JPH05271466A - Transparent radiation shielding material and preparation thereof - Google Patents
Transparent radiation shielding material and preparation thereofInfo
- Publication number
- JPH05271466A JPH05271466A JP7440892A JP7440892A JPH05271466A JP H05271466 A JPH05271466 A JP H05271466A JP 7440892 A JP7440892 A JP 7440892A JP 7440892 A JP7440892 A JP 7440892A JP H05271466 A JPH05271466 A JP H05271466A
- Authority
- JP
- Japan
- Prior art keywords
- gadolinium
- weight
- lead
- salt
- amount
- 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.)
- Granted
Links
- 230000005855 radiation Effects 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 29
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 36
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 150000000921 Gadolinium Chemical class 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 150000001408 amides Chemical class 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 7
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 5
- ZLWIERXFKXYFIT-UHFFFAOYSA-K gadolinium(3+) 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)[O-].[Gd+3].C(C(=C)C)(=O)[O-].C(C(=C)C)(=O)[O-] ZLWIERXFKXYFIT-UHFFFAOYSA-K 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- JEUDBARJOQFTCD-UHFFFAOYSA-K C(C=C)(=O)[O-].[Gd+3].C(C=C)(=O)[O-].C(C=C)(=O)[O-] Chemical compound C(C=C)(=O)[O-].[Gd+3].C(C=C)(=O)[O-].C(C=C)(=O)[O-] JEUDBARJOQFTCD-UHFFFAOYSA-K 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- BSLBENVVENBYIW-UHFFFAOYSA-L lead(2+);prop-2-enoate Chemical compound [Pb+2].[O-]C(=O)C=C.[O-]C(=O)C=C BSLBENVVENBYIW-UHFFFAOYSA-L 0.000 description 2
- 239000000113 methacrylic resin Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-M 9-cis,12-cis-Octadecadienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OYHQOLUKZRVURQ-HZJYTTRNSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OYHFUCHGJKUPMK-UHFFFAOYSA-K [Gd+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O Chemical compound [Gd+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O OYHFUCHGJKUPMK-UHFFFAOYSA-K 0.000 description 1
- OQESXYHBOJEPIJ-UHFFFAOYSA-N [Gd].[Pb] Chemical compound [Gd].[Pb] OQESXYHBOJEPIJ-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 150000002178 europium compounds Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GDHRQDYGUDOEIZ-UHFFFAOYSA-N n,n,2-trimethylpropan-1-amine Chemical compound CC(C)CN(C)C GDHRQDYGUDOEIZ-UHFFFAOYSA-N 0.000 description 1
- QYNZYUUXSVZDJO-UHFFFAOYSA-N n-propylbutan-2-amine Chemical compound CCCNC(C)CC QYNZYUUXSVZDJO-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、透明放射線遮蔽材及び
その製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent radiation shielding material and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】合成樹脂に、酸化鉛、ハロゲン化鉛、酢
酸鉛等の鉛化合物を含有せしめて、軽量で加工性、成形
性に富む放射線遮蔽材料が得られることは公知である。
しかし、透明性を有し、硬質の熱可塑性樹脂に、上述の
ような鉛化合物を含有せしめて、実質上満足な放射線遮
蔽能を有する材料は、しばしばその透明性を失い、ま
た、ブリード現象を起こしたり、脆弱になるなど実用上
種々の問題を有する。2. Description of the Related Art It is known that a radiation shielding material which is light in weight and excellent in processability and moldability can be obtained by incorporating a lead compound such as lead oxide, lead halide or lead acetate into a synthetic resin.
However, a material having a transparent and hard thermoplastic resin containing a lead compound as described above and having a substantially satisfactory radiation shielding ability often loses its transparency and causes a bleeding phenomenon. There are various problems in practical use, such as causing or becoming fragile.
【０００３】この問題を解決するために、例えば特開昭
53−9994号公報には、(Ａ)メタクリル酸メチルまたはス
チレンのうち少なくとも１種のモノマーを必須成分とし
て含み、熱変形温度６５℃以上を有し、かつ厚さ８ｍｍ
で測定した全光線透過率が７０％以上である重合体、ポ
リカーボネート、ポリ塩化ビニルよりなる群から選ばれ
た熱可塑性重合体３５〜８７重量％及び(Ｂ)一般式(Ｒ
ＣＯＯ)aＰｂ(ただしａは鉛の原子価に等しい整数、Ｒ
は炭素数５〜２０の飽和もしくは不飽和の炭化水素基を
表す)で表される有機酸鉛６５〜１３重量％からなる放
射線遮蔽用組成物が開示されている。To solve this problem, for example, Japanese Patent Laid-Open No.
JP-A-53-9994 contains (A) at least one monomer of methyl methacrylate or styrene as an essential component, has a heat distortion temperature of 65 ° C. or higher, and has a thickness of 8 mm.
35 to 87% by weight of a thermoplastic polymer selected from the group consisting of polymers having a total light transmittance of 70% or more, polycarbonates and polyvinyl chloride measured by
COO) a Pb (where a is an integer equal to the valence of lead, R
Represents a saturated or unsaturated hydrocarbon group having 5 to 20 carbon atoms) and a radiation shielding composition comprising 65 to 13 wt% of an organic acid lead.
【０００４】しかし、上述の放射線遮蔽用組成物はＸ線
やγ線のような電磁波及びα線、β線のような荷電粒子
に対しては有効な遮蔽能力を示す鉛が配合されているも
のの、熱中性子線に対しては不十分なものである。However, although the above-mentioned radiation shielding composition contains lead which exhibits an effective shielding ability against electromagnetic waves such as X-rays and γ-rays and charged particles such as α-rays and β-rays. , Is insufficient for thermal neutrons.
【０００５】一方、中性子線遮蔽の高分子材料として、
ポリエチレンまたはメタクリル樹脂に硼素化合物を添加
することも知られている。しかし、この方法も中性子線
吸収能は大きいものの、中性子吸収反応に伴い生成する
ヘリウム、リチウムは中性子吸収能がほとんどないた
め、中性子の吸収量の増加を伴わないその能力は減少し
て行く傾向をもつと共に、光学的及び機械的性質につい
て満足すべきところまで至っていない。On the other hand, as a polymer material for shielding neutron rays,
It is also known to add boron compounds to polyethylene or methacrylic resins. However, this method also has a large neutron absorption capacity, but since helium and lithium generated along with the neutron absorption reaction have almost no neutron absorption capacity, their capacity without increasing the absorption amount of neutrons tends to decrease. In addition, the optical and mechanical properties have not yet been satisfied.
【０００６】中性子線を吸収する物質として上記の硼素
化合物以外に、原子番号６２、６３及び６４の希土類元
素であるサマリウム、ユーロピウム及びガドリニウムが
熱中性子線の吸収能が硼素よりも更に大きいことが知ら
れている。このような成分が配合された組成物としては
例えば特開昭60−99150号公報に、可視領域においてメ
タクリル樹脂を除く透明な熱可塑性樹脂及び／または熱
硬化性樹脂からなる樹脂にガドリニウム、サマリウムま
たはユーロピウムの少なくとも１種からなる希土類元素
化合物を均一に分散し溶解してなる樹脂組成物が開示さ
れている。In addition to the above-mentioned boron compounds as substances that absorb neutron rays, it is known that samarium, europium and gadolinium, which are rare earth elements with atomic numbers 62, 63 and 64, have a thermal neutron ray absorption capacity higher than that of boron. Has been. As a composition containing such components, for example, in JP-A-60-99150, gadolinium, samarium or a resin made of a transparent thermoplastic resin and / or a thermosetting resin excluding methacrylic resin in the visible region is used. A resin composition in which a rare earth element compound containing at least one europium compound is uniformly dispersed and dissolved is disclosed.
【０００７】[0007]
【発明が解決しようとする課題】しかし、上記特開昭60
−99150号公報に開示された樹脂組成物には、ガドリニ
ウム等の希土類元素化合物が全樹脂分に対して希土類元
素として０.００１〜１０重量％の範囲でしか添加配合
されていない。この理由は該公報によると、配合量が１
０重量％を超えると樹脂組成物の機械的性質及び透明性
が損なわれるためとしている。しかし、上記上限量の希
土類元素を添加配合した樹脂組成物でも中性子線吸収能
は充分とは言えず、良好な性能を有する透明放射線遮蔽
材とは言えない。However, the above-mentioned Japanese Patent Laid-Open No. Sho 60 has been proposed.
The rare earth element compound such as gadolinium is added and blended to the resin composition disclosed in Japanese Patent Publication No. 99150 only as a rare earth element in the range of 0.001 to 10% by weight with respect to the total resin content. The reason for this is that according to the publication, the compounding amount is 1
If the amount exceeds 0% by weight, the mechanical properties and transparency of the resin composition will be impaired. However, it cannot be said that the resin composition containing the above-mentioned upper limit amount of the rare earth element added and blended has sufficient neutron absorption capacity, and cannot be said to be a transparent radiation shielding material having good performance.
【０００８】従って、本発明の目的は、透明性を損なう
ことなくより多量割合の希土類元素、特にガドリニウム
を添加、配合することができ、良好な放射線遮蔽性能を
有する透明放射線遮蔽材及びその製造方法を提供するこ
とにある。Therefore, an object of the present invention is to provide a transparent radiation shielding material having a good radiation shielding performance, which allows addition and blending of a large amount of rare earth elements, especially gadolinium, without impairing transparency, and a method for producing the same. To provide.
【０００９】また、本発明の他の目的は、透明性を損な
うことなくより多量割合の希土類元素、特にガドリニウ
ムを添加、配合することができ、同時に鉛をも添加、配
合することができ、良好な放射線遮蔽性能を有する透明
放射線遮蔽材及びその製造方法を提供することにある。Another object of the present invention is to add and blend a large amount of rare earth elements, especially gadolinium, without impairing transparency, and at the same time, lead can be added and blended. A transparent radiation shielding material having excellent radiation shielding performance and a method for producing the same are provided.
【００１０】[0010]
【課題を解決するための手段】本発明に係る透明放射線
遮蔽材は、ガドリニウム塩をガドリニウム換算量で１０
〜３０重量％、前記ガドリニウム塩を溶解するためのア
ミン系溶剤またはアミド系溶剤０.２〜２０重量％、樹
脂４０〜７０重量％及び反応開始剤０.０１〜１重量％
よりなることを特徴とする。A transparent radiation shielding material according to the present invention comprises a gadolinium salt in an amount of 10 gadolinium equivalent.
˜30 wt%, amine or amide solvent for dissolving the gadolinium salt 0.2 to 20 wt%, resin 40 to 70 wt% and reaction initiator 0.01 to 1 wt%.
Is characterized in that
【００１１】なお、この透明放射線遮蔽材は、ガドリニ
ウム換算量で１０〜３０重量％のガドリニウム塩を、前
記ガドリニウム塩を溶解するためのアミン系溶剤または
アミド系溶剤０.２〜２０重量％で溶解し、次に、ガド
リニウム含有溶液に樹脂４０〜７０重量％及び反応開始
剤０.０１〜１重量％を添加、混合して得た溶液を所定
の型枠にて注型することを特徴として製造することがで
きる。In this transparent radiation shielding material, 10 to 30% by weight of gadolinium equivalent of gadolinium salt is dissolved in 0.2 to 20% by weight of amine or amide solvent for dissolving the gadolinium salt. Then, 40 to 70% by weight of a resin and 0.01 to 1% by weight of a reaction initiator are added to a gadolinium-containing solution and mixed, and the resulting solution is cast in a predetermined mold. can do.
【００１２】更に、本発明に係る放射線遮蔽材は、ガド
リニウム塩をガドリニウム換算量で１０〜３０重量％、
鉛塩を鉛換算量で２０重量％以下、ガドリニウム換算量
及び鉛換算量でのガドリニウム塩と鉛塩の合計量３０重
量％以下、前記ガドリニウム塩及び鉛塩を溶解するため
のアミン系溶剤及びアミド系溶剤０.２〜２０重量％、
樹脂４０〜７０重量％及び反応開始剤０.０１〜１重量
％よりなることを特徴とする。Further, the radiation shielding material according to the present invention comprises a gadolinium salt in an amount of 10 to 30% by weight in terms of gadolinium.
20% by weight or less of lead salt in terms of lead, 30% by weight or less of gadolinium salt and lead salt in terms of gadolinium, amine solvent and amide for dissolving the gadolinium salt and lead salt System solvent 0.2 to 20% by weight,
The resin is characterized by comprising 40 to 70% by weight of a resin and 0.01 to 1% by weight of a reaction initiator.
【００１３】なお、この透明放射線遮蔽材は、ガドリニ
ウム換算量で１０〜３０重量％のガドリニウム塩及び鉛
換算量で２０重量％以下の鉛塩で、かつガドリニウム換
算量及び鉛換算量でのガドリニウム塩と鉛塩の合計量３
０重量％以下のガドリニウム塩及び鉛塩を、前記ガドリ
ニウム塩及び鉛塩を溶解するためのアミン系溶剤または
アミド系溶剤０.２〜２０重量％で溶解し、次に、ガド
リニウム及び鉛含有溶液に樹脂４０〜７０重量％及び反
応開始剤０.０１〜１重量％を添加、混合して得た溶液
を所定の型枠にて注型することを特徴として製造するこ
とができる。The transparent radiation shielding material is a gadolinium salt in an amount of 10 to 30% by weight in terms of gadolinium and a lead salt in an amount of 20% by weight or less in terms of lead, and a gadolinium salt in terms of gadolinium and lead. And total amount of lead salt 3
0% by weight or less of gadolinium salt and lead salt are dissolved in 0.2 to 20% by weight of an amine solvent or an amide solvent for dissolving the gadolinium salt and lead salt, and then dissolved in a solution containing gadolinium and lead. It can be manufactured by adding 40 to 70% by weight of a resin and 0.01 to 1% by weight of a reaction initiator, and mixing the resulting solution with a predetermined mold.
【００１４】[0014]
【作用】本発明の透明放射線遮蔽材は、中性子吸収能に
優れたガドリニウムを単独で、またはガドリニウムと鉛
を併用して配合するものであり、これらの成分をアミン
系溶剤またはアミド系溶剤に溶解した後に樹脂成分や反
応開始剤と混合することにより、これまでは透明性を損
なったり、機械的性質を損なう恐れがあるために添加、
配合することができなかった量のガドリニウムや鉛を配
合できるものである。The transparent radiation shielding material of the present invention comprises gadolinium having excellent neutron absorption ability alone or in combination with gadolinium and lead, and these components are dissolved in an amine solvent or an amide solvent. After that, by mixing with a resin component or a reaction initiator, there is a risk of impairing transparency and mechanical properties until now.
It is possible to add an amount of gadolinium or lead that could not be added.
【００１５】本発明の透明放射線遮蔽材に使用するガド
リニウム塩は後述するアミン系溶剤またはアミド系溶剤
に溶解するものであれば特に限定されるものではない
が、例えばアクリル酸ガドリニウム、アセチルアセトナ
ートガドリニウム、プロピオン酸ガドリニウムのような
有機塩を挙げることができる。ガドリニウム塩の添加、
配合量はガドリニウム換算量で１０〜３０重量％の範囲
である。The gadolinium salt used in the transparent radiation shielding material of the present invention is not particularly limited as long as it can be dissolved in an amine-based solvent or an amide-based solvent which will be described later, and examples thereof include gadolinium acrylate and acetylacetonato gadolinium. , And organic salts such as gadolinium propionate. Addition of gadolinium salt,
The compounding amount is in the range of 10 to 30% by weight in terms of gadolinium.
【００１６】次に、本発明の透明放射線遮蔽材に使用す
る鉛塩は後述するアミン系溶剤またはアミド系溶剤に溶
解するものであれば特に限定されるものではないが、例
えばアクリル酸鉛、オクチル酸鉛、リノレイン酸鉛のよ
うな有機塩を挙げることができる。鉛塩の添加、配合量
は鉛換算量で２０重量％以下である。なお、鉛塩とガド
リニウム塩を併用する場合の鉛塩とガドリニウム塩の合
計量は鉛換算量及びガドリニウム換算量で３０重量％以
下とする必要がある。これは合計量が３０重量％を超え
ると、透明放射線遮蔽材の透明性が損なわれることがあ
るためである。Next, the lead salt used in the transparent radiation shielding material of the present invention is not particularly limited as long as it can be dissolved in an amine-based solvent or an amide-based solvent which will be described later, and examples thereof include lead acrylate and octyl. Organic salts such as lead acid and lead linoleate can be mentioned. The amount of lead salt added and compounded is 20 wt% or less in terms of lead. When the lead salt and the gadolinium salt are used in combination, the total amount of the lead salt and the gadolinium salt needs to be 30% by weight or less in terms of the lead conversion amount and the gadolinium conversion amount. This is because if the total amount exceeds 30% by weight, the transparency of the transparent radiation shielding material may be impaired.
【００１７】本発明の特徴は、上記のようなガドリニウ
ム塩またはガドリニウム塩と鉛塩をアミン系溶剤または
アミド系溶剤に一旦溶解し、樹脂分及び反応開始剤と混
合するところにある。ガドリニウム塩や鉛塩をアミン系
溶剤またはアミド系溶剤に溶解してから、樹脂分及び反
応開始剤と混合することにより、得られる透明放射線遮
蔽材の透明性を損なうことなく、より多量割合のガドリ
ニウムや鉛を配合することができる。使用可能なアミン
系溶剤またはアミド系溶剤としては、Ｎ,Ｎ−ジメチル
ホルムアミド、Ｎ,Ｎ−ジメチルイソブチルアミン、Ｎ
−ｓｅｃ−ブチル−ｎ−プロピルアミン、シクロヘキシ
ルアミン、ジエチルアミン、Ｎ−エチルアミン、ヘキサ
メチル燐酸トリアミド、Ｎ−(２−ヒドロキシプロピル)
エチレンジアミン、ｎ−オクチルアミン、ｎ−ヘプチル
アミン等である。アミン系溶剤及びアミド系溶剤の添
加、配合量は全配合量に対して０.２〜２０重量％、好
ましくは５〜１０重量％の２〜２０重量％の範囲内であ
る。The feature of the present invention resides in that the above-mentioned gadolinium salt or gadolinium salt and lead salt are once dissolved in an amine solvent or an amide solvent and mixed with a resin component and a reaction initiator. By dissolving the gadolinium salt or lead salt in an amine-based solvent or an amide-based solvent and then mixing it with a resin component and a reaction initiator, a larger proportion of gadolinium is obtained without impairing the transparency of the resulting transparent radiation shielding material. Or lead can be added. Usable amine solvents or amide solvents include N, N-dimethylformamide, N, N-dimethylisobutylamine, N
-Sec-butyl-n-propylamine, cyclohexylamine, diethylamine, N-ethylamine, hexamethylphosphoric triamide, N- (2-hydroxypropyl)
Examples thereof include ethylenediamine, n-octylamine, and n-heptylamine. The addition amount of the amine solvent and the amide solvent is 0.2 to 20% by weight, preferably 5 to 10% by weight and 2 to 20% by weight, based on the total amount of the compound.
【００１８】本発明の透明放射線遮蔽材に使用する樹脂
は特に限定されるものではないが、例えばメタクリル樹
脂、スチレン樹脂、ヒドロキシ樹脂等の透明樹脂を挙げ
ることができる。樹脂の添加、配合量は４０〜７０重量
％の範囲内である。該添加、配合量が４０重量％未満で
あると、透明放射線遮蔽材の機械的強度が劣るために好
ましくない。また、７０重量％を超えると他の成分の添
加、配合量との関係で好ましくない。The resin used for the transparent radiation shielding material of the present invention is not particularly limited, but examples thereof include transparent resins such as methacrylic resin, styrene resin, and hydroxy resin. The amount of resin added and the amount added are in the range of 40 to 70% by weight. If the amount added or compounded is less than 40% by weight, the mechanical strength of the transparent radiation shielding material is poor, which is not preferable. Further, if it exceeds 70% by weight, it is not preferable in relation to the addition of other components and the blending amount.
【００１９】反応開始剤は使用する樹脂を硬化する成分
であり、使用する樹脂に応じて使用すれば良い。反応開
始剤の添加、配合量は通常樹脂に対して０.０１〜１重
量％の範囲内であり、特に０.１〜０.５重量％の範囲内
が好ましい。The reaction initiator is a component that cures the resin used, and may be used depending on the resin used. The amount of the reaction initiator to be added and compounded is usually in the range of 0.01 to 1% by weight, preferably 0.1 to 0.5% by weight, based on the resin.
【００２０】本発明の透明放射線遮蔽材は、上述のガド
リニウム塩またはガドリニウム塩と鉛塩をアミン系溶剤
またはアミド系溶剤で溶解し、次に、ガドリニウム及び
鉛含有溶液に樹脂及び反応開始剤を添加、混合して得た
溶液を所定の形状の型枠にて注型することにより製造す
ることができる。In the transparent radiation shielding material of the present invention, the above-mentioned gadolinium salt or gadolinium salt and lead salt are dissolved in an amine-based solvent or an amide-based solvent, and then a resin and a reaction initiator are added to a gadolinium- and lead-containing solution. It can be manufactured by casting a solution obtained by mixing with a mold having a predetermined shape.
【００２１】上記配合組成にアクリロニトリルを添加す
ることにより製品の靭性を上げることもできる。アクリ
ロニトリル添加量はスチレン樹脂に対して１：２〜１：
８の割合で添加してスチレン樹脂の靭性を向上し、それ
によって製品の靭性と強度が増大する。The toughness of the product can be increased by adding acrylonitrile to the above composition. The addition amount of acrylonitrile is 1: 2-1:
Add in a ratio of 8 to improve the toughness of the styrene resin, thereby increasing the toughness and strength of the product.
【００２２】[0022]
実施例１ メタクリル酸ガドリニウム ２６.８７重量％ メタクリル酸鉛 １０.４９重量％ メチルメタクリレート ２６.２９重量％ スチレン ２２.００重量％ アクリロニトリル ９.４５重量％ ヘキサメチル燐酸トリアミド ４.７２重量％ １,１−アゾビス(シクロヘキサン−１−カルボニトリル) ０.１８重量％ 上記割合でメタクリル酸ガドリニウムにヘキサメチル燐
酸トリアミドを添加した。一方、メタクリル酸鉛にメチ
ルメタクリレートを加え、加熱溶解する。両者を混合し
て９３℃で１０分間撹拌し溶解した後、更に、スチレン
を加え１００℃で５分間撹拌し透明液を得た。この液を
５０℃まで放冷した後、アクリロニトリルと１,１−ア
ゾビス(シクロヘキサン−１−カルボニトリル)を添加
し、ガラスの鋳型に流し込み６０℃で１５時間湯中固化
させ、更に、空気中１２０℃で２時間キュアーして重合
を完結させて本発明の透明放射線遮蔽材を得た。得られ
た透明放射線遮蔽材(寸法：１００×１５０×３ｍｍ)は
良好な透明性を有し、樹脂に対して１２.０６重量％の
ガドリニウム及び７.３７重量％の鉛を含有するもので
あった。Example 1 Gadolinium Methacrylate 26.87 wt% Lead Methacrylate 10.49 wt% Methyl Methacrylate 26.29 wt% Styrene 22.00 wt% Acrylonitrile 9.45 wt% Hexamethylphosphoric triamide 4.72 wt% 1,1- Azobis (cyclohexane-1-carbonitrile) 0.18% by weight Hexamethylphosphoric triamide was added to gadolinium methacrylate in the above proportion. Meanwhile, methyl methacrylate is added to lead methacrylate and heated and dissolved. After both were mixed and dissolved by stirring at 93 ° C. for 10 minutes, styrene was further added and stirred at 100 ° C. for 5 minutes to obtain a transparent liquid. After allowing this liquid to cool to 50 ° C., acrylonitrile and 1,1-azobis (cyclohexane-1-carbonitrile) were added, poured into a glass mold and solidified in hot water at 60 ° C. for 15 hours, and further in air 120 The transparent radiation-shielding material of the present invention was obtained by curing the composition at 2 ° C for 2 hours to complete the polymerization. The obtained transparent radiation shielding material (dimensions: 100 × 150 × 3 mm) had good transparency and contained 12.06% by weight of gadolinium and 7.37% by weight of lead with respect to the resin. It was
【００２３】実施例２ メタクリル酸ガドリニウム ２６.８９重量％ メチルメタクリレート ３１.１０重量％ スチレン ３７.１９重量％ ヘキサメチル燐酸トリアミド ４.７２重量％ １,１−アゾビス(シクロヘキサン−１−カルボニトリル) ０.１０重量％ 上記割合にて実施例１と同じ条件で鋳込み重合を行っ
た。その結果、透明性の良好な樹脂板が得られた。この
樹脂板は樹脂に対して１０.７３重量％のガドリニウム
含有量をもつものであった。Example 2 Gadolinium Methacrylate 26.89 wt% Methyl Methacrylate 31.10 wt% Styrene 37.19 wt% Hexamethylphosphoric Triamide 4.72 wt% 1,1-Azobis (cyclohexane-1-carbonitrile) 10 wt% Casting polymerization was carried out at the above ratio under the same conditions as in Example 1. As a result, a resin plate having good transparency was obtained. This resin plate had a gadolinium content of 10.73% by weight based on the resin.
【００２４】実施例３ アクリル酸ガドリニウム ２６.８７重量％ アクリル酸鉛 １０.４９重量％ メチルメタクリレート ２６.２９重量％ スチレン ３１.４５重量％ ヘキサメチル燐酸トリアミド ４.７２重量％ １,１−アゾビス(シクロヘキサン−１−カルボニトリル) ０.１８重量％ 上記割合にて実施例１と同じ条件で鋳込み重合を行っ
た。その結果、透明性が良好な樹脂板を得た。この透明
板は樹脂に対して１２.０１重量％のガドリニウム及び
７.３８重量％の鉛含有量をもつものであった。Example 3 Gadolinium acrylate 26.87% by weight Lead acrylate 10.49% by weight Methyl methacrylate 26.29% by weight Styrene 31.45% by weight Hexamethylphosphoric triamide 4.72% by weight 1,1-azobis (cyclohexane) -1-Carbonitrile) 0.18% by weight Casting polymerization was carried out at the above ratio under the same conditions as in Example 1. As a result, a resin plate having good transparency was obtained. The transparent plate had a gadolinium content of 12.01% by weight and a lead content of 7.38% by weight, based on the resin.
【００２５】実施例４ メタクリル酸ガドリニウム ２６.８８重量％ メタクリル酸鉛 １０.５０重量％ メチルメタクリレート １２.２６重量％ ヒドロキシエチルメタクリレート １４.０４重量％ ヘキサメチル燐酸トリアミド ４.５６重量％ １,１−アゾビス(シクロヘキサン−１−カルボニトリル) ０.１８重量％ スチレン ２２.０２重量％ アクリロニトリル ９.４４重量％ 離型剤 ０.１２重量％ 上記割合でメタクリル酸ガドリニウムにヘキサメチル燐
酸トリアミドを混合し、一方、メチルメタクリレートと
ヒドロキシエチルメタクリレートの混合液にメタクリル
酸鉛を加え加熱溶解した。この両者を混合して１００℃
で１０分間撹拌し透明液とした。この液を５０℃まで放
冷した後、アクリロニトリルと１,１−アゾビス(シクロ
ヘキサン−１−カルボニトリル)を添加し、ガラスの鋳
型に流し込み６０℃で１５時間湯中固化させ、更に、空
気中１２０℃で２時間キュアーして重合を完結させ透明
板を得た。この透明板は良好な透明性を有し、樹脂に対
して１２.０７重量％のガドリニウム及び７.３８重量％
の鉛含有量をもつものであった。Example 4 Gadolinium Methacrylate 26.88 wt% Lead Methacrylate 10.50 wt% Methyl Methacrylate 12.26 wt% Hydroxyethyl Methacrylate 14.04 wt% Hexamethylphosphoric Triamide 4.56 wt% 1,1-Azobis (Cyclohexane-1-carbonitrile) 0.18% by weight Styrene 22.02% by weight Acrylonitrile 9.44% by weight Release agent 0.12% by weight Hexamethylphosphoric triamide is mixed with gadolinium methacrylate in the above proportion, while methyl is added. Lead methacrylate was added to a mixed solution of methacrylate and hydroxyethyl methacrylate and dissolved by heating. Both are mixed at 100 ℃
And stirred for 10 minutes to obtain a transparent liquid. After allowing this liquid to cool to 50 ° C., acrylonitrile and 1,1-azobis (cyclohexane-1-carbonitrile) were added, poured into a glass mold and solidified in hot water at 60 ° C. for 15 hours, and further in air 120 It was cured at ℃ for 2 hours to complete the polymerization to obtain a transparent plate. This transparent plate has good transparency, 12.07% by weight of gadolinium and 7.38% by weight of resin.
It had a lead content of.
【００２６】[0026]
【表１】 密度(g/cm2) 透明性 全光線透過率(％) 曲げ強さ(kg/cm2) 実施例１ 1.21 良好 92 750 実施例２ 1.20 良好 91 720 実施例３ 1.21 良好 91 700 実施例４ 1.21 良好 90 750[Table 1] Density (g / cm 2 ) Transparency Total light transmittance (%) Bending strength (kg / cm 2 ) Example 1 1.21 Good 92 750 Example 2 1.20 Good 91 720 Example 3 1.21 Good 91 700 Example 4 1.21 Good 90 750
【００２７】[0027]
【発明の効果】本発明の透明放射線遮蔽材は、透明性を
損なうことなく、従来は添加、配合できないとされてい
たような多量割合のガドリニウムや鉛を含有するもので
あり、良好な放射線遮蔽能を有するものである。The transparent radiation shielding material of the present invention contains a large proportion of gadolinium or lead which could not be added or blended in the prior art without impairing the transparency, and thus has a good radiation shielding property. It has the ability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 33/04 ＬＨＺ 7921−4Ｊ 101/00 Ｇ０２Ｂ 1/04 7132−2Ｋ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C08L 33/04 LHZ 7921-4J 101/00 G02B 1/04 7132-2K
Claims (4)
１０〜３０重量％、前記ガドリニウム塩を溶解するため
のアミン系溶剤またはアミド系溶剤０.２〜２０重量
％、樹脂４０〜７０重量％及び反応開始剤０.０１〜１
重量％よりなることを特徴とする透明放射線遮蔽材。1. A gadolinium salt in an amount of 10 to 30% by weight in terms of gadolinium, an amine solvent or an amide solvent for dissolving the gadolinium salt in an amount of 0.2 to 20% by weight, a resin in an amount of 40 to 70% by weight, and a reaction start. Agent 0.01-1
A transparent radiation shielding material, characterized in that it is made up by weight%.
のガドリニウム塩を、前記ガドリニウム塩を溶解するた
めのアミン系溶剤またはアミド系溶剤０.２〜２０重量
％で溶解し、次に、ガドリニウム含有溶液に樹脂４０〜
７０重量％及び反応開始剤０.０１〜１重量％を添加、
混合して得た溶液を所定形状の型枠にて注型することを
特徴とする請求項１記載の透明放射線遮蔽材の製造方
法。2. A gadolinium equivalent amount of 10 to 30% by weight.
Gadolinium salt is dissolved in an amine-based solvent or an amide-based solvent for dissolving the gadolinium salt in an amount of 0.2 to 20% by weight, and then a resin containing 40 to 40 g of a gadolinium-containing solution is dissolved.
70% by weight and 0.01 to 1% by weight of a reaction initiator are added,
The method for producing a transparent radiation shielding material according to claim 1, wherein the solution obtained by mixing is cast with a mold having a predetermined shape.
１０〜３０重量％、鉛塩を鉛換算量で２０重量％以下、
ガドリニウム換算量及び鉛換算量でのガドリニウム塩と
鉛塩の合計量３０重量％以下、前記ガドリニウム塩及び
鉛塩を溶解するためのアミン系溶剤またはアミド系溶剤
０.２〜２０重量％、樹脂４０〜７０重量％及び反応開
始剤０.０１〜１重量％よりなることを特徴とする透明
放射線遮蔽材。3. A gadolinium salt in an amount of 10 to 30% by weight in terms of gadolinium, and a lead salt in an amount of 20% by weight or less in terms of lead,
The total amount of gadolinium salt and lead salt in terms of gadolinium equivalent and lead equivalent 30% by weight or less, 0.2-20% by weight of amine or amide solvent for dissolving the gadolinium salt and lead salt, resin 40 ˜70% by weight and 0.01 to 1% by weight of a reaction initiator, a transparent radiation shielding material.
のガドリニウム塩及び鉛換算量で２０重量％以下の鉛塩
で、かつガドリニウム換算量及び鉛換算量でのガドリニ
ウム塩と鉛塩の合計量３０重量％以下のガドリニウム塩
及び鉛塩を、前記ガドリニウム塩及び鉛塩を溶解するた
めのアミン系溶剤またはアミド系溶剤０.２〜２０重量
％で溶解し、次に、ガドリニウム及び鉛含有溶液に樹脂
４０〜７０重量％及び反応開始剤０.０１〜１重量％を
添加、混合して得た溶液を所定の形状の型枠にて注型す
ることを特徴とする請求項３記載の透明放射線遮蔽材の
製造方法。4. A gadolinium equivalent amount of 10 to 30% by weight.
Gadolinium salt and lead salt in an amount of 20% by weight or less in terms of lead, and a total amount of gadolinium salt and lead salt in an amount of gadolinium and in terms of lead of 30% by weight or less, the gadolinium salt And an amine-based or amide-based solvent for dissolving lead salts in an amount of 0.2 to 20% by weight, and then 40 to 70% by weight of a resin and 0.01 to 1 of a reaction initiator in a gadolinium and lead-containing solution. The method for producing a transparent radiation shielding material according to claim 3, wherein the solution obtained by adding and mixing the weight% is cast in a mold having a predetermined shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04074408A JP3105337B2 (en) | 1992-03-30 | 1992-03-30 | Transparent radiation shielding material and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04074408A JP3105337B2 (en) | 1992-03-30 | 1992-03-30 | Transparent radiation shielding material and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05271466A true JPH05271466A (en) | 1993-10-19 |
| JP3105337B2 JP3105337B2 (en) | 2000-10-30 |
Family
ID=13546336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04074408A Expired - Fee Related JP3105337B2 (en) | 1992-03-30 | 1992-03-30 | Transparent radiation shielding material and method of manufacturing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3105337B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016029154A (en) * | 2014-07-18 | 2016-03-03 | 三洋化成工業株式会社 | Polyurethane resin-formable composition for radiation shielding material |
-
1992
- 1992-03-30 JP JP04074408A patent/JP3105337B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016029154A (en) * | 2014-07-18 | 2016-03-03 | 三洋化成工業株式会社 | Polyurethane resin-formable composition for radiation shielding material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3105337B2 (en) | 2000-10-30 |
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