BS EN 71-11-2005 Safety of toys. Organic chemical compounds. Methods of analysis.pdf

BRITISH STANDARD BS EN ? 71-11:2005 Safety of toys Part 11: Organic chemical ? compounds Methods of analysis The European Standard EN 71-11:2005 has the status of a British Standard ICS 97.200.50 ? Copyright British Standards Institution Reproduced by IHS under license with BSI - Uncontrolled Copy Licensee=Hong Kong Polytechnic Univ/9976803100 Not for Resale, 01/23/2006 06:44:09 MSTNo reproduction or networking permitted without license from IHS -,-,- BS EN 71-11:2005 This British Standard was published under the authority of the Standards Policy and Strategy Committee? on 22 November 2005 © BSI 22 November 2005 ISBN 0 580 46391 5 National foreword This British Standard is the official English language version of ? EN 71-11:2005. The UK participation in its preparation was entrusted to Technical Committee CW/15, Safety of toys, which has the responsibility to: aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep UK interests informed; monitor related international and European developments and promulgate them in the UK. A list of organizations represented on this committee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “ International Standards Correspondence Index” , or by using the “ Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 69 and a back cover. The BSI copyright notice displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. DateComments Copyright British Standards Institution Reproduced by IHS under license with BSI - Uncontrolled Copy Licensee=Hong Kong Polytechnic Univ/9976803100 Not for Resale, 01/23/2006 06:44:09 MSTNo reproduction or networking permitted without license from IHS -,-,- EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM EN 71-11 November 2005 ICS 97.200.50 English Version Safety of toys - Part 11: Organic chemical compounds - Methods of analysis Sécurité des jouets - Partie 11 : Composés chimiques organiques dans les jouets - Méthodes d'analyse Sicherheit von Spielzeug - Teil 11: Organisch-chemische Verbindungen - Analysenverfahren This European Standard was approved by CEN on 27 June 2005. 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 Central Secretariat 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 Central Secretariat has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels © 2005 CENAll rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 71-11:2005: E Copyright British Standards Institution Reproduced by IHS under license with BSI - Uncontrolled Copy Licensee=Hong Kong Polytechnic Univ/9976803100 Not for Resale, 01/23/2006 06:44:09 MSTNo reproduction or networking permitted without license from IHS -,-,- EN 71-11:2005 (E) 2 Contents Page Foreword 3 Introduction4 1Scope.5 2Normative references .5 3Terms and definitions.5 4Environmental, health and safety precautions.6 5Methods of analysis6 5.1General 6 5.2Flame retardants.6 5.3Colourants.9 5.4Primary aromatic amines15 5.5Monomers and solvents.19 5.6Wood preservatives37 5.7Preservatives.41 5.8Plasticisers44 Annex A (informative) Methods of analysis for volatile solvents .48 Annex B (informative) Validation of test methods .65 Annex C (informative) Colourants conformational analysis 66 Annex ZA (informative) Clauses of this European Standard addressing essential requirements or other provisions of EU Directives68 Bibliography.69 Copyright British Standards Institution Reproduced by IHS under license with BSI - Uncontrolled Copy Licensee=Hong Kong Polytechnic Univ/9976803100 Not for Resale, 01/23/2006 06:44:09 MSTNo reproduction or networking permitted without license from IHS -,-,- ? EN 71-11:2005 (E) 3 Foreword This European Standard (EN 71-11:2005) has been prepared by Technical Committee CEN/TC 52 “ Safety of Toys” , the secretariat of which is held by DS. 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 May 2006, and conflicting national standards shall be withdrawn at the latest by May 2006. This European Standard has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association, and supports essential requirements of EU Directive(s). For relationship with EU Directive(s), see informative Annex ZA, which is an integral part of this European Standard. This European Standard constitutes part 11 of the European Standard on Safety of Toys. This part should be read in conjunction with parts 9 and 10. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Copyright British Standards Institution Reproduced by IHS under license with BSI - Uncontrolled Copy Licensee=Hong Kong Polytechnic Univ/9976803100 Not for Resale, 01/23/2006 06:44:09 MSTNo reproduction or networking permitted without license from IHS -,-,- ? EN 71-11:2005 (E) 4 Introduction The European Standard EN 71 for “ safety of toys” consists of the following parts: Part 1: Mechanical and physical properties Part 2: Flammability Part 3: Migration of certain elements Part 4: Experimental sets for chemistry and related activities Part 5: Chemical toys (sets) other than experimental sets Part 6: Graphical symbols for age warning labelling Part 7: Finger paints Requirements and test methods Part 8: Swings, slides and similar activity toys for indoor and outdoor family domestic use Part 9: Organic chemical compounds Requirements Part 10: Organic chemical compounds Sample preparation and extraction Part 11: Organic chemical compounds Methods of analysis The European Standards EN 71-9, EN 71-10 and EN 71-11 were mandated by the European Commission (M/229) to address the risks presented by organic chemical compounds in toys by taking into account the potential exposure and toxicological effects of those substances considered to present the greatest risk to health. This European Standard specifies methods of analysis to enable assessment of compliance with the chemical requirements specified in EN 71-9 when toy and toy material extracts have been prepared according to the sampling procedures in EN 71-10. This part on methods of analysis should be read in conjunction with EN 71-9, which contains requirements for certain organic chemical compounds in toys, and EN 71-10, which describes sample preparation and extraction procedures. This European Standard takes into account the opinion of the Toxicology Section of the Scientific Advisory Committee published in 1992 (EUR 13976), which recommended that certain groups of chemical compounds used in toys and toy materials need to be given special attention. In drafting this European Standard CEN/TC 52 has considered organic chemicals that can be classified within the following groups: Solvents Preservatives Plasticisers (excluding phthalate plasticisers)1 Flame retardants Monomers Biocides (wood preservatives) Processing aids Colouring agents 1 Phthalate plasticisers were specifically excluded from the scope of mandate M/229. Copyright British Standards Institution Reproduced by IHS under license with BSI - Uncontrolled Copy Licensee=Hong Kong Polytechnic Univ/9976803100 Not for Resale, 01/23/2006 06:44:09 MSTNo reproduction or networking permitted without license from IHS -,-,- ? EN 71-11:2005 (E) 5 1 Scope This Part 11 of the European Standard EN 71 for safety of toys specifies methods for the analysis of toy and toy material extracts prepared according to the sampling procedures in EN 71-10, to enable assessment of compliance with the chemical requirements specified in EN 71-9. This European Standard specifies analytical methods for the identification and determination of the following groups of organic chemicals: Flame retardants Colourants Primary aromatic amines Monomers and solvents Wood preservatives Preservatives Plasticisers NOTE 1 Methods for formaldehyde in accessible textile components of toys; accessible paper components of toys; and accessible resin-bonded wood components of toys are specified in EN 71-9. NOTE 2 The method for free formaldehyde as a preservative is specified in EN 71-10. 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 71-9:2005, Safety of toys Part 9: Organic chemical compounds Requirements EN 71-10:2005, Safety of toys Part 10: Organic chemical compounds Sample preparation and extraction EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) 3 Terms and definitions For the purposes of this European Standard, the following terms and definitions apply. 3.1 action limit routinely-achievable limit of quantification for a particular substance using the specified method of analysis 3.2 aqueous migrate liquid obtained after extracting a toy material according to the procedure specified in Clause 6 of EN 71- 10:2005 3.3 test portion portion of the laboratory sample prepared for analysis 3.4 toy material material from which toys and toy components are made NOTE This definition differs from that given in EN 71-3 Copyright British Standards Institution Reproduced by IHS under license with BSI - Uncontrolled Copy Licensee=Hong Kong Polytechnic Univ/9976803100 Not for Resale, 01/23/2006 06:44:09 MSTNo reproduction or networking permitted without license from IHS -,-,- ? EN 71-11:2005 (E) 6 4 Environmental, health and safety precautions When preparing this European Standard, consideration was given to the minimisation of environmental impacts caused by the use of the methods of analysis. It is the users responsibility to use safe and proper techniques in handling materials in the methods of analysis specified in this European Standard. Consult manufacturers for specific details such as material safety data sheets and other recommendations. Wear protective goggles and coats in all laboratory areas. Be careful about substances, which are toxic and/or human carcinogens. A fume cupboard shall be used during preparation of organic solvent solutions. Solvents shall be disposed of in accordance with environmental requirements. 5 Methods of analysis 5.1 General All chemicals used for analysis shall be of analytical grade (pro analysis) or, if unavailable, the best technical grade. Water shall be of grade 3 according to EN ISO 3696 or of a comparable quality, and demonstrably free from analytes of interest. The precision of volumetric glassware should be grade A. The analysis of toys and toy materials for chemical compounds for which limits are given in Tables 2 A to 2 I of EN 71-9:2005 shall be performed in accordance with the sampling procedures specified in EN 71-10 and the methods of analysis described in this European Standard. Alternative methods of analysis are acceptable only if they are capable of achieving at least the accuracy and precision of the methods described in this European Standard; an adequate sensitivity; and have been validated to show that the results are equivalent to those of these standard methods. 5.2 Flame retardants NOTE Methods are given for pentabromodiphenyl ether and octabromodiphenyl ether in order to enable compliance with Directive 2003/11/EC of the European Parliament and of the Council to be demonstrated for textile toy materials. 5.2.1 Principle Flame retardants are determined in acetonitrile extracts of toy materials by liquid chromatography with diode- array and mass spectrometry detection (LC-DAD-MS) using the external standard method of calibration. Copyright British Standards Institution Reproduced by IHS under license with BSI - Uncontrolled Copy Licensee=Hong Kong Polytechnic Univ/9976803100 Not for Resale, 01/23/2006 06:44:09 MSTNo reproduction or networking permitted without license from IHS -,-,- ? EN 71-11:2005 (E) 7 5.2.2 Standards, reagents and solvents 5.2.2.1 Standards 5.2.2.1.1 Pentabromodiphenyl ether2*, CAS No. 32534-81-9 5.2.2.1.2 Octabromodiphenyl ether3* , CAS No. 32536-52-0 5.2.2.1.3 Tri-o-cresyl phosphate, CAS No. 78-30-8 5.2.2.1.4 Tris(2-chloroethyl) phosphate, CAS No. 115-96-8 5.2.2.2 Reagents and solvents 5.2.2.2.1 Acetonitrile 5.2.2.2.2 Dichloromethane 5.2.2.2.3 Ammonium acetate, anhydrous 5.2.2.2.4 Acetic acid, glacial 5.2.2.2.5 Ammonium acetate, 10 mmol/l aqueous solution, pH 3,6 Transfer (0,77 ± 0,01) g ammonium acetate (5.2.2.2.3) int