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New developments
in radiation curable resins
for inks
European Coatings SYMPOSIUM Paul Gevaert
Dusseldorf, May 15th 2012
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?
Low VOC (100 % system)
Very high print quality with
high gloss and excellent resistance properties
Immediate drying enabling immediate further processing
Ideal for JUST IN TIME
Eye catching impressions
Lower System Cost (Short runs)
DIVERSIFICATION and INNOVATION in packaging design
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?
Pressure Sensitive
39%
Glue Applied
42%
Sleeving 12%
In-Mold
2%
Other
5%
2010 World Market Share by Labeling Technology
(42B linear M2)
Applications: Labels
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
Good pigment wetting
Good wrinkle resistance
Color brightness
Good Adhesion
EBECRYL® 571
50% shrink
Ink layer 5µ
Substrate 45µ
Substrate 90µ
Ink layer 6µ
Ink based on EBECRYL®571
Shrinkage (black) UV flexo ink - EBECRYL® 571
Substrate 90µ
Ink layer 10µ
GOOD
Colour aspect after shrinkage
BAD
Developments in radiation curable inks
Narrow web UV flexo:
IF…adhesion on uncoated substrates…
COST REDUCTION
on coated substrates: high cost
high quality labels
better adhesion
Developments in radiation curable inks
EBECRYL® 411
Good pigment wetting
High reactivity
Modified polyester in DPGDA
Good adhesion on uncoated substrates
PP, PE, PET, PS,PC, PLA…
Low viscosity
12
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®411 EBECRYL®812 EBECRYL®450
Developments in energy curable inks
Need for cleaner, safer energy curable resins
Food packaging:
Legislative pressure (e.g. Swiss ordinance)
…. more stringent migration limits
EBECRYL LEO® = low extractibles, low odor
Food packaging safety – NO CONTAMINATION of food!
NO DIRECT CONTACT with the food!
INK
Substrate = NO BARRIER
FOOD
MIGRATION Case # 1:
Food packaging safety – NO CONTAMINATION of food!
MIGRATION Case # 2:
INK
Inner liner
= NO BARRIER
FOOD
Substrate = NO BARRIER
NO DIRECT CONTACT with the food!
Food packaging safety – NO CONTAMINATION of food!
INK
Substrate = BARRIER
FOOD
MIGRATION
Case # 3:
Substrate = BARRIER INK
INVISIBLE SET OFF
Food packaging safety – functional barrier principle!
BARRIER?
YES NO
Shrink sleeves (Reverse printing)
Label
Substrate
Ink/Coating
Substrate = NO BARRIER
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?
Possibility of set-off or
vapour phase transfer
Potential
migration risk
Examples (not exhaustive!)
1 no inner (not relevant)
migration is possible
irrespective of the outer
wrap
(not relevant)
migration is possible
irrespective of the outer
wrap
High 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)
2 no outer no (not relevant)
migration is possible
irrespective of the outer
wrap
High - 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
yes High - aluminium lidding, or - printed pouch made of barrier
laminate material, or - packaging made of laminate material
with aluminium as inner layer
6 yes inner (not relevant)
Migration excluded
because of the presence
of a functional barrier
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
7 yes outer (not relevant)
Migration excluded
because of the presence
of a functional barrier
(not relevant)
Migration excluded
because of the presence
of a functional barrier
Low - glass bottle in printed outer container
Food packaging safety – Migration risks!
Food packaging chain – roles/responsabilities
EBECRYL LEO ®
LEO = Low Extractables-Low Odor
CYTEC
RESIN
PRODUCER
PRINTER
CONVERTER
INK
PRODUCER BRAND
OWNER
PRODUCER
BASE
Raw Materials
Development at different levels
CYTEC developments for UV/EB food packaging
RAW MATERIAL SELECTION
END PRODUCT SPECS
Quality Control
ADAPTED PROCESS
GMP GOOD
MANUFACTURING PRACTICES
Development at different levels
CYTEC developments for UV/EB food packaging
RAW MATERIAL SELECTION
What are potential migrants?
Migration potential Mw 1000 OK NOT “TOX RELEVANT”
Base
Raw materials
Additives:
End product
Process
Raw Material Selection
Compliant with EuPIA exclusion list
Listed in the Swiss Ordinance on Food Packaging
WORST CASE CALCULATION
< 10 ppb = OK
> 10 ppb = NOK
Migration test
EFSA listed NOT EFSA listed
EFSA = European Food Safety Authority
< SML = OK
SML = Specific Migration Limit
Worst Case Calculation
• Calculation:
- “Formulation” is 100% of acrylate concerned
- Y g/m2 print thickness
- 6 dm2 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
•Higher molecular weight •Higher purity (specs on residuals defined) •Additives used?
RAW MATERIAL SUPPLIER
Raw Material Selection
Development at different levels
CYTEC developments for UV/EB food packaging
ADAPTED PROCESS
Example: Monomers(“diluting acrylates”) process
Adapted Process
R
OH
HO
HO
OH
ACRYLIC ACID POLYOL
+ R
O
O
O
O
O
O
O
O
CATALYST STABILIZERS
HEAT SOLVENT
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
EB < 0.1
second
Liquid mixture
DRY FILM
Oligomers
Monomers UV
Oligomers
Monomers
Photoinitiator
Why limit amount of lower functional acrylates?
REACTION of AT LEAST 1 ACRYLATE FUNCTION:
NO MIGRATION
Development at different levels
CYTEC developments for UV/EB food packaging
GOOD MANUFACTURING PRACTICES (GMP)
GMP
Good Manufacturing Practices (GMP) at CYTEC:
ISO 9001
STANDARD
Products
Measures
against
cross
contamination
Traceability
at
EVERY
STAGE
specific
layout of
production log
sheets
Adapted
RM approval
process
EBECRYL LEO ® - Good Manufacturing Practices (GMP)
Impurity
specs
Extended
QC
Development at different levels
CYTEC developments for UV/EB food packaging
END PRODUCT SPECS
Quality Control
End Product Specifications
EBECRYL ® :
• Physical Properties
• Chemical Properties
EBECRYL LEO ® :
• Physical Properties
• Chemical Properties
• Residuals (process) A
B
C
• Impurities (RM) A
B
• Potential contaminants (process)
MUTAGENICITY assessment
MIGRATION limit
TOX DATA
OECD 471 (AMES)
OECD 476 (in
vitro)
OECD 473 (in
vitro)
10 ppb
50 ppb
NO OECD 408 - 90-day oral
NO accumulation
5 ppm
• AMES
• Mouse Micronucleus test – OECD 474 (in vivo)
(in vivo test results supersedes in vitro test results)
EBECRYL LEO ®
ACRYLATES: FALSE POSITIVES for OECD 476 or the OECD 473
• Brand Owners
• Converters,
• Institutes
• …
FULL composition
(under NDA)
Transfer of Compositional Information
on EBECRYL LEO ®
• CUSTOMERS
Food contact Information sheet
~ worst-case calculation of the Migration
RESIN
PRODUCER PRINTER
CONVERTER
INK
PRODUCER BRAND
OWNER
PRODUCER
BASE RM
End Product Specifications
• 3-f: EBECRYL LEO ® 10501
• 4-f: EBECRYL LEO ® 10502
DILUTING ACRYLATES
EBECRYL LEO ® Range
AMINO ACRYLATES
• EBECRYL LEO ® 10551
• EBECRYL LEO ® 10552
• EBECRYL LEO ® 10553
EPOXY ACRYLATES
• EBECRYL LEO ® 10601
• EBECRYL LEO ® 10620
• EBECRYL LEO ® 10801
POLYESTER ACRYLATES
Conclusion - CYTEC developments
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.
Resins for non-food contact Flexographic narrow web packaging applications:
To make UV/ EB successful in food packaging
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 UV/EB more ACCEPTABLE
for migration for Food packaging
ACCOUNTABILITY
at EACH stage
of the value chain
(GMP)
IMPROVE
INFORMATION STREAM
THANK YOU
FOR
YOUR
ATTENTION!
www.cytec.com
