EN 14362-1-2012 en Textiles - Methods for determination of certain aromatic amines derived from azo colorants - Part 1 Detection of the use of certain azo colorants accessible with.pdf

1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationTextiles Methods for determination of certain aromatic amines derived from azo colorantsPart 1: Detection of the use of certain azo colorants accessible with and without extracti

2、ng the fibresBS EN 14362-1:2012National forewordThis British Standard is the UK implementation of EN 14362-1:2012. It supersedes BS EN 14362-1:2003 and BS EN 14362-2:2003, which are withdrawn.The UK participation in its preparation was entrusted to Technical CommitteeTCI/80, Chemical testing of text

3、iles.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisions of acontract. Users are responsible for its correct application. The British Standards Institution 2012Published by BSI Stan

4、dards Limited 2012ISBN 978 0 580 69833 0ICS 59.080.01Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of the StandardsPolicy and Strategy Committee on 31 March 2012.Amendments issued since publicationAmd. No. Date

5、 Text affectedBRITISH STANDARDBS EN 14362-1:2012EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 14362-1 February 2012 ICS 59.080.01 Supersedes EN 14362-1:2003, EN 14362-2:2003English Version Textiles - Methods for determination of certain aromatic amines derived from azo colorants - Part 1: Det

6、ection of the use of certain azo colorants accessible with and without extracting the fibres Textiles - Mthodes de dtermination de certaines amines aromatiques drives de colorants azoques - Partie 1 : Dtection de lutilisation de certains azo-colorants accessibles avec ou sans extraction Textilien -

7、Verfahren fr die Bestimmung bestimmter aromatischer Amine aus Azofarbstoffen - Teil 1: Nachweis der Verwendung bestimmter Azofarbstoffe mit oder ohne Extraktion This European Standard was approved by CEN on 22 December 2011. CEN members are bound to comply with the CEN/CENELEC Internal Regulations w

8、hich 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

9、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 member

10、s are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, 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, S

11、weden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR 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 nationa

12、l Members. Ref. No. EN 14362-1:2012: EBS EN 14362-1:2012EN 14362-1:2012 (E) 2 Contents Page Foreword 41 Scope 52 Normative references 53 General 54 Principle 75 Safety precautions .76 Reagents .77 Apparatus .88 Test specimen sampling and preparation 108.1 General . 108.2 Textile article . 108.3 Fibr

13、e composition . 108.4 Case of the fibre blends . 118.5 Printed materials . 118.6 Colours 118.6.1 General . 118.6.2 Case of colour gathering . 118.6.3 Preparation of the three colour test specimen 129 Procedure 129.1 Colorant extraction for disperse dyes 129.1.1 Extraction of disperse dyes with chlor

14、obenzene 129.1.2 Textiles only dyed with disperse dyes . 129.1.3 Textiles dyed with disperse dyes and/or other dyes 129.2 Textiles dyed with dyes other than disperse dyes 129.3 Reductive cleavage 129.4 Separation and concentration of the amines . 139.5 Amine detection and quantification 139.6 Check

15、procedure. 139.6.1 General . 139.6.2 Calibration using internal standard (quantification performed by gas chromatography) 139.6.3 Calibration without internal standard . 1410 Evaluation 1410.1 General . 1410.2 Calculation of amine in the sample. 1510.3 Reliability of the method 1511 Test report . 15

16、Annex A (informative) Chromatographic analyses . 16A.1 Preliminary remark . 16A.2 Thin layer chromatography (TLC) . 16A.3 High performance liquid chromatography (HPLC) 17A.4 Capillary gas chromatography/mass selective detector (GC/MS) . 18A.5 Capillary electrophoresis (CE) 18Annex B (informative) Re

17、liability of the method . 20Annex C (informative) Assessment guide-interpretation of analytical results 22Annex D (informative) Explanatory table of dyestuffs used in various textile materials 23BS EN 14362-1:2012EN 14362-1:2012 (E) 3 D.1 General . 23D.2 Criteria for printed materials 24Annex E (inf

18、ormative) Procedure for liquid/liquid-extraction without diatomaceous earth 25E.1 Preliminary remark 25E.2 Additional reagents used 25E.3 Additional apparatus used . 26E.4 Procedure . 26Annex F (normative) Colorants - Methods for determination of certain aromatic amines 28F.1 Scope 28F.2 Principle 2

19、8F.3 Test specimen preparation . 28F.4 Procedure . 28F.5 Evaluation. 28F.6 Test report 28Bibliography 29BS EN 14362-1:2012EN 14362-1:2012 (E) 4 Foreword This document (EN 14362-1:2012) has been prepared by Technical Committee CEN/TC 248 “Textiles and textile products”, the secretariat of which is he

20、ld 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 2012, and conflicting national standards shall be withdrawn at the latest by August 2012. Attention is drawn to the possibility th

21、at 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 14362-1:2003, EN 14362-2:2003. EN 14362 is composed of the following parts: EN 14362-1, Textiles M

22、ethods 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; EN 14362-3, Textiles Methods for determination of certain aromatic amines derived from azo colorants Part 3: Detecti

23、on of the use of certain azo colorants which may release 4-aminoazobenzene. The following is a list of technical changes since the last edition: Part 2 of EN 14362 has been integrated into Part 1. This is mainly reflected in: changes to Clause 4 “Principle“; insertion of a new Clause 8 “Test specime

24、n sampling and preparation“; insertion of a new Subclause 9.1 “Colorant extraction for disperse dyes“; insertion of a new Subclause 9.2 “Textiles dyed with dyes other than disperse dyes“; addition of Annex D (informative) “Explanatory table of dyestuffs used in various textile materials“. Addition o

25、f Annex F (normative) “Colorants - Methods for determination of certain aromatic amines“; The calculation, previously Annex B (normative) has been moved to Subclause 9.6. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to i

26、mplement 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, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden,

27、 Switzerland, Turkey and the United Kingdom. BS EN 14362-1:2012EN 14362-1:2012 (E) 5 1 Scope This European Standard describes a procedure 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 accessi

28、ble to reducing agent with and without extraction. Azo colorants accessible to reducing agent without extraction are those used to dye: cellulosic fibres (e.g. cotton, viscose); protein fibres (e.g. wool, silk); synthetic fibres (e.g. polyamide, acrylic). Azo colorants accessible with extraction are

29、 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. For certain commodities made of cellulose and/or protein fibres blended with man-made fibres it is necessary to ext

30、ract the dye first. The method is relevant for all coloured textiles, e.g. dyed, printed and coated textiles. 2 Normative references The following referenced documents are indispensable for the application of this European Standard. For dated references, only the edition cited applies. For undated r

31、eferences, the latest edition of the referenced document (including any amendments) applies. EN ISO 3696:1995, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) 3 General Certain azo colorants may release, by reductive cleavage of azo group(s), one or more of the fol

32、lowing aromatic amines, which are proscribed 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. BS EN 14362-1:2012E

33、N 14362-1:2012 (E) 6 Table 1 Aromatic amines proscribed under Regulation REACH 1907/2006/Annex XVII 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 95-69-2 612-196-00-0 202-44

34、1-6 4-chloro-o-toluidine 4 91-59-8 612-022-00-3 202-080-4 2-naphthylamine 5a97-56-3 611-006-00-3 202-591-2 o-aminoazotoluene 4-amino-2,3-dimethylazobenzene 4-o-tolylazo-o-toluidine 6a99-55-8 612-210-00-5 202-765-8 5-nitro-o-toluidine 2-amino-4-nitrotoluene 7 106-47-8 612-137-00-9 203-401-0 4-chloroa

35、niline 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-

36、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-

37、(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-toluylendiam

38、ine 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 22b60-09-3 611-008-00-4 200-453-6 4-aminoazobenzene aThe CAS-numbers 97-56-3 (No. 5) and 99-55-8 (No. 6) are further reduced to CAS-numbers 95-53-4 (No. 18)

39、 and 95-80-7 (No. 19). bAzo 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. The presence of these colorants should be tes

40、ted by EN 14362-3. BS EN 14362-1:2012EN 14362-1:2012 (E) 7 4 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 dye

41、s. 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 discoloured during the applic

42、ation 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 concentrated and transferred to

43、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 the methanolic solution o

44、f 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 in the process is tran

45、sferred 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 chromatography (see Annex A).

46、 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 precautions 5.1 WARNING The substances amines liste

47、d in Clause 3 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. 5.2 It is the users responsibility to use safe and proper technique

48、s 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 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 Chlorobenzene. 6.2 Acetonitrile. 6.3 Methanol. BS EN 14362-1:2012EN 14362-1:2012 (E) 8 6.4 t-butyl methyl e