Pressure sensitive adhesive performance

The effect of chemistry

J.A. Fries

Regulatory and economic pressures are forcing reassessment of the value-in-use of the
various pressure sensitive adhesives now used. The emphasis has been directed mainly
towards the relative merit of physical forms: solvent solution, water-borne emulsion/
latex, and 100% solids hot melt. While form is a major concern, property variations due
to chemical differences in the two major types - rubber/resin and acrylic copolymer -
should also be an integral part of the alternative evaluation process. Each chemistry
involves advantages and disadvantages. An understanding of the differences between
them and of the effect o f the constraints imposed by that chemistry gives a basis for
rational selection for a given end-use.

Key words: adhesives; adhesive paper; pressure-sensitive materials

Pressure sensitives have been a major adhesive type since trade press and conference meetings. Most of this infor-
their introduction for self-adhesive labels in the mid-1930's. mation addresses problems caused by the use of high per-
For nrost of that forty-five or more years the majority of centages of solvents in conventional I'SAs.Such factors as
pressure-sensitive adhesives (eSAs) have been blends of rubber compliance with various regulations, relative process energy
and tackifying resins, carried in an organic solvent vehicle. demand and cost stabilization have been well reviewed. The
An alternative chemistry, that of the acrylic copolymers, coater now has sufficient information available regarding
was introduced in the late 1950's and rapidly gained a place the alternative forms to make a reasoned choice. Far less
in the market, particularly for plastic film and graphic arts information is available about the impact of the two major
applications. Other chemical approaches, based on silicone, chemistries -- rubber/resin and acrylic copolymer .... on pres-
urethane, polyvinyl ethers and ethylene-vinyl acetate back sure sensitive properties. Since both types are now provided
bones, have also been utilized, although to a much lesser in all three physical forms, the choice should also be based
degree. on considerations of perfornrance as related to chemistry.
The mix remained relatively static for several years, with
the rubber/resin solutions used for large volume applications
Pressure sensitive bonding
such as self-adhesive paper labels and most tapes, and the
acrylics for speciality applications. Two events of the 1970's, Tile unique distinguishing characteristic of PSA~is their
however, have had and are having today, major impacts on capability of forming an instantly usable bond upon bringing
the pressure sensitive adhesive industry. The 1973/74 oil a dry, adhesive coated surface into contact with an uncoated
embargo started a spiral of cost increases for solvents and surface under light contact pressure at room tenrperature.
other raw materials derived from petroleum: passage of the This property, 'tack'* requires that the adhesive mass make
1977 amendments to the Clean Air Act of 1970 require a almost instantaneous intimate contact with the second
major cutback in the amount of volatile organic compounds surface (a characteristic of a liquid'i'). Balancing this neces-
(vo(') emitted into the air. These two factors resulted in a sary liquidity with adequate cohesion {internal strength) is
search for less costly, regulatory-complying alternatives. As the perennial challange confronting the pressure sensitive
a consequence of the research and development effort, adhesive chemist.
several practical options are now available to the convertor
of pressure scnsitives. *The term 'tack' is used in a different sense with other adhesive
Manufacturers of I'SAshave accumulated considerable types. For example, in contact cements, tack is the open time during
which t w o freshly coated surfaces may be joined before crystaliz-
data about the relative merits of the three forms: solvent- ation makes film fusion impractical.
solution; water-borne dispersion; and 100'7csolids hot mehs. I"A second condition for wetting, the relative surface free energies
These data have been made available in forums such as the of the t w o materials, will be ignored as not relevant to this discussion.

0143-7496/82/030187-05 $03.00 © 1982 Butterworth & Co (Publishers) Ltd

INT.J.ADHESION AND ADHESIVES JULY 1982 187

 Liquid flow properties are easily obtained from low esters, polyterpenes, and/or, totally synthetic types.
cohesion materials, the extreme case being water which The mechanism by which a tough, non-tacky rubber and
wets most surfaces instantly. Such mobile liquids have no a brittle, also tack-free solid resin, combine to produce a new
utility as adhesives, of course, due to their very low internal material having a high degree of tack is not totally under-
strength. On the other hand, most high cohesion materials stood. Frank Wetzel 14 demonstrated the presence of a
such as plastics exhibit effectively zero flow properties, of resin-rich, plasticized phase at the surface of tacky pressure
the type needed here. There are two ways to achieve the sensitive films. Useful tack was found over a relatively
necessary balance: narrow range of resin to rubber concentrations, as shown in
1. By utilizing an essentially homogenous mass and depend- generalized form in Fig. 1.
ing on monomer and comonomer selection for desired
Anti-oxidants
mobility/cohesion. This is the approach used with
acrylic copolymers. Most rubbers and many tackifiers are unsaturated, ie contain
double bonds (-C = C-) in their structure. These sites are
2. By designing a heterogenous system, with a continuous,
reactive with oxygen and ozone, leading to property changes
relatively tough phase supplying cohesive strength and a (degradation). Anti-oxidants are chemicals which prefer-
discontinuous, partially incompatible mobile phase entially react with oxygen and are used to protect the
providing wetting at the surface. This method is used in system from such degradation. Their effectivenessdecreases
most rubber/resin PSas. with time as they are used up.
The differences in requirements of the two approaches
account for many of the performance variations between Miscellaneous ingredients
acrylic and rubber-based pressure sensitives. Other additives such as curing agents, fillers and pigments
may be present in specific formulations.

PSA composition and formulating Acrylic ¢opolymers

Rubber/resin Acrylic copolymer pressure sensitives are based on a totally
Rubber/resin PSAs, regardless of the physical form in which different chemical approach. These are essentially pure
they are supplied, are formulated as physical mixtures of polymeric systems, with external modifiers playing a mini-
several components, each contributing a specific property. mal role. Properties such as tack, cohesion, specific adhesion,
low temperature flexibility, etc are obtained from a com-
Rubber bination of:
The rubber* component provides cohesive strength and Monomer selection, and;
flexibility and functions as a matrix within which the other Degree of polymerization and/or cross-linking.
ingredients are dispersed and/or dissolved.
Before the introduction of synthetic rubbers during Monomers are low molecular weight compounds, eg 2 ethyl-
World War II, all PSAswere based on natural rubber. Natural hexyl acrylate. Two or more are selected, depending on the
rubber is still widely used, either alone or in combination properties required, and copolymerized into a polymer in
with synthetic types such as styrene-butadiene (SBR). which multiple monomer units are joined, forming the
Other PSAsare based totally on synthetics: SBR; poly- finished adhesive. One (or more) of the monomers is always
isobutylene; butyl; and the newer block copolymer types an acrylic acid ester, accounting for the generic term
such as styrene-isoprene-styrene. "acrylics' or 'acrylates'. Other, non-acrylic types are also
Unless drastically degraded by physical mastication used for specific properties, for example, vinyl acetate.
(milling) or chemical peptization, at which point cohesion Monomer selection and ratio determines specific adhesion,
is lost, rubbers by themselves have little or no pressure low temperature bonding and flexibility retention,
sensitive tack. Modification by the addition of tackifiers is
needed.
Tackifiers
A wide variety of compounds is available for addition to the
base rubber to provide ~ackification; solid, amorphous
resins (often brittle solids at room temperature) and liquid
plasticizers and oils are used. Early PSAsutilized naturally
occuring resins and plasticizers such as lanolin; current types
use these, chemically-modified variants such as the rosin
I i I I
0 20 40 60 80 100
*'Rubber' is properly reserved for the product of the rubber tree, ia
Resin (%)
natural rubber, but is used here in plo¢~ o f the mon~ general term,
'elastomer', which applies to any o f the cl=m o f materials having Fig. 1 Typical curve obtained for degree of 'tack' when adding
reversible extensibility. amorphous resins to rubber-bas~l adhesives

188 INT.J.ADHESION AND ADHESIVES JULY 1982

waocu.e on/9 ee,aetoee Se/z,e/ 've dAe tP

functionality for cross-linking and, to a large degree, tack. Ageing

The degree of polymerization or cross-linking determines Rubber/resin
cohesion, heat resistance, chemical resistance as well as Unsaturation in the polymer(s) make them susceptible to
influencing tack level. oxygen (and ozone) reactivity. The reaction products have
The polymers are completely saturated and no anti- properties differing from the original system: either softer
oxidants are needed: they are inherently inert to oxygen/ as with natural rubber-based grades; or embrittled, as with
ozone degradation. SBRs. Antioxidants give protection but are ultimately con-
sumed in performing their function. The consumption rate
Cohesion and molecular weight is proportional to the degree of exposure to air and to
With both rubber/resin acrylic copolymer PSAs, cohesive temperature, ie oxidation reaction rates roughly double for
strength and heat resistance are a function of molecular each 10°C temperature increase. Rubber/resin systems in
weight. In the water-borne form - acrylic emulsions or the hot melt form require special care. The need for heating
rubber/resin latex - molecular weight of the polymers has to up to 176°C can result in oxidation even before use as an
no effect on the viscosity of the liquid adhesive, the mass adhesive, therefore, high temperature exposure should be
being isolated from the water vehicle in discrete particles. In minimized, and the system protected by inert gas blanketing
solution types and in hot melts (100% solids), however, during processing.
molecular weight-induced viscosity is a limiting factor. Rubber/resin PSAsshould be carefully tested for suitability
Various mechanisms are used to attempt to compensate, in applications involving either porous face stocks such as
allowing reasonable coating viscosities without excessive lightweight papers or porous substrates such as fabrics,
sacrifice in cohesion. The most commonly used hot melt especially if long bond life is needed or if exposure to
PSAs are based on specially designed block polymers which elevated temperature is likely.
combine elastomeric and plastic segments in the same
polymer chain. On heating, the plastic segments melt, Acrylic copolymers
reducing viscosity to a point suitable for coating. The saturated polymers used in acrylate PSAs are inert to
With solutions, the situation is more complex. The ideal oxidation effects.
is generally the highest possible solids content, for process
efficiency and economic purposes, combined with low Clarity
viscosity for ease of coating, flow-out and drying.
An increase in cohesion/heat resistance in the case of Rubber/resin
rubber-based solution PSAs requires a post-curing step. Such Most rubber-based PSAshave some degree of colour, con-
reactions involve the use of highly reactive, short pot-life tributed by the polymer(s), or the tackifier(s), or both. A
additives and/or high initiation temperatures, while still few special purpose systems have been formulated with
leaving the tackifiers uncured - a source of thermoplasticity. water-white clarity but these are not suitable for general
Acrylic copolymer solutions are available in three types: applications.
In addition, rubber systems are usually susceptible to
thermoplasts in which cohesion is a simple function of
light-induced darkening, with the ultimate colour ranging
molecular weight;
from light yellow to dark brown. As such, these I'SAsare
heat-curing types; and not suitable for certain applications, for example, clear
self-curing types. decals, where water-whiteness and long term resistance to
The latter, since their introduction in the early 1970's, have discolouration under sunlight are needed.
quickly assumed a dominant position. The cross-linking
Acrylic copolymers
mechanism is built into the polymer, inhibited while in
solution and then spontaneously activated upon solvent Acrylic PSAs can be designed to exhibit both initial clarity
removal. This approach allows high solids, low viscosity and complete resistance to darkening on ageing in light.
systems tot efficiency and economics which then cross-link This is not universally true with acrylics, however, and where
to supply the cohesion/heat resistance associated with high this property is a consideration in use it should be specified
molecular weight. to the supplier or formulator.

Performance and chemistry Cohesion

The basic differences in approach between rubber/resin and Rubber/resin
acrylic copolymer PSAs impacts on most areas of performance. Rubber-based PSAsare capable of extremely high cohesive
For some uses the rubber/resin type is more satisfactory; strengths, even without post-cure. The more cohesive of the
for others, the acrylic. The choice between the two options, rubber grades surpasses the acrylics in this respect. Some of
for a particular use, should be based on a comparison of the advantage is lost, however, if the service temperature is
their performance capabilities in all the parameters pertinent even moderately elevated. The elastomeric portion of the
to the application. system is frequently resistant but the tackifiers - even those

INT.J.ADHESION AND ADHESIVES JULY 1982 189

, tocu.e Se/a.et 'v,r :t'he.e/ve..e

which are hard solids at room temperature - generally have Acrylic copolymers
low melting points resulting in softening of the entire mass. Acrylics are also softened by absorption of plasticizers and
However, service temperatures can be extended upwards via oils. The impact can be minimized through proper monomer
curing where this is practical. selection and grades are available which function with little
Hot melt rubber-based types are especially prone to heat- loss in properties, even on highly plasticized face stocks and/
induced softening and eohedon loss. Latex grades, where or substrates.
higher molecular weights are practical, generally retain a
somewhat greater percentage of original cohesion at Migration
moderately elevated temperatures.
Rubber/resin
Acrylic copolymers Rubber/resin PSAsare physical mixtures of formulating
Acrylics do not normally contain low melting point modi- ingredients. In many cases, particularly in adhesives designed
tiers and are, therfore, less thermoplastic (except in the, so for low temperature uses or as removables, these materials
far, developmental hot melt grades). Self cross-linking are mobile liquids. Such ingredients are migratory and can
solutions and the emulsion forms are particularly useful. penetrate into and through face stocks, causing staining.
Staining of labelled substrates is also a potential problem.
Low temperature properties Acrylic copolymers
Rubber~resin Acrylic PSAs contain little if any unbound additives. Staining
of face stocks or substrates is seldom a problem.
Rubber stiffens at low temperatures and, at some point,
embrittles. In PSAsintended for either application at
moderately low temperatures (below about 10°C) or where Specific Klhesion
retention of flexibility in extreme cold is needed, formulation Rubber~resin
with special low temperature plasticizers is needed. While Rubber-based PSAs are generally non-polar and, as such,
effective, such plasticization results in severe cohesion loss, tend to adhere poorly to polar substrates such as glass,
restricting the useful temperature range, especially the upper metals, and plastics (ie polyesters and most engineering
limit, at which the adhesive can function. Systems designed grades). Primers or plasticizer addition are frequently needed
for low temperatures generally have little cohesion at room to permit bonding to these surfaces, either as face stocks or
temperature. substrates.
Conversely, rubber/resin types generally have good
Acrylic copolymers specific adhesion to non-polar materials, and even, to a
Most acrylic copolymers remain flexible to about - 35°C. degree, untreated polyolefins.
Low temperature bonding properties are imparted through
monomer selection, without the need for external plastic- Acrylic copolgmers
izers. Such systems have good cohesion at higher The polar acrylics have superior adhesion to the polar
temperatures. surfaces mentioned above. Adhesion to non-polar materials
is generally lacking, except with softer (low molecular
weight) types.
Plasticizer resistance
The term 'plasticizer' encompasses the spectrum of liquid Chemical resistance
modifiers used to impart flexibility to plastics such as
PVC. These modifiers are un-bound and therefore, migratory.
Rubber~resin
Solubility also is a function of polarity. Non-polar rubber-
Rubber~resin based PSAs are dissolved in or swell in non.polar solvents
Rubber-based PSAs contain tackifier/plasticizers as part of their such as gasoline, turpentine and jet fuel (kerosene). They
basic formulation. As described above, optimum performance resist the effects of the oxygenated polar solvents such as
is achieved only when the ratio of rubber to tackifier is acetone and ethyl acetate.
restricted to a narrow range. If this ratio is skewed by Rubber grades tend to be more resistant to acid or
absorption of extra plasticizer from a substrate, cohesion alkaline attack and are usually the products of choice for
suffers. The dramatic softening effect of migratory phthalate end uses involving contact with such environments as, for
plasticizers from flexible Pvc is illustrative. Rubber/resin example, in battery labels.
PSAs, with a few specially formulated exceptions, are not
generally suitable for use with plasticized face stocks unless Acrylic copolymers
the mass is protected from the migratory components by a The polar acrylates respond in the opposite manner. They
barrier coating. The identical softening effect occurs when resist non-polar solvents but swell or dissolve in the oxygen-
(most) rubber PSAs are applied to plasticized substrates, as containing types. The effect is lessened, however, by cross-
for example with self-adhesive paper labels on vinyl luggage. linking.

190 INTJADHESION AND ADHESIVES JULY 1982

a ocu.e on/o e. tOee Se/' / Pe (TdAe. t'v

Acrylics are less resistant to exposure to strong acids and burdens in terms of time and resource investment, it can
alkalis than rubber/resin types. also be an opportunity to select a more nearly optimal
product mix from the variety of types and physical forms
Water resistance now available.
Both rubber/resin and acrylic copolymers, in their solvent-
borne or hot melt forms, are inherently water resistant Acknowledgement
insofar as the mass itself is concerned. Actual suitability in
This paper was first presented at a seminar entitled: 'Today's
a given use is more often a question of wetting and specific
Technology and Future Directions' held at Rosemont, IL,
adhesion. Intimate contact and anchorage to the face stock
USA in 1981 and organized by the Pressure Sensitive Tape
and/or substrate is necessary to prevent water from entering
Council (USA). It is published here by kind permission of
under the adhesive layer by capillary action and causing
the organizers. It has also appeared in Paper, Film and Foil
lifting through hydraulic forces.
Rubber latex and acrylic emulsion forms are more
Converter (October, 1981 ).
susceptible to property loss in the presence of water or
high moisture vapour levels due to the use of water-sensitive References
surfactants in their preparation. Both, however, can be 1 Wetzel, F. ASTM Bulletin No 221 (1957)
suitable for such uses when properly formulated.
2 Wetzel, F. RubberAge (November 1957)
3 Wetzel, F. Rubber Age (December 1957)
Conclusion
4 Wetzel, F. Adhesives age (January 1964)
Both rubber/resin and acrylic copolymer PSAs, in all their
physical forms, have a place in the pressure sensitive coating
Author
industry. No one type or form is optimum for all applications.
Regulatory constraints and rising raw material and energy Mr Fries is with National Adhesives, National Starch and
costs have motivated a search in the industry for complying, Chemical Corporation, PO Box 6500, Bridgewater, NJ
cost-effective systems. While the evaluation process imposes O8807, USA.

INT.J.ADHESION AND ADHESIVES JULY 1982 191