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Advances in the chemistry and technologies of organic pigments and additives for plastics: From appearance to functionality
Dr. Bansi L. Kaul, CEO
MCA Technologies GmbH 4105 Biel-Benken, Switzerland

It is all about: "Chemistry-our life, our future”

About us



 Co-sponsors and table-top exhibitors at this conference. Brochures of our products and services available at the table top exhibition.  Conducting/Supporting R&D & business development in environmentally friendly technologies and products; Today’s presentation is a demonstration of that.  Bridging gaps between science and technology to make lab curiosities as commercial realities.

Plastic processing



Besides the equipment, plastic processing requires not only the virgin polymer and anti-oxidations and processing aids but also: • Colorants-Pigments & polymer soluble dyes • Functional and effect additives such as fire retardants • Anti-aging, light-stabilizers & UV absorbs For the ease of incorporation of many of these ingredients into the polymer during processing, masterbatch form offers an ideal choice and opportunity

) and consumer conscience . packaging and toys regulations & requirements Recycling and cradle-to-grave concerns All-in-one masterbatches (for cost effectiveness and competitive edge) Regulations(REACH etc.Recent issues and opportunities for masterbatch industry M C A TECHNOLOGIES GmbH (Switzerland) Diarylide replacements Heavy-metal pigments replacements New Pigment Technologies (DPP Pigments) Halogen-free and cost-effective fire/flame retardants Food contact.

Pigment Oranges 13 & 34 R1 H2N R2 R2 R1 NH2 Only the tip of the ice-berg: Many azo pigments can also undergo similar thermal decomposition in plastics. generating toxic aromatic amines.e. Hence.e. . in the future the masterbatches. Pigment Yellows 17 & 83 I. and not the pigments. will have to be tested for the aromatic amine content.Thermal Decomposition of Benzidine/Diarylide Pigments in Plastics M C A TECHNOLOGIES GmbH (Switzerland) I.

Replacements of Diarylide Yellows in Plastics (middle-class) O O O O H N O N O H N N H O CH3 N N O O M C A TECHNOLOGIES GmbH (Switzerland) O H O O Pigment Yellow 155 (green shade) (Cost.& value-effective of most replacements) O H H N O N H N O H CH3 N N X N N H3C H O N O H H N O N H Pigment Yellow 139 (red shade) (Not compatible with HALS) Pigment Yellow 180 (middle shade) .

Pyrazolone Azo-Toner (Metal-Salt) Pigments R1 R5 N N O M R4 ++ N H N R2 R3 M C A TECHNOLOGIES GmbH (Switzerland) Pigment Yellow 183 Pigment Yellow 191 The new Basf Yellow (?) (Masterbatch 2011) For better heat stability .

green shade High colour strength Pigment Yellow 181. red shade Poor colour strength Pigment Yellow 110. red shade Poor colour strength .High-Performance Cadmium Yellows Replacements R4 R3 H M C A TECHNOLOGIES GmbH (Switzerland) R2 R1 N N H3C O N O H H N O N H Pigment Yellow 138.

Cadmium Orange/Red Replacements HO H N O N H CH3 O H N N N N H O M C A TECHNOLOGIES GmbH (Switzerland) H N O N H N Ni N O O Pigment Orange 64. yellow shade Pigment Orange 68. red shade One of the most stable of all organic pigments in engineering polymers (ABS. polyamides/nylons ) .

Disazo Condensation Pigments Cl O R5 N R3 R4 R6 R5 R4 R3 N N OH H N O R2 R1 HO H N O R4 R3 N N R6 R5 H O N N H O N H R2 R1 H N O CH3 H O H N N Cl N O R5 R3 R4 M C A TECHNOLOGIES GmbH (Switzerland) Pigment Yellow 93 Pigment Yellow 95 Pigment Red 144 Pigment Red 166 Pigment Red 214 Pigment Red 242 .

Red Azo-condensation Pigments M C A TECHNOLOGIES GmbH (Switzerland) R=CF3: Pigment Red 242 ( Scarlet) R=Cl: Pigment Red 214 (Blue Red) The most heat stable and lightfast of all azocondensation pigments .

BON-Azo Benzamidazolone Pigments R2 R3 R1 N N OH H N O N H H N O M C A TECHNOLOGIES GmbH (Switzerland) Pigment Red 176 Pigment Red 185 Pigment Brown 25 .

9-Dimethyl: Pigment Red 122 (Magenta) 2.9-Dichloro: Pigment Red 202 (For nylons) Perylene Pigment Red 149 .Quinacridone/Perylene Pigments 11 10 9 8 O H N O 1 2 N H 3 4 M C A TECHNOLOGIES GmbH (Switzerland) Quinacridone 2.

Dioxazine Violet M C A TECHNOLOGIES GmbH (Switzerland) Pigment Violet 23 One of the most cost effective and widely used organic pigment .

Phthalocyanine Pigments M C A TECHNOLOGIES GmbH (Switzerland) N X N N N Cu N N N N Pigment Blue 15 Pigment Green 7 Universal workhorse pigments .

Polymer Soluble Pigment Yellow 192 for Polyamides/Nylons M C A TECHNOLOGIES GmbH (Switzerland) Pigment Yellow 192 A polymer soluble dye with performance characteristics of a pigment in nylons. (like Pigment Yellow 147 in polyester ) .

Generally not as stable as azo-condensation pigments in plastics . but not for engineering polymers . styrenics.DPP Pigments M C A TECHNOLOGIES GmbH (Switzerland) O HN NH O Pigment Red 254 Pigment Red 264 Most successful of all recently introduced organic pigments suitable for polyolefins and PVC .

Green-Technologies of Pigments and additives M C A TECHNOLOGIES GmbH (Switzerland) Example: • MCA solvent-free greentechnology of DPP pigments .

State-of-the-art versus MCA• Solvent-free DPP Pigment Technology State-of-the-art synthesis M C A TECHNOLOGIES GmbH (Switzerland) MCAT synthesis Reactants Reactants 3-5 times solvent .

MCA• DPP Pigments Green Technology Less energy demand Less chemicals demand Less safety risk Less waste Higher productivity Better quality Products (nano-particles) M C A TECHNOLOGIES GmbH (Switzerland) .

fire & flame retardants.Fire & Flame retardants M C A TECHNOLOGIES GmbH (Switzerland) • Although not always a burning topic at the most masterbatch conferences. dispersion technology here is a very critical factor. with almost 2 million tons annual consumption are the largest volume but the least developed and therefore the most challenging of all polymer additives • Fire Retardancy is not a choice but mostly a legal requirement –And hence a major opportunity • Considering the loadings required. both for performance and economy . compared to any other colorant or additive.

“Burning” issues of fire and flame retardants M C A TECHNOLOGIES GmbH (Switzerland) High loadings required Halogen + Peak heat release rate and smoke density Non-compatibility & reactivity .

Promising of all future FRTechnologies: M C A TECHNOLOGIES GmbH (Switzerland) Fire-barrier technology • In the event of fire formation of a spongy charbarrier at the fire point by so-called “self-immolation mechanism” Extinguishing the fire and preventing its proliferation Lower loadings with low heat of glow & almost no smoke • • Novel “MCA PPM Triazines . is now a recognized milestone of this technology . to be presented.

8 Molecular Weight: 2757.75.4 Elemental Analysis: .38 .MCA• PPM Triazine HF: Novel. polymeric. O. halogen-free & chemically mostly inert universal nitrogen synergist M C A TECHNOLOGIES GmbH (Switzerland) Chemical Formula: C126H212N61O11 Exact Mass: 2755. 7. H. 6. .

acid scavenger Phosphates & Phosphinates MCA‚ PPM Triazine HF Minerals N-Mineral-C-O Char formation Low melting or liquids incl. NOR Nanoclays /PTFE Char + Antiplastification Char: Carbon scavenger for less smoke and heat glow Bromine based .Universal synergist of FRs and co-synergists Primary FR Polyols Effect N-P-C-O char formation.

MCA‚ PPM Triazines: Suitability for polymers & resins Polyolefins M C A TECHNOLOGIES GmbH (Switzerland) PU/Epoxides MCA• PPM Triazines PC and its blends PES/PA (particularly GF) .

epoxides). polyamides by cross-amidation and with primary FRs (APP) by “Pre–intumescent” reaction ((in processing). and even polymers (such as polyesters by amidation. can undergo gradual dissociation in the presence of water in the polar polymer itself).e. based on melamine and/or its derivatives have limitations due to any or many of the following reasons: • • • Sublimation and mould deposits Blooming (particularly incompatibility in polyolefins) Reactivity: Self-condensation and tridimensional (dendrimer) reactivity towards the monomers (urethanes. Heat stability Water solubility Hydrolytic & thermal stability/corrosivity (i. Value-in-use: “Cheap” is not always “cheap” • • • • .Why MCA‚ PPM Triazines as nitrogen-synergists? M C A TECHNOLOGIES GmbH (Switzerland) PPM Triazines are particularly recommended where state-of-theart nitrogen synergists. Melamine polyphosphate: being rather a weak acid-base salt.

MCA‚ PPM Triazine HF-Ammonium polyphosphate combination: PPMT 765 (IS=intumescent system) M Polypropylene (Switzerland) 80% Polypropylene + 765 A 20% PPMT C TECHNOLOGIES GmbH Almost no burningV-0 & no smoke+. Camino ĕt. low heat release+ Sample PP PP+20% PPMT 765 (5% HF) t1 (S) t2 (s) - Dripping/Ignition of Cotton Yes No Time to dripping 6 (s) UL 94 Rating 70 No Rating 1 3 No dripping V-0 (++) Prof.: Politecnico di Torino Alessandria.ăl. Italy .

C.1 12 (V-0) V-0 ? V-2 V-0 ? * t2 not recorded due to total burnout in t1.MCA‚ PPM Triazine 765 + Co-synergist in PP PPM Triazine 765 % Flamestab NOR 116 % Decabromodiphenyl ethane % Antimony Trioxide PTFE % Total Burning time(t1+t2 s) > 260* UL 94 (1. 40 (V-0) V-2 0.1 15 15 1 15 1 M C A TECHNOLOGIES GmbH (Switzerland) 15 15 10 0 10 0 0. N.C.6mm/1.5 mm) N.: no classification .

6 mm) 54.5 0. ***Melapur 200 (BASF) Dr. *(Ultramid B3S).5 25 15 5 0 3 V-0 54.5 0.5 25 10 10 0 14 V-0/V-1 M C A TECHNOLOGIES GmbH (Switzerland) 59.5 0 21 V-1/V-2 54. Rudolf Pfaendner Fraunhofer-Institut Darmstadt .5 25 0 0 20 32 n.MCA‚ PPM Triazine HF & a phosphinate combination in glass-filled PA 6 Polyamide 6* Additives Glass fibers Exolit OP 1230** MCA‚ PPM Triazine HF Melamine polyphosphate*** Average burning time(s) UL 94 (1.c.5 0.5 25 7.5 0.** Clariant.5 7.

Taiwan. Also in China.202.924) *The “handprint” of the technology . Japan Patent granted in the USA (Patent No. 8.MCA• Proprietary volatile-organicsolvent-free technology* M C A TECHNOLOGIES GmbH (Switzerland) Suspension polymerisation in the presence of catalysts Examples: PVC made by suspension polymerisation PP made using Ziegler-Natta process Patent applications : “Polytriazinyl compounds as flame retardants and light stabilizers” European Patent application 2130854. India.

   . Such properties are perhaps more important than even the flame for fire fighting. and for rescue and escape. and thereby improve the quality of the plastic items and reduce the ultimate waste for environmental impact MCA‚ PPM Triazines should enable achieve halogen-free fire retardancy. and in many polymers. MCA‚ PPM Triazines should enable reduce the total loadings of many FR-systems. the total cost of fire retardancy & processing. Ease of incineration at the disposal stage is an environmental plus. particularly if combined with brominated or even halogen-free (phosphorous based) flame retardants associated with this problem. and therefore.Summary   M C A TECHNOLOGIES GmbH (Switzerland) MCA‚ PPM Triazines: Universal synergist of most fire/flame retardants. at a reasonable cost if and wherever required or desired MCA‚ PPM Triazines should enable reduce the peaak heat release rate (pHRR) & smoke density for better fire safety.

Pigment Yellow 192)  Better efficacy (low loadings) and environmentally friendly (from cradle to grave) fire retardants  Multi-functional additives Thank You . total insolubility and inertness under the polymer processing conditions  Polymer soluble colorants with the characteristics of pigments (Pigment Yellow 147 . fully meeting the definition of a pigment i.Future Outlook M C A TECHNOLOGIES GmbH (Switzerland)  Novel masterbatching technologies that are gentle both towards the carrier as well as the colorants and additives  Novel pigments.e.