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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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Overview

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


Overview

Overview

  • Introduction

  • PR FAVV-AFSCA 2009/01

  • MIGRINKT

    • Overview 6 WP

    • WP 1 (15th of March)

  • Today


Introduction migration

Introduction: Migration

food

  • Classicalmigration (diffusion)

    • Via direct contact

    • Via gas phase

  • Unintentedpresence (set-off and residuesof technical aids)

     GMP

food


Overview1

Overview

  • Introduction

  • PR FAVV-AFSCA 2009/01

  • MIGRINKT

    • Overview 6 WP

    • WP 1 (15th of March)

  • Today


Pr favv afsca 2009 01

PR FAVV-AFSCA 2009/01

  • No harmonizedlegislation !!!

  • General list


Pr favv afsca 2009 01 general list of compounds used for inks and glues manufacture

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 used for inks and glues manufacturing

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 011

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

<

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


Pr favv afsca 2009 01 final list risk ranking list1

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


Overview2

Overview

  • Introduction

  • PR FAVV-AFSCA 2009/01

  • MIGRINKT

    • Overview 6 WP

    • WP 1 (15th of March)

  • Today


Migrinkt overview 6wp

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

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 41

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 6wp1

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


Migrinkt wp1 risk ranking list favv

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 wp1 photoinitiators

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 wp1 photoinitiators1

MIGRINKT – WP1 Photoinitiators


Migrinkt wp1 photoinitiators2

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


Overview3

Overview

  • Introduction

  • PR FAVV-AFSCA 2009/01

  • MIGRINKT

    • Overview 6 WP

    • WP 1 (15th of March)

  • Today: Questions


Are any of the selected photoinitiators still used in ink glue manufacturing

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 selected coinitiators still used in ink glue manufacturing

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 used in ink glue manufacturing

Solvents are usedin ink/glue-manufacturing?

  • Ethyl acetate?

  • Ethanol?


Use of mixtures of photoinitiators

Use of mixtures of photoinitiators?


Uv radiation

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

Can we retrieve pure substanceswhich are used in industry?


Practical questions

Practical questions?

  • Contact?

  • E.g. Mixture of

    • Photoinitiator

    • Coinitiator

    • Solvent

       concentrations?


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