JP2012037385A - Method and program for determining bromine-based flame retardant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and program for determining bromine-based flame retardants, which are capable of easily and quickly discriminating between PBB being substances prohibited by the RoHS and TBBPA not being substances prohibited by the RoHS.SOLUTION: The method for determining the bromine-based flame retardants is executed in a data analyzer for analyzing data obtained by an ion attachment type mass spectrometer and includes a first determination step and a determination step. In the first determination step, first determination means determines whether a first peak intensity ratio being a ratio of a peak intensity for a second mass number to a peak intensity for a first mass number is within a first range or not. In the determination step, determination means determines that a sample being a target to be inspected contains the bromine-based flame retardant not being prohibited by the RoHS if the first peak intensity ratio is within the first range.

Description

  Embodiments described herein relate generally to a brominated flame retardant determination method and program.

  The usage amount of hazardous substances contained in electronic equipment and electrical equipment is regulated by the RoHS Directive (Restriction on Hazardous Substances, Directive on Restricting Use of Specific Hazardous Substances contained in Electrical / Electronic Equipment).

  A brominated flame retardant, polybromobiphenyl (PBB), is a regulated substance of the RoHS Directive, and is currently hardly used in electronic devices manufactured in Japan. On the other hand, tetrabromobisphenol A-2, 3-dibromopropyl ether (TBBPA), which is a non-regulated substance, is widely used in products such as electronic devices as a brominated flame retardant instead of PBB. Electronic equipment manufactured at the factory needs to be measured before shipping for substances subject to the RoHS directive, but since PBB and TBBPA are very similar in mass number, simple analysis It is said that the method is difficult to identify.

  Conventionally, in order to distinguish between PBB and TBBPA, gas chromatograph mass spectrometry (GC / MS) (see Patent Document 1) or liquid chromatograph mass spectrometry (LC / MS) defined by the RoHS directive The measurement by (refer patent document 2) is used. In these GC / MS and LC / MS measurements, regulated substances can be detected quantitatively with high accuracy, but on the other hand, sample pretreatment is complicated, such as the sample must be dissolved in an organic solvent. Inspection time and inspection cost will be required. Therefore, it can be said that it is not suitable as a screening test used for all product inspections.

  Therefore, in recent years, inspection measurement by ion attachment mass spectrometry (IAMS) has attracted attention as a measurement method used for screening inspection (see Patent Document 3). In IAMS measurement, complicated pretreatment such as sample dissolution is unnecessary, and a solid sample can be used for measurement as it is, so that the inspection time and inspection cost can be reduced compared with GC / MS measurement and LC / MS measurement. It is possible. However, since the IAMS measurement is not the final inspection method defined by the RoHS command, if PBB is detected, it is precisely again by the GC / MS measurement or LC / MS measurement defined as the final inspection method by the RoHS command. Need to be inspected. However, when TBBPA is detected, it can be determined that the inspection has passed because the LoHS regulation has been cleared, so that it is possible to efficiently perform a pass determination for a product that satisfies the criteria.

  In IAMS measurement, scan measurement is performed to detect ions over a wide range of mass numbers. When a peak is detected near the mass number of the PBB in scan measurement, profile measurement that is a high resolution mode or SIM (Selected Ion Monitoring) measurement that performs measurement in a high resolution mode by limiting the mass number range is performed. Done.

JP 2010-66048 A JP 2007-85776 A JP 2008-164383 A

  However, when PBB and TBBPA are identified by IAMS measurement, after performing scan measurement, SIM measurement or profile measurement must be performed, and the measurement becomes two steps, which complicates the inspection work, and the inspection takes time. There is such a problem.

  This invention is made in view of the above, Comprising: The determination method of the brominated flame retardant which can identify easily and rapidly PBB which is a RoHS regulation subject substance, and TBBPA which is not a RoHS regulation subject substance, and The purpose is to provide a program.

  The method for determining a brominated flame retardant according to the embodiment is a method for determining a brominated flame retardant that is executed by a data analysis device that analyzes data obtained by an ion attachment mass spectrometer, and is determined as a first determination step. Process. In the first determination step, whether or not the first peak intensity ratio, which is the ratio of the peak intensity at the second mass number to the peak intensity at the first mass number, is within the first range. Determine whether. In the determination step, when the first peak intensity ratio is within the first range, the determination unit determines that the sample as the object to be inspected contains a brominated flame retardant that is not a restriction target.

  In addition, the program of the embodiment causes a computer that analyzes data obtained by the ion attachment mass spectrometer to function as a first determination unit and a determination unit. The first determination means determines whether or not a first peak intensity ratio that is a ratio of the peak intensity at the second mass number to the peak intensity at the first mass number is within the first range. When the first peak intensity ratio is within the first range, the determination unit determines that the sample that is the object to be inspected contains a brominated flame retardant that is not a restriction target.

FIG. 1 is a schematic diagram showing the configuration of the mass spectrometer of the present embodiment. FIG. 2 is an enlarged schematic view of the tip of the direct probe. FIG. 3 is a block diagram showing the configuration of the data analysis apparatus. FIG. 4 is a spectral pattern of IAMS calculated theoretically for PBB. FIG. 5 is a spectral pattern of IAMS calculated theoretically for TBBPA. FIG. 6 is a graph in which the peak intensity ratio of other peaks is plotted with respect to each mass number, with the peak intensity at a mass number of 950 m / z set to 1 for each substance. FIG. 7 is a distribution diagram showing the distribution of the peak intensity ratio I ₉₅₁ / I ₉₅₀ in PBB and TBBPA. FIG. 8 is a distribution diagram showing the distribution of the peak intensity ratio I ₉₅₄ / I ₉₅₃ in PBB and TBBPA. FIG. 9 is a flowchart for explaining a discrimination process between PBB and TBBPA performed by the data analysis apparatus according to the present embodiment. FIG. 10 is a block diagram illustrating a functional configuration of the data analysis apparatus.

<Mass spectrometer>
FIG. 1 is a schematic diagram illustrating a configuration of an ion attachment mass spectrometer 1 (hereinafter referred to as a mass spectrometer 1) according to the present embodiment. As shown in FIG. 1, the mass spectrometer 1 is provided with an ionization chamber 2, a mass analysis chamber 4, and a differential exhaust chamber 3 provided between the ionization chamber 2 and the mass analysis chamber 4. Yes. The ionization chamber 2 and the differential exhaust chamber 3 are partitioned by a partition plate 5, and the differential exhaust chamber 3 and the mass spectrometry chamber 4 are partitioned by a partition plate 6. In addition, opening portions 7 and 8 are provided in the central portions of the partition plates 5 and 6, and the detection gas can move between the chambers through the opening portions 7 and 8.

A vacuum pump 16 such as a turbo molecular pump is connected to the differential evacuation chamber 3 and the mass spectrometry chamber 4, and each chamber is adjusted until the pressure in each chamber reaches a predetermined pressure by adjusting a gate valve or the like. Exhaust the gas. As a specific example, the mass spectrometry chamber 4 is exhausted to 10 ⁻³ Pa, and the differential exhaust chamber 3 is exhausted to about 0.1 Pa to 1 Pa.

The differential exhaust chamber 3 is provided to connect or block the space of the ionization chamber 2 that is 10 Pa to 1000 Pa and the space of the high-vacuum mass analysis chamber 4 that is 1 × 10 ⁻³ Pa or less. When the gas in the differential evacuation chamber 3 is evacuated by the vacuum pump 16, the ionization chamber 2 is also evacuated through the opening 7, thereby reducing the pressure of the ionization chamber 2 to about 100 Pa. As a result, a pressure difference is generated between the ionization chamber 2 and the differential exhaust chamber 3, and the gas in the ionization chamber 2 flows out into the differential exhaust chamber 3.

  A direct probe 9 for holding the sample container 10 is connected to the ionization chamber 2. The sample container 10 can store an analysis sample or an analysis standard sample corresponding to the substance to be detected (hereinafter referred to as a sample unless otherwise specified).

  FIG. 2 is an enlarged schematic view of the tip portion of the direct probe 9. As shown in FIG. 2, a plurality of sample containers 10 can be installed in the direct probe 9, and after the analysis of one sample is completed, the direct probe 9 is slid by a predetermined distance, Analysis of another sample can continue. The sample to be analyzed may be cut into a size that fits in the sample container 10 and placed in the sample container 10, and complicated pretreatment such as dissolution in an acidic solution is unnecessary.

  The direct probe 9 is provided so as to be removable from the ionization chamber 2. When setting a sample, the direct probe 9 is pulled out from the ionization chamber 2 and the sample is placed in the sample container 10, and then directly. After inserting the probe 9 into the ionization chamber 2, the vacuum pump 16 is operated to perform evacuation. Thereby, the sample can be set without exposing the ionization chamber 2 to the atmosphere, and the degree of vacuum in the ionization chamber 2 and other chambers can be kept high.

  As shown in FIG. 1, the ionization chamber 2 includes a heating mechanism 11 that heats the sample container 10. For example, an infrared lamp or an infrared laser can be used as the heating mechanism 11. When the sample is heated by the heating mechanism 11, the components of the sample are vaporized, and a gas corresponding to the components is generated from the sample.

  An ion emitter 12 is provided in the ionization chamber 2, and a filament 13 for heating the ion emitter 12 is provided in the vicinity of the ion emitter 12. When a current is passed through the filament 13 to increase the temperature and the ion emitter 12 is heated, metal ions (for example, lithium ions (Li +)) are released from the ion emitter 12 into the ionization chamber 2.

  The metal ions emitted by the ion emitter 12 are not limited to Li +, and other examples include potassium ions (K +), sodium ions (Na +), rubidium ions (Rb +), cesium ions (Cs +), Aluminum ions (Al +), gallium ions (Ga +), indium ions (In +), or the like may be emitted.

  The released metal ions adhere to the gas generated from the sample and become an ionization detection gas (charged particle). The components of the analysis sample to which the metal ions are attached are discharged from the ion emitter 12 in the horizontal direction as charged particles having a charge, and proceed into the mass analysis chamber 4.

  The mass spectrometer 4 includes a mass spectrometer 15. In FIG. 1, a quadrupole (Q-pole) mass spectrometer is shown as the mass spectrometer 15. However, the type of the mass spectrometer 15 is not limited to this, and a magnetic field deflection type and a time-of-flight type are used. Other types of mass spectrometers such as (TOF) may be used. The mass spectrometer 15 detects the detection intensity for each mass number of charged particles (ionized detection gas) flying into the mass analysis chamber 4.

  The mass spectrometer 1 according to the present embodiment includes a data analyzer 20 that analyzes a mass spectrum measured by the mass spectrometer 1.

  FIG. 3 is a block diagram illustrating a configuration of the data analysis apparatus 20. The data analysis device 20 has a hardware configuration using a normal computer. As shown in FIG. 3, the data analysis device 20 includes a control device such as a CPU 31, a storage device such as a ROM (Read Only Memory) 32 and a RAM 33, an external storage device such as an HDD 34 and a CD drive device 35, and a display device. A display device such as 36, an input device such as a keyboard 37 and a mouse 38, and various interfaces (I / F) 39 are mainly provided, and these are connected via a bus 40.

  Further, the data analysis device 20 is connected to the vacuum pump 16 of the mass spectrometer 1, the gate valve (not shown), the heating mechanism 11, the ion emitter 12, the filament 13, the apertures 7 and 8 through the I / F 39. It is connected to the electrolens 14, the mass spectrometer 15, etc., and also functions as a control device for controlling them.

  The data analysis device 20 and the control device may be provided separately. For example, a general personal computer may be used as the data analysis device 20 separately from the control device connected to the mass spectrometer 1. In this case, the data analyzer 20 and the mass spectrometer 1 do not have to be connected, and the spectrum data measured by the mass spectrometer 1 is stored in the HDD of the data analyzer 20 by a communication line such as a storage medium or a LAN. The data analysis and the determination process of this embodiment may be performed.

<Method for judging brominated flame retardant>
(1) Difference in Peak Intensity Ratio in Spectrum Patterns of PBB and TBBPA Next, analysis results of spectrum patterns of PBB and TBBPA, which are the basis for the method for determining a brominated flame retardant according to the present embodiment, will be described. In order to distinguish between PBB and TBBPA by spectral pattern, the inventors have determined that the natural abundance ratio of bromine (Br) isotope ⁷⁹ Br (0.5069) and ⁸¹ Br (0.4931) Based on the above, the spectral pattern obtained by the scan measurement of IAMS measurement was theoretically calculated.

  FIG. 4 is an IAMS spectrum pattern theoretically calculated for Deca-BB as an example of PBB. FIG. 5 is an IAMS spectrum pattern theoretically calculated for TBBPA. 4 and 5, the peak intensity ratio of other peaks is plotted with respect to each mass number with the peak intensity having a mass number of 950 m / z being 1.

  As shown in FIG. 4 and FIG. 5, it was found from the calculation results that the spectral patterns of PBB and TBBPA have different shapes. For example, as shown in FIGS. 4 and 5, PBB and TBBPA have different intensity ratios of the peak intensity at a mass number of 951 m / z to the peak intensity at a mass number of 950 m / z. In addition, PBB and TBBPA have different intensity ratios of the peak intensity at a mass number of 954 m / z to the peak intensity at a mass number of 953 m / z.

  FIG. 6 is a graph obtained by plotting the peak intensity ratio of other peaks with respect to each mass number, assuming that the peak intensity at a mass number of 950 m / z is 1 for a substance containing PBB or TBBPA. PBB (PS) is a sample prepared by mixing a predetermined amount of PBB with a polystyrene (PS) resin, and PBB (PE) is a sample prepared by mixing a predetermined amount of PBB with a polyethylene (PE) resin. It is. Similarly, TBBPA (PS) and TBBPA (PE) are samples prepared by mixing a predetermined amount of TBBPA with PS resin and PE resin, respectively.

  As shown in FIG. 6, when the mass numbers are 948 m / z, 950 m / z, 952 m / z, and 954 m / z, there is not much difference in peak intensity ratio between PBB and TBBPA. On the other hand, at mass numbers of 949 m / z, 951 m / z, and 953 m / z, there is a difference in peak intensity ratio between PBB and TBBPA.

  Therefore, the inventors used a sample containing PBB and TBBPA to investigate whether there is a significant difference between the peak intensity ratio in PBB and the peak intensity ratio in TBBPA at a predetermined mass number. A t-test, which is one of statistical methods, was performed.

FIG. 7 shows the distribution (t distribution) of the peak intensity ratio I ₉₅₁ / I ₉₅₀ which is the ratio of the peak intensity I _{951 with} a mass number of 951 m / z to the peak intensity I _{950 with} a mass number of ₉₅₀ m / z in each of PBB and TBBPA. FIG. A1 and A4 shown in FIG. 7 indicate the average values of the peak intensity ratios I ₉₅₁ / I ₉₅₀ in PBB and TBBPA, respectively.

As shown in FIG. 7, the distribution of the peak intensity ratio I ₉₅₁ / I ₉₅₀ in TBBPA extends over a wide range from about 0.55 to 1.1, but the distribution of the peak intensity ratio I ₉₅₁ / I ₉₅₀ in PBB. Is substantially smaller than the threshold value Sh1.

That is, when the value of the peak intensity ratio I ₉₅₁ / I ₉₅₀ is larger than the threshold value Sh1, the brominated flame retardant contained in the sample is highly likely TBBPA and is unlikely to be PBB.

FIG. 8 shows the distribution (t distribution) of the peak intensity ratio I ₉₅₄ / I ₉₅₃ , which is the ratio of the peak intensity I _{954 with} a mass number of 954 m / z to the peak intensity I _{953 with} a mass number of 953 m / z in each of PBB and TBBPA. It is a distribution map showing. A2 and A3 shown in FIG. 8 indicate average values of the peak intensity ratios I ₉₅₄ / I ₉₅₃ in PBB and TBBPA, respectively.

As shown in FIG. 8, the distribution of the peak intensity ratio I ₉₅₄ / I ₉₅₃ in TBBPA extends over a wide range from about 0.5 to about 1.5, but the peak intensity ratio I ₉₅₄ / I _{953 in} PBB. Is within a value larger than the threshold value Sh3. Further, although not 100%, the peak intensity ratio I ₉₅₄ / I ₉₅₃ in PBB is almost within a value larger than the threshold value Sh2.

That is, when the value of the peak intensity ratio I ₉₅₄ / I ₉₅₃ is equal to or less than the threshold value Sh2, the brominated flame retardant contained in the sample is likely to be TBBPA and is unlikely to be PBB.

Further, when the value of the peak intensity ratio I ₉₅₄ / I ₉₅₃ is not more than the threshold value Sh3, the brominated flame retardant contained in the sample may be TBBPA more than the case where the peak intensity ratio I ₉₅₄ / I ₉₅₃ is not more than the threshold value Sh2. Higher and less likely to be PBB.

Therefore, for example, by determining a value such as the peak intensity ratio I ₉₅₁ / I ₉₅₀ or the peak intensity ratio I ₉₅₄ / I ₉₅₃ , whether the spectrum near the mass number of 950 m / z is a spectrum based on PBB or TBBPA. Can be identified. Thereby, it is possible to determine whether or not there is a possibility of containing PBB, which is a brominated flame retardant subject to restriction, with respect to a sample that is an object to be inspected.

(2) Determination method of this embodiment The determination method of the brominated flame retardant according to this embodiment is executed when the data analysis device 20 executes the program according to this embodiment.

  FIG. 10 is a block diagram showing a functional configuration of the data analysis apparatus 20. As actual hardware, the CPU 31 reads out the program according to the present embodiment from the ROM 32 to the RAM 33 and executes it, so that the first determination unit 21, the second determination unit 22, and the third determination are performed as shown in FIG. The control unit 30 including the unit 23 and the PBB determination unit 24 is generated on the main storage device.

  The program executed by the data analysis apparatus 20 of the present embodiment is a file in an installable format or an executable format and is a computer such as a CD-ROM, a flexible disk (FD), a CD-R, a DVD (Digital Versatile Disk). Recorded on a readable recording medium.

  In addition, the program executed by the data analysis apparatus 20 of the present embodiment may be stored on a computer connected to a network such as the Internet and provided by being downloaded via the network. Further, the program executed by the data analysis device 20 of the present embodiment may be configured to be provided or distributed via a network such as the Internet. Further, the program of this embodiment may be configured to be provided by being incorporated in advance in a ROM or the like.

The first determination unit 21, in the first determination step, to the peak intensity _{I 950} at mass numbers 950 meters / z (first mass number), mass number 951M / z peak intensity _{I 951} of the (second mass number) It is determined whether or not the value of the first peak intensity ratio I ₉₅₁ / I ₉₅₀ , which is the ratio, is within the first range, that is, greater than the threshold value Sh 1.

When the first peak intensity ratio I ₉₅₁ / I ₉₅₀ is larger than the threshold value Sh1 in the determination step, the PBB determination unit 24 is a TBBPA that is not a regulated substance according to the RoHS directive when the brominated flame retardant contained in the sample is It is determined that there is no possibility of containing PBB, which is a regulated substance.

In a preferred embodiment, the threshold value Sh1 is preferably set to a value in the range of 0.4 to 0.7. As a more preferable embodiment, for example, 0.65 is used as the threshold value Sh1 as a value obtained by adding twice the standard deviation σ to the average value A1 of the peak intensity ratio I ₉₅₁ / I _{950 in} the sample including PBB. More preferred.

  As shown in FIG. 6, there are a plurality of mass numbers having different peak intensity ratios between PBB and TBBPA. Therefore, as a preferred embodiment, in addition to the first determination step using the first peak intensity ratio, the second determination step is performed using a second peak intensity ratio that is different from the first peak intensity ratio. It is preferable to determine whether or not PBB is included in two stages.

The second determination unit 22, in the second determination step, to the peak intensity _{I 953} at mass number 953m / z (third mass number), mass number 954m / z peak intensity _{I 954} of (Fourth mass number) It is determined whether or not the value of the second peak intensity ratio I ₉₅₄ / I ₉₅₃ that is the ratio is equal to or less than the threshold value Sh2 (within the second range).

Then, the PBB determination unit 24 determines whether the first peak intensity ratio I ₉₅₁ / I ₉₅₀ is greater than the threshold value Sh1 and the second peak intensity ratio I ₉₅₄ / I ₉₅₃ is equal to or less than the threshold value Sh2 in the determination step. It is determined that the brominated flame retardant contained in is TBBPA that is not a regulated substance according to the RoHS directive, and there is no possibility of containing PBB that is a regulated substance.

In a preferred embodiment, the threshold value Sh2 is preferably set to a value in the range of 1.0 or more and 1.5 or less. In a more preferred embodiment, for example, 1.1 is preferably used as the threshold value Sh2 as a value obtained by subtracting the standard deviation σ from the average value A2 of the peak intensity ratio I ₉₅₄ / I _{953 in} the sample containing PBB.

As shown in FIG. 8, the threshold for determining the presence or absence of PBB is not limited to one for the same peak intensity ratio (for example, I ₉₅₄ / I ₉₅₃ ), and has a high probability of not being a PBB. A plurality can be set according to the size. Therefore, as a preferred embodiment, it is preferable to further set a range that is narrower than the second range and has a higher probability of not being the PBB than the second range as the third range.

In the third determination step, the third determination unit 23 determines whether or not the value of the second peak intensity ratio I ₉₅₄ / I ₉₅₃ is within the third range, that is, whether or not it is less than or equal to the threshold value Sh3. .

In the determination step, the PBB determination unit 24 determines whether the second peak intensity ratio I ₉₅₄ / I ₉₅₃ is less than or equal to the threshold value Sh3 even if the first peak intensity ratio I ₉₅₁ / I ₉₅₀ is outside the first range. It is determined that the brominated flame retardant contained in is TBBPA and there is no possibility of containing PBB.

In a preferred embodiment, the threshold value Sh3 is preferably set to a value in the range of 0.9 to 1.0. That is, it is preferable that the third range set by the threshold Sh3 has a lower probability of being a PBB than the second range set by the threshold Sh2. In a more preferred embodiment, the threshold value Sh3 is a value obtained by subtracting twice the standard deviation σ from the average value A2 of the second peak intensity ratio I ₉₅₄ / I ₉₅₃ in the sample including PBB, and in the sample including TBBPA. As a value obtained by adding the standard deviation σ to the average value A3 of the second peak intensity ratio I ₉₅₄ / I ₉₅₃ , for example, 0.96 is more preferably used.

  As a result, even if it is determined that “there is a possibility of PBB” in the first determination step under relatively strict determination conditions, it is determined that “there is no possibility of being PBB” by the third determination step. It can be repaired and the sample can be determined to have passed the inspection. Therefore, it can be determined that the sample that does not contain more PBB has passed the RoHS regulation, and the number of detailed inspections by the GC / MS method or the like can be further reduced.

(3) Procedure of PBB and TBBPA Discriminating Step Next, the procedure of the PBB and TBBPA discriminating step performed by the data analysis apparatus 20 of the present embodiment will be described. FIG. 9 is a flowchart for explaining a discrimination process between PBB and TBBPA performed by the data analysis apparatus 20 of the present embodiment.

  First, the direct probe 9 is pulled out from the ionization chamber 2 as described above, and a sample to be investigated whether or not PBB is contained is placed on the sample container 10. After inserting the direct probe 9 into the ionization chamber 2, The vacuum pump 16 is operated. (Sample setting)

  Then, the data analysis device 20 performs scan measurement on the sample (step S1). The scan measurement is a qualitative analysis measurement in which the mass number is roughly scanned (scanned) over a wide range (for example, 2 m / z to 1000 m / z). Specifically, whether the component of each mass number is detected by shortening the detection time per mass number or reducing the mass number resolution to, for example, 1 m / z and scanning the mass numbers in the above range. Qualitatively check whether or not. Although the scan measurement has low resolution, the presence or absence of ions of each mass number can be inspected at high speed over a wide range.

  Here, the mass number of PBB is 943.1 m / z, and the mass number when Li + having a mass number of 7 is attached is 950.1 m / z. On the other hand, the mass number of TBBPA is 943.6 m / z, and the mass number when Li + adheres is 950.6 m / z. Therefore, when PBB or TBBPA is detected, a peak is detected in the vicinity of 950 m / z. Therefore, first, in order to determine whether or not a detection intensity peak is detected in the vicinity of 950 m / z, a sample scan measurement is performed in step S1. In the scan measurement, since the resolution of the mass number is lowered to 1 m / z as described above, it is not possible to discriminate between PBB and TBBPA having a mass number difference of 0.5 only by the mass number difference. .

  Then, the data analysis device 20 determines whether or not a peak is detected at a mass number of 950 m / z by reading the detected intensity of each mass number into a storage area and analyzing it (step S2). If no peak is detected at a mass number of 950 m / z (step S2: No), the spectrum in the vicinity of the mass number of 950 m / z is based on TBBPA and does not contain PBB, which is a RoHS regulated substance. Therefore, the inspection result is passed (step S9).

On the other hand, when a peak is detected at a mass number of 950 m / z (step S2: Yes), the peak intensities I ₉₅₀ , I ₉₅₁ , I ₉₅₃ , and I ₉₅₄ are read from the spectrum data obtained by the scan measurement (step S 2: Yes) S11).

Then, it is determined whether the first peak intensity ratio I ₉₅₁ / I ₉₅₀ is greater than the threshold value Sh1 of 0.65 (step S12). If it is larger than the threshold value Sh1 (step S12: Yes), it is determined whether the second peak intensity ratio I ₉₅₄ / I ₉₅₃ is 1.1 or less of the threshold value Sh2 (step S15). When the threshold is Sh2 or less (step S15: Yes), it is determined that the spectrum in the vicinity of the mass number 950 m / z is based on TBBPA, and there is no possibility that the sample includes PBB (step S9). ).

On the other hand, if it is equal to or less than the threshold value Sh1 (step S12: No), it is determined whether the second peak intensity ratio I ₉₅₄ / I ₉₅₃ is equal to or less than 0.96 of the threshold value Sh3 (step S13). When the threshold value is less than or equal to the threshold Sh3 (step S13: Yes), it is determined that the spectrum in the vicinity of the mass number 950 m / z is based on TBBPA, and the sample is unlikely to contain PBB, and the determination is acceptable (step S9). ). If the threshold value Sh3 is greater than the threshold value Sh3 (step S13: No), it is determined that the sample may include PBB, and gray determination is performed (step S14).

  As described above, according to the present embodiment, PBB and TBBPA can be identified only by performing scan measurement (step S1 in FIG. 9) which is qualitative analysis measurement without using a standard sample. Therefore, there is an effect that it is possible to easily and quickly discriminate between PBB, which is a RoHS regulated substance, and TBBPA, which is not a RoHS regulated substance. Further, in the present embodiment, since the ion attachment mass spectrometer generally used conventionally can be used as it is, the above-described effects can be obtained without changing the apparatus.

  In a preferred embodiment, it is preferable to calibrate the mass spectrometer 15 using PBB and TBBPA standard substances before performing scan measurement. Thereby, the shift | offset | difference of the peak position with respect to mass number can be suppressed to less than 0.5 m / z, and a peak intensity ratio can be calculated correctly. Note that this calibration need not be performed every scan measurement, and may be performed every time the mass spectrometer 1 is started.

In the above description, after determining the value of the first peak intensity ratio I ₉₅₁ / I ₉₅₀ in the first determination step, the value of the second peak intensity ratio I ₉₅₄ / I ₉₅₃ is determined in the second determination step. However, the order of the determination steps is not limited to this. For example, the second determination step may be performed first, followed by the first determination step.

In the above description, the first peak intensity ratio is I ₉₅₁ / I ₉₅₀ and the second peak intensity ratio is I ₉₅₄ / I ₉₅₃ , but the first peak intensity ratio and the second peak intensity ratio are I ₉₅₁ / I _950. , I ₉₅₄ / I ₉₅₃ is not limited. The first peak intensity ratio may be I ₉₅₄ / I ₉₅₃ , the second peak intensity ratio may be I ₉₅₁ / I ₉₅₀ , and the peak intensity at other mass numbers is taken to obtain a new peak intensity ratio as the first peak intensity ratio. Ratio or the second peak intensity ratio.

  In the above description, the two determination steps are performed by the first determination step and the second determination step, but the number of determination steps is not limited to this. As described above, the determination based on other peak intensity ratios may be further performed to perform a determination process of three or more stages.

  Examples will be shown below to describe the present embodiment in more detail, but the present invention is not limited to the examples. Reference numerals correspond to the configuration of the mass spectrometer 1 described with reference to FIGS. 1 and 2.

(1) Preparation of PBB-containing sample PBB is not used in currently manufactured products. Therefore, a PBB (DeBB) reagent is dropped onto a resin powder such as PS or PE, and this mixed powder is used as a PBB-containing sample. Housed in a sample container 10. Twenty PBB-containing samples were produced.

(2) Production of TBBPA-containing sample TBBPA-containing samples were produced by two types of production methods. As a first type, a reagent of TBBPA (TBBPA-bis (2,3-dibromopropylene)) was dropped onto a resin powder such as PS or PE, and this mixed powder was stored in a sample container 10 as a TBBPA-containing sample. As the second type, a part of a product such as an electronic device in which TBBPA (TBBPA-bis (2,3-dibromopropyther)) is included in the resin portion can be prepared and accommodated in the sample container 10 The sample was cut into a size to obtain a TBBPA-containing sample. In addition, 60 TBBPA containing samples were produced.

(3) IAMS scan measurement The sample produced as described above was subjected to scan measurement and a brominated flame retardant determination step according to the present embodiment. The temperature raising condition of the heating mechanism 11 is that the temperature is raised at a rate of 128 ° C./min from an initial temperature of 10 ° C. to 170 ° C., and the temperature is raised at a rate of 64 ° C./min from 170 ° C. to a measured temperature of 290 ° C. The temperature was increased at a rate. After maintaining at 290 ° C. for 2.5 minutes, the ion emitter 12 and the filament 13 were operated to start scan measurement. The ion source temperature was 210 ° C.

(4) Inspection results Tables 1 to 4 show the results obtained. In the table, the gray determination is a determination that “PBB may be included”. Further, the pass determination is a determination that “there is no possibility of including PBB”.

  Table 1 is a table | surface which shows the determination result with respect to a PBB containing sample. As shown in Table 1, in this example, all 20 samples were determined to be gray. Therefore, PBB could be detected with a 100% inspection accuracy for the PBB-containing sample.

  Table 2 thru | or Table 4 is a table | surface which shows the determination result with respect to a TBBPA containing sample. In this example, four sample numbers 33, 36, 52, and 57 were erroneously determined to be gray determinations, but the other 56 samples other than these four samples were determined to be pass determinations. Therefore, 56 pieces out of 60 pieces could be correctly judged, and the judgment accuracy could be 93%.

  In the present embodiment, as described above, about 90% of the TBBPA-containing samples could be determined as TBBPA instead of PBB. Therefore, in this embodiment, only about 10% of mis-judged samples may be subjected to a precise inspection defined by the RoHS regulations such as GC / MS measurement, which is about 90% of the inspection time conventionally required for IAMS measurement. Could be reduced.

  Therefore, it was possible to easily and quickly discriminate between PBB, which is a RoHS regulated substance, and TBBPA, which is not a RoHS regulated substance.

  Further, in the present embodiment, even if it is erroneously determined that there is a possibility of containing PBB with respect to the TBBPA-containing sample, it is erroneously determined that there is no possibility of containing PBB with respect to the PBB-containing sample. There was no. Therefore, there was no PBB detection omission and a safe determination could be made.

  Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage. Moreover, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, the constituent elements over different embodiments may be appropriately combined.

DESCRIPTION OF SYMBOLS 1 Ion attachment mass spectrometer 2 Ionization chamber 3 Differential exhaust chamber 4 Mass analysis chamber 5, 6 Partition plate 7, 8 Opening part 9 Direct probe 10 Sample container 11 Heating mechanism 12 Ion emitter 13 Filament 14 Electrostatic lens 15 Mass spectrometry Total 16 Vacuum pump 20 Data analysis device 30 Control unit 21 First determination unit 22 Second determination unit 23 Third determination unit 24 PBB determination unit

Claims (10)

A method for determining a brominated flame retardant executed by a data analyzer that analyzes data obtained by an ion attachment mass spectrometer,
The first determination means determines whether or not a first peak intensity ratio, which is a ratio of the peak intensity at the second mass number to the peak intensity at the first mass number, is within the first range. A determination process;
When the determination means has the first peak intensity ratio within the first range, a determination step of determining that the sample to be inspected contains a brominated flame retardant that is not subject to regulation;
A method for determining a brominated flame retardant, comprising: The second determination means determines whether or not the second peak intensity ratio, which is the ratio of the peak intensity at the fourth mass number to the peak intensity at the third mass number, is within the second range. A judgment step,
The determination means determines that the sample is a bromine that is not subject to restriction when the first peak intensity ratio is within the first range and the second peak intensity ratio is within the second range. Determining that it contains a flame retardant,
The method for determining a brominated flame retardant according to claim 1. In the first determination step, the first mass number is 950 m / z, the second mass number is 951 m / z, and the first peak intensity ratio is different from that in the first range. Is greater than the first threshold,
In the second determination step, the third mass number is 953 m / z, the fourth mass number is 954 m / z, and the second peak intensity ratio is different from that in the second range. Is less than or equal to the second threshold,
The determination means is a case where the first peak intensity ratio is greater than a first threshold value, and when the second peak intensity ratio is equal to or less than a second threshold value, the sample is not a regulated brominated flame retardant. Determining that it contains TBBPA,
The method for determining a brominated flame retardant according to claim 2. The third determination means determines whether a third peak intensity ratio, which is a ratio of the peak intensity at the sixth mass number to the peak intensity at the fifth mass number, is within the third range. Further comprising 3 determination steps,
The determination means determines that the sample is not subject to the regulation when the third peak intensity ratio is within the third range even if the first peak intensity ratio is outside the first range. Determining that it contains a brominated flame retardant,
The method for determining a brominated flame retardant according to any one of claims 1 to 3. In the third determination step, the fifth mass number is 953 m / z, the sixth mass number is 954 m / z, and the third peak intensity is different from that in the third range. The ratio is below the third threshold,
When the first peak intensity ratio is less than or equal to a first threshold and the third peak intensity ratio is less than or equal to a third threshold, the determination means is a brominated flame retardant that is not subject to regulation. Determining that it contains a certain TBBPA;
The method for determining a brominated flame retardant according to claim 4. The first threshold value used in the first determination step is a value in a range of 0.4 to 0.7.
The second threshold value used in the second determination step is a value within a range of 1.0 or more and 1.5 or less;
The method for determining a brominated flame retardant according to any one of claims 3 to 5, wherein: The first threshold value used in the first determination step is 0.65,
The second threshold value used in the second determination step is 1.1,
The determination means is when the first peak intensity ratio is greater than 0.65, and when the second peak intensity ratio is 1.1 or less, the sample is a brominated flame retardant that is not subject to regulation. Determining that it contains TBBPA,
The method for determining a brominated flame retardant according to claim 5. The third threshold value used in the third determination step is a value in a range of 0.9 or more and 1.0 or less;
The method for determining a brominated flame retardant according to any one of claims 5 to 7, wherein: The third threshold value used in the third determination step is 0.96,
When the first peak intensity ratio is 0.65 or less and the third peak intensity ratio is 0.96 or less, the determination means is a brominated flame retardant that is not subject to regulation. Determining that it contains TBBPA;
The method for determining a brominated flame retardant according to claim 8. A computer that analyzes the data obtained with an ion attachment mass spectrometer,
First determination means for determining whether a first peak intensity ratio, which is a ratio of the peak intensity at the second mass number to the peak intensity at the first mass number, is within the first range;
When the first peak intensity ratio is within the first range, a determination unit that determines that the sample that is an object to be inspected contains a brominated flame retardant that is not a regulation target;
Program to function as.

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