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Plasticisers: An Update
David Cadogan
Plasttekniske Dager
Oslo, 8-9 November 2006
Outline
ECPI
Plasticiser requirements
Are phthalates a threat to human health
Legislative actions
– Classification and labelling
– Risk assessments
– Toys, food contact materials, medical devices
– Reach
Market trends
Summary
2
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 trade organisations in USA and Japan
3
Plasticiser requirements
Compatible with PVC
Efficient
Ease of processing
Low volatility
Low migration/extraction
Flexibility at low temperatures
High temperature performance
Electrical resistance
4
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
C8 – C10 alcohols
C11-C13 alcohols
>80% linear
: Lower viscosity, faster processing
: General purpose
: High temperature performance
: Better low / high temperature performance
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93% of Plasticisers are Phthalates
More polar groups – Increased compatibility with PVC and easier
processing
BBP – Fast processing and stain resistance
BBP
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Are phthalates a threat to human health?
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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, hypolipidaemic drugs and other chemicals cause tumours in
rodents by peroxisome proliferation (PP)
No PP or liver damage in monkeys fed DEHP and DINP
No PP or liver damage in humans taking hypolipidaemic drugs
No DEHP induced liver tumours in mice lacking PP receptor
2000 - IARC Reclassified DEHP - Phthalate induced liver cancer in
rats and mice is not relevant to humans
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Potential Health Impact - Reproductive Effects
High levels of some phthalates produce testicular atrophy 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?
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Adverse Effects on Human Health
The facts are:
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
Adverse effects not seen in non-human primates
However - There are now two studies claiming to see effects in humans
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Baby Boys Feminised by Prenatal Phthalate Exposure - Claims
Swan et al. (August 2005) measured Anogenital Index (AGI) in 85 boys
aged between 2 and 36 months. (AGI = AGD / Weight).
Smaller AGI in boys said to correlate with higher levels of metabolites of
DEP, DBP, DIBP and BBP in mothers urine during pregnancy
AGI is smaller in females than in males hence these phthalates are said
to have a feminising effect
Highly publicised – press conference more important than peer review.
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Prenatal Phthalates Feminise Baby Boys – The Facts
Inadequate measurement of maternal phthalate exposure
Only one urine sample taken during pregnancy
Studies by Hauser et al (2004) and Hoppin et al (2002) indicate that
repeated urine measurements are necessary to determine exposure
Concerns re measurement of AGD in boys
Poor planning. AGD changes rapidly with age but they measured at ages
ranging from 2 – 36 months. Hence needed extensive regression analysis
The only other study (Salazar-Martinez et al, 2004) was systematic - 45
boys measured at 6 hours old. No regression needed – apparently less
variation in AGD / weight
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Prenatal Phthalates Feminise Baby Boys – The Facts
Authors attempt to make case stronger than it is
Independent statisticians find the conclusions are unsound
US National Toxicology Programme panel of 11 toxicologists have
concluded that the findings are not reliable
No correlation between AGI and primary metabolite of DEHP in mother’s
urine but weak correlation with the level of secondary metabolites - not
logical
Strong correlation with MEP in urine – contrary to many other studies on
DEP
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Phthalates in Breast Milk Effect Baby Boys - Claims
Main et al. (February 2006) measured levels of phthalate monoesters in
breast milk of 130 mothers of baby boys at 1-3 months postnatally.
Subjects selected so that approximately half of the boys had
undescended testes.
No correlation found between undescended testes and monoesters in
breast milk – main aim of the study but gets little mention in the
report
Measured levels of reproductive hormones in boys at three months and
investigated link with levels of phthalate monoesters in breast milk.
A link is proposed between levels of some phthalate metabolites in breast
milk and some hormone levels in male offspring
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Phthalates in Breast Milk Effect Baby Boys – The Facts
Statistical treatment of data and interpretation of results questioned
Independent statisticians agree that there is no real correlation.
The authors discount results which do not fit their hypothesis as being
“random findings”
The lack of a link between MEHP and hormone levels is said to be due
to the “limited number of samples in the study”
Study rejected by EU Member States Experts in DEHP Risk Assessment
US Expert Panel on Human Reproduction believes that some hormone
measurements are not relevant and breast milk samples are most likely
contaminated
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Legislative Actions
Classification and labelling of dangerous substances
Existing substances legislation – Risk assessment and management
Toys and childcare articles
Food contact materials
Medical devices
REACH
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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 articles
Aim – To ensure safe handling and use in the workplace
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Classification and Labelling
DMP
DEP
DPrP
DIBP SCL = 25%
DBP
DPP
BBP
DIHP
DEHP
711P (Branched)
DINP
DIDP
79P (Linear)
911P (Linear)
Backbone
1
2
3
3
4
4-5
4-7
5-6
6
5-9
7-8
8-9
7-9
9 - 11
Fertility
None
None
None
Cat 3
Cat 3
Cat 2
Cat 3
None
Cat 2
Cat 3
None
None
None
None
Developmental
None
None
None
Cat 2
Cat 2
Cat 2
Cat 2
Cat 2
Cat 2
Cat 2
None
None
None
None
Existing Substances Legislation
Council Regulation EEC / 793 / 93 on the evaluation and control of the
risks of existing substances
To properly assess the risks imparted by all chemicals
To both humans and the environment
Margin of Safety (MOS) = NOAEL / Exposure
MOS > 100 = No Risk
To identify risk management requirements if necessary and implement a
Risk Reduction Strategy
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DBP, DINP, DIDP Risk Assessments / Reduction
Risk Assessments and Risk Reduction Strategies published in Official
Journal on 13 April 2006
Human health risks:
DBP – No consumer risks including cosmetics. Risk to workers assuming
worst case exposure – OEL to be implemented
DIDP – Theoretical risks for children via toys – Toy legislation
DINP – No risks in any current use – Toy legislation due to difference of
opinion between RAR and CSTEE
Environmental risks:
DBP – Possible risk to vegetation near some processing plants - Extra
monitoring data on exhaust air
DINP and DIDP – No risks
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DINP & DIDP Risk Assessments / Risk Reduction
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
Large shift in consumption to DINP and DIDP
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BBP & DEHP Risk Assessments / Risk Reduction
Risk assessments to be completed via “written procedure”
during Q4 2006. Publication in 2006 / 2007
Human health risks:
BBP – few, if any, risks anticipated – Consumption falling rapidly
DEHP
Workers – OEL to be defined and implemented
Children via toys – New legislation
Haemodialysis and long term transfusion in children / neonates
- Requested opinion of expert medical committee
Possibly children living near some processing plants – Agree
Marketing and Use Directive to control DEHP emissions
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Risk Assessments / Risk Reduction
Environmental risks:
BBP – Possible risk to water and sediment near processing plants - Fish
study and processing plant emission data
DEHP –Risks only seen for default emission levels from hypothetical
plants. No risks when using real emission data which are 1000 times
lower.
General population via the environment - Kemi wanted to ban DEHP in all
outdoor applications. Commission not convinced – no risk identified.
Biomonitoring more than 3.000 people - shows no risks to man at
regional level (MOS range from 280 to 1700)
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Legislative Actions - Toys and childcare articles
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Toys and Childcare Articles
Permanent measures published in the Official Journal on 27 December
2005
• DBP, BBP and DEHP banned in all toys and childcare articles
• DINP, DIDP and DNOP banned in toys and childcare articles which
can be put in the mouth
• National legislation to be enacted from 16 January 2007
• Entirely political decision ignoring science based risk assessments
A range of alternative plasticisers available – citrates, etc.
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Legislative Actions – Food contact materials
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Food Contact Materials
New legislation is expected to come into force in the EU during Q4 2006
EFSA Scientific Panel has re-examined the phthalate toxicity data and
published TDI values.
Concluded that phthalates may be used in a variety of repeat and single
use food contact applications
DEHA and polymeric plasticisers will continue to be used in a wide range
of food contact applications, especially clingfilm
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Flexible PVC in medical applications
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Medical Applications
DEHP Risk Assessment identifies risks to patients (MOS < 100) via :
• Long term haemodialysis (adults)
• Transfusions (neonates)
• Long term blood transfusion (children) (Lowest MOS via IV = 800)
It is possible that these three applications will move from DEHP to
alternatives such as ATBC, DINCH, trimellitates, acetylated glycerol
esters or polymeric plasticisers.
However this sector is conservative and reluctant to change away from
plasticisers which have given no adverse effects in patients
Threats from activists (HCWH) and from other polymers continue but it is
difficult to match the cost / performance characteristics of PVC
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Medical Applications
SCMPMD Opinion of September 2002 concluded that no specific
recommendation could be made to limit the use of DEHP
We must await the Opinion of the new Scientific Committee on Emerging
and Newly Identified Health Risks (SCENIHR) – February 2006
However the attacks continue:
EU Parliament Environment Committee (w/c 2nd October) agreed an
amendment to the Medical Devices Directive prohibiting the use of CMR
substances in medical devices. This still has to be voted on in plenary
Many drugs are CMR but are used on a risk/benefit basis
This amendment is based on hazard – there may be little exposure and
hence no risk
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Phthalate Alternatives Confer Special Properties
Adipates – Low temperature flexibility - food and medical
Polyesters – Low migration into oil, etc - food and medical
Trimellitates – High temperature cable sheathing
Citrates – PVdC film, some medical – Some adverse human reactions
Benzoates – Easy processing like BBP
Phosphates – Fire resistance
Alkyl sulphonates – Easy processing, weather resistance
DINCH – Possible use in medical and food contact – EFSA approval
Acetylated glycerol esters – Food contact
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REACH – Registration, Evaluation and Authorisation of Chemicals
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Impact of REACH on Plasticisers
The commonly used plasticisers are data-rich and have been subjected
to various risk assessments so no problems regarding registration.
CMR substances will be subject to authorisation to allow them to be used
in each application.
We have the risk assessment data but will it be accepted or will
substitution be demanded ?
Some Member States may propose that even those phthalates which are
not classified as CMR should be subject to authorisation because they
give rise to an “equivalent level of concern”
Environment Committee (10th October) voted to increase pressure for
substitution and reduce level of scientific evidence needed to prove
that a substance is of “equivalent concern”
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Source: ECPI, 2006
2005
2004
2003
2002
2001
2000
1999
1998
1997
1996
1995
1994
1993
1992
1991
1990
1989
1988
1987
1986
1985
1984
1983
1982
1981
1980
1979
Western Europe Plasticiser Consumption
(‘000s of tons)
1200
1000
800
600
400
200
0
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European Plasticiser Consumption - Trends
Other
Plasticisers
8%
Other
Phthalates
15%
1999
DINP/DIDP
35%
DEHP
42%
2005
Other
Phthalates
12%
Other
Plasticisers
7%
DEHP
21%
Source: ECPI, 2006
DINP/DIDP
60%
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Plasticisers – The Way Forward
The family of phthalates satisfy the performance, health and safety
requirements of the vast majority of applications.
Classification, labelling and risk assessment has resulted in a move to
DINP and DIDP and a decrease in DEHP, DBP and BBP consumption
Alternatives to phthalates already exist or are being developed for certain
applications
Food contact materials, medical devices, toys and childcare articles
• Low migrating plasticisers – polymerics and trimellitates
• Lower animal toxicity – adipates, citrates, terephthalates, DINCH,
acetylated glycerol esters
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Summary
Phthalates and speciality esters meet the needs of all PVC applications
Increase in DINP and DIDP use due to positive risk assessments
Decrease in DEHP, DBP and BBP due to Hazard Classification
Health effects not seen in primates - only in rodent studies
No human cancer concern. Investigating relevance to humans of rodent
reproductive effects
High profile human toxicological studies are not based on sound science
Biomonitoring data very helpful in risk assessment and risk reduction
There will be moves to new plasticisers due to new legislation and
concerns regarding toys, food contact and medical devices
There is still a very strong future for flexible PVC
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