORGANIC PIGMENTS
Organic pigments are characterised in general by high
colour strength and brightness and good transparency,
although they are somewhat variable in the range of
fastness properties which they offer. The most impor-
tant commodity yellow, orange and red organic pig-
ments currently in use in plastics are a long-established
series of azo pigments. A critical event in the develop-
ment of the organic pigment industry was the discovery
in the 1920s of copper phthalocyanine blue, the first
product to offer outstanding colouristics combined with
a range of excellent fastness properties. Since then a
wide range of chemical types of organic pigments emu-
lating the properties of copper phthalocyanines in the
yellow, orange, red and violet shade areas has been
introduced to meet the high performance demands of
many plastics, synthetic fibres and paint applications. A
number of comprehensive reviews of the chemistry of
organic pigments have appeared p r e v i o ~ s l y . ~ ~ ~ ~ ~ - ' ~ * ~
3.1 Classical azo pigments
Azo pigments, both numerically and in terms of
tonnage produced, dominate the yellow, orange and red
shade areas in the range of commercial organic pig-
ments. Azo colourants are generally described as struc-
tures containing one or more azo (-N=N-) groups,
even though they may exist preferentially in the alterna-
tive structural hydrazone form."
Simple classical monoazo pigments such as Hansa
356 Robert M . Christie

Yellow G (la), C I Pigment Yellow 1, and Toluidine
Red (2), C I Pigment Red 3, find little general use in
plastics since they are too soluble and hence liable to
migration. Migration resistance may be enhanced in azo
pigments by a variety of means, for example by increas-
ing the molecular size, by incorporating metal ions or
by introducing functionality, such as the amide group
(-NHCO-), leading to strong intermolecular associ-
ation in the crystal lattice and hence low solubility.
k3
Compound (lb), C I Pigment Yellow 97, is an example
of a higher molecular weight Hansa Yellow pigment
recommended for use in polystyrene, polypropylene and
rigid PVC. The most important yellow azo pigments,
used in polyethylene, polypropylene and flexible PVC,
are the disazoacetoacetanilides (Diarylide or Benzidine
Yellows) (3a-3e) which exhibit good colour strength and
migration resistance although somewhat inferior light-
fastness. The Pyrazolone Oranges (4a) and (4b) are
similar in structure and properties to the Diarylide
Yellows.
The most important classical red azo pigments are
metal salts (Sa-Sb), products of good colour strength
and brightness and migration resistance which are used
in many thermoplastics applications. These pigments,
commonly referred to as ‘toners’, have evolved from

1 Hansa Yellows
R’ R2 R3 R4 R5 R6
l a NO2 CH, H H H H
l b CH30 S02NHC6H5 CH,O CH,O CI CH30
1~ NO2 CI H H -NHCONH-

5 Metal salt pigments

C. I. Pigment R1 R2 M
5a Red48:l CH, CI Ba
5b Red48:2 CH, CI Ca
5c Red48:4 CH, CI Mn
2 Toluidine Red 5d Red57:l CH, H Ca

3 Benzidine Yellows
C. I. Pigment R1 R2 R3
3a Yellow 12 H H H
3b Yellow 13 CH, CH, H
3c Yellow14 CH, H H
3d Yellow 17 CH,O H H
3e Yellow83 CH,O CI CH,O

4 Pyrazolone Oranges
C. I. Pigment R
4a Orange 13 H
4b Orange34 CH,

POLYMER INTERNATIONAL VOL. 34, NO. 4, 1994

Pigments, dyes and fluorescent brightening agents for plastics
'lake' pigments, now largely obsolete, which were essen-
tially anionic azo dyestuffs precipitated on to inorganic
substrates such as alumina and barium sulphate. The
only commercially significant metal complex azo
pigment is Nickel Azo Yellow (6), C I Pigment Green
10, which exhibits good fastness properties and is suit-
able for use in polyethylene, PVC and cellulosics
although it suffers from a rather dull green colour.
6 Nickel Azo Yellow
'cl
3.2 Copper phthalocyanines
Copper phthalocyanine (7), C I Pigment Blue 15, is
arguably the single most important organic pigment.
Copper phthalocyanine finds widespread use in most
plastics applications because of its brilliant blue colour
and its excellent resistance towards light, heat, migra-
tion, acids and In addition, in spite of its
structural complexity, copper phthalocyanine is a rela-
tively inexpensive pigment as it is manufactured in high
yield from low cost starting materials. There are two
commercially important crystal modifications of the
pigment, the reddish-blue a-form and the more stable
greenish-blue p-form. The a-form of copper phthalocya-
nine pigments may be stabilised, e.g. by the presence of
a single chlorine substituent, and for plastics these pro-
ducts are preferred to unstabilised pigments which tend
to convert in application to the B-form with a corre-
sponding shade change. The most important green
organic pigments are copper phthalocyanines in which
most or all of the ring hydrogen atoms are replaced by
halogens. Polychloro, polybromo and polybromochloro
copper phthalocyanines are produced, the shade of the
pigments becoming progressively yellower with increas-
ing bromine content. These copper phthalocyanine
%q N cu
&iN'%
I \
7 Copper phthalocyanine
POLYMER INTERNATIONAL VOL. 34, NO. 4, 1994
357
greens, which exhibit properties comparable to the
blues, are also excellent pigments for plastics.
3.3 Miscellaneous high -performance organic
pigments
This section contains a brief survey of a range of
organic pigments encompassing a wide variety of struc-
tural types which are well suited to plastics applications
because of their excellent durability combined with high
colour strength and brightness, properties in many cases
comparable to those of copper phthalocyanines. They
tend, however, to be rather expensive.
There are two classes of high performance azo pig-
ments. Disazo condensation pigments, developed by
Ciba-Geigy, are a range of durable yellow, red, violet
and brown products with structures such as (8) which
derive their name, and also their relatively high cost,
8 Azo condensation pigment (A = aromatic ring)
from the rather elaborate synthetic procedures involved
in their manufacture. Hoechst have developed a range
of benzimidazolone azo pigments, e.g. the orange
product (lc), ranging in shades from yellow to bluish-
red and browns and with excellent fastness properties
including heat stability to 330°C. Their good stability to
light and heat and their insolubility is attributed to
extensive intermolecular association as a result of
hydrogen-bonding and dipolar forces in the crystal
lattice. A similar type of molecular association accounts
for the excellent range of fastness properties of the quin-
acridones (9). These pigments, developed initially by
DuPont, are used widely in plastics, offering red and
violet colours and heat stability to 400°C.22
H 0
R
9
0 H
Quinacridones (R = H. CI, or CH,)
A number of vat dyes developed originally for textile
applications are suitable, after conversion to an appro-
priate pigmentary physical form, for use in many plas-
tics applications. Examples of these so-called vat
pigments include the anthraquinones, Indanthrone Blue
358 Robert M . Christie

(lo), C I Pigment Blue 60, and Flavanthrone Yellow
(ll),C I Pigment Yellow 24, the red to violet thioindigo
derivatives (12) and the orange perinone (13). Other
high performance pigments used in plastics include the
red and maroon perylenes (14), the yellow to red tetra-
chloroisoindolinones (15), the violet dioxazine (16), C I
Pigment Violet 23, and the isoindolines, such as the
yellow pigment (17), C I Pigment Yellow 139. Arguably
0
the most significant development in organic pigments in
recent years has been the discovery and development of
diketopyrrolopyrrole (DPP) pigments (18).23These pig-
ments are capable of providing brilliant saturated red
shades with outstanding durability, including excellent
thermal stability. As such they are of considerable inter-
est for the pigmentation of plastics, and their use seems
certain to increase in years to come.

15 Tetrachloroisoindolinone (A = aromatic ring)

10 lndanthrone Blue 0

0 CI D
16 Dioxazine Violet

11 Flavanthrone Yellow 0
0

Hy4NH

12 Thioindigo pigments (Rl, R2 = H,CH,, CI)

17 lsoindoline 18
% \ R

DPP pigment

4 PIGMENTS FOR SPECIAL EFFECTS

4.I Fluorescent pigments

The striking brilliance of a fluorescent colour results

when a molecule absorbs visible radiation and re-emits
an intense narrow band of visible light at somewhat
13 Perinone higher wavelengths, reinforcing the colour already
present due to normal visible light absorption. Fluores-
cent pigments consist of low concentration solid solu-
tions of fluorescent dyes, such as aminonaphthalamide
(19), C I Disperse Yellow 11, and Rhodamine B (20), C I
Basic Violet 10, in a transparent resin, usually of the
toluenesulphonamide-melamine-formaldehyde type,
ground to a fine particle size.24 Fluorescent pigments
tend to show inferior lightfastness and thermal stability
14 Perylene (R = alkyl or aryl) compared with normal coloured pigments, factors

POLYMER INTERNATIONAL VOL. 34, NO. 4. 1994

Pigments, dyes and fluorescent brightening agents for plastics 359

5 DYES

Dyes are used much less extensively than pigments in

O 9 Y 0
- improved fastness properties suitable for use in more
N(C2H5)2
CI-
d in organic media. Solvent dyes are particularly impor-
which restrict their use to a certain extent in plastics.
Their main uses in plastics are for visual impact in toys,
packaging and safety application^.'^
4.2 Pearlescent pigments
Pearlescent pigments give rise to a white pearl effect,
often accompanied by a coloured irridescence. The most
important synthetic pearlescent pigments are thin plate-
lets of mica coated with titanium dioxide which partly
reflect and partly transmit incident light.26 Simulta-
neous reflection from many layers of oriented platelets
creates the sense of depth characteristic of pearlescent
lustre and, where the particles are of an appropriate
thickness, colours are produced by interference pheno-
mena. For maximum pearl effect in a plastic material,
sufficient shear to produce a good dispersion of the
pigment but avoiding disintegration of the platelets is
desired.
4.3 Metallic pigments
The most important metallic pigments are those based
on finely divided aluminium flakes.27They may be used
in plastics to simulate the colour of the metal or, in
the colouration of plastics. Nevertheless, there are
important applications of dyes in plastics which utilise
the particular merits which these colouring materials
possess. The advantages of dyes include high tinctorial
strength and brightness, excellent transparency, ease of
incorporation and low cost. Although dyes traditionally
are considered as having inferior resistance to migra-
tion, heat and light than pigments, the modern range of
dyes for plastics contain products with significantly
demanding applications.
By far the most important class of dyes used in plas-
tics because of their solubility in the polymer are
solvent dyes.” Solvent dyes are generally small non-
ionic aromatic molecules with relatively few substit-
uents, structural features which ensure good solubility
tant for the colouration of polystyrene where individual
dye molecules become fixed as a result of their affinity
for the polymer molecules. However, they are also used
to a certain extent in a wider range of thermoplastics,
including acrylics, cellulosics, ABS and rigid vinyls, and
in thermosets.
The yellow, orange and red shade areas are provided
mainly by simple inexpensive monoazo dyes, such as
compounds (21a)-(21c) and a few related disazo dyes
such as compound (21d). Red, violet, blue and green
shades are provided by simple anthraquinones, e.g.
(22a)-(22d). The anthraquinone dyes, in general, exhibit
R2 URl OH
21 Azo dyes for plastics
R’ R2
21a C.I. Solvent Red 14 H H
21b C.I. Solvent Orange 7 CH3 CH,
21c C.I. Solvent Red 1 CH3 H
21d C.I. Solvent Red 24 CH3 o-cH3c6H4-N=N-
0 R1

combination with transparent organic pigments, to

produce novel metallic colouristic effects. Pre-dispersed
preparations in liquid plasticiser or resin granules are
invariably used since dry aluminium flakes are poten-
tially explosive in a dust cloud. The shear used in dis-
22 Anthraquinone dyes for plastics
persing aluminium pigments into polymeric materials R’ R2
should be minimised in order to prevent disruption or 22a C.I. Solvent Red 111 CH3NH H
deformation of the flakes which would lead to a 22b C.I. Disperse Violet 1 NH, NH2
reduction in the metallic effect. Bronze pigments are 22c C.I. Solvent Blue 56 (CH3),CHNH (CH3),CHNH
used similarly to give a gold or copper effect.’* 22d C.I. Solvent Green 3 pCH,C,H,NHi pCH3C6H4NH

POLYMER INTERNATIONAL VOL. 34, NO. 4, 1994

360
superior weatherability and heat stability compared
with the azo dyes but they are more expensive. The
largest volume solvent dyes used by the plastics
industry are the nigrosine blacks whose high tinctorial
strength is used to produce jet blacks of an intensity
which cannot be matched using carbon black pigments.
Nigrosines are complex polymeric species containing
the phenazine ring system. A few solvent dyes of other
chemical types are used in plastics, including the fluo-
rescent yellow aminonaphthalimide (19), xanthenes,
perinones, quinophthalones and phthalocyanines.
Dyes of other application classes are used much less
in plastics, although anionic acid dyes, such as Metanil
Yellow (23), and cationic basic dyes, such as the fluores-
cent red Rhodamine B (20), may be used in some
thermosets.
SO3- Na+
23 Metanil Yellow
6 FLUORESCENT BRIGHTENING AGENTS
These materials, known variously as fluorescent or
optical brightening or whitening agents, are used to
offset a yellowish cast in a white substrate and further
to convert it into a brilliant b l u i ~ h - w h i t e . In
~ ~physi-
cal terms, an ideal white material would exhibit 100%
reflectance throughout the visible region of the spec-
trum (Fig. 2, curve a). However, white plastic substrates
commonly exhibit a strong absorption band in the UV
region of the spectrum which tails into the visible region
(curve b). This weak absorption of blue light gives rise
to a yellowish cast. The fluorescent brightening agent
absorbs UV radiation and re-emits the energy by means
of fluorescence in the blue to blue-violet region of the
I I I I
300 400 500 6w
WAVELENGTH Cnd
Fig. 2. Reflectance spectra of (a) ideal white substrate; (b)
white polymer substrate without FBA; (c)white polymer sub-
strate with FBA (total reflectance).
Robert M . Christie
visible region. The white substrate with the agent
incorporated exhibits a total reflectance spectrum (curve
c) showing increased UV absorption, but more impor-
tantly with the absorption of blue light by the substrate
more than offset by the fluorescent emission in that
region. The visual result is an appealing brilliant white
with a bluish cast.
The major applications of fluorescent brightening
agents are in textiles, paper and detergents. Their appli-
cation in plastics represents only a very small propor-
tion of the total tonnage produced. Nevertheless, they
are used in a range of thermoplastic and thermoset pro-
ducts in which a brilliant white appearance is desirable.
Of the many compounds available, only a few have the
necessary balance of properties for use in plastics. Fluo-
rescent brightening agents used commercially in plastics
generally have the structural features characteristic of
the solvent dye class, the most important types being
bis(benzoxazo1-Zyl) derivatives (24), coumarin deriv-
atives (25) and bis(styry1)biphenyls (26).
24 Bis (benzoxazol - 2- yl) FBA
(R = aromatic, heterocyclic or alkene group; R' = H, alkyl)
*~~
25 Coumarin FBA (R = heterocyclic)
26 Bis (styryl) biphenyl FBA
Since the optical effect of fluorescent brightening
agents relies on their absorption of UV radiation, the
presence of other UV-absorbing additives can have an
adverse effect on their performance. In consequence, a
more brilliant white is achievable from a fluorescent
brightening agent used in conjuction with anatase tita-
nium dioxide white pigments than with rutile form
which is more highly UV-absorbing (Fig. 1).
R EFER ENCES
700
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Wiley & Sons, New York, 1973; 2nd edn, ed. P. A. Lewis, John
Wiley & Sons, New York, 1988.
POLYMER INTERNATIONAL VOL. 34, NO. 4, 1994
Pigments, dyes and fluorescent brightening agents for plastics
3 Christie, R. M., Pigments: Structures and Synthetic Procedures. Oil
& Colour Chemists Association, London, 1993.
4 (a) Webber, T. G., ‘Colourants’ in Encyclopedia of Polymer Science
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5 Reeve, T. B., Plast. Eng., 33 (1977) 31.
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18. Verlag-Chemie, Weinheim, 1979.
10 Taylor, P. J., Rev. Prog. Coloration, 4 (1973) 37.
11 Ferguson, W. J., Plast. Rubber Int., 8 (1983) 32.
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13 Ressler, I., Plastuerarbeiter, 37, (1986) 48.
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15 Cowley, A. C. D., Rev. Prog. Coloration, 16 (1986) 16.
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Venkataraman. Academic Press, London, 1972, p. 313.
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361
17 Herbst, W. & Hunger, K., Industrielle Organische Pigmente. VCH
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18 Christie, R. M., Standring, P. N. & Griffths, J., Dyes Pigments, 9
(1988) 37.
19 Moser, F. H. & Thomas, A. L., Phthalocyanine Compounds. Rein-
hold Publishing Corporation, New York, 1963.
20 Moser, F. H. & Thomas, A. L., The Phthalocyanines, Vols I and 11.
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26 Reiger, C. J. & Novinski, S., Plastics Compounding, (1984) 56.
27 Kerr, G., Plastics Compounding, (1984) 59.
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