
REFERENCES
Cited Publications
1. A. A. Schoengood, ed., Plast. Eng. 32(3), 25 (1976).
2. M. McMurrer, ed., ‘‘Update: PVC Heat Stabilizers’’ in Plastic
Compounding, Resin Publications, Cleveland, OH, 1980, pp.
83–90.
3. L. R. Samuelson, Plast. Des. Process. 21(8), 14 (1981).
General References
P. Bredereck, J. of Vinyl Technology 1(4), 218–220 (1979). Guide to
Plastics, McGraw-Hill, New York, 1979, p. 27.
M. McMurrer, ed., Plastic Compounding 1984/85 Redbook, Vol. 7,
No. 6, Resin Publication, Cleveland, OH. 1985.
M. McMurrer, ed., ‘‘Update—U.V. Stabilizers,’’ Plastic Compound-
ing, Resin Publications, Cleveland, OH, 1985, pp. 40–57.
Thermal Stabilization of Vinyl Chloride Polymers, Technical
Report 3250, Rev. 7/68, Rohm & Haas, Philadelphia, 1968.
L. R. Samuelson, Plastics Design and Processing 21(8), 13–15
(1981).
V. Struber, Theory and Practice of Vinyl Compounding, Argus
Chemical Corp., New York, 1968.
FILM, SHRINK
GEORGE D. WOFFORD
Cryovac Division, W. R. Grace &
Co.-Conn., Duncan, South
Carolina
Shrink film is a name given to a unique family of films
that are distinguishable by their attributes, production
processes, and end uses. They are composed of two basic
categories: poly(vinyl chlorides) (PVCs) and polyolefins.
Although most plastics exhibit some amount of free shrink
and shrink force at elevated temperatures, true shrink
films (sometimes known as heat-shrinkable films) provide
a high degree of free shrink with a controlled level of
shrink force over a broad temperature range.
Shrink force must be controlled to prevent crushing or
deforming the product being packaged. Providing the
proper level is important to the marketing of toys; games;
cards, calendars, and other paper products; hardware;
food; and a variety of merchandise where a tight, glossy
package appearance is essential.
Shrink films are produced by uniaxially or biaxially
orienting a sheet or tube of film by imposing a draw force
at a temperature where the film is softened but kept below
its melting point, then quickly cooled to retain the physi-
cal properties generated during orientation. It is impor-
tant to note that the orientation temperature occurs
between the vicat softening point (ASTM D1525) and the
melting point, but is not directly related to the glass-
transition temperature (T
g
) as some literature would
indicate. This can be seen in Table 1, which compares
glass-transition temperatures to vicat softening points for
several polymers.
Prior to orientation, the molecules of the film are
randomly intertwined, exhibiting no particular align-
ment. However, when a draw force is imposed, the amor-
phous regions are straightened and oriented to the
direction of force. By applying proper cooling, the mole-
cules will be frozen in this state until sufficient heat
energy is applied to allow the chains to shrink back. One
can visualize this phenomenon by stretching a rubber
band and dipping it into liquid nitrogen. It will remain
stretched as long as it is kept at sufficiently cold tempera-
tures. However, when enough heat energy is applied, the
rubber band will shrink back to its original relaxed state.
Orientation on a commercial scale can be achieved
using either of two methods: a tenter-frame or a bubble
process. Tenter-frame technology produces a variety of
‘‘heat-set’’ products, of which biaxially oriented polypro-
pylene (BOPP) is the most common. Heat setting is a
process whereby a film is reheated in a constrained state
such that the shrink properties are destroyed. Other
important characteristics derived from orientation (optics,
tensile strength, and modulus) remain intact, however.
Current tenter-frame technology does not allow the pro-
duction of materials with a high degree of free shrink and
shrink force due to the mechanics and thermodynamics of
the process.
In the tenter-frame process, a flat sheet is produced and
cooled on a chill roll, which is usually immersed in a
waterbath. The sheet then proceeds through a machine-
direction orientation (MDO) unit, where it is heated and
stretched to the desired ratio. On exiting the MDO unit,
the sheet enters the transverse-direction orientation
(TDO) unit, where it is reheated and stretched. BOPP is
commonly stretched 700–800% in both the machine and
transverse directions. After exiting the TDO, the material
is wound into large mill rolls for aging (aging allows
secondary polymer crystallization, ensuring film flatness
and roll uniformity) and converting. Some tenter-frame
systems have additional downstream equipment for re-
tensilization and further heat setting or annealing. The
primary suppliers of tenter-frame systems are Bru
¨
ckner
(Germany), Mitsubishi (Japan), and Marshall & Williams
(United States).
The second commercial method is the bubble process,
sometimes referred to as a tubular process. A primary tube
is produced by blowing the film onto an external mandrel
or casting it onto an internal mandrel. Water is used to
help cool the tube at this point.
After it has been cooled, the tube is reheated and air is
used to inflate it into a bubble. On inflation, it is oriented
Table 1. Glass-Transition Temperatures and Vicat
Softening Points of Common Polymers
Polymer T
g
(1F) Vicat (1F)
Polystyrene 181–201 208
LLDPE 188 to 5 177–220
Polypropylene 7–41 307
PVC 158–176 183
498 FILM, SHRINK