Organic Pigments – The Basics - SII - Dec 2008

Public Tim Boyce ASEAN Regional Technical Servic

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

Public Corporate Presentation ASEAN Regional Technical Servic

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%

High Performance 14%

Azo 28%

Phthalocyanine 23%

Organic Pigment Market by Application (total market 2006 : ~ 260,000 T) Plastics 15%

Special Applications 5%

By volume Total : ~ 260,000 T


Coatings 23%

Printing Inks 56% NIP 1% Special Applications 13%

Printing Inks 35%

Plastics 19%


By value Total : ~ € 5 billion

Coatings 33%

Organic Pigment Market by Pigment Types Total Market 2006: 260,000 T

DIARYLIDE-YELLOW 22 LAKE RED 7

REFLEX-BLUE 3 HANSA-YELLOW 3 PYRAZOLONE 2 TOL.RED / ß-NAPHTOL 4

LITHOLRUBINE 12

NAPHTOL AS 4


SPECIAL AZO 4 QUINACRIDONE 2 OTHER POLYCYCLIC 2

OTHER LAKED 7

PHTHALOCYANINE 28

DIARYLIDE-YELLOW 18 REFLEX-BLUE 3 LAKE RED 3 HANSA-YELLOW 3 PYRAZOLONE 2 LITHOLRUBINE 7 TOL.RED / ß-NAPHTOL 2 NAPHTOL AS 5 OTHER LAKED 5 SPECIAL AZO 9 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service

QUINACRIDONE 8 PHTHALOCYANINE 27 OTHER POLYCYCLIC 8

Slide 6

Total Market 2006 : ~ 5.0 bn€

Organic Pigment Market (Value) by Region (total market 2006 : ~ € 5.0 billionT)


ROW 8% Americas 34 %

Asia 28 %


Europe 30 %


The Principles of Colour

Principles of Colour


1.

What is light? - Factorizing of light - Additive/subtractive mixing of colors

2.

Interaction of light and matter

3.

The creation of color - Color perception - Metamerism

4.

The CIE-Color system - The CIE La*b*-System - Color differences



1.


2.


3.


4.


Absorbing medium 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)


1023

1021

10-13

1019

10-11 10-9

1 Xe

400 nm

Organic Pigments The Basics Public ASEAN Regional Technical Service

1017

1 nm

1015

10-7

10-5

1011

10-3 1 mm

109

10-1

107

101

LW

MW

KW

UKW

dmW

mmW

1013

cmW

Radio waves

infrared

Light waves visible

X rays

ultraviolet

γ- rays

105

103

Frequency (Hz) (► decreasing)

Wavelength (m) (► increasing)

1 km

700 nm

Newton’s Experiment (1666) VIOLET INDIGO BLUE GREEN YELLOW ORANGE RED

Light source Wh


it e

Li g

ht

(400nm)

(540nm)

(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

White Violet Blue Green Yellow Orange Red

visible

350 nm - 400 nm > 770 nm

Ultraviolet Infrared

invisible

1 nm = 10 -9 m

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. Principles of Colour


Example of additive mixing

+

green Principles of Colour

red

The individual wavelengths are “added” together yellow Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 16

Subtractive Colour Mixing.


yellow

cyan

magenta incident light


Absorption and scattering

Example of Subtractive Colour Mixing


Transmission

1,0 0,8

Example: Yellow yellow/Cyan green Example: + Cyan = Green

0,6

0,4 0,2

380

cyan Organic Pigments The Basics Public ASEAN Regional Technical Service

440

+

520

yellow

600

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.

680 nm

green

Primary colours

blue

green

red


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) Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 21

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

Some green Light transmitted

Red absorbed



1.


2.


3.


4.


Apart from wavelengths and colour physics, some other aspects can affect the colour perception surface

Reflection (flop)


gloss

haze opacity Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 24

Standardized Illumination D 65, A and C

relative radiation intensity



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).

Depending on the illumination the colour impression changes



Metamerism Light source

Reflectance

Viewing angle

independent


red

metamerism - free dependent red

metamerism


Metamerism free

Metameric

Spectral Curve

same

different

Visual perception of

same

different under different lights

colour match



Deceptions


yellower

bluer Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 29

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

Brain Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 39

color perception hues (max. 2 Mio)

Measuring Instrument color intensity spectrum

Colorimetrics Color description: CIE La*b*-System ISO 7724-3, DIN 6174

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


cone cell

outer segment cell body

rod cell

• There are 3 types of cones each for blue, red, green detection

• The rod cells are for black & white detection, located in the outer part of the retina

• color impression, low light sensitivity

• no color, high light sensitivity • vision during night

• vision during daytime


Spectral sensitivity of the human eye Blue sensor Principles of Colour

Green sensor Red sensor


THE EYE RETINA CORNEA LENS LIGHT

LIGHT IRIS


PUPIL

Young Eyes Clear - Supple Lens

CORNEA

RETINA LENS LIGHT


Old Eyes Yellowing Rigid Lens

LIGHT IRIS

PUPIL

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 Principles of Colour

Different Races have different levels of deficiency and types of deficiencies Colour deficiencies in males according to race North America

8.00 %

Europe

8.76 %

Eastern Europe

9.31 %

China

6.15 %

Japan

4.50 %

Asia

6.00 %

Caucasian Population Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 44

Males

Females

Normal trichromats

91.9 %

99.6 %

Anomalous trichromats

5.5 %

0.4 %

Dichromats

2.6 %

0.05 %

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

Principles of Colour Eye b rig h t/d a rk b lu e , re d , g re e n

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 )

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

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 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 45

perception The human eye is represented by the color matching functions x, y and z

CIE - Chromaticity Diagram xy - Diagram 0,9

The standard tristimulus colour values X, Y and Z are calculated into the standard chromaticity coordinates (x, y and z) as follows :

0,8

0,7


0,6

x=

0,5

0,4

X (X+Y+Z)

y=

Y (X+Y+Z)

z=

Z (X+Y+Z)

To define the chromaticity only the values x and y are necessary.

0,3

0,2

Y is a dimension for the brightness of the colour.

0,1

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

Spectral colour co-ordinates :

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.

colour

nm

x

y

z

Red Orange Yellow Green Blue Violet

670 620 585 525 470 400

0,74 0,69 0,54 0,08 0,12 0,18

0,26 0,31 0,46 0,84 0,07 0,00

0,00 0,00 0,00 0,08 0,81 0,82

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 l´Eclairage.


Hue

Lightness

Chroma

CIE L*a*b* - Colour Model. L* White Principles of Colour

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.

Black

The colours are shown in their difference from one another as they are perceived by the eye.

Colour measurement CIElab - System

DIN 6174

Principles of Colour greenish yellow yellowish green

reddish yellow

Yellow

yellowish red

Greenish yellow

Reddish yellow Yellowish red

Yellowish green

Red Green bluish green

bluish red

greenish blue

reddish blue

Bluish green

Bluish red

Greenish blue Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 49

Reddish blue Blue

The CIE Lab Formula E*ab = (

L*)2 + ( a*)2 + (

b*)2

E*ab = (

L*)2 + ( H*)2 + (

C*)2

Chroma


C* =

( a *) + ( b *) 2

Shade/Hue angle 2

h ab

L* = Lightness a* = red/ green - Colourfulness b* = yellow/blue- Colourfulness

⎛b*⎞ = tan− 1 ⎜ ⎟ ⎝ a*⎠

L* b*

Derived designation: Organic Pigments The Basics Public ASEAN Regional Technical Service

C* = “intensity” difference H* = shade difference L* = lightness difference

a*

Colour measurement CIElab System

redder

dH Yellow

+

bluer

bluer

greener


yellower

Orange Red Violet Blue Green

dC

greener

Principles of Colour redder

Tolerances

yellower

yellower

redder

/=/

Equal

0.00 – 0.10

0.00 – 0.10

1

Trace

0.11 – 0.30

0.11 – 0.20

2

Slightly

0.31 – 0.80

0.21 – 0.50

3

Noticeably

0.81 – 1.40

0.51 – 0.80

4

Distinctly

1.40 – 2.20

0.81 – 1.40

5

Considerably

2.21 – 3.00

1.41 – 2.00

6

substantially

> 3.01

> 2.00

redder

bluer

dH

Chroma & Lightness Lighter

+

dL

-

Darker

Brighter

+

dC

-

Duller


Definition of Colourants

Definition of Colourants 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. Definition of Colourants






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 Definition of Colourants

inorganic Pigments


according to shade (DIN 55944)

organic Dyes

Pigments

Dyes

White Pigments

no commercial prominence

physically impossible

Colored Pigments

Colored PIgments

Colored Dyestuffs

Black Pigments

Black Pigments

Black Dyestuffs

Lustre Pigments

Lustre Pigments

physically impossible

Fluorescent Pigments

Fluorescent Pigments

Fluorescent Dyestuffs

Characteristics of Inorganic & Organic Pigments Characteristics of Organic & Inorganic Pigments Characteristic Definition of Colourants


Organic Pigments

Inorganic Pigments

Primary particles

Small

Large

Scattering

Weak

Strong

Absorption

High

Low

Surface

High area / hydrophobic

Small area / hydrophilic

Colour (hue)

Bright

Dull ► bright

Light/weatherfastness

Poor ► excellent

Good ► excellent

Tinting strength

Strong

Weak

Opacity

Transparent ► opaque

Opaque

Solvent fastness

Poor ► excellent

Excellent

Chemical fastness

Good ► excellent

Poor ► excellent

Dispersibility

Fair ► excellent

Good ► excellent

Heat stability

Good ► excellent

Good ► excellent

Toxicology

Mostly excellent

Heavy metals


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 (µ)

P.White 6 TiO2 280/300 2,75 1 very good abrasive 0,1-1,0

Coating *

organic/inorganic

Manufacturing process

Sulphate/Chloride

Shade

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

a little yellowish a little bluish

*Organic coating is destroyed at over 280°C .

chemical reaction bluish

Lead chromate pigments Colour area

Types of Inorganic pigments

Name

Formula

Colour-Index

Particle size (µ)

Chrome yellow

Pb(Cr,S)O4

P. Yellow 34

0,5-1,0

Chrome yellow

PbCrO4

P. Yellow 34

0,5-1,0

Molybdate red

Pb(Cr,Mo,S)O4

P. Red 104

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 Types of Inorganic pigments

ASEAN Regional Technical Service

Colour-Index particle size (µ)

Cadmium yellow greenish (Cd,Zn)S

P. Yellow 35

0.2-2

Cadmium yellow reddish

CdS

P. Yellow 37

0.2-2

Cadmium orange

Cd(S,Se)

P. Orange 20

0.2-2

Cadmium red

Cd(S,Se)

P. Red 108

0.2-2

Properties:

Organic Pigments The Basics Public

Formula

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 500-650°C. Disadvantage: Not for food packaging materials, environment- polluting.

Mixed phase / Metal complex pigments Name Types of Inorganic pigments

Formula

Nickel titanium (Ti,Ni,Sb)O 2 yellow Chrome titanium (Ti,Cr,Sb)O 2 yellow Cobalt blue Co(Al,Cr)O4 Cobalt green


P. Yellow 53 0.4-0.7 P. Brown 24 0.2-0.4 P. Blue 36

(Co,Ni,Zn)(Ti,Al)O4 P: Green 50

Zinc iron brown ZnFe2O4 Spinel black

Colour-Index Particle size (µ)

Cu(Fe,Cr)2O4

0.2 0.5

P. Yellow 119 1.0-2.6 P. Black 22

1.4-3.9

Properties: Excellent fastness properties in all concentrations Manufacturing is carried out in a calcining process at approx. 1000°C.

Oxide Pigments Colour area Types of Inorganic pigments

Name

Formula

Colour-Index particle size (µ)

Iron oxide yellow

FeOOH

P. Yellow 42 0.1-0.6

Iron oxide red

Fe2O3

P. Red 101

0.1-0.6

Iron oxide Fe3O4 black Chrome oxide greenCr2O3

P. Black 11

0.6-1.6

P. Green 17

0.3-2.0

Properties: Iron oxide yellow is limited in heat stability (180°C). All others have excellent fastness properties. All pigments are abrasive. Organic Pigments The Basics Public ASEAN Regional Technical Service

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 (µ)

Ultramarine blue Na6Al6Si6O24(Na S2-4)

P. Blue 29 0.3-8.0

Ultramarine violet Na6Al6Si6O24(NA S2-4 ) P. Violet 15 0.3-8.0 Manganese violet NH4Mn P2O7


P. Violet 16 0.3-8.0

Properties: Ultramarine blue Excellent light fastness Excellent heat resistance Dispersibility difficult

Sensitivity to acid Relatively high water content Moderate weather fastness

Properties: Manganese violet Excellent light fastness Excellent heat resistance Shading pigment

Sensitivity to acid and alkalis Very weak tinting power

Black pigments


Name

Formula

Colour Index Particle size (µ)

Carbon black

C

P. Black 7

0.01-0.1

Iron oxide black

Fe3O4

P. Black 11

0.6-1.6

Spinel black

Cu(Fe,Cr)2O

P. Black 28

1.4-3.9

4


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

Formula

Colour-Index

Aluminium

Al

P. Metal 1

Copper

Cu

P. Metal 2

Cooper/Zinc-alloy

Cu-Zn

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: Due to their flake structure, all metal pigments are shear sensitive. Bronze pigments can oxidise/tarnish

Effect pigments Types of Inorganic 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 Types of Inorganic pigments

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 Organic Pigments The Basics Public ASEAN Regional Technical Service

natural magnesium silicate hydrate natural aluminium silicate hydrate

French chalk

natural calcium aluminium silicate hydrate

Muscovite (Glimmer)

Kaolin, China Clay


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 1930’s. Huge range of azo pigments developed. These products met the demands of the colour using industries. 1950’s. The discovery of plastics and the requirement for automotive stoving paints led to the development of polycyclic and higher fastness azo pigments.


1960’s 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 Types of Organic pigments

Chromophores : - N = N -C=O -C=C-

-C=N-N=O

Substituent Groups : Auxchromes :

electron donors : electron acceptors :

Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service

Hypsochromes :

Slide 75

Br

Cl

CH3 OH ArNH2 COOH SO2 COOR

A chromophore complex forms the basic organic pigment molecule Types of Organic pigments

NO2

-

OH

-

-

NO2 -N=N-

2,4 - Dinitroaniline + B -Naphtol

Pigment Orange 5 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 76

There are 5 basic raw materials :

H3C

Types of Organic pigments

Benzene C6H6


Toluene C7H8

H3C

-

- CH

3

o, m, p - Xylene C8H10

Naphthalene

Anthracene

C10 H8

C14H10

Modified by a variety of chemical processes e.g. Types of Organic pigments


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 ………. Types of Organic pigments

• 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 :


Equivalent diameter (µm)


Volume distribution (%)

Volume portion (% per size class)

Volume distribution (%)


Volume portion (% per size class)

Size and distribution

Equivalent diameter (µm)

Narrow particle size distribution achieved by lower finish temperature for ink jet application

Shape P.R.122 Mixed crystal

P.R.122 Surface modified



Rod like Transparent Low viscosity

Viscosity design by modified shape

cubic Highly transparent Higher viscosity

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 Types of Organic pigments

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: Types of Organic pigments

Laked pigments : Chromophore F with acidic groups. SO3- / CO2F-SO3- / F-CO2-

M+ ------>

F-SO3- M+ / F-CO2- M+

Reaction with metal salt Large molecules : -N=N-


New Substitutients

From Monoazo to Dis-azo ---->

-N=N-A-N=N-

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

Fullshade Lightfastness 7 Overspray 2

Pigment Red 170 Novoperm Red F5RK

Fullshade Lightfastness 6-7 Overspray 3

Pigment Red 171 Permanent Bordeaux HFM

Fullshade Lightfastness 6 Overspray 5

Fullshade Lightfastness 7-8 Overspray 5

OCH3 N

N OH

1:46 TiO2 Lightfastness Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 86

1:55 TiO2 Lightfastness 4-5

1:85 TiO2 Lightfastness 4

CH3 NO2 N

CH3

NO2 N

N Cl OH

OC2H5 H

NH

N HO

O

1:80 TiO2 Lightfastness 6

H

OCH3

H N CONH2

N

H

NH HO O

H

N NO2

N

H N OH O

H N N H

O

Effects of Pigment Chemistry


Improve fastness properties e.g. increased substitution Shade e.g. new chromophores


Classes of synthetic organic pigments Azo


Classical Azo

Polycyclic

Special Azo

Naphtols

Monoazo

Azo condensation Laked Lake Red C

Benzimidazolone Anthraquinone Dioxazine Isoindolinone

Unlaked

Slide 88

Phthalocyanine Perylene

Toners


Quinacridone

Thioindigo

Hansa

DPP

Diazo Triphenylmethane

Chemistry

Yellow

Orange

Red

Brown

Violet

Monoazo

X

X

X

X

X

Diazo

X

X

X

X

Azo condensation

X

X

X

X

Azo salt

X

X

X

X

Azo metal complex

X

Benzimidazolone

X

Blue

Green

Black

AZO


X

X X

X

X X

POLYCYCLIC

Phthalocyanone Anthraquinone

X

Quinacridone

X

X

X

X

X

X

X

X

X X

Dioxazine Perylene Perinone

X

Pyranthrone

X

Indigoid

X

X

X

X

X

X

X

Thioindigo Isoindolinone

X

X

X

X

X

MISCELLANEOUS

X

Nitro Organic Pigments Nitroso The Basics Public Quinoline Tim Boyce ASEAN Regional Technical ServiceAzine Slide 89

Basic dye complexes

X X X X

X

X

X

X

X

X

Pigment classes


Azo Pigments

Monoazo Disazo Beta-Naphthol Naphthol AS Red Azo Lakes Benzimidazolone Disazo Condensation Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 90

Polycyclic Pigments

Phthalocyanine Quinacridone Perylene/Perinone Isoindolinone/Isoindoline Dioxazine Triphenylmethane Diketo-Pyrrolopyrrole DPP

Azo-Pigments Monoazo :

R2-N=N-R3 H3C


C.I.

O

Monoazo-Yellow

N

N O

N

Pigment Yellow 1

N H

+

O

O O N

Naphtol AS

O

O N

Cl

N

Pigment Red 14

H N

O NH

H3C

O

O

Benzimidazolone

CH 3

N H

HO

N H

HO

O N

N

Pigment Red 171

N

O

O N

β-Naphtol Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 91

O HO N

H3C

O

BONS laked

O S

O

Mn N

H3C

Pigment Red 3

N

O

N OH

O

2+

Pigment Red 48:4

Azo-Pigments Dis-Azo : Types of Organic pigments

R2-N=N-R3-N=N- R2

C.I.

Diarylyellow Cl

H3C O CH3 Cl

O H N

H3C O

O

N N

N N

O Cl

N H

O CH3

Pigment Yellow 83

O H3C

O

Cl H3C

Disazo-konden-sation Cl N Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service

Slide 92

H N

N OH

Cl

O

Cl Cl N H

O

OH N

Pigment Red 144 N Cl

Polycyclic Pigments N N

N

Phthalocyanin

Pigment Blue 15

N

Cu

N

N

N N


O

H N

Chinacridone

Pigment Violet 19 N H

O

Cl

Dioxazine

H5C2

N

N

O

O

N

N CH 2 5

Pigment Violet 23

Cl

O Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service

Slide 93

Cl

H N

Pigment Red 254

Diketo-Pyrrolopyrrol DPP Cl

N H

O

Polycyclic Pigments H N

O

Isoindolin

O H N

HN


Cl

Pigment Yellow 110 Cl

O

Slide 94

N

N

Cl Cl

Perylene

Pigment Yellow 139

O

Cl


O NH

O

Isoindolinon

H N

O

H3C N O

O Cl

O

Cl

Cl

O N CH3 O

Pigment Red 179

Azo Pigments Chemical structure and fastness properties


Pigment Class

Lightfastness

Migration fastness

monoazo

fair ►very good

poor

Β-Naphtol

good ►very good

poor

Naphtol AS

good ►very good

poor ►good

BONA, laked

good ►very good

good

excellent

excellent

fair ►very good

good ►very good

good ►very good

Very good ►excellent

poor

poor

Benzimidazolone Diarylide Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service

Slide 95

Disazocondensation Triphenylmethane

Polycyclic Pigments Chemical structure and fastness properties



Slide 96

Pigment Class

Lightfastness

Migration fastness

Dibromoanthanthrone

excellent

excellent

Phthalocyanine

excellent

excellent

Quinacridone

excellent

excellent

Diketo-Pyrrolopyrrole

excellent

excellent

Isoindolinone



Perylene/Perinone



Dioxazine



Isoindoline



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


Monoazo pigments 2,4,5 - trichloraniline Types of Organic pigments

HO

Cl Cl

CONH

N=N

CH 3

Cl

2-hydroxy-2-naphtho -ortho-toluidide Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service

Slide 98

Pigment Red 112 ( C.I. : 12370 )

Monoazo (Hansa) yellow pigments 4 RD

RD5 RD2


N

H N

N

RK2

H3C O

O RK5


Slide 99

RK4

C.I. Name

Const. No.

R2D

RD4

R5D

R2K

R4K

R5K

P.Y.1

11680

NO 2

CH 3

H

H

H

H

P.Y.3

11710

NO 2

Cl

H

Cl

H

H

P.Y.73

11738

NO 2

Cl

H

OCH 3

H

H

P.Y.74

11741

OCH 3

NO2

H

OCH 3

H

H

P.Y.97

11767

OCH 3

SO 2 NHC 6H 5

OCH3

OCH 3

Cl

OCH 3

Monoazo (Hansa) red pigments (β Naphtols) 2

R

N


N

4

R

OH


Slide 100

C.I. Name

Const. No.

R2

R4

P.O.5

12075

NO2

NO2

P.R.4

12085

Cl

NO2

P.R.3

12120

NO2

CH3

Monoazo pigments Naphtols AS R 2

K

R D2 N Types of Organic pigments

N HO

4

RD

4 RK

NH

O

5 RK

RD5


Slide 101

R2 D

R4 D

R5 D

R4 K

R5 K

1 24 60

Cl

H

Cl

OCH3

H

H

P .R .12

1 23 85

CH3

NO2

H

CH3

H

H

P .R .14

1 23 80

NO2

Cl

H

CH3

H

H

P .R .11 2

1 23 70

Cl

Cl

Cl

CH3

H

H

P .R .5

1 24 90

OCH3

H

S O 2 N (C 2 H 5 ) 2

OCH3

OCH3

Cl

P .R .14 6

1 24 85

OCH3

H

C O N H C 6H 5

OCH3

Cl

OCH3

P .R .17 0

1 24 75

H

CONH2

H

O C 2H 5

H

H

P .R .18 8

1 24 67

COOCH3

H

C O N H C 6H 3C l 2 (2 ,5 )

OCH3

H

H

P .R . 2 53

Cl

S O 2N H C H 3

Cl

CH3

Cl

H

P .O . 74

Cl

S O 2N H C H 3 S O 2 N (C H 3 ) 2

Cl

H

Cl

H

C .I. N a m e

C o n st. No .

P .R .9

R2 K

Monoazo red pigments red azo lakes CH3

Ba


2+

O

O S O

Cl

R2 N

N

N

O

N

OH

OH

R4

O

M2+

R5

P.R. 53:1 ( 15585:1 )

Ca

2+

CH3 N

O O S O


Slide 102

C onst. No.

R2

R4

R5

M

P .R .48:2

15865:2

S O 3-

CH3

Cl

Ca

P .R .48:3

15865:3

S O 3-

CH3

Cl

Sr

P .R .48:4

15865:4

S O 3-

CH3

Cl

Mn

P .R .57:1

15850:1

S O 3-

CH3

H

Ca

H N

N OH

N H

C .I. Nam e

O

O

P.R. 247 ( 15915 )

O CH3

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.


Slide 103

Not recommended for use in applications where the processing temperature exceeds 200°C.

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) Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service

Slide 104

Pigment Yellow 13 ( C.I. : 21100 )

Disazo pigments AAA arylide R2 Types of Organic pigments

H3C H N

Cl

O N

O

N

H N

N O

Cl

R5


Slide 105

R2

N

O

R4

CH3

C.I. Name

Const. No.

R2

R4

R5

P.Y.12

21090

H

H

H

P.Y.13

21100

CH3

CH3

H

P.Y.14

21095

CH3

H

H

P.Y.17

21105

OCH3

H

H

P.Y.83

21108

OCH3

Cl

OCH3

P.Y.127

21102

CH3

CH3

H

OCH3

H

H

P.Y.176

21103

CH3

CH3

H

OCH3

Cl

OCH3

P.Y.188

11767

CH3

CH3

H

H

H

H

R4 R5

Thermal decomposition of diarylide pigments.

A Diarylide pigment


>200 °C

B

>240 °C

soluble monoazo compound (coloured)

C

Dichlorbenzidine DCB

• Diarylide pigments partly dissolve above 200°C and split off into a soluble monoazo compound. •The monoazo compound starts to decompose above 240°C to produce DCB. Organic Pigments The Basics Public

• Monoazo dyes and DCB are considered carcinogenic in tests on animals.


Note : below 200’C diaryl pigments meet consumer goods regulations

Benzimidazolone pigments

Colour area Types of Organic pigments

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

3 RD


O

R D2 N

CH3 H N

N

H N O

O

4

RD

N H

RD5


Slide 108

C .I. Nam e

C onst. No.

RD2

3 RD

RD4

5 RD

P .Y.120

11783

H

COOCH3

H

COOCH3

P .Y.151

13980

COOH

H

H

H

P .Y.154

11781

CF3

H

H

H

P .Y.175

11784

COOCH3

H

H

COOCH3

P .Y.194

11785

OCH3

H

H

H

P .O .36

11780

NO2

H

Cl

H

P .O .62

11775

H

H

NO2

H

Benzimidazolone red and brown pigments

R2

D

N


R

H N

H N

N OH

4

O

O

N H

D

RD5


Slide 109

C .I. Nam e

C onst. No.

RD2

RD4

RD5

P .R .175

12513

COOCH3

H

H

P .R .176

12515

OCH3

H

CONHPh

P .R .185

12516

OCH3

S O 2N H C H 3

CH3

P .R .208

12514

C O O C 4H 9

H

H

P .V .32

12517

OCH3

S O 2N H C H 3

OCH3

P .B r.25

12510

Cl

H

Cl

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. Organic Pigments The Basics Public ASEAN Regional Technical Service

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 Types of Organic pigments

Q

N O


O N

H3C

R4

H N

N H

R2

CH3 N

O

O

N

Q

A

O

C.I. Name

Const. No.

R2

R4

A

Q

P.Y.93

20710

Cl

Cl

Cl

NH-C6H3-2- CH3,3-Cl

P.Y.95

20038

Cl

CH3

Cl

NH-C6H3-2- CH3,5-Cl

P.Y.128

20037

Cl

CH3

Cl

NH-C6H3-2-OAr,5-CF3

P.Y.155

200310

Ar = C6H4-4-Cl

H

H

COOCH3

OCH3

Disazo : Red azo condensation pigments RD5

O R D2


N N

OH

4

RD

4 RK

H N

N H

HO

N N

2 RD

R2 O K

4

RD5

RD


C.I. Name

Const. No.

R 2D

R 4D

RD5

R 2K

R 4K

P.R.144

20735

Cl

H

Cl

Cl

H

P.R.166

20730

Cl

H

Cl

H

H

P.R.214

200660

Cl

H

Cl

Cl

Cl

P.R.220

20055

CH 3

H

COOCH 2CH 2Cl

CH 3

CH 3

P.R.221

20065

Cl

H

COOCH(CH 3)2

Cl

Cl

P.R.242

20065

Cl

H

CF 3

Cl

Cl

P.R.262

-

Cl

H

Cl

CN

H

P.Br.23

20060

NO 2

Cl

H

Cl

H

Triphenylmethane Colour Colour area area Types of Organic pigments

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 Types of Organic pigments

H N

R2

-O3S +

C R2

HN


R2

C.I. Name

Const. No.

R2

P.Bl.56

42800

CH3

P.Bl.61

42765:1

H

Isoindolinone / Isoindoline Colour area Types of Organic pigments

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 : Types of Organic pigments

Cl Cl

N

N

Isoindoline : H N

Cl Cl

NH

CH3 HN

Cl

Cl Cl

N

O

Cl

N

N

N H

HN Cl


O

O

O O

O

N H

P.Y. 139 ( 56298 )

Cl

Cl Cl

H N

Cl

Cl NH

O

H N

O

P.Y. 109 ( 56284 ) Cl

O

H N

O

O N H

H N

O

CH3 N H N

O

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 10

R R


H N

8

R

1

R

9

R

N H

O

2

3

R R

4

C.I. Name

Const. No.

R2

R3

R4

R9

R 10

R 11

P.V.19

73900

H

H

H

H

H

H

P.R.122

73915

CH 3

H

H

CH 3

H

H

P.R.202

73907

Cl

H

H

Cl

H

H

P.R.207

73905

H

H

Cl

H

H

Cl

P.R.209

73905

H

Cl

H

H

Cl

H

P.O.49

-


O

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 Perinone :

Perylene : Types of Organic pigments

O

O

Q N

N Q

O

N

Slide 122

N

O

O


N

C.I. Name

Const. No.

Q

P.R.149

71137

3,5Me2-Ph

P.R.178

71155

4-Ph-N=N-Ph

P.R.179

71130

Me

N

O

P.O. 43 ( 71105 )

Dibromoanthranone


Brilliant yellowish red pigment. Excellent light and weathering resistance at all shade depths The dispersion is generally good. O

P.R.168 Organic Pigments The Basics Public ASEAN Regional Technical Service

O

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 Organic Pigments The Basics Public ASEAN Regional Technical Service

Diketo-pyrrolopyrrole R3

O Types of Organic pigments

N H

R4

R4

H N

O

R3


C.I. Name

Const. No.

R3

R4

P.O.71

561200

CN

H

P.O.73

561170

H

C(CH3 )3

P.R.254

56110

H

Cl

P.R.255

561050

H

H

P.R.264

561300

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 N

N

Cu N

N

N

Cu

N

N

N

N


N

N

N N

N

N

N

Cu N

N N

C .I. N a m e

m o d if ic a t io n

H a lo g e n s

m o d . s t a b i l iz e d

f lo c c u la t io n

P . B l. 1 5

α

-

no

-

P .B l. 1 5 :1

α

0 . 5 -1 C l

yes

u n s ta b le

P .B l. 1 5 :2

α

0 . 5 -1 C l

yes

s t a b le

P .B l. 1 5 :3

β

tr a c e s

-

u n s ta b le

P .B l. 1 5 :4

β

tr a c e s

-

s t a b le

P .B l. 1 5 :6

ε

tr a c e s

yes

P .G r. 7

-

1 4 -1 5 C l

P .G r. 3 6

-

4 - 9 B r ,8 - 2 C l

Slide 128

N N

Dioxazine


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

O

N Cl


P.V. 23 ( 51319 )

N


Synthesis and Production of Azo Pigments

Azo pigments are named for containing an azo-group Synthesis and Production of Azo Pigments

-N=NTwo nitrogen-atoms are connected with a double bond.


There can be one Azo group in so called monoazo pigments

NO2


H3C


Hansa Red B Pigment Red 3

HO

N N

or two azo groups, then it is called a disazo pigment (also called diaryl or diarylide) Synthesis and Production of Azo Pigments

Cl

Cl

O

O

H 3C

N

N

N

H N

O

CH N

H N O

Permanent Yellow DHG Pigment Yellow 12 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 134

You can also think about molecules with more then two Azogroups. This is actually done in the synthesis of azo dyes

3

Diazotization of an aromatic amine to form the diazonium compound NO2 NH2 Synthesis and Production of Azo Pigments

+ 2 HCl + NaNO2

H3C

+

NO2 N

N

Cl- + NaCl + 2 H2O

H3C Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 135

The unstable diazonium compound has to be cooled with ice to 5-7°C 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

Diazo kettle

CH 3


C=O CH 2

_

+

DCB

+ N

Cl

Dissolving kettle

≡N

N

≡N

_ Cl

+

AAA

CH 3 C=O CH 2 O=C NH

NH C=O KETTLE 2

+

KETTLE 1

Cl

Cl

KETTLE 2

+ 2 NaOH Coupling kettle CH 3

CH 3

C=O

C=O

HC

N=N

HN C=O Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 138

N= N CH Cl

DIARYLIDE YELLOW

Cl

( P.Y.12 )

PRECIPITATION

O=C NH

+

2 NaCl

+

2 H2O



Reactor vessel – Normally a sealed unit and as fully automated as possible

During coupling process, different conditions have to be control Synthesis and Production of Azo Pigments

Temperature pH value Time

These controlled conditions will have major effects on the synthesis, and therefore on the quality of the pigment Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 140

Finishing Optimizing the physical properties of the pigment, such as: Synthesis and Production of Azo Pigments

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

FILTRATION

NaOH

COUPLING COMPONENT

H 2O

DISSOLVING OF COUPLING COMPONENT

FILTRATION

COUPLING KETTLE Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 144

VAPOUR

FINISH KETTLE Synthesis and Production of Azo Pigments

FILTER

FILTRATION

PUMP

DRYING NAUTA BLENDER

VAPOUR


DRYING OVEN

GRANULES

GRANULATOR

PRESSCAKE

Filterpress with falling filtercake Synthesis and Production of Azo Pigments

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 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 147

After being dried, the priment granules fall from the beltdryer to the mill.

MILLING BLENDER


JET - MILL

1

2

3

4

STORAGE BINS


PIGMENT POWDER


Properties of Organic Pigments

Properties of organic pigments Pattern card data Colour Index Standard Shade Depth Properties of Organic Pigments

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 Properties of Organic Pigments


☺ Colour Index ☺ Colour & Shade Depth ☺ Tint Strength ☺ Physical Properties ☺ Fastness Properties







Colour Index Nomenclature system for pigments and dyestuffs Report to Colour Index : Properties of Organic Pigments

By producer, with trade name Structure (optional) Properties Application field

Classification in Colour Index : According to application, properties, shade and structure.

Listing in Colour Index :


Generic name Constitution number

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 Properties of Organic Pigments

CI Class

CI Class

Shade

Number

Pigment

Violet

19

Solvent

Red

135

Pigment Dye

Solvent, reactive, vat, basic, Acid, direct, disperse

Shade

yellow, orange, red, violet, blue, green, brown, black, white

Number Organic Pigments The Basics Public ASEAN Regional Technical Service

continuous

Colour Index – Constitution Numbers



Chemical Constitution

Constitution Number

Nitroso

10000 – 10299

Nitro

10300 – 10999

Monoazo

11000 – 19999

Disazo

20000 – 29999

Stilbene

40000 – 40799

Diphenylmethane

41000 – 41999

Triphenylmethane

42000 – 44999

Xanthene

45000 – 45999

Acridine

46000 – 46999

Quinoline

47000 – 47999

Methine

48000 – 48999

Thiazole

49000 – 49399

Indamine

49400 – 49699

Indophenol

49700 – 49999

Azine

50000 – 50999

Oxazine

51000 – 51999

Thiazine

52000 – 52999

Anthraquinone

58000 – 72999

Indigoid

73000 – 73999

Phthalocyanine

74000 – 74999

Inorganic pigments

77000 - 77999

Same Colour Index but .......

P.Y.16 Properties of Organic Pigments 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 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 158

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. Properties of Organic Pigments

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


FS

Fullshade

1/3 SD 1:2.5 TiO2


1/25 SD

1:29 TiO2

P.Y. 83

Fullshade

P.R. 112

Fullshade

P.B. 15:1

Fullshade

P.V. 23

Fullshade

1:15.3 TiO2

1: 5.5 TiO2

1:12.3 TiO2

1:19.7 TiO2

1:200 TiO2

1: 70 TiO2

1:175 TiO2

1:265 TiO2

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 Properties of Organic Pigments

can influence

can influence

colour colour purity fastness properties

particle size can influence

tinting strength shade hiding power

crystal structure


primary particles aggregates agglomerates

Organic pigment crystals Enlargement 32 000 X


Pigment Green 7


Pigment Red 247

Pigment Orange 43

Pigment Red 144

Particle composition of pigments Smallest unit of a material. Has its properties. In this case a mono crystal. Properties of Organic Pigments

Primary particle

Aggregates


Agglomerates

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.

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

α-modification

β-modification

P.B.15:1 Red shade

P.B.15:3 Blue shade

Crystal modifications C.I. Pigment Violet 19 full shade

white reduction


β Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 166

Hostaperm Red Violet ER 02 / ERX

γ Hostaperm Red E3B / E5B 02

β

γ

Hostaperm Red Violet ER 02 / ERX

Hostaperm Red E3B / E5B 02

SEM-micrograph of powder pigments C.I. Pigment Yellow 83


®Novoperm


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

Relationship between particle size and shade, opacity and tint strength Novoperm Yellow HR 02 (P.Y.83) Properties of Organic Pigments


Novoperm Yellow HR 70 (P.Y.83)



Specific surface area Relationship between particle size and surface area …………..


Cubic dimension

Number of particles in basic cube

Surface Area (m2)

1 cm

1

6 cm2

1 mm

103

60 cm2

1 nm

1012

60000 cm2

Assuming a spherical shape ………….


Particle diameter in µ

Surface Area (m2/g)

0.4

15

0.3

20

0.2

30

0.1

60

Effect of particle size on tint strength

0.50 Properties of Organic Pigments

0.45 0.40 0.35 0.30

P.Y.17 P.G.7

0.25 K/S 0.20 0.15 0.10 0.05 0.00 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 170

0.1

0.2

0.3 0.4 microns (u)

0.5

0.6

Typical surface areas


Most Monoazo Grades, 70 Series

< 25 sq m/g

Naphtol Grades, some Quinacridones

25-55 sq m/g

Some Quinacridones, Dioxazine Violet, Phthalocyanines Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 171

> 55 sq m/g

Dispersion of Pigments Pigment Powder Properties of Organic Pigments

Agglomerates

Aggregates Primary Particles Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 172

Decreasing Particle size

Dispersion of organic pigments 1. Deagglomeration - premixing of single pigments to break down larger, softer agglomerates. Initial wetting out. Properties of Organic Pigments


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 Type

Particle Size (µm)

Inorganic pigments


Pigment Black 7

Carbon black

0.01 – 1.0

Pigment White 6

Titanium dioxide

0.1 – 1.0

Pigment Yellow 34 / Pigment Red 104

Lead chromates / molybdates

0.5 – 1.0

Pigment Red 101

Iron oxide red

0.1 – 0.6

Pigment Blue 29

Ultramarine blue

0.3 – 8.0

Organic pigments


Pigment Yellow 13

Diarylide yellow

0.06

Pigment Yellow 180

Benzimidazolone

0.18

Pigment Orange 43

Perinone

0.15

Pigment Red 254

Diketopyrrolopyrrole

0.2

Pigment Violet 23

Dioxazine

0.06

Pigment Blue 15:3

Β-phthalocyanine

0.09

Flocculation



Effects of Flocculation Loss of colour strength Poor levelling (in paints) Poor flow Reduced gloss Hazing Shade variation

Flocculation v’s time

Properties of Organic Pigments 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


large

more opaque

low strength

low visc.

low Specific Surface Area

higher loading

properties

lower fastness

fastness

(flow)

viscosity

strength

opacity tint

transparency /


lower loading

concentration

high Specific Surface Area

high visc.

Surface area

high strength

specific

small

more trans.

millbase

particle size

higher fastness

* these are guidelines only and other factors may need to be considered


Pigment Technical Service Laboratory – ASEAN Region

Key fastness properties of organic pigments Migration Heat stability Lightfastness Weatherfastness



Migration fastness of organic colourants

Solvent fastness Bleeding Overspray Blooming

Solvent fastness Thepigment pigmentisisdissolved dissolvedby bythe thesolvent, solvent, The therebydiscolouring discolouringthe thesolvent solvent thereby Properties of Organic Pigments

• 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


Toluene

IPA


Toluene/IPA (70/30)

Slide 182

P-GRL 06 STD P.Y.13

DHG SPL STD P.Y.12

MX STD P.Y.13

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 – 120’C / 30 minutes

Migration fastness - overspray ► Bleeding in an overspray application (tested in thermosetting acrylic) Properties of Organic Pigments


P.R.170

P.R.3

Migration fastness - blooming


Example of blooming in Low Density Polyethylene Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 187

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 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service

1 week aged

Aromatic solvents or high heat (above 200’C) cause a crystal shift resulting in a greener, weaker product

Slide 188

Control

1 week aged

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” Properties of Organic Pigments

Initial matching designed for application at 240’C maximum

Final colour when processed at 280’C Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 191

Heat stability Heat stability - 0.5% pigment, 5 minute dwell time Pigment discolours Properties of Organic Pigments


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

70

120

100

160 140

200

160

180

120 100

120

160

Slide 196

80 120

100

80

160-180 160 120 140

140 180


100

160

70

120 100 80

180 160

180 160

Lightfastness – variation in radiation levels

160

180 Properties of Organic Pigments

170

190

160

200 200 190 180 170 160 150 140 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 197

160 150 140

160

160 150 140 130 120

Kilolangleys/year of radiation in Australia

150 140 130 120

Conversion Table 1 Langley = 1 cal/cm2


= 4,188 J/cm2

1 W/m2

= 0,0001 W/cm2

1 Luxh

= 0,581 x 10-3 cal/cm2

= 0,581 x 10-3 Ly

= 2,433 x 10-3 J/cm2

1 J/cm2

= 10 KJ/m2

= 0,2388 Ly

= 411 Luxh

1 Lux

= 0,161 x 10-6 cal/(cm2 x s)

= 0,676 x 10-6 W/cm2

1 Langley = 4,18 Joule/cm2 = 4,18 Ws/cm2 = 1,00 cal/cm2 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 198

The light energy of 1 year in Frankfurt is approximately 80 Kly = 3350 MJ/m2

Lightfastness – Blue Wool Scale


Step 1 Step 2 Rating

Step 3 Step 4

4–5

Step 5 Step 6

6

Step 7 8

Step 8 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 199

Exposed section 250 hours



Types of Accelerated UV/Weathering Apparatus



3. Light fastness (DIN EN ISO 4892) Different types of exposure

Blue wool scale Properties of Organic Pigments


Accelerated exposure* in hours

Normal daylight exposure* in days

(in Xenotest X 1200 W)

(in Frankfurt-Liederbach Germany)

1

6h

5 days

2

10 h

10 days

3

25 h

20 days

4

120 h

40 days

5

200 h

80 days

6

400 h

160 days

7

800 h

350 days

8

1.600 h

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

4 days

5.4 hrs

2.5 hrs

2.5 hrs

2.5 hrs

2

14 days

15 hrs

6.5 hrs

8 hrs

6.5 hrs

3

28 days

34 hrs

15 hrs

20 hrs

9 hrs

4

70 days

100 hrs

60 hrs

75 hrs

41 hrs

5

100 days

240 hrs

110 hrs

160 hrs

80 hrs

6

140 days

400 hrs

200 hrs

270 hrs

130 hrs

7

160 days

800 hrs

400 hrs

540 hrs

260 hrs

8

360 days

1600 hrs

800 hrs

1100 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

Exposure in daylight in days (in Liederbach)

Dyestuff

1

6h

5

Acilan Br. Blue FRR (Bayer)

2

15 h

10

Acilan Br. Blue FFB (Bayer)

3

34 h

20

Sypranolcyanine 6B (Bayer Bencylcyanine (Ciba)

4

120 h

40

Supramin Blue EG (Bayer)

5

240 h

80

Solmay Blue RN (ICI) Acilan Fast Blue RX (Bayer)

6

400 h

160

Alicarin Lightblue 4GL (Clariant)

7

800 h

350

Soledon Blue 4BC (ICI) Indigosol Blue 04B (Durand) Anthrasol Blue 04B (DyStar)

8

1.600 h

700

Indigosol Blue AGG (DyStar)



Resistance to Weathering

Weatherfastness It is a measure of all exposure conditions e.g. UV, rain, snow, industrial atmosphere etc Properties of Organic Pigments

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) Properties of Organic Pigments


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: Properties of Organic Pigments

Discoloration


Cracking

Rust

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

Energy (1 h)

Xenotest 1200 W (rotating panel)

1,764 MJ/m2

Relative Humidity 60 %

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 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 211

South East Asia

Wet

Dry

Wet

Dry

18 mins

102 mins

240 mins

240 mins

.

Fastness to weathering ISO 105-A02: 1993 Grey scale for assessing change in color



Fastness to weathering 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 Properties of Organic Pigments

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

Application Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 217

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

Test methods

Quality aspects

• 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


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 Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 219

Note : only used with reduced shade

Colour measurement CIElab - System

DIN 6174

Quality aspects greenish yellow yellowish green

reddish yellow

Yellow

yellowish red

Greenish yellow

Reddish yellow Yellowish red

Yellowish green

Red Green bluish green

bluish red

greenish blue

reddish blue

Bluish green

Bluish red

Greenish blue Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 220

Reddish blue Blue

Colour measurement CIElab System

redder

dH Yellow

+

bluer

bluer

greener


yellower

Orange Red Violet Blue Green

dC

greener

Quality aspects redder

Tolerances

yellower

yellower

redder

/=/

Equal

0.00 – 0.10

0.00 – 0.10

1

Trace

0.11 – 0.30

0.11 – 0.20

2

Slightly

0.31 – 0.80

0.21 – 0.50

3

Noticeably

0.81 – 1.40

0.51 – 0.80

4

Distinctly

1.40 – 2.20

0.81 – 1.40

5

Considerably

2.21 – 3.00

1.41 – 2.00

6

substantially

> 3.01

> 2.00

redder

bluer

dH

Chroma & Lightness Lighter

+

dL

-

Darker

Brighter

+

dC

-

Duller

Quality costs Total cost Prevention Quality aspects

Appraisal

Failure

Planning

Design

Replacement

Auditing

Inspection

Rework

Training

Test equipment

Repair

Quality Assurance

Evaluation

Re-inspection

Record Storage

Downtime Scrap Diagnosis


Up to 6%

Up to 11%

Up to ?? %

Technical & Quality complaint procedures Quality aspects

We need : - Sample and lot number of pigment ex delivery - Customer’s evaluation - ALL details of customer’s test method and application - Method of processing We check : Method of standardisation + customer’s application method

Technical decision Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 223

Commercial decision

Additional information

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 Clariant Product Range


Hostaperm

Highest Quality

Novoperm

Very High Quality

Permanent

Very Good / Good quality

Hansa

Specific Range with very good specific properties

Reflex Blue

Specific Range

PV Fast

Highest quality selectively tested for plastics

Graphtol

Very Good / Good quality selectively tested for plastics

Clariant product ranges – Dyestuffs Clariant Product Range


Savinyls

range of solvent dyes

Solvaperm

range of solvent dyes for plastics

Polysynthren

range of solvent dyes for plastics

Fat

range of solvent dyes

Hostasols

range of fluorescent solvent dyes for plastics

Duasyn

range of water soluble dyes

Vitasyn

range of water soluble food dyes

Cartasol


others


Clariant product ranges – Supply forms Clariant Product Range


Colourants Pigment

Dyestuff

Preparation

powder

powder

powder

granules presscake

liquid

paste fine granules granules flush pastes

Clariant product ranges – Pigments Standard Range Clariant Product Range

Hostaperm

Properties Excellent fastness properties

Chemistry Quinacridone Phthalocyanine Dioxazine Benzimidazolone Dibromoanthranthrone

Novoperm

Very good fastness

Benzimdazolone Naphtol AS

Permanent Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 229

Average to good fastness. High colour strength

Naphtol AS Diarylide

Hostaperm Most commonly used in High Quality applications such as : Clariant Product Range

• 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 : Clariant Product Range

• 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) Clariant Product Range


Standard Range

Properties

Chemistry

Hansa

Monoazo Good fastness to light but poor solvent fastness Beta naphtol

Reflex Blue

Low fastness. High colour strength

Triphenylmethane

PV Fast

High thermal stability and fastness

Selected Hostaperm and Novoperm grades

Graphtol

Moderate thermal stability and fair to good fastness

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 Clariant Product Range


Application field

Properties

Hostasol

Plastics

Fluorescent

Solvaperm

Plastics

Good fastness

Polysynthren

Higher performance plastics

High fastness

Fat

Solvent systems, waxes

Multiple applications

Duasyn

Special applications


Vitasyn

Foodstuffs, cosmetics

Registered products

Savinyl

Ink, coatings, Special applications


Clariant product ranges – Preparations Clariant Product Range


Paint

Printing Ink

Plastics

Specialised

Colanyl 100

Traditional

Hostaprint

Flexonyl

Colanyl 500

Flexonyl WF

Hostasin

Viscofil

Hostatint

Flexonyl A

Viscofil A

Hostatint E

NIP

Viscofil S

Hostatint A

Permajet liquid

Cosmenyl

Hostafine

Permajet 30

Cosmenyl gran.

Renol HW

Hostajet Hostacopy


Product safety


Product Safety Prior to marketing a product all legal requirements must be fulfilled! Mandatory Regulations:

Product safety

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 Voluntary Regulations:

Product safety

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


Internal Standards DIN EN ISO 9001 DIN EN ISO 14001

Worldwide Chemical Legislation In Force European Union

Eastern Europe

Switzerland

Russia, Baltic States, Bulgaria, Romania, Slowenia, Slovac Republic

USA Canada Australia

Product safety

Japan New Zealand Philippines South Korea China (partly) Czech Republic (partly) Hungary (partly) Poland (partly)


In Preparation

Mexico Malaysia Singapore Taiwan Thailand South Africa

Chemical Legislation Inventories EINECS

European Inventory of Existing Commercial Substances

REACH

Registration, Evaluation, Authorisation and Restriction of Chemicals

USA

TSCA

Toxic Substances Control Act

Canada

DSL

Domestic Substances List

Japan

ENCS

Japanese Existing and New Chemical Substances

Australia

AICS

Australian Inventory of Chemical Substances

Korea

ECL

Existing Chemicals List

Philippines

PICCS

Philippines Inventory of Chemicals and Chemical Substances

China

ECSC

Inventory of Existing Chemical Substances in China

EU

Product safety


Major worldwide regulations affecting pigments

Product safety


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)

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.


Colorants for the coloration of consumer goods, food packaging and toys Recommendation IX of BfR (former BgVV)

Product safety

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

Colorants for the coloration of consumer goods, food packaging and toys European Resolution AP (89) I "On the use of colorants in plastic materials coming into contact with food"

Product safety

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

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, ß-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

Colorants for the coloration of consumer goods, food packaging and toys Heavy metal limits (ppm*) for colorants in food packaging – Country overview Country/Metal

Product safety

Australia Belgium Germany (Rec. IX) EU/AP (89) I France Great Britain Greece Italy Japan (JHPA)** Japan (JHOSPA) Netherlands Portugal Switzerland


As

Ba

Cd

Cr

Hg

Pb

100 100 100 100 100 100 100 50 50 50** 100 100 100

100 100 100 100 100 100 100 100

100 100 100 100 100 100 100 100 100 100** 1000 100 100

1000 1000 1000 1000 1000 1000 1000 1000

50 50 50 50 50 50 50 50 50 50** 50 50 50

100 100 100 100 100 100 100 100 100 100* 100 100 100

* Soluble contents in diluted HCl

100 100 100 100

1000 1000 1000 1000

** Total content

Sb

Se

500 500 500 500 500 500 500 500

100 100 100 100 100 100 100 100

250 2000 500 500

100 100 100 100

Zn

2000

Colorants for the coloration of consumer goods, food packaging and toys Heavy metal limit values for toys (ppm) - Country overview

Product safety

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

(Art. 32) F 963-96a

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

Ba 500 250

Cd 75 50

Cr 60 25

Hg 60 25

Ni

Pb 90 90

Sb 60 60

Se 500 500

Sr

1,0

0,05

1,0

0,03

1,0

1,5

1,5

1,0

1,0

1000

75

60

60

90

60

500

250 350 1000

50 15 100

25 25 100

25 10 100

90 25 250

60 10 250

500 50

1000

75

60

60

90

60

1000 1000

75 75

60 60

60 60

90 90

60 60

[Cr(VI)]

500

Colorants for the coloration of consumer goods, food packaging and toys 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

Colorants for the coloration of consumer goods, food packaging and toys

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


Colorants for the coloration of consumer goods, food packaging and toys 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 POP’s 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.

The Issue of HCB (hexachlorobenzene) and TCPA (tetrachlorophthalicanhydride) 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.

Product safety

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.


The Issue of HCB (hexachlorobenzene) and TCPA (tetrachlorophthalicanhydride) C) Clariant products affected We generally do not use any HCB for the manufacturing of our colorants.

Product safety

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)

Note : this is an issue in Japan only and currently does not have relevance in any other country Organic Pigments The Basics Public Tim Boyce ASEAN Regional Technical Service Slide 255


Chlorine Free Pigments for Plastics

Chlorine free pigments/dyes (less than 1% chlorine) Pigment

Product safety


Colour Index

Chemical classification

Graphtol Yellow 3GP

P.Y.155

Bisacetoacetarylide

PV Fast Yellow H2G

P.Y.120

Benzimidazolone

PV Fast Yellow HG 01

P.Y.180

Benzimidazolone

PV Fast Yellow HG

P.Y.180

Benzimidazolone

Graphtol Yellow H2R

P.Y.139

Isoindolinone

PV Fast Yellow H3R

P.Y.181

Benzimidazolone

PV Fast Orange GRL

P.O.43

Perinone

PV Fast Red HB

P.R.247

Naphtol

Graphtol Red F3RK 70

P.R.170

Naphtol

Graphtol Red F5RK

P.R.170

Naphtol

Graphtol Rubine 6BP

P.R.57:1

Monoazo

PV Fast Red HFT

P.R.175

Benzimidazolone

Graphtol Red HF2B

P.R.208

Benzimidazolone

PV Fast Red E3B

P.V.19

β Quinacridone

PV Fast Red E5B

P.V.19

β Quinacridone

Graphtol Carmine HF3C

P.R.176

Benzimidazolone

Graphtol Carmine HF4C

P.R.185

Benzimidazolone

Chlorine free pigments/dyes (less than 1% chlorine) Pigment

Product safety


Colour Index


PV Fast Pink E

P.R.122

Dimethyl Quinacridone

PV Fast Pink E 01

P.R.122

Dimethyl Quinacridone

Graphtol Bordeaux HF3R

P.V.32

Benzimidazolone

PV Fast Violet ER

P.V.19

γ Quinacridone

Graphtol Blue AN

P.B.15:0

α Phthalocyanine

PV Fast Blue BG

P.B.15:3

β Phthalocyanine

Dyes

Colour Index


Sandoplast Yellow 2G

S.Y.114

Quinoline

Polysynthren Yellow GG

S.Y.133

Methine

Polysynthren Yellow NG

P.Y.147

Anthraquinone

Sandoplast Orange 3G

S.O.60

Perinone

Sandoplast Red 2G

S.R.179

Perinone

Sandoplast Red BB

S.R.195

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.

Product safety

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


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. > 100’C / 212’ F B – Boiling water sterilised C – Hot filled or pasteurised above 66’C ( 150’ F) D – Hot filled or pasteurised below 68’C (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.

Product safety

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


FDA Compliant Products (coloration at SD1/3 + 1% TiO2) Powder pigments

Product safety

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

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

PB15:3 PV Fast Blue BG

PB15:0 Graphtol Blue AN

PB15:1 PV Fast Blue A4R


PB15:1 PV Fast Blue A2R

DrizPearls

PY180 DrizPearl Yellow HG

PY181 DrizPearl Yellow H3R

PV19 DrizPearl Red E5B

PR122 DrizPearl Pink E

FDA Compliant Colorants with prescribed limitations Product

Product safety

Polymer

% upper concentration

Conditions of Use 21 CFR176.170

Food types

DrizPearl Yellow HG

P.Y.180

All

1

B–G

All foods

DrizPearl Yellow H3R

P.Y.181

All

1

B–H

All foods

DrizPearl Red E5B

P.V.19

All

1

A–H

All foods

DrizPearl Pink E

P.R.122

All

1

D–G

Aqueous, acidic,low alcohol

0.5

D–G

0.2

A-H

Graphtol Blue AN

P.B.15:0

PV Fast Yellow H9G

P.Y.214

All

1

A–H

All foods

PV Fast Yellow HG

P.Y.180

All

1

B-G

All foods

PV Fast Yellow H2GR

P.Y.181

All

1

B-H

All foods

PV Fast Yellow HGR

P.Y.191

All

1

B–H

All foods

PV Fast Yellow H3R

P.Y.181

All

1

B–H

All foods

PV Fast Scarlet 4RF

P.R.242

All

2 Maximum thickness 2 mm

A-H


PV Fast Red D3G

P.R.254

All

1

B–h

All foods

PV Fast Red HF4B

P.R.187

All

1

B–H

All foods

PV Fast Red E3B

P.V.19

FDA compliant colour without limitation in 21 CFR 178.3297

PV Fast Red E5B

P.V.19


PV Fast Pink E

P.R.122

PV Fast Pink E 01

Organic Pigments PV Fast Violet ER The Basics Public PV Fast Blue A4R Tim Boyce ASEAN Regional Technical ServicePV Fast Blue A2R Slide 265

Colour Index

PV Fast Blue BG PV Fast Green GNX

P.R.122


All

All

1

D–G


0.5

D–G

Fatty foods

0.2

A-H

All foods

1

D–G


0.5

D–G

Fatty foods

0.2

A-H

All foods

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

Product safety


PY151 Hostaperm Yellow H4G

PY147 Polysynthren Yellow NG

SBr53 Polysynthren Brown R

SR135 Polysynthren Red GFP

SR135 Solvaperm Red G

SB104 Polysynthren Blue RBL

SB104 Solvaperm Blue 2B

SG28 Sandoplast Green G

Optical Brighteners

Hostalux KS

Hosta;ux KS 1

Leucopure EGM

DY164 Solvaperm Yellow G

SR195 Solvaperm Red BB

FDA Compliant Colorants with prescribed limitations Product

Colour Index

Polymer

% upper concentration

Conditions of Use 21 CFR176.170

Food types

Hostaperm Yellow H4G

P.Y.151

PET

0.01

E–F–G


Polysynthren Yellow GG

S.Y.133

PET

0.2

E -F-G


Polysynthren Yellow NG

P.Y.147

PET

0.25

E–F–G

All foods

0.25

D–E –F-G

0.2

E–F-G


0.045

C–D


Polysynthren Red GFP

S.R.135

PET

Food types III, IV-A, VI

High alcohol, fatty foods Polysynthren Blue RBL

S.B.104

PET

0.2

E–F–G


Polysynthren Brown R

S.Br.53

PET

0.2

E–F–G


Solvent Yellow G

D.Y.64

PET

0.2

E–F–G


Solvaperm Red G

S.R.135

PET

0.2

E–F–G


0.045

C–D


Product safety

High alcohol, fatty foods Solvaperm Red BB

S.R.135

PET

0.2

E–F–G


Solvaperm Blue 2B

S.B.104

PET

0.2

E–F–G


Sandoplast Green G

S.G.28

PET

0.2

E–F–G


N/A

PVC

0.05

D–E–F–G

All foods

All

0.03

D–E–F–G

All foods

N/A

All

0.025

B – H < 275’F

FB238

Olefine

Hostalux KS

Hostalux KS 1 Leucopure EGM

PET


0.035

Food types I, II, VI-A, VII-B, VIII

E–F–G

All foods

A–H

All foods

Food contact conditions :

Product safety

A – Container is sterilised over 212’F B – Container is sterilised with boiling water C – Container is hot filled or pasteurised above 150’F D – Container is hot filled or pasteurised below 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 or microwaved in container at time of use

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)


Product safety


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Principles Behind REACH

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Organic Pigments – The Basics - SII - Dec 2008

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