d Packaging & Industrial Polymers

Specialty Resins for Extrusion

Coating & Films
Scott Marks
E. I. du Pont de Nemours & Company

TAPPI - “PLACE” Short Course

August 24 – 26, 2010
Charleston, SC m
 Selecting a Specialty
Resin

What do you have to consider?

³ Processability
³ Coextrudability
³ Physical Properties
³ Barrier Properties
³ End use requirements
³ Economics
 What Does A Specialty Resin
Have To Exhibit?

³ Good Processability: --- for the converter

³good melt quality
³good drawability
³good “green” adhesion to substrates
³good adhesion to coextruded layers
³runs on conventional equipment
³does not require excessive horsepower
³not too difficult to purge from extrusion system
³etc…..
 What Does A Specialty Resin
Have To Exhibit?
³ Good end-use properties: --- for the Packager
³sealability (through contaminants); peelability sometimes
³long term adhesion to adjacent layers and substrates
³contributes to machineability of structure on end user
equipment (if it does not run at customer, processing in your shop
does not mean a thing)
³proper COF, stiffness, durability, static, etc…
³durability of seals / adhesions / barrier, when exposed to;
³aggressive “chemicals” (oils, surfactants, spices,...)
³modified atmosphere gas pressures
³vacuum packaging
³etc…...
 Selecting a Specialty Resin:
The “Choices”

³ POLYETHYLENE FAMILY ³ SPECIALTY RESINS

³LDPE ³E / VA
³LLDPE ³E / acrylates
³HDPE ³E / terpolymers
³mPE ³Acid Copolymer
³Ionomer
³ POLYPROPYLENE ³PET
³CoPP extr/ctg ³Nylon, EVOH, ...
³CPP film
EVA (ethylene vinyl acetate)
CHEMISTRY

CH3 VA
l
C=O
l
O
l
— CH2 — CH2 — CH — CH2 — CH2 — CH2 —

Adding VA to the polymer gives:

1) lower crystallinity
2) slight polarity
 EVA
Characteristics

Increasing the percent Vinyl Acetate:

³ increases adhesion to many things
³ increases toughness
³ increases flexibility
³ increases optics
³ lowers seal initiation temperature
³ increases tackiness
³ increases “vinegar” odor
³ increases “chill roll sticking”
 EVA
Characteristics
³ EXTRUSION ISSUES:
³not moisture sensitive
³limited to processing temp max of 235C (455F)
³“Vinegar” (acetic acid) type odor
³Tackiness: with increasing VA content
³in coextrusion, EVA will bond with:
³PP, PE, PS, PVC, PVdC, and other resins to
various degrees
³you must purge it out well before raising extruder
temps back above 235C or before a shutdown.
 EVA Resins
Selection Factors
³ Resins typically available for extrusion coating and films:
³2.0% - 50% VA / 0.35 - 43.0 MI (dg/min)
³ Additive grades available containing slip, anti-block, chill roll
release
³ Suppliers: many worldwide in low VA levels (up to 15%);
several worldwide in high VA level (15 - 50%)
³DuPont, ExxonMobil, AT-Plastics, Equistar, Arkema, etc…...
³ A resin will be chosen FIRST based upon the end use
performance characteristics needed, and the processability for
extrusion coating, blown film, or cast film production.
 EVA application examples
in Extrusion Coating
³ Block Cheese package sealant
³OPP-ink / primer / 18% EVA with slip

³ Cookie / biscuit package sealant

³OPP-ink / adhesive // met-OPET / primer / PE / EVA

³ Condom package sealant

³OPET-ink / adhesive // foil / PE / EVA
³Cello-ink / primer / PE / foil / PE / EVA
 EVA application examples
in Film Extrusions
³ Cereal Box liner sealant:
³(HDPE - HDPE - 18% EVA with additives)

³ Vacuum Skin Packaging films:

³(ionomer - high% EVA)
 Ethylene Acrylate Copolymers

³ Features:
³similar to EVA, but with thermal stability up to 310C (590F).
³Used more in Industrial versus Packaging.
³will adhere to various materials in coextrusion
³have “acrylate” smell (instead of “vinegar” smell of EVA)
³ Suppliers:
³DuPont EBA, EEA, EMA; Mitsui-DuPont EEA;
³ExxonMobil EnBA, EMA; Arkema EBA, EMA;
³Dow EEA; Westlake EBA, EMA
³Mitsubishi EMA, EEA
³ MA=methyl acrylate, EA=ethyl acrylate, BA=butyl acrylate, nBA=normal
butyl acrylate, iBA=isobutyl acrylate
 Molecular structures

EBA (ethylene-butyl acrylate) C --O - CH2 CH2 CH2 CH3

EEA (ethylene-ethyl acrylate) C -- O - CH2 CH3

O

EMA (ethylene-methyl acrylate) C -- O - CH3

EVA (ethylene- vinyl acetate) O -- C - CH3

O
 Ethylene based Terpolymers

³ Polymers produced by polymerization of three feed streams,

of which one is ethylene to create the major components of
the molecular chains. These are “functionalized” resins.
³ The 2nd and 3rd monomers can come from a variety of
options;
³various acrylate types, maleic acid/anhydride, acrylic or
methacrylic acids, carbon monoxide, vinyl acetate, etc…
³ Suppliers:
³DuPont and Mitsui-DuPont
³Arkema, ExxonMobil, Sumitomo
 ACID COPOLYMER
CHEMISTRY
CH3
|
— CH2 — CH2 — CH2 — C — CH2 — CH2 — CH2 —
|
C
MAA O OH

HO O
C
|
— CH2 — CH2 — CH2 — C — CH2 — CH2 — CH2 —
|
CH3

Adding MAA (or AA) to the polymer gives:

³lower crystallinity
³strong polarity
³attraction between the polymer chains
 Types of Acid

Methacrylic acid: H

(E/MAA) H C H
O
H

C ⎯
⎯ C⎯C
H OH

Acrylic acid: H
H
O
(E/AA) C ⎯
⎯ C⎯C
H OH
 ACID COPOLYMER
CHARACTERISTICS

Excellent metal (aluminum) adhesion

Low sealing temperature
Very good hot tack strength (melt strength)
Broad sealing temperature range
Good Toughness
Good paper adhesion
 ACID COPOLYMER

³ Extrusion Issues:
³runs basically like LDPE
³not moisture sensitive
³can be used as tie layer for some resins
³requires corrosion protected equipment
³needs to be “purged” after use, and not left in the
equipment at shutdown
³some degree of tackiness
³can cross-link at high extruder temperature or
residence time.
 ACID COPOLYMER RESINS

E/MAA (ethylene methacrylic acid):

²DuPont
E/AA (ethylene acrylic acid):
²Dow, DuPont, and ExxonMobil

3% - 12% acid content common available commercially, but

higher weight percent grades are also available.

For extrusion: 0.8 - 20 MI (dg/min)

Additive grades available containing slip, antiblock, and / or

chill-roll release.
 ACID COPOLYMER end-use
Extrusion Coating examples

³Flavored edible oil sachet sealant

³ OPET or BONy - ink / primer / ACR

³Shampoo sachet foil adhesion/sealant

³ OPET-ink / primer / PE / foil / ACR

³Condiment foil adhesion/sealant

³ OPET-ink / primer / PE / foil / ACR
³ OPET-ink / primer / white ACR / foil / LLDPE

³Toothpaste tube tie layer

³ PE film / (white PE- ACR) / foil / (ACR – PE )/ PE film
 ACID COPOLYMER end-use
Film Extrusion examples

³Edible oil standup pouch sealant

³ OPET or BONy / ink / adhesive // (PE - ACR)

³Shampoo sachet sealant

³ OPET-ink / adhesive // vmPET / adhesive // (PE - ACR)

³Cable Shielding thermal laminating film

³ Black PE / (PE - ACR) //TL// 200u alu foil //TL// (ACR - PE) // cable
bundle
 IONOMER CHEMISTRY

CH3 CH3

— CH2 — CH2 — CH2 — C — CH2 — CH2 — CH2 — C

C C
Zn++ or O O- O OH
Na+ ION
O- O
CH3 C

— CH2 — C — CH2 — C — CH2 — CH2 — CH2 — CH2

C C
O OH

Partially neutralizing the acid:

• gives outstanding melt strength
• retains adhesion properties
 Ionomer Clusters

“Thermally reversible crosslinks”

 IONOMER
CHARACTERISTICS

Excellent hot tack strength

Excellent optics
Excellent oil/grease resistance
Excellent formability
Excellent seal through contamination
Very good metal (aluminum) adhesion
Low sealing temperature
Very broad sealing temperature range
 Film Stiffness
1%Secant Modulus(kpsi)

100
90 ionomer
80 SSC mPE's
70 cgct-
cgct-mpe CGCT mPE's
60
Z-N LPE's
50
40 EVA resins
ssc-
ssc-mpe
30 emaa Ionomers
zn-
zn-mpe
20 E/MAA
eva
10
0
0 2. 5 7. 10 12 1517 20 22 25
Stiffness
5 5 .5 .5 .5 increases
Weight Percent w/neutralization
Comonomer
 IONOMER

³ Extrusion Issues:
³runs basically like LDPE, but with slightly more
torque needed
³moisture sensitive
³some degree of tackiness
³needs to be “purged” after use, and not left in the
equipment at shutdown
³can cross-link at high extruder temperature or
residence time
³can be used as tie layer for some resins
³requires corrosion protected equipment
 IONOMER RESINS

Grades can be modified by:

³base acid content
³neutralization ion type and neutralization level
³viscosity (molecular weight) of the base resin
³viscosity of the final product (0.7 - 14 MI)
³Additive grades available containing slip, antiblock,
and/or chill-roll release
Suppliers:
³ DuPont (very long history of supply)
³ExxonMobil (medium history of supply)
³Dow, Schulman (newer entrants to market)
IONOMER end-use
examples

Processed meat sealant

Canister inner liner
Snack food sealants
Cookie/Biscuit sealants
Condom Package sealants
Skin Packaging films
Powdered Products
 Peel Seal Resins
³ Typically these are formulated resins.
³ They commonly use base resins of:
³LDPE, EVA, Acrylate copolymers, Acid copolymers, …
³they may contain one or more of the following modifiers:
³“tackifiers” --- modified phenols for example
³“rubberizers” --- EPR or mVLDPE for example
³“controlled contaminants” --- PB for example
³fillers and other materials……
³ Suppliers: - resin manufacturers; -converter’s own formulae
³‘ready to use’ resins from suppliers such as
³DuPont, Toyo Petrolite, Showa-Denko, Hirodyne, etc…...
 Selecting a resin for
Ext/Ctg as a Sealant:
Some Sealing Properties Some Processing Properties
Resin Hot Hot Low Seal Foil Draw- Low Ext Low
Type Tack Tack Seal Thru Adh ability Torque Neck-in
Peak Temp Temp Contam
Str Range
LDPE x x xx x X XX XXXX XX

mLLDPE xx x x xx X X X X

EVA xx xx xxxx xx NIL XX XX XX

EMA xx xx xxxx xx X XX XXX XX

mVLDPE xxxx x xxxx xxx X X X X

Acid xxx xxx xxxx xxx XXXX XXX XXX XXX

Copolymer
Ionomer xxxx xxxx xxxx xxxx XXX XXXX XXX XXXX

x=fair performance xxxx=high performance

 Selecting a resin for
Film as a Sealant:
Some Sealing Properties Some Processing Properties
Resin Hot Hot Low Seal Tackiness Draw Low Bubble
Type Tack Tack Seal Thru Ext Strength
Peak Temp Temp Contam Torque
Str Range
LDPE x x xx x X X XXXX XX

mLLDPE xx x x xx X XXX X X TO XX

EVA xx xx xxxx xx X TO XXXX XX XXX X TO XX

EMA xx xx xxxx xx X TO XXX XX XXX X

mVLDPE xxxx x xxxx xxx X TO XXX XXXX X X TO XX

Acid xxx xxx xxxx xxx XX XXX XXX XXX

Copolymer
Ionomer xxxx xxxx xxxx xxxx XX XXXX XXX XXXX

x=fair performance xxxx=high performance

 POLYPROPYLENE

H H
H

Made from propylene: C ⎯

⎯ C⎯C H

H H H

H H H H

H C H H C H H C H H C H
H H H H

Polypropylene: ⎯ C ⎯ C ⎯ C ⎯ C ⎯ C ⎯ C ⎯ C ⎯C ⎯
H H H H H H H H

Film is often oriented (“OPP”) to improve strength,

optics, and barrier properties
 PROPERTIES OF
POLYPROPYLENE

Good clarity

Relatively low cost

Good moisture barrier

Good seal strength

No oxidation needed
 POLYPROPYLENE
AS A SEALANT

“Copolymer” - propylene / ethylene

“Terpolymer” - propylene / ethylene / butene or others...
³reduced crystallinity
³lower sealing temperature (but still high vs. PE)

Snack package:
³ OPP-ink /primer/LDPE/metal-OPP/CoPP extr.ctg.
³ OPP-ink/CoPP extr.ctg.
³ OPP-ink/adhesive//vmCPP cast film
 Coextrudable Adhesive Resins
(“Tie” Resins)
³ Used to bond together resins in a “coextrusion”
³ Some resins will bond to others to various degrees of
strength
³ e.g.-- EVA bonds to many things if the VA level is high
enough, but perhaps not sufficiently.
³ Thus, “tie” resins are formulated with additions of grafted
materials, or other compounded modifiers to enhance
adhesion
³ Proper choice of the correct “tie” resin is based on many
variables. Processing parameters, enduse parameters,
etc…
³ Consult your “tie” resin supplier.
 Coextrudable Adhesive Resins
(“Tie” Resins)

³ Base Resins: Suppliers:

³LDPE, LLDPE, HDPE DuPont
³EVA, PP Mitsui
Equistar
³Acrylate copolymers
Mitsubishi
³Acid copolymers Arkema
³ Modifiers: Dow (Rohm & Haas)
³maleic anhydride DSM
…and several others.
³olefinic tougheners
³tackifiers
³rubbers
 Coextrudable Adhesive Resins
(“Tie” Resins)
³ Extrusion Issues:
³ get help to choose correct resin
³ watch for temp limits on EVA based tie resins
³ must match “rheology” with adjacent materials
³layer uniformity, no “interfacial instability”
³ there is a minimum temp needed for generating
adhesion with some materials
³ coextrusion feedblock and die design are also
influential factors for adhesion
³ extrusion “process time” is also an importanat factor.
Time of “cooling / drawing” of resins varies.
 Nylon

³ Types:
³Nylon 11 and 12: MP= 180C (360F)
³Nylon copolymers: MP= 210C (410C)
³Nylon 6: MP= 220C (430F)
³Nylon 66: MP= 250C (480F)
³Amorphous Nylon
³ Nylon screws are generally a different design than screws
for PE and ethylene copolymers
³ Suppliers:
³Honeywell, BASF, Bayer, DuPont, EMS,
³Mitsubishi, Ube, etc…
 Nylon

³ Features:
³Good gas barrier
³Good thermoformability
³Good toughness, abrasion resistance, tensiles...
³Good optics
³Good oil resistance
 Nylon

³ Extrusion Issues:
³crystalline melt point
³flow properties change rapidly from solid to melt
and back to solid. SAFETY!
³moisture sensitive
³various types, so need to choose extrusion
temperature profiles carefully
³“high” extrusion temperature needed
³almost always processed in coextrusion
 POLYESTER

Many types of polyester:

³most important type for films / sheet is PET
(polyethylene terephthalate)
PET is typically oriented to provide strength, clarity, and
barrier properties.
PET for extrusion coating is more challenging than olefins,
and requires special equipment. Use of coextrusion makes
it easier for running, but you still need dryers and proper
screw designs for the PET.
Suppliers of extrusion coating grades in the USA would be:
Eastman, DuPont, M&G (formerly Shell), ...
 EVOH
Ethylene Vinyl Alcohol
³ good oxygen barrier when dry
³ almost always run in coextrusion
³needs tie layers (except to Nylon)
³ moisture sensitive
³ thermal sensitivity
³needs short, smooth flow paths
³ good optical properties
³ high stiffness
³ flex crack sensitivity
³ Suppliers:
³Evalca, Kuraray, Nippon-Gohsei
What’s on the
Horizon?