21

Polyvinyl Acetate Emulsions

for Adhesives
HAROLD L. JAFFE
Chemical Consultant
Millburn, New Jersey
and
FRANKLIN M. ROSENBLUM AND WILEY DANIELS
Air Products and Chemicals, Inc.
Allentown, Pennsylvania

Polyvinyl acetate has been available commer- ticated polymer and copolymer products have
cially in the United States since the 1930s. been commercialized to meet the needs of
Growth was slow until the 1940s, when poly- changing technology.
vinyl acetate emulsions were introduced. The The excellent adhesion of polyvinyl acetate
volume of resin consumed has since grown emulsions to cellulosic and other materials gave
from a negligible amount in 1945 to 1.7 billion rise to an abundance of applications, including
pounds currently. bookbinding, paper bags, milk cartons, drink-
The adhesive industry is one of the most im- ing straws, envelopes, gummed tapes, convo-
portant outlets for polyvinyl acetate. An esti- lute tubes, folding boxes, multiwall shipping
mated 500 million pounds was used bags, labels, foils, film and paper board decals,
domestically in adhesives in 1987. Polyvinyl cigarette tips, lagging compounds, wood as-
acetate also goes into surface coatings, caulks, sembly, padding, automobile upholstery, pen-
etc. cils, leather binding, and tile cements.
Polyvinyl acetate came into widespread use Because of their relatively low cost, ready
in adhesives in the 1940s as a synthetic resin availability, wide compatibility, and excellent
substitute for hide glue. Superior properties of adhesive characteristics, many polyvinyl ace-
the synthetic resins offset their higher price. tate resins, solutions, and emulsions are treated
Polyvinyl acetate adhesives were adaptable to as commodity items by the adhesives industry.
new high-speed machinery in the paper con- Among the many U.S. manufacturers of poly-
verting and packaging fields and were enthu- vinyl acetate based resins are the following ma-
siastically received. They found a place in jor producers: Air Products, H. B. Fuller,
wood adhesives and later were introduced in National Starch, Reichhold, Rohm and Haas,
the familiar household "white glue." Signifi- Union Carbide, Union Oil, and W. R.Grace.
cant advances have taken place in polyvinyl The resulting competition has benefited adhe-
acetate technology. A large number of sophis- sives formulators with low prices, good qual-

I. Skeist (ed.), Handbook of Adhesives

381
© Van Nostrand Reinhold, New York, NY 1990
382 HANDBOOK OF ADHESIVES

ity, new improved products, and greater aqueous dispersions and (2) solid resins de-
technical service from the resin manufacturers. rived from aqueous dispersions.
Price variation is a common experience in this
competitive market. Grade of resin and volume Polymerization
are important factors in selling price.
Early studies of the polymerization of vinyl
Emphasis on the use of polyvinyl acetate in
acetate and the structure and properties of the
the adhesives industry alone gives a rather con-
polymer were made during the first quarter of
fining picture of the resin. Its use in other .in-
the century. 15,16 The first patents on polymeri-
dustries actually depends on its adhesive,
zation were also issued during that period. 17.18
binding, and film properties as much as it does
The real commercial development on the con-
in the adhesives industry. 1 Among the major
tinent began in 1925. Commercial polymeri-
outlets for polyvinyl acetate emulsions are in-
zation was underway by 1929. 19- 21 Since then,
terior and exterior flat paints, particularly for
a wealth of technical literature has been pub-
masonry surfaces. Leveling and color retention
lished dealing with polyvinyl acetate. 22 A par-
are the outstanding properties of these coat-
ticularly comprehensive article and bibliog-
ings. The textile industry utilizes polyvinyl
raphy on vinyl acetate polymerization and
acetates, mostly in emulsion fonn, for finishes
polymer properties is found in the "Encyclo-
that impart durability, strength, and "hand" to
pedia of Polymer Science and Technology." 12
woven cotton and other fabrics. Emulsions of
Vinyl acetate polymerizes by a free-radical
vinyl acetate and comonomers serve as binders
mechanism. Free radicals generated by the de-
for nonwoven or bonded fabrics. The paper in-
composition of organic peroxides such as ben-
dustry uses small particle size polyvinyl acetate
zoyl or hydrogen peroxide or of inorganic
emulsions as pigment binders for clays in paper
"per" salts such as potassium or ammonium
and paper board coatings.
persulfate are commonly used to initiate poly-
merization. Reactions ordinarily are accom-
Monomer
plished at temperatures above room temper-
Vinyl acetate is the most available and widely ature. Other techniques of polymerization have
used member of the vinyl ester family. This been used to make novel products; low tem-
colorless, flammable liquid was first prepared perature redox polymerization, irradiation, and
in 1912. Liquid-phase processes were com- ionic catalysis.
mercialized early in Germany and Canada, 3 but High molecular weight and essentially linear
these have been replaced generally by vapor- polymers, controlled particle size in the case of
phase processes. Earlier commercial processes emulsions, and even polymers with spatially
were based on the catalyzed reaction of acety- regulated structures are available. Vinyl acetate
lene with acetic acid. The more recent techni- copolymerizes with many other vinyl mono-
cal development is the production of vinyl mers. Acrylate esters; vinyl chloride and vi-
acetate monomer from ethylene and acetic acid. nylidene chloride; dibutyl and other dialkyl
Palladium catalyst is used for the vapor phase maleates and fumarates; crotonic, acrylic,
process. The ethylene route is the dominant methacrylic and itaconic acids; vinyl pyrroli-
route worldwide. done; and ethylene are commercially important
Vinyl acetate is manufactured in the U.S. by comonomers. 2 A monomer that does not com-
Borden, Celanese, duPont, Union Carbide, and bine with vinyl acetate alone may be combined
U.S.1. Chemicals. Its properties and reactions by use of a third monomer. "Grafting" can be
are reviewed in trade bulletins of the sup- used with monomers such as styrene that do not
pliers,6-9 and more extensive discussions are copolymerize with vinyl acetate.
presented in technical literature. 10-14 Laboratory processes for the polymerization
Domestic capacity for production of vinyl of vinyl acetate and some of the other vinyl es-
acetate in the U.S. was estimated to be 2.4 bil- ters are readily available from monomer sup-
lion pounds per year in 1987. pliers and in the patent literature. Commer-
The discussion that follows covers (1) cially, vinyl acetate polymers have been made
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 383

by all of the standard methods: bulk, suspen- hesives market is served by vinyl acetate and
sion, emulsion, and solution. 2 ,12 Manufactur- its copolymers.
ing processes are also available. 12

Emulsions ADVANTAGES OF POLYVINYL

ACETATE EMULSIONS
Polyvinyl acetate is most widely used in the
form of a dispersion of solid resin in water. Adhesion to a Wide Variety of Surfaces
These dispersions are produced by emulsion
Polyvinyl acetate resins adhere well to more
polymerization and are more commonly termed
surfaces than most other adhesive bases. Poly-
emulsions. In 1987, production volume was on
vinyl acetate homopolymers bond particularly
the order of 1.7 billion wet pounds for all uses
well to wood and paper substrates. Copolymers
and 500 million wet pounds for adhesives. Most
of polyvinyl acetates adhere to, or can be com-
products for adhesives are sold at 55 % solids
pounded to adhere to, a wide variety of plastic
at a sufficiently high viscosity level to facilitate
film and metal foils that are frequently lami-
use. These products are manufactured by one
nated or combined with paper and wood.
of several techniques23 - 26-batch, continuous,
or delay feed, depending on properties desired.
High Molecular Weight
The large volume usage depends not only on
the outstanding adhesive properties of the resin Polyvinyl acetate emulsions have the advan-
but also on the excellent compatibility of the tage of combining high molecular weight with
emulsions with many modifying agents. I low usable viscosity. Since the molecular
The properties, uses, and methods of for- weight of the polyvi~yl acetate does not affect
mulating emulsions are graphically and com- the viscosity of the emulsion, it is possible to
prehensively described in the trade literature, design adhesive bases which have high cohe-
which is an excellent source of information. sive strength and toughness, and yet also have
Most manufacturers specify properties of their viscosities that allow application by roller,
emulsions in terms of percent solids, emulsion spray, or extruder.
viscosity, pH, acid content, percent unreacted
monomer, and density. Other properties gen- High Solids
erally described are particle size, molecular
The emulsion form of polyvinyl acetate also al-
weight, film properties such as clarity, water
lows the production of high solids (55%) ad-
and grease resistance, and tolerance of the
hesives at low viscosities. It is possible,
emulsions to various organic and inorganic
therefore, to make rapid-setting, low shrinkage
chemicals.
adhesives at viscosities which permit them to
Although all components of an adhesive (film
be easily applied by roller, spray, or extruder.
formers, plasticizers, viscosity modifiers, tack-
Recent emulsions contain 65-66 % solids while
ifiers, solvents, fillers, and surfactants) have
maintaining low viscosity. 27
strong influence on the performance of the ad-
hesive, the film formers or polymer emulsions
Rapid Setting Speeds
are the most important. This is because the pol-
ymers, through molecular weight and struc- In the case of emulsion-based adhesives, the
ture, contribute such vital properties as tensile loss of a relatively small amount of water will
strength, toughness, flexibility, specific adhe- cause the inversion of the emulsion and rapid
sion, chemical resistance, mechanical stability, setting of the adhesive. This contrasts favora-
and compatibility with modifiers. bly to solution-based adhesives, both water and
The fundamental properties of the polymer organic solvent types, which require that most
background determine the suitability of a given of their solvent be lost to the atmosphere and/
type. of emulsion for a particular market. or absorbed into the substrate before they be-
Though styrene butadiene and acrylics are come tacky enough to hold the substrate to-
widely used, the largest portion of the U.S. ad- gether. In fact, even more solvent must be lost
384 HANDBOOK OF ADHESIVES

before strong, fiber-tearing bonds can be ob- Low Toxicity

tained.
Polyvinyl acetate adhesives have a low degree
of toxicity and have been used in food pack-
Easy Modification of Water and Solvent
aging for decades. They have been approved
Resistance
for this use by the Food and Drug Administra-
Polyvinyl acetate can be protected with colloid tion.
systems, surfactant systems, or a combination
of both. 12 By varying the protection system, it Minimal Environmental Impact
is possible to produce adhesive bases whose
Polyvinyl acetate emulsions, as a class, have a
relative water resistance will differ in range
low biological and chemical oxygen demand.
from water remoistenable to water resistant (24
hr) and even to boiling water resistant. The
HOMOPOLYMERS AND COPOLYMERS
choice of a protection system used in an adhe-
sive base will also affect the degree of solvent Homopolymers
resistance. 4o
The early polyvinyl acetate emulsions were ho-
mopolymers protected with partially hydro-
Good Machining Characteristics
lyzed polyvinyl alcohol. These high molecular
Polyvinyl acetate-based adhesives have a high weight polymers had great strength and set rap-
degree of mechanical stability and machine well idly to hard, horny films. Today, these homo-
in many different modes of application. At the polymers are the workhorses of the industry due
same time, they will set very rapidly. to their excellent adhesion to uncoated paper,
wood, concrete, ceramics, and glass. In addi-
Ease of Compounding tion, they exhibit a fair degree of water sensi-
tivity. This allows them to be easily cleaned
Polyvinyl acetate emulsion adhesives can be
from equipment and permits their use in re-
compounded using very basic mixing equip-
moistenable adhesives.
ment and procedures. Many resins, plasticiz-
ers, solvents, and fillers can be blended directly
Copolymers
into the emulsion without preemulsifying or
predispersing the additives. The ability to mod- Since polyvinyl acetate is a stiff material, the
ify polyvinyl acetate with a wide variety of ad- need for more flexible versions became appar-
ditives makes the adhesives more versatile and ent early in the development of the industry.
allows adhesion to a wider number of sub- The adhering of plastic films to paper and the
strates than adhesives made from other resin bonding of resin-coated paperboard in packag-
bases. ing applications are two examples of this need
for greater flexibility .
Resistance to Microorganisms Flexibility can be obtained either by com-
pounding with an external plasticizer or by co-
Dried polyvinyl acetate adhesive films are
polymerizing with a suitable monomer. When
highly resistant to attack by microorganisms.
a homopolymer adhesive is flexibilized with
The addition of biocides will prevent attack of
external plasticizers and/or solvents, the re-
microorganisms on a liquid emulsion or on a
sultant bonds frequently fail on aging because
dried adhesive film when animal or vegetable
of plasticizer migration. This may occur in any
modifying ingredients have been added to the
of three ways: (a) the plasticizer may migrate
emulsion.
into the plastic substrate, leaving a brittle ad-
hesive which loses its bond in as little as 7-10
Resistance to Oxidation and Ultraviolet
days; (b) if the substrate is plasticized PVC,
Radiation
the plasticizer in the substrate may migrate into
Polyvinyl acetate is a saturated molecule and is the adhesive, softening it to the point where it
therefore not subject to degradation by oxygen, has little cohesive strength; or (c) the plasti-
ozone, or ultraviolet radiation. cizer in the substrate may migrate to the inter-
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 385

face and, in effect, act as a release agent due to

incompatibility with the polyvinyl acetate.
When a polyvinyl acetate emulsion is fiexi-
bilized internally with a comonomer, the plas-
ticization is permanent and nonmigratory. This
is because the comonomers are part of the main
polymer chain, often with bulky side groups,
increasing the freedom of rotation of the chain.
The resulting softening and polymer mobility
allows better adhesion to plastic surfaces.
Monomers which are copolymerized with vi-
nyl acetate include alkylacrylates, alkylma-
leates, fumarates, and ethylene. The level of
comonomers may vary from a few weight per-
cent of the copolymer to as much as 70 weight -40+---'--r-r-"""T-""T"-'--~
percent. o 5 10 15 20 25 30 35
% COMONOMER

Ethylene vs. Ester Comonomers Fig. 1. Comonomer levels required to plasticize polyvi-
ny I acetate.
The early copolymers of vinyl acetate with di-
butyl maleate or acrylate esters offered distinct
advantages over the homopolymer in their abil-
ity to adhere to a vast number of difficult-to- 3.0 ......- - - - - - - - - - - - - ,
bond surfaces. However, they also had disad-
vantages, e.g., poor heat resistance, relatively
2.5
low strength, rather slow setting speed, and
·iii
comparatively poor machinability. The intro- a.
o
duction of vinyl acetate-ethylene copolymers ~ 2.0
changed this picture considerably. This class of I
~

emulsion had all the benefits of homopolymers Cl

a; 1.5
in strength, machinability and heat resistance II:
~

in addition to better adhesion characteristics rJ)

W
1.0
than those of the ester copolymers. ...J
iii
z
Ethylene is a much more effective internal w
~

plasticizer for polyvinyl acetate than are dibu- .5

tyl maleate and acrylate comonomers. Com-
pared with dibutyl maleate, smaller amounts of
ethylene are necessary to decrease the glass 30 20 10 0 -10 -20 -30
transition temperature of the homopolymer T9 (0C)
(Fig. 1). Vinyl acetate-ethylene copolymers
Fig. 2. Effect of Tg on vinyl acetate copolymer film ten-
also have much higher tensile strength than vi- sile strength.
nyl acetate-dibutyl maleate copolymers at
equivalent glass transition temperatures (Fig.
2). In fact, the ethylene copolymer emulsion
has a higher tensile strength than vinyl acetate-
Table 1. How Comonomers Affect
dibutyl maleate even though its glass transition
Copolymer Film Properties.
temperature is lower and its percent elongation
is about the same (Table 1). In addition, the VAclDibutyl
Property VAclEthylene Maleate
vinyl acetate-ethylene copolymer has the same
heat or creep resistance as the homopolymer Tensile Strength (psi) 960 618
and much better creep resistance than the vinyl Tg (0C) 0 6
Elongation (%) 1660 1550
acetate-dibutyl maleate type (Table 2). It should
386 HANDBOOK OF ADHESIVES

Table 2. Relative Creep Resistance of Effect of Accelerated Aging' on

Polyvinyl Acetate Copolymers
Polyvinyl Acetate Emulsions.
Emulsion Type Creep (mmlmin)
_ Belor. Aging
Homopolymer 0.02
DAfter Aging
VAc/ethylene 0.02
3
VAc/dibutyl maleate 7.6
.£
Homopolymer and 10% DBP" 0.6 0;
VAc/ethylene and 10% DBP" 0.6 Q)

-=
'DBP = Dibutyl phthalate. ".ci-=-
I 2
l-
t!)
Z
be noted that when it is plasticized with 10% W
II:
dibutyl phthalate, it still has less creep than the I-
en
neat vinyl acetate-dibutyl maleate and is equal ...J
w
W
to a homopolymer containing an equal amount 11.

of plasticizer.
VAE (vinyl acetate-ethylene) emulsions do
not require as much plasticizer to obtain a
strong bond to PVC as do vinyl acetate-dibutyl VAc/Ethylene' VAc/ VAc/Dlbutyl
maleate and vinyl acetate-acrylate (Fig. 3). Im- Acrylate' Maleate'
portantly, these copolymers do not soften I. Bonds aged one week at 120°F.
nearly as much as the other copolymers when 2. Prolective colloid: polyvinyl alcoh.ol.
plasticizer is added. This means that as lami- 3. Proteclive colloid: cellulosic.

nations of films to cellulosic substrates age, the Fig. 4. Peel strength of PVC to cloth bonds.
bond made by the VAE will not lose its cohe-
sive strength and weaken (Fig. 4).
Certain properties may best be explained by percent of dibutyl maleate may be visualized as
examining the molecular structure of polyvinyl a polyethylene chain with acetate groups on
acetate and some of its copolymers. Fig. 5 every other carbon atom for 16 atoms on the
compares polyethylene and polyvinyl acetate chain, and a butyl ester group on the 17th and
homopolymers. Polyethylene is, of course, a 18th carbon atoms (Fig. 6). These resins are
flexible polymer, whereas polyvinyl acetate flexible because the bulky pendant butyl ester
homopolymer is hard and brittle because steric groups allow intermolecular movement and also
hindrance between alternate acetate groups re- separate the chains of polymers so that they can
stricts movement of the molecules. A copoly- slip past one another rather easily. This ac-
mer of vinyl acetate containing 25 weight counts for the higher degree of creep in a vinyl

Effect of Plasticizer on Polyvinyl Acetate Copolymers

5
.5
-
0; VAc/Ethylene
Q) 4
~
-
.--------
-
g 3
I
l-
e> VAc/Dlbutyl Maleate
zw 2
II:
I-
en 0
VAcl Acrylate -
.
...J
W
W
11.

o 2
. .
4 6 8
,
10 12 14 16 18 20
•
PARTS OF PLASTICIZER (DIPROPYLENE GLYCOL DIBENZOATE) PER 100 PARTS OF EMULSION

Fig. 3. Peel strength of PVC to cloth bonds.

 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 387

copolymers is that they have greater resistance

to alkalis and acids than the older copolymers.
H, H. H. When acetate groups are present on alternate
carbons, the hydrolysis of one acetate group by
H. H. H. alkali exposes the next acetate group. The re-
/C~H/C~H/C~H/ action proceeds rapidly down the entire chain,
C C C unzipping the polymer. With vinyl acetate-eth-
I I I
000 ylene, the zipping is interrupted; therefore,
I I I rapid hydrolysis does not take place. In fact,
C-O C-O C-O
I I I test films of vinyl acetate-ethylene have been
CH, CH, CH, exposed to weak alkalis and acids for more than
Fig. 5. Polyethylene and polyvinyl acetate homopoly- a year without showing signs of deterioration.
mers.
Other Factors Affecting Adhesive
Properties
acetate-alkylmaleate or vinyl acetate-alkylacry-
late copolymer. In the case of vinyl acetate-eth- Polyvinyl acetate emulsions are among the most
ylene copolymers, the flexibility is achieved versatile bases for adhesives because they can
through much less steric hindrance, because the be modified during polymerization in many
acetate groups are not attached to alternate car- more ways than other resins used for adhesive
bons, and movement is not restricted along the compounding. Major changes can be made to
molecule (Fig. 7). Since the large, bulky side the adhesive properties of polyvinyl acetate by
chains are not present to achieve flexibility, changing the method of protecting the emul-
these polymers exhibit higher cohesive strength sion, by varying the glass transition tempera-
and much less creep. The use of polymer Tg as ture (Tg ), by modifying the degree of
a guide to latex specification for adhesive pur- branching, or by adding a variety of functional
poses has been described. 39 groups. These modifications may be made sin-
Another feature of the vinyl acetate-ethylene gly or in any combination of the above four.

H. H. H. H. H

/C~H/C~H/C~H/C~H/f~H/
C C C C c-o C
I I I I I I
o 0 0 0 0 c-o
I I I I I I
c-o c-o c-o c-o CH. 0
I I I I I I
CH, CH 3 CH 3 CH 3 CH. CH.
I I
CH. CH.
I I
CH 3 CH.
I
CH 3
Fig. 6. Vinyl acetate-dibutyl maleate copolymer.

H. H. H. H. H. H. H.

/C~H/C~H/C~H/C~H/C~H/C~H/C~
C C C C C C
I I I
0 0 0
I I I
C-O C-O c-o
I I I
CH, CH, CH,

Fig. 7. Vinyl acetate-ethylene copolymer.

 388 HANDBOOK OF ADHESIVES

As an indicator of the technical significance used with polyvinyl acetate) has a fine particle
to the adhesive industry of these emulsions, one size and a rather narrow particle size distribu-
finds 2,333 patents describing them and their tion.
uses listed in chemical abstracts from 1972 to Polyvinyl alcohol is a water-soluble mole-
the present. A total of 28 review articles have cule. It will therefore contribute a high degree
appeared worldwide in that time. 28 of wet tack to an emulsion that is not possible
with surfactant protection. Polyvinyl acetate
Protection by Colloids and/or Surfactants emulsions protected with partially hydrolyzed
polyvinyl alcohol have a combination of prop-
Polyvinyl acetate can be protected with colloid
erties usually described as "good machining, ' ,
systems, surfactant systems, or a combination
which include good flow, clean running, easy
of both. The type and amount of protection used
cleanup, and nonslinging or nonspitting. These
in the polymerization of polyvinyl acetate have
properties are generally not present in emul-
a great bearing on the physical properties of the
sions protected solely with surfactants. Surfac-
resin and on the working characteristics of the
tant-protected emulsions are much more
dispersion.
thixotropic than polyvinyl alcohol-protected
Table 3 compares emulsion and dried film
emulsions, and become thin under high-shear
properties controlled by the protection system.
conditions.
Since partially hydrolyzed polyvinyl alcohol is
Polyvinyl acetate emulsions set by losing
a poor emulsifier compared with a surfactant, a
water through evaporation into the air and also
polyvinyl acetate emulsion protected with this
by absorption into the porous substrates to
colloid would have a combination of large par-
which they are applied. 38 The polyvinyl acetate
ticles and a rather wide particle size distribu-
spheres in the emulsion pack together and form
tion. This combination of particle size and
capillaries which aid in the transport of the
distribution yields an emulsion that does not
water out of the film. The fine particles in an
change its viscosity very much as it experi-.
all-surfactant system form small capillaries
ences high shear conditions. On the other hand,
which drive water out at a rather rapid rate. In
an emulsion which is protected solely with a
a polyvinyl alcohol-protected system, the var-
surfactant (nonionic surfactants are generally
iously sized particles pack tighter and form
much finer capillaries, which drive the water
Table 3. How the Protection System out at a much more rapid rate. This causes the
Affects the Properties of an Adhesive emulsion to form a film and set more rapidly
Base. than an all-surfactant system.
Emulsion Properties- Emulsion Properties- The particles of polyvinyl acetate coated with
Colloid Protected Surfactant Protected partially hydrolyzed polyvinyl alcohol cannot
form a very tightly coalesced film. This is be-
Large particle size Fine particle size
Wide particle size dis- Narrow particle size cause polyvinyl alcohol has a higher Tg than,
tribution distribution and is not compatible with, polyvinyl acetate.
Strong wet tack Poor wet tack As a result, the dried film will have a hazy, flat
Good flow Poor flow appearance. This contrasts with a surfactant-
Good machining Relatively poor ma-
chining
protected acetate, which will coalesce more
Rapid setting Relatively slow set- tightly and will therefore form a clear, glossy
ting film. The dried film of a surfactant-protected
Near-Newtonian Thixotropic rheology emulsion will be much less water sensitive than
rheology (does not (thins with shear) that of a polyvinyl alcohol-protected emulsion.
shear thin)
This is attributable to the water solubility of
Film Properties- Film Properties- polyvinyl alcohol, and can be overcome to var-
Colloid Protected Surfactant Protected
ious degrees by crosslinking of the PVOH after
Hazy film Clear film film formation has occurred. 33 ,36,37
Flat film Glossy film Emulsions which combine surfactant and
Water sensitive Water resistant
colloid protection will display properties that
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 389

fall somewhere between those exhibited by col- The PVOH-protected emulsion has a greater
loid systems or surfactant systems alone. wet tack because of the water soluble polyvinyl
The effect of the protection system is illus- alcohol in its continuous phase. As discussed
trated in Table 4, which shows the properties earlier, polyvinyl alcohol protection contrib-
of three VAE copolymers with the same level utes to finer capillary formation and thereby
of ethylene and the same Tg • One is PVOH pro- promotes more rapid setting speed.
tected, one is surfactant protected, and the last The PVOH-protected emulsion and adhe-
is protected by a combination of surfactant and sives made with it spray very well in airless
cellulosic. spray systems, but relatively poorly in air spray
The first major difference among the three is systems.
that the PVOH-protected emulsion is incom- Table 4 further illustrates that the PVOH-
patible with borax and highly soluble dextrin, protected and the cellulosic emulsion are both
whereas the other two emulsions can accept excellent bases for adhesives to bond to poly-
these compounds without breaking. In addi- vinyl chloride. The PVOH-protected emulsion
tion, the PVOH-protected emulsion exhibits is usually chosen for wet laminations and the
less water resistance and more water spotting. cellulosic emulsion for heat-seal applications.
Water resistance denotes the ability of a lami- The surfactant emulsion shows much better
nation between two substrates, such as kraft adhesion to polystyrene than the other two
paper or cloth, to maintain its integrity or bond emulsions, but the other emulsions can be com-
strength after immersion in water for a speci- pounded with plasticizers and/or tackifier res-
fied time. Water spotting describes the appear- ins to make excellent polystyrene adhesive
ance of a dried film or emulsion after water is bases.
placed on that surface. A good or excellent film Though all three products exhibit the same
would not blush as rapidly as would the film glass transition temperature, the heat-seal tem-
indicated as fair. A lamination or bond made perature of the surfactant emulsion is below that
with the PVOH-protected emulsion has good of either the PVOH-protected or the cellulosic
water resistance, yet can be cleaned from ma- emulsions. Fig. 8 shows the difference between
chines more readily than the other two emul- the PVOH-protected and the surfactant emul-
sions. The water resistance of the PVOH- sion in laminating films of polyvinyl chloride
protected emulsion permits its use in glue laps, to each other, using a heat-seal technique. In
bag-seam adhesives, and polyvinyl chloride- this case, each emulsion was coated onto a PVC
laminating adhesives. film, allowed to dry, then heat sealed at the

Table 4. How Protection System Affects the Properties of

Three VAE Emulsions.
Protection System
Polyvinyl Nonionic Surfactant and
Propeny Alcohol Surfactant Cellulosic
Borax compatibility none good good
Dextrin compatibility poor good good
Water resistance good excellent very good
Water spotting fair excellent good
Wet tack excellent poor poor
Set speed rapid slower slower
Sprayability poor excellent excellent
PVC adhesion excellent fair excellent
Polystyrene adhesion fair excellent good
Heat sealability good fair excellent
Thickening response high moderate low
Solvent reactivation good fair excellent
Compatibility with rubber fair good excellent
Latices
390 HANDBOOK OF ADHESIVES

Effect of Heat-Sealing Temperature 60

on Two Types of Emulsions
10.5 .....--------~_ _
50

9
.5 ~
u
40
iii 0
e.
0
.~
<::
g >
l-
30
ii)
:I: 0
I- U
Cl 5 til
z :> 20
w
a:
I-
til
..J 10
W
W
11.
5
1.2
0.5 0 10 20 30
0~-r_~--,_~r__r-~_1
PARTS OF DIBUTYL PHTHALATE
o 80 90 100 110 120 130 140 (DBP)/l00 PARTS EMULSION
HEAT SEALING TEMPERATURE (OC)
Fig. 8. Peel strength of PVC-to-PVC bonds. 1. Brookfield Viscometer. Model RVF at 20 rpm. 2SoC.

Fig. 9. Thickening response of two Airflex emulsions to

plasticizer.
temperatures shown on the horizontal axis. The
laminations were then separated on an Instron®
tester. The measured resistance to delamination sive. This technique would be used if two non-
is shown on the vertical axis of the chart. It porous surfaces were to be joined together and
should be noted that the emulsions can be it was not possible to use heat to soften and
blended to obtain intennediate adhesion val- reactivate the adhesive. In this situation, small
ues. amounts of solvent could be used to reactivate
Plasticizer and solvent thickening response the adhesive, resulting in very low emissions.
are other important compounding properties This technique would also take advantage of
controlled by the protection system used in the much higher molecular weight, and there-
polymerization. Fig. 9 clearly shows that the fore greater tensile strength, of an emulsion-
polyvinyl alcohol-protected emulsion thickens polymerized adhesive resin compared with a
much more rapidly than the surfactant and cel- solvent-polymerized resin.
lulosic-protected emulsions. The rapid thick-
ening response of the PVOH-protected
emulsion is an economic advantage in com- Advantages of Polyvinyl Alcohol
pounding many packaging adhesives. There are Protection
times, however, when it is necessary to have a
high-solids, low-viscosity adhesive that con- As a protection system, polyvinyl alcohol con-
tains high amounts of either plasticizer or sol- fers unique properties on emulsions stabilized
vent. The surfactant emulsion would then have with it. Since polyvinyl alcohol enhances the
an advantage over the PVOH-protected emul- adhesive properties of polyvinyl acetate to such
sion; but again, it is possible to blend these two a great degree, a majority of adhesive emul-
emulsions to obtain intennediate properties. sions use this protection system. In addition to
The protection system used with polyvinyl the advantages listed in Table 5, polyvinyl al-
acetate emulsions also affects solvent reactiva- cohol-protected emulsions are easily modified
tion. Solvent reactivation describes the tech- to reinforce specific adhesive properties. Im-
nique whereby dried adhesive films are wet portantly, the resulting compounds exhibit ex-
with solvents in order to reactivate the adhe- cellent stability.
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 391

Table 5. Advantages of Polyvinyl 45

Alcohol Protection
;35
Good machinability
Easy cleanup
Good wet tack 25
Rapid setting speed
Rapid thickening response
15
Good heat resistance ~ VAc Homopolymer
Low degree of blocking 01
I-
Crosslinkability 5

-5
POLYMER STRUCTURE AND
PROPERTIES -15

Glass Transition Temperature -25

0 5 10 15 20 25
As indicated in Table 6, the glass transition
PARTS OF DIBUTYL PHTHALATE
temperature (Tg) has notable effects on prop- (DBP)/100 PARTS EMULSION
erties of adhesive emulsions. Varying the
amount of ethylene incorporated into a copol- Fig. 10. Effect of plasticizer on Tg of two emulsion types.

ymer has a direct relationship to the Tg : the

more ethylene, the lower the Tg • The glass
transition temperature affects such properties as Measured in % Bond Retention
flexibility, water resistance, PVC adhesion, 15~--------------------~

paper adhesion, and setting speed. The three

emulsions in Table 6 are all protected with ~
z
polyvinyl alcohol. The major difference among 0 10
j:::
them is the ethylene content as illustrated by z
UJ
the Tg • It should be noted that water resistance I-
UJ
a::
and ease-of-cleanup are inversely related. 0 5
z
The glass transition temperatures of polyvi- 0
al
nyl acetate emulsions may be lowered further
by adding a plasticizer such as dibutyl phthal- O~~~----~--~--~--~
ate (Fig. 10). Plasticizer addition will, in turn, o 5 10 15 20 25
PARTS OF DIBUTYL PHTHALATE
increase water resistance (Fig. 11). (DBP)/100 PARTS EMULSION
1. Cloth to cloth bonds
Branching
Fig. 11. Effect of plasticizer on water resistance of two
The linearity of a polyvinyl acetate resin can emulsion types.
be controlled during the polymerization pro-

Table 6. Effect of Tg on the Properties of Three VAE

Emulsions
Propeny Tg (O°C) Tg (-20°C) Tg (-30°C)

Wt % -CH2 -CH2 - (approx.) 17% 25% 31%

Water resistance good fair poor
PVC adhesion excellent poor poor
Paper adhesion excellent good fair
(Clay-coated board)
Setting speed excellent good fair
 392 HANDBOOK OF ADHESIVES

cess. Conditions such as high temperature and Table 7. Peel Strengtha of Cloth-to-
high catalyst concentration can favor the for- Metal Bondsb (lbs./linear in.)-Effect of
mation of pendant or branched segments on the Carboxyl Functionality on Vinyl Acetate-
linear chain. 29 This branching will increase Ethylene Polymers
tensile strength and toughness of the polymer. Conventional Vinyl Carboxylated Vinyl
It will also increase the heat resistance (creep Acetate-Ethylene Acetate-Ethylene
resistance) and reduce the tackiness of the pol- Aluminum 0.4 . 1.8
ymer's dried film. A branched polyvinyl ace- Brass 0.8 4.5
tate emulsion will accept greater amounts of Copper 0.6 3.9
polar and water-miscible solvent without Galvanized steel 0.6 3.5
breaking (destabilizing) than will a linear type. Lead 0.7 1.4
Steel 1.3 4.1
Some effects of branching and chain structure
'T Peel (180 0 peel on Instron~ tester, 2 in.lmin).
on adhesion have been reported. 34 bCotton poplin cloth. Laminated wet. Dried 24 hours.

Functional Groups
acetate-ethylene polymer adheres much better
Polyvinyl acetate emulsions can be further to metal substrates.
modified by the incorporation of functional The incorporation of a carboxyl functionality
groups. These groups permit the design of pol- reduces the softening range of vinyl acetate-
ymers which have the ability to bond a wider ethylene resin while enhancing its adhesion.
spectrum of surfaces, including difficult-to- Fig. 12 shows the difference in adhesion be-
bond substrates. The addition of functional tween carboxylated vinyl acetate-ethylene and
groups also permits crosslinkability of the pol- conventional vinyl acetate-ethylene polymer
ymer in order to achieve a high degree of water, when each is used as a heat-seal adhesive for
solvent, or heat resistance. bonding two pieces of commercial polyvinyl
N-Methylolacrylamide is commonly used to chloride film. For test purposes, these emul-
manufacture self-crosslinking vinyl acetate
polymers. 12
Rigid polymers are available which can be
used to make highly water resistant wood ad- 11
hesives. Other copolymers are available which
.5 10
are flexible enough to be used as water or sol- :a
G>
vent resistant nonwoven binder or as flocking .S
:::;
9
adhesives. The N-methylolacrylamide copol- g,
8
ymer will usually require the addition of an acid J:
I-
C!l
salt and a heat cure to achieve the desired ef- z 7
w
fect. a:
I-
CIl 6
Carboxyl functionality in a vinyl acetate-eth-
ylene emulsion offers three advantages over
noncarboxylated products. They are; increased
adhesion to metals and polymeric surfaces; re-
active sites for crosslinking; and a means for
thickening. 150 160 170 180 190 200 210
Carboxyl functionality increases the adhe- HEAT SEAL TEMPERATURE (OF)
sion of vinyl acetate-ethylene to several metals 1. Adhesion of PVC to PVC film; heat-sealed
on a Sentinel Heat Sealer using constant
(Table 7). A conventional vinyl acetate-ethyl- pressure of 40 psi; 8 seconds dwell time.
ene and a carboxylated vinyl acetate-ethylene
Fig. 12. Effect of carboxyl functionality on heat-seal
polymer both may have the same glass transi- adhesion. Adhesion of PVC to PVC film. Heat sealed on
tion temperature and the same ratio of vinyl a sentinel heat sealer using constant pressure of 40 psi; 8
acetate to ethylene, but the carboxylated vinyl seconds dwell time.
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 393

WITH UREA carboxylated vinyl acetate-ethylene with ami-

FORMALDEHYDE (AMINOPLASn RESIN
noplast increases the polymer's water and creep
o resistance, especially when the bond is heat-
II cured (Table.S).
o CH.OH /CH.o-c-a
II /
2R-C-OH + R, _R, 0 +2H;o
COMPOUNDING
\ \ II
CH.OH CH,O--C-R
Many polyvinyl acetate emulsions can be used
as adhesives without modification. However,
WITH PHENOLIC RESIN
an adhesive is usually compounded in order to
tailor the product for a particular application.
o

¢
o Compounding of adhesives facilitates applica-
II tion on equipment and bonding on specific sub-
2R--C-OH +
strates. It also imparts resistance to ambient
conditions. In addition to film formers, an ad-
CH.OH
hesive usually contains some of the following
WITH EPOXY RESIN
components; plasticizers, viscosity/rheology
modifiers, tackifiers/extenders, solvents, fill-
R, R, 0 ers, humectants, surfactants, and biocides.
I I II
o HC\ HC-O-C--R

2RJLOH + I 0- I ~ +H.O
Plasticizers
Copolymer emulsions are flexible and soft be-
HC/ HC-O-C-R
I I cause of bulky pendant groups or flexible back-
R, R,
bones. Polyvinyl acetate homopolymer
Fig. 13. Reactions of a carboxylated vinyl acetate-eth- emulsions series are hard and stiff due to the
ylene emulsion. steric hindrance of the acetate groups and the
strong intermolecular attraction. Any of these
sions were coated on one piece of film, allowed emulsion families may be compounded with
to dry, and then heat-sealed to the uncoated plasticizers to increase flexibility.
PVC film. Carboxylated vinyl acetate-ethylene Plasticizers are added to reduce the inter-
polymer will react with aminoplast, phenolic, molecular attraction of the polyvinyl acetate
and epoxy resins (Fig. 13). The reaction of the polymers. They cause the polyvinyl acetate

Table 8. How the Reaction of Carboxylated VAE Emulsion

with Urea Formaldehyde (Aminoplast) Resin Affects Water
and Creep Resistance. a
Peel Strength b (Ibs/linear inch)
Wet Wet Creep mm/minb
Pans UF Resin Dry (uncured) (cured)" (cured)"

0 13.0 3.0 5.8 0.96

3-Beetle 60 12.8 3.2 7.1 0.58
5-Beetle 60 12.6 3.4 7.4 0.23
10-Beetle 60 12.0 4.0 7.5 0.25
3-Beetle 65 12.0 2.9 8.3 0.36
5-Beetle 65 11.8 3.1 8.2 0.23
10-Beetle 65 11.0 3.6 7.9 0.01
Tests used cotton poplin to cotton poplin bonds. Cloth was laminated, then dried 7 days at room
temperature.
'T Peel (180° peel on Instron~ tester, 2 in.lmin).
~ Peel (500 g static load/linear/in., I70°F).
'Cured for 5 minutes at 275°F.
394 HANDBOOK OF ADHESIVES

particles to swell; this raises the viscosity of the 45

emulsion (Fig. 14) and destabilizes it for faster
breaking and setting speeds. In addition, the 35
resin particles in the emulsion gain mobility.
Increased mobility helps the resin to wet 25
smooth, nonporous surfaces, (e.g., films, foils,
and coated papers) and consequently to in- 15
crease its adhesion to these surfaces. More- E
over, softened polymer particles coalesce more ....C> 5
rapidly and more completely at lower temper-
atures. -5
When added to an emulsion, plasticizers will
also lower the glass transition temperature ( Tg) -15
of the polyvinyl acetate film, making it softer
and more flexible (Fig. 15). Finally, plasticiz-
25
ers will increase the tackiness of the film, re-
PARTS OF DIBUTYL PHTHALATE
duce its heat-sealing temperature, and improve (DBP)/l00 PARTS EMULSION
its water resistance (Fig. 16).30.31 Fig. 15. Effect of plasticizer on Tg of two emulsion types.
The general-purpose plasticizers listed in Ta-
ble 9 can be added to polyvinyl acetate homo-
polymer and copolymer emulsions. Fire- Viscosity IRheology Modifiers
retardant plasticizers, which are occasionally Adhesives are most commonly applied by ma-
needed, are also listed. chine. Each type of machine has its own vis-
cosity/rheology requirements. Most roll
applications use adhesives with a viscosity of
l00r---------------------~
1500-3000 cp and operate best with a slightly
thixotropic flow. Sprays require a more New-
tonian flow and use viscosities in the 200-800
cp range. Construction adhesives are applied
through a gun or trowel and use thixotropic or
pseudoplastic, high viscosity materials. The
proper choice of thickener will control viscos-
nu ity as well as rheology.

~ Measured in % Bond Retention

...>
8
Ul
;;;
15~--------------------~

~ 10
i=
z
w
....
w
a:
c 5
z
~ VAc Homopolymer

o 10 20 30 40 50 25
PARTS OF DIBUTYL PHTHALATE (DBP)I PARTS OF DIBUTYL PHTHALATE
100 PARTS EMULSION (DBP)/l00 PARTS EMULSION
Fig. 14. Thickening response of homopolymer emulsion Fig. 16. Effect of plasticizer on water resistance of two
to plasticizers. emulsion types.
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 395

Table 9. Plasticizers. lulosic, and fumed silica will also confer

General Purpose Fire Retardant pseudoplasticity.
Thickeners that can be added to all homo-
Acetyl tributy I citrate Cresyl diphenyl phos-
*Butyl benzyl phthalate phate
polymer and copolymer polyvinyl acetate ad-
Butyl phthalyl butyl *Tricresyl phosphate hesive emulsions include those shown in Table
glycolate Triphenyl phosphate 10.
*Dibutyl phthalate
Dibutyl sebacate Tackifiers/Extenders
Diethyl phthalate
*Diethylene glycol diben- Tackifiers increase the tackiness and the setting
zoate speed of adhesives. They increase tackiness by
Dipropylene glycol
*Dipropylene glycol di-
softening the polyvinyl acetate polymer, both
benzoate in the wet and in the dry adhesive film. They
Ethyl phthalyl ethyl gly- accelerate setting speed by raising the total sol-
colate ids content of the emulsion. This action has the
Ethyl-p-toluene sulfona- twofold result of "crowding" the aqueous
mide
Hexylene glycol
phase and making the emulsion less mechani-
Methyl phthalyl ethyl gly- cally stable.
colate Tackifier resins often increase the affinity of
Polyoxyethylene aryl adhesives for specific surfaces such as plastics
ether and metal foils. They also lower the softening
Tributoxyethyl phthalate
and heat-sealing temperatures of adhesive
*Denotes most frequently used.
films.
Tackifiers are insoluble in the continuous
Thickeners added to an adhesive will raise (water) phase of the emulsion and must be dis-
viscosity and pennit dilution with water. This solved in organic solvents and/or plasticizer
reduces the total solids of the adhesive and thus before they can be added.
lowers its (wet) cost. Thickeners release water By virtue of adding to the adhesive properties
slowly, and when combined with lower solids, of the polyvinyl acetate emulsion, tackifiers are
they also slow the setting (prolong open time) also extenders. (Most are too brittle to act as
of the adhesive. Thickeners such as polyvinyl adhesives in their own right and need the
alcohol, starch, and hydroxyethyl cellulose will toughness of polyvinyl acetate in order to func-
improve adhesion to porous substrates by re- tion). By raising the total solids content of the
ducing penetration of an emulsion into the sub- emulsion, tackifiers accelerate the breaking and
strate and decreasing the likelihood of a setting speeds and may reduce the cost of the
"starved joint. " adhesives to the extent that the active (polyvi-
Some thickeners can prevent adhesives from
spitting and throwing during high-speed appli- Table 10. Thickeners
cations. They pennit them to transfer cleanly
Alginates
and break short rather than draw to fibers. Bentonite
Polyvinyl alcohol is a good example of this type Casein
of thickener. Polyvinyl alcohol is also recom- Fumed silica
mended for high speed roll application because Guar gum
it does not shear thin as do other thickeners. Gum tragacanth
*Hydroxyethylcellulose
Some other specific effects of polyvinyl alcohol Locust bean gum
on emulsion adhesive properties have been re- *Methylcellulose
ported. 32 Polyacrylic acid salts (ammonium, potassium, sodium)
Pseudoplastic (shear thinning) adhesives can **Polyvinyl alcohol
be prepared by adding polyacrylates such as so- *Sodium carboxymethyl cellulose
*Starches
dium or ammonium polyacrylate. Starch, cel-
396 HANDBOOK OF ADHESIVES

nyl acetate) solids can be diluted by adding 100~--------------------,

water.
Plasticizers, solvents, tackified (borated) and
untackified polyvinyl alcohol, and certain
polyvinyl emulsions impart wet tack to poly-
vinyl acetate emulsions. Those additives spe-
cifically designated as tackifiers are listed in
Table 11.
ii
u
10
Solvents ~
Because of their volatility, solvents perform
...iii>
0
like plasticizers oom temporary basis. Solvents 0

increase the viscosity over that of emulsions;

'"
:>

they also dissolve wax or resin coatings, accel- 1.1.1. Trichloroethane

erate setting speed, reduce film-forming tem-
perature, reduce adhesive (wet) cost, increase
wet tack, dissolve tackifiers, and lower the
freezing point.
Like plasticizers, solvents cause the polyvi-
nyl acetate particles to soften and swell, raising
10 20 30 40 50
the viscosity of the emulsion (Fig. 17). Higher PARTS SOLVENT PER
viscosity allows dilution of the adhesive with 100 PARTS EMULSION -

water, thus reducing the adhesive wet cost. 1. Brooklield Viscometer, Model RVF at 20 rpm,
2S·C
Swelling and softening also destabilize the Fig. 17. Thickening response of homopolymer emulsion
emulsion. This increases the setting speed and to two solvent types.
also allows the adhesive to coalesce into a film
more rapidly and at a lower temperature than impart the necessary speed to the wet adhesive,
the neat emulsion. The improved coalescence but because they are volatile, will not cause the
results in greater water resistance for the film. dried bond to creep.
Low-boiling solvents impart only wet tack to Solvents promote adhesion to solvent-sensi-
the adhesive film, whereas high-boiling sol- tive adherends (plastic films and reconstituted
vents confer both dry and wet tack and lower cellulose films) by swelling and partially dis-
the heat sealing temperatures. High-boiling solving them, thus allowing the adhesive to wet
solvents behave like plasticizer except for and/or penetrate the surface. Coated adherends
eventual evaporation from the film. This evap- that resist adhesion, such as printed, lacquered,
oration aids wood glue or packaging adhesives or waxed papers, may also be partially dis-
that require fast setting speeds. Solvents can solved by solvents to promote adhesion. (Chlo-
rinated solvents are particularly effective on
Table 11. Tackifiers waxed surfaces).
Tackifier resins are usually dissolved in a
*Coumarone-indene
Ester gum solvent or a blend of solvent and plasticizer be-
Gum rosin fore being added to a polyvinyl acetate emul-
*Hydrocarbon resins sion. The compounded solvent and resin has a
Hydrogenated rosin crowding effect on the emulsion, which results
Phenolic modified hydrocarbon resins
in destabilization and a rapid setting speed.
*Rosin esters
Tall oil rosins The choice of solvents used with polyvinyl
Terpene phenolic acetate homo and copolymer emulsions de-
Terpene resins pends on the nature of the individual emulsion,
Toluenesufonamide-formaldehyde resin and importantly, on the degree of branching of
Wood rosin
each emulsion. For instance, highly branched
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 397

emulsions are more compatible with water- cooked starch fillers, in particular, reduce the
miscible solvents than other lesser-branched cold flow in wood glues.
emulsions. Clays and other fillers impart stiffness to ad-
Table 12 classifies various solvent types as hesive films. Clays reduce the penetration of
water-miscible or water-immiscible. adhesives into porous substrates. Large-parti-
cle clays are better able to control penetration
and also impart more rapid setting speed. A
Fillers
highly plastic clay, bentonite, makes adhesives
Fillers are added to emulsion adhesives to re- thixotropic-fluid under high shear, thicker
duce cost by replacing resin solids without de- upon application. A study has been made 3l of
creasing total solids, to reduce penetration into the effect of various fillers on the adhesive
porous substrate, and to change the rheology of properties of polyvinyl acetate.
the compound. Depending on their individual Table 13 lists general purpose fillers than can
properties, fillers can also add stiffness and be added to all polyvinyl acetate homo- and co-
strength or decrease tack and blocking. Un- polymer adhesive emulsions.

Table 12. Water Miscibility of Various Solvent Types.

Solvents Water Miscible Water Immiscible
ALCOHOLS
Ethanol •
*Isopropanol •
Methanol •
Chlorinated Compounds
Ethylene dichloride •
Methylene chloride •
Perchlorethylene •
*1, 1, 1-Trichlorethane •
Trichloroethylene •
Esters
Ethy I acetate •
Methyl acetate •
n-Butyl acetate •
Glycols, Ethers, and Oxides
Diethylene glycol diethyl ether •
Diethylene glycol monobutyl ether •
Diethylene glycol monoethyl ether •
Diethylene glycol monomethyl ether •
Dioxane •
Ethylene glycol monoethyl ether •
Ethylene glycol monobutyl ether •
Lower glycol ethers •
Hydrocarbons
Mineral spirits •
Naphtha •
*Toluene •
Xylene •
Ketones
Acetone •
Cyclohexanone •
Diacetone alcohol •
Isophorone •
*Methyl ethyl ketone •
Methyl isobutyl ketone •
Miscellaneous
Tetrahydrofuran •
398 HANDBOOK OF ADHESIVES

Table 13. Fillers. Table 15. Wetting Agents.

Bentonite Nut shell flours Alkyloxyl polyether alcohols
*Calcium carbonate Silica Dodecyl benzene sodium sulfonate
Calcium silicate Talc Polyoxy ethylene sorbitan monooleate
*Clay *Uncooked starches *Sodium alkyl benzene sulfonate
Mica Wood flour *Sodium dioctylsulfosuccinate
Sodium tetradecyl sulfate
*Acetylenic glycols
Humectants Tetrasodium pyrophosphate

A humectant is a hygroscopic substance, one

that absorbs and retains moisture from the Therefore, these should be added in minimal
atmosphere. In. emulsion adhesives, humec- amounts.
tants prevent the surface of the compound from Wetting agents that can be used with poly-
skinning by keeping it wet. When polyvinyl al- vinyl acetate homo- and copolymer emulsions
cohol or starch is present, the humectant holds are listed in Table 15. The effect of various sur-
water, which plasticizes these materials and factants on PV Ac latex film structure and prop-
keeps them flexible after drying. By retarding erties has been studied. 33
drying, humectants also slow setting speed and
extend the open time of the adhesive. Foam Control Agents
Humectants suitable for use in polyvinyl ace-
Foam control agents include antifoam and de-
tate homo and copolymer adhesive emulsions
foamer compounds. Foam causes problems in
are shown in Table 14.
the manufacturing and the application of ad-
hesives. Air in the formulation increases vis-
Wetting Agents
cosity, which can be misleading when adding
The surface-active agents (surfactants) added ingredients. A misleading viscosity also pre-
to polyvinyl acetate form two classes: wetting vents accurate metering during application of
agents and foam control agents. the adhesive, thereby preventing the deposit of
Wetting agents aid the adhesive to wet the sufficient solids on the glue line.
surface of the adherend, thereby improving A small amount of foam control agent, 0.1-
adhesion. When a vinyl acetate-ethylene poly- 0.2 % of the adhesive, is usually sufficient to
mer is used to bond PVC, the secondary plas- prevent or break foam.
ticizers in the film may exude to the surface, A foam control agent should be pretested in
making the film very difficult to wet and bond. each new adhesive formulation and each time
The addition of a good wetting agent amelio- an ingredient is changed. Changing the amount
rates this situation. of an ingredient can change foam control re-
Wetting agents help water penetrate the sur- quirements. The adhesive sample should age 6-
face of an adherend. This allows the polymer 8 weeks before analysis of foam control effi-
particles to coalesce and set rapidly. These ciency. Some foam controllers may emulsify or
compounds also disperse solids throughout the separate upon aging.
adhesive, which reduce settling.
Many of the anionic wetting agents cause Biocide
foaming if used to excess, and may also in-
Biocides are required when animal or vegetable
crease the water sensitivity of the adhesive film.
substances or their derivatives (starches, casein
and other proteins, nut shell flours, sugar, and
Table 14. Humectants. cellulosic resins) are incorporated into polyvi-
Calcium chloride Sodium nitrate nyl acetate homo- or copolymer emulsion ad-
Diethylene glycol Sorbitol hesives. Growing microorganisms digest these
*G\ycerine *Sucrose substances and can generate foul odors, dis-
Hexylene glycol *Urea
*Propylene glycol
color the adhesive, lower its viscosity, and
weaken the bond.
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 399

Table 16. Recommended Modifiers- Trademarks and Suppliers.

Plasticizers Thickeners
Abalyn® Hercules Inc. Natrosol® Hercules
Hercoflex® Hercules Inc. Cellosize® Union Carbide
Hercolyn® Hercules Inc. Methocel® Dow Chemical
Benzoflex® 2-45, 9-88, 50 Velsicol Chemical Corp. Polyco® 296W Borden Chemical
Pycal® 95 ICI Americas Polyoxy® WSRN 750 Union Carbide
Celluflex® CEF Stauffer Chemicals Carbopol® BF Goodrich Chemical
Resoflex® 296 Cambridge Industries Co.
Santicizerlll 8, 160, M17, Monsanto
140, 141 Solvents

Tackifiers-Extensing Resins Chlorothene® Dow Chemical Co.

Cellosolve® Union Carbide
Hercolyn® Hercules Carbitol® Union Carbide
Polpale® Resin Hercules
Stabelite® Ester 3, 10 Hercules Surfactants
Piccolite® Hercules
Surfynol® Air Products and Chemi-
Piccoflex® Hercules
cals, Inc.
Piccolastic® Hercules
Aerosol® OT American Cyanamid
Piccopale® Hercules
Nopcowet® 50 W. R. Grace and Co.
Foral® 85 Hercules
Foamasterlll JMY W. R. Grace and Co.
Vinsol® Hercules
Tween® ICI Americas
Santolite® MS Monsanto
Colloid® 682, 770 Colloid Inc.
MHP, MS80
Drew® 11250 Drew Chemical Corp.
Bakelite® CKM2400 Union Carbide
Bakelite® CKM2432 Union Carbide
Preservatives
Bakelite® CKROO36 Union Carbide
Bakelite® CKR2103 Union Carbide Dowicide® A, G Dow Chemical Corp.
Nevillac® Neville Chemical Co. Dowicil® 75 Dow Chemical Corp.
Proxcel® GXL ICI Americas
Thickeners
Merbac® 35 Merck and Co., Inc.
Cabosil® Cabot Corp. Kathon® LX Rohm and Haas

The inclusion of 0.1-0.2% of a biocide, The grade numbers indicated may not be ex-
based on the total wet weight of the formula- haustive of all those available; however, these
tion, prevents microbial growth. Nevertheless, are the most highly recommended.
microbes frequently adapt to a specific biocide
and flourish. Biocides should be changed reg- BIBLIOGRAPHY
ularly to prevent this occurrence.
1. Daniels, W. E., "Poly(Vinyl Acetate)" in "Kirk-
Polyvinyl Alcohol Othmer Encyclopedia of Chemical Technology," 3rd
Ed., pp. 817-847, New York, John Wiley and Sons,
Polyvinyl alcohol, a first class adhesive in its 1983.
2. Schildknecht, C. A., "Vinyl and Related Polymers,"
own right, also serves as an excellent additive
pp. 323, New York, John Wiley and Sons, 1952.
for modifying the properties of polyvinyl ace- 3. Skirrow, F. W., and Herzberg, O. W., U.S. Patent
tate emulsion adhesives. See Chapter 22 of this 1,638,713 (to Shawinigan Resins).
volume. 4. Hydrocarbon Processing, 46(4), 146 (1967).
5. Petroleum Refiner, 38, 304 (1959).
TRADEMARKS AND SUPPLIERS 6. Vinyl Acetate, Bulletin No. S-56-3, Celanese Chem-
ical Co., New York, 1969.
Table 16 lists the most commonly used modi- 7. Vinyl Acetate Monomer, F4l519, Union Carbide Co.,
New York, 1967.
fiers listed by their brand names and respective
8. Vinyl Acetate Monomer, BC-6, Borden Chemical Co.,
manufacturers. These modifiers are classified New York, 1969.
by functional uses, such as plasticizer, tacki- 9. Vinyl Acetate Monomer, Air Reduction Co., New
fiers, thickeners, solvents, and preservatives. York, 1969.
400 HANDBOOK OF ADHESIVES

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