Polyurethaneadhesives

Chr. Strdbech

(Casco Nobel A/S, Denmark)

This paper reports on the main types, uses and methods of application of polyurethane
adhesives, concentrating in particular on the one-component, moisture curing, solvent-
free and the two-component, hard types. For the latter, the development of strength
and hardness during cure is discussed, and the effects of pot life, application time and
pressing time are examined. Safety aspects of the use of polyurethane adhesives are
also considered, with particular reference to practice in the Scandinavian countries.

Key words: adhesives; polyurethanes; one-component types; two-component types;

strength; pot life; cure; safety

Due to the versatility of polyurethane chemistry, there
are many different types of polyurethane adhesives.
This means that when talking about polyurethane
adhesives for a specific purpose it is also necessary to
be specific about the adhesive type. The most
important types are as follows:
l one-component, moisture curing, solvent-free;
l one-component, moisture curing, with solvents;
0 one-component, moisture curing, elastic;
l one-component, moisture curing, hot melt;
l one-component contact adhesives, with solvents;
l two-component, hard;
l two-component, elastic; and
l two-component contact adhesives, with solvents.
Considering that nearly all the types may exist in
different variations, such as liquid or thixotropic. fast
or slow cure, and fire approved or not fire approved, it
is realized that there is a rich variety of adhesives to
select from.
Apart from some of the one-component, moisture
curing, elastic products (sealant adhesives), which
usually contain a little (below 0.5%) free toluene
diisocyanate (TDI), all the other types of adhesive are
based on polymeric methylene diphenyl diisocyanate
(MDI), the least volatile of the commonly used
isocyanates.
Polyurethane adhesives in Scandinavia
Health and Product Legislation in the Scandinavian
countries has always been very tough, forcing the
industry to develop products which are the least
harmful to man and environment.
In Denmark, for example, the formulations of all
polyurethane (and epoxy) products have to be
registered with the government, along with labels and
the material safety data sheets. If found acceptable, the
product is given a product registration number which
has to appear on labels, safety and technical data
sheets. In each factory using chemical products, a
safety group has to be established which, together with
the management, has responsibility for safety. The
safety groups work together with government inspectors
and a medical surveillance organization to find the
safest products, production methods and equipment.
Consequently, the polyurethane products and methods
developed in this constantly scrutinizing system are the
safest obtainable.
As an example, the use of solvent-borne spraying
adhesives is virtually unknown in Scandinavia, as
special systems and precautions have to be used for
spray systems. Even if a closed spray booth is used, it
is made difficult to use these adhesives because
solvents are released during the handling process,
demanding new safety considerations. Instead of the
solvent-borne adhesives, fast curing, solvent-free, one-
and two-component adhesives have been developed,
the use and application of which are described below.
Main uses for polyurethane adhesives
Due to their good adhesion, toughness, water and
chemical resistance, and the ability to tailor
polyurethanes to many specific uses, polyurethane
adhesives are used in many areas including:
l all kinds of sandwich element - bulkheads for ships
and trains, housing elements, cold store elements,
trucks, containers, recreational vehicles;
l tools (axes, hammers);
0 constructions - roof elements, metal/wood
constructions, bolts in laminated wood structures;
l repair (cars, containers, trucks);

0143-7496/90/030225-04 0 1990 Butterworth-Heinemann Ltd

INT.J.ADHESION AND ADHESIVES JULY 1990 225

• thin plate bonding;
• weld bonding and rivet bonding;
• bonding of plastic cars;
• bonding of reinforced plastic (glass fibre-reinforced
plastic (GRP), sheet moulding compound (SM¢),
etc).
The properties of adhesives used for the above
applications are shown in Tables 1 and 2.
Specific adhesive types
Of the different types of polyurethane adhesive listed
above, only the one-component, moisture curing,
solvent-free types and the two-component, hard types
will be dealt with more closely, these being the most
common adhesives.
One-component, moisture curing polyurethane
adhesives (solvent-free)
When supplied, these prepolymer (pre-reacted) types
are normally liquid and may be applied by hand, by
spraying (in closed cabins) or preferably by nozzles,
the easiest and safest method. Some automatic
application systems are up to about 3 m wide and may
apply adhesive at a speed of up to 15 m/min in an
amount of 100 to 300 g/m 2. Simultaneously with
application of the adhesive, water is sprayed onto the
adhesive/materials in an amount necessary for the
curing process. The most important production process
factors of these adhesives are the open time and cure
time at room temperature and elevated temperature,
since these adhesives may give pressing times down to
below 2 min at 70-80°C.
One-component polyurethane adhesives are
available both as filled and unfilled types. The filled
types contain less polyurethane and are consequently
used in bulkheads for ships and other places where fire
resistance of the adhesive is required (approved by
See-Berufsgenossenschaft (SBC)), or where the safest
adhesive has to be used. They are normally used for
sandwich elements with cores such as stonewool,
polyurethane and polystyrene foam and skin materials
such as GRP, lacquered metal or galvanized steel. The
unfilled types are excellent for bonding wood/wood,
even when the moisture content is high. During cure
with moisture the one-component polyurethane
adhesives liberate carbon dioxide, making the adhesive
foam slightly. This gives excellent bonding to porous
and uneven surfaces.
Some available adhesives are shown in Table 1,
ranked according to open time/cure time. As can be
seen, it is possible to select an adhesive for continuous
production where one element is made at a time, or for
stack pressing where a large stack of elements is
pressed at a time. Depending on the open time needed
for assembling an element, a fast or slow adhesive may
be selected. Heat greatly accelerates the cure process.

Table 1. One-component polyurethane adhesives

Open time at Press time, water spray, Press time, water spray, Notes Name/Number
23 ° C (min) 23°C (rain) 70°C (rain) Foss Than 1K (Casco)
1
7 15 1~-2 Filled, SBG 1828
10 20 2-3 Filled, SBG 1830
10 20 2-3 Non-filled 1812
20 40 4-5 Filled 1831
20 40 4-5 Non-filled 1843
30 60 5-6 Filled, SBG 1833
45 120 10 Non-filled 1894
45 120 10 Water clear 1809
200 12-18 h 120 Non-filled 1804

Table 2. Two-component polyurethane adhesives

Application Open time at Handling time Uses Application method/ Number Foss Than
time (rain) 230C (rain) at 230C fire resistance 2K (Casco)

5 10 50 rain Sandwich elements S 1807

12-15 20 60 min Sandwich elements S 1881
15 20 120 min Sandwich elements T, N, I 1862
20 40 4h Tools, bolts in wood N 1959
40 60 5h Metal, car repair, weld bonding B, N 1847
45 60 6h Roof elements N, T 1819
60 120 5-6 h Sandwich elements N, S, T, SBG 1899
90 45 6h Mounting, repair B, N, T 1897
120 60 8-12 h Sandwich elements N, T, R, SBG 1801
150 180 7h Sandwich elements B, N, T 1883
240 90 24 h Acoustic elements N, T, R, SBG 1867

B - - brush; N - - nozzles (machine application); R - - roller; S - - spraying; T - - t r o w e l (notched)

I - - non-combustible. I M C O A 4 7 2 (USCG); SBG - - f i r e approved (See-Berufsgenossenschaft)

226 INT.J.ADHESION AND ADHESIVES JULY 1990

Two-component polyurethane adhesives
Two-component polyurethane adhesives are used for a
large variety of applications (see above). They bond to
nearly all materials, either as-delivered or prepared for
bonding by proper industrial methods. The two-
component adhesives are normally applied by hand,
brush, nozzles, spray (closed cabin) or roller, and a
large range of m o d e m application equipment is
available for industrial bonding processes. An
automatic application machine for large elements is
shown in Fig. 1. For this purpose, the adhesives may be
made in different qualities (iiquid-pastelike, fast cure-
slow cure) to satisfy the requirements of the bonding
process.
Table 2 shows some typical two-component
adhesives grouped according to application time/cure Fig. 1 Application of two-component polyurethane adhesives on large
surfaces
speed. The application methods vary greatly, as do the
properties and application of the adhesives. After full
cure, they are all hard, tough adhesives, except 1867 60
which is a soft, sound-dampening adhesive for acoustic
panels. Pot life is about double the application time Pot life
5O
(see later). The adhesive has to be applied within the
application time and pressure has to be applied within Io
the open time. Handling time is equal to press time. q0
Final total cure takes days or weeks. For each 10°C x
temperature increase, the handling time is reduced by 3o
about half.

Curing "~ 20

Cure starts as soon as the two parts are mixed and the
base and curing agent molecules react. The viscosity of 10 A_~n
the mixture increases but, as the reaction proceeds, I
exothermic reaction heat develops which keeps the 0 10 20 30 qo 50 60 70 80
viscosity down or even lowers it for some time on faster
Time (min)
curing products.
Fig. 2 shows that the application time is the time Fig. 2 ~scosityincrease w i t h t i m e f o r F o s s T h a n 2K 1 8 9 9 / 1 8 2 1 =
from mixing to the time when the adhesive cannot be 100/22
applied, eg, using a notched trowel. For the specific
adhesive shown in Fig. 2 (Foss Than 2K 1899/1821), the 130[
viscosity is then about 50 to 70 Pa s or less, depending 120~ ~ . - " ~ ' ~ h e a r strength
on the application method. Pot life can be defined as
the time when the mixture cannot be stirred at all. The
viscosity at this stage is about 500 Pa s (start ,°° r
temperature 22°C). From the figure it can be seen that
a 80
the application time is about 45-50 min and pot life
=~ " 70 / /"O""""-- Shoed hardness
about 70 min (200 g mixture).
As cure continues, the adhesive turns slowly from
liquid to a soft, sticky material which slowly hardens. L 50
The hardness and strength increase for Foss Than 2K qO
1899/1821 adhesive is shown in Fig. 3. Strength is ¢. 30
t/1
measured on Al/A1 joints according to DIN 53283, and 20
Shore D is a measure of hardness. Shear strength takes 10
some 5-7 h to develop to handleable levels, depending I l I I I I l I I I I I I I I
on the construction bonded. Slower aftercure then 2 q 6 8 10 12 l q 16 18 20 22 2q 26 28 30
takes place, during which adhesion and water Time ( d a y s )
resistance develop.
Cure may be accelerated by adding catalysts. Fig. 4 Fig. 3 Hardness and strength increase with time for Foss Than 2K
1899/1821 = 100/22
shows the strength during the first few hours of cure
for the same adhesive as above but with different pot
lives. It can be seen that a reasonable strength can be and aluminium as a skin at a shear strength of only
obtained in less than 30 min if an adhesive with 31 min 1.2 MPa, then the pressing time, defined as the time
pot life is used. This time increases for longer pot lives. when the element can be handled without breakage in
Heat may greatly increase the cure speed. the foam, is shown in Table 3 as a function of pot life,
If it is assumed that breakages in the foam occur in application time and temperature. Combining these
a sandwich element using 60 kg PV¢ foam as a core measurements with those of flexural strength changes

INT.J.ADHESION AND ADHESIVES JULY 1 9 9 0 227

 Table 3. Relationship between pot life, application time and pressing time for Foss Then 2K 1899

Pot life (min) Application time, approx (min) Open time, approx (min) Press time, approx (min) Press time at 40°C,
approx (min)

3.5 1.5 3 20 5
10 5 12 90 25
30 15 18 180 45
50 25 60 240 60
70 45 120 300 75

Pot life (min)

This means that it is possible to work safely with
one- and two-component polyurethanes at room
5 a 3½
temperature with normal room ventilation, as long as
0.
normal hygienic conditions are followed. When heat
4 pressing is performed or the adhesives are sprayed,
£
special precautions have to be taken. The industrial
3 material safety data sheets should always be consulted,
and the production methods should be approved by

/J,/,
2 the local health and safety authorities.
.c
t~
1 Conclusion
- I I I
Polyurethane adhesives are widely used in many
I 2 3 4 5 6 7 8 different industries for bonding sandwich elements, for
Time {h) trucks and containers, tools and constructions, as well
as for repair, thin plate bonding and weld and rivet
Fig. 4 Strength during cure of Foss Than 2K 1 8 9 9 / I 821 with different
pot lifes
bonding. Modern application equipment is available
for applying the adhesives, and likewise effective
pressing and curing systems have been developed to
with time of the specific sandwich element gives a clear meet the demands of the latest one- or two-component
picture of what is happening during cure in the polyurethane adhesive technology. Modern application
bondline. and pressing systems most often have safety equipment
as an integral part of their construction.
Safety
The base resin of two-component polyurethanes Acknowledgement
normally consists of polyols, fillers and small amounts The author wishes to thank the European Commission
of additives. No safety markings are necessary. The for supporting the BRITE programme A B C O N
curing agent and the one-component, moisture curing (Adhesive Bonding Technology for Building
adhesives contain polymeric MDI, an isocyanate with a Construction). Part of the work reported in this paper
very low vapour pressure. Many measurements in stems from this BRITE programme.
actual industrial use, with hand or nozzle application,
show that the level of MDI in the air is much lower
than the threshold limit in Scandinavia (and now in Author
many other places) of 0.05 mg m -3, and normally Mr Strobech is with Casco Nobel A/S, 2-4
below the detection limit. Prmstemosevej, 3480 Fredensborg, Denmark.

228 INT.J.ADHESION AND ADHESIVES JULY 1990