WO2006054532A1 - 希土類賦活アルカリ土類金属弗化ハロゲン化物輝尽性蛍光体の製造方法 - Google Patents
希土類賦活アルカリ土類金属弗化ハロゲン化物輝尽性蛍光体の製造方法 Download PDFInfo
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- WO2006054532A1 WO2006054532A1 PCT/JP2005/020907 JP2005020907W WO2006054532A1 WO 2006054532 A1 WO2006054532 A1 WO 2006054532A1 JP 2005020907 W JP2005020907 W JP 2005020907W WO 2006054532 A1 WO2006054532 A1 WO 2006054532A1
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- rare earth
- earth metal
- alkaline earth
- photostimulable phosphor
- activated alkaline
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7732—Halogenides
- C09K11/7733—Halogenides with alkali or alkaline earth metals
Definitions
- the present invention relates to a method for producing a rare earth activated alkaline earth metal fluoride fluoride photostimulable phosphor (hereinafter also referred to simply as a photostimulable phosphor or phosphor).
- a radiation image recording / reproducing method using a stimulable phosphor described in JP-A-55-12145 is known as an effective diagnostic means to replace conventional radiography methods! / Speak.
- This method uses a radiation image conversion panel (also referred to as a stimulable phosphor sheet) containing a stimulable phosphor, and is capable of stimulating radiation transmitted through a subject or emitted from a subject.
- the stimulable phosphor is absorbed in a time-dependent manner and excited in a time series by electromagnetic waves (referred to as excitation light) such as visible light and ultraviolet light, and the accumulated radiation energy is fluorescent (referred to as stimulated emission light).
- excitation light such as visible light and ultraviolet light
- stimulated emission light fluorescent
- This fluorescence is photoelectrically read to obtain an electrical signal, and a radiographic image of the subject or subject is reproduced as a visible image based on the obtained electrical signal.
- the conversion panel after reading is erased for the remaining image and used for the next shooting.
- the radiation image conversion panel is composed of only a support and a photostimulable phosphor layer provided on the surface of the support or a self-supporting photostimulable phosphor layer. Some are composed of a photostimulable phosphor and a binder that disperses and supports the photostimulable phosphor, and others are composed only of aggregates of photostimulable phosphors formed by vapor deposition or sintering. Also known are those in which a gap between the aggregates is impregnated with a polymer substance. Furthermore, what is the support side of the photostimulable phosphor layer? A protective film made of a polymer film or an inorganic vapor deposition film is usually provided on the opposite surface.
- the photostimulable phosphor those that exhibit photostimulated luminescence in the wavelength range of 300 to 500 nm by excitation light in the range of 400 to 900 nm are generally used.
- Rare earth element activated alkaline earth metal fluorides such as those described in 27980, 59-56479, 59-56480, etc .; JP-A-59-75200, 60 -84381, 60-1 06752, 60-166379, 60-221483, 60-228592, 60-2 28593, 61-23679, 61-120882, 61 — Divalent europium-activated alkaline earth metal fluoride fluoride fluorides described in 120883, 61-12 0885, 61-235486, 61-235487, etc .; Rare earth elements described in No.
- bivalent europium activated alkaline earth metal fluoride halide phosphors containing iodine, rare earth elements containing iodine Oxyhalogenated phosphors and iodine-containing bismuth-activated alkali metal halide phosphors are known, but high brightness photostimulable phosphors are still required.
- the method for producing a photostimulable phosphor described above is a method called a solid phase method or a sintering method, and pulverization after firing is essential, and control of the particle shape that affects sensitivity and image performance is controlled. It has the problem of being difficult.
- it is effective to make the photostimulable phosphor finer and to make the particle size of the microstimulated phosphor uniform, that is, to narrow the particle size distribution. .
- a method for producing a phosphor from a liquid phase disclosed in JP-A-7-233369, 9-291278 and the like is carried out by adjusting the concentration of a phosphor raw material solution to produce fine-grained photostimulant.
- This is a method for obtaining a phosphor precursor, and is effective as a method for producing a stimulable phosphor powder having a uniform particle size distribution.
- rare earth activated alkaline earth metal fluorides and logenium-based stimulable phosphors having a high iodine content are preferable. This is because iodine has a higher X-ray absorption rate than bromine.
- the alkaline earth metal fluoroiodide-based stimulable phosphor produced in the liquid phase as described above is advantageous in terms of luminance and granularity, but obtains a precursor crystal in the liquid phase. In this case, it has the following problems. That is, as can be seen in the description of JP-A-10-88125 and 9-291278,
- the method 2) also requires an excess of barium iodide relative to the inorganic fluoride, and the yield is low.
- the liquid phase synthesis of barium fluoroiodide has the problem of low yield and poor productivity.
- Lowering the concentration of norium iodide in the mother liquor in order to increase the yield leads to particle enlargement, which is not preferable in terms of image quality characteristics.
- Patent Document 1 Japanese Patent Laid-Open No. 2003-236303
- An object of the present invention is to produce a photostimulable phosphor with good productivity that can withstand repeated use by X-ray exposure, and a photostimulable phosphor that provides high sensitivity and high image quality. It is to provide a manufacturing method.
- the object of the present invention is achieved by the following configurations.
- M 1 is at least one alkali metal atom selected from Li, Na, K, Rb, Cs
- M 2 is at least one alkali earth metal atom selected from Be, Mg, Sr and Ca
- Ln is Ce, Pr, Sm, Eu, Gd, Tb, Tm, Dy, Ho, Nd, Er, and Yb are at least one kind of rare earth elements
- X, y, a, b, and c are 0 ⁇ x ⁇ 0. 3, 0 ⁇ y ⁇ 0. 3, 0 ⁇ a ⁇ 0. 05, 0 ⁇ b ⁇ 0. 2, 0 ⁇ c ⁇ 0. 1)
- an inorganic fluoride aqueous solution is added to a reaction mother liquor in which a stimulable phosphor represented by the following general formula (1) is dissolved at a reaction temperature of 85 to 100 ° C. and barium halide is dissolved.
- a process for obtaining a precipitate of a rare earth-activated alkaline earth metal fluoride halide-based stimulable phosphor precursor crystal and a process for removing a solvent from the reaction mother liquor are carried out in parallel, thereby producing a stimulable phosphor. It is characterized in that it is obtained by obtaining a precursor and firing the photostimulable phosphor precursor. With these constitutions, the effects of the present invention can be obtained.
- M 1 is at least one alkali metal atom selected from Li, Na, K, Rb, Cs
- M 2 is at least one alkali earth metal atom selected from Be, Mg, Sr and Ca
- Ln is Ce, Pr, Sm, Eu, Gd, Tb, Tm, Dy, Ho, Nd, Er, and Yb are at least one kind of rare earth elements
- X, y, a, b, and c are 0 ⁇ x ⁇ 0. 3, 0 ⁇ y ⁇ 0. 3 , 0 ⁇ a ⁇ 0. 05, 0 ⁇ b ⁇ 0. 2, 0 ⁇ c ⁇ 0. 1)
- the precursor production method described in Japanese Patent Application No. 8-265525 and the precursor production apparatus described in Japanese Patent Application No. 8-266718 are preferable. Available.
- the photostimulable phosphor precursor refers to a state in which the substance of the general formula (1) has not been subjected to a high temperature of 600 ° C. or higher. 'Show little sex.
- the photostimulable phosphor represented by the general formula (1) is preferably produced by a liquid phase method in which the particle size can be easily controlled by the solid phase method in which the particle shape is difficult to control.
- the Bal concentration is 3. OmolZL or more, preferably 3.3 mol
- a solution of inorganic fluoride (ammonium fluoride or alkali metal fluoride) having a concentration of 3 molZL or more, preferably 6 molZL or more is added thereto.
- a raw material compound other than a fluorine compound is dissolved in an aqueous medium. That is, the halides of Bal and Ln, and optionally more M 2 halides, and more
- the Bal concentration is 3. Omol / L or more, preferably 3.3 mol / L
- the amount ratio between the Bal concentration and the aqueous solvent is adjusted so as to be L or more.
- reaction mother liquor is maintained at 85-: LOO ° C.
- an aqueous solution of an inorganic fluoride (ammonium fluoride, alkali metal fluoride, etc.) is added to a stirred aqueous solution maintained at 85 ° C to 100 ° C. Inject using etc. This injection is preferably carried out in the region where the stirring is particularly intense.
- an inorganic fluoride aqueous solution into the reaction mother liquor, a rare earth activated alkaline earth metal fluoride halide phosphor precursor crystal corresponding to the general formula (1) is precipitated.
- the reaction fluid solvent is removed.
- the removal amount of the solvent is preferably 2% or more by mass ratio before and after the removal. Below this, the crystal may not be fully BFI. Therefore, the removal amount is preferably 2% or more, more preferably 5% or more.
- the removal method Since the time required for solvent removal greatly affects the productivity, the shape and particle size distribution of the particles are also affected by the solvent removal method, so the removal method must be selected appropriately. .
- a method of heating the solution and evaporating the solvent is selected. This method is also useful in the present invention.
- By removing the solvent a precursor having the intended composition can be obtained.
- other solvent removal methods in combination.
- the method for removing the solvent used in combination is not particularly limited. It is also possible to select a method using a separation membrane such as a reverse osmosis membrane. Main departure In terms of productivity, it is preferable to select the following removal method from the viewpoint of productivity.
- the reaction vessel is a sealed type, and at least two holes through which gas can pass are provided, and dry gas is vented from there.
- the kind of gas can be selected arbitrarily. Air and nitrogen are preferable from the viewpoint of safety.
- the solvent is entrained in the gas and removed.
- a method of jetting gas as bubbles in the liquid phase and absorbing the solvent in the bubbles is also effective.
- the vapor pressure of the solvent decreases.
- the solvent can be removed efficiently by lowering the vapor pressure.
- the degree of reduced pressure can be appropriately selected depending on the type of solvent. If the solvent is water, 650mmHg or less is preferred.
- the heating method is a method of immersing the heating means in a liquid or mounting the heating means outside the container. Is common. According to this method, the heat transfer area is limited to the portion where the liquid and the heating means are in contact with each other, and the heat transfer area decreases with the removal of the solvent, and thus the time required for the solvent removal increases. In order to prevent this, it is effective to spread the heat transfer area by spraying on the wall of the reaction vessel using a pump or a stirrer.
- This method of spraying a liquid on the reaction vessel wall and forming a liquid film is known as a “wetting wall”.
- Examples of the method for forming the wet wall include a method using a pump and a method using a stirrer described in JP-A-6-335627 and 11-235522.
- the above phosphor precursor crystals are separated from the solution by filtration, centrifugation, etc., sufficiently washed with methanol or the like, and dried.
- This dry phosphor precursor crystal Add anti-sintering agent such as lumina fine powder, silica fine powder, etc., mix, and uniformly adhere the fine powder of sintering inhibitor to the crystal surface. It is also possible to omit the addition of the sintering inhibitor by selecting the firing conditions.
- the phosphor precursor crystals are filled in a heat-resistant container such as a quartz port, an alumina crucible, or a quartz crucible, and placed in the core of an electric furnace to be fired while avoiding sintering.
- the firing temperature is suitably in the range of 400-1300 ° C, preferably in the range of 500-1000 ° C.
- the firing time varies depending on the filling amount of the phosphor raw material mixture, the firing temperature, the furnace temperature, and the like, but generally 0.5 to 12 hours is appropriate.
- the firing atmosphere may be a neutral atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere, or a nitrogen gas atmosphere containing a small amount of hydrogen gas, or a carbon dioxide atmosphere containing carbon monoxide.
- An atmosphere or a trace oxygen introduction atmosphere is used.
- the method described in JP-A-2000-8034 is preferably used.
- the desired rare earth activated alkaline earth metal fluoride fluoride based stimulable phosphor can be obtained by the above firing.
- the support used in the radiation image conversion panel of the present invention various polymer materials, glass, metal and the like are used.
- materials that can be processed into flexible sheets or webs as information recording materials are suitable.
- a plastic film such as a film or a polycarbonate film, a metal sheet such as aluminum, iron, copper, or chromium, or a metal sheet having a coating layer of the metal oxide is preferable.
- the layer thickness of these supports varies depending on the material of the support to be used, but is generally from 80 m to 1000 m, and more preferably from 80 m to 500 m. is there.
- the surface of these supports may be a smooth surface, or may be a mat surface for the purpose of improving the adhesion to the photostimulable phosphor layer.
- these supports are used for the purpose of improving the adhesiveness with the stimulable phosphor layer.
- An undercoat layer may be provided on the surface on which the light body layer is provided.
- binder used in the stimulable phosphor layer in the present invention examples include proteins such as gelatin, polysaccharides such as dextran, or natural polymer materials such as gum arabic; and Polybutyllar, Polyacetate Bull, Nitrocellulose, Ethyl Cellulose, Salt-Vulyidene's Salt-Buyl Copolymer, Polyalkyl (meth) acrylate, Salty Vinyl-Buyl'Acetate Bull Copolymer, Polyurethane, Cellulose
- binders represented by synthetic polymer materials such as acetate butyrate, polyvinyl alcohol, and linear polyester.
- binders are nitrocellulose, linear polyesters, polyalkyl (meth) acrylates, mixtures of nitrocellulose and linear polyesters, nitrocellulose and polyalkyl (meth) acrylates. Mixtures and mixtures of polyurethane and polybutyral. These binders may be cross-linked by a cross-linking agent.
- the photostimulable phosphor layer can be formed on the undercoat layer by, for example, the following method.
- an iodine-containing stimulable phosphor, a compound such as phosphite for preventing yellowing, and a binder are added to a suitable solvent, and these are mixed well into the binder solution.
- a coating solution in which the phosphor particles and the compound particles are uniformly dispersed is prepared.
- binder used in the present invention examples include proteins such as gelatin, polysaccharides such as dextran, gum arabic, polybulbutyral, polyvinyl acetate, -trocellulose, ethylcellulose, burden chloride.
- a film-forming binder usually used for layer construction such as butyl copolymer, polymethyl methacrylate, butyl chloride butyl acetate copolymer, polyurethane, cellulose acetate butyrate, polybutyl alcohol and the like is used.
- the binder is used in the range of 0.01 to 1 part by mass with respect to 1 part by mass of the stimulable phosphor.
- it is preferable to use a small amount of binder Is more preferable.
- the mixing ratio of the binder to the stimulable phosphor in the coating solution (however, when the binder is an epoxy group-containing compound, it is equal to the ratio of the compound to the phosphor) Characteristics of radiation image conversion panels, types of phosphors, addition amount of epoxy group-containing compounds Generally, as an example of a solvent for preparing a bonding coating solution, methanol is used.
- Enothal, lower alcohols such as 1-propanol, 2-propanol, n-butanol; hydrocarbons containing chlorine atoms such as methylene chloride and ethylene chloride; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methyl acetate And esters of lower fatty acids and lower alcohols such as ethyl acetate, butyl acetate and butyl acetate; etherols such as dioxane, ethylene glycolenoethenoreethenore, ethyleneglycololeminomethinoreethenore; toluene; and mixtures thereof it can.
- Examples of the solvent used for the preparation of the stimulable phosphor layer coating solution include lower alcohols such as methanol, ethanol, isopropanol, and n-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- ketones such as ketones, methyl acetate, ethyl acetate, esters of lower fatty acids such as n-butyl acetate and lower alcohols, ethers such as dioxane, ethyleneglycolenomethinoreethenore, ethyleneglycololemonomethinoreethenore, Examples thereof include aromatic compounds such as triol and xylol, halogenated hydrocarbons such as methylene chloride and ethylene chloride, and mixtures thereof.
- the coating solution contains a dispersant for improving the dispersibility of the phosphor in the coating solution, and between the binder and the phosphor in the photostimulable phosphor layer after formation.
- a dispersant for improving the dispersibility of the phosphor in the coating solution, and between the binder and the phosphor in the photostimulable phosphor layer after formation.
- Various additives such as a plasticizer for improving the bonding force may be mixed.
- the dispersant used for such purposes include phthalic acid, stearic acid, cabronic acid, and lipophilic surfactants.
- plasticizers include phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate and diphenyl phosphate; phthalic acid esters such as jetyl phthalate and dimethochetyl phthalate; ethyl phthalyl glycolate, butyl phthalyl glycolate Examples thereof include glycolic acid esters such as butyl; polyesters of triethylene glycol and adipic acid, polyesters of polyethylene glycol and aliphatic dibasic acid such as polyesters of diethylene glycol and succinic acid, and the like.
- stearic acid such as may be mixed.
- phthalic acid such as jetyl phthalate and dibutyl phthalate.
- examples thereof include aliphatic dibasic acid esters such as tellurium, diisodecyl succinate and dioctyl adipate, and glycolic acid esters such as ethylphthalyl glycolate and butylphthalylbutyl glycolate.
- the coating liquid prepared as described above is uniformly applied to the surface of the undercoat layer to form a coating film of the coating liquid.
- This coating operation can be performed by using a normal coating means, for example, a doctor blade, a roll coater, a knife coater or the like.
- the formed coating film is dried by gradually heating to complete the formation of the photostimulable phosphor layer on the undercoat layer.
- the thickness of the photostimulable phosphor layer varies depending on the characteristics of the intended radiation image conversion panel, the type of stimulable phosphor, the mixing ratio of the binder and the phosphor, and is usually 20 ⁇ m. To lmm. However, this layer thickness is preferably 50 to 500 ⁇ m.
- the coating solution for the photostimulable phosphor layer is prepared using a dispersing device such as a ball mill, a sand mill, an attritor, a three-necked roll mill, a high-speed impeller disperser, a Kady mill, and an ultrasonic disperser. It is.
- the prepared coating solution is applied onto a support using a coating solution such as a doctor blade, a roll coater, or a knife coater, and dried to form a photostimulable phosphor layer.
- the stimulable phosphor layer and the support may be adhered after the coating solution is applied on the protective layer and dried.
- the thickness of the photostimulable phosphor layer of the radiation image conversion panel of the present invention depends on the characteristics of the intended radiation image conversion panel, the type of stimulable phosphor, the binder and the photostimulable phosphor.
- the range force is preferably selected from the range of 10 / ⁇ ⁇ to 1000 / ⁇ ⁇ , more preferably from 10 / ⁇ ⁇ to 500 ⁇ m.
- Example 1 In order to synthesize a stimulable phosphor precursor of europium-activated barium fluoride iodide, 2500 ml of Bal aqueous solution (3.35 molZL) and Eul aqueous solution (0.2
- the pressure in the reaction vessel was adjusted to 560 mmHg using a circulation aspirator, and the solvent was concentrated under reduced pressure.
- the mass ratio of the reaction solution before and after concentration was 0.90. Except this, the same operation as in Example 1 was performed to obtain a precipitate.
- the yield was calculated in the same manner as in Example 1, and the X-ray diffraction of the precipitate was performed.
- a precipitate was obtained in the same manner as in Example 1 except that the reaction temperature was 80 ° C.
- the mass ratio of the reaction solution before and after concentration was 0.91.
- the tube voltage and tube current are 80 kV and 100 mAo, respectively, and the fact that the half width is wide means that the crystallinity is broken compared to the narrow case.
- Each radiation image conversion panel was evaluated as follows.
- the panel After irradiating the radiation image conversion panel with X-rays with a tube voltage of 80 kVp, the panel is excited by operating with a He—Ne laser (633 nm) to receive the stimulated luminescence emitted from the phosphor layer.
- the light intensity was measured with a photosensitivity photomultiplier tube having a spectral sensitivity of S-5.
- sensitivity is shown as a relative value.
- the panel After irradiating the radiation image conversion panel with X-rays with a tube voltage of 80 kVp through a lead MTF chart, the panel is excited by operating with a He—Ne laser beam and emitted from the phosphor layer.
- the photostimulated luminescence is received by the same receiver as the sensitivity measurement and converted into an electrical signal, which is converted to analog Z-digital and recorded on magnetic tape, and the magnetic tape is analyzed by a computer.
- MTF modulation transfer function
- the panel After irradiating the radiation image conversion panel with X-rays (5R) with a tube voltage of 80 kVp, the panel is operated with halogen light to erase the information in the panel. This operation is repeated until the accumulated dose reaches 1000R, and the rate of decrease with respect to the initial sensitivity is obtained.
- High repetition durability (%) means high durability against X-rays with a low reduction rate.
- a photostimulable phosphor that can withstand repeated use by X-ray exposure and has an excellent effect with high sensitivity and high image quality is produced. I can do it.
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JP2006545049A JPWO2006054532A1 (ja) | 2004-11-22 | 2005-11-15 | 希土類賦活アルカリ土類金属弗化ハロゲン化物輝尽性蛍光体の製造方法 |
EP05806996A EP1826259A1 (en) | 2004-11-22 | 2005-11-15 | Process for producing rare earth activated alkaline earth metal fluorohalide photostimulable phosphor |
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JP2004337236 | 2004-11-22 | ||
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EP (1) | EP1826259A1 (ja) |
JP (1) | JPWO2006054532A1 (ja) |
CN (1) | CN101061201A (ja) |
WO (1) | WO2006054532A1 (ja) |
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WO2009116355A1 (ja) * | 2008-03-19 | 2009-09-24 | コニカミノルタエムジー株式会社 | 希土類賦活アルカリ土類金属弗化ハロゲン化物系輝尽性蛍光体の製造方法、希土類賦活アルカリ土類金属弗化ハロゲン化物系輝尽性蛍光体及び放射線像変換パネル |
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JP4760236B2 (ja) * | 2005-05-27 | 2011-08-31 | 日立化成工業株式会社 | 単結晶の熱処理方法 |
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CN103045237B (zh) * | 2011-10-17 | 2014-10-15 | 海洋王照明科技股份有限公司 | 钕镱双掺杂氯化钡上转换发光材料、制备方法及其应用 |
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US20060108565A1 (en) | 2006-05-25 |
JPWO2006054532A1 (ja) | 2008-05-29 |
EP1826259A1 (en) | 2007-08-29 |
CN101061201A (zh) | 2007-10-24 |
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