CN117121120A - Scintillator structure - Google Patents
Scintillator structure Download PDFInfo
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- CN117121120A CN117121120A CN202280024712.XA CN202280024712A CN117121120A CN 117121120 A CN117121120 A CN 117121120A CN 202280024712 A CN202280024712 A CN 202280024712A CN 117121120 A CN117121120 A CN 117121120A
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- resin
- gos
- scintillator
- curing agent
- scintillator structure
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- 229920005989 resin Polymers 0.000 claims abstract description 121
- 239000011347 resin Substances 0.000 claims abstract description 121
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 64
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 13
- 150000008065 acid anhydrides Chemical group 0.000 claims description 6
- 150000002903 organophosphorus compounds Chemical group 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical group C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000002834 transmittance Methods 0.000 description 50
- 239000000463 material Substances 0.000 description 40
- 239000003822 epoxy resin Substances 0.000 description 30
- 229920000647 polyepoxide Polymers 0.000 description 30
- 239000000843 powder Substances 0.000 description 26
- 230000005855 radiation Effects 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 239000000919 ceramic Substances 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000012795 verification Methods 0.000 description 14
- MCVAAHQLXUXWLC-UHFFFAOYSA-N [O-2].[O-2].[S-2].[Gd+3].[Gd+3] Chemical compound [O-2].[O-2].[S-2].[Gd+3].[Gd+3] MCVAAHQLXUXWLC-UHFFFAOYSA-N 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- -1 acid anhydride compound Chemical class 0.000 description 9
- 230000008901 benefit Effects 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 9
- 230000005283 ground state Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910052777 Praseodymium Inorganic materials 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 8
- 239000000470 constituent Substances 0.000 description 7
- 230000005281 excited state Effects 0.000 description 7
- 229910052771 Terbium Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- LSDYBCGXPCFFNM-UHFFFAOYSA-M dimethyl phosphate;tributyl(methyl)phosphanium Chemical compound COP([O-])(=O)OC.CCCC[P+](C)(CCCC)CCCC LSDYBCGXPCFFNM-UHFFFAOYSA-M 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 2
- OUWCMMDPQFNQHM-UHFFFAOYSA-N 3-ethylbutane-1,2,4-triol Chemical compound CCC(CO)C(O)CO OUWCMMDPQFNQHM-UHFFFAOYSA-N 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-M cyclohexanecarboxylate Chemical compound [O-]C(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
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- 230000007017 scission Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MIKCAECBBIRHCH-UHFFFAOYSA-N gadolinium(3+);oxygen(2-);trisulfide Chemical compound [O-2].[O-2].[O-2].[S-2].[S-2].[S-2].[Gd+3].[Gd+3].[Gd+3].[Gd+3] MIKCAECBBIRHCH-UHFFFAOYSA-N 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- HKNJOBDPCCDTNX-UHFFFAOYSA-N praseodymium terbium Chemical compound [Pr][Tb] HKNJOBDPCCDTNX-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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Abstract
The reliability of the scintillator structure is improved. The scintillator structure includes a plurality of cells and a reflective layer covering the plurality of cells. Here, the plurality of units each include a resin and a phosphor, the resin including a main agent and a curing agent, the main agent including bis-7-oxabicyclo [4.1.0] heptane. Alternatively, the plurality of units each include a resin and a phosphor, and the resin includes a main agent and a curing agent. The main agent comprises 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexane carboxylate and 2, 2-bis (hydroxymethyl) -1-butanol.
Description
Technical Field
The present invention relates to a scintillator structure, and for example, to an effective technique applied to a scintillator structure having a plurality of units each including a resin and a phosphor.
Background
Japanese patent application laid-open No. 63-100391 (patent document 1) describes a technique related to a phosphor molded body containing bisphenol A type epoxy resin.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 63-100391
Disclosure of Invention
Technical problem to be solved by the invention
The scintillator is a substance that absorbs energy of radiation to generate visible light when irradiated with radiation typified by X-rays or gamma rays. The scintillator is produced as a scintillator structure including a scintillator and a reflective layer, and an X-ray detector including a combination of the scintillator structure and a photoelectric conversion element such as a photodiode is used in, for example, medical equipment such as X-ray CT, analytical equipment, nondestructive inspection devices using radiation, radiation leakage inspection devices, and the like.
For example, the scintillator uses a material composed of gadolinium oxysulfide (Gd 2 O 2 S) a ceramic. Here, in the present specification, gadolinium oxysulfide is referred to as "GOS". In addition, gadolinium oxysulfide itself emits little light, and praseodymium, terbium, or the like is contained in gadolinium oxysulfide. Therefore, the term "GOS" in the present specification implies that a substance (phosphor) that emits light by using gadolinium oxysulfide itself containing praseodymium, terbium, or the like. However, when it is necessary to clearly indicate that gadolinium oxysulfide itself contains praseodymium, terbium, or the like, it is sometimes expressed as "GOS" containing praseodymium or as "GOS" containing praseodymiumTerbium "GOS".
In addition, in the case where the scintillator is composed of "GOS" monomers, the "GOS" is composed of ceramics. On the other hand, as described later, it has been studied to construct a scintillator from a mixture of "GOS" and a resin, and in this case, "GOS" is composed of powder. Therefore, in the present specification, when no particular explicit ceramic or powder is required, it is simply expressed as "GOS". In contrast, when explicit ceramics are required, they are called "GOS" ceramics. On the other hand, when the powder is required to be clearly illustrated, it is called "GOS" powder.
The GOS has a luminous output power ratio of visible light to cadmium tungstate (CdWO) 4 ) Great advantage, on the other hand, high manufacturing cost.
Therefore, in order to reduce the manufacturing cost of the scintillator structure, a mixture of "GOS" powder and resin is being studied for use as a scintillator.
In this regard, as an item requiring a high priority for the scintillator structure, reliability may be improved. This is because if the reliability of the scintillator structure can be improved, the life of the radiation detector can be prolonged. Therefore, in order to improve reliability, the scintillator is required to have high radiation resistance. In particular, as described above, in the case where the scintillator is composed of a mixture of "GOS" powder and resin, it is desirable that deterioration is not likely to occur when the resin is irradiated with radiation.
The purpose of the present invention is to improve the reliability of a scintillator structure.
Technical scheme for solving technical problems
The scintillator structure in one embodiment includes a plurality of cells and a reflective layer covering the plurality of cells. Here, the plurality of units each include a resin and a phosphor, the resin including a main agent and a curing agent, the main agent including bis-7-oxabicyclo [4.1.0] heptane.
The scintillator structure in one embodiment includes a plurality of cells and a reflective layer covering the plurality of cells. Here, the plurality of units each include a resin and a phosphor, and the resin includes a main agent and a curing agent. The main agent comprises 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexane carboxylate and 2, 2-bis (hydroxymethyl) -1-butanol.
Effects of the invention
According to one embodiment, the reliability of the scintillator structure can be improved.
Drawings
Fig. 1 is a diagram schematically showing an X-ray detector.
Fig. 2 is a flowchart illustrating a flow of a process for manufacturing a scintillator structure.
Fig. 3 is a diagram schematically showing steps from the dicing step to the reflective material application step.
Detailed Description
In all drawings for explaining the embodiments, the same members are denoted by the same reference numerals in principle, and repeated descriptions thereof are omitted. In order to facilitate understanding of the drawings, hatching may be added to the top view.
< summary of X-ray Detector >
Fig. 1 is a diagram schematically showing an X-ray detector.
In fig. 1, an X-ray detector 100 includes a scintillator structure 10 and a light receiving element 20. The scintillator structure 10 is composed of a plurality of scintillators 11 that generate visible light from X-rays incident on the X-ray detector 100, and a reflective layer 12 that covers each of these plurality of scintillators 11. On the other hand, the light receiving element 20 has a function of generating a current from the visible light generated by the scintillator 11, and is constituted by a photoelectric conversion element represented by a photodiode, for example. The light receiving element 20 is provided on the support 30, for example, and is provided corresponding to each of the plurality of scintillators 11.
The scintillator 11 has a function of absorbing X-rays to generate visible light, and is composed of a phosphor 11a and a resin 11 b. In this specification, a material obtained by mixing the resin 11b with the "GOS" powder constituting the phosphor 11a is sometimes referred to as "resin GOS". That is, the scintillator 11 in the present embodiment is constituted by "resin GOS". The phosphor 11a is gadolinium oxysulfide containing praseodymium, terbium, or the like, and the resin 11b is, for example, an epoxy resin. The reflective layer 12 is made of a resin 12b containing reflective particles 12a made of titanium oxide.
In recent years, as shown in fig. 1, in a scintillator structure 10, a scintillator 11 is divided into a plurality of Cells (CL). That is, from the viewpoint of improving the resolution of the X-ray image, the scintillator 11 is divided into a plurality of cells CL (array of the scintillator 11) corresponding to the plurality of light receiving elements 20, respectively. In this way, the scintillator structure 10 includes a plurality of cells CL and a reflective layer 12 covering the plurality of cells CL. Specifically, the upper surface and 4 sides of the cell CL are covered with the reflective layer 12. On the other hand, the lower surface of the cell CL needs to be in contact with the light receiving element 20, and is therefore not covered by the reflective layer 12.
The X-ray detector thus constructed operates as follows.
That is, when the X-rays are incident on the scintillator 11 of the scintillator structure 10, electrons in the phosphor 11a constituting the scintillator 11 receive the energy of the X-rays and are converted from the ground state to the excited state. Then, the electrons in the excited state are converted to the ground state. At this time, visible light corresponding to the energy difference between the excited state and the ground state is emitted. By such a mechanism, the scintillator 11 absorbs X-rays to generate visible light.
Then, a part of the visible light generated from the scintillator 11 is directly incident on the light receiving element 20, and another part of the visible light generated from the scintillator 11 is condensed on the light receiving element 20 while repeating the reflection by the reflection layer 12 covering the scintillator 11. Next, for example, when visible light is incident on the light receiving element 20 constituted by a photodiode, electrons of a semiconductor material constituting the photodiode are excited from a valence band to a conduction band by energy of the visible light. Thereby, a current caused by electrons excited in the conduction band flows through the photodiode. Then, an X-ray image is acquired based on the current output from the photodiode. In this way, according to the X-ray detector 100, an X-ray image can be acquired.
For example, as shown in fig. 1, the scintillator structure 10 is composed of a scintillator 11 in a rectangular parallelepiped shape and a reflective layer 12 covering the scintillator 11. Here, the scintillator 11 having a rectangular parallelepiped shape is formed by a processing step such as a dicing step or a grinding step, and a processed surface is formed on the surface of the rectangular parallelepiped shape. That is, the "machined surface" refers to a surface subjected to machining. Specifically, the "machined surface" includes a surface obtained by grinding with a grinding wheel when the workpiece is subjected to thickness setting, or a surface obtained by cutting the workpiece with a dicing blade in order to perform a cutting process.
For example, in the scintillator 11 using "resin GOS", the "processed surface" is defined as a surface where resin exposed and "GOS" powder broken surfaces are mixed. For example, fig. 1 schematically shows a case where the scintillator 11 using the "resin GOS" has a "processed surface" at the interface between the scintillator 11 and the reflective layer 12. In this case, it is known that a region where the resin 11b is cut and a region where the phosphor 11a ("GOS" powder) is broken are mixed in the "processed surface". Thus, the X-ray detector 100 is constituted.
Reasons for the adoption of "resin GOS
As described above, in the present embodiment, "resin GOS" is used as the scintillator 11. The reason for this will be explained below.
For example, cadmium tungstate (hereinafter referred to as "CWO") is used as the scintillator 11 constituting the scintillator structure 10, but the "CWO" contains cadmium as a substance to be subjected to the RoHS instruction/REACH rule. Therefore, as the scintillator 11, a "GOS" ceramic is used instead of a cadmium-containing "CWO". The "GOS" ceramic has a benefit of higher luminous output power of visible light than that of "CWO", and has a disadvantage of higher manufacturing cost.
Therefore, from the viewpoint of reducing the manufacturing cost, as the scintillator 11, it is being studied to use "resin GOS" in which a resin composed of an epoxy resin or the like and "GOS" powder are mixed, instead of "GOS" ceramics. That is, in order to suppress an increase in manufacturing cost due to the "GOS" ceramic, there is a trend to use "resin GOS" cheaper than the "GOS" ceramic for the scintillator 11.
Here, the "resin GOS" includes a "first resin GOS" obtained by mixing an epoxy resin with a "GOS" powder in which praseodymium (Pr) and cerium (Ce) are added to gadolinium oxysulfide, and a "second resin GOS" obtained by mixing an epoxy resin with a "GOS" powder in which terbium (Tb) and cerium (Ce) are added to gadolinium oxysulfide.
In addition, both the "first resin GOS" and the "second resin GOS" have an advantage of higher light emission output power than the "CWO". Furthermore, the afterglow characteristic of the "first resin GOS" is equivalent to that of the "CWO". That is, the scintillator structure 10 is required to have high luminous output and good afterglow characteristics.
Therefore, afterglow characteristics will be described. The scintillator 11 constituting the scintillator structure 10 is a substance that generates visible light when X-rays are irradiated. In the scintillator 11, the mechanism of generating visible light when X-rays are irradiated is as follows.
That is, when the scintillator 11 is irradiated with X-rays, electrons in the scintillator 11 receive energy from the X-rays and change from a ground state with low energy to an excited state with high energy. In addition, electrons in the excited state are converted to a ground state with low energy. At this time, most of the electrons excited immediately turn to the ground state. On the other hand, some of the electrons in the excited electrons are converted to the ground state after a certain amount of time has elapsed.
After the lapse of the predetermined period of time, the electrons generated are converted from the excited state to the ground state, and the visible light generated is afterglow. That is, afterglow is visible light generated at a point in time when transition from an excited state to a ground state occurs after a lapse of a certain amount of time from the point in time when X-rays are irradiated. The high afterglow means that the intensity of visible light generated from the irradiation of the X-rays until a certain time elapses is high. In this case, the afterglow generated in the previous X-ray irradiation remains until the next X-ray is irradiated, and the remaining afterglow becomes noise. Therefore, the afterglow is preferably small. That is, good afterglow characteristics means small afterglow. In this regard, the afterglow characteristic of the "first resin GOS" is the same as that of the "CWO".
Therefore, the "resin GOS" has the following advantages over the "CWO", and is therefore excellent as the scintillator 11 that can achieve both performance and manufacturing cost.
(1) The emission output power of the "resin GOS" is higher than that of the "CWO".
(2) The afterglow characteristics of the "first resin GOS" are the same as those of the "CWO".
(3) The "resin GOS" does not use cadmium.
(4) The "resin GOS" is lower in manufacturing cost than the "CWO".
In addition, cesium iodide (CsI) is used as the scintillator 11, and the "resin GOS" has the following advantages over the "CsI".
(1) The "second resin GOS" has a better stopping property of X-rays than the "CsI".
(2) The afterglow characteristic of the "second resin GOS" is about 1/70 of that of "CsI".
(3) "resin GOS" is a stable substance that is not deliquescent.
In addition, "resin GOS" has the following advantages as compared with "GOS" ceramics. That is, the "resin GOS" or "GOS" ceramic contains heavy metals such as "Gd", "Ga" or "Bi". These heavy metals are relatively expensive and may have adverse effects on living bodies and the environment due to the outflow. Therefore, it is desirable that the heavy metals contained in the scintillator 11 be as small as possible. In this regard, "resin GOS" composed of a mixture of "GOS" powder and resin is used in a smaller amount than "GOS" ceramic as a block. This means that the scintillator 11 having a heavy metal content smaller than that of the "GOS" ceramic can be constituted by the "resin GOS". Therefore, it can be said that "resin GOS" is superior to "GOS" ceramics in that the scintillator 11 having a small heavy metal content can be provided.
As described above, the "resin GOS" is expected to be the scintillator 11 capable of achieving both performance and manufacturing cost.
< concrete Material >
Next, specific materials constituting the constituent elements of the scintillator structure 10 will be described.
Phosphor 11a
The phosphor 11a used in the present embodiment is composed of gadolinium oxysulfide or gadolinium-aluminum-gallium garnet (GGAG), for example. Here, gadolinium oxysulfide has, for example"Gd" activated with at least one selected from praseodymium (Pr), cerium (Ce) or terbium (Tb) 2 O 2 S ", composition of S". On the other hand, "GGAG" has (Gd) activated with at least one kind selected from cerium (Ce), praseodymium (Pr), etc., for example 1-x Lu x ) 3+a (Ga u Al 1-u ) 5-a O 12 (x=0 to 0.5, u=0.2 to 0.6, a= -0.05 to 0.15). However, the phosphor 11a is not limited to a specific composition.
Resin 11b and resin 12b
The resin 11b and the resin 12b are made of a material that is not easily degraded when irradiated with radiation. The materials of the resin 11b and the resin 12b are characteristic points of the present embodiment, and the characteristic points will be described later.
Reflective particles 12a
Examples of the constituent material of the reflective particles 12a include "TiO 2 "(titanium oxide)," Al 2 O 3 "(alumina)," ZrO 2 "(zirconia) and the like. Here, for example, a block or a mixture of powder and resin can be used as the reflective particles 12 a. In particular from "rutile TiO 2 "the structured reflective particles 12a are preferable particles excellent in light reflection efficiency. From the viewpoint of improving the light receiving efficiency of the light receiving element 20, the light reflectance of the reflective particles 12a is preferably 80% or more, and further, the light reflectance of the reflective particles 12a is preferably 90% or more.
Other additives
Other additives may be blended in addition to the above components in the reflective material constituting the scintillator 11 and the reflective layer 12. For example, in order to shorten the curing time of the resin, it is preferable to blend a curing catalyst.
< study of improvement >
For example, epoxy resin is used as the resin contained in "resin GOS". The epoxy resin contains at least a main agent and a curing agent as constituent materials, and for example, bisphenol a type epoxy resin is often used as a main agent, and an amine type curing agent is often used as a curing agent. However, the present inventors have newly found that when a general epoxy resin containing bisphenol a type epoxy resin as a main agent and an amine type curing agent as a curing agent is used as a resin constituting "resin GOS", the resin is degraded and discolored by repeated irradiation of radiation (X-rays) for a long period of time.
Further, discoloration of the resin having light transmittance means that absorption of light increases, and as a result, light transmittance decreases. Therefore, light generated from the scintillator composed of "resin GOS" hardly reaches the light receiving element (photodiode), and thus the detection performance of the X-ray detector is degraded.
That is, according to the studies of the present inventors, it was found that if a general epoxy resin containing bisphenol a type epoxy resin as a main agent and an amine type curing agent as a curing agent is used as a resin constituting "resin GOS", it is difficult to exert stable detection performance for a long period of time in an X-ray detector. In other words, the present inventors have obtained new insight: if the above-mentioned general epoxy resin is used as the resin constituting the "resin GOS", it is difficult to secure the reliability of the X-ray detector for a long period of time.
Thus, based on the new findings described above, it is known that: in order to secure the reliability of the X-ray detector for a long period of time, it is preferable to use a resin which is hard to be discolored even when X-rays are irradiated for a long period of time as the resin constituting the "resin GOS" instead of the above-mentioned general epoxy resin. Accordingly, the present inventors found a resin having excellent radiation resistance, which is hardly discolored even when X-rays are irradiated for a long period of time, and the following description will be given.
< characteristics of embodiment (concrete embodiment 1) >)
The present embodiment is characterized in that an epoxy resin shown below is used as the resin contained in the "resin GOS" and the resin contained in the reflecting material as the epoxy resin containing at least the main agent and the curing agent. Thus, the reliability of the X-ray detector including the scintillator structure of the present embodiment as a constituent element can be ensured for a long period of time.
Main agent
The main agent comprises bis-7-oxabicyclo [4.1.0] heptane. In particular, bis-7-oxabicyclo [4.1.0] heptane is a material having no carbon double bond, and thus is less likely to cause discoloration due to cleavage of a carbon double bond by X-ray irradiation. That is, bis-7-oxabicyclo [4.1.0] heptane is a material excellent in radiation resistance.
Curing agent
In order to suppress discoloration caused by X-ray irradiation, the curing agent preferably uses a material having no carbon double bond. This is because the bonding strength of the carbon double bond is weaker than that of the carbon single bond, and the carbon double bond is easily cut off by irradiation with X-rays, and as a result, discoloration of the material is easily generated. For example, as the curing agent, an acid anhydride-based curing agent typified by a phthalic anhydride-based curing agent can be used. In particular, from the viewpoint of effectively suppressing discoloration caused by X-ray irradiation, one of polyvalent carboxylic acid anhydrides which are not aromatic and which have no carbon double bond chemically may be used, or two or more thereof may be used in combination.
Specifically, examples of the curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and dodecenyl succinic anhydride. In particular, methyl hexahydrophthalic anhydride is preferably used.
Specific examples of the acid anhydride compound include "RIKACID TH", "TH-1A", "HH", "MH-700G" (all manufactured by Nippon physicochemical Co., ltd.), and the like.
Curing catalyst
The curing catalyst is not necessarily a constituent material, but is preferably added from the viewpoint of promoting the curing reaction of the main agent. As the curing catalyst, an organic phosphorus compound which is hardly discolored even when X-rays are irradiated is preferably used. Specifically, examples of the curing catalyst include tetrabutylphosphonium 0, 0-diethyldithiophosphate (HISHICOLIN PX-4ET manufactured by Japanese chemical industry Co., ltd.), methyltributylphosphonium dimethylphosphate (HISHICOLIN PX-4MP manufactured by Japanese chemical industry Co., ltd.), and the like.
< verification of Effect >
The results of verification that the decrease in "total light transmittance" can be suppressed even after X-ray irradiation by the "resin GOS" containing the above-mentioned bis-7-oxabicyclo [4.1.0] heptane will be described.
The term "total light transmittance" as used herein is intended to include, among the transmitted light, light transmitted by scattering inside the scintillator so that the transmission direction deviates from the incident direction. That is, the "total light transmittance" means not only the transmitted light transmitted through the scintillator in a straight line from the incident direction but also the transmitted light scattered inside the scintillator and having a transmitted direction deviated from the straight line. The purpose of using this "total light transmittance" is that, in the scintillator structure, the cells made of the scintillator are covered with the reflective layer, and as a result, light scattered inside the cells is also repeatedly reflected and finally enters the light receiving element disposed on the bottom surface of the cells, and therefore, light scattered inside the cells also contributes to detection of radiation in the light receiving element. That is, in order to evaluate in consideration of all transmitted light contributing to radiation detection, "total light transmittance" is used.
In addition, "total light transmittance" in the present specification means total light transmittance measured using light having a wavelength of 542nm for a sample having a thickness of 1.5 mm. In the measurement of the "total light transmittance", a sample having a length×width×thickness of 15mmX15mm×1.5mm was prepared, and then the "total light transmittance" of each sample was measured using a sample having a mirror-finished surface.
The "total light transmittance" was measured by using an ultraviolet-visible-near-infrared spectrophotometer V-570 of Japanese spectroscopy to measure light having a wavelength of 542 nm.
Here, the total light transmittance was measured by focusing the diffuse transmission light and the straight forward transmission light on the detector using an integrating sphere device and a reflecting plate.
TABLE 1
Table 1 is a table showing the verification results of sample a and sample B.
In Table 1, sample A shows "resin GOS" in the present embodiment, which is a resin GOS using bis-7-oxabicyclo [4.1.0] heptane as a main component, and "Me-HHPA" (material name: methyl hexahydrophthalic anhydride product name: new Japanese chemical Co., ltd. "RIKACID MH-T") as a curing agent. On the other hand, sample B represents "resin GOS" in the related art, which is "resin GOS" using bisphenol a type epoxy resin as a main agent and using an amine compound as a curing agent.
As shown in table 1, regarding sample a, the initial "total light transmittance (0 kGy)" before X-ray irradiation was "92.489", while the "total light transmittance (100 kGy)" after X-ray irradiation at a dose of 100kGy was "86.087", and the "total light transmittance difference" was "6.402".
In contrast, with respect to sample B, the initial "total light transmittance (0 kGy)" before X-ray irradiation was "90.902", while the "total light transmittance (100 kGy)" after X-ray irradiation at a dose of 100kGy was "78.361", and the "total light transmittance difference" was "12.541".
As a result, the "total light transmittance reduction rate" of the sample a was "7.4%", whereas the "total light transmittance reduction rate" of the sample B was "16%". Therefore, as is clear from the results of table 1, it was confirmed that the decrease in "total light transmittance" can be suppressed even after the X-ray irradiation by the "resin GOS" in the present embodiment.
In particular, as can be seen from the results of table 1, the following excellent properties can be achieved by the "resin GOS" in the present embodiment: an initial total light transmittance of 90% or more to light having a wavelength of 542nm is ensured before the irradiation of the X-rays, while a decrease rate of the total light transmittance to light having a wavelength of 542nm is less than 8% after the irradiation of X-rays having a dose of 100 kGy. Therefore, by using the "resin GOS" in the present embodiment, a scintillator structure having high light emission output and excellent radiation resistance can be provided. As a result, by using the scintillator structure in the present embodiment, an X-ray detector excellent in reliability, which can maintain stable detection performance for a long period, can be provided.
In particular, the verification result in the present embodiment has great technical significance in that it is confirmed that the decrease in the total light transmittance of the "resin GOS" including bis-7-oxabicyclo [4.1.0] heptane can be suppressed even after irradiation of X-rays at a dose as high as 100 kGy.
For example, even if the radiation resistance to the material is known, if the radiation resistance to the X-ray irradiation of a certain dose is not known, it cannot be mentioned whether the reliability of the X-ray detector can be ensured for a long period of time in practice. That is, although only a material qualitatively having radiation resistance, the reliability of an X-ray detector using a high dose of X-rays cannot necessarily be ensured for a long period of time. In this regard, in the present embodiment, a verification result after irradiation with high-dose X-rays at a dose of 100kGy is shown, and based on the verification result, it was confirmed that the radiation resistance of the "resin GOS" including bis-7-oxabicyclo [4.1.0] heptane is excellent. That is, the present embodiment has a great technical significance in that it is verified that the decrease in "total light transmittance" can be suppressed even after the irradiation of X-rays of 100kGy by the "resin GOS" containing bis-7-oxabicyclo [4.1.0] heptane. This is because the verification result is data on the premise of 100kGy as a high dose, and thus, as a basis for ensuring the reliability of an X-ray detector using a high dose of X-rays for a long period of time, highly reliable data is provided.
< method for producing scintillator Structure >
Next, a method for manufacturing the scintillator structure will be described.
Fig. 2 is a flowchart illustrating a flow of a process for manufacturing a scintillator structure.
In fig. 2, first, predetermined amounts of raw material powder and flux components are weighed and mixed (S101), and then the mixture is filled into a crucible and fired in an atmosphere furnace at 1300 to 1400 ℃ for 7 to 9 hours (S102), thereby producing "GOS" powder. Then, the flux component and impurities contained in the "GOS" powder are removed by washing with hydrochloric acid and warm water (S103). Next, an epoxy resin is dropped into the "GOS" powder to impregnate the "GOS" powder with the epoxy resin (S104). Next, the epoxy resin is cured (S105), and then the epoxy resin not mixed with the "GOS" powder is removed (S106). Thus, a scintillator composed of "resin GOS" can be formed.
Next, the substrate on which the scintillator is formed is diced into a plurality of units by dicing (S107). The singulated units are rearranged (S108), and then a reflective material is applied so as to cover the units (S109). Then, after cutting off the unnecessary portion as the scintillator pack 10A (S110), the scintillator pack that passed the inspection is shipped (S111).
Fig. 3 is a diagram schematically showing steps from the dicing step to the reflective material application step.
As shown in fig. 3, the substrate WF on which the scintillator composed of the "resin GOS" is formed is diced, and the substrate WF is singulated into a plurality of cells CL. Then, the singulated cells CL are rearranged into a linear shape, for example. Then, the outer frame FR is arranged to enclose a plurality of cells CL rearranged in a linear shape. Next, a reflective material made of, for example, an epoxy resin containing titanium oxide is applied so as to cover the plurality of cells CL arranged in the outer frame FR. Then, the outer frame FR is removed. Thus, the scintillator structure 10A is manufactured.
In fig. 3, the linear scintillator structure 10A using 1×n cells is described as an example, but the technical idea in the present embodiment is not limited to this, and can be applied to, for example, a scintillator structure in an array (matrix) using n×n cells.
< advantage of the method >
The feature of this embodiment is that "resin GOS" containing bis-7-oxabicyclo [4.1.0] heptane is used, and that the bis-7-oxabicyclo [4.1.0] heptane has a low viscosity. As a result, the present embodiment can provide the following advantages, which will be described.
The viscosity of bis-7-oxabicyclo [4.1.0] heptane was 0.064 (Pa.s), very small. Here, as described in the above-described method for manufacturing the scintillator structure, the singulated cells CL are covered with the reflective material after being rearranged. Therefore, for example, if a resin containing bis-7-oxabicyclo [4.1.0] heptane is used as the resin constituting the reflecting material, the step of coating the reflecting material covering the rearranged plurality of cells CL can be easily performed. That is, according to the present embodiment, since the viscosity of bis-7-oxabicyclo [4.1.0] heptane is very small, if a resin containing bis-7-oxabicyclo [4.1.0] heptane is used as the resin constituting the reflective material, there can be obtained an advantage that the workability of the coating process of the reflective material can be improved. Further, according to the present embodiment, as a result of the improvement in workability, a significant effect that the manufacturing cost of the scintillator structure can be reduced can be obtained by the improvement in manufacturing yield. As described above, according to the present embodiment, not only the resin GOS but also the reliability of the X-ray detector can be ensured for a long period of time and the manufacturing cost of the scintillator structure can be reduced by using bis-7-oxabicyclo [4.1.0] heptane as the reflective layer 12, which is a very excellent technical idea.
< characteristics of embodiment (embodiment 2) >
The present embodiment is characterized in that an epoxy resin shown below is used as the resin contained in the "resin GOS" and the resin contained in the reflecting material as the epoxy resin containing at least the main agent and the curing agent. Thus, the reliability of the X-ray detector including the scintillator structure according to the present embodiment as a constituent element can be ensured for a long period of time.
Main agent
The main agent comprises a mixture of 3, 4-epoxycyclohexylmethyl (3, 4-epoxyethyl) cyclohexane carboxylate and 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol. In particular, these mixtures are materials having no carbon double bond, and therefore are less likely to cause discoloration due to cleavage of a carbon double bond by X-ray irradiation. That is, a mixture of 3, 4-epoxycyclohexylmethyl (3, 4-epoxycyclohexane carboxylate and 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol is a material excellent in radiation resistance.
Curing agent
In order to suppress discoloration caused by X-ray irradiation, the curing agent preferably uses a material having no carbon double bond. This is because the bonding strength of the carbon double bond is weaker than that of the carbon single bond, and the carbon double bond is easily cut off by irradiation with X-rays, and as a result, discoloration of the material is easily generated. For example, as the curing agent, an acid anhydride-based curing agent typified by a phthalic anhydride-based curing agent can be used. In particular, from the viewpoint of effectively suppressing discoloration caused by X-ray irradiation, one of polyvalent carboxylic acid anhydrides which are not aromatic and which have no carbon double bond chemically may be used, or two or more thereof may be used in combination.
Specifically, examples of the curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and dodecenyl succinic anhydride. In particular, methyl hexahydrophthalic anhydride is preferably used.
Specific examples of the acid anhydride compound include "RIKACID TH", "TH-1A", "HH", "MH-700G" (all manufactured by Nippon physicochemical Co., ltd.), and the like.
Curing catalyst
The curing catalyst is not necessarily a constituent material, but is preferably added from the viewpoint of promoting the curing reaction of the main agent. As the curing catalyst, an organic phosphorus compound which is hardly discolored even when X-rays are irradiated is preferably used. Specifically, examples of the curing catalyst include tetrabutylphosphonium 0, 0-diethyldithiophosphate (HISHICOLIN PX-4ET manufactured by Japanese chemical industry Co., ltd.), methyltributylphosphonium dimethylphosphate (HISHICOLIN PX-4MP manufactured by Japanese chemical industry Co., ltd.), and the like.
< verification of Effect >
The results of verification that the "resin GOS" comprising a mixture of the above-mentioned 3, 4-epoxycyclohexylmethyl (3, 4-epoxycyclohexane carboxylate and 1, 2-bis (hydroxymethyl) -1-butanol 1, 2-epoxyethyl-4- (2-epoxyethyl) cyclohexane adduct can suppress the decrease in "total light transmittance" even after X-ray irradiation will be described.
The term "total light transmittance" as used herein is intended to include, among the transmitted light, light transmitted by scattering inside the scintillator so that the transmission direction deviates from the incident direction. That is, the "total light transmittance" means not only the transmitted light transmitted through the scintillator in a straight line from the incident direction but also the transmitted light scattered inside the scintillator and having a transmitted direction deviated from the straight line. The purpose of using this "total light transmittance" is that, in the scintillator structure, the cells made of the scintillator are covered with the reflective layer, and as a result, light scattered inside the cells is also repeatedly reflected and finally enters the light receiving element disposed on the bottom surface of the cells, and therefore, light scattered inside the cells also contributes to detection of radiation in the light receiving element. That is, in order to evaluate in consideration of all transmitted light contributing to radiation detection, "total light transmittance" is used.
In addition, "total light transmittance" in the present specification means total light transmittance measured using light having a wavelength of 542nm for a sample having a thickness of 1.5 mm. In the measurement of the "total light transmittance", a sample having a length×width×thickness of 15mm×15mm×1.5mm was prepared, and then the "total light transmittance" of each sample was measured using a sample having a mirror-finished surface.
The "total light transmittance" was measured by using an ultraviolet-visible-near-infrared spectrophotometer V-570 of Japanese spectroscopy to measure light having a wavelength of 542 nm.
Here, the total light transmittance was measured by focusing the diffuse transmission light and the straight forward transmission light on the detector using an integrating sphere device and a reflecting plate.
TABLE 2
Table 2 is a table showing the verification results of sample C and sample D.
In Table 2, sample C shows "resin GOS" in the present embodiment, which is a mixture of 3, 4-epoxycyclohexylmethyl (3, 4-epoxygroup) cyclohexane carboxylate and 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol as a main component, and "Me-HHPA" (material name: methyl hexahydrophthalic anhydride product name: new Japanese chemical Co., ltd. "RIKACID MH-T") as a curing agent. On the other hand, sample D represents "resin GOS" in the related art, which is "resin GOS" using bisphenol a type epoxy resin as a main agent and an amine type compound as a curing agent.
As shown in table 2, regarding sample C, the initial "total light transmittance (0 kGy)" before X-ray irradiation was "92.661", while the "total light transmittance (100 kGy)" after X-ray irradiation at a dose of 100kGy was "86.292", and the "total light transmittance difference" was "6.369".
In contrast, with respect to sample D, the initial "total light transmittance (0 kGy)" before X-ray irradiation was "90.902", while the "total light transmittance (100 kGy)" after X-ray irradiation at a dose of 100kGy was "78.361", and the "total light transmittance difference" was "12.541".
As a result, the "total light transmittance reduction rate" of the sample C was "7.4%", whereas the "total light transmittance reduction rate" of the sample D was "16%". Therefore, as is clear from the results of table 2, it was confirmed that the decrease in "total light transmittance" can be suppressed even after the X-ray irradiation by the "resin GOS" in the present embodiment.
In particular, as can be seen from the results of table 2, the following excellent properties can be achieved by the "resin GOS" in the present embodiment: an initial total light transmittance of 90% or more to light having a wavelength of 542nm is ensured before the irradiation of the X-rays, while a decrease rate of the total light transmittance to light having a wavelength of 542nm is less than 8% after the irradiation of X-rays having a dose of 100 kGy. Therefore, by using the "resin GOS" in the present embodiment, a scintillator structure having high light emission output and excellent radiation resistance can be provided. As a result, by using the scintillator structure in the present embodiment, an X-ray detector excellent in reliability, which can maintain stable detection performance for a long period, can be provided.
In particular, the results of the verification in this embodiment are of great technical significance in that it was confirmed that the total light transmittance of the "resin GOS" comprising a mixture of 3, 4-epoxycyclohexylmethyl (3, 4-epoxyyl) cyclohexane carboxylate and 1, 2-bis (hydroxymethyl) -1-butanol, 1, 2-epoxy4- (2-epoxyethyl) cyclohexane adduct, was reduced even after irradiation with X-rays at a dose as high as 100 kGy.
For example, even if the radiation resistance to the material is known, if the radiation resistance to the X-ray irradiation of a certain dose is not known, it cannot be mentioned whether the reliability of the X-ray detector can be ensured for a long period of time in practice. That is, although only a material qualitatively having radiation resistance, the reliability of an X-ray detector using a high dose of X-rays cannot necessarily be ensured for a long period of time. In this regard, in the present embodiment, a verification result after irradiation with high-dose X-rays at a dose of 100kGy is shown, and based on the verification result, it was confirmed that the radiation resistance of the "resin GOS" of the mixture of 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct including 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexane carboxylate and 2, 2-bis (hydroxymethyl) -1-butanol is excellent. That is, this embodiment has a great technical meaning in that it is verified that the "resin GOS" comprising a mixture of 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexane carboxylate and 1, 2-bis (hydroxymethyl) -1-butanol, 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct can suppress the decrease in "total light transmittance" even after 100kGy of X-ray irradiation. This is because the verification result is data on the premise of 100kGy as a high dose, and thus, as a basis for ensuring the reliability of an X-ray detector using a high dose of X-rays for a long period of time, highly reliable data is provided.
< method for producing scintillator Structure >
Next, a method for manufacturing the scintillator structure will be described.
Fig. 2 is a flowchart illustrating a flow of a process for manufacturing a scintillator structure.
In fig. 2, first, predetermined amounts of raw material powder and flux components are weighed and mixed (S101), and then the mixture is filled into a crucible and fired in an atmosphere furnace at 1300 to 1400 ℃ for 7 to 9 hours (S102), thereby producing "GOS" powder. Then, the flux component and impurities contained in the "GOS" powder are removed by washing with hydrochloric acid and warm water (S103). Next, an epoxy resin is dropped into the "GOS" powder to impregnate the "GOS" powder with the epoxy resin (S104). Next, the epoxy resin is cured (S105), and then the epoxy resin not mixed with the "GOS" powder is removed (S106). Thus, a scintillator composed of "resin GOS" can be formed.
Next, the substrate on which the scintillator is formed is diced into a plurality of units by dicing (S107). The singulated units are rearranged (S108), and then a reflective material is applied so as to cover the units (S109). Then, after cutting off the unnecessary portion as the scintillator pack 10A (S110), the scintillator pack that passed the inspection is shipped (S111).
Fig. 3 is a diagram schematically showing steps from the dicing step to the reflective material application step.
As shown in fig. 3, the substrate WF on which the scintillator composed of the "resin GOS" is formed is diced, and the substrate WF is singulated into a plurality of cells CL. Then, the singulated cells CL are rearranged into a linear shape, for example. Then, the outer frame FR is arranged to enclose a plurality of cells CL rearranged in a linear shape. Next, a reflective material made of, for example, an epoxy resin containing titanium oxide is applied so as to cover the plurality of cells CL arranged in the outer frame FR. Then, the outer frame FR is removed. Thus, the scintillator structure 10A is manufactured.
In fig. 3, the linear scintillator structure 10A using 1×n cells is described as an example, but the technical idea in the present embodiment is not limited to this, and can be applied to, for example, a scintillator structure in an array (matrix) using n×n cells.
The invention completed by the present inventors has been specifically described based on the above embodiments, but the invention is not limited to the above embodiments, and various modifications may be made without departing from the gist thereof.
Description of the reference numerals
10: a scintillator structure; 11: a scintillator; 11a: a fluorescent body; 11b: a resin; 12: a reflective layer; 12a: reflective particles; 12b: a resin; 20: a light receiving element; 30: a support body; 100: an X-ray detector; CL: a unit.
Claims (9)
1. A scintillator structure is provided with:
a plurality of units; and
a reflective layer covering the plurality of cells,
the plurality of cells each include a resin and a phosphor,
the resin comprises:
a base agent comprising bis-7-oxabicyclo [4.1.0] heptane; and
and (3) a curing agent.
2. The scintillator structure according to claim 1, wherein,
the reflective layer also includes the resin.
3. The scintillator structure according to claim 1 or 2, wherein,
the curing agent is an acid anhydride-based curing agent.
4. The scintillator structure according to claim 3, wherein,
the acid anhydride-based curing agent is a phthalic acid anhydride-based curing agent.
5. The scintillator structure according to any one of claims 1 to 4, wherein the resin further contains a curing catalyst,
the curing catalyst is an organic phosphorus compound.
6. A scintillator structure is provided with:
a plurality of units; and
a reflective layer covering the plurality of cells,
the plurality of cells each include a resin and a phosphor,
the resin comprises:
a main agent; and
the curing agent is used for curing the resin,
the main agent comprises:
3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate; and
1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol.
7. The scintillator structure according to claim 6, wherein,
the curing agent is an acid anhydride-based curing agent.
8. The scintillator structure according to claim 7, wherein,
the acid anhydride-based curing agent is a phthalic acid anhydride-based curing agent.
9. The scintillator structure according to any one of claims 6 to 8, wherein,
the resin also comprises a curing catalyst which,
the curing catalyst is an organic phosphorus compound.
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| JP2021-063296 | 2021-04-02 | ||
| JP2021-063292 | 2021-04-02 | ||
| JP2021063292A JP2022158411A (en) | 2021-04-02 | 2021-04-02 | scintillator structure |
| PCT/JP2022/007653 WO2022209470A1 (en) | 2021-04-02 | 2022-02-24 | Scintillator structure |
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|---|---|
| CN117121120A true CN117121120A (en) | 2023-11-24 |
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| CN202280024712.XA Pending CN117121120A (en) | 2021-04-02 | 2022-02-24 | Scintillator structure |
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| JP (1) | JP2022158411A (en) |
| CN (1) | CN117121120A (en) |
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