EN 71-12-2016 en Safety of toys - Part 12 N-Nitrosamines and N-nitrosatable substances《玩具安全-第12部分 N-硝基胺和N-硝化物质》.pdf

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1、BS EN 71-12:2016Safety of toysPart 12: N-Nitrosamines and N-nitrosatablesubstancesBSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06BS EN 71-12:2016 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 71-12:2016. Itsupersedes BS EN 71-

2、12:2013 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee CW/15, Safety of toys.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a

3、contract. Users are responsible for its correctapplication. The British Standards Institution 2017. Published by BSI Standards Limited 2017ISBN 978 0 580 88627 0ICS 97.200.50Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the

4、authority of the Standards Policy and Strategy Committee on 31 January 2017.Amendments/Corrigenda issued since publicationDate Text affectedBS EN 71-12:2016EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 71-12 December 2016 ICS 97.200.50 Supersedes EN 71-12:2013English Version Safety of toys -

5、Part 12: N-Nitrosamines and N-nitrosatable substances Scurit des jouets - Partie 12 : N-Nitrosamines et substances N-nitrosables Sicherheit von Spielzeug - Teil 12: N-Nitrosamine und N-nitrosierbare Stoffe This European Standard was approved by CEN on 30 October 2016. CEN members are bound to comply

6、 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 M

7、anagement 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

8、 status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg,

9、Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2016

10、 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 71-12:2017 EBS EN 71-12:2016EN 71-12:2016 (E) 2 Contents PageEuropean foreword . 4 1 Scope 6 2 Normative references 6 3 Terms and definitions . 6 4 Requirements . 7 4.1 Requirements

11、for finger paints 7 4.2 Requirements for elastomers . 7 5 Principle . 8 6 Reagents and apparatus . 8 6.1 Reagents . 8 6.2 Standards . 9 6.3 Apparatus 10 7 Sample preparation . 11 7.1 General . 11 7.2 Finger paints 11 7.2.1 N-nitrosamines 11 7.2.2 N-nitrosatable substances 12 7.3 Elastomers 12 7.3.1

12、Sample preparation for balloons 12 7.3.2 Sample preparation for other toys or parts of toys than balloons . 12 7.3.3 Nitrosation 13 7.3.4 Preparation of solution for determination of N-nitrosamines by HPLC-MS/MS . 13 8 Methods of analysis . 13 8.1 General . 13 8.2 HPLC chromatographic conditions 14

13、8.3 MS/MS conditions 14 8.4 Confirmation of detected N-nitrosamines . 15 9 Calculation of results for N-nitrosamines and N-nitrosatable substances 16 9.1 Finger paint 16 9.1.1 General . 16 9.1.2 N-nitrosamines 16 9.1.3 N-nitrosatable substances 17 9.2 Elastomers 17 9.2.1 General . 17 9.2.2 N-nitrosa

14、mines 18 9.2.3 N-nitrosatable substances 18 10 Method performance 19 10.1 Finger paints 19 10.1.1 Repeatability, reproducibility and measurement uncertainty . 19 10.1.2 Limits of detection (LOD) and quantification (LOQ) . 19 10.2 Elastomers 19 10.2.1 Repeatability, reproducibility and measurement un

15、certainty . 19 10.2.2 Limits of detection and quantification . 20 BS EN 71-12:2016EN 71-12:2016 (E) 3 11 Test report 21 Annex A (informative) Background and rationale for this European Standard . 22 A.1 Definition of elastomer . 22 A.2 Requirements for finger paints (see 4.1) . 22 A.3 Requirements f

16、or elastomers (see 4.2) 23 A.4 Avoidance N-nitrosamines in finger paints . 24 A.5 Explanation for decision to do static migration for elastomers and for the specified migration times . 24 A.6 Reference to other standards and relevant deviations 25 A.7 Conditions for nitrosation . 25 A.8 NDELA in bal

17、loons 26 A.9 Selection of N-nitrosamines specified in this standard 26 Annex B (informative) Significant technical changes between this European Standard and the previous version 27 Annex C (informative) Adeviations . 29 Annex ZA (informative) Relationship between this European Standard and the esse

18、ntial requirements of EU Directive 2009/48/EC aimed to be covered . 30 Bibliography . 31 BS EN 71-12:2016EN 71-12:2016 (E) 4 European foreword This document (EN 71-12:2017) has been prepared by Technical Committee CEN/TC 52 “Safety of toys”, the secretariat of which is held by DS. This European Stan

19、dard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by June 2017, and conflicting national standards shall be withdrawn at the latest by June 2017. Attention is drawn to the possibility that some of the elements of this d

20、ocument may be the subject of patent rights. CEN shall not be held responsible for identifying any or all such patent rights. This document supersedes EN 71-12:2013. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association, and s

21、upports essential requirements of EU Directive 2009/48/EC. For relationship with EU Directive 2009/48/EC, see informative Annex ZA, which is an integral part of this document. Additional information on the rationale for various requirements is given in Annex A. Annex B provides details of significan

22、t technical changes between this European Standard and the previous edition. This European Standard constitutes the 12th part of the European Standard on safety of toys. This European Standard for safety of toys consists of the following parts: Part 1: Mechanical and physical properties; Part 2: Fla

23、mmability; 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 7: Finger paints Requirements and test methods; Part 8: Activity toys for domestic use; Part 9: Organic chemical compounds

24、 Requirements; Part 10: Organic chemical compounds Sample preparation and extraction; Part 11: Organic chemical compounds Methods of analysis; Part 12: N-nitrosamines and N-nitrosatable substances; Part 13: Olfactory board games, gustative board games, cosmetic kits and gustative kits; Part 14: Tram

25、polines for domestic use. BS EN 71-12:2016EN 71-12:2016 (E) 5 NOTE 1 In addition to the above parts of EN 71, the following guidance documents have been published: CEN Technical Report CEN/TR 15071, Safety of toys National translations of warnings and instructions for use in EN 71, and CEN Technical

26、 Report CEN/TR 15371 (all parts), Safety of toys Interpretations. NOTE 2 Words in italics are defined in Clause 3 (Terms and definitions). According to the CEN-CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard:

27、 Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain,

28、Sweden, Switzerland, Turkey and the United Kingdom. BS EN 71-12:2016EN 71-12:2016 (E) 6 1 Scope This European Standard specifies the requirements and test methods for N-nitrosamines and N-nitrosatable substances for: toys and parts of toys made from elastomers and intended for use by children under

29、36 months; toys and parts of toys made from elastomers and intended to be placed in the mouth; finger paints for children under 36 months. EXAMPLE Examples of toys made from elastomers are balloons and teethers. NOTE With regard to elastomers, up to now N-nitrosamines and N-nitrosatable substances h

30、ave mainly been detected in vulcanized materials. 2 Normative references The following documents, 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 editi

31、on of the referenced document (including any amendments) applies. EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696) 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 finger paint aqueous semi-solid or

32、liquid, coloured mixture specially designed for children to apply directly to suitable surfaces with the fingers and hands SOURCE: EN 71-7:2014, definition 3.1 3.2 elastomer flexible cross-linked macro-molecular material which returns rapidly to approximately its initial dimensions and shape after s

33、ubstantial deformation by stress and release of the stress at room temperature Note 1 to entry: Not all elastomers are likely to contain N-nitrosamines and N-nitrosatable substances. For further guidance on possible sources of N-nitrosamines and N-nitrosatable substances in elastomers the term elast

34、omer and other related aspects see A.1. SOURCE: EN ISO 472:2013, 2.327, modified: the phrases “flexible cross-linked”, “approximately” and “at room temperature” and note 1 to entry added and the phrase “a weak” deleted 3.3 N-nitrosamine substance characterised by the -N-N=O functional group, usually

35、 formed by the reaction of an amine with a nitrosating agent at acidic pH Note 1 to entry: The reacting amines primarily are secondary amines. Note 2 to entry: An example for a nitrosating agent is nitrite. BS EN 71-12:2016EN 71-12:2016 (E) 7 3.4 N-nitrosatable substance substance which when release

36、d into the test solution undergoes nitrosation to form a N-nitrosamine under specified conditions 4 Requirements 4.1 Requirements for finger paints The concentration of N-nitrosamines in finger paints shall not exceed 0,02 mg/kg when tested in accordance with 7.2 and Clause 8, calculated as sum of a

37、ll detected N-nitrosamines according to 9.1. The migration of N-nitrosatable substances from finger paints shall not exceed 1 mg/kg of toy material, calculated as sum of all detected N-nitrosamines after nitrosation. At least the substance in Table 1 shall be determined in finger paint. If there are

38、 indications of the presence of other N-nitrosamines, they shall also be determined. Table 1 List of N-nitrosamines in finger paints Name of the substance CAS number Abbreviation N-nitrosodiethanolamine 1116547 NDELA 4.2 Requirements for elastomers The migration of N-nitrosamines (calculated as sum

39、of all detected N-nitrosamines according to 9.2) and of N-nitrosatable substances (calculated as sum of all detected N-nitrosamines after nitrosation) from toys or parts of toys shall not exceed the limit values specified in Table 2 when tested in accordance with 7.3 and Clause 8. Table 2 Limit valu

40、es for elastomers Product type N-nitrosamines mg/kg N-nitrosatable substances mg/kg a) toys intended for use by children under 36 months and intended or likely to be placed into the mouth 0,01 0,1 b) toys intended for use by children under 36 months not covered by a) 0,05 1 c) toys intended for use

41、by children of 36 months and over and intended to be placed into the mouth 0,05 1 d) balloons 0,05 1 At least the substances in Table 3 shall be determined in elastomers. If there are indications of the presence of other N-nitrosamines they shall also be determined. BS EN 71-12:2016EN 71-12:2016 (E)

42、 8 Table 3 List of N-nitrosamines in elastomers Name of the substance CAS number Abbreviation N-nitrosodiethanolamine 1116547 NDELA N-nitrosodimethylamine 62759 NDMA N-nitrosodiethylamine 55185 NDEA N-nitrosodipropylamine 621647 NDPA N-nitrosodiisopropylamine 601774 NDiPA N-nitrosodibutylamine 92416

43、3 NDBA N-nitrosodiisobutylamine 997955 NDiBA N-nitrosodiisononylamine (N-Nitroso-N,N-di(3,5,5-trimethylhexyl)amine) 1207995627 NDiNA N-nitrosomorpholine 59892 NMOR N-nitrosopiperidine 100754 NPIP N-nitrosodibenzylamine 5336538 NDBzA N-nitroso-N-methyl-N-phenylamine 614006 NMPhA N-nitroso-N-ethyl-N-p

44、henylamine 612646 NEPhA 5 Principle N-nitrosamines and N-nitrosatable substances migrate into a test solution. N-nitrosatable substances are converted to N-nitrosamines by acidification. The final test solutions are analysed for N-nitrosamines by a suitable validated analytical technique. The N-nitr

45、osamines and N-nitrosatable substances are expressed in mg/kg of sample. The test solution for N-nitrosamines in finger paints is water. The test solution for N-nitrosatable substances in finger paints and for N-nitrosamines and N-nitrosatable substances in elastomers is saliva test solution. 6 Reag

46、ents and apparatus 6.1 Reagents Unless otherwise specified, all reagents shall be of analytical grade and distilled water, or water of equivalent purity conforming to at least grade 3 of EN ISO 3696. 6.1.1 Sodium hydrogen carbonate (CAS 144-55-8) 6.1.2 Sodium chloride (CAS 7647-14-5) 6.1.3 Potassium

47、 carbonate (CAS 584-08-7) 6.1.4 Sodium nitrite (CAS 7632-00-0) 6.1.5 Hydrochloric acid (CAS 7647-01-0), aqueous solution, c(HCL) = 0,1 mol/l BS EN 71-12:2016EN 71-12:2016 (E) 9 6.1.6 Sodium hydroxide (CAS 1310-73-2), aqueous solution, c(NaOH) = 0,1 mol/l 6.1.7 Saliva test solution Dissolve (4,2 0,02

48、1) g of the sodium hydrogen carbonate (6.1.1), (0,5 0,002 5) g of the sodium chloride (6.1.2), (0,2 0,001 0) g of the potassium carbonate (6.1.3) and (0,03 0,000 15) g of the sodium nitrite (6.1.4) in water and dilute to (950 5) ml with water. Adjust to pH 9,0 0,1 if necessary by adding the hydrochl

49、oric acid solution (6.1.5) or sodium hydroxide solution (6.1.6) drop by drop. Transfer into a 1 l volumetric flask and dilute to the mark with water. This solution has a limited stability. Saliva test solution kept for more than five days shall not be used. 6.1.8 Hydrochloric acid solution, c(HCL) = 1 mol/l. 6.1.9 Sodium hydroxide solution, c(NaOH) = 1 mol/l. 6.1.10 Methanol, 99,9 %, HPLC-grade. 6.1.11 Formic acid, 99,5 %, LC-MS grade. 6.1.12 Eluent A: 0,1 % (volume fraction) formic