EN ISO 14362-3:2017

Textiles - Methods for determination of certain aromatic amines derived from azo colorants - Part 3: Detection of the use of certain azo colorants, which may release 4-aminoazobenzene (ISO 14362-3:2017)

Azo colorants that are able to form 4-aminoazobenzene, generate under the conditions of ISO 14362-1, the amines aniline and 1,4-phenylenediamine. The presence of these 4-aminoazobenzene colorants cannot be reliably ascertained without additional information (e.g. the chemical structure of the colorant used) or without a special procedure.
ISO 14362-3:2017 is supplementary to ISO 14362-1 and describes a special procedure to detect the use, in commodities, of certain azo colorants, which may release 4-aminoazobenzene, and that are
-      accessible to reducing agent without extraction, particularly concerning textiles made of cellulose and protein fibres (e.g. cotton, viscose, wool, silk), and
-      accessible by extracting the fibres (e.g. polyester or imitation leather).
For certain fibre blends, in 9.3 and 9.4 (with and without extraction) may need to be applied.
The procedure also detects 4-aminoazobenzene (Solvent Yellow 1), which is already available as free amine in commodities without reducing pre-treatment.
The use of certain azo colorants, which may release, by reductive cleavage of their azo group(s), one or more of the other aromatic amines listed in the Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) as regards Annex XVII, except 4-aminoazobenzene, cannot be determined quantitatively with this method.

Textilien - Verfahren für die Bestimmung bestimmter aromatischer Amine aus Azofarbstoffen - Teil 3: Nachweis der Verwendung gewisser Azofarbstoffe, die 4-Aminoazobenzol freisetzen können (ISO 14362-3:2017)

Textiles - Méthodes de détermination de certaines amines aromatiques dérivées de colorants azoïques - Partie 3: Détection de l'utilisation de certains colorants azoïques susceptibles de libérer du 4-aminoazobenzène (ISO 14362-3:2017)

Les colorants azoïques capables de former du 4-aminoazobenzène génèrent, dans les conditions de l'ISO 14362‑1, des amines dont l'aniline et la 1,4-phénylènediamine. La présence de ces matières colorantes à base de 4-aminoazobenzène ne peut pas être déterminée de façon fiable sans informations supplémentaires (par exemple sur la structure chimique de la matière colorante colorant utilisé) ou sans mode opératoire spécifique.
ISO 14362-3:2017 est un complément à l'ISO 14362‑1 et décrit un mode opératoire spécifique permettant de détecter, dans des articles, l'utilisation de certains colorants azoïques pouvant libérer du 4-aminoazobenzène:
-      accessibles aux agents de réduction sans extraction, en particulier dans le cas des textiles fabriqués à partir de fibres de cellulose et de fibres animales (par exemple le coton, la viscose, la laine, la soie); et
-      accessibles par extraction des fibres (par exemple le polyester ou l'imitation du cuir).
Pour certains mélanges de fibres, il peut être nécessaire d'appliquer 9.3 et 9.4 (avec et sans extraction).
Le mode opératoire détecte également le 4-aminoazobenzène utilisé en tant que colorant (Solvent Yellow 1) qui est déjà disponible dans des articles sous la forme de l'amine libre, sans dégradation par traitement de réduction.
L'utilisation de certains colorants azoïques, qui peuvent libérer par clivage réducteur de leur(s) groupe(s) azoïque(s) une ou plusieurs des autres amines aromatiques répertoriées dans le Règlement CE n° 1907/2006 du Parlement européen et du Conseil concernant l'enregistrement, l'évaluation et l'autorisation des substances chimiques, ainsi que les restrictions applicables à ces substances (REACH) conformément à l'Annexe XVII, exception faite du 4-aminoazobenzène, ne peut pas être déterminée quantitativement avec cette méthode.

Tekstilije - Metode za določevanje nekaterih aromatskih aminov, izvirajočih iz azo barvil - 3. del: Zaznavanje prisotnosti določenih azo barvil, ki lahko sproščajo 4-aminoazobenzen (ISO 14362-3:2017)

Iz azo barvil, ki lahko tvorijo 4-aminoazobenzen, pod pogoji iz standarda ISO 14362-1 nastaneta amina anilin in 1,4-fenilenediamin. Prisotnosti teh barvil iz 4-aminoazobenzena ni mogoče zanesljivo ugotoviti brez dodatnih informacij (npr. kemijske strukture uporabljenega barvila) ali posebnega postopka.
Ta dokument dopolnjuje standard ISO 14362-1 in opisuje poseben postopek za zaznavanje prisotnosti (pri izdelkih) nekaterih azo barvil, ki lahko sproščajo 4-aminoazobenzen in so:
– reducentom dostopna brez ekstrahiranja, zlasti pri tekstilijah iz celuloznih in proteinskih vlaken (npr. bombaž, viskoza, volna, svila); ter
– dostopna z ekstrakcijo vlaken (npr. poliester ali umetno usnje).
Za nekatere mešanice vlaken (z ekstrahiranjem ali brez njega) bo morda treba uporabiti točki 9.3 in 9.4.
Postopek omogoča tudi zaznavanje 4-aminoazobenzena (Solvent Yellow 1 – topilo rumena 1), ki je v izdelkih že razpoložljiv kot prosti amin brez predhodne obdelave z redukcijo.
Kvantitativno določevanje uporabe določenih azo barvil, ki lahko z redukcijsko cepitvijo svojih azo skupin sproščajo enega ali več drugih aromatskih aminov iz Priloge XVII k Uredbi (ES) št. 1907/2006 Evropskega parlamenta in Sveta o registraciji, evalvaciji, avtorizaciji in omejevanju kemikalij (REACH), razen 4-aminoazobenzena, s to metodo ni mogoče.

General Information

• Status: Published
• Publication Date: 07-Feb-2017
• Withdrawal Date: 30-Aug-2017
• ICS: 59.060.01 - Textile fibres in general
• ICS: 59.080.01 - Textiles in general
• Technical Committee: CEN/TC 248 - Textiles and textile products
• Drafting Committee: CEN/TC 248/WG 26 - Methods of test for phthalates
• Current Stage: 6060 - Definitive text made available (DAV) - Publishing
• Start Date: 08-Feb-2017
• Due Date: 06-Jun-2017
• Completion Date: 08-Feb-2017
• Ref Project: SIST EN ISO 14362-3:2017 - Textiles - Methods for determination of certain aromatic amines derived from azo colorants - Detection of the use of certain azo colorants, which may release 4-aminoazobenzene (ISO 14362-3:2017)

Relations

• Replaces: EN 14362-3:2012 - Textiles - Methods for determination of certain aromatic amines derived from azo colorants - Part 3: Detection of the use of certain azo colorants, which may release 4-aminoazobenzene
• Effective Date: 08-Jun-2022

Overview

EN ISO 14362-3:2017 (ISO 14362-3:2017) is a CEN-adopted analytical standard for textiles that describes a special procedure to detect the use of certain azo colorants which may release 4‑aminoazobenzene. It is supplementary to ISO 14362-1 and targets azo dyes that are not reliably identified by standard screening because they can generate other aromatic amines (for example aniline and 1,4‑phenylenediamine) under ISO 14362‑1 conditions. The method also detects free 4‑aminoazobenzene (Solvent Yellow 1) when present in commodities.

Key topics and technical requirements

• Scope: Focuses on azo colorants accessible to reducing agent either without extraction (cellulose and protein fibres such as cotton, viscose, wool, silk) or after extraction (e.g. polyester, imitation leather). For some fibre blends both procedures (with and without extraction) in Clauses 9.3 and 9.4 may be required.
• Principle: Selected textile specimens (or extract residues) are treated with sodium dithionite in alkaline solution at about 40 °C in a closed vessel to reductively cleave azo bonds. Released 4‑aminoazobenzene is transferred by liquid–liquid extraction into a t‑butyl methyl ether phase.
• Analysis: Detection and (where applicable) determination of 4‑aminoazobenzene is performed by chromatographic methods (details and validation checks covered in Annex A).
• Limitations: The method is designed to detect 4‑aminoazobenzene; it cannot quantitatively determine other REACH‑listed aromatic amines released by reductive cleavage (except 4‑aminoazobenzene).
• Safety & reagents: Includes safety precautions and specifies analytical‑grade reagents and apparatus. Xylene is accepted as a less toxic substitute for chlorobenzene in revised procedures.

Applications and users

• Testing laboratories performing compliance checks for textile safety and chemical restrictions.
• Manufacturers and dye formulators verifying raw materials and finished textiles for prohibited aromatic amines.
• Regulatory and compliance teams ensuring conformity with REACH (Regulation (EC) No 1907/2006) Annex XVII restrictions on certain aromatic amines.
• Retailers, importers and forensic analysts investigating suspected contamination or non‑compliant dye use. Practical benefits include targeted detection of risky azo colorants and supporting product safety decisions where standard screening is inconclusive.

Related standards

• ISO 14362-1:2017 - main method for detection of azo colorants accessible with and without fibre extraction (this document is supplementary).
• REACH Regulation (EC) No 1907/2006, Annex XVII - regulatory context for restricted aromatic amines.

Keywords: ISO 14362-3:2017, EN ISO 14362-3:2017, 4‑aminoazobenzene, azo colorants, textiles, REACH, aromatic amines, detection method, sodium dithionite, chromatography.

Standards Content (Sample)

SLOVENSKI STANDARD
01-april-2017
1DGRPHãþD
SIST EN 14362-3:2012
7HNVWLOLMH0HWRGH]DGRORþHYDQMHQHNDWHULKDURPDWVNLKDPLQRYL]YLUDMRþLKL]D]R
EDUYLOGHO=D]QDYDQMHSULVRWQRVWLGRORþHQLKD]REDUYLONLODKNRVSURãþDMR
DPLQRD]REHQ]HQ,62
Textiles - Methods for determination of certain aromatic amines derived from azo
colorants - Detection of the use of certain azo colorants, which may release 4-
aminoazobenzene (ISO 14362-3:2017)
Textilien - Verfahren für die Bestimmung bestimmter aromatischer Amine aus
Azofarbstoffen - Nachweis der Verwendung bestimmter Azofarbstoffe, die 4-
Aminoazobenzol freisetzen können (ISO 14362-3:2017)
Textiles - Méthodes de détermination de certaines amines aromatiques dérivées de
colorants azoïques - Détection de l'utilisation de certains colorants azoïques susceptibles
de libérer du 4-aminoazobenzène (ISO 14362-3:2017)
Ta slovenski standard je istoveten z: EN ISO 14362-3:2017
ICS:
59.080.01 Tekstilije na splošno Textiles in general
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN ISO 14362-3
EUROPEAN STANDARD
NORME EUROPÉENNE
February 2017
EUROPÄISCHE NORM
ICS 59.060.01 Supersedes EN 14362-3:2012
English Version
Textiles - Methods for determination of certain aromatic
amines derived from azo colorants - Part 3: Detection of
the use of certain azo colorants, which may release 4-
aminoazobenzene (ISO 14362-3:2017)
Textiles - Méthodes de détermination de certaines Textilien - Verfahren für die Bestimmung bestimmter
amines aromatiques dérivées de colorants azoïques - aromatischer Amine aus Azofarbstoffen - Teil 3:
Partie 3: Détection de l'utilisation de certains colorants Nachweis der Verwendung gewisser Azofarbstoffe, die
azoïques susceptibles de libérer du 4- 4-Aminoazobenzol freisetzen können (ISO 14362-
aminoazobenzène (ISO 14362-3:2017) 3:2017)
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 14362-3:2017 E
worldwide for CEN national Members.

Contents Page
European foreword . 3

European foreword
This document (EN ISO 14362-3:2017) 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 14362-3:2012.
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 14362-3:2017 has been approved by CEN as EN ISO 14362-3:2017 without any
modification.
INTERNATIONAL ISO
STANDARD 14362-3
First edition
2017-02
Textiles — Methods for determination
of certain aromatic amines derived
from azo colorants —
Part 3:
Detection of the use of certain
azo colorants, which may release
4-aminoazobenzene
Textiles — Méthodes de détermination de certaines amines
aromatiques dérivées de colorants azoïques —
Partie 3: Détection de l’utilisation de certains colorants azoïques
susceptibles de libérer du 4-aminoazobenzène
Reference number
ISO 14362-3:2017(E)
©
ISO 2017
ISO 14362-3:2017(E)
© ISO 2017, Published in Switzerland
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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CH-1214 Vernier, Geneva, Switzerland
Tel. [phone]
Fax [phone]
[e-mail]
www.iso.org
ii © ISO 2017 – All rights reserved

ISO 14362-3:2017(E)
Contents Page
Foreword .iv
1 Scope . 1
2 Normative references . 1
3 Terms and definition . 1
4 General . 2
5 Principle . 2
6 Safety precautions . 2
7 Reagents . 2
8 Apparatus . 3
9 Procedure. 4
9.1 General . 4
9.2 Preparation of test specimens . 4
9.3 Colorant extraction for disperse dyes — Preparation with extraction . 5
9.4 Textiles dyed with dyes other than disperse dyes — Preparation without extraction . 5
9.5 Reductive cleavage . 5
9.6 Separation and concentration of 4-aminoazobenzene . . 5
9.7 Calibration solution . 6
9.7.1 Calibration solution for sample preparation without extraction . . 6
9.7.2 Calibration solution for sample preparation with extraction . 6
9.8 Check of the analytical system . 6
9.8.1 Sample preparation without extraction . 6
9.8.2 Sample preparation with extraction . 6
9.9 Chromatographic analyses . 6
10 Evaluation . 7
10.1 Calculation . 7
10.2 Reliability of the method . 7
11 Test report . 7
Annex A (informative) Chromatographic analyses . 8
Annex B (informative) Calculation.14
Annex C (informative) Reliability of the method .15
Annex D (informative) Assessment guide — Interpretation of analytical results .16
ISO 14362-3:2017(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 (see 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 (see 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 World Trade Organization (WTO) principles in the
Technical Barriers to Trade (TBT) see the following URL: www . i so .org/ iso/ foreword .html
This document was prepared by the European Committee Standardization (CEN) Technical Committee
CEN/TC 248, Textiles and textile products, in collaboration with ISO Technical Committee TC 38, Textiles,
in accordance with the agreement on technical cooperation between ISO and CEN (Vienna Agreement).
This first edition of ISO 14362-3 cancels and replaces ISO 24362-3:2014, which has been technically
revised.
The following is a list of the major technical changes between this edition and ISO 24362-3:2014:
— addition of a new Clause 3 and renumbered;
— changes to 7.1 to clarify the preparation and use of sodium dithionite solution;
— changes to Clause 9 “Procedure” to improve the method, including using xylene as substitute for
chlorobenzene (reasons: lower toxicity and lower adverse environmental effect of xylene).
A list of all parts in the ISO 14362 series can be found on the ISO website.
iv © ISO 2017 – All rights reserved

INTERNATIONAL STANDARD ISO 14362-3:2017(E)
Textiles — Methods for determination of certain aromatic
amines derived from azo colorants —
Part 3:
Detection of the use of certain azo colorants, which may
release 4-aminoazobenzene
1 Scope
Azo colorants that are able to form 4-aminoazobenzene, generate under the conditions of ISO 14362-1,
the amines aniline and 1,4-phenylenediamine. The presence of these 4-aminoazobenzene colorants
cannot be reliably ascertained without additional information (e.g. the chemical structure of the
colorant used) or without a special procedure.
This document is supplementary to ISO 14362-1 and describes a special procedure to detect the use, in
commodities, of certain azo colorants, which may release 4-aminoazobenzene, and that are
— accessible to reducing agent without extraction, particularly concerning textiles made of cellulose
and protein fibres (e.g. cotton, viscose, wool, silk), and
— accessible by extracting the fibres (e.g. polyester or imitation leather).
For certain fibre blends, in 9.3 and 9.4 (with and without extraction) may need to be applied.
The procedure also detects 4-aminoazobenzene (Solvent Yellow 1), which is already available as free
amine in commodities without reducing pre-treatment.
The use of certain azo colorants, which may release, by reductive cleavage of their azo group(s), one or
more of the other aromatic amines listed in the Regulation (EC) No 1907/2006 of the European Parliament
and of the Council on the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) as
regards Annex XVII, except 4-aminoazobenzene, cannot be determined quantitatively with this method.
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 14362-1:2017, 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
3 Terms and definition
No terms and definitions are listed in this document.
ISO 14362-3:2017(E)
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— IEC Electropedia: available at http:// www .electropedia .org/
— ISO Online browsing platform: available at http:// www .iso .org/ obp
4 General
Certain azo colorants may release, by reductive cleavage of azo group(s), 4-aminoazobenzene.
a
Table 1 — 4-aminoazobenzene
No. CAS number Index number EC number Substance
22 60–09–3 611–008–00–4 200–453–6 4-aminoazobenzene
a
Proscribed aromatic amine under Regulation (EC) No 1907/2006 of the European
Parliament and of the Council of 18 December 2006 concerning the Registration,
Evaluation, Authorization and Restriction of Chemicals (REACH), establishing a European
Chemicals Agency.
5 Principle
After selection of a coloured test specimen from the textile article, the test specimen is tested according
to the method of the colorant extraction for disperse dyes and/or the method of the direct reduction for
the other classes of colorants (pigments and/or dyes) (see ISO 14362-1).
The textile sample or the residue of the sample extraction is treated with sodium dithionite in an
alkaline solution at 40 °C in a closed vessel. 4-aminoazobenzene, which is released in the process, is
transferred to a t-butyl methyl ether phase by means of liquid-liquid extraction. An aliquot of the t-butyl
methyl ether phase is used for analysis. The detection and determination of 4-aminoazobenzene can be
performed using chromatography (see Annex A).
If 4-aminoazobenzene is detected by one chromatographic method, then confirmation shall be made
using one or more alternative methods.
6 Safety precautions
WARNING — 4-aminoazobenzene is classified as a substance known to be or suspected to be
human carcinogen.
Any handling and disposal of these substances shall be in strict accordance with the appropriate
national health and safety regulations.
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.
7 Reagents
Unless otherwise specified, analytical grade chemicals shall be used.
7.1 Aqueous sodium dithionite solution, ρ = 200 mg/ml freshly prepared: rest the solution in a
closed vessel for (55 ± 1) min, transfer it into an open glass beaker, rest for 5 min (−0 min, + 5 min) and
then use within 10 min.
1)
7.2 Sodium hydroxide aqueous solution, ω = 2 %.
1) ω = a mass fraction of 2%.
2 © ISO 2017 – All rights reserved

ISO 14362-3:2017(E)
7.3 Methanol.
7.4 Xylene (mixture of isomers) CAS No 1330-20-7.
7.5 t-butyl methyl ether.
7.6 Sodium chloride.
7.7 4-aminoazobenzene, highest available defined purity standard.
7.8 Internal standards for gas chromatography (IS), e.g. in the case of GC-MS analysis, one of the
following internal standards can be used:
— IS1: naphthalene-d8, CAS No.: 1146-65-2;
— IS2: 2,4,5-trichloroaniline, CAS No.: 636-30-6;
— IS3: anthracene-d10, CAS No.: 1719-06-8.
7.9 Standard solutions.
7.9.1 Internal standard solution, IS in t-butyl methyl ether, ρ = 10,0 µg/ml.
7.9.2 4-aminoazobenzene calibration solution for checking the experimental procedure and
preparation of calibration solutions
4-aminoazobenzene in methanol, ρ = 500 µg/ml.
7.10 Grade 3 water, complying with ISO 3696.
8 Apparatus
8.1 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 the specimen,
...