1、 ISO 2014Textiles 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 fibresTextiles Mthodes de dtermination de certaines amines aromatiques drives de colorants azoques Partie
2、 1: Dtection de lutilisation de certains colorants azoques accessibles avec ou sans extractionINTERNATIONAL STANDARDISO24362-1First edition2014-02-01Reference numberISO 24362-1:2014(E)ISO 24362-1:2014(E)ii ISO 2014 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2014All rights reserved. Unless o
3、therwise 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 addre
4、ss below 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 24362-1:2014(E) ISO 2014 All rights reserved iiiContents PageForeword ivIntro
5、duction v1 Scope . 12 Normative references 13 General 14 Principle 35 Safety precautions 36 Reagents 37 Apparatus . 58 Test specimen sampling and preparation 68.1 General . 68.2 Textile article 68.3 Fibre composition 78.4 Case of the fibre blends 78.5 Printed materials 78.6 Colours . 79 Procedure. 8
6、9.1 Colorant extraction for disperse dyes . 89.2 Textiles dyed with dyes other than disperse dyes 89.3 Reductive cleavage . 89.4 Separation and concentration of the amines 99.5 Amine detection and quantification . 99.6 Check procedure 910 Evaluation .1110.1 General 1110.2 Calculation of amine in the
7、 sample 1110.3 Reliability of the method . 1111 Test report 11Annex A (informative) Chromatographic analyses .12Annex B (informative) Reliability of the method 16Annex C (informative) Assessment guide Interpretation of analytical results 17Annex D (informative) Explanatory table of dyestuffs used in
8、 various textile materials .19Annex E (informative) Procedure for liquid-liquid-extraction without diatomaceous earth21Annex F (normative) Colorants-Methods for determination of certain aromatic amines 24Bibliography .25ISO 24362-1:2014(E)ForewordISO (the International Organization for Standardizati
9、on) 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 re
10、presented 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 de
11、velop 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 I
12、SO/IEC Directives, Part 2. www.iso.org/directivesAttention 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 d
13、evelopment of the document will be in the Introduction and/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 spe
14、cific terms and expressions related to conformity assessment, 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.ISO 2
15、4362 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
16、colorants, which may release 4-aminoazobenzeneiv ISO 2014 All rights reservedISO 24362-1:2014(E)IntroductionThis 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
17、All rights reserved vTextiles 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 fibres1 ScopeThis part of ISO 24362 describes a procedure to detect the use of certain azo co
18、lorants 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, vi
19、scose); 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, mo
20、dacrylic, 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 referencesThe following document
21、s, 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 analy
22、tical laboratory use Specification and test methods 3 GeneralCertain azo colorants may release, by reductive cleavage of azo group(s), one or more of the following aromatic amines.INTERNATIONAL STANDARD ISO 24362-1:2014(E) ISO 2014 All rights reserved 1ISO 24362-1:2014(E)Table 1 Aromatic amines subj
23、ectedNo. CAS number Index number EC number Substances1 92671 612072006 2021771 biphenyl-4-ylamine 4-aminobiphenyl xenylamine2 92875 612042002 2021991 benzidine3 95692 612196000 2024416 4-chloro-o-toluidine4 91598 612022003 2020804 2-naphthylamine5a97563 611006003 2025912 o-aminoazotoluene 4-amino-2,
24、3-dimethylazobenzene 4-o-tolylazo-o-toluidine6a99558 612210005 2027658 5-nitro-o-toluidine 2-amino-4-nitrotoluene7 106478 612137009 2034010 4-chloroaniline8 615054 612200000 2104061 4-methoxy-m-phenylenediamine 2,4-diaminoanisole9 101779 612051001 2029744 4,4-methylenedianiline 4,4-diaminodiphenylme
25、thane10 91941 612068004 2021090 3,3-dichlorobenzidine 3,3-dichlorobiphenyl-4,4-ylenediamine11 119904 61203600-X 2043554 3,3-dimethoxybenzidine o-dianisidine12 119937 612041007 2043580 3,3-dimethylbenzidine 4,4-bi-o-toluidine13 838880 612085007 2126588 4,4-methylenedi-o-toluidine14 120718 61220900-X
26、2044191 6-methoxy-m-toluidine p-cresidine15 101144 612078009 2029189 4,4-methylene-bis-(2-chloro-aniline) 2,2-dichloro-4.4-methylene-dianiline16 101804 612199007 2029770 4,4-oxydianiline17 139651 612198001 2053709 4,4-thiodianiline18 95534 61209100-X 2024290 o-toluidine 2-aminotoluene19 95807 612099
27、003 2024531 4-methyl-m-phenylenediamine 2,4-toluylendiamine 2,4-diaminotoluene20 137177 612197006 2052820 2,4,5-trimethylaniline21 90040 612035004 2019631 o-anisidine 2-methoxyaniline22b60093 611008004 2004536 4-aminoazobenzeneaThe CAS-numbers 97563 (No. 5) and 99558 (No. 6) are further reduced to C
28、AS-numbers 95534 (No. 18) and 95807 (No. 19).bAzo colorants that are able to form 4-aminoazobenzene, generate under the condition of this method aniline (CAS-number 62533) and 1,4-phenylenediamine (CAS number 106503). Due to detection limits, only aniline may be detected. The presence of these color
29、ants should be tested by ISO 24362-32 ISO 2014 All rights reservedISO 24362-1:2014(E)4 PrincipleAfter 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
30、 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 disco
31、loured 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 concentra
32、ted 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 th
33、e 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 i
34、n 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 chromato
35、graphy (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 precautionsWARNING The substances
36、 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 users responsibility to use safe and p
37、roper 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 han
38、dling 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 Chlorobenzene.WARNING This is a toxic chemical. To handle chlorobenzene, special care is required to prevent skin contact s
39、wallowing and aspiration. ISO 2014 All rights reserved 3ISO 24362-1:2014(E)6.2 Acetonitrile.6.3 Methanol.6.4 t-butyl methyl ether.6.5 n-pentane.6.6 Citrate/sodium hydroxide buffer solution, pH = 6, c = 0,06 mol/l1).6.7 Aqueous sodium dithionite solution, = 200 mg/ml2)freshly (daily) prepared.6.8 Dia
40、tomaceous 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 g of each amine per
41、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 = 15,0 g of each amine per millilitre of an
42、appropriate solvent.6.10.3 Calibration solutions of amines for quantification, concentration range from 2 g up to 50 g 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 i
43、n solution (IS), = 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
44、-06-8.NOTE If the confirmation analysis for benzidine is done with DAD or TLC the use of IS1: benzidine-d8, CAS No.: 92890636 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, c
45、omplying with ISO 3696:1987.1) c is citrate concentration.2) is the mass concentration.4 ISO 2014 All rights reservedISO 24362-1:2014(E)7 Apparatus7.1 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 plac
46、e so that the condensed solvent drips onto it; 100 ml round bottom flask NS 29/32; heating source.Figure 1 ApparatusNOTE 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 ves
47、sel (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
48、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 ap
49、paratus 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 releva
