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This document is drafted in accordance with the rules given in GB/T 1.1-2020 Directives for standardization - Part 1: Rules for the structure and drafting of standardizing documents.
This document replaces GB/T 22048-2015 Determination of certain phthalate esters in toys and children’s products. In addition to structural adjustments and editorial changes, the following main technical changes have been made with respect to GB/T 22048-2015:
a) DIBP ester and liquid materials are added in "Scope" (see Clause 1);
b) GB 6675.2-2014, GB/T 454 and GB/T 27417-2017 are added in "Normative References" (see Clause 2);
c) The composite test portion and limit of quantification in "Terms and definitions" are changed (see Clause 3; Clause 3 of Edition 2015);
d) The description of ultrasonic extractor is added in "Principle" (see Clause 4);
e) Apparatus used in ultrasonic method are added in "Apparatus" (see Clause 6);
f) Preparation of liquid material is added in "Sample preparation" (see Clause 7);
g) The reaction vessel, extraction procedure and quantification method for Method C are added (see 8.1, 8.2.3 and 8.3.2.2);
h) "The volume of dichloromethane may be adjusted according to the extraction equipment" is added (see 8.2.1 and 8.2.2);
i) The description of temperature setting for Method B is changed (see 8.2.2; 8.2.2 of Edition 2015);
j) Instructions for use of centrifuge are added (see 8.3.1);
k) Note on DPHP is added and the range of absolute deviation of retention time is deleted in "Qualitative analysis” (see 8.4.2; 8.4.2 of Edition 2015);
l) Notes on Method A and Method B are deleted [see 12c) of Edition 2015];
m) Notes on external standard method and internal standard method are deleted [see 12d) of Edition 2015];
n) Information about DIBP is added (see Annex A);
o) A normative annex for performance checking of ultrasonic extractor is added (see Annex E).
This standard is modified in relation to ISO 8124-6: 2018 Safety of toys - Part 6: Certain phthalate esters in toys and children’s products.
The technical differences with respect to ISO 8124-6: 2018 and their justifications are as follows:
a) In accordance with the national standards of China, “This document specifies a method for the determination of esters in 5.3.7, GB 6675.1-2014” and “is applicable to 5.3.7, GB 6675.1-2014” are added in Clause 1 of this document to expand its applicability;
b) In Clause 2 and Clause 3 hereof, three normative references, i.e., GB 6675.1-2014, GB 6675.4-2014 and GB/T 27417-2017, are added, among which, GB 6675.4-2014 replaces the international standard ISO 8124-3: 2010 to adapt to the technical conditions in China;
c) Two normative references, i.e., GB 6675.2-2014 and GB/T 454, which replaces ISO 8124-1: 2018 and ISO 2758, are added in Clause 2 and E.3.1 hereof to adapt to the technical conditions in China;
d) In accordance with the relevant national standards, in Clause 3 hereof, two terms and definitions, i.e., toy and children's product, are added, and the composite test portion and limit of quantification are modified;
e) 0.2mL pipette, which is referred to in 5.5.3 of ISO 8124-6: 2018, is added in 6.11 hereof;
f) Because different solvent extractors have different settings, the reasonable description of the temperature setting in Method B is changed in 8.2.2 hereof.
The following editorial changes have been made in this document:
a) This document is named as Determination of certain phthalate esters in toys and children’s products in accordance with relevant national standard;
b) “Warning” is deleted in this document;
c) The information in 6.13 is incorporated in 8.2.3;
d) 8.4.2 lists a textual description of the allowable range of abundance ratio of diagnostic ions;
e) The explanation of CAS numbers of DINP and DIDP is added in Table A.1;
f) Five materials free of phthalate esters, i.e., ABS, GPPS, MIPS, HIPS and SHIPS are added in G.5 hereof;
g) For the purpose of this document, ISO 8124-3: 2010, ASTMF963-11 and AfPS GS.2014: 01 PAK are replaced with ISO 8124-3: 2020, ASTM F963-17 and AfPS GS.2019:01 respectively.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. The issuing body of this document shall not be held responsible for identifying any or all such patent rights.
This document was proposed by China National Light Industry Council.
This standard is under the jurisdiction of National Technical Committee on Toys of Standardization Administration of China (SAC/TC 253).
The previous editions of this document are as follows:
——This standard was firstly issued in 2008 with the serial number of GB/T 22048-2008 and firstly revised in 2015;
——This is the second revision.
Determination of certain phthalate esters in toys and children’s products
1 Scope
This document specifies a method for the determination of esters in 5.3.7, GB 6675.1-2014.
This document specifies a method for the determination of di-iso-butyl ortho-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) (see Table A.1) in toys and children’s products.
This document is applicable to toys and children’s products containing polymers and similar materials, textiles, coatings and liquid materials, and is applicable to 5.3.7, GB 6675.1-2014. 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 materials of toys and children's products provided that adequate validation is demonstrated.
It might also be applicable to other phthalate esters provided that adequate validation is demonstrated.
2 Normative references
The following referenced documents are indispensable for the application 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.
GB/T 454 Paper - Determination of bursting strength (GB/T 454-2020, ISO 2758: 2014, MOD)
GB 6675.1-2014 Toys safety - Part 1: Basic code
GB 6675.2-2014 Safety of toys - Part 2: Mechanical and physical properties (ISO 8124-1: 2000, MOD)
GB 6675.4-2014 Safety of toys - Part 4: Migration of certain elements (ISO 8124-3: 2010, MOD)
GB/T 27417-2017 Confirmation assessment - Guidance on validation and verification of chemical analytical methods
3 Terms and definitions
For the purposes of this document, the terms and definitions given in GB 6675.1-2014, GB 6675.4-2014 and GB/T 27417-2017 and the following apply.
3.1
toy
all products and materials designed or intended for children under the age of 14 to play
[Source: GB 6675.1-2014, 3.1]
3.2
children's product
all products and materials specially designed or intended for children under the age of 14 to use, play and wear, including but not limited to school supplies, infant care products, children's clothing, children's shoes, children's furniture, child safety protectors, baby carriage toys and children's jewelry, etc.
3.3
laboratory sample
product in the form in which it is marketed or intended to be marketed
3.4
base material
material upon which coatings may be formed or deposited
[Source: GB 6675.4-2014, 3.1]
3.5
coating
all 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 may be removed by scraping with a sharp blade
[Source: GB 6675.4-2014, 3.2, modified]
3.6
scraping
mechanical removal of coatings down to but not including the base material
[Source: GB 6675.4-2014, 3.6]
3.7
test portion
portion of homogeneous material taken from a laboratory sample for analysis
3.8
composite test portion
mixed test portion formed by physically mixing several test portions of similar material. However, dissimilar materials, for example, textiles and paint coatings, should not be composited
3.9
composite test
test performed on the composite test portion
3.10
limit of quantification; LOQ
lowest mass concentration or lowest amount of the analyte in the sample that can be quantitatively determined with defined accuracy and precision
[Source: GB/T 27417-2017, 3.14, modified]
3.11
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, which is used to evaluate the contamination of the laboratory environment
4 Principle
The phthalate esters in test portion are extracted through a Soxhlet extractor or solvent extractor (see Annex C) with dichloromethane; after which, the phthalate esters in the extract are determined qualitatively and quantitatively by gas chromatograph-mass spectrometer (GC-MS).
5 Reagents and materials
5.1 Dichloromethane, CAS No. 75-09-2, analytical grade or higher. Before being used, each batch of dichloromethane should be subjected to acceptance confirmation to avoid contamination.
5.2 Phthalate reference substances, minimum of 95% purity, see Table A.1.
5.3 Standard stock solution: Weigh accurately an appropriate amount of phthalate standard substance (5.2) to prepare standard stock solution, 100mg/L of DIBP, DBP, BBP, DEHP and DNOP each, and 500mg/L of DINP, DIDP each in dichloromethane (5.1). Standard stock solution should be properly stored at 0~8℃, with a shelf life of three months.
5.4 Standard working solutions (external standard method): A series of standard working solutions (at least five solutions in the range of 0.4~10mg/L for DIBP, DBP, BBP, DEHP and DNOP, 2~50mg/L for DINP and DIDP) is prepared by transferring 0.2~5mL of the standard stock solution (5.3) to a 50mL volumetric flask and making up to the mark with dichloromethane. Standard working solutions should be stored at 0~8℃, with a shelf life of one month.
5.5 Standard working solutions (internal standard method).
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.
5.5.2 Internal standard stock solution: Accurately weigh an appropriate amount of internal standard substance (5.5.1), with 250mg/L of BB or DAP/DPP, in dichloromethane. Internal standard stock solution should be properly stored at 0~8℃, with a shelf life of three months.
5.5.3 Standard working solutions (internal standard method): A series of standard working solutions (at least five solutions in the range of 0.4~10mg/L for DIBP, DBP, BBP, DEHP and DNOP, 2~50mg/L for DINP and DIDP) is prepared by transferring 0.2~5mL of the standard stock solution (5.3) to a 50mL volumetric flask and adding 2mL of the internal standard stock solution (5.5.2) before making up to the mark with dichloromethane, each of the working solutions containing 10mg/L internal standard substance.
The mass concentration of the internal standard solution may be adjusted according to the mass concentration of the test portion, but the mass concentration of internal standard substance of the final sample solution (8.3.3) shall be consistent with that in the standard working solution. Standard working solutions containing internal standard substance should be stored at 0~8℃, with a shelf life of one month.
6 Apparatus
6.1 Phthalate esters are common contaminants which can affect the quantification result even at a low level of concentration. 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 Gas chromatography-mass spectrometer (GC-MS): with a capillary column coupled to a mass spectrometric detector (EI source) used for the analysis.
6.3 Soxhlet extractor, see Figure C.1. It is equipped with a refrigeration cycle device where necessary.
6.4 Solvent extractor (also known as fat extractor), see Figure C.2. It is equipped with a refrigeration cycle device where necessary.
6.5 Extraction thimble, cellulose.
6.6 Cotton wool.
6.7 Analytical balance, capable of measuring to an accuracy of 1mg.
6.8 Concentration apparatus, for example, a rotary evaporator.
6.9 Solid phase extraction (SPE) cartridge, 1g silica gel/6mL tubes, or equivalent.
6.10 Volumetric flasks, of 5mL, 10mL, 25mL, 50mL, and 100mL nominal capacity.
6.11 Pipettes, of 0.2mL, 0.5mL, 1mL, 2mL, 5mL, and 10mL nominal capacity.
6.12 Organic-phase microporous membrane filter, polytetrafluoroethylene (PTFE) membrane filter, of pore size 0.45μm.
6.13 Ultrasonic extractor, with the temperature controlled internally or externally, and the effective ultrasonic power density ranging from 0.25~2.0W/cm2.
Example:
The ultrasonic extractor with a gross power of 1,200W (including 200W ultrasonic power and 1,000W heating power) has a water bath area of 400cm2, and an ultrasonic effective power density of 0.50W/cm2(=200W/400cm2).
6.14 Ultrasonic basket, of which, the distance between the bottom of the basket and that of the ultrasonic water bath shall be 3~5cm when hanging on the ultrasonic extractor.
6.15 Sealed glass reaction vessel, which is capable of resisting a pressure of at least 0.2MPa, with a capacity of 2~10 times the volume of dichloromethane added. During ultrasonic extraction, the reaction vessel shall be sealed to prevent the evaporation of dichloromethane.
6.16 Centrifuge: with a centrifugal force of (5,000±500)g.
Foreword i
1 Scope
2 Normative references
3 Terms and definitions
4 Principle
5 Reagents and materials
6 Apparatus
7 Test portion preparation
8 Analysis procedure
9 Result calculation
10 Quality control
11 Precision
12 Test report
Annex A (Normative) Seven phthalate esters tested in this document
Annex B (Informative) Precision
Annex C (Informative) Diagrams of Soxhlet extractor and solvent extractor
Annex D (Informative) Composite test
Annex E (Informative) Performance checking of ultrasonic extractor
Annex F (Informative) Example of determination on phthalate esters
Annex G (Informative) Background and rationale
Bibliography
