1. Study of the stability and reactivity of migrant migrant components from printing inks and adhesives, used in packaging materials of foodstuffs - MIGRINKT.

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

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

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

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

6. PR FAVV-AFSCA 2009/01 – General list of compounds used for inks and glues manufacture
Swiss Ordinance on Food Contact materials
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)

7. 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)

8. PR FAVV-AFSCA 2009/01 General list  Final list 6097  399 compounds
Final list  risk ranking list: MW
SML

9. PR FAVV-AFSCA 2009/01 – Final list  Risk ranking listMW
<
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)

10. PR FAVV-AFSCA 2009/01 – Final list  Risk ranking listMW
<
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

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

12. 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

13. 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)

14. 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

15. 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

16. MIGRINKT – WP1 Risk ranking list FAVVMW
<
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)

17. 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

18. MIGRINKT – WP1 Photoinitiators

19. 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

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

21. 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

22. Are any of the selected coinitiators (still) used in ink/glue-manufacturing?
Ethyl-4-(dimethylamino)benzoate
4,4’-bis(dimethylamino)benzophenone)
CAS:
1-hydroxycyclohexyl-1-phenyl ketone
CAS:
2-ethylhexyl-4-dimethylaminobenzoate
CAS:
2-methyl-1(4-(methylthio)phenyl)-2-morpholino propan-1-one
CAS:

23. Solvents are used in ink/glue-manufacturing?
Ethyl acetate?
Ethanol?

24. Use of mixtures of photoinitiators?

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

26. Can we retrieve pure substances which are used in industry?

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