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Materials Science » "Adhesives - Applications and Properties", book edited by Anna Rudawska, ISBN 978-953-51-2784-0, Print ISBN 978-953-51-2783-3, Published: November 23, 2016 under CC BY 3.0 license. © The Author(s).

Chapter 9

What are the Health Risks of Occupational Exposure to Adhesive in the Shoe Industry?

By Imed Gargouri, Moncef Khadhraoui and Boubaker Elleuch
DOI: 10.5772/64936

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Map of (a) the center of Sfax city and (b) the old town of Sfax.
Figure 1. Map of (a) the center of Sfax city and (b) the old town of Sfax.
Atmospheric sampling (a) “individual” and (b) “stationary.”
Figure 2. Atmospheric sampling (a) “individual” and (b) “stationary.”

What are the Health Risks of Occupational Exposure to Adhesive in the Shoe Industry?

Imed Gargouri1, 2, Moncef Khadhraoui1 and Boubaker Elleuch1
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The term “shoe” covers a wide range of products made from various materials. Organic solvents (OS) are components of various products such as the adhesives which are used in many industries. The shoe industry consumes large amounts of adhesives. This chemical risk assessment (CRA) is to validate the hypothesis of decreasing gradient of RA craft enterprises to industrial enterprises through the semi-industrial. The simplified methodology CRA of INRS was applied. For each chemical, a hazard class is assigned based on the sign, and then the potential exposure class is determined according to parameters “quantity and frequency of use”. Our RA process is complete with ambient measurements for solvents to which employees are most frequently exposed. Adhesives being constituted as solvent mixture, we have conventionally used an exposure index which is compared with the limit values. The simplified method CRA of INRS was chosen because it is one of the reference methods in RA established from the Kinney model. If these atmospheric samples and toxicology tests were made for the first time in the shoe industry in Sfax, they concerned a sample of companies of the three shoe manufacturing processes preceded by a preliminary RA with post-study and inventory of products handled.

Keywords: risk assessment, chemical risk, shoes manufacturing, organic solvents, adhesive, occupational health

1. Introduction

The term “shoe” covers a wide range of products made from various materials. Boots, shoes, sandals, slippers, clogs, and others are made entirely or in part with leather, rubber, synthetic and plastic, cloth, rope, and wood [1]. Our study deals with the shoe industry, that is to say one based on traditional manufacturing methods. The rubber boots factory (or equivalent synthetic materials), which is one of the branches of the rubber industry, is excluded from this study [1, 2].

Shoes, boots and leather sandals, felt, or other materials have been for centurys hand. Quality shoes are still made entirely or partly in this way by craftsmen, but in all industrial countries, today the mass production predominates [2, 3].

Organic solvents (OS) are components of various products such as paints, inks, pesticides, degreasers, solvents, and glues, which are used in many industries [1]. The shoe industry consumes large amounts of adhesives, diluents, and strippers OS bases. Consequently, the employees in this sector are likely to present particular nerve pathologies [2].

2. History of the shoe in the Sfax city

Sfax is an industrial and agricultural pillar of the Tunisian economy [4]. Among its industries, shoemaking is highly developed sector, which employ about 10000 employees or 10 the workforce of the nonagricultural professional environment which 6000 artisans shoes located in the old city “the Medina.”


Figure 1.

Map of (a) the center of Sfax city and (b) the old town of Sfax.

As in many cities, Sfax had a craft of the shoe. But in addition, Sfax was a shoe industry. The manufacture of the shoes to form Sfax “industrial” dates back to the nineteenth century. It was well structured in the Medina in the shoe area called “Souk Blaghgias.” It consists of the main street shoes exhibition: The current street Mongi Slim known under its former name “Street of Bay.” Until now, along this road for approximately 300 m shoe shops displaying their products. In the level one called “the Ally” in every store or in the neighboring streets were their own manufacturing facilities.

In 1960, after independence, observers were predicting the rapid decline and disappearance of the craft before the competition of the modern shoe industry. Now, after more than 30 years, this craft, far from having disappeared, has prospered and it feeds today, modern shoes, more than half of the Tunisian market. The artisan district of the boot has grown in the old town of Sfax; we hear all the noise of machines whose artisans are equipped to modernize the sensitive points of their manufacturing (Figure 1) [4].

3. Manufacturing processes of the shoe

The realization of a shoe includes several operations. Each step has been mechanized, but the manual production is used as reference. The introduction of new materials has modified manufacturing processes without changing the outline [1, 2].

The manufacture of rods requires sorting and preparation of leather or other materials. The stems are cut with cutters on stitching presses (or burning). The various parties, including the linings, are then “assembled,” that is to say, stitched or glued together. Perforation, eyeletting, or making buttonholes are the procedures carried out further.

In the lower part, the outer and inner soles, heels and welts are cut using cutters to moving blades or molding presses. It manufactures heels compressing leather or wooden slats. The assembly is then cut, formed, cleaned, and labeled.

The upper and lower parts of the shoe are then assembled and then stitched, glued, nailed, or screwed together. After that the shoes are shaped and smoothed by means of rollers. The finishing of the shoe includes waxing, staining, spraying, polishing, and packaging.

Among the raw materials used in manufacturing, adhesives, including adhesive solids and liquids and natural adhesive solutions prepared from organic solvents, represent the largest occupational hazards [3].

4. The basic products used in the shoe industry

In the industry of the adhesive and its derivatives, products intended for the manufacture of the shoe are divided into three groups [2, 511]:

  • Four groups of adhesive,

  • Primers, hardeners, and additives,

  • Solvents, thinners, and strippers.

4.1. Four groups of adhesive (Table 1)

  • The polyurethane (PU) adhesive is used for assembling thermoplastic rubber soles (TR), rubber, polyvinyl chloride (PVC), leathers high in fat or synthetic fabrics requiring the use of high-performance adhesives.

  • The polychloroprene adhesives (neoprene) are used for making coatings soles, fast repair, and bonding of natural materials (leather, rubber). They are made from synthetic resins dissolved in ketone solvents.

  • The adhesives in aqueous emulsion (latex adhesives or white glues) may be natural or synthetic:

    • Natural latex adhesives are applied by machine gun or by hand. These are contact adhesives to attach soles, stitching, and lining.

    • The synthetic latex adhesives are used for laying the ends and bonding liners.

Polychloroprene adhesives
Implemented by
contact with the
– Coating the two sides to stick,
– Respect the drying time
(in ways that the two adhesive
films release their solvents)
– Assembly of parts (pressure)
after reactivation
– Solids based on polychloroprene
(15–30%) depending on use
Organic solvents (mixture): the most
used are, by decreasing
importance order:
* Gasoline C (up to 30% hexane)
* Acetone
* Ethyl acetate
* Toluene
* Cyclohexane
* The alcohols and chlorinated
hydrocarbons (little used)
– Welded shoe soles
The polyurethane
adhesives (PU)
1. based polyurethane
Polyvinyl chloride Elements (PCV)
– Solids of polyurethane elastomers
Organic solvents: mixture
* Ketones and / or
* Overheads
– Contact adhesive which is
taken after solvent evaporation
2. Two-componentPart A:
– Polypol (polyester or polyester)
Organic solvents (mixture) :
* Ketones and / or
* Overheads
Part B:
– Isocyanate prepolymers (small
amount of free isocyanate: Ex
diphenylmethane diisocyanate ….)
Very flexible assemblies
The mixture of A with B is carried
out at the time of use
– The adhesion is after solvent
Adhesives in aqueous
emulsion: latex adhesives
or white glues
– Solids (40–60% may be:
* Vinyl acetate
* polyisoprene
* Acrylic polymers
* Copolymers: acrylic, isoprene,
* polyurethane
* In general: WATER
* Optionally and low proportions:
– Alcohol
– Other solvents
– Installation of liners: manual
application by simply coating
and touch
– Water evaporation Making
Hot melt adhesives or
“hot melt”
Equipment cadence “very expensive”
Copolymer Ethylene-vinyl acetate ±
possibly: plasticizers or
Applying on one of the faces
to be bonded by a polymer
melt temperature rise

Table 1.

The basics products in the shoe manufacturing (part welded) [11].

The hot melt adhesive is a new generation of glue developed in order to reduce the use of solvents. It consists in applying on one of the faces to be bonded by a polymer melt temperature rise. It requires clock equipment which is expensive.

4.2. Primers, hardeners, and additives

  • The halogenations operation of TR soles with new functions (rubber look and matt or transparent), must be strictly control any change of model. There are several formulas ready to use (one or two components) for receiving an additive to control the regular application on the soles.

  • Catalysts, slow or fast, are used in polyurethane adhesives, polychloroprene or dispersion, as well as direct injection. They provide good resistance to the migration of fat leathers.

4.3. Solvents, thinners, and strippers

Beside adhesives preparations, there are other necessary preparations and complementary type of strippers, thinners, and solvents (Table 2).

PreparationsApplications and examples
The cleaning agent– PU soles: remove traces of mold release agent ;
– PCV soles: remove surface plasticizer contained in PCV compounds
The diluents– Dilute polychloroprene adhesives ;
– Clean the machine to glue and brushes, spray guns stained with paint,
screens for screen printing ink
The solvents– Clean the rubber soles, spray guns stained with
paint, screens for screen printing ink;
– Dilute paints and glues.

Table 2.

Other preparations used in the manufacture of shoes [13].

5. Risks of the solvents and the adhesives on the health

According to their properties, the solvents can be used in the manufacture of the shoe, of:

  • Degreasing (cleaning soles, textiles…)

  • Additives and solvents (paints, varnishes, inks, adhesives…)

  • Stripping (removal of paints, varnishes, glues…)

OS hydrocarbons are divided into eight main groups [1214]. Six families are used in the manufacturing industry adhesives and footwear (Table 3).

The intensive use of flammable liquids causes a high risk of fire, and the widespread use of presses and assembling machines has increased also the risk of accidents. The main danger to the health of workers is using toxic solvents, high concentrations of dust in the air, the risks due to ergonomic shortcomings, and noise from machinery.

OS can cause acute and chronic effects on the central nervous system. Benzene, which was once used in adhesives and solvents, has been replaced by toluene, xylene, hexane, methylethylketone (MEK), and methylbutylketone. The n-hexane and MEK can cause peripheral neuropathy and should be replaced by heptane or other solvents [2].

In many factories, there were outbreaks of a disease known as the “paralysis of the shoemaker” and characterized by clinical signs of a form of more or less serious paralysis. This is a flange type of paralysis, located in the upper and/or lower limbs resulting in deep tendon atrophy with areflexia, without altering the superficial or deep sensitivity. From the clinical point of view, this syndrome is due to an inhibition or a functional lesion of the lower motor neurons of the voluntary motor system (pyramidal system). Most often, it leads to a neurological regression with extensive proximodistal functional recovery [1, 2].

Groups of solventsApplications and examples
Aromatic hydrocarbonsHomologues of benzene (toluene, xylenes, ethylbenzene …) are used as lacquer thinners, adhesives and inks.
Petroleum solventsUsed as solvents in paints, adhesives and coatings:
Alkanes such as hexane (C6H14);
Cycloalkanes: The most used is cyclohexane (C6H12)
AlcoholsVery used as diluents inks, resins, varnishes, paints and glues. These are excellent dehydrating agents having good degreasing Action Example: isopropanol (or isopropyl alcohol).
KetonesMainly used as solvent paints, lacquers, varnishes, glues and adhesives. They are sometimes impregnated on wipes for small cleaning. They are good agents drying damp rooms.
The most commonly encountered are: acetone or MEK.
Acetates (esters)Often mixed with other solvents, for example, in the curing products and halogenation
Halogenated hydrocarbonsUsed as diluents glues, adhesives, paints.
Examples: Trichloroethylene (degreaser leather, thinner glue) or dichloromethane (thinner adhesives and cleaner)

Table 3.

The families of solvents used in the manufacture of adhesives and shoes [13, 15].

In the manufacture of shoes and boots, handling and leather processing can cause diseases by exposure to certain chemical substances mentioned above and in tanning and finishing. In addition, various chemicals can produce other diseases. Exposure to toxic solvents contained in adhesives and cleaning products, and to leather dust in the air is of particular concern. The use of benzene can cause thrombocytopenia (decreased number of red blood cells, platelets, and white blood cells in the blood) or pancytopenia. It has been almost eliminated from the footwear industry [3]. It was also found in some shoe factories cases of peripheral neuropathy due to n-hexane content in adhesives. This substance has also been largely replaced by less toxic solvents. Cases of electroencephalographic changes, liver damage, and behavioral alterations due to exposure to solvents have been reported in workers in the shoe industry [3].

6. Occupational chemical risk in shoe industry in Sfax

6.1. Methods

The prevention of occupational risks, particularly chemicals, is based on the risk assessment (RA) according to the specified procedures. Thus, we realized an exposure assessment in making shoes in a sample of volunteer companies (Table 4).

This chemical risk assessment (CRA) aims to validate the hypothesis of decreasing gradient of RC craft enterprises to industrial enterprises in passing by semi-industrial. The simplified assessment methodology for chemical risk (SAMCR) of National Institute of Research and Safety (INRS) [15] was applied only for strand “Health.” For each chemical, a hazard class (HC) is assigned based on the sign, and then the potential exposure class is determined based on the parameters “amount and frequency of use.”

Number of companies459
Equipment usedMechanization (workflow)Mechanization and manualManual
Number of employees>20[1020]<10
Installation locationIZIZ or MedinaMedina

Table 4.

Business definition.

IZ: industrial zone.


Table 5.

Hazard classes depending on the labeling [1315].

The HC was determined only on the labeling. The allocation of HC to a preparation based on the analysis of the pictogram on the packaging (Table 5). For preparations of glues or solvents “unidentified” (no information on the composition and/or the manufacturing company), it was decided that the assigned pictogram would be one that represents the greatest health risk and consequently the HC.”


Figure 2.

Atmospheric sampling (a) “individual” and (b) “stationary.”

la France
Our Study
SolventCAS1VEA5TLV-TWA6EAV adopted
(MEK, 2-butanone)

Table 6.

Values of atmospheric exposure limits [17].

1CAS: Chemical abstract service.

2EU: European Union.

3ACGIH: American Conference of Governmental Industrial Hygienists.

4MAK: Maximum Arbeitsplatz-konzentration.

5EAV: Exposure average value calculated over a reference period of 8 hours.

6TLV-TWA: Time-weighted average (weighted average values of 8 hours per day and 40 hours per week).

7ppm: Parts per million per volume of air.

  • Unidentified glue: The glue most dangerous to a symbol “Xn-Harmful” [5, 11] for the health and attributed HC is “3.” Thus, any unidentified glue the symbol “Xn-Harmful” and “3” class was assigned.

  • Unidentified solvent (solvents, thinners, and strippers): Two hypotheses “HC” were individualized [11, 1315]:

    • Let the symbol “T-Toxic” and class “4,” the highest existing level;

    • Let the symbol “Xn-Harmful” and “3” class more realistic for the majority of solvents.

alcohol (IPA)
Soften the
“strong against
chloride (2%)
in MEK
Washing, sole
DesmodurDESMODUR RCTDI (5%) in
Ethyl acetate
Diluent PU
DurcisseurDESMODUR RCXi-Irritant2
neoprene glue
98% Ethyl
TucosolveStripperMEK, AE,
Xn-Harmful or
3 or 4
Special ink
Solvent not

Table 7.

Inventory preparations “solvent” used in the footwear industry and hazard class.

Our approach to RA is complete, and ambient measurements [16] (Figure 2) for solvents (acetone, cyclohexane, n-hexane, MEK, toluene) to which employees are more frequently exposed are taken.

Adhesives being constituted as solvent mixture, an exposure index (I.exp) was used and compared with the limit values (Table 6) [17, 18]:

I.exp = C1/EAV1 + C2/EAV2  + Cn/EAVn

Cn and EAVn are respectively the concentration and the average value of n pollutants exposure.

If I.exp is greater than 1, the limit value is considered outdated. Calculated from stationary sampling, this index is called pollution index (I.pol).

6.2. CRA

However much the manufacturing process, the inventory of solvent borne formulations showed HC “2” and “3”. When the unidentified preparations, they were classified “3” or “4” (Table 7). For the 23 identified glue preparations, HC ranges from “1” to “3” (Table 8).

The potential risk score (PRS) process “industrial” 2 in case of danger class puts 13 chemical preparations to examine with high priority, including five of solvent preparations. For the HC “3,” PRS do not exceed “10000,” while with the hazard class “4” three of five solvent borne preparations pass a PRS 100000.

The situation of distinction for a process “semi-industrial” does not arise since we did not detect unidentified preparations. The preparations to consider with high priority are 2 solvents and 5 adhesives unidentified.

In the “artisanal” process, we have identified eight chemical preparations to examine with high priority: two solvents borne preparations and six adhesives.

110/Textile glueRubber 110FNatural rubber,
hexane, petroleum
or final
bonding of
420Ceylanprène 420Polycholoroprène,
MEK, Resin (phenol,
phenol terpene),
Bonding the
425SCeylanprène 425Polycholoroprène,
MEK, Resin (phenol,
phenol terpene),
Bonding the
715Bonding the
945Bonding the
C3Bonding the
C4Bonding the
MEK, Resin
phenol terpene) on
a ribbon
Polyester fabric
coated with an
CD11Gluing solesPolyurethaneXi-Irritant2
CN13Bonding the
Glue “Latex”Synthetic or
natural rubber in
an aqueous
For bonding
wood heel
Aqueous emulsionNo1
Vinyl glueEx: R10Polymer of
acetate, acrylic
polymer, water
Manufacture of
the shoe
D1Gluing solesPolyurethaneXi-Irritant2
Forestali/ICFGluing solesPolyurethaneXi-Irritant2
Gluing solesPolyurethaneXi-Irritant2
Gluing solesPolyurethaneXi-Irritant2
Gluing solesPolyurethaneXi-Irritant2
Gluing solesPolyurethaneXi-Irritant2
Colle geantNOT

Table 8.

Inventory preparations “glues” used in the footwear industry and hazard class.

6.3. Atmospheric measurements

Measurements of atmospheric concentrations (Table 9) show high levels especially in companies with semi-industrial process and type 1 craft.

ProcessBusinessNumber of
Personal samplingAtmosphere sampling
Exposure index*Pollution index**
IndustrialIndustrial 1530.3–1.10.720.5–0.80.6
Industrial 2211.810.3
Industrial 3540.9–9.43.710.8
Industrial 4540.8–19.86.810.0
Semi-industrial 1530.4–1.20.720.0–0.30.1
Semi-industrial 2540.5–
Semi-industrial 3420.2–2.51.320.2–0.40.3
Semi-industrial 4540.9–2.41.710.1
Semi-industrial 5415.634.3–8.86.8
ArtisanalType 1Craft 1210.110.4
Craft 21/10.7
Craft 31/10.8
Craft 4320.4–
Craft 5211.510.9
Craft 6221.6–3.42.5/
Craft 7216.415.1
Type 2Craft 81/10.5
Craft 91/10.6
Total = 33Total = 22

Table 9.

Atmospheric exposure of employees by industrial trial.

Stages of productionSources of pollution
1. Individual sizing
Solvent vapor:
– Glue container in use
– Piece glued
– Materials used for coating (pre-sizing operation)
2. The preparation of surfaces prior to bonding
– Clean and degrease the parts to be assembled (brush, cloth)
– Washing of soles
– Halogenation: Treatment of some soles (rubber)
3. DryingObjects are placed in general on fixed or movable shelves near collages positions
4. Finish– Cleaning after bonding to remove excess glue
(solvent-soaked rag)
– Coloring and application of polish (usually by spraying)
5. Cleaning equipmentBrushes and accessories: With solvents
6. Fractionation and storage
“Decanting” preparations
Adhesives wholesale packaging: A transfer in small containers used in gluing station

Table 10.

The steps of the shoe manufacturing (the welded Technique) and sources of pollution [11].

Exceedances of I.exp and/or I.pol are noted for exhibitors positions including the upper part makers, smelters and finishing (Table 10) within three manufacturing processes (Table 11).

All measurements in different companies show that exposure to OS varied from one process to another and from one position to another (Table 12). The average atmospheric concentrations of hexane are particularly high, especially with the exposure average value (EAV) which overruns the position of the upper part maker, the sole maker, and finishing in all production processes except the process artisan type 2. The other solvents (acetone, cyclohexane, MEK, and toluene) are relatively high without exceeding the EAV.

6.4. Comments and discussion

Despite significant exposures to solvent-based preparations, an almost total lack of use of personal protective equipment such as gloves, masks, and goggles by the manipulators of the adhesives formulations and/or solvents was noted. The equipment of rooms by adequate ventilation is not rated very often, while the Tunisian regulations require companies to preserve human capital and implement a preventive political.


Table 11.

Average atmospheric concentrations of solvents assayed.


Table 12.

Average atmospheric concentrations of solvents assayed.

The natural ventilation has been the main alternative ventilation: Some kind of artisans 2 working doors open because they have no other coming from vents (without windows), while others worked closed doors because of their irregular position (no statement to the National Case Social Security and/or cohabitation a group of craftsmen in a building intended for habitation and not commercial and industrial travailing each for its own account).

Semi-industrial footwear companies are craft enterprises working on a large scale with some mechanization, which paid their employees the number of parts produced per day (upper part makers and sole makers). They correspond to industrial companies that should be in IZ [19]. Another feature in this type of business is the presence of women in age mount positions rods and finishing [20]. Shoes manufacturing companies are increasing in the region with an extension to the new IZ south of the city of Sfax. The semi-industrial companies continue to invade Medina and especially the houses which are in most cases protected historical monuments.

The SAMCR of INRS was chosen because it is one of the reference methods in RA established from the Kinney model (mathematical model) [21].

If these atmospheric samples and toxicology tests were made for the first time in the shoe industry in Sfax, they concerned a sample of companies of the three shoes manufacturing processes (industrial, semi-industrial, and artisanal) preceded by a preliminary RA with a job and a study inventory of products handled.

Interest carcinogenic characteristics of certain preparations and especially their potential toxicity for reproduction must be taken, as a female presence in the shoe manufacturing sector increasingly important and cases of couple infertility [22] have been highlighted.

7. Conclusion

Identification and CRA are important steps in this process of prevention in the shoe industry. This detection was to (i) highlight the chemical preparations that are really harmful. This could be achieved by the inventory and prioritization of chemical preparations; and (ii) identify the nature of the manipulated chemical preparations. This identification was made by labeling of preparations. After this step, the semi-industrial process CRA is most at risk followed the industrial process and finally that of the artisanal process. When the study of exposure to workplace needs to know not only the average exposure over the EAV, but also to identify the polluting phases to determine the short-term exposure over the TLV.

Apart from the strengthening of health and safety measures in the shoe industry, two actions are to be undertaken in parallel: (i) the substitution of certain solvents by others in the manufacture of glues and derivatives seems necessary while maintaining the preparations use properties and (ii) a change in the Tunisian regulations on hygiene and safety, in particular, is necessary to mandate the RA in business.


This study was partly funded and supported by Sfax University. We are grateful to the director and staff of the adhesive company SIFCOL for their cooperation. We are also indebted to the workers who participated voluntarily in the study.


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