SIST EN ISO 14362-1:2017

SLOVENSKI STANDARD
SIST EN ISO 14362-1:2017
01-april-2017
1DGRPHãþD
SIST EN 14362-1:2012
7HNVWLOLMH0HWRGH]DGRORþHYDQMHQHNDWHULKDURPDWVNLKDPLQRYL]YLUDMRþLKL]D]R
EDUYLOGHO=D]QDYDQMHSULVRWQRVWLGRORþHQLKD]REDUYLOGRVWRSQLK]
HNVWUDKLUDQMHPYODNHQLQEUH]QMHJD,62
Textiles - Methods for determination of certain aromatic amines derived from azo
colorants - Part 1: Detection of the use of certain azo colorants accessible with and
without extracting the fibres (ISO 24362-1:2017)
Textilien - Verfahren für die Bestimmung gewisser aromatischer Amine aus
Azofarbstoffen - Teil 1: Nachweis der Verwendung gewisser Azofarbstoffe mit und ohne
Extraktion der Fasern (ISO 24362-1:2017)
Textiles - Méthodes de détermination de certaines amines aromatiques dérivées de
colorants azoïques - Partie 1 : Détection de l'utilisation de certains azo-colorants
accessibles avec ou sans extraction (ISO 24362-1:2017)
Ta slovenski standard je istoveten z: EN ISO 14362-1:2017
ICS:
59.080.01 Tekstilije na splošno Textiles in general
SIST EN ISO 14362-1:2017 sl,en,fr
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST EN ISO 14362-1:2017

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SIST EN ISO 14362-1:2017


EN ISO 14362-1
EUROPEAN STANDARD

NORME EUROPÉENNE

February 2017
EUROPÄISCHE NORM
ICS 59.060.01 Supersedes EN 14362-1:2012
English Version

Textiles - Methods for determination of certain aromatic
amines derived from azo colorants - Part 1: Detection of
the use of certain azo colorants accessible with and
without extracting the fibres (ISO 14362-1:2017)
Textiles - Méthodes de détermination de certaines Textilien - Verfahren für die Bestimmung gewisser
amines aromatiques dérivées de colorants azoïques - aromatischer Amine aus Azofarbstoffen - Teil 1:
Partie 1: Détection de l'utilisation de certains colorants Nachweis der Verwendung gewisser Azofarbstoffe mit
azoïques accessibles avec ou sans extraction (ISO und ohne Extraktion der Fasern (ISO 14362-1:2017)
14362-1:2017)
This European Standard was approved by CEN on 21 December 2016.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this
European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references
concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN
member.

This European Standard exists in three official versions (English, French, German). A version in any other language made by
translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.

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, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and United Kingdom.





EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2017 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 14362-1:2017 E
worldwide for CEN national Members.

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SIST EN ISO 14362-1:2017
EN ISO 14362-1:2017 (E)
Contents Page
European foreword . 3

2

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SIST EN ISO 14362-1:2017
EN ISO 14362-1:2017 (E)
European foreword
This document (EN ISO 14362-1:2017) has been prepared by Technical Committee ISO/TC 38
"Textiles" in collaboration with Technical Committee CEN/TC 248 “Textiles and textile products” the
secretariat of which is held by BSI.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by August 2017, and conflicting national standards shall
be withdrawn at the latest by August 2017.
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 EN 14362-1:2012.
According to the CEN-CENELEC Internal Regulations, the national standards organizations of the
following countries are bound to implement this European Standard: 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, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and the United Kingdom.
Endorsement notice
The text of ISO 14362-1:2017 has been approved by CEN as EN ISO 14362-1:2017 without any
modification.

3

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SIST EN ISO 14362-1:2017

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SIST EN ISO 14362-1:2017
INTERNATIONAL ISO
STANDARD 24362-1
First edition
2014-02-01
Textiles — Methods for determination
of certain aromatic amines derived
from azo colorants —
Part 1:
Detection of the use of certain azo
colorants accessible with and without
extracting the fibres
Textiles — Méthodes de détermination de certaines amines
aromatiques dérivées de colorants azoïques —
Partie 1: Détection de l’utilisation de certains colorants azoïques
accessibles avec ou sans extraction
Reference number
ISO 24362-1:2014(E)
©
ISO 2014

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SIST EN ISO 14362-1:2017
ISO 24362-1:2014(E)

COPYRIGHT PROTECTED DOCUMENT
© ISO 2014
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
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Tel. + 41 22 749 01 11
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E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2014 – All rights reserved

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SIST EN ISO 14362-1:2017
ISO 24362-1:2014(E)

Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Normative references . 1
3 General . 1
4 Principle . 3
5 Safety precautions . 3
6 Reagents . 3
7 Apparatus . 5
8 Test specimen sampling and preparation . 6
8.1 General . 6
8.2 Textile article . 6
8.3 Fibre composition . 7
8.4 Case of the fibre blends. 7
8.5 Printed materials . 7
8.6 Colours . 7
9 Procedure. 8
9.1 Colorant extraction for disperse dyes . 8
9.2 Textiles dyed with dyes other than disperse dyes . 8
9.3 Reductive cleavage . 8
9.4 Separation and concentration of the amines . 9
9.5 Amine detection and quantification . 9
9.6 Check procedure . 9
10 Evaluation .11
10.1 General .11
10.2 Calculation of amine in the sample .11
10.3 Reliability of the method .11
11 Test report .11
Annex A (informative) Chromatographic analyses .12
Annex B (informative) Reliability of the method .16
Annex C (informative) Assessment guide — Interpretation of analytical results .17
Annex D (informative) Explanatory table of dyestuffs used in various textile materials .19
Annex E (informative) Procedure for liquid-liquid-extraction without diatomaceous earth.21
Annex F (normative) Colorants-Methods for determination of certain aromatic amines .24
Bibliography .25
© ISO 2014 – All rights reserved iii

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SIST EN ISO 14362-1:2017
ISO 24362-1:2014(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.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2. www.iso.org/directives
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. Details of any
patent rights identified during the development of the document will be in the Introduction and/or on
the ISO list of patent declarations received. www.iso.org/patents
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical Barriers
to Trade (TBT) see the following URL: Foreword - Supplementary information
The committee responsible for this document is ISO/TC 38, Textiles.
ISO 24362 consists of the following parts, under the general title Textiles — Methods for determination of
certain aromatic amines derived from azo colorants:
— Part 1: Detection of the use of certain azo colorants accessible with and without extracting the fibres
— Part 3: Detection of the use of certain azo colorants, which may release 4-aminoazobenzene
iv © ISO 2014 – All rights reserved

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SIST EN ISO 14362-1:2017
ISO 24362-1:2014(E)

Introduction
This part of ISO 24362 is based on EN 14362-1:2012 which has been prepared by Technical Committee
CEN/TC 248 “Textiles and textile products”, the secretariat of which is held by BSI.
© ISO 2014 – All rights reserved v

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SIST EN ISO 14362-1:2017
INTERNATIONAL STANDARD ISO 24362-1:2014(E)
Textiles — Methods for determination of certain aromatic
amines derived from azo colorants —
Part 1:
Detection of the use of certain azo colorants accessible
with and without extracting the fibres
1 Scope
This part of ISO 24362 describes a procedure to detect the use of certain azo colorants that may not
be used in the manufacture or treatment of certain commodities made of textile fibres and that are
accessible to a reducing agent with and without extraction.
Azo colorants accessible to a reducing agent without extraction are those used to dye:
— cellulosic fibres (e.g. cotton, viscose);
— protein fibres (e.g. wool, silk);
— synthetic fibres (e.g. polyamide, acrylic).
Azo colorants accessible with extraction are those used to dye man-made fibres with disperse dyes. The
following man-made fibres can be dyed with disperse dyes: polyester, polyamide, acetate, triacetate,
acrylic, modacrylic, aramid and chlorofibre.
For certain commodities made of cellulose and/or protein fibres blended with man-made fibres it is
necessary to extract the dye first.
The method is relevant for all coloured textiles, e.g. dyed, printed and coated textiles.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated
references, the latest edition of the referenced document (including any amendments) applies.
ISO 3696:1987, Water for analytical laboratory use — Specification and test methods
3 General
Certain azo colorants may release, by reductive cleavage of azo group(s), one or more of the following
aromatic amines.
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SIST EN ISO 14362-1:2017
ISO 24362-1:2014(E)

Table 1 — Aromatic amines subjected
No. CAS number Index number EC number Substances
1 92–67–1 612–072–00–6 202–177–1 biphenyl-4-ylamine
4-aminobiphenyl
xenylamine
2 92–87–5 612–042–00–2 202–199–1 benzidine
3 95–69–2 612–196–00–0 202–441–6 4-chloro-o-toluidine
4 91–59–8 612–022–00–3 202–080–4 2-naphthylamine
a
5 97–56–3 611–006–00–3 202–591–2 o-aminoazotoluene
4-amino-2’,3-dimethylazobenzene
4-o-tolylazo-o-toluidine
a
6 99–55–8 612–210–00–5 202–765–8 5-nitro-o-toluidine
2-amino-4-nitrotoluene
7 106–47–8 612–137–00–9 203–401–0 4-chloroaniline
8 615–05–4 612–200–00–0 210–406–1 4-methoxy-m-phenylenediamine
2,4-diaminoanisole
9 101–77–9 612–051–00–1 202–974–4 4,4’-methylenedianiline
4,4’-diaminodiphenylmethane
10 91–94–1 612–068–00–4 202–109–0 3,3’-dichlorobenzidine
3,3’-dichlorobiphenyl-4,4’-ylenediamine
11 119–90–4 612–036–00-X 204–355–4 3,3’-dimethoxybenzidine
o-dianisidine
12 119–93–7 612–041–00–7 204–358–0 3,3’-dimethylbenzidine
4,4’-bi-o-toluidine
13 838–88–0 612–085–00–7 212–658–8 4,4’-methylenedi-o-toluidine
14 120–71–8 612–209–00-X 204–419–1 6-methoxy-m-toluidine
p-cresidine
15 101–14–4 612–078–00–9 202–918–9 4,4’-methylene-bis-(2-chloro-aniline)
2,2’-dichloro-4.4’-methylene-dianiline
16 101–80–4 612–199–00–7 202–977–0 4,4’-oxydianiline
17 139–65–1 612–198–00–1 205–370–9 4,4’-thiodianiline
18 95–53–4 612–091–00-X 202–429–0 o-toluidine
2-aminotoluene
19 95–80–7 612–099–00–3 202–453–1 4-methyl-m-phenylenediamine
2,4-toluylendiamine
2,4-diaminotoluene
20 137–17–7 612–197–00–6 205–282–0 2,4,5-trimethylaniline
21 90–04–0 612–035–00–4 201–963–1 o-anisidine
2-methoxyaniline
b
22 60–09–3 611–008–00–4 200–453–6 4-aminoazobenzene
a
The CAS-numbers 97–56–3 (No. 5) and 99–55–8 (No. 6) are further reduced to CAS-numbers 95–53–4 (No. 18) and
95–80–7 (No. 19).
b
Azo colorants that are able to form 4-aminoazobenzene, generate under the condition of this method aniline (CAS-
number 62–53–3) and 1,4-phenylenediamine (CAS – number 106–50–3). Due to detection limits, only aniline may be
detected. The presence of these colorants should be tested by ISO 24362-3.
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SIST EN ISO 14362-1:2017
ISO 24362-1:2014(E)

4 Principle
After selection of a coloured test specimen from the textile article, the test specimen is tested according
to the method of colorant extraction for disperse dyes and/or the method of direct reduction for the
other classes of dyes.
The application of the combined methods or one of the two methods is based on the nature of the fibre(s)
of the test specimen (composed of pure fibre or of fibre blends) and the colour treatment (dyeing or
printing process). When relevant, if the test specimen is not discoloured during the application of one of
the two methods, the other one is carried out.
When the method of the colorant extraction for disperse dyes is carried out, the colorant is first
extracted from the fibre in the headspace (see Figure 1) using chlorobenzene under reflux. The extract
is concentrated and transferred to the reaction vessel with methanol for subsequent reduction with
sodium dithionite in a citrate-buffered aqueous solution (pH = 6) at 70 °C. If the textile specimen is not
completely discoloured after chlorobenzene extraction, the specimen is added to the reaction vessel
with the methanolic solution of the dispersed dye for combined reduction.
When the method for the other classes of the dyes is carried out, the test specimen is treated with
sodium dithionite in a citrate-buffered aqueous solution (pH = 6) at 70 °C in a closed vessel.
After the reduction, any amine released in the process is transferred to a t-butyl methyl ether phase by
means of liquid-liquid extraction using diatomaceous earth columns. The t-butyl methyl ether extract is
then concentrated, and the residue is taken up in a solvent appropriate for detection and determination
of the amines using chromatography (see Annex A).
A screening method, using liquid-liquid extraction without diatomaceous earth columns, is described
in Annex E.
If any amine is detected by one chromatographic method, then confirmation shall be made using one or
more alternative methods.
5 Safety precautions
WARNING — The substances [amines] listed in Clause 3 are classified as substances known to be
or suspected of being human carcinogens.
5.1 Any handling and disposal of these substances shall be in strict accordance with the appropriate
national health and safety regulations.
5.2 It is the user’s responsibility to use safe and proper techniques in handling materials in this
test method. Consult manufacturers for specific details such as material safety data sheets and other
recommendations.
5.3 Good laboratory practice should be followed. Wear safety glasses in all laboratory areas and a
single-use dust respirator while handling powder colorants.
5.4 Users should comply with any national and local safety regulations.
6 Reagents
Unless otherwise specified, analytical grade chemicals shall be used.
6.1 Chlorobenzene.
WARNING — This is a toxic chemical. To handle chlorobenzene, special care is required to prevent
skin contact swallowing and aspiration.
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SIST EN ISO 14362-1:2017
ISO 24362-1:2014(E)

6.2 Acetonitrile.
6.3 Methanol.
6.4 t-butyl methyl ether.
6.5 n-pentane.
1)
6.6 Citrate/sodium hydroxide buffer solution, pH = 6, c = 0,06 mol/l .
2)
6.7 Aqueous sodium dithionite solution, ρ = 200 mg/ml freshly (daily) prepared.
6.8 Diatomaceous earth.
6.9 Amine substances, amines 1 to 21 (as specified in Table 1), and aniline and 1,4-phenylenediamine,
all of the highest available defined purity standard.
6.10 Standard solutions.
6.10.1 Stock solution of amines with a concentration of equal to or greater than 300 μg of each amine
per millilitre of an appropriate solvent.
NOTE Acetonitrile is an appropriate solvent for this stock solution, resulting in good stability of amines.
6.10.2 Calibration solution of amines for daily use.
Dilute from the stock solution 6.10.1 to a concentration of ρ = 15,0 µg of each amine per millilitre of an
appropriate solvent.
6.10.3 Calibration solutions of amines for quantification, concentration range from 2 µg up to 50 µg
of each amine per millilitre of an appropriate solvent.
NOTE It is the responsibility of each lab to choose appropriate concentrations for the calibration.
6.10.4 Internal standards in solution (IS), ρ = 1,0 mg of IS/ml of the appropriate IS solvent.
In case of GC-MS analysis, use one of the following internal standards:
— IS1: benzidine-d8, CAS No.: 92890-63-6;
— IS2: naphthalene-d8, CAS No.: 1146-65-2;
— IS3: 2,4,5-trichloroaniline, CAS No.: 636-30-6;
— IS4: anthracene-d10, CAS No.: 1719-06-8.
NOTE If the confirmation analysis for benzidine is done with DAD or TLC the use of IS1: benzidine-d8, CAS
No.: 92890–63–6 is not feasible, because the peak cannot be separated from the none deuterated benzidine.
6.11 Sodium hydroxide aqueous solution, a mass fraction of 10 %.
6.12 Grade 3 water, complying with ISO 3696:1987.
1) c is citrate concentration.
2) ρ is the mass concentration.
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SIST EN ISO 14362-1:2017
ISO 24362-1:2014(E)

7 Apparatus
7.1 Extraction apparatus, according to Figure 1, consisting of:
— coil condenser NS 29/32;
— a hook, made from an inert material to hold the specimen in place so that the condensed solvent
drips onto it;
— 100 ml round bottom flask NS 29/32;
— heating source.
Figure 1 — Apparatus
NOTE Similar apparatus may be used, if the same results are obtained.
7.2 Ultrasonic bath, capable of ultrasonic power 160 Watt RMS, with controllable heating equipment.
7.3 Reaction vessel (20 ml to 50 ml) of heat-resistant glass, with tight closure.
7.4 Heating source, capable of maintaining the temperature at (70 ± 2) °C.
7.5 Glass or polypropylene column, inside diameter 25 mm to 30 mm, length 130 mm to 150 mm,
packed with 20 g of diatomaceous earth (6.8), fitted with a glass-fibre filter at the outlet.
The diatomaceous earth columns are either bought pre-packed and used as is, or 20 g of diatomaceous
earth can be packed into a glass or polypropylene column of the dimensions given.
7.6 Vacuum rotary evaporator with vacuum control and water bath.
NOTE Other kinds of evaporation apparatus may be used, e.g. a water bath with a controlled flow of nitrogen
over the liquid.
7.7 Pipettes in required sizes or variable pipettes.
7.8 Chromatographic equipment selected from the following:
7.8.1 Thin layer chromatography (TLC) or high performance thin layer chromatography (HPTLC)
equipment, including relevant detection.
7.8.2 High performance liquid chromatography (HPLC) equipment, with gradient elution and
diode array detector (DAD) or mass selective detector (MS).
7.8.3 Gas chromatography (GC) equipment,with flame ionization detector (FID) or mass selective
detector (MS).
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SIST EN ISO 14362-1:2017
ISO 24362-1:2014(E)

7.8.4 Capillary electrophoresis (CE) equipment,with diode array detector (DAD).
NOTE A description of the chromatographic equipment is given in Annex A.
8 Test specimen sampling and preparation
8.1 General
The test specimen shall be selected based on the following criteria:
— Parts of the textile article;
— Nature of the fibre components (fibre composition);
— Printed materials;
— Colours.
Prepare the test specimen by cutting in order to obtain a total mass of 1 g. For specimens to be submitted
to colorant extraction (9.1) cut into strips (if apparatus described in 7.1 is used) or cut into small pieces
if other apparatus is used or for specimens to be submitted only to reductive cleavage (9.3).
8.2 Textile article
If the textile article is a semi-manufactured product, such as yarns, fabrics, etc., cut out test specimens
from it.
If the textile article is composed of several parts of textile products, such as a garment, cut out test
specimens from all the parts of the textile article that have direct and prolonged contact to skin or
mouth, which can be:
— principal fabric(s);
— lining(s);
— pocket fabric(s);
— embroideries;
— label(s) for textile article;
— drawstring(s);
— fastener(s);
— false fur;
— sewing threads.
If the mass of some parts (e.g. labels, sewing threads, embroideries of small size) does not reach the mass
(1 g) to be tested, gather identical parts when possible. If the total mass of material is below 0,5 g, this
material is defined as a minor component. (See NOTE 2, Annex C.)
Below 0,2 g of material the analysis is omitted.
NOTE If there are omitted portions of sampling because of less than 0,2 g, record the details in the test
report.
Embroideries shall be weighed with the ground fabric.
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SIST EN ISO 14362-1:2017
ISO 24362-1:2014(E)

8.3 Fibre composition
As the application of this part of ISO 24362 is partly based on the extraction of colorants, identify the
nature of the textile
...