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Determining the Most Effective Tie-Layer in

Response to New Material Developments

Barrier Film Conference


Brussels, Belgium

Dr. Maged Botros and Dr. Jean Merrick-Mack


February 22, 2006

Main Topics

Background
Exploring requirements and applications enabled
by new adhesives

Correlation of performance to interactions at


tie-layer/substrate interface

New developments in high-performance tie-layers


Summary and conclusions

Plexar Tie-Layer Resins


Background
PLEXAR products are tie-layer adhesives
manufactured in the United States by Equistar
Chemicals, a Lyondell company. They are
maleic anhydride modified polyolefins for highperformance packaging.

Functionalized polymers are used to bond


dissimilar materials in coextruded, coated or
laminated structures.

Market introduction in 1976


First tie-resin in North America
Equistar is one of the largest suppliers.
Key applications:
High-barrier food packaging
Metal bonding
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Plexar is a registered trademark of Equistar Chemicals, a Lyondell company.

Tie-Layer Adhesives
Product / Base Resin Selection
Plexar Adhesives Used in Food and Non-Food Applications
Plexars used in food contact applications are subject to Specific Migration Limits (SML)
under European Directive 2002/72/EC - Food Contact Plastics and Amendments. Not
all Plexar grades are suitable for all food applications. Please consult Lyondell Product
Safety for additional details

LLDPE-Based Tie-Layer Adhesives


LLDPE-based adhesives are the resin of choice for a
majority of EVOH/PA applications. These grades provide
cost-effectiveness, high adhesion, good processability,
and clarity.

Applications:
Flexible packaging for meat and cheese
Liquid packaging for wine, soups, sauces and
condiments

Lidstock for sealing to rigid containers


PE blow molding adhesive for EVOH
PE sheet for thermoformed containers

EVA- and LDPE-Based Tie-Layer Adhesives


Applications:

Films with high Clarity


Flexible meat and cheese packaging
Thermoformed trays
Products:

Medium VA content adhesive for flexible packaging


High VA content adhesive for flexible packaging and

thermoformed containers with adhesion to PE, EVOH, PA,


ionomer, PS and PET

LDPE-based tie-layer resins


Commonly used in flexible packaging
Exhibit excellent melt strength, clarity and taste/odor
characteristics.
Primarily used in coextrusion coating and bubble wrap

Polypropylene-Based Tie-Layer Adhesives


PP-based products provide high adhesion to EVOH
and PA, good processability, stiffness, and stress
crack resistance for flexible and rigid coextrusion.

PP-based Plexar product line is designed to offer a


variety of adhesion levels depending upon end use.

Applications:
Flexible packaging
Thermoformed sheets
Blow molded bottles

HDPE-Based Tie-Layer Adhesives


HDPE-based adhesives are designed for improved
moisture vapor barrier in flexible packaging, high
stiffness for rigid packaging, low taste and odor, and
high adhesion for mostly PA barrier structures.

Applications:
Cereal/cracker box liners
Meat/cheese packaging
Blow molded liquid packaging

Tie-Layer Coextrusion Applications

Blown/cast film:

Liquid packaging
Boil in bag
Dry food packaging
Bubble films
Paperboard cartons
Snack packaging
Ovenable board

Blow molding:

Meat and cheese packaging

Extrusion coating:

Bottles
Fuel tanks

Other applications:

Metal/foil laminations
Plastic pipe
Wire and cable
Sheet/thermoforming
Tubes

Coextrusion Coating
Plexar products for coextrusion coating are designed for
easy extrudability, high melt strength, and excellent
adhesion to polyamide (PA), ethylene vinyl alcohol
(EVOH), cellulose and foils.

Applications:
Liquid packaging
Flexible packaging
Truck panels

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Laminating Resins
Laminating resins are designed for high adhesion to
steel, aluminum, EVOH, PA and PE.

Applications:
Building panels
Truck trailer panels
Wire and cable coatings

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Metal Bonding Applications


Metal/foil lamination
Composite building panels
Composite truck trailer panels
Nail-collation tape

12

Metal Bonding Applications


Plastic pipe
Composite multi-layer pipe
XL-HDPE/Plexar/aluminum
XL-HDPE/Plexar/EVOH
Under-floor heating
Potable water applications

Wire and cable


Aluminum/Plexar/LDPE
Cable TV signal transmission

13

Metal Bonding Applications


External protective pipe coatings

Anti-corrosion coating
Large diameter metal pipes
Gas and crude oil (on- and offshore)
Coating: three-layer coated pipe
Pipe/epoxy/tie-layer (PE or PP)/HDPE + black (LLD, LDPE and
PP)

14

Sheet/Thermoforming and Tube Applications


Coextruded sheet/thermoformed containers
Examples/applications:
HDPE/tie/EVOH/tie/HDPE
Polystyrene/tie/EVOH/tie/PE
Single-portion containers
Coextruded tubes
LDPE/tie/EVOH/tie/LDPE
Application:
Highly-flavored toothpaste, specialty creams and lotions

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Correlation of Performance to Interactions at


Tie-Layer/Substrate Interface
Adhesion performance in flexible and rigid application
Interfacial interactions at tie-layer adhesives/EVOH
Relationship to performance
9 Performance of new developments
9 Applications: Film, blow molding, sheet and
thermoforming
Techniques applied:

16

Rheological investigation
FTIR spectroscopy

(A) Film Applications: Adhesion at Tie-Layer/


EVOH Interface for PP-Based Tie-Layers
8

Ad h esio n (N/1 5 mm)

6.2

Day 0

Day 1

6
5
4
3
2

2.3
1.7

2.8

3
2.5

1.8

1.9

1.8

1.3

1
0

PP Tie-1

PP Tie-2

PP Tie-3

Adhesive

17

PP Ref-1

PP Ref-2

(B) Blow Molding Application: Adhesion at TieLayer/EVOH Interface for PP-Based Tie-Layers
30

Adhesion (N/15 mm)

25

24

Day 1

23

20
15
10

5
0

PP Tie-2

PP Tie-3

Adhesive

18

PP Ref-1

Interfacial Interactions at Tie-Layer


Adhesives/EVOH
Relationship to Performance:
(I) Rheological Study
Parameters studied:
1. Complex viscosity
2. Storage modulus, G
3. Loss modulus, G
4. G, G relationship

19

Complex Viscosity Versus Frequency for


PP-Based Tie-Layer Blends With EVOH
1.E+06

Eta* , Poise

Tie-1

1.E+05

Tie-2
Tie-3
Ref-1
Ref-2

1.E+04

PP

1.E+03
0.01

0.1

10

Frequency (radians/second)

20

100

1000

G Versus Frequency for PP-Based Tie-Layer


Blends With EVOH
1.00E+06

PP
Ref-2

1.00E+05

Ref-1
Tie-3'

G'

Tie-2'
Tie-1'
1.00E+04

1.00E+03

1.00E+02
1.00E-02

1.00E-01

1.00E+00

1.00E+01

Frequency, rad/s

21

1.00E+02

1.00E+03

G and G Versus Frequency for PP-Based


Tie-Layer Blends With EVOH
1.00E+06
PP / G"

PP / G'

Ref-1/G"

Ref-1 / G'

Tie-3/G"

Tie-3 / G'

G", G'

1.00E+05

1.00E+04

1.00E+03

1.00E+02
1.00E-02

1.00E-01

1.00E+00

1.00E+01

Frequency, rad/s
22

1.00E+02

1.00E+03

Interfacial Interactions at Tie-Layer Adhesives/


EVOH
Relationship to Performance:
(II) FTIR Study

Main topics:
1. Detection of reaction
2. Correlation to performance

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FTIR Spectra For PP Tie and PP Blends With


EVOH
Acid Band

1.30
1.25
1.20

1740 cm-1
Ester Band

1.15

Absorbance

1.10
1.05
1.00
0.95
0.90

Tie - 3

0.85

Tie - 2
Tie - 1

0.80
0.75

Ref - 2
Ref - 1
PP

0.70
0.65
0.60
0.55
1850

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1800

1750
1700
Wavenumbers (cm-1)

1650

Correlation Between Adhesion and Ester


Formation in PP Tie/EVOH Structures
0.05

1.2

0.045

Normalized Ester Band

0.035

0.8

0.03
0.025

0.6

0.02
0.4

0.015
0.01

0.2

0.005
0

0
Tie-1

Tie-2

Tie-3

Ref-1

Adhesive

25

Ref-2

PP

Adhesion (Lbs./In)

0.04

Ester
Adhesion

New Developments in High-Performance


Tie-Layers
I.

High-clarity barrier films

Multi-layer film transparency

Challenges

New developments

II. High-performance tie-layer development for polystyrene


(PS)/high-impact polystyrene (HIPS) applications

Performance

26

Advantages of new development

Global Trend: Increasing Demand for


High-Clarity Barrier Films

Consumer preference for retail display


packages with excellent optics

Films with poor clarity detract from a


quality image.

Intense competition in film-converting


industry for distinguishing benefits

Clarity is a must-have feature.


Low-clarity films are at a disadvantage.

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Transparency Loss in Barrier Coextrusions


Measurement: narrow angle scattering (NAS)
Phenomena:
Coextruded barrier films with low optical transparency due to
apparent instability at tie-barrier interface
- Ground glass, graininess, orange peel appearance
Cause:
An uneven interface between tie layer and barrier layer, possibly
caused by covalent bonding, that amplifies interfacial stresses that
lead to nanometer scale distortions.

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Adhesion Versus Clarity in Standard


Multi-layer Films With EVOH Barrier
50

45
40
35

30
25

20
2

15
10

5
0

0
2MI LLDPE

Adh-A
Adhesive

29

Adh-B

NAS

Adhesion (N/15mm)

Adhesion
NAS Clarity

Performance of New Tie-Layer Developments in


Multilayer Films With EVOH Barrier
42

45
40

5X Adh (N/15 mm)

NAS

35
28

30
25

21

20

27

18.4

15
10

7.9

5
0

30

S tandard-A

Tie-Clarity1

Tie-Clarity-2

Key Attributes of New Developments


LLDPE-based tie-layer: 1.1 MI, 0.92 density
Specifically designed for EVOH blown film coextrusions
when excellent optics and transparency are required
9 Good viscosity and shear stress matched of most blown film EVOH grades
9 Optimized anhydride content for adhesion and transparency
9 Unique structure and graft architecture
9 Ability to absorb and dissipate interfacial stresses

High quality and unique benefits


Low gel levels
High melt strength, thermal stability, and good processability -- similar to
unmodified LLDPE

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Summary of High-Clarity Development

The effect of adhesion on multi-layer film clarity was


investigated.

It was concluded that the higher the adhesion, the


lower the clarity.

New adhesives maintain high clarity and high adhesion


at the same time.

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High-Performance Tie-Layer Development for


PS/HIPS Applications
Product characteristics
LLDPE-based tie-layer adhesive
Melt index = 3.30 g/10 min (D 1238)
Density = 0.9335 g/cc (D 1505)
Vicat softening point = 88.3C (D 1525)

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Plexar Tie-layer Performance


600 Micron Coex Sheet: PS+HIPS/PX/EVOH/PX/PS+HIPS
18
16

16.2

14
12
Adhesion 10
(N/2.54 cm) 8

8.3

7.5

Plexar
Reference

6
4

1.9

2
0
Inner

Outer
Tie-Layer

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Technical Summary for PS/HIPS Applications


Obtained excellent results with new Plexar tie-layer
development

Doubled performance compared to reference


Main advantages:
1. Excellent processability in sheet and
thermoforming applications
2. Improved adhesion
3. Low odor
4. Good cutability (no stringing)
5. High-temperature applications
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Summary and Conclusions

Plexar tie-layer adhesives produced by Equistar is the first maleic


anhydride tie-layer adhesive developed in North America.
Discussed requirements and applications are enabled by new
adhesives.
Investigated interactions between tie-layer adhesives and EVOH:

Direct relationship between adhesion and observed ester/acid


formation suggests a reaction between maleic anhydride groups
in the tie layer and OH groups in EVOH.

The techniques employed in this investigation were used as tools in


developing high-performance Plexar tie-layer adhesives that are
targeted for specific applications.
New tie-layer developments for high-performance applications:

High-clarity, multi-layer film application


High-performance tie-layer development for PS/HIPS applications
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Acknowledgments
The authors would like to thank Ms. Jennifer Nguyen,
Mr. Michael Grubb and Mr. William Shumake for their
significant contributions.

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