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GB/T 22048-2022 (GB/T22048-2022, GBT 22048-2022, GBT22048-2022)
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GB/T 22048-2022: PDF in English (GBT 22048-2022)

GB/T 22048-2022
GB
NATIONAL STANDARD OF THE
PEOPLE’S REPUBLIC OF CHINA
ICS 97.200.50
CCS Y 57
Replacing GB/T 22048-2015
Determination of certain phthalate esters in toys and
children’s products
(ISO 8124-6:2018, Safety of toys - Part 6: Certain phthalate esters in toys and
children’s products, MOD)
ISSUED ON: JULY 11, 2022
IMPLEMENTED ON: AUGUST 01, 2023
Issued by: State Administration for Market Regulation;
Standardization Administration of the People’s Republic of China.
Table of Contents
Foreword ... 3
1 Scope ... 6
2 Normative references ... 6
3 Terms and definitions ... 7
4 Principle ... 9
5 Reagents and materials ... 9
6 Instruments and equipment ... 10
7 Preparation of test portion ... 11
8 Analysis procedure ... 11
9 Calculation of results ... 17
10 Quality control ... 18
11 Precision ... 19
12 Test report ... 19
Annex A (normative) 7 phthalate esters tested in this document ... 20
Annex B (informative) Precision ... 21
Annex C (informative) Schematic diagrams of Soxhlet extractor and solvent extractor
... 25
Annex D (informative) Composite test ... 27
Annex E (normative) Ultrasonic extractor performance check ... 31
Annex F (informative) Determination examples of phthalate esters ... 34
Annex G (informative) Background and rationale ... 38
Bibliography ... 41
Determination of certain phthalate esters in toys and
children’s products
1 Scope
This document describes the determination methods for the plasticizer requirements in
5.3.7 of GB 6675.1-2014.
This document describes the determination methods for 7 kinds of phthalate esters
(according to the specifications in Table A.1) in toys and children’s products, i.e., 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).
This document is applicable to toys and children’s products containing polymers and
similar materials, textiles, coatings and liquid materials, and applicable to 5.3.7 of GB
6675.1-2014. This document has been validated for polyvinyl chloride (PVC),
polyurethane (PU) and some representative paint coatings, see Annex B. Other
materials for toys and children’s products can be determined with reference to this
document after validation.
The test of other phthalate esters can refer to this document after validation.
2 Normative references
The contents of the following documents constitute the essential provisions of this
document through normative references in the text. Among them, for dated references,
only the version corresponding to the date applies to this document; for undated
references, the latest version (including all amendments) applies to this document.
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)
prepare a series of standard working solutions (prepare at least 5 standard working
solutions, of which the mass concentration of DIBP, DBP, BBP, DEHP, DNOP is 0.4
mg/L ~ 10 mg/L, and the mass concentration of DINP, DIDP is 2 mg/L ~ 50 mg/L),
each of the working solutions contains 10 mg/L of the internal standard.
The mass concentration of the internal standard can be adjusted according to the mass
concentration of the test portion, but the mass concentration of the internal standard in
the final sample solution (8.3.3) shall be consistent with the mass concentration of the
internal standard in the standard working solution. The standard working solution
containing the internal standard should be stored at a temperature of 0 °C ~ 8 °C, and
the validity period is 1 month.
6 Instruments and equipment
6.1 For normal laboratory glassware, phthalate esters are common contaminants, and
even a small amount can affect quantitative results. It is recommended to avoid the use
of any plastic equipment that may contaminate the analysis. Glassware and equipment
should be cleaned before use.
6.2 Gas chromatography/mass spectrometry (GC-MS): equipped with a quartz capillary
column and a mass spectrometer detector (EI source).
6.3 Soxhlet extractor: see Figure C.1. When necessary, with a cooling circulation device.
6.4 Solvent extractor (also known as fat extractor), see Figure C.2. When necessary,
with a cooling circulation device.
6.5 Extraction thimble: made of cellulose.
6.6 Cotton wool.
6.7 Analytical balance: an accuracy of 1 mg.
6.8 Concentration apparatus: such as a rotary evaporator, etc.
6.9 Solid phase extraction cartridge (SPE): 1 g silica gel/6 mL tubes, or equivalent.
6.10 Volumetric flasks: of 5 mL, 10 mL, 25 mL, 50 mL and 100 mL capacity.
6.11 Pipettes: of 0.2 mL, 0.5 mL, 1 mL, 2 mL, 5 mL and 10 mL capacity.
6.12 Organic phase microporous membrane filter: of pore size 0.45 μm, recommended
to use polytetrafluoroethylene (PTFE) microporous membrane filter.
6.13 Ultrasonic extractor: thermostatically controlled internally or externally, with the
effective ultrasonic power density ranging from 0.25 W/cm2 to 2.0 W/cm2.
Example:
One of the following methods can be selected for extraction according to the actual
situation.
8.2.1 Method A
Place the test portion in the extraction thimble (6.5) of a 250 mL Soxhlet extractor (6.3).
In order to prevent the test portion from floating, cotton wool (6.6) can be placed on the
upper layer of the extraction thimble.
Add 120 mL of dichloromethane (5.1) into a 250 mL round-bottom flask, extract for 6
h, and reflux at least 4 times per hour. If necessary, use a cooling circulation device for
cooling and refluxing.
The volume of the dichloromethane can be adjusted according to the extraction
equipment.
After cooling, use a suitable concentration apparatus (6.8) to concentrate until about 10
mL of the extract remains, and take care to prevent it from being completely evaporated
to dryness.
It is recommended to control the temperature of the water bath of a rotary evaporator at
40 °C ~ 50 °C, while maintaining the pressure at 30 kPa ~ 45 kPa.
Care shall be taken to control the temperature of reflux and concentration to prevent the
loss of phthalate esters.
8.2.2 Method B
Place the test portion in the extraction thimble (6.5) of a solvent extractor (6.4). In order
to prevent the test portion from floating, cotton wool (6.6) can be placed on the upper
layer of the extraction paper tube.
Add 80 mL of dichloromethane (5.1) into the extraction bottle, set a suitable
temperature (such as 80 °C), make the dichloromethane boil and reflux, extract for 1.5
h, then rinse for 1.5 h; if necessary, use a cooling circulation device for cooling and
refluxing. Finally, concentrate the extract to about 10 mL.
The volume of the dichloromethane can be adjusted according to the extraction
equipment.
Care shall be taken to control the temperature of reflux and concentration to prevent the
loss of phthalate esters.
8.2.3 Method C
8.2.3.1 Solid materials
Place the test portion in an airtight glass reaction vessel (6.15), and add 25 mL of
dichloromethane. Place the container in an ultrasonic extractor (6.13), the liquid level
in the ultrasonic tank shall be higher than the liquid level of the dichloromethane in the
reaction vessel, start at (60 ± 2) °C, and continue ultrasonication for 60 min. The
ultrasonic extractor performance check shall be carried out according to Annex E.
NOTE: If the material does not dissolve or swell in dichloromethane, Method A or Method B might
be preferable.
8.2.3.2 Liquid materials
Place the test portion in an airtight glass reaction vessel (6.15), and add 15 mL of
dichloromethane. Place the container in the ultrasonic extractor (6.13), the liquid level
in the ultrasonic water tank shall be higher than the liquid level of the dichloromethane
in the reaction vessel, start at (60 ± 2) °C, and continue ultrasonication for 60 min. The
ultrasonic extractor performance check shall be carried out according to Annex E.
8.3 Preparation of analytical solutions
8.3.1 General
If the extract obtained in 8.2.1, 8.2.2 or 8.2.3 is turbid, it can be centrifuged with a
centrifuge (6.16) at a centrifugal force of 5000 g before filtration. If necessary, the
extract can be purified with a solid phase extraction cartridge (6.9). Before purification,
pre-wash and activate with 10 mL of dichloromethane, discard the activation solution,
and then load the test portion, rinse with 3 mL of dichloromethane for 3 times and
collect the eluate.
The extract or the eluent, at room temperature, can be made up to the mark by 8.3.2
external standard method or 8.3.3 internal standard method according to the actual
situation.
8.3.2 Constant volume (external standard method)
8.3.2.1 Method A and Method B
Transfer the extract or the eluent into a 25 mL volumetric flask, make up to the mark
with dichloromethane, filter through the organic phase microporous membrane filter
(6.12), for GC-MS (6.2) analysis.
The final constant volume can be adjusted according to the mass and concentration of
the test portion. Care should be taken not to affect the limit of quantification (10.1).
8.3.2.2 Method C
8.3.2.2.1 Solid materials
f) Determination method: identification by full scan mode (full scan), quantification
by selected ion monitoring (SIM).
8.4.2 Qualitative analysis
Qualitative analysis is performed by comparing the retention time of target substance
and the relative abundance of characteristic ions in the test portion and the standard
working solution.
The following conditions can be used to determine whether the sample contains the
corresponding phthalate esters:
a) The deviation between the retention time of the target substance in the sample and
the retention time of the target substance in the standard working solution is
within ± 0.5 %;
b) The characteristic ions (see Table F.1) appear at the retention time of the target
substance in the standard working solution;
c) The relative abundance of the characteristic ions is consistent with the relative
abundance of the target substance in the standard working solution (if the relative
abundance > 50 %, a deviation of ± 10 % is allowed; if the relative abundance is
between 20 % ~ 50 %, a deviation of ± 15 % is allowed; if the relative abundance
is between 10 % ~ 20 %, a deviation of ± 20 % is allowed; if the relative
abundance is ≤ 10 %, a deviation of ± 50 % is allowed).
NOTE: Certain isomers of DINP or DIDP can interfere with the qualitative and quantitative
determination of DINP or DIDP. For example, dipropyl heptyl phthalate (DPHP, CAS No. 53306-
54-0) is one of the isomers of DIDP. It is difficult to separate DPHP from DIDP, but they can be
identified by features such as peak shape, retention time and abundance ratio.
8.4.3 Quantitative analysis
8.4.3.1 General
The laboratory can choose the external standard method or internal standard method for
quantification according to the actual situation. See G.4 for the selection conditions.
Select at least 5 standard working solutions (5.4 or 5.5.3) with different mass
concentrations for determination, and plot a standard curve with peak area versus mass
concentration. The linear correlation coefficient of the standard curve is not less than
0.995, and the corresponding value of phthalate easters in the sample solution shall be
within the linear range of the instrument. If necessary, it can be diluted with
dichloromethane.
Since GC-MS responds differently to DINP and DIDP standard substances with
different CAS numbers, the laboratory shall try to select a standard substance similar to
the test portion, and at the same time indicate the CAS numbers of DINP and DIDP in
the report, see Clause 12 f).
When integrating the peak area of isomers of DINP and DIDP, the baseline shall be
flattened before integration.
NOTE: Due to the existence of inseparable isomers, the peaks of DNOP, DINP and DIDP are
partially overlapped. By selecting m/z = 279 (DNOP), m/z = 293 (DINP) and m/z = 307 (DIDP) as
quantitation ions, it can minimize the mutual interference.
8.4.3.2 Calibration curve (external standard method)
Calculate the slope and ordinate intercept of the standard curve according to formula
(1):
where:
A - the peak area or sum of peak areas of the quantification ions of the certain
phthalate esters in the standard working solution;
a1 - the slope of the calibration curve, in liters per milligram (L/mg);
ρ - the mass concentration of the certain phthalate esters in the standard working
solution, in milligrams per liter (mg/L);
b1 - the ordinate intercept of the calibration curve.
8.4.3.3 Calibration curve (internal standard method)
Calculate the slope and ordinate intercept of the standard curve according to formula
(2):
where:
A - the peak area or sum of peak areas of the quantification ions of the certain
phthalate esters in the standard working solution;
AIS - the peak area of the quantification ions of the internal standard in the standard
working solution;
a2 - the slope of the calibration curve;
ρ - the mass concentration of the certain phthalate esters in the standard working
solution, in milligrams per liter (mg/L);
ws - the content of the certain phthalate esters in the test portion, %;
A - the peak area or sum of peak areas of the quantitation ions of the certain phthalate
esters in the test solution;
AIS - the peak area of the quantitation ion of the internal standard in the test solution;
b2 - the ordinate intercept of the calibration curve, which can be obtained from
formula (2);
ρIS - the mass concentration of the internal standard in the sample solution, in
milligrams per liter (mg/L);
a2 - the slope of the calibration curve, which can be obtained from formula (2);
V - the constant volume of the test solution, in milliliters (mL);
m - the mass of the test portion, in grams (g);
D - the dilution factor.
NOTE: When the internal standard mass concentration of the sample solution is the same as that of
the standard working solution, it is usually set the internal standard mass concentration ρIS = 1 in
the internal standard method.
10 Quality control
10.1 Limit of quantitation
The limit of quantitation for the content of 7 phthalate esters in this document are:
DIBP, DBP, BBP, DEHP, DNOP: 0.001 %;
DINP, DIDP: 0.005 %.
10.2 Method blank test
A method blank test is required for each batch of samples. Except that no sample is
added, it uses the same test procedure as the sample test. The results of the blank test
can be used to assess the contamination of the test process. The result of the blank test
shall be less than the limit of quantitation (10.1).
10.3 Recovery rate
Take 1 mL of the standard stock solution (5.3) as a sample and operate according to the
procedures in Clause 8 and Clause 9. The recovery rate of each phthalate ester is 80 %
~ 120 %.
Annex D
(informative)
Composite test
D.1 Introduction
Composite test of similar materials is an effective screening method to reduce testing
costs. However, there are also many difficulties in composite test, such as the
complexity of the test matrix, interpretation of the analytical results and unpredictable
chemical reactions between different materials. These factors usually lead to wrong
conclusions. Therefore, composite test can only be used when a qualitative conclusion
is sufficient to determine that the material meets the requirements. The composite test
described in this annex is only for screening purposes.
It is worth noting that composite test is not used to solve the lack of mass of a test
portion, and composite test cannot get more accurate results. If the mass of a test portion
is not enough for a single test, it is also not possible to carry out a composite test either.
D.2 Preparation of composite test portions
Composite test portions shall meet the following conditions:
a) Only a maximum of three test portions can be combined to form a composite test
portion.
b) Only similar materials can be combined for composite test. Different types of
materials are not suitable for composite test, such as plastics and paint coatings
cannot be made into a composite test portion.
c) The mass of each test portion for composite test shall be similar. The difference
in mass between any two test portions shall not exceed 10 %. The mass of each
test portion in composite test shall be controlled within the range of 100 mg ~ 500
mg.
D.3 Test procedure
The test procedures specified in Clause 8 can be used for composite tests.
D.4 Calculation
The average content of the certain phthalate esters in composite tests and the maximum
content of the certain phthalate esters in the individual test portions can be calculated
by formula (D.1) and formula (D.2), respectively.
NOTE: Take into account the testing capability, the variability of different laboratories and the
diversity of materials, laboratories can select an appropriate safety factor based on their experience
and historical data accumulated. This document recommends 60 % as a safety factor, which is based
on practical analysis conclusions of phthalate esters.
D.6 Test report
In addition to the information given in Clause 12, the test report shall include the
following information:
a) indicate the test portions for the composite test;
b) the average content of the certain phthalate esters in the composite test portion
(based on the total amount), the value is expressed in %;
c) the maximum content of the certain phthalate esters in the composite test portion
(based on the minimum amount), the value is expressed in %.
D.7 Examples
Assume that a composite test portion consists of a physical mixture of three PVC
plastics, labeled A, B, and C, with corresponding masses of 0.3054 g, 0.3125 g and
0.3250 g, respectively. After constant volume, the volume of the composite test portion
solution is 25 mL, and the DEHP content in the test result of the composite test portion
solution is 5.90 mg/L.
Refer to the formula (D.4) for the calculation of the average content of phthalate esters
in the composite test portion:
Refer to the formula (D.5) for the calculation of the maximum content of phthalate
esters in the individual test portions:
If the regulated limit of DEHP is 0.1 %; the safety factor is set at 60 %.
- the maximum DEHP content in an individual test portion is 0.0483 %, which is
lower than the safety limit of 0.1 % × 0.6 = 0.06 %, and individual test is not
required.
- see Table D.1 for the test result report.
Annex E
(normative)
Ultrasonic extractor performance check
E.1 Introduction
Not all ultrasonic extractors are suitable for extracting phthalate esters from toys and
children’s products. It shall select a suitable ultrasonic extractor (6.13) and check its
performance regularly. This annex describes the performance check procedure.
E.2 Principle
The ultrasonic extractor includes an ultrasonic generator, an ultrasonic transducer and
a stainless steel tank. The ultrasonic generator generates a high-frequency oscillation
signal, which is converted into high-frequency mechanical oscillation waves by the
ultrasonic transducer to act on the liquid in the stainless steel tank, “tearing” the liquid
apart, leaving millions of microscopic “voids” or “partial vacuum bubbles” (cavitation).
These bubbles release enormous (mechanical) energy, which breaks down the contents
in the liquid into pieces. In this method, ultrasonic waves are applied to the aluminum
foil, forcing the foil to form small perforated holes. The intensity of ultrasonic waves is
related to the perforated rate of the aluminum foil. The performance check of the
ultrasonic extractor is carried out by calculating the perforated rate of the aluminum foil
during the ultrasonic process, not by measuring the sound intensity.
E.3 Instruments and equipment
E.3.1 Aluminum foil: the purity is not less than 85 %, the thickness is (0.020 ± 0.001)
mm, and the bursting strength is (185 ± 10) kPa.
Use a thickness measuring device to measure the thickness of aluminum foil according
to 5.10 in GB 6675.2-2014. The thickness is measured at 10 equidistant points across
the diagonal.
Use a bursting strength measuring device to measure the bursting strength of aluminum
foil according to GB/T 454.
E.4 Analysis procedure
Perform a performance check on the ultrasonic extractor as follows:
a) Spread a piece of aluminum foil on the bottom of the ultrasonic basket and smooth
it out, avoiding wrinkles.
b) Hang the hanging basket in the ultrasonic extractor, make sure that the distance
between the lower surface of the hanging basket and the bottom of the tank is
Annex G
(informative)
Background and rationale
G.1 Introduction
Plastics, including polyvinyl chloride (PVC), are the main materials for toys and
children’s products, and are widely used in industrial production. In the production
process of PVC, it is often necessary to add some plasticizers (such as phthalate esters)
to increase its plasticity. As certain phthalate esters are considered to be estrogens and
environmental hormones, and can accumulate in organisms through the food chain,
their impact on organisms and the environment has received more and more attention.
Therefore, since 1999, some countries and regions have gradually begun to formulate
regulations to restrict the use of certain phthalate esters. At the same time, some related
test methods have also been proposed, but there are large differences between these
methods.
In toys and children’s products, in addition to PVC, PU plastics, textiles and paint
coatings may also contain phthalate esters. This document aims to provide test methods
for phthalate esters in materials that may contain plasticizers in various toys and
children’s products.
G.2 Other phthalate eaters in toys and children’s products
This document has validated 7 phthalate esters, DIBP, DBP, BBP, DEHP, DNOP, DINP
and DIDP in toys and children’s products. Validated test of other phthalate esters can
also refer to this document.
G.3 Extraction and test techniques
When preparing samples, the sample can also be milled or ground into a representative
powder, but cross-contamination shall be avoided.
Soxhlet extraction, solvent extraction, microwave extraction and ultrasonic extraction
can all be used to extract phthalate esters in toys and children’s products. Among them,
Soxhlet extraction is a classic and most widely used organic extraction method, and its
apparatus is relatively simple and easy to obtain commercially. Solvent extraction is an
improvement of the classic Soxhlet extraction method to provide a simpler and faster
sample extraction method. Both methods have been validated as effective extraction
methods for phthalate esters.
Ultrasonic extraction has been validated as an effective extraction method (see 8.2.3).
......
 
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