Original Article

Proc IMechE Part L:

J Materials: Design and Applications
Adhesives in the footwear industry 0(0) 1–18
! IMechE 2015
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DOI: 10.1177/1464420715602441

Rosa MM Paiva1, Eduardo AS Marques2, Lucas FM da Silva3, pil.sagepub.com

Carlos AC António3 and Francisca Arán-Ais4

Abstract
Footwear manufacturing is basically a process of transformation and assembly of various components made up of several
materials where different adhesives play a key role, because without them, the shoe would lack shape and structure. This
paper aims to understand the importance of adhesives in the footwear industry. It is necessary to identify the different
processes in a shoemaking where adhesives are involved and the different adhesive joints produced, as well as their
technical requirements. The adhesive joint performance will depend on the different adherends’ nature used as footwear
materials, the joint design, the surface treatments, the adhesive properties which depend on their formulation, and so on.
Adhesive joints in a shoe act under different stress types (peel, shear, tensile, etc.). The most disfavourable are the peel
stress. For that reason, the peel strength test is one of the most common to evaluate adhesive joints’ performance.
When heat resistance is an important adhesive requirements, a creep test is carried out. Furthermore, aging tests are
undertaken in order to evaluate durability. This methodology is described in this paper.
In the literature, one can find several papers on adhesives, specifically on their mechanical properties. However, there is
little research related to footwear applications, including not only the mechanical properties that this industry demands,
but also the composition of the adhesives. Therefore, this paper aims to connect the important mechanical properties
for the footwear industry with the constituents of the adhesives. However, other properties are also important, such as
viscosity, wettability, compatibility, etc., depending on the materials and the adhesive joint type.

Keywords
Footwear, adhesives, raw materials, surface treatments, single lap joint, mechanical properties, contact adhesives

Date received: 29 May 2015; accepted: 30 July 2015

industry will be analysed and the properties and per-

Introduction
formance of different types of adhesives explained.
Nowadays, the footwear industry has a close associ- Each of these types of adhesive can be formulated
ation to the adhesives industry, using bonding tech- with several substances that will provide different per-
niques to join the variety of materials employed in the formance to the final adhesive, influencing the mater-
manufacture of shoes.1,2 To better understand the ials able to be joined, the application method, the
importance of adhesives in the footwear industry in surface treatment, the adhesion strength, the cohesive
respect to the manufacture process of the shoe, it is strength, the creep strength as well as the wetting,
very important to consider the operations that make drying time and adhesive hazard classification.3 This
up the process and the selection of the materials.1,2 work will only focus on the substances in the compos-
In the shoe manufacturing industry, there are several ition of the solvent-based adhesives that influence the
operations that use manual processing steps.1,2
The manufacturing of shoes is divided in eight main 1
CIPADE – Indústria e Investigação de Produtos Adesivos, S.A.,
operating processes: storaging, modeling, cutting, Avenida 1 de Maio, São João da Madeira, Portugal
2
sewing, lasting, assembling, finishing, and packaging.1 INEGI (Instituto de Ciência e Inovação em Engenharia Mecânica e
Engenharia Industrial), Rua Dr. Roberto Frias, Portugal
A wide range of materials is used in shoe manufac- 3
Departamento de Engenharia Mecânica, Faculdade de Engenharia,
turing, including natural and synthetic leather, plas- Universidade do Porto, Rua Dr. Roberto Frias, Portugal
tics materials, rubber and synthetic fibres, and 4
INESCOP, Spanish Footwear Technology Institute, Polı́gono Industrial
adhesives.2 The adhesives used in this industry are Campo Alto. C/Alemania, Elda (Alicante), Spain
varied and their producers are always developing
new products, following closely the market demands Corresponding author:
Rosa MM Paiva, CIPADE – Indústria e Investigação de Produtos
mainly due to the introduction of new materials Adesivos, S.A., Avenida 1 de Maio, 518, 3701-909 São João da Madeira,
according to fashion trends.1 During the course of Portugal.
this work, the importance of adhesives in the shoe Email: [email protected]

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2 Proc IMechE Part L: J Materials: Design and Applications 0(0)

type of materials to be joined, the peel strength and According to this construction, the shoe is formed
creep strength. Such adhesives can have in its consti- by two main parts: the upper and the sole, as identi-
tution elastomers, resins, additives and solvents.4 fied in Figure 1.10,11 The upper is formed by the vamp
For the manufacture of an adhesive joint, one must (that covers the front of the foot, covering the toecap),
take into account the materials which are intended to the counter (that covers the back of the foot), and
be joined, using this to identify the most appropriate joined by the quarter (covering the foot side).10–12
type of adhesive and surface treatments, enabling the The lining is a inner upper constituent. The sole
maximization of the join resistance and durability (known as outsole when is made of one piece) is the
through the adhesive joint design, as well technical underside of the shoe, comprising the insole, midsole,
requirements for such joint.2,5 There are four types bottom filler and the heel, as shown in Figure 1. These
of treatment usually employed in the footwear indus- components are usually produced outside of the foot-
try: physical, chemical, primer and solvent.5 wear manufacturer, in proper equipment for this
The footwear industry currently uses a large diver- purpose.12
sity of materials and over time this has increased the
challenges placed on the adhesives industry, since
bonding dissimilar materials with good performance
Footwear classification and composition
requires specially formulated adhesives. This perform- In the footwear industry, independently of the type of
ance is usually evaluated with two significant mech- materials used, to ensure its durability it is necessary
anical properties, which are the peel strength and the for adhesive joints to fulfil certain specifications.
creep strength.4 Standard EN 153076 establishes the minimum
strength values recommended for footwear bonding.
The peel strength values required for joining upper/
Footwear design and manufacturing sole are shown in Table 1.
Footwear components
In the past several years, the high quality footwear
market has proved to be a sector with a high potential
Table 1. Reference values of adhesion upper/soles, according
that has been growing.7 to standard EN 15307.
The prime goal of footwear was to protect the feet,
but wear comfort is also one of the biggest current Peel Strength per unit
concerns taken into account during shoe design and Shoes width (upper/sole)
the material selection. The aesthetic component is also Infants footwear, indoor 52.5 N/mm
extremely important,8,9 and all of these concerns lead footwear, fashion footwear
to a very careful selection of the materials employed Men town footwear, 53.0 N/mm, or 52.5 N/mm
for shoe manufacturing. Obviously, price is also a women town footwear, with material failure
main factor that must be balanced with all these cold weather footwear,
concerns. casual footwear
An item of footwear, commonly referred to as a Children footwear, 54.0 N/mm, or 53.0 N/mm
shoe, follows a particular construction, as identified general sports footwear with material failure
in Figure 1. Mountain footwear 55.0 N/mm, or 53.5 N/mm
Even taking into account this universal con- with material failure
struction, it is possible to create varied designs.

Figure 1. A typical construction of the shoe.

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Paiva et al. 3

Footwear materials Table 2. General properties of different footwear materials.

The quality and properties of the final product do not
Materials Properties
depend only on the correct execution of the shoemak-
ing steps but also on the materials used during the Natural CREPE Very good wear resistance
construction. Therefore, the material selection is cru- (natural Very soft
cial and one should take into account the technical rubber) Temperature sensitive
performance, comfort environmental impact and Easier to cut and trim when cold
economic aspect in the selection of materials. The Very good crack resistance
material properties that influence the functional per- Limited in colour
formance of the product that is being built should be Leather Fibrous and porous material
the focus the material selection process. The applic- Flexible material (has a low Young
ability of a material is then determined by the ideal modulus)
combination of properties, a combination capable to Easily damage by heat-shrinking
Good aesthetic appeal
provide the best performance according to the desired
Synthetic Leather
performance standards. The selection of materials can
PUR Easily moulded material
be made taking into account several factors: the price,
weight, size, ease of processing, durability, availability Good cold resistance
Limited shelf life
in the market, by mechanical, thermal, magnetic,
Good durability
physical, optical and electrical properties, or even by High resistance to wear, light
the environmental impact.3,4 Therefore, in the foot- weight, abrasion-resistance
wear industry, a wide variety of materials are used. Good thermal insulation
The upper can be produced in polyvinyl chloride Good flexibility at low temperatures
(PVC), natural or synthetic leather,4,13 etc. Excellent resistance to oils
Performance requirements for uppers as footwear TPU Good cold resistance
component, irrespective of the material, in order to Elasticity
assess the suitability for different end uses (sports, Low heat resistance
casual, men’s town, cold weather, women’s town, Has elasticity and durability
fashion, infants’ and indoor shoes) are established in Resistant to abrasion and impact
the Technical Report ISO/TR 20879:2007.14 This Tear resistant and high
report also establishes the test methods to be used temperatures
TR Moldable plastic soling
to evaluate the compliance with requirements, includ-
ing bondability, as described in Table 1. Excellent dry friction
Moldability into treated patter
The outsoles can be made by leather, natural (crepe
Offers potential for high wet friction
rubber) or synthetic polymers. The synthetic polymer Moderate abrasion resistance
materials used for the manufacture of this component Good performance in cold
are based on polyurethane (PUR), thermoplastic conditions
polyurethane (TPU), thermoplastic rubber (TR), styr- Very soft grades may give excessive
ene butadiene rubber (SBR), vinyl acetate (EVA), friction
polyamide (PA), polyvinyl chloride (PVC), polystyr- Cheaper
ene (PS) or Acrylonitrile Butadiene Styrene Rubbery aesthetic
(ABS).4,15–19 However, PS and ABS materials are Synthetic SBR Good temperature resistance
mainly used for heels. The selection of these materials Good cut resistance
will depend on their mechanical properties, price and EVA Porous and flexible material
design suitability, thereby determining the strength, Excellent crack resistance
quality and comfort desired for the final product, as PA Good impact, tensile, strong and
shown in Table 2.15–19 Performance requirements for flexural strengths from 0 to
outsoles as footwear component, irrespective of the 150 C
material, in order to assess the suitability for different Excellent flow friction properties
end uses are established in the Technical Report Good electrical resistivity
Very hard
ISO/TR 20880:2007.20 It also establishes the test
PVC Has a wide range of rigidity or
methods to be used to evaluate the compliance with flexibility
the requirements, including bondability.
Economical material
Easily injection moulded either dir-
Footwear manufacturing process ectly against a leather upper or
Molded as all-PVC wellington
For the manufacturing of shoes, it is necessary to take boots
into account the operating processes, divided in eight Durable material
distinct steps. The steps are storaging, modeling, cut- (continued)
ting, sewing, lasting, assembling, finishing, and

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4 Proc IMechE Part L: J Materials: Design and Applications 0(0)

Table 2. Continued. bonded to the sole3,9 in the upper-to-sole bonding

Materials Properties process – assembling step. Upper-to-sole is the adhe-
sive joint with higher technical requirements in the
Strength improves as it is made footwear construction.
softer In the assembling, soles may be attached to the
PS Rigid material
upper in a variety of ways, by welted, directed
Ease to process moulded, pre-formed as units, cemented or stitched
ABS Very good balance of physical
to it. When cemented, it is necessary to take into
properties
account the selection of the appropriate adhesive.2–4
In the finishing step, there is a rework process,
necessary to improve the aesthetic of the shoe. Here,
the shoe may be subjected to brushing, greasing, pol-
packaging, as shown in the diagram describing shoe ishing, waxing, and even to the application of paint
manufacture in Figure 2.9,21–23 (coloring).12–21 Accessories like cords and labels are
Many operations involving adhesives are made applied, excess adhesive is wiped and cleaned and the
generally out of the factory (i.e. heel, sole and insole finishing insoles are bonded into place.21 The process
preparation) and they should also be included. ends with the inspection, where the shoes are sub-
In storaging, the necessary raw materials for the jected to observation and comparison of the two
manufacture of footwear are identified and con- shoes of the same pair in order to verify if they meet
trolled.21 In modeling, the shoe is created and the the specification required by both the modeler and the
parts needed to build the shoe are defined. The cre- client.
ation of the model is determined by the fashion ten- The packaging step is where the shoe is placed in
dencies and the technical capabilities, setting up the boxes and labeled with an indication of the model and
shoe and attributes in its data sheet,21 defining the the number. Here, the final quality control is also
materials, the colors, the details, the control param- made, where the shoe is last checked for defects.
eters,21–22 the molds and scale the same for all sizes From this moment, the shoe is ready for expedition
that are intended to be produced.21 In the cutting step, and to be delivered to the final market.9,21
the materials are sorted and prepared, and then the As shown by the descriptions presented above,
pieces created by modeling in industrial quantities are during the manufacturing process of footwear, vari-
obtained.1,21,24 The cutting process can be manual or ous materials, including adhesives, are involved in the
automated systems are used to obtain all the parts of sewing, lasting, assembling, finishing, and packing
the shoes.21,24 When the cutting is manual, a work steps.21
table and a ‘‘cutter knife’’ are used. The knife consists
in a steel blade with a brass coating. To obtain the
pieces, the hand-held cutter knives or, alternatively, Adhesives used in footwear industry
cutting molds can be used.1,9 When the process is
Introduction
automated, a swing arm cutting press is used. An
example is shown in Figure 3. Currently, the cutting As for the other materials used in shoe manufactur-
is made by using machines with a laser or waterjet ing, the selection of the adhesive to manufacture the
cutting system integrated with the CAD/CAM soft- adhesive joint is very important to ensure a good
ware, as shown in Figure 4. quality and durable final product.1,3 The correct
The cutting step is followed by the sewing proced- choice of adhesive is fundamental to ensure the bond-
ure. In sewing, the pieces are skived (which consists in ing strength required by both the shoe manufacturers
reducing the leather thickness at the edge of the part, themselves and the applicable standards, such as EN
to allow for their overlap), folded (a step consisting of 1392:1998 and EN ISO 17708:2003.2,23 In the foot-
folding and fixing the edge of the workpiece with a wear industry, the most important method for joining
latex or cement (natural rubber-based glue),4,12,25 materials is the use of adhesives. The purpose of these
underlined, crossed out, glued and sewn together, all adhesives is both to fill gaps and act as a connecting
in accordance with the instructions set by the modeler bridge between the materials intended to be
for the model to be built. The placement of accessories bonded.26,27 There is not, however, a perfect adhesive
such as eyelets may also be required. In this phase, the that can be used in all situations. The selection of the
upper is manufactured,9 being stitched using stitching adhesives and the joint geometry is relatively complex
machines, as shown in Figure 5.24 and depends on various factors such as the intended
The next step is the lasting, where the insole is final joint strength and intended shoe use, the nature
prepared and adjusted to the upper using the last. of the substrates, thermal resistance, and the time
For the manufacturing of shoes, it is essential to use available to complete the bonding step, price, etc.
a last, made of wood or plastic, adjusted to the shoe The use of adhesives in the footwear industry is a
model and to the size. The last gives the shoe its constantly evolving process, always guided by
shape.12–21 After this step, the insole and upper are advances in chemical knowledge and methods.

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Paiva et al. 5

Figure 2. Diagram of a typical shoe manufacturing process.

Nitrocellulose adhesives were among the first to be The introduction of plastic materials to the footwear
introduced, as far back as 1906. The adhesives were industry containing high amounts of plasticisers made
mostly replaced in 1949 by polychloroprene (PCP) necessary the search of alternative adhesive, with
adhesives due to their versatility, as they present these anti-adherend plastic substances. For that
good results in bonding leather, textiles and reason, in 1970 adhesives based on thermoplastic
other materials, such as vulcanized rubbers. polyurethane were introduced, which are the most

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6 Proc IMechE Part L: J Materials: Design and Applications 0(0)

Figure 3. Swing arm cutting presses. Figure 5. Stitching machine.

requirements, and environmental concerns, such as

legal constraints imposed by Regulation (EC) n.
1907/2006 of 18 December 2006, also known as
REACH (Registration, Evaluation, Authorization
and Restriction of Chemicals). Lately, there is a
strong requirement for the replacement of solvent-
borne adhesives in order to improve workers’ health
and avoid environmental concerns. Furthermore, for
shoes with European Ecolabel, the use of organic
solvents is limited. However, solvent-based systems
still continue to be used because of their perform-
ance.27 Currently, there is a drive for the development
of water-based adhesives, strong enough to satisfy the
needs of the market. However, they do require adjust-
ments in the shoemaking process of the manufac-
turers, mainly due to the drying time and slight
Figure 4. Machine with laser cutting system. different application. For this reason and also because
of the low price of the solvent borne adhesives, the
footwear industry still mainly uses solvent-based
adhesives.4
common adhesive used currently for upper-to-sole In different steps of the footwear manufacture have
joints due to their high versatility. PCP and PU adhe- distinct requirements in the adhesives. For example,
sives are mainly used for high demanding strength during the lasting step, it is necessary to use a PCP or
resistance joints such as upper-to-sole. Furthermore, a hotmelt adhesive such as polyester and polyamide
other adhesives based on synthetic and natural poly- type.25 The hotmelt used on footwear manufacturing
mers such as styrene–isoprene–styrene (SIS), styrene– is a thermoplastic polymer that is applied on the sub-
butadiene–styrene (SBS), styrene–butadiene rubber strate at a temperature above the softening point,
(SBR) latex, hotmelt (polyamide, EVA based), etc., reaching high cohesive strength upon cooling.25 For
are used in the different footwear operations previ- bonding the lining to upper material, adhesives based
ously described.2,4,28 on NR (natural rubber), SIS, PCP solvent-based, or
The market constantly poses new challenges for the latex could all be used,29–33 generally with low bond-
adhesive manufacturers, guided by fashion trends, ing strength and tack. The choice can depend on fac-
innovative designs, increasing performance tors such as the kind of application (brush or spray)

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Paiva et al. 7

Table 3. Different kinds of adhesives used on sewing. percentage of rubber in the solution. It is character-
ized by easy handling due to its viscosity, it has a high
Spray Brush
solid content, it does not contain solvents,28,35 and is
Solvent-based With Without With Without thermo-oxidative stable.4
adhesives stitching stitching stitching stitching These adhesives are usually applied for bonding
porous substrates such as leather, paper, and tex-
NR 
tiles.28,29,35 Latex adhesives are used as water-based
PCP  contact adhesives, presenting an instant bond with
SIS  sufficient green strength.29,30
Latex  Polyurethane adhesives (PU): PU waterborne solu-
tions are applied as adhesives and coatings in textiles,
metals, plastics, and woods. These adhesives are
and if the bond is followed or not by the stitching, as widely used for upper-sole joints, presenting flexibil-
shown in Table 3. ity, good behavior at low temperature, and high
The following section describes in more detail the strength. Waterborne PU adhesives are a good alter-
most commonly used adhesives in the footwear native to PU solvent-based adhesives; however, they
industry. require additional heat in the process to remove water
before joining is completed.34
Types of adhesives
Solvent-based adhesives. Solvent-based adhesives are
Hotmelt. Hotmelts are thermoplastic adhesives, composed of a polymer dissolved in an organic
having 100% solid content and solid at room tem- solvent or mixture of solvents. They are currently
perature, but become fluid at higher temperatures. the most commonly used adhesives in the footwear
The main components of hotmelts are polymer, industry and hence are the ones subject to more atten-
wax, resin, etc. The application of heat melts the adhe- tion in this work.
sive, allowing the connection of the surfaces to be Polyurethane adhesives: Solvent-based PU adhe-
joined and producing a high degree of wetting sives are characterized by their flexibility and per-
between the adhesive and the adherend. After appli- formance at low temperatures, the excellent
cation, the temperature is reduced and the adhesive adhesion and cohesion strength, and also for rapid
solidifies, developing maximum strength. The use of curing. These adhesives have good wettability in a
hotmelt allows the quick production of an adhesive wide variety of materials. They form covalent bonds
joint, reducing time in the assembling step. In foot- with substrates that have active hydrogen atoms on
wear usage, these adhesives are characterized by their the surface.35,40,41 The mechanism is outlined in
flexibility and resistance to moisture and body oils Figure 6.35
without difficulty, which permit the easy fabrication In both systems of PU and PCP adhesives, we can
of complex shapes,25,32 depending on the adhesive find monocomponent and bicomponent adhesives
composition. types.
Monocomponent adhesives (1K), as the name sug-
Waterborne adhesives. Waterborne adhesives are dis- gests, are composed of only one component (adhesive
persions or emulsions composed of polymers in only), and depend only on themselves to form the
water. The main advantage of using this type of adhe- adhesive joint.42 The process of physically fixing
sives is the elimination of toxicity or flammability occurs after the adhesive joint is subjected to
problems. These types of adhesives are non-toxic pressure.4,42,36
and non-inflammable. Furthermore, one can obtain Bicomponent adhesives (2K) are composed of two
adequate bond strengths achieving good performance components, usually called A and B.42 Component A
adhesives. In some cases, the drying of these adhesives is an adhesive and component B is the crosslinking
may be slower, requiring the need of forced drying compound, commonly isocyanate-based. These adhe-
systems.34 sives are used when it is desired to accelerate the
These adhesives have higher price due to a curing of the adhesive and increase the temperature
higher solid content than the solvent-based ones. resistance of the adhesive joint as well as durability.
Therefore, the amount of adhesive applied should be Therefore, 2K adhesives are supplied separately,
lower. As a result, suitable and similar drying times because when they are mixed, the lifetime of the
are obtained, which results in optimum yield and combination is much reduced. It is necessary to be
efficiency.34 efficient when mixing the two components to ensure
Latex adhesives: The rubbers most commonly used a complete reaction. Only with a complete mixture of
for latex adhesives used for shoes manufacturing are the two components, the full mechanical properties of
natural rubber (cis-polyisoprene) and PCP types.4 the adhesive can be assured.3,4,40,36,37
Latex is an aqueous dispersion presenting approxi- In the particular case of the PU adhesive film, once
mately 60% solids, which corresponds to the it is applied and dried, it does not present any kind of

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8 Proc IMechE Part L: J Materials: Design and Applications 0(0)

Figure 6. Mechanism of typical covalent bond between the PU adhesive and a polar substrate.

(a) (b)
Adhesive film Developing of bond strength
Polymer Viscosity (MPa)
Polymer Viscosity (MPa)

Temperature (°C) seconds minutes days

(1) Cooling;
(2) Crystallization
(3) Crosslinking

Figure 7. Curing procedure of an adhesive with two compound (2K) PU-based solvent: (a) tack development in adhesive film, during
heat activation; (b) development along time of the bond strength in a single lap joint.

tackiness. Only when subjected to temperature, the using PU adhesive. The main difference between
film of adhesive softens and acquires the necessary these two products is the open time, which is longer
tack for attaching the substrates,4,36 as shown in in the case of PCP. In addition, the dry adhesive film
Figure 7(a). PU is a contact adhesive. Heat activation of PCP has tackiness at room temperature, allowing
is necessary in order to acquire tack to allow the in the fixation of the material without resorting to tem-
time joint of both adhesive layers. perature. The length of this phase with tackiness can
Figure 7(b) shows that the evolution of the curing range from a few minutes to hours, depending on the
time for a two-compound, PU solvent-based adhesive. type of resin used in the formulation.38,39,43,44
After the adhesive is applied, dried, reactivated with The solvent-based PCP adhesive, known as contact
temperature (where the adhesive softens), and bonded adhesive, refers to an adhesive that is applied to both
by pressing the materials, the adhesive joint cools and substrates to be bonded and allowed to dry before
the adhesive film dry in seconds. After a few minutes, pressing the two substrates together to complete the
the crystallization of the PU occurs and the curing bond. This type of adhesive requires high initial bond
process is almost complete. The action of isocyanate strength and the ability to form bonds with minimum
(second compound, 2K) occurs after a few days, cor- pressure after long open assembly periods.19,38
responding to the complete cure of the adhesive. At Styrene-isoprene-styrene adhesives: Solvent-based
this time, the curing process is irreversible, which styrene-isoprene-styrene (SIS) adhesive has with high
means that the adhesive is permanently crosslinked. solid content.4 These adhesives exhibit a good com-
After crosslinking, the adhesive joint is heat resistant, bination of high elasticity, low hardness, good balance
so if the adhesive film is subjected to high tempera- of tack and low viscosity. They adhere to a variety of
tures, degradation may occur.4,42 substrates, plastics, foam, and have high mechanical
Polychloroprene adhesives: The bonding strengths performance.
obtained using solvent-based polychloroprene adhe- This type of adhesives is not used in footwear
sives (PCP) adhesive are similar to those obtained industry, in upper-to-sole joints, because of they

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Paiva et al. 9

lack the abrasion resistance under rapid loading that

is required for high performance shoes.32

Natural rubber adhesives. Commonly named as cement

in the footwear industry, natural rubber (NR) do not
have a polar group attached to the polymer and for
that reason they do not bond to polar surfaces. These
rubbers have poor thermo-oxidative stability. These
adhesives are used in applications where the require-
ment is for temporary bonding,4 for example, before
sewing.
Solution adhesives consist of solid rubber dissolved
in aromatic hydrocarbon solvents, depending on the
drying time required.4,28 The adhesive is dried at
room temperature or in hot air ovens.28 Their main
property is a quite long open time (sometimes more
than 24 h).

Composition of solvent-based adhesives

Adhesives for the footwear industry are comprised of
a variety of chemical compounds, tailored to allow the
union of specific types of substrates. The components
of these adhesives must be carefully selected to Figure 8. Machine to bond insole to the upper.
improve the overall performance when bonding cer-
tain types of materials.27,37 The main components of
adhesives are elastomers, resins, additives, and solv- Table 4. Differences between high and low
ents.39 The following sections describe each one of degree of crystallization of polyurethanes.28,40
these components and their importance on the adhe-
sives properties. Degree of
crystallization Properties
Elastomers. Generally, elastomers improve the elasti- High High temperature resistance
city and the viscosity on the adhesive and serve also High the peel strength
as a carrier for the resins and additives.41,36,38 Various Low open time
types of elastomers can be used such as PUR, PCP, High cohesion
SIS, and NR.4,38 High wettability
The PUR used in solvent-based adhesives is of Low Low temperature resistance
thermoplastic nature and it has linear chains and is Low peel strength
composed primarily of crystalline segments. It has a High the open time
low glass transition temperature (Tg) and despite the
high degree of crystallization present, it gives good
flexural properties at low temperatures.4,26,45,46
The different types of PU existing in the market for thermoplasticity, which changes according to the
application on adhesives differ in the degree of crys- type of monomers used and its ratio. The degree of
tallization (due to a relationship between the hard and crystallization measures the rate at which the PU,
soft structures) and molecular weight (which deter- when cold, passes from the melt state to the crystalline
mines the viscosity). Higher molecular weight means state, as shown Figure 7(a). Therefore, the crystallin-
higher functionality of the polymer, which reflects ity will affect the rate of development of the connec-
into better cohesive properties.36 Very high molecular tion as well as the initial bond strength and tack
weight PU has quite high viscosity, low wettability time,42,36, as shown in Figure 7(b).
into porous materials such as leather and so high tem- Table 4 shows the main differences between high
perature activation. and low crystallization in PU.36,47
The balance between the crystalline and amorph- A typical composition of a PU solvent-based adhe-
ous segments of the PU allows softening at low tem- sive for upper-sole attachment is given in Table 5.
peratures, favoring the joining process. Increased PCP is a versatile material because the elastomer
thermoplasticity and tackiness of the adhesive are has a combination of properties that make it suitable
useful to ensure good bonding of materials. for many applications.42 The most important charac-
Therefore, different types of PU are mainly character- teristics of PCP are high mechanical strength, good
ized by their degree of crystallization and chemical resistance, good acid resistance, and very

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10 Proc IMechE Part L: J Materials: Design and Applications 0(0)

Table 5. Typical composition for PU solvent-based Table 7. Typical composition for SIS solvent
adhesive, phr (parts per hundred parts of rubber). based adhesive, phr (parts per hundred parts of
rubber).
Raw materials Quantity (phr)
Raw materials Quantity (phr)
PU 100
Resin 0–5 SIS 100
Fumaric acid 0–3 Resin 100
Silica/nitrocellulose 0–10 Antioxidant 2
Solvent mixture 500 Solvent mixture 300

Table 6. Typical composition for PCP solvent Table 8. Typical composition for NR solvent
based adhesive, phr (parts per hundred parts based adhesive, phr (parts per hundred parts
of rubber). of rubber).

Raw materials Quantity (phr) Raw materials Quantity (phr)

PCP 100 NR 100

Resin 30 Resin 100
MgO 4 Antioxidant 2
ZnO 5 Solvent mixture 700
Water 1
Antioxidant 2
Solvent mixture 500 adhesion.26 The gel content breaks down with the
mastication of the rubber, which causes the break-
down of the polymer chains and lowers their molecu-
good adhesion to metals and textiles.4 The adhesives lar mass, representing a decrease of the
made with PCP are easily crystallizable.39 The main viscosity, easing the manufacturing and the applica-
properties of these adhesive are adhesion to a wide tion process.43 The crystallization of the NR causes
variety of substrates, good initial bond strength, self-reinforcement, resulting in high tensile and tear
good cohesion, and good resistance to aging and strengths.43 A typical composition of a NR solvent-
chemical degradation agents.39,48 based adhesive is given in Table 8.
PCP adheres to a variety of substrates due to the
presence of a chlorine atom in each monomer of the Resins. Resins are used in adhesives when there is a
polymer, which gives it a very strong polarity and need to influence the tackiness, the cohesion strength,
enables the development of physical interactions.4 open time and temperature resistance.49 The resins
This characteristic is the reason behind PCP’s imme- allow increasing tackiness and the wettability, facili-
diate capacity to bond to itself when subjected to a tating the bonding formation and, therefore, improv-
small pressure. This happens regardless of its level of ing the strength by increasing the cohesive strength of
crystallization.47 A typical composition of a PCP sol- the adhesive.4,40,49 The improvement in properties
vent-based adhesive for upper-sole attachment is that they generate enables the adhesives to form a
given in Table 6. reasonable bond strength immediately on contact
SIS is a thermoplastic elastomer, belonging to a with another substrate, with or without the applica-
class of materials that combine elasticity of the elasto- tion of pressure.49 The most commonly used type of
mer and thermal reversibility. This elastomer can be resins in solvent-based adhesives are colophony,
used in applications where there is the need for flexi- hydrocarbon, alkyl phenolic, terpene phenolic, and
bility and elasticity at moderate temperature and coumarone-indene.
deformation conditions.41 The SIS type polymers Colophony, also known as rosin resin, increases
allow the production of adhesives with strong and tackiness but decreases the cohesion strength.39,50
lasting tack properties.43 Its means long open time. These resins are, however, very sensitive to oxidation.
A typical composition of a SIS solvent-based adhesive Hydrocarbon resins are thermoplastic, which
is given in Table 7. improves the initial bond strength.36,50,52 The
NR is quite sticky and it does not need any resin. improvements brought by the resin to the adhesive
Adhesives using NR have higher strengths and lower are varied depending on the resin type used. There
elongations than those using SIS rubber.35 NR is are resins that increase the open time of the adhesive,
prone to oxidative degradation due to their main increase resistance to fatigue, act as process aids,
chain double bond. It is necessary to add resins to increase the flexibility and improve the incorporation
the NR adhesives’ formulation to achieve high peel of fillers. Alkyl phenolics enhance adhesion and

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Paiva et al. 11

Table 9. General properties of resins.

Temperature
Resin Types Acidity Index Strength Tackiness Open time resistance Elasticity Life time

Colophony 155–175 # " " # # Long

Hydrocarbon <0.1 # # " " # Long
Alkyl phenolics – " # # " # Short
Terpene phenolics 60–70 # " " # médium Short
Coumarone-indene <0.5 " " – # " Short
Vinyl chloride/vinyl acetate – " # # " " Long

give an increase in the cohesive strength.38 Terpene adhesion promoters to soles of SBR. The most com-
phenolics’ tackiness increases with the increase of tem- monly used acids are fumaric acid and malonic acid.35
perature. Furthermore, terpene phenolics resin pro- Chlorinated rubber increases adhesion to rubber
motes the reduction of the crystallization degree of materials and increases resistance to temperature.35
the adhesive.42 Coumarone-indene resin’s tackiness Zinc oxide (ZnO) is an activator in NR and SBR,
increases with the increase of the temperature as the and acts as a curing agent for vulcanization of the
terpene phenolic resins, promotes the reduction of the PCP.38,39 It usually represents a very small proportion
crystallization degree of the adhesive, and increases on adhesive, around 5% of the weight of the rubber.35
the cohesive strength and elasticity of the adhesive.38 The magnesium oxide (MgO) is used in the com-
Vinyl chloride/vinyl acetate promotes adhesion of position of adhesives containing chlorine atoms and
PVC and metal to leather, paper, wood or plastics. acts as a chlorine acceptor in order to prevent the
It also gives flexibility or hardness, depending on formation of hydrochloric acid. This prevents oxida-
vinyl acetate content, and chemical resistance. Vinyl tion and aging of the adhesive, and thus prevents
chloride is responsible for increases in adhesive degradation of the adhesive properties.35,39
strength and resistance to water and chemicals. Antioxidants are used to prevent or retard the
Vinyl acetate increases the solubility and is respon- aging of the adhesives. Such aging manifests itself in
sible for increases in the flexibility. The resins are sol- variations of the hardness, color changes or degrad-
uble in the common solvent used in the adhesives and ation of the physical properties. In extreme cases, it
are compatible with almost any other polymers and can cause the appearance of cracks immediately after
resins, depending on the concentration. application of the adhesive on the substrate.35,38,39
In Table 9, a summary of the general properties of Aging occurs because of successive oxidation reac-
resins can be seen. It shows the relative influence of tions in the polymer chain. Thus, the oxygen absorbed
each type of resin in the general properties of the over time may be responsible for the degradation of
adhesive.19,35 macromolecules expressed by softening in the pres-
ence of heat or cold hardening and fragility.39 When
Additives. Additives give specific characteristics, such polymer degradation occurs due to attack by the
as preventing oxidation, higher adhesion, increase of oxygen produced by mixing the rubber with the
the viscosity and solids content among others.35,36 resins, there is a decrease in adhesion force. Such
A large variety of additives can be found in the for- attacks can be reduced with the addition of an anti-
mulation of adhesives for the footwear industry. oxidant.39 Thus, when an adhesive shows a loss of
Fumed silica, nitrocellulose, acids, chlorinated tack, attack by oxygen or environmental moisture
rubber, zinc oxide, magnesium oxide, and antioxi- can be suspected as causes. The compounds used in
dants are some of the most common.35,39 order to act as antioxidants are secondary amines,
Fumed silica is added to promote bonding to diamines and their derivatives, quinoline compounds,
porous substrates (for example leather, textile) dithiocarbamates, alkyl-phenols, esters of phosphoric
because it avoids the excessive penetration of the acid, phenolic.39 Thus, we can say that antioxidants
adhesive in the substrate. It is also used to adjust will inhibit or make a negative catalysis of auto-
the viscosity and rheology (thixotropic, pseudoplas- oxidation.38
tic).35,39 It also influences the mechanical properties,
and particularly it increases the resistance to initial Solvents. The liquid portion of the adhesives is com-
peel and increases the cohesion strength due to the posed of organic solvents. Their main role is to act as
presence of hydrogen bridge bonds that are formed carrier allowing adhesive application. The solvents are
between the silane and urethane groups, favored mainly responsible for the level of toxicity of the adhe-
by the presence of silica. Nitrocellulose can increase sive for the control of the drying time and for provid-
the viscosity of the adhesives. Acids act as ing better or worse wettability of the substrate. They

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12 Proc IMechE Part L: J Materials: Design and Applications 0(0)

also define the level of viscosity, influencing the fluid- machine for the application of the adhesive (hotmelt
ity, which can be an important parameter to be con- in this step) is used, as shown in Figure 8. Different
sidered (depending on application method).1,53,54 types of hotmelt adhesives are used depending on
Various types of solvents suitable to produce sol- forepart lasting, waist lasting or backlasting.
vent-based adhesives are available in the market. Furthermore, PCP with high thermal resistance is
Among these, the most used are aliphatic hydrocar- used for lasting.
bons (cyclohexane, toluene), chlorinated hydrocar-
bons (dichloromethane), ketones (acetone, MEK),
esters (ethyl acetate, methyl acetate) and tetrahydro-
Surface treatments
furan (THF).1,38 Poor bonding of materials in footwear can lead to
However, chlorinated hydrocarbons, due to their complaints, order returns and a loss of reputation.
toxicity and taking into account the legal require- To ensure a correct level of bond strength, surface
ments, have a tendency to disappear in the compos- treatment is often necessary and it can be a vital
ition of adhesives.1,36,38 Also to be taken into account step to guarantee the durability and the quality of
are the legal constraints imposed by Regulation (EC) the bonded assembly. To generate a good bond, the
no. 1907/2006 of 18 December 2006, also known as adhesive must adhere strongly to the surfaces. The
REACH.38 surface treatment must be carefully selected according
to the material. For this reason, it is important to
Manufacture of joints in footwear analyse the type of failure that occurs in the joint
when where is premature failure of a joint. There
industry
are different types of failure bond,56 as shown in
For the manufacture of an adhesive joint, the type of Figure 9.
materials that will be joined and the model of the shoe The surface treatment method has substantial
should take into account. These factors are crucial for effect on final adhesion characteristics.27 For the
the selection of an appropriate adhesive for the manu- application of the surface treatment, it is necessary
facture of a suitable resistant adhesive joint.2,3 to take into account the materials which are intended
Depending on the type of substrates, it can be neces- to be bonded.56–61 Four major types of surface treat-
sary or not to apply a surface treatment before pro- ments are available to use on the substrates: physical,
ceeding to the application of the adhesive, as described chemical, primer, and solvent wipping.61 Physical
in the Upper-to-sole bonding process section. treatment such as roughening using sandpaper or
In the footwear industry, depending on the model abrasives, increase the surface area. Chemical treat-
of the shoe, there are three methods of fixing ment changes the polarity of the surface. Use of
materials: primer allows minimizing the flow of the adhesive
into the porous of the material to prevent the forma-
– Fixing by glue, tion of weak points55,62 or improve the compatibility
– Fixing by stitching, adhesive substrate. The use of solvents eliminates the
– Fixing by glue and stitching.2 release agents on the surface of the materials that
might cause adhesion problems.27,56,57–60,63 Paiva
In the different upper preparation steps, the assem- et al.55 concluded that to maximize peel strength of
bly of the different components can be performed by the single lap joints leather/TR and leather/PUR
using adhesives and/or stitching. In this step, various joints, it is necessary to apply some surface treat-
types of adhesives can be used and then selection ments: on TR – chemical treatment, on leather –
depends on the type of materials and the adhesive mechanical treatment and primer and on PU – mech-
joint requirements.14 Table 10 shows the adhesives anical treatment and primer. Navarro-Bañón et al.64
more commonly used for each operation of the concluded that chemical treatment as surface treat-
sewing step.2,19,27 ment increases the SBS rubber surface energy
In lasting step, depending on the procedures used and introduced surface roughness, improving
for manufacturing footwear, the insole can be bonded the adhesion with PU and PCP adhesive types in
or stitched to the upper. If it is bonded, a specific upper-to-sole joints. Each material requires the

Table 10. Adhesives applied in the sewing step.

Units operations Types of adhesives Bond strength

Lining leather/leather Solvent-based NR adhesive, latex Moderate

Leather/leather Solvent-based PCP adhesive, solvent-based SIS adhesive High
Leather/woven Solvent-based NR adhesive, Latex Moderate
Leather/foam Solvent-based NR adhesive, Latex Moderate
Leather (folding) Hotmelt High

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Paiva et al. 13

Figure 9. Different types of failure.56 (a) Adhesion failure to either adherend, (b) Surface failure of either adherend, (c) deep failure
of either adherend, (d) tearing through either adherend, (e) No-coalescence of adhesive film, (f) cohesive failure, (g) coating tear
(peak force) then separation between coating and adherend.

application of a specific surface treatment, as shown Table 11. Surface treatment vs materials.
in Table 11.19,52,60,62,65–72
Chemical Mechanical Solvent
For example, Leather commonly has a layer of
Materials treatment treatment Primer wipping
grease at the surface, which causes problems in the
manufacture of the adhesive joint, thus the need to Leather  
perform an adequate surface treatment.63 The recom- PU  
mended surface treatment is to subject the leather to TPU  
a mechanical treatment (roughening), using a P24 TR  a
aluminium oxide abrasive cloth, to remove the pres- SBR  
ence of any greasy or fatty materials, like polyethylene EVA  
that creates adhesion problems on the surface.59
PA 
A primer is used to minimize adhesive penetration
PVC 
into the pieces of the leather. Sometimes, a specific
primer can be used to make more compatible the PS
PU adhesive with the greasy leather. After applica- ABS  
tion, it is allowed to dry for 5–20 minutes at room a
When a specific PCP adhesive on TR is used.
temperature.36,63
TR as a low surface energy material requires the
application of a surface treatment to achieve an two types of adhesives are mainly used: solvent-based
acceptable bond. The TR substrate must be subjected PCP adhesive, solvent-based PU adhesive.2,4
to a chemical treatment (halogenation) allowing react- Figure 10 shows the main steps of the upper-to-sole
ing it to dry at least 1 hour at room temperature to bonding process when a PU adhesive is applied.
improve material surface energy.52,56,63,67–72 Consequently, some fundamental shoemaking
parameters must be taken into account and controlled
to ensure the correct joint of the substrates. These
Upper-to-sole bonding process parameters include the activation temperature, work-
As mentioned in previous sections of this work, to ing time, and contact pressure. In addition, a correct
bond the upper to the sole in the footwear industry, adhesive application and a proper amount applied.

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14 Proc IMechE Part L: J Materials: Design and Applications 0(0)

Figure 10. Application of solvent-based PU adhesive on assembly step. (a) Adhesive application, (b) adhesive drying, (c) adhesive
heat activation, (d) attach the upper to sole, and (e) pressing upper-to-sole.

As shown in Figure 10, to bond uppers to soles, an adhesive in the footwear industry.63 There are two
the footwear industry takes the following steps:4,19,55 mechanical properties considered important in the
manufacture of footwear, peel strength, and creep
(a) Application of adhesive on the upper strength. Each property requires a specific test for
(Figure 10a); its evaluation.4
(b) Application of adhesive on the sole; The upper-to-sole requirements are defined on EN
(c) Allow the adhesive to dry, by solvents evapor- 15307,6 as shown in Table 1.
ation, about 5–10 min for solvent-based PU adhe-
sive and 15–20 minutes for solvent-based PCP
Peel strength
adhesive at room temperature (Figure 10b);
(d) For solvent-based PU adhesive, activate the The peel strength is the property that determines the
adhesive by heat (infrared radiation, IR), necessary force to separate two materials, in joints
approximately between 55 and 80  C for 2–6 s where at least one of the substrates is flexible. This
(Figure 10c) is required. In addition, PCP adhe- property is determined by a peel test, allowing to dis-
sive is also heat active when drying time is over tinguish if an adhesive is brittle or ductile. This test is
open time. Activation time depends on material performed in a tensile testing machine.7,57,63,73,74 The
colour; peel test is a standardized method and for the foot-
(e) Attach the uppers and soles, placing the desired wear industry, standard EN 1392 is used as a refer-
position (Figure 10d); ence standard.56 This standard determines the test
(f) Pressing for 4–5 s at a pressure of approximately method for obtaining the peel strength at an angle
2–4 bar (Figure 10e). The press depends on mater- of 180 , with the materials bonded in the specimen
ial nature and hardness. Press time depends on shape shown in Figure 11.56
crystallization rate. Seventy-two hours after the manufacture of the
adhesive joint, the peel test is performed in a testing
machine at a speed of 100 mm/min.7 The peel strength
per unit of width is determined by the ratio between
Joint properties the average force (Newton, N) and the average width
There are several factors that influence the strength of (millimetre, mm) of the overlap joint56,74 defined as
a bonded joint and to understand them, it is import-
ant to precisely measure the performance of the joints. F
P¼ ð1Þ
In this section, there is a discussion of the mechanical A
properties that are more relevant for the selection of

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Paiva et al. 15

A schematic diagram of the joint used for creep test

and the loading condition is shown in Figure 12.
After the complete cure of the adhesive joint, the
creep test is performed in a controlled environment at
a temperature of 60  C. This temperature is chosen to
simulate the warming of footwear in, for example,
non-temperature-controlled shop windows, in transit
in warm climates or on exposure to high temperatures
in service. The test procedure is started by carefully
bending apart the unbonded ends of the test specimen,
marking the beginning of the bonds, and inserting the
ends in the clamps of the peel test chamber. This is
followed by heating the test pieces in the test chamber
for 1 h to allow them to reach the specified tempera-
ture. After this heating up period, each of the test
specimens is loaded for 10 min with the specified con-
stant weight (1.5 kg). The peeling forces provided by
the 1.5 kg mass are sufficient for standard test. Higher
Figure 11. Adhesive joint for peel test (dimensions in
millimetres).
peeling forces, corresponding to the 2.0 and 2.5 kg
masses, may be used for special proposes, such as
adhesives with very high heat resistance. Finally, the
where P is the peel strength (N/mm), F is the average test chamber is opened and the deformation of speci-
force (N), and A represents the bonded area of the men is measured (in millimetres, mm) while still
specimen (mm).74 The values of F and A are obtained loaded. The time (in minutes, min) to complete
from the force/deformation plot obtained separation is then determined.6 With the creep experi-
experimentally. ment, a ‘‘creep rupture envelope’’ which can be
Paiva et al.55,63 concluded that applying solvent- obtained, is divided into three phases: primary, sec-
based PU adhesive to bond PU soles to leather ondary, and tertiary. The primary phase corresponds
upper, the peel strength is capable to satisfy the min- to instantaneous elastic strain, the secondary phase
imum requirements for the footwear industry, since represents the creep rate, and the tertiary phase
applied the correct surface treatment. Navarro- occurs with the rupture of the bond of the speci-
Bañóno et al.64 concluded that is possible to obtain men.4,37 The results are expressed as displacement
good results of peel strength using PU and PCP adhe- (millimetres, mm) versus time (minutes, min).
sive types to manufacture SBS/adhesive/leather joints; Gao et al.75 concluded that the effect of tempera-
however, to eliminate the reactivation process with ture on the creep loading is very evident, finding that
PCP adhesive, it is necessary to use thermoreactive the creep rate increases with an increase in tempera-
phenolic resin on the formulation. ture. The work of Paiva et al.76 has shown that, for
Furthermore, the type of failure can provide useful the footwear industry, good results for creep rate are
information about the performance of the adhesive reached when materials such as PU, caprolactone
joint or in case of improvement which parameter with extremely high crystallization type, and some
should be improved (material cohesion, heat additives, such as fumaric acid and chlorinated
activation, pressure, surface treatment, adhesive rubber, are included on the adhesive formulation.
viscosity, etc.) Inversely, when colophony and vinyl resin are
included, the creep results are noticeably worse.
Creep strength
Creep strength is a property that allows the assess-
Conclusions
ment of the temperature resistance that the adhesive This review shows that in the footwear industry, the
is able to withstand without suffering any loss of adhesives assume a very important role to ensure the
properties and without suffering damage to its struc- quality of the final product.
ture. This property is important for footwear because For that reason, before selection of the adhesive, it
footwear can be subjected to surprisingly large tem- is very important to define all the materials necessary
perature gradients. As an example, when the shoes are to manufacture the shoes and to define the intended
exhibited in shop window displays, they are subjected type of union of materials and the method of appli-
to large temperature variations. To quantify this cation. The surface treatment can then be selected in
property, the creep test is performed, which is normal- accordance with the materials to be used. Considering
ized according to the standard EN 1392.56 This prop- the most demanding joint on footwear, upper-to-sole,
erty is very important also for adhesives to be used for we can identify a few commonly used materials.
lasting where high thermal resistance is required. For the upper, PVC, natural and synthetic leather

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16 Proc IMechE Part L: J Materials: Design and Applications 0(0)

Figure 12. Adhesive joint for creep test.

are usually employed. For the sole, crepe, natural or 2. Petrie EM. The role of adhesives in the shoe industry,
synthetic leather, PU, TPU, TR, SBR, EVA, PA, www.specialschem.com 2007 (accessed 2014).
PVC, PS or ABS is used. 3. Falco APS. Avaliação da Adesivos utilizados em solados de
A correct surface treatment is important to achieve calçado de uso Marinha do Brasil. MSc. Thesis,
Universidade Federal do Rio de Janeiro, Brasil, 2007.
the required level of performance from the adhesive
4. da Silva LFM, Ochsner A and Adams RD. Handbook
joint. The effects of such treatment are varied, being
of adhesion technology. Volume I e II. Heidelberg:
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and/or to remove the surface finishes, improving the 5. Pastor-Blas MM, Martı́n-Martı́nez JM and Boerio FJ.
compatibility with the adhesive. In the footwear Influence of chlorinating solution concentration on the
industry, the most commonly used surface treatments interactions produced between chlorinated thermoplastic
are the primer, solvent cleaning and physical and rubber and polyurethane adhesive at the interface.
chemical treatment (halogenation). J Adhes 2001; 78(1): 39–77.
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resins, additives, and solvents in order to meet the wear materials. Sole-upper bonds. Minimum strength
intended mechanical properties. requirements.
7. Sapato Noticias, n. 21 – APPICCAPS, fonte, www.din-
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8. NOTÍCIAS RTP, n. 763488 – Economia, fonte,
properties are controlled. These are the peel strength www.rtp.pt, Indústria portuguesa do calçado e´
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