1、 ISO 2014 Safety of toys Part 6: Certain phthalate esters in toys and childrens products Scurit des jouets Partie 6: Jouets et produits pour enfants Dosage de certains phtalates desters dans les jouets et produits pour enfants INTERNATIONAL STANDARD ISO 8124-6 First edition 2014-08-15 Reference numb
2、er ISO 8124-6:2014(E) ISO 8124-6:2014(E)ii ISO 2014 All rights reserved COPYRIGHT PROTECTED DOCUMENT ISO 2014 All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocop
3、ying, or posting on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address below or ISOs member body in the country of the requester. ISO copyright office Case postale 56 CH-1211 Geneva 20 Tel. + 41 22 749 01 11 Fax + 41 22 749 09 47
4、 E-mail copyrightiso.org Web www.iso.org Published in Switzerland ISO 8124-6:2014(E) ISO 2014 All rights reserved iii Contents Page Foreword iv Introduction v 1 Scope . 1 2 T erms and definitions . 1 3 Principle 2 4 Reagents 2 5 Apparatus . 3 6 Selection of test portion 4 7 Procedure. 4 7.1 Sample w
5、eighing . 4 7.2 Extraction 4 7.3 Sample solution for analysis 5 7.4 Determination . 5 8 Calculation 8 8.1 External Standard (ES) calculation . 8 8.2 Internal Standard (IS) calculation 8 9 Quality control 9 9.1 Limit of quantification (LOQ) . 9 9.2 Method blank 9 9.3 Recovery . 9 9.4 Calibration chec
6、k . 9 10 Precision . 9 11 Test report . 9 Annex A (normative) Phthalate esters 10 Annex B (informative) Extraction apparatus 11 Annex C (informative) Example of GC-MS conditions .13 Annex D (informative) Precision of the method 16 Annex E (informative) Composite test .20 Annex F (informative) Backgr
7、ound and rationale .24 Bibliography .27 ISO 8124-6:2014(E) Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committ
8、ees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the Int
9、ernational Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the d
10、ifferent types of ISO documents should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives). Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO
11、shall not be held responsible for identifying any or all such patent rights. Details of any patent rights identified during the development of the document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents). Any trade name used in this docume
12、nt is information given for the convenience of users and does not constitute an endorsement. For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade
13、(TBT) see the following URL: Foreword - Supplementary information The committee responsible for this document is Technical Committee ISO/TC 181, Safety of toys. ISO 8124 consists of the following parts, under the general title Safety of toys: Part 1: Safety aspects related to mechanical and physical
14、 properties Part 2: Flammability Part 3: Migration of certain elements Part 4: Swings, slides and similar activity toys for indoor and outdoor family domestic use Part 6: Toys and childrens products Determination of certain phthalate esters in toys and childrens products The following parts are unde
15、r preparation: Part 5: Determination of total concentration of certain elements in toys Part 7: Finger paints Requirements and test methods Part 8: Age determination guidelinesiv ISO 2014 All rights reserved ISO 8124-6:2014(E) Introduction This part of ISO 8124 is largely based upon the existing Chi
16、nese national standard GB/T 22048-2008. Relevant standards of some countries and regions are referred to as well. Considering the diversity of laws and regulations in different countries, this International Standard has not set out limits for phthalate esters. It is intended to be used as a method s
17、tandard in conformity assessment. The user of this part of ISO 8124 is therefore advised to be aware of relevant national requirements. Whereas in some countries, phthalate ester requirements for toys are also applicable to children products and whereas children product materials are generally simil
18、ar to those of toys, this part of ISO 8124 whose scope covers various materials can be applicable to both toys and children products. Annex A is normative and Annex B, Annex C, Annex D, Annex E, and Annex F are for information purposes only, but they are crucial and helpful for the correct interpret
19、ation of this part of ISO 8124. ISO 2014 All rights reserved v Safety of toys Part 6: Certain phthalate esters in toys and childrens products WARNING Persons using this International Standard should be familiar with normal laboratory practice. This International Standard does not purport to address
20、all of the safety problems, if any, associated with 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. IMPORTANT It is absolutely essential that tests conducted in accordance with this I
21、nternational Standard be carried out by suitably trained staff. 1 Scope This part of ISO 8124 specifies a method for the determination of di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis-(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DNOP), di-iso-nonyl phthalate (DINP), and di-
22、iso-decyl phthalate (DIDP) (see Annex A) in toys and childrens products. This part of ISO 8124 is applicable to toys and childrens products which are made of plastics, textiles, and coatings, etc. This International Standard has been validated for polyvinylchloride (PVC) plastics, polyurethane (PU)
23、plastics, and some representative paint coatings (see Annex D). It might also be applicable to other phthalate esters and other products materials provided that adequate validation is demonstrated. 2 T erms an d definiti ons For the purposes of this document, the following terms and definitions appl
24、y. 2.1 laboratory sample toy or childrens product in the form in which it is marketed or intended to be marketed 2.2 base material material upon which coatings can be formed or deposited 2.3 coating all layers of material formed or deposited on the base material of toys or childrens products, includ
25、ing paints, varnishes, lacquers, inks, polymers, or other substances of a similar nature, whether they contain metallic particles or not, no matter how they have been applied to the toy or childrens product, and which can be removed by scraping with a sharp blade 2.4 scraping mechanical removal of c
26、oatings down to but not including the base material 2.5 test portion portion of homogeneous material taken from a corresponding part of the laboratory sample for analysis INTERNATIONAL ST ANDARD ISO 8124-6:2014(E) ISO 2014 All rights reserved 1 ISO 8124-6:2014(E) 2.6 composite test portion mixed tes
27、t portion formed by physically mixing several test portions of similar material Note 1 to entry: This term excludes the compositing of dissimilar materials, for example, compositing textiles and paint coatings are not permitted. 2.7 composite test test performed on the composite test portion 2.8 lim
28、i t of qu a nt i f ic at ion LOQ lowest amount of the analyte in the sample that can be quantitatively determined with defined precision under the stated experimental conditions 2.9 method blank aliquot of solvents that is treated exactly as a sample including exposure to glassware, apparatus, and c
29、onditions used for a particular test, but with no added sample Note 1 to entry: Method blank data are used to assess contamination from the laboratory environment. 3 Principle The test portion of a toy or childrens product is mechanically cut into small pieces which are then extracted through a Soxh
30、let extractor or solvent extractor (see Annex B) with dichloromethane; after which, the phthalate esters in the extract are determined qualitatively and quantitatively by gas chromatograph-mass spectrometer (GC-MS). 4 Reagents 4.1 Dichloromethane, CAS No. 75-09-2, analytical grade or higher, free of
31、 phthalate esters. 4.2 Phthalate reference substances, DBP , BBP , DEHP , DNOP , DINP , and DIDP (see Annex A), minimum of 95 % purity. 4.3 Stock solution, 100 mg/l of DBP , BBP , DEHP , DNOP each, and 500 mg/l of DINP , DIDP each in dichloromethane (4.1). Stock solution should be properly stored at
32、 0 C to 4 C to prevent change of concentration. It is recommended to prepare the solution at least every three months. 4.4 External Standard (ES) calibration solutions. A series of calibration standard solutions (of at least five equidistant calibrations in the range of 0,4 mg/l to 10 mg/l for DBP,
33、BBP, DEHP, and DNOP, 2 mg/l to 50 mg/l for DINP and DIDP) is prepared by transferring 0,2 ml to 5 ml of the stock solution (4.3) to a 50 ml volumetric flask and making up to the mark with dichloromethane. Calibration standard solutions should be properly stored at 0 C to 4 C to prevent change of con
34、centration. It is recommended to prepare the solution at least monthly.2 ISO 2014 All rights reserved ISO 8124-6:2014(E) 4.5 Internal Standard (IS) calibration solutions. 4.5.1 Internal reference substances, benzyl benzoate (BB, CAS No.120-51-4) or di-n-amyl phthalate (DAP , CAS No.131-18-0) also kn
35、own as di-n-pentyl phthalate (DPP), minimum of 95 % purity. The internal reference substances should not be present in the test portion matrix. Other compounds such as isotopically labelled phthalates can be used as alternative internal reference substances. 4.5.2 Internal stock solution, 250 mg/l o
36、f BB or DAP or others, in dichloromethane. IS solutions should be properly stored at 0 C to 4 C to prevent change of concentration. It is recommended to prepare these solutions at least every three months. 4.5.3 Internal Standard calibration solutions. A series of calibration standard solutions (of
37、at least five equidistant calibrations in the range of 0,4 mg/l to 10 mg/l for DBP, BBP, DEHP and DNOP, 2 mg/l to 50 mg/l for DINP and DIDP) is prepared by transferring 0,2 ml to 5 ml of the stock solution (4.3) to a 50 ml volumetric flask and adding 2 ml of the IS stock solution (4.5.2) before maki
38、ng up to the mark with dichloromethane, each of the calibration standards containing 10 mg/l IS. IS calibration solutions should be properly stored at 0 C to 4 C to prevent change of concentration. It is recommended to prepare these solutions at least monthly. 5 Apparatus Phthalate esters are common
39、 contaminants which can affect the test result even at a low level of concentration. In order to prevent interference and cross-contamination, any type of plastic apparatus that could affect the analysis should be avoided, and glassware and equipment should be scrupulously cleaned before use. 5.1 No
40、rmal laboratory glassware. 5.2 Gas chromatography-mass spectrometer (GC-MS), with a capillary column coupled to a mass spectrometric detector (electron ionization, EI) used for the analysis. See 7.4.1. 5.3 Soxhlet extractor, see Figure B.1. 5.4 Solvent extractor, see Figure B.2. 5.5 Extraction thimb
41、le, cellulose. 5.6 Cotton wool, for extraction thimble. 5.7 Analytical balance, capable of measuring to an accuracy of 0,001 g. 5.8 Concentration apparatus, for example, a rotary evaporator. 5.9 Solid phase extraction (SPE) cartridge, 1000 mg silica gel/6 ml tubes, or equivalent. 5.10 V olum etric f
42、lasks, of 5 ml, 10 ml, 25 ml, 50 ml, and 100 ml nominal capacity. 5.11 Pipettes, of 0,5 ml, 1 ml, 2 ml, 5 ml, and 10 ml nominal capacity. ISO 2014 All rights reserved 3 ISO 8124-6:2014(E) 5.12 P ol yt etr afluor oeth y lene (P TFE) membr ane filt er, of pore size 0,45 m. 6 Selection of test portion
43、Use a scalpel or other appropriate cutting utensils to cut a representative portion from the laboratory sample into small pieces. For coatings, remove each different coating from the laboratory sample by scraping. Extra care shall be taken to minimize the inclusion of the base material. Each piece s
44、hall, in the uncompressed condition, have no dimension greater than 5 mm and be mixed uniformly. A test portion of less than 10 mg from a single laboratory sample shall not be tested. NOTE Different countries or regions might have different legislation requirements for the minimum sample mass. Compo
45、site test can be used for screening. See Annex E. 7 Procedure 7.1 Sample weighing Weigh, to the nearest 1 mg, approximately 1 g of the test portion into an extraction thimble (5.5). If 1 g test portion cannot be obtained from a single laboratory sample, sampling as much as possible from more than on
46、e laboratory samples, but 0,1 g should be a minimum test portion. 7.2 Extraction Two optional extraction methods are described in the following, and the laboratory can select the most suitable one at its discretion. 7.2.1 Method A Place the thimble with test portion into the 150-ml Soxhlet extractor
47、 (5.3). In order to prevent the sample from floating, add cotton wool (5.6) to the top of the thimble. Add 120 ml of dichloromethane (4.1) into the 150-ml flask. Reflux for 6 h with no less than four reflux cycles per hour. After cooling, reduce the volume of the dichloromethane to about 10 ml using
48、 a suitable concentration apparatus (5.8). Take care to avoid reduction to dryness. When using a rotary evaporator, it is recommended that the temperature of the water bath is in the range of 40C to 50C with a constant pressure between 30 kPa and 45 kPa. NOTE During the refluxing and concentration s
49、teps, careful temperature control is necessary in order to avoid loss of phthalate esters. 7.2.2 Method B Place the thimble with test portion into the solvent extractor (5.4). In order to prevent the sample from floating, add cotton wool (5.6) to the top of the thimble. Add 80 ml of dichloromethane (4.1) into the receiver. Immerse for 1,5 h at about 80 C and reflux for 1,5 h. At the end, concentrate the dichloromethane extract to about 10 ml. NOTE During the refluxing and concentration steps, careful te
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