Brominated flame retardant compound quantitative analysis device

Abstract

To provide a technique by which the quantities of brominated flame-retardant compounds can be conveniently determined when a plurality of analyzers of the same type are used for an analysis of samples.SOLUTION: In a quantitative determination device 100 for brominated flame-retardant compounds, a storage section 41 holds a relative response factor 411 representing a relationship of a measured intensity of a compared compound to that of a reference compound selected from target compounds. A standard-sample measurer 43 acquires the intensity of the reference compound by measuring a standard sample, using an analyzer 10, 20. A target-sample measurer 45 acquires the intensities of the reference and compared compounds by measuring a target sample, using the analyzer. A reference-compound quantity determiner 46 determines a quantitative value of the reference compound in the target sample. A compared-compound quantity determiner 47 determines a quantitative value of the compared compound based on the quantity of the reference compound in the standard sample, intensity of the reference compound acquired by the standard-sample measurer, intensity of the compared compound acquired by the target-sample measurer, and relative response factor of the compared compound.SELECTED DRAWING: Figure 7

Description

[Technical field]

[0001] The present invention relates to a technique for quantifying brominated flame retardant compounds. [Background technology]

[0002] Polybrominated biphenyls (PBBs, molecular formula C 12 H (10-n) Br n (1≦n≦10)) and polybrominated diphenyl ethers (PBDEs, molecular formula C 12 H (10-m) Br m O(1≦m≦10)) is designated as a regulated compound in the RoHS Directive, and the total content of 10 types of PBBs and PBDEs permitted in each part of electrical and electronic products exported to Europe is set at 1000 mg / kg or less.

[0003] Conventionally, the content of PBBs and PBDEs has been measured as follows: Standard samples containing known concentrations of 10 types of PBBs, where n is 1 (Mono) to 10 (Deca), and 10 types of PBDEs, where m is 1 (Mono) to 10 (Deca), are measured in advance by gas chromatography / mass spectrometry (GC / MS) to obtain the retention time and peak intensity of each compound, and a calibration curve is created for each compound. After that, for the actual sample, PBBs and PBDEs extracted from the sample by pretreatment such as solvent extraction or heat extraction are measured by GC / MS to create a chromatogram, and the peaks of each compound are identified based on the retention time, and the content is determined by comparing the peak intensity of each compound with the calibration curve for that compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 129129 [Patent Document 2] International Publication No. 2020 / 152800 [Patent Document 3] International Publication No. 2020 / 161849 [Non-patent literature]

[0005] [Non-Patent Document 1] Yukihiko Kudo, et al., "Development of a screening method for phthalate esters in polymers using a quantitative database in combination with pyrolyzer / thermal desorption gas chromatography mass spectrometry", Journal of Chromatography A, Volume 1602, 27 September 2019, Pages 441-449 Summary of the Invention [Problem to be solved by the invention]

[0006] Normally, the above measurements require the creation of new calibration curves for each of the 10 PBBs and 10 PBDEs on each analysis date, which is time-consuming. In addition, a mixed standard solution that contains all of these can be expensive and difficult to obtain. Furthermore, when there are many samples to be analyzed, multiple mass spectrometers may be used. In such cases, the work of creating calibration curves for each of the 10 PBBs and 10 PBDEs using the above measurements must be performed for each mass spectrometer, which is time-consuming and labor-intensive.

[0007] The problem to be solved by the present invention is to provide a technique for easily quantifying brominated flame retardant compounds when it is difficult to prepare a calibration curve using a mixed solution containing 10 types of PBBs and 10 types of PBDEs, or when analyzing samples using multiple analytical instruments of the same type. [Means for solving the problem]

[0008] The present invention provides a quantitative determination apparatus for brominated flame retardant compounds, which is capable of solving the above problems. a memory unit in which a relative response coefficient is stored, the relative response coefficient representing the relationship between an intensity per unit amount of a reference compound, which is one of a plurality of target compounds that are some or all of a group of polybrominated biphenyl compounds and a group of polybrominated diphenyl ether compounds, measured by a predetermined analytical method under predetermined conditions, and an intensity per unit amount of a reference compound, which is a target compound other than the reference compound, measured under the predetermined conditions; an analytical device for measuring a sample by the predetermined analytical method; a standard sample measurement unit that measures a standard sample containing a known amount of the reference compound under the predetermined conditions using the analytical device to obtain an intensity of the reference compound; an analyte sample measurement unit that measures an analyte sample under the predetermined conditions using the analytical device to obtain intensities of the standard compound and the reference compound contained in the analyte sample; a reference compound quantification unit that determines a quantitative value of the reference compound contained in the analysis target sample based on the amount of the reference compound contained in the standard sample, the intensity of the reference compound obtained by the standard sample measurement unit, and the intensity of the reference compound obtained by the analysis target sample measurement unit; a reference compound quantification unit that determines a quantitative value of the reference compound based on the amount of the reference compound contained in the standard sample, the intensity of the reference compound obtained by the standard sample measurement unit, the intensity of the reference compound obtained by the analysis target sample measurement unit, and a relative response coefficient of the reference compound; Equipped with. Effect of the Invention

[0009] In the present invention, a standard compound is selected from a plurality of target compounds that are some or all of the polybrominated biphenyls and polybrominated diphenyl ethers, and a relative response coefficient that represents the relationship between the measured intensity per unit amount of the standard compound and the measured intensity per unit amount of the reference compound (a target compound other than the standard compound) is calculated and stored in a memory unit. When measuring a sample to be analyzed, a quantitative value is calculated using a calibration curve created by measuring only the standard sample for the standard compound, and a quantitative value of the reference compound is calculated from the measured intensity and relative response coefficient of the reference compound, the measured intensity of the standard compound obtained by measuring the standard sample, and the amount of the standard compound contained in the standard sample. In the present invention, the relative response coefficient of the target compound with respect to the standard compound is calculated in advance, and thereafter, a calibration curve is created for each analytical device only for the standard compound, so that brominated flame retardant compounds can be easily quantified when it is difficult to create a calibration curve using a mixed solution of all PBBs and PBDEs or when multiple analytical devices of the same type are used. [Brief description of the drawings]

[0010] [Figure 1] FIG. 2 is a diagram showing the configuration of the main parts of one embodiment of a gas chromatograph mass spectrometer used to create a relative response coefficient database in the present invention. [Diagram 2] Examples of measurement conditions used in the present embodiment. [Diagram 3] 4 is a flowchart showing a procedure for creating a relative response coefficient database in this embodiment. [Figure 4] 4 is an example of a relative response coefficient matrix in the present embodiment. [Diagram 5] 4 is an example of a relative response coefficient table in the present embodiment. [Figure 6] 1 is an example showing the correspondence relationship between a standard compound and a reference compound and the coefficient of variation of a relative response coefficient in this embodiment. [Figure 7] FIG. 1 is a diagram showing the configuration of a main part of an embodiment of a quantitative determination device for brominated flame retardant compounds according to the present invention. [Figure 8] 4 is a flowchart showing the procedure for quantifying compounds contained in an analysis sample using the relative response coefficient database in this embodiment. [Figure 9] 3 shows an example of a total ion current chromatogram and a mass chromatogram obtained in this embodiment. [Figure 10] Quantitative results and recovery rates of each compound in this example. [Figure 11] 4 shows another example of measurement conditions used in the present embodiment. [Figure 12] 13 is another example of a relative response coefficient table in the present embodiment. [Figure 13] 13 is another example showing the correspondence relationship between the standard compound and the reference compound and the coefficient of variation of the relative response coefficient in this embodiment. [Figure 14] 1 shows an example of the correspondence relationship with the reference compounds and the relative response coefficient when the compounds to be measured in this embodiment include TBBPA and HBCDD. [Figure 15] 1 is another example showing the correspondence relationship with the reference compounds and the relative response coefficient when the compounds to be measured in this embodiment include TBBPA and HBCDD. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] An embodiment of the quantitative determination apparatus for brominated flame retardant compounds according to the present invention will be described below with reference to the drawings. In this embodiment, a pyrolyzer-gas chromatograph mass spectrometer (Py-GC-MS) is used to determine the amount of polybrominated biphenyls (PBBs, molecular formula C 12 H (10-n) Br n (1≦n≦10)) and polybrominated diphenyl ethers (PBDEs, molecular formula C 12 H (10-m) Br m The present embodiment screens samples by quantifying the amount of m in the presence of 100% m ...

[0012] 1. Configuration of Py-GC-MS to create a relative response factor database FIG. 1 shows the configuration of the main components of a Py-GC-MS1 (first analyzer) used to create a relative response factor database used in quantifying PBBs and PBDEs in this example.

[0013] Py-GC-MS1 is broadly composed of a gas chromatograph section 10, a mass spectrometer section 20, and a control and processing section 30. Gas chromatograph section 10 includes a sample vaporization chamber 11, a pyrolyzer 12 provided in sample vaporization chamber 11, a carrier gas flow path 13 connected to the sample vaporization chamber, and a column 14 connected to the outlet of sample vaporization chamber 11. Column 14 is housed inside a column oven 15. Pyrolyzer 12 and column 14 in column oven 15 are each heated to a predetermined temperature by a heating mechanism (not shown).

[0014] In this embodiment, the column 14 is one capable of simultaneously analyzing PBBs and PBDEs. For example, considering that PBBs and PBDEs are highly polar compounds, it is desirable to use a column in which the liquid phase is a non-polar substance and the film thickness of the liquid phase is 1.0 μm or less, but this is not limited thereto. The length of the column may be appropriately determined according to the type and film thickness of the selected liquid phase. As the column 14 in this embodiment, for example, UA-PBDE (liquid phase: 100% dimethyl polysiloxane, length: 15 m, inner diameter: 0.25 mm, film thickness: 0.05 μm, manufactured by Frontier Labs) or SH-1MS with guard column (liquid phase: 100% dimethyl polysiloxane, length: 17 m, inner diameter: 0.25 mm, film thickness: 1.0 μm, manufactured by Shimadzu Corporation) can be suitably used.

[0015] The mass analysis section 20 includes an electron ionization source 22, an ion lens 23, a quadrupole mass filter 24, and an ion detector 25 within a vacuum chamber 21. Sample components separated over time inside the column 14 are sequentially introduced into the electron ionization source 22 and ionized by irradiation with thermoelectrons emitted from a filament (not shown).

[0016] The control and processing unit 30 has a storage unit 31. The storage unit 31 stores a method file used for measuring PBBs and PBDEs. The method file is a file that describes the measurement conditions for PBBs and PBDEs. The measurement conditions for PBBs and PBDEs include information such as the temperature of the pyrolyzer 12, the temperature of the column 14, the type and flow rate of the carrier gas, and two types of ions (quantitative ions and confirmatory ions) that characterize each of the PBBs and PBDEs. FIG. 2 shows an example of the measurement conditions. Although FIG. 2 shows only two types of ions for each compound, information on the mass-to-charge ratio of one or more preliminary ions for each compound is also stored in preparation for a case in which the mass-to-charge ratio of either the quantitative ion or the confirmatory ion is close to the mass-to-charge ratio of an ion generated from an impurity contained in the sample to be analyzed and an ion with that mass-to-charge ratio cannot be used.

[0017] The control / processing unit 30 includes, as functional blocks, a standard sample measuring unit 32, a retention index calculating unit 33, a relative response coefficient calculating unit 34, and a database creating unit 35. The actual substance of the control / processing unit 30 is a general personal computer, and a database creating unit 35 is installed in advance. Device These functional blocks are realized by executing a program on a processor. In addition, an input unit 36 ​​for a user to perform input operations and a display unit 37 for displaying various information are connected to the control / processing unit 30.

[0018] 2. Procedure for creating the relative response factor database Next, the procedure for creating the relative response coefficient database will be described with reference to the flowchart of FIG.

[0019] First, a standard sample (first standard sample) is prepared by mixing known amounts of the target compounds PBBs and PBDEs into a resin solution. To facilitate the calculation of the relative response factor described below, it is preferable that the contents of PBBs and PBDEs are the same, but they do not necessarily have to be the same. In this example, a standard sample based on a resin solution is prepared, but this is because, as described above, this example aims to screen resin products that are subject to the RoHS Directive, and the form of the standard sample may be appropriately determined depending on the shape and characteristics of the sample to be analyzed.

[0020] When a user introduces a standard sample into the pyrolyzer 12 and issues an instruction to start measurement, the standard sample measurement unit 32 reads out the method file stored in the memory unit 31 and measures the standard sample (first standard sample) based on the measurement conditions described in the method file (step 1). First, the pyrolyzer 12 is heated to vaporize the PBBs and PBDEs contained in the standard sample, and these are carried by the carrier gas flow and introduced into the column 14. The PBBs and PBDEs are separated in time according to the strength of their interaction with the liquid phase inside the column 14 and flow out. Each compound that flows out of the column 14 is introduced into the electron ionization source 22 in sequence.

[0021] Ions generated by the electron ionization source 22 are converged by the ion lens 23 near the central axis (ion optical axis C) in the flight direction, and then enter the quadrupole mass filter 24, where they are separated according to their mass-to-charge ratio and detected by the ion detector 25. Output signals from the ion detector 25 are sequentially transmitted to and stored in the memory unit 31.

[0022] During the measurement of the standard sample, the mass spectrometry unit 20 repeatedly performs scan measurement and selected ion monitoring (SIM) measurement. Specifically, one set is a scan measurement in which the mass-to-charge ratio of ions passing through the quadrupole mass filter 24 is scanned over a predetermined range (for example, a range of m / z from 50 to 1000), and 40 types of SIM measurements in which the mass-to-charge ratio of ions passing through the quadrupole mass filter 24 is fixed to the mass-to-charge ratio of a quantification ion or confirmation ion of each compound for a predetermined period of time, and this is repeated. Note that the scan measurement is not essential, and only the SIM measurement may be performed repeatedly.

[0023] In addition to the measurement of the standard sample, an n-alkane sample is also measured. The n-alkane sample is a standard sample containing a plurality of compounds with different lengths of hydrocarbon chain, and is used to obtain a retention index based on the retention time of each compound. As described in Non-Patent Document 1, the retention index I x is expressed by the following equation (1). I x =100(C n+i -C n ){(t x -t n ) / (t n+i -t n )}+100C n …(1) Here, C n , C n+i are the carbon numbers of the n-alkanes whose retention times are located before and after the retention time of the target compound, respectively, and t x is the retention time of compound x, t n , t n+i is the retention time of the n-alkanes located before and after the retention time of the compound in question.

[0024] After the standard sample is measured, the standard sample measurement unit 32 creates a total ion current chromatogram (TIC) based on the scan measurement data, and also creates a mass chromatogram based on the SIM measurement data. When these chromatograms are created, the retention index calculation unit 33 calculates the retention time and measurement intensity for each compound (step 2). The retention time of a compound is determined based on the peak top position of the peak that appears at the same retention time in the mass chromatogram of the quantitative ion and the mass chromatogram of the confirmation ion set for that compound. Once the retention time of each compound is determined, the retention index of each compound is calculated based on the retention time of each compound contained in the n-alkane sample (step 3).

[0025] Next, the relative response factor calculation unit 34 calculates the relative response factor (RRF) that represents the relationship between the measurement intensities of PBBs and PBDEs (a total of 20 types of compounds) (step 4). As described in Patent Documents 1 to 3 and Non-Patent Document 1, the relative response factor RRF of the reference compound a to the standard compound x is a / x is expressed by the following equation (2). RRF a / x =RF a / RF x …(2) Here, R.F. a and RF x are the response factors for reference compound a and standard compound x, respectively.

[0026] Response factor RF of reference compound a a is expressed by the following formula (3): Note that the following formulas are the same not only for the reference compound a but also for the standard compound x. RF a =A a / m a …(3) Here, A a and m a are the peak area and weight (mg) of reference compound a in the mass chromatogram, respectively. Also, the weight m a is expressed by the following equation (4). m a =M×Ca …(4) Here, M and C a are the weight (kg) of the standard sample and the concentration (mg / kg) of the reference compound a contained in the standard sample. As can be seen from equation (3) above, when a standard sample with the same content of PBBs and PBDEs is used, the ratio of the peak areas of each compound can be expressed as the RRF a / x This makes it easier to calculate the relative response coefficient.

[0027] The relative response coefficient calculation unit 34 determines the relative response coefficient when each of the 20 types of compounds is set as a standard compound x and the other compounds are set as reference compounds a. As a result, relative response coefficients (relative response coefficient matrix) corresponding to all combinations of the 20 types of compounds are created, as shown in FIG.

[0028] When the above processes by the retention index calculation unit 33 and the relative response coefficient calculation unit 34 are completed, the database creation unit 35 associates the retention index and the above relative response coefficient of each compound with the method file used in the measurement, and stores them in the memory unit 31 as a relative response coefficient database (step 5).

[0029] In addition, the same measurements and processing are also performed on another analytical instrument (Py-GC-MS) of the same type as the Py-GC-MS1 to obtain the relative response coefficients corresponding to all combinations of the 20 types of compounds, and a database of the relative response coefficients obtained in each instrument is created and read by the control and processing unit 30. When the database of the relative response coefficients obtained in the other analytical instruments is read, the database creation unit 35 extracts combinations of the standard compound and the reference compound that reduce the variation in the relative response coefficients between the analytical instruments and displays them on the screen of the display unit 37. The variation in the relative response coefficients can be evaluated, for example, by the %RSD value of the relative response coefficients obtained from the measurements using each analytical instrument. The %RSD is called the coefficient of variation, and is expressed as a percentage by dividing the standard deviation by the arithmetic mean. When evaluating the variation in the values ​​of the relative response coefficients using the coefficient of variation, it is preferable to select a combination of the standard compound and the reference compound whose coefficient of variation for each relative response coefficient is 20 or less. This is because if the coefficient of variation exceeds 20, the variation between the instruments is large, and the error in the quantitative value increases, which may result in poor screening accuracy.

[0030] The user refers to the combinations displayed on the display unit 37 and selects a standard compound and a reference compound to be associated with the standard compound. When all compounds have been selected as standard compounds or reference compounds, the database creation unit 35 stores the results in the memory unit 31. FIG. 5 shows an example of relative response coefficients stored in the memory unit 31. In this embodiment, Tetra-BDE, Penta-BDE, Deca-BDE, and Deca-BB are selected as standard compounds. The term "absolute calibration" in FIG. 5 and other figures refers to the relative response coefficients stored in the memory unit 31. is the reference compound This means that the amount of the compound is calculated using the calibration curve in the measurement of the sample to be analyzed, which will be described later. Figure 6 shows the results of performing the above process three times using each of the four Py-GC-MS1s to obtain relative response coefficients, and calculating the %RSD of each relative response coefficient. The relative response coefficient data thus created is appropriately adjusted for use in the Py-GC-MS100, which will be described later. record It is stored on a medium (CD-ROM, USB memory, etc.).

[0031] In this embodiment, the reference compound is determined in consideration of the small variation in the relative response factor between the devices, as well as the ease of obtaining a standard sample containing a known amount of the compound, which is used when measuring the sample to be analyzed, as described later. Certified reference material ERM-EC591, for example, is widely used as a standard sample containing PBBs and PBDEs. Certified reference material ERM-EC591 contains Tri-BDE, Tetra-BDE, Penta-BDE, Hexa-BDE, Hepta-BDE, Octa-BDE, Deca-BDE, and Deca-BB. Among these, Tetra-BDE, Penta-BDE, Deca-BDE, and Deca-BB are contained in large amounts (245 to 780 mg / kg). Since the RoHS Directive requires that the total content of PBBs and PBDEs does not exceed 1000 ppm (1000 mg / kg), it is preferable to use a compound contained in a standard material at a concentration close to that. This makes it possible to further reduce errors in the relative response coefficient caused by differences in measurement sensitivity due to concentration differences.

[0032] 3. Configuration of Py-GC-MS for measuring target samples FIG. 7 is a diagram showing the main configuration of the Py-GC-MS100 (second analyzer) used in screening the analysis target sample in this embodiment. The configurations of the gas chromatograph section 10 and the mass analyzer section 20 are the same as those in FIG. 1, so only the configuration of the control / processing section 40 will be described below. Note that the gas chromatograph section 10 and the mass analyzer section 20 need only be of the same type as the analyzer used to create the relative response coefficient database (here, a gas chromatograph mass analyzer), and do not necessarily need to have the exact same configuration. For example, the mass filter in the mass analyzer section 20 may be of a different type (for example, an ion trap or a time-of-flight mass separator).

[0033] The control / processing unit 40 includes a storage unit 41. A relative response coefficient database 411 (relative response coefficient matrix in FIG. 4 and relative response coefficient table in FIG. 5) created by the above-mentioned device described with reference to FIG. 1 and FIG. 3 and stored in a recording medium is read into the storage unit 41, and is stored in association with the measurement conditions (FIG. 2). The control / processing unit 40 also includes, as functional blocks, a reference compound determination unit 42, a standard sample measurement unit 43, a relative response coefficient evaluation unit 44, an analysis target sample measurement unit 45, a reference compound quantification unit 46, a reference compound quantification unit 47, a screening unit 48, and a database update unit 49. The actual entity of the control / processing unit 40 is a general personal computer, and the above-mentioned functional blocks are embodied by executing a pre-installed analysis sample measurement program on a processor. In addition, an input unit 50 for a user to perform input operations and a display unit 51 for displaying various information are connected to the control / processing unit 40.

[0034] 4. Screening Procedure for Analyte Samples Next, the procedure for screening the analysis sample will be described with reference to FIG.

[0035] When the user instructs screening of the sample to be analyzed, the reference compound determination unit 42 reads out the relative response coefficient database 411 from the storage unit 41 and displays the relative response coefficient table (FIG. 5) described therein on the display unit 51. The user checks this and changes the correspondence between the reference compound and the reference compound as necessary. For example, if it is difficult to obtain a standard sample containing the reference compound selected in the relative response coefficient table, the compound can be deleted from the reference compounds or another compound can be set as the reference compound. When the user changes the correspondence between the reference compound and the reference compound, the reference compound determination unit 42 refers to the relative response coefficient matrix (FIG. 4) and changes the relative response coefficient table to one corresponding to the changed reference compound. When the user finishes selecting the reference compound, the reference compound is determined (step 11). In this embodiment, the reference compound is not changed, and Tetra-BDE, Penta-BDE, Deca-BDE, and Deca-BB are determined as they are as the reference compounds.

[0036] Next, using the measurement conditions (related to the measurement of the reference compounds) described in the method file associated with the relative response factor database, standard samples (second standard samples) containing known amounts of each of the reference compounds (Tetra-BDE, Penta-BDE, Deca-BDE, Deca-BB) are measured (step 12). As the standard sample, the above-mentioned certified reference material ERM-EC591 can be suitably used.

[0037] Once the measurement of the reference compounds is completed, a calibration curve corresponding to each of the reference compounds is created (step 13). Here, only one standard sample is measured to create a one-point calibration curve. If there is a nonlinear relationship between the amount of the reference compound and the measurement intensity, multiple standard samples with different amounts of the reference compound may be measured to create a calibration curve based on two or more measurement points.

[0038] The relative response factor evaluation unit 44 determines the relative response factor from the relative response factor table by using one of the four reference compounds as the reference compound (e.g., Tetra-BDE) and the other one as the reference compound (e.g., Penta-BDE). The area of ​​the mass peak of the chromatogram obtained by measuring the standard sample is calculated, and the quantitative value is calculated using this and the relative response factor. The calculated quantitative value is then compared with the amount of the reference compound actually contained in the standard sample, and it is confirmed whether the degree of agreement between the two is within a predetermined range. The predetermined range is, for example, the actual content ±30%, and if the calculated quantitative value is within that range, it is determined that the relative response factor is valid (step 14). On the other hand, if the calculated quantitative value is outside that range, the process is interrupted, and the user is prompted to reselect the reference compound, re-create the relative response factor database, or use another relative response factor database if one is stored in the storage unit 41.

[0039] After creating the calibration curve for the reference compound, when the user sets the sample to be analyzed and issues an instruction to start measurement, the sample to be analyzed measurement unit 45 measures the sample to be analyzed using the measurement conditions described in the method file associated with the relative response coefficient database 411 (step 15). In addition to the measurement of the standard sample, the n-alkane sample is also measured. In the measurement of the sample to be analyzed, a scan measurement is not essential, and only the SIM measurement may be performed. However, by performing a scan measurement, if a large peak other than that of the compound to be analyzed is found after creating a total ion current chromatogram, the compound corresponding to the peak can be identified by analyzing the mass spectrum obtained at the retention time of the peak.

[0040] When the measurement of the sample to be analyzed is completed, the reference compound quantification unit 46 determines the peaks of the mass chromatogram of the quantification ion and confirmation ion based on the retention index of each reference compound, or the retention index and the predicted retention time calculated based on the measurement data of n-alkanes. Then, the peak area of ​​the quantification ion is compared with the calibration curve of the reference compound to obtain the quantitative value (step 16).

[0041] When the quantitative values ​​of the reference compounds are obtained, the reference compound quantification unit 47 determines the peaks of the mass chromatograms of the quantitative ions and the confirmation ions based on the retention indices of the reference compounds, or the predicted retention times calculated based on the retention indices and the measurement data of the n-alkanes, and calculates the quantitative values ​​of each reference compound based on the amount of the reference compound contained in the standard sample, the peak area of ​​the quantitative ions of the reference compounds detected by measuring the standard sample, the peak area of ​​the quantitative ions of the reference compounds, and the relative response coefficient (step 17).

[0042] When the quantitative values ​​of the standard compound and the reference compound are obtained, the screening unit 48 compares the quantitative values ​​with a predetermined threshold value to screen the sample to be analyzed. In this embodiment, based on the standard of the RoHS Directive (the total amount of PBBs and PBDEs is 1000 ppm or less), the screening unit 48 judges whether the total quantitative values ​​of PBBs and PBDEs contained in the sample to be analyzed are within the range of ±70% of the standard value (step 18). Specifically, if the total quantitative values ​​of PBBs and PBDEs contained in the sample to be analyzed is 300 ppm or less, the sample to be analyzed is judged to meet the standard of the RoHS Directive. If the total amount of PBBs and PBDEs exceeds 1700 ppn, the sample to be analyzed is judged to not meet the standard of the RoHS Directive. If the total amount of PBBs and PBDEs is within the range of 300 ppm to 1700 ppm, the judgment is withheld, and the sample to be analyzed is analyzed in detail by another method to calculate the quantitative values ​​more precisely.

[0043] The results of measuring an actual sample according to the above embodiment are shown in Figures 9 and 10. In this measurement, a polystyrene solution was added to a sample cup so that the amount of resin was 0.5 mg, and a mixed solution of PBBs and PBDEs was further added to the sample cup so that the concentration of each compound in the resin was 500 mg / kg (except for Deca-BDE, which was 1000 mg / kg), to prepare a sample to be analyzed.

[0044] Figure 9 shows the total ion current chromatogram and mass chromatogram of each compound obtained for the above-mentioned analysis sample. Figure 10 shows the quantitative values ​​of each compound obtained by the procedure explained in the above examples, and the calculation of the recovery rate of each compound.

[0045] The concentration values ​​in the table of FIG. 10 are the actual contents of PBBs and PBDEs contained in the above-mentioned analysis samples, and the values ​​shown below them are the quantitative values ​​obtained by the method of the above-mentioned Example. The recovery rates shown in the table are values ​​indicating the ratio of the quantitative values ​​to the actual contents, and correspond to the measurement error. In the measurement results, the recovery rates of each compound were in the range of 92 to 124%, and the recovery rates for the total amount of PBBs and the total amount of PBDEs were 105% and 109%, respectively. These values, especially the recovery rates for the total amount of PBBs and the total amount of PBDEs, have sufficient accuracy for screening analysis samples related to the RoHS Directive.

[0046] In the Py-GC-MS100 of this embodiment, not only can screening be performed using a relative response factor database 411 created using another analytical device and stored in the storage unit 41, but the relative response factor database 411 can also be created using the Py-GC-MS100 itself. When creating a new relative response factor database 411, the database creation program described for the Py-GC-MS1 can be executed to embody each functional block. Also, when a data file of a relative response factor database created by another analytical device is read, a new relative response factor database is saved in the storage unit 41 by the database update unit 49.

[0047] In addition, some samples may contain impurity compounds that were not anticipated when the relative response factor database was created. If the impurity compounds produce ions with mass-to-charge ratios close to the quantification ions or confirmation ions set for each compound, the impurity compounds will be measured simultaneously, and the correct measurement intensity of each compound will not be obtained. In such cases, it is necessary to set ions with mass-to-charge ratios different from those of the impurity compounds as the quantification ions or confirmation ions.

[0048] When the user instructs to change the settings of the quantitative ions or confirmation ions, the database update unit 49 reads out the relative response factor database 411 stored in the storage unit 41, and displays the measurement conditions on the screen of the display unit 51. When the user selects the quantitative ions or confirmation ions of the compound to be changed from the displayed measurement conditions, the database update unit 49 displays a field for inputting the mass-to-charge ratio of the ions to be newly set as quantitative ions or confirmation ions, and the ratio of the measured intensity of the ions after the change to the measured intensity of the quantitative ions or confirmation ions before the change. When the user inputs these, the mass-to-charge ratio of the quantitative ions or confirmation ions is updated. In addition, the relative response factor of the compound is updated to a value obtained by multiplying the original value by the above ratio. In addition, the method file is updated so that the ions after the change are measured as quantitative ions or confirmation ions.

[0049] The above embodiment is an example, and can be appropriately modified in accordance with the gist of the present invention. In the above embodiment, the measurement conditions when creating the relative response coefficient database using Py-GC-MS1 and the measurement conditions when screening and judging the analysis target sample using Py-GC-MS100 are the same, but they do not necessarily need to be completely the same. However, measurement parameters that affect the relative relationship of the measurement intensity between compounds must be common. Examples of such parameters include measurement parameters related to the heating of the sample by the pyrolyzer 12, the polarity of the column 14, the heating temperature of the column 14 by the column oven 15, the ionization method and ionization conditions (such as the energy of electron ions). In other words, the predetermined conditions in the present invention include those related to these measurement parameters.

[0050] 11 to 13 show an example of creating a relative response factor database by changing the measurement conditions using the Py-GC-MS1 of the above embodiment. This example is optimized to shorten the extraction time of the compound by the pyrolyzer (FIG. 11). The measurement conditions shown in FIG. 2 and FIG. 11 have different measurement parameters related to heating the sample by the pyrolyzer 12. In FIG. 2, the temperature of the pyrolyzer 12 is gradually increased and held at 340° C. for 1 minute, but in FIG. 11, the pyrolyzer is heated to 340° C. from the start of the measurement and held for 3 minutes. FIG. 12 shows the relative response factor of each compound obtained under these measurement conditions. Also, FIG. 13 shows the %RSD value of each relative response factor. In this way, by storing a plurality of relative response factor databases corresponding to a plurality of measurement conditions with different measurement parameters that affect the relative relationship of the measurement intensity between the compounds in the memory unit 41, screening judgment can be performed under measurement conditions suitable for the sample to be analyzed.

[0051] In the above embodiment, PBBs and PBDEs were used as the target compounds for measurement, but the same configuration as above can be used for the measurement of other compounds. For example, by previously determining the relative response factor for a compound having a structure or property similar to any of Tetra-BDE, Penta-BDE, Deca-BDE, and Deca-BB selected as the reference compound in the above embodiment, the compound contained in the sample to be analyzed can be quantified or screened. When performing measurements using Py-GC-MS as in the above embodiment, examples of such compounds include phthalates, tetrabromobisphenol A (TBBPA), and hexabromocyclododecane (HBCDD). These compounds are also subject to various chemical substance regulations, and by preparing a relative response factor database including these compounds, screening and judgment of the sample to be analyzed in accordance with various chemical substance regulations can be efficiently performed. Figure 14 shows the correspondence relationship and relative response factor of HBCDD and TBBPA with the reference compounds when the measurement conditions shown in Figure 2 are used. Also, Figure 15 shows the correspondence relationship and relative response factor with the reference compounds when the measurement conditions shown in Figure 11 are used.

[0052] The measurement method is not limited to the above GC / MS, and various measurement methods can be used as long as they can individually measure the target compounds. For example, a configuration can be adopted in which chromatography (gas chromatography, liquid chromatography, etc., which detects each compound by spectroscopic measurement, etc.) is performed using only a chromatograph device, and each compound separated in a column is measured. Also, a configuration can be adopted in which ions with mass-to-charge ratios characteristic of each compound are individually measured using only a mass spectrometer.

[0053] [Aspects] It will be appreciated by those skilled in the art that the exemplary embodiments described above are examples of the following aspects.

[0054] (Section 1) An apparatus for quantifying brominated flame retardant compounds according to one embodiment of the present invention comprises: a memory unit in which a relative response coefficient is stored, the relative response coefficient representing the relationship between an intensity per unit amount of a reference compound, which is one of a plurality of target compounds that are some or all of a group of polybrominated biphenyl compounds and a group of polybrominated diphenyl ether compounds, measured by a predetermined analytical method under predetermined conditions, and an intensity per unit amount of a reference compound, which is a target compound other than the reference compound, measured under the predetermined conditions; an analytical device for measuring a sample by the predetermined analytical method; a standard sample measurement unit that measures a standard sample containing a known amount of the reference compound under the predetermined conditions using the analytical device to obtain an intensity of the reference compound; an analyte sample measurement unit that measures an analyte sample under the predetermined conditions using the analytical device to obtain intensities of the standard compound and the reference compound contained in the analyte sample; a reference compound quantification unit that determines a quantitative value of the reference compound contained in the analysis target sample based on the amount of the reference compound contained in the standard sample, the intensity of the reference compound obtained by the standard sample measurement unit, and the intensity of the reference compound obtained by the analysis target sample measurement unit; a reference compound quantification unit that determines a quantitative value of the reference compound based on the amount of the reference compound contained in the standard sample, the intensity of the reference compound obtained by the standard sample measurement unit, the intensity of the reference compound obtained by the analysis target sample measurement unit, and a relative response coefficient of the reference compound; Equipped with.

[0055] The quantification apparatus for brominated flame retardant compounds in paragraph 1 is used to quantify a plurality of target compounds, which are some or all of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs), contained in a sample to be analyzed. Prior to measuring the sample to be analyzed, one or more reference compounds are selected from PBBs and PBDEs, and a first standard sample containing the reference compound and each reference compound at a known concentration is measured using an analytical apparatus (first analytical apparatus). Then, a relative response coefficient is obtained that represents the relationship between the measured intensity (first intensity) per unit amount of each reference compound and the measured intensity (first intensity) per unit amount of the reference compound.

[0056] When measuring a sample to be analyzed, a standard sample (second standard sample) containing a known concentration of a reference compound is measured using the analyzer (second analyzer) that is to measure the sample to be analyzed, and a calibration curve is created. For example, ERM-EC591, a commercially available certified reference material that is widely used for quantifying brominated flame retardant compounds, can be used as the standard sample. When ERM-EC591 is used as the standard sample, a reference compound is selected from the PBBs and PBDEs contained in it. After measuring the sample to be analyzed, the quantitative value of the reference compound is obtained using the calibration curve, and then the quantitative value of each reference compound is obtained based on the amount of the reference compound contained in the standard sample, the measured intensity (second intensity) of the reference compound obtained by measuring the standard sample, the measured intensity (third intensity) of the reference compound obtained by measuring the sample to be analyzed, and the relative response coefficient. In this way, with the quantitative analysis device for brominated flame retardant compounds in Section 1, the relative response coefficient of the reference compound for the standard compound is determined in advance, and thereafter, a calibration curve is created for each analytical device (second analytical device) only for the standard compound. This makes it easy to quantify brominated flame retardant compounds when it is difficult to obtain a mixed solution of all types of PBBs and PBDEs and create a calibration curve, or when multiple analytical devices of the same type are used.

[0057] (Section 2) In the quantitative determination apparatus for brominated flame retardant compounds according to claim 1, The reference compounds are Tetra-BDE, Penta-BDE, Deca-BDE, and Deca-BB.

[0058] (Section 3) In the quantitative determination apparatus for brominated flame retardant compounds according to the first or second aspect of the present invention, The relative response factors of Mono-BDE, Di-BDE, Tri-BDE, Mono-BB, Di-BB, Tri-BB, and Tetra-BB are stored with Tetra-BDE as the reference compound. The relative response factors of Hexa-BDE, Hepta-BDE, Penta-BB, Hepta-BB, and Hepta-BB are stored with Penta-BDE as the reference compound. The relative response factors of Octa-BDE and Nona-BDE are stored with Deca-BDE as the reference compound. The relative response factors of Octa-BB and Nona-BB are stored with Deca-BB as the reference compound.

[0059] (Section 12) Another aspect of the present invention is a computer-readable recording medium having recorded thereon data used for quantifying target compounds that are polybrominated biphenyl compounds and polybrominated diphenyl ether compounds by chromatography-mass spectrometry, the recording medium comprising: This data has a data structure in which the intensity per unit amount of the reference compounds Tetra-BDE, Penta-BDE, Deca-BDE, and Deca-BB when analyzed by chromatographic mass spectrometry under specified conditions is correlated with a relative response coefficient, which is information on the intensity per unit amount of a reference compound, which is a target compound other than the reference compounds, when measured under the same specified conditions.

[0060] (Section 13) 13. The computer readable medium according to claim 12, The relative response factors of Mono-BDE, Di-BDE, Tri-BDE, Mono-BB, Di-BB, Tri-BB, and Tetra-BB are associated with Tetra-BDE. The relative response factors of Hexa-BDE, Hepta-BDE, Penta-BB, Hepta-BB, and Hepta-BB are associated with Penta-BDE. The relative response factors of Octa-BDE and Nona-BDE are associated with Deca-BDE. Data having a data structure in which the relative response coefficients of Octa-BB and Nona-BB are associated with Deca-BB is recorded.

[0061] The commercially available certified reference material ERM-EC591 contains a large amount of Tetra-BDE, Penta-BDE, Deca-BDE, and Deca-BB (245-780mg / kg). The RoHS Directive requires that the total content of PBBs and PBDEs must not exceed 1000ppm (1000mg / kg). The quantitative determination devices for brominated flame retardant compounds described in paragraphs 2 and 3 and the computer-readable recording medium described in paragraphs 11 and 12 can determine the total content of PBBs and PBDEs at 1000ppm (1000mg / kg). ) Since a compound contained in a standard substance at a similar concentration is used as the reference compound, the error in the relative response coefficient caused by differences in measurement sensitivity due to concentration differences can be reduced.

[0062] (Section 4) In the quantitative determination apparatus for brominated flame retardant compounds according to any one of claims 1 to 3, For each of the plurality of different predetermined conditions, A relative response factor is stored that represents the relationship of the intensity per unit amount of the reference compound to the intensity per unit amount of the standard compound.

[0063] (Section 14) 14. The computer-readable recording medium according to claim 12 or 13, For each of the plurality of different predetermined conditions, Data having a data structure in which a relative response coefficient that indicates the relationship of the intensity per unit amount of the reference compound is associated with the standard compound is recorded.

[0064] In the quantitative determination apparatus for brominated flame retardant compounds described in paragraph 4 and the computer-readable recording medium described in paragraph 14, a measurement condition suitable for the sample to be analyzed can be selected from a plurality of measurement conditions having different measurement parameters that affect the relative relationship of the measurement intensities between the compounds, and the corresponding relative response factor can be used.

[0065] (Section 5) In the quantitative determination apparatus for brominated flame retardant compounds according to any one of claims 1 to 4, The predetermined condition is to perform chromatographic analysis and / or mass spectrometry.

[0066] In the quantitative determination device for brominated flame retardant compounds described in paragraph 5, in the case of chromatographic analysis, the measurement intensities of the standard compound and the reference compound can be obtained separately by separating them inside a column, and in the case of mass spectrometry, the measurement intensities of the standard compound and the reference compound can be obtained separately by detecting ions with different mass-to-charge ratios that are characteristic of each compound.

[0067] (Section 6) 6. The quantitative determination apparatus for brominated flame retardant compounds according to any one of claims 1 to 5, The predetermined conditions include performing the chromatographic analysis using a non-polar column.

[0068] The quantitative determination device for brominated flame retardant compounds described in paragraph 6 can simultaneously analyze polybrominated biphenyl compounds and polybrominated diphenyl ether compounds by using a non-polar column.

[0069] (Section 7) 7. The quantitative determination apparatus for brominated flame retardant compounds according to any one of claims 1 to 6, The predetermined conditions include performing mass spectrometry; the relative response factor is associated with each of a plurality of combinations of the mass-to-charge ratio of the standard compound and the mass-to-charge ratio of the reference compound; The analysis target sample measurement section receives an input for selecting one of the plurality of combinations, and performs mass spectrometry using the input combination.

[0070] The quantitative determination device for brominated flame retardant compounds described in paragraph 7 can obtain the measured intensities of these compounds by measuring ions with mass-to-charge ratios characteristic of the standard compound and the reference compound, respectively.

[0071] (Section 8) In the quantitative determination apparatus for brominated flame retardant compounds according to any one of claims 1 to 7, The target compounds further include one or more compounds other than the polybrominated biphenyl compound group and the polybrominated diphenyl ether compound group.

[0072] The quantitative measurement device for brominated flame retardant compounds described in paragraph 8 can quantify compounds other than PBBs and PBDEs.

[0073] (Section 9) 9. The quantitative determination apparatus for brominated flame retardant compounds according to any one of claims 1 to 8, The one or more compounds include any one of a phthalate ester compound group, tetrabromobisphenol A, and hexabromocyclododecane.

[0074] The quantitative determination device for brominated flame retardant compounds described in Section 9 can efficiently screen samples to be analyzed in accordance with the RoHS Directive and other chemical substance regulations.

[0075] (Section 10) In the quantitative determination apparatus for brominated flame retardant compounds according to any one of claims 1 to 9, moreover, a screening unit for determining whether or not the quantitative value of the standard compound and / or the quantitative value of the reference compound is within a predetermined range; Equipped with.

[0076] The quantitative determination device for brominated flame retardant compounds described in paragraph 10 enables easy screening of samples to be analyzed without the need for judgment by the user.

[0077] (Section 11) In the quantitative determination apparatus for brominated flame retardant compounds according to any one of claims 1 to 10, the storage unit stores relative response coefficients of one of the plurality of reference compounds with respect to the other reference compounds; moreover, a relative response coefficient evaluation unit that evaluates the validity of the relative response coefficient by comparing the amount of the one reference compound contained in the standard sample, the measurement intensity of the one reference compound and the measurement intensities of the other reference compounds obtained by the standard sample measurement unit, and the quantitative values ​​of the other reference compounds calculated based on the relative response coefficients of the other reference compounds with the amounts of the other reference compounds contained in the standard sample; Equipped with.

[0078] The quantitative determination device for brominated flame retardant compounds described in paragraph 11 can accurately determine the amount of target compounds after confirming the suitability of the relative response factor. [Explanation of symbols]

[0079] 1, 100... Pyrolyzer gas chromatograph mass spectrometer (Py-GC-MS) 10...Gas chromatograph section 11...Sample vaporizer 12. Pyrolyzer 13...Carrier gas flow path 14…Column 15…Column oven 20…Mass spectrometry department 21…Vacuum chamber 22...Electron ionization source 23…Ion lens 24...Quadrupole mass filter 25…Ion detector 30...Control and processing section 31...Storage section 32...Standard sample measurement section 33…Retention index calculation unit 34...Relative response coefficient calculation section 35…Database Creation Department 40...Control and processing section 41...Storage section 411...Relative response factor database 42...Reference compound determination section 43...Standard sample measurement section 44…Relative response factor evaluation section 45…Analysis sample measurement section 46...Reference compound determination section 47...Reference compound determination section 48…Screening Section 49…Database Update Division

Claims

1. a memory unit in which a relative response coefficient is stored, the relative response coefficient representing the relationship between an intensity per unit amount of a reference compound, which is one of a plurality of target compounds that are some or all of a group of polybrominated biphenyl compounds and a group of polybrominated diphenyl ether compounds, measured by a predetermined analytical method under predetermined conditions, and an intensity per unit amount of a reference compound, which is a target compound other than the reference compound, measured by the predetermined analytical method under the predetermined conditions; an analytical device for measuring a sample by the predetermined analytical method; a standard sample measurement unit that measures a standard sample containing a known amount of the reference compound under the predetermined conditions using the analytical device to obtain an intensity of the reference compound; an analyte sample measurement unit that measures an analyte sample under the predetermined conditions using the analytical device to obtain intensities of the standard compound and the reference compound contained in the analyte sample; a reference compound quantification unit that determines a quantitative value of the reference compound contained in the analysis target sample based on the amount of the reference compound contained in the standard sample, the intensity of the reference compound obtained by the standard sample measurement unit, and the intensity of the reference compound obtained by the analysis target sample measurement unit; a reference compound quantification unit that determines a quantitative value of the reference compound based on the amount of the reference compound contained in the standard sample, the intensity of the reference compound obtained by the standard sample measurement unit, the intensity of the reference compound obtained by the analysis target sample measurement unit, and a relative response coefficient of the reference compound; The quantitative determination apparatus for brominated flame retardant compounds is provided.

2. The apparatus for quantifying brominated flame retardant compounds according to claim 1, wherein the reference compounds are Tetra-BDE, Penta-BDE, Deca-BDE, and Deca-BB.

3. The relative response factors of Mono-BDE, Di-BDE, Tri-BDE, Mono-BB, Di-BB, Tri-BB, and Tetra-BB are stored with Tetra-BDE as the reference compound. The relative response factors of Hexa-BDE, Hepta-BDE, Penta-BB, Hepta-BB, and Hepta-BB are stored with Penta-BDE as the reference compound. The relative response factors of Octa-BDE and Nona-BDE are stored with Deca-BDE as the reference compound.

3. The apparatus for quantifying brominated flame retardant compounds according to claim 2, wherein the relative response factors of Octa-BB and Nona-BB are stored using Deca-BB as a reference compound.

4. For each of the plurality of different predetermined conditions, The quantitative determination device for a brominated flame retardant compound according to any one of claims 1 to 3, further comprising a relative response coefficient representing the relationship between the intensity per unit amount of the reference compound and the intensity per unit amount of the standard compound, the relative response coefficient being stored.

5. 5. The quantitative determination apparatus for brominated flame retardant compounds according to claim 1, wherein the predetermined condition is to perform chromatographic analysis and / or mass spectrometry.

6. 6. The apparatus for quantifying brominated flame retardant compounds according to claim 1, wherein the predetermined conditions include performing a chromatographic analysis using a non-polar column.

7. The predetermined conditions include performing mass spectrometry; the relative response factor is associated with each of a plurality of combinations of the mass-to-charge ratio of the standard compound and the mass-to-charge ratio of the reference compound; The analysis target sample measurement unit receives an input for selecting one of the plurality of combinations and performs mass spectrometry using the input combination. The quantitative determination apparatus for a brominated flame retardant compound according to any one of claims 1 to 4.

8. 8. The quantitative determination apparatus for brominated flame retardant compounds according to claim 1, wherein the target compounds further include one or more compounds other than the polybrominated biphenyl compound group and the polybrominated diphenyl ether compound group.

9. 9. The quantitative determination apparatus for brominated flame retardant compounds according to claim 8, wherein the one or more compounds include any one of a phthalate ester compound group, tetrabromobisphenol A, and hexabromocyclododecane.

10. moreover, a screening unit for determining whether or not the quantitative value of the standard compound and / or the quantitative value of the reference compound is within a predetermined range; The quantitative determination apparatus for a brominated flame retardant compound according to claim 1 , comprising:

11. the storage unit stores relative response coefficients of one of the plurality of reference compounds with respect to the other reference compounds; a relative response coefficient evaluation unit that evaluates the validity of the relative response coefficient by comparing the amount of the one reference compound contained in the standard sample, the measurement intensity of the one reference compound and the measurement intensities of the other reference compounds obtained by the standard sample measurement unit, and the quantitative values ​​of the other reference compounds calculated based on the relative response coefficients of the other reference compounds with the amounts of the other reference compounds contained in the standard sample; The quantitative determination apparatus for a brominated flame retardant compound according to any one of claims 2 to 10, comprising:

Images