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EAA Adhesivity
EAA Adhesivity
Background
Development of High Performance Ethylene Acrylic Acid (EAA) Copolymers
Chemical Structure of Ethylene Acrylic Acid (EAA) Copolymers
Physical Properties of Ethylene (E) and Acrylic Acid (AA) Copolymer
Ethylene Acrylic Acid Copolymer's Resistance to Light and High Temperature Exposure
Stability of Ethylene Acrylic Acid Copolymers
Wetting and Adhesion Properties of EAA Copolymer Dispersions
Modification to EAA Copolymer-based Coating
Uncrosslinked Ethylene Acrylic Acid Copolymers
Crosslinking Agents or Polymers for Ethylene Acrylic Acid Copolymers
Thermoplasticity of Ethylene Acrylic Acid Copolymers
Typical Coating Applications of Ethylene Acrylic Acid Copolymer Dispersions
Compatibility of Typical Coating Ingredients with Ethylene Acrylic Acid Copolymer
Dispersions
Compatibility of Two or More Binder Systems
Main Applications of EAA Copolymer Dispersions
Flexible Film Coatings of EAA Copolymers
Metal Coatings of EAA Copolymers
Paper coatings of EAA Copolymers
Textile Coatings of EAA Copolymers
Summary
Background
Michelman products that add value--and support that helps you win—are close at hand,
wherever you’re growing. Our products enhance the surface qualities of coatings and inks,
make composites tougher, and expand the possibilities of paper and film with barrier,
functional, and aesthetic features. Our extraordinary technical support helps ensure those
products deliver all they can to your bottom line.
Michelman can help you build next-generation performance into your products today. If
you’re looking for a product using established surface modifier or coating technology,
chances are we have it in stock. If you want something new, Michelman like to discuss
your needs. Many customer collaborations have resulted in product breakthroughs that still
lead their markets today.
This article will describe how new dispersion developments have evolved and discuss the
high performance properties now delivered on a wide variety of substrates. Requirements
for adhesion to non-polar substrates, faster line times and lower heat seal temperatures
are just a few of the developments explored in this paper.
On the other hand, acrylic acid brings polarity, toughness, crosslinkability, hot tack
strength, low temperature heat seal. The presence of AA reduces the crystallinity of E
segments. Increasing the AA content in an EAA copolymer will result in the formation of
more amorphous regions, disrupting the formation of crystals, as illustrated in Fig 1b. Just
as the increased branching in LDPE reduces the crystallinity of PE, so will the AA
behaves.
Furthermore, increasing the AA content will also increase adhesion to polar substrates,
decrease softening and melting point, improve optics and increase strength.
Fig 2 illustrated the properties brought by AA in the copolymer, whilst Table 1 summarizes
the properties of each individual monomer.
Hot tack
Modifying the ratio between the components can provide the balance needed to tailor the
copolymer properties in order to meet specific end-use application requirements. Those
properties and performances are reviewed in more details in the following sections.
Upon drying, both water and volatile neutralizing agent - such as ammonia or amine -
evaporate, leaving a surfactant - free EAA copolymer film on the coated substrate. Such
"clean" dispersions are less prone to water sensitivity, recoatability problems, optic defects
and reduced adhesion than polymer films deposited from surfactant -containing system.
Furthermore, EAA copolymers neutralized with aqueous or volatile amines are less water
sensitive compared to fixed alkali neutralized - EAA. Fixed alkali - neutralized EAA
dispersions result in the formation of ionomers. Ionomer films exhibit poorer adhesion and
increased water sensitivity, greater solvent and chemical resistance, and also higher
melting points. Modifying the type of neutralizing agent and also the degree of
neutralization, allows an EAA dispersion to be designed to meet specific properties.
Figure 3. Illustration of neutralised EAA copolymer chains in water and upon drying.
In house manufacturing experience and expertise in EAA copolymer dispersions give rise
to stable, small particle size colloidal dispersions. The dilution stability of EAA dispersions
is good, particularly with soft water, where an EAA content of 10 % solids remains stable
Whilst EAA copolymers with higher molecular weight resist freeze-thaw cycling better, care
should be taken with the lower molecular weight or low AA content species, which are
much more sensitive to low temperatures. One possible explanation could be that a higher
number of carboxylic functions present in high molecular chains, remains operational for
the electrostatic repulsion, as the electrolyte concentration increases on freezing.
Wetting and Adhesion Properties of EAA Copolymer
Dispersions
Adhesion is the result of interactions that develop between two dissimilar "bodies" when
they come into contact. It is a quantitative description of the work required to detach 2
surfaces. For a good adhesion to occur, good wetting of the substrate, high flexibility
polymer chain and maximized chemical interactions are necessary. EAA
copolymerdispersions meet all those requirements, which result in energetically good
adhesion conditions, as expressed by the surface energy.
H-Bonding 20 >C=O---HO-C=O
Corona treatment typically increases the surface energy of the surface by 5 to 20 mN/m,
depending on the treatment level. Although not an absolute number, a difference of at
least 10 mN/m is recommended to have good wetting / adhesion characteristics.
Crosslinking agents or
polymers
Melamine Formaldehyde
resins
Zn and Zr complexes
Epoxy resin
Polyethyleneimine
Thermoplasticity of Ethylene Acrylic Acid Copolymers
Some particular applications require large quantities of heat-seal film which can be sealed
to itself at a temperature which will not impair the film integrity. This is particularly the case
for flexible packaging. Polyolefins, particularly polypropylene, are in demand as film
materials owing to their strength and clarity but, in general, exhibit relatively poor heat seal
characteristics. This is due to the high crystallinity of such polymers. Introducing AA
segments in an ethylene chain will reduce the crystallinity, hence making the copolymer
softer and lowering the melting temperatures.
Application rates vary, based on intended use. As a primer on non-porous films or foil,
EAA copolymers should be applied at coating (dry) weights of 0,5 - 1,0 g/m2 . For porous
substrates, such as paper, the coating should be applied at slightly larger weights e.g. 0,8
- 1,2 g/m2.
Calcium Carbonate
+ +
Clay
+ +
Dyes +
Inorganic Pigments +
+
Colloidal Silica +
Organic Pigments +
+
Carbon Black +
Casein +
Starches +
+
Cationic Starch +
Methyl Cellulose +
+
Polyvinyl Alcohol +
Protein +
Di Octyl Adipate +
2-Ethyl Hexanol +
Mono Electrolytes
+
Di / Tri Electrolytes +
MF Resin +
SMA Resin +
+
Furthermore, the enhanced thermoplasticity behaviours of EAA make them attractive heat-
seal coatings. The presence of AA segments in the copolymer, will reduce the heat-seal
temperatures (sealing 20 - 30 °C lower than LDPE) and the high degree of hot tack will
improve line speeds and cut costs in most flexible packaging applications. EAA
copolymers can be used either in extrusion or in laminate coatings. Strong adhesive bonds
will enable EAA to be used in lamination of foil - foil, paper - foil and paper - paper. When
EAA copolymers are used as laminating coatings, the recommended coating (dry) weight
is 1,6 - 2,4 g/m2. Fig 5 illustrates the influence of AA content on the heat-seal temperatures
and bond strength.
Figure 5. Influence of AA content on the heat-seal temperatures and bond strength.
Metal coatings are another typical application where EAA dispersions can be very
useful. This includes coatings for cans, coils, industrial equipment, automotive …,
all applications where high adhesion properties are required. The literature reports
the use of Zn-crosslinked acrylate oligomers in UV-cured coatings for metals (6).
The ability of EAA copolymers to crosslink with metal ions, its excellent adhesion
properties to metal surfaces, and the flexibility and barrier properties obtained with
the E segments definitely open doors to numerous applications in metal coatings.
Can coatings are one area where waterborne paints are finding some growth.
Water-based coatings are easier to be approved in critical application areas such
as food packaging. Furthermore, the metal packaging area for food and beverage
is facing tough competition from PET bottles, due to restrictions on the use of
certain components such as dioxins and Bisphenol A. It is important for can coating
formulators to find acceptable alternatives, while maintaining the high level of
technical requirements. Coatings for cans have to have enough flexibility and
adhesion strength in demanding process conditions. Based on the EAA
performances as mentioned previously, it is worth thinking about the potential that
EAA copolymers can offer in this application. Furthermore, the fact that EAA
copolymers comply with BfR XIV and BfR XXXVI chapters as well as with most
FDA sections constitutes another non-negligible argument for their use in food
packaging.
In this application, EAA copolymer dispersions are frequently formulated with pigments or
fillers such as clay, Calcium carbonate, Titanium dioxide or Carbon black. For optimal
performance, the filler - typically 65 to 75 % solids - should be pre-dispersed with 0.1 to 0.3
% dispersing aids (polyacrylates) in water. An additional dispersant might be necessary to
minimize pigment shock, particularly with very fine particle size fillers.
Textiles come in many forms. Structurally, they are termed knits, weaves or nonwovens to
distinguish the process by which the fibers are arrayed in their final presentation. Thanks
to their particular properties, EAA copolymer dispersion can be used in textile application
for:
Back adhesive on a tufted carpet. EAA copolymers could be applied directly to the
back of tufted carpet that is made from rough fibers (e.g. jute), causing the tufted
fibers to adhere strongly to each other, and making the overall structure much
more stable. The backcoating formulation includes thickener, filler and additives.
The backcoating is applied by a wetted roller applicator and the coated carpet is
then dried. If a warranty for washability is required, the use of a crosslinker - such
as melamine / formaldehyde resin - can be envisaged.
Fusible interlining in garment manufacture. Fusible interlinings comprised of a
textile sheet which is coated with a thermoplastic adhesive, such as copolyamide,
copolyester and polyethylene, both LD and HD types. Fusing is the bonding of the
interlining to the outer fabric. It can be done with a hand-iron or with continuous
fusing presses with double pressing units. By application of heat over a certain
period of time, the thermoplastic adhesive turns soft or melts and penetrates the
yarn and woven structure of the textile.
Summary
In this article, we have provided a description of how EAA copolymer dispersions are used
in some industrial coating areas. Incorporating AA segments in a PE chain brings new
properties such as adhesion, whilst still offering barrier properties. Our intent herein is to
give readers a broader understanding of EAA copolymer technology applications in
coatings and to stimulate new ideas in research and development.
This information has been sourced, reviewed and adapted from materials provided by
Michelman.