1、BS EN 15777:2009ICS 59.080.01NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDTextiles Test methodfor phthalatesThis British Standardwas published underthe authority of theStandards Policy andStrategy Committee on 30November 2009. BSI 2009ISBN 978 0 580 61527 6Am
2、endments/corrigenda issued since publicationDate CommentsBS EN 15777:2009National forewordThis British Standard is the UK implementation of EN 15777:2009.The UK participation in its preparation was entrusted to TechnicalCommittee TCI/80, Chemical testing of textiles.A list of organizations represent
3、ed on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisionsof a contract. Users are responsible for its correct application.Compliance with a British Standard cannot confer immunityfrom legal obligations.BS EN 15777:2009EU
4、ROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15777August 2009ICS 59.080.01English VersionTextiles - Test method for phthalatesTextiles - Mthodes dessai des phtalates Textilien - Prfverfahren fr PhthalateThis European Standard was approved by CEN on 24 July 2009.CEN members are bound to comply wit
5、h the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the CEN Management Cent
6、re or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as theofficial v
7、ersions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, S
8、pain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: Avenue Marnix 17, B-1000 Brussels 2009 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Memb
9、ers.Ref. No. EN 15777:2009: EBS EN 15777:2009EN 15777:2009 (E) 2 Contents Page Foreword 3Introduction .41 Scope 52 Terms and definitions .53 Preparation of the test specimens .54 Apparatus and reagents 54.1 Apparatus .54.2 Reagents (analytical grade) 65 Test procedure .65.1 Principle 65.2 Reagent (s
10、tandard solutions) .65.3 Extraction of phthalates 75.4 Calculation of results 76 Test report 8Annex A (normative) Calculations .9A.1 Overall treated 9A.2 Locally treated . 10Annex B (informative) Suitable Gas Chromatography - Mass Spectrometry (GC-MS) apparatus, method and precision data for determi
11、nation of phthalate plasticizers 3 11Bibliography . 13BS EN 15777:2009EN 15777:2009 (E) 3 Foreword This document (EN 15777:2009) has been prepared by Technical Committee CEN/TC 248 “Textile and textile products”, the secretariat of which is held by BSI. This European Standard shall be given the stat
12、us of a national standard, either by publication of an identical text or by endorsement, at the latest by February 2010, and conflicting national standards shall be withdrawn at the latest by February 2010. Attention is drawn to the possibility that some of the elements of this document may be the s
13、ubject 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 Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium,
14、 Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, BS EN 15777:2009EN 15777:2009 (E) 4 Introduction This European Standard covers a test method for determination of phthal
15、ates in textile articles. 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 phthalates are toxic in reproduction. The level of media publicity will ensure that their use will continu
16、e to be of concern to consumers. Phthalates are an issue for textile manufacturers and retailers due to their use within motifs, coated fabrics, plastisol prints, buttons, etc. There are textile articles that have to comply with the Directive 2005/84/EC 1 and also articles that fall outside the scop
17、e of this legislation, that could be covered by the General Products Safety Directive (2001/95/EC) 2. WARNING Persons using this European Standard should be familiar with normal laboratory practice. This European Standard does not claim to address all of the safety problems, if any, associated with
18、its use. It is the responsibility of the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions. This European Standard calls for the use substances and/or procedures that may be injurious to health if appropriate precautions are no
19、t observed. It refers only to technical suitability and does not absolve the user from legal obligations relating to health and safety at any stage. Phthalates are controversial because high doses of many phthalates have shown hormonal activity in rodent studies. Studies on rodents involving large a
20、mounts of phthalates have shown damage to the liver, the kidneys, the lungs, and the developing testes. IMPORTANT It is absolutely essential that tests conducted according to this European Standard be carried out by suitably trained staff. BS EN 15777:2009EN 15777:2009 (E) 5 1 Scope This standard sp
21、ecifies a test method for taking representative specimens, extraction of phthalates from the material and determination of phthalates by gas chromatography mass spectrometry. This standard applies to textiles articles, where there is a possibility of the presence of some phthalates. 2 Terms and defi
22、nitions For the purposes of this European Standard, the following terms and definitions apply. 2.1 blank application of the method without test specimen 2.2 plasticized or softened materials plastic material (coating, pigment print binder, etc) that is treated with chemicals (for this specific stand
23、ard they are phthalates) to make it more flexible 2.3 overall treated textiles textiles with a continuous finish, coating or print 2.4 locally treated textiles textile with a discontinuous finish, coating or print 2.5 representative specimen specimen obtained by mixing pieces of all the different tr
24、eated parts and colours 3 Preparation of the test specimens Remove the untreated mass of the specimen if possible (see Annex A). If the untreated mass cannot be removed, see 5.4. Use a scalpel or other appropriate cutting tool to cut two representative specimens into small pieces. 4 Apparatus and re
25、agents 4.1 Apparatus 4.1.1 Balance (resolution of 1 mg). 4.1.2 150 ml flask. 4.1.3 Soxhlet extractor with siphon cup of approximately 20 ml. 4.1.4 Soxhlet cellulose thimble, approximately 15 mm in diameter and 50 mm height. 4.1.5 Water-cooled condenser. BS EN 15777:2009EN 15777:2009 (E) 6 4.1.6 Spar
26、k proof heating mantle/water bath. 4.1.7 Steam bath or rotary evaporator. 4.1.8 Calibrated volumetric flasks of suitable volume. NOTE Avoid direct contact between the samples and glassware and/or equipment to be used to minimize cross-contamination. Glassware, after washing, should have an extra rin
27、se with 0,1 N nitric acid and finally with acetone, acetone/methanol and/or cyclohexane. Dry at 110 C (1 h). Beware, the vapour of the organic solvents are highly flammable, especially at high temperature! Allow glassware to cool down before use. 4.1.9 Gas chromatography with mass selective detector
28、 (GC-MS). 4.2 Reagents (analytical grade) 4.2.1 n-Hexane, CAS No. 110-54-3. 4.2.2 Di-isononyl phthalate (DINP), CAS No. 28553-12-0 or 68515-48-0. 4.2.3 Di-(2-ethylhexyl) phthalate (DEHP), CAS No. 117-81-7. 4.2.4 Di-n-octyl phthalate (DNOP), CAS No. 117-84-0. 4.2.5 Di-iso-decyl phthalate (DIDP), CAS
29、No. 26761-40-0 or 68515-49-1. 4.2.6 Butyl benzyl phthalate (BBP), CAS No. 85-68-7. 4.2.7 Di-butyl phthalate (DBP), CAS No.84-74-2. 4.2.8 Dicyclohexyl phthalate (DCHP), CAS no.84-61-7 Internal Standard. 5 Test procedure 5.1 Principle The aim of the method is to extract phthalates in textiles and rela
30、ted accessories. This method uses Soxhlet extraction apparatus with n-hexane as solvent. However, any apparatus giving equivalent extraction as with Soxhlet can be used. The total n-hexane extractable phthalate plasticizer content is calculated by weight with Gas Chromatography-Mass-Spectrometry (GC
31、-MS) detection to identify and quantify individual phthalates. 5.2 Reagent (standard solutions) 5.2.1 Preparation of the internal standard solution. Prepare a 500 g/ml stock solution of the internal standard in n-hexane. 5.2.2 Standard solution. Prepare a series of individual stock standard solution
32、s of the individual phthalate in n-hexane as shown in Table 1. BS EN 15777:2009EN 15777:2009 (E) 7 Table 1 Stock solutions Phthalate DIDP DINP DBP BBP DNOP DEHP Concentration, g/ml 1000 1000 200 200 200 200 From the stock standard solutions prepare appropriate phthalate calibration solutions in n-he
33、xane. Use at least five appropriate dilutions of the calibration sets to create calibration graphs and add to each an appropriate amount of internal standard and perform GC-MS analysis. NOTE DIDP and DINP overlap in the chromatogram, choose target ions indicated in Annex B. 5.3 Extraction of phthala
34、tes Prepare the appropriate amount of internal standard solution. Weigh accurately (2,0 0,1) g of the pieces of a representative specimen into a Soxhlet thimble and add a filter paper disc to the top of the thimble. Extract every sample in duplicate and run a blank to control contamination. Add appr
35、oximately 50 ml of n-hexane into the flask. Reflux gently for 4 h. Allow sufficient time for the n-hexane to cool. Transfer the extract to a 100 ml volumetric flask. Rinse the flask with 2 aliquots of 20 ml n-hexane. Make up to the mark. Transfer a known volume into a suitable GC sampling vial and a
36、dd appropriate volume of internal standard solution and perform GC-MS analysis. Prepare if necessary further diluted solutions using the original solution and repeat the analysis after added the appropriate volume of internal standard solution. NOTE In some cases where the corrected mass of the spec
37、imen is very low, it will be necessary to increase the weight and/or concentrate the extract in order to reach at least 3 times the detection limit. 5.4 Calculation of results From the calibration graph determine the response of each phthalate, corrected for the internal standard peak area, and inte
38、rpolate the concentration of the phthalate in g/ml correcting for any dilutions. Subtract the blank concentration from the specimen concentration. 10000ma - b=VP (1) where P is the percentage of the individual phthalate; V is the volume of the volumetric flask (ml); m is the corrected mass of specim
39、en (g); a is the concentration of the individual phthalate of blank solution (g/ml); b is the concentration of the individual phthalate the specimen solution corrected for any dilutions (g/ml). If the corrected mass of test specimen cannot be obtained (see Annex A), give a remark in the test report.
40、 BS EN 15777:2009EN 15777:2009 (E) 8 An example of the calculation is given in Annex A. Overall treated material is illustrated in Figure A.1 and locally treated material in Figure A.2. 6 Test report The test report shall include the following information: a) reference to this standard; b) all detai
41、ls necessary for complete identification of the sample tested; c) description of the apparatus if Soxhlet is not used; d) preparation of the specimens and correction of the mass due to the untreated textile components; e) percent by mass of each listed phthalate in the plasticized material or textil
42、e product; f) any deviation by agreement or otherwise from the procedure specified. BS EN 15777:2009EN 15777:2009 (E) 9 Annex A (normative) Calculations A.1 Overall treated In the case of overall treated specimens, see Figure A.1: 12Key 1 Plastic Component (Coating) 2 Fabric Figure A.1 Overall treat
43、ed materials 1m = total mass of overall treated specimen (g); 2m = mass of textile component (g); m = mass of coating (g) NOTE Mass of coating is the corrected mass of the specimen as described in the formula in 5.4. From a test specimen, where (1m ) is measured (g), the plastic component (coating)
44、is removed by a mechanical, thermal or chemical procedure (or combination of these). The plastic component ( m ) shall be determined by comparison with the textile component (2m ). The part of the coating can be defined according to the following formula: 21mmm = (A.1) BS EN 15777:2009EN 15777:2009
45、(E) 10 A.2 Locally treated In the case of locally treated specimens, see Figure A.2. 21Key 1 Plastic Component (Coating) 2 Fabric Figure A.2 Locally treated specimen 1m = mass per unit area of treated area of specimen (gm-2); 2m = mass per unit area of textile material (gm-2); m = mass of the plasti
46、c component (coating) (g); NOTE Mass of the plastic component is the corrected mass of the specimen as described in the formula in 5.4. S = surface area of the treated area of the specimen (m2); Firstly, determine the mass per unit area from an untreated part (only textile material is involved) 2w F
47、rom a test specimen: measure the treated mass per unit area 1w ; measure the treated area, S . The mass of the plastic component can be calculated according to the following formula: ()Smmm =21, expressed in g (A.2) BS EN 15777:2009EN 15777:2009 (E) 11 Annex B (informative) Suitable Gas Chromatograp
48、hy - Mass Spectrometry (GC-MS) apparatus, method and precision data for determination of phthalate plasticizers 3 The following equipment, column and operating conditions have been found suitable: Equipment: 6890 Gas Chromatograph (GC) with a Hewlett Packard 5973N Mass Selective Device (MSD), quadru
49、pole. Column: 5 % phenyl methyl siloxane for MS; length 30 m; 0,32 mm I.D. & 0,25 m film thickness. Carrier gas: Helium. Flow rate: 2,0 ml/min. Injector temperature: 250 C. Injection volume: 1 l. Injection: splitless or split. Transfer line temperature: 280 C. MSD mode: Electron impact. Temperature programme: 150 C for 1 min to 250 C at 8 C/min to 290 C at 3 C/min Isothermal 5,00 min. Total run time is 34 min. Typical quantification ions for phthalate plasticizers
