禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

ALL RIGHTS RESERVED TO THE AUTHOR!!

For reference only

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

not for sale

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS 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 It supersedes BS EN 14362-1:2003 and BS EN 14362-2:2003, which are withdrawn.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 Committee TCI/80, Chemical testing of textiles. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.© The British Standards Institution 2012 Published by BSI Standards Limited 2012 ISBN 978 0 580 69833 0 ICS 59.080.01

Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 March 2012.

Amendments issued since publicationAmd. No. Date Text affected

Not for Resale

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM

BS EN 14362-1:2012

EN 14362-1

February 2012

Supersedes EN 14362-1:2003, EN 14362-2:2003

English Version

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 azo-colorants

accessibles avec ou sans extraction Textilien - Verfahren für 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 which 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 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 members 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, Sweden, Switzerland, Turkey and United Kingdom.

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

Contents Page

Foreword ..............................................................................................................................................................4 1 2 3 4 5 6 7 8 8.1 8.2 8.3 8.4 8.5 8.6 8.6.1 8.6.2 8.6.3 9 9.1 9.1.1 9.1.2 9.1.3 9.2 9.3 9.4 9.5 9.69.6.1 9.6.2 9.6.3 10 10.1 10.2 10.3 11

--`,,```,,,,````-`-`,,`,,`,`,,`---

Scope ......................................................................................................................................................5 Normative references ............................................................................................................................5 General ....................................................................................................................................................5 Principle ..................................................................................................................................................7 Safety precautions .................................................................................................................................7 Reagents .................................................................................................................................................7 Apparatus ...............................................................................................................................................8 Test specimen sampling and preparation ........................................................................................ 10 General ................................................................................................................................................. 10 Textile article ....................................................................................................................................... 10 Fibre composition ............................................................................................................................... 10 Case of the fibre blends ..................................................................................................................... 11 Printed materials ................................................................................................................................. 11 Colours ................................................................................................................................................ 11 General ................................................................................................................................................. 11 Case of colour gathering ................................................................................................................... 11 Preparation of the three colour test specimen ................................................................................ 12 Procedure ............................................................................................................................................ 12 Colorant extraction for disperse dyes .............................................................................................. 12 Extraction of disperse dyes with chlorobenzene ............................................................................ 12 Textiles only dyed with disperse dyes ............................................................................................. 12 Textiles dyed with disperse dyes and/or other dyes ...................................................................... 12 Textiles dyed with dyes other than disperse dyes .......................................................................... 12 Reductive cleavage ............................................................................................................................ 12 Separation and concentration of the amines ................................................................................... 13 Amine detection and quantification .................................................................................................. 13 Check procedure................................................................................................................................. 13 General ................................................................................................................................................. 13 Calibration using internal standard (quantification performed by gas chromatography) .......... 13 Calibration without internal standard ............................................................................................... 14 Evaluation ............................................................................................................................................ 14 General ................................................................................................................................................. 14 Calculation of amine in the sample................................................................................................... 15 Reliability of the method .................................................................................................................... 15 Test report ........................................................................................................................................... 15

Annex A (informative) Chromatographic analyses ..................................................................................... 16 A.1 Preliminary remark ............................................................................................................................. 16 A.2 Thin layer chromatography (TLC) ..................................................................................................... 16 A.3 High performance liquid chromatography (HPLC) .......................................................................... 17 A.4 Capillary gas chromatography/mass selective detector (GC/MS) ................................................. 18 A.5 Capillary electrophoresis (CE) .......................................................................................................... 18 Annex B (informative) Reliability of the method ......................................................................................... 20 Annex C (informative) Assessment guide-interpretation of analytical results ........................................ 22 Annex D (informative) Explanatory table of dyestuffs used in various textile materials ........................ 23

2

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

D.1 D.2 General ................................................................................................................................................. 23 Criteria for printed materials .............................................................................................................. 24

Annex E (informative) Procedure for liquid/liquid-extraction without diatomaceous earth .................... 25 E.1 Preliminary remark .............................................................................................................................. 25 E.2 Additional reagents used.................................................................................................................... 25 E.3 Additional apparatus used ................................................................................................................. 26 E.4 Procedure ............................................................................................................................................. 26 Annex F (normative) Colorants - Methods for determination of certain aromatic amines ...................... 28 F.1 Scope .................................................................................................................................................... 28 F.2 Principle................................................................................................................................................ 28 F.3 Test specimen preparation ................................................................................................................. 28 F.4 Procedure ............................................................................................................................................. 28 F.5 Evaluation............................................................................................................................................. 28 F.6 Test report ............................................................................................................................................ 28 Bibliography ...................................................................................................................................................... 29

3

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

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 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 August 2012, and conflicting national standards shall be withdrawn at the latest by August 2012.

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. This document supersedes EN 14362-1:2003, EN 14362-2:2003. EN 14362 is composed of the following parts:

EN 14362-1, 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; EN 14362-3, 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-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 specimen 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 of 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 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, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom.

4

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

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 accessible 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 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 extract 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 references, 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 following 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.

5

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

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 95-69-2 612-196-00-0 202-441-6 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. The presence of these colorants should be tested by EN 14362-3.

6

-

--`,,`,`,,`,,`-`-````,,,,```,,`--

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

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 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 discoloured 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 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 chlorobenzene extraction, the specimen is added to the reaction vessel with the 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 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 a solvent appropriate 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.

5 Safety precautions

5.1 WARNING — The substances [amines] listed 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 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. 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.

7

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

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, ρ = 200 mg/ml2) freshly (daily) prepared.

6.8 Diatomaceous earth.

6.9 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 standard. 6.10 Standard solutions.

6.10.1 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.

6.10.2 Calibration solution of amines for daily use.

Dilute from the stock solution 6.10.1 to a concentration of ρ = 15,0 µg of each amine per millilitre of an appropriate solvent.

6.10.3 Calibration solutions of amines for quantification, concentration range from 2 µg up to 50 µg of each amine per millilitre of an appropriate solvent.

NOTE

It is the responsibility of each lab to choose appropriate concentrations for the calibration.

6.10.4 Internal standards in solution (IS), ρ = 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.: 1719-06-8.

NOTE If the confirmation analysis for benzidine is done with DAD or TLC the use of IS1: benzidine-d8, CAS No.: 92890-63-6 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, complying with EN ISO 3696:1995.

7 Apparatus

7.1 Extraction apparatus, according to Figure 1, consisting of:

1) c is citrate concentration. 2) ρ is the mass concentration.

8

-

--`,,`,`,,`,,`-`-````,,,,```,,`--

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

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; 100 ml round bottom flask NS 29/32; heating source.

Figure 1 — Apparatus

NOTE

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

7.2 Ultrasonic bath, controllable heating.

7.3 Reaction vessel (20 ml to 50 ml) of heat-resistant glass, with tight closure. 7.4 Heating source that generates (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 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. 7.6

Vacuum rotary evaporator with vacuum control and water bath.

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

7.7 Pipettes in required sizes or variables 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 relevant detection.

--`,,```,,,,````-`-`,,`,,`,`,,`---

7.8.2 High performance liquid chromatography (HPLC) with gradient elution and diode array detector (DAD) or mass selective detector (MS).

7.8.3 Gas chromatography (GC) with flame ionisation detector (FID) or mass selective detector (MS). 7.8.4 Capillary electrophoresis (CE) with diode array detector (DAD).

NOTE

A description of the chromatographic equipment is given in Annex A.

9

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

8 Test specimen sampling and preparation

8.1 General

The test specimen shall be selected based on the following criteria: Parts of the textile article;

Nature of the fibre components (fibre composition); Printed materials; Colours.

Prepare the test specimen by cutting in order to obtain a total mass of 1 g. For specimens to be submitted to colorant extraction (9.1) cut into strips (if apparatus described in 7.1 is used) or cut into small pieces if other apparatus is used or for specimens to be submitted only to reductive cleavage (9.3).

8.2 Textile article

If the textile article is a semi-manufactured product, such as yarns, fabrics, etc., cut out test specimens from it. If the textile article is composed of several parts of textile products, such as a garment, cut out test specimens from all the parts of the textile article that have direct and prolonged contact to skin or mouth, which can be: principal fabric(s); lining(s); pocket fabric(s); embroideries;

label(s) for textile article; drawstring(s); fastener(s); false fur; sewing threads.

If the mass of some parts (e.g. labels, sewing threads, embroideries of small size) does not reach the mass (1 g) to be tested, gather identical parts when possible. If the total mass of material is below 0,5 g, this material is defined as a minor component. (See NOTE 2, Annex C.) Below 0,2 g of material the analysis is omitted. Embroideries shall be weighed with the ground fabric.

8.3 Fibre composition

textile components so that the possible use of disperse dyestuffs can be determined. Table 2 summarizes the four cases:

--`,,```,,,,````-`-`,,`,,`,`,,`---

10

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

Table 2 — Application of colorant extraction for disperse dyes (9.1) in relation to the fibre nature

Nature of fibre

Use of disperse

dyestuffs

No

Cases

Colorant extraction for disperse dyes (9.1)

necessary?

No

Natural fibre A

No B No

Man-made fibre

Undetermined C

Yes

Yes D Yes

NOTE

If a fibre is not dyed, the fibre shall not be tested.

Categories of dyestuffs used in either natural or man-made fibres are explained in Annex D.

8.4 Case of the fibre blends

In the case when fibres of different types are mixed, refer to Table 3 in order to decide if application of the colorant extraction for disperse dyes (9.1) shall be applied.

Table 3 — Application of colorant extraction for disperse dyes (9.1) in relation to the fibre blends Colorant extraction for disperse Other component of the blend dyes (9.1) necessary?

A B C D

A

Component

of the blend

B C D

NOTE

See Table 2 for meanings of A, B, C and D.

No No Yes Yes No No Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes

8.5 Printed materials

If material is printed with pigments (Annex D) the method in 9.2 has to be used.

8.6 Colours

8.6.1 General All colours shall be tested.

NOTE

"White" is not considered as "colour" and therefore "white" parts do not have to be tested.

8.6.2 Case of colour gathering

Up to three colours may be tested together.

In order to gather three colours, the following rules shall be applied. The rules have been listed in order of

preference:

Select the three colours from the same part of the textile article;

11

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

If the three colours do not come from the same part of the textile article, select these three colours from

textile parts made of the same type of textile fibre; If the three colours do not come from the same part of the textile article and do not come from the same

type of textile fibre, select these three colours from textile parts on which the same procedure shall be applied. 8.6.3 Preparation of the three colour test specimen

Each colour shall have approximately the same weight in order to obtain the total mass of 1 g.

If the result of the combined test specimen is in the range between 5 mg/kg and 30 mg/kg of any of the named amines, separate testing is necessary as the result of testing a single colour test specimen may exceed 30 mg/kg. The quantification limits shall be documented for every amine by internal validation procedures.

9 Procedure

9.1 Colorant extraction for disperse dyes

9.1.1 Extraction of disperse dyes with chlorobenzene

The textile specimen dyed with disperse dyes is kept in the extractor according to (7.1) for 30 min above 25 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 at a temperature of 45 °C to 60 °C to a small residual quantity. This residue is quantitatively transferred to the reaction vessel with two portions of 1 ml methanol using an ultrasonic bath to disperse the colorant. 9.1.2 Textiles only dyed with disperse dyes

Remove the textile specimen from the extractor and discard it if it is completely made of fibres dyed with disperse dyes and/or becomes decolourised after extraction. 9.1.3 Textiles dyed with disperse dyes and/or other dyes

Remove, from the extractor, the extracted textile specimen if it contains fibres belonging to cases A and/or B (8.4). Remove the solvent by washing the specimen with appropriate solvent e.g. n-pentane (6.5) or t-butyl methyl ether (6.4) 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 solution of the dispersed dye (in total 2 ml) for combined reduction.

--`,,```,,,,````-`-`,,`,,`,`,,`---

9.2 Textiles dyed with dyes other than disperse dyes

If the textile specimen contains fibres belonging only to cases A and/or B (8.4) put the test specimen directly in a reaction vessel and add 2 ml methanol (6.3).

9.3 Reductive cleavage

To the reaction vessel add 15 ml of citrate buffer solution (6.6) preheated to 70 °C. The reaction vessel is tightly closed and treated for (30 ± 1) min at (70 ± 2) °C.

Subsequently, 3,0 ml aqueous sodium dithionite solution (6.7), for reductive cleavage of the azo groups, are added to the reaction vessel, which is then shaken vigorously and immediately kept again at (70 ± 2) °C for another (30 ± 1) min whereupon it is cooled to room temperature (20 °C to 25 °C) within 2 min.

12

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

9.4 Separation and concentration of the amines

Add, to the reaction solution, 0,2 ml of the NaOH solution (6.11) and shake vigorously. Transfer the reaction solution to the diatomaceous earth column (7.5) and allow to be absorbed by the column for 15 min.

Meanwhile add 10 ml t-butyl methyl ether in the reaction vessel, shake vigorously and after the 15 min period the t-butylmethyl ether is decanted with the fibres onto the top of the column and the eluate is collected in a 100 ml round-bottom flask with standard ground joint or in a glass vessel for an evaporation apparatus (7.6). The reaction vessel is rinsed with 10 ml t-butylmethyl ether and the solvent is transferred to the column. Subsequently, 60 ml t-butyl methyl ether is poured directly on the column.

For amine detection and quantification, the t-butyl methyl ether extract is concentrated to about 1 ml (not to dryness!) at not more than 50 °C. If necessary, to exchange to another solvent, remove the remainder of the solvent very carefully by means of a weak flow of inert gas.

NOTE 1 Removal of the solvent (concentration in the rotary vacuum evaporator, evaporation to dryness) may lead to substantial amine losses if performed under uncontrolled conditions.

The extract or residue are immediately taken up to 2,0 ml of an appropriate solvent, e.g. acetonitrile or t-butyl methyl ether, and analysed without delay. If the complete analysis cannot be performed within 24 h, keep the extract below -18 °C.

NOTE 2 Owing to the matrix, individual amines, such as 2,4-diaminotoluene and 2,4-diaminoanisole are likely to exhibit a very poor stability. Where delays occur in the work routine, amines may be no longer detectable by the time of instrumental measurement.

9.5 Amine detection and quantification

Amine detection can be performed using the chromatographic techniques listed (7.8). Other validated methods may be used. If any amine is detected by one chromatographic method, then confirmation shall be made using one or more alternative methods. The result is positive only if both methods give a positive result. If any of the amines listed in Table 1 is identified, then at least a three point calibration curve is built up to quantify amine content.

NOTE

If the identified amines have isomers, care should be taken about the correct identification.

9.6 Check procedure

9.6.1 General

To check the procedure, 100 µl of the amine stock solution (6.10.1) (or a volume to give 30 µg of each amine in the reaction vessel) and 2,0 ml methanol are added to a reaction vessel (7.3) containing 15 ml of the preheated citrate/sodium hydroxide buffer solution (6.6). This check procedure shall be carried out with each batch of samples.

Then the procedure set out in 9.4 and 9.5 is carried out. Quantify this check standard based on the daily calibration (6.10.2).

9.6.2 Calibration using internal standard (quantification performed by gas chromatography)

ρS=ρc ×

where

As×AISC Vs

×

A c ×AISSV

ρs

concentration of the amine in the sample solution in µg/ml;

13

禁用偶氮染料释放芳香胺欧盟测试方法,替代原-1&-2方法。

BS EN 14362-1:2012

EN 14362-1:2012 (E)

As Ac Aiss Aisc V

peak area of the amine in the specimen solution in area units; peak area of the amine in the calibration solution in area units;

peak area of the internal standard in the specimen solution in area units; peak area of the internal standard in the calibration solution in area units; final specimen volume made up to according to 9.4 in ml; amine solution volume used for check procedure, in ml; concentration of the amine in the calibration solution in µg/ml.

Vs

ρc

9.6.3 Calibration without internal standard

ρS=ρc ×

where

AsVs

× A c V

ρs

As Ac V

concentration of the amine in the sample solution in µg/ml; peak area of the amine in the specimen solution in area units; peak area of the amine in the calibration solution in area units; final specimen volume made up to according to 9.4 in ml; amine solution volume used for check procedure, in ml; concentration of the amine in the calibration solution in µg/ml.

Vs

ρc

Amine recovery rates shall comply with the following minimum requirements:

amines No. 1 to 4, 7, 9 to 17 and 20 to 21: 70 %; amine No. 8: 20 %; amines No. 18 and 19: 50 %; amines No. 5, 6 and 22, see footnotes to Table 1

aniline: 70 %

NOTE

Currently, there is insufficient experience to give minimum requirements for the amines not listed above.

10 Evaluation

10.1 General

If any amine is detected and/or quantified using daily calibration (6.10.2) above 5 mg/kg, the quantification shall be done using a multipoint calibration graph (6.10.3).

Plot a calibration graph of the response against the known standard concentration (corrected for the response for the internal standard if used). From the calibration graph, interpolate the concentration of the amine in µg/ml (ρs).

14