JP2001354862A - Radiation-sensitive composition and dosimeter - Google Patents
Radiation-sensitive composition and dosimeterInfo
- Publication number
- JP2001354862A JP2001354862A JP2000178581A JP2000178581A JP2001354862A JP 2001354862 A JP2001354862 A JP 2001354862A JP 2000178581 A JP2000178581 A JP 2000178581A JP 2000178581 A JP2000178581 A JP 2000178581A JP 2001354862 A JP2001354862 A JP 2001354862A
- Authority
- JP
- Japan
- Prior art keywords
- radiation
- compound
- sensitive composition
- polycyclic aromatic
- condensed polycyclic
- Prior art date
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Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、放射線線量の検出
・測定に有用な感放射線組成物、およびこれを用いた線
量計に存する。The present invention relates to a radiation-sensitive composition useful for detecting and measuring a radiation dose, and a dosimeter using the same.
【０００２】[0002]
【従来の技術】医療器具の放射線滅菌あるいは放射線廃
棄物の管理などにおいて、放射線線量が簡便に評価でき
る線量計が使われている。従来の線量計は、メチルオレ
ンジなどｐＨインジケーターを用い、放射線反応に伴う
酸発生による変色など（山上他、Ｃｈｅｍ．Ｅｘｐｒｅ
ｓｓ ５，８０９（１９９０））を用いている。2. Description of the Related Art In radiation sterilization of medical instruments or management of radiation waste, a dosimeter capable of easily evaluating a radiation dose is used. Conventional dosimeters use a pH indicator such as methyl orange to change color due to the generation of acid due to radiation reaction (Yamagami et al., Chem. Expre.
ss 5, 809 (1990)).
【０００３】[0003]
【発明が解決しようとする課題】しかしながらこのよう
なｐＨインジケーターを用いた線量計は、大線量（５０
００グレイ以上）でのみ使用可能で、線量の低い領域で
は変色せず使用できない。また、一回のみ使用可能で、
再使用はできない。一方、フォトクロミック分子は、光
の作用により色の異なる２つの異性体を可逆的に生成す
る分子を言い、調光レンズ、光メモリ、光スイッチなど
への応用をめざし、研究開発がすすめられている。フォ
トクロミック分子には、光のみならず放射線照射によっ
ても可逆に変色するものがある。これらは、本質的に線
量計へ応用可能であるが、これまでそのような使用例は
ない。それは、従来のフォトクロミック分子では、いず
れにおいても放射線生成する着色体（逆フォトクロミッ
ク反応系では無色体）が熱的に不安定で、暗黒中におい
ても自然と無色体（逆フォトクロミック反応系では着色
体）にもどるため、線量測定のための着色体濃度を正確
に計測することができなかったためである。However, a dosimeter using such a pH indicator has a large dose (50%).
(More than 00 gray) and cannot be used without discoloration in low dose areas. Also, it can be used only once,
Cannot be reused. On the other hand, a photochromic molecule is a molecule that reversibly generates two isomers having different colors by the action of light, and research and development are being pursued with the aim of application to a light control lens, an optical memory, an optical switch, and the like. Some photochromic molecules change color reversibly by irradiation as well as light. They are essentially applicable to dosimeters, but there is no such use so far. In conventional photochromic molecules, the colored body that produces radiation (colorless body in the reverse photochromic reaction system) is thermally unstable in any case, and is naturally colorless in the dark (colored body in the reverse photochromic reaction system). This is because it was not possible to accurately measure the concentration of the colored body for dosimetry.
【０００４】このような課題を解決するために、既に発
明者らは、ポリスチレンなどの芳香環を側鎖あるいは主
鎖に含む高分子に熱不可逆性フォトクロミック化合物を
分散または溶解して使用することを提案している。（特
開平１１−２５８３４８号公報参照。）[0004] In order to solve such problems, the present inventors have already used a method in which a heat irreversible photochromic compound is dispersed or dissolved in a polymer having an aromatic ring such as polystyrene in a side chain or a main chain. is suggesting. (See JP-A-11-258348)
【０００５】[0005]
【課題を解決するための手段】本発明者らは更なる鋭意
検討の結果、系内に、ナフタレン環などの縮合多環芳香
族構造を有する化合物と、熱不可逆性フォトクロミック
化合物とを含む感放射線組成物は、放射線感受性が非常
に高く、これを用いることにより、前述のような熱退色
を生じず、かつ放射線量に応じてリニアに吸収強度が変
化し、また１０００グレイ以下、更には５００グレイ以
下の放射線量をも測定可能なフォトクロミック線量計を
提供できることを見出し、本発明に到達した。Means for Solving the Problems As a result of further intensive studies, the present inventors have found that a radiation-sensitive system containing a compound having a condensed polycyclic aromatic structure such as a naphthalene ring and a heat irreversible photochromic compound in the system. The composition has a very high radiation sensitivity. By using the composition, the thermal discoloration does not occur as described above, and the absorption intensity changes linearly according to the radiation dose. The present inventors have found that a photochromic dosimeter capable of measuring the following radiation dose can be provided, and have reached the present invention.
【０００６】すなわち本発明は、少なくとも、熱不可逆
性フォトクロミック化合物と、縮合多環芳香族構造を有
する化合物を含有する感放射線組成物、およびこれを用
いた線量計に存する。なお本発明における「縮合多環芳
香族構造を有する化合物」とは、後述するように、該基
を有するいわゆる高分子化合物であっても、ナフタレ
ン、アントラセン等の縮合多環芳香族の化合物であって
もよい。That is, the present invention resides in a radiation-sensitive composition containing at least a heat irreversible photochromic compound and a compound having a condensed polycyclic aromatic structure, and a dosimeter using the same. The “compound having a condensed polycyclic aromatic structure” in the present invention is a compound of a condensed polycyclic aromatic such as naphthalene or anthracene, even if it is a so-called polymer compound having the group, as described later. You may.
【０００７】[0007]
【発明の実施の形態】以下、本発明をより詳細に説明す
る。本発明に用いられる熱不可逆性フォトクロミック化
合物としては、作業環境において実質的な熱不可逆性を
有するものであればよいが、通常は４０℃以下、好まし
くは８０℃以下で実質的な退色を生じない化合物が好ま
しい。また放射線の作用により、色の異なる２つの異性
体を可逆的に生成する化合物が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The heat irreversible photochromic compound used in the present invention is not particularly limited as long as it has substantial heat irreversibility in a working environment, but usually does not substantially cause color fading at 40 ° C. or less, preferably 80 ° C. or less. Compounds are preferred. Further, a compound that reversibly generates two isomers having different colors by the action of radiation is preferable.
【０００８】このようなフォトクロミック化合物として
は、例えばフルギド系化合物やジアリールエテン系化合
物が挙げられ、例えば特開平６−２６３７５３号公報、
特開平８−２４５５７９号公報、特開平９−２４１２５
４号公報、特開平９−２４１６２５号公報等に記載され
たものより適宜選択することができる。より好ましくは
該熱不可逆性フォトクロミック化合物がジアリールエテ
ン系化合物であり、さらに好ましくは該熱不可逆性フォ
トクロミック化合物が、結晶フォトクロミズムを示すも
のである。Examples of such a photochromic compound include a fulgide compound and a diarylethene compound. For example, JP-A-6-263755,
JP-A-8-245579, JP-A-9-24125
No. 4, JP-A-9-241625 and the like can be appropriately selected. More preferably, the thermo-irreversible photochromic compound is a diarylethene-based compound, and even more preferably, the thermo-irreversible photochromic compound exhibits crystal photochromism.
【０００９】本発明の感放射線組成物は、系内に縮合多
環芳香族構造を有する化合物を含むことを特徴とする。
該縮合多環芳香族構造としては、例えば５員環および／
または６員環が２個以上縮合してなる環構造が挙げら
れ、具体的には例えば下記の構造が挙げられる。The radiation-sensitive composition of the present invention is characterized in that the system contains a compound having a condensed polycyclic aromatic structure.
As the fused polycyclic aromatic structure, for example, a 5-membered ring and / or
Alternatively, a ring structure formed by condensing two or more 6-membered rings is mentioned, and specific examples include the following structures.
【００１０】[0010]
【化３】 Embedded image
【００１１】これらは置換基を有していてもよく、該置
換基としては、例えばエチル基、メチル基、ブチル基、
オクチル基などの、炭素数１〜１０の直鎖または分岐の
アルキル基；フェニル基、ビフェニル基、または前述し
た縮合多環芳香族構造に対応する一価の基などのアリー
ル基；水酸基；フッ素原子、塩素原子などのハロゲン原
子等が挙げられる。These may have a substituent. Examples of the substituent include an ethyl group, a methyl group, a butyl group,
A linear or branched alkyl group having 1 to 10 carbon atoms such as an octyl group; an aryl group such as a phenyl group, a biphenyl group, or a monovalent group corresponding to the above-mentioned condensed polycyclic aromatic structure; a hydroxyl group; a fluorine atom And a halogen atom such as a chlorine atom.
【００１２】本発明における縮合多環芳香族構造には、
一重項励起状態の寿命が長く、本発明で用いる熱不可逆
性フォトクロミック化合物よりも高いエネルギーを有す
ることが要求される。使用する熱不可逆性フォトクロミ
ック化合物の種類によって、縮合する芳香族環の数の好
ましい範囲は異なるが、縮合する環の数が多くなると励
起状態のエネルギーが低くなる傾向があるため、概して
５員環および／または６員環が２〜４個縮合してなる縮
合多環芳香族構造が好ましく、中でもナフタレン環構造
が特に好ましい。The fused polycyclic aromatic structure in the present invention includes:
It is required that the singlet excited state has a long lifetime and has higher energy than the thermo-irreversible photochromic compound used in the present invention. The preferred range of the number of aromatic rings to be condensed varies depending on the type of the heat irreversible photochromic compound to be used. However, when the number of condensed rings increases, the energy of the excited state tends to decrease. A condensed polycyclic aromatic structure formed by condensing 2 to 4 6-membered rings is preferable, and a naphthalene ring structure is particularly preferable.
【００１３】本発明の縮合多環芳香族構造を有する化合
物については、該化合物が、主鎖または側鎖に縮合多
環芳香族基を有する高分子化合物である場合、および
縮合多環芳香族化合物である（いわゆるポリマーではな
い）場合、が考えられる。 −１ 側鎖に縮合多環芳香族基を有する高分子化合物
を含む感放射線組成物。With respect to the compound having a condensed polycyclic aromatic structure of the present invention, when the compound is a polymer compound having a condensed polycyclic aromatic group in the main chain or side chain, (Not a so-called polymer) is considered. -1 A radiation-sensitive composition containing a polymer compound having a condensed polycyclic aromatic group in a side chain.
【００１４】該高分子化合物として好ましくは側鎖に縮
合多環芳香族基を有するビニル重合体が挙げられ、具体
的には下記部分構造を有するものが挙げられる。The high molecular compound is preferably a vinyl polymer having a condensed polycyclic aromatic group in the side chain, and specifically, a compound having the following partial structure.
【００１５】[0015]
【化４】 Embedded image
【００１６】より好ましくは下記部分構造（Ｉ）および
（II）を繰り返し単位として有する重合体が挙げられ
る。More preferred are polymers having the following partial structures (I) and (II) as repeating units.
【００１７】[0017]
【化５】 Embedded image
【００１８】上記構造中、Ｒ1およびＲ2は各々独立に水
素原子または炭素数１〜３のアルキル基を表す。ベンゼ
ン環Ａは置換基を有していてもよく、該置換基としては
エチル基、メチル基、ブチル基、オクチル基などの、炭
素数１〜１０の直鎖または分岐のアルキル基；フェニル
基、ビフェニル基、または前述した縮合多環芳香族構造
に対応する一価の基などのアリール基；水酸基；フッ素
原子、塩素原子などのハロゲン原子等が挙げられる。ベ
ンゼン環Ａとしては、無置換のフェニル基が特に好まし
い。In the above structure, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The benzene ring A may have a substituent. Examples of the substituent include a linear or branched alkyl group having 1 to 10 carbon atoms such as an ethyl group, a methyl group, a butyl group, and an octyl group; a phenyl group; An aryl group such as a biphenyl group or a monovalent group corresponding to the above-mentioned condensed polycyclic aromatic structure; a hydroxyl group; a halogen atom such as a fluorine atom and a chlorine atom. As the benzene ring A, an unsubstituted phenyl group is particularly preferred.
【００１９】Ａｒ基は、前述した縮合多環芳香族構造に
対応する一価の縮合多環芳香族基を表し、好ましくは５
員環および／または６員環が２個以上縮合してなる縮合
多環芳香族基を表す。Ａｒ基が有していてもよい置換
基、およびＡｒ基として好ましいものは、前述した縮合
多環芳香族構造と同様である。該ビニル重合体におい
て、部分構造（Ｉ）は０〜９５mol％、構造（II）が５
〜１００mol％が好ましい。なお、該ビニル重合体の性
能を損なわない範囲で、その他のエチレン性不飽和結合
を有するモノマー由来の部分構造を有していてもよい。The Ar group represents a monovalent condensed polycyclic aromatic group corresponding to the above-mentioned condensed polycyclic aromatic structure.
Represents a condensed polycyclic aromatic group formed by condensing two or more membered rings and / or six-membered rings. Substituents that the Ar group may have, and preferable examples of the Ar group are the same as the condensed polycyclic aromatic structure described above. In the vinyl polymer, the partial structure (I) has 0 to 95 mol% and the structure (II) has 5
~ 100 mol% is preferred. The vinyl polymer may have a partial structure derived from a monomer having another ethylenically unsaturated bond as long as the performance of the vinyl polymer is not impaired.
【００２０】ビニル重合体として特に好ましくは、部分
構造（Ｉ）として２−ビニルナフタレン由来の構造を有
する２−ビニルナフタレン共重合体であり、最も好まし
くは部分構造（Ｉ）として２−ビニルナフタレン由来の
構造、および部分構造（II）としてスチレン由来の構造
を有するビニル重合体である。 −２ 主鎖に２価の縮合多環芳香族基を有する高分子
化合物を含む感放射線組成物。 主鎖に縮合多環芳香族基を有する高分子化合物として
は、ポリカーボネート、ポリアリレート、ポリエステ
ル、ノボラック等の、重縮合によって得られる重合体が
挙げられ、該２価の縮合多環芳香族基とは、前述した縮
合多環芳香族構造に対応する２価の基である。The vinyl polymer is particularly preferably a 2-vinylnaphthalene copolymer having a structure derived from 2-vinylnaphthalene as the partial structure (I), and most preferably a 2-vinylnaphthalene-derived copolymer as the partial structure (I). And a vinyl polymer having a structure derived from styrene as the partial structure (II). -2 A radiation-sensitive composition containing a polymer compound having a divalent fused polycyclic aromatic group in the main chain. Examples of the polymer compound having a condensed polycyclic aromatic group in the main chain include polymers obtained by polycondensation, such as polycarbonate, polyarylate, polyester, and novolak, and the divalent condensed polycyclic aromatic group and Is a divalent group corresponding to the above-mentioned condensed polycyclic aromatic structure.
【００２１】この２価の縮合多環芳香族基として好まし
いもの、および該基が有していてもよい置換基として
は、前述した縮合多環芳香族構造と同様のものが挙げら
れる。主鎖に縮合多環芳香族基を有する高分子化合物と
して、好ましくは下記部分構造を有するものが挙げられ
る。Preferred examples of the divalent condensed polycyclic aromatic group and the substituents that the group may have include those similar to the condensed polycyclic aromatic structure described above. As the polymer compound having a condensed polycyclic aromatic group in the main chain, a compound having the following partial structure is preferred.
【００２２】[0022]
【化６】 Embedded image
【００２３】[0023]
【化７】 Embedded image
【００２４】上記−１及び−２における高分子化合
物は、いわゆるオリゴマー程度の分子量であってもかま
わないが、後述するように本発明の感放射線組成物を用
いてフィルムを形成する場合には、ある程度高分子量で
ある方が好ましい。よって、分子量としては、特に制限
はないが、ＧＰＣで測定したポリスチレン換算の重量平
均分子量で通常３，０００〜１，０００，０００程度で
ある。 縮合多環芳香族化合物を含む感放射線組成物。The high molecular compound of the above-mentioned -1 and -2 may have a molecular weight of a so-called oligomer, but when forming a film using the radiation-sensitive composition of the present invention as described later, It is preferable that the molecular weight is high to some extent. Accordingly, the molecular weight is not particularly limited, but is generally about 3,000 to 1,000,000 in terms of polystyrene equivalent weight average molecular weight measured by GPC. A radiation-sensitive composition containing a condensed polycyclic aromatic compound.
【００２５】縮合多環芳香族化合物（いわゆるポリマー
ではない化合物）を含む場合は、本発明の感放射線組成
物中に縮合多環芳香族化合物が溶解または分散している
ものが挙げられる。縮合多環芳香族化合物とは、前述し
た縮合多環芳香族構造からなる化合物である。該化合物
として好ましいもの、および該化合物が有していてもよ
い置換基としては、前述した縮合多環芳香族構造と同様
のものが挙げられる。When a condensed polycyclic aromatic compound (compound which is not a polymer) is contained, a compound in which the condensed polycyclic aromatic compound is dissolved or dispersed in the radiation-sensitive composition of the present invention can be mentioned. The condensed polycyclic aromatic compound is a compound having the above-mentioned condensed polycyclic aromatic structure. Preferred examples of the compound and the substituents that the compound may have include those similar to the aforementioned condensed polycyclic aromatic structure.
【００２６】本発明の感放射線組成物は、少なくとも熱
不可逆性フォトクロミック化合物と、縮合多環芳香族構
造を有する化合物を含有しており、通常は、これらが適
当な有機溶媒に溶解した溶液または分散した分散液であ
るか、必要に応じて適当な有機溶媒やバインダー樹脂を
含んだ樹脂組成物である。これらの組成物を用いること
により、非常に精度よく放射線線量の検出・測定が可能
な線量計を得ることができる。これらの線量計を、放射
線暴露すると、線量に応じて色調が変化する。この色変
化を吸収スペクトルあるいは透過率変化により計測すれ
ば線量を見積もることができる。The radiation-sensitive composition of the present invention contains at least a heat irreversible photochromic compound and a compound having a condensed polycyclic aromatic structure. Usually, these are dissolved or dispersed in a suitable organic solvent. Or a resin composition containing an appropriate organic solvent or a binder resin as required. By using these compositions, a dosimeter capable of detecting and measuring a radiation dose with very high accuracy can be obtained. When these dosimeters are exposed to radiation, the color tone changes according to the dose. The dose can be estimated by measuring the color change by an absorption spectrum or transmittance change.
【００２７】本発明の感放射線組成物に放射線が照射さ
れると、まず放射線エネルギーによって高い励起状態へ
励起された媒体励起子が媒体間を移動し、系中の縮合多
環芳香族構造にトラップされ、そこからフォトクロミッ
ク化合物へ励起エネルギーが移動し、発色する。縮合多
環芳香族構造が存在しない系中ではすぐに基底状態に失
活し、失われてしまうエネルギーが、縮合多環芳香族構
造に安定にトラップされ、メディエーターとして有効に
利用されるのである。When the radiation-sensitive composition of the present invention is irradiated with radiation, first, a medium exciton excited to a high excited state by radiation energy moves between the media and is trapped in the condensed polycyclic aromatic structure in the system. Then, the excitation energy is transferred to the photochromic compound, and the color is developed. In a system in which a condensed polycyclic aromatic structure does not exist, the deactivated energy is immediately trapped in the ground state and stably trapped in the condensed polycyclic aromatic structure, and is effectively used as a mediator.
【００２８】本発明の感放射線組成物が溶液または分散
液の場合、具体的には、上述のフォトクロミック化合物
および縮合多環芳香族構造を有する化合物を、ベンゼン
あるいはトルエンなどの芳香族溶媒に溶解（濃度範囲と
しては、１０-5〜１０ｍｏｌ／ｌ）し、その溶液を線量
計とする。放射線照射後、可視域での吸収強度を測定す
ることにより、照射線量が見積もられる。When the radiation-sensitive composition of the present invention is a solution or a dispersion, specifically, the photochromic compound and the compound having a condensed polycyclic aromatic structure are dissolved in an aromatic solvent such as benzene or toluene ( The concentration range is 10 −5 to 10 mol / l), and the solution is used as a dosimeter. After irradiation, the irradiation dose can be estimated by measuring the absorption intensity in the visible region.
【００２９】本発明の感放射線組成物が樹脂組成物であ
る場合、必要に応じてバインダー樹脂や有機溶剤を加
え、基材となる樹脂製フィルム、シートまたはガラス基
板などに塗布・乾燥するか、または該樹脂組成物から公
知の方法にてフィルムを形成することにより、線量計が
得られる。これらフィルム状の線量計を放射線暴露し、
その後可視域の吸収スペクトル変化測定により、線量計
測が行われる。When the radiation-sensitive composition of the present invention is a resin composition, if necessary, a binder resin or an organic solvent is added, and the composition is applied to a resin film, sheet, glass substrate or the like as a base material and dried. Alternatively, a dosimeter can be obtained by forming a film from the resin composition by a known method. Radiation exposure of these film dosimeters,
Thereafter, dose measurement is performed by measuring the absorption spectrum change in the visible region.
【００３０】縮合多環芳香族構造を有する化合物が縮合
多環芳香族化合物である場合、これを含む感放射線組成
物を用いてフィルム状の線量計を形成するには、バイン
ダー樹脂が必要である。また、縮合多環芳香族構造を有
する化合物が高分子化合物である場合、これを含む感放
射線組成物を用いることにより、該高分子化合物自身を
主成分とするフィルム状の線量計を形成することは可能
であるが、本発明の感放射線組成物の性能を損なわない
範囲で、必要に応じてバインダー樹脂を含有していても
よい。When the compound having the condensed polycyclic aromatic structure is a condensed polycyclic aromatic compound, a binder resin is required to form a film-shaped dosimeter using the radiation-sensitive composition containing the compound. . When the compound having the condensed polycyclic aromatic structure is a polymer compound, a film-shaped dosimeter containing the polymer compound itself as a main component can be formed by using a radiation-sensitive composition containing the compound. Although it is possible, a binder resin may be contained, if necessary, as long as the performance of the radiation-sensitive composition of the present invention is not impaired.
【００３１】このようなバインダー樹脂としては、ポリ
ビニルアルコール、ポリビニルピロリドン、ニトロセル
ロース、酢酸セルロース、ケトン系樹脂、アクリル系樹
脂、ポリスチレン系樹脂、ウレタン系樹脂、ポリビニル
ブチラール、ポリカーボネート、ポリオレフィン等、バ
インダー樹脂として一般に使用される樹脂を使用するこ
とができる。Examples of such a binder resin include polyvinyl alcohol, polyvinyl pyrrolidone, nitrocellulose, cellulose acetate, ketone resin, acrylic resin, polystyrene resin, urethane resin, polyvinyl butyral, polycarbonate, polyolefin and the like. Commonly used resins can be used.
【００３２】さらに本発明の感放射線組成物は、その性
能を損なわない範囲で任意の添加剤を含有していてもよ
い。なお、本発明の感放射線組成物は、前述のおよび
をあわせたもの、すなわち、縮合多環芳香族化合物と
縮合多環芳香族基を有する高分子を、ともに含んだもの
であってもよい。Further, the radiation-sensitive composition of the present invention may contain an optional additive as long as its performance is not impaired. The radiation-sensitive composition of the present invention may be a combination of the above and the above, that is, a composition containing both a condensed polycyclic aromatic compound and a polymer having a condensed polycyclic aromatic group.
【００３３】本発明の感放射線組成物における縮合多
環芳香族構造を有する高分子化合物および／またはに
おける縮合多環芳香族化合物の含有量と、熱不可逆性フ
ォトクロミック化合物の含有量の重量比は１〜４０：９
９〜５である。In the radiation-sensitive composition of the present invention, the weight ratio of the content of the polymer compound having a condensed polycyclic aromatic structure and / or the content of the condensed polycyclic aromatic compound to the content of the heat irreversible photochromic compound is 1 ~ 40: 9
9 to 5.
【００３４】[0034]
【実施例】以下、本発明を実施例により更に具体的に説
明するが、本発明はこれら実施例に限定されるものでは
ない。 （実施例１〜４）下記一般式(ｉ)に示す繰り返し単位を
有するポリマー（共重合比n=0.05、ｍ＋ｎ＝１）を０．
９０ｇ、EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. (Examples 1 to 4) A polymer having a repeating unit represented by the following general formula (i) (copolymerization ratio n = 0.05, m + n = 1) was added to 0.1%.
90g,
【００３５】[0035]
【化８】 Embedded image
【００３６】および下記一般式（ii）で示されるジアリ
ールエテン０．１０ｇAnd 0.10 g of a diarylethene represented by the following general formula (ii)
【００３７】[0037]
【化９】 Embedded image
【００３８】をトルエンに溶解しキャストすることで、
厚さ０．２ｍｍの無色透明プラスチックフィルムを作成
した。これに放射線（60Ｃｏのγ線）照射を行ったとこ
ろ、１０００グレイ照射によりフィルムは青く着色し、
600nmにおける吸光度が照射前と比較して0.070増加し
た。同様に、共重合比をｎ＝0.1、0.2、0.5に変えて各
々厚さ０．２ｍｍのプラスチックフィルムを作成した。
前述と同様に放射線照射を行ったところ、表−１に示す
ように吸光度変化がみとめられた。Is dissolved in toluene and cast,
A colorless transparent plastic film having a thickness of 0.2 mm was prepared. When this was irradiated with radiation ( 60 Co gamma rays), the film was colored blue by 1000 Gray irradiation,
The absorbance at 600 nm increased by 0.070 compared to before the irradiation. Similarly, plastic films having a thickness of 0.2 mm were prepared by changing the copolymerization ratio to n = 0.1, 0.2, and 0.5.
When irradiation was performed in the same manner as described above, a change in absorbance was observed as shown in Table 1.
【００３９】なお、吸光度変化後のフィルムを室温にて
１日放置したが、吸収変化は無かった。さらにこれらの
フィルムに対し可視光を照射したところ、発色が消える
ことが確認できた。The film after the change in absorbance was left at room temperature for one day, but there was no change in absorption. Further, when these films were irradiated with visible light, it was confirmed that the coloring disappeared.
【００４０】[0040]
【表１】 [Table 1]
【００４１】表−１に示した吸光度変化の値から、実施
例１〜４にて得られたフィルム状線量計を使用すること
により、５００グレイ以下の放射線をも充分検出可能で
あることが明らかである。 （実施例５）ポリスチレン（ＧＰＣ換算による重量平均
分子量：１０万）０．４５ｇ、上記化合物（ii）０．０
５ｇ、およびナフタレン０．０５ｇをトルエンに溶解さ
せ、キャストすることで厚さ０．２ｍｍの無色透明プラ
スチックフィルムを作成した。得られたフィルムい対
し、実施例１と同様に放射線照射を行ったところ、１０
０0グレイ照射によりフィルムは青く着色し、600nmにお
ける吸光度が照射前と比較して0.08増加した。From the absorbance change values shown in Table 1, it is clear that the use of the film dosimeters obtained in Examples 1 to 4 can sufficiently detect radiation of 500 Gray or less. It is. (Example 5) 0.45 g of polystyrene (weight average molecular weight in terms of GPC: 100,000), the above compound (ii) 0.0
5 g and 0.05 g of naphthalene were dissolved in toluene and cast to prepare a 0.2 mm thick colorless transparent plastic film. When the obtained film was irradiated with radiation in the same manner as in Example 1, 10
Upon irradiation with 00 Gray, the film was colored blue, and the absorbance at 600 nm increased by 0.08 compared to that before irradiation.
【００４２】なお、吸光度変化後のフィルムを室温にて
１日放置したが、吸収変化は無かった。さらにこのフィ
ルムに対して可視光を照射したところ、発色が消えるこ
とが確認できた。 （実施例６）ナフタレンの添加量を表−２に示す量（ポ
リスチレン０．４５ｇ、式（ii）で表される化合物０．
０５ｇに対し、ナフタレン０．２５ｇ）に変えた他は、
実施例５と同様にフィルムを形成し、評価した。結果を
表−２に示す。実施例６と同様に、室温にて１日放置し
たが吸収変化は無く、又、これに可視光を照射したとこ
ろ、発色が消えることが確認できた。The film after the change in absorbance was left at room temperature for one day, but there was no change in absorption. Further, when this film was irradiated with visible light, it was confirmed that the color disappeared. (Example 6) The amount of naphthalene added was as shown in Table 2 (0.45 g of polystyrene, the amount of compound 0.1 represented by the formula (ii)).
05g, Naphthalene 0.25g)
A film was formed and evaluated in the same manner as in Example 5. Table 2 shows the results. As in Example 6, the sample was allowed to stand at room temperature for 1 day, but there was no change in absorption. When the sample was irradiated with visible light, it was confirmed that the color development disappeared.
【００４３】[0043]
【表２】 [Table 2]
【００４４】（比較例）実施例５で用いたものと同じポ
リスチレン0.8gと上記一般式（ii）0.2ｇをトルエンに
溶解させキャストすることで、厚さ０．２ｍｍの無色透
明プラスチックフィルムを形成した。得られたフィルム
に対し、実施例１と同様に放射線（60Ｃｏγ線）照射を
行ったところ、１００0グレイ照射によりフィルムは青
く着色した。１０００グレイ照射によりフィルムは青く
着色し、600nmにおける吸光度が照射前と比較して０．
０６５増加した。(Comparative Example) A colorless transparent plastic film having a thickness of 0.2 mm was formed by dissolving 0.8 g of polystyrene and 0.2 g of the above-mentioned general formula (ii) in toluene and casting the same as those used in Example 5. did. The obtained film was subjected to a similarly radiation (60 Co gamma-ray) irradiation as in Example 1, the film was colored blue by 1000 Gray irradiation. Upon irradiation with 1000 Gray, the film is colored blue, and the absorbance at 600 nm is 0.
065 increased.
【００４５】以上の結果より、ナフタレン基を有するポ
リマーやナフタレンを添加することによって、フォトク
ロミック化合物の放射線感受性がよくなることがわかっ
た。From the above results, it was found that the radiation sensitivity of the photochromic compound was improved by adding a polymer having a naphthalene group or naphthalene.
【００４６】[0046]
【発明の効果】本発明の感放射線組成物は、例えば放射
線増感紙、放射線量計、及び放射線画像変換パネル等に
好適に用いられる。また、該組成物を用いたフォトクロ
ミック線量計は、高感度で放射線計測ができる上に、再
使用可能である。The radiation-sensitive composition of the present invention is suitably used, for example, for radiation intensifying screens, radiation dosimeters, radiation image conversion panels, and the like. In addition, a photochromic dosimeter using the composition can measure radiation with high sensitivity and can be reused.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｆ 28/06 Ｃ０８Ｆ 28/06 212/06 212/06 212/08 212/08 Ｃ０８Ｋ 5/01 Ｃ０８Ｋ 5/01 Ｃ０８Ｌ 25/00 Ｃ０８Ｌ 25/00 25/04 25/04 25/16 25/16 37/00 37/00 39/04 39/04 41/00 41/00 Ｃ０９Ｋ 9/02 Ｃ０９Ｋ 9/02 Ｂ Ｇ０１Ｔ 1/04 Ｇ０１Ｔ 1/04 (72)発明者 入江 せつ子 福岡県福岡市早良区室見４丁目24番 25− 706号 (72)発明者 田中 由紀 神奈川県横浜市青葉区鴨志田町1000番地 三菱化学株式会社横浜総合研究所内 Ｆターム(参考） 2G088 BB09 4J002 BC011 BC031 BC041 BC081 BC091 BC101 BC111 BC121 BC131 BJ001 BQ001 CC031 CF131 CF161 CF181 CG001 EA036 EV306 FD096 FD206 GH00 GR00 GT00 4J100 AB00Q AB02P AB03P AB04P AB07P AQ01Q AQ25Q AQ26Q AQ28Q BA03P BB01P BB07P BC43P BC44P BD12Q CA01 CA04 DA00 JA00 JA24 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) C08F 28/06 C08F 28/06 212/06 212/06 212/08 212/08 C08K 5/01 C08K 5 / 01 C08L 25/00 C08L 25/00 25/04 25/04 25/16 25/16 37/00 37/00 39/04 39/04 41/00 41/00 C09K 9/02 C09K 9/02 B G01T 1 / 04 G01T 1/04 (72) Inventor Setsuko Irie 4-24-25-706 Muromi, Saara-ku, Fukuoka, Japan (72) Inventor Yuki Tanaka 1000 Kamoshida-cho, Aoba-ku, Yokohama, Kanagawa Prefecture F-term in Yokohama Research Institute (Reference) 2G088 BB09 4J002 BC011 BC031 BC041 BC081 BC091 BC101 BC111 BC121 BC131 BJ001 BQ001 CC031 CF131 CF161 CF181 CG001 EA036 EV306 FD096 FD206 GH00 GR00 GT00 4J100 AB00Q AB02P AB03AQQB02A BB07P BC43P BC44P BD12Q CA01 CA04 DA00 JA00 JA24
Claims (11)
ク化合物と、縮合多環芳香族構造を有する化合物を含有
する、感放射線組成物。1. A radiation-sensitive composition comprising at least a heat irreversible photochromic compound and a compound having a condensed polycyclic aromatic structure.
主鎖または側鎖に縮合多環芳香族基を有する高分子化合
物である、請求項１記載の感放射線組成物。2. A compound having a condensed polycyclic aromatic structure,
The radiation-sensitive composition according to claim 1, which is a polymer compound having a condensed polycyclic aromatic group in a main chain or a side chain.
族基を有するビニル重合体である、請求項２記載の感放
射線組成物。3. The radiation-sensitive composition according to claim 2, wherein the polymer compound is a vinyl polymer having a condensed polycyclic aromatic group in a side chain.
繰り返し単位として有することを特徴とする、請求項３
記載の感放射線組成物。 【化１】 （上記構造中、Ｒ1 は水素原子又は炭素数１〜３のアル
キル基を表し、Ａｒは縮合多環芳香族基を表す。）4. A vinyl polymer having the following partial structure (I) as a repeating unit.
The radiation-sensitive composition as described in the above. Embedded image (In the above structure, R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Ar represents a condensed polycyclic aromatic group.)
及び（II）を繰り返し単位として有することを特徴とす
る、請求項４記載の感放射線組成物。 【化２】 （上記構造中、Ｒ1およびＲ2は各々独立に、水素原子ま
たは炭素数１〜３のアルキル基を表し、Ａｒは５員環お
よび／または６員環が２個以上縮合してなる縮合多環芳
香族基を表す。ベンゼン環ＡおよびＡｒは置換基を有し
ていてもよい。）5. A vinyl polymer having the following partial structure (I)
The radiation-sensitive composition according to claim 4, wherein the radiation-sensitive composition has (I) and (II) as repeating units. Embedded image (In the above structure, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Ar is a condensed ring formed by condensing two or more 5-membered and / or 6-membered rings. Represents a ring aromatic group. The benzene rings A and Ar may have a substituent.)
環芳香族基を有する重合体である、請求項２記載の感放
射線組成物。6. The radiation-sensitive composition according to claim 2, wherein the polymer compound is a polymer having a divalent fused polycyclic aromatic group in the main chain.
縮合多環芳香族化合物である、請求項１記載の感放射線
組成物。7. A compound having a condensed polycyclic aromatic structure,
The radiation-sensitive composition according to claim 1, which is a condensed polycyclic aromatic compound.
ていてもよいナフタレン、アントラセン、フェナンスレ
ン、フルオレン、アセナフチレン、クリセン、ピレン、
トリフェニレン、ペリレン、ベンゾフラン、ベンゾチオ
フェン、インドール、キノリン、イソキノリン、アズレ
ン、フルオレン、カルバゾール、アクチジンまたはフェ
ナントリジンであることを特徴とする、請求項７記載の
感放射線組成物。8. The condensed polycyclic aromatic compound may be a substituted naphthalene, anthracene, phenanthrene, fluorene, acenaphthylene, chrysene, pyrene,
The radiation-sensitive composition according to claim 7, wherein the radiation-sensitive composition is triphenylene, perylene, benzofuran, benzothiophene, indole, quinoline, isoquinoline, azulene, fluorene, carbazole, actidine, or phenanthridine.
ジアリールエテン系化合物である、請求項１ないし８の
いずれかに記載の感放射線組成物。9. The heat irreversible photochromic compound,
The radiation-sensitive composition according to any one of claims 1 to 8, which is a diarylethene-based compound.
感放射線組成物を用いた線量計。10. A dosimeter using the radiation-sensitive composition according to claim 1.
ック化合物と、２−ビニルナフタレン共重合体を用いた
線量計。11. A dosimeter using at least a thermo-irreversible photochromic compound and a 2-vinylnaphthalene copolymer.
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|---|---|---|---|
| JP2000178581A JP3952664B2 (en) | 2000-06-14 | 2000-06-14 | Radiation sensitive composition and dosimeter |
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|---|---|---|---|
| JP2000178581A JP3952664B2 (en) | 2000-06-14 | 2000-06-14 | Radiation sensitive composition and dosimeter |
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| JP2001354862A true JP2001354862A (en) | 2001-12-25 |
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ID=18679989
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007031649A (en) * | 2005-07-29 | 2007-02-08 | Japan Atomic Energy Agency | Resin composition comprising organic molecule reversibly colored/decolored by quantum beam irradiation and photoirradiation or heating, and nano-pattern formation method |
| CN103635858A (en) * | 2011-07-07 | 2014-03-12 | 日产化学工业株式会社 | Resist underlayer film-forming composition which contains alicyclic skeleton-containing carbazole resin |
| WO2022250087A1 (en) * | 2021-05-25 | 2022-12-01 | 国立大学法人東海国立大学機構 | Organic scintillation material |
-
2000
- 2000-06-14 JP JP2000178581A patent/JP3952664B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007031649A (en) * | 2005-07-29 | 2007-02-08 | Japan Atomic Energy Agency | Resin composition comprising organic molecule reversibly colored/decolored by quantum beam irradiation and photoirradiation or heating, and nano-pattern formation method |
| CN103635858A (en) * | 2011-07-07 | 2014-03-12 | 日产化学工业株式会社 | Resist underlayer film-forming composition which contains alicyclic skeleton-containing carbazole resin |
| KR20140051931A (en) * | 2011-07-07 | 2014-05-02 | 닛산 가가쿠 고교 가부시키 가이샤 | Resist underlayer film-forming composition which contains alicyclic skeleton-containing carbazole resin |
| US20140235060A1 (en) * | 2011-07-07 | 2014-08-21 | Nissan Chemical Industries, Ltd. | Resist underlayer film-forming composition which contains alicyclic skeleton-containing carbazole resin |
| US9343324B2 (en) * | 2011-07-07 | 2016-05-17 | Nissan Chemical Industries, Ltd. | Resist underlayer film-forming composition which contains alicyclic skeleton-containing carbazole resin |
| KR101913101B1 (en) * | 2011-07-07 | 2018-10-31 | 닛산 가가쿠 가부시키가이샤 | Resist underlayer film-forming composition which contains alicyclic skeleton-containing carbazole resin |
| WO2022250087A1 (en) * | 2021-05-25 | 2022-12-01 | 国立大学法人東海国立大学機構 | Organic scintillation material |
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| Publication number | Publication date |
|---|---|
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