Yellow, Orange Lead Chromates & Molybdate Now It's Time for Sustainable Alternative

Mr. Dileep Patil Manager, Technical Business Development Plastic Additives South Asia
Singapore March 12, 2013

Table of content
Lead chromate: the time to change Legislation Impact on the plastic industry Alternatives Selection of alternatives
Matching of RAL shades: few examples Need for lead free non-diarylide pigment

Lead chromates: the time to change

Restrictions
Regulations Public awareness Envoromental issues Human health The desire to recycle

Current situation
Lead chromate pigments have excellent resistance combined with attractive coloristic properties, making them highly competitive as regard to "cost in use.

Alternatives from BASF

Wide product portfolio: organic as well as inorganic pigments Options that meet the economic and technical requirements

New legislation on lead chromate

The European Commission has included lead chromate pigments in Annex XIV of REACH regulation as substances with CMR* properties. Lead chromate pigments will be banned in Europe as from May 21, 2015.
Companies active in Europe will no longer be allowed to produce, sell, ship or store these products without authorization.

Requirements of authorization include

Chemical Safety Report

Analysis of possible alternatives

Substitution plan if alternatives available Socio-economic analysis

Authorization could be refused. * Risks with lead chromate are now considered greater than the benefits Carcinogenic, mutagenic and reprotoxic.
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Lead chromate: hazardous aspect

Lead(II) chromate is profoundly toxic, due to containing both lead and hexavalent chromium. Lead(II) chromate is a poison, and can be fatal if swallowed or inhaled, or absorbed through the skin.
Lead(II) chromate is a known carcinogen, developmental toxicant, and reproductive toxicant.

Children - more susceptible to the effects of lead

http://en.wikipedia.org/wiki/Lead(II)_chromate
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Impact on the plastic industry

Benefits
No segregation of raw materials and finished goods.

Challenges
No drop-in replacement.

Important to understand how and where the products are used. Innovation in sustainable systems will be accelerated. Complex reformulation work. New business opportunities . Authorization to continue (lead chromate) is likely to be granted only Enhance companies reputation and for a limited period, (if at all). image.

How BASF can help?

Can offer expertise and a broad, dedicated portfolio of lead-chromate-free products to cater for all types of chemistry. Committed to support customers in finding the best balance DPP between performance and color formulation efficiency. Quinacridone CICP and BiVa range of in-organic pigments help to enhance the opacity and performance. Cu-Phthalocyanine
Isoindolinone
Organic Pigments Quinophthalone Pteridine BiVa Inorganic Pigments

Disazo Condensation

Monoazo Salt Benzimidazolone

Isoindoline

BONA (2B-/4B-Toner)

Perylene

-Naphtol Anthraquinone

Iron oxide

Dioxazine
Cobalt pigments

Oxide pigments
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Diarylide

Chemistries yellow color space

CICP

Pteridine
Y215

BiVA
Y184

Performance scope

Isoindolinone

Isoindolinone
Y109

Y110

Quinophthalone Y138
Y180,

Benzimidazolone
PO 64

Isoindoline
Y139 Azo-salts & coupling PY 168, PY 62, PY 155, PY 183, PY 191 Diarylide PY 13, PY 14, PY 17, PY 83 Lead Chromes (PY 34)

Greenish Yellow

Reddish Yellow

Chemistries yellow color space

CICP

Pteridine
Y215

BiVA
Y184

Performance scope

Isoindolinone

Isoindolinone
Y109

Y110

Quinophthalone Y138
Y180,

Benzimidazolone
PO 64

Isoindoline
Y139 Azo-salts & coupling PY 168, PY 62, PY 155, PY 183, PY 191 Diarylide PY 13, PY 14, PY 17, PY 83

Greenish Yellow

Reddish Yellow

Chemistries in orange red space

CICP Anthraquinone PR177 Perylene
PR 264

PO 71
Performance scope

DPP transparent

Azo-condensation
PR 144, 166, 214
Benzimidazolone PO 64

PV19 red

Quinacridone PR202

PV19 violet

PR 104 Molybdate

DPP Opaque 254, 255

PR122

Azo salts, Naphtols

PR 276, 277, PO 79

Diaryls
PO 36

BONA red Lake Red C

PR 53 PR 48, PR 57

Orange

Scarlet

Red

Magenta

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Chemistries in orange red space

CICP Anthraquinone PR177 Perylene
PR 264

PO 71
Performance scope

DPP transparent

Azo-condensation
PR 144, 166, 214
Benzimidazolone PO 64

PV19 red

Quinacridone PR202

PV19 violet

DPP Opaque 254, 255

PR122

Azo salts, Naphtols

PR 276, 277, PO 79

Diaryls
PO 36

BONA red Lake Red C

PR 53 PR 48, PR 57

Orange

Scarlet

Red

Magenta

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Selection of alternatives
Lead chromate pigments usually offer high performance at low cost.
Rather bright shades with high color strength (vs. other inorganic pigments). Suitable for PVC, polyolefin, styrene and polyamide.

Very good resistance to heat and light exposure.

Fairly low cost per kilo.

BASF provides a broad range of alternatives available.

Based on organic and inorganic pigments. Covering the whole color space.

Covering all polymers and performance levels.

Coloration costs per kilo vary, depending on chemistry and performance.

Best balance between performance & color formulation efficiency

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Selection of alternatives - aspects to consider

There is no one-to-one solution available.
No single alternative with similar shade, performance profile and costs. Selection of alternative is like a new color matching process. It could be useful to define:
The respective polymers and select alternatives for each single one. Maximum processing requirements, bearing the possibility of compromise in mind. The most basic end-use properties.

An acceptable shade that could replace the current shade.

In the color matching process, it is worthwhile considering the following parameters:

Chromacity: achieved by organic pigments.

Opacity: achieved by inorganic pigments or TiO2.

Shading: organic or inorganic pigments that maintain the required performance.

Realize the need get to know the alternative

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Selection of alternatives - color positioning yellows

K 1070 K 1210

K 13201) K 14151)
K 1500 K 1420 K 17401) K 1841 K 1760

Lead chromate pigments Organic pigments Inorganic pigments

Increasing chroma C*

K 0990 FP

K 1300 K 1410 K 1310

K 1700

K 1120 FG

Mid shade PY34

K 2060 K 2070

Green shade PY34

Red shade PY34

K 1011

K 2001

Green shade
Color positioning according to 1/3 ISD in PVC.

Yellow

Red shade

1): Diarylide pigments should not be processed at temperatures above 200C. See general recommendations in ETAD information bulletin N 2.

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Selection of alternatives - color positioning oranges and reds

K 2920
K 29251) K 2960 K 3690 K 2890 K 3840
PR 104

Lead chromate pigments Organic pigments Inorganic pigments

Increasing chroma C*

K 3845 K 3845 LW
K 4060 FP

K 2430

Yellow shade
Color positioning according to 1/3 ISD in PVC.

Orange

Red

Red / blue shade

1): Diarylide pigments should not be processed at temperatures above 200C. See general recommendations in ETAD information bulletin N 2.

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Selection of alternatives - BASF Selection Guide

BASF selection guide is split into:

Polymer groups: PVC, polyolefin and polyamide.

Products for dispersion-critical applications.

For PVC and polyolefin.

Further split by performance level. Top performance - Applications for longest life outdoors.
PVC: roofing, siding, tarpaulins, decorative films for cars and advertisement light boxes.

PO: crates, shading net.

High performance - Applications for longest life indoors and specific outdoor end products.
PVC: higher quality flooring, decorative films for cars and advertisement light boxes. PO: crates, shading net.
1

Mid performance: indoor applications and items exposed to weather for short periods.
Pipes (storage time), fairly high quality packaging, standard flooring, furniture films and household machines.

Good enough performance/ cost driven: short lifetime applications.

Industrial and non-food packaging, self decorative films and low cost flooring.
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Chain of requirements
By OEM end-use By drivers & end-user EH&S Recycling requirements

By processing requirements Injection molding Heat resistance By color effect Warping Yellow Blow-molding Orange Extrusion Red Roto-molding Magenta Violet Blue, Green Transparent Opaque

Carpets
Pipes Yogurt cups Toys.. Outdoor use

Brand owners lists

Halogen free

Indoor use

By substrate

PE PP PVC

EP

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BASF Selection guide

Only those pigments were selected, which offer within the before mentioned areas the lowest cost at acceptable performance. To define these products, following color matching exercises were done:
A) Matching the shade of lead chromates Standard: 2% lead chromate Polymer: f-PVC Thickness: 0.4 mm Opacity: 1) Similar to the standard 2) Achieving highest transparency

B) Matching different yellow and orange RAL shades RAL (yellow): 1003, 1007, 1023, 1034 RAL (orange): 2000, 2004, 2010, 2012 Standard: RAL shades based on lead chromates formulation Polymer: HD-PE Thickness: 1.25 mm Opacity: Similar to the standard

Internal Use Only

Recipes that match shades with consideration of economics & Performance

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Cost saving by transparency - BASF selection guide: PVC

Lead chromates pigments are classified as high opaque.
Lead chromates formulations are develop for cost/performance reasons rather than opacity. Opacity given by lead chromate is not always a must Achieving similar opacity with lead free pigments is cost driver

Define highest achievable transparency to reduce costs

e.g. target: 2% Sicomin Yellow K 1922 in f-PVC Good enough level

Similar opacity 2.00% Paliotol Yellow K 1420 0.15% Paliotol Yellow K 1760 FP 0.50% TiO2 Cost factor: High

Highest transparency 0.085% Cromophtal Yellow K 1410 0.100% Paliotol Yellow K 1841 Cost factor: Low.

Create value with optimized cost/performance

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Selection of alternatives
- BASF selection guide: Examples (PO)
Selection guide by pigment shade area

Performance level
Top performance

Green shade yellows Cromophtal Y. K 0990 FP Sicotan Y. K 1011 Sicopal Y. K 1120 FG

Mid shade yellows Cromophtal Y. K 1310

Red shade yellows Sicotan Y. K 2001 Irgazin Y. K 20602)

Oranges and Reds Sicopal O. K 2430 Irgazin O. K 2890 Irgazin Red K 3845 LW

High performance

Sicotan Y. K 1011 Cromophtal Y. K 1210

Cromophtal Y. K 1500

Sicotan Y. K 2001 Irgazin Y. L 20602)

Sicopal O. K 2430 Irgazin O. K 2890 Irgazin Red K 38402)

Mid performance (Processing temp. > 200C)

Sicotan Y. K 1011 Paliotol Y. K 1070 Cromophtal Y. 2GF

Cromophtal Y. K 1410 Paliotol Y. K 1420 Paliotol Y. K 1700

Paliotol Y. K 1760 Paliotol Y. K 1841 Sicotan Y. K 2001

Sicopal O. K 2430 Cromophtal O. K 2960 Irgazin Red K 38402)

Good enough performance/ Cost driven (Processing temp. < 200C)

Sicotan Y. K 1011 Paliotol Y. K 1070 Irgalite Y. K 13201)

Irgalite Y. K 14151) Paliotol Y. K 1420

Irgalite Y. K 17401) Sicotan Y. K 2001

Sicopal O. K 2430 Paliotol O. K 2920 Irgalite O. K 29251) Irgalite Red K 3690 Irgalite Red K 4060 FP

1): Diarylide pigments should not be processed at temperatures above 200C. See general recommendations in ETAD information bulletin N 2. 2): Low warping solutions are available: Eupolen PE Y. 20-0501 and Irgazin Red K 3840 LW.

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Selection of alternatives
- BASF selection guide: Examples (PO)
Selection guide by RAL shade
Performance level RAL 1023 Traffic Yellow Irgazin Y. K 20602) Sicotan Y. K 1010 Cromophtal Y. K 1500 FP Eupolen Y. 11-5501 C/R * RAL 1003 Signal Yellow C/R * RAL 1007 Chrome Yellow C/R * RAL 1034 Pastel Yellow C/R *

Long lasting Outdoor

Sicopal Y. K 1120 FG +++

Irgazin Y. K 20602)
Sicopal Y. K 1120 Cromophtal Y. K 1500 Irgazin Y. K 20602) Paliotol Y. K 1420 Paliotol Y. K 1841

++++ Irgazin Y. K 20602) + Sicopal Y. K 1120 FG

++++ Irgazin Y. K 20602) Sicopal Y. K 1120 FG

+++++

Cromophtal Y. K 0990
Irgazin R. K 3845 LW

+++++

Seasonal outdoor & Long lasting indoor Indoor

+++

+++++

Cromophtal Y. K 1500 FP Irgazin R. K 38402) Paliotol Y. K 1841

+++

++

Paliotol Y. K 1841

++

Paliotol Y. K 1760FP

Irgazin R. K 38402)

Indoor / Diarylide pigments

Irgalite Y. K 14151) Irgalite Y. K 17401)

Irgalite Y. K 14151) Irgalite O. K 29251)

Irgalite Y. K 17401) Irgalite O. K 29251)

Irgalite Y. K 1740 Irgalite O. K 29251)

C/R : Cost Ratio. - Almost similar to formulation based on Lead Chromate +++++ Very High 1): Diarylide pigments should not be processed at temperatures above 200C. See general recommendations in ETAD information bulletin N 2. 2): Low warping solutions are available: Eupolen PE Y. 20-0501 and Irgazin Red K 3840 LW.

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Selection of alternatives
- BASF selection guide
Dispersion Critical Applications
Certain applications, e.g. thin film and fibers, require excellent dispersion properties.
Cromophtal Yellow K 0990 FP Cromophtal Yellow K 1210 FP Cromophtal Yellow K 1500 FP

Polyamide Applications
Alternatives are available, but be aware of limitations:
Sicotan Yellow K 1011 Sicopal Yellow K 1160 FG Cromophtal Yellow K 1310 Paliotol Yellow K 1700 Paliotol Yellow K 1760 Paliotol Yellow K 1800 Sicotan Yellow K 2001 Sicopal Orange K 2430 Paliogen Red K 3580 Cromophtal Red K 3830 Paliogen Red K 3911
: Suitable : Potential

Paliotol Yellow K 1760 FP

Paliotol Yellow K 1841 FP

Irgazin Yellow K 2060 FP

Certified quality from BASF

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Need for lead free non-diarylide pigment

Chemistry landscape (in red shade yellow pigments)

Megatrends
Plastic value chain willing to adopt good enough solutions Continued pressure on use of diarylide pigments

HPP organic: High coloring costs in relation to high performance Diarylides: Very strong and most cost effective pigments to formulate with after Lead chromes
Inorganic (Pb): Excellent combination of chroma, opacity and coloring costs. Inorganic (CICP): Titanates are opaque but weak and with low Chroma.

Ban the use of heavy metal containing pigments

Drivers are repeated increase of RM costs and potential for optimizing cost.

Take the initiative and achieve competitive advantage.

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Make the world a better place

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