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 Today Overview 6 WP WP 1 (15th of March) Today

Introduction: Migration Classical migration (diffusion) Via direct contact Via gas phase Unintented presence (set-off and residues of technical aids)  GMP food food

Overview Introduction PR FAVV-AFSCA 2009/01 MIGRINKT Today Overview 6 WP WP 1 (15th of March) Today

PR FAVV-AFSCA 2009/01 No harmonized legislation !!! General list

PR FAVV-AFSCA 2009/01 – General list of compounds used for inks and glues manufacture Swiss Ordinance on Food Contact materials 817.023.21 1st of 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: evaluated substances, sufficient toxicity data (SML based on TDIvalue) List B: “unevaluated” substances, insufficient toxicity data (10ppb or lower detection limit)

PR FAVV-AFSCA 2009/01 – General list of compounds used for inks and glues 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

PR FAVV-AFSCA 2009/01 – Final list  Risk ranking list MW < high SML 192 compounds low SML 207 compounds median value (202 Da) highest priority low MW 96 compounds high MW middle priority lowest SML > median value (1 mg/kg food) 399 compounds £ 104 compounds high 103 compounds median value (184 Da)

PR FAVV-AFSCA 2009/01 – Final list  Risk ranking list MW < high SML 192 compounds low SML 207 compounds median value (202 Da) highest priority low MW 96 compounds high MW middle priority lowest SML > median value (1 mg/kg food) 399 compounds £ 104 compounds high 103 compounds median value (184 Da) This list includes: 27 additives 60 monomers 2 solvents 5 photoinitiators 10 compounds from Plastic Directive

Overview Introduction PR FAVV-AFSCA 2009/01 MIGRINKT Today 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 stability selected migrants in water and acetic acid (WP2), ethanol (WP3) and MPPO (WP4) Not UV-activated compounds UV-activated compounds

Not UV-activated compounds WP 2, 3 & 4 : Not UV-activated compounds Dark Light 100% recovery ? 10 days/40°C 24h/reflux yes OK no Investigation different temperatures (20 – 60°C) and times (1 – 10 days)

UV-activated compounds WP 2, 3 & 4 : OK UV-activated compounds Dark Light 100% recovery ? 10 days/40°C 24h/reflux yes no Investigation different temperatures (20 – 60°C) and times (1 – 10 days) UV-activation No UV-activation

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 stability selected migrants in water and acetic acid (WP2), ethanol (WP3) and MPPO (WP4) WP 5: Validation kinetic models with packaging film WP 6: General coordination and reports

MIGRINKT – WP1 Risk ranking list FAVV MW < high SML 192 compounds low SML 207 compounds median value (202 Da) highest priority low MW 96 compounds high MW middle priority lowest SML > median value (1 mg/kg food) 399 compounds £ 104 compounds high 103 compounds median value (184 Da)

MIGRINKT – WP1 Photoinitiators 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 – WP1 Photoinitiators

MIGRINKT – WP1 Photoinitiators 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 Today: Questions Overview 6 WP WP 1 (15th of March) Today: Questions

Are any of the selected photoinitiators (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 selected coinitiators (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 used in ink/glue-manufacturing? Ethyl acetate? Ethanol?

Use of mixtures of photoinitiators?

UV-radiation? Glue: 300-500nm Ink: 365-400nm 365nm? Light intensity range: 50-5000mW/cm2  Narrow down?

Can we retrieve pure substances which are used in industry?

Practical questions? Contact? E.g. Mixture of Photoinitiator Coinitiator Solvent  concentrations?