New developments in anti-skinning and metal carboxylate technologies for oxidatively dried alkyd based coatings as an answer to the new legislative challenges. Western Coatings Symposium Las Vegas Oct 25-28, 2015 Stefan Bankov

THE DEVELOPMENT OF NEW OXIME FREE ANTI-SKINNING TECHNOLOGY TO WORK IN BOTH COBALT AND DRICAT ® 2700F SERIES DRIED COATINGS

Agenda Oxime based anti-skinning agents Legislation Non-oxime previous developments Dura’s development of new oxime free anti-skinning agents Summary and conclusions

Agenda Oxime based anti-skinning agents Legislation Non-oxime previous developments Dura’s development of new oxime free anti-skinning agents Summary and conclusions

Anti-skinning Agents - Oximes A range of oximes - available in the market place. Mode of action – complexation through the oxime group. Applicability varies due to the differences in evaporation rate. MEKO (methyl ethyl ketoxime) - the most common material used.

Agenda Oxime based anti-skinning agents Legislation Non-oxime previous developments Dura’s development of new oxime free anti-skinning agents Summary and conclusions

Legislation (I) MEKO was included in the Community Rolling Action Plan (CoRAP) in 2013 The tentative plan is to update the classification of MEKO as: –Carc. 1B, H350 –Acute Tox. 3, H301; –Acute Tox. 4, H312; Skin Sens. 1B, H317; STOT SE 3, H336 –Eye Dam. 1, H318 Date for intention:

Legislation (II) Reclassification as Carcinogen 1B, H350, will imply a generic restriction according to entry 28 of Annex XVII of the REACH Regulation which will affect sales to the general public of MEKO as a substance, as a constituent of other substances or in mixtures. The concentration of MEKO in coatings may exceed the generic concentration limits of ingredients of a mixture classified as carcinogen that trigger classification of the mixture according to the CLP Regulation. It is expected that a classification of MEKO as carcinogen 1B, H350, will lead to changes in consumer uses that may result in control of risks.

Agenda Oxime based anti-skinning agents Legislation Non-oxime previous developments Dura’s development of new oxime free anti-skinning agents Summary and conclusions

Non-oximes – Previous Developments Materials that have been extensively evaluated - Phenolics - Amines - Quinones and hydroquinones Work by complexing the primary drier

Non-oximes - Pros and Cons Pros They are effective as blocking / anti- skinning agents Wide range of possible variants Cons Non-evaporating - remain in the coating Retard drying time Can have unpleasant odour Can increase yellowing Difficult to work with – low dosage rates

Agenda Oxime based anti-skinning agents Legislation Non-oxime previous developments Dura’s development of new oxime free anti-skinning agents Summary and conclusions

Dura’s New Developments DriCAT ® 216 and DriCAT ® 232 To be used with cobalt and DriCAT ® 2700F series technology. DriCAT ® 2516 and DriCAT ® 2532 Combined directly with DriCAT ® 2700F series technology to maximise the performance into one easy to use product.

DriCAT ® 216 and 232 They complex the primary driers: Co, Mn, Fe Starting point recommendations are calculated depending on: -which and how much primary metal -which of the anti-skinning agents is used.

Working with Cobalt Example: 1000kg of a coating at 50% resin solids using Cobalt at 0.05% metal on resin solids % Resin solids x % Co metal on resin solids x batch size x = Addition of DriCAT ® 232 % Resin solids x % Co metal on resin solids x batch size x = Addition of DriCAT ® % x 0.05% x 1000 x = 5.59kg DriCAT ® % x 0.05% x 1000 x = 4.91kg DriCAT ® 216 Important factors for the calculations

Evaluations Commercially available paints without the driers and anti-skinning agents. Anti-skinning tests carried out in open and closed can – 2/3 full. All tests compared to the current standard drier and anti-skin combination used for the paint in use. Drying tests run on drying recorder.

Example

Working with Manganese* Example: 1000kg of a coating at 50% resin solids using Manganese at 0.05% metal on resin solids % Resin solids x % Mn metal on resin solids x batch size x = Addition of DriCAT ® 232 % Resin solids x % Mn metal on resin solids x batch size x = Addition of DriCAT ® % x 0.05% x 1000 x = 4.50kg DriCAT ® % x 0.05% x 1000 x = 3.95kg DriCAT ® 216 * For use with highly active manganese complexes we recommend DriCAT ® 2532 and 2516 Important factors for the calculations

DriCAT ® 2516 and DriCAT ® 2532 Why DriCAT ® 2516 and DriCAT ® 2532 ? –Ratio metal / amount of the new anti-skins is very important –Addition rates of the new anti-skins in a production environment could lead to errors of loading when working with Dura’s DriCAT ® 2700F series products. Incorporation of the new anti-skinning agents into Dura’s very high activity DriCAT ® 2700F series technology

DriCAT ® 2516 and Advantages Eliminate the requirement for: –Cobalt carboxylates –Oxime based anti-skinning agents. Do not impart a green coloration to the wet coating. Superior initial and long term color performance, especially in the reduction of dark yellowing of whites.

Cobalt Carcinogenicity Currently, there is no grouping paradigm for cancer. In the absence of any data or indication that two groups of cobalt substances exist (group 1 – Carc 1B, group 2 – NOT Carcinogenic), it is possible that an approach will be to assume carcinogenicity for any substance containing cobalt. The CoRC are attempting to show that there are a group of “biologically inert” cobalt compounds.

Initial Guidance Anti-skinning agent is removed from the formulation. Cobalt is replaced by DriCAT ® 2516 or 2532 by following the guidance provided. Adjustments to the co-driers are made to maximise the performance.

Example

Maximising Performance Achieving maximum performance is about finding the correct balance of DriCAT ® 2516 or 2532 with the co-driers. BALANCE IS THE KEY

Agenda Oxime based anti-skinning agents Legislation Non-oxime previous developments Dura’s development of new oxime free anti-skinning agents Summary and conclusions

Summary and Conclusions DriCAT ® 216 and DriCAT ® developed as oxime free anti-skinning agents to work with any primary drier. DriCAT ® 2516 and DriCAT ® developed as combined all-in-one cobalt and oxime free technology. Guidance available to provide starting point recommendations.

Thank you Any Questions?