TOPIC:- IV

TOPIC:- IV

Dr. S.C. Srivastava

K-TECH (INDIA) LIMITED

www.ktechindia.net

Industrial Classifications

1. High Performance Inorganic Pigments

2. High Performance Organic Pigments

Type

Volumes wise in Million Tons

FY 2005 FY 2020

1. High Performance Inorganic Pigments 2.0 Million Tons 6.0 Million Tons

2. Commodity Inorganic Pigments 4.0 Million Tons 14.0 Million Tons

Total 6.0 Million Tons 20.0 Million Tons

Inorganic

Pigment

Values wise in Billion US Dollars $

FY 2005 FY 2020

1. High Performance Inorganic Pigments 6.0 Billion USD $ 20.0 Billion USD $

2. Commodity Inorganic Pigments 8.0 Billion USD $ 20.0 Billion USD $

Total 14.0 Billion USD $ 40.0 Billion USD $

High Performance Organic Pigments

– Region Wise

Metric Tone

Region 2000 2020

Europe 8000 10000

NAFTA 8000 10000

ASIA CHINA 3000 5000

ROW INDIA 500 5000

High Performance Organic Pigments – Region Wise

Paradigm Shift in over 20 years

2000 2020

NAFTA 40 % 25 %

Europe 35 % 25 %

ASIA (India, China) 20 % 45 %

ROW < 5 % < 5 %

World Organic Pigments

(Classical & High Performance Pigment)

Organic pigment 2020 Volume Value

Classical Azo Pigments 4,50,000 MT 27000 Cr

High Performance Pigments 50,000 MT 18000 Cr

High Performance Pigment World - 2020

China 12,500 Cr

India 8,500 Cr

Europe 8,000 Cr

United States 8,000 Cr

Japan 5,000 Cr

Others 3,000 Cr

Special Effect Pigments Metallics – Al, Zn, Cu, Au, Ag, Fe

Oxide Coated

Mica Coated, MIO Pigments

Platelet Monocrystals Pigments

Phosphorescent Pigments

Fluorescent Pigment

Pearlescent High Performance Pigments

Luminescent High Performance Pigments

Semiconducting Pigment

Photo Chromic Pigment

Thermo Chromic Pigment

High Performance Pigments (Inorganic Chemistries)

Carbon Black Pigments

Aluminum Flakes Pigments

Metal Oxide Pigments

Mixed Metal Oxide

ZnFe2O4

CoAl2O4

Nitrides (Gallium)

Complex Inorganic Colour Pigments (Titanate/ Chromite, Oxide Coated Cobalt)

Cadmium Pigments (CDS/ CDSE)

Selenium Pigments

Cerium Pigments

Silicon Carbide

Bismuth Vandate Pigments

Arsenate (Gallium)

High Performance Pigments (Organic Chemistries)

Quinoptholone

Quinacridones

Perylene, Perinone

Benzimidazolone

Diketo pyrrolo pyrrole

Dis azo condensation

Dioxane Carbazole

Iso Indolinone, Iso Indolene

Pthalocyanines

• Rheological Properties

1. Flow Behavior in Application

2. Viscosity in application

3. Yield value in application

4. Shortness ratio in application

5. Thixotropy in application

6. Sagging in application

7. Settling in application

• Resistance Properties

1. Chemical Resistance – ASTM D 543 (Practice A)

2. Acid Resistance

3. Surfactant Resistance – ASTM F 903

4. Alcohol Resistance – ISO 23232:2009

5. Ketone Resistance – ASTM D 6754/ D6754M

6. Ester Resistance – ASTM D4293

7. Hydrocarbon Resistance – ASTM C868

8. Aromatic solvent Resistance

9. AR SR

10. Product Resistance

• Surface Properties

Surface Control = Fish eye

Dewetting

Crater

Cissing

Pinhole

Surface Control = Gloss

Sheen

Floating

Flooding

Crawling

Surface Control = Effect on Drying

Crystallization

• Functional Properties

1. Corrosion Inhibition – ASTM 420

2. Chalking Tendency

3. UV Stability

4. Microbial Properties

5. Flame Retardant properties

6. Antiskid Properties

7. Water Vapor Transmission rate

8. Oil repellency

9. Water repellency

10. Scratch hardness

Molecular Structure

Crystal Structure

Polar ability

Di Pole Moment

Confirmation

Constitution

Energy

Particle Size

Crystal Habit

Crystal Density

Crystal Defect

Surface Structure

Refraction Hardness

Cohesion

Zeta Potential

Solubility

Absorption

Conductivity

Magnetism

Agglomerates

Flocculation

Thermal Stability

Light Fastness

Weather Fastness

Filtration

Dispersion

Rheology

High Performance Pigments – Applications

%

Inks Digital Inks 05.00

Coatings Automotive, Industrial, Decorative 50.00

Plastics Engineering Plastics 35.00

Organic Electron CD, DVD, Chips, Solar, MICR, PCB 10.00

Total 100.00

High Performance Pigments – Key Characteristics

Key Parameters Minimum Requirements

Light Fastness (LF) 8 (on 1 – 8 scale)

Weather Fastness (WF) 5 (on 1 – 5 scale)

Heat Resistance (HR) > 300° C (dE 1.00 CIELAB)

Chemical Resistance (CR) 5 (on 1 – 5 scale)

Acid / Alkali Resistance (AR) 5 (on 1 – 5 scale)

Solvent Resistance (SR) 5 (on 1 – 5 scale)

Soap Resistance (SR) 5 (on 1 – 5 scale)

High Performance Pigments – Way ahead for India

Manufacturing (Chemistries)

Finishing Techniques & Standardization

Branding & Marketing

High Performance Pigments – Way ahead for India

Famous Proverb –

“Making of a country, community, company or chemistry is a never

ending process; it keeps going on, so keep moving, keep working, journey is better

than destination…”

“Our country has to keep learning, working and understanding high

performance pigment (HPP) synthesis & Functioning for end use requirement”

SYNTHETIC ORGANIC PIGMENT HPP CHEMISTRIES

Azomethine complex (PY153, PO59)

Isoindolinone (PY 173, 139)

Isoindolene (PY 185, PY 260)


Phthalocynine (PB15, 15.3, 15.4, PG7)

Quinacridone (PV19, PR122, 202, 206, 207, 209)

Carbaazole(PV23)

Perinone (PO44, 194)


oPerylene (PR123, 149, 178, 179, 190)

oAnthraquinone (PY147, 193, 199, 108, PR89, 177, 83)

oDPP (PO71, 72, 254, 255, 264, 272)

oQuinapthalene (PY138), Thio indigo (PR 88)

• Chemical Class – Mixed metal Oxide (MMO)

Complex Inorganic Colour pigment (CICP)

• Crystal Engineering - Metal : Oxygen ratio

Crystal Formula Oxygen Metal Ratio

Rutile MO2 2 1 2

Hematite M2O3 3 2 1.5

Spinel M3O4 4 3 1.33

• Cadmium Pigments :- Cd Produced Since 1817

Se Produced Since 1955

• Raw Material :- Cadmium (MP 321°C, BP765°C)

Selenium (MP 217°C, BP685°C)

CdD.CdSe (Highly insoluble)

• Technology:- 1. CdO3 + Na2S = CdS + Na2Co3

2. 3CdS + CdCO3 + Se = 3Cd.CdSe + CO2 + SO2

Colour Index Name Pigment Yellow 35 Pigment Orange 20 Pigment Red 108

Colour Index Number 77205 77119 7720

Chemistry CdS.ZnS CdS.CdSe CdS.CdSe

CAS No. 8042-0705 12656-574 58339-34-7

Oil Absorbance 20-25 20-22 20-22

Specific Gravity 4.6 4.8 5.1

Legislation & Regulation :- Cd

is Restricted

Application :- Paints, Plastics,

Ceramics, Coatings

• Serium Pigments:- Rare Earth Sulphide

La2S3 – White

Ce2S3 – Dark Red

Pr2S3 – Green

Nd2S2 – Light Green

Ti2S2 – Light Yellow

Dy2S3 – Orange

• Manufacturing :- Cerium Precursor, Sulfonation of Cerium Precursor, Final

tretament & preparation.

Colour Index Name Pigment Orange

78

Pigment Orange

75

Pigment Red 265 Pigment Red

75

Colour Index Number 772850 77283-1 77283-2 772830

Chemistry Ce2S3Ca2S3 Ce2S3 Ce2S3 Ce2S3

CAS No. 12014-93-6 12014-93-6 12014-93-6 12014-93-6

Application :- Paints, Plastics, Ceramics, Coatings

• Titanate based CICP (MMO) Pigments

• Application :- Plastics, Ceramics, Coatings

Shade Colour Index Name Chemistry Crystal

Green Colour Index Pigment Green 50 CoTi Spinel

Yellow Colour Index Pigment Yellow 157 BaNiTi Pridenli

Yellow Colour Index Pigment Yellow 53 NiSbTi Rutile

Yellow Colour Index Pigment Yellow 161 NiNbTi Rutile

Yellow Colour Index Pigment Yellow 189 NiWTi Rutile

Brown Colour Index Pigment Brown 24 CrSbTi Rutile

Yellow Colour Index Pigment Yellow 162 CrSbTi Rutile

Yellow Colour Index Pigment Yellow 163 CrSbTi Rutile

Black Colour Index Pigment Black 12 FeTi Spinel

Yellow Colour Index Pigment Yellow 37 MnSbTi Rutile

Brown Colour Index Pigment Brown 40 MnNbTi Rutile

Brown Colour Index Pigment Brown 45 MnCrTi Rutile

Brown Colour Index Pigment Brown MnWTi Rutile

• Titanate based CICP (MMO) Pigments

Shade Colour Index Name Colour Index Number CAS N-o.

Yellow Colour Index Pigment Yellow 53 77788 8007-18-9



Buff Colour Index Pigment Brown 24 77310 68186-90-3

Buff Colour Index Pigment Yellow 162 77896 68611-42-7

Buff Colour Index Pigment Yellow 163 77897 68186-92-5

Brown Colour Index Pigment Brown 164 77899 68412-38-4

Brown Colour Index Pigment Brown 37 77890 70248-09-8

Brown Colour Index Pigment Brown 45 N/A 19463-67-7

• Manufacturing:- Solids State reaction at high temperature with TiO2 Rutile &

Dopant

• Application :- Plastics, Ceramics, Coatings

• Metallic Pigments:- Al, Zn, Cu, Au, Ag, Fe

• Oxide Coated Metallic:- Sulphixode

• Platelets Pigment:- Cu, Zn, Fe2O3 Coated Aluminum

• Coated Mica:- Non Absorbing Coating- TiO2, ZrO2, SnO2 & SiO2

Total absorbing Coating- Fe3O4, Fe2O3, Cr2O3, TiO3, C,

As, Al, Mo, Cr, Pc.

• Platelet Monocrystal pigment :- BiOCl, Pb(OH)2, α − Fe3O3, Fe3O4, CuPC

• Comminuted thin PVD :- Al/Cr/SiO2

• Comminuted polymer film :- LCP (Liquid Crystal Polymers)

• Special Effects:-

• Pearlescent Pigments

• Interference Pigments

• Phosphorescent Pigments

• Thermal Pigments

• IR Reflecting Pigments

• UV Invisible Pigments

• Magnetic Pigments

• Conductive Pigments

• Laser Reflective Pigments

• Photo Sensitive Pigments

• Pearlescent Pigment :-

• Natural fish Silver

• Basic Lead Chron

• Binuth Oxy Chloride

• TiO2- Mica

• TiO2 2-X/ TiO2/ Mica

• Fe TiO3/ TiO2/ Mica

• Fe3O4/Mica

• Intra Red Reflective:- TiO2/ Mica

Doped Yttrium/ Indium.

Application IR reflecting Plastic

Roof Light

Exterior

• Magnetic Sensitive:- Fe3O4 γ Form

Hysteria Characteristics

Receptivity/ Coercivity

Magnetic Surface, types, DVD

• Laser Sensitive:- TiO2/ Mica/Sn,Sb

Laser marking of plastics, coatings

• Solar Semiconductor Photo Sensitive :- Gallium Nitrite

Silicon Carbide

Halfanium oxide, salts

• Electrical Conductive :- (SnSd)O2/ Mica

SnCo,F)2 Mica

Antistatic

Electrically Conducting

Coatings Packagings

Dust Reduction

Clean room

1. Chemical Class – Polycyclic Pigments

2. Since – 1952

3. Chemistry – Carbazole dioxazone Family.

4. Application – Paints, Printing Inks, Plastics

Shade Violet

Colour Index Name Pigment Violet 23

Colour Index Number 51319

CAS No. 215247-95-3

Crystal Area 100 Sq.m/ gm

Crystal Size 0.1 μ

Liquid Fastness (1-8) 8 Excellent

Specific Gravity (1-5) 5 Excellent Pigment Violet 23

3-amino-9-ethylcarbazole

2,3,5,6-tetrachloro

1,4- benzoquinone

+

1. Chemical Class – Polycyclic Pigments

2. Since – 1960

3. Chemistry – Thioindigoid Family.

4. Application – Paints, Printing Inks, Plastics.

Thioindigo

Colour Index Name Pigment indigo 88

Colour Index Number 773312

Chemistry Indigo

CAS No. 14295-43-3

Shade Reddish Voilet

Light Fastness Excellent

Whether Fastness Excellent

Heat Resistance 260°C

1. Chemistry Class – Benzimidazolone Pigments

2. Since – 1950

3. Key Coupling Component –

a. 5-Aceto acetyl amino benzimidazolone

b. 5-(2 Hychoxy – 3‘ Napthylamino) Benzimidazolone

4. Application – Paints, Printing Inks, Plastics. 5-Acetoacetyl amino

benzimidazolone intermediate

Shade Bright

Yellow

Greenish

Yellow

Warm

yellow

Reddish

Yellow

Yellow Orange Red Bluish

Red

Carmine

Red

Bordeaux

Red

Brown

C.I. Name PY 120 PY151 PY 180 PY181 PY 194 PO 36 PR175 PR176 PR185 PV 32 PB 25

C.I. No. 11783 13980 21290 11777 11785 11780 12513 12515 12516 12517 12510

CAS No. 29920-

31-8

31837-

42-0

77804-

81-0

74441-

05-7

82199-

12-0

12236-

62-3

6985-

92-5

12225-

06-8

5190-

12-8

12225-

08-0

6992-

11-6

1. Chemical Class – Diketo pyrolo Pyrolle (DPP) Pigments

2. Since – 1974

3. Chemistry – a.CN+ Br CH2CO2CH3 Zn

(Reformat sky reaction)

b. Cn + ROOC COOR base

4. Application – Photoconductive, Optical Informulation, OLED, LCD, Textile, Hair

Colourant, Laser Dyes, H2 Gas Sensor, Ca2+ Ion Indication, Fluorescent Dye,

Dendrite Dyes, Photorefractive Diketopyrrolo pyrrole

Shade Bright Red Red Orange Bright Orange

Colour Index Name PR 254 PR 255 PO 71 PO 73

Colour Index Number 56110 561050 561200 561170

CAS No. 84632-65-5 54660-00-3 84632-50-8 -

1. Chemical Class – Imidazolone Anellated

Triphenedioxozine Pigments

2. Since – 1960

3. Chemistry – Chloranil + 5amino Benzimidazole

4. Application – Paints, Coatings, Printing Inks, Plastics, Rubber.

5. Properties – Outstanding Colour Strenght

Excellent High Light fastness, Weather fastness, Solvent fastness

Excellent heat stability & durabiliy

R

5amino Benzimidazole

+

Chloranil

2-2 HCl

Oxidation

1. Chemical Class – Quinophthalone Pigments

2. Since – 1960

3. Chemistry – Quinaldine + Phthalic anhydride


Quinophthalone Compound

Shade Yellow Yellow Yellow

Colour Index Name PY 138 PY 139 PY 185

Colour Index Number 56300 - -

CAS No. 30125-47-4 36888-99-0 76199-85-4

Heat Resistance 250 250 250

Light/ Whether fastness Excellent Excellent Excellent

Quinaldine

+

Phthalic Anhydride

OH

1. Chemical Class – Iso Indoline Pigments

2. Since – 1946

3. Chemistry – a. Iso Indoline ring4. Application – Paints, Printing Inks, Plastics.

5. Manufacturing:- Barbituric acid, acetic acid coupled with isoindo linone post

distilled in DMF Iso-Indoline ring Compound

Shade Reddish Yellow Brown Yellowish Red Red Bright Yellow

Colour Index Name PY 139 PB 38 PO69 PR260 PY 185

Colour Index Number 56298 12367 58292 56295 56290

CAS No. 36888-99-0 12236-64-5 85959-60-0 71552-60-8 76199-85-4

1. Chemical Class – Phthalocyanine

2. Since – 1950

3. Chemistry – a. urea 4mole - Crude &Distillation

b. Phthalic anhydride 4mole - Pigmentation

c. Metalloids 1 mole - Post treatment

4. Application – Paints, Printing Inks, Plastics. Phthalocynine Compound

Shade Red Blue Red Blue Red Blue Green Blue Green Blue Green Blue Green Yellow Green

Colour Index

Name

PB 15 PB 15:1 PB 15:2 PB 15:3 PB 15:4 PB 15:6 PG 7 PG 36

Colour Index

Number

74160 74160 74160 74160 74160 74160 74260 74265

CAS No. 147-14-8 147-14-8 147-14-8 147-14-8 147-14-8 147-14-8 1328-53-6 14302-13-7

1. Chemical Class – Quinacridone Pigment

2. Since – 1958

3. Chemistry – a. Dimethyl succinate (DMS)

b. Sodium Methoxide

c. Claisen condensation

d. cyclization

e.DMSS (DIMETHYL SUCCINYL SUCCINATE)

f. PPA (Poly Phosphoric Acid)

Quinacridone


Quinandrone Compound

Dimethyl Succinate (DMS)

Sodium Methoxide (Catalyst)

DMSS (Dimethyl Succinyl Succinate)

Shade Red Violet

Colour Index Name Pigment Red 122 Pigment Violet 19

Colour Index Number 73915 980-26-7

CAS No. 73900 213-789-2

1. Chemical Class – Diazo Condensation Pigment

2. Since – 1950

3. Application – Paints, Printing Inks, Plastics. .

Diazo Condensation

C.I.

Name

PY93 PY94 PY128 PY166 PO31 PR 220 PR221 PBr23

C.I. No. 20710 20038 20037 20035 20050 20055 20065 20060

CAS No. 5580-57-4 5580-57-5 79953-

85-8

76223-

82-4

1344-38-3 68259-09-6 61815-09-6 35869-64-8

1. Chemical Class – Perylenes

2. Since – 1950 (discover 1913)

3. Chemistry – Acenapthene Converted to NN-disubtituted 3,4,9,10-tetra

carboxylic acid imide (PTCI)


Perylene Compound

Shade Scarlet Red Yellow Red Red Red Maroon Blue Red Red Bordeaux Black

Colour Index Name PR 123 PR 149 PR 178 PR 179 PR 190 PV 29 PB 31

Colour Index Number 71145 71137 71155 71130 71140 71129 71132

CAS No. 24108-89-2 4948-15-6 3049-71-6 5521-31-3 6424-77-7 81-33-4 67075-37-0

1.Finishing techniques

a. Partial Pigmentation & full activation of Crude HPP

(Technology & engineering)

b. Pigmentation (physics & technology) of activated HPP

c. Post treatment (chemistry & technology) of pigmented HPP

- Continued

1.Finishing techniques (Continuation)

a. Partial Pigmentation on & full activation of Crude HPP

(Technology & engineering)

Mechanical:-

a. Ball milling , Size reductions.

b. Shear . Cascading . Attrition milling. Sand milling

Chemical:-

a. Acid stable alkali stable

b. Reactant solvent removed

c. Impurities removed

d. Creating freshly prepared surface

e. Amenable to pigmentation

Finishing techniques (Continuation)

1.Pigmentation of Activated Crude

a. Solvent Reflux Techniques – solvent selection

b. Salt kneading techniques – salt selection

c. High pressure high temp bead milling .techniques

d. Other techniques


Post treatment of pigment crystals

1.Water - Aqueous application best treatment = textile,

leather, paper, artist colour.

2.Solvent – Non polary application = official inks, crayons, alkyd

paints post treatment.

3.Mid polar application = Liquid inks, decorative paints &

coatings.

4.Polar application = Industrial paints & coatings , liquid inks.

5.Solvent less = tp/ts = plastic master, batches

LD/HD/DD/NYLON/PET/PVC/ABS


Post treatment Application - pigment coated with coatings agent having

pigment affinity groups, forming, mono meduculars, layers all around

pigment crystal surface to optimize.

Surface charge. Zeta potential . lonic double layer.

Few recommended additives : PIGMESOL ® A 5541/ 5598/ 5093

PIGMESOL ® 5424 – Plastics & Rubber

PIGMESOL ® 5343 – Industrial Paints

PIGMESOL ® 5207 – Enamel Paints

PIGMESOL ® 5103 – Offset Printing Inks

PIGMESOL ® 5007 – Aqueous Application


Surface Active Agents – eg. PIGMEWET® (K-TECH)

-specialty wetting agents

Pigment coating agent– eg. PIGMESOL ® (K-TECH)

-specialty polymeric compounds

Pigment Synergists - PIGMECOL ® (K-TECH)

-Pigment Derrivatives

SPECIFICATIONS

Legislations (Safety Health & Environment)

ESHA (ETAD, EN 71:3, BIS, DIN, BS, ASTM))

Residual Metal Max ppm

Arsenic (As) ~ 50 ppm

Barium (Ba) ~ 100 ppm

Cadmium (Cd) ~ 100 ppm

Chromium (Cr) ~ 1000 ppm

Mercury (Hg) ~ 50 ppm

Lead (Pb) ~ 100 ppm

Tin (Sn) ~ 500 ppm

Selenium (Se) ~ 100 ppm

Zinc (Zn) ~ 2000 ppm

Residual Toxicants Max ppm

Aromatic Amines ~ 500 ppm

Carcinogen Amines ~ 10 ppm

Sulphonated Amines ~ 500 ppm

Polychloro Bisphenyl (PCB) ~ 25 ppm

AOX (Adsorable Organic Halides) ~

EPA ; Most HPP are NANO !!!

Documents

TOPIC:- IV