Paints and

colouring agents –
for chemical
technology

https://www.essentialchemicalindustry.org/
materials-and-applications/colorants.html
• Visible light -EMR( 400 - 800nm ).
• A black substance absorbs all wavelengths of visible light.
• Selective absorption of visible light by a substance imparts color, but the color is not
that of the light absorbed but instead of the residual light that the substance
transmits or reflects.
• For example, a compound that absorbs in the region 435 - 480nm removes blue
light from the visible spectrum, and the residual light is recognized by the eye as
being yellow.
 Colorants — impart color
• Pigments -- insoluble colorants
– usually inorganic compounds

• Dyestuffs -- soluble colorants Transition Metals

– usually organic compounds

• Lakes -- soluble dye attached to inert support

– Used as pigments

• Fillers -- inexpensive insoluble materials

– Can be organic or inorganic compounds
 Colorants — impart color
• Pigments -- insoluble colorants
– usually inorganic compounds
 Malachite and azurite — copper Cu
 Vermilion — mercury Hg
 Prussian Blue, yellow ochre, red ochre, magnitite — iron
Fe
 Cobalt blue, cerulean blue — cobalt Co
Transition Metals  Chrome oxide green, chrome yellow — chromium Cr

Ideal Properties of Pigments

• Lightfast — resists fading
• Chemically inert — resists oxidation
• Insoluble as possible — resists bleeding
• Good brightening or coloring power
• Uniform particles which can easily be dispersed in a binder
• High opacity or hiding power
The molecules of most coloured organic compounds contain two parts:

(i) a single aryl (aromatic) ring such as benzene or a benzene ring with a substituent.
Alternatively there may be a fused ring system such a naphthalene (two rings fused
together) or anthracene (three rings fused together).

(ii) an extensive conjugated double bond system containing unsaturated groups,

known as chromophores

The intensity of colour can be increased in a dye molecule by addition of

substituents containing lone pairs of electrons to the aryl ring - Auxochromes
The coloration of textiles
The chemical nature of a dye is determined by the chemical and physical properties
of the fibres of the textile to be coloured.
The four main types of fibres (Table 1) are protein, cellulosic, regenerated (based on
cellulose or derivatives) and synthetic.
Natural fibres Man made fibres

Protein Cellulose Regenerated Synthetic

Wool Cotton Viscose rayon Polyamides

Silk Linen Celulose ethanoates Polyesters

Mohair Ramie   Acrylics

Cashmere      

The term regenerated is used when a natural polymer has been treated chemically to
form another polymer.
For example, natural cellulose from plants, when treated
with ethanoic anhydride (acetic anhydride), produces a polymer, cellulose ethanoate,
which is rayon.
 Some common organic dyes

NH2 OH OH NH2
NaO3S N N N N SO 3Na

O2 N N N NH 2
CH3O OCH3
SO3Na SO3Na
Chicago Sky Blue 6B Disperse Orange 3
(Direct Blue 1) 4-(4-nitrophenylazo)aniline

CH3
N O
C OCH 2CH3
CH3 CH3
- Cl-
O 3S
OH
C CH3CH2 NH O NHCH2CH3

CH3 Rhodamine 6G
N (Basic Red 1)
CH3
O
Na+ -O3S H
N
Lissamine Green B
(Acid Green 50) N
N
H
N N indigo O

Na O3S
methyl orange
 Brief History of Synthetic Colorants

• After the Industrial Revolution…

– Synthetic pigments — 1704 “Prussian blue”
• Followed rapidly by…
– Synthetic ultramarine
– Cobalt blue
– Cadmium reds and yellows
– Chrome oxide green (Army green)
– Synthetic dyes — 1856 — “Mauve of Mauvine”
• Followed by…
– Synthetic Indigo
– Synthetic azo dyes in every color imaginable
 Artists’ Palettes Through the Ages
Red Yellow Green Blue White Black

Cave painting Ochre Ochre Chalk (CaCO3) Carbon

10,000 BC Fe2O3 Fe2O3 — — Gypsum (lampblack)
(CaSO4)

Egypt Red lead Orpiment Malachite Egyptian Blue Chalk (CaCO3) Carbon
1300 BC Pb3O4 As2S3 CuCO3. CaCuSi4O10 Gypsum (lampblack)
Cu(OH)2 (CaSO4)

Pompeii Vermilion Orpiment Malachite Egyptian Blue Lime Carbon

AD 79 HgS As2S3 CuCO3. CaCuSi4O10 Ca(OH)2 (lampblack)
Cu(OH)2

Renaissance Vermilion Lead/Tin Green Ultramarine Lead White Carbon

1400 AD HgS Yellow Earth Complex PbCO3.Pb(OH)2 (lampblack)
Complex aluminosilicate
iron Azurite
silicate
2CuCO3.Cu(OH)2

Impressionists Vermilion Chrome Viridian Cobalt Blue Lead White Carbon

1860 AD HgS yellow Cr2O3 CoO.Al2O3 PbCO3.Pb(OH)2 (lampblack)
PbCrO4
 Dyes
• Colorant which is homogeneously dispersed in the dye medium
• Usually soluble
• Naturally occurring or synthetic organics
• Categorized by...
1. Method of Application
2. Chemical Structure

Ideal Properties of Dyes

• Lightfast — resist fading
• Chemically inert
• Good brightening power
• Soluble as possible in order to apply
• Colorfast — resists washing out of fibers
 Uses of Dyes
• Coloring fibers and cloth

• Color photography

• Electronics — dye lasers, solar cells, display panels

• Biological and biochemical stains

• Foods and cosmetic

• Lakes used as pigments in modern paints

• Ink jet printer inks

 Sources of Natural Dyes – BUGS
• Tyrian Purple or “Royal Blue”
• 9000 snails to obtain 1 g of dye
• Used primarily before 8th century
A.D. to dye wool and silk
• Chemically it is 6,6’-dibromoindigo

• Kermes — the most ancient dye in

Europe
70,000 female oak beetles produce 1
pound dye
• Cochineal — Mexico and Central
America
Mexican cactus beetle
Kermes, Cochineal — Carmine

Chemically similar structure, light sensitive

Dyed wool and silk — “carmine red”
 Sources of Natural Dyes – PLANTS

• Indigo — used since 2000 B.C.

Extracted from Indigofera tinctoria
“Navy Blue” of English sailors
Blue jeans
• Insoluble in water
– Must be chemical reduced to
soluble leucoindigo to use as dye

O
H
N • Woad (poor man’s indigo)
– Member of the mustard family
N
H
– Common weed in temperate
O
climates
– Leaves contain same chemical as
indigo but in lower amounts
– Celtic war paint and tattoos
Braveheart
– Blue robes of priests
 Sources of Natural Dyes – PLANTS

• Madder — “Turkey Red”

– Root of madder plant found in
Europe and Asia
– Prepared as a “lake” with Al(OH)3
– British “Redcoats”
– Alexander the Great used it to
simulate blood

• Alizarin
• Synthetic alizarin prepared in 1875
O OH

OH

O
 Color Centers in Organic Dyes

• CHROMOPHORES — “color bearer” structural

part of colored molecule which is responsible for
its color
– Conjugated double bond systems
– Aromatic rings
– Azo groups —N=N—
– Carbonyl groups —C=O
– Quinoid rings O

O
 AUXOCHROMES
• “color augmenting” groups
• functional group with non-bonded
electrons which acts to strengthen or
deepen the color and hue

—NH2 —OH —OR

Classification of colorants by their chemical structure

a) azo dyes

b) anthraquinone dyes

c) phthalocyanines
 AZO Dyes
First prepared in 1863
Have widest range of colors of all dyes R—N = N—R
Azo group
Contain the AZO Chromophore
Generally lightfast
Brilliant colors ranging from reds to blues
HO

NaO3S N

HO HO
Orange II
OCH3

N N

NaO3S N NaO3S N

FD&C Red No. 40 FD&C Red No. 6

Allura Red SO3Na Sunset Yellow SO3Na
tructure Colour observed

yellow-green

yellow

red

blue

 
 CARBONYL Dyes/Anthraquinone dyes
• Anthroquinone Dyes O

– Contain several —C =O
groups
– Multiple aromatic rings
• Originate from plants & animals O

– Coloring agents in flowers, fruits, vegetables, bugs, etc.

HO

HO
O OH O OH O O OH

OH CO2H CO2H
HO

OH
HO OH HO OH

O CO2H O OH CO2H O OH
Alizarin Kermes Cochineal
(c) Phthalocyanines
 Mauveine — first synthetic dye
N

H2N N N
H

William Henry Perkin (18 years old), 1856

- Trying to make the antimalarial, quinine N
HO
- patent  dye company
H3CO

N
Quinine
 Lists the dyes under their technological names that indicate how
they are applied, along with the fibres to which they are applied

Dye Fibre
Group 1
Wool and other protein fibres,
Acid
polyamides
Wool and other protein fibres,
Metal-complex
polyamides
Direct Cotton, linen, viscose
Basic Acrylic
Disperse Polyesters, polyamides, ethanoates
Group 2
Reactive Cotton, linen, viscose, wool, silk
Vat Cotton, linen, viscose
Sulfur Cotton, linen

https://www.essentialchemicalindustry.org/materials-and-applications/colorants.html
 Fiber-Reactive Dye Structure
• Chromophore
• Reactive group
• Leaving group

SO 3-Na + OH

Cl
CH 3O N=N
N
N
Na+O 3S N
N
CH 3
OCH 3

Procion Scarlet H-R, Cibacron Scarlet RP, Chlorine Reactive Red 3

 Methods of Application
• Dye and Substrate can interact through...
1. ionic forces (+ and — charges)
2. hydrogen bonding
3. dispersion forces
4. covalent bonds

Dye Substrate
Types of Dyes by Application
• Acid or Basic Dyes (ionic forces)
• Mordant Dyes (ionic)
• Direct Dyes (hydrogen bonding)
• Vat Dyes
• Fiber-reactive Dyes (covalent)
 Direct Dyes
• Polar dye Polar Fibers
• Dye applied from a hot water solution

H
DYE N HO
Hydrogen Bond
Polar group H Polar group

• Cotton and cellulose-based fibers

• Synthetic dyes
 Acidic or Basic Dyes
• Acidic dye (-) (+) Basic fiber

• Basic dye (+) (-) Acidic fiber

DYE SO3- NH3+

Sulfonic acid group Basic amine group

DYE NH3+ -
OOC

Basic amine group Carboxylic acid group

• Wool, silk, nylon and leather have basic amine groups and acidic carboxylic
acid groups
 Fiber-Reactive Dyes
• Covalently bonded to fibers
R—C—O—fiber
R—C—S—fiber
R—C—NH—fiber
• Developed in 1950’s
• Used primarily on cellulosic and protein fibers
 Fiber-Reactive Dye Structure
• Chromophore
• Reactive group
• Leaving group

SO 3-Na + OH

Cl
CH 3O N=N
N
N
Na+O 3S N
N
CH 3
OCH 3

Procion Scarlet H-R, Cibacron Scarlet RP, Chlorine Reactive Red 3

 Vat Dyes
• Usually not soluble in water
• Must be converted to a soluble form to be used as a dye

Indigo: the Classic Vat Dye

• Indigo is insoluble in water
– Must be chemical reduced to leucoindigo

O H O- Na+ H

N NaOH/ Na 2 S 2 O4 N

C C C C

N N
Oxidation
O
H by Air (O 2 ) H O- Na+

• Leucoindigo is soluble
• Used to dye cellulose fibers — blue jeans
The Vat Dyeing Process
Reduction to soluble leucoindigo

Insoluble indigo in basic sodium dithionite

Dyeing of cotton textile

Oxidation in the cloth to reform insoluble indigo
 Synthesis of Methyl Orange

NH3 N N

NaNO2
HCl
O3 S O 3S

N N N
NaOH N N
+

O3 S methyl orange
(from part A) Na O3S
 Modern Blueprints
• The Diazo process
– Sensitized paper
– Exposed to light
– Developed with ammonia vapors — NH3(g)
• Developed for large scale operation

Diazo Blueprint Chemistry

• Paper contains HO
– A diazonium salt and a coupling molecule R

N2 +X-
R
• Diazonium salt is light sensitive — fades to colorless when exposed
to light

light
N2 +X- X + N2(g)
R R

• Expose paper to ammonia vapor (basic) to “develop” blueprint

HO HO
R
N2 +X- R
N=N
R R

Diazonium salt
Coupler Blue diazo dye

NH3
 Fastness in Dyes
• Stability of dyes towards light
• Dyes vary greatly in their lightfastness and
colorfastness
• Undergo photo-oxidation and photo-
reduction by light — dyes fade and
degrade
 What Controls Opacity?
• The more a paint scatters light the more
opaque it appears to be.
 Light scattering depends on...
• Pigment particle size

Glass pane Scratched Glass Ground Glass

Transparent Translucent Opaque

Malachite (dark green) Finely Ground (light green)

40-50m 10-12m
 What is the best size?
• Most effective scattering
– Particles in the 200 - 400nm range
– 1/2 the wavelength of visible light (400-
800nm)
• smaller particle size = more scattering
Light scattering also depends
on..
• Refractive Index differences of pigment
Pigment Particle
and binder
Binder

•If RI of pigment and binder are different = high scattering — opaque

•If RI of pigment and binder are similar = little scattering — transparent

•Higher RI means more bending of light in the medium.