JP6810941B1 - Plastic scintillator and its manufacturing method - Google Patents
Plastic scintillator and its manufacturing method Download PDFInfo
- Publication number
- JP6810941B1 JP6810941B1 JP2019156234A JP2019156234A JP6810941B1 JP 6810941 B1 JP6810941 B1 JP 6810941B1 JP 2019156234 A JP2019156234 A JP 2019156234A JP 2019156234 A JP2019156234 A JP 2019156234A JP 6810941 B1 JP6810941 B1 JP 6810941B1
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- JP
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- Prior art keywords
- plastic scintillator
- carboxylic acid
- plastic
- hydroxyl group
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920003023 plastic Polymers 0.000 title claims abstract description 73
- 239000004033 plastic Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 58
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 40
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 31
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 32
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 30
- -1 aliphatic monocarboxylic acid Chemical class 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims description 6
- 229930184652 p-Terphenyl Natural products 0.000 claims description 6
- QKLPIYTUUFFRLV-YTEMWHBBSA-N 1,4-bis[(e)-2-(2-methylphenyl)ethenyl]benzene Chemical compound CC1=CC=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=CC=C1C QKLPIYTUUFFRLV-YTEMWHBBSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- WMAXWOOEPJQXEB-UHFFFAOYSA-N 2-phenyl-5-(4-phenylphenyl)-1,3,4-oxadiazole Chemical compound C1=CC=CC=C1C1=NN=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)O1 WMAXWOOEPJQXEB-UHFFFAOYSA-N 0.000 claims description 4
- MASVCBBIUQRUKL-UHFFFAOYSA-N POPOP Chemical compound C=1N=C(C=2C=CC(=CC=2)C=2OC(=CN=2)C=2C=CC=CC=2)OC=1C1=CC=CC=C1 MASVCBBIUQRUKL-UHFFFAOYSA-N 0.000 claims description 4
- JMLYWQXLJYRYHL-UHFFFAOYSA-N 1-(2-butyloctoxy)-4-[4-[4-[4-(2-butyloctoxy)phenyl]phenyl]phenyl]benzene Chemical group C1=CC(OCC(CCCC)CCCCCC)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C=2C=CC(OCC(CCCC)CCCCCC)=CC=2)C=C1 JMLYWQXLJYRYHL-UHFFFAOYSA-N 0.000 claims description 3
- DCJKUXYSYJBBRD-UHFFFAOYSA-N 2,5-diphenyl-1,3,4-oxadiazole Chemical compound C1=CC=CC=C1C1=NN=C(C=2C=CC=CC=2)O1 DCJKUXYSYJBBRD-UHFFFAOYSA-N 0.000 claims description 3
- VLDFXDUAENINOO-UHFFFAOYSA-N 4-methyl-2-[4-(4-methyl-5-phenyl-1,3-oxazol-2-yl)phenyl]-5-phenyl-1,3-oxazole Chemical compound CC=1N=C(C=2C=CC(=CC=2)C=2OC(=C(C)N=2)C=2C=CC=CC=2)OC=1C1=CC=CC=C1 VLDFXDUAENINOO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 6
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 36
- 238000001514 detection method Methods 0.000 abstract description 17
- 238000010586 diagram Methods 0.000 abstract 1
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- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000005855 radiation Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
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- 238000002834 transmittance Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
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- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
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- BXSPZNVFEYWSLZ-UHFFFAOYSA-N (3-phenoxyphenyl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 BXSPZNVFEYWSLZ-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- GHPVDCPCKSNJDR-UHFFFAOYSA-N 2-hydroxydecanoic acid Chemical compound CCCCCCCCC(O)C(O)=O GHPVDCPCKSNJDR-UHFFFAOYSA-N 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
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- 150000004982 aromatic amines Chemical class 0.000 description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
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- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Measurement Of Radiation (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Luminescent Compositions (AREA)
Abstract
【課題】本発明は、高時間分解能で、高計数率かつ高検出効率のプラスチックシンチレータを提供することを目的とする。【解決手段】プラスチックと、有機蛍光化合物と、金属酸化物粒子とを含有するプラスチックシンチレータであって、前記金属酸化物粒子が水酸基不含有カルボン酸および水酸基含有カルボン酸で表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子である、プラスチックシンチレータ。【選択図】なしPROBLEM TO BE SOLVED: To provide a plastic scintillator having high time resolution, high counting rate and high detection efficiency. SOLUTION: A plastic scintillator containing a plastic, an organic fluorescent compound, and metal oxide particles, wherein the metal oxide particles are surface-treated with a hydroxyl group-free carboxylic acid and a hydroxyl group-containing carboxylic acid. A plastic scintillator that is a nanoparticle or hafnium oxide nanoparticles. [Selection diagram] None
Description
本発明は、放射線検出に用いるプラスチックシンチレータ、特に、金属酸化物を含有するプラスチックシンチレータおよびその製造方法に関する。 The present invention relates to a plastic scintillator used for radiation detection, particularly a plastic scintillator containing a metal oxide and a method for producing the same.
一般にα線、β線等の荷電粒子である放射線は、物質を通過する際にその物質中の原子又は分子を電離、励起又は解離し、エネルギーを失う。物質に伝達されたエネルギーはさらに熱運動エネルギーもしくは電磁波として放出される。この物質が蛍光を発する物質等である場合、そのエネルギーの多くの部分が可視領域の光として放出され、この現象をシンチレーション、放出される光をシンチレーション光という。 Generally, radiation, which is a charged particle such as α ray or β ray, ionizes, excites or dissociates an atom or molecule in the substance when passing through the substance, and loses energy. The energy transmitted to the substance is further released as thermal kinetic energy or electromagnetic waves. When this substance is a substance that emits fluorescence, most of its energy is emitted as light in the visible region, and this phenomenon is called scintillation, and the emitted light is called scintillation light.
Ｘ線、γ線、中性子線等の電荷を有しない放射線の場合も、これらの放射線が物質と相互作用する際に放出される二次的な荷電粒子により同様のシンチレーションが起こるため、これを利用して放射線を検出できる。 In the case of uncharged radiation such as X-rays, γ-rays, and neutrons, similar scintillation occurs due to the secondary charged particles emitted when these radiations interact with matter, so this is used. Radiation can be detected.
以上のようなシンチレーションを起こす物質を一般にシンチレータと総称し、素粒子物理学等の学術分野や医療、産業といった幅広い分野で放射線検出器に用いられている。これらの放射線検出器の中でも、陽電子断層撮像装置（ＰＥＴ）や陽電子消滅寿命測定装置等に用いられる放射線検出器に用いるシンチレータにおいては、特に高度な時間分解能、計数率、および検出効率をもつことが求められている。 Substances that cause scintillation as described above are generally collectively referred to as scintillators, and are used in radiation detectors in a wide range of fields such as academic fields such as particle physics, medicine, and industry. Among these radiation detectors, the scintillator used for the positron emission tomography device (PET), the positron annihilation lifetime measuring device, and the like may have particularly high time resolution, counting rate, and detection efficiency. It has been demanded.
シンチレータには、無機シンチレータと有機シンチレータとがある。
無機シンチレータは、実効原子番号が大きいことから一般に検出効率が高く発光量が大きいという利点を有しているが、無機シンチレータは発光の減衰時間が長いために時間分解能及び計数率が低いという問題があったり、減衰時間が短くても潮解性や自身の持つ放射性核種に起因するバックグラウンドの上昇などの問題点を有している。
Scintillators include inorganic scintillators and organic scintillators.
Inorganic scintillators generally have the advantage of high detection efficiency and large emission amount because of their large effective atomic number, but inorganic scintillators have the problem of low time resolution and count rate due to the long emission attenuation time. Even if it has a short decay time, it has problems such as deliquescent property and an increase in background due to its own radionuclide.
このような無機シンチレータとしては、例えば、ＮａＩ（Ｔｌ）シンチレータやＢａＦ２シンチレータ、ＬａＢｒ３（Ｃｅ）などが挙げられる。ＮａＩ（Ｔｌ）シンチレータは発光量が比較的大きいものの、発光の減衰時間が約２３０ｎｓと大きいために時間分解能が悪い。ＢａＦ２シンチレータは、減衰時間が０．６ｎｓである短寿命成分が含まれているものの、減衰時間が６２０ｎｓである長寿命成分が全発光量に対して７５％程度と多く含まれているため、やはり高計数率測定等に用いることは困難である。ＬａＢｒ３（Ｃｅ）シンチレータは、減衰時間が約２０ｎｓと比較的短寿命であるが、結晶中には放射性核種の１３８Ｌａと、不純物として混入する２２７Ａｃ系列核種とが存在しており、これらの自己放射能に起因するバックグラウンドが存在するというデメリットがある。 Examples of such an inorganic scintillator include a NaI (Tl) scintillator, a BaF 2 scintillator, and a LaBr 3 (Ce). Although the NaI (Tl) scintillator has a relatively large amount of light emission, the time resolution is poor because the light emission decay time is as large as about 230 ns. Although the BaF 2 scintillator contains a short-life component having an attenuation time of 0.6 ns, it contains a large amount of a long-life component having an attenuation time of 620 ns, which is about 75% of the total emission amount. After all, it is difficult to use it for high count rate measurement and the like. The LaBr 3 (Ce) scintillator has a relatively short life with a decay time of about 20 ns, but 138 La of radionuclides and 227 Ac series nuclides mixed as impurities are present in the crystal, and these There is a demerit that there is a background due to self-radioactivity.
他方、有機シンチレータとしては、ポリスチレン、ポリビニルトルエン等の高分子ポリマーに有機発光化合物を溶解した、いわゆるプラスチックシンチレータが代表的なものとして挙げられる。
例えば、非特許文献１には、いくつかのプラスチックシンチレータが記載されている。これらのプラスチックシンチレータは前記無機シンチレータと比較して発光の減衰時間が短いために、高度の時間分解能および高い計数率を達成することができるという利点を有しているが、シンチレータを構成する原子（Ｃ、Ｈ、Ｏ、Ｎ）の原子番号が小さく、Ｘ線やγ線とシンチレータ中の電子との電磁相互作用が起こる確率が低いために検出効率が低いという問題点を有していた。
On the other hand, as a typical example of the organic scintillator, a so-called plastic scintillator in which an organic luminescent compound is dissolved in a polymer polymer such as polystyrene or polyvinyltoluene is used.
For example, Non-Patent Document 1 describes some plastic scintillators. These plastic scintillators have the advantage of being able to achieve a high degree of time resolution and a high count rate because the emission decay time is shorter than that of the inorganic scintillator, but the atoms that make up the scintillator ( The atomic numbers of C, H, O, and N) are small, and there is a problem that the detection efficiency is low because the probability of electromagnetic interaction between X-rays and γ-rays and electrons in the scintillator is low.
そこで、Ｘ線やγ線に対する検出効率を上げるために、ポリビニルトルエンに重金属である鉛を１．５〜５質量％充填したプラスチックシンチレータ（ＥＪ−２５６、ＥＬＪＥＮ ＴＥＣＨＮＯＥＯＧＹ社）が市販されている。しかしながら、充填量が少ないために大きな検出効率の上昇は見込めず、また、鉛は有害金属であるため使用は避けられることが望ましい。 Therefore, in order to improve the detection efficiency for X-rays and γ-rays, plastic scintillators (EJ-256, ELJEN TECHNOEOGY) in which polyvinyl toluene is filled with 1.5 to 5% by mass of lead, which is a heavy metal, are commercially available. However, since the filling amount is small, a large increase in detection efficiency cannot be expected, and since lead is a harmful metal, it is desirable to avoid its use.
これらの問題点を改良するためいくつかの検討がなされている。例えば、非特許文献２には重金属としてジルコニアナノ粒子を用いたプラスチックシンチレータが提案されている。
また、非特許文献３にはフェニルプロピオン酸で表面処理された酸化ハフニウムナノ粒子を用いたもの、さらに、非特許文献４にはフェニルヘキサン酸で表面処理されたハフニアおよびジルコニアのナノ粒子を用いたプラスチックシンチレータが提案されている。
Several studies have been made to improve these problems. For example, Non-Patent Document 2 proposes a plastic scintillator using zirconia nanoparticles as a heavy metal.
Further, in Non-Patent Document 3, hafnium oxide nanoparticles surface-treated with phenylpropionic acid were used, and in Non-Patent Document 4, hafnia and zirconia nanoparticles surface-treated with phenylhexanoic acid were used. Plastic scintillators have been proposed.
非特許文献２〜４のプラスチックシンチレータは、重金属の含有量を高くできるため検出効率を上げることができたとしているが、分散性が悪く透明性にも問題があるため、その含有濃度はせいぜい１０質量％であり、シンチレータの厚みも薄くせざるを得ないため実用的な検出効率を達成できたといえるものではなかった。 The plastic scintillators of Non-Patent Documents 2 to 4 are said to have been able to improve the detection efficiency because the content of heavy metals can be increased, but the content concentration is at most 10 because of poor dispersibility and transparency. Since it was by mass% and the thickness of the scintillator had to be reduced, it could not be said that practical detection efficiency could be achieved.
そこで、本発明は、高時間分解能で、高計数率かつ高検出効率を達成できるプラスチックシンチレータを提供することを目的とする。 Therefore, an object of the present invention is to provide a plastic scintillator capable of achieving a high counting rate and a high detection efficiency with high time resolution.
本発明者は、鋭意検討した結果、水酸基不含有カルボン酸および水酸基含有カルボン酸で表面処理した酸化ジルコニウムナノ粒子および酸化ハフニウムナノ粒子が、プラスチックシンチレータの基材であるプラスチックに高濃度で分散できること、その結果、高時間分解能で、高計数率と高検出効率とを達成できることを見出し、本発明を完成した。 As a result of diligent studies, the present inventor has determined that zirconium oxide nanoparticles and hafnium oxide nanoparticles surface-treated with a hydroxyl group-free carboxylic acid and a hydroxyl group-containing carboxylic acid can be dispersed in a high concentration in the plastic which is the base material of the plastic scintillator. As a result, they have found that a high counting rate and a high detection efficiency can be achieved with high time resolution, and completed the present invention.
すなわち、本発明は、
（１）プラスチックと、有機蛍光化合物と、金属酸化物粒子とを含有するプラスチックシンチレータであって、前記金属酸化物粒子が水酸基不含有カルボン酸および水酸基含有カルボン酸で表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子である、プラスチックシンチレータ、
（２）前記プラスチックが、芳香族ビニルの少なくとも一つと（メタ）アクリレートの少なくとも一つとの重合体である、（１）記載のプラスチックシンチレータ、
（３）前記水酸基不含有カルボン酸が、炭素数が３以上２２以下の脂肪族モノカルボン酸または芳香族モノカルボン酸である、（１）または（２）記載のプラスチックシンチレータ、
（４）前記水酸基含有カルボン酸が、炭素数が３以上２２以下の水酸基含有脂肪族モノカルボン酸である、（１）から（３）のいずれか一つに記載のプラスチックシンチレータ、
（５）プラスチックシンチレータ全量に対して、前記酸化ジルコニウムナノ粒子または前記酸化ハフニウムナノ粒子の金属酸化物としての含有量が１０質量％以上７０質量％以下である、（１）から（４）のいずれか一つに記載のプラスチックシンチレータ、
（６）前記有機蛍光化合物が、２−（４−ビフェニリル）−５−フェニル−１，３，４−オキサジアゾール（ＰＢＤ）、２−（４−ｔｅｒｔ−ブチルフェニル）−５−（４−ビフェニリル）−１，３，４−オキサジアゾール（Ｂｕ−ＰＢＤ）、ｐ−テルフェニル（Ｐ−ＴＰ）、２，５−ジフェニルオキサゾール（ＤＰＯ）、１，４−ビス［２−（５−フェニルオキサゾリル）］ベンゼン（ＰＯＰＯＰ）、１，４−ビス［２−（４−メチル−５−フェニルオキサゾリル）］ベンゼン（ＤＭＰＯＰＯＰ）、１，４−ビス（２−メチルスチリル）ベンゼン（ビス−ＭＳＢ）および４,４’’’−ビス（２−ブチルオクチルオキシ）−ｐ−クアテルフェニル（ＢＩＢＵＱ）から選ばれる少なくとも１つである、（１）から（５）のいずれか一つに記載のプラスチックシンチレータ、
（７）重合性モノマーと、
有機蛍光化合物と、
水酸基不含有カルボン酸および水酸基含有カルボン酸によって表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子と、
を混合して分散体を得る第１の工程、
および、その得られた分散体中の前記重合性モノマーを重合させる第２の工程、
を含む、（１）から（６）のいずれか一つに記載のプラスチックシンチレータの製造方法、
（８）前記重合性モノマーが、芳香族ビニルの少なくとも一つおよび（メタ）アクリレートの少なくとも一つを含有する、（７）記載のプラスチックシンチレータの製造方法、
である。
That is, the present invention
(1) A plastic scintillator containing a plastic, an organic fluorescent compound, and metal oxide particles, wherein the metal oxide particles are surface-treated with a hydroxyl group-free carboxylic acid and a hydroxyl group-containing carboxylic acid. Plastic scintillators, which are particles or hafnium oxide nanoparticles,
(2) The plastic scintillator according to (1), wherein the plastic is a polymer of at least one of aromatic vinyl and at least one of (meth) acrylate.
(3) The plastic scintillator according to (1) or (2), wherein the hydroxyl group-free carboxylic acid is an aliphatic monocarboxylic acid or an aromatic monocarboxylic acid having 3 or more and 22 or less carbon atoms.
(4) The plastic scintillator according to any one of (1) to (3), wherein the hydroxyl group-containing carboxylic acid is a hydroxyl group-containing aliphatic monocarboxylic acid having 3 or more and 22 or less carbon atoms.
(5) Any of (1) to (4), wherein the content of the zirconium oxide nanoparticles or the hafnium oxide nanoparticles as a metal oxide is 10% by mass or more and 70% by mass or less with respect to the total amount of the plastic scintillator. One of the plastic scintillators,
(6) The organic fluorescent compound is 2- (4-biphenylyl) -5-phenyl-1,3,4-oxadiazole (PBD), 2- (4-tert-butylphenyl) -5- (4-). Biphenylyl) -1,3,4-oxadiazole (Bu-PBD), p-terphenyl (P-TP), 2,5-diphenyloxadiazole (DPO), 1,4-bis [2- (5-phenyl) Oxadiazole] benzene (POPOP), 1,4-bis [2- (4-methyl-5-phenyloxazolyl)] benzene (DMPOPOP), 1,4-bis (2-methylstyryl) benzene (bis) -MSB) and 4,4'''-bis (2-butyloctyloxy) -p-quaterphenyl (BIBUQ), which is at least one selected from any one of (1) to (5). Described plastic scintillator,
(7) Polymerizable monomer and
With organic fluorescent compounds
Zirconium oxide nanoparticles or hafnium oxide nanoparticles surface-treated with hydroxyl-free carboxylic acid and hydroxyl-containing carboxylic acid,
First step of mixing to obtain a dispersion,
And the second step of polymerizing the polymerizable monomer in the obtained dispersion,
The method for producing a plastic scintillator according to any one of (1) to (6), which comprises.
(8) The method for producing a plastic scintillator according to (7), wherein the polymerizable monomer contains at least one of aromatic vinyl and at least one of (meth) acrylate.
Is.
本発明のプラスチックシンチレータは、金属酸化物粒子として、分散性に優れた水酸基不含有カルボン酸および水酸基含有カルボン酸で表面処理された酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子を用い、かつ、基材となるプラスチックも透明で、これらの金属酸化物粒子および有機蛍光化合物との分散性に優れるため、これらの金属酸化物粒子を高濃度で含有させることができ、高濃度でも透明性に優れるので、高時間分解能で、高計数率と高検出効率とを達成できる。 The plastic scintillator of the present invention uses zirconium oxide nanoparticles or hafnium oxide nanoparticles surface-treated with a hydroxyl group-free carboxylic acid and a hydroxyl group-containing carboxylic acid having excellent dispersibility as metal oxide particles, and also as a base material. The plastic is also transparent and has excellent dispersibility with these metal oxide particles and organic fluorescent compounds. Therefore, these metal oxide particles can be contained in a high concentration, and even at a high concentration, the transparency is excellent. High count rate and high detection efficiency can be achieved with time resolution.
以下、本発明を実施するための形態を詳細に説明する。なお、本実施形態は、本発明を実施するための一形態に過ぎず、本発明は本実施形態によって限定されるものではなく、本発明の要旨を逸脱しない範囲で種々の変更、実施の形態が可能である。 Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the present embodiment is only one embodiment for carrying out the present invention, the present invention is not limited to the present embodiment, and various modifications and embodiments are made without departing from the gist of the present invention. Is possible.
本明細書中、「〜」は、特に明示しない限り、上限値と下限値を含むことを表す。 In the present specification, "~" means that an upper limit value and a lower limit value are included unless otherwise specified.
本発明のプラスチックシンチレータは、プラスチックと、有機蛍光化合物と、金属酸化物粒子とを含有するプラスチックシンチレータであって、前記金属酸化物粒子が水酸基不含有カルボン酸および水酸基含有カルボン酸で表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子である。 The plastic scintillator of the present invention is a plastic scintillator containing plastic, an organic fluorescent compound, and metal oxide particles, and the metal oxide particles are surface-treated with a hydroxyl group-free carboxylic acid and a hydroxyl group-containing carboxylic acid. These are zirconium oxide nanoparticles or hafnium oxide nanoparticles.
前記プラスチックは、芳香族ビニルの少なくとも一つと（メタ）アクリレートの少なくとも一つとの重合体である。 The plastic is a polymer of at least one of aromatic vinyl and at least one of (meth) acrylate.
前記芳香族ビニルは、スチレン、α−メチルスチレン、ビニルトルエン等のビニル基を有する芳香族化合物が例示できる。 Examples of the aromatic vinyl include aromatic compounds having a vinyl group such as styrene, α-methylstyrene, and vinyltoluene.
前記（メタ）アクリレートは、単官能（メタ）アクリレートであっても、多官能（メタ）アクリレートでもよく、特に選ぶものではないが、ベンゼン環等の芳香環をもつ（メタ）アクリレートおよびカルボン酸を有する（メタ）アクリレートの少なくとも一つが好ましく用いられる。 The (meth) acrylate may be a monofunctional (meth) acrylate or a polyfunctional (meth) acrylate, and is not particularly selected, but a (meth) acrylate having an aromatic ring such as a benzene ring and a carboxylic acid may be used. At least one of the (meth) acrylates having is preferably used.
前記したベンゼン環等の芳香環をもつ（メタ）アクリレートは、前記プラスチック中の芳香族ビニルに由来した部分との相溶性向上に寄与するものと考えられ、３−フェノキシベンジル（メタ）アクリレート、ｏ−フェニルフェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート等が例示される。 The (meth) acrylate having an aromatic ring such as the benzene ring is considered to contribute to the improvement of compatibility with the portion derived from the aromatic vinyl in the plastic, and 3-phenoxybenzyl (meth) acrylate, o. -Phenylphenoxyethyl (meth) acrylate, benzyl (meth) acrylate and the like are exemplified.
また、前記したカルボン酸を有する（メタ）アクリレートは、金属酸化物粒子の分散性向上に寄与すると考えられ、２−（メタ）アクリロイルオキシエチルサクシネート、２−（メタ）アクリロイロキシエチル−フタル酸等が例示される。 Further, the (meth) acrylate having the above-mentioned carboxylic acid is considered to contribute to the improvement of dispersibility of the metal oxide particles, and 2- (meth) acryloyloxyethyl succinate and 2- (meth) acryloyloxyethyl-phthal. Acids and the like are exemplified.
前記重合体中の前記芳香族ビニルと前記（メタ）アクリレートとの配合比率は、表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子の配合量にもよるが、前記芳香族ビニルを１００質量部としたとき前記（メタ）アクリレートが３〜１０質量部が好ましい。（メタ）アクリレートが３質量部未満では表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子の分散性が低下し、１０質量部を超えると発光量が低下するためシンチレータとして使用可能なレベルに到らない。 The blending ratio of the aromatic vinyl and the (meth) acrylate in the polymer depends on the blending amount of the surface-treated zirconium oxide nanoparticles or hafnium oxide nanoparticles, but 100% by mass of the aromatic vinyl. In terms of parts, the amount of the (meth) acrylate is preferably 3 to 10 parts by mass. If the amount of (meth) acrylate is less than 3 parts by mass, the dispersibility of the surface-treated zirconium oxide nanoparticles or hafnium oxide nanoparticles decreases, and if it exceeds 10 parts by mass, the amount of light emitted decreases, so that it can be used as a scintillator. It does not reach.
なお、本明細書中、「（メタ）アクリレート」はアクリレートとメタクリレートの両者を示すものとして使用される。 In addition, in this specification, "(meth) acrylate" is used as indicating both acrylate and methacrylate.
前記有機蛍光化合物としては、ｐ−テルフェニル（Ｐ−ＴＰ）、２，５−ジフェニルオキサゾール（ＤＰＯ）、２−（４−ｔｅｒｔ−ブチルフェニル）−５−（４−ビフェニリル）−１，３，４−オキサジアゾール（Ｂｕ−ＰＢＤ）、１，４−ビス［２−（５−フェニルオキサゾリル）］ベンゼン（ＰＯＰＯＰ）、１，４−ビス［２−（４−メチル−５−フェニルオキサゾリル）］ベンゼン（ＤＭＰＯＰＯＰ）、１，４−ビス（２−メチルスチリル）ベンゼン（ビス−ＭＳＢ）、４,４’’’−ビス（２−ブチルオクチルオキシ）−ｐ−クアテルフェニル（ＢＩＢＵＱ）等が例示され、その少なくとも１種が使用できる。
前記有機蛍光化合物の含有量は、得られるプラスチックシンチレータに対して０．０５質量％以上１０質量％以下が好ましい。これらの蛍光化合物の含有量が０．０５質量％未満では十分な発光量が得られず、含有量が１０質量％を超えると、濃度消光などによりかえって発光量が低下する。
Examples of the organic fluorescent compound include p-terphenyl (P-TP), 2,5-diphenyloxadiazole (DPO), 2- (4-tert-butylphenyl) -5- (4-biphenylyl) -1,3. 4-Oxadiazole (Bu-PBD), 1,4-bis [2- (5-phenyloxazolyl)] benzene (POPOP), 1,4-bis [2- (4-methyl-5-phenyloxa) Zolyl] Benzene (DMPOPOP), 1,4-bis (2-methylstyryl) benzene (bis-MSB), 4,4'''-bis (2-butyloctyloxy) -p-quaterphenyl (BIBUQ) ) Etc. are exemplified, and at least one of them can be used.
The content of the organic fluorescent compound is preferably 0.05% by mass or more and 10% by mass or less with respect to the obtained plastic scintillator. If the content of these fluorescent compounds is less than 0.05% by mass, a sufficient amount of light emission cannot be obtained, and if the content exceeds 10% by mass, the amount of light emission is rather lowered due to concentration quenching or the like.
本発明で用いる金属酸化物粒子は、水酸基不含有カルボン酸と水酸基含有カルボン酸とで表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子である。 The metal oxide particles used in the present invention are zirconium oxide nanoparticles or hafnium oxide nanoparticles surface-treated with a hydroxyl group-free carboxylic acid and a hydroxyl group-containing carboxylic acid.
前記水酸基不含有カルボン酸としては、脂肪族および芳香族のモノカルボン酸が挙げられ、脂肪族であれば、飽和、不飽和を問わず、枝分かれまたはフェニル基等の芳香族置換基を有してもよい炭素数が３以上２２以下のモノカルボン酸であり、好ましくは６以上２２以下である。６未満では金属酸化物粒子表面に十分な疎水性を付与できないためプラスチックやモノマーとの分散性が低下し、２２を越えると表面がべたつく傾向となるうえ、分子量が大きいため表面処理量が増えて金属酸化物粒子の濃度低下をもたらす。 Examples of the hydroxyl group-free carboxylic acid include aliphatic and aromatic monocarboxylic acids, and if it is an aliphatic, it has an aromatic substituent such as a branched or phenyl group regardless of whether it is saturated or unsaturated. It is a monocarboxylic acid having 3 or more and 22 or less carbon atoms, preferably 6 or more and 22 or less. If it is less than 6, the surface of the metal oxide particles cannot be sufficiently hydrophobic, so that the dispersibility with plastics and monomers decreases, and if it exceeds 22, the surface tends to be sticky, and the amount of surface treatment increases due to the large molecular weight. It causes a decrease in the concentration of metal oxide particles.
脂肪族の水酸基不含有モノカルボン酸としては、カプロン酸、カプリル酸、オクチル酸、ペラルゴン酸、カプリン酸、ネオデカン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、ヘプタデカン酸、ステアリン酸、ノナデカン酸、エイコサン酸、ヘネイコサン酸、ドコサン酸等の飽和モノカルボン酸、オレイン酸、リノール酸、リノレイン酸、魚油を鹸化分解して得られる脂肪酸等の不飽和脂肪酸およびそれらの幾何異性体、並びに、３−フェニルプロピオン酸、桂皮酸等が例示される。また、芳香族の水酸基不含有モノカルボン酸は、芳香環にカルボン酸残基が直接結合しているモノカルボン酸で、安息香酸、トルイル酸等が例示される。 Fatty acid-free monocarboxylic acids include caproic acid, capric acid, octyl acid, pelargonic acid, capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, and heptadecanoic acid. , Stearate, nonadecanic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid and other saturated monocarboxylic acids, oleic acid, linoleic acid, linoleic acid, unsaturated fatty acids such as fatty acids obtained by saponification and decomposition of fish oil, and their geometric isomerism. Examples include the body, 3-phenylpropionic acid, cinnamic acid and the like. The aromatic hydroxyl group-free monocarboxylic acid is a monocarboxylic acid in which a carboxylic acid residue is directly bonded to an aromatic ring, and examples thereof include benzoic acid and toluic acid.
前記水酸基含有カルボン酸としては、飽和、不飽和を問わず、枝分かれまたはフェニル基等の芳香族置換基を有してもよい炭素数が３以上２２以下のモノカルボン酸であり、炭素数が６以上２２以下の水酸基含有脂肪族モノカルボン酸が好ましく、具体的には、メバロン酸、パントイン酸、２−ヒドロキシデカン酸、３−ヒドロキシヘキサン酸、２−ヒドロキシステアリン酸、１２−ヒドロキシステアリン酸、リシノール酸等が例示される。 The hydroxyl group-containing carboxylic acid is a monocarboxylic acid having 3 or more and 22 or less carbon atoms which may have an aromatic substituent such as a branched or phenyl group regardless of whether it is saturated or unsaturated, and has 6 carbon atoms. Hydroxy group-containing aliphatic monocarboxylic acids having a hydroxyl group of 22 or more are preferable, and specifically, mevalonic acid, pantoic acid, 2-hydroxydecanoic acid, 3-hydroxyhexanoic acid, 2-hydroxystearic acid, 12-hydroxystearic acid, and ricinol. Examples include acids and the like.
前記水酸基不含有カルボン酸は、酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子表面に疎水性を与えることによりモノマーまたはその重合体中での分散安定性に寄与するものと考えられる。また、前記水酸基含有脂肪族カルボン酸は、詳細は不明であるが、その水酸基が、金属酸化物粒子とモノマーまたはその重合体との間で、カルボニル基もしくはカルボキシル基との水素結合により分散安定化に寄与しているものと考えられる。 It is considered that the hydroxyl group-free carboxylic acid contributes to the dispersion stability in the monomer or its polymer by imparting hydrophobicity to the surface of the zirconium oxide nanoparticles or the hafnium oxide nanoparticles. Although the details of the hydroxyl group-containing aliphatic carboxylic acid are unknown, the hydroxyl group is dispersed and stabilized between the metal oxide particles and the monomer or a polymer thereof by a hydrogen bond with a carbonyl group or a carboxyl group. It is considered that it contributes to.
なお、本発明で用いられる酸化ジルコニウムナノ粒子および酸化ハフニウムナノ粒子は、結晶形を選ばない。従って、両者とも製造の容易な単斜晶が好ましい。 The zirconium oxide nanoparticles and hafnium oxide nanoparticles used in the present invention may have any crystal form. Therefore, both are preferably monoclinic crystals that are easy to produce.
本発明の酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子はそれぞれが水酸基不含有カルボン酸と水酸基含有カルボン酸とで表面処理されていれば、その製造方法について、特に選ぶものではないが、例えば、オキシ塩化ジルコニウム水溶液またはオキシ塩化ハフニウム水溶液と、水酸基不含有カルボン酸および水酸基含有カルボン酸と、アミン化合物のアルカリ水溶液とを混合し、その得られた混合物を１４０〜３００℃の水熱反応に供して製造される。 If the zirconium oxide nanoparticles or hafnium oxide nanoparticles of the present invention are surface-treated with a hydroxyl group-free carboxylic acid and a hydroxyl group-containing carboxylic acid, respectively, the production method thereof is not particularly selected, but for example, oxychloride. It is produced by mixing a zirconium aqueous solution or a hafnium oxychloride aqueous solution, a hydroxyl group-free carboxylic acid and a hydroxyl group-containing carboxylic acid, and an alkaline aqueous solution of an amine compound, and subjecting the obtained mixture to a hydrothermal reaction at 140 to 300 ° C. To.
前記アミン化合物としては、非芳香族アミンが用いられる。非芳香族アミンとしては、脂肪族アミンがあげられる。例えば、プロピルアミン、ブチルアミン、オクチルアミン等の１級アミン、ジエチルアミン、ジプロピルアミン、ジオクチルアミン等の２級アミン、トリメチルアミン、トリエチルアミン等の３級アミンが例示できる。 As the amine compound, a non-aromatic amine is used. Examples of non-aromatic amines include aliphatic amines. For example, primary amines such as propylamine, butylamine and octylamine, secondary amines such as diethylamine, dipropylamine and dioctylamine, and tertiary amines such as trimethylamine and triethylamine can be exemplified.
また、アミノ基を２個以上もつもの、例えば、エチレンジアミン、ジエチレントリアミン、トリメチレンジアミン、トリエチレンテトラミン、Ｎ，Ｎ’−ジメチルエチレンジアミン、Ｎ，Ｎ−ジメチルエチレンジアミン、トリス（２−アミノエチル）アミン、テトラエチレンペンタミン等や、水酸基を持つもの、例えば、トリエタノールアミン、ジエタノールアミン、トリイソプロパノールアミン、ジイソプロパノールアミン、メチルジエタノールアミン、エチルジエタノールアミン等のアルカノールアミン、アミノカルボン酸化合物、例えば、グリシン、アラニン、アスパラギン酸、リシン等のα−アミノ酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、Ｎ−（２−ヒドロキシエチル）エチレンジアミン−Ｎ，Ｎ’，Ｎ’−三酢酸、トリエチレンテトラミン−Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’’，Ｎ’’’−六酢酸、１，３−プロパンジアミン−Ｎ，Ｎ，Ｎ’，Ｎ’−四酢酸等が例示できる。 Further, those having two or more amino groups, for example, ethylenediamine, diethylenetriamine, trimethylenediamine, triethylenetetramine, N, N'-dimethylethylenediamine, N, N-dimethylethylenediamine, tris (2-aminoethyl) amine, tetra. Ethylenepentamine and the like, those having a hydroxyl group, for example, triethanolamine, diethanolamine, triisopropanolamine, diisopropanolamine, methyldiethanolamine, ethyldiethanolamine and other alkanolamines, aminocarboxylic acid compounds, for example, glycine, alanine, aspartic acid , Α-amino acids such as lysine, ethylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid, N- (2-hydroxyethyl) ethylenediamine-N, N', N'-triacetic acid, triethylenetetramine-N, N, N', N' Examples thereof include', N''', N'''-hexacetic acid, 1,3-propanediamine-N, N, N', N'-tetraacetic acid and the like.
前記のアミン化合物の中では、水溶性で反応性が高いものが好ましく、脂肪族の総炭素数が２〜１２の１級、２級または３級のアルキルアミン、総炭素数が２〜１２のアルキレンジアミン、または総炭素数が２〜１２のアルカノールアミンが好ましく用いられるが、特に総炭素数が２〜１２のアルカノールアミンが好ましい。 Among the above amine compounds, those that are water-soluble and highly reactive are preferable, and the aliphatic total carbon number is 2 to 12, primary, secondary or tertiary alkylamine, and the total carbon number is 2 to 12. An alkylenediamine or an alkanolamine having a total carbon number of 2 to 12 is preferably used, and an alkanolamine having a total carbon number of 2 to 12 is particularly preferable.
好ましいアルカノールアミンの具体例として、トリエタノールアミン、ジエタノールアミン、トリイソプロパノールアミン、ジイソプロパノールアミン、メチルジエタノールアミン、エチルジエタノールアミン等の一種単独または二種以上の組み合わせが挙げられる。 Specific examples of preferable alkanolamines include triethanolamine, diethanolamine, triisopropanolamine, diisopropanolamine, methyldiethanolamine, ethyldiethanolamine, and the like alone or in combination of two or more.
本発明のプラスチックシンチレータは、プラスチックが熱可塑性である場合は、そのプラスチックと、前記有機蛍光化合物と、前記した水酸基不含有カルボン酸および水酸基含有カルボン酸によって表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子と、を混練して製造することもできるが、これらの金属酸化物粒子を高濃度で含んでも透明性が高いプラスチックシンチレータとするには、重合性モノマーと、前記有機蛍光化合物と、前記した水酸基不含有カルボン酸および水酸基含有カルボン酸によって表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子と、を混合分散させてから、その得られた分散体中の前記重合性モノマーを重合させて製造するのが好ましい。 The plastic scintillator of the present invention, when the plastic is thermoplastic, has zirconium oxide nanoparticles or oxidation surface-treated with the plastic, the organic fluorescent compound, and the hydroxyl group-free carboxylic acid and the hydroxyl group-containing carboxylic acid. Although it can be produced by kneading hafnium nanoparticles, in order to obtain a plastic scintillator having high transparency even if these metal oxide particles are contained in a high concentration, a polymerizable monomer, the organic fluorescent compound, and the organic fluorescent compound are used. The zirconium oxide nanoparticles or hafnium oxide nanoparticles surface-treated with the hydroxyl group-free carboxylic acid and the hydroxyl group-containing carboxylic acid are mixed and dispersed, and then the polymerizable monomer in the obtained dispersion is polymerized. It is preferable to carry out the production.
前記重合性モノマーは、芳香族ビニルの少なくとも一つと（メタ）アクリレートの少なくとも一つとを含む。 The polymerizable monomer contains at least one of aromatic vinyl and at least one of (meth) acrylate.
前記芳香族ビニルは、スチレン、α−メチルスチレン、ビニルトルエン等のビニル基を有する芳香族化合物が例示できる。 Examples of the aromatic vinyl include aromatic compounds having a vinyl group such as styrene, α-methylstyrene, and vinyltoluene.
前記（メタ）アクリレートは、単官能（メタ）アクリレートであっても、多官能（メタ）アクリレートでもよく、特に選ぶものではないが、ベンゼン環等の芳香環をもつ（メタ）アクリレートおよびカルボン酸を有する（メタ）アクリレートの少なくとも一つが好ましく用いられる。 The (meth) acrylate may be a monofunctional (meth) acrylate or a polyfunctional (meth) acrylate, and is not particularly selected, but a (meth) acrylate having an aromatic ring such as a benzene ring and a carboxylic acid may be used. At least one of the (meth) acrylates having is preferably used.
前記したベンゼン環等の芳香環をもつ（メタ）アクリレートとしては、３−フェノキシベンジル（メタ）アクリレート、ｏ−フェニルフェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート等が例示される。 Examples of the (meth) acrylate having an aromatic ring such as the benzene ring include 3-phenoxybenzyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, and benzyl (meth) acrylate.
また、前記したカルボン酸を有する（メタ）アクリレートとしては、２−（メタ）アクリロイルオキシエチルサクシネート、２−（メタ）アクリロイロキシエチル−フタル酸等が例示される。 Examples of the (meth) acrylate having the above-mentioned carboxylic acid include 2- (meth) acryloyloxyethyl succinate and 2- (meth) acryloyloxyethyl-phthalic acid.
本発明のプラスチックシンチレータは、前記重合性モノマーと、前記有機蛍光化合物と、前記した水酸基不含有カルボン酸および水酸基含有カルボン酸によって表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子と、を混合分散させた後、ラジカル発生剤の存在下で加熱するか、重合開始剤の存在下で活性エネルギー線照射することによって重合させ、製造できる。 The plastic scintillator of the present invention is a mixture of the polymerizable monomer, the organic fluorescent compound, and zirconium oxide nanoparticles or hafnium oxide nanoparticles surface-treated with the above-mentioned hydroxyl group-free carboxylic acid and hydroxyl group-containing carboxylic acid. After dispersion, it can be polymerized and produced by heating in the presence of a radical generator or by irradiating with active energy rays in the presence of a polymerization initiator.
このようにして得られたプラスチックシンチレータは、金属酸化物粒子を高濃度に含有しても透明性が高く、高時間分解能で、高計数率と高検出効率とを達成できる。 The plastic scintillator thus obtained has high transparency even if it contains metal oxide particles at a high concentration, can achieve high count rate and high detection efficiency with high time resolution.
なお、本発明において、透明性が高いとは、印刷物の上にプラスチックシンチレータの試験片をおいてその印刷物を認識できる程度をいい、具体的には可視光（３８０〜７８０ｎｍ）の平均透過率で６５％以上である。
また、高時間分解能の場合に高計数率を達成できる。すなわち、高計数率が達成できるということは、時間分解能が高いことを示している。
In the present invention, high transparency means a degree to which a test piece of a plastic scintillator is placed on a printed matter and the printed matter can be recognized, specifically, an average transmittance of visible light (380 to 780 nm). It is 65% or more.
In addition, a high counting rate can be achieved in the case of high time resolution. That is, the fact that a high counting rate can be achieved indicates that the time resolution is high.
以下に実施例及び比較例を示して本発明を更に具体的に説明するが、本発明はこれらに
限定されるものではない。なお、実施例および比較例中の部は質量部、％は質量％を意味する。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the part in an Example and a comparative example means a mass part, and% means a mass%.
（合成例１：酸化ジルコニウムナノ粒子の合成）
ジエタノールアミン２６．０ｇ、オクタン酸２０．０ｇ、リシノール酸４．０ｇ、４８％水酸化カリウム水溶液３０．０ｇを含有する混合液に、オキシ塩化ジルコニウム８水和物３６．０４ｇ、および純水２９．４４ｇの混合溶液を添加し、得られた混合物をオートクレーブ中で２２０℃、１０時間の水熱処理を行った。水熱処理後、上澄み液を除去し、白色沈殿物をアセトンおよび純水で洗浄、ポアサイズ３μｍフィルタで濾過し、得られた白色物を６０℃で一昼夜真空乾燥を行い、１６．４５ｇの白色粉末を得た。カルボン酸の表面処理量は、ＰｅｒｋｉｎＥｌｍｅｒ社製の熱質量測定装置ＴＧＡ８０００により、窒素雰囲気下４０℃／分の速度で９００℃まで昇温した質量減少率から２１．３４％で、ＸＲＤより結晶系は単斜晶であり、結晶子径は３．６ｎｍであった。
(Synthesis Example 1: Synthesis of Zirconium Oxide Nanoparticles)
36.04 g of zirconium oxychloride octahydrate and 29.44 g of pure water in a mixture containing 26.0 g of diethanolamine, 20.0 g of octanoic acid, 4.0 g of ricinoleic acid, and 30.0 g of a 48% potassium hydroxide aqueous solution. The mixed solution of the above was added, and the obtained mixture was subjected to hydrothermal treatment at 220 ° C. for 10 hours in an autoclave. After hydrothermal treatment, the supernatant is removed, the white precipitate is washed with acetone and pure water, filtered through a pore size 3 μm filter, and the obtained white product is vacuum dried at 60 ° C. for 24 hours to obtain 16.45 g of white powder. Obtained. The amount of surface treatment of the carboxylic acid is 21.34% from the mass reduction rate of heating up to 900 ° C. at a rate of 40 ° C./min under a nitrogen atmosphere by the thermal mass measuring device TGA8000 manufactured by PerkinElmer, and the crystal system is more crystalline than XRD. It was a monoclinic crystal with a crystallite diameter of 3.6 nm.
（合成例２：酸化ハフニウムナノ粒子の合成）
ジエタノールアミン２７．８ｇ、オクタン酸１４．４ｇ、リシノール酸７．２ｇ、４８％水酸化カリウム水溶液２１．６ｇを含有する混合液に、オキシ塩化ハフニウム８水和物３８．４ｇおよび純水３８．４ｇの混合溶液を添加し、得られた混合物をオートクレーブ中で２２０℃、１０時間の水熱処理を行った。水熱処理後、上澄み液を除去し、白色沈殿物をアセトンおよび純水で洗浄、ポアサイズ３μｍフィルタで濾過し、得られた白色物を６０℃で一昼夜真空乾燥を行い、２１．４３ｇの白色粉末を得た。カルボン酸の表面処理量は、ＰｅｒｋｉｎＥｌｍｅｒ社製の熱質量測定装置ＴＧＡ８０００により、窒素雰囲気下４０℃／分の速度で９００℃まで昇温した質量減少率から１４．８４％で、ＸＲＤより結晶系は単斜晶であり、結晶子径は３．９ｎｍであった。
(Synthesis Example 2: Synthesis of hafnium oxide nanoparticles)
In a mixture containing 27.8 g of diethanolamine, 14.4 g of octanoic acid, 7.2 g of ricinolic acid, and 21.6 g of a 48% potassium hydroxide aqueous solution, 38.4 g of hafnium oxychloride octahydrate and 38.4 g of pure water were added. The mixed solution was added and the resulting mixture was hydrothermally treated at 220 ° C. for 10 hours in an autoclave. After hydrothermal treatment, the supernatant is removed, the white precipitate is washed with acetone and pure water, filtered through a pore size 3 μm filter, and the obtained white product is vacuum dried at 60 ° C. for 24 hours to obtain 21.43 g of white powder. Obtained. The amount of surface treatment of the carboxylic acid is 14.84% from the mass reduction rate of heating up to 900 ° C. at a rate of 40 ° C./min under a nitrogen atmosphere by the thermal mass measuring device TGA8000 manufactured by PerkinElmer, and the crystal system is more crystalline than XRD. It was a monoclinic crystal with a crystallite diameter of 3.9 nm.
本発明において各ナノ粒子の平均粒子径は、Ｘ線回折装置（株式会社リガク製、全自動多目的Ｘ線回折装置 ＳｍａｒｔＬａｂ）を用い、測定条件を、Ｘ線管電圧４０ｋＶ、Ｘ線管電電流３０ｍＡ、走査範囲２θは１０．０−６５．０°とし、Ｘ線回折測定の２θ＝２８．４付近の（１１−１）面による回折強度からその半価幅βを求め、下記数１のＳｃｈｅｒｒｅｒ式において、Ｓｃｈｅｒｒｅｒ定数Ｋを０．９、Ｘ線管球の波長λを１．５４０５６として結晶子サイズＤを求め、その値とした。 In the present invention, the average particle size of each nanoparticle is measured by using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., fully automatic multipurpose X-ray diffractometer SmartLab), and the measurement conditions are X-ray tube voltage 40 kV and X-ray tube electric current 30 mA. The scanning range 2θ is set to 10.0-65.0 °, and the half-wavelength width β is obtained from the diffraction intensity of the (11-1) plane near 2θ = 28.4 in the X-ray diffraction measurement, and the Scherrer of the following equation 1 is obtained. In the formula, the Scherrer constant K was 0.9, the wavelength λ of the X-ray tube was 1.540556, and the crystallite size D was obtained and used as the value.
（数１）
Ｄ＝Ｋ ・λ／（β・ｃｏｓθ）
(Number 1)
D = K ・ λ / (β ・ cosθ)
合成例１および２のナノ粒子を用い、以下の実施例１〜１２のプラスチックシンチレータを製造した。 The following plastic scintillators of Examples 1 to 12 were produced using the nanoparticles of Synthesis Examples 1 and 2.
（実施例１）
合成例１の酸化ジルコニウムナノ粒子２．６部、スチレンモノマー９．４部、３−フェノキシベンジルアクリレート０．３部、２−アクリロイルオキシエチルサクシネート０．３部および２−（４−ｔｅｒｔ−ブチルフェニル）−５−（４−ビフェニリル）−１，３，４−オキサジアゾール０．７部をバイアルに添加、超音波分散させ、この混合液が透明になってから２，２’−アゾビス（２，４−ジメチルバレロニトリル)を０．０４部加え、アルゴン雰囲気下、６５℃のオーブンに２４時間静置し、酸化ジルコニウムを２０％含有するプラスチックシンチレータを得た。
(Example 1)
2.6 parts of zirconium oxide nanoparticles of Synthesis Example 1, 9.4 parts of styrene monomer, 0.3 part of 3-phenoxybenzyl acrylate, 0.3 part of 2-acryloyloxyethyl succinate and 2- (4-tert-butyl). 0.7 part of phenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole was added to the vial and ultrasonically dispersed, and after the mixed solution became transparent, 2,2'-azobis (2,2'-azobis) ( 0.04 part of 2,4-dimethylvaleronitrile) was added, and the mixture was allowed to stand in an oven at 65 ° C. for 24 hours under an argon atmosphere to obtain a plastic scintillator containing 20% of zirconium oxide.
（実施例２）
酸化ジルコニウムナノ粒子を４．６部としたほかは実施例１と同様にして、酸化ジルコニウムを３０％含有するプラスチックシンチレータを得た。
(Example 2)
A plastic scintillator containing 30% of zirconium oxide was obtained in the same manner as in Example 1 except that the number of zirconium oxide nanoparticles was 4.6 parts.
（実施例３）
酸化ジルコニウムナノ粒子を６．９部としたほかは実施例１と同様にして、酸化ジルコニウムを４０％含有するプラスチックシンチレータを得た。
(Example 3)
A plastic scintillator containing 40% of zirconium oxide was obtained in the same manner as in Example 1 except that the number of zirconium oxide nanoparticles was 6.9 parts.
（実施例４）
合成例１の酸化ジルコニウムナノ粒子２．６部を合成例２の酸化ハフニウムナノ粒子２．６部に変更したほかは、実施例１と同様にして、酸化ハフニウムを２０％含有するプラスチックシンチレータを得た。
(Example 4)
A plastic scintillator containing 20% hafnium oxide was obtained in the same manner as in Example 1 except that 2.6 parts of zirconium oxide nanoparticles of Synthesis Example 1 were changed to 2.6 parts of hafnium oxide nanoparticles of Synthesis Example 2. It was.
（実施例５）
酸化ハフニウムナノ粒子を４．５部としたほかは実施例４と同様にして、酸化ハフニウムを３０％含有するプラスチックシンチレータを得た。
(Example 5)
A plastic scintillator containing 30% of hafnium oxide was obtained in the same manner as in Example 4 except that the number of hafnium oxide nanoparticles was 4.5 parts.
（実施例６）
酸化ハフニウムナノ粒子を６．９部としたほかは実施例４と同様にして、酸化ハフニウムを４０％含有するプラスチックシンチレータを得た。
(Example 6)
A plastic scintillator containing 40% of hafnium oxide was obtained in the same manner as in Example 4 except that the number of hafnium oxide nanoparticles was 6.9 parts.
（実施例７）
合成例１の酸化ジルコニウムナノ粒子２．６部、４−ビニルトルエンモノマー９．４部、３−フェノキシベンジルアクリレート０．３部、２−アクリロイルオキシエチルサクシネート０．３部および２−（４−ｔｅｒｔ−ブチルフェニル）−５−（４−ビフェニリル）−１，３，４−オキサジアゾール０．７部をバイアルに添加、超音波分散させ、この混合液が透明になってから２，２’−アゾビス（２，４−ジメチルバレロニトリル)を０．０４部加え、この混合液をアルゴン雰囲気下、６５℃のオーブンに２４時間静置し、酸化ジルコニウムを２０％含有するプラスチックシンチレータを得た。
(Example 7)
2.6 parts of zirconium oxide nanoparticles of Synthesis Example 1, 9.4 parts of 4-vinyltoluene monomer, 0.3 parts of 3-phenoxybenzyl acrylate, 0.3 parts of 2-acryloyloxyethyl succinate and 2- (4-) 0.7 part of tert-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole was added to the vial and ultrasonically dispersed, and after the mixed solution became transparent, 2,2' 0.04 parts of −azobis (2,4-dimethylvaleronitrile) was added, and the mixed solution was allowed to stand in an oven at 65 ° C. for 24 hours under an argon atmosphere to obtain a plastic scintillator containing 20% of zirconium oxide.
（実施例８）
酸化ジルコニウムナノ粒子を４．５部としたほかは実施例７と同様にして、酸化ジルコニウムを３０％含有するプラスチックシンチレータを得た。
(Example 8)
A plastic scintillator containing 30% of zirconium oxide was obtained in the same manner as in Example 7 except that the number of zirconium oxide nanoparticles was 4.5 parts.
（実施例９）
酸化ジルコニウムナノ粒子を６．９部としたほかは実施例７と同様にして、酸化ジルコニウムを４０％含有するプラスチックシンチレータを得た。
(Example 9)
A plastic scintillator containing 40% of zirconium oxide was obtained in the same manner as in Example 7 except that the number of zirconium oxide nanoparticles was 6.9 parts.
（実施例１０）
合成例１の酸化ジルコニウムナノ粒子２．６部を合成例２の酸化ハフニウムナノ粒子２．６部に変更したほかは、実施例７と同様にして、酸化ハフニウムを２０％含有するプラスチックシンチレータを得た。
(Example 10)
A plastic scintillator containing 20% hafnium oxide was obtained in the same manner as in Example 7, except that 2.6 parts of zirconium oxide nanoparticles of Synthesis Example 1 were changed to 2.6 parts of hafnium oxide nanoparticles of Synthesis Example 2. It was.
（実施例１１）
酸化ハフニウムナノ粒子を４．５部としたほかは実施例１０と同様にして、酸化ハフニウムを３０％含有するプラスチックシンチレータを得た。
(Example 11)
A plastic scintillator containing 30% of hafnium oxide was obtained in the same manner as in Example 10 except that the number of hafnium oxide nanoparticles was 4.5 parts.
（実施例１２）
酸化ハフニウムナノ粒子を６．９部としたほかは実施例１０と同様にして、酸化ハフニウムを４０％含有するプラスチックシンチレータを得た。
(Example 12)
A plastic scintillator containing 40% of hafnium oxide was obtained in the same manner as in Example 10 except that the number of hafnium oxide nanoparticles was 6.9 parts.
各実施例で得られたプラスチックシンチレータを直径８ｍｍ、高さ３ｍｍの円柱に成形して評価用サンプルとした。 The plastic scintillators obtained in each example were molded into a cylinder having a diameter of 8 mm and a height of 3 mm to prepare a sample for evaluation.
（比較例１）
鉛を５％含有する直径８ｍｍ、高さ３ｍｍに成型したプラスチックシンチレータ（ＥＪ−２５６、ＥＬＪＥＮ ＴＥＣＨＮＯＥＯＧＹ）を比較例１（発光量評価の基準）とした。
(Comparative Example 1)
A plastic scintillator (EJ-256, ELJEN TECHNOEOGY) molded into a diameter of 8 mm and a height of 3 mm containing 5% of lead was used as Comparative Example 1 (standard for evaluating the amount of light emitted).
各実施例で得られたプラスチックシンチレータについて、以下の方法により可視光（３８０〜７８０ｎｍ）の平均光透過率、発光量および検出効率を求め、その結果を表１にまとめた。 For the plastic scintillators obtained in each example, the average light transmittance, light emission amount and detection efficiency of visible light (380 to 780 nm) were determined by the following methods, and the results are summarized in Table 1.
（平均光透過率）
実施例１〜１２の評価用サンプルについて、紫外可視近赤外分光光度計（ＵＨ４１５０、日立ハイテクサイエンス社製）を使用して可視光に相当する３８０〜７８０ｎｍの光透過率を０．５ｎｍ毎に測定し、それを相加平均して求めた。
(Average light transmittance)
For the evaluation samples of Examples 1 to 12, the light transmittance of 380 to 780 nm corresponding to visible light was measured every 0.5 nm using an ultraviolet visible near infrared spectrophotometer (UH4150, manufactured by Hitachi High-Tech Science Co., Ltd.). It was measured and calculated by arithmetic mean.
（発光量）
各実施例の評価用サンプルに６７．４ｋｅＶのＸ線を照射した際のシンチレーション光を光電子増倍管（商品名：Ｒ−７４００Ｐ、製造社：浜松ホトニクス）により検出し、電荷感応型前置増幅器（商品名：２００５、製造社：Ｃａｎｂｅｒｒａ）により増幅して得られた検出信号波高スペクトルから、実施例毎のピーク位置のチャンネル数（ピークチャンネル数）を求めた。
比較例１のシンチレータについて上記と同様にピークチャンネル数を求め、これを基準ピークチャンネル数とした。
この基準ピークチャンネル数に対する各実施例のピークチャンネル数の割合を求め、これを入射Ｘ線のエネルギー当たりの発光量（光子／ＭｅＶ）とした。
(Light emission amount)
The scintillation light when the evaluation sample of each example was irradiated with 67.4 keV X-ray was detected by a photomultiplier tube (trade name: R-7400P, manufacturer: Hamamatsu Photonics), and a charge-sensitive preamplifier. From the detection signal wave height spectrum obtained by amplification by (trade name: 2005, manufacturer: Canberra), the number of channels at the peak position (number of peak channels) for each example was determined.
For the scintillator of Comparative Example 1, the number of peak channels was obtained in the same manner as above, and this was used as the reference peak channel number.
The ratio of the number of peak channels of each example to the number of reference peak channels was obtained, and this was taken as the amount of light emitted per energy of incident X-rays (photon / MeV).
（検出効率）
前記発光量の測定と同様の条件で、厚さ５ｍｍのＮａＩ（Ｔｌ）シンチレータの測定を行い、得られた検出信号波高スペクトルの面積を１００としたときの各実施例の検出信号波高スペクトルの面積を求めた。この値は検出された全イベント数に相当するので、この値を検出効率（％）とした。
(Detection efficiency)
The area of the detected signal wave height spectrum of each embodiment when the area of the obtained detected signal wave height spectrum was set to 100 by measuring the NaI (Tl) scintillator having a thickness of 5 mm under the same conditions as the measurement of the amount of light emitted. Asked. Since this value corresponds to the total number of detected events, this value was used as the detection efficiency (%).
Claims (8)
有機蛍光化合物と、
水酸基不含有カルボン酸および水酸基含有カルボン酸によって表面処理されている酸化ジルコニウムナノ粒子または酸化ハフニウムナノ粒子と、
を混合して分散体を得る第１の工程、
および、その得られた分散体中の前記重合性モノマーを重合させる第２の工程、
を含む、請求項１から６のいずれか一つに記載のプラスチックシンチレータの製造方法。 With polymerizable monomers
With organic fluorescent compounds
Zirconium oxide nanoparticles or hafnium oxide nanoparticles surface-treated with hydroxyl-free carboxylic acid and hydroxyl-containing carboxylic acid,
First step of mixing to obtain a dispersion,
And the second step of polymerizing the polymerizable monomer in the obtained dispersion,
The method for producing a plastic scintillator according to any one of claims 1 to 6, which comprises.
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