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Study of the stability and reactivity of migrant migrant components from printing inks and adhesives, used in packaging materials of foodstuffs - MIGRINKT . Overview. Introduction PR FAVV-AFSCA 2009/01 MIGRINKT Overview 6 WP WP 1 (15th of March ) Today. Introduction : Migration.
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Study of the stability and reactivity of migrant migrant components from printing inks and adhesives, used in packaging materials of foodstuffs - MIGRINKT.
Overview • Introduction • PR FAVV-AFSCA 2009/01 • MIGRINKT • Overview 6 WP • WP 1 (15th of March) • Today
Introduction: Migration food • Classicalmigration (diffusion) • Via direct contact • Via gas phase • Unintentedpresence (set-off and residuesof technical aids) GMP food
Overview • Introduction • PR FAVV-AFSCA 2009/01 • MIGRINKT • Overview 6 WP • WP 1 (15th of March) • Today
PR FAVV-AFSCA 2009/01 • No harmonizedlegislation !!! • General list
PR FAVV-AFSCA 2009/01 –General list of compounds usedforinksandgluesmanufacture Swiss Ordinance on Food Contact materials 817.023.21 • 1stof April 2010 • Annex 1 (List I and II of EC Plastic Directive 2002/72/EC) and Annex 6 (List I-V) • Annex 6 lists 5 groups of substances (almost 6000 comp) • Monomers • Colorants • Solvents • Additives • Photoinitiators List A: evaluatedsubstances, sufficienttoxicity data (SML based on TDIvalue) List B: “unevaluated” substances, insufficienttoxicity data (10ppb or lowerdetection limit)
PR FAVV-AFSCA 2009/01 –General list of compounds usedforinksandglues manufacturing • All compounds listed in the Annex 6 of the Swiss Ordinance (Lists A and B) (5760 comp in total) • Missing substances listed in the Information letter to the Swiss Ordinance (218 compounds) • Compounds from Plastic Directive 2002/72/EC (Annex 1 of the Swiss Ordinance) not included in the Annex 6 of the Swiss Ordinance (65 compounds) • Compounds from FACET list not included in the Annex 6 of the Swiss Ordinance (54 compounds)
PR FAVV-AFSCA 2009/01 • General list Final list 6097 399 compounds • Final list risk ranking list: • MW • SML
MW < medianvalue (202 Da) low MW highest priority 104 compounds low SML 207 compounds high MW 103 compounds medianvalue (202 Da) MW < medianvalue (1 mg/kg food) SML £ middle priority 399 compounds MW medianvalue (184 Da) < medianvalue (1 mg/kg food) > SML low MW 96 compounds high SML high MW 192 compounds lowest priority 96 compounds MW < medianvalue (184 Da) PR FAVV-AFSCA 2009/01 – Final list Risk ranking list
MW < medianvalue (202 Da) low MW highest priority 104 compounds low SML 207 compounds high MW 103 compounds medianvalue (202 Da) MW < medianvalue (1 mg/kg food) SML £ middle priority 399 compounds MW medianvalue (184 Da) < medianvalue (1 mg/kg food) > SML low MW 96 compounds high SML high MW 192 compounds lowest priority 96 compounds MW < medianvalue (184 Da) PR FAVV-AFSCA 2009/01 – Final list Risk ranking list • This list includes: • 27 additives • 60 monomers • 2 solvents • 5 photoinitiators • 10 compounds from Plastic Directive
Overview • Introduction • PR FAVV-AFSCA 2009/01 • MIGRINKT • Overview 6 WP • WP 1 (15th of March) • Today
MIGRINKT – overview 6WP • WP 1: Study of literature concerning stability, reactivity and analyze methods of the most relevant migrants • WP 2, 3 & 4: Study of stabilityselected migrants in water and acetic acid (WP2), ethanol (WP3) and MPPO (WP4) • Not UV-activated compounds • UV-activated compounds
WP 2, 3 & 4 : Not UV-activated compounds 10 days/40°C 24h/reflux Light Dark Light Dark 100% recovery ? yes OK no Investigation differenttemperatures (20 – 60°C) and times (1 – 10 days)
WP 2, 3& 4 : UV-activated compounds UV-activation No UV-activation 10 days/40°C 24h/reflux 10 days/40°C 24h/reflux Light Dark Light Dark Light Dark Light Dark 100% recovery ? yes OK no Investigation differenttemperatures (20 – 60°C) and times (1 – 10 days)
MIGRINKT – overview 6WP • WP 1: Study of literature concerning stability, reactivity and analyze methods of the most relevant migrants • WP 2, 3 & 4: Study of stabilityselected migrants in water and acetic acid (WP2), ethanol (WP3) and MPPO (WP4) • WP 5: Validationkinetic models withpackaging film • WP 6: General coordinationand reports
MW < medianvalue (202 Da) low MW highest priority 104 compounds low SML 207 compounds high MW 103 compounds medianvalue (202 Da) MW < medianvalue (1 mg/kg food) SML £ middle priority 399 compounds MW medianvalue (184 Da) < medianvalue (1 mg/kg food) > SML low MW 96 compounds high SML high MW 192 compounds lowest priority 96 compounds MW < medianvalue (184 Da) MIGRINKT – WP1Risk ranking list FAVV
MIGRINKT – WP1Photoinitiators • High priority (5): Benzophenone 2-methylbenzophenone 3-methylbenzophenone 4-methylbenzophenone Ethyl-4-(dimethylamino)benzoate • Middle priority (7): Methyl-2-benzoylbenzoate 2-Isopropyl thioxanthone 4-Isopropyl thioxanthone 2-Benzyl-2-dimethylamino-4-morpholino butyrophenone 2-(4-Methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-1-butanon 2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl-2-methyl-2-propanone 1-(4-[(4-Benzoylphenyl)thio]phenyl)-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propan-1-one
MIGRINKT – WP1Photoinitiators • High priority (5): Benzophenone 2-methylbenzophenone – Type II 3-methylbenzophenone – Type II 4-methylbenzophenone – Type II Ethyl-4-(dimethylamino)benzoate – Type I and coinitiator • Middle priority (7): Methyl-2-benzoylbenzoate – Type II 2-Isopropyl thioxanthone – Type II 4-Isopropyl thioxanthone – Type II 2-Benzyl-2-dimethylamino-4-morpholino butyrophenone – Type I 2-(4-Methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-1-butanon 2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl-2-methyl-2-propanone – Type I 1-(4-[(4-Benzoylphenyl)thio]phenyl)-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propan-1-one – Type I
Overview • Introduction • PR FAVV-AFSCA 2009/01 • MIGRINKT • Overview 6 WP • WP 1 (15th of March) • Today: Questions
Are any of the selectedphotoinitiators (still) used in ink/glue-manufacturing? • High priority (5): Benzophenone 2-methylbenzophenone – Type II 3-methylbenzophenone – Type II 4-methylbenzophenone – Type II Ethyl-4-(dimethylamino)benzoate – Type I and coinitiator • Middle priority (7): Methyl-2-benzoylbenzoate – Type II 2-Isopropyl thioxanthone – Type II 4-Isopropyl thioxanthone – Type II 2-Benzyl-2-dimethylamino-4-morpholino butyrophenone – Type I 2-(4-Methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-1-butanon 2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl-2-methyl-2-propanone – Type I 1-(4-[(4-Benzoylphenyl)thio]phenyl)-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propan-1-one – Type I
Are any of the selectedcoinitiators(still) used in ink/glue-manufacturing? • Ethyl-4-(dimethylamino)benzoate • 4,4’-bis(dimethylamino)benzophenone) CAS: 90-93-7 • 1-hydroxycyclohexyl-1-phenyl ketone CAS: 947-19-3 • 2-ethylhexyl-4-dimethylaminobenzoate CAS: 21245-02-3 • 2-methyl-1(4-(methylthio)phenyl)-2-morpholino propan-1-one CAS: 71868-10-5
Solvents are usedin ink/glue-manufacturing? • Ethyl acetate? • Ethanol?
UV-radiation? • Glue: 300-500nm • Ink: 365-400nm 365nm? • Light intensity range: 50-5000mW/cm2 Narrow down?
Practical questions? • Contact? • E.g. Mixture of • Photoinitiator • Coinitiator • Solvent concentrations?