JP2012140262A - Cobalt-containing glass, blue filter, and radiation image reading apparatus - Google Patents
Cobalt-containing glass, blue filter, and radiation image reading apparatus Download PDFInfo
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- JP2012140262A JP2012140262A JP2010292668A JP2010292668A JP2012140262A JP 2012140262 A JP2012140262 A JP 2012140262A JP 2010292668 A JP2010292668 A JP 2010292668A JP 2010292668 A JP2010292668 A JP 2010292668A JP 2012140262 A JP2012140262 A JP 2012140262A
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- 239000011521 glass Substances 0.000 title claims abstract description 195
- 239000010941 cobalt Substances 0.000 title claims abstract description 94
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 94
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 93
- 230000005855 radiation Effects 0.000 title claims description 20
- 230000005284 excitation Effects 0.000 claims abstract description 53
- 150000001768 cations Chemical class 0.000 claims abstract description 45
- 150000001450 anions Chemical class 0.000 claims abstract description 23
- 238000002834 transmittance Methods 0.000 claims description 76
- 239000002994 raw material Substances 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 30
- 238000010521 absorption reaction Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 238000005191 phase separation Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- -1 chlorine ions Chemical class 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 3
- 230000002238 attenuated effect Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000004936 stimulating effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Glass Compositions (AREA)
- Conversion Of X-Rays Into Visible Images (AREA)
- Radiography Using Non-Light Waves (AREA)
- Optical Filters (AREA)
- Apparatus For Radiation Diagnosis (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
Description
本発明は、コバルト含有ガラス、青色フィルタおよび放射線画像読取装置に関するものである。 The present invention relates to a cobalt-containing glass, a blue filter, and a radiation image reading apparatus.
病気の診断等に広く用いられている放射線画像読取装置は、放射線画像が記録された輝尽性蛍光体プレートに励起光を照射する走査光学系と、励起光により発生する輝尽性蛍光体プレートからの輝尽光を光電変換素子に導く集光光学系とを備ており、放射線画像が記録された輝尽性蛍光体プレートに励起光を照射することにより生じた輝尽光を光電変換素子で電気信号に変換し、変換された電気信号を写真フィルムやディスプレイ上に放射線画像として再生するものである（特許文献１および２参照）。 A radiation image reading apparatus widely used for diagnosing diseases includes a scanning optical system that irradiates a stimulable phosphor plate on which a radiation image is recorded with excitation light, and a stimulable phosphor plate generated by the excitation light. And a condensing optical system that guides the photostimulated light from the photostimulable phosphor plate on which the radiation image is recorded to the photoelectric conversion device. Is converted into an electrical signal, and the converted electrical signal is reproduced as a radiation image on a photographic film or display (see Patent Documents 1 and 2).
励起光は輝尽光を生じさせないために必要であるが、輝尽性蛍光体プレート面で拡散された励起光が光電変換素子まで到達すると、ノイズとなって画像を劣化させるため、輝尽光を採取する導光板と光電変換素子との間に、励起光を吸収するための励起光カットフィルタが設けられており、励起光カットフィルタとして色ガラス材が用いられている。 Excitation light is necessary to prevent the generation of stimulating light, but when the excitation light diffused on the surface of the stimulable phosphor plate reaches the photoelectric conversion element, it becomes noise and degrades the image. An excitation light cut filter for absorbing excitation light is provided between the light guide plate that collects the light and the photoelectric conversion element, and a colored glass material is used as the excitation light cut filter.
ところで、放射線画像読取装置のサイズの小型化のためには放射線画像変換パネルと輝尽光検出手段との間の間隔をできるだけ短くしたいという要請があった。特に結像光学系を通して輝尽発光光を検出する手段を備えた装置の場合には、輝尽光検出手段を放射線画像変換パネルに接近させて結像光学系の開口数（NA）を大きくすることが、より解像力を高めることになる。そのようにするための方策のひとつとして、放射線画像変換パネルと輝尽光検出手段との間に配置された励起光カットフィルタの厚みを薄くすることが挙げられる。
しかしながら、励起光カットフィルタを構成している色ガラス材の材質を改良して、色ガラス材の励起光を遮断する特性を高めることにより、励起光カットフィルタの厚さを薄くすることは難しいとされてきた。
By the way, in order to reduce the size of the radiographic image reading apparatus, there has been a demand for minimizing the interval between the radiographic image conversion panel and the stimulating light detection means. In particular, in the case of an apparatus equipped with means for detecting stimulated emission light through an imaging optical system, the numerical aperture (NA) of the imaging optical system is increased by bringing the stimulated light detection means closer to the radiation image conversion panel. This will increase the resolution. One measure for doing so is to reduce the thickness of the excitation light cut filter disposed between the radiation image conversion panel and the stimulating light detection means.
However, it is difficult to reduce the thickness of the excitation light cut filter by improving the material of the color glass material constituting the excitation light cut filter and enhancing the characteristic of blocking the excitation light of the color glass material. It has been.
本発明は、励起光遮断特性を高めることにより、励起光カットフィルタの厚みを従来の色ガラス材よりも薄くできる色ガラス材を提供することを第１の目的とするものである。
また本発明は、上記色ガラス材からなるフィルタおよび該フィルタを用いた放射線画像読取装置を提供することを第２および第３の目的とするものである。
The first object of the present invention is to provide a colored glass material that can make the thickness of the excitation light cut filter thinner than a conventional colored glass material by enhancing the excitation light blocking characteristic.
It is a second and third object of the present invention to provide a filter made of the above colored glass material and a radiation image reading apparatus using the filter.
上記の第１、第２および第３の目的を達成する本発明は、下記の（１）〜（７）からなるものである。
（１）陽イオンとして、陽イオン％表示で、
Ｓｉ４＋ ２５〜６０％
Ａｌ３＋ ３〜１９％
Ｂ３＋ １８〜３８％
Ｋ＋ ９〜３１％
Ｃｏ２＋ ０．１〜１．５％
を含み、陰イオンとして、Ｏ２−を主成分として含み、さらに陰イオン％表示で、
Ｆ− １〜１２％
Ｃｌ− ０．０１〜２％
を含むことを特徴とするコバルト含有ガラス（以下、「コバルト含有ガラスＩ」という）、
（２）重量％表示で、
ＳｉＯ２ ２５〜６５％
Ａｌ２Ｏ３ ３〜１８％
Ｂ２Ｏ３ １０〜２７％
Ｋ２Ｏ ９〜２３％
ＣｏＯ ０．１〜１．５％
Ｆ２ １〜１３％
Ｃｌ２ ０．１〜５．５％
を含むガラス原料を熔解してなることを特徴とするコバルト含有ガラス（以下、「コバルト含有ガラスＩＩ」という）、
（３）上記（１）または（２）項に記載のコバルト含有ガラスからなることを特徴とする青色フィルタ、
（４）ガラスの厚みが５ｍｍの場合の波長６６０ｎｍの内部透過率が１×１０−１０以下であることを特徴とする上記（３）項に記載の青色フィルタ、
（５）励起光カット用であることを特徴とする上記（３）または（４）項に記載の青色フィルタ、
（６）放射線画像読取装置に用いられることを特徴とする上記（３）〜（５）項のいずれかに記載の青色フィルタ、および
（７）上記（３）〜（６）項のいずれかに記載の青色フィルタからなる励起光カットフィルタを含むことを特徴とする放射線画像読取装置、
を提供するものである。
The present invention for achieving the first, second and third objects comprises the following (1) to (7).
(1) As a cation, in cation% display,
Si 4+ 25-60%
Al 3+ 3-19%
B 3+ 18-38%
K + 9-31%
Co 2+ 0.1-1.5%
, As an anion, O 2− as a main component, and an anion% display,
F - 1-12%
Cl - 0.01-2%
A cobalt-containing glass (hereinafter referred to as “cobalt-containing glass I”),
(2) By weight% display
SiO 2 25~65%
Al 2 O 3 3-18%
B 2 O 3 10~27%
K 2 O 9~23%
CoO 0.1-1.5%
F 2 1~13%
Cl 2 0.1~5.5%
A cobalt-containing glass (hereinafter referred to as “cobalt-containing glass II”), characterized by melting a glass raw material containing
(3) A blue filter comprising the cobalt-containing glass according to (1) or (2) above,
(4) The blue filter as described in (3) above, wherein the internal transmittance at a wavelength of 660 nm when the thickness of the glass is 5 mm is 1 × 10 −10 or less,
(5) The blue filter as described in (3) or (4) above, which is used for cutting excitation light,
(6) The blue filter according to any one of (3) to (5) above, and (7) any one of (3) to (6) above, wherein the blue filter is used in a radiation image reading apparatus. A radiation image reading device comprising an excitation light cut filter comprising the blue filter described above,
Is to provide.
本発明によれば、励起光遮断特性が高められ、励起光カットフィルタの厚みを従来の色ガラスよりも薄くすることができるコバルト含有ガラスを提供することができた。
また本発明によれば、上記コバルト含有ガラスからなる青色フィルタおよび該青色フィルタを用いた放射線画像読取装置を提供することができた。
ADVANTAGE OF THE INVENTION According to this invention, the excitation light interruption characteristic was improved and the cobalt containing glass which can make thickness of an excitation light cut filter thinner than the conventional colored glass was able to be provided.
Moreover, according to this invention, the radiographic image reading apparatus using the blue filter consisting of the said cobalt containing glass and this blue filter was able to be provided.
［コバルト含有ガラスＩ］
本発明のコバルト含有ガラスＩは、
陽イオンとして、陽イオン％表示で、
Ｓｉ４＋ ２５〜６０％
Ａｌ３＋ ３〜１９％
Ｂ３＋ １８〜３８％
Ｋ＋ ９〜３１％
Ｃｏ２＋ ０．１〜１．５％
を含み、陰イオンとして、Ｏ２−を主成分として含み、さらに陰イオン％表示で、
Ｆ− １〜１２％
Ｃｌ− ０．０１〜２％
を含むことを特徴とするものである。
[Cobalt-containing glass I]
The cobalt-containing glass I of the present invention is
As a cation, in cation% display,
Si 4+ 25-60%
Al 3+ 3-19%
B 3+ 18-38%
K + 9-31%
Co 2+ 0.1-1.5%
, As an anion, O 2− as a main component, and an anion% display,
F - 1-12%
Cl - 0.01-2%
It is characterized by including.
（ガラスの組成）
先ず、本発明のコバルト含有ガラスＩの組成限定理由について説明する。
ＳｉＯ２はガラス内で、ガラス形成酸化物として働く。一般的に、ＳｉＯ２量が多くなるに従って、ガラスとしてより安定していくが、粘性は極端に増加していく。Ｓｉ４＋が６０陽イオン％より多くなると、６６０ｎｍの吸収が減少し、励起光遮断特性を高めることが困難になる。また、粘性が大きく増加するので、ガラス熔解性が極端に悪化する。一方、Ｓｉ４＋が２５陽イオン％より少なくなると、低粘性化しガラス熔解性は良化するが、化学的耐久性が悪化する。従って、本発明のコバルト含有ガラスＩにおいて、Ｓｉ４＋量は２５〜６０陽イオン％に限定される。
Ｓｉ４＋量は、３０〜５１陽イオン％が好ましく、３４〜４０陽イオン％がより好ましい。
(Glass composition)
First, the reasons for limiting the composition of the cobalt-containing glass I of the present invention will be described.
SiO 2 acts as a glass-forming oxide in the glass. Generally, as the amount of SiO 2 increases, the glass becomes more stable, but the viscosity increases extremely. If Si 4+ exceeds 60 cation%, the absorption at 660 nm decreases, and it becomes difficult to improve the excitation light blocking characteristic. Further, since the viscosity is greatly increased, the glass meltability is extremely deteriorated. On the other hand, when Si 4+ is less than 25 cation%, the viscosity is lowered and the glass melting property is improved, but the chemical durability is deteriorated. Accordingly, in the cobalt-containing glass I of the present invention, the amount of Si 4+ is limited to 25-60 cation%.
The amount of Si 4+ is preferably 30 to 51 cation%, and more preferably 34 to 40 cation%.
Ａｌ２Ｏ３はガラス内で、ガラス中間酸化物として働く。一般的に、多成分系ガラスにおいて、化学的耐久性を上げる役目をＡｌ２Ｏ３が担う。Ａｌ３＋が１９陽イオン％より多いときには、分相傾向を増す。一方、Ａｌ３＋が３陽イオン％より少ないときにも、分相傾向が増し、化学的耐久性が減少し、６６０ｎｍの吸収が減少する。従って、本発明のコバルト含有ガラスＩにおいて、Ａｌ３＋量は、３〜１９陽イオン％に限定される。
Ａｌ３＋量は、５〜１７陽イオン％が好ましく、７〜１３陽イオン％がより好ましい。
Al 2 O 3 acts as a glass intermediate oxide in the glass. Generally, in a multicomponent glass, Al 2 O 3 plays a role of increasing chemical durability. When Al 3+ is more than 19 cation%, the phase separation tendency increases. On the other hand, even when Al 3+ is less than 3 cation%, the phase separation tendency increases, the chemical durability decreases, and the absorption at 660 nm decreases. Therefore, in the cobalt-containing glass I of the present invention, the amount of Al 3+ is limited to 3-19 cation%.
The amount of Al 3+ is preferably 5 to 17 cation%, and more preferably 7 to 13 cation%.
Ｂ２Ｏ３はガラス内で、ガラス形成酸化物として働く。一般的に、Ｂ２Ｏ３はガラス熔解性を向上させる役目を担う。Ｂ３＋が３８陽イオン％より多いときには、透過率において、６６０ｎｍの吸収が増加するが、化学的耐久性が大きく減少する。一方、Ｂ３＋が１８陽イオン％より少ないときには、６６０ｎｍの吸収が減少する。従って、本発明のコバルト含有ガラスＩにおいて、Ｂ３＋量は１８〜３８陽イオン％に限定される。
Ｂ３＋量は、２１〜３５陽イオン％が好ましく、２４〜３５陽イオン％がより好ましい。
B 2 O 3 acts as a glass forming oxide in the glass. In general, B 2 O 3 plays a role of improving glass meltability. When B 3+ is greater than 38 cation%, the absorption at 660 nm increases in transmittance, but the chemical durability is greatly reduced. On the other hand, when B 3+ is less than 18 cation%, the absorption at 660 nm decreases. Therefore, in the cobalt-containing glass I of the present invention, the amount of B 3+ is limited to 18 to 38 cation%.
The amount of B 3+ is preferably 21 to 35 cation%, more preferably 24 to 35 cation%.
Ｋ２Ｏはガラス内で、ガラス修飾酸化物として働く。一般的に、Ｋ２Ｏはガラス粘性を下げてガラスを安定化させる役目を担う。Ｋ＋が３１陽イオン％より多いときには、分相傾向が増し、化学的耐久性を減少させる。一方、Ｋ＋が９陽イオン％より少ないときには、粘性が高くなり熔解性を減少させる。従って、本発明のコバルト含有ガラスＩにおいて、Ｋ＋量は９〜３１陽イオン％に限定される。
Ｋ＋量は、１１〜２８陽イオン％が好ましく、１３〜２６陽イオン％がより好ましい。
K 2 O acts as a glass modifying oxide in the glass. In general, K 2 O plays a role of lowering the glass viscosity and stabilizing the glass. When K + is greater than 31 cation%, the phase separation tendency increases and the chemical durability decreases. On the other hand, when K + is less than 9 cation%, the viscosity increases and the meltability decreases. Accordingly, in the cobalt-containing glass I of the present invention, the amount of K + is limited to 9 to 31 cation%.
The K + amount is preferably 11 to 28 cation%, and more preferably 13 to 26 cation%.
ＣｏＯは本ガラスでは塩素イオンと一緒になって、着色を担う。コバルト含有ガラスにおいて、コバルトイオン（Ｃｏ２＋）に塩素イオン（Ｃｌ−）が４個配位した錯イオンがあたかも形成されたかのような着色部分と、ＣｏＯが単独で発色した着色部分とが共存して５００−７５０ｎｍの吸収帯を形成する。Ｃｏ２＋が１．５陽イオン％より多いときには、５００−６００ｎｍの吸収が増加し、励起光カットフィルタに必要な厚みのガラスにしたとき、４００ｎｍ付近までその吸収が裾を引き、４００ｎｍ付近の透過率を悪化させる。一方、Ｃｏ２＋が０．１陽イオン％より少ないときには、 ６６０ｎｍの吸収を減少させる。従って、本発明のコバルト含有ガラスＩにおいて、Ｃｏ２＋量は０．１〜１．５陽イオン％に限定される。
Ｃｏ２＋量は、０．１〜１．２陽イオン％が好ましく、０．１〜０．７陽イオン％がより好ましい。
In this glass, CoO is colored together with chloride ions. In a cobalt-containing glass, a colored portion as if a complex ion in which four chlorine ions (Cl − ) are coordinated to cobalt ions (Co 2+ ) and a colored portion in which CoO is colored alone coexist. An absorption band of 500-750 nm is formed. When Co 2+ is more than 1.5 cation%, the absorption at 500-600 nm increases, and when the glass has a thickness necessary for the excitation light cut filter, the absorption extends to the vicinity of 400 nm, and the transmission near 400 nm. Worsen the rate. On the other hand, when Co 2+ is less than 0.1 cation%, the absorption at 660 nm is decreased. Therefore, in the cobalt-containing glass I of the present invention, the amount of Co 2+ is limited to 0.1 to 1.5 cation%.
The amount of Co 2+ is preferably 0.1 to 1.2 cation%, and more preferably 0.1 to 0.7 cation%.
上述したように、コバルト含有ガラスにおいては、コバルトイオン（Ｃｏ２＋）に塩素イオン（Ｃｌ−）が４個配位した錯イオンがあたかも形成されたかのような着色部分が形成されるが、Ｆ２は、この着色部分の発色性を補助する役目がある。Ｆ２が少ないと十分な吸収の大きさやピーク値が得られない。また、Ｆ２は粘性を下げる効果があり、粘性を上げるＣｌ２と共存させることにより、熔解に適した粘性を生み出すことができる。Ｆ−が１２陰イオン％より多いときには、６５０〜７００ｎｍの吸収帯はより急峻な透過率カーブを示し、透過率特性は良化するが、化学的耐久性が減少し、極薄い分相を示すようにもなる。一方、Ｆ−が1陰イオン%より少ないときには、粘性が高くなり熔解性が落ち、６６０ｎｍの吸収も減少して、５００−６００ｎｍの吸収が増加し、励起光カットに必要な厚みのガラスにしたとき、４００ｎｍ付近までその吸収が裾を引き、400nm付近の透過率を悪化させたる。従って本発明のコバルト含有ガラスＩにおいて、Ｆ−量は１〜１２陰イオン％に限定される。
Ｆ−量は、２〜１１陰イオン％が好ましく、３〜９陰イオン％がよりに好ましい。
As described above, in the cobalt-containing glass, cobalt ions (Co 2+) chlorine ions (Cl -) is four coordinated colored portions, such as if the complex ions are though formed is formed, F 2 is , Has the role of assisting the coloring of the colored portion. When the amount of F 2 is small, sufficient absorption magnitude and peak value cannot be obtained. Further, F 2 has an effect of reducing the viscosity, and by coexisting with Cl 2 that increases the viscosity, a viscosity suitable for melting can be generated. When F − is more than 12 anion%, the absorption band of 650 to 700 nm shows a steeper transmittance curve, and the transmittance characteristic is improved, but the chemical durability is reduced and an extremely thin phase separation is exhibited. It becomes like. On the other hand, when F − is less than 1 anion%, the viscosity becomes higher and the meltability is lowered, the absorption at 660 nm is decreased, the absorption at 500 to 600 nm is increased, and the glass has a thickness necessary for the excitation light cut. At that time, the absorption is extended to around 400 nm, and the transmittance around 400 nm is deteriorated. Therefore, in the cobalt-containing glass I of the present invention, the amount of F − is limited to 1 to 12 anion%.
The amount of F − is preferably 2 to 11 anion%, more preferably 3 to 9 anion%.
Ｃｌ２は、コバルトイオンと一緒になって着色を担い、コバルトイオンにＣｌ−が４個配位した錯イオンがあたかも形成されたかのような着色部分を作り出す。Ｃｌ−が２．０陰イオン％より多いときには、６５０〜７００ｎｍの吸収帯はより急峻な透過率カーブを示し、透過率特性は良化するが、粘性が高くなり熔解性が減少し、化学的耐久性も減少する。一方、Ｃｌ−が０．０１陰イオン％より少ないときには、６６０ｎｍの吸収が減少し、５００−６００ｎｍ領域では吸収が増加し、励起光カットに必要な厚みのガラスにしたとき、４００ｎｍ付近までその吸収が裾を引き、４００ｎｍ付近の透過率を悪化させる。従って本発明のコバルト含有ガラスＩにおいて、Ｃｌ−量は０．０１〜２．０陰イオン％に限定される。
Ｃｌ−量は、０．０５〜１．３陰イオン％が好ましく、０．１〜０．８陰イオン％がよりに好ましい。
Cl 2 is colored together with cobalt ions to create a colored portion as if a complex ion in which four Cl − are coordinated to cobalt ions is formed. When Cl − is more than 2.0 anion%, the absorption band of 650 to 700 nm shows a steeper transmittance curve, and the transmittance characteristics are improved, but the viscosity becomes higher and the meltability is decreased. Durability is also reduced. On the other hand, when Cl − is less than 0.01 anion%, the absorption at 660 nm decreases, the absorption increases at the 500-600 nm region, and when the glass has a thickness necessary for excitation light cut, the absorption is up to around 400 nm. Pulls the bottom and deteriorates the transmittance around 400 nm. Therefore, in the cobalt-containing glass I of the present invention, the amount of Cl − is limited to 0.01 to 2.0 anion%.
The amount of Cl − is preferably 0.05 to 1.3 anion%, more preferably 0.1 to 0.8 anion%.
本発明のコバルト含有ガラスＩは、他の陽イオンとして、Ｐ５＋、Ｎａ＋、Ｃｓ＋、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｂａ２＋、Ｚｎ２＋、Ｌａ３＋、Ｔｉ４＋、Ｙ３＋、Ｚｒ４＋、Ｎｂ５＋、Ｔａ５＋、Ｗ６＋、Ｂｉ３＋、Ｆｅ３＋、Ｓｂ３＋、Ａｓ３＋を、他の陰イオンとしてＢｒ−、Ｉ−を本発明の目的を損わない範囲で含むことができる。 The cobalt-containing glass I of the present invention includes, as other cations, P 5+ , Na + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , La 3+ , Ti 4+ , Y 3+ , Zr 4+. , Nb 5+ , Ta 5+ , W 6+ , Bi 3+ , Fe 3+ , Sb 3+ , As 3+ and Br − and I − as other anions can be included within a range that does not impair the object of the present invention.
特に、Ｐ５＋、Ｎａ＋、Ｃｓ＋、Ｂａ２＋、Ｚｒ４＋の好ましい含有量は下記のとおりである。
Ｐ５＋としては、０〜８陽イオン％
Ｎａ＋として、０〜６陽イオン％
Ｃｓ＋として、０〜１陽イオン%
Ｂａ２＋として、０〜１陽イオン%
Ｚｒ４＋として、０〜２陽イオン%
In particular, preferable contents of P 5+ , Na + , Cs + , Ba 2+ , and Zr 4+ are as follows.
As P 5+ , 0 to 8 cations%
Na + as 0-6 cations%
Cs + as 0 to 1 cation%
Ba 2+ , 0 to 1 cation%
0 to 2 cations% as Zr 4+
本発明のコバルト含有ガラスＩは、Ｐ５＋、Ｎａ＋、Ｃｓ＋、Ｂａ２＋、Ｚｒ４＋などを含有しても、３００〜５００ｎｍの透過範囲および６００〜７００ｎｍの吸収範囲における透過率をほとんど悪化させることがない。 Even if the cobalt-containing glass I of the present invention contains P 5+ , Na + , Cs + , Ba 2+ , Zr 4+ and the like, the transmittance in the transmission range of 300 to 500 nm and the absorption range of 600 to 700 nm is almost deteriorated. There is nothing.
（ガラスの特性）
次に本発明のコバルト含有ガラスＩの特性について説明する。
１．励起光遮断特性
本発明のコバルト含有ガラスＩは、これに限定されるものではないが、励起光カットフィルタ、特に放射線画像読取装置に設けられる励起光カットフィルタに用いられるものであるため、必須の特性として励起光遮断特性を有する。
(Characteristics of glass)
Next, the characteristics of the cobalt-containing glass I of the present invention will be described.
1. Excitation light blocking characteristics The cobalt-containing glass I of the present invention is not limited to this, but is used for an excitation light cut filter, particularly an excitation light cut filter provided in a radiation image reading apparatus. It has an excitation light blocking characteristic as a characteristic.
本発明のコバルト含有ガラスＩは励起光遮断特性に優れており、これを励起光カットフィルタに用いたときに厚みを従来より励起光カットフィルタとして用いられている市販フッ素、塩素含有ホウケイ酸系色ガラス材に比べて薄くできる。このことを以下に説明する。 The cobalt-containing glass I of the present invention has excellent excitation light blocking characteristics, and when this is used in an excitation light cut filter, the commercially available fluorine and chlorine-containing borosilicate colors that have been used as excitation light cut filters in the past. It can be made thinner than glass. This will be described below.
励起光カットフィルタが励起光強度をどの程度減衰できれば、放射線像読取装置に適用できるかは、特許文献１によれば、励起光カットフィルタの透過率を１×１０−１０に、すなわち励起光強度を１０桁程度減衰させることが適当であると例示されており、特許文献２には、励起光カットフィルタの透過率を１×１０−８に、すなわち励起光強度を８桁減衰させることが適当であると例示されているが、これ以降では、より厳しい前者の透過率１×１０−１０に、すなわち励起光強度を１０桁減衰させ得るものが必要特性であるとして述べていく。 According to Patent Document 1, the transmittance of the excitation light cut filter is set to 1 × 10 −10 , that is, the excitation light intensity can be applied to the radiation image reading apparatus if the excitation light cut filter can attenuate the excitation light intensity. It is exemplified that it is appropriate to attenuate about 10 orders of magnitude. In Patent Document 2, it is appropriate to reduce the transmittance of the excitation light cut filter to 1 × 10 −8 , that is, to reduce the excitation light intensity by 8 orders of magnitude. However, in the following, it will be described that the more severe former transmittance of 1 × 10 −10 , that is, what can attenuate the excitation light intensity by 10 orders of magnitude is a necessary characteristic.
市販フッ素、塩素含有ホウケイ酸系色ガラス材の１０ｍｍ厚での内部透過率曲線を図１ａに示す。横軸は波長を表し、波長範囲を３００ｎｍから８００ｎｍとし、縦軸は対数表示の内部透過率を表したものである。図１ｂは、波長範囲及び透過率範囲を狭めて、吸収帯を拡大して示したものである。図１ａおよび図１ｂによれば、６６０ｎｍの内部透過率は、１×１０−１０以下に、すなわち励起光強度は１０桁以上減衰している。そして、輝尽発光光が存在する３００〜５００ｎｍは十分な透過特性を示す。よって、輝尽性蛍光体を励起させる励起光波長が、特に６５０〜７００ｎｍの範囲であるとき、その波長範囲に吸収ピークを持つ１０ｍｍ厚の市販フッ素、塩素含有ホウケイ酸系色ガラス材は、励起光強度を１０桁以上減衰させる能力を持つ励起光カットフィルタとして有用である。 An internal transmittance curve of a commercially available fluorine- and chlorine-containing borosilicate color glass material at a thickness of 10 mm is shown in FIG. The horizontal axis represents wavelength, the wavelength range is 300 nm to 800 nm, and the vertical axis represents logarithmic internal transmittance. FIG. 1b shows the absorption band enlarged with the wavelength range and transmittance range narrowed. According to FIGS. 1a and 1b, the internal transmittance at 660 nm is 1 × 10 −10 or less, that is, the excitation light intensity is attenuated by 10 orders of magnitude or more. And 300-500 nm in which stimulated emission light exists shows sufficient transmission characteristics. Therefore, when the excitation light wavelength for exciting the photostimulable phosphor is in the range of 650 to 700 nm, the commercially available fluorine and chlorine-containing borosilicate color glass material having an absorption peak in the wavelength range is excited. It is useful as an excitation light cut filter having the ability to attenuate the light intensity by 10 digits or more.
本発明のコバルト含有ガラスＩは、後述する実施例１〜２８（表１〜表５および図２ａ、図２ｂ〜図１０ａ、図１０ｂ参照）で実証されているように、厚みが市販フッ素、塩素含有ホウケイ酸系色ガラス材の厚み１０ｍｍの１／２である５ｍｍであっても波長６６０ｎｍの内部透過率を市販フッ素、塩素含有ホウケイ酸系色ガラス材と同様に１×１０−１０以下とすることができ、励起光強度を１０桁以上減衰させることができる。 The cobalt-containing glass I of the present invention has commercially available fluorine and chlorine thicknesses as demonstrated in Examples 1 to 28 (see Tables 1 to 5 and FIGS. 2a, 2b to 10a, and 10b) described later. The internal transmittance at a wavelength of 660 nm is 1 × 10 −10 or less as in the case of commercially available fluorine and chlorine-containing borosilicate color glass materials even when the content is 5 mm which is ½ of the thickness of 10 mm of the borosilicate color glass material. The excitation light intensity can be attenuated by 10 orders of magnitude or more.
２．化学的耐久性
本発明のコバルト含有ガラスＩは、励起光カットフィルタとして用いたときの長時間使用可能性を確保するために化学的耐久性を有することが好ましい。
本発明のコバルト含有ガラスＩのうちのあるものは、後述する実施例１〜１９および２８（表１〜３および表５参照）で実証されているように、市販フッ素、塩素含有ホウケイ酸系色ガラス材と同等ないしそれ以上の化学的耐久性を有する。
2. Chemical Durability The cobalt-containing glass I of the present invention preferably has chemical durability in order to ensure long-term useability when used as an excitation light cut filter.
Some of the cobalt-containing glasses I of the present invention are commercially available fluorine, chlorine-containing borosilicate colors as demonstrated in Examples 1-19 and 28 (see Tables 1-3 and Table 5) described below. Has chemical durability equivalent to or better than glass.
［コバルト含有ガラスＩＩ］
本発明のコバルト含有ガラスＩＩは、重量％表示で、
ＳｉO２ ２５〜６５％
Ａｌ２O３ ３〜１８％
Ｂ２O３ １０〜２７％
Ｋ２O ９〜２３％
ＣｏO ０．１〜１．５％
Ｆ２ １〜１３％
Ｃｌ２ ０．１〜５．５％
を含むガラス原料を熔解してなることを特徴とするものである。
[Cobalt-containing glass II]
The cobalt-containing glass II of the present invention is expressed by weight%,
SiO 2 25~65%
Al 2 O 3 3-18%
B 2 O 3 10-27%
K 2 O 9-23%
CoO 0.1-1.5%
F 2 1~13%
Cl 2 0.1~5.5%
It is characterized by melting a glass raw material containing.
本発明のコバルト含有ガラスＩＩは、ガラスを作製するために熔解されるガラス原料である金属酸化物およびハロゲン分子の各成分を含有量（重量％）で規定したものであり、ガラス原料であるＳｉO２、Ａｌ２O３、Ｂ２O３、Ｋ２O、ＣｏO、Ｆ２およびＣｌ２の含有量（重量％）は、ガラスを構成する陽イオン成分であるＳｉ４＋、Ａｌ３＋、Ｂ３＋、Ｋ＋、Ｃｏ２＋および陰イオン成分であるＦ−およびＣｌ−の含有量を陽イオン％および陰イオン％で規定した本発明のコバルト含有ガラスＩと同様の組成が得られるように定められているものである。 The cobalt-containing glass II of the present invention is defined by the content (% by weight) of each component of a metal oxide and a halogen molecule, which are glass raw materials that are melted to produce glass, and is a glass raw material, SiO. 2 , Al 2 O 3 , B 2 O 3 , K 2 O, CoO, F 2 and Cl 2 content (% by weight) are determined as Si 4+ , Al 3+ , B 3+ , which are cation components constituting the glass. It is determined so as to obtain a composition similar to that of the cobalt-containing glass I of the present invention in which the contents of K + , Co 2+, and F − and Cl − which are anionic components are defined by cation% and anion%. Is.
上記のガラス原料の熔解によるガラスの製造は、ガラス原料である各成分を所定の含有量となるように秤量したのち混合し、例えば１２００〜１４５０℃に保持された熔解炉中で３〜１０時間加熱して熔解し、清澄することにより行われる。 Production of the glass by melting the glass raw material described above is performed by weighing each component of the glass raw material so as to have a predetermined content, and mixing them, for example, in a melting furnace maintained at 1200 to 1450 ° C. for 3 to 10 hours. It is done by heating, melting and clarifying.
なお、実際のガラス原料の熔解によるガラスの製造においては、ガラス原料としてＡｌ（ＯＨ）３などの金属水酸化物、Ｈ３ＢＯ３などの酸、Ｋ２ＣＯ３、Ｋ２ＳｉＦ６、ＫＣｌなどの金属塩が用いられ、Ａｌ２O３、Ｂ２O３、Ｋ２Oなどの金属酸化物やＦ２、Ｃｌ２などのハロゲン分子がガラス原料として直接用いられることは少ないが、本発明のコバルト含有ガラスＩＩにおけるＡｌ２O３、Ｂ２O３、Ｋ２O、Ｆ２、Ｃｌ２の含有量（重量％）は上記の対応する金属水酸化物、酸、金属塩の含有量（重量％）からの換算値である。 In the production of glass by melting actual glass raw materials, metal hydroxides such as Al (OH) 3 , acids such as H 3 BO 3 , K 2 CO 3 , K 2 SiF 6 , KCl, etc. Although metal oxides such as Al 2 O 3 , B 2 O 3 and K 2 O and halogen molecules such as F 2 and Cl 2 are rarely used directly as glass raw materials, The content (weight%) of Al 2 O 3 , B 2 O 3 , K 2 O, F 2 , and Cl 2 in the cobalt-containing glass II is the content (weight) of the corresponding metal hydroxide, acid, and metal salt. %).
上記したように本発明のコバルト含有ガラスＩＩは、本発明のコバルト含有ガラスＩと同様の組成を有するものであるので、本発明のコバルト含有ガラスＩと同様の特性、例えば優れた励起光遮断特性および優れた化学的耐久性を有する。 As described above, since the cobalt-containing glass II of the present invention has the same composition as the cobalt-containing glass I of the present invention, the same characteristics as the cobalt-containing glass I of the present invention, for example, excellent excitation light blocking characteristics. And has excellent chemical durability.
［青色フィルタ］
本発明の青色フィルタは、上述の本発明のコバルト含有ガラスＩまたは上述の本発明のコバルト含有ガラスＩＩからなることを特徴とするものである。
本発明の青色フィルタは、その好ましい態様において、ガラスの厚みが５ｍｍの場合の波長６６０ｎｍの内部透過率が１×１０−１０以下であり、励起光カットフィルタ、特に放射線画像読取装置に設けられる励起光カットフィルタとして好ましく用いられる。
[Blue filter]
The blue filter of the present invention comprises the above-described cobalt-containing glass I of the present invention or the above-described cobalt-containing glass II of the present invention.
In the preferred embodiment, the blue filter of the present invention has an internal transmittance of 1 × 10 −10 or less at a wavelength of 660 nm when the thickness of the glass is 5 mm, and is provided in an excitation light cut filter, particularly an excitation provided in a radiation image reading apparatus. It is preferably used as a light cut filter.
［放射線画像読取装置］
本発明の放射線画像読取装置は、上述の本発明の青色フィルタからなる励起光カットフィルタを含むことを特徴とするものである。
本発明の放射線画像読取装置は、励起光カットフィルタが本発明の青色フィルタからなるという構成に特徴があり、他の構成は従来公知の放射線画像読取装置をそのまま採用することができる。
[Radiation image reader]
The radiation image reading apparatus of the present invention includes an excitation light cut filter composed of the above-described blue filter of the present invention.
The radiation image reading apparatus of the present invention is characterized in that the excitation light cut filter is composed of the blue filter of the present invention, and a conventionally known radiation image reading apparatus can be employed as it is for the other structure.
以下、実施例１〜２８により本発明をさらに説明するが、本発明はこれらの実施例に限定されるものではない。
実施例１
ａ．ガラス原料バッチの作製
表１に示すように、ガラス原料組成が、重量基準でＳｉＯ２ ４８．１％、Ａｌ２Ｏ３ ９．７％、Ｂ２Ｏ３ １８．８％、Ｋ２Ｏ １６．０％、ＣｏＯ ０．３２８％、 Ｆ２ ４．４％、 Ｃｌ２ ２．７％となるように、ＳｉＯ２、Ａｌ（ＯＨ）３、Ｈ３ＢＯ３、Ｋ２ＣＯ３、ＣｏＯ、Ｋ２ＳｉＦ６、ＫＣｌを所定量秤量し、これらを調合してガラス原料バッチ１００ｇを作製した。
EXAMPLES Hereinafter, although this invention is further demonstrated by Examples 1-28, this invention is not limited to these Examples.
Example 1
a. Production of Glass Raw Material Batch As shown in Table 1, the glass raw material composition was 48.1% SiO 2 , 9.7% Al 2 O 3 , 18.8% B 2 O 3 , K 2 O 16. SiO 2 , Al (OH) 3 , H 3 BO 3 , K 2 CO 3 , CoO, K 2 to be 0%, CoO 0.328%, F 2 4.4%, Cl 2 2.7%. Predetermined amounts of SiF 6 and KCl were weighed and prepared to prepare 100 g of a glass raw material batch.
ｂ．熔解によるガラスの製造
２００ｃｃのシリカビーカーをガラス原料熔解容器として用い、このシリカビーカーに、ガラス原料バッチ１００ｇを入れ、シリカビーカーを１３５０℃に保持された炉の中に入れた。約１時間熟成させた後、シリカビーカーを取り出し、直径６ｍｍのシリカ棒で熔融ガラスを撹拌し、撹拌後、炉に戻した。１時間後、同じ撹拌を繰り返し、その１時間後、鉄板の上にガラスをキャストした。ある程度、ガラスが固まるのを待ち、４５０℃のアニール炉の中にキャストしたガラスを入れ、１時間その温度で保持し、５０℃／時間の速度で温度を下げて、表１に示すようにＳｉ４＋ ４２．７％、Ａｌ３＋ １０．１％、Ｂ３＋ ２８．８％、Ｋ＋ １８．１％、Ｃｏ２＋ ０．２３３％、 Ｆ− ５．４％、 Ｃｌ− ０．５５％、Ｏ２− ９４．０％のガラス組成を有する実施例１のコバルト含有ガラスを得た。
b. Production of Glass by Melting Using a 200 cc silica beaker as a glass raw material melting vessel, 100 g of a glass raw material batch was placed in this silica beaker, and the silica beaker was placed in a furnace maintained at 1350 ° C. After aging for about 1 hour, the silica beaker was taken out, and the molten glass was stirred with a silica rod having a diameter of 6 mm. After stirring, the glass was returned to the furnace. After 1 hour, the same stirring was repeated, and after 1 hour, the glass was cast on an iron plate. Wait for the glass to harden to some extent, put the cast glass in a 450 ° C. annealing furnace, hold at that temperature for 1 hour, lower the temperature at a rate of 50 ° C./hour, and as shown in Table 1, 4+ 42.7%, Al 3+ 10.1%, B 3+ 28.8%, K + 18.1%, Co 2+ 0.233%, F − 5.4%, Cl − 0.55%, O 2 - to obtain 94.0% of the cobalt-containing glasses of example 1 having a glass composition.
実施例２〜２８
実施例１において、ガラス原料組成（重量％）を表１〜表５に示すように変動させた以外は実施例１−ａと同様にガラス原料バッチを作製し、得られたガラス原料バッチを実施例１−ｂと同様に熔解して、表１〜表５に示すガラス組成（陽イオン％、陰イオン％）を有する実施例２〜２８のコバルト含有ガラスを得た。
Examples 2-28
In Example 1, a glass raw material batch was produced in the same manner as in Example 1-a except that the glass raw material composition (% by weight) was varied as shown in Tables 1 to 5, and the obtained glass raw material batch was carried out. It melted similarly to Example 1-b, and obtained the cobalt containing glass of Examples 2-28 which has the glass composition (cation%, anion%) shown in Table 1-Table 5.
比較例１〜６
実施例１において、ガラス原料組成（重量％）を表６〜表７に示すように変動させた以外は実施例１−ａと同様にガラス原料バッチを作製し、得られたガラス原料バッチを実施例１−ｂと同様に熔解して、表６〜表７に示すガラス組成（陽イオン％、陰イオン％）を有する比較例１〜６のコバルト含有ガラスを得た。
Comparative Examples 1-6
In Example 1, a glass raw material batch was prepared in the same manner as in Example 1-a except that the glass raw material composition (% by weight) was varied as shown in Tables 6 to 7, and the obtained glass raw material batch was carried out. By melting in the same manner as in Example 1-b, cobalt-containing glasses of Comparative Examples 1 to 6 having the glass compositions (cation% and anion%) shown in Tables 6 to 7 were obtained.
比較例１〜６のガラスは、コバルトを含有するものの、ガラス組成が本発明のコバルト含有ガラスＩの組成（陽イオン％、陰イオン％）を満足しない比較のガラスである。 Although the glass of Comparative Examples 1-6 contains cobalt, it is a comparative glass whose glass composition does not satisfy the composition of the cobalt-containing glass I of the present invention (cation%, anion%).
ガラスの物性測定試験
ａ．透過率測定用試料の加工
アニール後の実施例１〜２８および比較例１〜６のガラスを、ダイヤモンドカッターを用いて、厚み３ｍｍ程度、約２ｃｍ四方の大きさに切り出し、研磨加工を行い、最終厚み０．５ｍｍに揃えた透過率測定用試料を作製した。
Glass physical property measurement test a. Processing of Sample for Transmittance Measurement After annealing, the glasses of Examples 1 to 28 and Comparative Examples 1 to 6 were cut into a size of about 3 mm and a size of about 2 cm by using a diamond cutter, and polished. A transmittance measurement sample having a thickness of 0.5 mm was prepared.
ｂ．透過率測定
上記ａで得られた厚み０．５ｍｍの透過率測定用試料について、透過率を分光光度計（メーカ名：（株）島津製作所、型番：ＵＶ−３６００）を用いて測定した。
b. Transmittance Measurement The transmittance of the 0.5 mm thick sample for transmittance measurement obtained in the above a was measured using a spectrophotometer (manufacturer name: Shimadzu Corporation, model number: UV-3600).
ｃ．５ｍｍ厚内部透過率の計算
通常、内部透過率は、同一ガラスから3種の厚みの異なる透過率測定用サンプルを用意し、３種の厚みのサンプルをそれぞれ透過率測定し、計算により反射率を取り除いて、厚みに対する内部透過率の直線を最小二乗法で求め、この直線から、その厚みについての内部透過率が計算される。
c. Calculation of 5mm thickness internal transmittance Usually, the internal transmittance is prepared by preparing three types of transmittance measurement samples from the same glass, measuring the transmittance of each of the three thickness samples, and calculating the reflectance by calculation. The straight line of the internal transmittance with respect to thickness is calculated | required by the least square method, and the internal transmittance about the thickness is calculated from this straight line.
ここでは簡易方法を用いて内部透過率を算出することにする。すなわち、反射係数を９３%と仮定して算出する方法をここでは採用する。例えば、０．９７ｍｍ厚で外部透過率８．１%であれば、１０ｍｍ厚の内部透過率は、（８．１／９３）＾（１０／０．９７）で求まり、１．１８Ｅ−１１となる。これは、上記市販の色ガラス材が１０ｍｍ厚で励起光を１０桁以上減衰させる性能をもつことを意味する。本発明は、上記市販の色ガラス材の厚み１０ｍｍの半分の厚み５ｍｍで上記市販の色ガラス材と同等の性能を有するコバルト含有ガラスを提供することを目的としているので、実施例１〜２８のコバルト含有ガラスは厚みを５ｍｍに統一して、１０ｍｍ厚の上記市販のフッ素、塩素含有ホウケイ酸系色ガラス材と透過率を比較した。なお、実際の透過率測定に用いたガラス厚みは前述の０．５ｍｍとした。 Here, the internal transmittance is calculated using a simple method. That is, a calculation method assuming that the reflection coefficient is 93% is adopted here. For example, if the thickness is 0.97 mm and the external transmittance is 8.1%, the internal transmittance of the 10 mm thickness is obtained by (8.1 / 93) ^ (10 / 0.97), and is 1.18E-11. Become. This means that the commercially available colored glass material has a thickness of 10 mm and has the ability to attenuate excitation light by 10 digits or more. Since this invention aims at providing the cobalt containing glass which has the performance equivalent to the said commercially available colored glass material by thickness 5mm of the thickness 10mm of the said commercially available colored glass material, it is the Example 1-28. Cobalt-containing glass was unified to a thickness of 5 mm, and the transmittance was compared with the commercially available fluorine- and chlorine-containing borosilicate color glass material having a thickness of 10 mm. In addition, the glass thickness used for the actual transmittance | permeability measurement was 0.5 mm mentioned above.
１０ｍｍ厚の上記市販のフッ素、塩素含有ホウケイ酸系色ガラス材の内部透過率曲線を図１ａ、図１ｂに、５ｍｍ厚の実施例１〜２８のコバルト含有ガラスの内部透過率曲線を図２ａ、図２ｂ〜図１０ａ、図１０ｂに、５ｍｍ厚の比較例１〜６のコバルト含有ガラスの内部透過率曲線を図１１ａ、図１１ｂ〜図１２ａ、図１２ｂに示した。 The internal transmittance curves of the commercially available fluorine- and chlorine-containing borosilicate color glass material having a thickness of 10 mm are shown in FIGS. 1 a and 1 b, and the internal transmittance curves of the cobalt-containing glasses of Examples 1 to 28 having a thickness of 5 mm are shown in FIG. FIGS. 2b to 10a and 10b show internal transmittance curves of the cobalt-containing glasses of Comparative Examples 1 to 6 having a thickness of 5 mm in FIGS. 11a, 11b to 12a, and 12b.
表１〜表７に示す実施例１〜２８のコバルト含有ガラスおよび比較例１〜６のコバルト含有ガラスの６６０ｎｍ透過率（５ｍｍ厚）において、１０ｍｍ厚の上記市販の色ガラス材と同等である１×１０−１０以下の内部透過率であれば、記号「○」を表記し、１×１０−１０を上まわる内部透過率であれば、記号「×」を表記した。 In the 660 nm transmittance | permeability (5 mm thickness) of the cobalt containing glass of Examples 1-28 shown in Table 1-Table 7, and the cobalt containing glass of Comparative Examples 1-6, it is equivalent to the said commercially available colored glass material of 10 mm thickness 1 When the internal transmittance was less than or equal to × 10 −10 , the symbol “◯” was written, and when the internal transmittance exceeded 1 × 10 −10 , the symbol “x” was written.
ｄ．２．５ｍｍ厚外部透過率の計算
上述した計算法により、５ｍｍ厚内部透過率はすでに計算されて求められており、この値をもとに２．５ｍｍ厚の外部透過率を算出した。例えば、５ｍｍ厚で内部透過率が７９．７%であれば、２．５ｍｍ厚の外部透過率は、９３×０．７９７＾（２．５／５）で求まり、８３．０%となる。波長−透過率の数値データからＴｍａｘ、λＳ１、λ１５を導き出した。
d. Calculation of 2.5 mm-thick external transmittance The 5 mm-thick internal transmittance has already been calculated by the above-described calculation method, and the 2.5 mm-thick external transmittance was calculated based on this value. For example, if the internal transmittance is 59.7% with a thickness of 5 mm, the external transmittance with a thickness of 2.5 mm is obtained as 93 × 0.797 ^ (2.5 / 5), and becomes 83.0%. Tmax, λ S1 , and λ 15 were derived from the numerical data of wavelength-transmittance.
ここにＴｍａｘは、２．５ｍｍ厚のガラスの波長３００〜５００ｎｍにおける最高外部透過率であり、λＳ１は、透過帯域の短波長側で透過率が１%以下になる波長であり、λ１５は、透過帯域の長波長側で透過率が１５%以下になる波長である。 Here, Tmax is the maximum external transmittance at a wavelength of 300 to 500 nm of glass having a thickness of 2.5 mm, λ S1 is a wavelength at which the transmittance is 1% or less on the short wavelength side of the transmission band, and λ 15 is The wavelength at which the transmittance is 15% or less on the long wavelength side of the transmission band.
表１〜表７に示す実施例１〜２８のコバルト含有ガラスおよび比較例１〜６のコバルト含有ガラスの２．５ｍｍ厚３００〜５００ｎｍ外部透過率において、Ｔｍａｘが83%以上であれば、記号「○」と表記し、８３%を下まわれば、記号「×」を表記した。λｓ１が２５０ｎｍ以上に存在するときには、記号「○」を表記し、２５０ｎｍより短波長側に出現したときには、記号「×」を表記した。最後にλ１５が６００ｎｍより短波長側に存在したときには、記号「○」を表記し、６００ｎｍを上まわったときには、記号「×」を表記した。 In 2.5 mm thickness 300-500 nm external transmittance of the cobalt-containing glasses of Examples 1 to 28 and Comparative Examples 1 to 6 shown in Table 1 to Table 7, if Tmax is 83% or more, the symbol “ The symbol “X” was written when it was less than 83%. When λ s1 is present at 250 nm or more, the symbol “◯” is indicated, and when λ s1 appears on the shorter wavelength side than 250 nm, the symbol “X” is indicated. Finally, when λ 15 is present on the shorter wavelength side than 600 nm, the symbol “◯” is shown, and when it exceeds 600 nm, the symbol “X” is shown.
ｅ．化学的耐久性
化学的耐久性を評価するための耐候性試験は、ガラスを６５℃、９０%ＲＨの環境下に１００〜１０００時間放置し、放置後の表面状態を観察することにより行った。用いた耐候性試験器はメーカ名：エスペック（株）、型番：ＰＲ−３ＫＰである。耐久性がかなり悪いものは、表面に結晶が析出したり、表面に割れが出現したりし、耐久性が少し悪いものは、雨上がり後のガラス窓表面に現れる様な「曇り」がサンプル表面に出現する。この曇りが少ないほど耐久性が高いと判断できる。更に、耐久性が良くなれば、その曇りがサンプル表面の一部に薄く出現するようになる。上記市販の色ガラス材はこのレベルの耐久性に相当する。そして、更に耐久性が良いものは、まったく曇らないのである。実施例１〜２８のコバルト含有ガラスおよび比較例１〜６のコバルト含有ガラスについて、上記市販の色ガラス材をリファレンスとして試験を行い、上記市販の色ガラス材との比較を行った。
e. Chemical Durability A weather resistance test for evaluating chemical durability was performed by leaving the glass in an environment of 65 ° C. and 90% RH for 100 to 1000 hours and observing the surface condition after being left. The used weather resistance tester is manufacturer name: ESPEC Co., Ltd., model number: PR-3KP. If the durability is quite poor, crystals will be deposited on the surface or cracks will appear on the surface. If the durability is slightly low, the cloudy surface that appears on the surface of the glass window after the rain will appear on the sample surface. Appear. It can be judged that durability is so high that there is little this cloudiness. Furthermore, when the durability is improved, the cloudiness appears thinly on a part of the sample surface. The commercially available colored glass material corresponds to this level of durability. And those with better durability do not fog at all. About the cobalt containing glass of Examples 1-28 and the cobalt containing glass of Comparative Examples 1-6, it tested using the said commercially available colored glass material as a reference, and compared with the said commercially available colored glass material.
表１〜表７に示す実施例１〜２８のコバルト含有ガラスおよび比較例１〜６のコバルト含有ガラスの耐候性試験において、ガラス表面の変化が上記市販の色ガラス材と同等もしくはそれより小さければ、記号「○」を表記した。ガラス表面の変化が上記市販の色ガラス材より大きければ、記号「×」を表記した。評価をしなかったものについては、記号「−」を表記した。例えば、分相性が現れたものについては「化学的耐久性」の評価をしなかった。 In the weather resistance test of the cobalt-containing glasses of Examples 1 to 28 and the cobalt-containing glasses of Comparative Examples 1 to 6 shown in Tables 1 to 7, if the change in the glass surface is equal to or smaller than the commercially available colored glass material The symbol “◯” was written. If the change of the glass surface was larger than the above-mentioned commercially available colored glass material, the symbol “x” was written. For those not evaluated, the symbol “-” was written. For example, the evaluation of “chemical durability” was not performed for those in which phase separation occurred.
ｆ．分相性
実施例１〜２８のコバルト含有ガラスおよび比較例１〜６のコバルト含有ガラスについて、キャストしたガラスを観察して、分相現象の出現の程度で分相性を評価した。
表１〜表７に示す実施例１〜２８のコバルト含有ガラスおよび比較例１〜６のコバルト含有ガラスにおいて、キャストしたガラスに分相現象が現れなければ、記号「○」を表記し、キャストしたガラスに分相現象が現れれば、記号「×」を表記した。
f. Phase separation The cast glass was observed for the cobalt-containing glasses of Examples 1 to 28 and the cobalt-containing glasses of Comparative Examples 1 to 6, and the phase separation was evaluated by the degree of appearance of the phase separation phenomenon.
In the cobalt-containing glasses of Examples 1 to 28 shown in Tables 1 to 7 and the cobalt-containing glasses of Comparative Examples 1 to 6, if the phase separation phenomenon does not appear in the cast glass, the symbol “◯” is written and cast. If a phase separation phenomenon appears in the glass, the symbol “x” is shown.
図２ａ、図２ｂ〜図１２ａ、図１２ｂおよび表１〜表７の結果より、次のことが明らかとなった。
（ｉ）本発明のコバルト含有ガラスＩに相当する実施例１〜２８のコバルト含有ガラスは、分相性を示さず、また厚みが５ｍｍであっても、厚みが１０ｍｍである市販のフッ素、塩素含有ホウケイ酸系色ガラス材と同様に６６０ｎｍの内部透過率を１×１０−１０以下とすることができ、励起光強度を１０桁以上減衰させることができた。
（ｉｉ）本発明のコバルト含有ガラスＩに相当する実施例１〜１９および２８のコバルト含有ガラスは、上記市販のフッ素、塩素含有ホウケイ酸系色ガラス材と同等それ以上の化学的耐久性を有していた。
（ｉｉｉ）比較例１〜４のコバルト含有ガラスは、ガラス組成（陽イオン％）が本発明のコバルト含有ガラスＩのガラス組成を満足しないので、必要な透過率特性が得られず、比較例５〜６のコバルト含有ガラスは、分相性を示した。
From the results shown in FIG. 2a, FIG. 2b to FIG. 12a, FIG. 12b and Tables 1 to 7, the following became clear.
(I) The cobalt-containing glasses of Examples 1 to 28 corresponding to the cobalt-containing glass I of the present invention do not exhibit phase separation, and even if the thickness is 5 mm, commercially available fluorine and chlorine containing 10 mm in thickness. Similar to the borosilicate color glass material, the internal transmittance at 660 nm could be 1 × 10 −10 or less, and the excitation light intensity could be attenuated by 10 digits or more.
(Ii) The cobalt-containing glasses of Examples 1 to 19 and 28 corresponding to the cobalt-containing glass I of the present invention have chemical durability equivalent to or higher than that of the above-mentioned commercially available fluorine and chlorine-containing borosilicate color glass materials. Was.
(Iii) In the cobalt-containing glasses of Comparative Examples 1 to 4, the glass composition (cation%) does not satisfy the glass composition of the cobalt-containing glass I of the present invention. The cobalt-containing glasses of ˜6 showed phase separation.
本発明によれば、励起光遮断特性が高められ、励起光カットフィルタの厚みを従来の色ガラスよりも薄くすることができるコバルト含有ガラスを提供することができた。
また本発明によれば、上記コバルト含有ガラスからなる青色フィルタおよび該青色フィルタを用いた放射線画像読取装置を提供することができた。
ADVANTAGE OF THE INVENTION According to this invention, the excitation light interruption characteristic was improved and the cobalt containing glass which can make thickness of an excitation light cut filter thinner than the conventional colored glass was able to be provided.
Moreover, according to this invention, the radiographic image reading apparatus using the blue filter consisting of the said cobalt containing glass and this blue filter was able to be provided.
Claims (7)
Ｓｉ４＋ ２５〜６０％
Ａｌ３＋ ３〜１９％
Ｂ３＋ １８〜３８％
Ｋ＋ ９〜３１％
Ｃｏ２＋ ０．１〜１．５％
を含み、陰イオンとして、Ｏ２−を主成分として含み、さらに陰イオン％表示で、
Ｆ− １〜１２％
Ｃｌ− ０．０１〜２％
を含むことを特徴とするコバルト含有ガラス。 As a cation, in cation% display,
Si 4+ 25-60%
Al 3+ 3-19%
B 3+ 18-38%
K + 9-31%
Co 2+ 0.1-1.5%
, As an anion, O 2− as a main component, and an anion% display,
F - 1-12%
Cl - 0.01-2%
Cobalt-containing glass characterized by containing.
ＳｉＯ２ ２５〜６５％
Ａｌ２Ｏ３ ３〜１８％
Ｂ２Ｏ３ １０〜２７％
Ｋ２Ｏ ９〜２３％
ＣｏＯ ０．１〜１．５％
Ｆ２ １〜１３％
Ｃｌ２ ０．１〜５．５％
を含むガラス原料を熔解してなることを特徴とするコバルト含有ガラス。 In weight% display
SiO 2 25~65%
Al 2 O 3 3-18%
B 2 O 3 10~27%
K 2 O 9~23%
CoO 0.1-1.5%
F 2 1~13%
Cl 2 0.1~5.5%
A cobalt-containing glass obtained by melting a glass raw material containing
A radiation image reading apparatus comprising the excitation light cut filter comprising the blue filter according to claim 3.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51127110A (en) * | 1975-04-14 | 1976-11-05 | Corning Glass Works | Reinforced photochromic glass |
| JPS54160413A (en) * | 1978-04-12 | 1979-12-19 | Corning Glass Works | Phtochromic glass |
| JPS5738341A (en) * | 1980-06-09 | 1982-03-03 | Corning Glass Works | Photochromic glass for eye glass lens |
| JPS61219740A (en) * | 1985-03-26 | 1986-09-30 | Toshiba Glass Co Ltd | Blue glass for aeronautical sign lamp |
| JP2004250285A (en) * | 2003-02-20 | 2004-09-09 | Hoya Corp | Colored glass and blue filter |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1472953A1 (en) * | 1987-02-10 | 1989-04-15 | Предприятие П/Я В-2268 | Electro insulating composition |
| JP2526129B2 (en) * | 1989-08-04 | 1996-08-21 | 宇部興産株式会社 | Magneto-optical recording medium |
| JP3315136B2 (en) * | 1991-09-04 | 2002-08-19 | トピー工業株式会社 | Composite mica powder and ultraviolet screening agent containing said mica powder |
| EP1171393A1 (en) * | 1999-01-21 | 2002-01-16 | Corning Incorporated | GeAs SULPHIDE GLASSES CONTAINING P |
| JP5072657B2 (en) * | 2008-03-05 | 2012-11-14 | 株式会社松風 | Color tone adjusting composition for aluminosilicate glass and ceramic crown ceramics |
-
2010
- 2010-12-28 JP JP2010292668A patent/JP5183730B2/en not_active Expired - Fee Related
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2011
- 2011-10-18 CN CN201110319286.6A patent/CN102531382B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51127110A (en) * | 1975-04-14 | 1976-11-05 | Corning Glass Works | Reinforced photochromic glass |
| JPS54160413A (en) * | 1978-04-12 | 1979-12-19 | Corning Glass Works | Phtochromic glass |
| JPS5738341A (en) * | 1980-06-09 | 1982-03-03 | Corning Glass Works | Photochromic glass for eye glass lens |
| JPS61219740A (en) * | 1985-03-26 | 1986-09-30 | Toshiba Glass Co Ltd | Blue glass for aeronautical sign lamp |
| JP2004250285A (en) * | 2003-02-20 | 2004-09-09 | Hoya Corp | Colored glass and blue filter |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102531382A (en) | 2012-07-04 |
| CN102531382B (en) | 2015-01-21 |
| JP5183730B2 (en) | 2013-04-17 |
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