PIGMENT

Pigment
• What is pigment

• A pigment is a material that changes the color of reflected or

transmitted light as the result of wavelength-selective
absorption. This physical process differs from fluorescence,
phosphorescence, and other forms of luminescence, in which a
material emits light

• Many materials selectively absorb certain wavelengths of

light. Materials that humans have chosen and developed for
use as pigments usually have special properties that make them
ideal for coloring other materials. A pigment must have a high
tinting strength relative to the materials it colors. It must be
stable in solid form at ambient temperatures.
 PIGMENT
is a particulate solid dispersed into a medium without
solution or significant interaction

Differences between Pigments and Dyes

Pigments are dispersions in medium but dyes are

solutions
Pigments posses particulate properties but dyes do not

Pigments are far more durable and resistant to fading

than dye
Differences between Pigments and
Dyes

Pigment

Dye
 Applications of Pigments

1 Inks : water and solvent based

2 Paints : water and solvent based
3 Plastics : all types including EVA
4 Rubber
5 Glass
6 Ceramic
7 Textile
8 Cement Products
9 Cosmetics
 Required Properties of Pigments

Colour Weather Stability

Colour Strength Opacity

Heat Resistant: IK Insolubility

Light Fastness: sun light, Solvent Fastnesss

xenon
Color Strength
Full-Tinting Strength
Two Roll Mill
Two Roll Mill
Solvent Fastness
 Effect of particle size of the pigment

1 Tinting strength
2 Gloss
3 Viscosity
4 Weatherfastness
 Forms of Pigments

Solid Minimum 95% Pigment

content
Presscake Maximum 40 % Pigment
Content

Chip, masterbatch Usually 20-25 % Pigment

Content
BASIC / PRIMARY COLOURS (2nd & 3ry
?)
Organic Pigments vs Inorganic Pigments

Particular Inorganic Pigment Organic pigment

Color Dull Bright
Color strength Low High
Opacity Opaque Transparent
Light Fastness Good Vary from poor to
good
Heat Fastness Good Vary from poor to
good
Chemical Fastness Poor Very Good
Solubility Insoluble in sovents Have little degree of
solubility
Degree of safety May be unsafe Usually safe
Classification of Organic Pigments

• Azo Pigments
• Non-Azo Pigments = Polycyclic Pigments

Azo Pigments
Azo Pigments have the azo group (-N = N-)
There are 2 stages for the synthesis of azo pigments:
- Diazonium salt formation
- Coupling reaction
Monoazo Yellow and Orange Pigments

1. They are obtained by coupling a diazonium salt with

acetoacetic arylides to give greenish to medium Yellow
Pigments

2. While coupling with 1 – arylpyrazolones-5 produces

reddish orange shade

3. Their process good light fastness but poor solvent &

migration resistance

4. commercial application in certain inks ( flexo & offset inks)

Monoazo yellow
Monoazo Orange
 Disazo Pigments

• Disazo Pigments : 2 classes

1. The coupling of di – and tetra – substituted
diaminodiphenyls with acetoacetic arylides or pyrazolones

2. The coupling of diazotization of aromatic amines with

bisacetoaceticarylides

3. These pigments cover the colour range from greeny yellow to

reddish yellow & orange & red

4. They have better solvent & migration fastness than mono azo
pigments & are use in printing inks & plastic

The color potential of disazo pigments covers the color range from
very greenish yellow and orange and red
Disazo Pigments(2 Oxygens missing)
 β- Naphthol Pigments

Beta Naphthol Pigments provide colours from orange

to medium red

Production by coupling reaction with beta naphthol

Solvent resistant, migration fastness & light fastness are
comparable to mono azo yellow pigments

Commercial application in paints

Beta Naphthol Pigment
 Naphthol AS Pigments
(Naphthol Reds)

These pigments provide colour from yellowish &

medium red to brown & violet

They are obtain by coupling reaction of aryl diazonium

salt with aryllides of 2-hydroxy-3-naphthoic acid

Their solvent fastness & migration resistance marginal

Commercial application in printing inks & paints

Naphthol AS Pigment (2 N missing)
 Azo Pigment Lake
(Salt Type Pigments)

These pigments provide colours between medium red

to bluish red
They are from by precipitating a monoazo compound with
contain sulfo & / or carboxy groups with metal cations such as
calcium, barium, magnesium, strontium or manganese.

These pigments have limited light fastness & migration

resistance but good heat fastness.

Their commercial application are in printing inks, plastic

& paints
Naphthol AS Pigment Lakes
Beta Naphthol Pigment Lakes
Azo Metal Complexes
Bona Pigment Lakes
Naphthalenesulfonate Pigment
Lakes
Azomethine Metal Complexes
 Benzimidazolone Pigments

These pigments cover the spectrum from greenish

yellow to orange & medium red to maroon
There two type : the first one is obtain by coupling with 5-
acetoacetylaminobenzymidazolone,the second one the coupling
components is 5-2-hydroxy-3-naphthoaylamino-
benzymidazolone

Pigment performance including light fastness & weather ability is

excellent
Application in plastics & hybrid printing inks
Benzimidalone Pigment
Benzimidazolone Pigment
 Disazo Condensation Pigments

The spectral range of these pigments covers from greenish

yellow to orange & blueish red or brown

They are obtained from the condensation of two carboxylic

monoazo with one aromatic diamine

They have wood solvent & migration resistance & light

fastness
Application in plastic & spin dyeing
Disazo Condensation Pigments
Yellow (missing R, CONHAr)
Disazo Condensation Pigments, Red
(missing R, CONH2)
 Isoindolinone & Isoindoline
Pigments

These pigments produce greeny to reddish yellow

They show good light & weather fastness, solvent &

migration resistance

Commercial application in plastic & high grade coatings

Isoindolinone
Isoindoline Pigments
 Polycylic Pigments

These are pigments with condendsed aromatic or

heterocyclic ring systems

They have good light, heat and weather fastness and

good solvent and migration resistance

They are more expensive than azo pigments except the

phthalocyanine pigments
They are use in all application ranging from water &
solvent base inks, water & solvent base paints, plastic,
rubber, cement & textile
 Phthalocyanine Pigments

These pigments are the most produced organic pigment in the

world. They cover the colour from greenish blue to reddish blue
& blueish green to yellowish green

They are produce by reacting metal salt with nitrogen source

compound & phthalic acid derivative

They show good solvent & migration resistance, good , light,

heat, chemical & weather fastness

Commercial application cover a whole range of product

Phthalocyanine Pigment
 Quinacridone Pigments

These pigments available in a reddish violet and a blueish red

Like the phthalocyanine pigments ,quinacridone are make in two

stages , the preparation of crude quinacridone and the
pigmentation the crude

They have outstanding light & weather fastness & solvent &
migration resistance
Commercial application are for high grade coating ( automotive),
for plastics & special inks
Quinacridone Pigments
 Perylene and Perinone Pigments

The color of perylene is red while for perinone is orange

They provide excellent light , heat and weather fastness

Commercial application are for spin dyeing, polyolefin, special

printing inks for metal decoration and poster printing and
automotive paints
Perylene Pigments
Perinone
 Diketopyrrolo Pyrrole (DPP)
Pigments

They provide colour range from orange to blueish red

The pigment consist of two anelated five membered rings each

of which contain a carbonamide in the ring

They have excellent light and weather fastness as well as good

heat stability

Commercial application are for plastics and automotive finishes

Diketopyrrolo Pyrrole pigment
 Thioindigo Pigments

This is reddish violet shade pigments

They show good light fastness and weather fastness

They are generally used in plastics and industrial

coating such as automotive finishes
Thioindigo Pigments
 Anthrapyrimidine Pigments

This class of pigment provide a greenish to medium

yellow coloration

They have excellent heat & weather fastness

Commercial application are for industrial coating such

as automotive metallic finishes
Anthrapyrimidine
 Flavanthrone Pigments

Flavanthrone yellow .the only commercially use

flavanthrone is a brilliant reddish yellow

Excellent light and weather fastness combined with

good solvent and migration resistance
Commercial application for automotive finishes
Flavanthrone
 Pyranthrone Pigments

Most pigments are orange but others are blueish red

colour

These are derivatives of pyranthrone molecule with

varying level of halogenation
They have good weather fastness
Commercial application for high grade industrial
finishes.
Pyranthrone Pigments
 Anthanthrone Pigments

The only commercial pigments is

dibromoanthanthrone which provides shade of scarlet
for metallic finishes

They have outstanding weather fastness

Commercial application are in high grade

Anthanthrone
 Dioxazine Pigments

These pigments produced violet colouration and in

combination with phthalocyanine blue pigment
produces a very reddish shade
Dioaxazine Pigments are derived from
triphenodioxazine, linear system of five anelated rings
They show extreemly light and weather fastness as well
as excellent solvent and migration resistance
Commercial application include the pigmentation of
plastics, printing inks, spin dyeing and coating
Dioxazine Pigments, violet 23 & 37
 Triarylcarbonium Pigments

The colour covers from green,violet and victoria blue

There are two types of these pigments: salt of triphenylmethane sulfonic acid
salt of heteropolyacid with tungsten,
molybdenum, silicon or iron

They have poor solvent resistance and limited light fastness but have
excellent colour brilliant and clarity of hue better than any other organic and
/organic pigments

Commercial application is for printing inks especially are for packaging inks
Triarylcarbonium Pigments
 Quinophthalone Pigments

They are mostly greenish yellow

These pigments have a polycylic structure derived from

quinaldine and phthalic anhydride

They have excellent temperatures resistance

The main market for these pigments are in the plastics

and coating industries
Quinophthalone
Synthesis of Pigments
azo pigment & copper phthalocyanine
 Production of CI Pigment Yellow 1, 11680

Diazotization
In a vessel 912 kg of 4-methyl-2-nitroaniline is stirred over night
with water.
Then 3395 L of 5 mol / L HCl is added, together with some ice
to lower the temperatures to 0 C.
Sodium nitrite solution, 792 L of 40 wt % is then run in
underneath the surface.
Any excess sodium nitrite is removed by addition of 3- nitro- p-
toluidine.
Active charcoal is added as clarifying agent and then filtered

Dissolution the coupling component

AcetoAcetanilide, 1098kg, is strirred with water for 1 H at 25C
then 510 kg of CaCO 3 and 206 kg of 33% NaOH solution is then
added.
 Production of CI Pigment Yellow 1, 11680

Coupling

The reaction mixture is heated to 33 C and the clarified

diazonium salt solution is then run in.

After 30 minutes HCl is added to adjust the pH to 3-4.

After 20 minutes the pigment is separated by filtering through

a filter press and wash with water to remove salt.

The filter cake ( press cake ) is dried at 60-65C

The yield is 2042 kg

Production of CI Pigment Red 112, 12370

Diazotization

In a steel-enamel stirred tank, 1000 kg of glacial acetic acid is

heated to 65 C , and 552 kg of 2,4,5-trichloroaniline is added.

The soln is run into a mixture of 7000 L of water and 2240 L of 5

mol/L of HCl. The reaction mixture is cooled to 0C by addition
of ice and repeatedly diazotizide with 370 L of 40 wt %NaN02
soln. The temp must not exceed 0 C.

After 2 h, 214 kg of CaCO3 suspended in water is added, The

volume is made up to 28500L with water; active charcoal are
added and the soln is filtered thro a clarifying filter.
Dissolution of the coupling component

At 30 C, 840 kg of naphthol AS/D is dissolved in 644 L of 33% of

NaOH and 6000L of water ; 20 kg of active charcoal is then
added and the soln is filtered. Then 168 g of Igepon T in 400 L
of water is added and the mixture is cooled to 3 C with ice.

The coupling component is precipitated by rapid addition of

470 L of glacial acetic acid.

Coupling
The reaction mixture is heated to 38 C, and the filter diazonium
salt soln is run in under the surface of the suspension of the
coupling component within 3,5 h. After completion of coupling,
the pigment is isolated by filtering the suspension thro a press,
washing to remove salt and drying at 50-55 C. The yield is 1400
kg
 Copper Phthalocyanine Blue

 BLUE PIGMENT CuPc (Copper Phthalocyanine)

Blue pigment CuPc is one of the most stable pigments
towards light, temperature and chemicals and hence,
combined with its attractive colors, this pigment is widely
used in many applications such as in paints water & solvent
based paints including automotive paints), in water & solvent
based inks, in textiles and in plastics with temperature of
operations up to 350 C.

 In industry, this pigment is produced in two stages

The first stage is the preparation of the Blue Crude
CuPc while the 2nd is the Pigmentation of
crude CuPc ie the reduction of particle size of
Crude CuPc.
 Copper Phthalocyanine Blue
CRUDE CuPc Blue

Crude CuPc is commonly prepared by reacting copper chloride urea, phthalic

anhydride, catalyst with solvent.
• CuCl + 12 H2NCONH2 + 4 C6H4 (CO)2O CuPc + NH3 + CO2 + H2O + NH4Cl

(produced in Malaysia)

• Structure of CuPc Yield 90%

 Production of Crude CuPc
according to Patent
Phthalic anhydride 1000 kg, urea 1350 kg, and trichlorobenzene 3000 kg are
mixed in a vessel equipped with an oil bath and stirrer: 240 kg of copper(II)
chloride and 5 kg of ammonium molybdate are then added.

The mixture are heated up slowly within 1 hour to 200 C . Gas evolution
mostly CO2 and some NH3 with formation of phthalimide begins at 130 C.

Formation of CuPc begins at 160-170 C, with simultaneous released of CO

and NH3. After stirring at 200-205 C for 1 hour, formation of the pigment is
complete.

The Phthalocyanine is filtered of ; washed with hot trichlorobenzene at 50 C,

methanol and hot water; and dried.

The yield of CuPc is 870 kg( 90%)

GLASS LINED PRESSURE REACTOR
ROTARY VACUUM DRYER
Filter Press
Spin Flash Dryer
Department Duty
Purchasing To buy raw materials, machinery, lab equipments,
spare parts of machinery and packaging etc

QC To set the standard and control the quality of the raw

materials, finish products and packaging

R&D To produce new cheap products which satisfy

customers requirements based on preliminary research
by Technical Support

Production To produce consistent products

Marketing To find the market for the products and to set the
quarterly sale forecast

Engineering To repair the damage and worn out parts of machinery

Technical Support To research customer complains regarding with quality
& packaging problems and to prepare test methods for
the finish products suitable for customers and to do
preliminary research for new products based on
customer’s requirements
 Product Specification of Crude CuPc

Parameter Specification Test Method Number

Purity 97 % min TM 1
Moisture Content 1 % max TM 2
Water Soluble Matter 1.5 % max TM 3
Alcohol Soluble Matter 2.0 % max TM 4
pH 4-8 TM 5
Conductivity 800 mho TM 6
Total Grit 300 ppm max TM 7
Iron 20 pieces max /100 g TM 8
Sand 30 pieces max / 100 g TM 9
Fiber Trace TM 10
Free Copper Content 3000 ppm max TM 11
PCB 0.1 ppm max TM 12
PROBLEMS OF MANUFACTURING CRUDE
CuPc

1. Yield
The yield of reaction is max 90% based on copper chloride
used (see List of Patents). There are therefore about 10 %
of the reagents used are disposed as waste.

2.. Environmental Effect

Most of the waste of the production of crude CuPc (11,000
tons/yr) is precipitated using Na2S and then is buried
underground
 Pigmentation Process

Methods Pigments Produced Notes

Dissolving in conc H2SO4 Blue Pigment 15:0 Reddish blue pigment with
and then sprayed into heat stability up to 170 C
aqueous solution and poor solvent resistant
containing certain additives
Blue Pigment 15:1 Reddish blue pigment with
heat stability up to 350 C
but poor solvent resistant

Blue Pigment 15:2 Reddish blue pigment with

heat stability up to 350 C
and good solvent resistant
Grinding with inorganic Blue Pigment 15:3 Greenish blue pigment
salts with the aids of polyol with tendency to
solvent in the presence of agglomerate
certain additive in kneader Blue Pigment 15-4
or ball mill Greenish blue pigment
with solvent fastness
Kneader for Beta-CuPc
Ball mill for Beta-CuPc
Ball Mill
 Pigmentation by Sulfuric Acid

Production of alpha –CuPc Pigment from crude CuPc

Crude CuPc 700 kg is added quickly to conc. H2SO4 (96%) 6300 kg , and the
temp is allowed to rise to 50 C . The suspension is stirred overnight.

When the phthalocyanine is completely dissolved , the suspension is

sprayed into 35000 L of water at 70 C, and the temp is allowed to rise to 85 C
– 90 C. The precipitated pigment is filtered off in a filter press and washed
until acid free.

The presscake is then mixed with 25000 L of water, and the remaining acid is
neutralized with K2CO3 and ammonia. After addtion of 35 kg of Lorol
sulfonate the suspension is heated for 1 h until a clear filtrate is obtained.

After filtration of the suspension, the presscake is washed with hot water
and homogenized with sufficient water to give a 20% paste, which is past 3-
5 times thro a disintegrator (3000 rpm).
 Pigmentation by Grinding

Production of Beta-CuPc Pigment from Crude CuPc

In a kneader , 283kg of crude CuPc is ground for 8 hours with
1131 kg of NaCl and 283 kg of Diethylene Glycol (DEG).

Then this paste is boiled in 6000 L of water and filtered using

filter press to remove water/soluble substances.
Washing with hot water is continued until no water soluble
substances can be found.

The presscake is then dried at 70 C – 75 C or using spin flash

drier. A intensive greenish blue beta-CuPC is obtained.
 Copper phthalocyanine Green
The most common organic green pigments are Phthalocyanine
green
The Phthalogreens are made by halogenating CuPc blue to
produce mixtures of CuPc in which many of the 16 hydrogen
atoms on CuPc have been replaced by chlorine or mixture of
chlorine and bromine atoms
The pigment vary from blue green to yellow green depending on
the ratios of bromine to chlorine
The yellowish green are obtained with nine to ten bromine
atoms per molecule
The Phthalogreens are economical and have good light fastness
 Copper Phthalocyanine Green

1 The most common organic green pigments are

Phthalocyanine green
2 The Phthalogreens are made by halogenating CuPc blue to
produce mixtures of CuPc in which many of the 16 hydrogen
atoms on CuPc have been replaced by chlorine or mixture of
chlorine and bromine atoms
3 The pigments vary from blue green to yellow green
depending on the ratios of bromine to chlorine
4 The yellowish green are obtained with nine to ten bromine
atoms per molecule
5 The Phthalogreens are economical and have good light
fastness
Copper Phthalocyanine Green
 MARKET DEMAND for Copper Phthalocyanine
World production of this product is over 110,000
tons/year while the gap between the world demand
and the supply according to Business Analyst for
Asahi Songwon Colors Ltd for 2011 is 19,000 tons /
year.

 PRODUCTION COUNTRIES
Crude CuPc was used to be produced in Japan,
Europe and America but now it has been shifted to
mainly China and India due to lower labor cost and
also mainly as the waste regulations of these
countries are not strictly followed.
 COST OF RAW MATERIALS USED
(Jan 2011)

Phthalic anhydride $ 1,500 / MT

Cuprous Chloride $ 6,565 / MT

Urea $ 350 / MT

Ammonium $ 24,000 / MT
molybdate

CuPc (just raw $ 3,517 / MT

materials cost)

FOB Price of CuPc $ 5,760 /MT

(from Baiyan China)
 CALCULATIONS

Material Weight used for 1 Unit Price / MT Cost

MT CuPc

CuCl 191 kg $ 6,565 $ 1,254.00

Phthalic Anhydride 1143 kg $ 1,500 $ 1,714.50

Urea 1390 kg $ 350 $ 487.00

Catalyst 2.60 kg $ 24,000 $ 62.40

Total Cost CuPc $ 3,517.90 / MT

 Profit

The profit for the manufacturers of this product would increase

tremendously by using this new process. For example, a medium size
manufacturer that produces 5000 MT CuPc/ year with the FOB price of the
low quality CuPc is $5.76/kg, the expenses are as follow:

If the cost of raw materials ($3.52), packaging ($0.04) and energy ($0.44) to
be $4.00/kg then to produce 5000 MT = $20m

And if the cost for machinery is assumed to be $1m

so a 5 yrs depreciation= $0.2m/yr

And if the number of workers employed is 100 with

salary assumed to be $300/month each,
so salary = $0.36m/yr
 Profit

Then Profit :

(5000 MT x $5.76) - $20m - $0.2m - $0.36m + (10% x 5000 MT x

$5.76) = $8.24m + $2.88m
$11.12m/yr (before depreciation of building, Interest & Tax)

The profit should be more than this as the saving cost for the
waste treatment should be added to this amount.
 SOLUTION TO THE PROBLEM
• Adding a small amount of another co catalyst
would improve the yield tremendously up to
99.9%
• The co-catalyst could be added at the same
time as other reagents before the reaction
starts or in the middle of the reaction before
the temperature reaches 160 C
• The general chemical formula of this chemical
is a complex of X-fatty acid ester sodium salt