JP5463909B2 - Method for detecting Br in resin, resin sorting apparatus, and method for producing recycled resin product - Google Patents

Description

  The present invention relates to a technology for detecting a resin containing a specific element from a recovered resin, separating a resin from which the element is detected from a resin not having been detected, and manufacturing a recycled resin product that does not contain the specific element. .

  For resins such as plastics used for home appliances, some flame retardant resins containing a flame retardant are used. The flame retardant content is usually 1 to 30% by weight, and brominated flame retardants are mainly used as the flame retardant.

  Therefore, the resin obtained by discarding and recovering these resin products includes those containing bromine (hereinafter abbreviated as Br). This Br is a target substance of the hazardous substance regulation represented by the European RoHS Directive (Directive concerning the restriction on the use of specific hazardous substances contained in electrical and electronic equipment). This Br is an element which is inconvenient for the production and use of the resin, and it is important to exclude Br from the recovered resin.

  The content of Br in the resin can be detected by fluorescent X-ray analysis. For example, in Patent Document 1, an X-ray or an electron beam is irradiated to a resin transported by a transport device, a generated characteristic X-ray is detected to detect an element such as Br in the resin, and the resin is detected from the detection result. It has been shown to sort out.

  Patent Document 2 discloses a fluorescent X-ray whose peak-to-background ratio is improved by irradiating a sample with X-rays having a low energy component reduced by a filter, and further detecting the generated fluorescent X-ray through the filter. An analyzer is shown.

JP 2004-219366 A JP 2006-38822 A

  In a conventional method for detecting a specific element in a resin using fluorescent X-ray analysis, an X-ray detector having a function of detecting X-ray energy has been used. In the X-ray detector having such energy resolution, the intensity of the X-ray having the energy is detected for each different energy. For this reason, in the conventional method, the configuration of the detector is complicated, and a long time is required for detection. Moreover, it was not easy to detect a resin piece containing a specific element from a large amount of resin pieces at high speed.

  Therefore, an object of the present invention is to realize a method for detecting a specific element in a resin piece with high accuracy and high speed even when an X-ray detector having no function of detecting energy is used. In particular, an object is to detect a resin containing Br such as a flame retardant resin at a high speed with Br as a specific element. It is another object of the present invention to realize the separation of the resin and a recycled resin product containing almost no Br.

The method for detecting Br in a resin according to the present invention comprises simultaneously irradiating a plurality of resin pieces with a characteristic X-ray of any one of Sr-Kα , Y-Kα, Zr-Kα, Nb-Kα, and Mo-Kα. The step of simultaneously detecting the intensity of the first X-ray transmitted through the piece as a visible image obtained by image processing, and the intensity of the first X-ray is less than or less than the first threshold value for each of the plurality of resin pieces Determining the position of the resin piece that is less than or less than the first threshold value among the plurality of resin pieces, and irradiating the resin piece with characteristic X-rays of Zr-Kα, Detecting the intensity of the X-rays generated in step 1 as the intensity of the second X-rays through the first filter containing Rb and the second filter containing Se in order, And detecting the content of Br based on In the step of detecting the intensity of the second X-ray when the intensity of the first X-ray is less than or less than the first threshold, and the intensity of the first X-ray is less than or equal to the first threshold If not, or less than, have the resin piece skip the step of detecting the intensity of the second X-ray as not containing Br .

Any of Sr-Kα , Y-Kα, Zr-Kα, Nb-Kα, and Mo-Kα that is closer to the absorption edge of the K shell of Br and closer to the K shell of Mo than the characteristic X-ray of Mo By simultaneously irradiating a plurality of resin pieces with X-rays, the intensity of transmitted X-rays is greatly reduced in the resin pieces containing Br, and the generation of fluorescent X-rays of Br becomes strong. Since at the same time to detect the content of Br in the plurality of resin pieces based on the X-ray intensity transmitted through the plurality of resin pieces, characteristic of the Br in the resin even with low performance X-ray detector Mo X It becomes possible to detect with higher accuracy than in the case of irradiating a line, and has a unique effect of detecting and sorting Br in a plurality of resin pieces at high speed .

It is sectional drawing explaining the structure of the Br-in-resin detection apparatus used for the Br-in-resin detection method of this Embodiment 1. FIG. It is explanatory drawing of the data obtained in the in-resin Br detection method of this Embodiment 1. FIG. It is a flowchart which determines the presence or absence of Br in the resin piece by the method for detecting Br in resin according to the first embodiment. It is a characteristic view explaining the principle of the Br detection method in resin of this Embodiment 1. It is a characteristic view explaining the principle of the Br detection method in resin of this Embodiment 1. 4 is a chart for explaining the principle of a resin Br detecting method according to the first embodiment. It is a characteristic view explaining the principle of the Br detection method in resin of this Embodiment 1. It is a block diagram of the X-ray detection experiment apparatus used in the experiment example of the Br detection method in resin of this Embodiment 1. FIG. It is a characteristic view which shows the result of the experiment example of this Embodiment 1. FIG. 6 is a chart showing the results of an experimental example of the first embodiment. It is a characteristic view which shows the result of the 2nd experiment example of this Embodiment 1. It is the schematic explaining the structure of the resin separation apparatus of this Embodiment 2. It is a perspective view explaining the structure of the resin separation apparatus of this Embodiment 2. It is explanatory drawing which shows the example of the data detected with the resin separation apparatus of this Embodiment 2. It is a perspective view explaining a part of structure of the resin separation apparatus of this Embodiment 3. It is sectional drawing explaining a part of structure of the resin separation apparatus of this Embodiment 3. It is a figure which shows the time change of the signal of the resin separation apparatus of this Embodiment 3. It is sectional drawing explaining the structure of the Br-in-resin detection apparatus used for the Br-in-resin detection method of this Embodiment 4. It is explanatory drawing which showed the example of the data measured by the Br detection method in resin of this Embodiment 4. FIG. It is a flowchart which determines the presence or absence of Br in the resin piece by the method for detecting Br in resin according to the fourth embodiment. It is a characteristic view explaining the measurement principle of the Br detection method in resin of this Embodiment 4. It is a block diagram of the in-resin Br detection apparatus used in the experiment example of the in-resin Br detection method of this Embodiment 4. It is a characteristic view which shows the experimental result of the experiment example of the Br detection method in resin of this Embodiment 4. FIG. It is a characteristic view which shows the experimental result of the comparative example of the Br detection method in resin of this Embodiment 4. It is a figure which shows the experimental result of the experiment example of the Br detection method in resin of this Embodiment 4. FIG. It is a figure which shows the experimental result of the experiment example of the Br detection method in resin of this Embodiment 4. FIG. It is a figure which shows the experimental result of the other comparative example of the Br detection method in resin of this Embodiment 4. FIG. It is a figure which shows the experimental result of the other comparative example of the Br detection method in resin of this Embodiment 4. FIG. It is a figure which shows the experimental result of the other comparative example of the Br detection method in resin of this Embodiment 4. FIG. It is a flowchart which determines the presence or absence of Br in a resin piece combining the Br detection method in resin which concerns on this Embodiment 4, and the Br detection method in resin which concerns on Embodiment 1 mentioned above. It is another flowchart which determines the presence or absence of Br in a resin piece combining the Br detection method in resin which concerns on this Embodiment 4, and the Br detection method in resin which concerns on Embodiment 1 mentioned above. It is the schematic explaining the structure of the resin separation apparatus of this Embodiment 5. It is explanatory drawing which shows the example of the detection data obtained with the resin separation apparatus of this Embodiment 5. It is the schematic which shows the structure of a deformation | transformation of the resin sorting apparatus which concerns on this Embodiment 5. FIG. It is the schematic which shows the structure of the resin separation apparatus which concerns on this Embodiment 6. FIG. It is explanatory drawing which shows the example of the data detected with the resin sorting apparatus which concerns on this Embodiment 6. It is the schematic which shows the structure of a deformation | transformation of the resin sorting apparatus which concerns on this Embodiment 6. FIG. It is the schematic which shows the structure of another deformation | transformation of the resin separation apparatus which concerns on this Embodiment 6. FIG. It is a flowchart explaining the manufacturing method of the recycled resin product of this Embodiment 7.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Primary X-ray source, 2 Secondary target, 3 Sample stand, 4 Resin piece, 4a Br containing resin piece, 4b Br non-containing resin piece, 5 X-ray detector, 6 Collimator, 7 Feeding device, 8 Conveying device, 9 motor, 10 data processor, 11 sorting mechanism, 12 Br-containing resin piece storage box, 13 Br-free resin piece storage box, 14 screen, 15 filter, 15a first filter, 15b second filter, 16 Partition, 31 sorting mechanism controller, 34 images, 40 filter moving mechanism, 101 continuous X-ray, 102 characteristic X-ray.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and description thereof will not be repeated and will be omitted.

<Embodiment 1. >
FIG. 1 is a cross-sectional view for explaining the configuration of the in-resin Br detecting device used in the in-resin Br detecting method of the first embodiment. The detection apparatus includes a primary X-ray source 1 that generates continuous X-rays 101 and a target 2 that is irradiated with the continuous X-rays 101. When the target 2 is irradiated with the continuous X-ray 101, characteristic X-rays 102 peculiar to the element contained in the target 2 are generated. As the primary X-ray source 1, an X-ray tube using rhodium (hereinafter abbreviated as Rh) as an internal target (primary target) can be used. The target 2 is a material containing any element of Sr, Y, Zr, Nb, and Mo. As a result, the primary X-ray source 1 and the target 2 become X-ray sources that generate characteristic X-rays 102 of any one of Sr, Y, Zr, Nb, and Mo.

  In addition, the detection apparatus includes a sample stage 3 on which the resin pieces 4a and 4b, which are detection objects, are placed at positions where the generated characteristic X-ray 102 is irradiated, and is opposite to the X-ray source with respect to the sample stage 3. An X-ray detector 5 is provided on the side. The resin piece 4a is a resin piece containing Br, and the resin piece 4b is a resin piece containing no Br. The sample stage 3 is made of a resin material that easily transmits any one of the characteristic X-rays 102 of Sr, Y, Zr, Nb, and Mo, or a member having a mesh or lattice structure. The X-ray detector 5 is an X-ray detector that detects any characteristic X-ray 102 of Sr, Y, Zr, Nb, and Mo. With this configuration, the characteristic X-ray 102 of any one of Sr, Y, Zr, Nb, and Mo generated by the X-ray source passes through the resin material, mesh, and lattice of the sample stage 3 after passing through the resin pieces 4a and 4b. And detected by the X-ray detector 5. The transmitted X-ray intensity data detected by the X-ray detector 5 is input to the data processor 10, and the data processor 10 calculates the concentration of Br in the resin piece based on the transmitted X-ray intensity. Further, the data processor 10 may have a function of determining that the resin piece contains Br when, for example, the transmitted X-ray intensity exceeds a predetermined value based on the intensity.

  As the X-ray detector 5, an X-ray detector 7 having no energy resolution such as an X-ray scintillator or a position-sensitive proportional counter can be used. The X-ray detector 5 uses a detector in which a plurality of X-ray detectors are arranged one-dimensionally or two-dimensionally, such as an X-ray line sensor, an X-ray imaging intensifier, or an X-ray CCD camera. Can do. Thereby, Br of the some resin piece mounted in the sample stand 3 can be detected simultaneously.

  FIG. 2 is an explanatory diagram of data obtained in the method for detecting Br in resin according to the first embodiment. The data shown in the figure is, for example, an image 34 displayed on the screen 14 of the data processor 10 when an X-ray CCD camera is used for the X-ray detector 5. This image 34 shows the distribution of transmitted X-ray intensity. The detection surface of the X-ray CCD camera is installed in parallel with the mounting surface of the resin piece of the sample table 3. A plurality of resin pieces having different Br-containing concentrations are placed on the placement surface of the sample stage 3 so as not to overlap each other. Since the X-ray transmission characteristics are different depending on the concentration of Br contained in the resin piece, the image 34 is an image having a distribution with different shades depending on the position of the resin piece. Since any characteristic X-ray of Sr, Y, Zr, Nb, and Mo is used as the X-ray source, the X-ray transmittance decreases as the concentration of Br increases. The figure shows a brighter image as the X-ray intensity is higher. The resin piece 4a containing Br is darker, and the resin piece 4b not containing it is brighter than 4a. In addition, since the resin piece which does not contain Br is also slightly absorbed by the resin, it is slightly darker than the place between the resin piece on which the resin piece is not placed. For example, the data processor 10 calculates the concentration of Br based on the difference in density and determines whether the resin piece contains Br. Further, when the X-ray detector 5 outputs the transmitted X-ray intensity as the signal intensity, the determination of containing Br may be performed based on the signal intensity.

  FIG. 3 is a flowchart for determining the presence or absence of Br in the resin piece by the method for detecting Br in resin according to the first embodiment. First, the characteristic X-ray of any one of Sr, Y, Zr, Nb, and Mo is irradiated onto the resin piece, and the intensity of the first X-ray that has passed through the resin piece is detected (step S1). Next, it is determined whether the first X-ray is less than or less than a preset first threshold value (step S2). If the determination in step S2 is YES, the resin piece contains Br, and if NO, the resin piece does not contain Br (steps S3a and S3b). Thus, in the resin Br detecting method according to the first embodiment, the resin piece is irradiated with the characteristic X-ray of any one of Sr, Y, Zr, Nb, and Mo, and the first piece that has passed through the resin piece. A step of detecting the intensity of the X-ray and a step of detecting the content of Br in the resin piece based on the intensity of the first X-ray.

Next, the principle of measurement will be described. 4 and 5 are characteristic diagrams for explaining the principle of the in-resin Br detection method according to the first embodiment. The characteristic diagram of FIG. 4 is a graph showing calculated values of X-ray transmission spectra of a resin containing 10% by mass of Br and a reference resin containing no Br. In this graph, the horizontal axis represents the energy of X-rays, and the vertical axis represents the transmittance with 1 indicating no absorption. In the figure, the line indicated by REF indicates the transmittance of the reference resin piece containing no Br, and the line indicated by BR10 indicates the transmittance of the resin piece containing 10% by mass of Br. The energy indicated by ABEBR in the figure is the energy at the absorption edge of the K shell of Br. In the calculation, a calculation condition was used in which the density of the resin containing Br and the reference resin was 0.9 g / cm ^3, which is a general resin density, and the thickness of the resin was 1 mm.

  Since the absorption edge of the K shell of Br is about 13.5 keV, as shown in the figure, the resin containing Br has a lower transmittance of X-rays having higher energy than the absorption edge compared to the reference resin. Further, X-rays having higher energy than the absorption edge tend to decrease the transmittance of the resin containing Br as the energy approaches from the high energy to about 13.5 keV at the absorption edge. Therefore, the decrease in transmittance is particularly large between about 13.5 keV and 20 keV at the absorption edge. In the resin used for the calculation, the transmittance between 13.5 keV and 20 keV is as high as 60% or less, and the absorption effect is large. Further, as the energy becomes higher, the transmittance gradually increases and the absorption effect decreases. Further, on the lower energy side than the K absorption edge, there is no great difference in the spectrum between the resin containing Br and the reference resin, and the transmittance gradually decreases as the energy becomes lower. There is a transmittance of 60% or more up to about 10 keV on the lower energy side than the K absorption edge, the absorption effect is small, and when the energy becomes lower, the transmittance gradually decreases and the absorption effect increases. These are considered to be mainly absorbed by the resin.

  The characteristic diagram of FIG. 5 shows the characteristic X-ray intensity of the K shell of each element of Rb, Sr, Y, Zr, Nb, and Mo, and the intensity of continuous X-rays generated from the X-ray source of Rh. It is the graph which showed the energy of X-ray and the vertical axis | shaft with the intensity | strength of arbitrary units. In FIG. 5, the spectrum of the transmittance of the resin containing Br shown in FIG. 4 is also indicated by a dotted line BR10. Moreover, the intensity | strength of the continuous X-ray used in FIG. 5 was shown with the broken line CONX. Note that Kα1 and Kα2 of the characteristic X-ray of each element are shown as Kα of one peak because the energy is close. The characteristic X-rays of these elements occupy most of the intensity of Kα, and Kβ1 generated on the higher energy side is considerably smaller than the intensity of Kα. Among the above elements, the Kα energy of Sr, Y, Zr, Nb, and Mo is between about 13.5 keV to about 20 keV at the Br absorption edge, which is a resin containing Br and has a large decrease in transmittance. On the other hand, the continuous X-ray used has an intensity peak between 5 and 10 keV as in CONX in FIG. 5, and the intensity gradually decreases in the energy range higher than 13.5 keV at the Br absorption edge. It has a spectrum that

  FIG. 6 is a chart for explaining the principle of the resin Br detecting method according to the first embodiment. The data in the chart of FIG. 6 are calculated values of transmittance when a continuous X-ray and characteristic X-rays of each element are irradiated to a resin (thickness 1 mm) containing Br 0 mass%, 1 mass% and 10 mass%, and reference It is the result of having calculated the ratio of the transmittance | permeability of Br containing resin with respect to the transmittance | permeability of Br non-resin which is resin. The transmittance of each continuous X-ray with respect to the resin of each Br concentration is normalized by the X-ray intensity at the energy value in the continuous X-ray plot CONX in FIG. 5 (the X-ray intensity of the energy value having the highest X-ray intensity). ). Further, the transmittance of monochromatic X-rays was calculated using Kα rays of each element having a high intensity as a representative.

  As shown in the figure, the ratio of the transmittance is larger when the characteristic X-rays of Sr, Y, Zr, Nb, and Mo are irradiated than when the continuous X-ray is used. From the above results, it is possible to detect to some extent even using continuous X-rays, but the characteristic X-rays of Sr, Y, Zr, Nb, and Mo, which are X-ray light sources of 13.5 keV to 20 keV at the Br absorption edge, can be obtained. It can be seen that the sensitivity of Br detection is greatly improved. On the other hand, in the characteristic X-rays of Tc and Ru, the ratio of transmittance is smaller than that of continuous X-rays, and the sensitivity is not improved. Further, since the Rb-Kα ray is on the lower energy side than the K absorption edge of Br, there is no improvement in sensitivity due to the monochromatization of the X-ray.

  FIG. 7 is a characteristic diagram illustrating the principle of the in-resin Br detection method of the first embodiment. FIG. 7 shows the thickness dependence of the transmitted X-ray intensity when the resin containing continuous X-rays, Sr, and Zr characteristic X-rays is irradiated onto a resin containing Br mass 0%, 1 mass%, and 10 mass%. In the characteristic diagram of FIG. 7, (a) is a continuous X-ray, (b) is a graph using Sr characteristic X-ray, and (c) is a graph using Zr characteristic X-ray. In these graphs, the vertical axis represents the normalized transmission X-ray intensity with 1 in the absence of absorption, and the horizontal axis represents the resin thickness (mm). In addition, PBR00 indicated by square dots is Br0 mass%, PBR01 indicated by round dots is Br1 mass%, PBR10 indicated by triangular dots is the normalized transmission X-ray intensity of a resin piece of Br 10 mass% Indicates. In addition, since it was normalized, the transmitted X-ray intensity is the same value as the transmittance. In any X-ray, the transmitted X-ray intensity tends to decrease as the resin thickness increases and as the Br concentration increases. Even in the case of Br0% by mass of the resin, the transmission X-ray intensity is reduced depending on the thickness because the resin material alone has an X-ray absorption effect to some extent.

  Whether or not the resin contains Br can be determined based on the transmitted X-ray intensity. For example, a broken line shown in the figure is an example of a threshold value of transmitted X-ray intensity for discriminating between a Br-containing resin and a Br-non-containing resin. However, in the case of continuous X-rays, when the transmission X-ray intensity of 1 mm resin containing 1% by mass Br is used as a threshold value and the resin below the threshold value is discriminated as Br-containing resin, the resin of 2 mm thickness and 3 mm thickness of Br0% by mass is below the threshold value. Therefore, it is discriminated as a Br-containing resin. On the other hand, when the Sr-Kα ray and the Zr-Kα ray are used, even if the transmission X-ray intensity of the 1 mm-thick resin containing 1% by mass of Br is used as a threshold value and the threshold value or less is determined as Br-containing resin, the Br mass is 0 % Thickness 2 mm resin is equal to or greater than the threshold value, so it is not mistakenly determined as Br-containing resin. Therefore, when the Sr-Kα line and the Zr-Kα line are used, the accuracy of determining whether or not Br is contained is improved. The use of characteristic X-rays of Y, Nb, and Mo, which are X-ray light sources of 13.5 keV to 20 keV at the Br absorption edge, similarly has the effect of improving the discrimination accuracy.

  As described above, in continuous X-ray irradiation, there are energy regions where the absorption effect by Br is large and energy regions are small, and in the method of detecting the total X-ray transmission intensity, the absorption effect corresponding to the inclusion of Br is small and the sensitivity is high. There is a low problem. On the other hand, since the inclusion of Br is detected based on the transmitted X-ray intensity using an X-ray light source of 13.5 keV to 20 keV at the Br absorption edge as in the first embodiment, sensitivity and discrimination accuracy are improved. Further, since an X-ray light source having a large effect of absorbing Br is used by generating characteristic X-rays of any one of Sr, Y, Zr, Nb, and Mo, improvement in accuracy can be realized with a relatively simple configuration. it can. Further, since detection is performed with this configuration, the X-ray detector does not need to have energy resolution, and the apparatus can be simplified. Furthermore, since a plurality of resin pieces can be easily detected simultaneously using a detector that detects the X-ray intensity in two dimensions, such as an X-ray CCD camera, the detection can be easily performed at high speed.

  Similarly, when detecting that a specific element other than Br is contained in a resin or a substance to be detected, an X-ray light source having energy equal to or higher than the X-ray absorption edge of the specific element and in the vicinity of the X-ray absorption edge. The same effect can be obtained by measuring the transmitted X-ray intensity using.

  Hereinafter, an experimental example for detecting Br detection using the in-resin Br detection method of the first embodiment will be described. FIG. 8 is a configuration diagram of an X-ray detection experimental apparatus used in an experimental example of the in-resin Br detection method of the first embodiment. In the figure, when primary X-rays, which are continuous X-rays 101 generated from the primary X-ray source 1, are irradiated to the secondary target 2 via the collimator 6, characteristic X-rays derived from the secondary target 2 (2 Secondary X-ray) 102 passes through the resin piece 4 and the X-ray detector 5 detects characteristic X-rays derived from the secondary target 2. The collimator 6 is provided for the function of restricting primary X-rays emitted from the primary X-ray source 1.

  In the experimental example, the primary X-ray source 1, the X-ray detector 5, and the collimator 6 were all those attached to JEOL fluorescent X-ray analyzer JSX-3000 type. The primary X-ray source 1 is an X-ray tube using rhodium (hereinafter Rh) as an internal target (primary target). In the experiment, a lithium drift type silicon detector, which is a semiconductor detector having energy separation ability, was used as the X-ray detector 5. Here, by using a semiconductor detector having energy separation capability as the X-ray detector 5, the X-rays derived from the secondary target 2 and the resin piece 4 are energy-separated, and the respective detection intensities are measured. The effectiveness of 2 was verified.

  As measurement conditions, the output of the X-ray tube of the primary X-ray source 1 was set to a tube voltage of 50 kV, a tube current of 1 mA, and the inner diameter of the collimator 6 was set to 7 mm. As the resin piece 4, an impact-resistant polystyrene (HIPS) plate (thickness 1 mm) having a Br content of 10 mass%, 1 mass%, and 0 mass% was used. This resin piece 4 is made of a decabromodiphenyl ether reagent (manufactured by Wako Pure Chemical Industries, Ltd.) which is a kind of brominated flame retardant so that the Br content is as described above in HIPS pellets (manufactured by PS Japan, model number H8672). What was mixed and kneaded was produced into a plate shape by hot pressing. In this experiment, strontium oxide (manufactured by Wako Pure Chemical Industries) or a Zr metal plate (thickness 1 mm, purity 99.999%) was used as the secondary target 2.

  FIG. 9 is a characteristic diagram showing the results of the experimental example of the first embodiment. 9A shows an X-ray detection after passing through each resin piece 4 having a Br content of 0% by mass, (b) having a Br content of 1% by mass, and (c) having a Br content of 10% by mass. It is a graph showing the X-ray spectrum which measured the intensity | strength. In addition, the thickness of the resin piece 4 was 1 mm, and strontium oxide was used for the secondary target 2. In these graphs, the horizontal axis represents the characteristic X-ray energy value (keV), and the vertical axis represents the X-ray intensity (cps / mA).

  As shown in FIGS. 9A to 9C, the X-ray intensities of the Sr-Kα line and the Sr-Kβ1 line decrease as the Br content increases to 0, 1, and 10% by mass. That is, the greater the Br content, the lower the transmitted X-ray intensity.

  FIG. 10 is a chart showing the results of the experimental example of the first embodiment. This chart shows the transmittance when each of continuous X-rays, characteristic X-rays of Sr and Zr elements is irradiated to a resin containing 0% by mass, 1% by mass, and 10% by mass (thickness 1 mm). Here, the transmittance is a value normalized by 1 when there is no attenuation, and the same value as the transmission X-ray intensity normalized by 1 when there is no attenuation. The figure also shows the ratio of the transmittance of Br 1 mass% and 10 mass% resin to the transmittance of the reference resin of Br 0 mass%.

  When the characteristic X-rays of Sr or Zr are irradiated, the transmittance ratio is larger than the transmittance ratio of the continuous X-rays to the transmittance of the reference resin. Therefore, the sensitivity for detecting Br is improved by irradiating with characteristic X-rays of Sr or Zr. Similar effects can be obtained by irradiating the resin piece with characteristic X-rays of Y, Nb, and Mo instead of these elements. Further, the ratio of the transmittance was increased by the irradiation of the characteristic X-rays of Sr than the characteristic X-rays of Zr, and the sensitivity was improved. This is presumably because the characteristic X-rays of Sr are closer to the Br absorption edge than the Zr characteristic X-rays, and the closer to the Br absorption edge, the greater the reduction in transmittance due to the inclusion of Br.

  In the case of this experimental example, for example, when a resin having a transmittance of 0.8 or less is contained in Br, a resin containing 1% by mass or more of Br can be easily detected.

  In the following, a second experimental example for detecting Br detection using the in-resin Br detection method of the first embodiment will be described. In the second experimental example, an impact-resistant polystyrene (HIPS) plate having a Br content of 10 mass%, 1 mass%, and 0 mass% was used for the resin piece 4. The configuration of the apparatus used is the same as in the above experimental example.

  FIG. 11 is a characteristic diagram showing the results of the second experimental example of the first embodiment. In the characteristic diagram of FIG. 11, (a) is a continuous X-ray, (b) is a graph using Sr Kα characteristic X-ray, and (c) is a Zr Kα characteristic X-ray. When the characteristic X-rays of continuous X-rays, Sr, and Zr are irradiated to a resin containing Br mass 0%, 1 mass%, and 10 mass%, the normalized transmission X-ray intensity changes depending on the thickness of the resin. It shows. In the second experimental example, the resin thickness was 1, 2 and 3 mm. The horizontal axis represents the resin thickness (mm), and the vertical axis represents the normalized transmitted X-ray intensity. The normalized transmitted X-ray intensity is a value normalized with the value when there is no resin as 1. The open square point PBR00 indicates the normalized transmission X-ray intensity of the resin piece of Br0 mass%, the round point PBR01 indicates the Br1 mass%, and the open triangular point PBR10 indicates the Br 10 mass%.

  In any X-rays, the normalized transmission X-ray intensity tended to decrease as the resin thickness increased and the Br concentration increased. The reason why the transmitted X-ray intensity is reduced even in the case of Br0% by mass resin is that the resin material alone has a small X-ray absorption effect. The threshold value of the transmitted X-ray intensity for discriminating between the Br-containing resin and the Br-free resin can be, for example, the normalized transmitted X-ray intensity indicated by a broken line shown in the drawing.

  In the case of continuous X-rays, if the transmission X-ray intensity of 1 mm resin containing 1% by mass Br is used as a threshold value, and the threshold value or less is determined to be Br-containing resin, the thickness of 2 mm and 3 mm resins at Br 0% by mass will be below the threshold value. It will be identified as resin. On the other hand, with Sr-Kα and Zr-Kα rays, the transmission X-ray intensity of 1 mm thick resin containing 1% by mass Br is used as a threshold, and even if it is discriminated as Br containing resin below the threshold, the thickness is Br 0% by mass. Since 2 mm resin is equal to or greater than the threshold value, it is not mistakenly determined as a Br-containing resin.

  As described above, the plastic detection device including the brominated flame retardant according to the first embodiment converts the continuous X-rays generated from the X-ray source that generates the primary X-rays into Sr, Y, Zr, Nb, and Mo. Since the X-ray absorption effect of Br is particularly increased and the X-ray absorption effect of only the resin is reduced because the plastic is irradiated with monochromatic X-rays specific to each element using a secondary target containing any of the above. The difference in transmitted X-ray intensity between the plastic and the non-containing plastic can be increased and the sensitivity can be improved, and the discrimination accuracy of Br-containing / non-containing plastic can be improved.

  In the resin Br detection method according to the first embodiment, the resin piece is irradiated with an X-ray source between about 13.5 keV and 20 keV at the Br absorption edge, which is a resin containing Br and has a large decrease in transmittance. Based on the transmission intensity, Br in fat is detected. As X-rays having these energies, characteristic X-rays of any one of Sr, Y, Zr, Nb, and Mo, particularly Kα characteristic X-rays are used. In order to generate characteristic X-rays of Sr, Y, Zr, Nb, and Mo, for example, a target of any one of Sr, Y, Zr, Nb, and Mo is irradiated with continuous X-rays. And irradiating the resin piece with one of the characteristic X-rays of Sr, Y, Zr, Nb, and Mo to detect the intensity of the first X-ray transmitted through the resin piece; Detecting the content of Br in the resin piece based on the strength. As is clear from the experimental examples described above, it is possible to accurately detect Br in the resin using the X-ray detector that does not need to detect energy by the method of the first embodiment. Become. In addition, since it is not necessary to detect energy, Br in the resin can be detected at high speed.

  In the above description, the characteristic X-ray is used as the X-ray to be irradiated to the resin piece. However, the X-ray to be irradiated is a resin containing Br and is attenuated if it is an X-ray in an energy range with a large decrease in transmittance. Increases and the effect of the present invention is obtained. For example, an X-ray having a maximum intensity in an energy range of not less than the absorption edge of the K shell of Br and not more than the characteristic X-ray of the K shell of Mo may be used. Even if the range does not have a single intensity peak, the main X-ray intensity is in the energy range from about 13.5 keV which is the absorption edge of the K shell of Br to about 20 keV, for example. I just need it.

<Embodiment 2. >
FIG. 12 is a schematic diagram illustrating the configuration of the resin sorting apparatus according to the second embodiment. The resin separation device is configured to drive a feeding device 7 such as a feeder for feeding the resin pieces 4a and 4b, a feeding device 8 such as a belt conveyor for feeding the resin pieces 4a and 4b supplied from the feeding device 7, and the feeding device 8. A motor 9 is provided. In the figure, the resin piece 4a is a resin piece containing Br, and the resin piece 4b is a resin piece containing no Br. Further, the in-resin Br detecting device portion having the same configuration as that used in the in-resin Br detecting method of the first embodiment, that is, the primary X-ray source 1, the secondary target 2, and the X-ray that generate continuous X-rays. A detector 5 is provided. However, the resin pieces 4 a and 4 b are placed on the transport device 8 instead of the sample stage 3. The secondary target 2 is irradiated with continuous X-rays from the primary X-ray source 1 to generate any one of Sr, Y, Zr, Nb, and Mo characteristic X-rays. It is installed so as to irradiate the placed resin pieces 4a, 4b. The X-ray detector 5 is installed on the opposite side of the secondary target 2 with respect to the transfer device 8 on which the resin pieces 4a and 4b are placed. In the figure, a characteristic X-ray transmitted through the resin pieces 4a and 4b is detected by being installed under the conveying device 8 on which the resin pieces 4a and 4b are placed. Conversely, the X-ray source may be disposed below the transport device 8 and the X-ray detector 5 may be disposed above the transport device 8.

  The resin separation device includes a data processor 10 that detects Br in the resin based on the X-ray intensity detected by the X-ray detector 5, and a resin that is transported by the transport device 8 based on the detection result of the data processor 10. A separation mechanism 11 that separates the pieces 4a and 4b according to the content and presence of Br, a storage box 12 for sorted Br-containing resin pieces, and a storage box 13 for resin pieces not containing Br are provided.

  FIG. 13 is a perspective view illustrating the configuration of the resin sorting apparatus according to the second embodiment. In order to make it easy to understand, in the figure, the portions where the characteristic X-rays such as the primary X-ray source 1 and the secondary target 2 are irradiated are shown shifted from the transfer device 8, but in reality, they are located immediately above the transfer device 8. . Although not shown in FIG. 12, a power source 21 is connected to the primary X-ray source 1 so that X-rays emitted from the primary X-ray source 1 and irradiated on the resin pieces from the secondary target 2 are not leaked to the outside. And an X-ray shield 22 for shielding. The X-ray shield 22 has an opening on the transport device 8 side so that characteristic X-rays from the secondary target 2 are irradiated to the resin.

  A motor control device 29 is connected to the motor 9, and the motor control device 29 receives a signal indicating the detection status from the data processor 10, and executes rotation and stop of the motor 9 based on the signal, Controls the conveyance of the resin piece.

  13 is a belt conveyor, for example. The belt is made of a material having a high X-ray transmittance as in the sample table 3 of the first embodiment. The belt has a belt width orthogonal to the conveying direction (X direction in the figure). A plurality of resin pieces are placed from the supply device 7 within this width. Therefore, a plurality of resin pieces are placed in the width direction (Y direction in the figure, hereinafter abbreviated as the width direction) of the transport device 8 perpendicular to the transport direction.

  The supply device 7 stores a resin piece to be placed on the transport device 8 inside. The supply device 7 has an opening on the conveying device 8 side, and carries a resin piece from the opening onto the conveying device 8 by a vibration device or the like (not shown) provided inside. The opening is substantially the same width as the belt and the height is slightly larger than the resin piece. The resin pieces are placed on the conveying device 8 in a substantially uniform ratio in the belt width direction without overlapping the resin pieces. Further, by scanning an opening having a size that allows the resin piece to pass in the belt width direction, the resin piece can be placed in a substantially uniform ratio in the belt width direction.

  The separation mechanism 11 is installed near the conveyance end of the conveyance device 8 and changes the path of the resin piece after conveyance. For example, FIG. 13 shows an example of the separation mechanism 11 including a slope 11c and shutters 11a and 11b. The separation mechanism 11 in FIG. 13 is provided with a slope 11 c after being transported from the transport device 8, and a plurality of shutters 11 a and 11 b having a size slightly larger than the resin piece are arranged in a line in the width direction of the transport device 8. is there. When the shutter is closed (11b in the figure), the resin piece slides down the slope as it is, and when the shutter is open (11a in the figure), the resin piece falls down from the slope through the shutter opening. A storage box 12 for Br-containing resin pieces and a storage box 13 for resin pieces not containing Br are installed below the slope and under the opening of the shutter. The opening / closing of the shutter is controlled by the sorting mechanism controller 31. The sorting mechanism controller 31 receives a signal indicating the detection status from the data processor 10, and controls opening and closing of the shutter based on the signal. Alternatively, the separation mechanism 11 may be a separation mechanism that includes a mechanism that blows off the resin that is transported and dropped by the pressure of air and changes the path by the pressure.

  Since a plurality of resin pieces are placed in the width direction of the transport device 8 as described above, the X-ray detector 5 also has a transmission X-ray intensity distribution in the width direction so that the transmission X-ray intensity can be detected simultaneously. What can measure is good. As the X-ray detector 5 that measures the intensity distribution of transmitted X-rays in the width direction, for example, an X-ray CCD camera that detects a two-dimensional X-ray intensity distribution can be used. Instead of the X-ray CCD camera, for example, a line sensor in which a plurality of X-ray detectors are arranged in the width direction may be used.

  In addition, it is desirable that the intensity of characteristic X-rays applied to a plurality of resin pieces placed in the width direction is approximately uniform. For example, a primary X-ray source 1 that generates X-rays having a substantially uniform intensity distribution along the width direction of the transport device 8 is used, or the X-ray absorption distribution is such that the intensity is uniform in the width direction. The adjusted uniformizing filter may be inserted into the X-ray irradiation path. Further, the shape in the secondary target 2 may be adjusted to make the strength in the width direction uniform.

  The secondary target 2 has any element of Sr, Y, Zr, Nb, and Mo, generates characteristic X-rays by continuous X-rays irradiated from the primary X-ray source 1, and generates the generated characteristic X Irradiate the resin piece with the wire.

  Next, the operation of the resin sorting apparatus according to the second embodiment will be described. First, a resin piece as a separation target is supplied from the supply device 7 to the carry-in side of the transport device 8. This may be a mixture of resin pieces of different materials, or may be preliminarily separated and resin pieces of the same material, regardless of the extent to which the resin pieces containing Br are mixed. Here, it is a mixture of resin pieces that are crushed to a size of several millimeters and have a thickness of several millimeters. The motor control device 29 rotates the motor 9 to move the resin pieces 4a and 4b placed on the transport device 8 to the detection position. When time is required for detection, the rotation of the motor 9 may be stopped during the detection period to stop the conveyance. Characteristic X-rays are irradiated onto the resin pieces 4 a and 4 b at a predetermined detection position, and the X-ray intensity transmitted through them is detected by the X-ray detector 5. The detection signal is sent to the data processor 10. Then, the resin piece 4a containing Br and the resin piece 4b containing no Br are discriminated from the relationship between the transmitted X-ray intensity after passing through the resin pieces 4a and 4b and the threshold value.

  FIG. 14 is an explanatory diagram showing an example of data detected by the resin sorting apparatus according to the second embodiment. This data is an image 34 displayed on the screen 14 of the data processor in FIG. 13 when an X-ray visualization detector such as an X-ray CCD camera is used as the X-ray detector 5. In the image 34, the direction from the top to the bottom is the transport direction (X direction), and the left and right are the width direction (Y direction) of the transport device 8. The resin piece 4a containing Br is displayed with a low luminance due to the reduced transmitted X-ray intensity due to the X-ray absorption of Br. On the other hand, the brightness of the resin piece 4b not containing Br is brightly displayed because there is no Br absorption. Even if the resin piece 4b does not contain Br, there is a little absorption by the resin, so that the luminance is displayed slightly lower than the absorption part of the belt of the conveying device 8 between the resin piece and the resin piece. Whether the resin piece contains Br or how much its content can be calculated by the luminance of the resin piece portion. For example, the ratio of the luminance of the resin piece portion is calculated based on the luminance of the absorption portion consisting only of the transport device 8. A case where this ratio is equal to or less than a predetermined value is determined to contain Br. In addition, the luminance is measured in advance with a standard sample containing a known bromine amount, and the value is stored in a memory in the data processor 10, and the value in the memory is compared with the luminance of the detected resin piece. From the above, the amount of Br contained in the resin piece may be calculated.

  From the detection image based on the distribution of the transmitted X-ray intensity, the position and size of the resin piece in the predetermined region can be specified by image processing. The data processor 10 first determines whether or not there is a resin piece containing Br as described above in a predetermined area, and if there is, specifies the position. Next, the time point when the resin piece 4a determined to contain Br enters the separation mechanism 11 is calculated based on the conveyance speed and operation state of the conveyance device 8, and the shutter controller 31 that controls the separation mechanism 11 at that time is calculated. Send a signal. Based on this signal, the shutter controller 31 opens and closes the shutter, and operates the separation mechanism 11 so that the resin piece 4a containing Br and the resin piece 4b containing no Br are carried along different paths.

  As described above, the resin sorting apparatus according to the second embodiment irradiates one of the characteristic X-rays of Sr, Y, Zr, Nb, and Mo to the transport device 8 that transports the resin piece 4 and the transported resin piece 4. The X-ray source to detect, the X-ray detector 5 for detecting the intensity of the X-ray transmitted through the resin piece 4 by the characteristic X-ray, and the presence or absence of Br in the resin piece 4 is determined from the detected X-ray intensity. A data processor 10 and a sorting mechanism 11 that sorts the resin pieces 4 transported by the transport device 8 based on the presence or absence of Br determined by the data processor 10 are provided. With this configuration, the analysis object is irradiated with X-rays having energy slightly higher than the X-ray absorption edge of the specific element, and the inclusion of the specific element in the analysis object is detected based on the transmitted X-ray intensity. Therefore, even if an X-ray detector having no energy resolution is used as the X-ray detector 5, the specific element can be detected with high accuracy. Moreover, since energy resolution is not required, detection can be speeded up, and as a result, sorting can be speeded up. In particular, as shown in the second embodiment, when an X-ray detector capable of detecting the X-ray intensity distribution in the direction perpendicular to the transport direction is used, it becomes easy to detect a plurality of analytes simultaneously. A large amount of analysis objects can be separated at high speed.

  The X-ray source that irradiates the resin piece does not necessarily generate characteristic X-rays. If X-rays that irradiate X-rays in an energy range with a large decrease in transmittance can be generated with a resin containing Br, attenuation is reduced. It becomes large and the effect of this invention is acquired. For example, a material capable of generating X-rays having a maximum intensity in an energy range not less than the absorption edge of Br K-shell and not more than the characteristic X-ray of Mo K-shell may be used. Even if the range does not have a single intensity peak, the main X-ray intensity is in the energy range from about 13.5 keV which is the absorption edge of the K shell of Br to about 20 keV, for example. An X-ray source may be used.

<Embodiment 3. >
FIG. 15 is a perspective view for explaining a part of the configuration of the resin sorting apparatus according to the third embodiment. The basic structure of the resin sorting apparatus according to the third embodiment is the same as that of the second embodiment, but the transfer device 8 and the X-ray detector 5 are different. FIG. 15 is a view in which the periphery of the transmission X-ray detection region of the transport device 8 is cut out and displayed. As shown in the figure, the transport device 8 is partitioned into a plurality of rows in the transport direction (X direction) by partition plates 28a and 28b. The resin pieces 4a and 4b are transported in each partitioned row. Each column is irradiated with any characteristic X-ray of Sr, Y, Zr, Nb, and Mo from above (Z direction). The X-ray detector 5 includes a plurality of X-ray detection elements arranged in the width direction (Y direction) of the transport device 8. The X-ray detection element is, for example, a Si photodiode in which a fluorescent material that emits visible light when irradiated with X-rays is installed on the light receiving side. Each of the X-ray detection elements detects the transmitted X-ray intensity for each transport row. The intensity of each X-ray detection element is input to the data processor 10, and a signal is sent to the data processor 10 based on the intensity. Based on this signal, the data processor 10 operates the sorting mechanism 11 so that the resin pieces enter the respective storage boxes 12 and 13 depending on whether or not Br is contained.

  FIG. 16 is a cross-sectional view for explaining a part of the configuration of the resin sorting apparatus according to the third embodiment. The figure is a cross-sectional view of the periphery of the transmission X-ray detection region of the transport device 8 as viewed from the transport direction side. The belt 38 of the transport device 8 has a fold formed in a valley shape so that the vicinity of the center of each transport row is slightly depressed downward. A groove may be formed instead of the fold. Further, the mountain-shaped crease portion of the belt 38 is positioned directly below the partition plates 28a and 28b installed at the boundary of each row. Each mountain-like fold portion is held by a roller 28 c installed at the lower part of the belt 8. Since the resin pieces 4a and 4b are conveyed by such a conveying device 8, the resin pieces are positioned near the center of each row by gravity. X-ray detection elements 5a to 5i for detecting the X-ray intensity of each row are arranged directly below the center of each transport row.

  FIG. 17 is a diagram showing a time change of a signal of the X-ray detection signal intensity output from the X-ray detection element of the resin sorting apparatus according to the third embodiment. When the resin piece passes right above the X-ray detection element, the output signal OUTPUT for X-ray detection becomes small. In the resin piece 4a containing Br, the decrease in the output signal OUTPUT is larger than that of the resin piece 4b not containing Br. Therefore, as indicated by a dotted line in the figure, a predetermined value LVL is set as a detection level, and a time T1 when the value is equal to or lower than that value and a time T2 when the value is equal to or lower than the value are detected. It can be known that a resin piece containing a large amount of Br is passing between T1 and T2. Based on this time, the data processor 10 operates the sorting mechanism 11 to sort the resin pieces based on the content of Br.

  As described above, since the resin sorting apparatus according to the third embodiment is partitioned for each column and the transmitted X-ray intensity is detected by the X-ray detection element for each column, the image is performed as in the second embodiment. There is no need for processing, and the configuration is simplified. In addition, since the depression is provided so that the resin piece is positioned at the center of the transport row and the detector is placed directly under the depression, even a small X-ray detection element can be detected with high accuracy. Even if there is a distribution in which the irradiation intensity of characteristic X-rays differs in the width direction, it is possible to easily realize the same detection reference in the width direction by adjusting the detection signal level for each transport row.

<Embodiment 4. >
FIG. 18 is a cross-sectional view for explaining the configuration of the in-resin Br detecting device used in the in-resin Br detecting method of the fourth embodiment. This in-resin Br detecting device is the same as that used in the in-resin Br detecting method of Embodiment 1, but the secondary target 2 contains Zr. The X-ray detector 5 detects fluorescent X-rays generated in the separation target irradiated with the Zr characteristic X-rays. As the X-ray detector 5, a detector such as an X-ray line sensor, an X-ray imaging intensifier, an X-ray CCD camera, and an X-ray scintillator having no energy resolution can be used.

  Furthermore, a first filter 15 a and a second filter 15 b are provided below the sample stage 3 and on the X-ray detector 5. In the figure, the sample stage 3, the resin piece 4, the first filter 15 a, and the second filter 15 b are installed in parallel to the detection surface of the X-ray detector 5. The first filter 15a contains rubidium (hereinafter abbreviated as Rb), and the second filter 15b contains selenium (hereinafter abbreviated as Se). For example, the first filter 15a is made of a resin in which an appropriate amount of Rb or a compound thereof is mixed in a resin material having a high X-ray transmittance. For example, the second filter 15b is made of a resin in which an appropriate amount of Se or a compound thereof is mixed in a resin material having a high X-ray transmittance. Each of them may be a substrate having a high X-ray transmittance and a material containing Rb or Se applied or formed into a film. Further, when the X-ray detector 5 has a plurality of first X-ray detection elements, the filter 15a and the second filter 15b may be fixed to the detection surface side for each X-ray detection element. Good.

  The characteristic X-rays from the secondary target 2 that have passed through the resin piece are effectively attenuated by sequentially passing through the first filter 15a and the second filter 15b. When characteristic X-rays from the secondary target 2 are irradiated onto the resin piece, if the resin piece contains Br, fluorescent X-rays of Br are generated. Since this fluorescent X-ray passes through the first filter 15a and the second filter 15b, it is detected by the X-ray detector 5. This detection signal is input to the data processor 10, and if the signal is equal to or greater than a predetermined value, it is determined that it contains Br, and the content of Br is calculated based on the value of the signal. That is, the in-resin Br detection method according to the fourth embodiment is a method for detecting the inclusion of a specific element based on the intensity of fluorescent X-rays generated in a separation target.

  FIG. 19 is an explanatory diagram showing an example of data measured by the method for detecting Br in resin according to the fourth embodiment. This data is an image 34 displayed on the data processor screen 14 in FIG. 18 when an X-ray visualization detector such as an X-ray CCD camera is used as the X-ray detector 5. The resin piece 4b that does not contain Br and the portion of only the sample size 3 have low luminance because no fluorescent X-rays are generated. Compared with this, since the fluorescent X-rays are generated at the position of the resin piece 4a containing Br, the luminance is increased. Therefore, whether or not Br is present in the resin piece can be determined based on the magnitude of the luminance. If the luminance of a standard sample containing a certain amount of Br is measured in advance, the content of Br in the resin piece can be determined by comparison with the luminance of the standard sample.

  FIG. 20 is a flowchart for determining the presence or absence of Br in the resin piece by the method for detecting Br in resin according to the fourth embodiment. First, Zr characteristic X-rays are irradiated onto a resin piece, and the intensity of X-rays generated through the resin piece passes through a first filter containing Rb and a second filter containing Se in order. 2 is detected as the X-ray intensity (step S11). Next, it is determined whether the second X-ray is greater than or equal to a preset second threshold value (step S12). If the determination in step S12 is YES, the resin piece contains Br, and if NO, the resin piece does not contain Br (steps S13a and S13b). As described above, in the resin Br detecting method according to the fourth embodiment, the resin piece is irradiated with the characteristic X-ray of Zr, and the intensity of the X-ray generated through the resin piece is changed to the first filter containing Rb. And detecting the intensity of the second X-ray through the second filter containing Se in turn, and detecting the content of Br in the resin piece based on the intensity of the second X-ray. ,have.

Hereinafter, the measurement principle of the method for detecting Br in resin according to the fourth embodiment will be described. FIG. 21 is a characteristic diagram illustrating the measurement principle of the in-resin Br detection method according to the fourth embodiment. In this characteristic diagram, the horizontal axis is X-ray energy, and the vertical axis is a transmittance with 1 representing no absorption. Energy positions of characteristic X-rays (Kα line and Kβ1 line) of each element of Se, Br, Rb, Sr, Y, Zr in the vicinity of the Br absorption edge, and each energy of absorption curves ABRB, Rb of each energy value of Se The absorption curve ABSE of the value is represented. The absorption curve shows the case where the film thickness of each element of Se and Rb is 100 μm. When the density of the Rb density of 1.5 g / cm ^3, Se and 4.5 g / cm ^3, the film deposition amount becomes 15 mg / cm ^2, Se in 45 mg / cm ² in Rb.

  In the following, first, consider a case in which the filter 15 installed before the irradiated X-ray passes through the resin piece and reaches the X-ray detector is composed of only one element.

  For example, when the filter 15 is composed only of Rb, the Br-Kα line, Br-Kβ1 line, Sr-Kα line, and Y on the energy side lower than the energy 15.2 keV of the absorption edge of the K shell of Rb The transmittance of -Kα rays and the like is high, that is, the absorptance is low. The transmittance of Zr-Kα line, Sr-Kβ1 line, Y-Kβ1 line, and Zr-Kβ1 line located on the higher energy side than the absorption edge of the K shell of Rb is low, that is, the absorption rate is high. Therefore, when the secondary target 2 is made of Zr, the filter 15 containing only Rb can transmit the characteristic X-rays of Br while absorbing the secondary X-rays from Zr.

  For example, when the filter 15 is composed only of Se, the transmittance of Br-Kα rays on the energy side lower than the energy of 12.7 keV at the absorption edge of the Se K shell is high. The transmittance of the Sr-Kα line, the Y-Kα line, the Zr-Kα line, the Sr-Kβ1 line, the Y-Kβ1 line, the Zr-Kβ1 line, etc. on the higher energy side than the energy of the absorption edge of the Se K shell is Low. Accordingly, when the secondary target 2 is composed of any one of Sr, Y, and Zr, the filter 15b containing only Se transmits the characteristic X-rays of Br while absorbing the secondary X-rays generated by them. can do.

  Therefore, the characteristic X-rays of Br are efficiently generated by the secondary X-rays derived from the secondary target 2, and only the secondary X-rays are absorbed by the filter 15 so as not to reach the X-ray detector 5. As a combination of the constituent elements of the secondary target 2 and the filter 15, the following four conditions are considered effective. That is, by setting (secondary target, filter) = (Sr, Se), (Y, Se), (Zr, Se), (Zr, Rb), the above object can be achieved.

  However, characteristic X-rays are generated not only in the secondary target 2 but also in the filter 15. Therefore, the filter 15 is not composed of only one element (one-stage structure), but has a two-stage structure of a first filter 15a and a second filter 15b, and the first filter 15a has a secondary target. It is considered effective to absorb characteristic X-rays derived from 2 or second-order X-rays and absorb characteristic X-rays derived from the first filter 15a in the second filter 15b. That is, by setting (secondary target, first filter, second filter) = (Zr, Rb, Se), the above object can be achieved.

  In the resin Br detection method of the fourth embodiment, Zr characteristic X-rays are used as excitation X-rays. The Zr characteristic X-ray has a strong Kα-ray energy of 15.7 keV, and the next-highest Kβ1 ray has an energy of 17.7 keV, which is larger than the energy of the K-shell absorption edge of Se of 12.7 keV. The energy at the absorption edge of the K shell of Rb is a little larger than 15.2 keV. Therefore, the Kr line of Zr is first absorbed by Rb of the first filter. At this time, fluorescent X-rays that are characteristic X-rays of Rb are also generated. The Rb characteristic X-ray Kα ray energy 13.4 keV and Kβ1 ray energy 15.0 keV are both slightly larger than the energy of the Se K-shell absorption edge of about 12.6 keV. For this reason, these fluorescent X-rays are absorbed by Se of the second filter. Further, Se fluorescent X-rays are also generated by the Rb fluorescent X-rays, but the intensity of the fluorescent X-rays generated is significantly smaller than the excitation X-rays. As described above, the intensity of the fluorescent X-rays of Rb generated from the characteristic X-rays of Zr, and further the intensity of the fluorescent X-rays of Se generated from the fluorescent X-rays of the Rb are gradually decreased. If the Se fluorescent X-ray is small to some extent with respect to the intensity of Br fluorescent X-rays generated from this resin piece, even if Se fluorescent X-rays enter the X-ray detector, the effect is small. Br can be detected from the total X-ray intensity detected by the X-ray detector. That is, Br can be detected without detecting energy.

  Since the energy 15.7 keV of the Kr ray of Zr is larger than the energy 13.5 keV of the absorption edge of Br, when the resin piece containing Br is irradiated with the Kα ray of Zr, a fluorescent X-ray of Br is generated. The intensity is much smaller than the characteristic X-rays of Zr. In the first embodiment described above, the influence of the fluorescent X-rays can be ignored, and the inclusion of Br is detected from the intensity of the transmitted X-rays. . On the other hand, in the second embodiment, only the fluorescent X-ray is taken out and detected by the X-ray detector 5. Zr characteristic X-ray energy Since it is higher than the energy of the Rb absorption edge of the first filter 15a and the Se absorption edge of the second filter 15b, it is absorbed by the respective filters, and the X-ray detector 5 Hardly reach. Since the characteristic X-ray energy of Br is smaller than the energy of Rb of the first filter 15a and the Se absorption edge of the second filter 15b, the fluorescent X-rays of Br generated in the resin piece are not absorbed so much. The line detector 5 is reached. As a result, the X-ray detector 5 can mainly detect the fluorescent X-rays of Br.

  As described above, X-rays (Zr Kα rays) irradiating a resin piece that is an object from the higher energy, the absorption edge of the first filter 15a (Rb), and the first filter 15a. The characteristic X-ray of the element (Rb), the absorption edge of the second filter 15b (Se), and the characteristic X-ray of the detection element (Br) are in this order. Since the first filter 15a and the second filter 15b are sequentially passed in this way, the X-rays to be excited hardly reach the X-ray detector, and the fluorescent X-rays of the detection elements generated in the resin pieces are not detected. Reach the X-ray detector. For this reason, even X-ray detectors that do not have energy resolution can detect the generation and intensity of fluorescent X-rays of the detected element, and know the presence and content of the detected element in the object based on the intensity. It becomes. The output of the X-ray detector 5 is input to the data processor 10, and the presence / absence and content of the X detection element may be calculated by the data processor 10.

  Further, in the method for detecting Br in resin of the fourth embodiment, the characteristic X-ray of the element (Zr) that is relatively close to the absorption edge of the detection element (Br) is used as the excitation X-ray, so that the detection element (Br) Of X-rays can be generated efficiently.

  When an element having a large X-ray absorption other than Br is contained in the resin piece, if it is detected using only the transmitted X-ray intensity, the resin piece containing such an element other than Br may also contain Br. There is sex. In the fourth embodiment, since the fluorescent X-rays specific to Br are detected to detect Br, the detection accuracy is increased.

  As the X-ray detector 5, an X-ray detector that does not have energy resolution, has a relatively large detection area, and can visualize the intensity distribution of X-rays can be used. When a detector capable of visualizing X-rays is used, the brightness of the Br-containing resin piece 4a is higher than that of the Br-non-containing resin piece 4b, so that the resin piece 4 can be distinguished. As such a detector, for example, an inexpensive detector such as an X-ray line sensor, an X-ray imaging intensifier, an X-ray CCD camera, or an X-ray scintillator can be used. If the detection area is relatively large so that objects containing a plurality of Br can be detected simultaneously, a large number of objects can be detected quickly.

  As Zr for the secondary target 2, a Zr metal plate, Zr powder, or a Zr compound such as an oxide or a chloride can be used. The Zr compound is preferably a compound that does not contain an element that generates characteristic X-rays within the sensitivity range of the X-ray detector 5.

  As Rb for the first filter 15a, a resin sheet on which an Rb compound such as Rb, oxide, chloride, or carbonate is formed, or an attached resin sheet or paper can be used. The Rb compound is preferably a compound that does not contain an element that generates characteristic X-rays within the sensitivity range of the X-ray detector 5.

  As Se for the second filter 15b, a resin sheet on which a Se compound such as Se, oxide, or chloride is formed, or an attached resin sheet or paper can be used. In addition, in Se compound, the compound which does not contain the element which generate | occur | produces the characteristic X ray in the sensitivity range of the X-ray detector 5 is preferable.

  Hereinafter, an experimental example of the in-resin Br detection method of the fourth embodiment will be described. FIG. 22 is a configuration diagram of the in-resin Br detecting device used in the experimental example of the in-resin Br detecting method of the fourth embodiment. The secondary target 2 of the in-resin Br detection device used in the experimental example in Embodiment 1 shown in FIG. 7 is used as a target containing Zr, and further between the resin piece 4 and the X-ray detector 5. It is the structure which inserted the 1st filter containing Rb and the 2nd filter containing Se in order from the secondary target 2 side. In FIG. 22, for example, the resin piece 4, the first filter 15 a, and the second filter 15 b are installed perpendicular to the detection surface of the X-ray detector 5. Irradiated X-rays (secondary X-rays) derived from the secondary target 2 pass through the resin piece 4, the first filter 15a, and the second filter 15b in this order, and the X-ray detector 5 is detected.

  In the experimental example, the effectiveness of the filter 15 including the first filter 15a and the second filter 15b was verified using a semiconductor detector having energy separation as the X-ray detector 5. A Zr metal plate (thickness 1 mm, purity 99.999%) was used as the secondary target 2, an Rb film was used as the first filter 15a, and an Se film was used as the second filter 15b.

The Rb film of the first filter 15a was prepared by dripping and drying an aqueous solution of rubidium carbonate Rb ₂ CO ₃ (manufactured by Wako Pure Chemical Industries) on filter paper, and the Rb adhesion amount was 15, 30, 60, 90, 120 mg. The film was / cm ² . The Se film of the second filter 15b was prepared by dripping and drying an aqueous solution of selenium oxide SeO ₂ (manufactured by Wako Pure Chemical Industries) on filter paper, and the Se adhesion amount was 30, 60, 120, 180, 240 mg / cm. ^The film was ² .

FIG. 23 is a characteristic diagram showing an experimental result of an experimental example of the method for detecting Br in resin according to the fourth embodiment. In the figure, (a) shows a Br content of 0% by mass, (b) shows a Br content of 1% by mass, and (c) shows a Br containing content of 10% by mass, the first filter 15a and the second filter 15b. It is a graph which shows the X-ray spectrum measured by X-ray detector 5 after that. The Rb deposition amount of the Rb film of the first filter 15a was 60 mg / cm ² , and the Se deposition amount of the Se film of the second filter 15b was 180 mg / cm ² . In FIG. 23, the horizontal axis represents the characteristic X-ray energy value (keV), and the vertical axis represents the X-ray intensity (cps / mA).

  As shown in FIG. 23A, in the X-ray spectrum of the resin piece 4 having a Br content of 0% by mass, the Zr-Kα line and the Zr-Kβ1 line derived from the secondary target 2 and the second filter 15b Se-Kα rays and Se-Kβ1 rays derived from Se have been detected.

  On the other hand, as shown in FIGS. 23 (b) to 23 (c), in the X-ray spectrum of the resin piece 4 having a Br content of 1 mass% and 10 mass%, in addition to the above peaks, the Br of the resin piece 4 is The excited characteristic X-rays, that is, Br-Kα ray and Br-Kβ1 ray are also detected. 23A to 23C, in any X-ray spectrum, the Zr-Kα line and the Zr-Kβ1 line are absorbed by the first filter 15a and the second filter 15b, and their intensities can be ignored. It is getting smaller. Since the transmittance of the filter 15 is relatively high, the Br-Kα line is detected with a greater intensity than the Zr-Kα line and the Zr-Kβ1 line as shown in FIG. The intensity of Br fluorescent X-ray increases as the Br content increases from 1% by mass in (b) to 10% by mass in (c). Also, from (a) to (c), it can be seen that the intensity of Se fluorescent X-rays decreases as the Br content increases. This is presumably because the intensity of the characteristic X-ray of Zr that passes through the resin piece decreases as the amount of Br increases. Further, the fluorescent X-rays of Rb were absorbed by the second filter 15b and were hardly detected in any case.

  When the X-ray detector 5 does not have energy resolution, the X-ray detector 5 uses the Xr characteristic X-ray for excitation, the fluorescent X-ray of Br, the fluorescent X-ray of Rb, and the total transmission X of the fluorescent X-ray of Se. The total intensity of the line is detected. The first filter 15a and the second filter 15b attenuate the excitation Xr characteristic X-ray and the Rb fluorescent X-ray to a negligible level. Se fluorescent X-rays are detected a little, but their magnitude is relatively small with respect to the intensity of Br fluorescent X-rays. As the Br content in the resin piece increases, the intensity of the Br fluorescent X-ray with respect to the Se fluorescent X-ray increases, and when the Br content increases to some extent, the Br fluorescent X-ray becomes the main component of the total transmitted X-ray. It becomes. Therefore, the fluorescent X-rays of Br can be detected by detecting the total transmitted X-rays with the X-ray detector 5.

  FIG. 24 is a graph showing experimental results of a comparative example of the method for detecting Br in resin according to the fourth embodiment. In the comparative example, the first filter 15a and the second filter 15b are not installed. 24A is an X-ray spectrum measured with an X-ray detector 5 for a resin piece 4 having a Br content of 0 mass%, (b) a Br content of 1 mass%, and (c) a Br content of 10 mass%. It is a graph which shows.

  As shown in FIG. 24A, only the Zr-Kα ray and the Zr-Kβ1 ray derived from the secondary target 2 are detected in the X-ray spectrum of the resin piece 4 having a Br content mass of 0%. As shown in FIGS. 24B to 24C, in the X-ray spectrum of the resin piece 4 having a Br content of 1% by mass and 10% by mass, the Zr-Kα line and the Zr-Kβ1 line derived from the secondary target 2 are used. In addition, Br-Kα ray and Br-Kβ1 ray, which are characteristic X-rays in which Br of the resin piece 4 is excited, are also slightly detected. 24 (b) to 24 (c), the X-ray detection intensity of the Zr-Kα line and the Zr-Kβ1 line is reduced compared to FIG. Absorption phenomenon is observed.

  At this time, the total ΣI (e) of the X-ray intensities of the Zr-Kα line, Zr-Kβ1 line, Br-Kα1 line, and Br-Kβ1 line in each resin piece 4 is about 30000 cps / mA at Br0 mass%, It was about 27000 cps / mA at 1% by mass of Br and about 12400 cps / mA at 10% by mass of Br. The ratio of the total X-ray intensities ΣI (e) is ΣI (e) [Br10 mass%] / ΣI (e) [Br0 mass%] = 0.41, ΣI (e) [Br1 mass%] / ΣI ( e) [Br0 mass%] = 0.89. For example, when a detector capable of visualizing X-rays is used as the X-ray detector 5, the brightness of the Br-containing resin piece 4a is smaller than that of the Br-non-containing resin piece 4b.

  As described above, when an element other than Br that absorbs X-rays is included, the sum ΣI (e) detected by the X-ray detector having the X-ray intensity is small as in the case where Br is included. In order to detect Br by generation of fluorescent X-rays, a resin piece containing Br is used rather than ΣI (e) [Br0 mass%] which is the intensity of all X-rays transmitted through a resin piece containing no Br. It is necessary to increase the intensity of all X-rays. That is, ΣI (e) [Br 10 mass%] / ΣI (e) [Br 0 mass%] and ΣI (e) [Br 1 mass%] / ΣI (e) [Br 0 mass%] must be larger than 1. It becomes. Thereby, for example, when a detector capable of visualizing X-rays is used as the X-ray detector 5, the Br-containing resin piece 4a has a higher luminance than the Br-non-containing resin piece 4b.

  25 and 26 are diagrams showing experimental results of experimental examples of the method for detecting Br in resin according to the fourth embodiment. These are the sums of all transmitted X-rays with resin pieces not containing Br when the amount of Rb and Se contained in each of the first filter 15a and the second filter 15b in FIG. 22 is changed. On the other hand, it shows how the total sum of transmitted X-rays of Br 1 mass% and Br 10 mass% changes. FIG. 25 shows the ratio of the total ΣI (e) of each X-ray intensity when Br is 10% by mass. Each data in the table is expressed by ΣI (e) [Br10% by mass] / ΣI (e) [Br0% by mass]. Represented. FIG. 26 shows the ratio of the total ΣI (e) of each X-ray intensity in the case of Br1% by mass. Each data in the table is expressed by ΣI (e) [Br1% by mass] / ΣI (e) [Br0% by mass]. Represented.

As shown in FIG. 23, when the Rb deposition amount of the Rb film of the first filter 15a is 60 mg / cm ² and the Se deposition amount of the Se film of the second filter 15b is 180 mg / cm ² , the detection is performed by the X-ray detector 5. The total amount of X-rays is about 7.5 cps / mA when the resin piece is Br 0% by mass, about 10 cps / mA when Br is 1% by mass, and about 17 cps / mA when Br is 10% by mass. As shown in FIGS. 25 and 26, the ratio of the total X-ray intensities ΣI (e) is ΣI (e) [Br10 mass%] / ΣI (e) [Br0 mass%] = 2.25, ΣI (e) [Br1 mass%] / ΣI (e) [Br0 mass%] = 1.29.

  The amount of Rb adhering to the first filter 15a such that the ratio value based on the total X-ray intensity of Br0 mass% is greater than 1 and increases according to the Br content, the second filter 15b Br can be detected by fluorescent X-rays within the range of Se adhesion.

As shown in FIG. 25, the range of the conditions of the filter 15 in which the ratio ΣI (e) [Br10 mass%] / ΣI (e) [Br0 mass%] is larger than 1 is the Rb adhesion amount of the first filter 15a. Is 30 to 120 mg / cm ² , and the Se deposition amount of the second filter 15b is in the range of 60 to 240 mg / cm ² . Preferably, the Rb deposition amount of the first filter 15a is 120 mg / cm ² , and the Se deposition amount of the second filter 15b is 120 to 240 mg / cm ² . In that case, a ratio ΣI (e) [Br 10 mass%] / ΣI (e) [Br 0 mass%] can be obtained with a sensitivity of about 2. Also, preferably, Rb adhesion amount of the first filter 15a is a 60 to 120 mg / cm ^2, and Se deposition amount of the second filter 15b is 180 mg / cm ^2. In that case, a ratio ΣI (e) [Br 10 mass%] / ΣI (e) [Br 0 mass%] can be obtained with a sensitivity of about 2.

  The conditions for the Rb adhesion amount of the first filter 15a and the Se adhesion amount of the second filter 15b are as follows. The ratio ΣI (e) [Br1 mass%] / ΣI (e) [Br0] shown in FIG. The same tendency is obtained in [mass%].

27, 28, and 29 are diagrams showing experimental results of other comparative examples of the method for detecting Br in resin according to the fourth embodiment. FIG. 27 shows the experimental results in the comparative example in which Rb is not contained as the first filter 15a, that is, the Rb adhesion amount is 0 mg / cm ^{2 under} the same conditions as FIG. 25 and FIG. (A) of FIG. 27 is the ratio of the sum of all transmitted X-rays of 10 mass% of Br to the sum of all transmitted X-rays of a resin piece not containing Br. Each data is represented by the formula, ΣI (e) [Br10%] / ΣI (e) [Br0%]. FIG. 27B shows the ratio of the total transmission X-rays of Br1 mass% to the total transmission X-rays of the resin pieces not containing Br. Each data is represented by the formula, ΣI (e) [Br1%]. / ΣI (e) [Br0%]. As shown in FIG. 27, the ratio of the total X-ray intensity ΣI (e) of the resin pieces after passing through the second filter 15b is the ratio ΣI (e) [Br10 mass%] / ΣI (e) [Br0 mass%]. And the ratio ΣI (e) [Br1% by mass] / ΣI (e) [Br0% by mass] does not greatly exceed 1.

FIG. 28 is a diagram showing experimental results in a comparative example in which Se is not contained as the second filter 15b, that is, the Se adhesion amount is 0 mg / cm ^{2 under the} same conditions as in FIGS. (A) of FIG. 28 is a ratio of the sum of all the transmitted X-rays of 10 mass% of Br to the sum of all transmitted X-rays of the resin piece not containing Br, and each data is represented by the formula: ΣI (e) [Br10%] / ΣI (e) [Br0%]. (B) of FIG. 28 is the ratio of the sum of all transmitted X-rays of Br1 mass% to the sum of all transmitted X-rays of a resin piece not containing Br, and each data is represented by the formula: ΣI (e) [Br1%] / ΣI (e) [Br0%]. As shown in FIG. 28, the ratio between the total ΣI (e) of the X-ray intensities after the resin pieces have passed through the second filter 15b is the ratio ΣI (e) [Br10 mass%] / ΣI (e) [Br0 mass%]. And the ratio ΣI (e) [Br1% by mass] / ΣI (e) [Br0% by mass] does not greatly exceed 1.

FIG. 29 shows the same conditions as FIG. 25 and FIG. 26 except that the secondary target 2 is replaced with Zr and contains Sr, and the first filter 15a does not contain Rb, that is, the Rb adhesion amount is 0 mg. It is a figure which shows the experimental result in the comparative example made into / cm < ² >. As Sr for the secondary target 2, strontium carbonate SrCO ₃ (manufactured by Wako Pure Chemical Industries, Ltd.) powder was used in a measuring cup for powder sample. (A) of FIG. 29 is a ratio of the sum of all the transmitted X-rays of 10 mass% of Br to the sum of all transmitted X-rays of the resin piece not containing Br, and each data is represented by the formula: ΣI (e) [Br10%] / ΣI (e) [Br0%]. FIG. 29B shows the ratio of the total transmission X-rays of Br1 mass% to the total transmission X-rays of the resin pieces not containing Br. Each data is represented by the formula, ΣI (e) [Br1%]. / ΣI (e) [Br0%]. As shown in FIG. 29, the ratio between the total ΣI (e) of the X-ray intensities after passing through the second filter 15b is the ratio ΣI (e) [Br10 mass%] / ΣI (e) [Br0 mass%] and the ratio ΣI. (E) None of [Br1% by mass] / ΣI (e) [Br0% by mass] greatly exceeds 1.

  Therefore, also from the experimental results of any of the comparative examples in FIGS. 27, 28, and 29, the X-ray detector 5 shows that the X-ray detection intensity of the Br-containing resin piece 4a is higher than that of the non-Br-containing resin piece 4b. The resin piece 4 cannot be distinguished.

  In the method for detecting Br in resin according to the present embodiment, the X-ray intensity generated by irradiating the resin piece 4 with Zr characteristic X-rays and passing through the resin piece 4 is compared with the first filter containing Rb and Se. It has a step of detecting the X-ray intensity through the second filter contained in order, and a step of detecting the content of Br in the resin piece 4 based on the detected X-ray intensity. Since the filter 15 having a two-stage configuration including the first filter 15a containing Rb and the second filter 15b containing Se is used, irradiation X-rays derived from the secondary target 2 (Zr-Kα rays and Zr-Kβ1) Line) and X-rays derived from the filter 15 (consisting of Rb-Kα ray, Rb-Kβ1 ray, Se-Kα ray and Se-Kβ1 ray) while reducing the arrival intensity of the X-ray detector 5 to the resin The arrival intensity of Br-derived X-rays (Br-Kα ray and Br-Kβ1 ray) in the piece 4 can be maintained.

  Therefore, the total X-ray detection intensity of the resin piece 4 having a Br content of 1 to 10% by mass can be made stronger than the total X-ray detection intensity of the resin piece 4 having a Br content of 0% by mass. Therefore, a detector capable of visualizing X-rays such as an X-ray line sensor, an X-ray imaging intensifier, an X-ray CCD camera, and an X-ray scintillator position sensitive proportional counter was used as the X-ray detector 7. In this case, the Br-containing resin piece 4a has higher brightness than the Br-non-containing resin piece 4b, and the resin piece 4 can be distinguished. Thereby, Br can be detected easily and at low cost. Also, the characteristic X-rays of Zr used for irradiating the resin pieces are easily absorbed by Br having the maximum intensity in the energy range of the K K shell absorption edge or higher and the Mo K shell X or lower energy range. Is a line. For this reason, the fluorescent X-rays of Br can be generated relatively strongly.

  The X-ray detector 5 is not necessarily limited to a detector capable of visualizing X-rays, and may be any device that can detect the intensity of X-rays generated in the sample (resin piece 4). For example, a detector having no energy resolution such as a scintillation counter or a proportional counter can be used. Since no energy resolution is required, the detection speed can be improved.

  Further, the in-resin Br detection method according to the fourth embodiment may be combined with the in-resin Br detection method according to the first embodiment described above. FIG. 30 is a flowchart for determining the presence or absence of Br in a resin piece by combining the method for detecting Br in resin according to the fourth embodiment and the method for detecting Br in resin according to the first embodiment described above. The characteristic X-ray of any one of Sr, Y, Zr, Nb, and Mo is irradiated onto the resin piece, and the intensity of the first X-ray that has passed through the resin piece is detected (step S1). Further, Zr characteristic X-rays are irradiated onto the resin piece, and the intensity of the X-rays generated through the resin piece is first passed through the first filter containing Rb and the second filter containing Se. 2 is detected as the X-ray intensity (step S11). It is determined whether the intensity of the first X-ray is less than or less than a preset first threshold and whether the intensity of the second X-ray is greater than or greater than a preset second threshold (step) S22). If the determination in step S22 is YES, it is assumed that the resin piece contains Br, and if NO, the resin piece does not contain Br (steps S23a and S23b). Thus, since the inclusion of Br is detected based on the intensity of the first X-ray and the intensity of the second X-ray by combining the first embodiment and the fourth embodiment, a plurality of detection methods The detection accuracy is improved by combining.

  As described above, the Br detection by transmission X-ray absorption in the first embodiment also detects a resin piece containing an element having a large absorption other than Br. However, as in the fourth embodiment, the fluorescence X peculiar to Br is detected. Since the detection is further performed with a line, the accuracy is improved.

  The in-resin Br detecting method of the fourth embodiment may be further performed on the resin piece that is supposed to contain Br in the in-resin Br detecting method of the first embodiment. FIG. 31 is another flowchart for determining the presence or absence of Br in a resin piece by combining the method for detecting Br in resin according to the fourth embodiment and the method for detecting Br in resin according to the first embodiment described above. . First, the characteristic X-ray of any one of Sr, Y, Zr, Nb, and Mo is irradiated onto the resin piece, and the intensity of the first X-ray that has passed through the resin piece is detected (step S1). Next, it is determined whether the first X-ray is less than or less than a preset first threshold value (step S2). If determination of step S22 is YES, it will progress to the detection step of following step S11. On the other hand, if NO, the detection step of the next step S11 is skipped, and the resin piece does not contain Br (step S43b). In step S11, the resin piece for which the determination in step S22 is YES is irradiated with Zr characteristic X-rays, and the generated X-rays are a first filter containing Rb and a second filter containing Se. The intensity of the second X-ray is detected in order. Next, it is determined whether the intensity of the second X-ray is greater than or greater than a preset second threshold value (step S12). If the determination in step S12 is YES, the resin piece contains Br, and if NO, the resin piece does not contain Br (steps S43a and S43b).

  Since the resin piece not containing Br is removed by the Br detection by the transmission X-ray absorption of the first embodiment, it is not necessary to perform the fluorescent X-ray detection of the fourth embodiment for all the resins. That is, detection by the in-resin Br detection method of the first embodiment is performed prior to the detection of the fourth embodiment, and the X-ray intensity by the in-resin Br detection method of the first embodiment is a preset value. If it is not less than or less than this, the detection of the fourth embodiment is skipped because the resin piece does not contain Br. The detection of the fourth embodiment is performed only when the X-ray intensity in the resin Br detection method is less than or less than a preset value. Accordingly, if the ratio of the Br-containing resin pieces contained in all the resin pieces is small, the fluorescent X-ray detection of the fourth embodiment can be skipped, so that there is an effect of increasing the detection speed while ensuring the detection accuracy.

<Embodiment 5. >
FIG. 32 is a schematic diagram illustrating the configuration of the resin sorting apparatus according to the fifth embodiment. This is a configuration in which the in-resin Br detecting device portion of the second embodiment is replaced with a device using the in-resin Br detecting method of the fourth embodiment.

  In FIG. 32, a filter 15 including a first filter 15a and a second filter 15b is installed between the transport device 8 and the X-ray detector 5, and the secondary target contains Zr. Of the two filters, the first filter 15a arranged on the X-ray source side contains Rb, and the second filter 15b arranged on the X-ray detector 5 side contains Se.

The X-ray intensity detected by the X-ray detector 5 is input to the data processor 10, and the data processor 10 determines whether or not the resin piece contains Br based on the X-ray intensity. For example, as in the experimental example of the fourth embodiment, the Rb deposition amount of the Rb film of the first filter 15a is 60 mg / cm ² , and the Se deposition amount of the Se film of the second filter 15b is 180 mg / cm ² . A resin piece whose X-ray intensity is increased 1.29 times or more compared to the strength of a resin not containing Br is determined as a Br-containing resin. Thereby, the resin piece containing 1 mass% or more of Br is detectable. The relationship between the Br content and the X-ray intensity may be stored in a memory in advance, and the Br content may be calculated by comparing the relationship with the measured intensity. The sorting mechanism 11 sorts the resin pieces according to the discrimination of the data processor 10.

  The resin sorting apparatus according to the fifth embodiment may be used so as to further sort only the resin pieces that are supposed to contain Br in advance by the resin sorting apparatus according to the third or fourth embodiment. For example, the resin pieces 4 sorted in the storage box 12 for Br-containing resin pieces in the second embodiment are supplied from the supply device 7 to the transport device 8 as a separation object. The supplied resin piece is a resin piece whose transmitted X-ray intensity is equal to or less than a set threshold value in the resin separation of the third and fourth embodiments. Most of these are usually resins containing Br, which is a flame retardant, but may contain resin pieces containing elements similar to the X-ray absorption effect of Br, such as Zn, Pb, Sr, etc. There is sex. Alternatively, it is a resin piece that does not contain Br but is significantly thicker than a standard resin piece to be processed.

  Hereinafter, the sorting operation in such a case will be described. The resin piece 4 is moved by the transport device 8, and X-rays monochromated by the primary X-ray source 1 and the secondary target 2 of Zr at a predetermined position are converted into resin pieces 4 (Br-containing resin pieces 4 a or Br). The X-ray detector 5 detects the fluorescent X-rays derived from the resin pieces 4, and the detection signal is sent to the data processor 10. And it distinguishes from the resin X 4 intensity | strength derived from each resin piece 4, and the resin piece 4b which does not contain Br from the relationship of a threshold value. FIG. 33 is an explanatory diagram showing an example of detection data obtained by the X-ray detector 5 of the resin sorting apparatus according to the fifth embodiment. The data in this figure is an image 34 displayed on the screen 14 of the data processor 10 when an X-ray visualization detector such as an X-ray imaging intensifier is used as the X-ray detector 5. In the image 34, the Br-containing resin piece 4a is displayed with high luminance due to the fluorescent X-rays derived from Br, and the luminance of the resin piece 4b not containing Br that does not generate Br-derived fluorescent X-rays is displayed low. Also, the resin piece 4c that contains an element having an effect similar to the X-ray absorption effect of Br or does not contain Br but has a large thickness also has a low luminance. From such determination, a command signal corresponding to the determination is output to the sorting mechanism 11 at an appropriate timing, and the sorting object is sorted. In this way, it is possible to further improve the separation accuracy of the resin containing Br.

  FIG. 34 is a schematic view showing a modified configuration of the resin sorting apparatus according to the fifth embodiment. This is a configuration in which the filter 15 and the X-ray detection unit 5 having the configuration of FIG. Since the fluorescent X-rays generated from the resin piece 4 radiate in all directions centering on the resin piece 4, the arrangement of the filter 15 and the X-ray detector 5 is arranged above the resin piece 4 as shown in FIG. The structure to do may be sufficient. In addition, regardless of the arrangement of the filter 15 and the X-ray detector 5, a partition 16 is provided between the filter 15 and the X-ray detector 5 to block the fluorescent X-rays generated from the other resin pieces 4. The position of the plastic piece 4 that generates the line can be determined more accurately.

  Note that, in the same configuration as in the third embodiment, a filter 15 is formed on the detection side of each of a plurality of X-ray detection elements constituting the X-ray detector 5, and the X-rays detected by the X-ray detection elements Similar detection is possible using intensity.

  In the fifth embodiment, the resin piece is irradiated with the characteristic X-ray of Zr, which is an X-ray having the maximum intensity in the energy range not less than the absorption edge of the Br K-shell and not more than the characteristic X-ray of the Mo K-shell. Since the fluorescent X-rays of Br can be generated relatively strongly, an X-ray detector having no energy resolution can be used.

<Embodiment 6. >
FIG. 35 is a schematic diagram showing the configuration of the resin sorting apparatus according to the sixth embodiment. The resin sorting device according to the sixth embodiment is a resin sorting device having a function of detecting the content of Br using the in-resin Br detecting method of the first embodiment and the in-resin Br detecting method of the fourth embodiment. In addition to the configuration of the resin sorting device of the second and third embodiments, the configuration of the detection device portion of the resin sorting device of the fifth embodiment is also provided.

  As in FIG. 35, the X-rays detected by the primary X-ray source 1, the conveyor device 8 such as a belt conveyor, the X-ray detector 5, and the X-ray detector 5, as in the resin sorting apparatus of the second and third embodiments. A data processor 10 that detects Br in the resin piece 4 based on the strength, and a separation mechanism 11 that separates the resin piece 4 based on the detection result of the data processor 10 are provided.

  The resin separation device according to the sixth embodiment includes means for irradiating the resin piece 4 with characteristic X-rays of Sr, Y, Zr, Nb, and Mo and detecting Br based on the intensity of the transmitted X-rays; And a means for detecting Br based on the intensity of Br fluorescent X-rays generated from the resin piece by irradiating the resin piece 4 with the characteristic X-ray of Zr. For example, in the X-ray detector unit without the secondary filter 15, the data processor 10 is configured to determine whether or not Br is contained by attenuation of transmitted X-rays after the irradiated X-rays pass through the object to be sorted. With a processing circuit. In addition, the X-ray detector unit having the secondary filter 15 has a processing circuit configured to discriminate whether or not Br is contained based on the fluorescent X-ray intensity derived from Br generated from the object to be sorted. The data processor 10 detects Br based on the attenuation data of the transmitted X-rays and the fluorescent X-ray data of Br, and information signals such as the position of the resin piece from which the Br is detected and the time when it passes through the sorting unit. Is output to the sorting mechanism 11. When the data processor 10 detects a resin piece having a transmitted X-ray intensity equal to or lower than the threshold and a Br-derived fluorescent X-ray intensity equal to or higher than the threshold, it is determined as a Br-containing resin piece.

  The means for detecting Br based on the intensity of the transmitted X-ray and the means for detecting Br based on the intensity of the fluorescent X-ray are configured separately for each X-ray source part and X-ray detector part. You can also. If the X-ray source part and the X-ray detector part are used in common, the number of components is reduced, so that a low-cost apparatus can be realized. Therefore, in FIG. 35, the secondary target 2 is a target containing Zr. The resin piece 4 is irradiated with Zr characteristic X-rays. Further, a part of the light receiving side of the X-ray detector 5 is covered with the filter 15. The X-ray detector 5 uses an X-ray CCD camera that can detect the in-plane X-ray intensity, an X-ray sensor array, or the like. The X-ray intensity detected in the detection region 5b of the X-ray detector 5 covered with the filter 15 is used as data for detecting Br based on the intensity of the fluorescent X-ray. The X-ray intensity detected in the detection region 5a of the X-ray detector 5 not covered with the filter 15 is used as data for detecting Br based on the intensity of the transmitted X-ray.

  Hereinafter, the operation of the resin sorting apparatus according to the sixth embodiment will be described. The resin piece 4 composed of the Br-containing resin piece 4a and the non-Br-containing resin piece 4b is first moved to a position on the X-ray detector 5 where there is no secondary filter 15 by the transport device 8. At this position, the resin piece 4 is irradiated with X-rays monochromatic to characteristic X-rays by the primary X-ray source 1 and the secondary target 2. Here, the characteristic X-ray is a Zr characteristic X-ray. The X-rays irradiated and transmitted to the resin piece 4 are detected by the detector portion of the X-ray detector 5 in the region 5 a where the secondary filter 15 is not present. The detection signal detected here is sent to the data processor 10.

  Next, the resin piece 4 is moved to a position where the secondary filter 15 is installed on the X-ray detector 5. The fluorescent X-rays generated by the X-rays irradiated on the resin piece 4 at this position are detected by the X-ray detector 5 through the first filter 15a and the second filter 15b of the secondary filter 15 in this order. The first filter 15a contains Rb, and the second filter 15b contains Se. For this reason, fluorescent X-rays detected in this region 5b are mainly fluorescent X-rays derived from Br. The detection signal detected at this position is sent to the data processor 10.

  The data processor 10 first determines whether the resin piece 4 contains Br based on the X-ray intensity detected at the position of the X-ray detector 5 without the secondary filter 15. For example, it is assumed that the resin piece 4 contains Br when the transmitted X-ray intensity is equal to or less than a preset threshold value.

  Next, the data processor 10 determines whether or not the resin piece 4 contains Br based on the X-ray intensity detected at the position of the X-ray detector 5 where the secondary filter 15 is installed. For example, it is assumed that the resin piece 4 contains Br when the fluorescent X-ray intensity is equal to or higher than a preset threshold value.

  Thus, since the data processor 10 discriminates the resin piece using the transmitted X-ray intensity and the fluorescent X-ray intensity, it can be discriminated with high accuracy. Note that the detection order of transmitted X-ray intensity and fluorescent X-ray intensity may be reversed. Further, when the transmitted X-ray intensity detected in the area without the secondary filter 15 is all greater than the threshold value, the resin piece in the area does not contain Br. The fluorescent X-ray intensity may be measured only when there is a resin piece. In this case, when the ratio of the Br-containing resin pieces contained in all the resin pieces is relatively small, and the measurement of the fluorescent X-ray intensity requires more time than the transmitted X-ray intensity, it is effective in increasing the processing speed. Is big.

  FIG. 36 is an explanatory diagram showing an example of data detected by the resin sorting apparatus according to the sixth embodiment. This data is an image 34 displayed on the screen 14 of the data processor 10 when an X-ray visualization detector such as an X-ray CCD camera is used as the X-ray detector 5. The direction from the top to the bottom of the image 34 is the transport direction (X direction), and the left and right are the width direction (Y direction) of the transport device 8. 36A is an image detected at a certain time point, and FIG. 36B is an image detected after the resin piece is moved after (a). In (a) and (b), the upper half 34 a is an image detected in the light receiving area 5 a not including the filter 15, and the lower half 34 b is an image detected in the light receiving area 5 b including the filter 15. The resin piece 4a displayed with low luminance in the upper half 34a of (a) is the resin piece 4a displayed with high luminance in the lower half 34b of (b).

  36, in the image 34a detected in the light receiving region 5a that does not include the filter 15, the transmitted X-ray intensity is reduced at the portion of the Br-containing resin piece 4a where the transmitted X-ray is absorbed by Br, and the luminance is increased. It is displayed small. In the resin piece 4b that does not contain Br, or in the region where there is no resin, the transmitted X-ray intensity hardly changes and the luminance is displayed large. Note that even the resin piece 4b without Br is slightly absorbed by the resin, so that the luminance is slightly lowered as compared with the region without the resin. Similar to the X-ray absorption effect of Br, a resin piece containing an element other than Br or a resin piece 4c that does not contain Br but is thicker than a standard resin piece is displayed with low brightness. Therefore, if Br is contained only with a low transmitted X-ray intensity, a resin piece that does not contain Br, such as the resin piece 4c, may also become a Br-containing resin piece.

  Next, the resin piece 4 is moved to the light receiving region 5 b including the filter 15. In the detected image 34b, the Br-containing resin piece 4a that generates fluorescent X-rays derived from Br is displayed with high luminance. The non-Br containing resin piece 4b that does not generate Br-derived fluorescent X-rays is displayed without luminance. Similarly, the area where the resin piece is not placed is displayed dark without luminance. Also, a resin piece 4c containing an element having an effect similar to the X-ray absorption effect of Br or not containing Br but having a large thickness is displayed without luminance.

  For example, the data processor 10 extracts and stores a portion displayed with a luminance equal to or lower than a predetermined threshold value from the image 34a detected in the light receiving region 5a that does not include the filter 15. Next, after the same resin piece detected in the light receiving area 5a is moved to the light receiving area 5b by the transport device 8, a portion displayed with a luminance equal to or higher than a predetermined threshold is extracted from the detected image 34b and stored. And the part extracted with the image 34a and the part extracted with the image 34b are collated, and let the part extracted together be a part in which a Br containing resin piece exists.

  The data processor 10 outputs a command signal corresponding to the two-stage discrimination to the sorting mechanism 11 at an appropriate timing, and sorts the sorting object. Since two types of detection methods can be performed with one X-ray detection apparatus, it can be realized at low cost. In addition, by combining the data of the two types of detection methods on the same transport device, it is possible to more reliably determine whether or not Br is contained, and it is possible to determine the exact position on the transport device. The resin separation accuracy can be further improved.

  Moreover, in the apparatus described above, the filter 15 is configured to partially cover the light receiving side of the X-ray detector 5, but instead, a mechanism for inserting and removing the filter 15 on the light receiving side of the X-ray detector 5 is provided. Also good. FIG. 37 is a schematic view showing a modified configuration of the resin sorting apparatus according to the sixth embodiment. Based on the configuration of FIG. 35, a filter moving mechanism 40 is further provided that allows the filter 15 to move between the light receiving region of the X-ray detector 5 and the outside thereof. The filter moving mechanism 40 allows the filter 15 to be inserted and removed from the light receiving area of the X-ray detector 5 and outside the area.

  For example, in the case of the configuration of FIG. 37, detection is performed according to the following procedure. First, when the resin piece is transported to the top of the X-ray detector 5, the transport is temporarily stopped. At that time, the transmitted X-ray intensity is detected by the X-ray detector 5 with the filter 15 removed from the light receiving side of the X-ray detector 5. Next, a filter 15 is inserted on the light receiving side of the X-ray detector 5. The X-ray detector 5 detects the fluorescent X-ray intensity. The method for detecting Br from the transmitted X-ray intensity and the fluorescent X-ray intensity may be the same procedure as described above. When the measurement is completed, the filter 15 is pulled out to the light receiving side of the X-ray detector 5 and the next resin piece is conveyed to the top of the X-ray detector 5. Repeat these steps.

  FIG. 38 is a schematic view showing another modified configuration of the resin sorting apparatus according to the sixth embodiment. The secondary target 2 shown in FIG. 37 has a portion 2a for generating Zr characteristic X-rays and a portion 2b for generating Sr characteristic X-rays, and includes a target switching mechanism 42 for switching between these portions. For example, the portion 2a that generates the characteristic X-ray of Zr and the portion 2b that generates the characteristic X-ray of Sr are fixed to a rotatable shaft so that the surface that generates the characteristic X-ray is on the opposite side. 42 switches between 2a and 2b by rotating the shaft 180 degrees. The target switching mechanism 42 detects the transmitted X-ray intensity so that the continuous X-rays from the primary X-ray source 1 are irradiated to the portion 2b that generates the characteristic X-rays of Sr so that the fluorescent X-rays are emitted. At the time of detecting the intensity, the continuous X-ray from the primary X-ray source 1 is irradiated to the portion 2a that generates the characteristic X-ray of Zr. With this configuration, Sr characteristic X-rays having a large change in transmittance due to the absorption of Br can be used when the transmitted X-ray intensity is detected. For this reason, there exists an effect which improves a detection precision with a transmitted X-ray intensity. Further, since only one primary X-ray source 1 that generates continuous X-rays can generate two energy characteristic X-rays separately, the apparatus is simplified.

  As described above, the resin sorting apparatus according to the sixth embodiment has a characteristic X-ray of any one of Sr, Y, Zr, Nb, and Mo on the conveying device 8 that conveys the resin piece and the resin piece 4 that is conveyed. An X-ray source for irradiating, an X-ray detector 5 for detecting the intensity of the first X-rays whose characteristic X-rays have passed through the resin piece 4, and an X-ray for irradiating the resin piece 4 with Zr characteristic X-rays The intensity of the X-rays after being irradiated with the Zr characteristic X-rays and passing through the resin piece 4 is passed through the first filter 15a containing Rb and the second filter 15b containing Se in order. X-ray detector 5 for detecting the X-ray intensity of 2 and a data processor for determining the presence or absence of Br in the resin piece 4 based on the intensity of the first X-ray and the intensity of the second X-ray 10 is provided. For this reason, it is possible to accurately detect Br in the resin piece 4 even when using the X-ray detector 5 having no function of detecting energy, and it is possible to detect Br in the resin at high speed.

<Embodiment 7. >
FIG. 39 is a flowchart for explaining a method for producing a recycled resin product according to the seventh embodiment. First, a discarded resin product and a discarded home appliance are prepared (step T0). Next, in step 1 (SS1), a resin part containing resin is crushed from a discarded resin product or a discarded household electrical appliance and processed into a resin piece. The resin piece is, for example, a rectangular parallelepiped having a thickness of 0.5 to 20 mm and a side of about 5 mm to 5 cm, or an indeterminate shape having the same volume. More preferably, it is desirable to have a thickness in the range of about 1 to 3 mm.

  Next, in step 2 (SS2), metal or ceramic mixed in the resin piece is removed. Since metal and ceramic generally have a higher specific gravity than resin, a method may be used in which crushed pieces are placed in a solution having an appropriate specific gravity, and the submerged one is separated from metal or ceramic, and the floated one is separated from resin pieces. Separately, metal and ceramic are reused by processing such as metal (T1).

  Next, Step 3 (SS3) is a process of separating a resin piece containing Br from a plurality of resin pieces using the method and apparatus described in the first to sixth embodiments. Since it can be detected by an X-ray detector having no energy resolution, high-speed detection can be realized. The resin piece containing Br is separately separated and reused by Br-containing resin treatment (T2). The resin piece not containing Br proceeds to the subsequent steps.

  Next, in the process of Step 4 (SS4), the material is sorted for each material such as polypropylene and polystyrene, for example, by electrostatic sorting using the difference in the charged series of the resin or sorting using the specific gravity difference. Next, in step 5 (SS5), the resin piece from which the Br-containing resin piece has been removed is heated and melted, or a mixed resin material, a property modifying material, or the like is newly added to the resin piece to perform a mixing process. . In addition, the process of step 5 is not essential if it can be reused as it is after the process of step 4 (SS4). The resin obtained in step 4 or step 5 is a recycled resin material (T3), which is a raw material for manufacturing a recycled resin product.

  Finally, in step 6 (SS6), the mixed material is processed into a resin part or resin product by a method such as extrusion molding or pressure molding. A recycled resin product (T4) is manufactured by the series of steps described above. The SS3 separation process is performed between the crushing process of SS1 and the mixing process of SS5. Further, the process of removing the mixed metal of SS2 and the process of selecting the resin material of SS4 are not necessarily performed.

  As described above, in the method for producing a recycled resin product according to the seventh embodiment, Br in a resin piece obtained by chopping a collected resin product is detected in Br in Embodiments 1 and 4 and a combination thereof. A recycled resin product comprising: a detection step that is detected by a method; a separation step that excludes a resin piece that is supposed to contain Br in the detection step; and a step of mixing the resin piece after the separation step and molding the resin piece into a resin part. It is a manufacturing method. Moreover, the apparatus shown in Embodiment 2, 3, 5, 6 is used as a resin classification apparatus used for a detection process and a classification process. For this reason, even if it uses the X-ray detector which does not have the function to detect energy, the method of detecting Br which is a specific element in resin accurately and at high speed is realizable. Moreover, since the resin is fractionated, a recycled resin product containing almost no Br can be realized.

  As described above, all of the embodiments have the maximum energy in this range so that the main energy component is in the energy range above the absorption edge of Br K shell and below the characteristic X-ray of Mo K shell. Irradiate the resin piece with the wire. For this reason, the absorption in Br is large, the change in transmittance is large, and the generation of fluorescent X-rays is large, so that Br in the resin can be removed even if an X-ray detector having no function of detecting energy is used. It becomes possible to detect with high accuracy, and Br in the resin can be detected at high speed.

Claims (6)

A plurality of resin pieces are simultaneously irradiated with one of the characteristic X-rays of Sr-Kα , Y-Kα, Zr-Kα, Nb-Kα, and Mo-Kα, and the first X-rays transmitted through the plurality of resin pieces Simultaneously detecting the intensity of as a visible image obtained by image processing;
For each of the plurality of resin pieces, determining whether the intensity of the first X-ray is less than or less than a first threshold;
Identifying a position of a resin piece that is less than or less than the first threshold value among the plurality of resin pieces;
The resin piece is irradiated with characteristic X-rays of Zr-Kα, and the intensity of X-rays generated in the resin is secondly passed through a first filter containing Rb and a second filter containing Se in order. Detecting as the X-ray intensity of
Detecting the content of Br based on the intensity of the second X-ray,
In the step of determining, when the intensity of the first X-ray is less than or less than a first threshold, the process proceeds to a step of detecting the intensity of the second X-ray, and the intensity of the first X-ray is A method for detecting Br in resin, wherein the step of detecting the intensity of the second X-ray is skipped on the assumption that the resin piece does not contain Br if it is not less than or less than a threshold value of 1 . 2. The resin according to claim 1, wherein the determining step is a step of determining whether the value is equal to or less than a first threshold value by comparing data relating to a standard sample containing a known bromine amount. Middle Br detection method. A transport device for transporting a plurality of resin pieces;
An X-ray source that simultaneously irradiates one of the characteristic X-rays of Sr-Kα, Y-Kα, Zr-Kα, and Nb-Kα to the plurality of resin pieces to be conveyed;
For each of the plurality of resin pieces, an X-ray detector that simultaneously detects the intensity of transmitted X-rays as a visible image obtained by image processing;
For each of the plurality of detected resin pieces, a determiner for determining the presence or absence of Br in the plurality of resin pieces from the intensity of transmitted X-rays;
A resin separation device comprising: a separation mechanism that separates the resin pieces based on a determination result of the determination device. A transport device for transporting a plurality of resin pieces;
An X-ray source that simultaneously irradiates one of the characteristic X-rays of Sr-Kα, Y-Kα, Zr-Kα, and Nb-Kα to the plurality of resin pieces to be conveyed;
For each of the plurality of resin pieces, an X-ray detector that simultaneously detects the intensity of the first X-rays through which the irradiated characteristic X-rays have passed through the resin piece as a visible image obtained by image processing;
An X-ray source for irradiating the resin piece with a characteristic X-ray of Zr-Kα;
The intensity of the X-rays generated in the resin by irradiation with the characteristic X-rays of Zr-Kα is changed to the second X-ray intensity through the first filter containing Rb and the second filter containing Se in order. An X-ray detector that detects the intensity;
Determining the presence or absence of Br in the resin piece based on the intensity of each X-ray obtained by each X-ray detector, and in the determining step, A determinator that determines to contain Br when the intensity is less than or less than a first threshold and the intensity of the second X-ray is greater than or greater than a second threshold;
Resin sorting device with The resin according to claim 4, wherein the determining step is a step of determining whether the value is equal to or less than a first threshold value by comparing with data relating to a standard sample containing a known bromine amount. Sorting device. A separation step of separating Br in a resin piece obtained by shredding the collected resin product by the resin separation device according to any one of claims 3 to 5, and a resin piece after the separation step are mixed. And a step of molding the resin part into a recycled resin product.

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