ISO 8124-6:2023
(Main)Safety of toys — Part 6: Certain phthalate esters
Safety of toys — Part 6: Certain phthalate esters
This document specifies a method standard for the determination of di-iso-butyl phthalate (DIBP), 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-iso-decyl phthalate (DIDP) in toys. It can also be applied to other phthalate esters (see G.2) if adequate validation is demonstrated. This document applies to toys made of plastics, textiles, coatings and liquids. This document has been validated for polyvinylchloride (PVC) and polyurethane (PU) plastics and some representative paint coatings (see Annex B). This document can also be applied to other product categories.
Sécurité des jouets — Partie 6: Certains esters de phtalates
General Information
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Buy Standard
Standards Content (Sample)
INTERNATIONAL ISO
STANDARD 8124-6
Third edition
2023-08
Safety of toys —
Part 6:
Certain phthalate esters
Sécurité des jouets —
Partie 6: Certains esters de phtalates
Reference number
ISO 8124-6:2023(E)
© ISO 2023
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ISO 8124-6:2023(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2023
All rights reserved. Unless otherwise specified, or required in the context of its implementation, no part of this publication may
be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on
the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address below
or ISO’s member body in the country of the requester.
ISO copyright office
CP 401 • Ch. de Blandonnet 8
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Phone: +41 22 749 01 11
Email: copyright@iso.org
Website: www.iso.org
Published in Switzerland
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ISO 8124-6:2023(E)
Contents Page
Foreword .v
Introduction . vi
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 3
5 Reagents . 3
6 Apparatus . 4
6.1 General . 4
6.2 Normal laboratory apparatus . 4
7 Selection of test portions .5
7.1 General . 5
7.2 Individual test . 5
7.3 Composite test . 5
8 Procedure .6
8.1 General . 6
8.2 Sample weighing . 6
8.2.1 Individual test . 6
8.2.2 Composite test . 6
8.3 Extraction . 6
8.3.1 General . 6
8.3.2 Method A . . . 6
8.3.3 Method B . 6
8.3.4 Method C . 7
8.4 Sample solution for analysis . 7
8.4.1 General . 7
8.4.2 Quantification by external standard (ES) calibration . 7
8.4.3 Quantification by IS calibration . 8
8.5 Determination . 8
8.5.1 GC-MS conditions . 8
8.5.2 Identification . 8
8.5.3 Calibration . . . 9
9 Calculation .10
9.1 Individual test . 10
9.1.1 External standard (ES) calculation . 10
9.1.2 Internal standard (IS) calculation . 11
9.2 Composite test .12
9.2.1 Maximum concentration calculation.12
9.2.2 C onformity assessment of the composite test result .12
9.2.3 Examples of composite testing . 13
10 Quality control .14
10.1 Limit of quantification (LOQ) . 14
10.2 Method blank . 14
10.3 Recovery . 14
10.4 Calibration check . 14
11 Precision .14
12 Test report .14
Annex A (normative) Phthalate esters .16
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ISO 8124-6:2023(E)
Annex B (informative) Precision of the method.17
Annex C (informative) Soxhlet extractor and solvent extractor .21
Annex D (informative) Composite test .23
Annex E (normative) Ultrasonic bath performance check .30
Annex F (informative) Example of GC-MS conditions .33
Annex G (informative) Background and rationale .37
Bibliography .40
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ISO 8124-6:2023(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 committees. 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 International 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
different types of ISO document 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).
ISO draws attention to the possibility that the implementation of this document may involve the use
of (a) patent(s). ISO takes no position concerning the evidence, validity or applicability of any claimed
patent rights in respect thereof. As of the date of publication of this document, ISO had received notice
of (a) patent(s) which may be required to implement this document. However, implementers are
cautioned that this may not represent the latest information, which may be obtained from the patent
database available at www.iso.org/patents. ISO shall not be held responsible for identifying any or all
such patent rights.
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation of the voluntary nature of standards, the meaning of ISO specific terms and
expressions related to conformity assessment, as well as information about ISO's adherence to
the World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT), see
www.iso.org/iso/foreword.html.
This document was prepared by Technical Committee ISO/TC 181, Safety of toys.
A list of all parts in the ISO 8124 series can be found on the ISO website.
This third edition cancels and replaces the second edition (ISO 8124-6:2018), which has been technically
revised.
The main changes are as follows:
— removal of “children’s products” from the title, scope and other parts of this document;
— addition of new definitions for instrument detection limit (3.9) and action limit in (3.11);
— replacement of “4 °C” with “0 °C to 8 °C” in 5.3, 5.4, 5.5.2 and 5.5.3;
— addition of the composite test in 7.3 and 9.2;
— addition of the maximum total mass of composite test portions for the composite test in 8.2.2;
— addition of a clean-up procedure in 8.4.1;
— the volume of the final solution adjusted from 1 ml to 50 ml in 8.4.2.1, 8.4.2.2.1 and 8.4.2.2.2;
— addition of the composite test mathematic model in Annex D;
— addition of a list including other phthalate esters in G.2.
Any feedback or questions on this document should be directed to the user’s national standards body. A
complete listing of these bodies can be found at www.iso.org/members.html.
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ISO 8124-6:2023(E)
Introduction
This document does not determine the limits for certain phthalate esters. It is intended to be used as a
method standard in conformity assessment. The user of this document is therefore advised to be aware
of relevant national requirements.
In some countries, phthalate ester requirements for toys are also applicable to other product categories
with materials similar to those of toys. The scope of this document covers various materials used in
toys and other product categories.
Annex A and Annex E are normative, whereas Annex B, Annex C, Annex D, Annex F and Annex G are for
information only. However, they are crucial and helpful for correctly interpreting this document.
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INTERNATIONAL STANDARD ISO 8124-6:2023(E)
Safety of toys —
Part 6:
Certain phthalate esters
WARNING — Persons using this document should be familiar with normal laboratory practice.
This document does not purport to address 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.
IMPORTANT — It is absolutely essential that tests conducted in accordance with this document
should be carried out by suitably trained staff.
1 Scope
This document specifies a method standard for the determination of di-iso-butyl phthalate (DIBP), 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-iso-decyl phthalate (DIDP) in toys. It can also
be applied to other phthalate esters (see G.2) if adequate validation is demonstrated.
This document applies to toys made of plastics, textiles, coatings and liquids. This document has been
validated for polyvinylchloride (PVC) and polyurethane (PU) plastics and some representative paint
coatings (see Annex B).
This document can also be applied to other product categories.
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
ISO 2758, Paper — Determination of bursting strength
ISO 8124-1:2022, Safety of toys — Part 1: Safety aspects related to mechanical and physical properties
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminology databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https:// www .iso .org/ obp
— IEC Electropedia: available at https:// www .electropedia .org/
3.1
laboratory sample
toy in the form in which it is marketed or intended to be marketed
3.2
base material
material upon which coatings (3.3) may be formed or deposited
[SOURCE: ISO 8124-3:2020, 3.1]
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ISO 8124-6:2023(E)
3.3
coating
layers of material formed or deposited on the base material (3.2) of toys, including 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 children’s product and which can be removed
by scraping with a sharp blade
[SOURCE: ISO 8124-3:2020, 3.2]
3.4
scraping
mechanical process for removal of coatings (3.3) down to the base material (3.2)
[SOURCE: ISO 8124-3:2020, 3.7]
3.5
test portion
portion of homogeneous material taken from a corresponding part of the laboratory sample (3.1) for
analysis
3.6
composite test portion
mixed test portion (3.5) formed by physically mixing several test portions of similar materials
Note 1 to entry: This term excludes the compositing of dissimilar materials; for example, compositing textiles
and paint coatings (3.3) are not permitted.
3.7
composite test
test performed on the composite test portion (3.6)
3.8
limit of quantification
LOQ
lowest concentration of target in a test sample that can be quantitatively determined with an acceptable
level of precision and accuracy under the experimental conditions specified in the method
Note 1 to entry: The LOQ is related to the mass of the test portion (3.5) and the final volume of the solvent.
[SOURCE: ISO 15216-1:2017, 3.18, modified — Note 1 to entry revised.]
3.9
instrument detection limit
IDL
lowest concentration at which an instrument can distinguish the presence of analyte from the
background generated by a matrix, such as a reagent blank, having a minimal amount of analyte
[SOURCE: ISO 18158:2016, 2.3.5, modified — Definition revised.]
3.10
method blank
aliquot of solvents that is treated exactly as a sample, including exposure to glassware, apparatus and
conditions 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.
3.11
action limit
acceptable limit of quantification (3.8) that, if exceeded, requires further individual tests
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ISO 8124-6:2023(E)
4 Principle
The test portion of a toy or children’s product is extracted through a Soxhlet extractor, solvent extractor
(see Annex C) or ultrasonic bath with dichloromethane. Phthalate esters in the extract are determined
qualitatively and quantitatively by gas chromatography-mass spectrometry (GC-MS).
5 Reagents
®1)
5.1 Dichloromethane, CAS Registry Number (CAS No.) 75-09-2, analytical grade or higher, free of
phthalate esters.
5.2 Phthalate esters reference substances, DIBP, DBP, BBP, DEHP, DNOP, DINP and DIDP (as
specified in Annex A), minimum of 95 % purity.
5.3 Stock solution, 100 mg/l each of DIBP, DBP, BBP, DEHP and DNOP and 500 mg/l each of DINP and
DIDP in dichloromethane (5.1).
Stock solution should be properly stored at 0 °C to 8 °C to prevent change of concentration. It is
recommended that these solutions be prepared at least every three months.
5.4 External standard (ES) calibration solutions
A series of calibration standard solutions (of at least five equidistant calibrations in the range of 0,2 mg/l
to 10 mg/l for DIBP, DBP, BBP, DEHP and DNOP, 1 mg/l to 50 mg/l for DINP and DIDP) are prepared by
transferring 0,1 ml to 5 ml of the stock solution (5.3) to a series of 50 ml volumetric flasks and making
up to the mark with dichloromethane.
Calibration standard solutions should be properly stored at 0 °C to 8 °C to prevent change of
concentration. It is recommended that these solutions be prepared at least monthly.
5.5 Internal standard (IS) calibration solutions
5.5.1 Internal reference substances
Benzyl benzoate (BB, CAS No. 120-51-4) or di-n-amyl phthalate (DAP, CAS No. 131-18-0) [also known 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 phthalate esters, can be used as alternative internal reference substances.
5.5.2 Internal standard stock solution
250 mg/l of BB, DAP or others, in dichloromethane.
IS solutions should be properly stored at 0 °C to 8 °C to prevent change of concentration. It is
recommended that these solutions be prepared at least every three months.
5.5.3 Internal standard calibration solutions
A series of calibration standard solutions (of at least five equidistant calibrations in the range of
0,2 mg/l to 10 mg/l for DIBP, DBP, BBP, DEHP and DNOP, 1 mg/l to 50 mg/l for DINP and DIDP) are
prepared by transferring 0,1 ml to 5 ml of the stock solution (5.3) to a series of 50 ml volumetric flasks
®
1) Chemical Abstracts Service (CAS) Registry Number is a trademark of the American Chemical Society (ACS).
This information is given for the convenience of users of this document and does not constitute an endorsement by
ISO of the product named. Equivalent products may be used if they can be shown to lead to the same results.
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ISO 8124-6:2023(E)
and adding 2 ml of the IS stock solution (5.5.2) before making up to the mark with dichloromethane.
Each of the calibration standards contains 10 mg/l IS.
IS calibration solutions should be properly stored at 0 °C to 8 °C to prevent change of concentration. It is
recommended that these solutions be prepared at least monthly.
6 Apparatus
6.1 General
Phthalate esters are common 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.
6.2 Normal laboratory apparatus
6.2.1 Gas chromatography-mass spectrometer (GC-MS), with a capillary column coupled to a
mass spectrometric detector (electron ionization, EI) used for the analysis. See 8.4.1.
6.2.2 Soxhlet extractor, see Figure C.1.
6.2.3 Solvent extractor, see Figure C.2.
6.2.4 Extraction thimble, made of cellulose.
6.2.5 Cotton wool, for extraction thimble.
6.2.6 Analytical balance, capable of measuring to an accuracy of 0,001 g.
6.2.7 Concentration apparatus, for example a rotary evaporator.
6.2.8 Solid phase extraction (SPE) cartridge, 1 000 mg silica gel/6 ml tubes or equivalent.
6.2.9 Volumetric flasks, of 5 ml, 10 ml, 25 ml, 50 ml and 100 ml nominal capacity.
6.2.10 Pipettes, of 0,1 ml, 0,5 ml, 1 ml, 2 ml, 5 ml and 10 ml nominal capacity.
6.2.11 Polytetrafluoroethylene (PTFE) membrane filter, of pore size 0,45 μm.
6.2.12 Ultrasonic bath, thermostatically controlled internally or externally, with the effective
2 2
ultrasonic power intensity ranging from 0,25 W/cm to 2,0 W/cm . The performance check of the
ultrasonic bath shall be performed as specified in Annex E.
EXAMPLE An ultrasonic bath with a total power consumption of 1 200 W, including 200 W of effective
2
ultrasonic power and 1 000 W of heating power, with an internal bath base area of 400 cm , will provide an
2 2
effective ultrasonic power intensity of 0,50 W/cm (=200 W/400 cm ).
6.2.13 Ultrasonic basket, usually supplied together with the ultrasonic bath. When hung on the
ultrasonic bath, its lowest level is approximately 3 cm to 5 cm above the bottom of the bath.
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ISO 8124-6:2023(E)
6.2.14 Airtight glass reaction vessel, pressure-resistant to at least 0,2 MPa and with a gross volume
of 2 to 10 times the volume of dichloromethane. The reaction vessel should be tightly closed to prevent
the evaporation of dichloromethane during ultrasonic extraction.
6.2.15 Centrifuge, capable of centrifuging at (5 000 ± 500) g.
7 Selection of test portions
7.1 General
Individual test for one test portion and composite test for multiple test portions are used in this
document.
7.2 Individual test
For solid materials, use a scalpel or other appropriate cutting equipment to cut a representative portion
from the laboratory sample into small pieces. For coatings, remove each different coating from the
laboratory sample by scraping if possible. Extra care shall be taken to minimize the inclusion of base
material. In the uncompressed condition, each piece shall have no dimension greater than 5 mm and be
uniformly mixed.
For liquid materials, use an appropriate apparatus, such as a pipette or syringe, to transfer a
representative portion from the laboratory sample. Extra care shall be taken to minimize cross-
contamination.
Analysis of toy materials present in amounts less than 0,010 g is not required.
NOTE The requirement does not preclude the taking of test portions from materials used to manufacture
the toy, provided they are representative of the final toy.
7.3 Composite test
When used properly, the composite test can reduce costs and improve efficiency without affecting the
accuracy of the test. A composite test used for quantitative assessment shall meet all the following
conditions:
a) Only similar materials can be combined to form a composite test portion. The compositing of
dissimilar materials is not appropriate (e.g. compositing plastics and coatings).
b) Similar masses shall be weighed for each constituent test portion. The mass between any two
constituent test portions should not differ by more than 10 %.
c) The limit of quantification (LOQ) of target phthalate esters is lower than 50 mg/kg.
When a composite test is used for the quantitative assessment, the number of the constituent test
portions (K) shall be less than or equal to 3 (i.e. K ≤ 3). Composite tests with K more than 3 can be
performed with reference to Annex D.
A composite test is used for judging conformity with requirements. If the result of the composite test is
above the action limits, further individual tests are needed.
NOTE Composite testing cannot be used to solve the problem of insufficient mass of a test portion. If the mass
of a constituent test portion is not enough to perform an individual test, it is impossible to get a representative
result via composite testing.
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ISO 8124-6:2023(E)
8 Procedure
8.1 General
Except for 8.2, the following procedures are applicable to both the individual test and the composite
test.
8.2 Sample weighing
8.2.1 Individual test
In general, weigh to the nearest 1 mg approximately 1 g of a single test portion into an extraction
thimble (6.2.4) or airtight glass reaction vessel (6.2.14). If 1 g test portion cannot be obtained from a
single laboratory sample, then as many test portions as possible shall be taken from multiple laboratory
samples; 0,05 g is recommended as a minimum test portion.
8.2.2 Composite test
The total amount of all composite test portions shall not exceed 2 g. The mass deviation of each
constituent test portion should not exceed 10 %. The mass of constituent test portions shall be recorded
and used for subsequent calculation.
8.3 Extraction
8.3.1 General
Three options of extraction procedures, Method A (
...
DRAFT INTERNATIONAL STANDARD
ISO/DIS 8124-6
ISO/TC 181 Secretariat: DS
Voting begins on: Voting terminates on:
2022-06-27 2022-09-19
Safety of toys —
Part 6:
Certain phthalate esters in toys and children's products
Sécurité des jouets —
Partie 6: Dosage de certains esters de phtalates dans les jouets et produits pour enfants
ICS: 97.200.50
THIS DOCUMENT IS A DRAFT CIRCULATED
FOR COMMENT AND APPROVAL. IT IS
THEREFORE SUBJECT TO CHANGE AND MAY
This document is circulated as received from the committee secretariat.
NOT BE REFERRED TO AS AN INTERNATIONAL
STANDARD UNTIL PUBLISHED AS SUCH.
IN ADDITION TO THEIR EVALUATION AS
BEING ACCEPTABLE FOR INDUSTRIAL,
TECHNOLOGICAL, COMMERCIAL AND
USER PURPOSES, DRAFT INTERNATIONAL
STANDARDS MAY ON OCCASION HAVE TO
BE CONSIDERED IN THE LIGHT OF THEIR
POTENTIAL TO BECOME STANDARDS TO
WHICH REFERENCE MAY BE MADE IN
Reference number
NATIONAL REGULATIONS.
ISO/DIS 8124-6:2022(E)
RECIPIENTS OF THIS DRAFT ARE INVITED
TO SUBMIT, WITH THEIR COMMENTS,
NOTIFICATION OF ANY RELEVANT PATENT
RIGHTS OF WHICH THEY ARE AWARE AND TO
PROVIDE SUPPORTING DOCUMENTATION. © ISO 2022
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ISO/DIS 8124-6:2022(E)
DRAFT INTERNATIONAL STANDARD
ISO/DIS 8124-6
ISO/TC 181 Secretariat: DS
Voting begins on: Voting terminates on:
Safety of toys —
Part 6:
Certain phthalate esters in toys and children's products
Sécurité des jouets —
Partie 6: Dosage de certains esters de phtalates dans les jouets et produits pour enfants
ICS: 97.200.50
COPYRIGHT PROTECTED DOCUMENT
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NOT BE REFERRED TO AS AN INTERNATIONAL
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PROVIDE SUPPORTING DOCUMENTATION. © ISO 2022
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ISO/DIS 8124-6:2022(E)
Contents Page
Foreword .v
Introduction . vi
1 Scope (mandatory) . 1
2 Normative references (mandatory) . 1
3 Terms and definitions (mandatory) . .1
4 Principle . 2
5 Reagents . 2
6 Apparatus . 3
7 Selection of test portion . 4
7.1 General principle . 4
7.2 Individual test . 4
7.3 Composite test . 5
8 Procedure .5
8.1 General . 5
8.2 Sample weighing . 5
8.2.1 Individual test . 5
8.2.2 Composite test . 5
8.3 Extraction . 5
8.3.1 Options of extraction method . 5
8.3.2 Method A . . . 5
8.3.3 Method B . 6
8.3.4 Method C . 6
8.4 Sample solution for analysis . 6
8.4.1 General . 6
8.4.2 Quantification by external standard (ES) calibration . 7
8.4.3 Quantification by IS calibration . 7
8.5 Determination . 8
8.5.1 GC-MS conditions . 8
8.5.2 Identification . 8
8.5.3 Calibration . . . 9
9 Calculation .10
9.1 Individual test . 10
9.1.1 External standard (ES) calculation . 10
9.1.2 Internal standard (IS) calculation . 10
9.2 Composite test . 11
9.2.1 Concentration calculation . 11
9.2.2 Judgment for next action . 11
9.2.3 Examples .12
10 Quality control .13
10.1 LOQ of method (LOQ ) . .13
m
10.2 Method blank . 13
10.3 Recovery .13
10.4 Calibration check . 13
11 Precision .13
12 Test report .13
Annex A (normative) Phthalate esters .14
Annex B (informative) Precision of the method .15
Annex C (informative) Soxhlet extractor and solvent extractor .19
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ISO/DIS 8124-6:2022(E)
Annex D (informative) Composite test .22
Annex E (normative) Ultrasonic bath performance check .28
Annex F (informative) Example of GC-MS conditions .31
Annex G (informative) Background and rationale .36
Bibliography .39
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ISO/DIS 8124-6:2022(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 committees. 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 International 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
different 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 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 document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation of the voluntary nature of standards, the meaning of ISO specific terms and
expressions related to conformity assessment, as well as information about ISO's adherence to
the World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT), see
www.iso.org/iso/foreword.html.
This document was prepared by Technical Committee ISO/TC 181, Safety of toys.
A list of all parts in the ISO 8124 series can be found on the ISO website.
This third edition of ISO 8124-6 cancels and replaces the second edition (ISO 8124-6:2018), which has
been technically revised.
The main changes compared to ISO 8124-6:2018 are as follows:
— addition of a new definition for instrument detection limit in (3.9);
— replacement of “4 °C” with “0 °C to 8 °C” in (5.3, 5.4, 5.5.2, and 5.5.3);
— addition of a maximum test portion for the composite test in (8.1);
— addition of a clean-up step in (8.3.1);
— addition of the volume of the final solution may be adjusted from 1 ml to 50 ml in (8.3.2.1, 8.3.2.2.1
and 8.3.2.2.2);
— addition of the composite test model in Annex D status;
— addition of a list including other phthalate esters in G.2;
— Clause 7 has been modified significantly. The normative requirements have been moved from
Annex D to Clause 7 and Annex D has subsequently been changed into an informative annex.
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ISO/DIS 8124-6:2022(E)
Introduction
This document is largely based upon the existing Chinese national standard GB/T 22048-2015. Relevant
standards of some countries and regions are referred to as well.
This document does not set out limits for phthalate esters. It is intended to be used as a method
standard in conformity assessment. The user of this document is therefore advised to be aware of
relevant national requirements.
In some countries phthalate ester requirements for toys are also applicable to children’s products and
children’s product materials are generally similar to those of toys. This document, whose scope covers
various materials, is therefore applicable to both toys and children’s products.
Annex A and Annex E are normative, whereas Annex B, Annex C, Annex D, Annex F, and Annex G are for
information only. However, they are crucial and helpful for the correct interpretation of this document.
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DRAFT INTERNATIONAL STANDARD ISO/DIS 8124-6:2022(E)
Safety of toys —
Part 6:
Certain phthalate esters in toys and children's products
WARNING — Persons using this document should be familiar with normal laboratory practice.
This document does not purport to address 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.
IMPORTANT — It is absolutely essential that tests conducted in accordance with this document
should be carried out by suitably trained staff.
1 Scope (mandatory)
This document specifies a method for the determination of di-iso-butyl phthalate (DIBP), 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-iso-decyl phthalate (DIDP) (as specified in
Annex A) in toys and children’s products.
This document is applicable to toys and children’s products which are made of plastics, textiles, coatings
and liquids. This document has been validated for polyvinylchloride (PVC) plastics, polyurethane
(PU) plastics and some representative paint coatings (see Annex B). It might also be applicable to
other phthalate esters (see G.2) and other product materials provided that adequate validation is
demonstrated.
2 Normative references (mandatory)
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
ISO 2758, Paper — Determination of bursting strength
ISO 8124-1:2018, Safety of toys — Part 1: Safety aspects related to mechanical and physical properties
3 Terms and definitions (mandatory)
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https:// www .iso .org/ obp
— IEC Electropedia: available at https:// www .electropedia .org/
3.1
laboratory sample
toy or children’s product in the form in which it is marketed or intended to be marketed
Note 1 to entry: Text of the note.
3.2
base material
material upon which coatings may be formed or deposited
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ISO/DIS 8124-6:2022(E)
3.3
coating
layers of material formed or deposited on the base material of toys or children’s products, including
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 children’s product
and which can be removed by scraping with a sharp blade
3.4
scraping
mechanical process for removal of coatings (3.3) down to the base material (3.2)
3.5
test portion
portion of homogeneous material taken from a corresponding part of the laboratory sample for analysis
3.6
composite test portion
mixed test portion formed by physically mixing several test portions of similar materials
Note 1 to entry: This term excludes the compositing of dissimilar materials; for example, compositing textiles
and paint coatings are not permitted.
3.7
composite test
test performed on the composite test portion (3.6)
3.8
limit of quantification
LOQ
lowest amount of the analyte in the sample that can be quantitatively determined with defined precision
and accuracy under the stated experimental conditions
3.9
method blank
aliquot of solvents that is treated exactly as a sample, including exposure to glassware, apparatus and
conditions 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.
4 Principle
The test portion of a toy or children’s product is extracted through a Soxhlet extractor, solvent extractor
(see Annex C) or ultrasonic bath with dichloromethane. Phthalate esters in the extract are determined
qualitatively and quantitatively by gas chromatography-mass spectrometry (GC-MS).
5 Reagents
5.1 Dichloromethane, CAS No. 75-09-2, analytical grade or higher, free of phthalate esters.
5.2 Phthalate esters reference substances, DIBP, DBP, BBP, DEHP, DNOP, DINP and DIDP (as
specified in Annex A), minimum of 95 % purity.
5.3 Stock solution, 100 mg/l of DIBP, DBP, BBP, DEHP, DNOP each, and 500 mg/l of DINP, DIDP each in
dichloromethane (5.1).
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ISO/DIS 8124-6:2022(E)
5.4 External standard (ES) calibration solutions
A series of calibration standard solutions (of at least five equidistant calibrations in the range of 0,2 mg/l
to 10 mg/l for DIBP, DBP, BBP, DEHP and DNOP, 1 mg/l to 50 mg/l for DINP and DIDP) is prepared by
transferring 0,1 ml to 5 ml of the stock solution (5.3) 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 8 °C to prevent change of
concentration. It is recommended that the solution be prepared at least monthly.
5.5 Internal standard (IS) calibration solutions
5.5.1 Internal reference substances
Benzyl benzoate (BB, CAS No. 120-51-4) or di-n-amyl phthalate (DAP, CAS No. 131-18-0) (also known 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 phthalate esters, can be used as alternative internal reference substances.
5.5.2 Internal stock solution
250 mg/l of BB, DAP or others, in dichloromethane.
IS solutions should be properly stored at 0 °C to 8 °C to prevent change of concentration. It is
recommended that these solutions be prepared at least every three months.
5.5.3 Internal standard calibration solutions
A series of calibration standard solutions (of at least five equidistant calibrations in the range of
0,2 mg/l to 10 mg/l for DIBP, DBP, BBP, DEHP and DNOP, 1 mg/l to 50 mg/l for DINP and DIDP) is
prepared by transferring 0,1 ml to 5 ml of the stock solution (5.3) to a 50 ml volumetric flask and
adding 2 ml of the IS stock solution (5.5.2) before making up to the mark with dichloromethane. Each
of the calibration standards contains 10 mg/l IS.
IS calibration solutions should be properly stored at 0 °C to 8 °C to prevent change of concentration. It
is recommended that these solutions be prepared at least monthly.
6 Apparatus
6.1 General
Phthalate esters are common 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.
6.2 Normal laboratory glassware
6.3 Gas chromatography-mass spectrometer (GC-MS), with a capillary column coupled to a mass
spectrometric detector (electron ionization, EI) used for the analysis. See 8.4.1.
6.4 Soxhlet extractor, see Figure C.1.
6.5 Solvent extractor, see Figure C.2.
6.6 Extraction thimble, made of cellulose.
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ISO/DIS 8124-6:2022(E)
6.7 Cotton wool, for extraction thimble.
6.8 Analytical balance, capable of measuring to an accuracy of 0,001 g.
6.9 Concentration apparatus, for example, a rotary evaporator.
6.10 Solid phase extraction (SPE) cartridge, 1 000 mg silica gel/6 ml tubes, or equivalent.
6.11 Volumetric flasks, of 5 ml, 10 ml, 25 ml, 50 ml and 100 ml nominal capacity.
6.12 Pipettes, of 0,1 ml, 0,5 ml, 1 ml, 2 ml, 5 ml and 10 ml nominal capacity.
6.13 Polytetrafluoroethylene (PTFE) membrane filter, of pore size 0,45 μm.
6.14 Ultrasonic bath, thermostatically controlled internally or externally, with the effective ultrasonic
2 2
power intensity ranging from 0,25 W/cm to 2,0 W/cm . The performance check of the ultrasonic bath
is performed as specified in Annex E.
EXAMPLE An ultrasonic bath with a total power consumption of 1 200 W, including 200 W of effective
2
ultrasonic power and 1 000 W of heating power, with an internal bath base area of 400 cm , will provide an
2 2
effective ultrasonic power intensity of 0,50 W/cm (=200 W/400 cm ).
6.15 Ultrasonic basket, usually supplied together with the ultrasonic bath. When hung on the
ultrasonic bath, its lowest level is approximately 3 cm to 5 cm above the bottom of the bath.
6.16 Airtight glass reaction vessel, pressure-resistant to at least 0,2 MPa and with a gross volume of
2 to 10 times the volume of dichloromethane. The reaction vessel should be tightly closed to prevent the
evaporation of dichloromethane during ultrasonic extraction.
6.17 Centrifuge, capable of centrifuging at (5 000 ± 500) g.
7 Selection of test portion
7.1 General principle
Individual test and composite test are used in this document.
7.2 Individual test
For materials in solid form, use a scalpel or other appropriate cutting instrument 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 shall, in the uncompressed condition, have no dimension greater than
5 mm and be mixed uniformly.
For materials in liquid form, use appropriate apparatus, such as a pipette or syringe, to transfer
a representative portion from the laboratory sample. Extra care shall be taken to minimize cross
contamination.
A test portion of less than 10 mg from a single laboratory sample shall not be tested.
The requirement does not preclude the taking of reference portions from toy or children’s product
materials in a different form, provided that they are representative of the relevant material specified
above and the substrate upon which they are deposited.
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ISO/DIS 8124-6:2022(E)
7.3 Composite test
When used properly, the composite test serves the purpose of reducing test costs and improving
efficiency, without affecting the accuracy of the test. A composite test used for quantitative screening
shall meet all of the following conditions:
a) Only similar materials can be combined to form a composite test portion. The compositing of
dissimilar materials is not appropriate (e.g. compositing plastics and coatings);
b) Similar mass shall be weighed for each constituent test portion, the mass between any two
constituent test portions should not differ by over 10 %;
c) The LOQ of target phthalate esters is lower than 50 mg/kg;
m
When a composite test is used, the number of the constituent test portions shall be less than or equal to
3 (i.e. K ≤ 3). When the number greater than 3 (i.e. K>3) is used in forming the composite test portion in
accordance with Annex D.
Composite test is only allowed in cases when it is enough for judging conformance with requirements.
And if the conclusion of composite test is failed, further individual tests are needed to find failed
samples among composite test portions.
NOTE The composite testing cannot be used to solve the lack of mass of a test portion. If a constituent test
portion’s mass is not enough to perform an individual test, it is not possible to get a representative result through
composite testing either.
8 Procedure
8.1 General
Except for clause 8.2, following procedure are applicable to both individual test and composite test.
8.2 Sample weighing
8.2.1 Individual test
In general, weigh, to the nearest 1 mg, approximately 1 g of a single test portion into an extraction
thimble (6.6) or reaction vessel (6.16). If 1 g test portion cannot be obtained from a single laboratory
sample, sample as much as possible from more than one laboratory sample, but 0,05 g is recommended
as a minimum test port
...
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