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(LIFE08 ENV/E/000140)

MANUAL FOR
OXAZOLIDINE
TANNED LEATHER
LIFE+ Proyect Enviromentally Friendly
Oxazolidine-Tanned Leather (OXATAN)
PROJECT COORDINATOR

CENTER FOR TECHNOLOGY


AND INNOVATION

PROJECT PARTNERS

Manual for oxazolidine leather tanning


LIFE08 ENV/E/000140

CONTENTS

1. INTRODUCTION ............................................................................................................. 3
2. THE MANUFACTURE OF LEATHER........................................................................... 4
2.1. The origins of tanning................................................................................................. 4
2.2. The industrial processing of the hides and skins. ..................................................... 11
2.2.1. Beamhouse operations. ...................................................................................... 15
2.2.2. Tanning. ............................................................................................................. 19
2.2.3. Post-tanning. ...................................................................................................... 23
2.2.4. Finishing ............................................................................................................ 27
3. THE OXAZOLIDINE LEATHER TANNING TECHNOLOGY................................... 33
3.1. Background............................................................................................................... 33
3.2. Starting materials: hides and skins, equipment and chemicals................................. 41
3.3. Technical procedure.................................................................................................. 44
3.4. Technical validation of oxazolidine-tanning technology.......................................... 57
3.5. Basic safety and health guidelines for the oxazolidine-tanning process. ................. 63
ANNEX I. SAFETY DATA SHEETS OF (GENERIC) CHEMICALS ............................. 77
ANNEX II. LEATHER QUALITY STANDARDS (PHYSICAL PARAMETERS). ........ 86
ANNEX III. BIBLIOGRAPHY......................................................................................... 100

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1. INTRODUCTION.
The traditional tanning process, used in more than 90% of leather tanned worldwide,
consists in the application of trivalent chromium salts, which interact with the skins
collagen, acting this way as a tanning agent. This process confers leather excellent physical
properties and a high stability to manufacturing processes and the passage of time.
However, in some cases, it can cause allergies to chromium and even on some occasions
the chemical characteristics of chromium can change and be harmful to the environment.
Given the growing environmental pressure to which tanning industries are subjected and
the tendency to increase the environmental requirements for leather, recently INESCOP,
Centre for Innovation and Technology, has been carrying out different R&D actions to
develop new tanning techniques, alternative to the traditional chrome tanning, that allow
the environmental performance of tanneries to be improved. As a result of these actions,
the project titled Environmentally-friendly Oxazolidine-tanned Leather (OXATAN) was
launched, co-funded by the European Commission through the LIFE+ Environment
Programme. This project proved that tanning with oxazolidine, combined with other
vegetable or synthetic tanning agents, makes it possible to obtain high performance leather
while avoiding the presence of metals (chromium) both in liquid and solid waste; this way,
the environmental impact generated during the whole tanning process can be dramatically
reduced.
This Manual describes the methodology for oxazolidine leather tanning developed in the
framework of the project Environmentally-friendly Oxazolidine-tanned Leather
(OXATAN).

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2. THE MANUFACTURE OF LEATHER.


Tanning is one of the oldest trades of humanity, with references on the use of leather in
cave paintings and archaeological sites worldwide that prove this.
Tanning had an accidental nature in its prehistoric origins, slowing evolving until turning
in the Middle Ages into a craft. At the end of the nineteenth century, the first scientific
studies were started which, with the industrial revolution and the development of the
relevant machinery, derived into the current leather production technology.

2.1. The origins of tanning.


Primitive man hunted wild animals for food; he removed the hides and skins from the dead
animal carcass and used them as crude tents, clothing and footwear. The earliest record of
the use of leather dates from the Palaeolithic period, cave paintings discovered in caves
near Lerida in Spain depict the use of leather clothing. Excavation of Palaeolithic sites has
yielded bone tools used for scraping hides and skins to remove hair.
The main problem for the prehistoric man was to avoid the rapid putrefaction of the skins,
by first drying and then rubbing them with fat to give them a greater softness. It is assumed
that primitive man also discovered accidentally that the smoke from wood fires could
preserve the hides and skins, as did softening them with tannin-containing barks, leaves,
twigs and fruits of certain trees and plants.
With the passage of time, they discovered ways to remove the hair using wood ash and
burnt limestone and, much later, the capacity of certain minerals (alum) to stabilise the
skins obtaining whiter and softer leather thanks to their content in aluminium.
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Figure 1. Cave paintings of La Valltorta in Castelln-Spain and a cowhide shoe found in Armenia,
3.500 BC.

The first civilisations (Mesopotamia, Sumer, Assyria, Persia, etc.) used tanned leather for
footwear manufacturing and other articles as shown in different icons drawn on ceramic
pots, jars and engravings found in burial tombs.
The Egyptian civilisation is the one that has brought the most information on leather
tanning, in the form of engraving in papyruses or in wall paintings and objects in Egyptian
tombs; sandals, clothes, gloves, buckets, bottles, shrouds for burying the dead and military
equipment, due to their belief that the dead should be buried with all of their possessions to
enjoy them in the next life.

Figure 2. Reproduction of an Egyptian papyrus showing leather tanning.

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The ancient Greeks and Romans also made extensive use of leather. The Romans used
leather on a wide scale for footwear, clothes, and military equipment including shields,
saddles and harnesses.

Figure 3. Roman leather footwear. Oiasso, Irn, Basque Country.

The tanning process evolved with time until turning, during the Middle Ages, into a craft.
Most towns and villages had a tannery, situated on the local stream or river, which they
used as a source of water for processing and as a source of power for their machines. In
many towns there is still evidence of this in street names.
Also, at that time religious communities had a prominent role in the progress of this
activity, since their monks were expert at making leather, especially vellum and parchment
for writing purposes and bookbinding.
During the Middle Ages, rawhides and skins were treated by first immersing them in a
fermenting solution of organic matter in which bacteria grew and attacked the hides or
skins, resulting in a loosening of the hair or wool and some dissolving out of skin protein.

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The hair or wool was then scraped off with primitive scrapers and fat or meat still adhering
to the flesh side was removed in a similar manner. Tanning was done by dusting the
rawstock with ground up bark or other organic matter and placing them in shallow pits or
vats of tannin solution.
The skins remained immersed for a long time in these tannin solutions given that it was a
static process, finalizing it when the tannin solution had penetrated right through the skin
structure. The majority of the leather was tanned with oak bark but softer and whiter
clothing, gloving and footwear leathers were tanned with alum, oil, and combinations of
these two materials.
The leather was then hung up for several days in open sheds. The dressing of the leather
involved paring or shaving it to a level thickness, colouring and treatment with oils and
greases to produce attractive surface finishes. Finally the grain surface was treated with
waxes, proteins such as blood and egg albumins, to produce attractive surface finishes.

Figure 4. Medieval tanneries from the poor area of San Segundo in Avila (Spain).

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At that time, leather was used for all kinds of purposes such as: footwear, clothes, leather
bags, cases and trunks, leather bottles, saddlery and harness, for the upholstery of chairs,
and couches, bookbinding and military uses. It was also used to decorate coaches, sedan
chairs and walls.
From the Middle Ages till the end of the seventeenth century, there were not many changes
in the skin transformation processes, until Colbert, minister of King Louis XIV of France,
gave a strong impetus to scientific analysis of tanning methods. This way, at his request,
Des Billettes wrote in 1708 a work called La tannerie et la prparation des cuirs, which
marked the end of the oral tradition in this technical field.
At the end of the eighteenth century, the growth of industrialisation created a demand for
many new kinds of heavier-duty leathers, e.g. belting leathers to drive the machines being
introduced into industry, special leathers for use in looms in the textile industry, leathers
for use as diaphragms and washers, leathers for use in transport and for furniture
upholstery, etc. as well as other softer, suppler, colourful leather for clothing, footwear and
glove making that the traditional vegetable tanning could not provide.
Similarly, the progress in chemistry at the end of the nineteenth century was critical for the
development of the tanning industry, with the discovery and introduction of basic
chemicals like lime and sulphuric acid, the range of coal tar dyes, etc.
Finally, the discovery of new tanning products, mainly chromium and aluminium, marked
the beginning of industrial scale tanning.

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In 1853, the French Cavalin discovered the use of trivalent chromium salts that reacted
with the collagen fibres of the skin, thus obtaining strongly tanned leathers with never
before obtained characteristics, like the boiling and tear resistance, as well as a good
elasticity and water vapour permeability.
In 1858, Knapp patented tanning with two baths and finally, between 1887 and 1892, A.
Schultz achieved the first tanning with only one bath. Since then, trivalent chromium salts
have been used as a tanning agent, and presently 90% of leather is tanned this way
worldwide.
Likewise, various artificial substitutes of the natural substances always used for tanning
were discovered. These synthetic tannins marked an important field of application of
chemistry to the leather industry and since then they have continued to be studied. This
change in what refers to tanning substances was accompanied by something similar with
regard to processes applied to tanning, which were mechanized in an extremely rapid way.
The tanneries of the beginning of the twentieth century were big factories where the
treatment of hides and skins, with all its complexity, was slowly carried out, manually and
with very few mechanical means.
In recent years, the work conditions have been radically transformed with the incorporation
of the instrumentation that engineering, electronics and computing provide, so that a
spectacular optimization could be achieved both from the output of the process and the
final quality of the leathers, trying also, to minimize the impact of this activity on the
environment by developing clean and innovative technologies.

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Figure 5. Paddles and drums in tanneries in Igualada, Barcelona (Spain) at the end of the nineteenth
century and appearance of a current tannery.

In the current industrial process, leather tanning is carried out dynamically in drums and
paddles, in which the hides and skins interact with different chemical agents, mainly
trivalent chromium salts, which react with the collagens fibres to obtain stable and durable
leather.
After tanning, the skins are drained and shaved, obtaining an intermediate product named
wet-blue due to the blue-greenish colour of chromium sulphate.
If other tanning products are used, this intermediate product is known as wet-white.
Then, different operations are conducted to improve its aspect and feel and confer it
different textures.
All the process is carried out using a sequence of well-known chemical processes and
mechanical operations that are described below.

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2.2. The industrial processing of the hides and skins.


The tanning process consists in turning a putrescible organic product, fresh animal skin,
into a resistant, durable and very nice-looking material that can be used for the
manufacture of footwear, leathergoods, upholstery, garments, etc.
The hides and skins used are mainly those of cattle, sheep, goat, pig and, in a lesser
amount, reptiles, birds and fish. Leather processing can start little after slaughtering the
animal, but in many cases the hides and skins are stored for a long time, a preservation
treatment being necessary to prevent the growing of microorganisms and the associated
putrefaction.
The curing process is carried out in collection centres, inside or outside abattoirs, to avoid
the putrefaction and loss of quality of the raw material, which requires the time between
collection and preparation to be as brief as possible. For this, when the material cannot be
processed immediately, it must be cured by one of the available methods: refrigeration
(chilling) for short periods, drying (by air or in chamber), salting, dry salting and use of
biocides or products to prevent bacterial attack.
Hides and skins are usually cured in abattoirs and sometimes the gatherers/ wholesalers represerve them, putting hides and skins in pallets, leaving them in cold areas of the
warehouse or refrigerated. The degrees of curing of the skin vary, although currently all the
skins are prepared to be able to be transported to any place in the world, which involves
undergoing a curing treatment that prevents them from deteriorating over long periods of
time and enduring very aggressive transport conditions.

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Once in the tannery, if the skins are to be stored for long time, they are kept in refrigerated
to avoid deterioration and quality loss.
In the industrial process numerous chemical and mechanical operations are carried out,
using different technologies and reactives according to the type of skin that needs to be
processed and the use of the final product, each tannery adapting basic processes to their
needs.
The process to obtain finished leather from fresh hides or skins can be divided into
multiple steps, which in turn can include four stages:
Beamhouse operations,
Tanning,
Post-tanning
Finishing.
The Beamhouse operations for a conventional process are the following: soaking,
dehairing, liming, fleshing and splitting.
The objective of this stage of the process is to clean the skin, remove the adipose tissue and
the hair and adapt the thickness of the skin to the desired value.
The Tanning steps for a conventional process are the following: deliming, bating, pickling
and tanning.

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The objective of this stage of the process is to partially degrade the structure of the skin to
facilitate the penetration and the subsequent fixing of chemicals, to adjust the pH to the
adequate value for tanning, and to stabilise the structure of the collagen by adding tanning
agents (the most common ones are chromium salts or vegetable extracts).
Also, for sheepskin there is usually a degreasing step after pickling. After the tanning step
the skins are now stable and in this state they are called wet-blue, if tanned with
chromium, or wet-white, if another tanning agent was used.
The Post-tanning steps for a conventional process are the following: shaving,
neutralisation, retanning, dyeing, fatliquoring, sammying and drying.
The objective of this stage of the process is to adjust the desired thickness for the skin,
achieving the characteristics of fullness and colour, and to bring the skin to a suitable
moisture content. In this stage the skin is called crust.
The Finishing stage for a conventional process consists in diverse mechanical operations
and/or the application of various products on the surface to give the leather the final texture
and appearance desired.
According to the type of starting hide or skin or the final product to be obtained these
stages can be carried out in a different way. Consequently, many variations to the
conventional process can be found.

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The stages of the tanning process are listed in Table 1:


RAW HIDES OR SKINS
Sorting - Trimming
BEAMHOUSE

Soaking - Liming
Fleshing Pelt splitting
Deliming - Bating
Degreasing

TANNING

Pickling
Tanning
Sammying
Splitting
Shaving
Retanning
Neutralisation

POST-TANNING

Dyeing
Fatliquoring
Sammying
Drying
Staking
Finishing

FINISHING

Mechanical operations
Sorting Packing - Dispatching
FINISHED LEATHER
Table1. Stages of the tanning process.

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2.2.1. Beamhouse operations.


In this stage the initial steps for the processing of skins are carried out from its arrival to
the factory until the tanning is carried out. These are chemical processes and mechanical
operations to remove all unwanted components from the skin, which are not adequate to
obtain the leather, as well as to prepare the structure of collagen for the tanning stage.
Most processes are carried out by immersing the skins in water and adding different
chemicals in adequate containers, which can be:
-

Pits: These are used when the skins must remain static in the presence of liquids. In
these vessels there is no considerable mechanical action, although in some cases the
skins have a slight rocking motion or the liquid is re-circulated using a pump.
Normally they are used in soaking and in vegetable tanning although at present
they are obsolete.

Paddle vats: The skins are immersed in a bath inside a vat fitted with a rotating
paddle wheel. In this case the skins are bent and there is a soft mechanical action
that facilitates the penetration of products.

Drums: In these the mechanical action is much greater than in pits and paddle vats.
It is internally fitted with shelves or pegs to tumble the skins. As the drum rotates,
the skins are hit, bent and subjected to strong tensions and they finally fall, all of
which favours the penetration of chemicals. These are cylindrical vessels that can
be made of wood or stainless steel and are fitted with an airtight door to load and
unload the skins.

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Figure 6. Diagram of paddle vats, drums and mixers used in different stages of the tanning process.

In addition to the traditional drums, there are those called cement mixers or mixers, Yshape drums, etc. The sequence of steps in the beamhouse stage is described below.

Soaking.
The aim is to remove all foreign matter from the skins and to return the skins to the
hydration state they were in when fresh. This operation can be carried out both in drums,
and in paddle vats. Fresh skins do not require soaking, just a wash to remove blood, dirt
and dung.
Cowhides present some problems in soaking, as they are thicker and therefore salt is more
adhered to the fibres, which makes it more difficult for water to penetrate. The water that is
used for soaking must be free from organic matter, at a temperature of around 25-28 C and
free from ferric salts that can produce stains on the skin.
The products added to the soaking bath are:
-

Alkaline products: when the hair is not relevant given that these products break the
hydrogen bridges that exist in collagen molecules and subsequently favour
rehydration.

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Surfactants: the function of which is to decrease the surface tension of water and
thus facilitate water penetration in the skin. They are also able to emulsify the
natural fats of the skin.

Prepared enzyme products: the function of which is to accelerate the soaking of the
skin in a controlled way.

Bactericides: to avoid bacterial growth problems during soaking.

The wastewater of this operation shows high organic matter content and high salinity,
which can cause putrefaction problems with bad odours.

Liming.
The hydrated, cleaned skin, some of the proteins of which having been removed in the
soaking stage, now passes to the liming stage. This operation aims to remove the epidermis
and hair and to loosen the fibrous structure of collagen. To achieve this, it is necessary to
use lime. However, in most hides the desired effect is not achieved, so the bath has to be
reinforced with sulphides. The skins must not be left for an excessive time in this bath,
since otherwise the hair would be attacked by the alkaline bath, which would dissolve hair
and would not be able to be separated in the filter.
The pH of the skins after leaving the bath is of about 12.5. After draining the bath the skins
are subjected again to some washes.
At present, the hair removed in this process is filtered out from wastewater and the lime
liquor is re-circulated. This hair can be used as a fertiliser.

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Figure 7. Facility for hair filtering from the liming bath.

Trimming and Fleshing.


The dehaired skins are brought to the fleshing area. The aim of fleshing is to clean the skin
by removing the adhering fat and tissues on the underside of the skin to facilitate the
penetration of chemicals applied in subsequent stages. This operation is carried out using a
fleshing machine. With this process we obtain the skin ready to be split and a by-product
called tallow that can be marketed.

Figure 8. Cowhide fleshing stage.

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The operation ends with a manual retouch to removes what the machine hasnt removed
properly.

Splitting.
This operation consists in placing the skin on two cylinders and using a knife, separating
horizontally the skin in two layers, one called grain, which will be used do produce leather,
and another one called split, which is the flesh part that can be tanned in the same factory,
to obtain another external layer or can be applied to other uses.

2.2.2. Tanning.
Deliming.
After the splitting process, the grain layer of the skin and the suitable split undergo a
deliming process. Deliming is the process that removes lime and alkaline products from the
inside of the skin. This way the swelling of the limed skin is achieved.
The lime dissolved in interfibrillary liquids and the one deposited on the fibres can be
easily removed using some washes prior to liming. The rest of the lime is removed by
adding buffered solutions of ammonium or organic salts, or carbon dioxide. These agents,
combined with the alkaline products of the limed skin, provide readily water-soluble
products that can be removed by a simple wash. When adding theses acids, the pH has to
be equal to or greater than 7.5, otherwise the skin would undergo undesired acidic
swelling.

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Bating.
The objective of bating is to achieve, using proteolytic enzymes, the de-swelling and
relaxation of the skin, while cleaning up any remaining epidermis, globulins, elastins, hair
and fat, as a secondary effect, making the grain finer and softer grain.
Traditionally, animal dung, mainly dog and chicken dung would have been used as the
source of the enzymes. The digestive tracts of these animals are a rich source of the
relevant enzymes. In more recent times the enzyme was extracted from pancreas of cattle.
This gland produces a series of active substances able to decompose the proteins and fats.
Bating with such extracts, being unhygienic and hard to control, has been displaced by
artificial bates that simplify the exact dosage and correct control of the operation. Some
interesting bates are:
-

Pancreatic enzymes-based bates.

Fungal and bacteria proteases-based bates, their activity being lower than that of
the pancreatic trypsin.

Degreasing.
At this stage the natural fat of the skin is removed to facilitate the penetration of reagents
and to avoid undesired reactions and stains on the skin. This operation is carried out by
direct emulsion of fat in an aqueous medium using surfactants or solvents. When
degreasing using surfactants, the process can be improved using lipolytic enzymes that
degrade the skins fat, which facilitates fat emulsion and solubility to reduce its molecule
size.

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Pickling.
This stage can be considered as a complement of deliming and definitive interruption of
the enzymatic effect of the bating process. Also, after pickling the skin is prepared for the
tanning operation.
The pickling operation is more important with respect to the subsequent tanning operation,
since, if unpickled, the pH of the skin would be high and the salts of the mineral tanning
agent would gain higher basicity. In these pH conditions, over-tanning would affect the
outer layers, which would make it difficult for the tanning agent to diffuse into the internal
layers, thus shrinking the grain layer and precipitating the hydrolyzed mineral agent on it.
In the pickling operation, the skin is treated with acid products that add an important
quantity of acids to the skin and at the same time manage to lower its pH to 3-3.5,
removing totally the skins alkali. The acids that are used are: sulphuric acid, formic acid
and acetic acid.
Neutral salts are also added to the pickling bath before adding acid so as to be able to
prevent the acidic swelling of the collagen. The salt that is normally used is sodium
chloride, which is practically not combined with the skin, so its concentration remains
almost unchanged in the waste bath. In addition to sodium chloride, it is also possible to
use sodium sulphate, sodium formiate and polyphosphates.

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Tanning.
The skin, once adequately prepared in previous processes, is subjected to the tanning
process in which it turns into leather, namely, the skin becomes rot-proof, stabilizing its
protein structure by crosslinking collagen chains with the tanning agent by means of
chemical bonds.
Due to the wide variety of hides and skins, it is easy to assume that there are many
different types of tannages.
All these tannage types can be grouped into:
Tanning with inorganic products or mineral tanning, using chromium salts,
aluminium, iron, titanium, etc.
Vegetable tanning, using natural vegetable extracts.
Tanning with organic products like syntans, aldehydes and quinones,
sulphochlorinated paraffins and multiple resins.

Figure 9. Unloading cowhides from tanning drums.

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Sammying.
Chromium-tanned leather contains between 90-100% of water, but in order for the leather
to be adequately split and shaved, it must not contain more than 50-55%.
Leather sammying is easier if the skin has been previously split. This operation is carried
out making the leather go through two rollers covered with filter nets. The pressure of the
cylinders is transmitted to the leathers fibres and forces them to squeeze the water out,
while the filters absorb the water and drain it to the outside.

2.2.3. Post-tanning.
Shaving.
The leather is passed through a cutting machine subjecting it to a knife that adjusts its final
thickness, generating waste called shavings.

Re-tanning.
In the re-tanning stage, one or various tanning products are added to provide the leather
with certain qualities that are not easily obtained using only one tanning agent.
There are many types of re-tanning agents that can be grouped as follows:
Cationic products such as metallic salts like chromium, aluminium, zirconium,
organo-chromium and organo-aluminium salts.
Anionic products such as vegetable extracts like mimosa, quebracho, chestnut,
tara, sumac, synthetic substitution products, neutral or acidic auxiliary synthetic
products, auxiliary-substitution and vegetable extract-substitution products or
mixed blends.

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Resins:

anionic,

cationic,

amphoteric,

pre-polymerized,

polymerized,

monomeric, urea-based, melamine, dicyandiamide and acrylic resins.


Various re-tanning agents, like silicate, aldehydes, polyphosphates, tanning oils
and fillers of different types.

Neutralisation.
The main purposes of neutralisation are to remove the remains of shavings adhered to the
skin, to remove unfixed tanning agents and to remove part of the initial acidity of the skin
by adding alkaline salts to facilitate the penetration of the dyestuff and fatliquoring
products.

Dyeing.
Leather dyeing includes a group of operations aiming to confer a certain coloration to the
tanned skin, be it superficial, partial or total.
From a chemical point of view, dyes are classified as natural and synthetic; the same way
there are vegetable and synthetic tanning agents. The commercial series of dyes gather
dyes of very different chemical composition, but of similar dyeing behaviour with regard
to fastness, penetration power, matching capability, degree of opacity, method of use, etc.
According to these characteristics dyes are classified as: acid dyes, direct dyes, basic dyes,
metal-complex dyes and reactive dyes.

Fatliquoring.
The fibres of the wet leather move easily since it is a very flexible material; but when the
leather dries it can become hard due to the fact that the fibres have dehydrated and have
grouped forming a compact substance.

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The fatliquoring operation is carried out with the aim to obtain flexible and soft-feeling
leather, which is achieved by the incorporation of water soluble or insoluble fats. These
maintain the fibres separated and lubricate them so that they can glide off each other.
The greater or lesser degree of flexibility of leather depends on the quantity and type of fat
used, which conditions the product that needs to be obtained so that by varying the fat
percentages and the combinations of fatliquoring agents different products are obtained.

Drying.
Through this operation, the moisture content of the skin is reduced to be able to carry out
the finishing operations. Drying can be achieved through different systems:
Drying chamber: is the oldest and most economical system and consists in natural
air drying but, to avoid problems that ambient humidity can produce, it is carried
out inside a chamber equipped with fans and heating batteries until the leather
dries. The air can go in and out completely or be recirculated in a controlled way.
Drying tunnel: consist of a tunnel through which the leathers pass slowly, hanging
from a conveyor, while the hot air circulates perpendicularly to the leathers path.
The drying tunnel can be divided into various sections; each one has its own
temperature and air recirculation. This drying method is mainly used for leather that
must have a very soft touch. If used for vegetable-tanned leather, low temperatures
must be used to avoid a darkening of the leathers colour.
Paste drying: consists in sticking the leathers grain side onto a glass plate. The
glass plates covered with leather circulate slowly and vertically inside a drying
tunnel. At the end of the process the leathers have dried, and they are removed from
the glass, the glasses are washed and wet leather is stuck once again.

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Using this drying system very flat leathers are obtained with high surface yield,
since the leather cannot shrink during drying because it is stuck to the glass. The
grain is very fine.
Secoterm drying: the leather is stuck, on its grain side, on a metallic plate inside
which hot liquid circulates. The leather moisture evaporates on the grain side and
must go through the whole leather thickness to be able to come out so the leather is
less compact than after paste drying. It is usually used for suede and industrial
leathers, being not recommended for vegetable-tanned leather because the
operating temperature is 85-95 C.
Vacuum drying: the leather is spread out on a heated horizontal plate, the machines
airtight hood is placed over the leather and a strong vacuum is applied to quickly
remove moisture from the leather. The drying duration depends on the thickness of
the leather and will take several minutes. This drying method is normally used as
previous drying to obtain a finer grain, the still humid leathers needing to be
hanged for complete drying. Currently, this is the most commonly used method.

Figure 10. Vacumm drying.

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2.2.4. Finishing
The finishing operations include a series of processes aimed to improve the leathers
surface appearance, protect it against chemical and mechanical effects, even out colour and
shine and improve the feel of the leather.
The finish provides resistance to rain, blows, rubbing and any type of external mechanical
stress, and at the same time gives the desired appearance to the leather.
Depending on the appearance of the leathers surface and the desired result, the finish
application will be different, so if the leathers characteristics are to be highlighted, finer
coats will be applied that give it shine and texture but if the leathers imperfections need to
be corrected it is necessary to apply thicker coats. Also, pigments are generally added to
the finish to even out and adjust the colour achieved in the previous stages.
Prior to the application of the finishing products it is necessary to carry out a series of
mechanical operations, some of them optional:
Moisture conditioning: during drying, the leather was left with a very low moisture
content, so it is necessary to carry out a conditioning with the aim to achieve a
relative humidity of 20-22%.
Staking: this operation intends to obtain more flexible leather. This is achieved by
applying a bending and/or stretching mechanical action to the leather which
separates the fibres from each other, which were joined before to confer stiffness.
The softening can be carried out manually or with staking machines. Usually
vibrating pivot machines are used to soften leather for footwear and leather goods,
and roller machines or blades are used for garment leather.

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Final drying: the softened leather still contains certain moisture that must be
removed before continuing the finishing operations. This can be achieved by
nailing the skin on a board and leaving it to air dry, using a vacuum dryer, or a peg
dryer. In this latter, the skins are stretched out using pegs that are placed at the
edges of the leather and then fixed on perforated plates. With this final drying, the
leather moisture is reduced to 12-14%.
Trimming and ironing: in these operations, the creased parts or defects such as peg
marks, holes, etc. are removed to give a better presentation and obtain a completely
flat leather surface so that the application of finish products can be as uniform as
possible.
Buffing: the leather surface must be sanded with emery paper. When it is done on
the grain side, it can serve to obtain nubuck or to smooth surface defects. When it is
done on the flesh side, it serves to remove flesh and improve the final appearance,
and if it is on split, velvety skins are obtained. If done thoroughly, suede can be
obtained. The buffing machine has a metallic cylinder on which an emery paper is
placed. It is applied with two simultaneous movements, one circular on its axis and
the other to and fro.
Dedusting: after buffing, dedusting is necessary to remove the dust from the surface
of the leather. For this, air blast or brushing machines are used. The brushing
machines are of a very simple construction and have two cylinders provided with
brushes which rotate in an opposite direction and between which the leathers are
fed. Air blast machines remove the dust using a powerful jet of air projected
perpendicularly to the leather surface using some special blowers.
Finishing products can be classified in different groups:

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Dyestuffs: are substances that are used to dye undyed or dyed leather in which it is
intended to level, correct or make the colour brighter, without hiding the support
(they are transparent)

Pigments: are coloured, insoluble substances that are used in aqueous or organic
dispersion. Unlike the colourants, pigments hide the supports appearance so they
are used to conceal defects in the leather (scratches, insect damage, etc.)

Binders: are polymers able to form films and retain the rest of the finishing
products in them. They can be of various types:

Protein binders (albumin, casein), which are soluble in water, insensitive


to heat, form hard and discontinuous films and need rubbing or glazing
to provide a glossy look;

Cellulosic binders, which are insoluble in water, giving a lot of shine


and are heat sensitive; and

Thermoplastic binders.

Finishing auxiliaries: are substances that change the characteristics of the binder
used. Some of these products are: wax, plasticizers, matting agents, fillers,
thickeners, etc.

Solvents: are the ones that contain the dissolved finish products. Once applied they
evaporate. These can be organic solvents or water.

With regard to the type of finish, there are multiple possible combinations between the
different components.
Depending on the type of binder used, the most usual finishes are:

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Glazable finishes: they have a smooth pore, are transparent and have an excellent
gloss because protein binders (casein) are used and the leather is subjected to a
glazing operation.

Nitrocellulose finishes: use nitrocellulose as a binder.

Thermoplastic finishes: consist in the application of a thermoplastic emulsion


(acrylic resin or polyurethane) on the leather which results in a very homogeneous
coat able to cover all imperfections.

Furthermore, depending on the amount of pigment contained in the finish, the following
types of finish can be found:
-

Full aniline finish, which is completely transparent without any type of pigment,

Semi-aniline finish, which is a finish with a certain covering power that is achieved
by moderately adding pigments and dyestuffs,

Pigmented finish, which has a great covering effect by adding high quantities of
covering pigments.

Regarding the methods of application, we can distinguish:


-

Spray guns: it is the most commonly used method and with it, it is possible to
achieve a very thin, uniform coat that enhances the leather quality. The system is
basically comprised of a conveyor belt, a spray booth and a drying tunnel.
The spray booth contains the spray guns from which air and pigment are atomised
(< 5 g/foot2 in one row) in a fine mist that is not completely deposited on the leather
and the excess finish must be removed using fans at the exit. The drying tunnel is
made up of different sections, in each of which the air temperature can be regulated.

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Figure 11. Spray gun for the application of finishing products.

Roller coating machine: in this case, the finish is transferred to the leather by
passing between two rollers. The quantity applied in just one coat ranges between
5-50 g/sq.foot. This system has a disadvantage of being very sensitive to the
differences in leather feel and thickness. The machine has a metallic roller and a
blade. The space between the roller and the blade is filled with the finish
preparation. By rotating the engraved roller, it ends up covered with a finish layer
that is later deposited on the leather while being able to impart special effects.

There are other machines that do not apply finishing products but are used in the finishing
section as an intermediate step in the application of the different finish coats, like the
ironing press, the plating press, the glazing machine, the polishing wheel, etc.
In short, after this laborious production process comprising numerous chemical processes
and mechanical operations, tanned hides and skins are obtained, which are suitable for use
in the manufacture of different articles. Also, as in every industrial activity, the process has
a significant impact on the environment, which is summarised in Figure 12:

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INPUTS
Salted raw hide
Water

Chemicals

Energy

OUTPUTS
1 000 kg

20 40 m2

400 600 kg

9 42 GJ

Leather 200 250 kg


Water

20 40 m2
QOD
BOD5
SS
Chrome (III)
Sulphides

230 250 kg
100 kg
150 kg
5 6 kg
10 kg

Solid waste 450 730 kg


Untanned trimmings
20 kg
Untanned fleshings 170 350 kg
Untanned scraps
225 kg
Finishing dust
2 kg
Finishing trimmings
30 kg
Wastewater sludge
500 kg
Air

40 kg

Organic solvents

Figure 12. Mass balance of the tanning process.

However, the integrated pollution prevention and control policies and the new clean
production technologies, which are increasingly known and implemented, reduce this
environmental impact at source, in both the consumption of natural resources and in the
generation of contaminated effluents and waste.

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3. THE OXAZOLIDINE LEATHER TANNING TECHNOLOGY.


This section describes the developed methodology, based on the use of oxazolidine as a
main tanning agent combined with vegetable or synthetic tanning agents and the final
conditioning treatment to remove the free formaldehyde from leather. This technology is
applied in those cases where it is required to tan hides and skins without using mineral
tanning agents, obtaining metal-free leather but with similar appearance, quality, properties
and technical applications.

3.1. Background.
As described in previous sections, the transformation of the animal skin into leather
involves a series of chemical processes and mechanical operations, where a putrescible
material, constituted mainly by proteins, is transformed into a resistant material, suitable
for use in the manufacture of footwear, leathergoods, upholstery, garments, etc.
In the traditional tanning process, used in more than 90% of the leather tanned worldwide,
the stabilization of the protein structure is carried out using trivalent chromium salts that
interact through chemical bonds with the carboxyl groups of the collagen present in the
skin, providing the leather with its stability and resistance properties (see Figure 13).
COLLAGEN-CHROMIUM CROSSLINKING

Figure 13. Collagen-chromium crosslinking.

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This process gives the leather excellent physical, mechanical and chemical properties and a
high stability to manufacturing processes and the passage of time, with shrinkage
temperatures over 100 C. However, in some cases, chromium allergies may arise or even,
under certain conditions, trivalent chromium can oxidize to hexavalent chromium, which is
a carcinogenic compound that can be present in tannery wastewater and solid waste with a
considerable impact on the environment and human health.
There is also recent environmental pressure on tanning industries and a tendency to stricter
environmental requirements for leather, which has led to the implementation of
improvements in the tanning processes to reduce pollution, and the search for innovative
tanning technologies alternative to chromium, thus avoiding at source the problems derived
from its use. In this context, among the existing alternatives, the use of mineral tanning
agents combined with other metallic ions, like aluminium (III), zirconium (IV) or titanium
(IV) has been proposed. However, similar restrictions could be faced with when the market
demands metal-free leather. As a result, organic tanning is an alternative technology that
has been widely studied in recent years.
Organic tanning products, including vegetable tannins, glutaraldehyde, oxazolidine,
phosphonium salts, melamine and methacrylic resins, show different properties and
collagen reaction capacity. Depending on the type of organic radical, the leathers obtained
can reach shrinkage temperatures of up to 80 - 85C which gives them a thermal stability
adequate for the manufacture of footwear, leathergoods, garments, etc. However, in some
cases the leathers can show an unnatural appearance, little fullness and flexibility, as seen
in the case of phosphonium salts and melamine and methacrylic resins, or cause a greater
degree of contamination of the process wastewater, as it happens with vegetable tannins.

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In the case of glutaraldehyde, the leather obtained shows adequate appearance and physical
properties, but has the drawback of being a substance of high risk in its handling and use
for the operators. Also, the leather shows little fastness to light and yellowing problems.
Therefore, there is a need to develop a new tanning technology that provides, using
processes with less environmental impact, quality leathers that comply with the markets
requirements in terms of quality and content in restricted substances. In this sense,
previous research studies carried out by INESCOP have proved that the use of oxazolidine
as a tanning agent, combined with other agents (vegetable or synthetic) allow quality
leathers to be obtained, which can be employed by footwear, upholstery and leathergoods
industries.
The main advantage of oxazolidine tanning is that it allows high performance leather to be
obtained, while managing to avoid the presence of metals both in liquid and solid waste
derived from the tanning process, given that to date there is no record of problems derived
from the use of oxazolidine.
This way, it is possible to considerably reduce the environmental impact generated during
the tanning process and also at the end of the leather lifecycle, either in the form of leather
trimmings when different goods are manufactured or when they are disposed of after use.
Oxazolidines are saturated heterocyclic compounds prepared by reacting primary amino
alcohols with formaldehyde. Monocyclic or bicyclic oxazolidine ring structures are formed
depending on the choice of starting chemicals. It is therefore possible to synthesize a
variety of oxazolidines from different amino alcohols.

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Oxazolidines are highly useful chemicals for a wide variety of applications: corrosion
inhibitors, emulsifiers, diluents or tanning agents, etc. The oxazolidines marketed for use
as tanning agents are water soluble compounds, compatible with most chemicals
commonly used in tanning operations. Table 2 shows the main types of oxazolidines used
as tanning agents:

Type
Name

Oxazolidine A

Oxazolidine E

Oxazolidine T

4,4-Dimethyl-1-oxa-3aza -cyclopentane

5-Ethyl-1-aza3,7-dioxabyciclo
[3,3,0] octane

5-Hydroxymethyl-1aza-3,7-dioxabyciclo
[3,3,0] octane

51200-87-4

7747-35-5

6542-37-6

101.17

143.18

145.18

11.0

11.2

Yellowish liquid

Yellowish liquid

White powder

Molecular structure

CAS number
Molecular weight
(g/mol)
pH
Appearance

Table 2. Properties of the oxazolidines used as tanning agents

The capacity of oxazolidine as a tanning agent is based on the formation of a reaction


intermediate due to two possible mechanisms:
-

the protonation of oxygen of each ring in acid medium, which weakens the C-O
bond, or;

the opening up of oxazolidine rings, by hydrolysis in acid medium, to provide an


intermediate with two N-(hydroxymethyl) groups

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and the subsequent nucleophilic attack of this intermediate species to the amino groups of
collagen (lysine, hydroxylysine, tyrosine and methionine) by means of stable covalent
bonds. (Figure 14).

COLLAGEN-OXAZOLIDINE CROSSLINKING

COLLAGEN-OXAZOLIDINE CROSSLINKING

Figure 14. Collagen-oxazolidine cross-linking

Leather tanned with chromium salts has high stability, determined by a shrinkage
temperature (Tg) over 100 C, while leather tanned with oxazolidine alone reaches a
shrinkage temperature below 75 C. It is therefore necessary to carry out oxazolidine
tanning in combination with synthetic or vegetable tanning agents to achieve higher
shrinkage temperatures and obtain leather of comparable quality to mineral tanned leather.
Synthetic or vegetable re-tanning agents react directly through their hydroxyl groups (-OH)
with the collagens amino acids by means of hydrogen bridges and also indirectly with
oxazolidines reactive groups by means of covalent bonds (see Figure 15).

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Figure 15. Collagen-oxazolidine- retanning agent bond.

This way, the tanning structure stability is improved and an increase between 5-10 C in
the shrinkage temperature is achieved.
Furthermore, aldehyde tanning, including oxazolidine tanning, tends to give positive
results in the free formaldehyde content of the leather, so it is necessary to carry out a final
conditioning treatment of the leather to comply with increasingly strict limitations.
The initial approach to control formaldehyde in oxazolidine-tanned hides is based on the
intensification of the skin washing (closed door to avoid great water consumption) and the
prevention of formaldehyde using formaldehyde-free syntans and natural vegetable
tanning agents, that is, free from dispersants or other products that could contain
formaldehyde.

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Given the strict limitations existing on the market, a conditioning procedure was optimized
to remove free formaldehyde by adding a reducing substance with the capacity to react
with the leathers free formaldehyde, converting it into a soluble product which is removed
by washing without affecting the leathers properties. In the reaction an oxime is formed,
which is a soluble compound that is removed from leather by washing (see Figure 16):

Formaldehyde

Hydroxylamine

Oxime

Figure 16. Formaldehyde reacting with hydroxylamine sulphate to form a soluble oxime.

It was determined that adding 2% of hydroxylamine sulphate in the final wash of the
leather reduces formaldehyde content to less than 50 ppm.
Moreover, the use of a greater percentage of this product reduces the formaldehyde content
even more, obtaining values of less than 15 ppm with 4% of hydroxylamine sulphate,
although this involves an increase in the production costs that must be assessed by the user.
Likewise, it was found that adding this product did not cause the un-tanning of the leather,
given that the shrinkage temperature and the physical properties of the leather were
maintained. Under these operating conditions, it was possible to obtain white, odourless
leather with good physical resistance, with a thin grain and with an adequate smoothness,
softness, fullness and flexibility, showing no significant differences between both
combinations (synthetic or vegetable re-tanning).

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Regarding the oxazolidine ratio used (3 or 5%), no differences were found in the leathers,
neither in their appearance nor in their physical properties, so adding 3% was considered
enough, reaching a Tg of 80 C which also saves costs in the process. With regard to the
selection of a synthetic or vegetable re-tanning agent, in each case it will depend on the
specific use of the leather, choosing synthetic products for lighter colours and with a high
fastness to light, and vegetable re-tanning agents for darker colours and with no light
fastness requirements.
Likewise, the leather obtained meets the quality standards recommended for the
manufacture of different leather articles as well as the criteria established for the European
Ecolabel for Footwear (Commission Decision 2002/231/EC).
With regard to the manufacture of leather for different uses (footwear, leathergoods,
garments, upholstery, etc.) the process to be carried out is quite similar, the most important
being to make an adequate choice of the re-tanning and fatliquoring products for the
requirements for each use, as well as of the intermediate mechanical operations to be
performed (milling, staking, etc.) and the final finish applied to the leathers that gives them
their final appearance.
Moreover, the quality of the leathers tanned with oxazolidine was checked by
manufacturing different leather articles. In all cases, the manufacturing process was carried
out as usual and no differences were observed in the processes or in the final appearance of
the produced articles with regard to those obtained from mineral tanned leather.

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With regard to the environmental impact of this technology, both the effluents and the
waste derived from oxazolidine tanning are metal-free and proved to be more
biodegradable than those derived from chrome tanning.
In short, oxazolidine tanning implies a significant benefit given that it is possible to
dramatically reduce the environmental impact produced during the tanning process and at
the end of the lifecycle of articles made of this type of leather.

3.2. Starting materials: hides and skins, equipment and chemicals.


The tanning methodology was developed using pickled cowhide, sheepskin and pigskin as
starting materials, obtained from raw skins subjected to a standard beamhouse process
made up of the following stages: soaking, dehairing/liming, splitting, deliming, bating and
pickling. These operations were performed as usual, without making any change in the
processes and reagents used.
With regard to the necessary equipment, the chemical operations were conducted in
tanning drums of suitable size for the weight of the hides and skins to be processed and
equipped with the control systems usually found in tanneries:
water dosage and temperature control,
reagents dosage,
drum rotation speed, and
manual or automatic mode operation.

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The mechanical operations for shaving, staking, milling, etc. were carried out as usual,
using normal tannery equipment. In the case of the shaving machine, if the machine is to
be used in both processes (tanning with or without metals), the skin shavings were
adequately separated (with or without metals) to be suitably managed. Likewise, in
trimming operations, both types of tanned leather trimmings were separated for their
separate management.
Furthermore, given the limit on the metal content of metal-free leather (<0.1%), in the
sammying operation precaution should be taken to carry out an adequate wash of the
sammying machines felt mat to avoid the contamination from leathers with metals, if the
machine is used in both processes (metal and metal-free tannage). Finally, it is very
important to control and adjust the operating temperature in the drying chambers and
tunnels and, above all, in the vacuum drying, due to the lower shrinkage temperature of the
oxazolidine-tanned leather.
With regard to chemicals, in the different stages generic products were used, like sodium
formiate and bicarbonate, formic acid, etc., together with commercial products selected for
their chemical composition for this specific application. It is important to adequately select
the substitutive synthetic re-tanning products with a very low content in formaldehyde to
minimize its content in processed leathers.
Likewise, in the dyestuff selection, those which contain azo groups (-N=N-) must be
avoided since they may form aromatic aryl amines of demonstrated carcinogenic potential,
as well as metal complex dyes to avoid the metal contamination from leather waste
(shavings and trimmings) in wastewater and treatment sludge.

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Table 3 shows the products used in the process stages:

STAGE

CHEMICALS
Sodium chloride

TANNING

Pre-fatliquoring: combination of phosphoric esters and


synthetic fats
Oxazolidine: type E

Substitutive synthetic re-tanning agent:


condensation product of sulphone and aromatic
sulfphonic acid, with low formaldehyde content.
Vegetable reagent: mix of tara, quebracho and mimosa.
NEUTRALISATION

Sodium formiate
Sodium bicarbonate

DYEING /
FATLIQUORING

Dyestuffs
Fatliquoring: sulphonated triolein
Fatliquoring: waterproofing agent

Reagent with low formaldehyde content


Formic acid
CONDITIONING

Sequestering agent

AUXILIARIES

Indicators: bromcresol green

Table 3. Main chemicals used in the oxazolidine tanning process

The safety data sheets of the chemicals used with their most relevant data are included in
Annex I.

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3.3. Technical procedure.


The tanning procedure developed allows metal-free leathers to be obtained with similar
appearance, qualities, properties and technical application possibilities.
This technology is based on a group of chemical and mechanical operations intended to
achieve stabilization of the protein structure of the skin by means of the reaction of
collagen proteins with oxazolidine and the subsequent treatments to improve their physical
and chemical properties.
This procedure comprises the following stages:
- tanning with oxazolidine
- re-tanning using synthetic or vegetable products
- neutralisation using sodium salts
- dyeing and fatliquoring
- leather conditioning to remove free formaldehyde
The oxazolidine tanning process, which is described in detail below, is carried out without
substantial modifications to the conventional processes used in traditional tanning with
trivalent chromium salts.
Moreover, the described process is adequate for pickled cowhide, sheepskin, and pigskin,
no important differences being found in tanning these three types of hides and skins with
oxazolidine.

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(1) Oxazolidine tanning.


The oxazolidine tanning procedure starts by soaking the skins in a saline pickling bath.1
This bath is made of 70% water at 25 C and 7% sodium chloride (by pelt weight), letting
the drum rotate at slow speed (4-6 rpm) for 10 min in order for salt to dissolve. Next, the
salinity of the bath is checked (6-7 Baum) using a densimeter.
If this value is not achieved, the parameters of the bath are readjusted by adding salt
(successive doses of 0.2%), the drum is left to rotate at a slow speed (4-6 rpm) for 10 min
and the salinity is checked again until reaching the values indicated.
Once the pickled baths salinity is adjusted, the skins are loaded in the drum and they are
left to rotate for 15 min for them to get re-moisturized, checking the pH of the bath that
must have a value of 3.
Otherwise, the parameters of the bath are readjusted by adding formic acid (successive
doses of 0.2%) and the drum is left to rotate at a slow speed (4-6 rpm) for 10 min, checking
again the pH until reaching the indicated value.
Then, a pre-fatliquoring is done to lubricate the fibres, facilitate the penetration of the
products and improve the feel of the skins.

This stage can be avoided if the process is carried out after beamhouse operations and the skins are already
in the pickling bath.

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This process is carried out adding 5% (by pelt weight) of a commercial product
combination of phosphoric esters and synthetic fats, leaving them to rotate in the drum for
30 min at a slow speed (4-6 rpm).
After the pre-fatliquoring, a tanning agent is added, in this case 3% (by pelt weight) of
oxazolidine, and the skins are left to rotate for 90 min at a speed of 6-8 rpm and for the
whole night with the drum working automatically (5 minutes in motion, with the previous
speed and 55 minutes stopped).
Once the reaction of oxazolidine with the skin collagen has finished, the pH of the leather
is checked, which must have a value of 4.5-5.0, and the penetration of oxazolidine is also
checked by cutting a small sample and applying the indicator (bromcresol green) to the
cross section.
If the oxazolidine has penetrated through the whole cross section of the skin, the cross
section will show a homogeneous greenish coloration, while if it has not penetrated the
whole cross section there will be a lighter shade at the centre of the cross section.
In this case, the rotation of the drum will be extended for 60 min and the penetration will
be checked again, repeating this operation as much as needed2. Table 4 shows the formula
used:

If the tanning has been carried out during the whole night with the drum turning automatically, the
penetration should be complete and it would then not necessary to extend the tanning stage.

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PROCESS/PRODUCTS

%
pelt
weight

T
(C)

Time
(min)

pH

Remarks

TANNING
Soaking/pickling bath
Water
NaCl

70
7

25
10
Add the skins
15

Check 8 Be 3
Check pH<34

Pre-fatliquoring
Pre-fatliquoring agent

30

90

Tanning
Oxazolidine (100%)

Automatic over night


Check pH (4.5-5.0) and cross section
Table 4. Formulation of oxazolidine tanning stage.

(2) Retanning.
At this stage, according to the type of re-tannage selected (synthetic or vegetable), the
following products are added to the same oxazolidine tanning bath:

3
4

If it not reached, successive doses of 0.20% sodium chloride are added (although it is not usually necessary)
If the pH>3, successive doses of 0.20% formic acid are added (although it is not usually necessary)

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15% (by pelt weight) of substitution synthetic retanning agent: sulphone


condensation product and aromatic sulphonic acid or

15% (by pelt weight) of vegetable retanning agent: mix of tara, quebracho and
mimosa.

The addition is carried out in three successive doses of 5% (by pelt weight), separated by a
60 min interval, with the drum rotating at a speed of 8-10 rpm.
Once the reaction of synthetic and vegetable retanning agents with oxazolidine and with
the skin collagen has finished, the pH of the leather is checked, which must have a value in
the range of 5.0-5.5 and the penetration of the retanning products is also checked by
cutting a small leather sample and applying the indicator (bromcresol green) to the cross
section.
If the retanning agents have penetrated through the whole cross section of the leather, the
cross section will show a homogeneous green-bluish coloration, while if it has not
penetrated the whole cross section, the centre of the cross section will have a lighter shade.
In this case, the rotation of the drum will be extended for 60 min and the penetration will
be checked again, repeating this operation as much as needed.5
Finally, the bath is drained and the drum unloaded, leaving the leathers to rest on a horse
for 12 hours to stabilize the tanning bonds formed.

In general, the products used, both synthetic and vegetable, have a good penetration in the skin so it is not
necessary to extend the retanning stage.

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The mechanical operations required for the article to be processed are then carried out,
which mainly consist of sammying and shaving the leathers to give them the desired
thickness. Table 5 shows the formula used:

PROCESS/PRODUCTS

%
pelt
weight

T
(C)

Time
(min)

pH

Remarks

RETANNING
Synthetic/vegetable tanning

60

Synthetic/vegetable tanning

60

Synthetic/vegetable tanning

60

Check pH6

Check pH (5.0 5.5) and cross section


Drain and remove leathers
Leathers are left to rest for 12 hours
Sammying and shaving
Table 5. Retanning formulation.

(3) Neutralisation.
The leathers shaved to the desired thickness are loaded in the drum for neutralisation. The
alkaline nature of oxazolidine simplifies the neutralisation stage, reaching the final tanning
pH with a lower addition of basifying agent. In these conditions, the bath is formulated
with 200% water at 30 C, 1% sodium formiate and 0.5% sodium bicarbonate (by shaved
leather weight), and the drum is rotated at 10 rpm.

If the pH>3, successive doses of 0.20% formic acid are added (although it is not usually necessary)

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After 40 min, the pH of the leather is checked, which must have a value in the range of 5.56.0 and the penetration of the neutralising products is also checked by cutting a small
leather sample and applying the indicator (bromcresol green) to the cross section.
If the neutralizing agents have penetrated through the whole cross section of the leather,
the cross section will show a homogeneous bluish coloration, while if it has not penetrated
the whole cross section; the centre of the cross section will have a lighter shade.
In this case, successive additions of 0.2% sodium chloride will be made to reach this pH
value, extending drum rotation for 30 min and repeating this operation as much as needed.7
Once the desired pH has been reached, the leathers are gently washed to remove the excess
neutralising reagents and the bath is drained. Table 6 shows the formula used:

%
shaved
weight

T
(C)

Water

200

30

Sodium formiate

1.0

Sodium bicarbonate

0.5

PROCESS/PRODUCTS

Time
(min.)

pH

Remarks

NEUTRALISATION

40

Check pH8

Check pH (5.5 6.0) and cross section


Drain bath and wash leathers
Table 6. Neutralisation stage formulation.
7

In general, leather neutralisation is achieved with an initial dose of formiate and bicarbonate so it is not
necessary to extend the neutralization stage.
8
If the pH >3, successive doses of 0.20% formic acid are added (although it is usually not necessary)

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(4) Dyeing/fatliquoring.
Once the leathers have been neutralized, washed and the bath has been drained, the dyeing
operation is carried out, if desired. For this, the desired dyestuff is added on the wet
leathers (dry dyeing, without water, to improve the dyestuff penetration crossing through
the whole section of the leather) on a ratio (by shaved leather weight) of 3% for sheep and
pigskin and 5% for cowhide (for its greater thickness), and the drum is rotated for 30 min
at 10 rpm so that the colour can penetrate.
Next, the colour penetration is checked by cutting a small leather sample. If the dyestuff
has penetrated through the whole cross section of the leather, the cross section will show a
homogeneous coloration, while if it has not penetrated the whole cross section; the centre
of the cross section will show a lighter shade.
In this case, successive additions of 0.5% dyestuff are made in order for the dyestuff to
penetrate the leather, extending the rotation of the drum for 20 min and repeating this
operation as much as needed.
Once the colour has penetrated the leather, the fatliquoring is carried out; in this case, it is
done in two successive doses. The fatliquoring bath is formulated (by shaved leather
weight) with 100% hot water (40 C), 2% sulphonated triolein and 4% waterproofing
fatliquor, and the leathers are tumbled at 12-15 rpm for 30 min.
Next, a similar bath is prepared; it is added to the drum and left to rotate at 12-15 rpm for
30 min.

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After this time, in which the fatliquor has penetrated the leather lubricating the fibres, 5%
re-tanning agent (by shaved leather weight) is added to the bath to improve the appearance
and properties of the leather, such as its fullness, feel, compactness, physical resistance,
improvement on the retention capacity of the print, of the buffing, etc.
The type of final re-tanning agent used will depend on the appearance and intended use for
which each leather is processed, but it must have a low formaldehyde content. The retanning agent is left to act for 30 min with the drum rotating at 12-15 rpm.
Finally, 2% formic acid (dilution 1:10) is added (by shaved leather weight and on two
consecutive doses separated by 15 minutes), which causes a decrease in the leather pH (<3)
and a change in the polarity of the leather that favours the fixation of the dyestuff and
fatliquoring products.
The formic acid is left to act for 20-30 min, with the drum rotating at 12-15 rpm.
Once the dyestuff and fatliquor are fixed, the drum is drained and the leathers are washed
to remove the excess unfixed reagents, using 200% water (by shaved leather weight), in a
closed-door drum for 5 min and then the bath is drained.
Table 7 shows the formula used:

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PROCESS/PRODUCTS

%
shaved
weight

T
(C)

Time
(min.)

pH

Remarks

<3

Check pH and Tg

DYEING/FATLIQUORING
Dyeing
Dyestuff

3-5

30
Check cross section

Fatliquoring
Water
Fatliquor (sulphonated
triolein)
Waterproofing fatliquor
Water
Fatliquor (sulphonated
triolein)
Waterproofing fatliquor
Synthetic/vegetable tanning
agent
Formic acid (1:10 v/v)
Formic acid (1:10 v/v)

100

40

2
4
100

30
40

2
4

30

30

1
1

15
15
Check pH <3

Drain bath and wash leathers


Table 7. Dyeing/fatliquoring stage formulation

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(5) Final conditioning.


The conditioning treatment of the drained and washed leathers is carried out to remove the
free formaldehyde. For this, the formaldehyde sequestering bath is added, which is
formulated with 100% water at 35 C and 2% hydroxylamine sulphate (by shaved leather
weight), leaving it to act for 60 min.
Finally the bath is drained and the leathers are unloaded, leaving them to rest for their
subsequent sammying, drying, mechanical operations and finishing in accordance with
their desired final appearance. Table 8 shows the formula used:

PROCESS/PRODUCTS

%
shaved
weight

T
(C)

Time
(min)

pH

Remarks

FINAL CONDITIONING
Water
Sequestering agent

100
45
2
60
Check Tg
Drain and remove leathers
Rest
Sammying, drying and mechanical operations
Finishing operations
Table 8. Final conditioning stage formulation.

Table 9 shows the overall formulation used for the complete monitoring of the process:

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PROCESS/PRODUCTS

%
pelt
weight

T
(C)

Time
(min.)

pH

Remarks

TANNING
Soaking/pickling bath
Water
NaCl

70
7

25
10
Add the skins
15

Check 8 Be 9
Check pH<310

Pre-fatliquoring
Pre-fatliquoring agent

30

90

Tanning
Oxazolidine(100%)

Automatic over night


Check pH (4.5-5.0) and cross section
RETANNING
Retanning
Synthetic/vegetable tanning
agent
Synthetic/vegetable tanning
agent
Synthetic/vegetable tanning
agent

60

60

60

Check pH11

Check pH (5.0 5.5) and cross section


Drain and remove leathers
Leathers are left to rest for 12 hours
Sammying and shaving
9

If this salinity is not reached, successive doses of 0.20% sodium chloride are added (although it is usually
not necessary)
10
If the pH>3, successive doses of 0.20% formic acid are added (although it is usually not necessary)
11
If the pH>3, successive doses of 0.20% formic acid are added (although it is usually not necessary)

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%
shaved
weight

PROCESS/PRODUCTS

T
(C)

Time
(min.)

pH

Remarks

NEUTRALISATION
Neutralisation
Sodium formiate

1,0

Sodium bicarbonate

0,5

Check pH12

40

Check pH (5.5 6.0) and cross section


Drain bath and wash leathers
DYEING/FATLIQUORING
Dyeing
Dyestuff

3-5

30
Check cross section

Fatliquoring
Water
Fatliquor(sulphonated
triolein)
Waterproofing fatliquor
Water
Fatliquor (sulphonated
triolein)
Waterproofing fatliquor
Synthetic/vegetable tanning
agent
Formic acid (1:10 v/v)
Formic acid (1:10 v/v)

100

40

2
4
100

30
40

2
4

30

30

1
1

15
15
Check pH <3

<3

Check pH and Tg

Drain bath and wash leathers

12

If the pH>3, successive doses of 0.20% formic acid are added (although it is usually not necessary)

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PROCESS/PRODUCTS

%
shaved
weight

T
(C)

Time
(min.)

pH

Remarks

FINAL CONDITIONING
Final conditioning
Water
Sequestering agent

100
45
2
60
Check Tg
Drain and remove leathers
Rest
Sammying, drying and mechanical operations
Finishing operations

Table 9. Overall formulation of the oxazolidine-tanning process.

In these operating conditions, white, odourless leathers are obtained, with a thin grain and
with similar properties to leathers tanned with chromium salts. However, these leathers are
metal-free and have a lower impact on the environment due to their higher degree of
biodegradability.
3.4. Technical validation of oxazolidine-tanning technology.
The results derived from the development of oxazolidine tanning technology, in
combination with synthetic or vegetable tanning agents, showed that the obtained leather
had good physical strength and adequate appearance and feel for the manufacture of
different articles. Moreover, no significant differences between the two tanning agent
combinations were detected.

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Therefore, the selection of a synthetic or vegetable tanning agent will depend on each
individual case, choosing syntans for lighter colours and high light-fastness, while
vegetable tanning agents can be used for darker colours with no light-fastness requirement,
as they are cheaper. Regarding the ratio of oxazolidine used, it was considered that 3% was
the optimum dose, which favours the financial viability of this technology.
The tanning degree of leather was assessed through the determination of the Shrinkage
Temperature (Tg), giving values between 75 and 82 C, which were acceptable for the
production of most products (footwear, handbags, jackets, etc.).
The technical validation of oxazolidine tanning technology was first assessed according to
standardised quality control tests to check the compliance with recommended values and
the suitability of leather for footwear manufacturing. Table 10 shows the results obtained
in the different tests carried out, compared with recommended values.

PARAMETERS
Thickness
(mm)
Tear strength
(N)
Tensile strength
(N/mm2)
Elongation at break
(%)
Grain burst
(mm)
Shrinkage temperature
(C)

CATTLE
HIDES

SHEEP
SKINS

RECOMMENDED
VALUES

ISO 2589:2002

1.9

1.5

> 1.1

ISO 3377-2:2002

187

69

> 50

ISO 3376:2002

20

16

> 15

ISO 3376:2002

103.5

76

> 40

ISO 3379:1976

9.3

9.9

>8

ISO 3380:2002

80

77

> 70

STANDARD

Table 10. Physical characterisation of oxazolidine-tanned cattle hides and sheepskins

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Likewise, some footwear styles (even incorporating vulcanised soles) and upholstery,
leathergoods and apparel products were manufactured and no differences were observed in
leather processing or in the final appearance of the articles produced, as shown in Figures
17, 18 and 19.

Figure 17. Childrens footwear (DECHICS), mens penny loafers (MOSEIPE) and occupational
footwear - clogs (DIAN) made from oxazolidine tanned leather.

Figure 18. Womens footwear (TPSP), casual and vulcanised footwear (CALZADOS CANS
GARCA, S.L.) made from oxazolidine tanned leather.

Figure 19. Upholstery, leathergoods and apparel products made from oxazolidine tanned leather.

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Furthermore, oxazolidine-tanned leather meets the requirements relative to the limit


content in hazardous substances according to the criteria of the European Ecolabel for
footwear set forth in the Commission Decision 2002/231/EC:

PARAMETERS

STANDARD

LIMITED VALUES (*)

Chromium (VI)

ISO 17075:2007

10 ppm

Formaldehyde

ISO 17226-1:2008

150 ppm

Pentachlorophenol

ISO 17070:2006

Not detected (*)

Lead (Pb)

ISO 17072-2:2011

Not detected (*)

Cadmiun (Cd)

ISO 17072-2:2011

Not detected (*)

Arsenic (As)

ISO 17072-2:2011

Not detected (*)

Aromatic amines
(derived from azo-colorants)

ISO 17234-1:2010

Not detected (*)

Not detected (*): below the detection limit

Table 11. Chemical characterisation of oxazolidine-tanned leather

Regarding the environmental impact of this technology, the characterisation of the


effluents from oxazolidine tanning processes showed similar values to those obtained in
chrome tanning. However, oxazolidine tanning effluents are chrome-free and consequently
the oxidation of trivalent chromium to its hexavalent state is avoided and the metal-free
sludge derived from wastewater treatment is more likely to be reused, e.g. for agriculture.
Furthermore, the respirometry tests conducted on activated sludge proved that oxazolidine
tanning effluents are more biodegradable, which reduces the environmental impact of the
process and a priori implies a higher feasibility of the biological treatment of wastewater.

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Finally, biodegradability tests were performed on leather, which allowed the different
tanning technologies to be compared with regard to the environmental impact of their
resulting waste. Since there is currently no test method or specific standard for the
determination of the biodegradability of leather, we employed a method jointly designed
and optimised by INESCOP and the University Miguel Hernandez (Elche-Spain).
In the tests carried out, the biodegradation of chrome-tanned leather and oxazolidine Etanned leather was compared with a pure collagen standard. As expected, pure collagen,
used as a test standard, showed a biodegradation rate of 85% after 700 hours, while
chrome-tanned leather showed 12% and oxazolidine-tanned leather 55%. This implies an
increase by 43% (see Figure 20).

85%

55%

12%

Figure 20. Graph comparing the biodegradability rate of collagen, oxazolidine-tanned leather and
chrome-tanned leather.

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These results showed a significant improvement in the biodegradation of oxazolidine


tanned leather waste with regard to chrome tanned leather, and prove the use of
oxazolidine as an alternative to chromium salts in the tanning process, since the generated
waste is more biodegradable, thus reducing the environmental impact of the process in
terms of waste generated
Oxazolidine tanning allows high performance leather to be obtained, while it avoids metal
(chrome) presence in liquid and solid waste derived from the tanning process. To date
there is no record of problems derived from the use of oxazolidine.
This way, it is possible to dramatically reduce the environmental impact generated during
the tanning process and also at the end of the leather lifecycle, either in the form of leather
trimmings when different goods are manufactured or when they are disposed of after use.

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3.5. Basic safety and health guidelines for the oxazolidine-tanning process.
Tanning industries constitute an industrial sector with very specific characteristics, mainly
with regard to the great variety of products and materials used, the amount of workforce
needed and the diversity of machinery and of equipment used in the different stages.
The scale and typology of tanning facilities are very varied due to:
-

the processed raw material: raw hides and skins, tanned hides and skins, or crust
leather,

the processes carried out: complete process, starting from tanned leather or only
finishing operations,

the formulation used: mineral, vegetable, organic or combination tanning, etc.

the industrys automation degree; automatic dosage, bath recirculation, etc.

In this context, there is a wide range of hazard circumstances due to the different stages
carried out both in the traditional chrome tanning process and in the oxazolidine tanning
process described in this Manual, given that both processes are very similar.
Below there is a list of the risks that most frequently occur in tanning industries, briefly
indicating the stages where the risk is most likely to appear, its possible consequences and
the prevention measures to take in the form of recommendations.

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Chemical hazards.
Contact with chemical substances is made in the different stages of the process by handling
or using chemicals, and contact can be made in different ways:
-

inhalation in the form of substances present in the air (gases, dust, vapours, fog and
smokes)

ingestion, when the workers are eating, drinking or smoking in the work area
without washing their contaminated hands

by skin contact or absorption, normally through the pores or cuts/wounds in hands,


arms, or unprotected body areas

Although not all chemicals are necessarily dangerous for human health, we must take into
account that the inherent source of danger can be both the product itself and the containers
used for the storage and transport of such products.
Some of the especially problematic substances are: sodium sulphide; chromium salts,
which can cause contact dermatitis; aldehyde derivatives, which are irritating and
sensitizing; synthetic resins, like urea-formol or urea-acrylics, which are sensitizing; acids
and alkalis, which are corrosive, etc. The consequences of contact with toxic substances
depend on different factors; the toxicity of the substance, its ease to penetrate the skin,
organs or systems which it affects, the amount of substance or the affected skin surface,
and time of exposure.The result of the contact can cause temporary effects, like fainting,
headache, eye, skin or lung irritation, allergic reactions, poisoning of the liver, kidney or
nervous system, or fainting due to the lack of oxygen. It can also cause long-term illnesses
like occupational asthma, ulcers, bronchitis or genetic defects and, in some specific cases,
even instant death.

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It is therefore important to know:


-

the characteristics of the chemicals used mainly with regard to their toxicity,
corrosiveness, irritability, etc. according to the information provided in the
products safety data sheets and the indications on the labels of their containers

collective and personal protection equipment that must be used to avoid contact
with chemicals

In addition to the adverse effect on the human body, chemicals can be the source and cause
of fire, corrosion and damage to electric installations and structures, and can have
detrimental effects on the surrounding environment when they are released in an
uncontrolled way.
For the handling and storage of chemicals in the tannery, the following recommendations
shall be taken into consideration:
-

use adequately labelled products, including information such as trade name,


product identification, suppliers details, hazard symbols, type of risk, safety
precautions, etc.

know the products used and refer to the safety data sheets, which shall include:

identification of the product and of the company

information about the ingredients/ composition of the product

classification of the possible risks and first aid

fire-fighting measures and measures in the case of accidental spillage

recommendations for storage, handling and disposal

information about how to control exposure and what measures and


personal protective equipment shall be used

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where possible, avoid dangerous products in the workplace, for example, replace
solvent-based products with water-based ones in the degreasing and finishing
operations, partially replace sodium sulphide with enzymes in liming, replace
metal-complex dyestuffs with other less toxic ones, etc.

limit the possibilities of exposure to hazardous products:

dosing or transferring products to fully or partly closed systems

correctly closing the products containers,

using pumps for the transfer of hazardous products,

reducing the number of workers in contact with hazardous products and


limiting the access to the work area where these products are found,

controlling the unloading of paddle vat and drum baths with pipes
connected to the drain,

reducing the concentration of pollutants in the surrounding air, using


general ventilation and natural airflow,

using low emission equipment, like roller machines instead of spraying


units, whenever possible,

using extraction systems in dry shaving machines, wheeling and buffing


machines, dedusting machines and spraying booths,

ensuring adequate hygiene practice, like regular cleaning of work area,


floors, walls and machines, removal of waste and adoption of safe
practice in storage and handling.

prevent the exposure to hazardous chemicals using protective equipment:

ensuring the availability of gloves, boots and aprons for each worker

using respirators and gloves in the handling of liquid and powdered


chemicals

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have suitable storage areas:

separate from production areas, occupied buildings, other warehouses,


work areas or areas with potential ignition sources

with flat, uniform and waterproof floors, to prevent soil contamination,


with emergency drainage connected to the wastewater treatment plant

equipped with emergency services (shower and eyewash), electrical


installation, fire-extinguishing means and suitable spill and leak
containment buckets

with restricted access to authorized and qualified staff

grouping and storing the different products according to their


compatibility, creating designated areas for each group

ensuring sufficient room for movement of staff and materials

storing the solvents and inflammable products in a separate warehouse

never mixing products randomly and indiscriminately

avoiding the inhalation of smokes, dust and vapours, using suitable


respirators and masks

avoiding skin contact with chemicals, using safety goggles and other
protective equipment specified in the applicable safety data sheet

maximising hygiene measures taken by operators before and after the


use of chemicals

informing of possible leakages or spillages

properly managing chemicals containers

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Same-level or elevated falls


This type of risk can occur in usual work activities and while walking along corridors,
entrance doors, etc. due to the floors state, fixed obstacles, objects that get in the way, etc.
In the tanning sector this risk is particularly important due to the use in some processes
(beamhouse operations, tanning, dyeing) of great quantities of water that, coupled with
skin scraps and other by-products, make the floor quite slippery.
Furthermore, falls into pits and vats are also frequent, if not adequately protected, as well
as walking up and down fixed or service stairs to move between levels (platforms,
overhead compartments, etc.), using ladders to access elevated places, etc. The
consequences of this risk are injuries, bruises, scratches, sprains, dislocations, fractures,
etc. depending on the type of fall.
For the prevention of falls during tanning operations the following recommendations shall
be taken into account
-

keep passageways and exit areas clearly marked and free from obstacles respecting
their widths to ease, as far as possible, the simultaneous passage of people and load
transport vehicles and prevent blows on objects and falls, keeping the necessary
safety distance

signpost workplace areas in which there is a risk of falling, because of uneven and
irregular floors, wet floors, etc. and install handrails, doorstops, etc.

rapidly remove spillages, leakages, oil and grease stains, as well as waste and
residues

install sufficient lighting in busy areas

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Heavy falling objects


This type of risk is mainly produced in the raw material reception, material storage and
preparation in intermediate processes, and storage and dispatching of finished products,
due to poor piling up, packaging defects and/or improper way of fastening them, exceeding
the capacity both in volume or weight of the vehicle, driving at excessive speed, poor
fastening of loads, etc. The consequences of this risk are injuries, bruises, crushing, etc.,
due to the impact of chemical product containers, leather batches, etc. on the upper and
lower limbs, which will be more or less severe depending on the weight of the object.
To prevent falls of heavy objects the following recommendations shall be taken into
account
-

limit the pile height (boxes, equipment, etc.).

securing materials in warehouses so as to prevent slipping

secure well the loads during transport

use mechanical means in the handling of heavy and/or bulky objects.

define and mark the area of influence of suspended load and avoid staying under it

Collision with moving objects


This risk is usually related to the use in tanneries of forklifts or other loading and transport
vehicles and contact with moving parts of the machines and motor-driven tools. The most
probable consequences are wounds, cuts, fractures, etc., due to the impact of the different
parts of the forklift with the operators body, mainly the lower limbs (legs and feet).
To prevent collision with moving objects the following recommendations shall be taken
into account:

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regarding transport means:

always drive with care, especially at intersections and points without


good visibility and in the manoeuvres

look in the forward direction and keep eyes on the route, avoiding abrupt
stops and starts and fast turns

avoid blocking the visibility with the load

after use, place the transport means in their designated area without
leaving them in walkways or any other place where they can be
dangerous

keep traffic and exit areas clearly marked and free from obstacles
respecting their widths to ease, as far as possible, the simultaneous
passage of people and load transport equipment and prevent blows on
objects and falls, keeping the necessary safety distance

on purchasing work equipment, compliance with the minimum legally defined


requirements for safety and health in machines and components (RD 1435/1992
modified by RD 56/1995) shall be ensured

on operating machines and motor-driven tools with moving elements:

keep protection devices or guards in place, which prevent direct access


to operative areas of the moving parts

do not stay in the operation angle of moving parts and avoid contact
with them

servicing, maintenance, repair, and cleaning shall be performed on


turned-off, disconnected equipment

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Blows and cuts by objects or tools


Most blows and cuts occur during raw or finished material handling due to the use of
machinery and during machinery maintenance operations.
In the tanning process, the leathers are subjected to different manual trimming operations
using knives or scissors, with the risk of cutting by direct contact with the tool.
Furthermore, the majority of machinery used in tanneries has as main element a cylinder
fitted with blades (fleshing, splitting, shaving, shearing machines, etc.) which can be
accessed in maintenance operations or accidentally while working with them.
Finally, the generalised used of rotating drums for tanning and dyeing adds the risk of
blows and trapping. As a consequence of these risks, there are frequent injuries such as
cuts, tears, pricks, wounds, bruises, scratches, etc.
To prevent blows and cuts by objects or tools, the following recommendation shall be
taken into account:
-

the machinery shall have the relevant declaration of conformity and the CE mark,
as a guarantee from the manufacturer of compliance with the requirements of
harmonized European standards and R.D. 1435/92 on machine safety.

use the appropriate tool in each operation.

before using a tool, check that it is in a good condition, without debris, with
isolation and handles in place, etc.

keep tools clean and tidy in a safe place.

use suitable protection for each tool (gloves, goggles, etc.)

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Projection of fragments or particles


In some of the tannery machines there can be a risk of tool particle or fragment projection,
like in the band saw, polishing wheel, etc. that can cause cuts, tears or injuries by particle
projection to the face or eyes.

To prevent particle or fragment projection it is

recommended to install guards or protective devices in the machines that limit the
projection of fragments or particles.

Trapping by or between objects


This risk can apply to machines that have moving parts at the reach of operators. In most of
the tannery machinery there is this risk of trapping, given that, in the majority of operations
the leather has to be directly held and brought to the operation area manually. In cleaning
and maintenance work it may be caused by transmission parts like belts, gears, etc.
Trapping can cause wounds, cuts, tears, multiple injuries, etc.
The machines which have a greater risk of trapping are:
-

in the beamhouse process: fleshing, splitting, shearing machines, etc.

in operations prior to finishing: sammying, shaving, buffing, setting, shearing,


dedusting machines, etc.

in the finishing process: ironing, polishing, and splitting machines.

To prevent trapping, the following recommendations shall be taken into account:


-

do not remove guards or protective devices that prevent direct access to moving
parts of the machines,

do not stay in the operating angle of moving parts of the equipment and avoid
contact with them,

turn off and disconnect machinery during servicing or maintenance.

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Overexertion
In material handling, mainly in unloading or storage, overexertion may occur due to the
weight or volume of the materials handled, or to the need to adopt awkward or forced
posture with a risk of back injuries. As a consequence of this overexertion, muscle and
bone injuries can occur, which, if the situation is not corrected, can become chronic.
To prevent these injuries, the following recommendations shall be considered:
-

avoid awkward postures when handling loads.

decrease the weight of the loads

whenever possible, use mechanical aids to handle materials and, if necessary, loads
should be handled by more than one person.

Thermal contact.
The risk of thermal contact in tanneries occurs mainly in drying and finishing processes by
contact with hot presses and cylinders that can cause more or less severe burns, caused by
contact with hot parts of the machinery.
To prevent injuries it is recommended to maximise the precautions while operating
equipment with hot surfaces, like dryers, ironing presses, boilers and hot water pipes, etc.

Direct or indirect electrical contact.


The risk of direct or indirect contact is common to all types of operations and, especially,
to the ones conducted with voltage, by incompliance of the basic rules of electrical safety
or by faulty electrical devices.

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Depending on the intensity of voltage there may be cramps, contractions or tetanisation of


the muscles, respiratory arrest, asphyxia, erratically heart beating, ventricular fibrillation,
etc. even causing the death of the victim under certain negative circumstances.
To avoid these injuries it is recommended to establish suitable maintenance protocols for
the facilities and electric appliances, working with the necessary PPE and the most suitable
safety material in each case.

Fire.
In tanneries the fire risk level is considered of medium degree. The high calorific power of
the finished product (fur, leather, buffing dust, etc.) is counteracted by a low activation
coefficient of these materials. Depending on the type of fire, there can be consequences for
people such as asphyxia, smoke intoxication, multiple injuries, fire burns, etc.
To prevent fire, it is recommended:
-

to install the necessary fire extinguishing and detection means and to establish their
maintenance procedures,

to keep emergency exits free from obstacles and work areas clean,

not to smoke in work areas,

to carry out adequate maintenance operations in electrical facilities likely to cause


fire,

to avoid the accumulation of inflammable/combustible materials

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Explosions
Explosions can happen in tanneries when using solvents due to vapour concentration in
certain work areas or the use of pressure equipment, like compressors, boilers, etc.
Depending on the scope and type of explosion, nearby workers will be affected by severe
burns, multiple injuries by projected pieces and materials, etc. even causing the death of
the victim under certain negative circumstances.
To prevent explosions, it is recommended to carry out adequate maintenance operations in
pressure equipment and use solvent-free products.

Exposure to noise
Noise as a physical contaminant is also present in tanneries, mainly in beamhouse and
tanning processes, and above all in operations prior to finishing due to the great number of
mechanical operations performed, which can occasionally exceed 90 dbA.
Depending on the equivalent daily level of exposure, the consequence of this risk, in the
long term, can be hearing loss, for high noise level exposure. As additional symptoms there
may be temporary auditory fatigue, blood pressure disorders, anxiety, etc. so it is
recommended to use hearing protection.

Exposure to vibrations
In activities with portable tools, hand-arm vibrations can be transmitted which can generate
specific

long-term

pathologies

that

can

cause

musculoskeletal,

vasomotor

or

neuromuscular disorders considered as professional illnesses (osteoarthritis, osteonecrosis,


Reynaud syndrome, acroparesthesia, etc.).

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Activities in wet environments


Humidity is a risk factor inherent to the majority of processes of the tanning sector and can
generate both accidents and illnesses so it is necessary to give greater importance to its
control.
Many of the beamhouse operations (leather preparation) are carried out by processing
hides and skins in big pits or drums. The solutions are usually transferred into containers
through pipes or are poured into them and are subsequently emptied through pipes or open
drains in the work area.
The tasks where the presence of humidity is most important are the following: drum
loading and unloading, soaking and unhairing, pre-tanning and tanning, dyeing and
fatliquoring, fleshing, splitting, piling and trimming, sammying and cutting into sides,
shaving and setting out.
Excessive humidity critically affects the comfort or heat sensation by affecting the
environmental humidity; furthermore, certain humidity levels favour the growing of
microorganisms with possible detrimental effects on health.
Among the detrimental effects of humidity are skeletal system diseases (arthritis and
rheumatism), respiratory disorders caused by frequent colds and rhinitis, and dermatitis. To
prevent these conditions, it is recommended to wear waterproof clothes and suitable
(waterproof and non-skid) footwear and masks.

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ANNEX I. SAFETY DATA SHEETS OF (GENERIC) CHEMICALS.

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I.1. PRE-FATLIQUORING PRODUCT


1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product name: emulsifiable oils in aqueous medium
Recommended use: pre-fatliquoring of hides and skins
2. HAZARDS IDENTIFICATION
R36 Irritating to eyes.
3. COMPOSITION/INFORMATION ON INGREDIENTS
Chemical nature of the preparation: Preparation based on synthetic oils and phosphoric esters
emulsifiable in aqueous medium.
Active substance: 45%
4. PHYSICAL AND CHEMICAL PROPERTIES
State: liquid
Colour: white
Odour: characteristic
pH: 6- 7(10 % solution) at 20C
Boiling point: 100C
Melting point: Not applicable
Flash point: >60 C- closed cup
Density: 0,96g/cm (20C)
Solubility in water: Miscible
Viscosity: 460cP (20C) Brookfield LVT
Conductivity: 65 10% (uS/cm. sol. 10 g/l.)
5. FIRST AID MEASURES
Skin contact: wash immediately with plenty of soap and water.
Eye contact: bathe the yes immediately with water and seek medical advice.
Inhalation: move to fresh air and seek medical advice.
Ingestion: wash out mouth with water and seek medical advice.
6. FIRE-FIGHTING AND/OR ACCIDENTAL RELEASE MEASURES
Extinguishing media: Carbon dioxide (CO2), water spray, foam, dry chemical powder.
Thermal decomposition can lead to release of irritating gases and vapours.
Ensure there is sufficient ventilation of the area. Avoid contact with skin and eyes.
Do not discharge into drains or rivers.
Soak up with inert absorbent material (eg. sand, diatomaceous earth, acid binders, universal
binders). Transfer to a container for disposal by a mechanical method.
7. HANDLING AND STORAGE
Ensure there is sufficient ventilation of the area.
Use personal protective equipment. When using do not smoke. Handle and open container with care.
Handle with adequate industrial hygiene measures and respect safety practice.
Keep container tightly closed and store in a cool, well-ventilated place. Keep only in the original
container.
8. STABILITY AND REACTIVITY
Stable under recommended storage conditions..
Chemically stable under normal storage conditions.

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I.2. OXAZOLIDINE
1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product name: Oxazolidine
Recommended use: Tanning
2. HAZARDS IDENTIFICATION
Classification:
R43 May cause sensitisation by skin contact.
R50/53 Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic
environment.
R36/38 Irritating to eyes and skin.
R20/21 Harmful by inhalation and in contact with the skin.
Potential health effects:
May cause sensitisation by skin contact.
Harmful by inhalation and in contact with the skin.
Irritating to eyes and skin.
Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment.
3. COMPOSITION/INFORMATION ON INGREDIENTS
Chemical nature of the preparation: Cyclic aldehyde.
Ingredients: 7a-ethyldihydro-1H,3H,5H oxazolo[3,4-c]oxazole
% by weight: > 90%
CAS No.: 7747-35-5
UE-N EINECS: 231-810-4
4. PHYSICAL AND CHEMICAL PROPERTIES
State: Yellowish liquid
Odour: Characteristic.
pH: 8- 10
Melting point: 0,2C
Flash point: 79C- Closed cup
Density: 1,08g/cm (20C)
Solubility in water: totally soluble
Viscosity: 20cP (25C) Brookfield LVT
Conductivity: 37 10% (uS/cm. sol. 10 g/l.)
Vapour pressure: 6.65 hPa 25C
5. FIRST AID MEASURES
Skin contact: wash immediately with plenty of soap and water.
Eye contact: bathe the yes immediately with water and seek medical advice.
Inhalation: move to fresh air and seek medical advice.
Ingestion: wash out mouth with water and seek medical advice
6. FIRE-FIGHTING AND/OR ACCIDENTAL RELEASE MEASURES
Extinguishing media: Carbon dioxide (CO2), water spray, foam, dry chemical powder.
Thermal decomposition can lead to release of irritating gases and vapours.
Ensure there is sufficient ventilation of the area. Avoid contact with skin and eyes.
Do not discharge into drains or rivers.
Soak up with inert absorbent material (eg. sand, diatomaceous earth, acid binders, universal
binders). Transfer to a container for disposal by a mechanical method.

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7. HANDLING AND STORAGE


Ensure there is sufficient ventilation of the area.
Use personal protective equipment. When using do not smoke. Handle and open container with care.
Handle with adequate industrial hygiene measures and respect safety practice.
Keep container tightly closed and store in a cool, well-ventilated place. Keep only in the original
container.
8. STABILITY AND REACTIVITY
Stable under recommended storage conditions..
Keep away from extreme temperatures, direct sunlight, strong oxidising agents and acids.
Thermal decomposition can lead to release of irritating gases and vapours.

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I.3. SYNTHETIC RETANNING AGENT


1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product name: Synthetic retanning agent
Recommended use: Tanning
2. HAZARDS IDENTIFICATION
R36 Irritating to eyes.
3. COMPOSITION/INFORMATION ON INGREDIENTS
Chemical nature of the preparation: sulphone and aromatic sulphonic acid condensate, with low
formaldehyde content
Solids content: 42%
4. PHYSICAL AND CHEMICAL PROPERTIES
State: Liquid
Colour: yellowish brown.
Odour: characteristic
pH: 4,5 (10 % solution) at 20C
Water miscible at any ratio
Compatible with all conventional anionic retanning agents.
Low phenol and formaldehyde content.
Low salt content.
High fastness.
5. FIRST AID MEASURES
Skin contact: wash immediately with plenty of soap and water.
Eye contact: bathe the yes immediately with water and seek medical advice.
Inhalation: move to fresh air and seek medical advice.
Ingestion: wash out mouth with water and seek medical advice
6. FIRE-FIGHTING AND/OR ACCIDENTAL RELEASE MEASURES
Extinguishing media: Carbon dioxide (CO2), water spray, foam, dry chemical powder.
Thermal decomposition can lead to release of irritating gases and vapours.
Ensure there is sufficient ventilation of the area. Avoid contact with skin and eyes.
Do not discharge into drains or rivers.
Soak up with inert absorbent material (eg. sand, diatomaceous earth, acid binders, universal
binders). Transfer to a container for disposal by a mechanical method.
7. HANDLING AND STORAGE
Ensure there is sufficient ventilation of the area.
Use personal protective equipment. When using do not smoke. Handle and open container with care.
Handle with adequate industrial hygiene measures and respect safety practice.
Keep container tightly closed and store in a cool, well-ventilated place. Keep only in the original
container.
8. STABILITY AND REACTIVITY
Stable under recommended storage conditions..
Chemically stable under normal storage conditions.

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I.4. VEGETABLE RETANNING AGENT


1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product name: Vegetable retanning agent.
Recommended use: Retanning
2. HAZARDS IDENTIFICATION
S 7/8 Keep container tightly closed and dry.
S20/21 When using do not drink, eat or smoke.
S36/37 Wear suitable protective clothing and gloves..
3. COMPOSITION/INFORMATION ON INGREDIENTS
Chemical nature of the preparation: Vegetable extracts
4. PHYSICAL AND CHEMICAL PROPERTIES
State: Powder
Colour: Beige.
Odour: characteristic
pH: 2.5 - 4.5(10 % solution) at 20C
Solubility in water: dispersible
Conductivity: 2400 10% (uS/cm. sol. 10 g/l.)
5. FIRST AID MEASURES
Skin contact: wash immediately with plenty of soap and water.
Eye contact: bathe the yes immediately with water and seek medical advice.
Inhalation: move to fresh air and seek medical advice.
Ingestion: wash out mouth with water and seek medical advice
6. FIRE-FIGHTING AND/OR ACCIDENTAL RELEASE MEASURES
Extinguishing media: Carbon dioxide (CO2), water spray, foam, dry chemical powder.
Thermal decomposition can lead to release of irritating gases and vapours.
Ensure there is sufficient ventilation of the area. Avoid contact with skin and eyes.
Do not discharge into drains or rivers.
Soak up with inert absorbent material (eg. sand, diatomaceous earth, acid binders, universal
binders). Transfer to a container for disposal by a mechanical method.
7. HANDLING AND STORAGE
Ensure there is sufficient ventilation of the area.
Use personal protective equipment. When using do not smoke. Handle and open container with care.
Handle with adequate industrial hygiene measures and respect safety practice.
Keep container tightly closed and store in a cool, well-ventilated place. Keep only in the original
container.
8. STABILITY AND REACTIVITY
Stable under recommended storage conditions..
Chemically stable under normal storage conditions.

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I.5. FATLIQUORING PRODUCT


1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product name: Fatliquoring product
Recommended use: Fatliquoring hides and skins
2. HAZARDS IDENTIFICATION
R36/38 Irritating to eyes and skin.
3. COMPOSITION/INFORMATION ON INGREDIENTS
Chemical nature of the preparation: Preparation based on polymers and synthetic oils
emulsifiable in an aqueous medium.
4. PHYSICAL AND CHEMICAL PROPERTIES
State: liquid
Colour: white
Odour: characteristic
pH: 7,4 - 9,4(10 % solution) @ 20C
Solubility in water: completely miscible
5. FIRST AID MEASURES
Skin contact: wash immediately with plenty of soap and water.
Eye contact: bathe the yes immediately with water and seek medical advice.
Inhalation: move to fresh air and seek medical advice.
Ingestion: wash out mouth with water and seek medical advice
6. FIRE-FIGHTING AND/OR ACCIDENTAL RELEASE MEASURES
Extinguishing media: Carbon dioxide (CO2), water spray, foam, dry chemical powder.
Thermal decomposition can lead to release of irritating gases and vapours.
Ensure there is sufficient ventilation of the area. Avoid contact with skin and eyes.
Do not discharge into drains or rivers.
Soak up with inert absorbent material (eg. sand, diatomaceous earth, acid binders, universal
binders). Transfer to a container for disposal by a mechanical method.
7. HANDLING AND STORAGE
Ensure there is sufficient ventilation of the area.
Use personal protective equipment. When using do not smoke. Handle and open container with care.
Handle with adequate industrial hygiene measures and respect safety practice.
Keep container tightly closed and store in a cool, well-ventilated place. Keep only in the original
container.
8. STABILITY AND REACTIVITY
Stable under recommended storage conditions..
Chemically stable under normal storage conditions.

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I.6. FORMALDEHYDE SEQUESTERING AGENT


1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product name: Formaldehyde complexing agent
Recommended use: Final conditioning of leather.
2. HAZARDS IDENTIFICATION
R2: Risk of explosion by shock, friction, fire or other sources of ignition.
R21/22: Harmful in contact with the skin and if swallowed.
R36/38: Irritating to eyes and skin.
R40: Limited evidence of a carcinogenic effect.
R43: May cause sensitisation by skin contact.
R48/22: Danger of serious damage to health by prolonged exposure and if swallowed.
R50: Very toxic to aquatic organisms.
S2: Keep out of the reach of children.
S36/37: Wear suitable protective clothing and gloves.
S61: Avoid release to the environment. Refer to special instructions/safety data sheets.
3. COMPOSITION/INFORMATION ON INGREDIENTS
Chemical nature of the preparation:
4. PHYSICAL AND CHEMICAL PROPERTIES
State: crystalline
Odour: odourless
Colour: white
pH: 3.6 ( 10 g/l, 20 C)
Specific weight: 1,100 kg/m3
n-octanol/water partition coefficient (log Pow): -3.6 ( 25 C)
Solubility in water, g/100 ml at 20C: 58.7
Solubility in other solvents: 370 g/kg ( 20 C)
Melting point: 120C
5. FIRST AID MEASURES
Skin contact: wash immediately with plenty of soap and water.
Eye contact: bathe the yes immediately with water and seek medical advice.
Inhalation: move to fresh air and seek medical advice.
Ingestion: wash out mouth with water and seek medical advice
6. FIRE-FIGHTING AND/OR ACCIDENTAL RELEASE MEASURES
Extinguishing media: Carbon dioxide (CO2), water spray, foam, dry chemical powder.
Thermal decomposition can lead to release of irritating gases and vapours.
Ensure there is sufficient ventilation of the area. Avoid contact with skin and eyes.
Do not discharge into drains or rivers.
Soak up with inert absorbent material (eg. sand, diatomaceous earth, acid binders, universal
binders). Transfer to a container for disposal by a mechanical method.

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7. HANDLING AND STORAGE


Ensure there is sufficient ventilation of the area.
Use personal protective equipment. When using do not smoke. Handle and open container with care.
Handle with adequate industrial hygiene measures and respect safety practice.
Keep container tightly closed and store in a cool, well-ventilated place. Keep only in the original
container.
8. STABILITY AND REACTIVITY
Stable under recommended storage conditions..
Chemically stable under normal storage conditions.

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ANNEX II. LEATHER QUALITY STANDARDS (PHYSICAL PARAMETERS).

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ANNEX II. QUALITY STANDARDS FOR LEATHER (PHYSICAL PARAMETERS).


In the broad sense, the quality of a product is defined as its degree of fitness to meet the needs and
desires of the consumer. In the case of leather, its quality is defined by two properties:

aesthetic values, like colour evenness, grain fineness, pore appearance, absence of
defects, surface feel, flexibility, stretch and, in general, those properties that can be
perceived by senses and assessed subjectively.

use properties, which measure the fitness of the leather material to withstand
environmental conditions and physical efforts to which it will be subjected in practical
use by the consumer, by conducting the corresponding tests or standard analyses.

In the near future a new eco quality factor shall have to be considered, which will imply meeting
new requirements like using the best available technologies, bio-compatibility, the absence of
substances harmful to the user and the environment, and others related to the products
environmental impact.
The weight of each property will depend on the type of leather and its intended final use. So, in a
fashion good, the aesthetic factors have a great importance, while in leather used in protective
goods for professional use, the use properties are the vital factors to assess the materials quality.
For other types of leather, like upholstery leather, both aesthetic and practical factors have a similar
importance.
This annex refers exclusively to quality related to the leather performance in applications
considered in the LIFE-OXATAN project: footwear, leathergoods, upholstery and clothing,
regarding its resistance, fastness, breathability, etc. by carrying out standard analyses and tests and
by complying with the regulations and/or existing recommendations.

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The different quality guidelines or quality recommendations have been drafted by the
Specifications Committee of the European Group of Leather Research Institutes (GERIC), the
United Nations Industrial Development Organization (UNIDO), companies, etc. In Germany, the
Leather Industry Association has drafted some official quality guidelines, with similar values to the
ones established as a recommendation.

II.1. Quality specifications for footwear upper leather.


Establishing quality guidelines for footwear upper leather is a problematic task given that it
includes the use of different types of leather, tannages, re-tannages, and finishes, for different types
of footwear: mens loafers, childrens shoes, womens court shoes, sandals, military boots, trekking
boots, occupational footwear, football shoes, sports shoes, etc. For this reason, there are no official
generic quality specifications for footwear upper leather but there are some technical specifications
only for occupational or protective footwear, military footwear, or large companies requirements,
etc. However, in order to be able to contrast the results of the tests it is necessary to have reference
values provided by quality guidelines or recommendations.
In summary, these are the main requirements that upper leather shall meet in the manufacture and
in the practical use of the footwear:

The leather and its finish shall have high flexibility to prevent the appearance of cracks
and tears in the ball area of the footwear upper.

The adhesion of the finish shall be enough to avoid its detachment with use.

Provide adequate fastness to rubbing, so that rubbing does not substantially change the
leather appearance. For unlined footwear, it is important to provide a good fastness on
the grain side to avoid staining on stockings or feet.

The grain layer shall have a high elasticity, which allows it to withstand the elongation
stresses to which it is subjected during footwear lasting, especially on the toe area.

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The elongation at break shall provide a medium value, so that the leather has enough
elasticity to adapt to the users feet and to the movements derived from the use of
footwear but not too excessive to avoid the footwear deformation.

Water resistance is a much demanded property so the dynamic water resistance test is
particularly important, as well as the water vapour permeability test to assess the
leathers breathability, mainly in leather coated with very thick films.

The soluble inorganic matter content must be low to prevent the formation of salt spew.

For suede split, it is essential to check for a sufficient structural resistance by


determining its tensile strength.

Table II.1 shows the main requirements for footwear upper leather according to the quality
guidelines or recommendations established by GERIC.

GENERAL RECOMMENDATION
PROPERTY
Tensile strength

UNIT
N/mm

METHOD

REMARKS

15
15

(1)
(2)

40

(3)

UNE-EN ISO
3376:03

Leather in general
Split
Elongation at break

UNE-EN ISO
3376:03

Tear strength
General purpose footwear
Unlined footwear
Lined footwear
Sports and childrens footwear
Unlined footwear
Lined footwear

UNE-EN ISO
3377-2:03

Damage on lasting
Thin leather
Cattle hides

MINIMUM
VALUES

50
35
100
70
mm

UNE-EN
13511:02

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GENERAL RECOMMENDATION
PROPERTY

UNIT

Flex resistance
Finished leather
Coated split
Adhesion of finish
Thin leather
Full grain cattle hides
Corrected grain cattle hides
Patent leather
Coated split
Water resistance
Football shoes
Penetration time
Water absorption after 2 h
Water penetration after 2 h
Waterproof footwear
Penetration time
Water absorption after 3 h
Water penetration after 3 h

MINIMUM
VALUES

UNE-EN
13512:02
UNE-EN ISO
5402:03

Dry
50 000
150 000

Wet
12 000
30 000

(6)

N/10 mm

UNE-EN ISO
11644:04

Dry
2.0
3.0
5.0
6.0
10.0

Wet
1.0
2.0
3.0
4.0
10.0

(7) (8)

min
%
g

UNE-EN
13518:02
UNE-EN ISO
5403:03

min
%
g

30
30 maximum
3 maximum
180
25 maximum
---

UNE-EN ISO
11640:99

Change in colour
Dry (150 rubs)
Wet (50 rubs)

Leather in
general:
10 N load
Sueded
leather:
5 N load

Colour discharge
Dry (10 rubs)
Wet (10 rubs)
Rubbing resistance using
rubber
General purpose footwear
Sports and childrens
footwear
pH

(flesh

REMARKS

No. flexes
No significant
damage

Rubbing fastness

Fastness to perspiration
Unlined footwear
side)

METHOD

UNE
59231:97

3
3
3
3
Dry
30
60

Wet
20
40

pH

UNE-EN ISO
4045:99

3.5

Grey Scale
rate

UNE-EN ISO
11641:04

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GENERAL RECOMMENDATION
PROPERTY

UNIT

METHOD

MINIMUM
VALUES

Fastness to artificial light

Blue Scale
rate

UNE-EN ISO
105-B02:01

Colour migration
At 50 C and 100 C

Grey Scale
rate

4
(No staining on PVC)

Water vapour permeability


Unlined footwear

mg/cm.h

UNE-EN
13517:02
UNE-EN ISO
15701:00
UNE-EN
13515:02
UNE-EN ISO
14268:03

REMARKS

1,5
(if pH<4, difference
figure 0,7)

Water-soluble inorganic matter

UNE-EN ISO
4098:06

1 maximum

Shape retention (dome


plasticity apparatus)

BS 3144-10

60

Table II.1. Quality recommendations for footwear upper leather (GERIC).


(1)

(2)
(3)
(4)
(5)
(6)
(7)
(8)

NOTE:

Usual values for different types of leather:


- Goatskin: 14-15 N/mm below these values the leather could be faulty.
- Cattle hide: 20 N/mm
- Thin goatskin and crossbred leather (0.5-0.7 mm): 120-150 N
Good values over 20 N/mm.
It is recommended not to exceed 70-80% elongation. Higher values would require taking measures to avoid leather
deformation.
For calfskins 0,6-0,7 mm thick 7.5 mm can be accepted for lasting, but precautions should be taken on lasting. It should be
ensured that the leather shows good tear and elongation performance.
For cattle hides used in cowboy boots with sharp bevelled toes, the minimum recommended value is around 9.0 mm.
Test also in cold conditions (-10 C). Minimum 30 000 flexes without damage.
This recommendation is valid for cracking finishes.
For constructions that do not require prior preparation (direct injection), the adhesion test shall be passed in dry and wet
conditions.
For metallised leather, the finish requirements are the same as those for full grain leather. The most relevant characteristics
to be checked are flex resistance and rub fastness.

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II.2. Quality specifications for footwear lining and insock leather.


The lining performs an important function in the footwear that can be summed up into three main
objectives:

Improving the aesthetical function of the shoe,

Contributing to the foots comfort and hygiene.

Ensuring a good fastness to colour staining of the inner side of the footwear.

To be able to perform satisfactorily, lining leather shall meet certain requirements; the most
important of which are summarised below:

Good rubbing fastness, valuing above colour fastness to staining on adjacent materials..

Fast dyeing to avoid migration by leaching in wet conditions (sweat) to other footwear
components or stockings.

Low concentration of soluble mineral salts, which can cause whitish spew on the
footwear upper by migration.

pH value high enough to guarantee the absence of free strong acids, which in addition
to eventually producing a deterioration of the leather, are particularly undesirable in
footwear lining for being in direct contact with the users foot.

Absorbent and breathable. Consequently it must have a minimum water vapour


absorption capacity, and minimum water vapour permeability.

As for mechanical properties, the main one is the elongation at break.

For a normal lining, the fat content shall not be high to avoid limiting the humidity
absorption capacity.

Table II.2 shows the main requirements footwear lining and insock leather according to the quality
guidelines or recommendation established by GERIC.

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GENERAL RECOMMENDATION
PROPERTY

UNIT

Elongation at break

Tear strength

Rubbing fastness

Grey Scale
rate

Change in colour
Dry (150 rubs)
Wet (50 rubs)
Colour discharge
Dry (150 rubs)
Wet (50 rubs)

Water vapour permeability

Abrasion resistance

No. cycles

Indoor footwear
Womens footwear
Mens footwear
Sports and childrens
footwear
Water-soluble inorganic matter

MINIMUM
VALUES

UNE-EN ISO
3376:03
UNE-EN ISO
3377-2:03
UNE-EN ISO
11640:99
Linings and
inside of
unlined
uppers:
10 N load

REMARKS

30
30

3
3
3
3

Grey Scale
rate
mg/(cm.h)

Fastness to perspiration

METHOD

UNE-EN ISO
11641:04
UNE-EN
13515:02
UNE-EN ISO
14268:03
UNE-EN
13520:02

No significant
damage

3
1.5

Dry
6 400
25 600
25 600
25 600

Wet
1 600
3 200
6 400
12 800

UNE-EN ISO
4098:06

Leather lining
Insole and insock
Cattle hide

1.5 maximum
1.0 maximum
2.0 maximum

pH

pH

UNE-EN ISO
4045:99

3.5
(if pH<4, difference
figure 0.7)

Shap retation (dome plasticity


apparatus)

BS 3144-10

55

Table II.2. Quality recommendations for footwear lining and insock leather (GERIC).
(1)
(2)
(3)

(1)
(1)
(2)

For quarter and counter lining, wet conditions, 12 800 cycles minimum.
For quarter and counter lining, dry conditions 52 200 cycles minimum, wet conditions: 25 600 cycles.
Up to 2% is within usual values, but it should be recommended to carry out periodical checks to ensure that they do not
increase.

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II.3. Quality specifications for leathergoods.


Similarly to footwear upper leather, these quality specifications apply to leather made with
different types of hides and skins, tannages, re-tannages and finishes for its use in the manufacture
of suitcases, briefcases, handbags, portfolios, belts, wallets, purses, cases, key rings, and the like.
Leathers for leathergoods make up a too disperse and heterogeneous set to abide by general quality
standards, valid for the entirety of this type of leather. For this reason, there are no official quality
guidelines or specifications for this type of leather. However, as an internal reference, the values
used were the ones recommended by the Tanning School of Igualada.
The following summarises the main requirements that are considered necessary for the majority of
leathers for leathergoods:

Good rubbing fastness, so that the friction with textile materials does not lead to leather
fading or staining.

Water resistance is an interesting added value, an important selling argument, and a


compulsory requirement to be met by leather intended for high-quality products, such
as briefcases for executives, or high-end bags.

Possibly the most important requirement in leathergoods is the fastness to water


spotting. The user demands for the rain drops not to change the leather appearance
once dry. In particular stains, aureoles or swellings should not be accepted. A certain
degree of waterproofing is very convenient to pass this test.

For suitcases and certain bags it is interesting to check the scratching resistance.

Metal elements in contact with leather, like buckles, fasteners, decorations and the like
sometimes suffer from corrosion problems. An overly acidic pH and an excessive
content in soluble inorganic salts are related to the corrosive power of leather.

Table II.3 shows the main requirements for leather to be used in leathergoods in accordance with
the quality guidelines or recommendations indicated by the Tanning School of Igualada.

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GENERAL RECOMMENDATION
PROPERTY

UNIT

METHOD
VALUES

Tensile strength

N/cm

Elongation at break

Tear strength

Rubbing fastness

Grey Scale rate

UNE-EN ISO
3376 :03
UNE-EN ISO
3376:03
UNE-EN ISO
3377-2:03
UNE-EN ISO
11640:99

Change in colour
Dry felt (100 rubs)
Wet felt (25 rubs)

Water-soluble inorganic matter


pH

(1)
(2)

> 1 500
< 75
> 40

>4
>4

Fastness to water spotting


Abrasion resistance

REMARKS

1 kg/100 cycles
%
pH

UNE-EN ISO
11642:99
UNE-EN
13520:02
UNE-EN ISO
4098:06
UNE-EN ISO
4045:99

(1)
(2)

<1.0
> 3.5
(if pH<4, difference
figure 0.7)

After 30 min, check and record if the water drop has been absorbed. Once the leather has dried, assess the appearance of the
area where the water drop had been deposited, indicating if any stain, swelling, change in colour, shine loss, etc. occurred.
No visible damage

Table II.3. Quality recommendations for leathergoods according to the Tanning School of Igualada.

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II.4. Quality specifications for upholstery leather.


Upholstery leather is a high quality product from which high performance is demanded. The
qualities required for upholstery leather depend firstly on its use, differentiating especially
upholstery for common furniture and automotive upholstery. The second consideration is the type
of leather, i.e. this can range from leather with light and barely covered finishes to corrected grain
leather with a high opacity finish, passing through various possible intermediate articles.
In general it is essential for upholstery leather to offer high rubbing and light fastness. The finish
shall feature a high degree of flexibility and adhesion to the grain layer, and the tear resistance shall
be enough to withstand mechanical stress on seams and stitches.
In the case of automotive upholstery leather, different brands have established their own quality
requirements that their suppliers shall meet, mainly focusing on the following aspects:
-

Fastness to UV radiation and to different washing products,

Adhesion of finish,

Flex resistance at different temperatures (-10C and 20 C),

Heat resistance (144 hours at 100C),

Break in cold conditions (-30C),

Water vapour permeability,

Fogging test

Table II.4 shows the main requirements for upholstery leather in accordance with the quality
guidelines or recommendations established by GERIC.

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GENERAL RECOMMENDATION
PROPERTY

UNIT

METHOD
MINIMUM VALUES

Tear strength

UNE-EN ISO
3377-2:03

50

Flex resistance

Flexes

UNE-EN ISO
5402:2003

20 000

Rubs
(Grey Scale
rate)

UNE-EN ISO
11640:99

Rubbing fastness
Change in colour
Dry felt:
Wet felt:
Felt wetted with perspiration
(pH 9)
Fastness to artificial light

Blue Scale rate

IUF 401

Colour fastness to migration

Blue Scale rate

UNE-EN ISO
15701:2000

N/cm

UNE-EN
11644:2004

2.5

pH

UNE-EN ISO
4045:99

>3.5

Adhesion of finish

pH
(1)

1000
200
100

4
4
4

No damage on finish coat.

Table II.4. Quality recommendations for upholstery leather (GERIC).

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II.5. Quality specifications for garment leather.


According to the International Union of Leather Technologists and Chemists Societies (IULTCS)
the most important tests to assess the garment leather quality are: tear strength, rubbing fastness,
fastness to dry cleaning and break in cold conditions. Fastness to artificial light, fastness to water
spotting, and fastness to mild washing (water) should all be added to this list of essential tests, all
of them particularly valid for unfinished leather.
Table II.5 shows the main requirements for garment leather in accordance with the quality
guidelines or recommendations established by GERIC.
GENERAL RECOMMENDATION
PROPERTY
Tear strength

UNIT
N

Tensile strength

N/cm2

Flex resistance
- finished nappa

Flexes

Rubbing fastness
Change in colour
Dry felt:
- suede, nubuck and aniline
nappa
- finished nappa
Wet felt:
- suede, nubuck and aniline
nappa
- finished nappa
Felt wetted with perspiration
(pH 9)
- suede, nubuck and aniline
nappa
- finished nappa

Rubs
(Grey Scale
rate)
20

METHOD
UNE-EN
ISO 33772:03
UNE-EN
ISO 3376 :03
UNE-EN
ISO
5402:2003
UNE-EN
ISO
11640:99

MINIMUM
VALUES
20 (suede and nubuck)
30 (nappa)
> 1 200

> 50 000

50

10

20

10

20

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GENERAL RECOMMENDATION
PROPERTY
Fastness to artificial light

UNIT

METHOD

Blue Scale
rate

UNE-EN
ISO
11640:99

- suede, nubuck and aniline


nappa
- finished nappa
Adhesion of finish
Finished nappa
pH
Fastness to water spotting
- suede, nubuck and aniline
nappa
- finished nappa
Fastness to mild washing (water)
- suede, nubuck

N/cm

UNE-EN
11644:2004

pH

UNE-EN
ISO 4045:99
UNE-EN
15700 :2000

Penetration
time

MINIMUM
VALUES

REMARKS

4
4
>2.5

>3,5

>10 min.
>15 min.

UNE-EN
ISO
15703:2000

No change in handle
No change in colour:
>3 grey scale rate
Change in area <3%

(1) Assessment of leather appearance after washing, drying and light staking.

Table II.5. Quality recommendations for garment leather (GERIC).

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LIFE08 ENV/E/000140

ANNEX III. BIBLIOGRAPHY.

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Bibliography.
[1]

Angus Chemie GmbH. Oxazolidinas Technical Data Sheet.

[2]

Kitty Qu, Jeff Yang and Patrick Brutto, ANGUS Chemical Company, a Subsidiary of the

Dow Chemical Company. Oxazolidines-The versatile leather Curticin agents. Leather, 2008, pag.
38.
[3]

DAquino A., Barbani N., DElia G., et al. Combined organic Curticin based on mimosa

and oxazolidina: development of a semi-industrial scale process for high-quality bovine upper
leather. Journal of the Society of Leather Technologists and Chemists. Vol. 88, p 47-55.
[4]

De la Casa Lillo M.A., Daz Tahoces A., Mazn Canales P., De Aza Moya P.N., Segarra

Orero V., Martnez Sanchez M.A., Bertazzo M. Biodegradation of leather: establishment of a


valuation method using aerobic microorganisms from tannery wastewater". XI National Congress
of Materials. Zaragoza. June 2010.
[5]

X.

Guardino.

SISTEMA

DE

REGISTRO

REACH:

NUEVA

POLTICA

DE

PRODUCTOS QUMICOS. Centro Nacional de Condiciones de Trabajo. Instituto Nacional de


Seguridad e Higiene en el Trabajo. Boletn tcnico AQEIC. Vol 57. N4, 2006.
[6]

Equipo tcnico AIICA. Revisin de las recomendaciones tcnicas internacionales sobre

pieles de confeccin. Boletn tcnico AQEIC. Vol. 60 N1, 2009. EUROPEAN CHEMICALS
POLICY Leather, v.205 n. 4732, 2003.
[7]

Font, J., Rius, A., Marsal, A., Sanchez, D., Hauber, C., Tommaselli, M. Como evitar la

formacin de Cromo VI, Revista do couro, ediao 186, p. 108 110, 2006.
[8]

Glasspool, J. Hazardous Substances Update, SATRA Bulletin, 2007.

[9]

Hauber, C. Sources, Detection and Avoidance of Hexavalent Chromium in Leather and

Leather Products United Nations Industrial Development Organization, 1999.


[10]

One Leather Training. Self-Training for the leather industry. Education and Culture.

Leonardo da Vinci. Transnational Networks.


[11]

Dr. Joaquim Font. Anlisis y ensayos en la industria del curtido. Consorci Escola Tcnica

dIgualada. ISBN 84-931837-5-X.

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[12]

Christine DeJong, ASTM International, Wet Conshohocken, PA. ASTM OVERVIEW.

ALCA. 106th Annual Meeting. Lake Geneva. WI. June 2010.


[13]

W.F.Fuck, M. Gutterres, Produtos qumicos perigosos e de uso restrito no couro,

Universidade Federal do Rio Grande do Sul, Departamento de Engenharia Qumica Laboratrio de


Estudos em Couro e Meio Ambiente (LACOURO). TC 309, TR 16178 (WI309136:2009).
[14]

Manuel Carb Martnez. Visin general para la aplicacin del REACH por las autoridades

competentes. Secretara de Estado del Cambio Climtico. Inspeccin general de calidad y


evaluacin ambiental. Ministerio de Medio Ambiente y Medio Rural y Marino. Gobierno de
Espaa.
[15]

Integrated Pollution Prevention and Control (IPPC). Reference Document on Best

Available Techniques for the Curticin of Hides and Skins. European Commission. February 2003.
[16]

Gua de las mejores tcnicas disponibles en Espaa del sector de curtidos. Ministerio de

Medio Ambiente. Direccin General de Calidad y Evaluacin Ambiental. 2003.


[17]

J.C. Castell. Innovation in the Leather Industry. The REACH challenge & innovation in

the European Leather Industry. Who does what?. COTANCE Round Table. Bologna 2008.
[18]

Bugra Ocak, Ahmet Aslan, Grbz Glmser. Utilization of chromium-tanned leather solid

wastes in microencapsulation. Leather Waste Microencapsulation, 2011 vol. 16, pag 232-238.
[19]

Li Jing, Sun Qingyong, Wu Chao, Xuepin Liao and Shi Bi. A novel oxazolidine Curticin

agent and its use in vegetable combination Curticin. SLTC Journal, 2011 vol. 95, pag 165-170.
[20]

Samir DasGupta. Modern oxazolidine tannages. Jilta, 2010, pag. 739-758.

[21]

Gladstone Christopher Jayakumar, L. Santana Bala, Swarna V. Kanth, B. Chandrasekaran,

J.R. Rao and B.U.Nair. Combination Curticin system based on dialdehyde alginic acid: an
ecofriendly organic approach. Jalca 2011, vol. 105, pag 51-58.
[22]

Lu Yan, Luo Zhaoyang, Fan Haojun, Liu Yuansen, Li Hui, Peng Biyu and Shi Bi. Nano-

SiO2/Oxazolidine Combination Tannage: Potential for Chrome-Free Leather. Journal of the


Society of leather Technologists and Chemists. 2008 vol. 92, pag. 252.

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[23]

A.D. Covingtyon, L. Song, O. Suparno, H.E.C.Koon and M. J. Collins. Link-Lock: An

Explanation of the Chemical Stabilisation of Collagen. Journal of Society of Leather Technologists


and Chemists, 2007 vol. 92, pag. 1.
[24]

A.E Musa, B. Madhan, R. Aravindhan, J. Raghave Rao, B. Chandrasekaran and G.A.

Gasmelseed. Studies on Combination Curticin Based on Henna and Oxazolidine. Jolca, 2009 vol.
104, pag. 335-343.
[25]

O. Suparno, A.D. Covington, and C. S. Evans. Novel Combination Curticin Using

Diphenols and Oxazolidine for High Stability Leather. Journal of the Society of Leather
Technologists and Chemists. 2006 Vol. 91, pag. 188.
[26]

Qiang Tao-Tao, Wang Xue-Chuan, Ren Long-Fang and Ren Yong-Qiang. Airconium-

Oxazolidine Combination Tannage for Sheep Garment Leather. 2008 Vol. 93, pag. 35.
[27]

Samir DasGupta. Zirconium Acetate-Oxazolidine Combination Tannages. SLTC Journal.

2009-2010 Vol. 94, pag. 167.


[28]

Anthony D. Covington, Lijiang Song, Ono Suparno, Applied Collagen Research Group,

The University of Northampton and Hannah E. C. Koon, Matthew J. Collins, BioArch, Depts. Of
Biology and Archeology, The university of York. Link-Lock: an explonation of the chemical
stabilisation of collagen. World Leather. 2010 October/November, pag. 35.
[29]

Formaldehyde in leathergoods: remedies and solutions. Leather International. 2005, pag. 24

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