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INTERNATIONAL ISO
STANDARD 14362-1

First edition
2017-02

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 14362-1:2017(E)

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ISO 14362-1:2017(E)


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ISO 14362-1:2017(E)


Contents Page

Foreword...........................................................................................................................................................................................................................................v
1 Scope.................................................................................................................................................................................................................................. 1
2 Normative references....................................................................................................................................................................................... 1
3 Terms and definitions...................................................................................................................................................................................... 1
4 General............................................................................................................................................................................................................................. 1
5 Principle......................................................................................................................................................................................................................... 3
6 Safety precautions............................................................................................................................................................................................... 3
7 Reagents......................................................................................................................................................................................................................... 3
8 Apparatus...................................................................................................................................................................................................................... 4
9 Test specimen sampling and preparation................................................................................................................................... 6
9.1 General............................................................................................................................................................................................................ 6
9.2 Textile article............................................................................................................................................................................................. 6
9.3 Fibre composition................................................................................................................................................................................. 6
9.4 Case of the fibre blends.................................................................................................................................................................... 7
9.5 Coloured materials with pigments......................................................................................................................................... 7
9.6 Colours............................................................................................................................................................................................................ 7
9.6.1 General...................................................................................................................................................................................... 7
9.6.2 Case of colour gathering............................................................................................................................................. 7
9.6.3 Preparation of the three colour test specimen....................................................................................... 8
10 Procedure..................................................................................................................................................................................................................... 8
10.1 Colorant extraction for disperse dyes with xylene................................................................................................... 8
10.2 Textiles coloured with pigments and/or dyed with colorants other than disperse dyes........ 8
10.3 Reductive cleavage................................................................................................................................................................................ 8
10.4 Separation and concentration of the amines................................................................................................................. 8
10.5 Amine detection and quantification...................................................................................................................................... 9
10.5.1 Detection of aniline and 1,4-phenylenediamine (indicators
of 4-aminoazobenzene).............................................................................................................................................. 9
10.5.2 In relation to quantification equipment / other sources of false positive results.... 9
10.6 Check procedure.................................................................................................................................................................................. 10
10.6.1 General................................................................................................................................................................................... 10
10.6.2 Calibration using internal standard (quantification performed by
gas chromatography)................................................................................................................................................. 10
10.6.3 Calibration without internal standard........................................................................................................ 11
10.6.4 Amine recovery............................................................................................................................................................... 11
11 Evaluation..................................................................................................................................................................................................................11
11.1 General......................................................................................................................................................................................................... 11
11.2 Calculation of amine in the sample..................................................................................................................................... 12
11.3 Reliability of the method.............................................................................................................................................................. 12
12 Test report................................................................................................................................................................................................................. 12
Annex A (informative) Chromatographic analyses..............................................................................................................................13
Annex B (informative) Reliability of the method...................................................................................................................................17
Annex C (informative) Assessment guide — Interpretation of analytical results...............................................19
Annex D (informative) Explanatory table of dyestuffs used in various textile materials............................25
Annex E (informative) Procedure for liquid/liquid extraction without diatomaceous earth................26
Annex F (normative) Colorants — Methods for determination of certain aromatic amines...................29
Annex G (informative) Pigments.............................................................................................................................................................................30

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Bibliography.............................................................................................................................................................................................................................. 32

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ISO 14362-1:2017(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​.iso​.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  14362-1 cancels and replaces ISO  24362-1:2014, which has been technically
revised.
The following is a list of the major technical changes between this edition and ISO 24362-1:2014:
— addition of a new Clause 3 and renumbered;
— changes to Clause 5 “Principle,” where the combined method has been removed as it had been found
that results were not accurate in certain cases;
— changes to Clause 9 “Test specimen sampling and preparation” to be more explanatory;
— changes to Clause 10 “Procedure” to improve the method, including using xylene as substitute for
chlorobenzene (reasons: lower toxicity and lower adverse environmental effect of xylene);
— extension of Annex C “Assessment guide — Interpretation of analytical results” to give examples for
false-positive results, suggested procedures and suggested comments in test report;
— addition of Annex G “Pigments.”
A list of all parts in the ISO 14362 series can be found on the ISO website.

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INTERNATIONAL STANDARD ISO 14362-1:2017(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 document describes a method 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
reducing agent with and without extraction.
Azo colorants accessible to reducing agent without extraction are those used to colour with pigments
or to dye
— cellulosic fibres (e.g. cotton, viscose),
— protein fibres (e.g. wool, silk), and
— 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 and chlorofibre.
The method is relevant for all coloured textiles, e.g. dyed, printed and coated textiles.

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

3 Terms and definitions

No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— IEC Electropedia: available at http://​w ww​.electropedia​.org/​
— ISO Online browsing platform: available at http://​w ww​.iso​.org/​obp

4 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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Table 1 — Targeted aromatic aminesc

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
5a 97-56-3 611-006-00-3 202-591-2 o-aminoazotoluene
4-amino-2’,3-dimethylazobenzene
4-o-tolylazo-o-toluidine
6a 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
22b 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. If aniline is detected above 5 mg/kg, then the presence of these colorants should be tested by ISO 14362-3.
c The targeted aromatic amines are the proscribed aromatic amines under Regulation (EC) No 1907/2006 of the
European Parliament and of the Council of 18 December 2006 concerning the Registration, Evaluation, Authorisation and
Restriction of Chemicals (REACH), establishing a European Chemicals Agency.

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ISO 14362-1:2017(E)


5 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 colorants (pigments and/or dyes).
The application of 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
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 xylene 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 xylene extraction, a new test specimen needs
to be prepared again and reprocessed with the method for non-extractable classes of the colorants.
When the method for non-extractable classes of the colorants 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 an appropriate solvent 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.

6 Safety precautions
WARNING — The substances [amines] listed in Clause 4 are classified as substances known to be
or suspected of being human carcinogens.
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 Xylene (mixture of isomers) CAS No 1330-20-7.

7.2 Acetonitrile.

7.3 Methanol.

7.4 t-butyl methyl ether.

7.5 Citrate/sodium hydroxide buffer solution, pH = 6, c = 0,06 mol/l1).

1) c is citrate concentration.

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7.6 Aqueous sodium dithionite solution, ρ = 200 mg/ml2) freshly prepared (which means to be used
within 1 h).

7.7 Diatomaceous earth.

7.8 Amine substances — amines 1 to 4, 7 to 21 (as specified in Table 1), and aniline and
1,4-phenylenediamine — all of highest available defined purity standards.

7.9 Standard solutions.

7.9.1 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.

7.9.2 Calibration solution of amines for daily use.

Dilute from the stock solution (7.9.1) to a concentration of ρ = 15,0 μg of each amine per millilitre of an
appropriate solvent.

7.9.3 Calibration solutions of amines for quantification, concentration range from 2 μg up to 50 μg
of each amine per millilitre of an appropriate solvent. If gas chromatography is used, 10 μl of internal
standard solution (7.9.4) per millilitre must be added before injection.
NOTE It is the responsibility of each lab to choose appropriate concentrations for the calibration.

7.9.4 Internal standards in solution (IS), ρ = 1,0 mg /ml in the appropriate solvent.

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.

7.9.5 Indicator for later eluting amines: benzidine-d8, CAS No.: 92890-63-6.

ρ = 0,5 mg/ml of benzidine-d8 in solution (7.9.4)

benzidine-d8 (CAS 92890-63-6) is a suitable indicator for interferences in the later part of the GC
chromatogram (10.5).

7.10 Sodium hydroxide aqueous solution, a mass fraction of 10 %.

7.11 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 it,

2) ρ is the mass concentration.

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— 100 ml round bottom flask NS 29/32, and

— heating source.

Figure 1 — Apparatus

Similar apparatus may be used, if the same results are obtained.

8.2 Ultrasonic bath.

8.3 Reaction vessel (20 ml to 50 ml) of heat-resistant glass, with tight closure.

8.4 Heating source that generates (70 ± 2) °C.

8.5 Glass or polypropylene column, inside diameter 25 mm to 30 mm, length 130 mm to 150 mm,
packed with 20 g of diatomaceous earth (7.7), fitted with 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.

8.6 Vacuum rotary evaporator with vacuum control and water bath.

Other kinds of evaporation apparatus may be used, e.g. a water bath with a controlled flow of nitrogen
over the liquid.

8.7 Pipettes in required sizes or variables pipettes.

8.8 Chromatographic equipment, selected from the following:

8.8.1 Thin layer chromatograph (TLC) or high-performance thin layer chromatograph (HPTLC),
including relevant detection.

8.8.2 High-performance liquid chromatograph (HPLC) with gradient elution and diode array
detector (DAD) or mass selective detector (MS).

8.8.3 Gas chromatograph (GC) with flame ionization detector (FID) or mass selective detector (MS).

8.8.4 Capillary electrophoresis (CE) with diode array detector (DAD).

8.8.4.1 Membrane filter PTFE (polytetrafluoroethylene), pore size 0,2  µm, adapted for capillary
electrophoresis (8.8.4)
NOTE A description of the chromatographic conditions is given in Annex A.

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