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Pigments for Printing Inks

By: Adesh Katariya

Pigment
Industrially, a pigment is any finely divided insoluble
black, white or colored solid material, a major
function of which is to improve the appearance of or
give color to the medium in which it is to be used.

Colour
Color phenomena is the electromagnetic
radiation in the wavelength range of 400 to
700 nm.
When a photon enters a pigmented film
following events may occur:
1. It may be absorbed by a Pigment particle
2. It may be scattered by a Pigment particle
3. It may simply pass through the film

Pigments : How they appear?


Pigment must have light absorption and light-scattering
properties.
If absorption is very small compared with scattering,
the pigment is a white pigment.
The absorption is much higher than scattering over the
entire visible region, and then the pigment is a black
pigment.
In a colored pigment, absorption is selective.
A wide variety of wavelengths (colors)
encounter a pigment. This pigment
absorbs red and green light, but
reflects blue, creating the color blue.

Colour Index Generic Name


C.I. Generic Name describes a commercial
product by its recognised usage class, its hue
and a serial number (which simply reflects the
chronological order in which related colorant
types have been registered with the Colour
Index)
Like C.I. Red 122, C.I. Pigment Yellow 176

Quality and performance of


Pigments
Governed by :
Crystal type
Crystal shape (nodular, spherical, prismatic, acicular or lamellae )
Crystal size : Typical ranges for average diameter of
primary particles are:
Carbon black 0.01 to 0.08 m
Titanium dioxide 0.22 to 0.24 m.
organic 0.01 to 1.00 m;
Inorganic 0.10 to 5.00 m;
Crystal surface properties

Performance of pigments in Ink


System

Performance is governed by application type,


technology in use and interaction with formulating
Ingredients
Parameters which have to be taken into consideration,
as well modified, are physical form, dispersion
property, ability to stand dispersion condition,
rheological behavior, colouristic properties, heat &
light fastness properties, storage properties, etc.

Pigments are classified as either


organic or inorganic.
Organic pigments are based on carbon chains
and carbon rings.
Inorganic pigments, chemical compounds not
based on carbon, are usually metallic salts
precipitated from solutions

Inorganic v/s Organic pigments


Inorganic pigments have a much larger average particle
size than organic pigments. This is the main reason why
most organic pigments are considered transparent and
most inorganic pigments opaque.
With their larger surface area, organic pigments give
much higher color strength. However, for similar
reasons, their dispersibility is usually poorer.
As a result of their chemical composition, inorganic
pigments are stable in the presence of organic solvents
unlike many of the simpler organic pigments, which
can dissolve and have high resistance to pigment
bleeding and migration.
With a few exceptions, inorganic pigments have higher
heat stability than organic pigments. However, light
fastness and weatherability vary more widely.

Cont.
Particulars

Inorganic Pigments

Organic Pigments

Source

Minerals

Chemically refined oil

Color

Often dull

Bright

Dyeing / Coloring Strength

Low

High

Opacity

Opaque

Transparent

Light fastness

Very good

Vary from poor to good

Solubility

Insoluble in solvents

Have have little degree of


solubility

Degree of safety

May be unsafe

Usually safe

Chemical Stability

Often sensitive

Usually good

Cost

Moderate

Mostly too expensive

Organic Pigments
Azo Pigments: Pigment class containing the azo
group (-N=N-) in common. The synthesis of azo
pigments is economically attractive.
Poly Cyclic Pigments : Pigments with condensed
aromatic or heterocyclic ring systems are known as
polycyclic pigments. Their chief characteristics are
good light and weather-fastness and good solvent
resistance. They are typically costlier than azo
pigments.

Key features and characteristics of


Organic Pigments
Very good stability to solvents, light, heat, and
weathering
Good tinctorial strength
Cost effectiveness
Consistency and unique shades
Completely non-toxic
Very bright, pure, rich colors
Organic pigments shows good color strength

Azo Pigments
o
o
o
o
o
o
o
o

Mono-azo Yellow and Orange pigments


Disazo
Naphthol
Naphthol AS
Azo lakes
Benzimidazolone
Disazo condensation
Metal complex

Polycyclic pigments

Phthalocyanine
Quinacridone
Perylene and perinone
Thioindigo
Anthraquinone
Dioxazine
Isoindolinone and isoindolin
Diketo-pyrrolo-pyrrole (DPP)
Triarylcarbonium
Quinophthalone

Monoazo Yellow and Orange Pigments


Monoazo yellow pigments that are obtained by a
coupling a diazonium salt with acetoacetic acrylides, as
coupling components, cover the spectral range between
greenish and medium yellow; while coupling with 1acrypyrazolone-5 affords reddish yellow to orange
shades.
All members of this family share good light fastness,
combined with poor solvent and migration resistance.
PY1, PY3, PY 74, PY 73 etc.

Diazo Pigments
Major products :PY12, PY13, PY17, PY83
Diazo Pigments divided into two groups
The first and most important group includes compounds
whose synthesis involves the coupling of di- and tetrasubstituted diaminodiphenyls as diazonium salt with
acetoacetic arylides (diarylide yellows) or pyrazolones (disazo
Pyrazolones) as coupling components.
The second group, bisacetoacetic arylide pigments, are
obtained by diazotization of aromatic amines, followed by
coupling on to biacetoacetic arylides. The color potential of
disazo pigments covers the color range from very greenish
yellow to reddish yellow and orange and red.

-Naphthol Pigments
-Naphthol Pigments provide colors in the range
from orange to medium red.
The typical coupling reaction with -naphthol, as a
coupling component, yields such wellknown
pigments as Toluidine Red and Dinitroaniline
Orange.
Available hues are toluidine red (PR3, PR49, PR53,
PR68) and a few orange (dinitraline orange PO5,
PO17, PO46)

Naphthol AS Pigments (Naphthol


Reds)

These pigments are obtained by substituting coupling aryl


diazonium salt with arylides of 2-hydroxy-3-naphthoic acid
(2- hydroxy-3-naphthoic acid anilide = Naphthol AS).

They provide a broad range of colours from yellowish and


medium red to bordeux, carmine, brown, and violet; their
solvent fastness and migration resistance are only marginal.

The color range is concentrated in the long wavelength end of


the spectrum, including warm orange (PO24, PO38), scarlet
(PR188, PR261), many reds (PR2, PR3, PR5, PR7, PR8, PR9,
PR17, PR22, PR112, PR150, etc.), carmines (PR23, PR146,
the many pigments listed under PR170), maroon violet (PV13,
PV25, PV44), and brown (PBr1).

Azo Pigment Lakes


These pigments are formed by precipitating a
monazo compound, which contains sulfo and/or
carboxy groups.
The coupling component in the reaction may vary: b-naphthoic acid
lakes are derived from 2-naphthol, BONA pigments lakes use 2hydroxy-3-naphthoic acid (Beta-Oxy- Naphthoic Acid); and Naphthol
AS pigment lakes contains anilides of 2-hydroxy- 3-naphthoic acid,
as a coupling component.

Lakes may also be prepared from naphthalene


sulfonic acids. Lake Red C is one of the
commercially significant b-naphthol lakes.

Benzimidazolone pigments
Benzimidazolone pigments feature the
benzimidazolone structure, introduced as part of the
coupling components.
These pigment obtained by coupling onto 5-acetoacetyl
aminobenzimidazolone cover the spectrum from greenish yellow
to orange; while 5-(2-hydroxy-3-naphthoylamino)benzimidazolone as a coupling components affords products that
range from medium red to carmine, maroon, bordeaux, and
brown shades.

Broad range of hues, from yellow (PY120,PY151,PY154,PY175,


PY180, PY181, PY194), through orange (PO36,PO37,
PO60,PO62, PO72) and red (PR171,PR175,PR176, PR185,
PR208) to a maroon of fair lightfastness (PV32).

Disazo Condensation
These pigments can formally be viewed as resulting from the
condensation of two carboxylic monoazo components with one
aromatic diamine.
The resulting high molecular weight pigments show good heat stability
and light fastness.
Their main markets are in the plastic field and in spin dyeing.
The spectral range of disazo condensation pigments extends from
greenish yellow to orange and bluish red or brown.
Available hues range from yellow (PY93, PY95, PY128, PY166),
orange (PO31), red (PR144, PR166) and brown (PBr23,PBr42).

Metal Complex Pigments


All combine a symmetrical pair of carbon (organic)
compounds with a metal atom (usually nickel or copper).

Included in this group are the azo-methine metal complexes. Colors range
from green (PG8) to green gold (PG10,PY117, PY129), yellow
(PY150, PY153, PY177, PY179), orange (PO59, PO65), and red (PR257,
PR271).

Those species that provide the required light fastness and


weather resistance are used in automotive finishes and
other industrial coatings.
They are nontoxic but may (depending on the metal atom
used) irritate the skin.

Phthalocyanine pigments

Phthalocyanine pigments are derived from the


phthalocyanine structure, a tetraaza-tetra-benzo-porphine.
Although this basic molecule can chelate with a large
variety of metals under various coordination conditions,
today only the copper (II) complexes are of practical
importance as pigments.
Commercial varieties include the reddish blue alpha form, as
stabilized and non-stabilized pigments; the greenish blue beta
modification. Bluish to yellowish shades of green pigments may be
produced by introduction of chlorine or bromine atoms into the
phthalocyanine molecule.

Cont..
An important pigment from the family of
Copper phthalocyanine is the C.I. Pigment
Blue 15:3.
The production steps of which is given
here.

Quinacridone pigments
Highly recommended for high light fast and High
resistance application.
As on now major consumption in ink jet inks as
well as high quality process magenta shades
Due to better transparency, the combination with
pearlescent and metallic pigments creates
outstanding effects that can easily be applied for
coatings and inks.
The available hues range from golden yellow (PO49), through
reddish orange (PO48), middle red (PR209), coral (PR207),
red (PV19), rose (PV19 and PV42), magenta (PR122, PR202),
maroon (PR206), and a dark reddish violet (PV19).

Isoindolinone and Isoindoline Pigments


Although of comparatively good light and weather
fastness, solvent and migration resistance, only a
few members of the isoindolinone and isoindoline
families are commercially available as pigments.
Chemically classified as heterocyclic pigments,
they are preferably supplied for high grade inks.
Colors range from yellow (PY109, PY110, PY139,
PY173, PY185) to orange (PO61, PO66, PO69) and red
(PR260).

Perylene Pigments
Perylene pigments are prepared by the condensation of
perylenetetracarboxylic monoanhydride monoimides with primary
amines.
Perylene pigments are very stable thermally together with photo
stability .

Available colors are limited to moderately saturated scarlets (PR123,PR149,


PR190), reds (PR178), dark maroons (PR190, PR179, PR224, PV29), and a
very dark green (PBk31).

Dioxazine
The pigment is obtained by dissolving the dye
in a very hot acid, then washing and salt
grinding the precipitate that results.
The pigment exists in two crystal modifications, a red and a
blue shade, whose hue can be modified by different methods
of manufacture or grinding: both have the same color index
name, are poorly distinguished by manufacturers, and are
apparently confused in the lightfastness testing literature

Pigment Violet 23 and 37

Anthraquinone
A small group of about 10 pigments, most of them
with a long history as textile vat dyes.
They made dull, weak pigments until methods of
purification, careful precipitation and grinding were
discovered that retained most of the dye's color
brilliance.

The group includes anthrapyrimidine yellow (PY108), anthraquinoid red


(PR177) and my favorite, indanthrone blue (PB60).

Good Re-solubility in Solvent based Inks: Use to improve resolubility

Diketo-pyrrolo-pyrrole (DPP)
A small but very important group of new synthetic
organic pigments, discovered in the early 1980's and
systematically developed into pigments with very
good lightfastness.
About six are currently offered, in the shades orange
(PO71, PO73), scarlet (PR255), red (PR254) and
carmine (PR264, PR274).
All the pyrroles are nontoxic, extremely lightfast,
semitransparent to semi-opaque, and staining.

Triarylcarbonium.
Two groups of triphenylmethane pigments, obtained by
laking basic dyes.
Color range is green (PG1, PG2, PG4, PG45), blue (PB1, PB2,
PB9, PB10, PB14, PB18, PB19, PB56, PB61, PB62), red
(PR81, PR169) or violet (PV1, PV2, PV3, PV27, PV39).
Their lightfastness ranges from poor to worthless and no paint
containing these pigments or any unlaked basic dye should be
used in professional quality artworks.

Quinophthalone
Quinophthalone pigments prepared with using of
phthalic anhydride and 2-methylquinoline derivatives as
starting materials and BF3 as catalyst under solvent-free
and reflux conditions.
These pigments are opaque in nature, fastness to
weathering , Low migration nature, satisfactory HR, gloss
stability and flow properties; the outstanding color strength
makes it the preferred product for economic formulations.
These are non-Toxic to animals by oral, so widely used for
fish foods.
PY 138, PY 139, PY 185

Inorganic pigments

Titanium dioxide white


Carbon black
Iron oxide
Ultramarine blue
Chrome based pigments
Effect Pigments ( Pearl, Metallic etc.)

Carbon black
Carbon black (PBK-7) is the name of a common
black pigment, traditionally produced from charring
organic materials such as wood or bone.
It appears black because it reflects very little light
in the visible part of the spectrum, with
an albedo near zero.

High strength, good colour, light & weather


resistant

Titanium dioxide-TiO2 (PW6)


Titanium dioxide Is the naturally occurring oxide of titanium.
The three common phases of titanium dioxide are rutile, anatase and
brookite. Rutile is the most stable form of titanium dioxide. Anatase
and brookite are stable at normal temperatures but slowly convert to
rutile upon heating to temp. above 550 and 750 C, respectively.
Approximately 4.6 million tons of pigmentary TiO2 are used
annually worldwide.
High strength, high opacity, cheap, good UV resistance.
Major problem: forms radicals that degrade the binder.

Manufacturing of Titanium
Dioxide
Chloride Process

Sulfate Process

Iron oxide Pigments


Usually mined although can be synthesized
Natural iron oxides are derived from hematite, which is a red iron oxide
mineral; limonites, which vary from yellow to brown, such as ochers,
siennas, and umbers; and magnetite, which is black iron oxide.
Also can be produced synthetically by thermal decomposition of iron
salts or iron compounds, precipitation of iron salts usually accompanied
by oxidation, and reduction of organic compounds by iron
Light and weather resistant, unreactive
India is world leader in production of Iron Oxide Pigments
Cannot produce clean shades

Chrome Pigments
These pigments are chromium based pigments.
Ink companies are avoiding to use these
pigments due to presence of Heavy Metals.
Light, weather, alkali and acid resistant;
thermally stable
Main products are Strontium Chromate, Lemon Chrome, Middle
Chrome, Primrose Chrome, Scarlet Chrome and Zinc Chromate .

Ultramarine Blue
Ultramarine Blue is Synthetic Inorganic. It
is a blue pigment of sodium aluminosilicate
containing sulphur.
It is prepared by heating kaolin, sodium
carbonate, sulphur and other inexpensive
ingredients together.
It is heat and alkali resistant.

Effect Pigments
The theory of optics as a wave
and
combination of Chemistry

Pearl luster pigments


Regular reflection takes place on highly
refractive parallel pigment platelets
Titanium dioxide on mica

Metal effect pigments


Regular reflection takes place

Types:
o Aluminium Pigments( Leafing/Non-Leafing)
o Vacuum Metallized Pigments
o Goldbronze Pigments

Interference pigments
The optical effect of colored luster pigments
is caused mainly due to interference of
light.
Iron oxide on mica

UV Fluorescent Pigments

UV Fluorescence Pigment absorbs radiation of a


certain wavelength, or group of wavelengths, and reemits photons of a different wavelength , without a
delay

Most of these pigments are excited by short


wavelength UV light (around 254 nm).
Silver-doped zinc sulfide
Under Normal Light

Under UV Light

Phosphorescent pigments
These pigment has ability to absorb light and
then emitted the light of longer wavelength
within several hours after excitation.
When ambient darkness occurs, it becomes
highly visible.
Examples: copper-doped zinc sulfide
Commonly called glow-in-the-dark
Used in Screen Inks for Sign Boards

IR Fluorescent (Anti-Stokes)
Coding and MarkingPigments
Purposes in Security Printing

Applications for Offset and Solvent Based inks.


Special near IR lasers or LEDs are needed for detection.
Under Visible light, they appear white and in Near IR
Region, they appear coloured.
IR fluorescent pigments do not Stokes law, they are
excited by IR energy, and either emit in the visible region
or in the IR region but at a shorter wavelength.

Same Pigmented Coating


In Visible Region

In 980 nm IR Region

White

Yellow

Optically Variable Pigments


PVP show angle-dependent color and lightness
effects which are based on reflection, interference
and absorption phenomena of visible light in
pigmentary multilayer systems.

Thermochromic Pigments
Thermochromic Pigments change change
their color because of the Change of
Temperature
Change in the molecular structure as per
temperature.
Also pressure dependent pigments are using
Uses in Offset and Screen Inks
Same coating have

At 15 DC

At 30 DC

White

Orange

..

Thank You