The Current Plasticiser Situation in Europe

1. The Current Plasticiser Situation in Europe David Cadogan, ECPI Phthalates and new plasticisers for PVC Conference Copenhagen, Denmark 20 September 2007

2. Outline • ECPI • Is there a move away from phthalates – Why? • Are phthalates a threat to human health? • Legislation • The plasticisers of yesterday and today • The plasticisers of today and tomorrow - Alternatives to phthalates • Summary

3. ECPI • European Council for Plasticisers and Intermediates • A Sector Group of CEFIC – the European Chemical Industry Council • European producers of plasticisers, alcohols and acids • Sponsorship of scientific studies by independent experts • Provide users, legislators and other interested bodies with information on safety, health and the environment • Close liaison with equivalent organisations in USA and Japan

4. Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl CI CI Cl Cl O O O O PVC plus DEHP

5. 93% of Plasticisers are Phthalates • Phthalates have : • Optimum balance of polar / non-polar groups • Best all round performance / price ratio DEHP • Performance can be fine tuned by using appropriate alcohol C4 - C7 alcohol : Lower viscosity, faster processing C8 – C10 alcohols : General purpose C11-C13 alcohols : High temperature performance >80% linear : Better low / high temperature performance

6. Is there a move away from phthalates?..... Why? • Yes • There is move away from somephthalates • New plasticisers are being developed • Why? • Concern that some phthalates may be a threat to human health • Increasing legislation limiting the use of some phthalates • Need Speciality Plasticisers to meet changing performance requirements

7. Are phthalates a threat to human health?

8. Potential Health Impact - Carcinogenicity • 1982 – Liver tumours in rodents caused IARC to classify DEHP as “possibly carcinogenic to humans” 18 years of research showed : • Phthalates, drugs used to lower cholesterol levels and some other chemicals cause tumours in rodents by peroxisome proliferation (PP) • No effects in monkeys fed DEHP and DINP • No liver damage in humans taking cholesterol lowering drugs • 2000 - IARC Reclassified DEHP - Liver cancer caused by phthalates in rats and mice is not relevant to humans

9. Potential Health Impact - Reproductive Effects • High levels of some phthalates produce adverse effects in rodents • Little, if any, effects seen with DMP, DEP, DINP and DIDP • Levels can be defined at which no effects occur (NOAEL) • In general NOAELs are orders of magnitude higher than levels of exposure. Therefore no risk • Studies ongoing to identify the mechanism underlying the reproductive effects in rodents – are they relevant to humans?

10. Potential Health Impact - Structure / Activity Phthalate toxicity to rodents depends on number of carbon atoms in the alcohol backbone 1-3 C (DMP, DEP) Minimal 4-6 C (DBP, DEHP) Maximum > 7 C (DINP, DIDP) Minimal

11. Do Phthalates have Adverse Effects on Humans? • No evidence of any phthalate having an adverse effect on human health • 20 year follow-up study on 242 low birth weight individuals (high DEHP exposure in intensive care) showed no effects on male fertility • Adolescents exposed to DEHP via ECMO as neonates show no adverse effects on growth or sexual maturity • Adverse effects are only seen in rodent studies – not in non-human primates • The only studies claiming to see effects in humans are considered by independent epidemiologists and statisticians: • To be poorly designed • To use questionable statistical treatment of data and interpretation of results.

12. Legislative Actions and Expert Opinions • Classification and labelling of substances • Existing substances legislation – Risk assessment and management • Indoor Air • Norwegian proposed ban • Toys and childcare articles • Food contact materials • Medical devices

13. Classification and Labelling

14. Hazard - Classification and Labelling • Category 1 Substances known to cause effects in humans. Based on epidemiological data. • Category 2 Substances to be regarded as if they cause effects in humans. Based on clear evidence in animal studies. • Category 3 Substances causing concern for humans. Based on less convincing evidence in animal studies. Classification and labelling does not apply to flexible PVC articles Aim – To ensure safe handling and use in the workplace

15. Classification and Labelling Backbone Fertility Developmental DMP 1 None None DEP 2 None None DPrP 3 None None DIBP SCL = 25% 3 Cat 3 Cat 2 DBP 4 Cat 3 Cat 2 DPP 4 - 5 Cat 2 Cat 2 BBP 4 - 7 Cat 3 Cat 2 DIHP 5 - 6 None Cat 2 DEHP 6 Cat 2 Cat 2 711P (Branched) 5 - 9 Cat 3 Cat 2 DINP 7 - 8 None None DIDP 8 - 9 None None 79P (Linear) 7 - 9 None None 911P (Linear) 9 - 11 None None

16. Existing substances legislationRisk assessment and management

17. DINP & DIDP Risk Assessments / Risk Reduction • Risk Assessments published in Official Journal on 13 April 2006 • Two versatile high volume phthalates • Finally perceived as being “Risk Free” following revision of legislation for use in toys • For both health and environmental effects • Can be used in all applications except toys and childcare articles “which can be put in the mouth” • Not hazardous - not classified CMR or Dangerous to the Environment • Driving a large shift in consumption to DINP and DIDP

18. DEHP Risk Assessment / Risk Reduction • Anticipate publication in Q4, 2007 • Human Health • Workers inhalation exposure – Waiting for OEL to be identified. It will be enforced across the EU • Children via toys – New legislation in place • Haemodialysis in adults and long term transfusion in children / neonates – Awaiting opinion of expert Committee (SCENIHR) • Theoretical risk to children living near some processing plants – Marketing and Use Directive to control DEHP emissions

19. DEHP Risk Assessment / Risk Reduction • Environment • Emissions to water. No risk to aquatic organisms. Only possible risk is a theoretical one to predators eating fish. • DEHP is a “Priority Substance” under the Water Framework Directive and so must meet certain Environmental Quality Standards - These EQS stipulate the level allowed in water to manage these theoretical risks.

20. Phthalates in indoor air - Expert opinion

21. SCHER Opinion on Phthalates in Indoor Air • Opinion adopted by the Scientific Committee on Health and Environmental Risks (SCHER) on May 29th 2007 • “Based on the lack of mechanistic support and taking into account the low exposure level of phthalates by inhalation, SCHER does not find consistent scientific evidence which indicate that phthalates should be high concern chemicals in indoor air. • The RA report on DEHP (European Union Risk Assessment report, 2007) suggests that the MOSs from exposure in indoor air to reproductive effects, which are the basis for risk characterisation, remain large (over 200 for children, over 1000 for adults).”

22. Proposed Norwegian ban on 19 substances

23. Proposed Norwegian ban on DEHP in consumer products • Norway is proposing to ban a range of hazardous substances (including DEHP) in consumer products • “to limit the harmful effects on human health and the environment from consumer products, as well as to limit the content of hazardous substances in waste”. • It would be prohibited to produce, import, export or sell consumer products that contain more than 0.1% DEHP • Excludes construction materials for outdoor use

24. Response by EFTA and EU Commission • The EFTA Surveillance Authority reminds the Norwegian Government that under the Marketing and Use Directive the MS seeking to limit the use of a substance must : • Provide all the relevant health and environmental impact data on the substance and alternatives • Conduct an adequate risk assessment • The Commission points out that there is no need to exceed the measures defined by the DEHP RAR and being developed in the risk reduction strategy. Norway is invited to fully participate in the discussions

25. Legislative Actions - Toys and childcare articles

26. Toys and Childcare Articles Permanent measures published in the Official Journal on 27 December 2005 • DBP, BBP and DEHP restricted (0.1 wt%) in all toys and childcare articles • DINP, DIDP and DNOP restricted (0.1 wt%) in toys and childcare articles which can be put in the mouth • National legislation was enacted from 16 January 2007 • Entirely political decision ignoring science based risk assessments • Toys and childcare articles which can be put in the mouth are being produced with alternative plasticisers – citrates, DINCH, etc.

27. Food contact materials

28. Food Contact Materials Published in the Official Journal on 31st March 2007: • The amendment of Directive 2002/72 (Plastics materials intended to come into contact with food) and Directive 85/572 (Simulants to be used for migration testing). Published in the Official Journal on 3rd April 2007: • Commission Regulation laying down transitional migration limits for plasticisers in lid gaskets.

29. Food Contact Materials In practical terms the amendment of Directive 2002/72 will mean: Repeat Use Applications (tubes, conveyor belts, etc) • BBP, DINP and DIDP – all food types – meet SMLs based on full TDIs • DEHP – only aqueous foods – SML based on 50% TDI • DBP - only aqueous foods – SML based on 50% new TDI - too low Single Use Applications (cap seals, etc) • BBP, DINP and DIDP – aqueous only – SML based on full TDI • DBP and DEHP may not be used

30. Food Contact Materials Timetable • Manufacturers and importers have 14 months from adoption of the Directive before having to meet the requirements • Therefore DEHP can continue to be used in bottle caps for aqueous foods until April 2008 • Additives other than phthalates have until February 2009 to meet the requirements • Transitional migration limits for plasticisers in lid gaskets – Higher migration limits allowed for ESBO, citrates, polymerics, etc for 14 months to allow new formulations to be developed

31. Food Contact Materials Non-phthalates • DINCH included with no SML or application restrictions. • DEHA and polymerics already included Simulants to represent milk products • Distilled water to be replaced by 50% ethanol. Most likely excludes phthalates from milk tubing, etc. Conclusions • Biggest impact is on DEHP in bottle caps • Lower impact on other phthalates because already used mainly for non-fatty foods. Increased use of speciality plasticisers in lid gaskets.

32. Why use flexible PVC in medical devices?

33. Flexible PVC in Medical Applications - Benefits • Used successfully for more than 40 years • Flexible PVC containing DEHP is approved by European Pharmacopoeia for medical containers and tubes • Excellent biocompatibility and ease of processing • Wide variety of applications with significant benefits • Steam sterilisation • Low temperature storage • Gas permeability • Withstands centrifugation forces. No kinking

34. DEHP in Medical Applications - Risk Assessment • RAR states – Risk / benefit analysis is not taken into account • Conservative NOAEL = 4.8 mg/kg bw/day (oral) • Should use NOAEL based on IV studies • Risks to patients (MOS < 100) associated with exposure to DEHP via : • Long term haemodialysis (adults) • Transfusions (neonates) • Long term blood transfusion (children) (Lowest MOS via IV = 800) • There are no risks associated with : • Lifetime exposure to DEHP during infusions • Long term blood transfusion (adults)

35. Expert opinions on medical devices

36. SCMPMD, SCENIHR and UK MHRA Opinions • EU Scientific Committee on Medicinal Products and Medical Devices (SCMPMD) September 2002 • Opinion - Risk / benefit analysis is needed and no specific recommendations can be made to limit the use of DEHP or PVC • EU Scientific Committee on Emerging and Newly Identified Health Risks (SCENIHR) • July 2007 – Opinion expected on whether alternatives to PVC and DEHP should be used in certain applications. • UK Medicines and Healthcare Products Regulatory Agency (MHRA) conclude that no phase out or substitution of DEHP in medical devices should be considered until the SCENIHR has delivered its opinion.

37. Legislative position on medical devices

38. Legislative position • EU Parliament, Council and Commission came to a first reading agreement on 27 February 2007 (Did not wait for SCENIHR Opinion) • DEHP is not banned in medical devices • “Phthalate containing” label must be placed on device or packaging for all medical devices in contact with bodily fluids or medicines, where phthalates classified as CMR are used • Label to be defined by CEN • Medical device manufacturers to justify use of CMR phthalates in applications for children or pregnant women. • Increasing quantities of speciality plasticisers becoming available for certain medical applications

39. Plasticiser consumption trends

40. Western Europe Plasticiser Consumption (‘000s of tons) Source: ECPI, 2007

41. Plasticiser Consumption • Total plasticiser consumption relatively stable • A marked trend to less hazardous phthalates • DEHP replaced by DINP and DIDP • DBP being replaced by DIBP and others • BBP consumption diminishing and being replaced by benzoates • ECPI statistics not very sensitive to changes in non-phthalates usage

42. European Plasticiser Consumption - Trends 1999 2006 Source: ECPI, 2007

43. Alternatives to phthalates

44. Adipates • Confer good flexibility at low temperatures • Low plastisol viscosity • Approved for use in food contact applications • Relatively volatile • Limited compatibility with PVC • Rapid migration • Higher adipates usually regarded as 'secondary' plasticisers

45. Polyesters (Polymeric plasticisers) • Most commonly based on propyleneglycol and adipic acid • Used only where high resistance to migration (into oils, solvents, adhesives etc.) is a requirement. Hence used in some medical applications • Approved for use in materials in contact with food • Polyesters have very high viscosity which can make processing difficult • Confer poor low temperature flexibility

46. O O O O O O Trimellitates • Low volatility in high temperature cable compounds • Non-fogging automotive interior trim • Generally good balance of properties • Low migration hence some use in medical applications • Limited supply of trimellitic anhydride and its precursor pseudocumene

47. Citrates • Low tonnage products • The most important is acetyl tributyl citrate, ATBC • Has a variety of food contact approvals and is used in PVdC film • Process costs for citrate manufacture are relatively high • Used in limited medical applications but some adverse human reactions

48. Benzoates • Main commercial product is dipropyleneglycol dibenzoate • Competes with butyl benzyl phthalate • Speciality fast fusing stain-resistant plasticiser in vinyl flooring • Poor flexibility at low temperatures and relatively high volatility prevent general purpose use

49. Alkyl sulphonate esters • Used in some applications where their chemical stability (resistance to hydrolysis) is beneficial • Generally good all-round technical performance • Good PVC fusion characteristics • Single source • Large scale expansion in production likely to be feedstock constrained

50. Di-2-ethylhexyl terephthalate (DEHT) • Based on terephthalic acid (para) rather than phthalic anhydride (ortho) • Metabolised differently in rats • 2-generation reproduction study in rats – much lower potency than DEHP. Similar to higher phthalates, eg DINP • Plasticising performance similar to DEHP