1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationDD CEN ISO/TS 16181:2011Footwear Critical substancespotentially present in footwearand footwear components Determination of phthalatesin footwear materials (ISO/TS16181:2011)DD C
2、EN ISO/TS 16181:2011 BRITISH STANDARDNational forewordThis Draft for Development is the UK implementation of CEN ISO/TS 16181:2011.This publication is not to be regarded as a British Standard.It is being issued in the Draft for Development series of publications and is of a provisional nature. It sh
3、ould be applied on this provisional basis, so that information and experience of its practical application can be obtained.Comments arising from the use of this Draft for Development are requested so that UK experience can be reported to the international organization responsible for its conversion
4、to an international standard. A review of this publication will be initiated not later than 3 years after its publication by the international organization so that a decision can be taken on its status. Notification of the start of the review period will be made in an announcement in the appropriate
5、 issue of Update Standards.According to the replies received by the end of the review period, the responsible BSI Committee will decide whether to support theconversion into an international Standard, to extend the life of the Technical Specification or to withdraw it. Comments should be sent to the
6、 Secretary of the responsible BSI Technical Committee at British Standards House, 389 Chiswick High Road, London W4 4AL.The UK participation in its preparation was entrusted to Technical Committee TCI/69, Footwear, leather and coated fabrics.A list of organizations represented on this committee can
7、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. BSI 2011 ISBN 978 0 580 74887 5 ICS 61.060 Compliance with a British Standard cannot confer immunity from legal obligati
8、ons.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 August 2011.Amendments issued since publicationDate T e x t a f f e c t e dTECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN ISO/TS 16181 July 2011 ICS 61.060 En
9、glish Version Footwear - Critical substances potentially present in footwear and footwear components - Determination of phthalates in footwear materials (ISO/TS 16181:2011) Chaussures - Substances critiques potentiellement prsentes dans les chaussures et les composants des chaussures - Dtermination
10、des phtalates dans les matriaux des chaussures (ISO/TS 16181:2011) Schuhe - Mglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische Substanzen - Bestimmung von Phthalaten in Schuhwerkstoffen (ISO/TS 16181:2011) This Technical Specification (CEN/TS) was approved by CEN on 21 May 2011 for
11、 provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to a
12、nnounce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion o
13、f the CEN/TS into an EN is reached. 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, P
14、ortugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any me
15、ans reserved worldwide for CEN national Members. Ref. No. CEN ISO/TS 16181:2011: EDD CEN ISO/TS 16181:2011CEN ISO/TS 16181:2011 (E) 3 Foreword This document (CEN ISO/TS 16181:2011) has been prepared by Technical Committee CEN/TC 309 “Footwear“, the secretariat of which is held by AENOR, in collabora
16、tion with Technical Committee ISO/TC 216 “Footwear“. 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 Inte
17、rnal Regulations, the national standards organizations of the following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
18、Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. DD CEN ISO/TS 16181:2011ISO/TS 16181:2011(E) ISO 2011 All rights reserved iiiForeword ISO (the International Organization for Standardization) is a worldwide fede
19、ration of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that commi
20、ttee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordan
21、ce with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires
22、approval by at least 75 % of the member bodies casting a vote. In other circumstances, particularly when there is an urgent market requirement for such documents, a technical committee may decide to publish other types of document: an ISO Publicly Available Specification (ISO/PAS) represents an agre
23、ement between technical experts in an ISO working group and is accepted for publication if it is approved by more than 50 % of the members of the parent committee casting a vote; an ISO Technical Specification (ISO/TS) represents an agreement between the members of a technical committee and is accep
24、ted for publication if it is approved by 2/3 of the members of the committee casting a vote. An ISO/PAS or ISO/TS is reviewed after three years in order to decide whether it will be confirmed for a further three years, revised to become an International Standard, or withdrawn. If the ISO/PAS or ISO/
25、TS is confirmed, it is reviewed again after a further three years, at which time it must either be transformed into an International Standard or be withdrawn. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held r
26、esponsible for identifying any or all such patent rights. ISO/TS 16181 was prepared by the European Committee for Standardization (CEN) Technical Committee CEN/TC 309, Footwear, in collaboration with Technical Committee ISO/TC 216, Footwear, in accordance with the Agreement on technical cooperation
27、between ISO and CEN (Vienna Agreement). DD CEN ISO/TS 16181:2011ISO/TS 16181:2011(E) iv ISO 2011 All rights reservedIntroduction Phthalates are commonly used as plasticizers in polymers. Toxicological concern has arisen due to their potential effect as endocrine disruptors and some of the listed pht
28、halates are toxic in reproduction. The level of media publicity will ensure that their use continues to be of concern to consumers. Phthalates are controversial because high doses of many phthalates have shown hormonal activity in rodent studies. Studies on rodents involving large amounts of phthala
29、tes have shown damage to the liver, the kidneys, the lungs, and the developing testes. This Technical Specification calls for the use of substances and/or procedures that can be injurious to health if appropriate precautions are not observed. It refers only to technical suitability and does not abso
30、lve the user from legal obligations relating to health and safety at any stage. DD CEN ISO/TS 16181:2011TECHNICAL SPECIFICATION ISO/TS 16181:2011(E) ISO 2011 All rights reserved 1Footwear Critical substances potentially present in footwear and footwear components Determination of phthalates in footw
31、ear materials SAFETY PRECAUTIONS Persons using this Technical Specification should be familiar with normal laboratory practice. This Technical Specification does not claim to address all of the safety problems, if any, associated with its use. It is the responsibility of the user to establish approp
32、riate safety and health practices and to ensure compliance with any national regulatory conditions. IMPORTANT It is absolutely essential that tests conducted according to this Technical Specification be carried out by suitably trained staff. 1 Scope This Technical Specification specifies a test meth
33、od to determine the presence of phthalate compounds. This test method is applicable to all types of footwear materials. NOTE 1 This test method can also be used to determine plasticizers other than those listed in 3.2, subject to validation. NOTE 2 ISO/TR 16178 defines which materials are concerned
34、by this determination. 2 Principle The aim of the method is to extract phthalates in footwear materials such as leather, textile, polymer, coated materials or others. This method uses extraction apparatus with n-hexane/acetone as solvent. The total n-hexane/acetone extractable phthalate plasticizer
35、content is calculated by weight with gas chromatography-mass spectrometry (GC-MS) detection to identify and quantify individual phthalates. 3 Apparatus and reagents 3.1 Apparatus 3.1.1 Scales, resolution of 1 mg. 3.1.2 Flask, 50 ml. 3.1.3 Water-cooled condenser. 3.1.4 Spark-proof heating mantle/wate
36、r bath. 3.1.5 Ultrasonic bath. 3.1.6 Microwave extractor. 3.1.7 Steam bath or rotary evaporator. DD CEN ISO/TS 16181:2011ISO/TS 16181:2011(E) 2 ISO 2011 All rights reserved3.1.8 Calibrated volumetric flasks of suitable volume. Avoid direct contact between the samples and glassware and/or equipment u
37、sed in order to minimize cross-contamination. Glassware, after washing, should be given an extra rinse with 0,1 N nitric acid and finally with acetone, acetone/methanol and/or cyclohexane. Dry at 110 C for 1 h. WARNING The vapour of the organic solvents are highly flammable, especially at high tempe
38、rature. Allow glassware to cool down before use. 3.1.9 Gas chromatograph with mass-selective detector (GC-MS). 3.2 Reagents Unless otherwise specified, use only reagents of recognized analytical grade. 3.2.1 Water, distilled or of equivalent purity. 3.2.2 n-Hexane, CAS1)number: 110-54-3. 3.2.3 Di-is
39、o-nonyl phthalate (DINP), CAS number: 28553-12-0 or 68515-48-0. 3.2.4 Di-(2-ethylhexyl) phthalate (DEHP), CAS number: 117-81-7. 3.2.5 Di-n-octyl phthalate (DNOP), CAS number: 117-84-0. 3.2.6 Di-iso-decyl phthalate (DIDP), CAS number: 26761-40-0 or 68515-49-1. 3.2.7 Butyl benzyl phthalate (BBP), CAS
40、number: 85-68-7. 3.2.8 Di-butyl phthalate (DBP), CAS number: 84-74-2. 3.2.9 Di-cyclohexyl phthalate (DCHP), CAS number: 84-61 -7, internal standard. 3.2.10 Acetone, CAS number: 67-64-1. 3.2.11 Mixture of n-hexane/acetone, 80 %/20 % volume fraction. 3.2.12 Di-isobutyl phthalate (DIBP), CAS number: 84
41、-69-5. 4 Sampling The test piece consists of a single material taken from the footwear, such as leather, textile, polymer, coated material or others. The preparation of the sample should involve removal of the individual materials from the footwear, and preparation of a test piece made of particles
42、as small as possible (but of at least 4 mm). NOTE It is possible to grind the sample. 1) CAS: Chemical Abstract Service. DD CEN ISO/TS 16181:2011ISO/TS 16181:2011(E) ISO 2011 All rights reserved 35 Test procedure 5.1 Preparation of solutions 5.1.1 Preparation of the internal standard solution Prepar
43、e a 500 g/ml stock solution of the internal standard in n-hexane. 5.1.2 Standard solution Prepare a series of individual stock standard solutions of the individual phthalate in n-hexane, as shown in Table 1. Table 1 Stock solutions Phthalate DIDP DINP DBP BBP DNOP DEHP DIBP Concentration, g/ml 1 000
44、 1 000 200 200 200 200 200 From the stock standard solutions, prepare appropriate phthalate calibration solutions in n-hexane. Use at least five appropriate dilutions of the calibration sets to create calibration graphs, add to each an appropriate amount of internal standard and perform GC-MS analys
45、is. NOTE DIDP and DINP overlap in the chromatogram; the target ions to be chosen are indicated in Annex A. 5.2 Extraction procedures 5.2.1 General Prepare the appropriate amount of internal standard solution. 5.2.2 Blank For each series of tests, a blank shall be prepared. For the preparation of the
46、 blank, the complete procedure (extraction either 5.2.3 or 5.2.4 and GC-MS analysis) shall be done in a 50 ml glass flask (3.1.2) without the sample. 5.2.3 Ultrasonic extraction Weigh accurately (2,0 0,1) g of the pieces of a representative specimen into a 50 ml glass flask (3.1.2) fitted with teflo
47、n stopcock. Add 40 ml of n-hexane/acetone (3.2.11) to wet the entire specimen. Extract the phthalate in the ultrasonic bath (3.1.5) for 1 h at 50 C and transfer the extract to a 50 ml volumetric flask (3.1.8) after filtration or centrifugation. Fill to the mark with n-hexane. Transfer a known volume
48、 of organic phase into a suitable GC sampling vial, add an appropriate volume of internal standard solution and perform GC-MS analysis. If necessary, prepare further diluted solutions using the original solution and repeat the analysis after adding the appropriate volume of internal standard solutio
49、n. DD CEN ISO/TS 16181:2011ISO/TS 16181:2011(E) 4 ISO 2011 All rights reserved5.2.4 Microwave extractor Weigh accurately (2,0 0,1) g of the pieces of a representative specimen into a polytetrafluoroethylene (PTFE) vessel. Add a sufficient quantity of the n-hexane/acetone mixture (3.2.11) to wet the whole specimen. Extract the phthalate in the microwave extractor. The following parameters could be used as a basis for optimizing the extraction: power: 600 W; time: 15 min; temperature: 100 C; pressure: 10 bars (1 MPa). Tran
