CEN ISO/TR 16178:2012

SLOVENSKI STANDARD
01-november-2012
1DGRPHãþD
kSIST-TP FprCEN ISO/TR 16178:2010
Obuvala - Nevarne snovi, ki so lahko prisotne v obuvalih in njihovih sestavnih
delih (ISO/TR 16178:2012)
Footwear - Critical substances potentially present in footwear and footwear components
(ISO/TR 16178:2012)
Schuhe - Möglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische
Substanzen (ISO/TR 16178:2012)
Chaussures - Substances critiques potentiellement présentes dans la chaussure et les
composants de chaussures (ISO/TR 16178:2012)
Ta slovenski standard je istoveten z: CEN ISO/TR 16178:2012
ICS:
61.060 Obuvala Footwear
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL REPORT
CEN ISO/TR 16178
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
September 2012
ICS 61.060 Supersedes CEN ISO/TR 16178:2010
English Version
Footwear - Critical substances potentially present in footwear
and footwear components (ISO/TR 16178:2012)
Chaussures - Substances critiques potentiellement Schuhe - Möglicherweise in Schuhen und
présentes dans la chaussure et les composants de Schuhbestandteilen vorhandene kritische Substanzen
chaussures (ISO/TR 16178:2012) (ISO/TR 16178:2012)

This Technical Report was approved by CEN on 30 July 2012. It has been drawn up by the Technical Committee CEN/TC 309.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United
Kingdom.
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COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2012 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN ISO/TR 16178:2012: E
worldwide for CEN national Members.

Contents Page
Foreword .3
Foreword
This document (CEN ISO/TR 16178:2012) has been prepared by Technical Committee CEN/TC 309
“Footwear", the secretariat of which is held by AENOR, in collaboration with Technical Committee ISO/TC 216
"Footwear".
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
This document supersedes CEN ISO/TR 16178:2010.
TECHNICAL ISO/TR
REPORT 16178
Second edition
2012-07-15
Footwear — Critical substances
potentially present in footwear and
footwear components
Chaussures — Substances critiques potentiellement présentes dans la
chaussure et les composants de chaussures
Reference number
ISO/TR 16178:2012(E)
©
ISO 2012
ISO/TR 16178:2012(E)
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,
electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or ISO’s
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Published in Switzerland
ii © ISO 2012 – All rights reserved

ISO/TR 16178:2012(E)
Contents Page
Foreword .iv
1 Scope . 1
2 Terms and definitions . 1
3 Presence of chemicals in footwear materials . 2
Annex A (informative) Materials used in the footwear industry . 7
Annex B (informative) Critical substances potentially present in footwear and footwear components .13
Bibliography .40
ISO/TR 16178:2012(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies
(ISO member bodies). The work of preparing International Standards is normally carried out through ISO
technical committees. Each member body interested in a subject for which a technical committee has been
established has the right to be represented on that committee. International organizations, governmental and
non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International
Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
In exceptional circumstances, when a technical committee has collected data of a different kind from that
which is normally published as an International Standard (“state of the art”, for example), it may decide by a
simple majority vote of its participating members to publish a Technical Report. A Technical Report is entirely
informative in nature and does not have to be reviewed until the data it provides are considered to be no longer
valid or useful.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO/TR 16178 was prepared by Technical Committee ISO/TC 216, Footwear.
ISO/TR 16178 was prepared by the European Committee for Standardization (CEN) Technical Committee
CEN/TC 309, Footwear, in collaboration with ISO Technical Committee TC 216, Footwear, in accordance with
the Agreement on technical cooperation between ISO and CEN (Vienna agreement).
This second edition cancels and replaces the first edition (ISO/TR 16178:2010), which has been technically revised.
iv © ISO 2012 – All rights reserved

TECHNICAL REPORT ISO/TR 16178:2012(E)
Footwear — Critical substances potentially present in footwear
and footwear components
1 Scope
This Technical Report establishes a list of critical chemical substances potentially present in footwear and
footwear components.
This Technical Report describes the critical chemical substances, their potential risks, the materials in which
they can be found and the test method(s) which can be used to quantify them. It does not include requirements;
it is the responsibility of the user of this Technical Report to fix his/her level of acceptance, for instance using
a defined concentration or detection limit or quantification limit.
NOTE The proposed test methods indicate the state of the art. Some substances do not include a test method, as no
test method is available at the time of publication of this Technical Report. If possible, it is intended to include a test method
in a revision of this Technical Report.
This Technical Report applies to any kind of footwear and footwear components.
2 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
2.1
allergen
substance that is capable of inducing an allergic reaction
2.2
allergy
immunologically mediated response to certain specific substances
NOTE 1 The specific substances are allergens.
NOTE 2 Type-1 allergy (respiratory allergy) is mediated by IgE antibodies and can cause asthma, rhinitis and urticaria.
NOTE 3 Type-4 allergy (dermal allergy) is mediated by T-cells and can cause dermatitis.
2.3
detection limit
value from which a substance is considered detectable
NOTE This means that the signal associated to the substance is three times bigger than the background noise signal.
The limit of detection is determined experimentally by the laboratory for each substance.
2.4
quantification limit
value from which a substance is considered measurable
NOTE It is the value where the uncertainty of measurement is equal to 50 % of the determined value.
2.5
absence of a chemical
state in which a chemical is lacking from a material, where the test method is unable to detect it
NOTE The amount of the chemical is smaller than the detection limit of the test method.
ISO/TR 16178:2012(E)
2.6
critical substance
chemical substance that can be found in footwear or footwear components and that can have an effect on the
wearer and/or environmental impact due to its chemical reactivity
NOTE 1 The effects caused by critical substances vary. They can be carcinogenic or mutagenic effects, allergy,
reaction to toxics, etc.
NOTE 2 Legislations can change; this Technical Report gives the information available at the time of publication. It is
the responsibility of the user of this Technical Report to ensure that no changes have occurred.
2.6.1
critical substances category 1
substances with proven dangerous effect on the wearer
NOTE These substances are restricted by regulation at European level.
2.6.2
critical substances category 2
substances with dangerous effect on the wearer
NOTE These substances are restricted by regulation at national level in some countries.
2.6.3
critical substances category 3
substances with environmental impact
NOTE These substances are mentioned in European Ecolabel.
2.6.4
critical substances category 4
substances that are highly suspected to have an effect on the wearer
NOTE Possibly, these substances are not restricted by regulation at the time of publication of this Technical Report.
2.6.5
critical substances category 5
substances that are suspected to have an effect on the wearer
NOTE Possibly, these substances are not restricted by regulation at the time of publication of this Technical Report.
3 Presence of chemicals in footwear materials
A number of chemicals are present in footwear materials. Table 1 gives:
a) materials in which they are supposed to be (for information, see Annex A);
b) the list of the critical chemicals, (for information, see Annex B);
c) test methods which can be used to provoke and quantify them;
d) the potential risk associated with and assessed by the use of the critical substances category scale (see 2.6).
For composite materials, the tests should be conducted on the entire component.
EXAMPLE 1 Coated textile (cotton plus PVC coating): the test on PVC and the test on cellulosic natural fibres should
be carried out.
EXAMPLE 2 Mixed textile (PES plus cotton): the test on cellulosic natural textile and the test on PES textile should
be carried out.
2 © ISO 2012 – All rights reserved

ISO/TR 16178:2012(E)
Table 1 — Critical chemicals potentially present in footwear and footwear components
Leather Synthetic material Natural material Miscellaneous

Substance
Test method
(see Annex B)
Acrylonitrile   5   5  5
AZO - arylamines ISO 17234-1 1 1 1
When 4-aminoazobenzene
AZO - arylamines ISO 17234-2 1 1 1
is suspected
AZO - arylamines EN 14362-1     1 1 1 1 1  1
AZO - arylamines EN 14362-2    1     1
When 4-aminoazobenzene
AZO - arylamines EN 14362-3    1 1 1 1 1 1  1
is suspected
Cadmium All plastics (mainly PVC) EN 1122 1 1 1 1 1 1     1
Chloroorganic carriers DIN 54232    3
Chromium VI
ISO 17075 2 2 2
Colophony         5
Dimethylformamide (DMF)  4  4
Dimethylfumarate (DMFU)
ISO/TS 16186 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Disperses dyes and dyestuffs DIN 54231    2 2 2 2 2 2
Only for product claiming
Flame retardant 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
FR properties
ISO 17226-1 and
Formaldehyde 2 2 2
ISO 17226-2
Leather
Coated leather
Leather fibre board
PVC
EVA
Rubber
PU – TPU elasthan
PE- PP
Polyester
Polyamide
Chloride fibre
Polyacrylic
Latex
Cellulosic natural textile
Proteinic natural textile
Wood - cork
Adhesives
Metal hardware
Prints for textile
Cellulosic materials
ISO/TR 16178:2012(E)
4 © ISO 2012 – All rights reserved
Table 1 (continued)
Leather Synthetic material Natural material Miscellaneous

Substance
Test method
(see Annex B)
Formaldehyde EN 120 EN 717-3        2  2
Formaldehyde ISO 14184-1    2 2 2 2 2 2
Extractible
ISO 17072-1 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4
(Sb – As – Pb – Cd – Cr –
Co – Cu – Ni – Hg – Zn)
Extractible
Footwear for children less
than 36 months old
ISO 17072-1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
(Sb – As – Pb – Cd – Cr
Heavy metals
– Co – Cu – Ni – Hg – Zn
– Ba – Se)
Total content
ISO 17072-2 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4
(Sb – As – Pb – Cd – Cr –
Co – Cu – Ni – Hg – Zn)
Total content
EN 14602:2004 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3
(As – Cd – Pb)
Mercaptobenzothiazole   5
Extractible latex proteins EN 455-3      4
N-ethylphenylamine    5   4
EN 1811
CR 12471
Nickel Skin contact         1
(with or without
EN 12472)
Footwear for children less
Nitrosamines EN 12868   2
than 36 months old
Leather
Coated leather
Leather fibre board
PVC
EVA
Rubber
PU – TPU elasthan
PE- PP
Polyester
Polyamide
Chloride fibre
Polyacrylic
Latex
Cellulosic natural textile
Proteinic natural textile
Wood - cork
Adhesives
Metal hardware
Prints for textile
Cellulosic materials
ISO/TR 16178:2012(E)
Table 1 (continued)
Leather Synthetic material Natural material Miscellaneous

Substance
Test method
(see Annex B)
Nitrosamines EN 12868   3
OP, NP, OPEO, NPEO Alkylphenols and 4 4 4   3 3 3 3 3 3
alkylphenolethoxylates)
Organotin compounds(TBT, TPT) ISO/TS 16179 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Organotin compounds(MBT, DBT, DOT), ISO/TS 16179 4 4 4 4 4 4 4 4 3 3 3 3 4 3 3 4 4 4 4
Ortho-phenylphenol ISO 13365 5 5 5 5  5 5 5 5 5 5 5 5  5
Ozone depleting substances     3 3 3 3 3 3
PAH – polycyclic aromatic hydrocarbons 4 4 4 4 4 4 4 4
PCP -TeCP – TriCP - polychlorophenols ISO 17070 2 2 2
PCP -TeCP – TriCP - polychlorophenols CEN/TR 14823        2
PCP -TeCP – TriCP - polychlorophenols XP G 08-015       2 2
Pesticides 5 5 5     3 3  5
Only for product claiming
PFOS/PFOA (Perfluorooctane
FR properties and water CEN/TS 15968 1 1 1   1 1 1 1 1 1
sulfonate/perfluorooctanoic acid)
resistance
pH ISO 4045 4 4 4
pH ISO 3071    4 4 4 4 4 4
Phenol 4 4 4 4    4 4 4 4
ISO/TS 16181  3 3 3 3 3
Phthalates
Footwear for children less
ISO/TS 16181 2 2 2 2 2 2 2 2 2 2 2 2  2
than 36 months old
PCB - Polychlorinated biphenyls 5 5 5   3 3 3 3 3 3
Polychloroprene or neoprene   5     5
Leather
Coated leather
Leather fibre board
PVC
EVA
Rubber
PU – TPU elasthan
PE- PP
Polyester
Polyamide
Chloride fibre
Polyacrylic
Latex
Cellulosic natural textile
Proteinic natural textile
Wood - cork
Adhesives
Metal hardware
Prints for textile
Cellulosic materials
ISO/TR 16178:2012(E)
6 © ISO 2012 – All rights reserved
Table 1 (continued)
Leather Synthetic material Natural material Miscellaneous

Substance
Test method
(see Annex B)
PPD Paraphenylene diamine 5 5 5   5 5 5 5 5  5 5
PTBF Paratertiary butyl phenol formaldehyde         5
Short-chained chloroparaffins (C -C ) 3 3 3 3 3 3 3 3 3 3
10 13
TCMTB (2-(thiocyanatomethylthio)-1,3-benzothiazole) ISO 13365 5 5 5
Thiuram and thiocarbamate   5
Vinyl chloride monomer ISO 6401 4 4
Leather
Coated leather
Leather fibre board
PVC
EVA
Rubber
PU – TPU elasthan
PE- PP
Polyester
Polyamide
Chloride fibre
Polyacrylic
Latex
Cellulosic natural textile
Proteinic natural textile
Wood - cork
Adhesives
Metal hardware
Prints for textile
Cellulosic materials
ISO/TR 16178:2012(E)
Annex A
(informative)
Materials used in the footwear industry
A.1 Leather
Leather is a general term for hide or skin, with its original fibrous structure more or less intact, tanned to be
rot-proof. The hair or wool can be removed or not. Leather is also made from a hide or skin, which has been
split into layers or segmented, either before or after tanning. However, if the tanned hide or skin is disintegrated
mechanically and/or chemically into fibrous particles, small pieces or powders and then, with or without the
combination of a binding agent, is made into sheets or other forms, such sheets or forms are not leather. If
the leather has a surface coating, no matter what is applied, or a glued-on finish, such surface coating layers
should not be thicker than 0,15 mm.
A.2 Coated leather
Leather, of which the applied surface coating does not exceed one third of the total thickness of the product,
but is in excess of 0,15 mm.
A.3 Leather fibre board
Leather fibre board is the term for materials where tanned hides or skins are disintegrated, mechanically and/or
chemically, into fibrous particles, small pieces or powders and then, are made into sheets or other forms,
with or without the combination of a binding agent. A minimum amount of 50 % mass fraction of dry leather is
necessary to use the term leather fibre board.
A.4 PVC
PVC is a polymer constituted of polymerized vinyl chloride. In footwear material, PVC is used with plasticizer in
order to create flexibility. It can also be used as polymeric coating in a coated fabric or patent leather.
A.5 EVA foam
EVA foam is a polymer composed of ethylene vinyl acetate; it can be expanded to foam. It is used as a
lightweight midsole in some trainers and as an outsole in some summer sandals where resistance to abrasion
is not required.
A.6 Rubber, synthetic rubber and rubber foam
Rubbers are polymers based on either synthetic or natural materials, which are cross-linked to give required
physical performance properties and chemical resistance. They are extensively used as outsoles in many
styles of footwear (see ISO 1382).
A.7 Thermoplastic polyurethanes
Thermoplastic polyurethanes (TPU) are compounds formed from the condensation of isocyanates and polyols
and can be remoulded on the application of heat. They can be moulded in compact or cellular forms.
ISO/TR 16178:2012(E)
A.8 Thermoplastic elastomers or thermoplastic rubbers
Thermoplastic elastomers or thermoplastic rubbers (not vulcanized) (TPE or TPR) combine the processability
of plastics with the flexibility and durability of rubbers, while more lightweight and formable. These properties
provide favourable conditions for the production of thermoplastic materials due to a structure consisting of
block copolymers, which combine elastic chain segments with rubbery properties, and very rigid segments
(at room temperature). They play the same role as the sulfur bonds formed during vulcanization process, i.e.
to prevent the chain displacement against stress. However, due to the absence of a cross-linked structure,
cohesion is lost where exceeding the glass transition temperature and the hot material can flow and is suitable
for injection moulding. For example:
— Polyethylene (PE) is a thermoplastic polymer consisting of long chains, and produced by combining the
ingredient monomer ethylene; it is used in a wide variety of applications, including packaging, textiles,
vessels and construction;
— Polypropylene (PP) is a thermoplastic polymer consisting of long chains, and produced by combining the
ingredient monomer propylene; it is used in a wide variety of applications, including packaging, textiles
(e.g. ropes, thermal underwear and carpets) and construction.
A.9 Latex
Rubber latex is a water-based colloidal solution, which includes spherical rubber particles with a diameter
smaller than 1 µm, dispersed in an aqueous continuous phase and relatively stable. Due to its hydrophobic
nature, it is non-miscible with water, and the suspension is stabilized because every rubber particle is coated
with a layer of natural or synthetic emulsifiers (see ISO 1382).
A.10 Blown material — Foam
Blown material is a synthetic expanded polymer with a closed-cell or open-cell structure, which can be flexible
or rigid, and is used for a variety of products.
A.11 Composite materials
Composites, also known as composite materials or reinforced plastics, consist of a polymeric matrix or
continuous phase and a discrete phase, made up of one or more loads or reinforcements in the form of mineral
and/or synthetic fibres. As a result, a structural material is obtained, whose mechanical properties are, at least,
higher than the values obtained from the lineal combination of the individual properties of both constituents.
For instance, carbon or glass fibres are commonly used as reinforcing materials.
A.12 Polyurethane
Polyurethane (PU) includes those polymers with urethane groups in the molecular backbone, regardless of
the chemical composition of the rest of the chain. Urethane groups (see Figure A.1) are produced through a
chemical reaction between a diisocyanate and a polyol. Thus, typical polyurethane may contain, in addition
to the urethane linkages, aliphatic and aromatic hydrocarbons, esters, ethers, amides, urea and isocyanates
groups. A wide range of properties can be obtained depending on the chemical composition used: thermoplastic,
thermoset, rigid or flexible, cellular or compact polyurethanes, etc. Polyurethanes are used as structural
materials, coatings, adhesives and sealants.
Figure A.1 — Urethane groups
8 © ISO 2012 – All rights reserved

ISO/TR 16178:2012(E)
A.13 Textile
The word textile was originally used to describe a woven fabric. The term now applies to fibres, filaments or
yarns, which are natural or man-made, and the products obtained from them.
EXAMPLE Threads, cords, ropes, braids, lace, embroidery, nets and fabrics made by weaving, knitting, felting,
bonding and tufting are textiles.
A.14 Polyester
Polyester is a polymer with ester bonds in its main string (see Figure A.2). The definition of polyester includes
the large family of synthetic polymers, with polycarbonate being the most used and poly(ethylene terephthalate)
(PET) the most of all.
Figure A.2 — Ester bond
A.15 Polyester fibre
Polyester fibre are fibres composed of synthetic linear macromolecules having in the chain at least 85 % (mass
fraction) of an ester of a diol and benzene-1,4-dicarboxylic acid (terephthalic acid).
A.16 Polyamides
A synthetic linear polymer in which the linkage of the simple chemical compound or compounds used in its
production takes place through the formation of amide groups, for example
[— R — CO — NH — R — CO — NH —] , or
n
[ — R — NH — CO — R — CO — NH —] ,
1 2 n
where R, R , and R are generally, but not necessarily, linear divalent hydrocarbon chains (— CH —) .
1 2 2 m
ISO/TR 16178:2012(E)
Polyamides are distinguished from one another by quoting the number of carbon atoms in the repeating unit or
units for polyamides made from two reactants. In the latter case, the number of carbon atoms in the diamine is
given first, followed by the number in the dicarboxylic acid, for example
- hexanolactam ( E – caprolactam)
[— NH — (CH ) — CO — ] (Nylon 6)
2 5 n
- 1,6 – diaminohexane + hexanedioic acid (adipic acid)
[— NH — (CH ) — NH — CO — (CH ) — CO — ] (Nylon 6:6)
2 6 2 4 n
- 1,6 – diaminohexane + decanedioic acid
[— NH — (CH ) — NH — CO — (CH ) — CO — ] (Nylon 6:10)
2 6 2 8 n
1)
Polyamide (synthetic fibre) and Nylon (synthetic fibre) are used to describe fibres composed of synthetic linear
macromolecules, having in the chain, recurring amide groups, at least 85 % of which are attached to aliphatic
or cyclo-aliphatic groups.
Nylon is a thermoplastic polymer belonging to the polyamide group (PA). It has good tensile properties, high hardness
and toughness. Nylon fibres are commonly used by the textile industry in the shape of threads. This material is
comprised of long-chain synthetic polyamides containing amide groups (-CONH-), in the core of the polymeric
chain. Although there are different varieties of Nylon, the most commonly known are Nylon 6.6 and Nylon 6.
A.17 Chlorofibres
Chlorofibres is a term used to describe fibres composed of synthetic linear macromolecules with more than
50 % (mass fraction) of chloroethene (vinyl chloride) or I,J-dichloroethene (vinylidene chloride) groups in their
chains. [More than 65 %, in the case where the rest of the chain is made up of cyanoethene (acrylonitrile)
groups, the modacrylic fibres being thus excluded.]
A.18 Polyacrylic
Polyacrylics are a synonym for copolymer fabrics with polyacrylnitrile (PAN) and polymethyl-methacrylates
2)
(PMMA). The content of PAN shall be higher than 85 %. Typical materials are Dralon, Orlon or Dolan .
A.19 Natural textile
A.19.1 General
Natural textile describes articles of clothing and textile commodities, which are produced from natural fibres by
special criteria. Natural fibres should be untreated or, at least, treated to the least extent possible. The porosity of
the fibres should be guaranteed, in any case, and the natural textile articles should be water vapour permeable.
NOTE Natural fibres are fibres made from animals, plants or minerals (cotton, wool, silk, linen, etc.). Fibres of natural
origin, which are intended to be spinnable by means of chemical preparation, just like viscose rayon or modal, are not
considered natural fibres.
A.19.2 Proteinic textile
Proteinic textile is textile issued from animal fibres.
1) Nylon is a trademark. This information is given for the convenience of users of this document and does not constitute
an endorsement by ISO. Equivalent products may be used if they can be shown to lead to the same results.
2) Dralon, Orlon and Dolan are trademarks. This information is given for the convenience of users of this document and
does not constitute an endorsement by ISO. Equivalent products may be used if they can be shown to lead to the same
results.
10 © ISO 2012 – All rights reserved

ISO/TR 16178:2012(E)
A.19.3 Cellulosic textile
Cellulosic textile is textile issued from vegetable fibres.
A.19.4 Man-made textile fibres
Man-made textile fibres are textiles which are not issued from proteinic or cellulosic fibres.
A.19.5 Mixed textile
Mixed textiles consist of a mix of natural fibres and chemical fibres.
A.20 Print for textile
Textile printing is a process of applying colour to fabric or non-woven textile in definite patterns or designs. In
properly printed fabrics, the colour is bonded with the fibre so as to resist washing and friction. Textile printing
is related to dyeing but, whereas in dyeing proper the whole fabric is uniformly covered with one colour, in
printing, one or more colour(s) are applied to the fabric in certain parts only and in sharply defined patterns.
In printing, wooden blocks, stencils, engraved plates, rollers or silkscreen are used to place colours on fabric.
Colourants used in printing contain dyes or pigments.
NOTE Traditional textile printing techniques can be broadly categorized into four styles:
— direct printing, in which colourants containing dyes, thickener and the mordents or substances necessary for
fixing the colour on the textile are printed in the desired pattern;
— the printing of a mordent in the desired pattern prior to dyeing cloth; the colours adhere only where the
mordent is printed;
— resist dyeing, in which a wax or other substance is printed on to fabric, which is subsequently dyed, leaving
uncoloured patterns against a coloured ground;
— discharge printing, in which a bleaching agent is printed into previously dyed fabrics to remove some or the
entire colour.
All printing pastes, whether containing colouring matter or not, are known technically as colours and these
colours, over colouring matter, contain thickening agents as vehicles in printing. Thickening agents include
starch, flour, arabic gum, dextrin or albumen, filler and mordent agent to enable fixing of the colours in textile.
A.21 Wood
Wood is a hard, fibrous, lignified structural tissue produced as secondary xylem in the stems of woody plants,
notably trees, but also shrubs. Wood is a heterogeneous, hygroscopic, cellular and anisotropic material. Wood
is composed of fibre of cellulose and hemicelluloses, impregnated with lignin.
In the footwear industry, wood can find some application mostly in particular types of shoes, i.e. sandals, where
hardness and structural resistance of raw materials are required.
Wood is often preserved by chemical treatments.
A.22 Cork
Cork material is a subset of generic cork tissue, harvested for commercial use primarily from the cork oak tree,
Quercus suber. Cork’s elasticity, light weight combined with is near impermeability makes it a suitable material
for many uses.
The cork material is also used in the footwear industry for application where a high structural resistance is not
required, typically as an insole material for certain types of shoes.
ISO/TR 16178:2012(E)
A.23 Adhesives
An adhesive is a non-metallic substance capable of joining materials by surface bonding (adhesion) and by the
bond possessing adequate internal strength (cohesion).
In the footwear industry, many types of adhesives are used in bonding upper and sole as the major joint, but
also for the minor joint in footwear.
EN 923 contains a systematic classification of all adhesives, with the corresponding definitions.
The formulation of the adhesives is classified in EN 923. Due to the large number of adhesives used, there are
no corresponding typical formulations available for adhesives used for the minor joint in footwear.
A.24 Metallic hardware
Metallic hardware is any material composed entirely of a single metallic element or a combination of metallic
elements (alloys). This may be coated to give a desired appearance. This may be achieved by painting, plating
or varnishing.
Uses of metallic components include fastenings, ornamental decorations, structural component and assembling.
A.25 Cellulosic material
Cellulosic material is material made from cellulose fibre (for example paper). Where is used as insole material,
it contains a binder.
12 © ISO 2012 – All rights reserved

ISO/TR 16178:2012(E)
Annex B
(informative)
Critical substances potentially present in footwear and footwear
components
B.1 General
This annex describes the critical substances potentially present in footwear and footwear components.
Depending on the tested product and application (see Table 1), different test methods can be used.
B.2 Acrylonitrile
B.2.1 General
Chemical compound with the formula CH CHCN.
Figure B.1 — Acrylonitrile molecular structure
This pungent-smelling colourless liquid often appears yellow due to impurities. It is an important monomer for
the manufacture of useful plastics. In terms of its molecular structure, it consists of a vinyl group linked to a nitrile.
Acrylonitrile is used principally as a monomer in the manufacture of synthetic polymers, especially
polyacrylonitrile, which comprises acrylic fibres. Acrylic fibres are, among other uses, precursors for well-known
carbon-fibre. It is also a component of synthetic rubber.
Synthetic rubber, essentially based on SBR (styrene-butadiene rubber) and containing acrylonitrile has
some properties which are suitable for use as a material for soles, especially for a sole in professional high-
resistance footwear.
B.2.2 Potential risks
Acrylonitrile is highly flammable and toxic. It undergoes explosive polymerization. The burning material releases
fumes of hydrogen cyanide and oxides of nitrogen. Acrylonitrile is classified as a recognized human carcinogen.
Where polymerized or in composition as synthetic rubber, it is considered inert material and no particular
problems rise in using acrylonitrile.
In footwear products, the problems of the use of acrylonitrile are essentially correlated with waste management,
in order to avoid uncontrolled burning process, which can release dangerous fumes into the environment.
B.2.3 Test methods
At the time of publication of this Technical Report, there is no standard available for acrylonitrile analysis in
footwear and footwear components.
ISO/TR 16178:2012(E)
B.3 Aromatic amines
B.3.1 General
Aromatic amines are amines with an aromatic substituent, that is -NH , -NH- or nitrogen group(s) attached
to an aromatic hydrocarbon, whose structure usually contains one or more benzene rings. Benzidine is an
example (see Figure B.2).
Figure B.2 — Example of aromatic amines molecular structure —Benzidine
Aromatic amines are produced during the degradation of azo-dyes.
The list of the critical amines is given in Table B.1.
Table B.1 — List of critical aromatic amines developed by azo-dyestuffs
Compound CAS number Compound CAS number
4-aminobiphenyl 92-67-1 3,3’-dimethyl-4,4’-diaminodiphenylmethane 838-88-0
Benzidine 92-87-5 p-cresidine 120-71-8
4-chloro-o-toluidine 95-69-2 4,4’-methylen-bis(2-chloraniline) 101-14-4
2-naphthylamine 91-59-8 4,4’-oxydianiline 101-80-4
o-aminoazotoluene 97-56-3 4,4’-thiodianiline 139-65-1
2-amino-4-nitrotoluene 99-55-8 o-toluidine 95-53-4
p-chloroaniline 106-47-8 2,4-toluylendiamine 95-80-7
2,4-diaminoanisole 615-05-4 2,4,5-trimethylaniline 137-17-7
a
4,4’- diaminodiphenylmethane 101-77-9 2,4-dimethylaniline (=2,4-Xylidine) 95-68-1
a
3,3’-dichlorobenzidine 91-94-1 2,6-dimethylaniline (=2,6-Xylidine) 87-62-7
3,3’-dimethoxybenzidine 119-90-4 2-methoxyaniline (=o-anisidine) 90-04-0
3,3’-dimethylbenzidine 119-93-7 4-aminoazobenzene 60-09-3
a
This is not requested by the European Directive 2002/95/EC, but may be considered in some other countries.
B.3.2 Potential risks
The aromatic amines given in Table B.1 are known to be carcinogenic (4-aminobiphenyl, benzidine,
4-chlor-o-toluidine, 2-naphthylamine) or suspected to be carcinogenic (others). These substances are restricted
in many countries.
B.3.3 Test methods
For the purposes of this Technical Report, the content of aromatic amines can be tested with one of the
test methods in
— ISO 17234-1,
— ISO 17234-2,
— EN 14362-1,
— EN 14362-2, or
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ISO/TR 16178:2012(E)
— EN 14362-3.
B.4 Cadmium — Cd
For cadmium (Cd), see B.13.
B.5 Chloroorganic carriers
B.5.1 General
The halogenated carriers, are mainly used in the manufacture of polyester. Table B.2 includes a list of some
of these compounds.
Table B.2 — List of chloroorganic carriers
Substance CAS number
1,2-DICHLOROBENZENE [95-50-1] 1,4-DICHLOROBENZENE [106-46-7]
Dichlorobenzenes
1,3-DICHLOROBENZENE [541-73-1]
1,2,3-TRICHLOROBENZENE [87-61-6] 1,3,5-TRICHLOROBENZENE [108-70-3]
Trichlorobenzenes
1,2,4-TRICHLOROBENZENE [120-81-1]
Tetrachlorobenzenes TETRACHLOROBENZENE [634-66-2]
Pentachlorobenzene PENTACHLOROBENZENE [608-93-5]
Hexachlorobenzene HEXACHLOROBENZENE [118-74-1]
2-CHLOROTOLUENE [95-49-9] 4-CHLOROTOLUENE [106-43-4]
Chlorotoluene
3-CHLOROTOLUENE [108-41-8]
2,3-DICHLOROTOLUENE [32768-54-0] 2,6-DICHLOROTOLUENE [118-69-4]
Dichlorotoluenes 2,4-DICHLOROTOLUENE [95-73-8] 3,4 DICHLOROTOLUENE [95-75-0]
2,5-DICHLOROTOLUENE [19398-61-9]
2,3,6-TRICHLOROTOLUENE [2077-46-5] alpha, 2,4 TRICHLOROTOLUENE [94-99-5]
Trichlorotoluenes 2,4,5-TRICHLOROTOLUENE [6639-30-1] alpha, 2,6 TRICHLOROTOLUENE [2014-83-7]
alpha, alpha alpha TRICHLOROTOLUENE [98-07-7] alpha, 3,4 TRICHLOROTOLUENE [102-47-6]
alpha, alpha, 2,6 TETRACHLOROTOLUENE [81-19-6] alpha, 4 – TETRACHLOROTOLUENE [5216-25-1]
Tetrachlorotoluenes alpha, alpha, alpha, 2 – TETRACHLOROTOLUENE
[2136-89-2]
Pentachlorotoluene 2,3,4,5,6-PENTACHLOROTOLUENE [877-11-2]
B.5.2 Potential risks
The substances listed in Table B.2 are toxic and some of them carcinogenic.
B.5.3 Test methods
For the purposes of this Technical Report, the content of chloroorganic carriers can be tested using the test
method in DIN 54232.
B.6 Chromium and chromium VI
For chromium and chromium VI, see B.13.
B.7 Colophony
B.7.1 General
Colophony is also called Greek pitch or rosin. The major part of rosin used is obtained as a by-product of the
pulp industry and is known as tall oil rosin. These two types of rosin do not have the same composition although
ISO/TR 16178:2012(E)
they have major products in common; however, a variation in the amounts of the different compounds is seen.
They are often used for the same purposes and, probably, in shoes modified tall oil rosin is found most often .
Both types of rosin consist of 90 % resin acids and 10 % neutral material. In colophony of the gum rosin type,
the major resin acid is abietic acid, while dehydroabietic acid dominates in tall oil rosin. 7-Oxo-dehydroabietic
acid is a stable oxidation product, which is used as a marker for the presence of other autoxidation products in
rosin, e.g. 15-hydroperoxyabietic acid. The latter is identified as the major allergen in colophony. However, this
hydroperoxide is not suitable for analysis since it is not stable enough.
Colophony is an ingredient in printing inks, varnishes, adhesives (glues), soap, paper sizing, soda, and, in past
times, was an ingredient in sealing wax.
B.7.2 Potential risks
Prolonged exposure to colophony fumes released during soldering can cause occupational asthma in sensitive
individuals, therefore, it is considered an allergen.
Colophony is one of the most common causes of skin (contact) allergy, which is caused by contact with
colophony on the skin. It is on the ten top list of all skin allergens tested worldwide. Colophony in shoes is
considered to be a dominating cause of sensitization in this aspect.
NOTE Colophony is classified in the EU legislation due to its skin sensitizing properties and products containing more
than 1 % of colophony are marked with R 43 (i.e. can cause skin sensitization). However, in the EU legislation, there is no
demand for R 42 (lung allergy).
B.7.3 Test methods
At the time of publication of this Technical Report, there is no standard available for colophony analysis in
footwear and footwear components.
B.8 Dimethylformamide
B.8.1 General
Dimethylformamide (DMF) is the organic compound with the formula (CH ) NC(O)H. Commonly abbreviated
3 2
as DMF, this colourless liquid is miscible with water and the majority of organic liquids. DMF is a common
solvent for chemical reactions. Pure dimethylformamide is odourless, whereas technical grade or degraded
dimethylformamide often has a fishy smell due to impurity of dimethylamine (CAS number is [68-12-2]).
Figure B.3 — Dimethylformamide molecular structure
Its name is derived from the fact that it is a derivative of formamide, the amide of formic acid. The primary use
of dimethylformamide is as a solvent with low evaporation rate. Dimethylformamide is used in the production
of acrylic fibres and plastics. It is also used in the manufacture of adhesives, synthetic leathers, fibres, films,
and surface coatings.
B.8.2 Potential risks
Dimethylformamide is harmful by inhalation, ingestion or skin contact and can act as a carcinogen. Ingestion
or absorption through skin can be fatal. Exposure can result in foetal death. Long-term exposure can result in
kidney or liver damage. It is also an irritant.
16 © ISO 2012 – All rights reserved

ISO/TR 16178:2012(E)
B.8.3 Test methods
At the time of publication of this Technical Report, there is no standard available for DMF analysis in footwear
and footwear components.
B.9 Dimethylfumarate
B.9.1 General
Dimethylfumarate (DMFU) (CAS number [624-49-7]) is used to treat psoriasis. It is a lipophilic, highly mobile
molecule in human tissue. However, as an α,β-unsaturated ester, dimethylfumarate reacts rapidly with the
detoxifying agent glutathione by Michael addition.
Another use for dimethylfumarate is mould inhibition. Dimethylfumarate is used also as a biocide.
Figure B.4 — Dimethylfumarate molecular structure
B.9.2 Potential risks
Dimethylfumarate has been found to be a sensitizer at very low concentrations, producing extensive, pronounced
eczema, which is difficult to treat. Low concentrations of about 1 ppm (0,998 859 mg/L) can produce allergic reactions.
NOTE The extreme sensitizing risk was brought to public attention by the “poison chair” incident, where a Chinese
manufacturer produced two-seater sofas, which contained DMFU sachets in the interior in order to inhibit mould while they
were in storage or transport. The cause was identified as dimethylfumarate-induced allergic reaction.
B.9.3 Test methods
For the purposes of this Technical Report, the content of DMFU can be tested using the test method in
ISO/TS 16186.
B.10 Disperses dyes
B.10.1 General
A dye can generally be described as a coloured substance, which has an affinity for the substrate to which it
is being applied. The dye is generally applied in an aqueous solution, and can require a mordant to improve
the fastness of the dye on the fibre. Both dyes and pigments appear to be coloured because they preferentially
absorb some wavelengths of light. In contrast with a dye, a pigment generally is insoluble and has no affinity
for the substrate. Some dyes can be precipitated with an inert salt to produce a lake pigment.
A list of allergenic dyes and of carcinogenic dyes is included in Table B.3 and Table B.4, respectively.
...