1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 14362-3:2012T e x t i l e s M e t h o d s f o r determination of certain aromatic amines derived from azo colorantsPart 3: Detection of the use of certain azo colorants, wh
2、ich may release 4-aminoazobenzeneCopyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 14362-3:2012 BRITISH STANDARDNational forewordThis British Standard is the UK implementatio
3、n of EN 14362-3:2012.The UK participation in its preparation was entrusted to TechnicalCommittee TCI/80, Chemical testing of textiles.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisi
4、ons of a contract. Users are responsible for its correctapplication. The British Standards Institution 2012. Published by BSI StandardsLimited 2012ISBN 978 0 580 70790 2ICS 59.080.01Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published un
5、der the authority of theStandards Policy and Strategy Committee on 31 July 2012.Amendments issued since publicationDate Text affectedCopyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,
6、-,-BS EN 14362-3:2012EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 14362-3 June 2012 ICS 59.080.01 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-aminoazobe
7、nzene Textiles - Mthodes de dtermination de certaines amines aromatiques drives de colorants azoques - Partie 3: Dtection de lutilisation de certains colorants azoques susceptibles de librer du 4-aminoazobenzne Textilien - Verfahren fr die Bestimmung bestimmter aromatischer Amine aus Azofarbstoffen
8、- Teil 3: Nachweis der Verwendung gewisser Azofarbstoffe, die 4-Aminoazobenzol freisetzen knnen This European Standard was approved by CEN on 24 May 2012. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the st
9、atus 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,
10、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, Cro
11、atia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR
12、STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 14362-3:2012: ECopyright European Committee for
13、 Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 14362-3:2012EN 14362-3:2012 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 General 44 Principle 55 Safety precautions .56 Reagents .57 App
14、aratus .68 Procedure .79 Evaluation .910 Test report . 10Annex A (informative) Chromatographic analyses . 11Annex B (normative) Calculation 16Annex C (informative) Reliability of the method . 18Annex D (informative) Assessment guide - Interpretation of analytical results 20Copyright European Committ
15、ee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 14362-3:2012EN 14362-3:2012 (E) 3 Foreword This document (EN 14362-3:2012) has been prepared by Technical Committee CEN/TC 248 “Textiles and textile p
16、roducts”, 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 December 2012, and conflicting national standards shall be withdrawn at the latest by December 20
17、12. 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. According to the CEN/CENELEC Internal Regulations, the national standards organiza
18、tions of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portug
19、al, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 14362-3:2012EN 14362-3:2012 (E)
20、4 1 Scope Azo colorants that are able to form 4-aminoazobenzene, generate under the conditions of EN 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 th
21、e colorant used) or without a special procedure. This part of EN 14362 is supplementary to Part 1 and describes a special procedure to detect the use of certain azo colorants in commodities, which may release 4-aminoazobenzene, accessible to reducing agent without extraction, particularly concerning
22、 textiles made of cellulose and protein fibres (e.g. cotton, viscose, wool, silk); accessible by extracting the fibres (e.g. polyester or imitation leather). For certain fibre blends both parts of this standard (without or with extraction) may need to be applied. The procedure detects as well 4-amin
23、oazobenzene (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 o
24、f the European Parliament and of the Council on the Registration, Evaluation, Authorisation 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, in whole or in part,
25、 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. EN 14362-1:2012, Textiles Methods for determination
26、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 EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696) 3 General Certain azo colorants may release, by red
27、uctive 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 Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) as regards Annex XVII. Table 1 4-aminoazobenzene proscribed und
28、er Regulation REACH 1907/2006/Annex XVII No. CAS number Index number EC number Substance 22 60-09-3 611-008-00-4 200-453-6 4-aminoazobenzene Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license fr
29、om IHS-,-,-BS EN 14362-3:2012EN 14362-3:2012 (E) 5 4 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 the
30、 dyes (see EN 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 extra
31、ction. 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 altern
32、ative methods. 5 Safety precautions 5.1 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. 5.2 It is the users
33、 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 si
34、ngle-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 aqueous sodium dithionite solution, = 200 mg/ml1), freshly prepared, to use immediate
35、ly after resting for one hour in a closed vessel 6.2 sodium hydroxide aqueous solution, = 2 %2) 6.3 n-pentane 6.4 methanol 6.5 chlorobenzene 6.6 t-butyl methyl ether 6.7 sodium chloride 1) = mass concentration 2) = mass portion (% by weight) Copyright European Committee for Standardization Provided
36、by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 14362-3:2012EN 14362-3:2012 (E) 6 6.8 4-aminoazobenzene, highest available defined purity standard 6.9 internal standards for gas chromatography (IS), e.g.: IS1: benzidine-d8, CAS No
37、.: 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. 6.10 standard solutions 6.10.1 internal standard solution, IS in t-butyl methyl ether, = 10,0 g/ml 6.10.2 4-aminoazobenzene calibration solution for checking
38、the experimental procedure and preparation of calibration solutions 4-aminoazobenzene in methanol, = 500 g/ml 6.11 grade 3 water, complying with EN ISO 3696. 7 Apparatus 7.1 reaction vessel (20 ml to 50 ml) of heat-resistant glass, with tight closure 7.2 extraction apparatus, according to Figure 1,
39、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 ml round bottom flask NS 29/32; heating source. Figure 1 Apparatus NOTE Similar apparatus can be used, if the same results are obtained.
40、 7.3 heating source that generates a temperature of (40 2) C Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 14362-3:2012EN 14362-3:2012 (E) 7 7.4 centrifuge, more than 300
41、0 r/min 7.5 vacuum rotary evaporator 7.6 pipettes in required sizes or variable pipettes 7.7 ultrasonic bath, at least ultrasonic power RMS 160 Watt, with controllable heating 7.8 horizontal shaker with sufficient frequency of 5 s-1, path length 2 cm to 5 cm 7.9 instrumental equipment 7.9.1 gas chro
42、matography (GC) with mass selective detector (MS) 7.9.2 high performance liquid chromatography (HPLC) 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 chromatography (HPTLC) equipment, including
43、relevant detection 7.9.4 capillary electrophoresis (CE) with DAD NOTE A description of the equipment is given in Annex A. 8 Procedure 8.1 General Apply this standard to the test specimen that gave a positive result for aniline and 1,4-phenylenediamine or only aniline using EN 14362-1. Choose 8.3 or
44、8.4 depending of the sample composition. 8.2 Preparation of test specimens In 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, specimens of the various qualities
45、(in terms of fibre and/or colour) shall be analyzed 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 small pieces if other apparatus
46、is used or for specimens to be submitted only to reductive cleavage (8.4). 8.3 Colorant extraction for disperse dyes 8.3.1 Extraction if disperse dyes with chlorobenzene The textile specimen dyed with disperse dyes (see Annex D from EN 14362-1:2012) is kept in the extractor (7.2) for 30 min above 25
47、 ml boiling chlorobenzene. The chlorobenzene extract is allowed to cool down to room temperature before detaching it from the extractor. Concentrate the chlorobenzene extract in the evaporation apparatus (7.5) at a temperature of 45 C to 60 C to a small residual quantity. This residue is quantitativ
48、ely transferred to the reaction vessel with 7 ml methanol (6.4) in total, using an ultrasonic bath to disperse the colorant. NOTE 1 It is recommended to carry out the transfer in multiple steps; e. g. to 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. Copyright European Committee for Standardization Provided
