EP0348172B1 - Radiation image storage panel - Google Patents

Radiation image storage panel Download PDF

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Publication number
EP0348172B1
EP0348172B1 EP19890306261 EP89306261A EP0348172B1 EP 0348172 B1 EP0348172 B1 EP 0348172B1 EP 19890306261 EP19890306261 EP 19890306261 EP 89306261 A EP89306261 A EP 89306261A EP 0348172 B1 EP0348172 B1 EP 0348172B1
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Prior art keywords
storage panel
protective layer
layer
radiation image
image storage
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German (de)
French (fr)
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EP0348172A3 (en
EP0348172A2 (en
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Akiko Kano
Masaaki Nitta
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Konica Minolta Inc
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Konica Minolta Inc
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    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21KTECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K4/00Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens

Definitions

  • This invention relates to a radiation image storage panel having a stimulable phosphor layer, more particularly to a radiation image storage panel having excellent sharpness of image due to small spreading of stimulation excitation light by scattering of light within the protective layer.
  • a radiation image such as X-ray image has been frequently used for diagnosis of disease, etc.
  • This method is a method in which radiation (generally X-ray) transmitted through an object to be photographed is absorbed onto a phosphor, and then the phosphor is excited by, for example, light or heat energy, thereby radiating the radiation energy accumulated in the phosphor by the above radiation absorption as fluorescent light, and the fluorescent light is detected to form an image.
  • radiation generally X-ray
  • the phosphor is excited by, for example, light or heat energy, thereby radiating the radiation energy accumulated in the phosphor by the above radiation absorption as fluorescent light, and the fluorescent light is detected to form an image.
  • U.S. Patent No. 3,859,527 and Japanese Provisional Patent Publication No. 12144/1980 disclose radiation image storage methods with visible light rays or IR-rays as the stimulation excitation light by use of a stimulable phosphor.
  • This method comprises using a radiation image storage panel (hereinafter abbreviated as “storage panel”) having a stimulable phosphor layer (hereinafter abbreviated as “stimulable layer”) formed on a support, and radiation having passed through an object to be photographed is irradiated on the stimulable layer of the storage panel to form a latent image through accumulation of the radiation energy corresponding to the radiation transmittance at the respective portions of the object to be photographed, and thereafter the stimulable layer is scanned with a stimulation excitation light, thereby irradiating the radiation energy accumulated in the respective portions to convert it to light and obtain an image according to the optical signals depending on the intensity of the light.
  • the final image may be reproduced as a hard copy or reproduced on CRT.
  • the storage panel used in the radiation image storage panel releases the accumulated energy by scanning of the stimulation excitation light after accumulation of the radiation image information, and therefore accumulation of the radiation image can be effected again after scanning, so that repeated use is possible.
  • the above storage panel should desirably be able to withstand repeated use for a long time without deterioration of the radiation image obtained.
  • the stimulable layer of the above storage panel should be protected sufficiently from external physical or chemical stimulations.
  • a protective layer for covering the stimulable layer surface on the support of the storage panel has been provided in order to solve the above problem.
  • Such protective layer may be formed by coating directly a coating solution for the protective layer on a stimulable layer or by adhering a protective layer previously formed separately on a stimulable layer, as disclosed in Japanese Provisional Patent Publication No. 42500/1984.
  • a thin protective layer comprising an organic polymer is generally used. Such a thin protective layer is used because a reduction in the sharpness of the storage panel should be prevented.
  • the relationship between sharpness and protective layer thickness of a storage panel having a stimulable layer is shown in Table 1 by use of MTF (modulation transfer function) at a spatial frequency of 1 lp/mm and 2 lp/mm.
  • MTF modulation transfer function
  • PET is a polyethylene terephthalate film.
  • MTF exhibits about 65 % in the case of 1 lp/mm and about 35 % in the case of 2 lp/mm. It is therefore preferred that in the storage panel the MTF should not be inferior to that of the above screen-film system so that the thickness of the protective layer is desirably 10 ⁇ m or less.
  • a thin protective layer of an organic polymer conventionally used is permeable to some extent to water and/or humidity, and therefore the stimulable layer absorbs water which results in a great lowering in radiation sensitivity of the storage panel or attenuation of the accumulated energy until receiving stimulation excitation light irradiation, whereby variations and/or deterioration in image quality of the radiation image obtained is brought about.
  • moisture permeability of PET with a thickness of 10 ⁇ m is about 60 (g/m2 ⁇ 24 hr), and as much as 60 g of water permeates per unit area per day.
  • OPP oriented polypropylene
  • an object of the present invention is to provide a durable and use-resistant storage panel which can protect sufficiently the stimulable layer against physical stimulation and chemical stimulation, particularly water without impairing sharpness of the image at all, and can be used under ordinary conditions while maintaining high sensitivity, high sharpness and high graininess of the stimulable layer for a long term.
  • the storage panel of the present invention has a stimulable phosphor layer, a low refractive index layer and a protective layer in this order on a support, the protective layer having a haze ratio of 3 % or less as defined according to JIS K6714 (Japanese Industrial Standard, Methacryl resin plates for air plane, JIS K6714-1977, pp. 13 to 14).
  • Fig. 1 and Fig. 2 are schematic sectional views of radiation image storage panels of the present invention and Fig. 3 is a schematic view of a radiation image storage method using the storage panel of the present invention.
  • Fig. 1 and Fig. 2 are schematic sectional views each showing an example of a storage panel of the present invention.
  • the numerals in the drawings show the following, namely 1 is a protective layer, 2 is a low refractive index layer, 3 is a stimulable layer, 4 is a support and 5 is a protective layer supporting member.
  • the storage panel of the present invention has a stimulable layer 3, a low refractive index layer 2 and a protective layer 1 in this order on a support 4. Also, in the storage panel of the present invention, as shown in Fig. 2, it may also has a protective layer supporting member 5. One end of the protective layer supporting member 5 is adhered to the support 4, and the other end is adhered to the protective layer 1. The peripheral portion of the stimulable layer 3 and the protective layer supporting member 5 may be in contact or apart from each other.
  • the low refractive index layer 2 is constructed shielded from the outer atmosphere with the protective layer 1, the stimulable layer 3 (or stimulable layer 3 and support 4) and the protective layer supporting member 5.
  • the protective layer in the storage panel of the present invention has a haze ratio (haze value) as defined according to JIS K6714 of 3 % or less, preferably 1 % or less.
  • haze ratio haze value
  • expansion of the stimulation excitation light becomes greater due to expansion of scattering of light internally of the protective layer, whereby sharpness of the image is lowered.
  • the haze value as defined in JIS K6714 is expressed by the ratio of transmittance of diffused light to the transmittance of whole light in terms of percent (%).
  • the protective layer should otherwise have good light transmitting characteristics and also be moldable into a sheet. Further, the protective layer, for permitting transmission of stimulation excitation light and stimulation emission with good efficiency, preferably exhibits high transmittance over wide wavelength range, preferably a transmittance of 80 % or higher.
  • the thickness of the protective layer is determined in relation to the haze ratio and the humidity preventive characteristics of the constituent material, but it is practically 10 ⁇ m to 4 mm, and preferably 100 ⁇ m or more for having a certain haze ratio and obtaining good humidity preventive characteristics.
  • the protective layer has a thickness of 500 ⁇ m or more, a storage panel with excellent durability and use resistance can be obtained.
  • a protective layer for example plate glasses such as of quartz, borosilicate glass and chemically reinforced glass, organic polymeric compounds such as PET, OPP and polyvinyl chloride may be included.
  • a borosilicate glass with a thickness of 500 ⁇ m has a haze ratio of 0.6 % and exhibits a transmittance of 80 % or higher within the wavelength range of 330 nm to 2.6 ⁇ m.
  • An example of a quartz glass with a thickness of 500 ⁇ m has a haze ratio of 0.0 % and exhibits higher transmittance even at shorter wavelength than in the case of the borosilicate glass.
  • the haze ratio will vary depending on the thickness of the protective layer and the surface treatment. If the protective layer is a plate glass, one having a higher polishing grade has generally a lower haze ratio. On the other hand, if it is a plastic film, one which has been laminated or one with the surface subjected to matting or embossing working has generally a higher haze ratio.
  • the above-mentioned plate glass is preferred for excellent transmittance and humidity preventive characteristic along with haze ratio.
  • a reflection preventive layer such as MgF2 is preferred for permitting transmission of the stimulation excitation light and stimulation emission as well as for the effect of making lowering in sharpness smaller.
  • the refractive index of the protective layer is not particularly limited, but it is generally within the range of 1.4 to 2.0 in practical applications.
  • the protective layer can be provided as two or more layers, if desired.
  • the low refractive index layer of the storage panel of the present invention is a layer comprising a material having lower refractive index than the protective layer.
  • the material for constituting the low refractive index layer is not limited, provided that it has a lower refractive index than the protective layer.
  • a low refractive index layer is present as shown in Fig. 1 between the protective layer and the stimulable layer.
  • the low refractive index layer can be a layer comprising, for example, CaF2 (refractive index: 1.23 - 1.26), Na3AlF6 (refractive index: 1.35), MgF2 (refractive index: 1.38) or SiO2 (refractive index: 1.46), for example.
  • the low refractive index layer can be applied according to a physical vapor deposition method such as vacuum deposition on the surface of the stimulable layer and the protective layer or a thin film formed previously according to a similar method is laminated on the surface of the stimulable layer or the protective layer.
  • the low refractive index layer is shielded by the protective layer supporting member from the external atmosphere.
  • the thickness of the protective layer can be made substantially thicker, whereby humidity preventive characteristic and durability of the storage panel can be further improved.
  • the same material as described above can be used, but when a protective layer supporting member is included, for example, it is preferably made using a liquid such as ethanol (refractive index: 1.36), methanol (refractive index: 1.33) and diethyl ether (refractive index: 1.35); or a layer comprising a gas and having a refractive index of substantially 1, such as air, nitrogen, argon or a vacuum layer, for example.
  • a liquid such as ethanol (refractive index: 1.36), methanol (refractive index: 1.33) and diethyl ether (refractive index: 1.35); or a layer comprising a gas and having a refractive index of substantially 1, such as air, nitrogen, argon or a vacuum layer, for example.
  • the low refractive index layer of the storage panel including a protective layer supporting member is preferably a gas layer or vacuum layer to prevent a lowering in sharpness.
  • the thickness of the low refractive index layer is generally from 0.05 ⁇ m to 3 mm.
  • the low refractive index layer and the stimulable layer should be adhered to one another.
  • the low refractive index layer is a liquid layer, a gas layer or a vacuum layer, it may be as such, but when the low refractive index layer is formed on the surface of the protective layer with the above-mentioned CaF2, Na3AlF6, MgF2, SiO2, etc., the stimulable layer and the low refractive index layer are adhered with the use of an adhesive, for example.
  • the refractive index of the adhesive should preferably approximate to that of the stimulable layer.
  • any material capable of shielding the low refractive index layer from the external atmosphere can be used without particular limitation, including glasses, ceramics, metals and plastics.
  • the protective layer supporting member preferably has a moisture permeability of 10 g/m2 ⁇ 24 hr or less. If the moisture permeability is too great, the stimulable phosphor will undesirably deteriorate due to water penetration from the outside.
  • the thickness of the protective layer supporting member (a in Fig. 2) may be the thickness of the stimulable layer or thicker. That is, the thickness of the protective layer supporting member is generally equal to or greater than the thickness of the stimulable layer.
  • the case where the protective layer and the stimulable layer have the same thickness is, for example, the case where the low refractive index layer is a vacuum layer.
  • the low refractive index layer is sufficient if there exists a vacuum layer so as to be optically discontinuous between the stimulable layer and the protective layer, and therefore the two layers may be in contact with each other.
  • the thickness of the low refractive index layer can be determined in relation to the thickness of the low refractive index layer to be formed.
  • the width of the protective layer supporting member (b in Fig. 2) is determined in relation to the humidity preventive characteristic (above-mentioned moisture permeability) of the adhered portions between the protective layer supporting member and the support and the protective layer, and is preferably 1 to 30 mm.
  • the width of the protective layer supporting member is too small, it is not preferred for stability, strength and humidity preventive characteristic of the protective layer supporting member.
  • the storage panel becomes unnecessarily enlarged. It is preferred that the moisture permeability of the portion between the protective layer supporting member and the support and the protective layer should be 10 g/m2 ⁇ 24 hr or less.
  • the protective layer supporting member should be adhered to the support and the protective layer for imparting humidity preventive characteristic and for maintaining the layer thickness of the low refractive index layer constant.
  • an adhesive may be employed and one having humidity preventive characteristics is preferred.
  • organic polymeric adhesives such as epoxy resins, phenol type resins, cyanoacrylate resins, vinyl acetate resins, vinyl chloride resins, polyurethane resins, acrylic resins, ethylene-vinyl acetate resins, polyolefinic resins, chloroprene rubbers or nitrile rubbers, for example, or silicone adhesives.
  • epoxy resins or silicone resins used for encapsulation of semiconductors or electronic parts are preferred for excellent humidity resistance, and particularly epoxy resins for low moisture permeability.
  • the stimulable phosphor constituting the stimulable layer in the storage panel of the present invention is a phosphor exhibiting stimulation emission corresponding to the irradiation dosage of the initial light or high energy radiation by optical, thermal, mechanical, chemical or electrical stimulation (stimulation excitation) after irradiation of the initial light or high energy radiation, and is preferably a phosphor which exhibits stimulation emission by an excitation light of 500 nm or higher.
  • Examples of such stimulable phosphors may include the phosphors as represented by BaSO4:Ax as disclosed in Japanese Provisional Patent Publication No. 80487/1973, SrSO4:Ax as disclosed in Japanese Provisional Patent Publication No. 80489/1973, Li2B4O7Cu,Ag, etc.
  • the ZnS:Cu,Pb phosphor the barium aluminate phosphor represented by the formula BaO ⁇ xAl2O3:Eu, and the alkaline earth metal silicate type phosphor represented by the formula M II O ⁇ xSiO2:A as disclosed in Japanese Provisional Patent Publication No. 12142/1980.
  • the alkaline earth fluoride halide phosphor represented by the formula (Ba 1-x-y Mg x Ca y )FX:eEu as disclosed in Japanese Provisional Patent Publica-tion No. 12143/1980
  • the phosphor represented by the formula LnOX:xA as disclosed in Japanese Provisional Patent Publica-tion No.
  • the phosphors represented by the formulae ZnS:A, (Zn,Cd)S:A, ZnS:A,X and CdS:A,X the phosphor represented by either one of the following formulae xM3(PO4)2 ⁇ NX2:yA M3(PO4)2:yA as disclosed in Japanese Provisional Patent Publication No. 8278/1984, the phosphor represented by either one of the following formulae nRex3 ⁇ maX′2 ⁇ xEu, nReX3 ⁇ mAX′2:xEu,ySm as disclosed in Japanese Provisional Patent Publication No.
  • an alkali halide phosphor represented by the formula M I X ⁇ aM II X′2 ⁇ bm III X ⁇ :cA as disclosed in Japanese Provisional Patent Publication No. 72087/1986.
  • an alkali halide phosphor is preferred because a stimulable layer can be readily formed according to such method as vapor deposition or sputtering.
  • the stimulable phosphor to be used in the storage panel of the present invention is not limited to the phosphors as described above, as any phosphor may be employed which can exhibit stimulation emission when stimulation excitation light is irradiated (after irradiation).
  • the stimulable layer in the storage panel of the present invention may be one containing at least one stimulable phosphor as described above or a group of stimulable layers comprising two or more stimulable layers. Also, the stimulable phosphors contained in the respective layers may be the same or different.
  • the layer thickness of the stimulable layer of the storage panel may depend on the sensitivity of the desired storage panel to radiation and the kind of the stimulable phosphor, for example, but when no binder is used, may be preferably from 10 to 1000 ⁇ m, more preferably 20 to 800 ⁇ m, and when binder is used, it may preferably be 20 to 1000 ⁇ m, more preferably 50 to 500 ⁇ m.
  • the support to be used in the present invention may include various polymeric materials, glasses, ceramics and metals.
  • polymeric materials include films of cellulose acetate, polyester, polyethylene terephthalate, polyamide, polyimide, triacetate and polycarbonate.
  • metal sheets or plates of aluminum, iron, copper or chromium or metal sheets or plates having coated layers of said metal oxides may be included.
  • glass chemically reinforced glasses and crystallized glasses may be included.
  • ceramics sintered plates of alumina or zirconia may be included.
  • the layer thickness of these supports may differ depending on the material of the support used, but is generally 80 ⁇ m to 5 mm, and preferably 200 ⁇ m to 3 mm for ease in handling.
  • the surface of these supports may be smooth, or alternatively made matte for the purpose of improvement of adhesiveness with the stimulable layer.
  • the surface of the support can be also made uneven, or made to have a surface structure in which close packed fine plates shaped like tiles are arranged.
  • a subbing layer may be also provided on the surface of the support where the stimulable layer is provided for the purpose of improving adhesiveness with the stimulable layer.
  • the side edge portion of the protective layer and the support or the peripheral portion of the protective layer supporting member it is preferred to seal the side edge portion of the protective layer and the support or the peripheral portion of the protective layer supporting member.
  • glass fusion or sealing with an adhesive such as epoxy resin system are applicable.
  • the protective layer can also function as the support.
  • the storage panel of the present invention may be used in the radiation image storage method as shown schematically in Fig. 3.
  • the radiation from the radiation generating device 41 is incident on the storage panel 43 through an object 42 to be photographed.
  • the incident radiation is absorbed by the stimulable layer of the panel 43, and its energy is accumulated to form the accumulated image of the radiation transmitted image.
  • the accumulated image is excited with the stimulation excitation light from the stimulation excitation light source 44, and since the strength of the stimulation emission is proportional to the radiation energy quantity, the optical signal is converted photoelectrically by a photoelectric converting device 45 such as a photomultiplier, to reproduce it as an image by the image reproducing device 46 and display it by an image displaying device 47, whereby the radiation transmitted image of the object to be photographed can be observed.
  • a photoelectric converting device 45 such as a photomultiplier
  • an alkali halide phosphor (RbBr: 0.0006Tl) was vapor deposited by a vacuum deposition device to a thickness of 300 ⁇ m to form a stimulable layer.
  • a protective layer with the thickness and the haze ratio as shown in Table 2 CaF2 (refractive index: 1.25) was vapor deposited to a thickness of 0.1 ⁇ m to provide a low refractive index layer.
  • the above support and protective layer were adhered so that each stimulable layer was in contact with the low refractive index layer with an epoxy resin type adhesive to obtain a storage panel.
  • Soda glasses (A) and (B) have the same composition, but are different in the extent of polishing.
  • PET (a) is the transparent type
  • (b) is the commercially available standard type
  • (c) is the hazy type.
  • the image storage panels obtained in these Examples and Comparative examples were vacuum dried at 80 °C and 10 ⁇ 3 torr for one hour, and then the support and the side edge portion of the glass protective layer and the peripheral portion of the protective layer supporting member were sealed with an epoxy type adhesive to provide samples. For these samples, sharpness according to MTF was evaluated. Table 4 shows MTF at spatial frequencies of 1 lp/mm and 2 lp/mm.
  • the storage panels of the present invention have excellent sharpness, but the storage panels of Comparative examples with great haze ratios of the protective layers have lower sharpness.
  • an alkali halide phosphor (RbBr: 0.0006Tl) was vapor deposited by a vapor deposition device to a thickness of 300 ⁇ m to form a stimulable layer.
  • a glass sheet with a width of 5 mm and a thickness of 1 mm was adhered with an epoxy resin type adhesive so as to surround the above stimulable layer.
  • vacuum drying was effected at 80 °C and 10 ⁇ 3 Torr for one hour.
  • the other surface of the above glass sheet was adhered to each protective layer having a haze ratio as shown in Table 4 in the same manner as described above.
  • the storage panels of the present invention have excellent sharpness, but the panels of Comparative examples with great haze ratios of the protective layers have low sharpness.
  • the image storage panel of the present invention has excellent sharpness due to small expansion of the stimulation excitation light by scanning of the light within the protective layer.

Description

  • This invention relates to a radiation image storage panel having a stimulable phosphor layer, more particularly to a radiation image storage panel having excellent sharpness of image due to small spreading of stimulation excitation light by scattering of light within the protective layer.
  • A radiation image such as X-ray image has been frequently used for diagnosis of disease, etc.
  • For obtaining such an X-ray image, attempts have been made to devise an X-ray image storage method which takes out directly an image from the phosphor layer in place of a silver halide photosensitive material.
  • This method is a method in which radiation (generally X-ray) transmitted through an object to be photographed is absorbed onto a phosphor, and then the phosphor is excited by, for example, light or heat energy, thereby radiating the radiation energy accumulated in the phosphor by the above radiation absorption as fluorescent light, and the fluorescent light is detected to form an image.
  • Specifically, for example, U.S. Patent No. 3,859,527 and Japanese Provisional Patent Publication No. 12144/1980 disclose radiation image storage methods with visible light rays or IR-rays as the stimulation excitation light by use of a stimulable phosphor.
  • This method comprises using a radiation image storage panel (hereinafter abbreviated as "storage panel") having a stimulable phosphor layer (hereinafter abbreviated as "stimulable layer") formed on a support, and radiation having passed through an object to be photographed is irradiated on the stimulable layer of the storage panel to form a latent image through accumulation of the radiation energy corresponding to the radiation transmittance at the respective portions of the object to be photographed, and thereafter the stimulable layer is scanned with a stimulation excitation light, thereby irradiating the radiation energy accumulated in the respective portions to convert it to light and obtain an image according to the optical signals depending on the intensity of the light.
  • The final image may be reproduced as a hard copy or reproduced on CRT.
  • The storage panel used in the radiation image storage panel releases the accumulated energy by scanning of the stimulation excitation light after accumulation of the radiation image information, and therefore accumulation of the radiation image can be effected again after scanning, so that repeated use is possible.
  • Accordingly, the above storage panel should desirably be able to withstand repeated use for a long time without deterioration of the radiation image obtained. For that purpose, the stimulable layer of the above storage panel should be protected sufficiently from external physical or chemical stimulations.
  • Such a panel is disclosed in EP-A-102089.
  • In the storage panels of the prior art, a protective layer for covering the stimulable layer surface on the support of the storage panel has been provided in order to solve the above problem. Such protective layer may be formed by coating directly a coating solution for the protective layer on a stimulable layer or by adhering a protective layer previously formed separately on a stimulable layer, as disclosed in Japanese Provisional Patent Publication No. 42500/1984.
  • As the protective layer, a thin protective layer comprising an organic polymer is generally used. Such a thin protective layer is used because a reduction in the sharpness of the storage panel should be prevented.
  • The relationship between sharpness and protective layer thickness of a storage panel having a stimulable layer is shown in Table 1 by use of MTF (modulation transfer function) at a spatial frequency of 1 lp/mm and 2 lp/mm. In Table 1, PET is a polyethylene terephthalate film.
    Figure imgb0001
  • As shown in Table 1, sharpness is lowered as the protective layer is thicker. It is believed that the reason for this is that the reflected scattered light of the incident stimulation excitation light against the stimulable layer surface is reflected against the protective layer-air interface to be reincident on the stimulable layer. The reflected scattered light will go farther as the protective layer is thicker to entrain information of a pixel other than the target pixel, whereby sharpness is lowered.
  • In the general type screen-film system to be used in X-ray photographing, MTF exhibits about 65 % in the case of 1 lp/mm and about 35 % in the case of 2 lp/mm. It is therefore preferred that in the storage panel the MTF should not be inferior to that of the above screen-film system so that the thickness of the protective layer is desirably 10 µm or less.
  • However, a thin protective layer of an organic polymer conventionally used is permeable to some extent to water and/or humidity, and therefore the stimulable layer absorbs water which results in a great lowering in radiation sensitivity of the storage panel or attenuation of the accumulated energy until receiving stimulation excitation light irradiation, whereby variations and/or deterioration in image quality of the radiation image obtained is brought about.
  • For example, moisture permeability of PET with a thickness of 10 µm is about 60 (g/m²·24 hr), and as much as 60 g of water permeates per unit area per day. In an oriented polypropylene (hereinafter abbreviated as "OPP") with a film thickness of 10 µm, it is about 15 (g/m²·24 hr).
  • Thus, although the defect on account of a thin layer can be cancelled by making the protective layer thicker, sharpness will be lowered. It is therefore, desired to have improvements in aspects of humidity resistance, strength and impact resistance without impairing sharpness.
  • As described above, in the storage panel using a stimulable phosphor of the prior art, when a thin protective layer is used in order to improve sharpness of the image, variations and deterioration of the radiation image obtained will be generated particularly by penetration of water or humidity from the outside, and also there is the problem that breaking of the stimulable layer, etc. may be caused by physical stimulation from outside. On the other hand, when a thick protective layer is used for the purpose of protection from such chemical and physical stimulations, there sometimes occurs a lowering in image quality depending on the optical properties of the protective layer. More specifically, there is the problem that sharpness of the image is lowered, because the degree of expansion due to scattering of the excited light internally of the protective layer amplified is greater as the protective layer is thicker.
  • Accordingly, an object of the present invention is to provide a durable and use-resistant storage panel which can protect sufficiently the stimulable layer against physical stimulation and chemical stimulation, particularly water without impairing sharpness of the image at all, and can be used under ordinary conditions while maintaining high sensitivity, high sharpness and high graininess of the stimulable layer for a long term.
  • The storage panel of the present invention has a stimulable phosphor layer, a low refractive index layer and a protective layer in this order on a support, the protective layer having a haze ratio of 3 % or less as defined according to JIS K6714 (Japanese Industrial Standard, Methacryl resin plates for air plane, JIS K6714-1977, pp. 13 to 14).
  • Fig. 1 and Fig. 2 are schematic sectional views of radiation image storage panels of the present invention and Fig. 3 is a schematic view of a radiation image storage method using the storage panel of the present invention.
  • The construction of the storage panels A and B can be described by referring to the accompanying drawings. Fig. 1 and Fig. 2 are schematic sectional views each showing an example of a storage panel of the present invention. The numerals in the drawings show the following, namely 1 is a protective layer, 2 is a low refractive index layer, 3 is a stimulable layer, 4 is a support and 5 is a protective layer supporting member.
  • The storage panel of the present invention, as shown in Fig. 1, has a stimulable layer 3, a low refractive index layer 2 and a protective layer 1 in this order on a support 4. Also, in the storage panel of the present invention, as shown in Fig. 2, it may also has a protective layer supporting member 5. One end of the protective layer supporting member 5 is adhered to the support 4, and the other end is adhered to the protective layer 1. The peripheral portion of the stimulable layer 3 and the protective layer supporting member 5 may be in contact or apart from each other. Accordingly, in the case of a storage panel having the protective layer supporting member 5 as a constituent element, the low refractive index layer 2 is constructed shielded from the outer atmosphere with the protective layer 1, the stimulable layer 3 (or stimulable layer 3 and support 4) and the protective layer supporting member 5.
  • The protective layer in the storage panel of the present invention has a haze ratio (haze value) as defined according to JIS K6714 of 3 % or less, preferably 1 % or less. When the haze ratio exceeds 3 %, expansion of the stimulation excitation light becomes greater due to expansion of scattering of light internally of the protective layer, whereby sharpness of the image is lowered.
  • The haze value as defined in JIS K6714 is expressed by the ratio of transmittance of diffused light to the transmittance of whole light in terms of percent (%).
  • The protective layer should otherwise have good light transmitting characteristics and also be moldable into a sheet. Further, the protective layer, for permitting transmission of stimulation excitation light and stimulation emission with good efficiency, preferably exhibits high transmittance over wide wavelength range, preferably a transmittance of 80 % or higher.
  • The thickness of the protective layer is determined in relation to the haze ratio and the humidity preventive characteristics of the constituent material, but it is practically 10 µm to 4 mm, and preferably 100 µm or more for having a certain haze ratio and obtaining good humidity preventive characteristics. When the protective layer has a thickness of 500 µm or more, a storage panel with excellent durability and use resistance can be obtained.
  • As the material for forming such a protective layer, for example plate glasses such as of quartz, borosilicate glass and chemically reinforced glass, organic polymeric compounds such as PET, OPP and polyvinyl chloride may be included. For example, a borosilicate glass with a thickness of 500 µm has a haze ratio of 0.6 % and exhibits a transmittance of 80 % or higher within the wavelength range of 330 nm to 2.6 µm. An example of a quartz glass with a thickness of 500 µm has a haze ratio of 0.0 % and exhibits higher transmittance even at shorter wavelength than in the case of the borosilicate glass.
  • The haze ratio will vary depending on the thickness of the protective layer and the surface treatment. If the protective layer is a plate glass, one having a higher polishing grade has generally a lower haze ratio. On the other hand, if it is a plastic film, one which has been laminated or one with the surface subjected to matting or embossing working has generally a higher haze ratio.
  • As the material for forming the protective layer, the above-mentioned plate glass is preferred for excellent transmittance and humidity preventive characteristic along with haze ratio.
  • Also, provision of a reflection preventive layer such as MgF₂ is preferred for permitting transmission of the stimulation excitation light and stimulation emission as well as for the effect of making lowering in sharpness smaller.
  • The refractive index of the protective layer is not particularly limited, but it is generally within the range of 1.4 to 2.0 in practical applications.
  • The protective layer can be provided as two or more layers, if desired.
  • The low refractive index layer of the storage panel of the present invention is a layer comprising a material having lower refractive index than the protective layer. The material for constituting the low refractive index layer is not limited, provided that it has a lower refractive index than the protective layer.
  • In a storage panel containing no protective layer supporting member, a low refractive index layer is present as shown in Fig. 1 between the protective layer and the stimulable layer.
  • The low refractive index layer can be a layer comprising, for example, CaF₂ (refractive index: 1.23 - 1.26), Na₃AlF₆ (refractive index: 1.35), MgF₂ (refractive index: 1.38) or SiO₂ (refractive index: 1.46), for example. The low refractive index layer can be applied according to a physical vapor deposition method such as vacuum deposition on the surface of the stimulable layer and the protective layer or a thin film formed previously according to a similar method is laminated on the surface of the stimulable layer or the protective layer.
  • In the storage panel comprising the protective layer supporting member, the low refractive index layer is shielded by the protective layer supporting member from the external atmosphere. Thus, by use of a protective layer supporting member, the thickness of the protective layer can be made substantially thicker, whereby humidity preventive characteristic and durability of the storage panel can be further improved.
  • As the low refractive index layer, the same material as described above can be used, but when a protective layer supporting member is included, for example, it is preferably made using a liquid such as ethanol (refractive index: 1.36), methanol (refractive index: 1.33) and diethyl ether (refractive index: 1.35); or a layer comprising a gas and having a refractive index of substantially 1, such as air, nitrogen, argon or a vacuum layer, for example.
  • The low refractive index layer of the storage panel including a protective layer supporting member is preferably a gas layer or vacuum layer to prevent a lowering in sharpness.
  • The thickness of the low refractive index layer is generally from 0.05 µm to 3 mm.
  • In order to impart sufficiently the reduction in sharpness lowering to the low refractive index layer used in the present invention, the low refractive index layer and the stimulable layer should be adhered to one another. Accordingly, when the low refractive index layer is a liquid layer, a gas layer or a vacuum layer, it may be as such, but when the low refractive index layer is formed on the surface of the protective layer with the above-mentioned CaF₂, Na₃AlF₆, MgF₂, SiO₂, etc., the stimulable layer and the low refractive index layer are adhered with the use of an adhesive, for example. In this case, the refractive index of the adhesive should preferably approximate to that of the stimulable layer.
  • As the protective layer supporting member to be used in the storage panel of the present invention, any material capable of shielding the low refractive index layer from the external atmosphere can be used without particular limitation, including glasses, ceramics, metals and plastics.
  • The protective layer supporting member preferably has a moisture permeability of 10 g/m²·24 hr or less. If the moisture permeability is too great, the stimulable phosphor will undesirably deteriorate due to water penetration from the outside.
  • The thickness of the protective layer supporting member (a in Fig. 2) may be the thickness of the stimulable layer or thicker. That is, the thickness of the protective layer supporting member is generally equal to or greater than the thickness of the stimulable layer.
  • The case where the protective layer and the stimulable layer have the same thickness is, for example, the case where the low refractive index layer is a vacuum layer. In this case, the low refractive index layer is sufficient if there exists a vacuum layer so as to be optically discontinuous between the stimulable layer and the protective layer, and therefore the two layers may be in contact with each other.
  • When the thickness of the protective layer supporting member exceeds the thickness of the stimulable layer, the thickness of the low refractive index layer can be determined in relation to the thickness of the low refractive index layer to be formed.
  • The width of the protective layer supporting member (b in Fig. 2) is determined in relation to the humidity preventive characteristic (above-mentioned moisture permeability) of the adhered portions between the protective layer supporting member and the support and the protective layer, and is preferably 1 to 30 mm. When the width of the protective layer supporting member is too small, it is not preferred for stability, strength and humidity preventive characteristic of the protective layer supporting member. On the other hand, if it is too large, the storage panel becomes unnecessarily enlarged. It is preferred that the moisture permeability of the portion between the protective layer supporting member and the support and the protective layer should be 10 g/m²·24 hr or less.
  • It is required that the protective layer supporting member should be adhered to the support and the protective layer for imparting humidity preventive characteristic and for maintaining the layer thickness of the low refractive index layer constant. Here, for making the protective layer supporting member adhered to the support and the protective layer, for example, an adhesive may be employed and one having humidity preventive characteristics is preferred. Specifically, there can be employed organic polymeric adhesives such as epoxy resins, phenol type resins, cyanoacrylate resins, vinyl acetate resins, vinyl chloride resins, polyurethane resins, acrylic resins, ethylene-vinyl acetate resins, polyolefinic resins, chloroprene rubbers or nitrile rubbers, for example, or silicone adhesives. Among them, epoxy resins or silicone resins used for encapsulation of semiconductors or electronic parts are preferred for excellent humidity resistance, and particularly epoxy resins for low moisture permeability.
  • Also, for the purpose of enhancing adhesion at the adhered portion between the protective layer supporting member and the support or between the protective layer supporting member and the protective layer, it is possible to provide a subbing layer or apply a roughening treatment at the contact surface of the protective layer supporting member, the support and the protective layer with the other layer.
  • The stimulable phosphor constituting the stimulable layer in the storage panel of the present invention is a phosphor exhibiting stimulation emission corresponding to the irradiation dosage of the initial light or high energy radiation by optical, thermal, mechanical, chemical or electrical stimulation (stimulation excitation) after irradiation of the initial light or high energy radiation, and is preferably a phosphor which exhibits stimulation emission by an excitation light of 500 nm or higher. Examples of such stimulable phosphors may include the phosphors as represented by BaSO₄:Ax as disclosed in Japanese Provisional Patent Publication No. 80487/1973, SrSO₄:Ax as disclosed in Japanese Provisional Patent Publication No. 80489/1973, Li₂B₄O₇Cu,Ag, etc. as disclosed in Japanese Provisional Patent Publication No. 39277/1978, Li₂O·(B₂O₂)x:Cu and Li₂O·(B₂O₂)x:Cu,Ag, etc. as disclosed in Japanese Provisional Patent Publication No. 47883/1979, SrS:Ce,Sm, SrS:Eu,Sm, La₂O₂S:Eu,Sm and (Zn,Cd)S:Mn,X as disclosed in U.S. Patent No. 3,859,527.
  • Also, there may be included the ZnS:Cu,Pb phosphor, the barium aluminate phosphor represented by the formula BaO·xAl₂O₃:Eu, and the alkaline earth metal silicate type phosphor represented by the formula MIIO·xSiO₂:A as disclosed in Japanese Provisional Patent Publication No. 12142/1980. Further, there may be included the alkaline earth fluoride halide phosphor represented by the formula

            (Ba1-x-yMgxCay)FX:eEu


    as disclosed in Japanese Provisional Patent Publica-tion No. 12143/1980, the phosphor represented by the formula LnOX:xA as disclosed in Japanese Provisional Patent Publica-tion No. 12144/1980, the phosphor represented by the formula

            (Ba1-xMII x)FX:yA


    as disclosed in Japanese Provisional Patent Publication No. 12145/1980, the phosphor represented by the formula

            BaFX:xCe,yA


    as disclosed in Japanese Provisional Patent Publication No. 84389/1980, the rare earth element activated divalent metal fluorohalide phosphor represented by the formula

            MIIFX·xA:yLn


    as disclosed in Japanese Provisional Patent Publication No. 160078/1980, the phosphors represented by the formulae ZnS:A, (Zn,Cd)S:A, ZnS:A,X and CdS:A,X, the phosphor represented by either one of the following formulae

            xM₃(PO₄)₂·NX₂:yA



            M₃(PO₄)₂:yA


    as disclosed in Japanese Provisional Patent Publication No. 8278/1984, the phosphor represented by either one of the following formulae

            nRex₃·maX′₂·xEu,



            nReX₃·mAX′₂:xEu,ySm


    as disclosed in Japanese Provisional Patent Publication No. 155487/1984 and the alkali halide phosphor represented by the formula

            MIX·aMIIX′₂·bmIIIX˝:cA


    as disclosed in Japanese Provisional Patent Publication No. 72087/1986. Particularly, an alkali halide phosphor is preferred because a stimulable layer can be readily formed according to such method as vapor deposition or sputtering.
  • However, the stimulable phosphor to be used in the storage panel of the present invention is not limited to the phosphors as described above, as any phosphor may be employed which can exhibit stimulation emission when stimulation excitation light is irradiated (after irradiation).
  • The stimulable layer in the storage panel of the present invention may be one containing at least one stimulable phosphor as described above or a group of stimulable layers comprising two or more stimulable layers. Also, the stimulable phosphors contained in the respective layers may be the same or different.
  • The layer thickness of the stimulable layer of the storage panel may depend on the sensitivity of the desired storage panel to radiation and the kind of the stimulable phosphor, for example, but when no binder is used, may be preferably from 10 to 1000 µm, more preferably 20 to 800 µm, and when binder is used, it may preferably be 20 to 1000 µm, more preferably 50 to 500 µm.
  • The support to be used in the present invention may include various polymeric materials, glasses, ceramics and metals.
  • Examples of polymeric materials include films of cellulose acetate, polyester, polyethylene terephthalate, polyamide, polyimide, triacetate and polycarbonate. As the metal, metal sheets or plates of aluminum, iron, copper or chromium or metal sheets or plates having coated layers of said metal oxides may be included. As the glass, chemically reinforced glasses and crystallized glasses may be included. As the ceramics, sintered plates of alumina or zirconia may be included.
  • The layer thickness of these supports may differ depending on the material of the support used, but is generally 80 µm to 5 mm, and preferably 200 µm to 3 mm for ease in handling.
  • The surface of these supports may be smooth, or alternatively made matte for the purpose of improvement of adhesiveness with the stimulable layer. The surface of the support can be also made uneven, or made to have a surface structure in which close packed fine plates shaped like tiles are arranged.
  • Further, on these supports, a subbing layer may be also provided on the surface of the support where the stimulable layer is provided for the purpose of improving adhesiveness with the stimulable layer.
  • For imparting further humidity preventive characteristic to the storage panel of the present invention, it is preferred to seal the side edge portion of the protective layer and the support or the peripheral portion of the protective layer supporting member. As the method for such sealing, glass fusion or sealing with an adhesive such as epoxy resin system are applicable.
  • In the storage panel of the present invention, the protective layer can also function as the support.
  • The storage panel of the present invention may be used in the radiation image storage method as shown schematically in Fig. 3.
  • More specifically, the radiation from the radiation generating device 41 is incident on the storage panel 43 through an object 42 to be photographed.
  • The incident radiation is absorbed by the stimulable layer of the panel 43, and its energy is accumulated to form the accumulated image of the radiation transmitted image.
  • Next, the accumulated image is excited with the stimulation excitation light from the stimulation excitation light source 44, and since the the strength of the stimulation emission is proportional to the radiation energy quantity, the optical signal is converted photoelectrically by a photoelectric converting device 45 such as a photomultiplier, to reproduce it as an image by the image reproducing device 46 and display it by an image displaying device 47, whereby the radiation transmitted image of the object to be photographed can be observed.
  • The present invention is described by referring to the following Examples.
  • Examples 1 to 4 and Comparative examples 1 and 2
  • On a crystallized glass support with a thickness of 1 mm, an alkali halide phosphor (RbBr: 0.0006Tl) was vapor deposited by a vacuum deposition device to a thickness of 300 µm to form a stimulable layer. Next, on the surface a protective layer with the thickness and the haze ratio as shown in Table 2, CaF₂ (refractive index: 1.25) was vapor deposited to a thickness of 0.1 µm to provide a low refractive index layer. Then, the above support and protective layer were adhered so that each stimulable layer was in contact with the low refractive index layer with an epoxy resin type adhesive to obtain a storage panel.
  • Storage panels of the Comparative examples were obtained in the same manner as in Examples.
  • Soda glasses (A) and (B) have the same composition, but are different in the extent of polishing. PET (a) is the transparent type, (b) is the commercially available standard type and (c) is the hazy type.
    Figure imgb0002
  • The image storage panels obtained in these Examples and Comparative examples were vacuum dried at 80 °C and 10⁻³ torr for one hour, and then the support and the side edge portion of the glass protective layer and the peripheral portion of the protective layer supporting member were sealed with an epoxy type adhesive to provide samples. For these samples, sharpness according to MTF was evaluated. Table 4 shows MTF at spatial frequencies of 1 lp/mm and 2 lp/mm.
    Figure imgb0003
  • As is apparent from the Table, the storage panels of the present invention have excellent sharpness, but the storage panels of Comparative examples with great haze ratios of the protective layers have lower sharpness.
  • Examples 5 to 8 and Comparative examples 3 and 4
  • On a crystallized glass support with a thickness of 1 mm, an alkali halide phosphor (RbBr: 0.0006Tl) was vapor deposited by a vapor deposition device to a thickness of 300 µm to form a stimulable layer. Next, on the support, a glass sheet with a width of 5 mm and a thickness of 1 mm was adhered with an epoxy resin type adhesive so as to surround the above stimulable layer. Then, vacuum drying was effected at 80 °C and 10⁻³ Torr for one hour. Next, the other surface of the above glass sheet was adhered to each protective layer having a haze ratio as shown in Table 4 in the same manner as described above. By performing a series of steps in a conventional atmosphere, storage panels of the present invention were obtained with the low refractive index layer as the air layer.
  • Also, except for having different protective layers, storage panels of Comparative examples were obtained in the same manner as in Examples.
    Figure imgb0004
  • By use of the image storage panels obtained in these Examples and Comparative examples, MTF at the spatial frequencies of 1 lp/mm and 2 lp/mm was measured as in Example 1. The results are shown in Table 5.
    Figure imgb0005
  • As is apparent from Table 5, the storage panels of the present invention have excellent sharpness, but the panels of Comparative examples with great haze ratios of the protective layers have low sharpness.
  • The image storage panel of the present invention has excellent sharpness due to small expansion of the stimulation excitation light by scanning of the light within the protective layer.

Claims (18)

  1. A radiation image storage panel comprisinq a stimulable phosphor layer, a layer having a lower refractive index than a protective layer and the protective layer in this order on a support, the protective layer having a haze ratio of 3 % or less as defined according to JIS K6714.
  2. A radiation image storage panel according to Claim 1, wherein the haze ratio is 1 % or less.
  3. A radiation image storage panel according to Claim 1 or 2, wherein the protective layer exhibits a transmittance of 80 % or higher.
  4. A radiation image storage panel according to anyone of Claims 1 to 3, wherein the protective layer has a thickness of 10 µm to 4 mm.
  5. A radiation image storage panel according to Claim 4, wherein the protective layer has a thickness of 100 µm or more.
  6. A radiation image storage panel according to Claim 5, wherein the protective layer has a thickness of 200 µm or more.
  7. A radiation image storage panel according to anyone of Claims 1 to 6, wherein the protective layer is composed of a plate glass or an organic polymeric compound.
  8. A radiation image storage panel according to Claim 7, wherein the glass plate is a quartz glass, a borosilicate glass or a chemically reinforced glass.
  9. A radiation image storage panel according to Claim 7, wherein the organic polymeric compound is polyethylene terephthalate, oriented polypropylene or polyvinyl chloride.
  10. A radiation image storage panel according to anyone of Claims 1 to 9, wherein the low refractive index layer is composed of at least one of CaF₂, Na₃AlF₆, MgF₂ and SiO₂.
  11. A radiation image storage panel according to anyone of Claims 1 to 9, wherein the low refractive index layer is composed of at least one of methanol, ethanol and diethyl ether.
  12. A radiation image storage panel according to anyone of Claims 1 to 9, wherein the low refractive index layer is composed of at least one of air, nitrogen and argon.
  13. A radiation image storage panel according to anyone of Claims 1 to 12 , wherein the low refractive index layer is a vacuum layer.
  14. A radiation image storage panel according to anyone of Claims 1 to 13, wherein the low refractive index layer has a thickness of 0.05 µm to 3 mm.
  15. A radiation image storage panel according to anyone of Claims 1 to 14, wherein the stimulable phosphor layer contains at least an alkali halide phosphor.
  16. A radiation image storage panel according to anyone of Claims 1 to 15, wherein the moisture permeability of the protective layer is 10.0 g/m²·24 hr according to JIS Z0208.
  17. A radiation image storage panel according to Claim 16, wherein the moisture permeability of the protective layer is 5.0 g/m²·24 hr according to JIS Z0208.
  18. A radiation image storage panel according to anyone of Claims 1 to 17, wherein the panel further comprises a protective layer supporting member.
EP19890306261 1988-06-21 1989-06-21 Radiation image storage panel Expired - Lifetime EP0348172B1 (en)

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Application Number Priority Date Filing Date Title
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JP151123/88 1988-06-21

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JPH077119B2 (en) * 1987-11-19 1995-01-30 コニカ株式会社 Radiation image conversion panel having an intermediate layer with restricted physical properties
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DE68917808D1 (en) 1994-10-06
EP0348172A2 (en) 1989-12-27

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