organic pigments – the basics - sii - dec 2008

Public

ASEAN Regional Technical ServicTim Boyce

Organic Pigments –The Basics

(revised October 2008)

Public

ASEAN Regional Technical Service

Organic Pigments -The Basics

Tim Boyce

Principles of Principles of ColourColour

Types of Inorganic PigmentsTypes of Inorganic Pigments

Properties of Organic PigmentsProperties of Organic Pigments

Types of Organic PigmentsTypes of Organic Pigments

Clariant Product RangeClariant Product Range

Quality AspectsQuality Aspects

Synthesis of Synthesis of AzoAzo PigmentsPigments

Global Pigment MarketGlobal Pigment Market

Product SafetyProduct Safety

Agenda

Definition of Definition of ColourantsColourants

Public

ASEAN Regional Technical ServicCorporate Presentation

Global Pigment Market

Public



Tim Boyce

Phthalo-cyanine

23%

Chromium3%

Iron oxide13%

Complex metal oxide

13%

Azo28%

Other inorganic

6%

High Per-formance

14%

Organic Pigments ~ 65% by value azo pigmentsphthalocyanine pigmentspolycyclics

Inorganic Pigments ~ 35% by value Iron oxidesComplex metal oxidesChrome pigmentsOthers * excluding titanium dioxide/fillers

Global PigmentMarket

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

Public



Tim Boyce

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

Printing Inks56%

NIP1%

Coatings23%

Plastics15%

Special Applications

5%

Printing Inks35%

Coatings33%

Plastics19%

Special Applications

13%

By volumeTotal : ~ 260,000 T

By valueTotal : ~ € 5 billion


Public



Tim Boyce

DIARYLIDE-YELLOW 22

LAKE RED 7

LITHOLRUBINE 12

OTHER LAKED 7

PHTHALOCYANINE 28

OTHER POLYCYCLIC 2QUINACRIDONE 2

SPECIAL AZO 4

NAPHTOL AS 4

TOL.RED / ß-NAPHTOL 4

PYRAZOLONE 2HANSA-YELLOW 3

REFLEX-BLUE 3

DIARYLIDE-YELLOW 18

LAKE RED 3

LITHOLRUBINE 7

OTHER LAKED 5

PHTHALOCYANINE 27OTHER POLYCYCLIC 8

QUINACRIDONE 8

SPECIAL AZO 9

NAPHTOL AS 5

TOL.RED / ß-NAPHTOL 2PYRAZOLONE 2

HANSA-YELLOW 3REFLEX-BLUE 3

Total Market 2006 : ~ 5.0 bn€

Total Market 2006: 260,000 T

Organic Pigment Market by Pigment Types


Public



Tim Boyce

ROW8 %

Asia28 %

Americas34 %

Europe30 %

Organic Pigment Market (Value) by Region

(total market 2006 : ~ € 5.0 billionT)


Public


The Principles of Colour

Public



Tim Boyce

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

Principles of Colour

Public



To see objects we need lightTo see objects we need light.

Of the entire spectrum of waves in the universe, mancan visually perceive only a small wavelength range (400 - 700 nm), which we call light.

Rays with long wavelengths and extremely short wavelengths are invisible to the human being.

Light beam

Colour of light

Absorbing medium

Reflected residual light produces sensation of colour

Illumination


Public



Spectrum of the electromagnetic waves.Spectrum of the electromagnetic waves.(logarithmic scale)

ultr

avio

let

infr

ared

Radio wavesLight wavesX raysγ- rays

Frequency (Hz)

(► decreasing)

Wavelength (m)(► increasing)

1 Xe 1 nm 1 mm 1 km

1023 1021 1019 1017 1015 1013 1011 109 107 105

visi

ble

mm

W

cmW

dmW

UK

W

KW

MW

LW

10-7 10310110-110-310-510-13 10-11 10-9

400 nm 700 nm


Public



Tim Boyce

Newton’s Experiment (1666)

Light source

PRISM

White Light

VIOLET (400nm)INDIGOBLUEGREEN (540nm)YELLOWORANGERED (700nm)

400 nm - 770 nm WhiteWhite400 nm - 435 nm VioletViolet435 nm - 480 nm BlueBlue500 nm - 560 nm GreenGreen580 nm - 595 nm YellowYellow595 nm - 605 nm OrangeOrange605 nm - 770 nm RedRed

350 nm - 400 nm Ultraviolet> 770 nm Infrared

visible

invisible

1 nm = 10 -9 m


Public



Tim Boyce

blue magenta

whiteyellow

Wavelengths mean colour


Public



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.


Public



Tim Boyce

Example of additive mixing

yellow

green red+

The individual wavelengthsare “added” together


Public



Subtractive Colour Mixing.

yellow cyan magenta

incident light

Absorption and scattering


Public



Example of Subtractive Colour Mixing

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

0,2

0,4

0,6

0,8

1,0

nm380 440 520 600 680

Tran

smis

sion

greenyellowcyan +

Only the wavelengthscommon to both contributing colours are responsible for the final colour. The final colour will alwaysbe lower in intensity than the initial colours.


Public



Tim Boyce

blue redgreen

yellowmagentacyan

Subtractive primary colours

Additive primary colours

Primary colours


Public



Tim Boyce





Public



Tim Boyce

absorption(structure)

Reflection(surface)

Interaction of light and matter

scattering(particles /

particle size)

transmission(surface)

When light hits a surface ….


Public



Tim Boyce

Scattering, absorption, transmission, reflection

Blue lighttransmitted

Some greenLight transmitted

Yellow absorbed Red absorbed

Some red lightscatteredPrinciples of Colour

Public



Tim Boyce






Public



Tim Boyce

Apart from wavelengths and colour physics, some otheraspects can affect the colour perception

opacity

haze

Reflection (flop)

gloss

surface


Public



Tim Boyce

Standardized Illumination D 65, A and C

rela

tive

radi

atio

n in

tens

ity

The standard illumination Acorresponds to An incandescent (tungsten) light bulb (2800 K), also called evening color.

The standard illumination Chas 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).


Public



Tim Boyce

Depending on the illumination the colour impression changes


Public



Metamerism

red

dependent

metamerism - free

metamerism

Light source Viewing angleReflectance

independent

red

Metamerism free Metameric

Spectral Curve same different

Visual perception ofcolour match

same different under different lights


Public



Tim Boyce

DeceptionsPrinciples of Colour

Public



Tim Boyce

InducedInducedColourColour

yelloweryellowerbluerbluer


Public



Tim Boyce


Public



Tim Boyce

…….. And one last piece of fun

Public



Tim Boyce






Public



Tim Boyce

Color impression and color measuring

incident light

Object

absorption, reflection, scattering

emitted light

Eyebright/darkblue, red, green

Brain

color perceptionhues (max. 2 Mio)

Measuring Instrumentcolor intensityspectrum

Colorimetrics

Color description: CIE La*b*-SystemISO 7724-3, DIN 6174


Public



Tim Boyce

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.


Public



Tim Boyce

The human eye

The human eye has 2 different sensors for the detection of light. There are cone cells (3) and rod cells.

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

• color impression, low light sensitivity

• vision during daytime

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

• no color, high light sensitivity

• vision during night

rod cell

cell body

outer segmentsynaptic. region

cone cell


Public



Tim Boyce

Spectral sensitivity of the human eye

Red sensor

Blue sensor

Green sensorPrinciples of Colour

Public



Tim Boyce

THE EYE

RETINACORNEA

LENS

IRIS

LIGHT

PUPIL

LIGHT

Young EyesClear - Supple Lens

RETINA CORNEA

LENS

IRIS

LIGHT

PUPIL

LIGHT

Old Eyes Yellowing -Rigid Lens


Public



Tim Boyce

Color Vision DefectsMore than 200 million people worldwide have some color vision deficiencyOver 8% of males have this problem but only 0.5% of females

Different Races have different levels of deficiency and types ofdeficiencies

Colour deficiencies in males according to raceNorth America 8.00 %

Europe 8.76 %

Eastern Europe 9.31 %

China 6.15 %

Japan 4.50 %

Asia 6.00 %

Caucasian Population Males Females91.9 % 99.6 %

0.4 %

0.05 %

5.5 %

2.6 %

Normal trichromats

Anomalous trichromats

Dichromats


Public



Tim Boyce

We need:

1. Light2. Object3. Observer / Spectrophotometer + Software for

comparing the electric signal with the visual perception

incident ligh t

ob jectA bsorption , reflexion , scattering

em itted ligh t

E yebright/darkb lue, red , green

B ra incolour perceptionhues (m ax. 2 M io )

M easuring instrum entcolour in tensityspectrum

C olorim etrics

Color description: CIE La*b*-SystemISO 7724-3, DIN 6174

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

Color measurement


Public



0,1 0,2 0,5 0,60,40,3 0,70,0

0,8

0,9

0,1

0,2

0,5

0,6

0,4

0,3

0,7

xy - Diagram

The chromaticity diagram is a chart of all possible chromaticities in the axis based chart of colour coordinates.

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

CIE - Chromaticity Diagram

Spectral colour co-ordinates :

colour nm x y zRed 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

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)

y = Y(X+Y+Z)

z = Z(X+Y+Z)

Y is a dimension for the brightness of the colour.


Public



CIE Colour Model of 1931.

The three dimensional colour system defines coloursaccording to brightness and chroma, but does not show colours in the difference from each other in which they are perceived by the eye.

Later the CIE* XYZ Model (“shoe sole”) was developed from this.

Hue Lightness Chroma

*CIE = Commission International de l´Eclairage.


Public



CIE L*a*b* - Colour Model.

GreenGreen--a*a*

Black

WhiteL*

Red+a*

YellowYellow

+b*+b*

Blue-b* 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.


Public



Tim Boyce

Colour measurement

greenish yellow

yellowish green

greenish blue reddish blue

reddish yellow

bluish redbluish green

yellowish red

CIElab - System DIN 6174

Greenish yellow

Yellowish green

Bluish red

Reddish blue

Bluish green

Greenish blue

Yellow

Red

Blue

Green

Reddish yellow

Yellowish red


Public



The CIE Lab Formula

a*C* = “intensity” differenceH* = shade differenceL* = lightness difference

a* = red/ green - Colourfulnessb* = yellow/blue- Colourfulness

L* = Lightness

Derived designation:

L*

b*

E*ab = ( L*)2 + ( a*)2 + ( b*)2

E*ab = ( L*)2 + ( H*)2 + ( C*)2

22 *)(*)(* baC +=

Chroma Shade/Hue angle

⎟⎠⎞

⎜⎝⎛= −

**1

abtanh ab


Public



Tim Boyce

CIElab System

- dH + Tolerances

dC dH/=/ 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

Chroma & Lightnessgreener Blue redder

Lighter + dL - Darker+ dC -yellower Green Dullerbluer Brighter

bluer Violet redder

bluer Red yellower

redder Orange yellower

redder Yellow greener

Colour measurement


Public


Definition of Colourants

Public



Tim Boyce

Definition of Definition of ColourantsColourants

Bulls and horses in a cave near

Lascaux (France)

Egyptian receptaclewith painted boatand ornaments


Public



Tim Boyce

Egypt 1500 bc . Painting on limestone.


Public



Tim Boyce

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


Public



Tim Boyce

PigmentsInsoluble in mediumHigher light/weather fastnessBetter chemical resistanceMore opaque

DyestuffsSoluble in mediumLimited light/weather fastnessHigh colour strengthLimited chemical fastnessLimited migration fastnessHigh transparency

What’s the

What’s the

difference

difference ??

Pigments and dyes


Public



Tim Boyce

according to shade (DIN 55944)

organic

Pigments

White Pigments

Colored Pigments

Black Pigments

Lustre Pigments

Fluorescent Pigments

Dyes

inorganic

Colorants

Pigments Dyes

no commercialprominence

Colored PIgments

Black Pigments

Lustre Pigments

physicallyimpossible

Colored Dyestuffs

Black Dyestuffs

physicallyimpossible

Classification of Colorants

Fluorescent Dyestuffs

Fluorescent Pigments


Public



Tim Boyce

Characteristics of Inorganic & Organic Pigments

Characteristics of Organic & Inorganic PigmentsCharacteristic Organic Pigments Inorganic Pigments

Primary particles Small LargeScattering Weak StrongAbsorption High LowSurface High area / hydrophobic Small area / hydrophilicColour (hue) Bright Dull ► brightLight/weatherfastness Poor ► excellent Good ► excellentTinting strength Strong WeakOpacity Transparent ► opaque OpaqueSolvent fastness Poor ► excellent ExcellentChemical fastness Good ► excellent Poor ► excellentDispersibility Fair ► excellent Good ► excellentHeat stability Good ► excellent Good ► excellentToxicology Mostly excellent Heavy metals


Public


Types of Inorganic Pigments

Public



Tim Boyce

Public



White pigments.

*Organic coating is destroyed at over 280°C .

Titanium dioxide - rutile

Titanium Dioxide - anatase Zinc sulphide

Colour-Index P.White 6 P.White 6 P.White 7Formula TiO2 TiO2 ZnSHeat resistance °C 280/300 280/300 300Refraction index n 2,75 2,55 2,35Scattering index 1 1,5 2Dispersibility very good good very goodAbrasion abrasive less abrasive low abrasiveParticle size (µ) 0,1-1,0 0,1-1,0 1Coating * organic/inorganic organic/inorganic no

Manufacturing process Sulphate/Chloride Sulphate chemical reaction

Shade a little yellowish a little bluish bluish

Types of Inorganic pigments

Public



Lead chromate pigments

Colour area

Name Formula Colour-Index

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

Particle size (µ)

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:Disadvantage: Not for food packaging materials, environmentNot for food packaging materials, environment--polluting, toxicpolluting, toxic


Public



Cadmium pigments

NameName FormulaFormula ColourColour--IndexIndex particle size (µ)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 0.2-2Cadmium red Cd(S,Se) P. Red 108 0.2-2

Properties: Excellent general properties.Bright, clean fullshades.Lithopone types contain BaSO4Greenish types have lower weather resistance.

Manufacturing is carried out in a calcining process at 500-650°C.

Colour area

Disadvantage:Disadvantage: Not for food packaging materials, Not for food packaging materials, environmentenvironment-- polluting.polluting.

Main usage is in plastics or ceramics.


Public



Mixed phase / Metal complex pigmentsMixed phase / Metal complex pigmentsName Formula Colour-Index Particle size (µ)

Nickel titanium yellow

(Ti,Ni,Sb)O2 P. Yellow 53 0.4-0.7

Chrome titaniumyellow

(Ti,Cr,Sb)O2 P. Brown 24 0.2-0.4

Cobalt blue Co(Al,Cr)O4 P. Blue 36 0.2

Cobalt green (Co,Ni,Zn)(Ti,Al)O4 P: Green 50 0.5

Zinc iron brown ZnFe2O4 P. Yellow 119 1.0-2.6

Spinel black Cu(Fe,Cr)2O4 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.


Public



Oxide Pigments

Colour area

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 black

Fe3O4 P. Black 11 0.6-1.6

Chrome oxide greenCr2O3 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.

Disadvantage: The thermal ageing of polypropylene and PVC is negatively affected by the use of iron oxide pigments.


Public



Ultramarine/ Manganese pigments

Excellent light fastnessExcellent heat resistanceShading pigment

Properties: Manganese violet

Excellent light fastnessExcellent heat resistanceDispersibility difficult

Properties: Ultramarine blue

Sensitivity to acid and alkalisVery weak tinting power

Sensitivity to acidRelatively high water contentModerate weather fastness

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


Public



Black pigments

Properties: Carbon black.

Improves the fastness to weathering of polymers

Multipurpose applicationsLow cost pigmentExcellent fastness properties

Improves the electrical conductivity of polymers

HygroscopicDispersibility is difficultThe tenacity of polymers is negatively affected

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)2O4

P. Black 28 1.4-3.9

Name Formula Colour Index Particle size (µ)Types of Inorganic pigments

Public



Name Formula Colour-IndexAluminium Al P. Metal 1Copper Cu P. Metal 2

Cooper/Zinc-alloy Cu-Zn P. Metal 2

Metal pigments

Aluminium powder is explosive in mixturewith air, dust-free metal pastes are availableSolvents where used smell like white spirit.The particle size and shape is variedLarge size particle - good metal effectSmall particle - high covering power

Properties:

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


Public



Effect pigments

Mica with TiO2-coating Pearl effect pigmentsPearl effect pigments

Mica with iron oxide andtitanium dioxide coatings

Interference pigmentsInterference pigments

Disadvantage: Because of their flake structure, all micaceous pigments are shear sensitive.Require high loadings to be effective


Public



Fillers

1.Carbonates1.Carbonatesnatural calcium carbonate from fossilsnatural calcium carbonate, crystallinechemical calcium carbonatenatural calcium-magnesium carbonate

2. 2. SulphatesSulphatesnatural barium saltssynthetic barium salts

3. Silicates3. Silicatesnatural magnesium silicate hydratenatural aluminium silicate hydrate

natural calcium aluminium silicate hydrate

ChalkCalcite, MarbleCCPDolomite

BarytesBlanc fix

French chalkKaolin, China ClayMuscovite (Glimmer)


Public


Types of Organic Pigments

Public



Tim Boyce

History and Chemistry of Organic Pigments

1899 Pigment Red 1. The first true organic pigment.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.

Types of Organic pigments

Public



Tim Boyce

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 = N -- C = O - N = O- C = C -

Substituent Groups ::Auxchromes : electron donors : CHCH33 OH OH

ArNHArNH22electron acceptors : COOH SOCOOH SO2 2

COORCOORHypsochromes : BrBr ClCl


Public



Tim Boyce

A chromophore complex formsthe basic organic pigment

molecule

- -- - N = N -

NO2

NO2

OH

2,4 - Dinitroaniline+

B -Naphtol

Pigment Orange 5


Public



Tim Boyce

There are 5 basic raw materials :

-H3C -H3C - CH3

Benzene

C6H6

Naphthalene

C10 H8

o, m, p - Xylene

C8H10

Toluene

C7H8

Anthracene

C14H10


Public



Tim Boyce

Modified by a variety of chemical processes e.g.

Substitution AdditionNitration SulphonationOxidation ReductionHalogenation Alkali fusionHydrolysis AcylationAlkylation

In many cases there can be multiple reactions required in the preliminary synthesis of the raw materials as well as the finalpigment synthesis


Public



Tim Boyce

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 :


Public



Tim Boyce

Size and distribution

Equivalent diameter (µm) Equivalent diameter (µm)

Vol

ume

porti

on (%

per

siz

e cl

ass)

Vol

ume

porti

on (%

per

siz

e cl

ass)

Vol

ume

dist

ribut

ion

(%)

Vol

ume

dist

ribut

ion

(%)

Narrow particle size distribution achieved by lower finishtemperature for ink jet application


Public



Tim Boyce

Shape

P.R.122Mixed crystal

P.R.122Surface modified

Rod likeTransparentLow viscosity

cubicHighly transparentHigher viscosity

Viscosity design by modified shape


Public



Tim Boyce

The Surface• Influence of the polarity of the pigment on the wetting behaviour

Type A – hydrophobic – floating on thewater surface

Type B – hydrophillic – excellent wettingin water

Surface design for perfect fit


Public



Tim Boyce

Intermediates Derived From NitrobenzeneIntermediates Derived From Nitrobenzene

Public



Tim Boyce

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


Public



Tim Boyce

Pigment Chemistry

Three options to reduce solubility:

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

-

Reaction with metal salt

Large molecules : From Monoazo to Dis-azo

F-SO3- / F-CO2

- M+

------>F-SO3

- M+ / F-CO2- M+

---->-N=N- -N=N-A-N=N-

New Substitutients for example: -CONH- group

-CONH- group


Public



Tim Boyce NN

OHCH3

NO2

NN

OH

OCH3

Cl

NO2

CH3

H

ON

O

N NH

HHCONH2

HOC2H5

H

ON

O

N NH

HH NO2

OCH3

N N

O N

NON

OH

H H

H

Solvent Red 1 Pigment Red 3 Pigment Red 14 Pigment Red 170 Pigment Red 171Fat Red G Hansa Red B Permanent Novoperm Red Permanent

Bordeaux FGR F5RK Bordeaux HFM

FullshadeLightfastness 7Overspray 2

FullshadeLightfastness 6-7Overspray 3

1:85 TiO2Lightfastness 4

FullshadeLightfastness 7-8Overspray 5

1:46 TiO2Lightfastness -

1:55 TiO2Lightfastness 4-5

FullshadeLightfastness 6Overspray 5

1:80 TiO2Lightfastness 6

Effect of substitution on colour and fastness properties

Public



Tim Boyce

Effects of Pigment Chemistry

Improve fastness propertiese.g. increased substitution

Shade e.g. new chromophores


Public



Tim Boyce

Classical Azo

Laked

Quinacridone

Phthalocyanine

Perylene

Anthraquinone

Dioxazine

Isoindolinone

Thioindigo

DPP

Lake Red C

Toners

Unlaked

Hansa

Diazo

Monoazo

Special Azo

Naphtols

Azo condensation

Benzimidazolone

Triphenylmethane

Classes of synthetic organic pigments

Azo Polycyclic


Public



Tim Boyce

Chemistry Yellow Orange Red Brown Violet Blue Green Black

AZO

Monoazo X X X X X

Diazo X X X X X

Azo condensation X X X X

Azo salt X X X X

Azo metal complex X X X

Benzimidazolone X X X X

POLYCYCLIC

Phthalocyanone X X

Anthraquinone X X X X X X X

Quinacridone X X X

Dioxazine X

Perylene X X

Perinone X

Pyranthrone X

Indigoid X X X X

Thioindigo X

Isoindolinone X X X

MISCELLANEOUS

Nitro X

Nitroso X

Quinoline X

Azine X

Basic dye complexes X X X X X X X


Public



Tim Boyce

Azo Pigments Polycyclic Pigments

MonoazoDisazoBeta-NaphtholNaphthol ASRed Azo LakesBenzimidazoloneDisazo Condensation

PhthalocyanineQuinacridonePerylene/PerinoneIsoindolinone/IsoindolineDioxazineTriphenylmethaneDiketo-Pyrrolopyrrole DPP

Pigment classes


Public



Tim Boyce

Azo-Pigments

Monoazo : R2-N=N-R3 C.I.CH3

NN

+

O O

NNH

O

O

NN

NOH

O

CH3

O

NN

NOH

O

Cl

ONH

OCH3

NN

OH O

OS

CH3

OOO

Mn2+

NN

OH NH

O

NO

OO

CH3NH

NH O

Monoazo-Yellow

Naphtol AS

Benzimidazolone

β-Naphtol

BONS laked

Pigment Yellow 1

Pigment Red 14

Pigment Red 171

Pigment Red 3

Pigment Red 48:4


Public



Tim Boyce

Azo-Pigments

Dis-Azo : R2-N=N-R3-N=N- R2 C.I.

Diarylyellow

Disazo-konden-sation

Pigment Yellow 83

Pigment Red 144

Cl

Cl

NNN

NNH

O

CH3

O

OCH3

NH

OO

O Cl

Cl

O

O

CH3CH3

CH3

CH3

Cl

Cl

NN

OH O

NH

NH

ClO

NN

Cl

Cl

OH


Public



Tim Boyce

Polycyclic Pigments

Phthalocyanin Pigment Blue 15

Pigment Red 254

N

N

N

N

N

N

N

N

Cu

Chinacridone

Dioxazine

Diketo-Pyrrolopyrrol DPP

NH

NH

O

O

Pigment Violet 19

Pigment Violet 23

O

N

N

O

Cl

Cl

N

N

H5C2

C2H5

NH

NH

O

O

Cl

Cl


Public



Tim Boyce

Polycyclic Pigments

Isoindolin Pigment Yellow 139

Pigment Red 179

NH

NH

NH NH

NHO

O

OO

O

O

Isoindolinon

Perylene

N NCl

Cl

ClCl

O OCl

Cl

Cl

Cl Pigment Yellow 110

N N

O

O

O

O

CH3CH3


Public



Tim Boyce

Azo PigmentsChemical 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

Benzimidazolone excellent excellent

Diarylide fair ►very good good ►very good

Disazocondensation good ►very good Very good ►excellent

Triphenylmethane poor poor


Public



Tim Boyce

Polycyclic PigmentsChemical structure and fastness properties

Pigment Class Lightfastness Migration fastness

Dibromoanthanthrone excellent excellent

Phthalocyanine excellent excellent

Quinacridone excellent excellent

Diketo-Pyrrolopyrrole excellent excellent

Isoindolinone Very good ►excellent Very good ►excellent

Perylene/Perinone Very good ►excellent Very good ►excellent

Dioxazine Very good ►excellent Very good ►excellent

Isoindoline Very good ►excellent Very good ►excellent


Public



Their fastness properties vary considerably.Only few pigments are suitable for shading.

Colour area

Monoazo pigments range from greenish yellow to bluish red. Can be pure monoazo (Hansa, Naphtol) or laked/toner.

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


Public



Tim Boyce Pigment Red 112 ( C.I. : 12370 )

3

CONH

CH

HOCl

Cl

Cl

N = N

2,4,5 - trichloraniline

2-hydroxy-2-naphtho-ortho-toluidide

Monoazo pigments


Public



Tim Boyce

N

RD5

RD4

RD2

H RK2

RK5

O O

CH3

N N

RK4

C.I. Name Const. No. R2 R4 R5 R2 R4 R5

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 3SO 2 NH-C 6 H 5

OCH3 OCH 3 Cl OCH 3

D D D K K K

Monoazo (Hansa) yellow pigments


Public



Tim Boyce

NN

OH

R4

R2

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 (Hansa) red pigments(β Naphtols)


Public



Tim Boyce

RD5

RD4

RD2

R2K

R4K

ON

O

N NH

R5K

H

C.I. Nam e Const. No. R 2 R 4 R 5 R 2 R 4 R 5

P.R.9 12460 Cl H Cl O CH 3 H H

P.R.12 12385 CH 3 NO 2 H CH 3 H H

P.R.14 12380 NO 2 Cl H CH 3 H H

P.R.112 12370 Cl C l C l CH 3 H H

P.R.5 12490 O CH 3 H SO 2N(C 2H 5)2 O CH 3 O CH 3 Cl

P .R.146 12485 O CH 3 H CO NHC 6H 5 O CH 3 Cl O CH 3

P.R.170 12475 H CO NH 2 H O C 2H 5 H H

P.R.188 12467 CO O CH 3 H CO NHC 6H 3-C l2(2 ,5) O CH 3 H H

P.R. 253 Cl SO 2NHCH 3 Cl CH 3 C l H

P.O . 74 C l SO 2NHCH 3SO 2N(CH 3)2

C l H Cl H

D D D K K K

Monoazo pigments -Naphtols AS


Public



Tim Boyce

NOH

NS

O

O

O

CH3Cl

Ba2+

OH O

NH

NN

CH3

NH

O

SO

OO

OCH3

Ca2+

NN

OHR4

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

P.R. 247 ( 15915 )

R2

R5

O

O

M2+

C.I. Name Const. No. R2 R4 R5 M

P.R.48:2 15865:2 SO 3- CH3 Cl Ca

P.R.48:3 15865:3 SO 3- CH3 Cl Sr

P.R.48:4 15865:4 SO 3- CH3 Cl Mn

P.R.57:1 15850:1 SO 3- CH3 H Ca

Monoazo red pigments -red azo lakes


Public



Tim Boyce

Colour area

Disazo pigments

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 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.


Public



Tim Boyce

Pigment Yellow 13 ( C.I. : 21100 )

3,3-dichlorobenzidine(3,3-dcb)

2,4- acetoacet -meta-xylidide(aamx)

Disazo pigments


Public



Tim Boyce

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 21102CH3

OCH3

CH3

H

H

H

P.Y.176 21103CH3

OCH3

CH3

Cl

H

OCH3

P.Y.188 11767CH3

H

CH3

H

H

H

Cl

O

NH

CH3 O

NN

R2

R4

R5

N

CH3

N

O

NH

O

R5R4

R2

Cl

Disazo pigments -AAA arylide


Public



Thermal decomposition of diarylide pigments.

• 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.

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

A B C>200 °C >240 °C

Diarylidepigment

soluble monoazocompound (coloured)

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

DichlorbenzidineDCB


Public



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 pigments


Public



Tim Boyce

RD5

RD4

RD2 CH3

N

O

NO N

NO

NR3D

H H

H

C.I. Name Const. No. R2 R3 R4 R5

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 NO 2 H Cl H

P.O.62 11775 H H NO 2 H

D D D D

Benzimidazolone yellow and orange pigments


Public



Tim Boyce

RD5

RD4

RD2

N N

O N

NON

OH

H H

H

C.I. Name Const. No. R2 R4 R5

P.R.175 12513 COOCH3 H H

P.R.176 12515 OCH3 H CONHPh

P.R.185 12516 OCH3 SO 2NHCH3 CH3

P.R.208 12514 COOC4H9 H H

P.V.32 12517 OCH3 SO 2NHCH3 OCH3

P.Br.25 12510 Cl H Cl

D D D

Benzimidazolone red and brown pigments


Public



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.

Colour area

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

Azo condensation pigments


Public



Tim Boyce

N

NH

NH

R4

R2O

N

CH3O

NO

N

CH3

A

AQ

O

Q

OO

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 H H COOCH3 OCH3

Ar = C6H4-4-Cl

Disazo :Bis AAA Arylide / Yellow azo condensationpigments


Public



Tim Boyce

R2K

R4K

NH

O

NH

O

OHN

OH N

N

N RD2

RD2

RD4

RD4

RD5

RD5

C.I. Name Const. No. R2 R4 R5 R2 R4

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 CH3 H COOCH2CH2Cl CH3 CH3

P.R.221 20065 Cl H COOCH(CH3)2 Cl Cl

P.R.242 20065 Cl H CF3 Cl Cl

P.R.262 - Cl H Cl CN H

P.Br.23 20060 NO2 Cl H Cl H

D D D K K

Disazo : Red azo condensation pigments


Public



Colour areaColour area

Deep blue shade with excellent colour strength.

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

Used to tone black printing inks for offset applications

Triphenylmethane


Public



Tim Boyce

NH

C+

NH

NH

R2

R2

R2

-O3S

C.I. Name Const. No. R2

P.Bl.56 42800 CH3

P.Bl.61 42765:1 H

Triphenylmethane : Reflex (Alkali) blue


Public



Colour area

Shade from yellow to orange to red , good colourstrength.

The fastness properties are good to excellent.

The dispersibility is generally good.

Reaction with alkaline additives can cause discoloration and a reduction in fastness properties.

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


Public



Tim Boyce

Isoindolinone :

NHCl

Cl

ClCl N

N

CH3

N

NH

ClCl

ClClO

NHCl

Cl

ClCl O

N N

NH

ClCl

ClClO

P.Y. 109 ( 56284 )

P.Y. 110 ( 56280 )

Isoindoline :

H

HN

NO

O

O

N

N

NO

O

O

H H

H

NH

NH

O

O

NH N

H

OO

N

CH3

P.Y. 139 ( 56298 )

P.Y. 185 ( 56290 )

Isoindolinone / Isoindoline


Public



Greenish yellow pigments.

Excellent fastness properties.

Colour area

P.Y.138

Quinophthalone


Public



Yellowish to bluish red, pink and redYellowish to bluish red, pink and red--violet violet pigments.pigments.

Excellent fastness properties.Excellent fastness properties.

Suitable as shading pigment.Suitable as shading pigment.

Colour area

Optimum dispersion is often difficult.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


Public



Tim Boyce

N

N

RR

RR O

R

R

RR

OH

H

1

2

3

4

11

10

9

8

C.I. Name Const. No. R2 R3 R4 R9 R10 R11

P.V.19 73900 H H H H H H

P.R.122 73915 CH3 H H CH3 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 - unsubst. Quinacridone+ Quinacridonequinone

Quinacridone


Public



Yellowish to bluish red shade.Excellent fastness properties.Suitable as shading pigment.

Colour area

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

Perylene


Public



Brilliant orange pigment.

Excellent lightfastness.High weathering resistance in reduced shades.

Colour area

Not suitable as shading pigment Not suitable as shading pigment in plasticsin plastics( solubility) but ( solubility) but in paintsin paints is best suited for is best suited for shading.shading.

The dispersion is generally good.

P.O.43, P.R.194

Perinone


Public



Tim Boyce

Perylene :

NN

O

OO

O

QQ

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

Perinone :

N O

N

N

NO

P.O. 43( 71105 )

Perylene / Perinone


Public



Brilliant yellowish red pigment.

Excellent light and weathering resistanceat all shade depths

Colour area


P.R.168

O

O

Dibromoanthranone


Public



Reddish blue shade.Excellent fastness properties.

Colour area

P.B.60

Optimum dispersion is often difficult.

Indanthrone


Public



Orange to bluish red pigments.

Excellent fastness properties.


P.O.71, P.O.73, P.R.254, P.R.255, P.R.64, P.R.270, P.R.272

Colour area

Diketo-pyrrolopyrrole


Public



Tim Boyce

NH

NH

O

O

R3

R3

R4

R4

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

Diketo-pyrrolopyrrole


Public



Reddish and greenish blue pigments.Yellowish and bluish green pigments.Excellent fastness properties.Universal suitability, low coloration costs

Colour area

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


Public



Tim Boyce

N

N N

N

NNNN

Cu

N

N N

N

NNNN

Cu

N

N N

N

NNNN

Cu

C .I. N a m e m o d if ic a tio n H a lo g e n s m o d . s ta b il iz e d flo c c u la t io n

P .B l. 1 5 α - n o -

P .B l. 1 5 :1 α 0 .5 -1 C l y e s u n s ta b le

P .B l. 1 5 :2 α 0 .5 -1 C l y e s s ta b le

P .B l. 1 5 :3 β t ra c e s - u n s ta b le

P .B l. 1 5 :4 β t ra c e s - s ta b le

P .B l. 1 5 :6 ε t ra c e s y e s

P .G r. 7 - 1 4 -1 5 C l

P .G r. 3 6 - 4 -9 B r,8 -2 C l

Copper (II) complex oftetraazatetrabenzoporphine

Phthalocyanine


Public



Very reddish violet pigment.Excellent fastness properties.

Colour area

Not suitable in low concentration Not suitable in low concentration in plastics due to solubility.in plastics due to solubility.

The dispersion is often difficult.The dispersion is often difficult.

P.V.23

Dioxazine


Public



Tim Boyce

N O

N

N

O N

Cl

Cl

P.V. 23 ( 51319 )

Dioxazine


Public


Synthesis and Production of Azo

Pigments

Public



Tim Boyce

Azo pigments are named for containing an azo-group

-N=N-Two nitrogen-atoms are

connected with a double bond.

Synthesis and Production of AzoPigments

Public



Tim Boyce

There can be one Azo group in so called monoazo pigments

NNCH3

OHNO2

Hansa Red BPigment Red 3


Public



Tim Boyce

or two azo groups, then it is called a disazopigment (also called diaryl or diarylide)

NH

O

CH 3

O

NN N

NC H 3

O

ONH

Cl Cl

Permanent Yellow DHGPigment Yellow 12

You can also think about molecules with more then two Azo-groups. This is actually done in the

synthesis of azo dyes


Public



Tim Boyce

Diazotization of an aromatic amine to form the diazonium compound

CH3

NN

NO2

+

Cl- + NaCl + 2 H2O

NH2

CH3

NO2

+ 2 HCl + NaNO2

The unstable diazonium compound has to be cooled with ice to 5-7°C to avoid any side reaction


Public



Tim Boyce

Dissolving of the coupling component

ONa

+ 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

+ NaOH

OHSynthesis and Production of AzoPigments

Public



Tim Boyce

CH3

NN

NO2

+

Cl-ONa

NNCH3

OHNO2

+ NaCl

Hansa Red B, P.R. 3

Synthesis of the pigment

By coupling the two components, the pigment precipitates as primary particles.There is no longer a solution but a suspension.

couplingSynthesis and Production of AzoPigments

Public



Tim Boyce

Disazo Pigment

+ +

Coupling kettle

Dissolving kettle

Diazokettle

+

+

KETTLE 2

CHC=OCH

2

3

NH C=O O=C NHCHC=OCH AAA

2

3

KETTLE 2

Cl_ +

N ≡ N

Cl Cl

N ≡ N

+

Cl_

DCB

KETTLE 1

DIARYLIDE YELLOW ( P.Y.12 )

ClClHN C=O

C=O

CH CH

O=C NH

C=O

HC N = N N N CH=

3 3

PRECIPITATION

2 NaOH

2 NaCl

2 H2O

+

Dissolving kettle


Public



Tim Boyce

Reactor vessel –Normally a sealedunit and as fully automated as possible


Public



Tim Boyce

During coupling process, different conditions have to be control

TemperaturepH valueTime

These controlled conditions will have major effects on the synthesis, and therefore on the quality of the pigment


Public



Tim Boyce

important process to reach optimum application properties

thermal treatmentheating the crude pigment

suspension in water and/or organic solvents

surface treatmentadding appropriate auxiliaries

with different chemical structures

Optimizing the physical properties of the pigment, such as:Crystal shapeCrystal sizeCrystal qualityParticle size distribution

Finishing


Public



Tim Boyce

Public



Tim Boyce

VAPOUR

FILTRATION

H2 O

NaOHCOUPLING COMPONENT

HCl

+ ICE

AROMATIC AMINE

Na NO2

DIAZOTISATIONKETTLE

DISSOLVING OF COUPLING COMPONENT

FILTRATION

COUPLING KETTLE


Public



Tim Boyce PRESSCAKEGRANULES

VAPOUR

PUMP

NAUTA BLENDER

DRYING

DRYING OVEN

FILTRATIONFILTER

GRANULATOR

FINISHKETTLE


Public



Tim Boyce

Filterpress with falling filtercakeBy opening the filterplates,the filtercake falls to a beltand is transferred to thenauta-blender.

Drum filter withfiltercake

The filter sucks up thesuspension, the liquor moves through the clothand leaves behind the filtercake.


Public



Tim Boyce

Granulation in frontof belt dryerTo give a large surface area to the filtercake it is granulatedbefore drying.

Dry pigment granules After being dried, the priment granulesfall from the beltdryerto the mill.


Public



Tim Boyce

1 2 3 4

BLENDER

MILLING

STORAGE BINS

PIGMENT POWDER

JET - MILL


Public


Properties of Organic Pigments

Public



Tim Boyce

Properties of organic pigmentsPattern card dataColour IndexStandard Shade DepthTinting StrengthPigment Physics

– Particle size and distribution– Crystallography and shape– Specific surface area

Dispersion of organic pigmentsFlocculationFastness properties

– Migration / solvent fastness– Heat stability– Lightfastness– weatherfastness

Properties ofOrganic Pigments

Public



Tim Boyce

☺ Colour Index

☺ Tint Strength☺ Physical Properties

☺ Colour & Shade Depth

☺ Fastness Properties

Pattern Card Data


Public



Tim Boyce


Public



By producer, with trade nameStructure (optional)PropertiesApplication field

Report to Colour Index :

Constitution numberGeneric nameTrade name

Listing in Colour Index :

According to application, properties, shade and structure.

Classification in Colour Index :

Generic name

Constitution number

Nomenclature system for pigments and dyestuffs

The Colour Index is published by the Society of Dyers and Colorists (GB) and the American Association of Textile Chemists and Colorists.

Colour Index

4th EDITION: online ( www.colour-index.org )different search modes


Public



Colour Index

Generic Names

CI Class Shade Number

PigmentSolvent

VioletRed

19135

PigmentCI Class

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

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

Number continuous

Generic NameProperties ofOrganic Pigments

Public



Tim Boyce

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

Colour Index –Constitution Numbers


Public



Tim Boyce

Same Colour Index but .......

Permanent Yellow NCG Permanent Yellow NCG 71 Permanent Yellow NCG Permanent Yellow NCG 71

Hansa Brilliant Yellow 5GX Hansa Brilliant Yellow 2GX 70

Novoperm Yellow HR 02 Novoperm Yellow HR 70

Hansa Brilliant Yellow 5GX Hansa Brilliant Yellow 2GX 70

Novoperm Yellow HR 02 Novoperm Yellow HR 70

P.Y.16

P.Y.83

P.Y.74


Public



Tim Boyce

Standard Shade Depth (SD) - DIN 53235

The “depth of shade” is a degree of intensity of visual colourperception. 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 colourwhich is settled by convention.

1/1 SD, 1/3 SD or 1/25 SD which are used for illustration ortesting procedure are standardised according to DIN 53235

The colorimetric calculation is according to CIE-lab system(standardised in DIN 6174)


Public



Tim Boyce

P.Y. 3 P.Y. 83 P.R. 112 P.B. 15:1 P.V. 23

Fullshade Fullshade Fullshade Fullshade Fullshade

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

1/3 SD

1/25 SD

FS

Standard Shade Depth (SD) - DIN 53235


Public



Tim Boyce

•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 colouredpigment 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 either5% TiO2 (PVC) or 1% TiO2 (PO) needed to reach the indicated depth

e.g. 2.5g strong (HR) ; 14.59 weak (H3R)

Tinting strengthThe evaluation method is depending very much on the application, thus the information varies in different pattern cards .


Public



Tim Boyce

can influence

can influence

can influence

particle composition

particle size

crystal structure

primary particlesaggregatesagglomerates

colourcolour purityfastness properties

tinting strengthshadehiding power

Pigment physics


Public



Pigment Green 7 Pigment Orange 43

Pigment Red 247 Pigment Red 144

Enlargement 32 000 X

Organic pigment crystals


Public



Primary particle

Agglomerates

Aggregates

Smallest unit of a material. Has its properties. In this case a mono crystal.

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.

Particle composition of pigments


Public



Tim Boyce

C.I. Pigment Blue 15

α-modification β-modification

Crystals in same directionSpacing is smallerAngle is smaller

Crystals in alternate directionSpacing is biggerAngle is greater

Crystal modifications


P.B.15:1Red shade

P.B.15:3Blue shade

Public



Tim Boyce

white reduction

β γ

full shade

β γ

Hostaperm RedViolet ER 02 / ERX

Hostaperm RedE3B / E5B 02

Hostaperm RedViolet ER 02 / ERX

Hostaperm RedE3B / E5B 02

C.I. Pigment Violet 19

Crystal modifications


Public



Tim Boyce

SEM-micrograph of powder pigmentsC.I. Pigment Yellow 83

®Novoperm Yellow HRSpecific surface area 69 m2/gAverage partice size 40 nm

®Novoperm Yellow HR 70Specific surface area 22 m2/gAverage partice size 325 nm


Public



Tim Boyce

Relationship between particle size and shade, opacity and tint strength

Novoperm YellowHR 02

(P.Y.83)


(P.Y.83)


(P.Y.83)


(P.Y.83)Properties ofOrganic Pigments

Public



Tim Boyce

Relationship between particle size and surface area …………..Cubic dimension Number of particles

in basic cubeSurface 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)

0.4 150.3 200.2 300.1 60

Specific surface area


Public



Tim Boyce

0.000.050.100.150.200.250.300.350.400.450.50

0.1 0.2 0.3 0.4 0.5 0.6microns (u)

K/SP.Y.17P.G.7

Effect of particle size on tint strength


Public



Tim Boyce

Most Monoazo Grades, 70 Series

< 25 sq m/g

Some Quinacridones, Dioxazine Violet,Phthalocyanines

> 55 sq m/g

25-55 sq m/g

Naphtol Grades, some Quinacridones

Typical surface areas


Public



Tim Boyce

Dispersion of Pigments

Pigment Powder

DecreasingParticle

size

Agglomerates

Aggregates

Primary Particles


Public



Tim Boyce

1. 1. DeagglomerationDeagglomeration -- premixing of single pigments to premixing of single pigments to break down larger, softer agglomerates. Initialbreak down larger, softer agglomerates. Initialwetting out.wetting out.

2. Dispersion2. Dispersiona) a) WettingWetting –– most important stepmost important step. Often requires use . Often requires use of auxiliaries to improve pigment wetting. of auxiliaries to improve pigment wetting. Solvent and resin should cover entire pigment Solvent and resin should cover entire pigment surface. Polar carriers and solvents have surface. Polar carriers and solvents have better wetting power.better wetting power.b) b) DispersionDispersion –– all pigment agglomerates are broken all pigment agglomerates are broken down. This is done by friction and pressure down. This is done by friction and pressure (shear forces).(shear forces).c) c) DistributionDistribution –– optimal statistical distribution of the optimal statistical distribution of the

dispersed pigment within the carrier materialdispersed pigment within the carrier materiald) d) StabilisationStabilisation –– protection of the system against protection of the system against

reagglomerationreagglomeration or flocculationor flocculation

Dispersion of organic pigments


Public



Tim Boyce

Step 1> 100 u

Step 250 - 100 u

Step 7< 1 u

Step 61 - 5 u

Step 55 - 10 u

Step 410 - 20 u

Step 320 -50 u

Microscopic DispersionEvaluationScale (x 110 times)


Public



Tim Boyce

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

Organic pigments

Pigment Yellow 180 Benzimidazolone 0.18

Pigment White 6 Titanium dioxide 0.1 – 1.0Pigment Yellow 34 / Pigment Red 104

Lead chromates / molybdates

0.5 – 1.0

Pigment Blue 29 Ultramarine blue 0.3 – 8.0

Pigment Yellow 13 Diarylide yellow 0.06

Pigment Orange 43 Perinone 0.15Pigment Red 254 Diketopyrrolopyrrole 0.2Pigment Violet 23 Dioxazine 0.06Pigment Blue 15:3 Β-phthalocyanine 0.09

Pigment Red 101 Iron oxide red 0.1 – 0.6


Public



Tim Boyce

Effects of FlocculationLoss of colour strengthPoor levelling (in paints)Poor flowReduced glossHazingShade variation

Flocculation


Public



Tim Boyce

0 min 25 min

40 min 60 min

90 min 120 min

Flocculation v’s time

Test system

CPP gravure ink5% pigment conc.

Magnification x 110


Public



Tim Boyce

particle size

moreopaque

lowstrength

lowvisc.

higherfastness

higherloading

lowSpecificSurface

Area

lower fastness

lowerloading

highSpecificSurface

Area

highvisc.

highstrength

moretrans.

trans

pare

ncy

/

opac

itytin

t

stre

ngth

visc

osity

(flow

)

spec

ific

Sur

face

are

a

millb

ase

conc

entra

tion

fast

ness

prop

ertie

s

large

small

Particle size & distribution – general rules

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


Public

ASEAN Regional Technical ServicTim BoycePigment Technical Service Laboratory – ASEAN Region

Key fastness propertiesof organic pigments

MigrationHeat stabilityLightfastnessWeatherfastness

Public


Migration fastnessof organic colourants

Solvent fastnessBleedingOversprayBlooming

Public



Tim Boyce

• 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)

The pigment is dissolved by the solvent, thereby discolouring the solvent

The pigment is dissolved by the solvent, thereby discolouring the solvent

Solvent fastness


Public



Tim Boyce

Toluene

IPA

Toluene/IPA(70/30)

GR200 P-GRL 06 DHG SPL MXSTD STD STD STDP.Y.12 P.Y.13 P.Y.12 P.Y.13

Solvent Fastness Test - tested on pigment powder

Solvent fastness


Public



Tim Boyce

Bleeding pigment moves from the colouredmaterial to directly contacting material

Overspraypigment moves into subsequentpaint layers thereby discolouring them

Bloomingpigment migrates to the surfaceand can be wiped off

Migration fastness


Public



Bleeding / Blooming.

White contact film

Red coloured filmWhite paper covered with colour

Plaques with coloured dust on the surface.

► 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


Public



Tim Boyce

Migration fastness - bleeding

Retort fastness – 120’C / 30 minutes


Public



Tim Boyce

P.R.170 P.R.3

► Bleeding in an overspray application(tested in thermosetting acrylic)

Migration fastness - overspray


Public



Tim Boyce

Example of blooming inLow Density Polyethylene

Migration fastness - blooming


Public



Tim Boyce

Recrystallisation due to poor solvent fastnessin aromatic solvents (tested in medium oil alkyd)

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

Non flocculating version ofPigment Blue 15:1 i.e.it is a non-recrystallising or flocculatinggrade

Control 1 week aged Control 1 week aged

Pigment Blue 15:0 Pigment Blue 15:2

Solvent fastness - Recrystallisation


Public


Heat stability /Limit concentration

Public



Tim Boyce

Pigment is either discoloured or destroyed depending on the conditions and / or the nature of the pigment


Heat stability

Public



Tim Boyce

Pigment is “burnt out” in polypropylene polymer and colour “disappears”

Heat stability

Initial matching designed for applicationat 240’C maximum

Final colour when processed at280’C


Public



Tim Boyce

Heat stability - 0.5% pigment, 5 minute dwell timePigment discolours

Heat stability


Public



Tim Boyce

Heat resistance (DIN EN 12877)Heat resistance test


Public


Lightfastness –resistance to UV radiation

http://www.q-panel.com/UserFiles/File/PDFs-EN/Q-SUN-Xenon-Test-Chambers-LX5050.pdf

http://www.q-panel.com/UserFiles/File/PDFs-EN/QUV-Accelerated-Weathering-Tester-LU0819-EN.pdf

Public



Tim Boyce

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 glassEvaluated against the Blue Wool Scale according to

DIN EN ISO 105-BO 2Blue Wool Scale must be exposed at same time

as sample and result must specify timeand conditions

Blue Wool Scale is geometric - each successivestep is twice the previous step

Limited rating system of 1 (very poor) to 8 (very good)Final lightfastness is system dependent

Lightfastness


Public



Tim Boyce

Global radiation in Kly (DIN EN ISO 4892)

70

70

70

70

60 60

60

8080

80

80 100

100

100100

100

120120

120

120

120120

140

140 140

160

160160160

160 160

160-180

180180180

180

160

200


Public



Tim Boyce

160160

170

170

180

180190

190

200

200

160160

150150

140140

160150140

130

120

160

150140

130

120

Kilolangleys/year of radiation in Australia

Lightfastness – variation in radiation levels


Public



Tim Boyce

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

Conversion Table

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


Public



Tim Boyce

Lightfastness – Blue Wool Scale

Step 1

Step 8

Step 2

Step 3

Step 4

Step 5

Step 6

Step 7

Exposed section250 hours

Rating

4 – 5

6

8


Public



Tim Boyce


Public



Tim Boyce

Types of Accelerated UV/Weathering Apparatus


Public



Tim Boyce

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

Blue wool scale

Accelerated exposure* in hours

(in Xenotest X 1200 W)

Normal daylight exposure* in days

(in Frankfurt-Liederbach Germany)

1 6 h 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


Public



Tim Boyce

Light fastness (DIN EN ISO 4892)Comparison of various accelerated exposures

Blue Wool Scale

Normal daylight

exposure in days *

Accelerated exposure in

hours in XenotestX 1200 W


hours in Xenotest XE

1200 GL


hours in Weathero-

meter


hours in Suntest

2.5 hrs 2.5 hrs

6.5 hrs

9 hrs

41 hrs

80 hrs

130 hrs

260 hrs

520 hrs

8 hrs

20 hrs

75 hrs

160 hrs

270 hrs

540 hrs

1100 hrs

2.5 hrs

6.5 hrs

15 hrs

60 hrs

110 hrs

200 hrs

400 hrs

800 hrs

1 4 days 5.4 hrs

2 14 days 15 hrs

3 28 days 34 hrs

4 70 days 100 hrs

5 100 days 240 hrs

6 140 days 400 hrs

7 160 days 800 hrs

8 360 days 1600 hrs

Note : The time for outdoor exposure of stages 1 – 7 is very dependent on thetime of year at which the test began.

* The outdoor exposure test is tested behind window glass


Public



Tim Boyce

Blue wool scale

Exposure time Xenotest X 1200 W

Exposure in daylight in days (in Liederbach)

Dyestuff

1 6 h 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)

Dyes used in Blue Wool Scale


Public


Resistance to Weathering

Public



Tim Boyce

It is a measure of all exposure conditionse.g. UV, rain, snow, industrial atmosphere etc

Can be accelerated e.or actual exposuree.g. Florida or Allunga, Xenotest or QUV

Evaluated against the Grey Scale and/or bycolour difference measurement

Carried out as per DIN 54001

Results can be different to lightfastness

Results are highly system dependent


Weatherfastness

Public



Tim Boyce

Global Climate Classification (Koeppen)


Public



Tim Boyce

Primary effectsSolar radiation (light energy)Temperature and temperature differencesWater (moisture)

Secondary effectsAirborne pollutantsAcid rainBiological effects (mold, mildew)

Weatherfastness factors

Primary + Secondary effects

Weathering


Public



Tim Boyce

The result is unwanted and premature product failures

This could mean:

Effects of weathering

Discoloration

Cracking Peeling Paint

Rust


Public



Tim Boyce

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 thestrength 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 (accelerated ageing, DIN EN ISO 4892)

Public



Tim Boyce

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 inFrankfurt is 80 Kly = 3350 MJ/m2

Accelerated test cyclesEurope South East Asia

Wet Dry Wet Dry18 mins 102 mins 240 mins 240 mins


Public



Tim Boyce

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


Public



Tim Boyce

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


Public



Tim Boyce

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

Parameters affecting fastness properties – general rules


Public


Quality Aspects

Public



Tim Boyce

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

Quality aspects

You should know that ……

Public



Tim Boyce

Volatile matter (moisture)Sieve residuepH valueSpecific conductivitySolvent fastnessViscositySpecific gravity

ColourStrengthOpacity / TransparencyGlossDispersibilityMigration fastness RheologySpecific customer tests

Pigment / Preparation

Application

Quality aspectsWhat do we standardise ?

Quality aspects

Public



Tim Boyce

• 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

Test methods

Quality aspects

Public



Tim Boyce

dH (Hue)

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

CIElab system

dL (Lightness)

dC (Chroma)

Colour measurement

Quality aspects

Public



Tim Boyce

Colour measurement

greenish yellow

yellowish green

greenish blue reddish blue

reddish yellow

bluish redbluish green

yellowish red

CIElab - System DIN 6174

Greenish yellow

Yellowish green

Bluish red

Reddish blue

Bluish green

Greenish blue

Yellow

Red

Blue

Green

Reddish yellow

Yellowish red

Quality aspects

Public



Tim Boyce

CIElab System

- dH + Tolerances

dC dH/=/ 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

Chroma & Lightnessgreener Blue redder

Lighter + dL - Darker+ dC -yellower Green Dullerbluer Brighter

bluer Violet redder

bluer Red yellower

redder Orange yellower

redder Yellow greener

Colour measurement

Quality aspects

Public



Tim Boyce

Up to 6% Up to 11% Up to ?? %

Total cost

Planning

Auditing

Training

Quality Assurance

PreventionDesign

Inspection

Test equipment

Evaluation

Record Storage

Replacement

Rework

Repair

Re-inspection

Downtime

Scrap

Diagnosis

FailureAppraisal

Quality costs

Quality aspects

Public



Tim Boyce

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 Additional information

Commercial decision

Technical & Quality complaint procedures

Quality aspects

Public



Tim Boyce

• Product Reports : specific, new release, deletions, changes….

• 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

Literature & information

• It is important that these are up to date• It is important that the information is clearly understood

Quality aspects

Public


Clariant Product Range

Public



Tim Boyce

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 –Pigments

Clariant ProductRange

Public



Tim Boyce

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 range of water soluble dyes

others range of water soluble dyes

Clariant product ranges –Dyestuffs


Public



Tim Boyce

Colourants

Pigment

powdergranulespresscake

Dyestuff

powderliquid

Preparation

powderpastefine granulesgranulesflush pastes

Clariant product ranges –Supply forms


Public



Tim Boyce

Standard Range

Properties Chemistry

QuinacridonePhthalocyanineDioxazineBenzimidazoloneDibromoanthranthrone

Naphtol AS

Diarylide

BenzimdazoloneNovoperm Very good fastness

Naphtol ASPermanent Average to good fastness. High colourstrength

Hostaperm Excellent fastness properties

Clariant product ranges –Pigments


Public



Tim Boyce

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)


Hostaperm

Public



Tim Boyce

Most commonly used in High Quality applications such as :

• Automotive paints (mainly Refinish)

• High quality industrial paints

• Decorative paints (where light and weatherfastnessare critical)

• Inks (where high fastness properties are required - metal dec)


Novoperm

Public



Tim Boyce

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

Permanent


Public



Tim Boyce

Standard Range

Properties Chemistry

MonoazoHansa 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

Clariant product ranges –Pigments (continued)


Public



Tim Boyce

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

Hansa


Public



Tim Boyce

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)

Permanent


Public



Tim Boyce

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

PV Fast & Graphtol


Public



Tim Boyce

Clariant product ranges –Dyestuffs

Standard 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 Multiple applications

Vitasyn Foodstuffs, cosmetics Registered products

Savinyl Ink, coatings, Special applications

Multiple applications


Public



Tim Boyce

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

Clariant product ranges –Preparations


Public


Product safety

Public



Tim Boyce

Product Safety

Prior to marketing a product all legal requirements must be fulfilled!

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

Mandatory Regulations:

Product safety

Public



Tim Boyce

International Environmental LabelsUSA: Green SealJapan: Eco MarkScandinavia: White SwanCanada: Environmental ChoiceGermany: Blue AngelEurope: Flower

EU-Eco-Labels- Textile products- Footwear- Bed mattresses- Indoor paints- Bed linen and T-shirts- Copy paper

Internal StandardsDIN EN ISO 9001DIN EN ISO 14001

Voluntary Regulations:

Product Safety

Product safety

Public



Tim Boyce

In Force In Preparation European Union Switzerland USA Canada Australia Japan New Zealand Philippines South Korea China (partly) Czech Republic (partly) Hungary (partly) Poland (partly)

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

Mexico Malaysia Singapore Taiwan Thailand South Africa

Worldwide Chemical Legislation

Product safety

Public



Tim Boyce

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

Public



Tim Boyce

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/ECFDA-Approval (US)French Positive List (FR)JHOSPA (JP)JHPA (JP)REACHStandard 2070.6 (AU)

Major worldwide regulations affecting pigments

Product safety

Public



Tim Boyce

PurityMigration fastnessToxicological properties

For colorants that are used for coloring consumer goods, food packaging and toys the parameters relating to

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

Product safety

Public



Tim Boyce

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 limitsThe following limiting values must not be exceeded (extractable in 0.1 N HCl)

As 100 ppmBa 100 ppmCd 100 ppmCr 1000 ppm

Hg 50 ppmPb 100 ppmSb 500 ppmSe 100 ppm


toys

Product safety

Public



Tim Boyce

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 limitsThe following limiting values must not be exceeded (extractable in 0.1 N HCl)

Primary aromatic aminesThe 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 ppm2-methyl-4-chloroaniline should be treated in the same wayThe content of polychlorinated biphenyls (PCB) should not exceed 25 ppm

As 100 ppmBa 100 ppmCd 100 ppmCr 1000 ppm

Hg 50 ppmPb 100 ppmSb 500 ppmSe 100 ppm

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

Product safety

Public



Tim Boyce

Heavy metal limits (ppm*) for colorants in food packaging –Country overview

Country/Metal As Ba Cd Cr Hg Pb Sb Se Zn Australia 100 100 100 1000 50 100 500 100 Belgium 100 100 100 1000 50 100 500 100 Germany (Rec. IX) 100 100 100 1000 50 100 500 100 EU/AP (89) I 100 100 100 1000 50 100 500 100 France 100 100 100 1000 50 100 500 100 Great Britain 100 100 100 1000 50 100 500 100 Greece 100 100 100 1000 50 100 500 100 Italy 50 100 100 1000 50 100 500 100 Japan (JHPA)** 50 100 50 100 Japan (JHOSPA) 50** 100 100** 1000 50** 100* 250 100 Netherlands 100 100 1000 1000 50 100 2000 100 Portugal 100 100 100 1000 50 100 500 100 2000 Switzerland 100 100 100 1000 50 100 500 100

* Soluble contents in diluted HCl ** Total content


toys

Product safety

Public



Tim Boyce

Heavy metal limit values for toys (ppm) - Country overview

Country/Metal As Ba Cd Cr Hg Ni Pb Sb Se Sr Australia (toy coatings) 25 500 75 60 60 90 60 500 Australia (modeling clay,

finger paints) 25 250 50 25 25 90 60 500

Australia (total content in modeling compounds)

1,0 1,0 0,05 1,0 0,03 1,0 1,5 1,5 1,0 1,0

EU EN 71/3 Tab. 1 (surface coatings etc.)

25 1000 75 60 60 90 60 500

EU EN 71/3 Tab. 2 (modeling clay) 25 250 50 25 25 90 60 500 EU EN 71/7 (finger paints) 10 350 15 25 10 25 10 50 United Kingdom (coatings of

pencils, pens, etc.)

100 1000 100 100 [Cr(VI)]

100 250 250

Switzerland (Art. 31) (coatings of paints, drawing etc.)

25 1000 75 60 60 90 60

Switzerland (Art. 32) (water colors) 25 1000 75 60 60 90 60 USA ASTM F 963-96a (surface coatings) 25 1000 75 60 60 90 60 500


toys

Product safety

Public



Tim Boyce

Purity of our products


toys

Antimony 60 ppm (EN 71-3)Arsenic 25 ppmBarium 100 ppmCadmium 50 ppmChromium 60 ppmLead 90 ppm (EN 71-3)Mercury 25 ppmSelenium 100 ppmZinc 1000 ppm

Primary aromatic amines 500 ppm*

4-aminobiphenyl, benzidine2-naphthylamine, 2-methyl-4-chloroaniline 10 ppm

* = calculated as aniline

Products which are subject to regular analytical tests meet the following purity criteria:

The maximum soluble content (in 0.1 N respect. 1N HCl) of the following elements is:

Product safety

Public



Tim Boyce

Migration fastness


toys

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.The migration is among others dependent upon

the properties of the packaging material usedthe 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 colorantsthe application procedurethe food and the storage conditions

Product safety

Public



Tim Boyce

Toxicological Properties

Important toxicological tests for pigments are:

acute toxicityirritation of skin and mucous membranetoxicity after repeated applicationsensitizationmutagenicitychronic toxicity, especially carcinogenicity

The most important property of organic pigments is their extremeinsolubility in water and the application media.


toys

Product safety

Public



Tim Boyce

The Issue of HCB (hexachlorobenzene) and TCPA (tetrachlorophthalicanhydride)A) IntroductionOn 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

In Japan HCB is a Class I specified substance under the ChemicalSubstances 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.

Product safety

Public



Tim Boyce

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.

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

Product safety

Public



Tim Boyce

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 concernPigment Green 7 (e.g. PV Fast Green GNX / Hostaperm Green GNX)

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

Note : this is an issue in Japan only and currently does not have relevance in any other country

Product safety

Public


Chlorine Free Pigments for Plastics

Public



Tim Boyce

Chlorine free pigments/dyes (less than 1% chlorine)Pigment Colour Index Chemical classification

Graphtol Yellow 3GP P.Y.155 Bisacetoacetarylide

Benzimidazolone

Benzimidazolone

Benzimidazolone

Isoindolinone

Benzimidazolone

Perinone

Naphtol

Naphtol

Naphtol

Monoazo

Benzimidazolone

Benzimidazolone

β Quinacridone

β Quinacridone

Benzimidazolone

Benzimidazolone

PV Fast Yellow H2G P.Y.120

PV Fast Yellow HG 01 P.Y.180

PV Fast Yellow HG P.Y.180

Graphtol Yellow H2R P.Y.139

PV Fast Yellow H3R P.Y.181

PV Fast Orange GRL P.O.43

PV Fast Red HB P.R.247

Graphtol Red F3RK 70 P.R.170

Graphtol Red F5RK P.R.170

Graphtol Rubine 6BP P.R.57:1

PV Fast Red HFT P.R.175

Graphtol Red HF2B P.R.208

PV Fast Red E3B P.V.19

PV Fast Red E5B P.V.19

Graphtol Carmine HF3C P.R.176

Graphtol Carmine HF4C P.R.185

Product safety

Public



Tim Boyce

Chlorine free pigments/dyes (less than 1% chlorine)Pigment Colour Index Chemical classification

PV Fast Pink E P.R.122 Dimethyl Quinacridone

Dimethyl Quinacridone

Benzimidazolone

γ Quinacridone

α Phthalocyanine

β Phthalocyanine

Chemical classification

Quinoline

Methine

Anthraquinone

Perinone

Perinone

Monoazo

PV Fast Pink E 01 P.R.122

Graphtol Bordeaux HF3R P.V.32

PV Fast Violet ER P.V.19

Graphtol Blue AN P.B.15:0

PV Fast Blue BG P.B.15:3

Dyes Colour Index

Sandoplast Yellow 2G S.Y.114

Polysynthren Yellow GG S.Y.133

Polysynthren Yellow NG P.Y.147

Sandoplast Orange 3G S.O.60

Sandoplast Red 2G S.R.179

Sandoplast Red BB S.R.195

Product safety

Public


FDA Compliant Colorants from Clariant

Public



Tim Boyce

1. General remarksThe 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

FDA ApprovalSummary of the regulations concerning food packaging

Product safety

Public



Tim Boyce

2. Legal and Regulatory Background – FDA Compliance for Food AdditivesA 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)

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 orHolding 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.

Product safety

Public



Tim Boyce

2.1 Regulated Colorants for Polymers2.1.1 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

Conditions of use describe the temperature conditions the coloured polymer may be subjectto and are described as follows :

A – High temperature heat sterilised e.g. > 100’C / 212’ FB – Boiling water sterilisedC – 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

Product safety

Public



Tim Boyce

2.1 Regulated Colorants for Polymers2.1.2 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 theFDA webpage. For a complete listing of FDA cleared substances, both 21 CFR § 178.3297and 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 thecompany who is listed with the cleared substance on the FDA webpage may declaretheir product as FDA compliantProduct safety

Public



Tim Boyce

PY214PV Fast Yellow

H9G

PB15:1PV Fast Blue A4R

PG7PV Fast Green

GNX

PV19PV Fast Violet

ER

PR122PV Fast Pink

E 01

PR122PVFast Pink

E

PV19PV Fast Red

E5B

PV19PV Fast Red

E3B

PR187PV Fast Red

HF4B

PY254PV Fast Red

D3G

PY242PV Fast Scarlet

4RF

PY181PV Fast Yellow

H3R

PY191PV Fast Yellow

HGR

PY191PV Fast Yellow

H2GR

PY180PV Fast Yellow

HG

PR122DrizPearl Pink

E

PV19DrizPearl Red

E5B

PY181DrizPearl Yellow

H3R

PY180DrizPearl Yellow

HG

PB15:0Graphtol Blue

AN

PB15:3PV Fast Blue

BG

PB15:1PV Fast Blue A2R

Powder pigments

DrizPearls

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

Product safety

Public



Tim Boyce

FDA Compliant Colorants with prescribed limitations

Product Colour Index 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

1 D – G Aqueous, acidic,low alcohol

0.5 D – G

0.2 A - H

Graphtol Blue AN P.B.15:0 FDA compliant colour without limitation in 21 CFR 178.3297

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 Red E5B P.V.19 FDA compliant colour without limitation in 21 CFR 178.3297


PV Fast Yellow H2GR P.Y.181 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 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 Aqueous, acidic,low alcohol

PV Fast Red D3G P.R.254 All 1 B – h All foods

0.5 D – G Fatty foods

0.2 A - H All foods


0.5 D – G Fatty foods

0.2 A - H All foods

PV Fast Violet ER P.V.19 FDA compliant colour without limitation in 21 CFR 178.3297

PV Fast Blue A4R P.B.15:1 FDA compliant colour without limitation in 21 CFR 178.3297

PV Fast Blue A2R P.B.15:1 FDA compliant colour without limitation in 21 CFR 178.3297

PV Fast Blue BG P.B.15:3 FDA compliant colour without limitation in 21 CFR 178.3297

PV Fast Green GNX P.G.7 FDA compliant colour without limitation in 21 CFR 178.3297

PV Fast Pink E 01 P.R.122 All

PV Fast Pink E P.R.122 All

DrizPearl Pink E P.R.122 All

Product safety

Public



Tim Boyce

SBr53Polysynthren Brown

R

DY164Solvaperm Yellow

G

PY147Polysynthren Yellow

NG

PY151Hostaperm Yellow

H4G

SY133Polysynthren Yellow

GG

Colorants in PET

Optical Brighteners

LeucopureEGM

Hosta;uxKS 1

HostaluxKS

SG28Sandoplast Green

G

SB104Solvaperm Blue

2B

SB104Polysynthren Blue

RBL

SR195Solvaperm Red

BB

SR135Solvaperm Red

G

SR135Polysynthren Red

GFP

Product safety

Public



Tim Boyce

FDA Compliant Colorants with prescribed limitations

Product Colour Index Polymer % upper concentration Conditions of Use 21 CFR176.170 Food types

Polysynthren Red GFP S.R.135 PET

High alcohol, fatty foods

0.2 E – F – G Aqueous, acidic,low alcohol

0.05 D – E – F – G All foods

Hostalux KS 1 N/A All

OlefineLeucopure EGM FB238

Hostaperm Yellow H4G P.Y.151 PET 0.01 E – F – G Aqueous, acidic,low alcohol

Polysynthren Yellow GG S.Y.133 PET 0.2 E - F - G Aqueous, acidic,low alcohol

0.25 E – F – G All foods

0.25 D – E – F - G Food types III, IV-A, VI

0.2 E – F - G Aqueous, acidic,low alcohol

Aqueous, acidic,low alcohol0.045 C – D

Polysynthren Blue RBL S.B.104 PET 0.2 E – F – G Aqueous, acidic,low alcohol

Polysynthren Brown R S.Br.53 PET 0.2 E – F – G Aqueous, acidic,low alcohol

PVCHostalux KS N/A

0.03 D – E – F – G All foods

Solvent Yellow G D.Y.64 PET 0.2 E – F – G Aqueous, acidic,low alcohol

Solvaperm Blue 2B S.B.104 PET 0.2 E – F – G Aqueous, acidic,low alcohol

Sandoplast Green G S.G.28 PET

0.2 E – F – G Aqueous, acidic,low alcohol

Aqueous, acidic,low alcohol0.045 C – D

High alcohol, fatty foods

Solvaperm Red BB S.R.135 PET 0.2 E – F – G Aqueous, acidic,low alcohol

All

0.025 B – H < 275’F Food types I, II, VI-A, VII-B, VIII

E – F – G All foods

PET 0.035 A – H All foods

Solvaperm Red G S.R.135 PET

Polysynthren Yellow NG P.Y.147 PET

Product safety

Public



Tim Boyce

Food contact conditions :A – Container is sterilised over 212’FB – Container is sterilised with boiling waterC – Container is hot filled or pasteurised above 150’FD – Container is hot filled or pasteurised below 150’FE – Room temperature filled and stored. No thermal treatment in the containerF – Refrigerated storage. No thermal treatment in the containerG – Frozen storage. No thermal treatment in the containerH – 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 contentIV-B – Oil-in-water emulsions, high or low fatVI-A – Beverages containing up to 8 percent alcoholVI-B – Beverages, non alcoholicVII-B – Moist bakery products with surface containing no free fat or oilVIII – Dry solids with the surface containing no free fat or oil (no end test required)

Product safety

Public



Tim Boyce

Product safety

Public



Tim Boyce

Principles Behind REACH

Product safety

Public



Tim Boyce

Product safety

organic pigments – the basics - sii - dec 2008

Documents