JP4821721B2 - Manufacturing method of radiation image conversion panel - Google Patents

Description

The present invention relates to a method for producing a radiation image conversion panel employing a phosphor.

  Radiation images such as X-ray images are often used in fields such as disease diagnosis. The X-ray image is obtained by irradiating the phosphor layer (phosphor screen) with X-rays that have passed through the subject, thereby generating visible light, and then using this visible light as when taking a normal photograph. Thus, a so-called radiographic method in which a silver halide photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material) is irradiated and then developed to obtain a visible silver image is widely used.

  However, in recent years, a new method for taking out an image directly from a phosphor layer has been developed instead of an image forming method using a photosensitive material having a silver halide salt. In this method, after the radiation transmitted through the subject is absorbed by the phosphor, the phosphor is excited by light or thermal energy, for example, so that the radiation energy accumulated by the phosphor is absorbed as fluorescence. There is a method of emitting and detecting this fluorescence and imaging.

  Specifically, for example, a radiation image conversion method using a photostimulable phosphor as described in US Pat. No. 3,859,527 and JP-A-55-12144 is known. Yes. This method uses a radiation image conversion panel using a stimulable phosphor layer containing a stimulable phosphor, and the radiation transmitted through the subject is applied to the stimulable phosphor layer of the radiation image conversion panel. , By storing radiation energy corresponding to the radiation transmission density of each part of the subject and then exciting the stimulable phosphor in time series with electromagnetic waves (excitation light) such as visible light and infrared light. Radiation energy accumulated in the body is emitted as stimulated emission, and a signal based on the intensity of this light is photoelectrically converted to obtain an electrical signal, which is used as a recording material such as a photosensitive material, CRT, etc. The image is reproduced as a visible image on the display device.

  According to the above radiographic image reproduction method, a radiographic image with abundant information can be obtained with a much smaller exposure dose as compared with a radiographic method using a combination of a conventional radiographic film and an intensifying screen. Has the advantage.

  Radiation image conversion panels using these photostimulable phosphors can store radiation image information after storing radiation image information, and can store radiation images again after scanning. Is possible. In other words, the conventional radiographic method consumes a radiographic film for each radiographing, whereas in this radiographic image conversion method, the radiographic image conversion panel is repeatedly used. It is advantageous.

  Furthermore, in recent years, a radiographic image conversion panel with higher sharpness has been required for analysis of diagnostic images. As means for improving the sharpness, for example, an attempt has been made to improve the sensitivity and sharpness by controlling the shape of the photostimulable phosphor itself.

  As one of these attempts, for example, from a fine pseudo-columnar block described in JP-A No. 61-142497, which is formed by depositing a photostimulable phosphor on a support having a fine concavo-convex pattern. There is a method using a stimulable phosphor layer.

  Further, as described in JP-A-61-142500, a crack between columnar blocks obtained by depositing a photostimulable phosphor on a support having a fine pattern is subjected to shock treatment for further development. Method using a radiation image conversion panel having a photostimulable phosphor layer formed, and further, radiation image conversion in which a photostimulable phosphor layer formed on the surface of a support is cracked from the surface side to form a pseudo columnar shape A method using a panel (see, for example, Patent Document 1), and further a method in which a stimulable phosphor layer having a cavity is formed on the upper surface of a support by vapor deposition, and then a cavity is grown by heat treatment to provide a crack, etc. (For example, refer to Patent Document 2).

  Further, there has been proposed a radiation image conversion panel having a photostimulable phosphor layer in which elongated columnar crystals having a certain inclination with respect to the normal direction of the support are formed on the support by vapor deposition (for example, And Patent Document 3).

  Recently, a radiation image conversion panel using a stimulable phosphor activated with Eu based on an alkali halide such as CsBr has been proposed, and in particular, high X-rays that have not been obtained by using Eu as an activator. It became possible to derive the conversion efficiency.

  Also known is a technique intended to improve sensitivity by evaporating one or more evaporation sources including a phosphor base material and an activator component such as EuOX or a mixture of EuOX and EuXm in an atmosphere having a predetermined oxygen partial pressure. (For example, see Patent Document 4).

Patent Document 5 discloses that when the pH value A of the phosphor layer and the pH value B of the phosphor material are in the range of 0 to 7, high brightness and high sharpness are obtained. , B difference and afterglow characteristics are not mentioned and are different from the present invention.
JP 62-39737 A JP-A-62-110200 JP-A-2-58000 Japanese Patent Laid-Open No. 2004-233134 JP 2003-344594 A

The present invention has been made in view of the above situation, the problem to be solved is to provide a radiation image conversion panel brightness, afterglow, a manufacturing method excellent radiation image conversion panel workability .

As a result of various studies, the present inventors have found that the phosphor raw material has a pH of 5.degree. 3 to 5.9 , and adjusting the difference between the pH of the phosphor material and the pH of the phosphor layer to be 0.1 to 0.6, the afterglow is reduced along with the improvement in luminance. As a result, the present invention has been achieved.

  That is, the said subject which concerns on this invention is solved by the following means.

1. In a method for manufacturing a radiation image conversion panel including a step of forming a phosphor layer by heating a deposition source containing a phosphor material and depositing a generated substance on a substrate, the pH of the phosphor material at 25 ° C. A method for producing a radiation image conversion panel, which is 5.3 to 5.9, and the difference between the pH of the phosphor material and the pH of the phosphor layer is 0.1 to 0.6.
2. 2. The method for producing a radiation image conversion panel according to item 1, wherein the phosphor layer contains a phosphor based on an alkali halide represented by the following general formula (1).
The general formula ^{(1) M 1 X · aM} 2 X '· bM 3 X ": eA
[Wherein, M ¹ is at least one alkali metal atom selected from Li, Na, K, Rb and Cs atoms, and M ² is Be, Mg, Ca, Sr, Ba, Zn, Cd, Cu. And at least one divalent metal atom selected from each atom of Ni, and M ³ is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, At least one trivalent metal atom selected from each atom of Tm, Yb, Lu, Al, Ga and In, and X, X ′ and X ″ are at least selected from each atom of F, Cl, Br and I 1 type of halogen atom, A is Eu, Tb, In, Ce, Tm, Dy, Pr, Ho, Nd, Yb, Er, Gd, Lu, Sm, Y, Tl, Na, Ag, Cu and Mg. At least one metal atom selected from each atom; And, a, b, e each represent a number between 0 ≦ a <0.5,0 ≦ b <0.5,0 ≦ e ≦ 0.2.]
3. The phosphor layer, the phosphor of alkali halide represented by the general formula (1) as a matrix is CsBr: radiation image conversion according to prior Symbol second term, which is a Eu phosphor Panel manufacturing method.

By the means of the present invention, as the radiation image conversion panel luminance afterglow characteristics, it is possible to provide a manufacturing method excellent radiation image conversion panel in workability.

The method for producing a radiation image conversion panel of the present invention includes a step of forming a phosphor layer by heating a vapor deposition source containing a phosphor raw material and depositing a generated substance on the substrate. The pH of the phosphor material at 25 ° C. is 5. 3 to 5.9 , and the difference between the pH of the phosphor material and the pH of the phosphor layer is 0.1 to 0.6. This feature is a technical feature common to the inventions according to claims 1 to 3.

(Preferred embodiment of the present invention)
The method for producing a radiation image conversion panel of the present invention includes a step of forming a phosphor layer by heating a vapor deposition source containing a phosphor raw material and depositing a generated substance on the substrate. The pH of the phosphor material at 25 ° C. is 5. 3 to 5.9 , and the difference between the pH of the phosphor material and the pH of the phosphor layer is 0.1 to 0.6. An embodiment containing a phosphor having an alkali halide represented by 1) as a base is preferable.

  In the present invention, the phosphor crystal component in the radiation image conversion panel obtained under the above conditions has a crystal structure in which columnar particles have high transparency and crystallinity (interstitial) stability is increased. It is estimated that the light characteristics have been improved.

  The pH of the phosphor material is measured under a constant temperature (25 ° C.) condition using a pH meter after the phosphor material is dissolved in pure water and sufficiently stirred. The pH of the phosphor layer is measured in the same manner as the phosphor material by collecting the phosphor film.

  When preparing a pH measurement sample, a part of the phosphor component may precipitate over time. In such a case, the pH measurement is performed immediately after sufficiently stirring the aqueous solution (aqueous dispersion).

  Hereinafter, the present invention, its components, and the best mode for carrying out the invention will be described in detail.

(Phosphor raw material)
The compound represented by the general formula (1) according to the present invention will be described.

M ¹ represents at least one alkali metal atom selected from each atom such as Na, K, Rb and Cs, among which at least one alkaline earth metal atom selected from each atom of Rb and Cs is preferable. Preferably it is a Cs atom.

M ² represents at least one divalent metal atom selected from atoms such as Be, Mg, Ca, Sr, Ba, Zn, Cd, Cu, and Ni, and among them, Be, Mg, It is a divalent metal atom selected from each atom such as Ca, Sr and Ba.

M ³ is at least selected from each atom such as Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Ga and In. One kind of trivalent metal atom is represented, and among these, a trivalent metal atom selected from each atom such as Y, Ce, Sm, Eu, Al, La, Gd, Lu, Ga and In is preferred. is there.

  A is at least selected from each atom of Eu, Tb, In, Ga, Ce, Tm, Dy, Pr, Ho, Nd, Yb, Er, Gd, Lu, Sm, Y, Tl, Na, Ag, Cu, and Mg. One kind of metal atom.

  From the viewpoint of improving the stimulated emission luminance of the compound represented by the general formula (1), X, X ′ and X ″ each represent at least one halogen atom selected from F, Cl, Br and I atoms. At least one halogen atom selected from F, Cl and Br is preferred, and a Br atom is more preferred.

  In the general formula (1), when e> 0, the compound itself represented by the general formula (1) is a phosphor, which becomes a phosphor base material.

  In the general formula (1), when e = 0, specific examples of the compound represented by the general formula (1) according to the present invention will be given.

  (A) At least one compound selected from NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbF, RbCl, RbBr, RbI, CsF, CsCl, CsBr and CsI is used.

_{(B) MgF 2, MgCl 2} , MgBr 2, MgI 2, CaF 2, CaCl 2, CaBr 2, CaI 2, SrF 2, SrCl 2, SrBr 2, SrI 2, BaF 2, BaCI 2, BaBr 2, BaBr 2 2H ₂ O, BaI ₂ , ZnF ₂ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ , CdF ₂ , CdCl ₂ , CdBr ₂ , CdI ₂ , CuF ₂ , CuCl ₂ , CuBr ₂ , CuI, NiF ₂ , NiCl ₂ , NiBr _At least one or two or more compounds selected from ₂ and NiI ₂ compounds are used.

When e = 0 in the general formula (1), it is preferable to use a mixture of the compound of the general formula (1) and the following compound (2) as the phosphor raw material.
Compound (2) At least selected from each atom of Eu, Tb, In, Ce, Tm, Dy, Pr, Ho, Nd, Yb, Er, Gd, Lu, Sm, Y, Tl, Na, Ag, Cu, and Mg A compound having one kind of atom A preferred compound (2) is a europium compound. Examples of the europium compound used in the present invention include EuX ₂ , EuX ₃ and EuOX (X is a group consisting of F, Cl, Br, I and combinations thereof). Among them, EuBr ₃ , EuBr ₂ , EuCl ₂ and EuOBr gave excellent results.

(substrate)
As the substrate used in the radiation image conversion panel of the present invention, various glasses, polymer materials, metals and the like are used. For example, plate glass such as quartz, borosilicate glass, chemically tempered glass, cellulose acetate film, polyester, etc. Examples include films, polyethylene terephthalate films, polyamide films, polyimide films, triacetate films, polycarbonate resin and other organic resin films, metal sheets such as aluminum sheets, iron sheets, and copper sheets, or metal sheets having a coating layer of the metal oxide. .

  Among these, an organic resin film is preferable. The organic resin film is controlled by controlling the substrate temperature above the softening point, so that the deposited crystal can enter the substrate. Further, the amount of penetration can be controlled not only by the substrate temperature but also by the vapor incidence speed, vapor temperature, and the like. These incident speeds and temperatures can be controlled by the temperature at which the deposition material is evaporated.

(Phosphor vapor phase growth method)
Further, the phosphor layer according to the present invention is formed by a vapor phase growth method. Vapor deposition, sputtering, CVD, ion plating, and others can be used as the vapor phase growth method of the phosphor.

  In the present invention, for example, the following methods can be mentioned.

In the vapor deposition method of the first method, after the substrate is first installed in the vapor deposition apparatus, the inside of the apparatus is evacuated to a degree of vacuum of about 1.333 × 10 ⁻⁴ Pa. Next, at least one of the phosphors is heated and evaporated by a resistance heating method, an electron beam method, or the like to grow the phosphor on the substrate surface to a desired thickness. As a result, a phosphor layer containing no binder is formed, but the phosphor layer can be formed in a plurality of times in the vapor deposition step.

  In the vapor deposition step, a plurality of resistance heaters or an electron beam may be co-deposited to synthesize the target phosphor on the substrate and simultaneously form the phosphor layer.

  After the vapor deposition is completed, a radiation image conversion panel according to the present invention is manufactured by providing a protective layer on the side opposite to the substrate side of the phosphor layer as necessary. In addition, after forming a fluorescent substance layer on a protective layer, you may take the procedure of providing a board | substrate.

  Furthermore, in the vapor deposition method, the vapor deposition target (substrate, protective layer or intermediate layer) may be cooled or heated as necessary during vapor deposition.

Moreover, you may heat-process a fluorescent substance layer after completion | finish of vapor deposition. Further, in the above evaporation process, it may be carried out reactive deposition for depositing by introducing O _2, H ₂ etc. of the gas if necessary.

In the sputtering method as the second method, as in the vapor deposition method, a substrate having a protective layer or an intermediate layer is placed in a sputtering apparatus, and then the apparatus is evacuated to a vacuum of about 1.333 × 10 ⁻⁴ Pa. Then, an inert gas such as Ar or Ne is introduced as a sputtering gas into the sputtering apparatus to obtain a gas pressure of about 1.333 × 10 ⁻¹ Pa. Next, a phosphor layer is grown to a desired thickness on the substrate by sputtering using the phosphor as a target.

  Various applied treatments can be used in the sputtering step as in the vapor deposition method.

  The third method is a CVD method, and the fourth method is an ion plating method.

  In addition, the growth rate of the phosphor layer in the vapor phase growth is preferably 0.05 to 300 μm / min. When the growth rate is less than 0.05 μm / min, the productivity of the radiation image conversion panel according to the present invention is poor, which is not preferable. Further, when the growth rate exceeds 300 μm / min, it is difficult to control the growth rate.

  When the radiation image conversion panel is obtained by the above-described vacuum deposition method, sputtering method, etc., since there is no binder, the packing density of the phosphor can be increased, and a preferable radiation image conversion panel can be obtained in terms of sensitivity and resolution. preferable.

  Although the film thickness of the phosphor layer varies depending on the purpose of use of the radiation image conversion panel and the type of phosphor, it is 50 μm to 1 mm, preferably 100 to 800 μm, more preferably from the viewpoint of obtaining the effects of the present invention. Is 100-700 μm.

  In preparation of the phosphor layer by the vapor phase growth method, the temperature of the substrate on which the phosphor layer is formed is preferably set to 40 ° C. or higher, more preferably 80 ° C. or higher, and particularly preferably 100 to 400. ° C.

(Sealing-protective film)
The protective film is for moisture-proofing the phosphor layer and suppressing deterioration of the phosphor layer, and is composed of a film with low moisture permeability. For example, a polyethylene terephthalate film (PET) can be used. Besides PET, a polyester film, a polymethacrylate film, a nitrocellulose film, a cellulose acetate film, a polypropylene film, a polyethylene naphthalate film, or the like can be used. Moreover, it can also be set as the structure which laminated | stacked several vapor deposition films which vapor-deposited metal oxide etc. on these films according to the moisture-proof property required.

  In addition, on the surfaces of the image conversion panel on the substrate side and the phosphor layer side facing each other, a fusion layer for fusing and sealing each other is formed. As the fusion layer, a resin film that can be fused with a commonly used impulse sealer can be used. For example, an ethylene vinyl acetate copolymer (EVA), a polypropene (PP) film, a polyethylene (PE) film, etc. are mentioned, However, it is not restricted to this.

  It can be sealed by sandwiching the image conversion panel between upper and lower protective films and fusing the end portions in contact with the upper and lower protective films in a reduced pressure atmosphere.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1
[Preparation of phosphor material]
A phosphor material was prepared by the following method. That is, cesium carbonate and hydrogen bromide were added and mixed and stirred, followed by filtration at the neutralization point to evaporate and evaporate the water in the filtrate to produce crystals. At this time, the amount of hydrogen bromide added was controlled so that the pH of the phosphor raw material became the value shown in Table 1.

[Production of Radiation Image Conversion Panel 1]
As phosphor materials, 1.7 g of europium oxide bromide (EuOBr) powder and 1000 g of cesium bromide (CsBr) powder were weighed and mixed in an environment with a relative humidity of 25%. Next, the phosphor raw material mixed in this way is taken into a resistance heating crucible, and the inside of the vapor deposition apparatus is evacuated to a high vacuum, and then Ar gas is introduced to become 1.0 × 10 ⁻² Pa. The degree of vacuum was adjusted as follows. Next, the resistance heating crucible was heated to vapor-deposit phosphor material at a rate of 2 μm / min, and CsBr: Eu phosphor was deposited. After vapor deposition, the inside of the apparatus was returned to atmospheric pressure, and the substrate was taken out from the apparatus. On the aluminum substrate, there was formed a phosphor layer (layer thickness: 150 μm) having a structure in which phosphor columnar crystals were densely planted in a substantially vertical direction.

  The phosphor plate thus obtained is covered with a moisture-proof protective film, and the periphery of the moisture-proof raw protective film is fused and sealed with an impulse sealer under reduced pressure to produce a radiation image conversion panel 1 did.

[Production of radiation image conversion panels 2 to 7]
Radiation image conversion panels 2 to 7 were prepared in the same manner except that the phosphor raw material having a value described in Table 1 was used in the production of the radiation image conversion panel 1.

[Evaluation]
The pH of the phosphor material was measured by dissolving 10 g of the phosphor material in 90 g of pure water and allowing to stand for 5 minutes, and then using a handy pH meter / WAT-1 manufactured by Shimadzu Corporation under a constant temperature (25 ° C.) condition. Carried out in The pH measurement of the phosphor layer was performed in the same manner as the phosphor material by collecting 10 g of the phosphor film.

  The radiation image conversion panels 1 to 7 were evaluated as follows.

(Luminance)
The luminance was evaluated using Regius 350 manufactured by Konica Minolta MG Co., Ltd. As in the sharpness evaluation, X-rays were irradiated with a tungsten tube at 80 kVp and 10 mAs at a distance of 2 m between the bombardment source and the plate, and then a plate was set on the Regius 350 and read. Relative evaluation was performed based on the electrical signal from the obtained photomultiplier. The brightness of the radiation image conversion panel 1 was set to 1.0, and the other samples were represented by their relative values.

(afterglow)
Each sample is cut into a 50 mm square, affixed to a plate, and placed in a photo cassette. X-ray irradiation is performed, and a signal difference from the 50th pixel is used as an afterglow value at the time of reading.

  The above evaluation results are summarized in Table 1.

  From Table 1, it can be seen that the radiographic image conversion panel according to the production method of the present invention is superior to the comparative radiographic image conversion panel in both luminance and afterglow characteristics.

Claims (3)

In a method for manufacturing a radiation image conversion panel including a step of forming a phosphor layer by heating a deposition source containing a phosphor material and depositing a generated substance on a substrate, the pH of the phosphor material at 25 ° C. 5). 3 to 5.9 , and the difference between the pH of the phosphor material and the pH of the phosphor layer is 0.1 to 0.6. The method for producing a radiation image conversion panel according to claim 1, wherein the phosphor layer contains a phosphor based on an alkali halide represented by the following general formula (1).
The general formula ^{(1) M 1 X · aM} 2 X '· bM 3 X ": eA
[Wherein, M ¹ is at least one alkali metal atom selected from Li, Na, K, Rb and Cs atoms, and M ² is Be, Mg, Ca, Sr, Ba, Zn, Cd, Cu. And at least one divalent metal atom selected from each atom of Ni, and M ³ is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, At least one trivalent metal atom selected from each atom of Tm, Yb, Lu, Al, Ga and In, and X, X ′ and X ″ are at least selected from each atom of F, Cl, Br and I 1 type of halogen atom, A is Eu, Tb, In, Ce, Tm, Dy, Pr, Ho, Nd, Yb, Er, Gd, Lu, Sm, Y, Tl, Na, Ag, Cu and Mg. At least one metal atom selected from each atom; And, a, b, e each represent a number between 0 ≦ a <0.5,0 ≦ b <0.5,0 ≦ e ≦ 0.2.] The phosphor layer, the phosphor of alkali halide represented by the general formula (1) and maternal, CsBr: radiation image conversion according to 請 Motomeko 2 you being a Eu phosphor Panel manufacturing method.