Organic Pigments - The Basics - SII - Dec 2008

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Tim Boyce ASEAN Regional Technical Servi
Organic Pigments The Basics

(revised October 2008)
Global Pigment Market Principles of Colour Definition of Colourants
Agenda
Types of Inorganic Pigments Types of Organic Pigments Synthesis of Azo Pigments Properties of Organic Pigments Quality Aspects
Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 2
Clariant Product Range Product Safety
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Corporate Presentation ASEAN Regional Technical Servi
Global Pigment Market
Total Pigment Market (Value) (total market 2006 : ~ 7.5 billion)

Organic Pigments ~ 65% by value azo pigments phthalocyanine pigments polycyclics Inorganic Pigments ~ 35% by value Iron oxides Complex metal oxides Chrome pigments Others * excluding titanium dioxide/fillers
Other Chromium inorganic 6% Complex 3% metal oxide 13% Iron oxide 13%
Azo 28%
High Performance 14%
Phthalocyanine 23%
Organic Pigment Market by Application

(total market 2006 : ~ 260,000 T)
Plastics 15%
Special Applications 5%
By volume Total : ~ 260,000 T

Printing Inks 56% NIP 1%
Special Applications 13% Plastics 19%
Coatings 23%
Printing Inks 35%
By value Total : ~ 5 billion
Coatings 33%
Organic Pigment Market by Pigment Types

DIARYLIDE-YELLOW 22 LAKE RED 7
Total Market 2006: 260,000 T

REFLEX-BLUE 3 HANSA-YELLOW 3 PYRAZOLONE 2 TOL.RED / -NAPHTOL 4
LITHOLRUBINE 12
NAPHTOL AS 4 SPECIAL AZO 4

OTHER LAKED 7
QUINACRIDONE 2 OTHER POLYCYCLIC 2
PHTHALOCYANINE 28
DIARYLIDE-YELLOW 18 REFLEX-BLUE 3 LAKE RED 3 HANSA-YELLOW 3 PYRAZOLONE 2 LITHOLRUBINE 7 TOL.RED / -NAPHTOL 2 NAPHTOL AS 5 OTHER LAKED 5 SPECIAL AZO 9
QUINACRIDONE 8 PHTHALOCYANINE 27 OTHER POLYCYCLIC 8
Total Market 2006 : ~ 5.0 bn
Organic Pigment Market (Value) by Region

(total market 2006 : ~ 5.0 billionT)
ROW 8% Asia 28 % Americas 34 %
Europe 30 %
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The Principles of Colour
Principles of Colour
1.
What is light? - Factorizing of light - Additive/subtractive mixing of colors Interaction of light and matter The creation of color - Color perception - Metamerism The CIE-Color system - The CIE La*b*-System - Color differences
2. 3.
4.
1.
2. 3.
4.
Absorbing medium Principles of Colour Light beam Colour of light Illumination Reflected residual light produces sensation of colour
To see objects we need light. light Of the entire spectrum of waves in the universe, man can visually perceive only a small wavelength range (400 - 700 nm), which we call light.
Organic Pigments The Basics Public ASEAN Regional Technical Service
Rays with long wavelengths and extremely short wavelengths are invisible to the human being.
Spectrum of the electromagnetic waves.

(logarithmic scale)
ultraviolet - rays X rays Light waves
infrared
Radio waves
mmW dmW cmW UKW MW KW LW
visible
1023
1021
1019
1017
1015
1013
1011
109
107
105
Frequency (Hz) ( decreasing)
10-13
1 Xe
10-11 10-9
1 nm
10-7
10-5
10-3
1 mm
10-1
101
103
1 km
Wavelength (m)
( increasing)
400 nm
700 nm
Newtons Experiment (1666)

Light source
Wh
VIOLET INDIGO BLUE GREEN YELLOW ORANGE RED (400nm)
(540nm)
it e
Li g
ht
(700nm)
PRISM
400 nm - 770 nm 400 nm - 435 nm 435 nm - 480 nm 500 nm - 560 nm 580 nm - 595 nm 595 nm - 605 nm 605 nm - 770 nm 350 nm - 400 nm > 770 nm
White Violet Blue Green Yellow Orange Red Ultraviolet Infrared
visible 1 nm = 10 -9 m
invisible
Wavelengths mean colour

blue magenta
yellow
white
Additive Colour Mixing.

In additive colour mixing, the single colours are added together to make white. This is only possible with light not pigments or dyes.
Example of additive mixing
green
red
The individual wavelengths are added together yellow

Subtractive Colour Mixing.
yellow
cyan
magenta
incident light
Absorption and scattering
Example of Subtractive Colour Mixing

1,0
Example: yellow/Cyan green Example: Yellow + Cyan = Green
0,8
0,6
0,4 0,2
Only the wavelengths common to both contributing colours are responsible for the final colour. The final colour will always be lower in intensity than the initial colours.
Transmission
380
440
520
600
680 nm
cyan
yellow
green
Primary colours
green red
blue
Additive primary colours
cyan
magenta
yellow
Subtractive primary colours
1.
2. 3.
4.
Interaction of light and matter

When light hits a surface .
absorption
(structure)
scattering
(particles / particle size)
transmission
(surface)
Reflection (surface)
Scattering, absorption, transmission, reflection

Some red light scattered
Yellow absorbed
Organic Pigments Blue light The Basics transmitted Public Tim Boyce ASEAN Regional Technical Service Slide 22
Red absorbed
Some green Light transmitted
1.
2. 3.
4.
Apart from wavelengths and colour physics, some other aspects can affect the colour perception
surface
Reflection (flop)
gloss
haze opacity
Standardized Illumination D 65, A and C

The standard illumination A corresponds to An incandescent (tungsten) light bulb (2800 K), also called evening color. The standard illumination C has a radiation distribution similar to the northern daylight and was fixed in 1931 using a 2 observer The standard illumination D 65 (daylight) corresponds to a black body radiation at 6500 K In addition there are standard fluorescent illuminations (F11, discontinuous spectrum etc).
Illuminant C was defined in 1931 (CIE 2 standard observer) and illuminant D65 was extended in 1964 (CIE 10 observer).
relative radiation intensity
Depending on the illumination the colour impression changes
Metamerism
Light source Reflectance Viewing angle independent
red
metamerism - free
dependent
red
metamerism
Metamerism free
Metameric different different under different lights
Spectral Curve Visual perception of colour match
same same
Deceptions
bluer
yellower
Induced Colour
.. And one last piece of fun
1.
2. 3.
4.
Color impression and color measuring

incident light Object
absorption, reflection, scattering
emitted light Eye

bright/dark blue, red, green
Measuring Instrument
color intensity spectrum
Brain
Colorimetrics
Color description: CIE La*b*-System ISO 7724-3, DIN 6174
color perception hues (max. 2 Mio)
The Color Appearance
Color of light of a light source goes direct to the eye. Color of light of a light source goes through a filter and then to the eye. Color of light of a light source hits the surface of a body and goes then to the eye.
The human eye

The human eye has 2 different sensors for the detection of light. There are cone cells (3) and rod cells.
synaptic. region outer segment cell body
cone cell
rod cell
There are 3 types of cones each for blue, red, green detection color impression, low light sensitivity
The rod cells are for black & white detection, located in the outer part of the retina no color, high light sensitivity vision during night
vision during daytime
Spectral sensitivity of the human eye

Blue sensor
Green sensor Red sensor
THE EYE
RETINA CORNEA LENS LIGHT IRIS LIGHT PUPIL
Young Eyes Clear - Supple Lens
RETINA LENS LIGHT
CORNEA
LIGHT IRIS PUPIL
Old Eyes Yellowing Rigid Lens
Color Vision Defects

More than 200 million people worldwide have some color vision deficiency Over 8% of males have this problem but only 0.5% of females
Different Races have different levels of deficiency and types of deficiencies

Colour deficiencies in males according to race North America Europe Eastern Europe China Japan Asia Caucasian Population 8.00 % 8.76 % 9.31 % 6.15 % 4.50 % 6.00 % Males 91.9 % 5.5 % 2.6 % Females 99.6 % 0.4 % 0.05 %
Normal trichromats Anomalous trichromats Dichromats
Color measurement
in c id e n t lig h t o b je c t
A b s o rp tio n , re fle x io n , s c a tte rin g
e m itte d lig h t
Eye
b rig h t/d a rk b lu e , re d , g re e n
M e a s u rin g in s tru m e n t
c o lo u r in te n s ity s p e c tru m
B ra in
c o lo u r p e rc e p tio n h u e s (m a x . 2 M io )
C o lo rim e tric s
Color description: CIE La*b*-System ISO 7724-3, DIN 6174
We need: 1. Light 2. Object 3. Observer / Spectrophotometer + Software for comparing the electric signal with the visual
perception The human eye is represented by the color matching functions x, y and z
CIE - Chromaticity Diagram

xy - Diagram
0,9
0,8
0,7
0,6
The standard tristimulus colour values X, Y and Z are calculated into the standard chromaticity coordinates (x, y and z) as follows : x=
X (X+Y+Z)
0,5
y=
0,4
0,3
Y (X+Y+Z)
z=
Z (X+Y+Z)
To define the chromaticity only the values x and y are necessary. Y is a dimension for the brightness of the colour.
0,1 0,2 0,3 0,4 0,5 0,6 0,7
0,2 0,1
0,0
Spectral colour co-ordinates : colour nm 670 620 585 525 470 400 x 0,74 0,69 0,54 0,08 0,12 0,18 y 0,26 0,31 0,46 0,84 0,07 0,00 z 0,00 0,00 0,00 0,08 0,81 0,82 Red Orange Yellow Green Blue Violet
The chromaticity diagram is Organic Pigments a chart of all possible The Basics Public chromaticities in the axis ASEAN Regional Technical Service based chart of colour coordinates.
CIE Colour Model of 1931.

The three dimensional colour system defines colours according to brightness and chroma, but does not show colours in the difference from each other in which they are perceived by the eye. Principles of Colour Later the CIE* XYZ Model (shoe sole) was developed from this. *CIE = Commission International de lEclairage.
Hue
Lightness
Chroma
CIE L*a*b* - Colour Model.

L* White
Yellow +b* Green -a* -b* Blue Red +a*
The CIE L*a*b* System was introduced in1976. All modern measurement systems are based on it. The colours are shown in their difference from one another as they are perceived by the eye.
Black
Colour measurement
CIElab - System
greenish yellow yellowish green reddish yellow
DIN 6174
Yellow
Greenish yellow
yellowish red
Reddish yellow Yellowish red Red
Yellowish green
Green
bluish green greenish blue bluish red reddish blue
Bluish green
Bluish red Reddish blue Blue
Greenish blue
The CIE Lab Formula

E*ab = ( E*ab = (
Principles of Colour Chroma
L*)2 + ( a*)2 + ( L*)2 + ( H*)2 + (
b*)2 C*)2
Shade/Hue angle
2
C* =
( a *) + ( b *)
2
h ab
b* = tan 1 a*
L* = Lightness a* = red/ green - Colourfulness b* = yellow/blue- Colourfulness

Derived designation:
L* b*
C* = intensity difference H* = shade difference L* = lightness difference
a*
Colour measurement
CIElab System
redder
dH Yellow Orange Red Violet Blue Green
+
greener
Tolerances dC /=/
Equal Trace Slightly Noticeably Distinctly Considerably substantially
0.00 0.10 0.11 0.30 0.31 0.80 0.81 1.40 1.40 2.20 2.21 3.00 > 3.01
dH
0.00 0.10 0.11 0.20 0.21 0.50 0.51 0.80 0.81 1.40 1.41 2.00 > 2.00
redder yellower
1 2 3 4 5 6
bluer
yellower
bluer
redder
greener
redder
Chroma & Lightness Lighter + + dL dC Darker Duller Brighter
yellower
bluer
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Definition of Colourants
Bulls and horses in a cave near Lascaux (France)
Egyptian receptacle with painted boat and ornaments
Egypt 1500 bc . Painting on limestone.



A modern pigment shop in Venice, Italy, where the "traditional" painter/artist can buy pigments to mix into paints themselves.
Pigments and dyes

Pigments Insoluble in medium Higher light/weather fastness Better chemical resistance More opaque Dyestuffs Soluble in medium Limited light/weather fastness High colour strength Limited chemical fastness Limited migration fastness High transparency
W di hat ffe s re t h nc e e ?
Classification of Colorants
Colorants
according to shade (DIN 55944)
inorganic Pigments
White Pigments Colored Pigments Black Pigments Lustre Pigments Fluorescent Pigments
organic Dyes Pigments

no commercial prominence Colored PIgments Black Pigments Lustre Pigments Fluorescent Pigments
Dyes
physically impossible Colored Dyestuffs Black Dyestuffs physically impossible Fluorescent Dyestuffs
Characteristics of Inorganic & Organic Pigments

Characteristics of Organic & Inorganic Pigments
Characteristic Primary particles
Organic Pigments Small Weak High High area / hydrophobic Bright Poor excellent Strong Transparent opaque Poor excellent Good excellent Fair excellent Good excellent Mostly excellent
Inorganic Pigments Large Strong Low Small area / hydrophilic Dull bright Good excellent Weak Opaque Excellent Poor excellent Good excellent Good excellent Heavy metals
Scattering Absorption Surface Colour (hue) Light/weatherfastness Tinting strength Opacity Solvent fastness Chemical fastness Dispersibility Heat stability Toxicology
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Types of Inorganic Pigments
White pigments.
Types of Inorganic pigments
Titanium dioxide - rutile Colour-Index Formula Heat resistance C Refraction index n Scattering index Dispersibility Abrasion Particle size () Coating *
Manufacturing process
P.White 6 TiO2 280/300 2,75 1 very good abrasive 0,1-1,0

organic/inorganic Sulphate/Chloride
Titanium Dioxide - anatase P.White 6 TiO2 280/300 2,55 1,5 good less abrasive 0,1-1,0
Zinc sulphide P.White 7 ZnS 300 2,35 2 very good low abrasive 1
organic/inorganic no
Sulphate
chemical reaction bluish
Shade
a little yellowish a little bluish
*Organic coating is destroyed at over 280C .
Lead chromate pigments

Colour area
Name Chrome yellow Chrome yellow Molybdate red Formula Pb(Cr,S)O4 PbCrO4 Pb(Cr,Mo,S)O4 Colour-Index P. Yellow 34 P. Yellow 34 P. Red 104
Particle size ()
0,5-1,0 0,5-1,0 0,5-1,0
Properties: Lead chromate pigments have different crystal modifications: rhombic-monoclinic-tetragonal. They are distinguished by medium to high heat resistance, high covering power and brilliant shades. For fastness properties, they are coated with inorganic compounds e.g. silicates, alumina. This allows improvements on their resistance to light, heat, weathering and chemicals which varies from good to excellent. Their resistance to acid/alkaline is moderate. Disadvantage: Not for food packaging materials, environment-polluting, toxic
Cadmium pigments
Colour area
Name
Formula
Colour-Index particle size () P. Yellow 35 P. Yellow 37 P. Orange 20 P. Red 108 0.2-2 0.2-2 0.2-2 0.2-2
Cadmium yellow greenish (Cd,Zn)S Cadmium yellow reddish Cadmium orange Cadmium red CdS Cd(S,Se) Cd(S,Se)
Properties:
Excellent general properties. Bright, clean fullshades. Lithopone types contain BaSO4 Greenish types have lower weather resistance. Main usage is in plastics or ceramics.
Manufacturing is carried out in a calcining process at 500-650C. Disadvantage: Not for food packaging materials, environment- polluting.
Mixed phase / Metal complex pigments

Name
Formula
Colour-Index Particle size () P. Yellow 53 0.4-0.7 P. Brown 24 0.2-0.4 P. Blue 36 0.2 0.5
Nickel titanium (Ti,Ni,Sb)O 2 yellow Chrome titanium (Ti,Cr,Sb)O 2 yellow Cobalt blue Co(Al,Cr)O4 Cobalt green
(Co,Ni,Zn)(Ti,Al)O4 P: Green 50
Zinc iron brown ZnFe2O4 Spinel black

P. Yellow 119 1.0-2.6 P. Black 22 1.4-3.9
Cu(Fe,Cr)2O4
Properties: Excellent fastness properties in all concentrations Manufacturing is carried out in a calcining process at approx. 1000C.
Oxide Pigments
Colour area
Name Iron oxide yellow Iron oxide red
Formula FeOOH Fe2O3
Colour-Index particle size () P. Yellow 42 0.1-0.6 P. Red 101 P. Black 11 P. Green 17 0.1-0.6 0.6-1.6 0.3-2.0
Iron oxide Fe3O4 black Chrome oxide greenCr2O3
Properties: Iron oxide yellow is limited in heat stability (180C). All others have excellent fastness properties. All pigments are abrasive.
Disadvantage: The thermal ageing of polypropylene and PVC is negatively affected by the use of iron oxide pigments.
Ultramarine/ Manganese pigments

Colour area
Name
Formula
Colour IndexParticle size () P. Blue 29 0.3-8.0
Ultramarine blue Na6Al6Si6O24(Na S2-4)
Ultramarine violet Na6Al6Si6O24(NA S2-4 ) P. Violet 15 0.3-8.0 Manganese violet NH4Mn P2O7
P. Violet 16 0.3-8.0 Sensitivity to acid Relatively high water content Moderate weather fastness Sensitivity to acid and alkalis Very weak tinting power
Properties: Ultramarine blue Excellent light fastness Excellent heat resistance Dispersibility difficult
Properties: Manganese violet Excellent light fastness Excellent heat resistance Shading pigment
Black pigments
Name Carbon black Iron oxide black Spinel black
Formula C Fe3O4 Cu(Fe,Cr)2O

4
Colour Index Particle size () P. Black 7 P. Black 11 P. Black 28 0.01-0.1 0.6-1.6 1.4-3.9
Properties: Carbon black. Multipurpose applications Low cost pigment Excellent fastness properties Improves the fastness to weathering of polymers Improves the electrical conductivity of polymers Hygroscopic Dispersibility is difficult The tenacity of polymers is negatively affected
Metal pigments
Name Aluminium Copper Cooper/Zinc-alloy Formula Al Cu Cu-Zn Colour-Index P. Metal 1 P. Metal 2 P. Metal 2
Properties:
Aluminium powder is explosive in mixture with air, dust-free metal pastes are available
Solvents where used smell like white spirit. The particle size and shape is varied Large size particle - good metal effect Small particle - high covering power Disadvantage: to their flake structure, all metal Due pigments are shear sensitive. Bronze pigments can oxidise/tarnish
Effect pigments
Pearl effect pigments

Mica with TiO2-coating
Interference pigments
Mica with iron oxide and titanium dioxide coatings Disadvantage: Because of their flake structure, all micaceous pigments are shear sensitive. Require high loadings to be effective ASEAN Regional Technical Service
Organic Pigments The Basics Public
Fillers
1.Carbonates
natural calcium carbonate from fossils natural calcium carbonate, crystalline chemical calcium carbonate natural calcium-magnesium carbonate
Chalk Calcite, Marble CCP Dolomite
2. Sulphates
natural barium salts synthetic barium salts Barytes Blanc fix
3. Silicates
natural magnesium silicate hydrate natural aluminium silicate hydrate
French chalk Kaolin, China Clay Muscovite (Glimmer)
natural calcium aluminium silicate hydrate
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Types of Organic Pigments
History and Chemistry of Organic Pigments

1899 Pigment Red 1. The first true organic pigment.
Types of Organic pigments
1900 to 1930s. Huge range of azo pigments developed. These products met the demands of the colour using industries. 1950s. The discovery of plastics and the requirement for automotive stoving paints led to the development of polycyclic and higher fastness azo pigments. 1960s to the present saw the improvement in the physical characteristics of pigments like improved opacity, better dispersion properties etc. A few new chromophores were also developed.
What are organic pigments?

Organic pigments are a system of conjugated double bonds connected by chromophores and modified by substituent groups
Chromophores : - N = N -C=O -C=C-
-C=N-N=O
Substituent Groups :
Auxchromes : electron donors : electron acceptors :
CH3 OH ArNH2 COOH SO2 COOR
Hypsochromes :
Br
Cl
A chromophore complex forms the basic organic pigment molecule

NO2
OH
NO2
-N=N-
2,4 - Dinitroaniline + B -Naphtol
Pigment Orange 5
There are 5 basic raw materials :
H3C
Toluene C7H8
H3C
- CH
C8H10
Benzene C6H6
o, m, p - Xylene
Naphthalene C10 H8
Anthracene C14H10
Modified by a variety of chemical processes e.g.

Substitution Nitration Oxidation Halogenation Hydrolysis Alkylation
Addition Sulphonation Reduction Alkali fusion Acylation
In many cases there can be multiple reactions required in the preliminary synthesis of the raw materials as well as the final pigment synthesis
And further modified by a series of physical processes .

Heat
Dissolution and re-precipitation in organic solvent or aqueous media Pressure Surface treatment
These are usually carried out under carefully controlled conditions and can affect :
Size and distribution

Volume portion (% per size class) Volume portion (% per size class)
Volume distribution (%)
Equivalent diameter (m)
Equivalent diameter (m)
Narrow particle size distribution achieved by lower finish temperature for ink jet application
Volume distribution (%)
Shape
P.R.122 Mixed crystal
P.R.122 Surface modified
Rod like Transparent Low viscosity
cubic Highly transparent Higher viscosity
Viscosity design by modified shape
The Surface
Influence of the polarity of the pigment on the wetting behaviour Type A hydrophobic floating on the water surface Type B hydrophillic excellent wetting in water
Surface design for perfect fit
Intermediates Derived From Nitrobenzene
Pigments or Dyes ???

Pigments and dyes often have a similar molecular structure Solubilising or insolubilising constituents determine the category
Insolubilising groups : carbonamide groups, nitro groups or chlorine (azo pigments), nitrogen, chlorine and bromine for polycyclic pigments. Polar substituents decrease solubility in non polar solvents whilst increased substitution increases insolubility Solubilising groups : long chain alkyl, alkoxy or alkylamino groups and sulphonic acid functions Many pigments have partial solubility depending on the application medium,solvents and the processing conditions (particularly temperature)
For pigments, fastness properties are a function of both their chemical structure and, most importantly, their physical characteristics (crystallinity, particle size and distribution etc) whereas for dyes it is purely their chemical structure
Pigment Chemistry
Three options to reduce solubility:
Laked pigments : Chromophore F with acidic groups. SO3- / CO2F-SO3- / F-CO2M+

------>
F-SO3- M+ / F-CO2- M+
Reaction with metal salt Large molecules : -N=NFrom Monoazo to Dis-azo ----> -N=N-A-N=N-
New Substitutients
for example: -CONH- group

-CONH- group
Effect of substitution on colour and fastness properties

Solvent Red 1 Fat Red G Pigment Red 3 Hansa Red B Pigment Red 14 Permanent Bordeaux FGR Pigment Red 170 Novoperm Red F5RK Pigment Red 171 Permanent Bordeaux HFM
Fullshade Lightfastness 7 Overspray 2

OCH3 N N OH
Fullshade Lightfastness 6-7 Overspray 3
Fullshade Lightfastness 6 Overspray 5
Fullshade Lightfastness 7-8 Overspray 5
1:46 TiO2 Lightfastness Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 86 NO2 N N Cl OH
1:55 TiO2 Lightfastness 4-5

CH3 NO2 N N H O H O H H H
1:85 TiO2 Lightfastness 4

OC2H5 N CONH2 N N H H O O H H NO2
1:80 TiO2 Lightfastness 6

OCH3 N N O O H H N H N N H
CH3
Effects of Pigment Chemistry
Improve fastness properties e.g. increased substitution Shade e.g. new chromophores
Classes of synthetic organic pigments Azo Polycyclic
Classical Azo
Special Azo
Monoazo
Naphtols Azo condensation
Quinacridone Phthalocyanine Perylene
Laked Lake Red C Toners Unlaked

Benzimidazolone Anthraquinone Dioxazine Isoindolinone Thioindigo DPP Triphenylmethane
Hansa Diazo
Chemistry
AZO Monoazo Diazo Azo condensation Azo salt Azo metal complex Benzimidazolone
Yellow
Orange
Red
Brown
Violet
Blue
Green
Black
X X X X X X
X X X X
X X X X X
X X X X
X X
X X
POLYCYCLIC
Phthalocyanone Anthraquinone Quinacridone Dioxazine Perylene Perinone Pyranthrone Indigoid Thioindigo Isoindolinone
MISCELLANEOUS
X X X X X X X X X X X X X X X X X X X X X X X
X X
Nitro
Organic Pigments Nitroso The Basics Public Quinoline Tim Boyce ASEAN Regional Technical ServiceAzine Slide 89
X X X X X X X X X X X
Basic dye complexes
Pigment classes
Azo Pigments
Polycyclic Pigments
Monoazo Disazo Beta-Naphthol Naphthol AS Red Azo Lakes Benzimidazolone Disazo Condensation
Phthalocyanine Quinacridone Perylene/Perinone Isoindolinone/Isoindoline Dioxazine Triphenylmethane Diketo-Pyrrolopyrrole DPP
Azo-Pigments
Monoazo :
H3C
R2-N=N-R3
O N O N
+
C.I.
Pigment Yellow 1
Monoazo-Yellow
O
O N
N O
N H
O HO N N
O N H CH 3
Naphtol AS
Cl
Pigment Red 14
O NH
H N
H3C O
O HO N N N H
Benzimidazolone
O N O
Pigment Red 171
O N O HO H3C N N
-Naphtol
Pigment Red 3
O S
O N N OH O O
Mn
2+
BONS laked
H3C
Pigment Red 48:4
Azo-Pigments
Dis-Azo :
R2-N=N-R3-N=N- R2
H3C O CH3 O Cl N N O Cl H3C N N O N H O O CH3 H N Cl
C.I.
Diarylyellow
H3C O
Pigment Yellow 83
Cl H3C
Disazo-konden-sation
Cl N
Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service
N OH O
H N
Cl Cl N H O OH N N Cl
Pigment Red 144
Cl
Slide 92
Polycyclic Pigments
N
Phthalocyanin
N N N N Cu
N N N
Pigment Blue 15
Chinacridone
H N
Pigment Violet 19
N H
Cl N O N Cl N CH 2 5
Pigment Violet 23
Dioxazine
H5C2
O
H N
Cl
Diketo-Pyrrolopyrrol DPP
Cl
Pigment Red 254

N H O
Slide 93
Polycyclic Pigments
O H N HN O O H N O O H N NH O
Isoindolin
Pigment Yellow 139
Cl
Cl Cl
Isoindolinon
Pigment Yellow 110

Cl
Cl Cl O Cl O Cl
O
O N CH3 O
Perylene
H3C N O
Pigment Red 179
Slide 94
Azo Pigments
Chemical structure and fastness properties
Pigment Class monoazo -Naphtol Naphtol AS BONA, laked Benzimidazolone Diarylide
Lightfastness
fair very good good very good good very good good very good excellent fair very good good very good poor
Migration fastness
poor poor poor good good excellent good very good Very good excellent poor
Disazocondensation Triphenylmethane
Slide 95
Polycyclic Pigments
Chemical structure and fastness properties
Pigment Class
Lightfastness
excellent excellent excellent excellent Very good excellent Very good excellent Very good excellent Very good excellent
Migration fastness
excellent excellent excellent excellent Very good excellent Very good excellent Very good excellent Very good excellent
Dibromoanthanthrone Phthalocyanine Quinacridone Diketo-Pyrrolopyrrole Isoindolinone Perylene/Perinone
Dioxazine Isoindoline
Slide 96
Monoazo pigments
Colour area
Monoazo pigments range from greenish yellow to bluish red. Can be pure monoazo (Hansa, Naphtol) or laked/toner. Their fastness properties vary considerably. Only few pigments are suitable for shading. The dispersibility is generally good. P.Y.1, P.Y.3, P.Y.73, P.Y.74, P.Y.75, P.Y.97, P.O.5, P.Y.191, P.R.3, P.R.48, P.R.49, P.R.53, P.R.57, P.R.112, P.R.170, P.R.9, P.R.146, P.R.12
ASEAN Regional Technical Service
Monoazo pigments
2,4,5 - trichloraniline
Cl Cl Cl N=N
HO
CONH CH 3
2-hydroxy-2-naphtho -ortho-toluidide
Pigment Red 112 ( C.I. : 12370 )
Slide 98
Monoazo (Hansa) yellow pigments

4 RD 5 RD
2 RD
N H3C O
H N
2 RK
O
5 RK
4 RK
C.I. Name P.Y.1 P.Y.3

Const. No. 11680 11710 11738 11741 11767
R2 D NO 2 NO 2 NO 2 OCH 3 OCH 3
R4 D CH 3 Cl Cl NO2 SO 2 NHC 6H 5
R5 D H H H H OCH3
R2K H Cl OCH 3 OCH 3 OCH 3
R4K H H H H Cl
R5K H H H H OCH 3
P.Y.73 P.Y.74 P.Y.97
Slide 99
Monoazo (Hansa) red pigments ( Naphtols)

R
2
N R
4
OH
C.I. Name P.O.5 P.R.4
Const. No. 12075 12085 12120
R2 NO2 Cl NO2
R4 NO2 NO2 CH3
P.R.3
Slide 100
Monoazo pigments Naphtols AS R

K
2 2 RD
N
N HO O
NH
5 RK
4 RK
RD
5 RD
C .I. N a m e P .R .9 P .R .12 P .R .14 P .R .11 2 P .R .5 P .R .14 6 P .R .17 0

C o n st. No . 1 24 60 1 23 85 1 23 80 1 23 70 1 24 90 1 24 85 1 24 75 1 24 67
R2 D Cl CH3 NO2 Cl OCH3 OCH3 H COOCH3 Cl Cl
R4 D H NO2 Cl Cl H H CONH2 H S O 2N H C H 3 S O 2N H C H 3 S O 2 N (C H 3 ) 2
R5 D Cl H H Cl S O 2 N (C 2 H 5 ) 2 C O N H C 6H 5 H C O N H C 6H 3C l 2 (2 ,5 ) Cl Cl
R2 K OCH3 CH3 CH3 CH3 OCH3 OCH3 O C 2H 5 OCH3 CH3 H
R4 K H H H H OCH3 Cl H H Cl Cl
R5 K H H H H Cl OCH3 H H H H
P .R .18 8 P .R . 2 53 P .O . 74
Slide 101
Monoazo red pigments red azo lakes

CH3 O O S O Cl
Ba
2+
R2
N N OH
N R4 R5
N OH O
O M2+
P.R. 53:1 ( 15585:1 )
C .I. Nam e P .R .48:2 P .R .48:3 P .R .48:4
C onst. No. 15865:2 15865:3 15865:4 15850:1
R2 S O 3S O 3S O 3S O 3-
R4 CH3 CH3 CH3 CH3
R5 Cl Cl Cl H
M Ca Sr Mn Ca
Ca O O S O
2+
P .R .57:1
CH3 N N OH N H O O H N O CH3
Slide 102
P.R. 247 ( 15915 )
Disazo pigments
Colour area
Disazo pigments are in the same colour range as monoazo pigments. The lightfastness is good to very good. Very high colour strength i.e. excellent in ink applications. Not suitable in low concentrations in plastics due to high solubility of the pigments. The dispersibility is normally good.
Not recommended for use in applications where the processing temperature exceeds 200C.
Slide 103
P.Y.12, P.Y.13, P.Y.14, P.Y.17, P.Y.174, P.Y.176, P.Y.188, P.Y.83, P.O.34, P.R.38
Disazo pigments
3,3-dichlorobenzidine (3,3-dcb)
2,4- acetoacet -meta-xylidide (aamx)

Pigment Yellow 13 ( C.I. : 21100 )
Slide 104
Disazo pigments AAA arylide

R2
H3C H N O
O N N
Cl
O N N
Cl
CH3 H N O
R5 H H H H OCH3 H H H OCH3 H H
R2
R4 R5
R4 R5
C.I. Name P.Y.12 P.Y.13 P.Y.14 P.Y.17 P.Y.83 P.Y.127

Const. No. 21090 21100 21095 21105 21108 21102
R2 H CH3 CH3 OCH3 OCH3 CH3 OCH3 CH3 OCH3 CH3 H
R4 H CH3 H H Cl CH3 H CH3 Cl CH3 H
P.Y.176
21103
Slide 105
P.Y.188
11767
Thermal decomposition of diarylide pigments.
A
>200 C
>240 C
Diarylide pigment
soluble monoazo compound (coloured)
Dichlorbenzidine DCB
Diarylide pigments partly dissolve above 200C and split off into a soluble monoazo compound. The monoazo compound starts to decompose above 240C to produce DCB.
Monoazo dyes and DCB are considered carcinogenic in tests on animals.

Note : below 200C diaryl pigments meet consumer goods regulations
Benzimidazolone pigments
Colour area
Benzimidazolone pigments range from greenish yellow, orange to bluish red. Mostly high fastness properties. Some pigments have very good weathering fastness. Good to excellent migration fastness. The dispersibility is generally very good
P.Y.120, P.Y.151, P.Y.154, P.Y.180, P.Y.181, P.O.36, P.O.62, P.R.175, P.R.176, P.R.185, P.R.208, P.V.32, P.Br.25
Benzimidazolone yellow and orange pigments

2 RD
O N N
3 RD
CH3 H N O
H N O N H
RD
5 RD
C .I. Nam e P .Y.120 P .Y.151 P .Y.154 P .Y.175 C onst. No. 11783 13980 11781 11784 11785 11780 11775
2 RD
3 RD
4 RD
5 RD
H COOH CF3 COOCH3 OCH3 NO2 H
COOCH3 H H H H H H
H H H H H Cl NO2
COOCH3 H H COOCH3 H H H
P .Y.194 P .O .36 P .O .62
Slide 108
Benzimidazolone red and brown pigments
R2
N R
4 5 RD
H N N OH O
H N O N H
C .I. Nam e P .R .175 P .R .176 P .R .185

C onst. No. 12513 12515 12516 12514 12517 12510
R2 D COOCH3 OCH3 OCH3 C O O C 4H 9 OCH3 Cl
R4 D H H S O 2N H C H 3 H S O 2N H C H 3 H
5 RD
H CONHPh CH3 H OCH3 Cl
P .R .208 P .V .32 P .B r.25
Slide 109
Azo condensation pigments

Colour area
Azo condensation pigments range from greenish yellow to bluish red. Mostly high fastness properties. Some pigments have very good weathering fastness. Good to excellent migration fastness.
The dispersibility in some cases is not easy.

P.Y.93, P.Y.94, P.Y.95, P.Y.128, P.R.144, P.R.166, P.R.214, P.R.220, P.R.242, P.R.248
Disazo :Bis AAA Arylide / Yellow azo condensation pigments

O A
CH3 N N A
O N O
R4 N H
H N R2 O
O Q
Q O
H3C
C.I. Name P.Y.93 P.Y.95

Const. No. 20710 20038 20037 200310
R2 Cl Cl Cl
R4 Cl CH3 CH3
A Cl Cl Cl
Q NH-C6H3-2- CH3,3-Cl NH-C6H3-2- CH3,5-Cl NH-C6H3-2-OAr,5-CF3

Ar = C6H4-4-Cl
P.Y.128 P.Y.155
COOCH3
OCH3
Disazo : Red azo condensation pigments

5 RD
RD
O
2 RD
4 RK
N N
OH
N H
K
H N R2 O
HO
N N
2 RD
RD
5 RD
C.I. Name P.R.144 P.R.166 P.R.214 P.R.220 P.R.221

Const. No. 20735 20730 200660 20055 20065 20065 20060
R2 D Cl Cl Cl CH 3 Cl Cl Cl NO 2
R 4D H H H H H H H Cl
5 RD
R2 K Cl H Cl CH 3 Cl Cl CN Cl
R4 K H H Cl CH 3 Cl Cl H H
Cl Cl Cl COOCH 2CH 2Cl COOCH(CH 3)2 CF 3 Cl H
P.R.242 P.R.262 P.Br.23
Triphenylmethane
Colour Colour area area
Deep blue shade with excellent colour strength. Used to tone black printing inks for offset applications The fastness properties are very poor The dispersibility is very poor and thus they are normally supplied as flushpastes or powder preparations P.B.56, P.B.61
Triphenylmethane : Reflex (Alkali) blue
H N
H N C
+
R2
-O3S R2
HN
R2
C.I. Name
Const. No. 42800 42765:1
R2 CH3 H
P.Bl.56 P.Bl.61
Isoindolinone / Isoindoline
Colour area
Shade from yellow to orange to red , good colour strength. The fastness properties are good to excellent. Reaction with alkaline additives can cause discoloration and a reduction in fastness properties.
The dispersibility is generally good. P.Y.109, P.Y.110, P.Y.139, P.Y.173, P.Y.185 P.O.61, P.O.66, P.O.69, P.R.260
Isoindolinone / Isoindoline
Isoindolinone :
Cl Cl Cl N O Cl Cl Cl Cl NH CH3 HN Cl
O N H O
Isoindoline :
H N
O
H N
H N O N H
P.Y. 109 ( 56284 )

Cl Cl Cl Cl
P.Y. 139 ( 56298 )

O O N H N
O
N NH O HN
Cl Cl Cl
O
H N N H
H N
CH3
Cl
P.Y. 110 ( 56280 )
P.Y. 185 ( 56290 )
Quinophthalone
Colour area
Greenish yellow pigments. Excellent fastness properties.
P.Y.138
Quinacridone
Colour area
Yellowish to bluish red, pink and red-violet pigments. Excellent fastness properties. Suitable as shading pigment. Optimum dispersion is often difficult.
P.R.122, P.R.202, P.R.207, P.R.209, P.V.19, P.R.206, P.O.48, P.O.49, P.V.42
Quinacridone
R11 R
10
H N
R N H R R
4
R
C.I. Name P.V.19 P.R.122 P.R.202 P.R.207 P.R.209
O
R3 H H H H Cl
Const. No. 73900 73915 73907 73905 73905 -
R2 H CH 3 Cl H H
R4 H H H Cl H
R9 H CH 3 Cl H H
R 10 H H H H Cl
R 11 H H H Cl H
P.O.49
unsubst. Quinacridone + Quinacridonequinone
Perylene
Colour area
Yellowish to bluish red shade. Excellent fastness properties. Suitable as shading pigment. The dispersibility is generally fair to good
P.R.123, P.R.149, P.R.178, P.R.179, P.R.190, P.R.224, P.V.29
Perinone
Colour area
Brilliant orange pigment. High weathering resistance in reduced shades. Excellent lightfastness. The dispersion is generally good. Not suitable as shading pigment in plastics ( solubility) but in paints is best suited for shading.
P.O.43, P.R.194
Perylene / Perinone
Perylene :
Perinone :
O N Q
O Q N O
O
O
N
C.I. Name P.R.149 P.R.178 P.R.179 Const. No. 71137 71155 71130 Q 3,5Me2-Ph 4-Ph-N=N-Ph Me
P.O. 43 ( 71105 )
Dibromoanthranone
Colour area
Brilliant yellowish red pigment. Excellent light and weathering resistance at all shade depths The dispersion is generally good.
O
P.R.168
Indanthrone
Colour area
Reddish blue shade. Excellent fastness properties.

Optimum dispersion is often difficult. P.B.60
Diketo-pyrrolopyrrole
Colour area
Orange to bluish red pigments. Excellent fastness properties. The dispersion is generally good. P.O.71, P.O.73, P.R.254, P.R.255, P.R.64, P.R.270, P.R.272
Diketo-pyrrolopyrrole
R3 H N R4
O
R4 R3
C.I. Name P.O.71 P.O.73 P.R.254 P.R.255 P.R.264 Const. No. 561200 561170 56110 561050 561300
N H
R3 CN H H H H
R4 H C(CH3 )3 Cl H Ph
Phthalocyanine
Colour area
Reddish and greenish blue pigments. Yellowish and bluish green pigments. Excellent fastness properties. Universal suitability, low coloration costs The dispersibility can be difficult. P.B.15, P.B.15:1, P.B.15:2, P.B.15:3, P.B.15:4, P.B.15:6, P.G.7, P.G.36
Phthalocyanine Copper (II) complex of tetraazatetrabenzoporphine

N N N Cu N
N
N N N
N N
N
N
N
N N
N Cu N
N N
Cu N
N
C .I. N a m e P . B l. 1 5 P .B l. 1 5 :1 P .B l. 1 5 :2 P .B l. 1 5 :3
m o d if ic a t io n -
H a lo g e n s 0 . 5 -1 C l 0 . 5 -1 C l tr a c e s tr a c e s tr a c e s 1 4 -1 5 C l 4 - 9 B r ,8 - 2 C l
m o d . s t a b i l iz e d no yes yes yes
f lo c c u la t io n u n s ta b le s t a b le u n s ta b le s t a b le
P .B l. 1 5 :4 P .B l. 1 5 :6 P .G r. 7 P .G r. 3 6
Dioxazine
Colour area
Very reddish violet pigment. Excellent fastness properties. The dispersion is often difficult. Not suitable in low concentration in plastics due to solubility.
P.V.23
Dioxazine
Cl N N O Cl O N N
P.V. 23 ( 51319 )
Public Corporate Presentation ASEAN Regional Technical Servi
Synthesis and Production of Azo Pigments
Azo pigments are named for containing an azo-group

-N=NTwo nitrogen-atoms are connected with a double bond.
There can be one Azo group in so called monoazo pigments

NO2 H3C N N
HO
Hansa Red B Pigment Red 3
or two azo groups, then it is called a disazo pigment (also called diaryl or diarylide)
Cl
Cl O N N O CH H N
O
H 3C H N N N
Permanent Yellow DHG Pigment Yellow 12

You can also think about molecules with more then two Azogroups. This is actually done in the synthesis of azo dyes
Diazotization of an aromatic amine to form the diazonium compound

NO2 NH2
+ 2 HCl + NaNO2
H3C
NO2 N H3C
+
N
Cl- + NaCl + 2 H2O
The unstable diazonium compound has to be cooled with ice to 5-7C to avoid any side reaction
Dissolving of the coupling component
OH
ONa
NaOH
+ H2O
There is a huge variety of coupling components but the technically most significant groups are : compounds containing activated methylene groups pyrazolone derivates and 2-Hydroxynaphthalene and its 3-carboxylic acid derivatives
Synthesis of the pigment
NO2
+
N N
coupling
ONa
Cl-
H3C
By coupling the two components, the pigment precipitates as primary particles. There is no longer a solution but a suspension.
NO2 HO H3C N N
Hansa Red B, P.R. 3
+ NaCl
Disazo Pigment
Dissolving kettle
CH 3 + N
Diazo kettle DCB

+
Dissolving kettle
CH 3 C=O CH 2 O=C NH KETTLE 2
AAA
C=O CH 2 NH C=O KETTLE 2
_ Cl
N
Cl Cl
_ Cl
KETTLE 1
+ 2 NaOH Coupling kettle

CH 3 C=O HC N=N Cl Cl CH 3 C=O N= N CH O=C NH
+ +
2 NaCl 2 H2O
HN C=O
DIARYLIDE YELLOW
( P.Y.12 )
PRECIPITATION
Reactor vessel Normally a sealed unit and as fully automated as possible
During coupling process, different conditions have to be control

Temperature pH value Time
These controlled conditions will have major effects on the synthesis, and therefore on the quality of the pigment
Finishing
Optimizing the physical properties of the pigment, such as:
Crystal shape Crystal size Crystal quality Particle size distribution

important process to reach optimum application properties thermal treatment heating the crude pigment suspension in water and/or organic solvents surface treatment adding appropriate auxiliaries with different chemical structures
HCl Na NO 2
AROMATIC AMINE + ICE DIAZOTISATION KETTLE
COUPLING COMPONENT
NaOH
H 2O
DISSOLVING OF COUPLING COMPONENT
FILTRATION
FILTRATION
COUPLING KETTLE
VAPOUR
FINISH KETTLE Synthesis and Production of Azo Pigments

PUMP FILTER FILTRATION
DRYING NAUTA BLENDER
VAPOUR
DRYING OVEN
GRANULATOR
GRANULES
PRESSCAKE
Filterpress with falling filtercake

By opening the filterplates, the filtercake falls to a belt and is transferred to the nauta-blender.
Drum filter with filtercake

The filter sucks up the suspension, the liquor moves through the cloth and leaves behind the filtercake.
Granulation in front of belt dryer

To give a large surface area to the filtercake it is granulated before drying.
Dry pigment granules

After being dried, the priment granules fall from the beltdryer to the mill.
MILLING BLENDER
JET - MILL
STORAGE BINS
PIGMENT POWDER
Properties of Organic Pigments
Properties of organic pigments

Pattern card data Colour Index Standard Shade Depth
Tinting Strength Pigment Physics Particle size and distribution Crystallography and shape Specific surface area Dispersion of organic pigments Flocculation Fastness properties Migration / solvent fastness Heat stability Lightfastness weatherfastness
Pattern Card Data

Colour Index Colour & Shade Depth Tint Strength Physical Properties Fastness Properties
Colour Index
Nomenclature system for pigments and dyestuffs
Report to Colour Index :
By producer, with trade name Structure (optional) Properties Application field
Classification in Colour Index :

According to application, properties, shade and structure. Generic name Constitution number
Listing in Colour Index :
Constitution number Generic name Trade name
The Colour Index is published by the Society of Dyers and Colorists (GB) and the American Association of Textile Chemists and Colorists.
4th EDITION: online ( www.colour-index.org ) different search modes
Colour Index
Generic Names Generic Name
CI Class Pigment Solvent
Shade Violet Red
Number 19 135
CI Class
Pigment Dye Solvent, reactive, vat, basic, Acid, direct, disperse
Shade Number
yellow, orange, red, violet, blue, green, brown, black, white continuous
Colour Index Constitution Numbers
Chemical Constitution
Constitution Number
Nitroso Nitro Monoazo Disazo Stilbene Diphenylmethane
10000 10299 10300 10999 11000 19999 20000 29999 40000 40799 41000 41999 42000 44999 45000 45999 46000 46999 47000 47999 48000 48999 49000 49399 49400 49699 49700 49999 50000 50999 51000 51999 52000 52999 58000 72999 73000 73999 74000 74999 77000 - 77999
Triphenylmethane Xanthene Acridine Quinoline Methine Thiazole Indamine Indophenol Azine Oxazine Thiazine Anthraquinone Indigoid Phthalocyanine Inorganic pigments
Same Colour Index but .......
P.Y.16
Permanent Yellow NCG Permanent Yellow NCG 71 Permanent Yellow NCG Permanent Yellow NCG 71
P.Y.74
Hansa Brilliant Yellow 5GX Hansa Brilliant Yellow 2GX 70
Hansa Brilliant Yellow 5GX Hansa Brilliant Yellow 2GX 70
P.Y.83
Novoperm Yellow HR 02
Standard Shade Depth (SD) - DIN 53235

The depth of shade is a degree of intensity of visual colour perception. It denotes the visual spacing between a given coloration and a pure white specimen.
With increasing saturation the intensity is higher and with increasing luminosity the intensity of colour perception in general will decrease. Standard depth of shade (SD) is a level of depth of colour which is settled by convention. 1/1 SD, 1/3 SD or 1/25 SD which are used for illustration or testing procedure are standardised according to DIN 53235
The colorimetric calculation is according to CIE-lab system (standardised in DIN 6174)
Standard Shade Depth (SD) - DIN 53235

P.Y. 3 P.Y. 83 P.R. 112 P.B. 15:1 P.V. 23
FS
Fullshade
Fullshade
Fullshade
Fullshade
Fullshade
1/3 SD 1:2.5 TiO2
1:15.3 TiO2
1: 5.5 TiO2
1:12.3 TiO2
1:19.7 TiO2
1:29 TiO2
1:200 TiO2
1: 70 TiO2
1:175 TiO2
1:265 TiO2
1/25 SD
Tinting strength
The evaluation method is depending very much on the application, thus the information varies in different pattern cards .
PRINTING INK : Pigment concentration required to give indicated shade depth at 1.5 g/m2. The lower the figure, the stronger the pigment. e.g. 7.0g strong (GRX 80) ; > 25g weak (H4G) PAINT : Parts of TiO2 needed to bring 1 part of coloured pigment to the indicated shade depth. The larger the figure, the stronger the pigment. e.g. 1:132 strong (5GX 02) ; 1:26 weak (H3G)
PLASTIC : The grams of pigment / kg plastic with either 5% TiO2 (PVC) or 1% TiO2 (PO) needed to Organic Pigments The Basics reach the indicated depth Public Tim Boyce ASEAN Regional Technical Service e.g. 2.5g strong (HR) ; 14.59 weak (H3R)
Slide 161
Pigment physics
particle composition
can influence
primary particles aggregates agglomerates
crystal structure
can influence
colour colour purity fastness properties tinting strength shade hiding power
particle size can influence
Organic pigment crystals

Enlargement 32 000 X
Pigment Green 7
Pigment Orange 43
Pigment Red 247
Pigment Red 144
Particle composition of pigments

Smallest unit of a material. Has its properties. In this case a mono crystal.
Primary particle
Bundle of primary particles, coupled on the surface (face to face). The surface is smaller than the surface of all single primary particles together. There is no inner accessible surface.
Aggregates
Agglomerates
Primary particles and aggregates coupled at the corners and edges. The surface is not much different from the sum of the surface of all particles. The inner surface is accessible.
Crystal modifications
C.I. Pigment Blue 15
Crystals in same direction Spacing is smaller Angle is smaller Crystals in alternate direction Spacing is bigger Angle is greater
-modification
P.B.15:1 Red shade
-modification
P.B.15:3 Blue shade
Crystal modifications
C.I. Pigment Violet 19 full shade
white reduction
Hostaperm Red E3B / E5B 02
Hostaperm Red Violet ER 02 / ERX
Hostaperm Red E3B / E5B 02
Hostaperm Red Violet ER 02 / ERX
SEM-micrograph of powder pigments

C.I. Pigment Yellow 83
Yellow HR Specific surface area 69 m2/g Average partice size 40 nm
Novoperm
Yellow HR 70 Specific surface area 22 m2/g Average partice size 325 nm
Novoperm
Relationship between particle size and shade, opacity and tint strength
Novoperm Yellow HR 02 (P.Y.83)
Specific surface area

Relationship between particle size and surface area .. Cubic dimension
Number of particles in basic cube 1 103 1012
Surface Area (m2) 6 cm2 60 cm2 60000 cm2
1 cm 1 mm 1 nm
Assuming a spherical shape . Particle diameter in 0.4 0.3

Surface Area (m2/g) 15 20 30 60
0.2 0.1
Effect of particle size on tint strength
0.50
0.45 0.40 0.35 0.30 0.25 K/S 0.20 0.15 0.10 0.05 0.00 0.1 0.2 0.3 0.4 microns (u) 0.5 0.6 P.Y.17 P.G.7
Typical surface areas

Most Monoazo Grades, 70 Series < 25 sq m/g
Naphtol Grades, some Quinacridones Some Quinacridones, Dioxazine Violet, Phthalocyanines

25-55 sq m/g > 55 sq m/g
Dispersion of Pigments
Pigment Powder
Agglomerates
Aggregates Primary Particles

Decreasing Particle size
Dispersion of organic pigments

1. Deagglomeration - premixing of single pigments to break down larger, softer agglomerates. Initial wetting out.
2. Dispersion a) Wetting most important step. Often requires use of auxiliaries to improve pigment wetting. Solvent and resin should cover entire pigment surface. Polar carriers and solvents have better wetting power. b) Dispersion all pigment agglomerates are broken down. This is done by friction and pressure (shear forces). c) Distribution optimal statistical distribution of the dispersed pigment within the carrier material d) Stabilisation protection of the system against reagglomeration or flocculation
Step 1 > 100 u
Step 2 50 - 100 u
Step 3 20 -50 u
Step 4 10 - 20 u
Step 5 5 - 10 u
Step 6 1-5u
Step 7 <1u
Microscopic Dispersion Evaluation Scale (x 110 times)
Dispersion of pigments relative particle size of some inorganic and organic pigments
Colour Index Pigment Black 7
Pigment Type Inorganic pigments Carbon black Titanium dioxide Lead chromates / molybdates Iron oxide red Ultramarine blue Organic pigments Diarylide yellow Benzimidazolone Perinone Diketopyrrolopyrrole Dioxazine -phthalocyanine
Particle Size (m) 0.01 1.0 0.1 1.0 0.5 1.0 0.1 0.6 0.3 8.0 0.06 0.18 0.15 0.2 0.06 0.09
Pigment White 6 Pigment Yellow 34 / Pigment Red 104 Pigment Red 101 Pigment Blue 29 Pigment Yellow 13 Pigment Yellow 180 Pigment Orange 43 Pigment Red 254 Pigment Violet 23 Pigment Blue 15:3
Flocculation Effects of Flocculation Loss of colour strength Poor levelling (in paints) Poor flow Reduced gloss Hazing Shade variation
Flocculation vs time

0 min 25 min
Test system CPP gravure ink 5% pigment conc. Magnification x 110

40 min 60 min
90 min
120 min
Particle size & distribution general rules

particle size
small
more trans.
high strength
high visc.
high Specific Surface Area
lower loading
lower fastness
transparency /
concentration
Surface area
large
millbase
more opaque
low strength
low visc.
low Specific Surface Area
higher loading
higher fastness
* these are guidelines only and other factors may need to be considered
properties
strength
viscosity
specific
fastness
opacity tint
(flow)
Pigment Technical Service Laboratory ASEAN Region
Public Tim Boyce ASEAN Regional Technical Servi
Key fastness properties of organic pigments

Migration Heat stability Lightfastness Weatherfastness
Migration fastness of organic colourants
Solvent fastness Bleeding Overspray Blooming
Solvent fastness
The pigment is dissolved by the solvent, The pigment is dissolved by the solvent, thereby discolouring the solvent thereby discolouring the solvent
Paint : This is tested on the pigment powder itself, using individual solvents or a solvent mixture. Ink : For offset ink, this is tested on the print application using either individual solvents or a solvent mixture. For gravure pigments it is tested on the individual pigments using either individual solvents or a solvent mixture.
evaluation is against the 5 step Grey Scale (DIN 54002)
Solvent fastness
Solvent Fastness Test - tested on pigment powder
GR200 STD P.Y.12 P-GRL 06 STD P.Y.13 DHG SPL STD P.Y.12 MX STD P.Y.13
Toluene
IPA
Toluene/IPA (70/30)
Migration fastness
Bleeding pigment moves from the coloured material to directly contacting material Overspray pigment moves into subsequent paint layers thereby discolouring them Blooming pigment migrates to the surface and can be wiped off
Bleeding / Blooming.
Incorrect pigment selection Dyestuff used in partly crystalline polymers Pigments soluble in the binder or polymer Pigments soluble in the solvent or plasticiser High processing temperatures / poor heat stability
White contact film
Plaques with coloured dust on the surface.
Red coloured film White paper covered with colour
Migration fastness - bleeding
Retort fastness 120C / 30 minutes
Migration fastness - overspray

Bleeding in an overspray application (tested in thermosetting acrylic)
P.R.170
P.R.3
Migration fastness - blooming
Example of blooming in Low Density Polyethylene

Solvent fastness - Recrystallisation

Recrystallisation due to poor solvent fastness in aromatic solvents (tested in medium oil alkyd)
Pigment Blue 15:0
Pigment Blue 15:2
Control
1 week aged
Control
1 week aged
Aromatic solvents or high heat (above 200C) cause a crystal shift resulting in a greener, weaker product
Non flocculating version of Pigment Blue 15:1 i.e.it is a non-recrystallising or flocculating grade
Heat stability / Limit concentration
Heat stability Pigment is either discoloured or destroyed depending on the conditions and / or the nature of the pigment
Heat stability
Pigment is burnt out in polypropylene polymer and colour disappears
Initial matching designed for application at 240C maximum
Final colour when processed at 280C

Heat stability
Heat stability - 0.5% pigment, 5 minute dwell time Pigment discolours
Heat resistance (DIN EN 12877)

Heat resistance test
Lightfastness resistance to UV radiation
Lightfastness
Is a measure of the resistance to UV radiation ONLY i.e. It is not a measure of exterior durability Can be accelerated or actual exposure under glass Evaluated against the Blue Wool Scale according to DIN EN ISO 105-BO 2 Blue Wool Scale must be exposed at same time as sample and result must specify time and conditions Blue Wool Scale is geometric - each successive step is twice the previous step Limited rating system of 1 (very poor) to 8 (very good) Final lightfastness is system dependent
Global radiation in Kly (DIN EN ISO 4892)
60
60 70 60 70 80 120 160-180 160 120 140
70
80 120 140 100 160 120 100 140 180 160 120 100 80
100
100
80
160
200 180 120 180 160
160
180 160
70
Lightfastness variation in radiation levels
180
160 170 160
190 200 200 190 180 170 160 150 140
160 150 140 160 160 150 140 130 120 150 140 130 120
Kilolangleys/year of radiation in Australia
Conversion Table
1 Langley = 1 cal/cm2 1 W/m2 Properties of Organic Pigments 1 Luxh 1 J/cm2 1 Lux = 0,0001 W/cm2 = 0,581 x 10-3 cal/cm2 = 10 KJ/m2 = 0,161 x 10-6 cal/(cm2 x s) = 0,581 x 10-3 Ly = 0,2388 Ly = 0,676 x 10-6 W/cm2 = 2,433 x 10-3 J/cm2 = 411 Luxh = 4,188 J/cm2
1 Langley = 4,18 Joule/cm2 = 4,18 Ws/cm2 = 1,00 cal/cm2

The light energy of 1 year in Frankfurt is approximately 80 Kly = 3350 MJ/m2
Lightfastness Blue Wool Scale
Step 1 Step 2 Step 3 Step 4 Step 5 Step 6 Step 7 Step 8 8 Exposed section 250 hours 45 6 Rating
Types of Accelerated UV/Weathering Apparatus
3. Light fastness (DIN EN ISO 4892)

Different types of exposure
Accelerated exposure* in hours
(in Xenotest X 1200 W)
Blue wool scale

Normal daylight exposure* in days

(in Frankfurt-Liederbach Germany)
1 2 3 4 5 6 7 8
6h 10 h 25 h 120 h 200 h 400 h 800 h 1.600 h
5 days 10 days 20 days 40 days 80 days 160 days 350 days 700 days
(16.800 hours)
*test with a glass filter / behind glass
Light fastness (DIN EN ISO 4892)

Comparison of various accelerated exposures
Blue Wool Scale Normal daylight exposure in days * Accelerated exposure in hours in Xenotest X 1200 W Accelerated exposure in hours in Xenotest XE 1200 GL Accelerated exposure in hours in Weatherometer Accelerated exposure in hours in Suntest
1 2 3 4 5 6 7 8
4 days 14 days 28 days 70 days 100 days 140 days 160 days 360 days
5.4 hrs 15 hrs 34 hrs 100 hrs 240 hrs 400 hrs 800 hrs 1600 hrs
2.5 hrs 6.5 hrs 15 hrs 60 hrs 110 hrs 200 hrs 400 hrs 800 hrs
2.5 hrs 8 hrs 20 hrs 75 hrs 160 hrs 270 hrs 540 hrs 1100 hrs
2.5 hrs 6.5 hrs 9 hrs 41 hrs 80 hrs 130 hrs 260 hrs 520 hrs
Note :
The time for outdoor exposure of stages 1 7 is very dependent on the time of year at which the test began. * The outdoor exposure test is tested behind window glass
Dyes used in Blue Wool Scale

Blue wool scale Exposure time Xenotest X 1200 W 6h 15 h 34 h 120 h 240 h 400 h 800 h Exposure in daylight in days (in Liederbach) 5 10 20 40 80 160 350 Dyestuff
1 2 3 4 5 6 7
Acilan Br. Blue FRR (Bayer) Acilan Br. Blue FFB (Bayer) Sypranolcyanine 6B (Bayer Bencylcyanine (Ciba) Supramin Blue EG (Bayer) Solmay Blue RN (ICI) Acilan Fast Blue RX (Bayer) Alicarin Lightblue 4GL (Clariant) Soledon Blue 4BC (ICI) Indigosol Blue 04B (Durand) Anthrasol Blue 04B (DyStar) Indigosol Blue AGG (DyStar)
1.600 h
700
Resistance to Weathering
Weatherfastness
It is a measure of all exposure conditions e.g. UV, rain, snow, industrial atmosphere etc
Can be accelerated e.or actual exposure e.g. Florida or Allunga, Xenotest or QUV Evaluated against the Grey Scale and/or by colour difference measurement Carried out as per DIN 54001 Results can be different to lightfastness
Results are highly system dependent
Global Climate Classification (Koeppen)

Weatherfastness factors
Primary effects Solar radiation (light energy) Temperature and temperature differences Water (moisture) Secondary effects Airborne pollutants Acid rain Biological effects (mold, mildew)
Primary + Secondary effects
Weathering
Effects of weathering
The result is unwanted and premature product failures This could mean:
Discoloration
Rust
Cracking
Peeling Paint
Fastness to weathering (accelerated ageing, DIN EN ISO 4892)

The weather fastness properties of a colorant are a feature of molecular structure and particle size. Many factors, most importantly polymer stabilization, pigment concentration and the strength of UV radiation can influence the result. Accelerated weathering in a weather-o-meter can provide a good indication of the performance of a given formulation however, a pre-test under the applied conditions of use is always recommended. Visual evaluation with the 5-step grey scale for assessing change in color in accordance with ISO 105-A02 : 1993 5 = very good; 1 = very bad The test can be run until Stage 3 of the Grey Scale is reached. The hours of the exposure or the energy values (Kly) can be recorded and compared. Alternatively a fixed exposure time e.g. 3000 hours can be used and results rated on the Grey Scale
Fastness to weathering
Test machine: accelerated weathering (DIN EN ISO 4892)
Machine
Xenotest 1200 W (rotating panel) Relative Humidity 60 %
Energy (1 h)
1,764 MJ/m2 Black Panel = 60 C
1 Langley
= 4,18 Joule/cm2 = 4,18 Ws/cm2 = 1,00 cal/cm2
The light energy of 1 year in Frankfurt is 80 Kly = 3350 MJ/m2
Accelerated test cycles Europe Wet

South East Asia Dry Wet 240 mins Dry 240 mins
18 mins
102 mins
ISO 105-A02: 1993 Grey scale for assessing change in color
Summary (DIN EN ISO 4892)
It is a total system test, where all components and exposure conditions must be taken into account - polymer/binder type and stabilization - pigment type and concentration - UV radiation, temperature, moisture etc The important criteria is how long the final article is in actual outdoor use and where it is placed locally and in the world (Global radiation and climate conditions vary considerably)
Testing should be carried out as per the final pigment formulation in the defined polymer/binder system, including stabilization
Parameters affecting fastness properties general rules

Various fastness properties depend on :

Entire system e.g. resin,additives,pigments,fillers Pigment concentration / film thickness Pigment type (chemical constitution) Shade depth / pigment mixtures Temperature Time Nature of process e.g. dispersion method, solvents
Quality Aspects
Quality aspects
You should know that
Quality aspects
Reference standards
* Exist for all sales products
* Represent average production quality * Tested together with each production batch * Used in all decisions regarding quality * For new standards - everyone is notified * Customers must be notified * Sample stock is held for customers
Quality aspects
What do we standardise ?
Quality aspects
Pigment / Preparation
Volatile matter (moisture) Sieve residue pH value Specific conductivity Solvent fastness Viscosity Specific gravity Colour Strength Opacity / Transparency Gloss Dispersibility Migration fastness Rheology Specific customer tests
Application
Test methods
Description of test conditions : type of binder dispersion method and conditions application evaluation criteria Test methods based on : DIN or ISO or ASTM Standards specific requirements
Quality aspects
Colour measurement
dH (Hue)
Quality aspects
CIElab system
dC (Chroma) dL (Lightness)
Adjustment of shade depth : relative tinctorial strength (+/- 5% or 105%) residual dH, dC, dL, and dE (at dL = 0) d means difference against standard
Note : only used with reduced shade
Colour measurement
CIElab - System
Quality aspects
greenish yellow yellowish green reddish yellow
DIN 6174
Yellow
Greenish yellow
yellowish red
Reddish yellow Yellowish red Red
Yellowish green
Green
bluish green greenish blue bluish red reddish blue
Bluish green
Bluish red Reddish blue Blue
Greenish blue
Colour measurement
CIElab System
redder
dH Yellow Orange Red Violet Blue Green
+
greener
Tolerances dC /=/
Equal Trace Slightly Noticeably Distinctly Considerably substantially
0.00 0.10 0.11 0.30 0.31 0.80 0.81 1.40 1.40 2.20 2.21 3.00 > 3.01
dH
0.00 0.10 0.11 0.20 0.21 0.50 0.51 0.80 0.81 1.40 1.41 2.00 > 2.00
Quality aspects
redder yellower
1 2 3 4 5 6
bluer
yellower
bluer
redder
greener
redder
Chroma & Lightness Lighter + + dL dC Darker Duller Brighter
yellower
bluer
Quality costs
Total cost Prevention
Quality aspects
Appraisal
Design Inspection Test equipment Evaluation Record Storage
Failure
Replacement Rework Repair Re-inspection Downtime Scrap Diagnosis
Planning Auditing Training Quality Assurance
Up to 6%
Up to 11%
Up to ?? %
Technical & Quality complaint procedures

Quality aspects
We need : - Sample and lot number of pigment ex delivery - Customers evaluation - ALL details of customers test method and application - Method of processing We check : Method of standardisation + customers application method
Technical decision
Additional information
Commercial decision
Literature & information

Product Reports : specific, new release, deletions, changes.
Quality aspects
Pattern cards : specific applications, sales range, product information & illustration, fastness properties Technical specifications : QC, product quality, fastness properties Certificates of analysis : certification, test results, Safety data sheets : chemistry, safety, transport, toxicology, ecology, accidents, health
It is important that these are up to date It is important that the information is clearly understood
Clariant Product Range
Clariant product ranges Pigments

Hostaperm
Highest Quality Very High Quality Very Good / Good quality Specific Range with very good specific properties Specific Range Highest quality selectively tested for plastics
Novoperm Permanent Hansa Reflex Blue PV Fast Graphtol
Very Good / Good quality selectively tested for plastics
Clariant product ranges Dyestuffs

Savinyls
range of solvent dyes range of solvent dyes for plastics range of solvent dyes for plastics range of solvent dyes range of fluorescent solvent dyes for plastics range of water soluble dyes range of water soluble food dyes range of water soluble dyes range of water soluble dyes
Solvaperm Polysynthren Fat Hostasols Duasyn Vitasyn Cartasol others
Clariant product ranges Supply forms

Colourants
Pigment Dyestuff Preparation
powder granules presscake

powder liquid
powder paste fine granules granules flush pastes
Clariant product ranges Pigments

Standard Range
Properties Excellent fastness properties
Chemistry
Quinacridone Phthalocyanine Dioxazine Benzimidazolone Dibromoanthranthrone
Hostaperm
Novoperm Permanent
Very good fastness Average to good fastness. High colour strength
Benzimdazolone Naphtol AS Naphtol AS Diarylide
Hostaperm
Most commonly used in High Quality applications such as :
Automotive Paints (OEM & Refinish) High quality industrial paints Decorative paints (where light and weatherfastness are critical) Inks (where high fastness properties are required - metal dec)
Novoperm
Most commonly used in High Quality applications such as :
Automotive paints (mainly Refinish) High quality industrial paints Decorative paints (where light and weatherfastness are critical) Inks (where high fastness properties are required - metal dec)
Permanent
These grades are most commonly used in ink applications although a number are suitable for paint applications (mainly reds) : Offset inks (Sheetfed, Heatset, Coldset) Solvent & water based liquid inks (Gravure, Flexo) General industrial paints Decorative paints
Clariant product ranges Pigments (continued)

Standard Range Hansa Reflex Blue PV Fast Graphtol
Properties
Chemistry
Monoazo Good fastness to light but poor solvent fastness Beta naphtol
Low fastness. High colour strength High thermal stability and fastness Moderate thermal stability and fair to good fastness
Triphenylmethane Selected Hostaperm and Novoperm grades Selected Novoperm and Permanent grades
Hansa
These grades are most commonly used in decorative paint applications although a some are used in ink applications. They are sensitive to strong solvents e.g.aromatics Screen inks Solvent & water based liquid inks (gravure, flexo) General industrial paints Decorative paints
Permanent
These grades are almost exclusively used in offset ink applications although some are used in other ink applications or special fields. They are sensitive to strong solvents e.g.aromatics Offset inks (Sheetfed, Heatset, Coldset) Water based flexo inks (Powder grades only) Special applications (carbon paper etc)
PV Fast & Graphtol

These grades are primarily used for plastics applications. Selected pigments are from Hostaperm, Novoperm and Permanent ranges with all grades standardised in PVC Polyolefines & PVC Elastomers Engineering resins Powder coatings
Clariant product ranges Dyestuffs

Standard range
Application field Plastics Plastics Higher performance plastics Solvent systems, waxes Special applications Foodstuffs, cosmetics Ink, coatings, Special applications
Properties Fluorescent Good fastness High fastness Multiple applications Multiple applications Registered products Multiple applications
Hostasol Solvaperm Polysynthren Fat Duasyn Vitasyn
Savinyl
Clariant product ranges Preparations

Paint
Printing Ink Traditional Flexonyl WF Flexonyl A NIP Permajet liquid Permajet 30 Hostajet Hostacopy
Plastics Hostaprint Hostasin
Specialised Flexonyl Viscofil Viscofil A Viscofil S Cosmenyl Cosmenyl gran.
Colanyl 100 Colanyl 500 Hostatint Hostatint E Hostatint A Hostafine Renol HW
Product safety
Product Safety
Prior to marketing a product all legal requirements must be fulfilled! Mandatory Regulations: Worldwide Chemical Legislation - Chemical Registration - Quantity Monitoring - Classification and Labeling of hazardous substances and preparations Transport Classification Special Regulations - Chemical Prohibition Ordinance - Consumer Goods Ordinance - Positive/Negative Lists REACH
Product safety
Product Safety
Voluntary Regulations: International Environmental Labels USA: Green Seal Japan: Eco Mark Scandinavia: White Swan Canada: Environmental Choice Germany: Blue Angel Europe: Flower EU-Eco-Labels - Textile products - Footwear - Bed mattresses - Indoor paints - Bed linen and T-shirts - Copy paper
Product safety
Internal Standards DIN EN ISO 9001 DIN EN ISO 14001
Worldwide Chemical Legislation

In Force
European Union Switzerland USA Canada Australia
In Preparation
Eastern Europe
Russia, Baltic States, Bulgaria, Romania, Slowenia, Slovac Republic
Mexico Malaysia Singapore Taiwan Thailand South Africa
Product safety
Japan New Zealand Philippines South Korea China (partly) Czech Republic (partly) Hungary (partly) Poland (partly)
Chemical Legislation Inventories

EU EINECS REACH USA TSCA DSL ENCS AICS ECL PICCS ECSC European Inventory of Existing Commercial Substances Registration, Evaluation, Authorisation and Restriction of Chemicals Toxic Substances Control Act Domestic Substances List Japanese Existing and New Chemical Substances Australian Inventory of Chemical Substances Existing Chemicals List Philippines Inventory of Chemicals and Chemical Substances Inventory of Existing Chemical Substances in China
Product safety
Canada Japan Australia Korea Philippines China
Major worldwide regulations affecting pigments

Austrian Approval (AT) ASTM: Safety of Toys (US) BfR Requirements (G) CONEG-Regulation (US) Consumer Goods Ordinance (G) Chemical Prohibition (G) EU-Resolution AP (89) I (EU) EU-Toys Standard EN 71/3 (EU) EU-Preparations Directive 1999/45/EC FDA-Approval (US) French Positive List (FR) JHOSPA (JP) JHPA (JP) REACH Standard 2070.6 (AU)
Product safety
Colorants for the coloration of consumer goods, food packaging and toys
For colorants that are used for coloring consumer goods, food packaging and toys the parameters relating to
Product safety
Purity Migration fastness Toxicological properties are of essential importance. With these criteria the risk evaluation of colorants serves as the basis for the suitability of the colorants for specific areas of application.
Recommendation IX of BfR (former BgVV)
Purity criteria for colorants for the coloration of plastic materials and other polymers for consumer goods - Heavy metal limits - Limit for primary aromatic amines Heavy metal limits The following limiting values must not be exceeded (extractable in 0.1 N HCl) As Ba Cd Cr 100 ppm 100 ppm 100 ppm 1000 ppm Hg Pb Sb Se 50 ppm 100 ppm 500 ppm 100 ppm
Product safety
European Resolution AP (89) I
"On the use of colorants in plastic materials coming into contact with food"
Purity criteria for colorants - Heavy metal limits - Limit for primary aromatic amines - Limit for polychlorinated biphenyls (PCB) Heavy metal limits The following limiting values must not be exceeded (extractable in 0.1 N HCl)
As Ba Cd Cr 100 ppm 100 ppm 100 ppm 1000 ppm Hg Pb Sb Se 50 ppm 100 ppm 500 ppm 100 ppm
Product safety
Primary aromatic amines The content of unsulphonated primary aromatic amines soluble in 1N HCl should not exceed 500 ppm (calculated as aniline) The content of sulphonated aromatic amines should not exceed 500 ppm (calculated as aniline sulphonic acid) The content of benzidine, -naphthylamine and 4-aminobiphenyl, singly or in total, should not exceed 10 ppm 2-methyl-4-chloroaniline should be treated in the same way The content of polychlorinated biphenyls (PCB) should not exceed 25 ppm
Heavy metal limits (ppm*) for colorants in food packaging Country overview
Country/Metal As
100 100 100 100 100 100 100 50 50 50** 100 100 100
Ba
100 100 100 100 100 100 100 100 100 100 100 100
Cd
100 100 100 100 100 100 100 100 100 100** 1000 100 100
Cr
1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000
Hg
50 50 50 50 50 50 50 50 50 50** 50 50 50
Pb
100 100 100 100 100 100 100 100 100 100* 100 100 100
Sb
500 500 500 500 500 500 500 500 250 2000 500 500
Se
100 100 100 100 100 100 100 100 100 100 100 100
Zn
Product safety
Australia Belgium Germany (Rec. IX) EU/AP (89) I France Great Britain Greece Italy Japan (JHPA)** Japan (JHOSPA) Netherlands Portugal Switzerland
2000
* Soluble contents in diluted HCl
** Total content
Heavy metal limit values for toys (ppm) - Country overview
Country/Metal Australia Australia Australia EU EN 71/3 Tab. 1 EU EN 71/3 Tab. 2 EU EN 71/7 United Kingdom Switzerland (Art. 31)
Organic Pigments Switzerland The Basics Public USA ASTM Tim Boyce ASEAN Regional Technical Service Slide 249
As
(toy coatings) 25 (modeling clay, 25 finger paints) (total content in 1,0 modeling compounds) (surface coatings 25 etc.) (modeling clay) 25 (finger paints) 10 (coatings of 100 pencils, pens, etc.) (coatings of 25 paints, drawing etc.) (water colors) 25 (surface coatings) 25
Product safety
Ba 500 250 1,0 1000 250 350 1000 1000 1000 1000
Cd 75 50 0,05 75 50 15 100 75 75 75
Cr 60 25 1,0 60 25 25 100 60 60 60
Hg 60 25 0,03 60 25 10 100 60 60 60
Ni
Pb 90 90 1,5 90 90 25 250 90 90 90
Sb 60 60 1,5 60 60 10 250 60 60 60
Se 500 500 1,0 500 500 50
Sr
1,0
1,0
[Cr(VI)]
(Art. 32) F 963-96a
500
Purity of our products
Products which are subject to regular analytical tests meet the following purity criteria:
Product safety
The maximum soluble content (in 0.1 N respect. 1N HCl) of the following elements is:
Antimony Arsenic Barium Cadmium Chromium Lead Mercury Selenium Zinc 60 ppm (EN 71-3) 25 ppm 100 ppm 50 ppm 60 ppm 90 ppm (EN 71-3) 25 ppm 100 ppm 1000 ppm Primary aromatic amines 4-aminobiphenyl, benzidine 2-naphthylamine, 2-methyl4-chloroaniline * = calculated as aniline 500 ppm*
10 ppm
Migration fastness
For the suitability of colorants for the coloration of food packaging, consumer goods and toys lowest possible migration from the colored article onto the food is of essential importance.
Product safety
The migration is among others dependent upon

the properties of the packaging material used the type and quantity of other additives (and their possible interaction with the colorant) contained in the packaging material such as anti-oxidizing agents etc. the concentration and the properties of the colorants the application procedure the food and the storage conditions
Toxicological Properties
Important toxicological tests for pigments are:
Product safety
acute toxicity irritation of skin and mucous membrane toxicity after repeated application sensitization mutagenicity chronic toxicity, especially carcinogenicity The most important property of organic pigments is their extreme insolubility in water and the application media.
The Issue of HCB (hexachlorobenzene) and TCPA (tetrachlorophthalicanhydride)

A) Introduction On February 24, 2006 the Japanese Authorities published an official letter announcing the prohibition of the use of Tetra Chloro Phthalic Anhydride (TCPA) due to its contamination with Hexachlorobenzene (HCB). Additionally the industry has been asked to stop using TCPA and also to stop the distribution of products made from TCPA
Product safety
In Japan HCB is a Class I specified substance under the Chemical Substances Control Law. In the scope of this law the production, import and usage of HCB is prohibited. Moreover HCB belongs to the "dirty dozen" which have been prohibited in the scope of the international POPs convention. The authorities have identified Solvent Red 135 as a colorant containing HCB impurities due the manufacturing process using TCPA.
No official limit with regard to trace impurities of HCB in colorants has been published yet.

B) Actions taken by the industry for the time being Because of the complexity of the whole matter a task force of the Japanese industry has been formed to develop a common strategy. As an initial step the authorities have been informed that also other colorants than those based on TCPA may contain HCB impurities. The HCB content of a colorant is related to the raw materials and solvents used for the production and the production process. The first step is to define voluntary HCB limits for the individual colorants and to harmonize the limits with the authorities followed by a stepwise reduction of the impurity levels.
Product safety

C) Clariant products affected We generally do not use any HCB for the manufacturing of our colorants. 1. TCPA based colorants within our range are Solvent Red 135 (Solvaperm Red G / Polysynthren Red GFP) Pigment Red 257 (Hostaperm Red Violet 3RL) 2. Other colorants of concern Pigment Green 7 (e.g. PV Fast Green GNX / Hostaperm Green GNX)
Product safety
Note : this is an issue in Japan only and currently does not have relevance in any other country
Chlorine Free Pigments for Plastics
Chlorine free pigments/dyes (less than 1% chlorine)

Pigment Colour Index Chemical classification
Graphtol Yellow 3GP PV Fast Yellow H2G PV Fast Yellow HG 01 PV Fast Yellow HG Graphtol Yellow H2R PV Fast Yellow H3R PV Fast Orange GRL
P.Y.155 P.Y.120 P.Y.180 P.Y.180 P.Y.139 P.Y.181 P.O.43 P.R.247 P.R.170 P.R.170 P.R.57:1 P.R.175 P.R.208 P.V.19 P.V.19 P.R.176 P.R.185
Bisacetoacetarylide Benzimidazolone Benzimidazolone Benzimidazolone Isoindolinone Benzimidazolone Perinone Naphtol Naphtol Naphtol Monoazo Benzimidazolone Benzimidazolone Quinacridone Quinacridone Benzimidazolone Benzimidazolone
Product safety
PV Fast Red HB Graphtol Red F3RK 70 Graphtol Red F5RK Graphtol Rubine 6BP PV Fast Red HFT Graphtol Red HF2B PV Fast Red E3B PV Fast Red E5B Graphtol Carmine HF3C Graphtol Carmine HF4C
Chlorine free pigments/dyes (less than 1% chlorine)

Pigment Colour Index Chemical classification
PV Fast Pink E PV Fast Pink E 01 Graphtol Bordeaux HF3R PV Fast Violet ER Graphtol Blue AN PV Fast Blue BG
P.R.122 P.R.122 P.V.32 P.V.19 P.B.15:0 P.B.15:3

Colour Index
Dimethyl Quinacridone Dimethyl Quinacridone Benzimidazolone
Quinacridone Phthalocyanine
Phthalocyanine
Chemical classification
Product safety
Dyes
Sandoplast Yellow 2G Polysynthren Yellow GG Polysynthren Yellow NG Sandoplast Orange 3G Sandoplast Red 2G Sandoplast Red BB
S.Y.114 S.Y.133 P.Y.147 S.O.60 S.R.179 S.R.195
Quinoline Methine Anthraquinone Perinone Perinone Monoazo
FDA Compliant Colorants from Clariant
FDA Approval
Summary of the regulations concerning food packaging 1. General remarks The Food and Drug Administration (FDA) regulates cosmetics, medical devices, drugs (including food additives and food packaging) in the United States. FDA regulations are compiled in Title 21 of the Code of Federal Regulations(21 CFR). These regulations can be amended in the Federal Register, or as described below. FDA regulations are organised in Parts.The parts that are most relevant to food contact are : > Part 175 Adhesives and Coatings > Part 176 Paper and Paperboard > Part 177 Polymers > Part 178 Adjuvants, Production Aids, Sanitisers > Part 181 Prior Sanctions > Part 184 Affirmed GRAS Substances > Part 186 Food Contact Substances Affirmed as GRAS Detailed regulatory information is found in paragraphs such as 178.3297, Colorants for Polymers
Product safety
2. Legal and Regulatory Background FDA Compliance for Food Additives A food additive is a substance which, when used as intended, is reasonably expected to become a component of food. Afood additive must be already regulated, exempt or precleared. Three types of food additives are recognised : > Direct (food ingredients) > Secondary Direct (added to food during processing but removed) > Indirect (food packaging and other food contact)
Product safety
An indirect food additive, also called a food contact substance, is any substance intended for use as a component of materials used in manufacturing, packaging, transporting or Holding food. Such use is not intended to have a technical effect in food. Food contact substances must also be already regulated, exempt or precleared. However, food contact substances are likely to have exemptions or preclearances.
2.1 Regulated Colorants for Polymers 2.1.1 21 CFR, 178.3297, Colorants for Polymers Colorants for polymers are listed in 21 CFR 178.3297, Colorants for Polymers. The colorants are listed with their chemical names and/or with their Colour Index generic Names. Many of the colorants are subject to restrictions on : > Upper limit colour concentrations in the polymer > Polymer types > Food types (aqueous, acidic, fatty, low alcohol, high alcohol) and/or > Conditions of use
Product safety
Conditions of use describe the temperature conditions the coloured polymer may be subject to and are described as follows : A High temperature heat sterilised e.g. > 100C / 212 F B Boiling water sterilised C Hot filled or pasteurised above 66C ( 150 F) D Hot filled or pasteurised below 68C (150 F) E Room temperature filled and stored (no thermal treatment in the container) F Refrigerated storage (no thermal treatment in the container) G Frozen storage (no thermal treatment in the container) H Frozen or refrigerated storage : ready prepared foods intended to be reheated in the container at time of use
2.1 Regulated Colorants for Polymers 2.1.2 Food contact Notifications As of January, 2000, the FDA no longer lists cleared substances in 21 CFR 178.3297. Rather, substances cleared by the FDA as food contact substances will be listed on the FDA webpage. For a complete listing of FDA cleared substances, both 21 CFR 178.3297 and the FDA webpage must be researched. The same restrictions as are found in 21 CFR 178.3297 would be utilised in substances cleared by food contact notifications. It is important to note that only the company who is listed with the cleared substance on the FDA webpage may declare their product as FDA compliant
Product safety
FDA Compliant Products (coloration at SD1/3 + 1% TiO2)

Powder pigments
PY214 PV Fast Yellow H9G
PY180 PV Fast Yellow HG
PY191 PV Fast Yellow H2GR
PY191 PV Fast Yellow HGR
PY181 PV Fast Yellow H3R
Product safety
PY242 PV Fast Scarlet 4RF
PY254 PV Fast Red D3G
PR187 PV Fast Red HF4B
PV19 PV Fast Red E3B
PV19 PV Fast Red E5B
PR122 PVFast Pink E
PR122 PV Fast Pink E 01
PV19 PV Fast Violet ER
PG7 PV Fast Green GNX
PB15:1 PV Fast Blue A4R
PB15:1 PV Fast Blue A2R
PB15:3 PV Fast Blue BG
PB15:0 Graphtol Blue AN
DrizPearls
PY180 DrizPearl Yellow HG
PY181 DrizPearl Yellow H3R
PV19 DrizPearl Red E5B
PR122 DrizPearl Pink E
FDA Compliant Colorants with prescribed limitations

Product
DrizPearl Yellow HG DrizPearl Yellow H3R DrizPearl Red E5B DrizPearl Pink E
Colour Index
P.Y.180 P.Y.181 P.V.19 P.R.122
Polymer
All All All All
% upper concentration
1 1 1 1 0.5 0.2
Conditions of Use 21 CFR176.170

BG BH AH DG DG A-H
Food types
All foods All foods All foods Aqueous, acidic,low alcohol
Graphtol Blue AN PV Fast Yellow H9G PV Fast Yellow HG PV Fast Yellow H2GR PV Fast Yellow HGR PV Fast Yellow H3R
P.B.15:0 P.Y.214 P.Y.180 P.Y.181 P.Y.191 P.Y.181 P.R.242 P.R.254 P.R.187 P.V.19 P.V.19 P.R.122 All 1 0.5 0.2 All All All All All All All All 1 1 1 1 1
FDA compliant colour without limitation in 21 CFR 178.3297 AH B-G B-H BH BH A-H Bh BH FDA compliant colour without limitation in 21 CFR 178.3297 FDA compliant colour without limitation in 21 CFR 178.3297 DG DG A-H DG DG A-H FDA compliant colour without limitation in 21 CFR 178.3297 FDA compliant colour without limitation in 21 CFR 178.3297 FDA compliant colour without limitation in 21 CFR 178.3297 FDA compliant colour without limitation in 21 CFR 178.3297 FDA compliant colour without limitation in 21 CFR 178.3297 Aqueous, acidic,low alcohol Fatty foods All foods Aqueous, acidic,low alcohol Fatty foods All foods All foods All foods All foods All foods All foods Aqueous, acidic,low alcohol All foods All foods
Product safety
PV Fast Scarlet 4RF PV Fast Red D3G PV Fast Red HF4B PV Fast Red E3B PV Fast Red E5B PV Fast Pink E
2 Maximum thickness 2 mm 1 1
PV Fast Pink E 01
P.R.122
All
1 0.5 0.2
Organic Pigments PV Fast Violet ER The Basics Public PV Fast Blue A4R Tim Boyce ASEAN Regional Technical ServicePV Fast Blue A2R Slide 265
PV Fast Blue BG PV Fast Green GNX
P.V.19 P.B.15:1 P.B.15:1 P.B.15:3 P.G.7
Colorants in PET
SY133 Polysynthren Yellow GG
PY151 Hostaperm Yellow H4G
PY147 Polysynthren Yellow NG
DY164 Solvaperm Yellow G
Product safety
SBr53 Polysynthren Brown R
SR135 Polysynthren Red GFP
SR135 Solvaperm Red G
SR195 Solvaperm Red BB
SB104 Polysynthren Blue RBL
SB104 Solvaperm Blue 2B
SG28 Sandoplast Green G
Optical Brighteners
Hostalux KS
Hosta;ux KS 1
Leucopure EGM
FDA Compliant Colorants with prescribed limitations

Product
Hostaperm Yellow H4G Polysynthren Yellow GG Polysynthren Yellow NG
Colour Index
P.Y.151 S.Y.133 P.Y.147
Polymer
PET PET PET
% upper concentration
0.01 0.2 0.25 0.25
Conditions of Use 21 CFR176.170

EFG E -F-G EFG DE F-G EF-G CD
Food types
Aqueous, acidic,low alcohol Aqueous, acidic,low alcohol All foods Food types III, IV-A, VI Aqueous, acidic,low alcohol Aqueous, acidic,low alcohol High alcohol, fatty foods
Polysynthren Red GFP
S.R.135
PET
0.2 0.045
Polysynthren Blue RBL Polysynthren Brown R Solvent Yellow G Solvaperm Red G
S.B.104 S.Br.53 D.Y.64 S.R.135
PET PET PET PET
0.2 0.2 0.2 0.2 0.045
EFG EFG EFG EFG CD
Aqueous, acidic,low alcohol Aqueous, acidic,low alcohol Aqueous, acidic,low alcohol Aqueous, acidic,low alcohol Aqueous, acidic,low alcohol High alcohol, fatty foods
Product safety
Solvaperm Red BB Solvaperm Blue 2B Sandoplast Green G Hostalux KS S.R.135 S.B.104 S.G.28 N/A PET PET PET PVC All Hostalux KS 1 Leucopure EGM N/A FB238 All Olefine PET 0.035 0.2 0.2 0.2 0.05 0.03 0.025 EFG EFG EFG DEFG DEFG B H < 275F EFG AH
Aqueous, acidic,low alcohol Aqueous, acidic,low alcohol Aqueous, acidic,low alcohol All foods All foods Food types I, II, VI-A, VII-B, VIII All foods All foods
Food contact conditions :

A Container is sterilised over 212F B Container is sterilised with boiling water C Container is hot filled or pasteurised above 150F D Container is hot filled or pasteurised below 150F E Room temperature filled and stored. No thermal treatment in the container F Refrigerated storage. No thermal treatment in the container G Frozen storage. No thermal treatment in the container H Frozen or refrigerated storage. Ready prepared foods intended to be reheated or microwaved in container at time of use
Product safety
Food types :
I Non acid,aqueous: may contain salt/sugar (pH above 5.0) II Acid, aqueuous; may contain salt/sugar and oil-in-water emulsions of low or high fat content IV-B Oil-in-water emulsions, high or low fat VI-A Beverages containing up to 8 percent alcohol VI-B Beverages, non alcoholic VII-B Moist bakery products with surface containing no free fat or oil VIII Dry solids with the surface containing no free fat or oil (no end test required)
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Principles Behind REACH
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Organic Pigments - The Basics - SII - Dec 2008

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Organic Pigments - The Basics - SII - Dec 2008

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Public

Tim Boyce ASEAN Regional Technical Servi

Organic Pigments The Basics

Global Pigment Market Principles of Colour Definition of Colourants

Clariant Product Range Product Safety

Corporate Presentation ASEAN Regional Technical Servi

Global Pigment Market

Total Pigment Market (Value) (total market 2006 : ~ 7.5 billion)

Global Pigment Market

High Performance 14%

Organic Pigment Market by Application

By volume Total : ~ 260,000 T

Printing Inks 35%

By value Total : ~ 5 billion

Organic Pigment Market by Pigment Types

Total Market 2006: 260,000 T

NAPHTOL AS 4 SPECIAL AZO 4

Global Pigment Market

QUINACRIDONE 2 OTHER POLYCYCLIC 2

QUINACRIDONE 8 PHTHALOCYANINE 27 OTHER POLYCYCLIC 8

Total Market 2006 : ~ 5.0 bn

Organic Pigment Market (Value) by Region

Global Pigment Market

ROW 8% Asia 28 % Americas 34 %

Corporate Presentation ASEAN Regional Technical Servi

The Principles of Colour

Spectrum of the electromagnetic waves.

Frequency (Hz) ( decreasing)

Organic Pigments The Basics Public ASEAN Regional Technical Service

Newtons Experiment (1666)

White Violet Blue Green Yellow Orange Red Ultraviolet Infrared

Wavelengths mean colour

Additive Colour Mixing.

Organic Pigments The Basics Public ASEAN Regional Technical Service

Example of additive mixing

The individual wavelengths are added together yellow

Subtractive Colour Mixing.

Organic Pigments The Basics Public ASEAN Regional Technical Service

Absorption and scattering

Example of Subtractive Colour Mixing

Additive primary colours

Subtractive primary colours

Interaction of light and matter

Scattering, absorption, transmission, reflection

Some green Light transmitted

Standardized Illumination D 65, A and C

relative radiation intensity

Depending on the illumination the colour impression changes

Metameric different different under different lights

Spectral Curve Visual perception of colour match

.. And one last piece of fun

Color impression and color measuring

emitted light Eye

color perception hues (max. 2 Mio)

The Color Appearance

The human eye

vision during daytime

Spectral sensitivity of the human eye

Green sensor Red sensor

Young Eyes Clear - Supple Lens

RETINA LENS LIGHT

LIGHT IRIS PUPIL

CIE Lab* - Colour Model.

L)2 + ( a)2 + ( L)2 + ( H)2 + (