New developments in radiation curable resins for inks European Coatings SYMPOSIUM Dusseldorf, May 15t h 2012 Paul Gevaert
Content Why and where UV/EB? Development in resins for Shrink sleeves Development in resins for Narrow web flexo Development in resins for Indirect Food Packaging
Why are radiation curable inks/coatings used? Very high print quality with high gloss and excellent resistance properties Eye catching impressions DIVERSIFICATION and INNOVATION in packaging design Immediate drying enabling immediate further processing Ideal for JUST IN TIME Lower System Cost (Short runs) Low VOC (100 % system) Can be used on a variety of substrates (paper & board, foils, metal, )
Where are radiation curable products used?
Where are radiation curable inks/coatings used? Applications: Labels 2010 World Market Share by Labeling Technology (42B linear M 2 ) Sleeving 12% In-Mold 2% Other 5% Pressure Sensitive 39% Glue Applied 42%
Developments in radiation curable inks Shrink sleeves - advantages: Entire surface for messaging Innovation in design. product differentiation Inside printing..scratch/chemical/moisture resistance No glue is required
Developments in radiation curable inks Shrink sleeves challenges for inks: High shrinkage Maintain optical density (black metallic inks) Compromise flexibility reactivity (high speed printing) Adhesion to PVC, PET-G, OPS EBECRYL 571
Developments in radiation curable inks EBECRYL 571 Good pigment wetting Good wrinkle resistance Color brightness Good Adhesion
Shrinkage (black) UV flexo ink - EBECRYL 571 Ink layer 5µ Substrate 45µ 50% shrink Ink layer 6µ Ink layer 10µ Substrate 90µ Substrate 90µ Colour aspect after shrinkage BAD GOOD Ink based on EBECRYL 571
Developments in radiation curable inks Narrow web UV flexo: high quality labels on coated substrates: high cost better adhesion IF adhesion on uncoated substrates COST REDUCTION
Developments in radiation curable inks EBECRYL 411 Modified polyester in DPGDA Low viscosity Good pigment wetting High reactivity Good adhesion on uncoated substrates PP, PE, PET, PS,PC, PLA
Water immersion test (ICE-water) Beer labels Substrate: uncoated OPP Adhesion is tested after 2h water-immersion; water at max. 2 C (melting ice) EBECRYL 812 EBECRYL 450 EBECRYL 411 12
Developments in energy curable inks Food packaging: Legislative pressure (e.g. Swiss ordinance). more stringent migration limits Need for cleaner, safer energy curable resins EBECRYL LEO = low extractibles, low odor
Food packaging safety NO CONTAMINATION of food! NO DIRECT CONTACT with the food! MIGRATION Case # 1: Substrate = NO BARRIER INK FOOD
Food packaging safety NO CONTAMINATION of food! NO DIRECT CONTACT with the food! MIGRATION Case # 2: Substrate = NO BARRIER INK FOOD Inner liner = NO BARRIER
Food packaging safety NO CONTAMINATION of food! MIGRATION Case # 3: INK Substrate = BARRIER INVISIBLE SET OFF Substrate = BARRIER INK FOOD
Food packaging safety functional barrier principle! YES BARRIER? NO
Food packaging safety Migration risks! Shrink sleeves (Reverse printing) Label Substrate = NO BARRIER Substrate Ink/Coating
Food packaging safety Migration risks! EuPIA: 7 cases to define migration risk Case Is the inner wrap a barrier to ink ingredients? Wrap to be printed Is the outer wrap a barrier to ink ingredients? 1 no inner (not relevant) migration is possible irrespective of the outer wrap Possibility of set-off or vapour phase transfer (not relevant) migration is possible irrespective of the outer wrap 2 no outer no (not relevant) migration is possible irrespective of the outer wrap Potential migration risk High High Examples (not exhaustive!) single wrap packaging, e.g. - printed paper bag or cardboard box, also PE coated ones, - printed flexible pouch or rigid container made of non-barrier material (e.g. PP or PE), - plastic bottle with printed label (which counts as one wrap, as it is not easily separable) - food products in PP pouch in a printed cardboard box 3 no outer yes yes High - printed box made of aluminium laminated board, containing food products wrapped in paper or PP 4 no outer yes no Low - printed tinplate box without internal lacquer, containing food products which are packed separately in unprinted PP pouches 5 yes inner (not relevant) migration is possible irrespective of the outer wrap 6 yes inner (not relevant) Migration excluded because of the presence of a functional barrier 7 yes outer (not relevant) Migration excluded because of the presence of a functional barrier yes High - aluminium lidding, or - printed pouch made of barrier laminate material, or - packaging made of laminate material with aluminium as inner layer no Low - glass bottle or can with printed label, or - coated/printed cans where set-off can be excluded, e.g. without internal lacquer, or printed/coated after forming (not relevant) Migration excluded because of the presence of a functional barrier Low - glass bottle in printed outer container
Food packaging chain roles/responsabilities PRODUCER BASE Raw Materials RESIN PRODUCER INK PRODUCER PRINTER CONVERTER BRAND OWNER CYTEC EBECRYL LEO LEO = Low Extractables-Low Odor
CYTEC developments for UV/EB food packaging Development at different levels RAW MATERIAL SELECTION ADAPTED PROCESS END PRODUCT SPECS Quality Control GMP GOOD MANUFACTURING PRACTICES
CYTEC developments for UV/EB food packaging Development at different levels RAW MATERIAL SELECTION
What are potential migrants? Migration potential Mw 1000 OK NOT TOX RELEVANT Base Raw materials Additives: Process End product
Raw Material Selection Compliant with EuPIA exclusion list Listed in the Swiss Ordinance on Food Packaging EFSA listed NOT EFSA listed WORST CASE CALCULATION < SML = OK < 10 ppb = OK > 10 ppb = NOK Migration test EFSA = European Food Safety Authority SML = Specific Migration Limit
Raw Material Selection Worst Case Calculation Calculation: - Formulation is 100% of acrylate concerned - Y g/m 2 print thickness - 6 dm 2 packaging in contact with 1 l food - 100% migration: Migration (ppb) = 0.06 x Y x Component content in acrylate (ppm) Ex: 0.06 x 3 g/m² x 50 ppm = 9 ppb
Raw Material Selection RAW MATERIAL SUPPLIER Higher molecular weight Higher purity (specs on residuals defined) Additives used?
CYTEC developments for UV/EB food packaging Development at different levels ADAPTED PROCESS
O O Adapted Process Example: Monomers( diluting acrylates ) process ACRYLIC ACID POLYOL O OH CATALYST STABILIZERS HO O + R R OH HO HEAT SOLVENT O O O O 4 functional DILUTING ACRYLATE Longer stripping to minimize residuals (solvent and acrylic acid) LOW ODOR Higher conversion degree to limit mono and di-acrylates LOW MIGRATION
Why limit amount of lower functional acrylates? Liquid mixture Oligomers Monomers Photoinitiator UV < 0.1 second EB Oligomers Monomers DRY FILM REACTION of AT LEAST 1 ACRYLATE FUNCTION: NO MIGRATION
CYTEC developments for UV/EB food packaging Development at different levels GMP GOOD MANUFACTURING PRACTICES (GMP)
EBECRYL LEO - Good Manufacturing Practices (GMP) Good Manufacturing Practices (GMP) at CYTEC: Extended QC Adapted RM approval process ISO 9001 specific layout of production log sheets Impurity specs STANDARD Products Measures against cross contamination Traceability at EVERY STAGE
CYTEC developments for UV/EB food packaging Development at different levels END PRODUCT SPECS Quality Control
End Product Specifications EBECRYL : EBECRYL LEO : Physical Properties Chemical Properties Physical Properties Chemical Properties Residuals (process) A B C Impurities (RM) A B Potential contaminants (process)
MUTAGENICITY assessment MIGRATION limit 10 ppb 50 ppb 5 ppm NO TOX DATA OECD 471 (AMES) OECD 476 (in vitro) OECD 473 (in vitro) OECD 408-90-day oral NO accumulation ACRYLATES: FALSE POSITIVES for OECD 476 or the OECD 473 EBECRYL LEO AMES Mouse Micronucleus test OECD 474 (in vivo) (in vivo test results supersedes in vitro test results)
End Product Specifications Transfer of Compositional Information on EBECRYL LEO PRODUCER BASE RM RESIN PRODUCER INK PRODUCER PRINTER CONVERTER BRAND OWNER Brand Owners Converters, Institutes CUSTOMERS FULL composition (under NDA) Food contact Information sheet ~ worst-case calculation of the Migration
EBECRYL LEO Range DILUTING ACRYLATES 3-f: EBECRYL LEO 10501 4-f: EBECRYL LEO 10502 EPOXY ACRYLATES EBECRYL LEO 10601 EBECRYL LEO 10620 AMINO ACRYLATES POLYESTER ACRYLATES EBECRYL LEO 10551 EBECRYL LEO 10552 EBECRYL LEO 10553 EBECRYL LEO 10801
Conclusion - CYTEC developments Resins for non-food contact Flexographic narrow web packaging applications: EBECRYL 571 for heat shrink sleeves providing better adhesion wrinkle resistance color brightness good pigment wetting properties. EBECRYL 411 for narrow web applications providing improved adhesion impact, mar and scratch resistance On UNCOATED BOPP, OPP, OPS and other commonly used filmic substrates.
Conclusion CYTEC development in food packaging UV (EB) technology DIVERSIFICATION INNOVATION in packaging design NEGATIVE IMAGE due to photoinitiator migration issues CYTEC: EBECRYL LEO REDUCED RISK for migration UV/EB more ACCEPTABLE for Food packaging To make UV/ EB successful in food packaging ACCOUNTABILITY at EACH stage of the value chain (GMP) IMPROVE INFORMATION STREAM
THANK YOU FOR YOUR ATTENTION! paul.gevaert@cytec.com www.cytec.com