Thermoplastic Polyurethane

Technologies for the Textile Industry*

LARRY JOHNSON** AND JULIE SAMMS
The BFGoodrich Company
9911 Brecksville Rd.
Cleveland, OH 44141-3247

INTRODUCTION

(TPU) has been meeting the needs of a

POLYURETHANE
THERMOPLASTIC
worldwide marketplace for many years. Its versatile property mix has
made it a candidate for many applications in various markets where a tough,
durable, elastomeric material is required. These polymers offer design free-
dom not found in other materials due to a unique and broad-ranging port-
folio of characteristics, including outstanding abrasion resistance, strength
and toughness, chemical and hydrolysis resistance, fungal growth resistance,
low temperature flexibility, clarity, colorability, ease of decoration, and a
wide processing window in many plastic processes. These properties are so
well established in the marketplace that there are very few market areas
where TPU does not have some utility. Some of the segments that utilize
TPU include, wire and cable, footwear, automotive, healthcare/medical,
hose and tube, and film and sheet.
A less well-known market for TPU is in the textile industry where TPU is
laminated onto a fabric to provide protection, comfort and aesthetics to the
user or wearer. BFGoodrich has developed several new and novel thermo-

plastic polyurethane materials to meet the special needs ofthis segment. These
TPU materials can be extruded into thin monolithic films that can be lami-
nated onto a textile substrate to provide the above mentioned benefits.

*Copyright held by The BFGoodrich Company.

**Author to whom correspondence should be addressed.

48 JOURNAL OF COATED FABRICS, 1/olume 27-July 1997

0093-4658/97/01 0048-15 $10.00/0

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The TPU technologies in question are high moisture vapor transmission

(HMVTR), flame retardant, inherently static dissipative, and rubber-like. The
attributes ofthese TPU materials extend the use of these polymers into apphca-
tions where it is important to balance functionality and comfort with an effec-
tive protective barrier between the user and his/her environment such as
sportswear, hygiene, outerwear, medical apparel, protective apparel, and diapers.
The purpose of this paper is to discuss the above mentioned BFGoodrich
EstaneO thermoplastic polyurethane material technologies that are now com-
mercially available.
Brief History of TPU in Textiles

Thermoplastic polyurethane has been in use as a fabric coating material in

the textile industry for nearly thirty years. Its first application was as a replace-
ment for PVC where the &dquo;look and feel&dquo; of PVC was of value, but the per-
formance of PVC was lacking in areas, such as flex properties, plasticizer
migration, abrasion resistance, low temperature properties, and cleanability.
These deficiencies opened the door for TPU to replace PVC because TPU
could solve these problems, albeit at a higher price. In addition to the above
properties, TPU offered excellent &dquo;drape&dquo; properties, softness and suppleness
of hand, and could be processed to a very high gloss surface (wet look) or for-
mulated to look and feel like leather (shoes).
TPU was also known to have much better moisture vapor transmission
properties than PVC. Although this was not the prime motivating factor in
TPU’s moving into textile applications, it was a very desirable feature even
then.
Today, the property portfolio that TPU offers the textile industry is still of
prime importance and TPU is still very much a problem solver for the indus-
try.

Thermoplastic Polyurethanes
,

Offering characteristics ofboth rubbery elastomers and rigid plastics, ther-

moplastic polyurethanes (TPUs) have a number of features that make them
desirable for use in a variety of applications. Their versatility and durability of-

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50

fer strength and toughness that is greater than that of traditional thermoset
systems. They are also flexible enough to be processed on a broad range of
thermoplastic equipment.
TPU materials offer a wide range of properties. High tensile
strength and
elongation combined with superior resistance to tearing and cutting make
TPU exceptionally tough. With abrasion resistance that is better than nylon,
rubber, polystyrene, or high-density polyethylene; TPUs are suitable for the
most demanding applications. Members of the TPU family offer good
chemical-, UV-, and hydrolysis resistance, excellent low temperature flexibil-
ity, and excellent flex fatigue properties. Characteristics, such as clarity, color-
ability, and ease of decoration make TPUs ideal for applications where
aesthetics are important. The materials are also sterilizable and bondable to a
number of different substrates. Finally, the recyclability of TPU satisfactorily
addresses growing environmental concerns.
Several characteristics make TPU especially well suited for use in the textile
industry. Their flexibility, especially at low temperatures, yields a soft hand and
quiet sound to articles manufactured with TPU. The materials maintain good
barrier properties while providing high breathability-a combination of at-
tributes required by the outdoor and performance sportswear industries. Re-
sistance to fungal growth, washability, rubber-like elasticity, resistance to
tearing and punctures, and the ability to be processed into fibers further add to
TPUs utility in textile manufacture. TPU can also be compounded with a va-
riety offiller materials, such as flame retardants, minerals, lubricants, and proc-
essing aids to achieve specific functionality objectives.
General TPU Chemistry
Thermoplastic polyurethanes are part of the thermoplastic elastomer fam-
ily, a group ofpolymers that can be formed and reformed by the application of
heat and pressure. All TPUs are manufactured from three primary raw mate-
rials : an isocyanate, a macroglycol, and a cham extender. The choice of each of
these components affects the structure of the polymer and thus influences its
final physical properties. Other materials such as stabilizers, lubricants, fillers,
and pigments can also be used in TPU manufacture.
Isocyanate: Isocyanate used to produce TPU can be either aliphatic (HMDI,
IPDI) or aromatic (MDI,TDI). Whereas aliphatic isocyanates demonstrate
better light stability, are soluble in mild solvents, are more resistant to weather-
ing, and offer better abrasion resistance; the aromatic materials are lower-cost,
more solvent-resistant, and yield urethanes with better tensile strength and re-

covery. Hydrolysis of the final polymer is somewhat more likely with the aro-
matic materials, but this characteristic is more greatly influenced by the choice
of polyol.

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 51

Macroglycol: Macroglycols react with the isocyanate to form the soft-

segment backbone of the polymer, and give the material its amorphous
characteristics. Higher molecular weight macroglycols yield a longer
polymer backbone and more flexibihty in the final product. Choice of
macroglycol type (polyester, polyether, or polycaprolactone) influences
chemical and hydrolysis resistance of final TPU. Whereas polyesters pro-
vide better UV-, oxidation-, and chemical resistance, and typically yield
better physical properties,polyethers provide hydrolytic stability and good
low temperature properties. Polycaprolactones provide a combination of
these characteristics; they are more expensive and can be varied in chain
length only [2].
Chain Extender: Chain extenders react with the isocyanate to form the ac-
tual urethane structure, or hard segment of the polymer. Chain extenders are
typically either diols, which react with the isocyanate to form urethane or dia-
mines, which react with the isocyanate to form urea. The urethane and/or
urea can further react with isocyanate to form biuret and allophonate struc-
tures that are undesirable side reactions. Use of a higher percentage of chain
extender or a short-chain low molecular weight chain extender in the formu-
lation yields more urethane segments and a more crystalline polymer, thus
providing strength and toughness to the finished product.

BREATHABLE THERMOPLASTIC POLYURETHANES

What Is &dquo;Breathable&dquo; and Why Is It Important?

Breathability is the ability of a textile construction to allow water vapor to
pass out from the body through it, but not to allow liquid from the outside to
pass into it. This property is expressed as &dquo;moisture vapor transmission rate&dquo; or
MVTR. It is &dquo;the steady water vapor flow in unit time through unit area of
body, normal to specific parallel surfaces, under specific conditions of tem-
perature and humidity at each surface&dquo; [1]. The value is expressed in number
of grams per square meter over a given period of time. ASTM Test Methods
E96B and E96E were used to determine breathability ofEstane@ 58237 and
58245 thermoplastic polyurethane.
Protection is discussed in two different terms in today’s textile market. Itt
can mean protecting the wearer from elements from the outside environ-
ment such as rain, blood or other liquids, virus, wind, and microbial attack.
It can also mean protecting the outside environment from the human
wearer in applications, such as cleanroom apparel and surgical gowns. In

the case of cleanroom apparel, the protection could be from particulate

matter, such as skin, flaking onto the very sensitive electronics being

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 52

worked on. In the case of surgical gowns, the protection is prevention of

the contamination of the patient from microorganisms that could be re-
leased by the gown wearer.
In 1991 the Occupational Safety and Health Administration issued a rule
that requires all employers with personnel at risk of occupational blood expo-
sure to provide &dquo;appropiate&dquo; protection that &dquo;does not permit blood or other
infectious material to pass through onto healthcare workers skin or inner
clothing&dquo; [3]. This rule has called into questions the requirements for protec-
tive clothing in healthcare institutions. It has also been the impetus for a
number of orgamzations, including ASTM, to issue test methods to evaluate
the barrier effectiveness of protective apparel against body fluids and blood-
borne viruses (ASTM ES 21, ASTM ES 22).
The importance of comfort and protection in today’stextiles cannot be ar-
gued even though one can debate how much breathability is necessary for a
textile to be comfortable. Preventing water vapor produced by the body from
escaping to the outside interferes with the basic chemical prmcipal of achiev-
ing equilibrium. The challenge, then, is to create a film that is a barrier to liq-
uids yet remains permeable to water vapor so that the fabric can relatively
quickly reach equilibrium between the inside and the outside [4,5]. Meeting
this objective produces a textile construction that achieves the goals ofprotec-
tion and comfort.

Monolithic vs. Microporous Film Technology

In constructions where a barrier film (such as the form in which TPU
would be used) is employed to provide protection and also provide comfort,
there are two technologies that are used to accomplish these objectives. Both
technologies provide the above mentioned benefits. Which is better is a mat-
ter of degree of effectiveness.

Microporous membranes are produced by stretching a blend oftwo incom-

&dquo;
patible partners, such as a polymer filled with inorganic particles. This stretch-
ing induces micro cavities around the filler particles [4,5]. These membranes
can be made of any number of polymer systems, from polyolefins to
out
PTFE. Figure 1 illustrates microporous membranes.
Monolithic membranes are dense, pinhole free polymer membranes that
are produced by simply casting or extruding a solid film via one of several

processing techniques and laminating it onto a fabric. These membranes can

also be made out of a variety of polymer systems, but they are generally of
higher cost because specialty polymer systems (like thermoplastic polyure-
thane) are needed to achieve the goals ofprotection and comfort to the degree
needed. Figure 2 illustrates monolithic moisture vapor transmission.
Features of both technologies are listed in Figure 3.

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 53

FIGURE 1. Microporous moisture vapor transmission

FIGURE 2. Monolithic moisture vapor transmission

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54

FIGURE 3. Characteristics of monolithic and microporous film technologies

Because there are no pores in monolithic films, they are generally the ac-

cepted technology applications requiring viral barrier. Estanee thermo-

in a

plastic polyurethane technology is used to make monolithic protective films

that exhibit the above characteristics as well as comfort.

The Effect of Chemistry on Breathability

There are a number ofproperties that affect the permeability or breathability
of a polymer. Its hydrophilic nature, glass temperature ( Tg), crystallinity, and filler
content can all effect the ability of the material to transmit water vapor.
The chemical structure of polyurethane can be manipulated to improve
permeability. Incorporation of a hydrophilic backbone into the ure-
thane-includmg the use of hydrophilic structures such as ether, hydroxyl,
and carboxyl groups-increases the affinity of the polymer to water and im-
proves permeability. Additionally, greater solubility of water in the polymer
also improves permeability. The greater potential concentration gradient pro-
vides a stronger driving force for moisture vapor transmission, thus creating a
&dquo;wicking&dquo; action in the material.
An amorphous polymer exhibits higher permeability when in a rubbery
state at temperatures above its glass transition temperature (TJ than when in a
glassy state at temperatures below its Tg. In a polymer containing both hard
and soft segments (including most TPUs), permeation occurs primarily
through the soft (rubbery) segment rather than through the hard (crystalline)
segment. As a result, permeability is inversely proportional to crystallinity.
Therefore, a more crystalline polymer is less permeable, and a polymer with
lower urethane content/hard segment will have higher MVT properties. Per-
meability can also be effected by the addition of insoluble inorganic fillers. Of
low permeability themselves, these materials act to increase the diffusion path

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 55

length of water through the polyurethane and thus reduce the rate of trans-
port.

High Moisture Vapor Transmission

Estaneg 58237 and Estaneg 58245
Two TPUs specifically formulated for high moisture vapor transmission
characteristics are The BFGoodrich Company’s Estane 58237 and Estane
58245. These aromatic materials perform very favorably and economically
when compared to traditional TPUs and to other TPE materials.
Estane 58237 polyether-based polyurethane has a Shore hardness of 90A,
tensile strength of 7300 psi, ultimate elongation of 500%, and tear strength of
480 psi. It exhibits a moisture vapor transmission rate of 9,OOOg/m2/day at
38°C/90%RH (E-96E). Estane 58245 TPU, a somewhat softer polyether-
based material, offers better breathability. With a Shore hardness of80A, ten-
sile strength of 4000 psi, ultimate elongation of 800%, and tear strength of 390
psi, it exhibits a moisture vapor transmission rate of 14,000 g/m2/day at
38°C/90%RH (E-96E). A summary of physical properties and breathability
characteristics can be found in Figures 4 and 5.
The moisture vapor transmission properties of Estanes 58237 and 58245
are much better than standard polyester- and polyether-based TPUs. Estane

58237 is comparable in both price and MVT performance to COPE and

PEBA. The breathability ofEstane 58245 is superior to that of these materials,
and in fact approaches that of microporous PTFE.

RUBBER-LIKE THERMOPLASTIC POLYURETHANES

The ability of an elastic material to be deformed with relatively low levels of

and to recover almost completely with very little induced set is of tre-
stress
mendous value in many applications. In fact, this property is what gives natural
rubber its utility and value in many of the markets it serves.

FIGURE 4. Typical physical properties of Estane 58237 and 58245.

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56

FIGURE 5. Moisture vapor transmission data for Estane 58237 and 58245 1 mil extruded
film .

Thermoplastic polyurethanes have not traditionally offered this par-

ticular property to the degree natural rubber has in the past. The property
mix that TPU has offered consists of the properties expressed previously
in this paper, along with the processing advantages that a thermoplastic has
over thermoset materials (like natural rubber). TPUs have not exhibited
the same degree of elasticity and rebound that natural rubber offers. Until
now, this has limited the application opportumties for TPUs to areas
where high rebound and low set properties are not important aspects of
the specification.
BFGoodrich has developed new TPU technology that provides polyure-
thanes with more &dquo;rubber-like&dquo; elastic behavior while maintaining the tradi-
tional properties TPU has become known for. These materials are Estane
58238 and 58661 polyester TPUs. The typical properties summary is found in
Figure 6.
In studies that were done in comparison with conventional TPU technol-
ogy some important difference were found in the elastic behavior that 58661
and 58238 exhibited as opposed to these other TPUs.

FIGURE 6. Typical physical properties for Estane 58238 and 58661.

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 57

FIGURE 7. &dquo;Rubber-like&dquo; TPU’s stress-stram to 100%.

First, as illustrated in Figure 7, Estane 58238 and 58661 have substantially

lower 100% modulus. This indicates that these materials deform with less
stress at low elongations.
The behavior of 58238 and 58661 at low elongations is ofparticular impor-
tance as most &dquo;real-world&dquo;applications involve deformations ofunder 50%.
Another key attribute of&dquo;rubber-like&dquo; behavior is recovery after deformation.
Figure 8 below shows the behavior of 58238 and 58661 TPUs compared to a
control TPU and natural rubber. This figure shows very clearly the advantages of
rubber-like TPU, compared to other TPU, and also shows that rubber-like TPUs
approach natural rubber With respect to this important property.
Both Estane 58238 and 58661 exhibit significantly better &dquo;rubber-like&dquo;
behavior than conventional TPU products. Although they do not replicate
natural rubber in this regard, they make a significant jump toward this goal and
allow the textile engineer the design versatility to work with a material that can

FIGURE 8. &dquo;Rubber-hke&dquo; TPU’s tensile recovery.

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58

be easily melt processed and still maintain highly elastic properties in a mono-
lithic film laminate.

INHERENTLY STATIC DISSIPATIVE

THERMOPLASTIC POLYURETHANE ALLOYS

Electrostatic discharge (ESD) happens when an electrostatic charge is trans-

ferred between bodies of different electrostatic potential. This discharge
causes a rapid release of energy from excess positive or negative charge trying
to reach equilibrium. A common example of this discharge is the shock a per-
son experiences when, after walking across a carpet, they touch a door knob

[6]. This type of &dquo;ESD&dquo; event is very common and, if it occurs under the
wrong circumstance such as in a cleanroom environment, can be very costly.
In today’s cleanroom environment contamination-free manufacturing
drives to eliminate all impurities from the processing environment, even those
caused by humans (such as skin flaking). The reason for this elimination is the
static sensitivity, and the high value of the products manufactured in this type
of environment.
The Mitech Corporation, a subsidiary of the BFGoodrich Estane Division,
has introduced three inherently static dissipative thermoplastic polyurethane
alloy compounds that can prevent the above-described ESD event. They are
Stat-Rite Tm E-1150 (polyether), E-1050 (polyether) and E-1140 (polyester).
Figure 9 shows where Stat-Rite static control polymers lie in terms of surface
resistivity.
These products provide the textile industry with a reliable, controlled dis-
charge of static charge buildup that is cost-effective, humidity independent,
colorable, non-contaminating, permanent, non-gassing, and non-migrating.
In addition they can be converted into thm films that can be laminated onto
fabrics for ESD safe and comfortable cleanroom type apparel applications,

FIGURE 9. Stat-Rite’s resistmty.

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 59

FIGURE 10. Stat-Pite physical and ESD performance properties.

while maintaining TPU type properties. Typical properties and ESD per-
formance data are found in Figure 10.
Stat-R.ite’s unique combination of performance properties also provides
the textile industry with an alternative to the traditional coatings, chemical
antistats, and filled systems that are currently being used. These products don’t
provide all of the features that Stat-Rite provides. Figure 11 illustrates this
competitive comparison.
Stat-Rite Thermoplastic Polyurethane Alloys provide cost effective ESD
protection to the textile industry that can easily be converted into a mono-
lithic membrane, laminated onto a fabric construction, and provide comfort
and protection for reusable and throwaway apparel applications where this
type of protection is needed. ’-

FLAME RETARDANT (FR) THERMOPLASTIC

POLYURETHANE TECHNOLOGY

Flame retardant thermoplastic polyurethane has been used extensively in

the wire and cable industry for years with excellent results. Its use extends into

FIGURE 11. Stat-Rite competitive comparison.

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60

FIGURE 12. Flame retardant thermoplastic polyurethane summary.

every imaginable environment from the frigid cold of the South Pole to the
extreme heat of the equator.
Although it has not, so far, been used as extensively in the textile industry,
thermoplastic polyurethane does present properties that make it a material re-
source for membrane laminants onto fabrics to achieve flame retardant speci-

fications. BFGoodrich Estane thermoplastic polyurethane features an

extensive portfolio of flame retardant TPUs. This portfolio includes opaque
and clear non-halogen as well as halogen FR materials. The flame retardant
additives that are used in these materials reduce both the ease of ignitability
and the rate of burn of the polymer system. Figure 12 gives a summary of the
thermoplastic polyurethane flame retardant materials.
These products provide flame retardancy while maintaining the tough du-
rable properties that TPU is known for. They also provide good bondability
to fabric substrates as well as excellent flex properties. They are an option for
textile applications requiring flame retardancy.

MARKETS AND APPLICATIONS FOR THERMOPLASTIC

POLYURETHANES IN THE TEXTILE INDUSTRY

The thermoplastic polyurethane technologies discussed above provide for

numerous application opportunities in the textile industry. Figure 13 lists
some of these application areas.

SUMMARY

Thermoplastic polyurethanes are some of the most versatile polymers in

the plastics/rubber world. They offer the traditional excellent properties for
which TPU has become known and also offer features that are of specific in-
terest to the textile industry. These materials can be converted into mono-
lithic membranes and laminated onto fabrics to achieve certain objectives

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 61

FIGURE 13. Possible textile applications for thermoplastic polyurethane technologies.

such as breathability, rubber-like behavior, flame retardancy, and static dissipa-

tion as well as other objectives. The end result is protection, comfort, and
pleasing aesthetics.
REFERENCES

1. American Society of Testing and Material. 1995. Standard Test Methods for Deter-
mining Water Vapor Transmission of Materials, Designation E96-95
, Philadelphia, PA.
2. Gasparrim, F.J. 1995. "Formulation Requirements for Urethane Fabric Coatings,"
Urethanes in Coated Fabrics, Vol 3
, Technomic Publishing Company, Inc., Lancaster,
PA, pp. 51-64.
3. Krishnan, K. 1993. "Hydrophilic Urethanes for Textiles,"
Journal of Coated Fabrics,
23(1):54-66.
4. Pinchard, G. and G. Fous. 1996. "Breathable Film: Now There is a Choice," Insight
96 Absorbent Products Conference, 1996, Section XII-2.
5. Pinchard, G. and G. Fous. 1996. Ibid., Section XII-4.
6. Madden, T. E. and T. E. Fahey. 1993. "Cleanroom Safe Electrostatic Dissipa-
tive(ESD) Plastics," The Cleanrooms Show, Boston, MA, March, 1993.

BIBLIOGRAPHY

Davis, D. G. and J. B. Conke. 1991. "New Hydrophilic Polyether-Ester-Amide Block

Copolymers."
Day, R.C. "Rubber-Like" Thermoplastic Polyurethanes."
"Estane Thermoplastic Polyurethane," Product Brochure by the BFGoodrich Com-
pany, 1996.
Gasparrini, F.J. 1979. "The Design of Solution Polyurethanes for Textile Coating,"
Urethanes in Coated Fabrics Volume 2: Major Papers from The Journal of
Coated Fabrics, pp. 93-111. First printed in 1974.
Gillibrand, J. 1979. "Polyurethane Coated Fabrics," Urethanes in Coated Fabrics
Volume 2: Major Papers from The Journal of Coated Fabrics, 1979, pg. 1-11.
First printed in 1973.

Downloaded from jit.sagepub.com at NANYANG TECH UNIV LIBRARY on April 28, 2015
62

Hayashi, S. andC. Giordano. 1993. "High Moisture Permeability Polyurethane for

Applications," of Coated Fabrics
Textile
Journal , 23(1):74-83.
McCullough, E.A. 1993. "47 Methods for Determining the Barrier Efficacy of Surgi-
cal Gowns," Institute for Environmental Research, Kansas State University,Man-
hattan, Kansas.
McCullough, E.A. and L. K. Schoenberger, L.K., "Liquid Barrier and Thermal Prop-
Surgical Gowns," Study done for Kansas State University Department of
erties of
Clothing and Textiles, Manhattan, Kansas.
"Morton Breathable Thermoplastic Polyurethanes for Monolithic Membrane
Films," Product Brochure by Morton International.
Ward, Robert S. and K. A. White. 1991. "Barrier Films that Breathe," CHEMTECH,
November, pp.670-676.

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