KR940007115B1 - X-ray imagine plate, method of producing x-ray imagine plate, phosphor of photostimulated luminescence material & method of producing phosphor of photostimulated luminescence materi - Google Patents

Abstract

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Description

[Name of invention]

PHOSPMOR OF PHOTO STIMULATED LUMINESCENCE MATERIAL AND MANUFACTURING METHOD AND X-RAY IMAGING PLATE MANUFACTURING THE FLUOMETER AND THE METHOD OF MANUFACTURING THE SAME (X-RAY IMAGING PLATE)

[Brief Description of Drawings]

1 is a band chart illustrating the action of a phosphor made of a photo-stimulatory light emitting material,

2A is a cross sectional view of a phosphor layer structure made of a photo-stimulatory light emitting material as a first method of achieving the second object of the present invention,

2B is a cross sectional view of a phosphor layer structure made of a photo-stimulatory light emitting material as a second of the methods for achieving the second object of the present invention,

3 is a cross-sectional view of the phosphor layer structure made of a photo-stimulatory light emitting material used in the prior art as a reference diagram of FIGS. 2A and 2B,

4 is a graph showing the results of the method of achieving the second object of the present invention, that is, a graph showing the correlation between the exposure time and the signal intensity when the test piece is exposed to a humid environment. In FIG. The moisture resistance test results of the X-ray image conversion plate having the layer structure shown in Fig. 3 shows the moisture resistance test results of the X-ray image conversion bled having the layer structure shown in Fig. 3B, and the solid line (9). ) Shows the results of the moisture resistance test of the prior art X-ray image conversion plate, and the broken line 10 shows the inside of the X-ray image conversion plate having the layer structure shown in FIG. Indicates wet test results,

FIG. 5 is a graph showing the results of the embodiment of item A (2) below, ie, the correlation graph between the emission intensity and the wavelength of the excitation light (dashed line 11) illustrating the results of the method of achieving the first object. ),

6 is a view showing an example of the X-ray image conversion plate,

7 is an excitation spectrum diagram of BaFClEu: ²⁺ of the prior art (Japanese Patent Laid-Open No. 51-28591),

8 is an excitation spectrum diagram of BaClBr: Eu ²⁺ of the prior art (Japanese Patent Laid-Open No. 63-28952),

9 is an excitation spectrum diagram of BaCl ₂ -BaBr ₂ -yCaS: zEu ^{2+ in} the method of achieving the sixth object of the present invention.

Detailed description of the invention

[Field of Invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor made of a photo-stimulatory light emitting material and a manufacturing method thereof, and an improved X-ray image conversion plate made of the phosphor and a manufacturing method thereof.

More specifically, the present invention includes the above object, and the light emission intensity and moisture resistance of the X-ray image conversion plate and the curvature correction ability of the X-ray image conversion plate and the light emission intensity of the phosphor made of a photo-stimulatory light emitting material In order to improve and also to reproduce the X-ray image stored in the X-ray image conversion plate made of the phosphor by using a semiconductor laser, it has several wavelengths among the wavelengths emitted by the ordinary semiconductor laser of this phosphor. The purpose of the present invention is to improve the light emitting ability by excitation of light.

X-rays are widely used for the diagnosis of the animal body of the human body by using the difference in their absorption rate. Since the tissue of the animal body is destroyed by X-ray exposure, it is preferable to use as little X-ray exposure amount as possible as long as it can detect a pattern representing regions having different X-ray absorption rates. Therefore, it is necessary to develop a technique for detecting a pattern representing an X-ray absorption region and / or forming a visible image representing an X-ray absorption region with as little X-ray exposure as possible. The opposite principle applies between the sensitivity and resolution of a no-screen type X-ray film.

That is, increasing the sensitivity inevitably reduces the resolution.

In order to eliminate the above drawbacks, whenever a phosphor made of a photo-stimulatory light emitting material is exposed to X-rays, the energy of the X-rays is accumulated, and each time it is exposed to light such as a laser of a special wavelength, the accumulated energy is visible. An X-ray image conversion plate has been developed that uses natural phenomena that can be converted into fluorescence having a wavelength that is local or reactive to silver halides or exhibits sensitivity.

Examples of phosphors made of a photo-stimulatory light emitting material that can be used for this purpose include alkali earth metals activated by divalent europium, which are activated by alkaline earth metals and divalent europium, for example, divalent europium. Compounds formed from a combination of barium chloride or BaClBr: Eu ²⁺ .

1 is a band chart of a phosphor made of a photo-stimulatory light emitting material composed of barium chloride bromide (BaClBr / Eu ²⁺ ) activated by divalent europium.

In FIG. 1, (C ₁ ) and (V ₁ ) represent the conduction band and the valence band, respectively, and (C ₂ ) and (V ₂ ) represent the excited state and the ground state of europium, respectively. , (T) represents each defect or bandage generated when anion is removed from an atom of BaClBr. (T) serves as a light emitting center.

When the phosphor made of the photo-stimulatory light emitting material, shown in the band diagram of FIG. 1, is exposed to X-rays, electrons in the ground state V ₂ of divalent europium become excited and move to the conduction band C _{1 of} BaClEr. When the X-ray exposure is momentarily stopped, electrons in the excited state lose energy and are trapped at the emission center close to the X-ray exposure area.

The phenomenon is the same as the electrons of the divalent europium in the X-ray exposure region moved to the emission center T in the X-ray exposed europium region, which has a lower excitation energy from a geometrical point of view. It means that the X-ray energy is stored in some storage means capable of emitting reactive or sensitive fluorescence to a screenless X-ray film when exposed to light having less energy or light having a wavelength of 500 to 900 mm.

Therefore, it is possible to specify a phosphor made of a photo-stimulatory light emitting material in which the electrons of the divalent europium are moved to the emission center T (the level at which fluorescence can be emitted by smaller energy) located in the region to be exposed to X-rays. When exposed to light, for example, with a laser, electrons trapped in the emission center T are excited to the conduction band C ₁ of the alkaline earth metal constituting the phosphor.

When the supply of the specific light which has spared the electrons is momentarily stopped, the electrons fall through the excited state C _{2 of} europium to the ground state V ₂ of europium. At this time, fluorescence having a wavelength corresponding to the level difference between the excited state C ₂ of the divalent europium and the ground state V ₂ is emitted at an intensity proportional to the amount of electrons trapped at the emission center T.

In theory, by producing a plate from the phosphor made of the photo-stimulatory light emitting material, an X-ray image conversion plate using the phosphor made of the photo-stimulatory light emitting material can be produced. However, from a practical point of view, as shown in Fig. 3, a photo-stimulatory light emitting material is formed on a base film made of a transparent resin such as polyethylene terephthalate (hereinafter referred to as " trademark of polyethylene terephthalate " Mylar). An X-ray image conversion plate may be manufactured by forming a phosphor layer.

In other words, after forming a mixture layer of an alkaline earth metal halide and europium halide having a large atomic weight and a high X-ray absorption rate in a transparent film made of miracle, etc., the second layer is formed of a mixture of nitrogen hydride or a mixed gas of carbon monoxide carbon dioxide. The trivalent europium is reduced to divalent europium by firing in a reducing atmosphere. As a result, after forming a phosphor layer made of a photo-stimulatory light emitting material composed of alkaline earth metal activated by divalent europium, the two layers are pulverized into powder. This powder is mixed with a binder made of a polymer such as polymethyl methacrylate and a solvent such as toluene.

As shown in Fig. 3, the liquid mixture was applied to a base film 5 made of a mummy or the like having a thickness of about 70 µm, thereby forming a phosphor layer 1 made of a light-stimulating light emitting material having a thickness of 250 to 300 µm. Thereafter, a protective thin film 6 made of a mummy or the like having a thickness of about 10 μm is formed thereon via the adhesive layer 4.

The X-ray image conversion plate manufactured as described above can be used in two ways.

One way is to make an image on a photofilm.

In this case, the X-ray image conversion plate is exposed with weak X-rays through which an object such as a human body passes. During this process, the pattern representing the X-ray absorption region and the X-ray non-absorption region of the object is stored as a pattern consisting of a light emitting center group included in the X-ray image conversion plate. Thereafter, the X-ray image conversion plate is placed on a photo-flip sensitive to fluorescence, and then exposed to a laser such as a He-Ne laser having a wavelength of 630 nm. By this step, a pattern representing the X-ray absorption region and the X-ray non-absorption region of the object, stored as a pattern consisting of the light emitting center group, is copied to the photo film.

Another way is to burn the image on a CRT tube.

In this case, each picture element forming a pattern representing an X-ray absorption region and an X-ray non-absorption region of the object, in which a laser such as a He-Ne laser having a wavelength of 630 nm is stored as a pattern consisting of a light emitting center group. Inject along.

By this process, each image element emits a small fluorescent spot, which is captured by a photomultiplier or the like.

As a result, train of electric pulses representing the X-ray absorption region and the X-ray non-absorption region of the object are output. An image is formed on a CRT tube or the like in accordance with the electric pulse trains representing the X-ray absorption region and the X-ray non-absorption region of the object.

In both of these methods, the sensitivity of the X-ray image conversion plate is proportional to the amount of electrons trapped at the emission center.

As described above, the pattern stored in the X-ray image conversion plate is normally reproduced by a He-Ne laser having a wavelength of almost 630 nm. However, since the He-Ne laser is large in size, it is necessary to develop a technology that enables the use of a semiconductor laser such as an AlGaAs laser having a wavelength of almost 830 nm. As the wavelength of the memory for reproducing laser increases, the light emission intensity of the phosphor made of the photo-stimulatory light emitting material decreases, so that the X-ray image conversion plate cannot use a semiconductor laser having a wavelength of 830 nm and a small size as the laser for memory reproducing. Always have.

Secondly, an X-ray image conversion plate having a structure in which a plate made of a mixture of a phosphor and a binder made of a photo-stimulatory light emitting material is formed between a mummy base film and a mummy cover film, If the moisture resistance is weak and used after being left in a humid environment, the luminous intensity is lowered.

Thirdly, a powder obtained by sintering a mixture of europium halide and an alkaline earth metal halide, pulverized phosphor made of a photo-stimulatory light emitting material, and a mixture of the binder was applied to a resin film such as a mummy film, After making a sheet containing the phosphor and the binder made of a light emitting material, and heating and purifying the sheet, another resin film such as a mira film contains a fluorescent agent and a binder made of the photo-stimulatory light emitting material. The X-ray image conversion plate according to the conventional method, which is deposited on the drying sheet, does not satisfy the sensitivity and the resolution.

As a solution to the problems, it may be considered to decrease the relative amount of the binder and increase the relative amount of the phosphor made of a photo-stimulatory light emitting material. However, if the decrease in the relative amount of the binder is excessive, the formation of a flat mummy resin film This becomes difficult, and as a result, the laser is scattered on the surface of the fluorescent agent made of the photo-stimulatory light emitting material, and the resolution is reduced. In addition, the phosphor made of the photo-stimulatory light emitting material is damaged during the crushing process, and the sensitivity is lowered.

Fourthly, a liquid mixture of a powder of a conjugate made of a photo-stimulatory light emitting material and a binder is applied to a resin film such as a mira film, and the liquid mixture film is dried to form a sheet of phosphor and a binder made of a photo-stimulatory light emitting material. After the preparation, the resin film was removed from the sheet, and the photostimulatory light emission was performed to recover the defects generated during the grinding process, to increase the relative amount of the phosphor made of the photo-stimulatory light emitting material and to decrease the relative amount of the binder. An improved method of producing an X-ray image conversion plate has been developed by firing a sheet of phosphor and a binder made of material in a reducing atmosphere at 800 to 900 ° C.

However, this method has the disadvantage of facilitating the manufacturing process.

The X-ray image conversion plate of the present invention is characterized in that it comprises a phosphor made of a photostimulatory light emitting material made of a halide of alkaline earth metals activated by divalent europium, wherein BaXX'Eu (where X or X 'is F , At least one halogen selected from the group consisting of Cl, Br, and I).

The phosphor made of the photo-stimulatory light emitting material is useful as a material for an X-ray image conversion plate because it has photo-stimulatory light emission or near-ultraviolet light emission when excited by electromagnetic waves such as visible light and infrared light after X-ray exposure.

Examples of available ones include fluoride halide phosphors of divalent metals activated by divalent europium, and are represented by the following formulas.

(Ba _1-xyp Sr _x Ca _y EU _p ²⁺ ) F (Cl _1-ab Br _a Ib)

In the formula, the symbols x, y, p, a and b are numbers satisfying the inequality of (x + y + p) ≦ 1, y ≧ 0.2, 0.01 ≦ p ≦ 0.2 and (a + b) ≦ 1.

The phosphor made of the photo-stimulatory light emitting material emits a near-ultraviolet spectrum having a peak near 390 nm upon exposure by X-rays, ultraviolet rays and electron beams.

The phosphor made of the photo-stimulatory light emitting material has high sensitivity to X-rays and emits fluorescence having a wavelength belonging to the highest spectral sensitivity range, and thus is widely used as a phosphor for a sensitizer of an X-ray film. (Japanese Patent Application No. 51-28591)

In FIG. 7, the correlation between the fluorescence intensity and the wavelength of the excitation light or the spectrum of the fluorescence intensity with respect to the excitation light wavelength is shown, and a peak appears near 580 nm. Therefore, He-Ne lasers are commonly used for excitation of phosphors made of photo-stimulatory light emitting materials.

In recent years, the fluorescent substance (Japanese Unexamined-Japanese-Patent No. 63-28952) which consists of another photo-stimulatory light emitting material useful as a material of an X-ray image conversion plate has the following formula.

MX ₂ -aMX ' ₂ : xEu ²⁺

Wherein M is at least one alkaline earth metal selected from the group containing Ba, Sr and Ca, X or X 'is at least one halogen selected from the group containing Cl, Br and I, and X is X' A is a positive number of 0.1 or more and 10 or less and x is a positive number of 0.2 or less). Specifically, a phosphor made of a photostimulatory light emitting material belonging to BaClBr: Eu is 410 nm when exposed by X-rays, ultraviolet rays and electron beams. It has an emission spectrum peak in the vicinity.

In addition, referring to FIG. 8, the correlation between the fluorescence intensity and the wavelength of the excitation light or the spectrum of the fluorescence intensity with respect to the wavelength of the excitation light is shown, and peaks are shown near 580 nm and around 700 nm.

That is, not only He-Ne laser but also semiconductor laser can be used for excitation.

The phosphor made of the photo-stimulatory light emitting material described above can be produced by firing the light emitting material at a temperature in the range of 600 to 1000 占 폚.

As described above, a conventional phosphor made of a photostimulatory light emitting material, specifically, a phosphor made of a photostimulatory light emitting material belonging to BaClBr: Eu has a large peak in the visible wavelength range of the excitation light spectrum and is a semiconductor. It has a reduced sensitivity in the emission wavelength range of the laser.

In other words, the phosphor made of a photo-stimulatory light emitting material has a reduced sensitivity within the emission wavelength range of a semiconductor laser, which is a convenient device for reproducing stored patterns expressing an X-ray absorption region and an X-ray non-absorption region of an object. As a result, there is a disadvantage inconvenient to use.

[Explanation and purpose of the invention]

It is an object of the present invention to obviate the aforementioned disadvantages.

It is a first object of the present invention to provide an X-ray image conversion plate having a large luminous intensity and a manufacturing method thereof.

A second object of the present invention is to provide an X-ray image conversion plate having moisture resistance and moisture resistance.

A third object of the present invention is to provide an X-ray image conversion plate having a large luminous intensity and a method of manufacturing the same, since the amount of the phosphor made of the photo-stimulatory light emitting material is relatively larger than that of the binder.

A fourth object of the present invention is to provide a method for producing an X-ray image conversion plate without warping during the firing process.

A fifth object of the present invention is to provide a phosphor made of a photo-stimulatory light emitting material having a large luminous sensitivity and a manufacturing method thereof.

A sixth object of the present invention is a phosphor made of a photo-stimulatory light emitting material, in which a semiconductor laser has a light emission wavelength of around 700 nm used for pattern reproduction representing an X-ray absorption region and an X-ray non-absorption region of an object, and It is to provide a method for producing the same.

A method of achieving the first object is described below.

A first method for achieving the first object is to prepare a sheet from a mixture of phosphor powder and a binder made of a photo-stimulatory light emitting material, and then to prepare a first firing process and an X-ray image conversion plate for manufacturing the phosphor, which is essential in the prior art. Instead of performing a two-stage firing step as a second firing step for the production of the X-ray image conversion plate using only one step litigation process (this method corresponds to claims 1 and 2).

In the method according to claims 1 and 2, it is advantageous to use a heat resistant substrate based on a ceramic substrate (this method corresponds to claims 7 and 8).

A second method for achieving the first object comprises a first step of producing a phosphor made of a photo-stimulatory light emitting material by performing a firing step, and a second process of making a powder of phosphor made of the photo-stimulatory light emitting material by a pulverizing process. And a third step of forming a sheet of a mixture of the phosphor and a binder made of the photo-stimulatory light emitting material on the base film and a fourth step of removing the mixture sheet of the phosphor and the binder made of the photo-stimulatory light emitting material from the base film. And a fifth step of plastically purifying the binder to reduce the relative amount of the binder in the X-ray image conversion plate (the method corresponds to claims 4 and 5).

In the above methods corresponding to claims 4 and 5, it is advantageous to use a polymer film (this method corresponds to claims 27 and 28).

The method for achieving the second object is, up, down as comprising a fluorescent layer of a light stimulating light-emitting material formed between the protective film In addition, the upper and lower protection for the reinforcement of at least one of the protective functions of the film, SiO ₂ It is to provide an X-ray image conversion plate further comprising at least one moisture resistant film, such as, ITO film (this method corresponds to claim 9).

A method for achieving the third object comprises the above-mentioned method for combustion of a binder for increasing a relative amount of a phosphor made of a photo-stimulatory light emitting material and during the grinding and mixing of the phosphor made of the photo-stimulatory light emitting material. In order to recover the defects of the phosphor made of the photo-stimulatory light emitting material, a step of oxidizing the mixture sheet of the phosphor made of the photo-stimulatory light emitting material and the binder is included (this method corresponds to claims 10 and 13).

More specifically, the method is a method for producing an X-ray image conversion plate, comprising: (i) preparing a mixture of a compound made of a halogen and group IIa element with a compound made of another halogen and group IIa element and a europium halogen compound; And (ii) preparing a mixture of a compound of halogen and group Ia elements and a compound of halogen and europium or thallium, or a compound of halogen and group IIa elements and another halogen and group IIa element. A process for preparing a mixture, wherein one of these two compounds is a compound selected from the group consisting of silicon oxide, phosphorous oxide, sulfur compounds of Mg, Ca, Sr or Ba, or yttrium oxide and europium halides (iii ), Grinding the mixture, preparing a mixture of powder and binder of the mixture, preparing a sheet of the mixture, The sheet is calcined, and the binder is removed, and the mixture is reduced-baked to convert it into a phosphor made of a photo-stimulatory light emitting material.

In general, the method comprises the steps of preparing a mixture of a phosphor and a binder of a photo-stimulatory light emitting material represented by the following formula,

aMX _2- (1-a) MX ' ₂ : bEu

(Wherein M is an element selected from Mg, Ca, Sr and Ba, X and X 'are individually selected elements from the halogen group, a is a positive number less than 1 and b is a positive number less than or equal to 0.2)

or

MA: aA

(Wherein M is an element selected from group Ia, X is halogen, A is europium or thallium and a is a positive number less than 1)

or

aMX _2- (1-a) MX ' ₂ -cB: bEu

Wherein m is an element selected from Mg, Ca, Sr and Ba, X and X 'are individually selected elements from the halogen group, B is one of the sulfides of Mg, Ca, Sr or Ba, silicon oxide, phosphorus oxide or Is a compound in yttrium oxide, a is a positive number less than 1, b and c are positive numbers less than or equal to 0.2)

A process comprising preparing a mixture of a powder of one phosphor and a binder among phosphors of the photo-stimulatory light emitting material, preparing a sheet of the mixture, and firing the sheet to remove the binder; The X-ray image conversion plate according to the above method includes a sintered body of phosphor made of a photo-stimulatory light emitting material represented by the following formula.

aMX _2- (1-a) MX ' ₂ : bEu

(Wherein M is an element selected from Mg, Ca, Sr and Ba, X and X 'are individually selected elements from the halogen group, a is a positive number less than 1 and b is a positive number less than or equal to 0.2)

or

MX: aA

(Wherein M is an element selected from group Ia, X is halogen, A is europium or thallium and a is a positive number less than 1)

or

aMX _2- (1-a) MX ' ₂ -cB: bEu

Wherein M is an element selected from Mg, Ca, Sr and Ba, X and X 'are individually selected elements from the halogen group, B is one of the sulfides of Ma, Ca, Sr or Ba, silicon oxide, phosphorus oxide or Is a compound in yttrium oxide, a is a positive number less than 1, b and c are positive numbers less than or equal to 0.2)

A method for achieving the fourth object includes the steps of: installing a quartz plate or a ceramic plate on a phosphor layer made of a photostimulatory light emitting material; and firing a phosphor layer made of the photostimulatory light emitting material in a reducing atmosphere to form a photostimulatory light emitting material. And a step of correcting warping of the phosphor layer (this method corresponds to claims 3 or 6).

A method of achieving the fifth object is to perform a calcination process (a process of reducing trivalent europium and trivalent thallium to divalent thallium) in a mixed gas of hydrogen and nitrogen (this method corresponds to claim 14). .

A method for achieving the sixth object is to use BaCl ₂ -xBaBr ₂ -yCaS: zEu ²⁺ or the like as a phosphor made of a photo-stimulatory light emitting material. More specifically, this method is a method for producing a phosphor of a complex alkaline earth metal halide compound activated by europium, which is a process for preparing a mixture of raw materials having a relative amount represented by the following formula;

(1-X) MeX ₂ -xMeX ' ₂ -yMe'S: zEu

Wherein Me and Me 'are at least one element selected from the group comprising Mg, Ca, Sr and Ba, and X and X' are different elements selected from the group containing F, Cl, Br and I, and x Is a number greater than or equal to 0.4 and less than or equal to 0.6, y is a positive number less than or equal to 0.1, and z is a number greater than or equal to 0.0001 and less than or equal to 0.03)

A process comprising calcining the mixture at a temperature of 500 to 1100 ° C. in a weak reducing atmosphere, which provides a phosphor of a complex alkaline earth metal halogen compound activated by europium represented by the following formula:

(1- x) MeX ₂ -xMeX ' ₂ -yMe'S: zEu

Wherein Me and Me 'are at least one element selected from the group comprising Mg, Ca, Sr and Ba, and X and X' are different elements selected from the group containing F, Cl, Br and I, and x Is a number greater than or equal to 0.4 and less than or equal to 0.6, y is a positive number less than or equal to 0.1, and z is a number greater than or equal to 0.0001 and less than or equal to 0.03)

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Some preferred embodiments of the invention are described in detail below.

A. Embodiment of the method of achieving the first object

(1) Embodiments corresponding to claims 1 and 2

In this embodiment, an X-ray image conversion plate is manufactured by firing or sintering a phosphor made of a strong stimulating light emitting material or by using a phosphor made of a photo stimulating light emitting material without crushing.

BaCl ₂ ... … … … … … … … … … … … … … … … … … … … … … … … … … 208.246 g

BaBr ₂ ... … … … … … … … … … … … … … … … … … … … … … … … … … 297.148 g

EuBr ₃ ... … … … … … … … … … … … … … … … … … … … … … … … … … 0.783 g

PMMA… … … … … … … … … … … … … … … … … … … … … … … … … … 40 g

Dibutyl phthalate... … … … … … … … … … … … … … … … … … … … … 30 g

toluene… … … … … … … … … … … … … … … … … … … … … … … … … … 400 g

Raw materials including the mixture were mixed for 24 hours in a ball mill to prepare a liquid mixture. This liquid mixture was applied to an alumina plate using a bar coater to form a thin film of the mixture of this composition. The thin film of the mixture having the composition applied on the alumina plate was dried in a dryer at 50 ° C. for 7 hours, and then treated in an electric furnace (e: ectricfurnace) for 1 hour in aeration to remove the binder.

In a H ₂ and N ₂ -containing atmosphere, firing was performed at 895 ° C. for 1 hour to prepare a 300 μm-thick phosphor made of a sintered BaClBr: Eu ²⁺ photostimulating light emitting material.

An X-ray image conversion plate was prepared by adhering a 0.5 mm thick transparent glass plate to both surfaces of the phosphor plate made of the photo-stimulatory light emitting material with an adhesive.

For comparison, an X-ray image conversion plate was prepared by a conventional method.

In other words, a 300 μm-thick mixed layer made of a phosphor made of a photo-stimulatory light emitting material and a binder was formed on a 250 μm-thick Mira sheet, and another 50 μm-thick Mira sheet was deposited on the phosphor layer made of the photo-stimulative light emitting material.

The X-ray image conversion plates were exposed to X-rays through a phantom under conditions of 120 kV, 200 mA and an irradiation time of 0.05 seconds, and then irradiated with a laser having a wavelength of 830 nm and 10 mW by a semiconductor laser to emit fluorescence. The fluorescence was measured by photomultipliers.

Table 1 shows the results of the above test with signal strength of 100 according to the prior art.

TABLE 1

(2) Embodiments corresponding to claims 4 and 5

In this embodiment, a process of forming a mixture sheet of phosphor and a binder made of a photo-stimulatory light emitting material on a base sheet, separating the mixture sheet from a base sheet, and a relative amount of phosphor made of the photo-stimulatory light emitting material Firing process to remove the binder to increase.

After obtaining a powder of phosphor made of a photo-stimulatory light emitting material, polymethyl methacrylate as a binder and a solvent were mixed with the powder, and a phosphor sheet made of the photo-stimulating light-emitting material was formed on a mummy film.

After drying, only the phosphor sheet made of the photo-stimulatory light emitting material was separated from the mummy film.

The sheet was heated in 600 占 폚 for 1 to 40 hours in an atmosphere containing N ₂ and O ₂ having a mixed concentration ratio in the range of 10: 1 to 1: 5, and then the binder was removed in an atmosphere containing H ₂ and N ₂ . It baked at 850 degreeC for 1 hour, and obtained the 300 micrometer thickness baking agent plate or the sintering agent plate of the fluorescent substance which used the photo-stimulatory light emitting material.

Finally, a quartz glass plate was attached to both surfaces of the fluorescent plate made of a photo-stimulatory light emitting material with an adhesive to prepare an X-ray image conversion plate.

The X-ray image conversion plate was compared with an X-ray image conversion plate obtained by applying a mixture of phosphor powder made of a photo-stimulatory light emitting material and a binder PMMA on a substrate according to the prior art, to prepare a sheet having a thickness of 300 μm. .

In the comparative test, the X-ray image conversion plates were exposed to X-rays through a pantom under conditions of 120 kV, 200 mA and an irradiation time of 0.05 seconds, and then irradiated with a laser having a wavelength of 830 m and 10 mW by a semiconductor laser to emit fluorescence. And fluorescence was measured using a photomultiplier tube.

Table 2 shows the results of the above test, indicated with a signal strength of 100 according to the prior art.

TABLE 2

From the above table, it can be seen that the X-ray image conversion plate by the phosphor made of the photo-stimulatory light emitting material of the present invention is remarkably improved in terms of its luminescence intensity as compared with that of the prior art. This is because the relative amount of the phosphor of the photo-stimulatory light emitting material is larger, the relative amount of the binder is smaller, and the crystal defects during the grinding process are corrected by the growth of the crystals in the predetermined process.

A similar test to the above was carried out on the X-ray image conversion plate of the above example, using X-rays emitted at 800 kV and 100 mW and an excitation laser having a wavelength of 500 to 900 nm.

5 is a diagram showing the results of the test, showing the correlation between the emission intensity and the wavelength of the excitation light (shown by broken line 11).

In FIG. 5, the solid line 12 shows the emission intensity and the excitation light wavelength when the phosphor made of the photo-stimulatory light emitting material of the present embodiment, which is fired in a mixed gas of N ₂ and H ₂ , is measured under the same conditions as described above. The dotted line 13 shows the correlation between the emission intensity and the excitation light wavelength when BaFBr: Eu according to the prior art is measured under the same conditions as described above (Japanese Patent Laid-Open No. 63-28954). .

From the graph, it is clear that the X-ray image conversion plate of the present invention has excellent sensitivity to excitation light in the wavelength range of 500 to 900 nm.

Therefore, referring to FIG. 6, the X-ray image conversion plate of the present invention, which is exposed to the X-ray 15 transmitted through the object 14, is exposed to an excitation curreut having a wavelength of 500 to 900 nm. When the fluorescence is emitted, the fluorescence is collected by the optical system 18, sensed by a light sensor (photomultiplier tube) 19, and converted into an electrical signal.

B. Examples of a method of achieving the second object

In this embodiment, one or two further protective layers made of SiO ₂ , ITO, or the like are added to the protective layer of the X-ray image conversion plate having one or two protective layers on both sides or one side thereof.

Using a method similar to that described in item A (1) above, a 300 μm-thick phosphor made of a photo-stimulatory light emitting material was formed on a mummy-thick 50 μm base film.

After drying, the phosphor made of the photo-stimulatory light emitting material is cut into A ₄ size, the base film is removed, and a layer made of silicon dioxide (SiO ₂ ) and indium tin oxide (ITO), etc. that the mummy film having one surface on the length and width of 5mm longer than the cut a ₄ size, was laminated with an adhesive to both sides of the phosphor layer with the stimulating light emitting material.

2A is a cross sectional view of an X-ray image conversion plate manufactured by the above method.

In FIG. 2A, the phosphor layer 1 made of a photo-stimulatory light emitting material is adhered to each other by an adhesive 4 between piles made of the mira film layer 3 and the SiO ₂ film layer 2. It is.

Since the dropper 4 surrounds the edge of the phosphor layer 1 made of the photo-stimulatory light emitting material, the phosphor layer 1 made of the photo-stimulatory light emitting material is not exposed to the outside air.

FIG. 2B shows a case where the base film 5 does not need to be removed from the phosphor layer 1 made of the photo-stimulatory light emitting material.

In other words, the laminate including the phosphor layer 1 made of the photo-stimulatory light emitting material can be adhered to each other with an adhesive between the laminate made of the mira film 3 and the SiO ₂ film 2.

4 is a laminate of an X-ray image conversion plate according to the present invention having a layer structure of FIGS. 2A and 2B, and a phosphor layer 1 made of a photo-stimulatory light emitting material, such as a mira film 3 and a SiO ₂ film 2. A graph showing the results of a moisture resistance test performed on a condition of a temperature of 60 ° C. and a relative humidity of 90% for an X-ray image conversion plate according to the prior art having a layer structure laminated by an adhesive 4 between laminated laminates. to be.

From FIG. 4, the moisture resistance (shown by the dashed line 7 and the solid line 8, respectively) of the X-ray image conversion plate having the layer structure described in FIGS. 2A and 2B, respectively, is described in FIG. It can be clearly seen that it is greater than the moisture resistance (shown by the solid line 9) of the conventional X-ray image conversion plate having a layer structure.

In addition, in FIG. 4, the broken line 10 is a line showing the moisture resistance of the X-ray image conversion plate having a similar structure except the edge portion of the phosphor layer 1 made of the light emitting material. Or much smaller than in the case of the X-ray image conversion plate of FIG. 2B, because the laminates of the mira film 3 and the SiO ₂ film 2 are made of a phosphor 1 made of a photo-stimulatory light emitting material and This is because the size of the laminate made of the base film 5 becomes the same. As a gas for reducing trivalent euroforms in a mixture of alkaline earth metal halides and euroform halides to divalent euroforms, when a mixed gas of helium and hydrogen gas is used, the size of helium atoms is small, so that the atoms enter the alkaline earth metal. Since it diffuses effectively and removes undesirable gas, it is effective in increasing the luminous intensity of the phosphor made of the photo-stimulatory light emitting material produced therefrom. "E. Embodiment of the method of achieving the fifth object (corresponding to claim 14) ) ".

One or two protective films made of inorganic materials such as SiO ₂ and ITO are prepared by using a mixed gas of helium and hydrogen for reduction of trivalent euroforms into divalent euroforms. When added to the X-ray image conversion plate, the result of the present embodiment and the fifth object achieving method is combined, which is effective in improving the performance of the X-ray image conversion plate.

C. Embodiments of the method of achieving the fourth object (corresponding to claims 3 and 6)

The embodiments are embodiments related to warpage correction of the X-ray image conversion plate.

BaCl ₂ ... … … … … … … … … … … … … … … … … … … … … … … 208.246 g

BaBr ₂ ... … … … … … … … … … … … … … … … … … … … … … … 297.148 g

EuBr ₃ ... … … … … … … … … … … … … … … … … … … … … … 0.783 g

Distilled water… … … … … … … … … … … … … … … … … … … … … 400 g

After mixing and the like to obtain a liquid mixture, and dried at almost 80 ℃, the dried mixture was ground to a powder.

After the powder was calcined in the air at about 500 ° C. for 2 hours using an electric furnace, the calcined body of the phosphor made of the photo-stimulatory light emitting material was pulverized so as to have a particle size of 30 to 50 μm.

30 g of phosphor powder 500 g PMMA, 3 g of dibutyl phthalate and 150 g of toluene made of the photo-stimulatory light emitting material were mixed for 24 hours in a bowl for ball grinding to obtain a liquid mixture. This liquid mixture was applied onto a mummy film using a duct blade, then dried to prepare a 400 μm thick mixture chic of a phosphor and a binder made of a photo-stimulatory light emitting material and then removed from the mummy film.

The temperature of the sheet was raised to 600 ° C. over 6 hours in an electric furnace, and then maintained at this temperature for 1 hour and lowered to 200 ° C. or less over 5 hours.

Thereafter, the semi-sintered sheet was placed in an electric furnace filled with a nitrogen gas mixture of hydrogen, the temperature of the sheet was raised to 900 ° C. over 9 hours, and maintained at that temperature for 3 hours, and then over 5 hours. The temperature was lowered to 200 ° C.

However, warpage always occurred in the phosphor sheet made of the photo-stimulatory light emitting material manufactured as described above.

In order to correct this warp, while performing the baking step again in a mixed gas of hydrogen and nitrogen, a 0.5 mm thick quartz plate was placed on the phosphor sheet made of the photo-stimulatory light emitting material. This method was effective in correcting the warpage, and was also effective in obtaining a 300 μm thick sheet of a phosphor made of a photo-stimulatory light emitting material with no warpage.

Subsequently, the X-ray image conversion plate was manufactured by contacting the phosphor sheet made of the photo-stimulatory light emitting material with an adhesive between the 50 μm thick mummy films.

D. Embodiments of the method of achieving the third object (corresponding to claims 10 to 13)

This embodiment includes a step of heating a mixture sheet of a phosphor powder and a binder made of a photo-stimulatory light emitting material to remove the binder and correcting crystal defects generated during the mixing process.

[First Embodiment]

BaCl ₂ ... … … … … … … … … … … … … … … … … … … … … … … … … 208.246 g

BaBr ₂ ... … … … … … … … … … … … … … … … … … … … … … … … … 297.148 g

EuBr ₃ ... … … … … … … … … … … … … … … … … … … … … … … … 0.652 g

After mixing the raw material comprising a ball mill for 6 hours, the lid was opened and left for 3 hours, the mixture was dried at 150 ℃ in vacuum for about 3 hours.

Using the ball mill again, the dried mixture was further mixed for 6 hours.

Using an electric furnace, the mixture was calcined at about 900 ° C. for about 2 hours in a reducing atmosphere containing hydrogen and helium to obtain a phosphor powder made of a photo-stimulatory light emitting material.

The mixture containing 500 g of the phosphor powder of the photo-stimulatory light emitting material, 3 g of PMMA 30 g of dibutyl phthalate, and 150 g of toluene was mixed in a ball mill vessel for about 20 hours to obtain a liquid mixture. The liquid mixture was applied onto the mummy film using duct blades.

After drying at nearly 120 [deg.] C., the mirafilm was removed from the phosphor sheet of the photo-stimulatory light emitting material.

The phosphor sheet made of the photo-stimulatory light emitting material was placed on a quartz plate in an electric furnace. The temperature of this sheet was raised to approximately 150 ° C. in an oxidizing atmosphere (atmosphere), held at that temperature for 2 hours, and then further raised to a temperature of 600 ° C., and maintained at that temperature for approximately 2 hours. . Finally, the temperature of the sheet was lowered to 100 ° C or lower. By this process, the semi-sintered compact sheet from which the binder and the warpage were removed was obtained.

The semi-sintered sheet placed on the graphite plate was placed in an electric furnace. The temperature of the sheet is raised to nearly 800 ° C. in a reducing atmosphere containing a mixed gas of hydrogen and nitrogen or a mixed gas of hydrogen and helium, and maintained at that temperature for about 2 hours, and then the temperature of the sheet is 100 Lowered below ℃. By this process, about 300 μm-thick sintered sheet or sheet of phosphor made of a photo-stimulatory light emitting material was obtained.

In order to protect the fluorescent material made of the photo-stimulatory light emitting material from moisture, a tempered glass sheet or a quartz glass sheet is adhered to one side of the sintered sheet by epoxy resin, and a mira film, The tempered glass film or the quartz glass film was bonded with an epoxy resin. An X-ray image conversion plate was produced by this method.

The prepared X-ray image conversion plate was installed at a distance of 70 cm from the focus of the X-ray tube stimulated under the conditions of a tube voltage, 120 kV, and a tube current of 50 mA, and X-ray exposure was performed for 0.2 seconds using this X-ray tube.

After the exposure, the exposed X-ray image conversion plate was irradiated with a laser of wavelength 780 nm and power 10 kV.

The intensity of fluorescence emitted from the X-ray image conversion plate was sensed by photomultipliers. As a result, the light emission intensity of the X-ray image conversion plate was 3.7 times that of the prior art.

Second Embodiment

BaCl ₂ ... … … … … … … … … … … … … … … … … … … … … … … … 208.246 g

BaBr ₂ ... … … … … … … … … … … … … … … … … … … … … … … … 297.148 g

EuCl ₃ ... … … … … … … … … … … … … … … … … … … … … … … 0.652 g

After mixing the raw material comprising a for 6 hours in a ball mill, the lid was opened and left for 3 hours, the mixture was dried at almost 150 ℃ in vacuum for 3 hours.

Using the ball mill again, the dried mixture was further mixed for 6 hours. When the mixture was wet, vacuum drying or heat treatment was performed in air. A mixture containing 500 g of the mixture (phosphor raw material made of a photo-stimulatory light emitting material), 30 g of PMMA, 3 g of dibutyl phthalate, and 150 g of toluene was mixed in a ball grinding vessel for about 20 hours to obtain a liquid mixture. The liquid mixture was applied onto the mirafilm using duct blades. After drying at nearly 120 [deg.] C., the mirafilm was removed from the phosphor sheet of the photo-stimulatory light emitting material.

The sheet made of the phosphor raw material of the photo-stimulatory light emitting material was placed on a quartz plate and placed in a battery furnace.

The temperature of this sheet was raised to approximately 150 ° C. in an oxidizing atmosphere (atmosphere), held at that temperature for 2 hours, and then further raised to a temperature of 600 ° C., and maintained at that temperature for approximately 2 hours. .

Finally, the temperature of the sheet was lowered to 100 ° C or lower. This process yielded a semi-sintered sheet with no binder and no warpage.

The semi-sintered sheet was placed in an electric furnace on a graphite plate.

The temperature of the sheet is raised to nearly 800 ° C. in a reducing atmosphere containing a mixture of hydrogen and nitrogen or a mixture of hydrogen and helium, and maintained at that temperature for approximately 2 hours, and then the temperature of the sheet is 100 ° C. Lowered below. By this process, a sintered compact sheet or sheet having a thickness of about 300 µm of a phosphor made of a photo-stimulatory light emitting material was obtained.

In order to protect the phosphor made of the photo-stimulatory light emitting material from moisture, a sheet of tempered glass sheet or quartz glass is bonded to one side of the sintered body sheet with an epoxy resin and a mirafilm-reinforced glass film on the other side of the sintered body sheet. Or the quartz glass film was bonded by epoxy resin. An X-ray image conversion plate was produced by this method.

The X-ray image conversion plate prepared above was installed at a distance of 70 cm from the focus of the X-ray tube stimulated under a condition of a tube voltage of 120 kV and a tube current of 50 mA, and subjected to 0.2 second X-ray exposure using this X-ray tube.

After the exposure, the exposed X-ray image conversion plate was irradiated with a laser of wavelength 780 nm and power 10 mW. The intensity of fluorescence emitted from the X-ray image conversion plate was sensed by photomultipliers.

As a result, the light emission intensity of the X-ray image conversion plate was 3.6 times that according to the prior art.

Third Embodiment

RbBr… … … … … … … … … … … … … … … … … … … … … … … 164.4 g

TlBr… … … … … … … … … … … … … … … … … … … … … … … 0.568 g

After mixing the raw material comprising a for 6 hours in a ball mill, the lid was opened and left for 3 hours, the mixture was dried at almost 150 ℃ in vacuum for 3 hours.

Using the ball mill again, the dried mixture was further mixed for 6 hours.

The mixture was calcined at about 650 ° C. for about 2 hours in a reducing atmosphere containing hydrogen and helium using an electric furnace to obtain a phosphor powder made of a photo-stimulatory light emitting material.

A mixture containing 500 g of the phosphor powder of the photo-stimulatory light emitting material, 30 g of PMMA, 3 g of dibutyl phthalate, and 150 g of toluene was mixed in a ball grinding vessel for 20 hours to obtain a liquid mixture. The liquid mixture was applied onto the mirafilm using duct blades. After drying at nearly 120 ° C., the mirafilm was removed from the phosphor sheet of photo-stimulatory light emitting material.

The phosphor sheet made of the photo-stimulatory light emitting material was placed in a cell furnace on a quartz plate. The temperature of this sheet was raised to approximately 150 ° C. in an oxidizing atmosphere (atmosphere), held at that temperature for 2 hours, and then further raised to a temperature of 600 ° C., and maintained at that temperature for approximately 2 hours. .

Finally, the temperature of the sheet was lowered to 100 ° C or lower.

This process yielded a semi-sintered sheet with no binder and no warpage.

The semi-sintered sheet was placed in an electric furnace on a graphite plate.

The temperature of the sheet is raised to nearly 800 ° C. in a reducing atmosphere containing a mixture of hydrogen and nitrogen or a mixture of hydrogen and helium, and maintained at that temperature for approximately 2 hours, and then the temperature of the sheet is 100 ° C. Lowered below. By this process, about 300 μm thick sintered sheet or sheet of the phosphor made of the photo-stimulatory light emitting material was obtained.

In order to protect the phosphor made of the photo-stimulatory light emitting material from moisture, a sheet of tempered glass sheet or quartz glass is bonded to one side of the sintered body sheet by epoxy resin, and a mirafilm, reinforced on the other side of the sintered body sheet. A glass film or a quartz glass film was bonded with an epoxy resin.

An X-ray image conversion plate was produced by this method.

The prepared X-ray image conversion plate was installed at a distance of 70 cm from the focal point of the X-ray tube stimulated under the condition of a tube voltage of 120 kV and a tube current of 50 mA, and the X-ray tube was subjected to X-ray exposure for 0.2 seconds.

After the exposure, the exposed X-ray image conversion plate was irradiated with a laser of wavelength 780 nm and power 10 mW. The intensity of fluorescence emitted from the X-ray image conversion plate was sensed by photomultipliers.

As a result, the light emission intensity of the X-ray image conversion plate was 3.7 times that according to the prior art.

[Example 4]

RbBr… … … … … … … … … … … … … … … … … … … … … … … … 164.4 g

TlBr… … … … … … … … … … … … … … … … … … … … … … … … 0.568 g

After mixing the raw material containing a for 6 hours in a ball mill, the lid was opened and left for 3 hours, and the mixture was dried at almost 150 DEG C for 3 hours in a vacuum.

Using the ball mill again, the dried mixture was further mixed for 6 hours. If the mixture was wet, vacuum drying or heat treatment was performed in air.

A mixture containing 500 g of the above-mentioned mixture (phosphor raw material made of a photo-stimulatory light emitting material), 30 g of PMMA, 3 g of dibutyl phthalate, and 150 g of toluene was mixed in a ball grinding vessel for about 20 hours to obtain a liquid mixture. The liquid mixture was applied onto the mirafilm using duct blades.

After precursoring at nearly 120 ° C., the mirafilm was removed from the phosphor sheet of photo-stimulatory light emitting material.

The sheet of the phosphor raw material of the photo-stimulatory light emitting material was placed on a quartz plate and placed in an electric furnace.

The temperature of this sheet was raised to nearly 150 ° C. in an oxidizing atmosphere (atmosphere), held at that temperature for 2 hours, and then the temperature of the sheet was further raised to 550 ° C. and maintained at that temperature for almost 2 hours. .

Finally, the temperature of the sheet was lowered to 100 ° C or lower.

This process yielded a semi-sintered sheet with no binder and no warpage.

The semi-sintered sheet was placed on a graphite plate and placed in an electric furnace.

The temperature of the sheet is raised to nearly 600 ° C. in a reducing atmosphere containing a mixture of hydrogen and nitrogen or a mixture of hydrogen and helium, and maintained at that temperature for approximately 2 hours, and then the temperature of the sheet is 100 ° C. Lowered below. By this process, about 300 μm thick sintered sheet or sheet of the phosphor made of the photo-stimulatory light emitting material was obtained.

In order to protect the phosphor made of the photo-stimulatory light emitting material from moisture, a sheet of tempered glass sheet or quartz glass is bonded to one side of the sintered body sheet by epoxy resin, and a mirafilm, reinforced on the other side of the sintered body sheet. A glass film or a quartz glass film was bonded with an epoxy resin.

An X-ray image conversion plate was produced by this method.

The prepared X-ray image conversion plate was installed at a distance of 70 cm from the focus of the X-ray tube stimulated under the condition of a tube voltage of 120 kV and a tube current of 50 mA, and X-ray exposure was performed for 0.2 seconds using this X-ray tube.

After the exposure, the exposed X-ray image conversion plate was irradiated with a laser of wavelength 780 nm and power 10 mV. The intensity of fluorescence emitted from the X-ray image conversion plate was sensed by photomultipliers.

As a result, the light emission intensity of the X-ray image conversion plate was 3.2 times that according to the prior art.

[Example 5]

BaCl ₂ ... … … … … … … … … … … … … … … … … … … … … … … 208.246 g

BaBr ₂ ... … … … … … … … … … … … … … … … … … … … … … … 297.148 g

CaS… … … … … … … … … … … … … … … … … … … … … … … 0.721 g

EuCl ₃ ... … … … … … … … … … … … … … … … … … … … … … 0.652 g

After mixing the raw material containing for 6 hours in a fire crusher, the lid was opened and left for 3 hours, the mixture was dried at almost 150 ℃ in vacuum for 3 hours.

Using the ball mill again, the dried mixture was further mixed for 6 hours.

The mixture was calcined at about 900 ° C. for about 2 hours in a reducing atmosphere containing hydrogen and helium using an electric furnace to obtain a phosphor powder made of a photo-stimulatory light emitting material.

A mixture containing 500 g of the phosphor powder of the photo-stimulatory light emitting material, 30 g of PMMA, 3 g of dibutyl phthalate and 150 g of toluene was mixed in a ball grinding vessel for about 20 hours to obtain a liquid mixture. The liquid mixture was applied onto the mirafilm using duct blades.

After drying at nearly 120 ° C., the mirafilm was removed from the phosphor sheet of photo-stimulatory light emitting material.

The phosphor sheet made of the photo-stimulatory light emitting material was placed on a quartz plate and placed in a battery furnace. The temperature of this sheet was raised to approximately 150 ° C. in an oxidizing atmosphere (atmosphere), held at that temperature for 2 hours, and then further raised to a temperature of 600 ° C., and maintained at that temperature for approximately 2 hours. .

Finally, the temperature of the sheet was lowered to 100 ° C or lower.

This process yielded a semi-sintered sheet that eliminated the binder and warpage.

The semisintered sheet was placed on a graphite plate and placed in an electric furnace.

The temperature of the sheet is raised to nearly 800 ° C. in a reducing atmosphere containing a mixture of hydrogen and nitrogen or a mixture of hydrogen and helium, and maintained at that temperature for approximately 2 hours, and then the temperature of the sheet is 100 ° C. Lowered below. By this process, about 300 μm thick sintered sheet or sheet of the fluorescent material made of the photo-stimulatory light emitting material was obtained.

In order to protect the phosphor made of the photo-stimulatory light emitting material from moisture, a sheet of tempered glass sheet or quartz glass is bonded to one side of the sintered body sheet with an epoxy resin, and a mira film, on the other side of the sintered body sheet, The tempered glass film or the quartz glass film was bonded with an epoxy resin. An X-ray image conversion plate was produced by this method.

The prepared X-ray image conversion plate was installed at a distance of 70 cm from the focal point of the X-ray tube stimulated under the condition of a tube voltage of 120 kV and a tube current of 50 mA, and the X-ray tube was subjected to X-ray exposure for 0.2 seconds.

After the exposure, the exposed X-ray image conversion plate was irradiated with a laser of wavelength 780 nm and power 10 mW. The intensity of fluorescence emitted from the X-ray image conversion plate was sensed by photomultipliers.

As a result, the light emission intensity of the X-ray image conversion plate was 1.8 times that according to the prior art.

[Example 6]

BaCl ₂ ... … … … … … … … … … … … … … … … … … … … … … … … 208.246 g

BABr ₂ ... … … … … … … … … … … … … … … … … … … … … … … … 297.148 g

EuCl ₃ ... … … … … … … … … … … … … … … … … … … … … … … 0.652 g

CaS… … … … … … … … … … … … … … … … … … … … … … … … 0.721 g

After mixing the raw material comprising a for 6 hours in a ball mill, the lid was opened and left for 3 hours, the mixture was dried at almost 150 ℃ in vacuum for 3 hours.

Using the ball mill again, the dried mixture was further mixed for 6 hours. When the mixture was wet, vacuum drying or heat treatment was performed in air.

A mixture containing 500 g, 500 g, PMMA 30 g, 3 g dibutyl phthalate and 150 g toluene was mixed in a ball grinding vessel for 20 hours to obtain a liquid mixture. The liquid mixture was applied onto the mirafilm using duct blades.

After drying at nearly 120 ° C., the mirafilm was removed from the phosphor sheet of photo-stimulatory light emitting material.

The sheet of the phosphor raw material made of the photo-stimulatory light emitting material was placed on a quartz plate and placed in a battery furnace.

The temperature of this sheet was raised to approximately 150 ° C. in an oxidizing atmosphere (atmosphere), held at that temperature for 2 hours, and then further raised to a temperature of 600 ° C., and maintained at that temperature for approximately 2 hours. .

Finally, the temperature of the sheet was lowered to 100 ° C or lower.

This process yielded a semi-sintered sheet with no binder and no warpage.

The semi-sintered sheet was placed on a graphite plate and placed in an electric furnace.

The temperature of the sheet is raised to nearly 800 ° C. in a reducing atmosphere containing a mixture of hydrogen and nitrogen or a mixture of hydrogen and helium, and maintained at that temperature for approximately 2 hours, and then the temperature of the sheet is 100 ° C. Lowered below. By this process, about 300 μm thick sintered sheet or sheet of the phosphor made of the photo-stimulatory light emitting material was obtained.

By protecting the phosphor made of the photo-stimulatory light emitting material from moisture, a sheet of tempered glass sheet or quartz glass is bonded to one surface of the sintered body sheet with an epoxy resin, and a mirafilm, reinforced on the other side of the sintered body sheet. A glass film or a quartz glass film was bonded with an epoxy resin.

An X-ray image conversion plate was produced by this method.

The prepared X-ray image conversion plate was installed at a distance of 70 cm from the focal point of the X-ray tube stimulated under the condition of a tube voltage of 120 kV and a tube current of 50 mA, and the X-ray tube was subjected to X-ray exposure for 0.2 seconds.

After the exposure, the exposed X-ray image conversion plate was irradiated with a laser of wavelength 780 nm and power 10 mW.

The intensity of fluorescence emitted from the X-ray image conversion plate was sensed by photomultipliers.

As a result, the light emission intensity of the X-ray image conversion plate was 3.7 times that according to the prior art.

[Seventh Embodiment]

BaCl ₂ ... … … … … … … … … … … … … … … … … … … … … … … … … 208.246 g

BaBr ₂ ... … … … … … … … … … … … … … … … … … … … … … … … … 297.148 g

EuCl ₃ ... … … … … … … … … … … … … … … … … … … … … … … … … 0.652 g

Y ₂ O ₃ . … … … … … … … … … … … … … … … … … … … … … … … … 2.256g

After mixing the raw material comprising a for 6 hours in a ball mill, the lid was opened and left for 3 hours, the mixture was dried at almost 150 ℃ in vacuum for 3 hours.

Using the ball mill again, the dried mixture was further mixed for 6 hours.

The mixture was calcined at about 900 ° C. for about 2 hours in a reducing atmosphere containing hydrogen and helium using an electric furnace to obtain a phosphor powder made of a photo-stimulatory light emitting material.

A mixture containing 500 g of the phosphor powder of the photo-stimulatory light emitting material, 30 g of PMMA, 3 g of dibutyl phthalate, and 150 g of toluene was mixed in a ball grinding vessel for 20 hours to obtain a liquid mixture. The liquid mixture was applied onto the mirafilm using duct blades.

After drying at nearly 120 ° C., the mirafilm was removed from the phosphor sheet of photo-stimulatory light emitting material.

The phosphor sheet made of the photo-stimulatory light emitting material was placed on a quartz plate and placed in a battery furnace. The temperature of this sheet was raised to nearly 150 ° C. in an oxidizing atmosphere (atmosphere), and maintained at that temperature for 2 hours, after which the temperature of the sheet was further raised to 600 ° C. and maintained at that temperature for almost 2 hours. . Finally, the temperature of the sheet was lowered below 100 ° C.

This process yielded a semi-sintered sheet with no binder and no warpage.

The semi-sintered sheet was placed on a graphite plate and placed in an electric furnace.

The temperature of the sheet is raised to nearly 800 ° C. in a reducing atmosphere containing a mixed gas of hydrogen and nitrogen or a mixed gas of hydrogen and helium, and maintained at that temperature for almost 2 hours, and then the temperature of the sheet is 100 ° C. Lowered below. By this process, about 300 µm-thick sintered sheet or sheet of the phosphor made of the photo-stimulatory light emitting material was obtained. In order to protect the phosphor made of the photo-stimulatory light emitting material from moisture, a sheet of tempered glass sheet or quartz glass is adhered to one side of the sintered sheet by epoxy resin, and the other side of the sintered sheet is mirafilm, reinforced A glass film or a quartz glass film was bonded with an epoxy resin. An X-ray image conversion plate was produced by this method.

The prepared X-ray image conversion plate was installed at a distance of 70 cm from the focal point of the X-ray tube stimulated under the condition of a tube voltage of 120 kV and a tube current of 50 mA, and the X-ray tube was subjected to X-ray exposure for 0.2 seconds. After the exposure, the exposed X-ray image conversion plate was irradiated with a laser of wavelength 780 nm and power 10 mW. The intensity of fluorescence emitted from the X-ray image conversion plate was sensed by photomultipliers. As a result, the light emission intensity of the X-ray image conversion plate was 1.7 times that according to the prior art.

[Example 8]

BaCl ₂ ... … … … … … … … … … … … … … … … … … … … … … … 208.246 g

BaBr ₂ ... … … … … … … … … … … … … … … … … … … … … … … 297.148 g

EuCl ₃ ... … … … … … … … … … … … … … … … … … … … … … … 0.652 g

Y ₂ O ₃ . … … … … … … … … … … … … … … … … … … … … … … 2.259 g

After mixing the raw material comprising a for 6 hours in a ball mill, the lid was opened and left for 3 hours, the mixture was dried at almost 150 ℃ in vacuum for 3 hours.

Using the ball mill again, the dried mixture was further mixed for 6 hours. When the mixture was wet, vacuum drying or heat treatment was performed in air. A mixture containing 500 g of the above-mentioned mixture (phosphor material made of a photo-stimulatory light emitting material), 30 g of PMMA, 3 g of dibutyl phthalate and 150 g of toluene was mixed in a ball grinding vessel for about 20 hours to obtain a liquid mixture. The liquid mixture was applied onto the mirafilm using duct blades. After drying at nearly 120 ° C., the mirafilm was removed from the phosphor sheet of photo-stimulatory light emitting material.

The phosphor sheet made of the photo-stimulatory light emitting material was placed on a quartz plate in an electric furnace. The temperature of this sheet was raised to nearly 150 ° C. in an oxidizing atmosphere (atmosphere), held at that temperature for 2 hours, and then further raised to a temperature of 600 ° C., and maintained at that temperature for almost 2 hours. . Finally, the temperature of the sheet was lowered below 100 ° C.

This process yielded a semi-sintered sheet with no binder and no warpage.

The semi-sintered sheet was placed on a graphite plate and placed in an electric furnace. The semi-sintered sheet was placed on a graphite plate and placed in an electric furnace.

The temperature of the sheet is raised to nearly 800 ° C. in a reducing atmosphere containing a mixed gas of hydrogen and nitrogen or a mixed gas of hydrogen and helium, and maintained at that temperature for almost 2 hours, and then the temperature of the sheet is 100 ° C. Lowered below. By this process, about 300 µm-thick sintered sheet or sheet of the phosphor made of the photo-stimulatory light emitting material was obtained.

In order to protect the phosphor made of the photo-stimulatory light emitting material from moisture, a sheet of tempered glass sheet or quartz glass is adhered to one side of the sintered sheet by epoxy resin, and the other side of the sintered sheet is mirafilm, reinforced A glass film or a quartz glass film was bonded with an epoxy resin. An X-ray image conversion plate was produced by this method. The prepared X-ray image conversion plate was installed at a distance of 70 cm from the focal point of the X-ray tube stimulated under the condition of a tube voltage of 120 kV and a tube current of 50 mA, and the X-ray tube was subjected to X-ray exposure for 0.2 seconds. After the exposure, the exposed X-ray image conversion plate was irradiated with a laser of wavelength 780 nm and power 10 mW. The intensity of fluorescence emitted from the X-ray image conversion plate was sensed by photomultipliers. As a result, the light emission intensity of the X-ray image conversion plate was 3.5 times that according to the prior art.

Further, any of the sintered body sheets of the phosphor made of the photo-stimulatory light emitting material according to the above embodiments, the phosphor made of the photo-stimulatory light emitting material described in the above item "C. The sheet warping correction method can be applied.

In other words, warpage of any of the sintered sheet may be corrected by a second firing step at a temperature of 800 to 900 ° C. in a reducing atmosphere containing helium and hydrogen, and the second firing step may include It is performed under the conditions which laminated | stacked the quartz plate on the sintered compact sheet.

E. An example of a method of achieving a fifth object (corresponding to claim 14)

The present embodiment is a reducing gas of reduction of trivalent europium into divalent europium contained in a mixture of at least one alkaline earth metal halide and europium halide, using a mixed gas of helium and hydrogen, The embodiment converts the mixture into a phosphor made of a photo-stimulatory light emitting material.

BaCl2... … … … … … … … … … … … … … … … … … … … … … … 208.246 g

BaBr2... … … … … … … … … … … … … … … … … … … … … … … 297.148 g

EuBr3... … … … … … … … … … … … … … … … … … … … … … … 0.783 g

Distilled water… … … … … … … … … … … … … … … … … … … … … … … 1,000g

The mixture was mixed in a reaction vessel to obtain a liquid mixture. The mixture was treated with water for about 6 hours at 80 DEG C and dried, and further heated at 80 DEG C for 5 hours in a drier.

The dried mixture was placed in a calcination boat and placed in an electric furnace supplied with a mixture having a mass ratio of H ₂ and He of 20: 1 to 1: 100. The oven was calcined at 800 ° C. for 30 minutes to 10 hours. By this step, a phosphor made of a photo-stimulatory light emitting material was obtained.

The phosphor made of the photo-stimulatory light emitting material prepared as above can be used as the X-ray image conversion plate. However, using a conventional method, the phosphor made of the photo-stimulatory light emitting material is pulverized into powder, and then mixed with the conjugated dibutyl phthalate and toluene solvent, and at least the phosphor made of the photo-stimulating light emitting material and PMMA are 1: 9.5. The liquid mixture contained in mass ratio was obtained.

The liquid mixture was applied onto a ummy film having a thickness of 250 μm using a duct blade, and then the liquid mixture thin plate was dried to obtain a 300 μm thick solid sheet of a fluorescent material made of a photo-stimulatory light emitting material. On the solid sheet of the phosphor, a mirafilm having a thickness of 12 µm was adhered.

For comparison, other X-ray image conversion plates were prepared using a mixed gas of H ₂ and Ar or a mixed gas of H ₂ and N ₂ as a reducing gas. Of course, other conditions were made the same as the above.

The comparative X-ray image conversion plates were irradiated with X-rays (80 kV, 200 mA) and then exposed with a He-Ne laser (wavelength 630 nm, power 10 mW) and a semiconductor laser (wavelength 830 nm, power 10 mW). The fluorescence emitted was sensed by light conduit.

The results are shown in Table 3 and show the results when a mixed gas of H ₂ and N ₂ was used as the reference or 100 as the reducing gas.

TABLE 3

In the above method for producing a phosphor made of a photo-stimulatory light emitting material, which includes a step of reducing in a mixture gas of H ₂ and He, He diffuses into a crystal and easily removes an undesirable gas from the crystal. The small size of is believed to be due to its intrinsic properties.

F. Embodiments of the method of achieving the sixth object (corresponding to claims 15 to 26)

This embodiment is an embodiment in which a phosphor composition made of a photo-stimulatory light emitting material is selected to change the effective or sensitive wavelength range of excitation light and the wavelength range of emission light of a semiconductor laser such as an AlGaAs laser.

It demonstrates with reference to the following composition example.

BaCl ₂ -xBaBr ₂ -yCaS: ZEu ²⁺ .

BaCl ₂ 8.553 g

(99.999%, Asian injury Kabuki Kaisha),

(48.0 mol%)

BaBr ₂ 12.175 g

(99.999%, Asian injury Kabuki Kaisha),

(48.0 mol%)

CaS 0.2464 g

(99.999%, product made by Kazuki Kaisha)

(4.0 mol%)

The raw material including was mixed with a ball mill. In addition, EuCl ₃ (99.9%, manufactured by Furuchi Chemical Industries, Ltd.) effective for activating the raw material was added to the mixture by the mill in a mass ratio of 0.0004 mole (0.08820 g) to 1 mole of the raw material mixture. . In addition, sulfur (99.999%, manufactured by Furuuchi Chemical Co., Ltd.) was added to the mixture by the ball mill in an amount of 4 moles (0.010942 g), which is the same amount as the CaS amount, to prevent sulfur deficiency contained in CaS. Thereafter, mixing was performed for 12 hours.

The mixed raw materials as described above were placed in a quartz boat and calcined in a tube furnace. This calcining treatment was performed for 90 minutes at a temperature of 882 ° C in He gas containing 20 vol% of H ₂ and having a flow rate of 10 pi / min. After completion of the firing step, the fired raw material was gradually cooled to ambient temperature in the above-described atmosphere. The phosphor made of the sintered photo-stimulatory light emitting material was pulverized to obtain a phosphor powder made of the photo-stimulatory light-emitting material. Its spectrum is shown in FIG.

From the above description, the phosphor made of the photo-stimulatory light emitting material according to the present invention is less sensitive to the excitation light of the visible wavelength and has a large sensitivity to the wavelength range of the emitted light by the semiconductor laser. It is possible to use as excitation light.

In the method according to the present embodiment, when a phosphor made of a photo-stimulatory light emitting material is produced, the raw materials must be mixed to a sufficient degree, and the mixing process is a conventional mixer such as a mixer, a ball mill, a V-type blender, a rod mill, or the like. You should be able to use When the activation raw material is used in the liquid phase, it is preferable to dry the mixture of the raw material containing the activation raw material, and then the mixing step is performed. Since the raw material of the phosphor has absorbency, the mixing step is preferably carried out in a dry atmosphere or in an inert gas atmosphere.

Thereafter, the phosphor raw material is placed in a heat resistant container such as an alumina crucible, a quartz crucible, or a quartz boat, and a firing step is performed.

Examples of the atmosphere that can be used as the minor component atmosphere include an atmospheric atmosphere (oxidation atmosphere), a reducing atmosphere, an inert gas atmosphere, and the like.

However, since the air atmosphere is an oxidizing atmosphere, a reducing atmosphere or an inert gas atmosphere is preferable.

As a preferable reducing atmosphere, there is a nitrogen atmosphere containing 30 vol% or less of hydrogen. Suitable inert gas atmospheres include nitrogen gas atmospheres, argon gas atmospheres, helium gas atmospheres, and the like.

The divalent europium is used as the activator for the phosphor made of a photostimulatory light emitting material of the complexed halide sulfide of alkaline earth metal activated by divalent europium according to the present invention.

Therefore, in the case of producing a phosphor made of a photo-stimulatory light emitting material, trivalent europium is contained in the raw material, so that it is reduced to divalent europium during the firing process.

That is, a phosphor made of a photo-stimulatory light emitting material using divalent europium as an activator is produced, and a firing step must be performed in a reducing atmosphere.

Preferred firing temperatures depend on the type and composition of the phosphor raw material of the photo-stimulatory light emitting material. In general, the temperature range is preferably 600 to 1,000 占 폚. Moreover, the temperature range of 700-950 degreeC is more preferable. The preferred firing time is determined by the type and / or composition of the raw material, the amount of the raw material input into the heat resistant container, the firing temperature and the like. When the temperature is selected within the above preferred temperature range, the firing time is preferably 30 minutes to 48 hours, more preferably 1 hour to 12 hours. After the firing process in which sintering occurs, the grinding process and the classification process are essential. This grinding step and the classification step are preferably carried out in a dry atmosphere, an inert atmosphere or a similar atmosphere.

The phosphor made of the photo-stimulatory light emitting material according to the present invention exhibits a peak sensitive to excitation light in the infrared wavelength region when irradiated by X-ray, UV, electron beam or the like. Accordingly, the photostimulatory light emission according to the present invention is compared with the phosphor made of a photostimulatory light emitting material, which is a divalent metal halide activated by a rare earth metal having an excitation light spectrum as shown in FIG. 7 or 8. Phosphors made of a material have less luminous intensity in the visible wavelength range, and consequently have the advantage of reading the phosphors using a semiconductor laser. For example, as illustrated in FIG. 9, the luminescence intensity of BaClBr—CaS: Eu ²⁺ for 630 nm is almost 60% of that for 780 nm. Therefore, when the phosphor made of the photo-stimulatory light emitting material of the present invention is used in an image processing system, it is possible to use a semiconductor laser rather than a He-Ne laser for reproducing an X-ray pattern stored in an X-ray image conversion plate. The size and weight of the image processing system equipment can be reduced.

Claims (46)

Applying a liquid mixture containing at least an alkaline earth metal halide and europium halide onto a base film to produce a composite layer having a composition corresponding to the mixture on the base film; Phosphor layer in a reducing atmosphere of a hydrogen and helium mixture having a flow ratio of 20: 1 to 1: 100 at a temperature of 1100 ° C, and a photostimulatory light emitting material made of alkaline earth metal halides activated by divalent europium; X-ray image conversion plate manufactured by the method for producing an X-ray image conversion plate, characterized in that it comprises a step of forming a. Applying a liquid mixture containing at least an alkaline earth metal halide and europium halide onto a base film to produce a composite layer having a composition corresponding to the mixture on the base film; Phosphor layer in a reducing atmosphere of a hydrogen and helium mixture having a flow ratio of 20: 1 to 1: 100 at a temperature of 1100 ° C, and a photostimulatory light emitting material made of alkaline earth metal halides activated by divalent europium; Method for producing an X-ray image conversion plate, characterized in that it comprises a step of forming a. 3. The method of claim 2, further comprising the step of placing a quartz or ceramic plate on the phosphor layer after the phosphor layer is manufactured, and calcining the phosphor layer in a reducing atmosphere to correct warpage of the phosphor layer. A method for producing an X-ray image conversion plate. Calcining a composite containing at least an alkaline earth metal halide and a europium halide in a first reducing atmosphere to convert the complex into a phosphor made of a photostimulatory light emitting material of an alkaline earth metal halide activated by a divalent europium; And applying a liquid mixture of the phosphor and the binder on the base film to form the phosphor layer on the base film, separating the phosphor layer and the binder from the base film, and separating the phosphor. Heating the layer and the binder to remove the binder from the phosphor layer, and firing the phosphor layer in a second reducing atmosphere to convert the phosphor layer into the sintered body. At least one of the second reduction quarries is a mixture of helium and hydrogen having a flow ratio of 20: 1 to 1: 100. The X-ray image converting plate is manufactured by the manufacturing method of the X- ray image converting plate characteristics. Calcining a complex containing at least an alkaline earth metal halide and a europium halide in a first reducing atmosphere to convert the complex into a phosphor made of a photostimulating light emitting material of an alkaline earth metal halide activated by divalent europium; And applying a liquid mixture of the phosphor and the binder on the base film to form the phosphor layer on the base film, separating the phosphor layer and the binder from the base film, and separating the phosphor. Heating the layer and the binder to remove the binder from the phosphor layer, and firing the phosphor layer in a second reducing atmosphere to convert the phosphor layer to the sintered body. At least one of the second reducing atmospheres is a mixture of helium and hydrogen having a flow ratio of 20: 1 to 1: 100 It is a method for manufacturing the X- ray image converting plate characteristics. 6. The method of claim 5, further comprising the step of placing a quartz or ceramic plate on the phosphor layer after the phosphor layer is manufactured, and calcining the phosphor layer in a reducing atmosphere to correct warpage of the phosphor layer. The manufacturing method of phosphorus X-ray image conversion plate. The X-ray image conversion plate according to claim 1, wherein the base film is a heat resistant substrate or a ceramic substrate. The X-ray image conversion plate according to claim 2, wherein the base film is a heat resistant substrate or a ceramic substrate. Base film 3 and: at least one protective layer 2 formed on the base film 3 and the phosphor layer 1 formed between the laminates of the base film 3 and the protective layer 2 And an adhesive layer (4) surrounding the edge thereof so as not to expose the phosphor layer (1) to the outside. (1-X) MeX ₂ -xMeX ' ₂ -yMe'S: composition of zEU ₂ ⁺ (wherein Me and Me' are at least one element selected from Mg, Ca, Sr and Ba, and X and X 'are F, Cl , Selected independently from the group comprising Br and I, different from each other, x is a number from 0.4 to 0.6, y is a positive number below 0.1, and z is a number from 0.001 to 0.03. An X-ray image conversion plate characterized by being a sintered compact sheet of phosphor. (Ii) a compound of halogen and group IIa elements, a compound of other halogen and group IIa elements and a europium halide, or a compound of a compound of halogen and group Ia and a compound of halogen and europium or thallium, or , Complexes of compounds of halogen and group IIa elements with compounds of other halogen and group IIa elements, wherein one of the two compounds is silicon oxide, phosphorus oxide, silicon oxide of Mg, Ca, Sr or Ba, phosphorus oxide, Mg Preparing a composite (iii) selected from the group consisting of one of sulfides of Ca, Sr or Ba, or yttrium oxide and europium halide, pulverizing any one of the compounds to obtain a composite powder; Forming a mixture of the powder and the binder of the composite, forming a sheet of the mixture, and baking the sheet to form the binder. Step, by heating in the mixture sheet to a reducing atmosphere, to methods for manufacturing the X-ray image converting plate characterized in comprising a step of conversion to the light emitting material of a light stimulating phosphor. aMX _2- (1-a) MX ' _2: composition of bEu (wherein M is an element selected from Mg, Ca, Sr and Ba, X and X' are individually selected elements in the halogen, a is less than 1 Positive, b is less than or equal to 0.2) or MX: an ancestor of aA (wherein M is an element selected from group Ia, X is halogen, A is europium or thallium and a is a positive number less than 1) or aMX _2- (1-a) MX ' ₂ -cB: The composition of bEu (wherein M is an element selected from Mg, Ca, Sr and Ba, X and X' are individually selected from halogen groups, B is Mg, Ca Phosphor of one of the sulfides of Sr or Ba, of silicon oxide, phosphorus oxide or yttrium oxide, a being a positive number less than 1 and b and c positive numbers less than 0.2) Forming a composite containing a powder and a binder, forming a layer by the composite, and layering the layer in an oxidizing atmosphere. Heating to from the layer, the method for producing characterized in, X-ray image converting plate, which comprises the steps of removing the binder standing. The method according to claim 12, further comprising the step of heating the layer from which the binder is removed in a reducing atmosphere. Calcining a mixture containing at least an alkaline earth metal halide and a europium halide in a reducing atmosphere, and producing a phosphor using a photo-stimulatory light emitting material of the alkaline earth metal halide activated by divalent europium. In the method for producing a phosphor, the reducing atmosphere is a mixture of helium and hydrogen, characterized in that the phosphor manufacturing method using a photo-stimulatory light emitting material. A phosphor with a photo-stimulatory light emitting material, characterized in that it comprises a complex having the following composition, comprising a sulfide and europium of an alkaline earth metal halide and an alkaline earth metal activated by divalent europium. _(1-x) Mex2-xMeX ' ₂ -yMe'S: zEu Wherein Me and Me 'are at least one element selected from the group containing Mg, Ca, Sr and Ba, X and X' are different elements selected from the group containing F, Cl, Br and I, x Is a number greater than or equal to 0.4 and less than or equal to 0.6, y is a positive number less than or equal to 0.1, and z is a number greater than or equal to 0.0001 and less than or equal to 0.03). The phosphor according to claim 15, wherein x is a number of 0.45 or more and 0.55 or less. The fluorescent agent according to claim 15, wherein y is a positive number of 0.001 or more and 0.05 or less. The fluorescent agent according to claim 15, wherein z is a positive number of 0.0001 or more and 0.01 or less. 16. A phosphor according to claim 15, wherein said Me is barium. 16. A phosphor according to claim 15, wherein said Me 'is calcium. A method for producing a phosphor comprising a complex compound comprising an alkaline earth metal halide, an sulfide of an alkaline earth metal, and europium activated by divalent europium, the method comprising the steps of: preparing a mixture of raw materials having a complex compound having the following composition; _(1-x) Mex ₂ -xMeX ' ₂ -yMe'S: zEu Wherein Me and Me 'are at least one element selected from the group containing Mg, Ca, Sr and Ba, X and X' are different elements selected from the group containing F, Cl, Br and I, x Is a number greater than or equal to 0.4 and less than or equal to 0.6, y is a positive number less than or equal to 0.1, and z is a number greater than or equal to 0.0001 and less than or equal to 0.03) And a step of baking the mixture in a temperature range of 500 to 1,100 ° C. in a weak reducing atmosphere. 22. The phosphor according to claim 21, wherein x is a number of 0.45 or more and 0.55 or less. The phosphor according to claim 21, wherein y is a positive number of 0.001 or more and 0.05 or less. The phosphor according to claim 21, wherein y is a positive number of 0.0001 or more and 0.01 or less. A phosphor according to claim 21, wherein said Me is barium. 16. A phosphor according to claim 15, wherein said Me 'is calcium. The X-ray image conversion plate according to claim 4, wherein the base film is a polymer film. The method of claim 5, wherein the base film is a polymer film. 6. The X-ray image conversion plate according to claim 5, further comprising the step of placing the phosphor layer on a heat resistant plate, and heating the phosphor layer on the heat resistant plate to remove the binder from the phosphor layer. Manufacturing method. 13. The X-ray image conversion plate of claim 12, further comprising the step of placing the phosphor layer on a heat resistant flat plate, and heating the phosphor layer on the heat resistant plate to remove the binder from the phosphor layer. Manufacturing method. 31. The method of manufacturing an X-ray image conversion plate according to claim 29 or 30, wherein the heat resistant flat plate is a quartz flat plate. The method of manufacturing an X-ray image conversion plate according to claim 13, further comprising the step of placing the layer from which the binder is removed on a graphite plate and the step of baking the layer in a reducing atmosphere. The X-ray image conversion plate according to claim 10, further comprising a heat resistant plate, a graphite plate or a glass plate on one side of the sintering agent sheet of the phosphor, and a glass sheet or a polymer sheet on the other side. A base film: at least one protective layer formed on the base film; a phosphor layer formed between the laminate of the base film and the protective layer; and surrounding edges of the phosphor layer so as not to expose the phosphor layer to the outside. The process of absorbing the radiation of the X-ray image conversion plate composed of an adhesive layer, the radiation transmitted from the object or the radiation emitted from the object fire, and the phosphor of the X-ray image conversion plate with an electromagnetic wave having a wavelength range of 500 ~ 900nm And exposing the radiation energy stored in the phosphor to emit light as fluorescence. The method of claim 9, wherein the base film is a polyethylene terephthalate film, a polyethylene terephthalate film having at least one of a silicon oxide layer and a metal oxide layer, a tampered glass plate, a quartz glass plate, a heat resistant substrate or a graphite substrate, characterized in that X-ray image conversion plate. The X-ray image conversion plate according to claim 9, wherein the protective layer is a polyethylene terephthalate film tampered glass plate or a quartz glass plate having at least one of a polyethylene terephthalate film, a silicon oxide layer or a metal oxide layer. 10. The X-ray image conversion plate according to claim 9, wherein the phosphor layer is a sintered layer of a phosphor made of a photostimulatory light emitting material which is a halide of an alkaline earth metal activated by a divalent europium having the following composition: _{aMX 2 - (1-a)} MX '2: bEu 2- (Wherein M is an element selected from the group consisting of Mg, Ca, Sr and Br, X and X 'are individually selected elements from the halogen group, a is a positive number less than 1 and b is a positive number less than or equal to 0.2) 10. The X phosphor according to claim 9, wherein the phosphor layer is made of a sintered layer of phosphor of a photostimulatory light emitting material made of a compound of halogen and group Ia element having the following composition activated by divalent europium or divalent thallium. Line conversion plate; MX: aA (Wherein M is an element selected from group Ia or halogen, A is halogen, A is divalent europium or divalent thallium, a is less than 1 positive) 10. The X-ray image conversion plate according to claim 9, wherein the phosphor layer is a sintered layer of phosphor made of a photo-stimulatory light emitting material which is a halide of an alkaline earth metal of the following composition activated by divalent europium: aMX _2- (1-a) MX ' ₂ -cB: bEu ²⁺ (Wherein M is a group IIa element, one of X and X 'is an element selected individually from the halogen group, and B is a group consisting of silicon oxide, phosphorus oxide, one of sulfides of Mg, Ca, Sr or Ba and irioxide) Is a compound selected from a, a is less than 1 positive, and one of b and c is positive less than or equal to 0.2) 40. The composite according to any one of claims 37, 38 or 39, wherein the sintered layer of the phosphor is a compound (i) consisting of a compound of halogen and group IIa elements, a compound of another halogen and group IIa elements and a europium halide, or a halogen and (Ii) a complex of a compound of group Ia with a compound of halogen and europium or thallium, or a complex of a compound of halogen and group Ia with another compound of halogen and group IIa, either of which is silicon jade A mixture of complex (iii) selected from the group consisting of one of the sulfides of seed, phosphorus oxide, Mg, Ca, Sr or Ba, yttrium oxide and europium halides is hydrogen having a flow ratio of 20: 1 to 1: 100. By firing in a reducing atmosphere containing a mixture of and helium, trivalent europium (Eu ³⁺ ) or trivalent thallium (Tl ³⁺ ) is ^converted to divalent europium (Eu ²⁺ ) or divalent thallium (Tl ²⁺ ), respectively. Reducing process X-ray image conversion plate, characterized in that manufactured by. 10. The X-ray image conversion plate according to claim 9, wherein the phosphor layer comprises a solid layer made of a mixture of a phosphor and a binder made of a photostimulatory light emitting material, and the phosphor has the following composition. _{aMX 2 - (1-a)} MX'2: bEu 2+ (Wherein M is an element selected from the group consisting of Mg, Ca, Sr and Ba, X and X 'are elements individually selected from halogen groups, a is a positive number of less than 1 and b is a positive number of 0.2 or less) 10. An X-ray image conversion plate according to claim 9, wherein said phosphor layer comprises a solid layer made of a mixture of a photostimulatory light emitting material phosphor and a binder, said phosphor having the following composition. MX: aA (Wherein M is an element selected from Group Ia, X is halogen, A is europium or thallium, and a is a positive number less than 1) 10. The X-ray image conversion plate according to claim 9, wherein the phosphor layer comprises a solid layer comprising a mixture of a phosphor and a binder of a photo-stimulatory light emitting material, wherein the phosphor has the following composition. aMX _2- (1-a) MX ' ₂ -cB: bEu ²⁺ Wherein M is an element belonging to group IIa, one of X 'and X is an element selected individually from the halogen group, B is silicon oxide, phosphorus oxide, one of the sulfides of Mg, Ca, Sr or Ba and yttrium oxide Is a compound selected from the group 1, a is less than one positive number, and one of b and c is positive or less than 0.2). 43. The complex according to any one of claims 41, 42 or 43, wherein the phosphor is a compound of halogen and group IIa elements, a compound of other halogen and group IIa elements and a europium halogen compound, or of a halogen and group Ia element. (Ii) a complex of a compound with a compound of halogen and europium or thallium, or a compound of a compound of halogen and group IIa elements with a compound of other halogen and group IIa elements, either of which is silicon oxide, oxide A mixture of the composite agent (iii), which is a compound selected from the group consisting of one of the sulfides of phosphorus, Mg, Ca, Sr and Ba, yttrium oxide and europium halide, has hydrogen and helium having a flow ratio of 20: 1 to 1: 100. The trivalent europium (Eu ³⁺ ) or trivalent thallium (Tl ³⁺ ) is reduced to divalent europium (Eu ²⁺ ) or divalent thallium (Tl ²⁺ ) by firing in a reducing atmosphere containing a mixture of Do the process Which it is characterized by the manufacture by the X-ray image converting plate. 10. The X-ray image conversion plate according to claim 9, wherein the phosphor is activated by a divalent europium having the following composition, and is composed of a complex compound consisting of a halide of alkaline earth metals, a sulfide of alkaline earth metals, and europium. (1-x) MeX ₂ -xMeX ' ₂ -yMe'S: zEu ²⁺ Wherein Me and Me 'are at least one element selected from the group consisting of Mg, Ca, Sr and Ba, X and X' are different elements selected from the group consisting of F, Cl, Br and I, and x is 0.4 Is a number of ˜0.6, y is a positive number of 0.1 or less, and z is a number of 0.001 to 0.03.) 10. The substrate film 3 and the protective layer 2 having a width and a length of about 5 mm larger than those of the shaped layer 1.

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