JP2006038470A - Radiation image conversion panel and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a radiation image conversion panel for improving photostimulated emission quantity greatly. <P>SOLUTION: The method for manufacturing the radiation image conversion panel 1 comprises a process for dipping a phosphor panel 4 in which a stimulable phosphor layer 3 is formed on a prescribed substrate 2 by a vapor deposition method into a halogenation agent; and a process for heating the phosphor panel 4 at 60-200°C under an atmosphere of vacuum, air, or inert gas after the dipping process. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing a radiation image conversion panel used when forming a radiation image of a subject.

  Conventionally, radiographic images such as X-ray images have been widely used for diagnosis of medical conditions in the medical field. In particular, radiographic images using intensifying screen-film systems have been developed as an imaging system that combines high reliability and excellent cost performance as a result of high sensitivity and high image quality in the long history. Used in the medical field. In recent years, computed radiography (CR (computed radiography)) using a photostimulable phosphor panel as a radiation image conversion panel has been commercialized, and high sensitivity and improvement in image quality have been continued day and night.

The above-mentioned “stimulable phosphor panel” is a type that accumulates radiation that has passed through a subject and stimulates the stored radiation to emit light with an intensity corresponding to the dose by irradiation with excitation light or the like. The photostimulable phosphor is formed in a layer on the substrate. An example of a method for producing such a photostimulable phosphor panel is disclosed in Patent Document 1. In the manufacturing method described in Patent Document 1, a photostimulable phosphor panel is manufactured by forming a photostimulable phosphor layer on a predetermined substrate by a known vapor deposition method. Heat treatment is performed (see paragraph numbers 0034 and 0035).
JP 2003-279696 A

Here, when the photostimulable phosphor panel is heat-treated as in the manufacturing method described in Patent Document 1, water components are removed from the crystals of the photostimulable phosphor, and the photostimulable light emission of the photostimulable phosphor layer is performed. However, the amount of stimulated luminescence can only be increased to a certain level by simply heat-treating the photostimulable phosphor panel. Linear noise may occur.
An object of the present invention is to drastically improve the amount of stimulated light emission.

In order to solve the above-mentioned problem, the manufacturing method of the radiation image conversion panel of the invention of claim 1
An immersion step of immersing a phosphor panel in which a photostimulable phosphor layer is formed on a predetermined substrate by a vapor deposition method in a halogenated solvent;
A heating step of heating the phosphor panel to 60 to 200 ° C. in a vacuum, air or inert gas atmosphere after the immersion step;
It is characterized by having.

The invention described in claim 2
In a state where a phosphor panel having a photostimulable phosphor layer formed on a predetermined substrate by a vapor deposition method is immersed in a halogenated solvent, the halogenated solvent is boiled at 60 to 200 ° C. It is characterized by heating.

The invention according to claim 3
In the manufacturing method of the radiation image conversion panel according to claim 1 or 2,
The halogenated solvent is a nonflammable solvent having no flash point.

The invention according to claim 4
In the manufacturing method of the radiographic image conversion panel as described in any one of Claims 1-3,
The halogenated solvent is HFE.

The invention described in claim 5
In the manufacturing method of the radiographic image conversion panel as described in any one of Claims 1-4,
The halogenated solvent contains a coloring material that absorbs excitation light.

The radiation image conversion panel of the invention according to claim 6 is,
A phosphor panel manufactured according to the method for manufacturing a radiation image conversion panel according to any one of claims 1 to 5,
A first protective film disposed on the photostimulable phosphor layer and having a peripheral edge extending outside the peripheral edge of the phosphor panel;
A second protective film disposed under the substrate and having a peripheral edge extending outside the peripheral edge of the phosphor panel;
With
The peripheral portions of the first protective film and the second protective film are fused to each other.

  In the first aspect of the invention, since the phosphor panel is not simply heated, but is immersed in a halogenated solvent and then the phosphor panel is heated, the brightness of the radiation image conversion panel after manufacture is increased. The amount of exhaust light can be dramatically improved. Therefore, it is possible to prevent the occurrence of image unevenness and linear noise in the radiographic image.

  In the invention according to claim 2, since the phosphor panel is heated by boiling the halogenated solvent in a state where the phosphor panel is immersed in the halogenated solvent instead of simply heating the phosphor panel, The amount of stimulated emission of the radiation image conversion panel can be dramatically improved. Therefore, it is possible to prevent the occurrence of image unevenness and linear noise in the radiographic image.

  In the third and fourth aspects of the invention, since the halogenated solvent is a non-flammable solvent having no flash point, the type of the halogenated solvent to be used is not considered when heating the phosphor panel. The heating temperature can be set arbitrarily.

  In the invention according to claim 5, since the halogenated solvent contains an excitation light absorbing colorant, the colorant penetrates into the stimulable phosphor layer and enters the stimulable phosphor layer. Scattering of the excited light can be prevented.

  In the invention described in claim 6, since the first and second protective films are fused to each other at the peripheral edges, the phosphor panel is sealed with the first and second protective films, and the phosphor panel It is possible to reliably prevent moisture from entering the photostimulable phosphor layer.

  The best mode for carrying out the present invention will be described below with reference to the drawings. However, the scope of the invention is not limited to the illustrated examples.

[First Embodiment]
FIG. 1 is a sectional view of a radiation image conversion panel 1 according to the present invention.
As shown in FIG. 1, the radiation image conversion panel 1 includes a phosphor panel 4 in which a stimulable phosphor layer 3 is formed on a predetermined substrate 2, and the phosphor panel 4 includes two second panels. 1 and the second protective films 5 and 6 are completely sealed.

  The substrate 2 has a rectangular shape. The substrate 2 is made of a polymer material, glass, metal, etc., and in particular, a plastic film such as cellulose acetate film, polyester film, polyethylene terephthalate, polyamide film, polyimide film, triacetate film, polycarbonate film, quartz, borosilicate It is good to be comprised by glass sheets, such as glass, chemically tempered glass, or a metal sheet which has a coating layer of metal sheets, such as aluminum, iron, copper, chromium, or those metal oxides.

  The surface 2a (upper surface in FIG. 1) of the substrate 2 may be a smooth surface or a mat surface for the purpose of improving the adhesion to the stimulable phosphor layer 3, and on the surface 2a. May be provided with an undercoat layer for the purpose of improving the adhesiveness with the photostimulable phosphor layer 3, and the excitation light is transmitted to the photostimulable phosphor layer 3 through the substrate 2 on the surface 2 a. A light reflecting layer may be provided for the purpose of preventing the incident light.

  The photostimulable phosphor layer 3 is made of a known photostimulable phosphor such as CsBr: Eu, and includes a vapor deposition method, a sputtering method, a CVD (Chemical Vapor Deposition) method, a PVD (Physical Vapor Deposition) method, and an ion plate. It is formed by a known vapor deposition method such as a ting method. The photostimulable phosphor layer 3 may be composed of one layer or may be composed of two or more layers.

FIG. 2 is an enlarged cross-sectional view of the phosphor panel 4 and is a cross-sectional view of the stimulable phosphor layer 3 viewed macroscopically.
As shown in FIG. 2, the photostimulable phosphor layer 3 has a columnar structure in which a large number of columnar crystals 3a, 3a,... Composed of photostimulable phosphors are arranged at intervals. Each columnar crystal 3 a is inclined at a predetermined angle with respect to the normal line R of the surface 2 a of the substrate 2.

  As shown in FIG. 1, the phosphor panel 4 having the above configuration includes a first protective film 5 disposed on the stimulable phosphor layer 3 and a second protective film 6 disposed below the substrate 2. Is intervening between.

  The first protective film 5 has a slightly larger area than the phosphor panel 4, and the peripheral portion of the first protective film 5 is not substantially bonded to the photostimulable phosphor layer 3 of the phosphor panel 4. It extends outside from the peripheral edge of. “The state in which the first protective film 5 is not substantially bonded to the photostimulable phosphor layer 3” means that the first protective film 5 and the photostimulable phosphor layer 3 are optically integrated. More specifically, the contact area between the first protective film 5 and the photostimulable phosphor layer 3 is the surface of the photostimulable phosphor layer 3 (the surface facing the first protective film 5). The state is 10% or less of the area.

  On the other hand, the second protective film 6 also has a slightly larger area than the phosphor panel 4, and the peripheral edge extends outward from the peripheral edge of the phosphor panel 4.

  In the radiation image conversion panel 1, the peripheral portions of the first and second protective films 5 and 6 are fused together over the entire circumference. Thereby, the phosphor panel 4 is completely sealed with the protective films 5 and 6, and moisture can be reliably prevented from entering the photostimulable phosphor layer 3 of the phosphor panel 4.

  As the first and second protective films 5 and 6, cellulose acetate, nitrocellulose, polymethyl methacrylate, polyvinyl butyral, polyvinyl formal, polycarbonate, polyester, polyethylene terephthalate, polyethylene naphthalate, polyethylene, polyvinylidene chloride, nylon, poly It is possible to use a resin film such as tetrafluoroethylene, polytrifluoride-ethylene chloride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer. it can. The resin film is easy to process, and even if the thickness is reduced to 100 μm or less, there is no problem in strength during the manufacturing process, and since it is a thin layer, it is preferable in terms of initial image quality.

The first and second protective films 5 and 6 may be laminated with an inorganic substance layer having low moisture permeability and oxygen permeability. Examples of such inorganic substances include SiO _x (SiO, SiO ₂ ), Al ₂ O ₃ , ZnO ₂ , SnO ₂ , SiC, SiN, etc. Of these, Al ₂ O ₃ and SiO _x are particularly light transmittances. It is particularly preferable because it has a high moisture permeability and oxygen permeability, that is, it can form a dense film with few cracks and micropores. SiO _x and Al ₂ O ₃ may be laminated alone, but if both are laminated, moisture permeability and oxygen permeability can be further improved. Therefore, both SiO _x and Al ₂ O ₃ are laminated. Good.

  For the lamination of the inorganic substance on the first and second protective films 5 and 6, methods such as PVD method, sputtering method, CVD method, PE-CVD (Plasma enhanced CVD) can be used. The lamination treatment may be performed after the photostimulable phosphor layer 3 is coated with a resin film, or may be performed before the photostimulable phosphor layer 3 is coated, and the lamination thickness is 0.01 to The thickness is preferably about 1 μm.

  In addition, as the first and second protective films 5 and 6, a laminated film formed by laminating a metal film such as an aluminum film may be used, or a commercially available moisture-proof resin film on which a vapor deposition layer is formed in advance. May be used. Examples of such a moisture-proof resin film include Toppan Printing Co., Ltd. GL-AE. A plurality of the above films may be laminated to form the first and second protective films 5 and 6.

  As a method for sealing the photostimulable phosphor layer 3 by the first and second protective films 5 and 6, any known method can be applied. For example, the outermost layer is made of a heat-fusible resin. The constructed moisture-proof first and second protective films 5 and 6 are arranged above and below the phosphor panel 4, and the first and second protective films 5 and 6 are positioned outside the peripheral edge of the phosphor panel 4. The photostimulable phosphor layer 3 can be sealed by heating and fusing the peripheral edges of each other with an impulse sealer.

  Then, the manufacturing method of the radiographic image conversion panel 1 which concerns on this invention is demonstrated.

FIG. 3 is a schematic drawing showing each process of the manufacturing method of the radiation image conversion panel 1 over time.
First, a predetermined substrate 2 is prepared, and a photostimulable phosphor layer 3 is formed on the substrate 2 by a known vapor deposition method (stimulable phosphor layer forming step).

  For example, the case where the photostimulable phosphor layer 3 is formed by vapor deposition among a plurality of well-known vapor deposition methods will be briefly described. As shown in FIG. It is fixed and installed on the substrate holder, and the inside of the deposition apparatus is evacuated to a vacuum state. Thereafter, the stimulable phosphor is heated and evaporated by a resistance heating method, an electron beam method or the like using the stimulable phosphor as a deposition source, and the stimulable phosphor is deposited on the surface 2a of the substrate 2 to a desired thickness. Then, the stimulable phosphor layer 3 is formed on the substrate 2.

  Here, as shown in FIG. 2, with respect to the normal R of the surface 2a of the substrate 2 fixed to the substrate holder in the vapor deposition apparatus, the incident angle of the vapor flow of the stimulable phosphor is θ2, and the columnar shape to be formed is formed. Assuming that the tilt angle of the crystal 3a is θ1, the tilt angle θ1 is empirically about half of the incident angle θ2, and a large number of columnar crystals 3a, 3a,... Are formed at the tilt angle θ1 corresponding to the incident angle θ2. That is, if the vapor flow of the stimulable phosphor is incident on the surface 2a of the substrate 2 at an incident angle θ2 = 60 °, a large number of columnar crystals 3a having an inclination angle θ1 = 30 ° are incident on the surface 2a of the substrate 2. 3a,... Can be formed.

  As a method of supplying the vapor flow of the stimulable phosphor to the surface 2a of the substrate 2 at a predetermined incident angle, a method of arranging the substrate 2 to be inclined with respect to the vapor deposition source, There is a method in which only the oblique components of the vapor flow of the stimulable phosphor are evaporated from the vapor deposition surface by installing them in parallel with each other by a slit or the like.

  When the photostimulable phosphor layer forming step is finished, as shown in FIG. 3B, the phosphor panel 4 having the photostimulable phosphor layer 3 formed on the substrate 2 is immersed in a halogenated solvent for a predetermined time. (Immersion process)

  “Halogenated solvent” that can be used in the dipping process is a hydrocarbon compound consisting of carbon and hydrogen atoms, in which at least one of the hydrogen atoms is replaced with a fluorine, chlorine, bromine or iodine atom belonging to the halogen group element. Which is a liquid at room temperature and pressure. The halogenated solvent may structurally be a compound in which the bonds between elements are composed of only saturated bonds, a compound containing unsaturated bonds, or a cyclic compound. It may be a chain compound, or a compound in which atoms or molecules in the compound are substituted with a hydroxyl group, an ether group, a carbonyl group, a carboxyl group, or the like.

As a preferable compound as the halogenated solvent,
(1) Points to be subjected to heat treatment (see below) (Characteristics such as having no flash point are required from the viewpoint of fire fighting law related to flammability and explosiveness)
From this point of view, it is preferable to apply a nonflammable solvent having no flash point. In this case, in the heating step described later, the heating temperature can be arbitrarily set without considering the type of halogenated solvent to be used.

Furthermore, including the viewpoint of (1) above,
(2) Environmental suitability (3) From the viewpoints of harmfulness to living organisms, it has been considered that chlorofluorocarbon substitute materials, which have been discussed recently, are useful. Among them, “HFE (hydrofluoroether)” which is the latest fluorocarbon substitute material excellent in the above (2) and (3) can be suitably used as the halogenated solvent.

  HFE consists of carbon, fluorine, hydrogen, one or more ether oxygen atoms, and may further contain one or more additional heteroatoms, such as sulfur or trivalent nitrogen atoms, incorporated into the carbon backbone. . HFE may have a straight chain shape, may have a branched shape, may have a ring shape, or may have a structure composed of a combination thereof, for example, Alkyl alicyclic may also be used. However, it is preferable that HFE does not contain an unsaturated bond.

  As a specific HFE, a compound represented by the following general formula (4) can be used as an example.

(R ⁴ -O) _a -R ⁵ (4)

In the general formula (4), “a” is a number from 1 to 3, and “R ⁴ ” and “R ⁵ ” are groups selected from the group consisting of an alkyl group and an aryl group, and are the same as each other. It may be different or different. At least one of “R ⁴ ” and “R ⁵ ” includes at least one fluorine atom and at least one hydrogen atom, and one of “R ⁴ ” and “R ⁵ ”. Or both may contain one or more hetero atoms in the chain, and HFE preferably has a total number of fluorine atoms in the HFE equal to or greater than the total number of hydrogen atoms. “R ⁴ ” and “R ⁵ ” may be linear, branched, cyclic, or more specifically one or more unsaturated groups. Although it may contain a carbon-carbon bond, both “R ⁴ ” and “R ⁵ ” are preferably atomic groups in which each element is saturatedly bonded.

  Examples of HFEs having such properties include Novec (registered trademark) HFE-7100, 7100DL, 7200 manufactured by Sumitomo 3M Limited, HFE-S7 (trade name) manufactured by Daikin Industries, Ltd., and the like. HFE can be suitably used as a halogenated solvent that can be used in the dipping process.

  The halogenated solvent may contain a “coloring material” that absorbs excitation light. Since the coloring material is contained in the halogenated solvent, the coloring material penetrates to every corner of the gap between the columnar crystals 3a in the dipping process, and prevents scattering of excitation light incident on the gap between the columnar crystals 3a. can do.

  The color material to be used is preferably determined according to the type of stimulable phosphor. In the radiation image conversion panel 1, a stimulable phosphor that exhibits a stimulable light emission with a wavelength of 300 to 500 nm by excitation light with a wavelength of 400 to 900 nm is usually used, and as a coloring material, an organic color of blue to green is used. It is preferable to use a material or an inorganic color material.

Examples of blue to green organic colorants include Neozapon Blau 807 (BASF), Zavon First Blue 3G (Hoechst), Estrol Brill Blue N-3RL (Sumitomo Chemical Co., Ltd.), Sumacryl Blue N -3RL (manufactured by Sumitomo Chemical Co., Ltd.), D & C Blue No. 1 (made by National Aniline), Spirit Blue (made by Hodogaya Chemical Co., Ltd.), Oil Blue No. 1 603 (manufactured by Orient Co., Ltd.), Kitten Blue A (manufactured by Ciba-Geigy), Eisen Cachiron Blue GLH (manufactured by Hodogaya Chemical Co., Ltd.), Lake Blue AFH (manufactured by Kyowa Sangyo), Primocyanin 6GX (Inabata Sangyo ( Co., Ltd.), Brill Acid Green 6BH (Hodogaya Chemical Co., Ltd.), Cyanine Blue BNRS (Toyo Ink Co., Ltd.), Lionol Blue SL (Toyo Ink Co., Ltd.) and the like. On the other hand, examples of blue to green inorganic color materials include ultramarine blue, cobalt blue, cerulean blue, chromium oxide, and TiO ₂ —ZnO—CoO—NiO pigments.

  In addition to the color material, the halogenated solvent may contain a filler such as a high light absorption substance and a high light reflection substance. Filling the gaps between the columnar crystals 3a with a filler such as a highly light-absorbing substance or a highly light-reflecting substance is effective in reducing the lateral diffusion of the stimulated excitation light incident on the stimulable phosphor layer 3. It is.

  When the immersion process is completed, as shown in FIG. 3C, the phosphor panel 4 immersed in the halogenated solvent is placed in a known thermostatic chamber 10 and the interior of the thermostatic chamber 10 is vacuum, air or In an atmosphere of inert gas (nitrogen, argon, etc.), the phosphor panel 4 is heated at a temperature of 60 to 200 ° C. for a predetermined time in that state, and from each columnar crystal 3 a of the stimulable phosphor layer 3 of the phosphor panel 4. The water component is removed (heating process).

  In the heating step, the higher the heating temperature is set within a temperature range of 60 to 200 ° C., the shorter the heat treatment can be completed, and the sensitivity (luminance) of the stimulable phosphor layer 3 The image quality of the manufactured radiation image conversion panel 1 can be improved. When the heating temperature in the heating step is less than 60 ° C., it is possible to exert the above effects, but in order to obtain such effects sufficiently, the heating time must be set long, and a radiographic image The productivity of the conversion panel 1 is inferior. Therefore, the heating temperature is preferably set at 60 ° C. or higher. On the other hand, when the heating temperature in the heating step exceeds 200 ° C., harmful hydrogen halide may be generated from the halogenated solvent. Therefore, the heating temperature is preferably set to 200 ° C. or less.

  In addition, as above-mentioned, the process of a heating process is good also as one process performed continuously on the same heating conditions, However, a heating process is divided into two or more processes, and heating conditions ( The atmosphere, heating temperature, heating time, etc. in the thermostat 10 may be changed. For example, the heating process is divided into two processes, and the phosphor panel 4 is heated at 100 ° C. for 1 hour in a nitrogen atmosphere in the first heat treatment, and then in the air atmosphere in the second heat treatment. The phosphor panel 4 may be heated at 140 ° C. for 2 hours.

  Moreover, between the immersion process and the heating process, the phosphor panel 4 is placed in a thermostatic chamber 10 and heated at a predetermined temperature for a short time for the purpose of drying the phosphor panel 4 immersed in the halogenated solvent. It is good (drying process). For example, the drying process can be realized by heating the phosphor panel 4 at 100 ° C. for 2 minutes inside the thermostatic chamber 10.

  After finishing the heating process, the phosphor panel 4 is left in the constant temperature bath 10 as it is for a predetermined time, and the phosphor panel 4 is cooled until the phosphor panel 4 is lowered to a predetermined temperature (a standing cooling process). For example, the phosphor panel 4 is left in the thermostat 10 for 1 hour or longer, and the phosphor panel 4 is cooled until the phosphor panel 4 is lowered to around 50 ° C.

  When the standing cooling process is finished, the phosphor panel 4 is taken out from the thermostat 10 and the taken-out phosphor panel 4 is placed between the first and second protective films 5 and 6 as shown in FIG. The peripheral portions of the first and second protective films 5 and 6 are sandwiched and heated and fused with an impulse sealer, and the phosphor panel 4 is sealed with the first and second protective films 5 and 6 (sealing). Process). Thereby, manufacture of the radiation image conversion panel 1 is completed.

  In the sealing step, the production of the radiation image conversion panel 1 may be completed by simply attaching the first protective film 5 to the substrate 2 so as to cover the stimulable phosphor layer 3.

  In the manufacturing method of the radiation image conversion panel 1 according to the first embodiment described above, the phosphor panel 4 is not simply heated, but the phosphor panel 4 is immersed in a halogenated solvent in the immersion step, and the subsequent heating step. Since the phosphor panel 4 is heated in step 1, the amount of stimulated light emission of the manufactured radiation image conversion panel 1 can be dramatically improved. Therefore, it is possible to prevent the occurrence of image unevenness and linear noise in the radiographic image.

[Second Embodiment]
The radiation image conversion panel 1 according to the second embodiment has the same configuration as that of the radiation image conversion panel 1 according to the first embodiment. This is different from the manufacturing method described in the embodiment. Below, the manufacturing method of the radiographic image conversion panel 1 is demonstrated centering on a different process from the manufacturing method demonstrated in the said 1st Embodiment.

FIG. 4 is a drawing showing a method for manufacturing the radiation image conversion panel 1 according to the second embodiment, and is a schematic drawing expressing each step of the manufacturing method over time.
First, as shown in FIG. 4 (a), the same stimulable phosphor layer forming process as described above is performed, and after the stimulable phosphor layer forming process is finished, as shown in FIG. 4 (b). The phosphor panel 4 having the photostimulable phosphor layer 3 formed on the substrate 2 is immersed in the halogenated solvent in the container 20 containing the halogenated solvent, and the halogenated solvent is added in the state 60 to 60. The phosphor panel 4 is heated by boiling at 200 ° C. (boiling step).

As the boiling container 20, for example, a stainless steel sealed container can be applied.
In the boiling step, usable halogenated solvents are those described in the first embodiment and may contain the coloring materials and fillers described above. For the same reason as the heating temperature in the heating step described in the first embodiment, it is preferable to set within a temperature range of 60 to 200 ° C.

  When the boiling process is completed, as shown in FIG. 4C, the same drying process as described above is performed. When the drying process is completed, the same cooling process as described above is performed. When finished, as shown in FIG. 4D, the same sealing process as described above is performed, and the production of the radiation image conversion panel 1 according to the second embodiment is completed.

  In the manufacturing method for the radiation image conversion panel 1 according to the second embodiment described above, the phosphor panel 4 is not simply heated, but the halogenated solvent is immersed in the halogenated solvent in the boiling step. Since the phosphor panel 4 is heated by boiling, the amount of stimulated emission of the radiation image conversion panel 1 after manufacture can be dramatically improved. Therefore, it is possible to prevent the occurrence of image unevenness and linear noise in the radiographic image.

  In this example, a plurality of types of samples were prepared assuming a radiation image conversion panel, and the sensitivity (luminance) and image quality (the presence or absence of image unevenness and linear noise) were measured and evaluated for each sample.

(1) Preparation of sample 17 transparent crystallized glasses having a size of 10 cm × 10 cm and a thickness of 500 μm were prepared as substrates, and a light reflecting layer was formed on one surface of each substrate. The light reflecting layer was formed by vapor-depositing titanium oxide (manufactured by Furuuchi Chemical Co., Ltd.) and zirconium oxide (manufactured by Furuuchi Chemical Co., Ltd.) on a substrate using a known vapor deposition apparatus. The thickness of the light reflecting layer was adjusted so that the reflectance for light with a wavelength of 400 nm was 85% and the reflectance for light with a wavelength of 660 nm was 20%.

  Thereafter, a stimulable phosphor composed of CsBr: Eu was vapor-deposited on the light reflecting layer of each substrate, and a stimulable phosphor layer was formed on the light reflecting layer of each substrate. Specifically, first, each substrate is fixed in a vacuum chamber in the vapor deposition apparatus with the surface on which the light reflection layer of each substrate is formed facing the vapor deposition source of the vapor deposition apparatus, and the inside of the vacuum chamber is kept at 240 ° C. In this state, nitrogen gas was introduced into the vacuum chamber, and the degree of vacuum was adjusted to 0.1 Pa. At this time, the distance between the vapor deposition source and the substrate was 60 cm. Thereafter, an aluminum slit is disposed between the vapor deposition source and the substrate so that the vapor of the stimulable phosphor is incident at an angle of 30 ° with respect to the normal direction of the surface on which the light reflecting layer of the substrate is formed. did. Thereafter, vapor deposition was carried out while transporting the substrate in the surface direction, and a stimulable phosphor layer having a columnar structure with a thickness of 300 μm was formed on the light reflecting layer of each substrate, thereby producing 17 phosphor panels.

(1-1) Preparation of Sample 1 Two liquids of 12 μm-thick polyethylene terephthalate (PET12) subjected to various mat processing and 12 μm-thick PET (VMPET12, Toyo Metallizing Co., Ltd.) vapor-deposited with alumina. A reactive type urethane adhesive was used and bonded together by dry lamination to produce a protective film. Thereafter, one phosphor panel is selected from the 17 manufactured phosphor panels, and a protective film is arranged on the phosphor panel so as to cover the stimulable phosphor layer with the prepared protective film. Then, a protective film was attached to the substrate of the phosphor panel, and this was designated as “Sample 1”. Details of the manufacturing process and the like of the sample 1 are as shown in Table 1 below.

(1-2) Preparation of Sample 2 One phosphor panel was selected from the 17 manufactured phosphor panels, and the phosphor panel was placed in a well-known thermostat and 100 ° C. in an air atmosphere. For 2 hours. Thereafter, a protective film was attached to the heated phosphor panel in the same manner as in (1-1) above, and this was designated as “Sample 2”. Details of the manufacturing process and the like of the sample 2 are as shown in Table 1 below.

(1-3) Production of Sample 10 One phosphor panel was selected from the 17 produced phosphor panels, and the phosphor panel was immersed in a 10 cc halogenated solvent for 3 minutes. Thereafter, the immersed phosphor panel was placed in a known thermostat and dried at 100 ° C. for 2 minutes, and then heated at 100 ° C. for 2 hours in an air atmosphere. In the heating process here, the halogenated solvent used in the dipping process may remain attached to the phosphor panel, and it can be said that the phosphor panel is heated in the halogenated solvent atmosphere. Then, the protective film was affixed with respect to the heated fluorescent substance panel like said (1-1), and this was made into the "sample 10". Details of the manufacturing process and the like of the sample 10 are as shown in Table 1 below.

(1-4) Preparation of Samples 11 to 15 Five phosphor panels were selected from the 17 prepared phosphor panels, and each phosphor panel was replaced with 0.03% by weight of a color material (BASF Corporation). It was immersed for 3 minutes in 10 cc of a halogenated solvent containing Neozapon Blau 807). Thereafter, each immersed phosphor panel was placed in a well-known thermostat and dried at 100 ° C. for 2 minutes, and then each phosphor panel was heated under different conditions for each phosphor panel. The heating conditions for each phosphor panel were as shown in Table 1 below. In the heating process here, the halogenated solvent used in the dipping process may remain attached to the phosphor panel, and it can be said that the phosphor panel is heated in the halogenated solvent atmosphere.

  Separately from the heating step, a 12 μm thick polyethylene terephthalate (PET12) subjected to various mat processing and a 12 μm thick PET (VMPET12, manufactured by Toyo Metallizing Co., Ltd.) vapor-deposited with alumina are two-component reaction type. The first protective film is made by laminating with a urethane-based adhesive material, and then 9 μm thick aluminum foil and 100 μm thick PET are pasted together by dry lamination, and heat fusion is applied to the aluminum foil side. A second protective film was prepared by applying an adhesive lacquer.

  After producing the first and second protective films, the first protective film is disposed above the stimulable phosphor layer of each phosphor panel, and the second protective film is disposed below the substrate of each phosphor panel. In this state, these were placed in a vacuum chamber, and helium gas was introduced into the vacuum chamber while the pressure in the vacuum chamber was reduced to 200 Pa, thereby replacing the gas in the vacuum chamber. Thereafter, the atmospheric pressure in the vacuum chamber is readjusted to 7000 Pa, and the peripheral portions of the first and second protective films are fused together with an impulse sealer (with a heater width of 8 mm) under this reduced pressure. The body panel was sealed between the two first and second protective films, and these were designated as “Samples 11 to 15”, respectively. Details of the manufacturing steps and the like of the samples 11 to 15 are as shown in Table 1 below.

In Table 1, “halogenated solvent” indicates the type of halogenated solvent used in the dipping step, and specifically, “(A) to (E), (H)” are the following compounds.
(A): Sumitomo 3M Co., Ltd. Novec HFE-7100 (C ₄ F ₉ OCH ₃ )
(B): Sumitomo 3M Co., Ltd. Novec HFE-7100DL (C ₄ F ₉ OCH ₃ )
(C) ... Sumitomo 3M Novec _{HFE-7200 (C 4 F 9} OC 2 H 5)
(D) HAI-S7 (CHF ₂ CF ₂ OCH ₂ CF ₃ ) manufactured by Daikin Industries, Ltd.
(E) Asahi Clin AK-225 (CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF) manufactured by Asahi Glass Co., Ltd.
(H) ... SC52S (HCBr) manufactured by Dipsol Co., Ltd.

(1-5) Preparation of Sample 20 One phosphor panel is selected from the 17 manufactured phosphor panels, and the phosphor panel is immersed in a 100 cc halogenated solvent and halogenated in that state. The solvent was boiled at 60 ° C. for 24 hours. In the boiling treatment, a stainless steel sealed container was used as a boiling container, and 100 cc of the halogenated solvent was placed in the sealed container to boil the halogenated solvent. Thereafter, the boiled phosphor panel was placed in a known thermostatic bath and dried at 100 ° C. for 2 minutes. Thereafter, a protective film was attached to the dried phosphor panel in the same manner as in (1-1) above, and this was designated as “Sample 20”. Details of the manufacturing process of the sample 20 are as shown in Table 2 below.

(1-6) Preparation of Samples 21 to 28 Eight phosphor panels were selected from the 17 prepared phosphor panels, and 0.03% by weight of each phosphor panel (manufactured by BASF) It was immersed in 100 cc halogenated solvent containing Neozapon Blau 807), and the halogenated solvent was boiled under different conditions for each phosphor panel in that state. The boiling conditions of each phosphor panel were as shown in Table 2 below. In the boiling treatment, a stainless steel sealed container was used as a boiling container, and 100 cc of the halogenated solvent was put into the sealed container to boil the halogenated solvent. Thereafter, each of the boiled phosphor panels was placed in a well-known constant temperature bath and dried at 100 ° C. for 2 minutes. After that, each phosphor panel is sealed between two first and second protective films in the same manner as in (1-4) above for each dried phosphor panel. ~ 28 ". Details of the manufacturing steps and the like of the samples 21 to 28 are as shown in Table 2 below.

In Table 2, “halogenated solvent” indicates the type of halogenated solvent used in the boiling step, and specifically, “(A) to (H)” are the following compounds.
(A) to (E), (H) ... same as above (F) ... ZEOLORA H (annular C ₅ H ₃ F ₇ ) manufactured by ZEON CORPORATION
(G) ... eClean-21F (C ₄ H ₅ F ₅ ) manufactured by Kaneko Chemical

(2) Measurement of sensitivity (luminance) X-rays having a tube voltage of 80 kVp were irradiated from the back surfaces (surfaces on which the photostimulable phosphor layer was not formed) of each sample 1, 2, 10-15, 20-28. Thereafter, a semiconductor laser is scanned on the surface of each sample 1, 2, 10-15, 20-28 (surface on which the photostimulable phosphor layer is formed) to excite the photostimulable phosphor layer, The amount of stimulated luminescence emitted from the photostimulable phosphor layer (light intensity) is measured for each sample with a light receiver (photoelectron image multiplier of spectral sensitivity S-5), and the measured value is expressed as “sensitivity (luminance). " The measurement results are shown in Table 3 below. However, in Table 3, the values indicating the sensitivities of the samples 1, 2, 10 to 15, and 20 to 28 are relative values with the sensitivity of the sample 1 being 1.00.

(3) Evaluation of image quality (image unevenness, presence or absence of linear noise) X-ray with tube voltage of 80 kVp is used for the back surface of each sample 1, 2, 10-15, 20-28 (no photostimulable phosphor layer is formed) Surface). Thereafter, a semiconductor laser is scanned on the surface of each sample 1, 2, 10-15, 20-28 (surface on which the photostimulable phosphor layer is formed) to excite the photostimulable phosphor layer, The amount (light intensity) of the photostimulated luminescence emitted from the photostimulable phosphor layer was received for each sample by a photoreceiver (photoelectron image multiplier of spectral sensitivity S-5) and converted into an electrical signal. After that, the image based on the converted electrical signal is printed out from a known printer in a state of being magnified twice, and the image after the printout is visually observed to check the image quality (image unevenness, presence of linear noise). evaluated.

The evaluation of the image quality described above was performed twice for each sample, immediately after production (initial stage) and after being held in a temperature environment of 80 ° C. for 2 days after production. The reason why each sample was kept in a temperature environment of 80 ° C. for 2 days after the manufacture in the evaluation of image quality is that the deterioration (fluctuation) of each sample over time was evaluated in a short period of time. The evaluation results are shown in Table 3 below. However, in Table 3, the evaluation criteria of “◎”, “◯”, and “△” are as follows.
◎… No image unevenness and linear noise ○ ○: Light image unevenness and linear noise are observed in 1 and 2 places of image △… Light image unevenness and linear noise are recognized in 3 and 4 places of image

It is sectional drawing of a radiographic image conversion panel. It is an expanded sectional view of a phosphor panel. It is the schematic drawing which expressed the manufacturing method of the radiation image conversion panel over time. It is the schematic drawing which expressed the manufacturing method of the radiographic image conversion panel concerning a 2nd embodiment over time.

Explanation of symbols

1 Radiation Image Conversion Panel 2 Substrate 3 Stimulable Phosphor Layer 4 Phosphor Panel 5 First Protective Film 6 Second Protective Film

Claims (6)

An immersion step of immersing a phosphor panel in which a photostimulable phosphor layer is formed on a predetermined substrate by a vapor deposition method in a halogenated solvent;
A heating step of heating the phosphor panel to 60 to 200 ° C. in a vacuum, air or inert gas atmosphere after the immersion step;
A method for manufacturing a radiation image conversion panel.   In a state where a phosphor panel having a photostimulable phosphor layer formed on a predetermined substrate by a vapor deposition method is immersed in a halogenated solvent, the halogenated solvent is boiled at 60 to 200 ° C. A method for producing a radiation image conversion panel, comprising heating the substrate. In the manufacturing method of the radiation image conversion panel according to claim 1 or 2,
The method for producing a radiation image conversion panel, wherein the halogenated solvent is a nonflammable solvent having no flash point. In the manufacturing method of the radiographic image conversion panel as described in any one of Claims 1-3,
The method for producing a radiation image conversion panel, wherein the halogenated solvent is HFE. In the manufacturing method of the radiographic image conversion panel as described in any one of Claims 1-4,
The method for producing a radiation image conversion panel, wherein the halogenated solvent contains a coloring material that absorbs excitation light. A phosphor panel manufactured according to the method for manufacturing a radiation image conversion panel according to any one of claims 1 to 5,
A first protective film disposed on the photostimulable phosphor layer and having a peripheral edge extending outside the peripheral edge of the phosphor panel;
A second protective film disposed under the substrate and having a peripheral edge extending outside the peripheral edge of the phosphor panel;
With
The radiation image conversion panel, wherein the peripheral portions of the first protective film and the second protective film are fused to each other.

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