1、 ISO 2014Textiles 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-aminoazobenzeneTextiles Mthodes de dtermination de certaines amines aromatiques drives de colorants azoques Partie 3: Dtection
2、de lutilisation de certains colorants azoques susceptibles de librer du 4-aminoazobenzneINTERNATIONAL STANDARDISO24362-3First edition2014-02-01Reference numberISO 24362-3:2014(E)ISO 24362-3:2014(E)ii ISO 2014 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2014All rights reserved. Unless otherwi
3、se 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 bel
4、ow or ISOs member body in the country of the requester.ISO copyright officeCase postale 56 CH-1211 Geneva 20Tel. + 41 22 749 01 11Fax + 41 22 749 09 47E-mail copyrightiso.orgWeb www.iso.orgPublished in SwitzerlandISO 24362-3:2014(E) ISO 2014 All rights reserved iiiContents PageForeword ivIntroductio
5、n v1 Scope . 12 Normative references 13 General 14 Principle 25 Safety precautions 26 Reagents 27 Apparatus . 38 Procedure. 48.1 General . 48.2 Preparation of test specimens . 48.3 Colorant extraction for disperse dyes . 48.4 Textiles dyed with dyes other than disperse dyes 58.5 Reductive cleavage .
6、 58.6 Separation and concentration of 4-aminoazobenzene . 58.7 Calibration solution 68.8 Check of the analytical system . 68.9 Chromatographic analyses . 69 Evaluation 69.1 Calculation 69.2 Reliability of the method 710 Test report . 7Annex A (informative) Chromatographic analyses 8Annex B (informat
7、ive) Calculation.15Annex C (informative) Reliability of the method 16Annex D (informative) Assessment guide Interpretation of analytical results .17Bibliography .18ISO 24362-3:2014(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodi
8、es (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
9、, 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 m
10、aintenance 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/directivesAttenti
11、on 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 a
12、nd/or on the ISO list of patent declarations received. www.iso.org/patentsAny 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 assess
13、ment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary informationThe committee responsible for this document is ISO/TC 38, Textiles.This international standard consists of the following parts,
14、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-aminoaz
15、obenzeneiv ISO 2014 All rights reservedISO 24362-3:2014(E)IntroductionThis part of ISO 24362 is based on EN 14362-3:2012 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 vTextiles Methods
16、for determination of certain aromatic amines derived from azo colorants Part 3: Detection of the use of certain azo colorants, which may release 4-aminoazobenzene1 ScopeAzo colorants that are able to form 4-aminoazobenzene, generate under the conditions of ISO 24362-1 the amines aniline and 1,4-phen
17、ylenediamine. 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 part of ISO 24362 is supplementary to ISO 24362-1 and describes a special procedure to
18、detect the use of certain azo colorants in commodities, which may release 4-aminoazobenzene, accessible to reducing agent without extraction, particularly concerning textiles made of cellulose and protein fibres (e.g. cotton, viscose, wool, silk); accessible by extracting the fibres (e.g. polyester
19、or imitation leather).For certain fibre blends both parts of ISO 24362 (without or with extraction) may need to be applied.The procedure detects as well 4-aminoazobenzene (Solvent Yellow 1) which is already available as free amine in commodities without reducing pre-treatment.The use of certain azo
20、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 An
21、nex XVII, except 4-aminoazobenzene, cannot be determined quantitatively with this method.2 Normative referencesThe 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. Fo
22、r undated references, the latest edition of the referenced document (including any amendments) applies.ISO 24362-1:2014, 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 extracti
23、ng the fibresISO 3696, Water for analytical laboratory use Specification and test methods3 GeneralCertain azo colorants may release, by reductive cleavage of azo group(s), 4-aminoazobenzene, which is proscribed under Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the R
24、egistration, Evaluation, Authorization and Restriction of Chemicals (REACH) as regards Annex XVII.INTERNATIONAL STANDARD ISO 24362-3:2014(E) ISO 2014 All rights reserved 1ISO 24362-3:2014(E)Table 1 4-aminoazobenzene proscribed under Regulation REACH 1907/2006/Annex XVIINo. CAS number Index number EC
25、 number Substance22 60093 611008004 2004536 4-aminoazobenzene4 PrincipleAfter 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 class
26、es of the dyes (see ISO 24362-1).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-liq
27、uid 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 mor
28、e alternative methods.5 Safety precautions5.1 WARNING 4-aminoazobenzene is classified as a substance known to be or suspected to be human carcinogen.Any handling and disposal of this substance shall be in strict accordance with the appropriate national health and safety regulations.5.2 It is the use
29、rs 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 s
30、ingle-use dust respirator while handling powder colorants.5.4 Users should comply with any national and local safety regulations.6 ReagentsUnless otherwise specified, analytical grade chemicals shall be used.6.1 aqueous sodium dithionite solution, = 200 mg/ml1), freshly prepared, to use immediately
31、after resting for one hour in a closed vessel.6.2 sodium hydroxide aqueous solution, = 2 %2)6.3 n-pentane6.4 methanol6.5 chlorobenzene1) = mass concentration2) = mass fraction (% by weight)2 ISO 2014 All rights reservedISO 24362-3:2014(E)6.6 t-butyl methyl ether6.7 sodium chloride6.8 4-aminoazobenze
32、ne, with highest available defined purity standard6.9 internal standards (IS) for gas chromatography, e.g.:IS1: benzidine-d8, CAS No.: 92890-63-6IS2: naphthalene-d8, CAS No.: 1146-65-2IS3: 2,4,5-trichloroaniline, CAS No.: 636-30-6IS4: anthracene-d10, CAS No.: 1719-06-8.6.10 standard solutions6.10.1
33、internal standard solution, prepared by IS (6.9) in t-butyl methyl ether, = 10,0 g/ml6.10.2 4-aminoazobenzene calibration solution for checking the experimental procedure and preparation of calibration solutions4-aminoazobenzene in methanol, = 500 g/ml6.11 grade 3 water, complying with ISO 3696.7 Ap
34、paratus7.1 reaction vessel (20 ml to 50 ml) of heat-resistant glass, with tight closure7.2 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; 100
35、ml round bottom flask NS 29/32; heating source.Figure 1 Apparatus ISO 2014 All rights reserved 3ISO 24362-3:2014(E)NOTE Similar apparatus can be used, if the same results are obtained.7.3 heating source, capable of maintaining the temperature at (40 2) C7.4 centrifuge, capable with a rotation of mor
36、e than 3 000 r/min7.5 vacuum rotary evaporator7.6 pipettes in required sizes or variable pipettes7.7 ultrasonic bath, capable of ultrasonic power 160 Watt RMS, with controllable heating equipment7.8 horizontal shaker, capable of frequency of 5 s1, path length 2 cm to 5 cm7.9 instrumental equipment7.
37、9.1 gas chromatography (GC) equipment, with mass selective detector (MS)7.9.2 high performance liquid chromatography (HPLC) equipment, with gradient elution and diode array detector (DAD) or mass selective detector (MS)7.9.3 thin layer chromatography (TLC) or high performance thin layer chromatograp
38、hy (HPTLC) equipment, including relevant detection7.9.4 capillary electrophoresis (CE) equipment, with DADNOTE A description of the equipment is given in Annex A.8 Procedure8.1 GeneralApply this standard to the test specimen that gave a positive result for aniline and 1,4-phenylenediamine or only an
39、iline using ISO 24362-1. Choose 8.3 or 8.4 depending on sample composition.8.2 Preparation of test specimensIn the case of fabrics with multicoloured patterns, the various colours have to be taken into account separately as far as possible. For commodities consisting of various textile qualities, sp
40、ecimens of the various qualities (in terms of fibre and/or colour) shall be analysed separately.Prepare the test specimen by cutting in order to obtain a total mass of 1 g. For specimens to be submitted to colorant extraction (8.3) cut into strips (if apparatus described in 7.2 is used) or cut into
41、small pieces if other apparatus is used or for specimens to be submitted only to reductive cleavage (8.4).8.3 Colorant extraction for disperse dyes8.3.1 Extraction of disperse dyes with chlorobenzeneThe textile specimen dyed with disperse dyes (see Annex D from ISO 24362-1) is kept in the extraction
42、 apparatus (7.2) for 30 min above 25 ml boiling chlorobenzene. The chlorobenzene extract is allowed to cool down to room temperature before detaching it from the extraction apparatus.4 ISO 2014 All rights reservedISO 24362-3:2014(E)Concentrate the chlorobenzene extract by the vacuum rotary evaporato
43、r (7.5) at a temperature of 45 C to 60 C to a small residual quantity. This residue is quantitatively transferred to the reaction vessel with 7 ml methanol (6.4) in total, using an ultrasonic bath to disperse the colorants.NOTE 1 It is recommended to carry out the transfer in multiple steps; e.g. to
44、 add 4 ml of methanol and to dissolve the residue from the glass flask using an ultrasonic bath, then to transfer the suspension quantitatively into the reaction vessel using a pipette, subsequently to rinse three times with 1 ml of methanol and to transfer the solution quantitatively.NOTE 2 For dir
45、ect determination of a 4-aminoazobenzene-releasing dispersion colorants (e.g. Disperse Yellow 23) an aliquot of this methanolic solution may be immediately used for analysis by LC-DAD-MS.8.3.2 Textiles only dyed with disperse dyesRemove the textile specimen from the extraction apparatus (7.2), and d
46、iscard it if it is completely made of fibres dyed with disperse dyes and/or becomes decolourised after extraction.8.3.3 Textiles dyed with disperse dyes and/or other dyesRemove the extracted textile specimen from the extraction apparatus (7.2), if it contains fibres belonging to cases A and/or B (se
47、e 8.4 of ISO 24362-1). Remove the solvent by washing the specimen with appropriate solvent e.g. npentane (6.3) or t-butyl methyl ether (6.6) and let it dry. If necessary cut it into small pieces for reductive cleavage. Add the extracted textile specimen to the reaction vessel with the methanolic sol
48、ution of the dispersed dyes (in total 7 ml) for combined reduction.8.4 Textiles dyed with dyes other than disperse dyesIf the textile specimen contains fibres belonging only to cases A and/or B (see 8.4 of ISO 24362-1) put the test specimen directly in a reaction vessel.8.5 Reductive cleavageA quant
49、ity of 9 ml of sodium hydroxide solution (6.2) is added to the reaction vessel (8.3.1, 8.3.3 or 8.4). The reaction vessel is tightly closed and shaken vigorously.Subsequently, 1,0 ml aqueous sodium dithionite solution (6.1) is added for reductive cleavage. The mixture is shaken vigorously and immediately kept without shaking at (40 2) C for exactly 30 min, whereupon it is cooled to room temperature 20 C to 25 C within 1 min.8.6 Separation and concentration of 4-aminoazobenzene5 ml t-
