Study of the stability and reactivity of migrant migrant components from printing inks and...

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

- Classical migration (diffusion)- Via direct contact

- Via gas phase

- Unintented presence (set-off and residues of technical aids)

GMP

food

food

Overview



• 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)

1. Monomers 2. Colorants 3. Solvents 4. Additives 5. 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)

• General list Final list 6097 399 compounds• Final list risk ranking list:

– MW– SML

PR FAVV-AFSCA 2009/01

PR FAVV-AFSCA 2009/01 – Final list Risk ranking list

MW <

high SML

192 compounds

MW <

MW <

low SML

207 compounds

MW < median value (202 Da)

highest priority

low MW

96 compounds

high MW

96 compounds

middle priority

lowest priority

SML >median value (1 mg/kg food)

399 compounds

SML £median value (1 mg/kg food)

low MW

104 compounds

high MW

103 compounds

median value (184 Da)



PR FAVV-AFSCA 2009/01 – Final list Risk ranking list

MW <

high SML

192 compounds

MW <

MW <

low SML

207 compounds


highest priority

low MW

96 compounds

high MW

96 compounds

middle priority

lowest priority


399 compounds


low MW

104 compounds

high MW

103 compounds



median value (202 Da)This list includes:• 27 additives• 60 monomers• 2 solvents• 5 photoinitiators• 10 compounds from Plastic Directive

Overview



• 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

WP 2, 3 & 4 :

Not UV-activated compounds

DarkLight

100% recovery ?

10 days/40°C 24h/reflux

yesOK

no

Investigation different temperatures (20 – 60°C) and times (1 – 10 days)

DarkLight

WP 2, 3 & 4 :

OK

UV-activated compounds

DarkLight

100% recovery ?


yes

no

Investigation different temperatures (20 – 60°C) and times (1 – 10 days)

DarkLight

UV-activation No UV-activation


Light Dark Light Dark

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 – WP1Risk ranking list FAVV

MW <

high SML

192 compounds

MW <

MW <

low SML

207 compounds


highest priority

low MW

96 compounds

high MW

96 compounds

middle priority

lowest priority


399 compounds


low MW

104 compounds

high MW

103 compounds




MIGRINKT – WP1Photoinitiators

• High priority (5):Benzophenone2-methylbenzophenone3-methylbenzophenone4-methylbenzophenoneEthyl-4-(dimethylamino)benzoate• Middle priority (7):Methyl-2-benzoylbenzoate 2-Isopropyl thioxanthone 4-Isopropyl thioxanthone2-Benzyl-2-dimethylamino-4-morpholino butyrophenone2-(4-Methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-1-butanon2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl-2-methyl-2-propanone1-(4-[(4-Benzoylphenyl)thio]phenyl)-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propan-1-one

MIGRINKT – WP1 Photoinitiators

MIGRINKT – WP1Photoinitiators

• High priority (5):Benzophenone2-methylbenzophenone – Type II3-methylbenzophenone – Type II4-methylbenzophenone – Type IIEthyl-4-(dimethylamino)benzoate – Type I and coinitiator• Middle priority (7):Methyl-2-benzoylbenzoate – Type II2-Isopropyl thioxanthone – Type II4-Isopropyl thioxanthone – Type II2-Benzyl-2-dimethylamino-4-morpholino butyrophenone – Type I2-(4-Methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-1-butanon2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl-2-methyl-2-propanone – Type I1-(4-[(4-Benzoylphenyl)thio]phenyl)-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propan-1-one – Type I

Overview



• Today: Questions

Are any of the selected photoinitiators (still) used in ink/glue-manufacturing?

• High priority (5):Benzophenone2-methylbenzophenone – Type II3-methylbenzophenone – Type II4-methylbenzophenone – Type IIEthyl-4-(dimethylamino)benzoate – Type I and coinitiator• Middle priority (7):Methyl-2-benzoylbenzoate – Type II2-Isopropyl thioxanthone – Type II4-Isopropyl thioxanthone – Type II2-Benzyl-2-dimethylamino-4-morpholino butyrophenone – Type I2-(4-Methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-1-butanon2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl-2-methyl-2-propanone – Type I1-(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: 365-400nm365nm?• 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?

Study of the stability and reactivity of migrant migrant components from printing inks and...

Documents

Transcript of Study of the stability and reactivity of migrant migrant components from printing inks and...