Adhesive Properties of

Ethylene – Acrylic Ester – Maleïc Anhydride

Terpolymers
in Extrusion Coating / Lamination

TAPPI PLACE Conference, Roma 2003,12-14th May

Jérôme PASCAL
 Aim of the Presentation

To analyze the conditions of adhesion

development in extrusion coating and extrusion
lamination

To present the possibilities of Ethylene –

Acrylic Ester – Maleïc Anhydride (E-AE-MAH)
Terpolymers in these processing technologies
 Adhesion - What does it mean ?
Starting requirement :
ƒ Chemical or physical interactions connecting polymer chains
to solid surface sites

Polymer
Semi-crystalline

Oxidized, hydroxylated,
Metal contaminated top layers

But also :
ƒ Number of these connecting links per unit of interface area
ƒ Entanglement or crystallisation of these connecting chains
with the bulk
 From Adhesion to Peel Strength

Peel Force F Peeling arm deformation

(macroscopic plasticity)

Stress transfer
inducing
Interfacial interactions plasticity
(molecular) (nano to microscopic)

Schema of crack propagation during peel test

showing the contributions to peel strength
 From Adhesion to Peel Strength
Peel Force F
Peeling arm deformation
(macroscopic plasticity)

Stress transfer
(nanometric to
microscopic plasticity)
Interfacial interactions
(molecular)

Peel Strength = Chemical Ties + Plasticity

Reactivity + Entanglement + Yield stress

 Requirements Regarding Adhesion

Reactivity, which has to be given by polar and reactive chemical

groups carried by polymer chains
Diffusion and reaction kinetics, which have to be suitable for the
process conditions of coating
Ability to crystallise or entangle the polymer chains reacted at the
interface with the bulk of the adhesive
Mechanical properties (E modulus, Yield strength σy) which, from
the connecting chains, have to allow high plastic energy dissipation

A sophisticated set of
Chemical + Physical + Mechanical properties !
Adhesion Development in which
Conditions ?

High drawing rate

=> Strong molecular orientation
Drawing time : 0.5 to O.1 s
Drawing rate dα/dt = 10 to 100 s-1

High cooling rate

=> Quenching of the first nm
 Cooling Computation Example

(T°C)
Temperature (°C)
Alu side
Middle
Chill roll side
(1µm from surfaces)

Coating : 30 µm
Terpolymer at 300°C
(Alu 20°, Chill 15°,
Air 50°, Air Gap 85 mm)

Time
0 0.257 0.262 0.852 (s)
Alu contact Enlarged scale End of solidification
Die exit
Solidification time : 5 ms
 Consequences

Very hard conditions for adhesion development !

ƒ Strong orientation + Very little time left in molten state

Direct consequences
ƒ Only immediately available functional groups can react
ƒ Crystallisation state of the adhesive is far below equilibrium state

Delayed consequences
ƒ Solid state relaxation and post crystallisation will take place at
room temperature
ƒ => Slow increase of Yield stress σy close to the interface
ƒ => Peel strength will slowly and monotonically vary with time
 Processing Requirements

Usual requirements in extrusion coating

ƒ Good general processability and melt quality
ƒ Drawability
ƒ Low neck-in
ƒ Low power consumption

Additional requirements for a “perfect” adhesive

ƒ Runs on conventional equipment
ƒ Wide processing temperature range, without cross-linking risk
ƒ No corrosion of extrusion equipment
ƒ Easy purging
ƒ Versatile adhesive properties in coating / Lamination
ƒ Versatile adhesive properties in coextrusion
ƒ Reliability
 Extrusion Coating/Lamination Adhesive
«Chemical Structure» Requirements

Combining processing requirements and adhesion

development requirements, we need to control
ƒ Rheological behaviour, to suit coating specificities
ƒ Neutrality towards extrusion equipment
ƒ Reactivity in molten state
ƒ Crystallisation behaviour
ƒ Solid state mechanical properties E modulus and Yield stress
to lead to easy processable and as versatile as
possible adhesives, for many kinds of laminates
 A Really Flexible Chemistry
E – AE – MAH Terpolymers

Ethylene – Acrylic Ester – Maleïc Anhydride

--- (CH2 - CH2 -)x -- (CH2 - CH - )y --- (CH2 - CH2 -)z --- (CH - CH - )t
I I I
C=O O=C C=O
I \ /
O O
I
R

Random terpolymers made by high pressure radical polymerization

in autoclave reactor. Trademark Lotader®.
 E-AE-MAH Terpolymers
derive closely from LDPE
Ethylene – Acrylic Ester – Maleïc Anhydride

Basically ethylene copolymers, made by high pressure radical

polymerization, in the same autoclave reactor as coating LDPE
Chemical structure and long chain branching giving the best
rheology for extrusion coating process
Fully miscible with LDPE
 Effect of Acrylate Comonomer

Ethylene – Acrylic Ester – Maleïc Anhydride

Possibly Methyl, Ethyl or Butyl Acrylate

Basically 2 effects : reduces crystallinity and increases polarity
compared to LDPE
From 5 to 30 weight % comonomer
Varying gradually comonomer content allows tailor-made
ƒ crystallinity control,
ƒ crystallisation temperature control
ƒ E modulus (flexibility) and Yield stress (plasticity) control
Excellent thermal stability allowing high processing temperatures
 Effect of Maleïc Anhydride

Ethylene – Acrylic Ester – Maleïc Anhydride

Introduces reactivity in the polymer chain

Same effect on crystallinity as acrylate comonomer
From 1 to 4 weight %
Excellent heat stability allowing high processing temperatures
Paticularly reactive with hydroxyl groups, amine groups, and Corona
treatment induced species
Not corrosive
Not self cross-linking
Moisture sensitive (equilibrium anhydride + water ÅÆ diacid)
 What use are E-AE-MAH Terpolymers ?

Generally speaking these are polyvalent adhesives in

extrusion coating and extrusion lamination

Three main uses can be described

ƒ Adhesion enhancer for LDPE : to increase and make more
reliable adhesive performance of LDPE, most often on
aluminium foil.
ƒ Adhesive for plain plastic films OPET, OPP, CPP, OPA
(especially without primers), metallized films, printed
substrates, etc.
ƒ Coating adhesive for coextrusion with PA, EVOH, in
combination with all kinds of polyethylenes or ethylene
copolymers
 Example of performances as
LDPE Adhesion Enhancer
Peel strength of LDPE alone on Aluminium foil
Processing at 330°C - Drawing rate d α / d t = 10 s
-1

3,5
Peel Strength (N/15mm)

2,5

1,5

0,5
Pure LDPE
0
0 10 20 30 40 50 60

Time after extrusion (days)

 Example of performances as
LDPE Adhesion Enhancer
Effect of introducing 20% Lotader 3210 terpolymer
E - BA6% - MAH3% in LDPE (MFI 4, density 924)
Processing at 330°C - Drawing rate d α / d t = 10 s
-1

Terpolymer content (%)

3,5
Peel Strength (N/15mm)

3
20 % Terpolymer
2,5 20
2 0

1,5 + 50 %
1

0,5
Pure LDPE
0
0 10 20 30 40 50 60

Time after extrusion (days)

 Example of performances as
LDPE Adhesion Enhancer
Effect of introducing 20% to 100% of Lotader 3210
terpolymer
E - BA6% - MAH3% in LDPE (MFI 4, density 924)
Processing at 330°C - Drawing rate d α / d t = 10 s
-1

Terpolymer content (%)

3,5
100
Peel Strength (N/15mm)

3 80
60
2,5
40
2 30
1,5
20
0
1

0,5

0
0 10 20 30 40 50 60

Time after extrusion (days)

 Adhesion Performance on Plain OPET

Effect of processing temperature on peel strength of Lotader

3430 (E-MA-MAH terpolymer) on Corona treated OPET
Structure : OPET 12µm / terpolymer 10µm / LDPE 25µm

5
After 1 week
Peel Strength (N/15mm)

1
Just after extrusion

0
220 240 260 280 300 320

Temperature (°C)
 Which Terpolymer for which Use ?
General rules
1 - The more difficult the substrate (regarding adhesion), the “softer”
the terpolymer to be chosen, i.e. the higher the comonomer content
2 – Blending in LDPE allows to modulate performance/cost ratio
3 – Adhesion increases with increasing processing temperature

Easy Difficult

ƒ Paper ƒ PE ƒ Alu foils ƒ Primerless plastic films

ƒ Board ƒ Ethylene ƒ Metallized films ƒ OPET, OPP, CPP, OPA
copolymers ƒ Primerized films ƒ Inks, special surfaces, etc

Recommended Terpolymers
Low Medium High comonomer content
 Some examples of laminates

OPET/Ink/Primer/Terpo blend/Alu foil/Terpo blend/LDPE

Instant coffee sachet
Paper/Terpo blend/Alu foil/Sealing layer
Liner for potato chips board tube
Cello/Terpo blend/Alu foil/Terpo blend
Tablet laminates
OPET/Terpo/Alu foil/Sealing layer
Fresh food
OPET/Terpo/EVOH/Terpo/LDPE
Barrier laminates
OPET/Print/Primer/Terpo blend/Alu foil/Terpo blend
Condom packaging
OPP/Terpo/Alu foil
Flexible structure replacing paper based laminate
Terpo blend/HDPE web/Alu foil
Roof thermal insulation
 Summary of Processing Properties

Runs basically like LDPE : power consumption, melt

stability, drawability
Typical low neck-in of autoclave resins
Very large temperature processing window, up to 320-
330°C
Fully compatible with LDPE, blendable in all
proportions
Easy purging with LDPE, short transitions in production
No corrosion of extrusion equipment
Packed in waterproof bags to prevent MAH hydrolysis
Typical “acrylate smell”
 Other Autoclave Co and Terpolymers

Ethylene – Methyl Acrylate or Butyl Acrylate

copolymers (Trademark Lotryl®)
ƒ Physical description similar to Terpolymers, except reactivity
ƒ Excellent processability (autoclave polymerization process)
ƒ Main use in flexible packaging : seal and seal peel
applications, used either pure or blended, with or without
processing additives

Ethylene – Glycidyl Methacrylate copolymers

Ethylene - Methyl Acrylate - Glycidyl Methacrylate
Terpolymers
ƒ High reactivity of epoxy in GMA functional groups
ƒ As coating adhesive, mainly used out of food packaging
 Adhesive Properties of
Ethylene – Acrylic Ester – Maleïc Anhydride
Terpolymers
in Extrusion Coating / Lamination

Thank You !
 LOTADER 4210 Benefits and
Highlights
Performance Cost
ƒ Increase adhesion level over
LDPE
ƒ Increase line speed
ƒ Decrease power consumption
ƒ Decrease purging time
ƒ No corrosion problem
Ease in processing
ƒ Process like LDPE
ƒ Miscible with LDPE (can be
blended)
ƒ Processing Temperature in blend
320°C
Sealing in extrusion coating
applications
ƒ Decrease sealing
temperature of LDPE
ƒ Seal trough contamination
ƒ Better hot tack versus LDPE
Versatile adhesion
ƒ Good adhesion to Met PET
ƒ Good adhesion to PU inks
and nitrocellulose inks (
100% ink coverage)
 Conventional Structures with Lotader
PET 12µ/ full print/ AC / 33% LOTADER-PE blend 15µ/ FOIL 7µ / dry lam. / Lldpe 30 – 40µ
Î for coffee bags, instant powder chocolate pouch

PET 12µ/ full print/ AC / 33% LOTADER-PE blend 15µ/ FOIL 7µ /33% Lotader blend 30µ
Î for small 15gr coffee bags and chocolate pouches

BOPP 20µ/ full print/ AC / 33% LOTADER-PE blend 12-15µ/ FOIL 7µ / dry lam. / Lldpe 30 – 40µ
Î for Snack food

PET 12µ/ full print/ AC / 33% Lotader-PE blend 12 –15µ / m-PET 12µ/ dry lamination / Lldpe 30-40µ
Î Frequent structure, mainly for Instant coffee bags

BOPP 20µ/ full print/ AC / 33% LOTADER-PE blend 12-15µ/m-PET 12µ/ dry lamination / Lldpe 30-40µ
Î Frequent used structure for Snack food

Paper 18gr|m²/ 33% LOTADER-PE blend 12-15µ/FOIL 7µ/ dry lamination / Lldpe 30-40µ
Î for mint Candy “FOX”and Bubble gum

PET 12µ/ full print/ AC / 33% LOTADER-PE blend 15µ/ FOIL 7µ / dry lam. /33% Lotader blend 15µ/Lldpe
Î for Coffee packaging