WO2007029492A1 - Radiation image transformation panel - Google Patents

Radiation image transformation panel Download PDF

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Publication number
WO2007029492A1
WO2007029492A1 PCT/JP2006/316447 JP2006316447W WO2007029492A1 WO 2007029492 A1 WO2007029492 A1 WO 2007029492A1 JP 2006316447 W JP2006316447 W JP 2006316447W WO 2007029492 A1 WO2007029492 A1 WO 2007029492A1
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WIPO (PCT)
Prior art keywords
layer
radiation image
image conversion
conversion panel
protective layer
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Application number
PCT/JP2006/316447
Other languages
French (fr)
Japanese (ja)
Inventor
Hirobumi Yamashita
Original Assignee
Konica Minolta Medical & Graphic, Inc.
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Application filed by Konica Minolta Medical & Graphic, Inc. filed Critical Konica Minolta Medical & Graphic, Inc.
Priority to JP2007534314A priority Critical patent/JPWO2007029492A1/en
Publication of WO2007029492A1 publication Critical patent/WO2007029492A1/en

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Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
    • 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
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/779—Halogenides

Definitions

  • the present invention relates to a radiation image conversion panel, and more specifically, the radiation image conversion panel is protected from physical impact in the periphery of the radiation image conversion panel, and the panel is deteriorated due to moisture absorption of the photostimulable phosphor layer.
  • the present invention relates to a radiation image conversion panel in which the above is prevented.
  • Radiation images such as X-ray images are often used for disease diagnosis and the like.
  • the phosphor fluorescent screen
  • the phosphor is irradiated with X-rays that have passed through the subject, thereby generating visible light, and this visible light is applied to silver salt in the same way as when taking a normal picture.
  • So-called radiographs developed by irradiating and developing the used film have been widely used in the past.
  • a radiation image conversion method using a stimulable phosphor as described in Patent Documents 1 and 2 is known as an alternative to the conventional radiographic method.
  • This method uses a radiation image conversion panel (accumulative phosphor sheet) containing a stimulable phosphor.
  • the panel transmits the radiation transmitted through the subject or emitted from the subject.
  • the stimulable phosphor is then absorbed and then accumulated in the stimulable phosphor by exciting the stimulable phosphor in a time series with electromagnetic waves (excitation light) such as visible light and infrared light.
  • Radiation energy is emitted as fluorescence (stimulated luminescence light), this fluorescence is photoelectrically read to obtain an electrical signal, and then a radiographic image of the subject or subject is visualized based on the obtained electrical signal. As something to play.
  • the panel which has been read is prepared for the next photographing after the remaining image is erased. That is, the radiation image conversion panel is used repeatedly.
  • radiographic image conversion method a radiographic image having a large amount of information can be obtained with a much smaller exposure dose than in the case of radiography using a combination of a conventional radiographic film and an intensifying screen. There is an advantage that can be obtained.
  • conventional radiography consumes radiographic film for each shot, whereas this radiographic image is used.
  • the conversion method uses a radiation image conversion panel repeatedly, which is advantageous in terms of resource protection and economic efficiency.
  • Such a stimulable phosphor is a stimulable phosphor that exhibits stimulating luminescence when irradiated with radiation and then irradiated with excitation light.
  • the wavelength is in the range of 400 to 900 nm.
  • Stimulable phosphors that exhibit stimulated emission in the wavelength range of 300 to 500 nm by excitation light are generally used.
  • a protective layer is usually provided on the surface of the photostimulable phosphor layer (the surface not facing the support), and the phosphor layer is subjected to chemical alteration or physical impact. It protects from.
  • the protective layer was formed by applying a solution prepared by dissolving a transparent organic polymer substance such as cellulose derivative or polymethylmetatalylate in an appropriate solvent on the phosphor layer.
  • an organic polymer film such as polyethylene terephthalate, or a sheet for forming a protective layer such as a transparent glass plate, which is fixed to the surface of the phosphor layer with an appropriate adhesive, or an inorganic compound is deposited.
  • a film formed on a phosphor layer is known.
  • the radiation image conversion panel When implementing the radiation image conversion method, the radiation image conversion panel is used to irradiate radiation (record radiation images), irradiate excitation light (read out recorded radiation images), and then apply erasing light. It is used repeatedly in a cycle of (erasing the remaining radiation image).
  • the transition to each step of the radiation image conversion panel is performed by a conveying means such as a belt and a roller, and after completion of the site, the panels are usually laminated and stored.
  • the radiation image conversion panel having the protective layer formed by coating as described above is repeatedly used in this manner, for example, the surface of the protective layer may be contaminated or scratched. For the reason, the image quality of the radiation image formed by the radiation image conversion panel tends to be gradually lowered.
  • the radiographic image conversion panel is also desired to provide an image with high sensitivity and good image quality (sharpness, graininess, etc.) as in the conventional radiographic method, as described above. It is an important issue to prevent the occurrence of various stains and scratches.
  • Patent Document 3 a protective layer provided with a resin composition layer containing a crosslinkable fluororesin is laminated (laminated) on the surface of the photostimulable phosphor layer to obtain antifouling property, scratch resistance and A method for obtaining a radiation image conversion panel having excellent durability is disclosed.
  • This method is antifouling and scratchproof
  • a thin film is difficult, and a scattering layer is necessary on the surface to prevent stretching unevenness of the PET used for the protective layer. Due to the thick film, there is a problem that sharpness and contrast are lowered.
  • Patent Document 4 a phosphor sheet having a stimulable phosphor layer on a support, and a phosphor sheet that is disposed above and below the phosphor sheet and covers the entire surface of the phosphor sheet are provided. Further, a radiation image conversion panel having a protective film (la, so-called sealing film) is disclosed. Although this method is antifouling and scratch resistant, it has the problem of poor productivity.
  • Patent Document 1 US Pat. No. 3,859,527
  • Patent Document 2 JP-A-55-12144
  • Patent Document 3 Japanese Patent Publication No. 2001-13298
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-131498
  • Patent Document 5 Japanese Patent Laid-Open No. 2002-148395
  • Patent Document 6 Japanese Unexamined Patent Application Publication No. 2002-174698
  • the present invention has been made in view of the above problems, and its purpose is to protect the radiation image conversion panel from physical impact at the periphery of the radiation image conversion panel and to absorb moisture from the stimulable phosphor layer. It is an object of the present invention to provide a radiation image conversion panel in which deterioration of the panel due to, for example, is prevented.
  • the radiation image conversion panel has a small amount of the stimulable phosphor layer. Both have a covering portion having a softening point that seals the end portion together with the protective layer, and the difference between the softening point of at least one of the protective layer and the covering portion is 0 to 30 ° C. Characteristic radiation Line image conversion panel.
  • At least one of the protective layers and the covering portion each contain a thermoplastic elastomer, and each thermoplastic elastomer contains the same monomer unit, and the same monomer unit.
  • M 1 is at least one alkali metal atom selected from Li, Na, K, Rb and Cs
  • M 2 is at least one alkali earth metal atom selected from Be, Mg, Sr and Ca
  • L ⁇ Ce, Pr, Sm, Eu, Gd, Tb, Tm, Dy, Ho, Nd, Er, and Yb force are selected from at least one rare earth element, x, y, a, b, and c, respectively.
  • a radiation image conversion panel that protects the radiation image conversion panel from physical impact at the periphery of the radiation image conversion panel and prevents deterioration of the panel due to moisture absorption or the like of the stimulable phosphor layer. Can be provided.
  • FIG. 1 is a cross-sectional view of a radiation image conversion panel showing a first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a radiation image conversion panel showing a second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view of a radiation image conversion panel showing a third embodiment of the present invention.
  • the radiation image conversion panel has at least a stimulable phosphor layer and a protective layer having a softening point on the support.
  • a coating portion having a softening point that seals at least an end of the photostimulable phosphor layer together with the protective layer, and a difference in softening point between at least one layer of the protective layer and the coating portion is 0 to
  • the radiation image conversion panel which is characterized by 30 ° C, protects the radiation image conversion panel from physical impacts at the periphery of the radiation image conversion panel, which does not deteriorate the sensitivity and image quality.
  • the inventors have found the effect of the present invention that a radiation image conversion panel in which deterioration of the panel due to moisture absorption of the layer is prevented can be obtained.
  • the photostimulable phosphor layer is sealed by a covering portion, a protective layer, and a support.
  • at least one of the protective layer and the coating are also used.
  • the effect of the present invention is achieved by the difference in the softening point of the part between S0 and 30 ° C.
  • FIG. 1 is a sectional view of a radiation image conversion panel showing a first embodiment of the present invention
  • FIG. 2 is a sectional view of a radiation image conversion panel showing a second embodiment of the present invention
  • FIG. It is sectional drawing of the radiation image conversion panel which shows three embodiment.
  • a photostimulable phosphor layer 12 is laminated on a support 11, and the photostimulable phosphor is displayed.
  • a protective layer 13 is further laminated on the layer 12, and the end portion of the stimulable phosphor layer 12 is sealed with the covering portion 14.
  • the covering portion 14 only needs to seal the photostimulable phosphor layer 12, and wraps the entire support 11, the photostimulable phosphor layer 12, and the protective layer 13 as shown in FIG. It is preferable to encapsulate the photostimulable phosphor layer 12.
  • the covering portion 24 may be placed on the edge portion of the support 21 to seal the stimulable phosphor layer 22.
  • the covering portion 24 may be provided up to the side portion of the protective layer 23.
  • the stimulable phosphor layer 32 is smaller than the support 31 and smaller than the protective layer 33, the stimulable phosphor layer
  • a covering portion 34 is preferably provided so as to cap the photostimulable phosphor layer 32 as shown in FIG.
  • the thickness of the end face of the photostimulable phosphor layer of the covering portion is in contact with the end face of the stimulable phosphor layer of the covering portion with respect to the end face of the stimulable phosphor layer. Thickness in the vertical direction, which is dl in Fig. 1, d2 in Fig. 2, and d3 in Fig. 3.
  • the thickness of the coating portion is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, from the viewpoint of moisture resistance and strength with respect to the stimulable phosphor layer and productivity.
  • each layer of the radiation image conversion panel of the present invention will be described in the order of a stimulable phosphor layer, a support, a protective layer, and a covering portion.
  • the photostimulable phosphor layer according to the present invention will be described.
  • the photostimulable phosphor layer contains at least a binder and photostimulable phosphor particles.
  • a photostimulable phosphor is a material that is exposed to the initial light or high energy radiation by stimulating (stimulated excitation) such as optical, thermal, mechanical, scientific or electrical after the initial light or high-energy radiation. Phosphors exhibiting stimulated emission corresponding to the irradiation dose of engineering radiation. From a practical standpoint, phosphors that exhibit stimulated emission by light stimulation (stimulated excitation) have a preferred wavelength of 500 nm ⁇ A phosphor exhibiting stimulated emission by 1 ⁇ m stimulated excitation light is preferred.
  • M represents at least one alkali metal of Li, Na, K, Rb, and Cs, and M represents Be, Mg,
  • An alkali halide photostimulable phosphor represented by
  • lx IXI represents at least one of g, Ca, Sr, Zn, and Cd
  • X represents at least one of Cl, Br, and I
  • A represents Eu, Tb, Ce, Tm, Dy, Pr, Ho, It represents at least one of Nd, Yb and Er
  • x and y represent numbers satisfying 0 ⁇ x ⁇ 0.6 and 0 ⁇ y ⁇ 0.2.
  • ⁇ represents at least one of ThO
  • Ln is Eu, Tb, Ce, Tm, Dy, Pr, Ho, Nd, Yb
  • X is at least one of Cl, Br, I, x, y are 5 X 10— 5 ⁇ x ⁇ 0. 5, 0 ⁇ y ⁇ 0. Represents a number satisfying 2.
  • Stimulable phosphor represented by
  • stimulable phosphors represented by the following general formula (1) are preferable.
  • M 1 is at least one alkali metal atom selected from Li, Na, K, Rb and Cs
  • M 2 is at least one alkali earth metal atom selected from Be, Mg, Sr and Ca
  • Ln is At least one rare earth element selected from Ce, Pr, Sm, Eu, Gd, Tb, Tm, Dy, Ho, Nd, Er, and Yb, x, y, a, b, and c is 0 ⁇ 0 ⁇ 3, 0 ⁇ y ⁇ l. 0, 0 ⁇ a ⁇ 0. 05, 0 ⁇ b ⁇ 0. 2, 0 ⁇ c ⁇ 0.1.
  • the photostimulable phosphor precursor refers to a state in which the substance represented by the general formula (1) has not been subjected to a high temperature of 600 ° C. or higher. , which shows almost no sexual activity or instantaneous luminescence.
  • the precursor is preferably obtained by the following liquid phase synthesis method.
  • the photostimulable phosphor composed of the general formula (1) is preferably produced by a liquid phase method in which the particle size is easily controlled as compared with the solid phase method in which the particle shape is difficult to control.
  • Production method It contains a halide of Bal and Ln, and if x in the general formula (1) is not 0, it further contains a halide of M 2 , if y is not 0, BaBr, and M 1
  • Inorganic fluoride with a concentration of 5 mol / L or more, preferably 8 mol / L or more, while maintaining a temperature of C or more
  • a process comprising: separating the precursor crystal precipitate from the reaction solution; and firing the separated precursor crystal precipitate while avoiding sintering.
  • the particles have an average particle size of 1 to 10 ⁇ m
  • monodisperse particles preferably have an average particle size of 1 to 5 xm and an average particle size distribution of Those having a particle size of 20% or less are preferred. Particularly, those having an average particle size of: ⁇ 3 ⁇ m and a distribution of average particle size of 15% or less are preferable.
  • the average particle diameter in the present invention is obtained by randomly selecting 200 particles from an electron micrograph of particles (crystals) and calculating the average with a volume particle diameter in terms of a sphere.
  • a raw material compound other than a fluorine compound is dissolved in an aqueous medium. That is, the halides of Bal and Ln, and if necessary, further M 2 halides, and further M 1 halides are placed in an aqueous medium and mixed thoroughly to dissolve them. Prepare an aqueous solution.
  • Bal concentration is 3.3molZL or more, preferably 3.5mol
  • the amount ratio between the Bal concentration and the aqueous solvent is adjusted so as to be equal to or higher than ZL.
  • a small amount of acid, ammonia, alcohol, water-soluble polymer, water-insoluble metal oxide fine particle powder or the like may be added. It is also preferable to add an appropriate amount of lower alcohol (methanol or ethanol) within a range where the solubility of Bal does not significantly decrease.
  • This aqueous solution (reaction mother liquor) is maintained at 80 ° C.
  • an aqueous solution of an inorganic fluoride (ammonium fluoride, alkali metal fluoride, etc.) is poured into the aqueous solution maintained at 80 ° C and stirred. This injection is preferably carried out in the region where stirring is particularly intense.
  • an inorganic fluoride ammonium fluoride, alkali metal fluoride, etc.
  • the timing for removing the solvent is not particularly limited as long as it is in the additive.
  • the ratio (hereinafter referred to as the removal ratio) of the total mass after removal of the solvent to the mass before removal (the sum of the mass of the reaction mother liquor and the mass of the added aqueous solution) is preferably 0.97 or less. If it exceeds 0.9, the crystal may not be BaFI. Therefore, the removal ratio is preferably 0.97 or less, more preferably 0.95 or less. Moreover, even if it is removed too much, the viscosity of the reaction solution may increase excessively, which may cause inconvenience in handling.
  • the solvent removal ratio is preferably up to 0.5 (0.50 or more).
  • the time required to remove the solvent is not a force that greatly affects the productivity.
  • the shape and particle size distribution of the particles are also affected by the method of removing the solvent, 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.
  • the method for removing the solvent used in combination is not particularly limited. Reverse immersion It is also possible to select a method using a separation membrane such as a permeable membrane. In the present invention, it is preferable to select the following removal method from the viewpoint of productivity.
  • the reaction vessel through which dry gas is vented is sealed, and at least two or more holes through which gas can pass are provided, and dry gas is vented from there.
  • the type of gas can be selected arbitrarily. Air and nitrogen are preferable from the viewpoint of safety. Depending on the amount of saturated water vapor in the gas being aerated, 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 efficiently removed by the vapor pressure drop.
  • the degree of reduced pressure can be appropriately selected depending on the type of solvent. When the solvent is water, 86 kPa or less is preferable.
  • the solvent can be efficiently removed by enlarging the liquid film evaporation area.
  • the heating method is generally either by immersing the heating means in a liquid or by attaching the heating means outside the container. It is. 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 solvent removal increases. In order to prevent this, it is effective to spread the heat transfer area by spraying it on the wall of the reaction vessel using a pump or a stirrer.
  • This method of spraying a liquid on the reaction vessel wall to form a liquid film is known as a “wetting wall”.
  • a method for forming the wetting wall in addition to a method using a pump, a method using a stirrer described in JP-A Nos. 6-335627 and 11-235522 can be mentioned.
  • the phosphor precursor crystal is separated from the solution by filtration, centrifugation, or the like, sufficiently washed with methanol or the like, and dried.
  • a sintering inhibitor such as alumina fine powder or silica fine powder is added to and mixed with the dried phosphor precursor crystal, and the sintering inhibitor fine powder is added to the crystal surface. Apply the powder uniformly. 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, a quartz crucible, and the like, and placed in an electric furnace core to be sintered while avoiding sintering.
  • the firing temperature is suitably from 400 to 1,300 ° C, and preferably from 500 to 1,000 ° C.
  • the firing time varies depending on the filling amount of the phosphor raw material mixture, the firing temperature, the removal temperature from the furnace, etc., 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, or the like.
  • An atmosphere or a trace oxygen introduction atmosphere is used.
  • the method described in JP-A-2000-8034 is preferably used.
  • the target photostimulable phosphor is obtained by the above firing, and a radiation image conversion panel having a phosphor layer formed using the phosphor is produced.
  • binder also referred to as binder
  • the binder used in the photostimulable phosphor layer according to the present invention will be described.
  • binder used in the present invention examples include proteins such as gelatin, polysaccharides such as dextran, or natural high molecular substances such as gum arabic; and polybuleptyl, polyacetic acid bule, nitrocellulose, ethyl Represented by synthetic polymer materials such as cellulose, vinylidene chloride 'butyl chloride copolymer, polyalkyl (meth) acrylate, butyl chloride' acetic acid butyl copolymer, polyurethane, cellulose acetate butyrate, polybutyl alcohol, linear polyester, etc.
  • the binder is preferably a resin whose main component is a thermoplastic elastomer.
  • thermoplastic elastomers examples include polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polybutadiene-based thermoplastics.
  • Elastomer ethylene acetate butyl thermoplastic elastomer, polychlorinated butyl thermoplastic elastomer, natural rubber thermoplastic elastomer, fluororubber thermoplastic elastomer 1, polyisoprene-based thermoplastic elastomers, chlorinated polyethylene-based thermoplastic elastomers, styrene-butadiene rubber, silicone rubber-based thermoplastic elastomers, and the like.
  • polyurethane-based thermoplastic elastomers and polyester-based thermoplastic elastomers have good dispersibility due to their strong bonding strength with phosphors, and are also highly ductile, and are flexible against radiation intensifying screens. Is preferable.
  • These nodes may be crosslinked with a crosslinking agent.
  • the mixing ratio of the binder and the photostimulable phosphor in the coating solution varies depending on the target haze ratio setting value of the radiation image conversion panel. 1 to 20 parts by mass is preferable with respect to the phosphor. 2 to: 10 parts by mass are more preferable.
  • Examples of the organic solvent used for the preparation of the stimulable phosphor layer coating solution include lower alcohols such as methanol, ethanol, isopropanol and n-butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, Esters of lower fatty acids and lower alcohols such as methyl acetate, ethyl acetate and n-butyl acetate; ethers such as dioxane, ethylene glycol monoethyl ether and ethylene glycol monomethyl ether; aromatic compounds such as triol and xylol; And halogenated hydrocarbons such as methylene chloride and ethylene chloride, and mixtures thereof.
  • lower alcohols such as methanol, ethanol, isopropanol and n-butanol
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone
  • the coating liquid contains a dispersant for improving the dispersibility of the phosphor in the coating liquid, and a bond 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 liquid, and a bond between the binder and the phosphor in the photostimulable phosphor layer after formation.
  • Various additives such as a plasticizer for improving the strength may be mixed.
  • the dispersant used for such purpose include phthalic acid, stearic acid, cabronic acid, lipophilic surfactant and the like.
  • plasticizers include phosphoric esters such as triphenyl phosphate, tricresyl phosphate and diphenyl phosphate; phthalate esters such as jetyl phthalate and dimethochetyl phthalate; ethyl phthalyl glycolate, butylphthalyl 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.
  • Dispersants such as stearic acid, phthalic acid, cabronic acid, and lipophilic surfactants may be mixed.
  • Preparation of the stimulable phosphor layer coating liquid is performed by, for example, a dispersing device such as a ball mill, a bead mill, a sand mill, an attritor, a three-roll mill, a high-speed impeller-dispersing machine, a Kady mill, or an ultrasonic dispersing machine. It is performed using.
  • a dispersing device such as a ball mill, a bead mill, a sand mill, an attritor, a three-roll mill, a high-speed impeller-dispersing machine, a Kady mill, or an ultrasonic dispersing machine. It is performed using.
  • a coating film is formed by uniformly coating the coating solution prepared as described above on the surface of a support described later.
  • a coating method that can be used, a usual coating means such as a doctor blade, a roll coater, a knife coater, a comma coater, a lip coater or the like can be used.
  • the coating film formed by the above means is then heated and dried to complete the formation of the photostimulable phosphor layer on the support.
  • the film 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 binder and phosphor, etc. 10 to 1000 / im force S is preferable, and more preferably 10 to 500 / im.
  • a material made from various materials such as glass, wool, cotton, paper, metal, etc. can be used as a force information recording material.
  • a material that can be processed into a flexible sheet or roll is preferable.
  • metal sheets such as cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, triacetate film, polycarbonate film, etc., aluminum foil, aluminum alloy foil, etc.
  • General paper and printing paper such as photographic paper, coated paper, or art paper, baryta paper, resin coated paper, polysaccharides as described in Belgian Patent No. 784,615, etc.
  • processed papers such as paper sized with, pigment paper containing pigments such as titanium dioxide, and paper sized with polyvinyl alcohol.
  • the film thickness of these supports varies depending on the material of the support to be used, but is generally 80 to 1000 zm, and more preferably 80 to 500 zm from the viewpoint of handling.
  • the surface of these supports may be a smooth surface, or a mat surface for the purpose of improving the adhesive strength with the undercoat layer.
  • the edge of each layer of the radiation image conversion panel that is, the edge of the radiation image conversion panel is made of resin or the like. Covering and sealing the photostimulable phosphor layer is performed.
  • the present invention provides a radiation image conversion panel having at least a stimulable phosphor layer and a protective layer having a softening point on a support, the radiation image conversion panel comprising at least the stimulable phosphor layer. It has a covering portion having a soft saddle point that seals the end portion together with the protective layer, and the difference between the softening point of at least one layer of the protective layer and the covering portion is 0 to 30 ° C. Is a feature. The difference between the soft spot of at least one of the protective layers and the covering is more preferably 0 to: 15 ° C.
  • the softening point can be obtained by TMA (thermomechanical analysis) penetration measurement or DSC (differential scanning calorimetry) measurement.
  • thermoplastic elastomer hereinafter also referred to as TPE
  • TPE thermoplastic elastomer
  • thermoplastic elastomer referred to in the present invention indicates the properties of vulcanized rubber (properties as an elastomer) at room temperature, but can be plastically deformed at high temperatures and molded with a plastic processing machine or the like. It refers to a polymer material that can be used. TPE is formed from a rubber component (soft segment) and a resin component (node segment), and the monomer unit of the thermoplastic elastomer referred to in the present invention represents the soft segment and the hard segment.
  • TPE used in the present invention polystyrene-based TPE using polystyrene as a hard segment and polyethylene as a soft segment, polyolefin such as polypropylene as a hard segment, and rubber such as ethylene and propylene as a soft segment are used.
  • Polyolefin TPE crystalline polybutadiene as a hard segment, polygen TPE using amorphous polybutadiene as a soft segment, polychlorinated butyl as a hard segment, and polyalloyed using rubber such as partially crosslinked NBR as a soft segment Bure chloride TPE, polyurethane obtained by reaction of short chain glycol and isocyanate as hard segment, and polyurethane obtained by reaction of long chain glycol and isocyanate as soft segment
  • Polyurethane TPE which is a linear multi-block copolymer
  • polyester which is a multi-block copolymer using polyester or hard segment as a hard segment and polyether or polyester having a low glass transition temperature (Tg) as a soft segment
  • Polyamide which is a multiblock copolymer using TPE, polyamide as the node segment, and low-polyether or polyester with a low glass transition temperature (Tg) as the soft segment
  • TPE fluorine-based TPE made of fluororesin as hard segment and fluoro-rubber as soft segment, etc., such as ⁇ Thermoplastic Elastomer Basics & Applications 'Kiba' Future Prospects '' (Nikkan Kogyo Shimbun) or ⁇ Plastic molding materials Examples include TPE described in “Handbook of Commercial Transactions 2005” (Chemical Industry Daily).
  • the polyol that forms the soft segment or hard segment of polyurethane-based TPE and the polyester-polyether that forms the hard segment of polyester-based TPE or polyamide-based TPE have the same structure, they are regarded as the same monomer unit. Can do.
  • the TPE used in the protective layer and covering portion of the radiation image conversion panel of the present invention is preferably an elastomer that is preferred in terms of softness when the soft segment amount is 10% by mass or more as the ratio of the soft segment to the hard segment.
  • the physical properties are also preferable. If this amount is 90% by mass or less, the average chain length of the hard segments will not be too short, and the hard blocks, which are physical crosslink points, can resist external forces and have good mechanical strength and function as an elastomer material. I like it.
  • the amount of the soft segment is more preferably 25 to 75% by mass. This hard Z soft segment ratio can be accurately quantified using 1 H-NMR.
  • an adjustment method (polyol component and polyisotope based on the molecular weight of the soft segment or hard segment of the TPE is used.
  • (Molar ratio with cyanate component, use of high molecular weight polyol, use of high molecular weight polymer, etc.) adjustment method by crystal of ethylene chain of polyester polyol, adjustment by structure of aromatic ring of polyol component or polyisocyanate component Examples thereof include a method and an adjustment method depending on the amount of urethane bonds.
  • Table 1 shows thermoplastic elastomers preferably used in the present invention.
  • TPA terephthalic acid
  • the physical properties and chemical structures of the materials constituting the protective layer and the covering portion are similar.
  • at least one of the protective layers and the covering portion contain a thermoplastic elastomer.
  • the monomer unit of the thermoplastic elastomer constituting at least one layer of the protective layer and the monomer unit of the thermoplastic elastomer constituting the covering portion are 30 to 100% identical.
  • “30 to 100% identical” means that 30 to 100% of the monomer units are the same based on the thermoplastic elastomer of the protective layer.
  • the monomer unit of the thermoplastic elastomer in the outermost protective layer and the monomer unit of the thermoplastic elastomer constituting the covering portion are 30 to 100% identical.
  • thermoplastic elastomer of the protective layer A force A different chemical formula Al, A2, A3 It consists of three types of monomer units, and the mass fractions of Al, A2 and A3 are 30, respectively. /. , 30%, 40%, thermoplastic elastomer of the coating part B force Consists of two types of monomer units, Bl and B2, with different chemical formulas.
  • the protective layer of the radiation image conversion panel of the present invention is required to have a very high optical transparency in addition to maintaining the relationship with the softening point of the covering portion.
  • the haze ratio measured by the method described in ASTMD-1003 is preferably 5% or more and less than 60%, more preferably 10% or more, from the viewpoint of the effect of eliminating image unevenness and linear noise and the effect of improving sharpness. Less than%.
  • the protective layer is required to have moisture resistance in consideration of prevention of moisture absorption deterioration of the stimulable phosphor.
  • the moisture permeability is preferably at least 5.0 g / m 2 'day or less.
  • Optimum moisture resistance can be achieved by laminating a plurality of vapor-deposited films obtained by vapor-depositing a thin film such as a metal oxide or silicon nitride on the resin film or resin film.
  • a method for stacking the resin film any known method with no particular limitation may be used.
  • an excitation light absorption layer in the protective layer from the viewpoint of improving the image quality.
  • the excitation light absorption layer is physically impacted. It is preferable to maintain stable plate performance for a long time, protected from chemical alteration.
  • a plurality of excitation light absorption layers may be provided, or an excitation light absorption layer may be formed by containing a coloring material in an adhesive layer for lamination.
  • the method for forming the protective layer is generally a method of laminating a protective layer (protective film) such as a PET film provided with a resin composition layer on the surface of the stimulable phosphor layer (laminating method), on the support.
  • a protective layer such as a PET film provided with a resin composition layer on the surface of the stimulable phosphor layer (laminating method)
  • laminating method laminating method
  • a method of forming a protective layer by applying and drying a protective layer coating solution on the stimulable phosphor layer (coating method).
  • the laminate method has antifouling properties and scratch resistance, it is difficult to form a thin film. Due to the thick film, there is a problem that sharpness and contrast tend to decrease. Although the sealing method has antifouling property and scratch resistance, there is a problem that productivity is poor.
  • the coating method generally has the advantage that the adhesive strength with the stimulable phosphor layer is strong and can be manufactured by a relatively simple process.
  • the protective layer is formed by coating, coating unevenness and coating defects This may cause unevenness on the image of the obtained radiation image conversion panel and may interfere with subtle diagnosis, and it has been desired to reduce it conventionally.
  • Examples of the layer configuration of the transfer foil include the following examples.
  • the transfer foil support described above (a support separate from the support provided under the stimulable phosphor layer, which is peeled off and removed before the radiation image conversion panel is used) Acrylates, methacrylates, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polychlorinated butyl, polyethylene, polypropylene, polystyrene, nylon, aromatic polyamide, poly Examples of the resin film include ether ether ketone, polysulfone, polyether sulfone, polyimide, and polyetherimide, and a resin film formed by laminating two or more layers of the above resins. Of these, polyethylene terephthalate (PET) is preferred.
  • the thickness of the support is usually about 5 to about 100 zm, preferably 10 to 50 xm.
  • the transfer foil according to the present invention has a transfer layer (protective layer) on the temporary support as described above.
  • the transfer layer of the transfer foil is preferably made of a resin layer.
  • the resin layer is preferably formed by coating a resin emulsion.
  • Resin emulsion does not dissolve completely in the solvent, It means a dispersion in which resin fine particles having a certain particle size distribution are dispersed using a dispersion aid such as a surfactant as necessary.
  • a resin that completely dissolves in the solvent is used, the coating film after coating and drying becomes uniform and flat, so that the adhesiveness to the support for the transfer foil is increased, so that the photostimulable phosphor layer is heated and pressurized. The transferability at the time is reduced, so that the adhesiveness after transfer becomes insufficient.
  • the thermoplastic elastomer is used as a main component.
  • polyester resins urethane resins, styrene butadiene copolymers, styrene rubber copolymers such as styrene isobutylene copolymers, etc.
  • Polymer resins Acrylic resins, vinyl acetate resins, ethylene vinyl acetate copolymers, ethylene ethyl acrylate copolymers, and other ethylene resins; Polybutylacetal resins such as polyvinyl butyral, vinyl chloride-vinyl acetate Examples thereof include a vinyl chloride resin such as a polymer.
  • polyester resins are particularly preferred in terms of adhesion and durability.
  • the glass transition temperature (Tg) of this resin is preferably 20 to 70 ° C., and the content thereof is preferably 50% by mass or more based on the total solid content of the transfer layer.
  • the above resin emulsion is one in which a resin is present in the form of a fine particle dispersion in a dispersion solvent.
  • a dispersion solvent having poor resin solubility or a mixture of two or more of them is used. And preferably used.
  • the resin emulsion dispersion solvent that is preferably used is preferably water or alcohols such as methanol, ethanol, linear or branched propanol, and butanol. In addition to these, other organic solvents may be mixed and used as long as the dispersibility is not impaired.
  • the thickness of the transfer layer of the transfer foil used in the present invention is preferably 2 to 15 zm. If it is thinner than this, sufficient durability cannot be secured, and if it is thicker than this, sufficient adhesion will not be obtained when the support is peeled off after the transfer foil is adhered and heated and pressed. There is a case.
  • the silicone resin compound is used for the purpose of improving the durability after transfer of the transfer layer of the transfer foil. It is preferable to add lubricants such as tass, solid molybdenum compounds, and Teflon (registered trademark) powder. The addition amount of these lubricants is usually from 0.:! To 50 mass%, preferably from 1 to: 10 mass%, based on the total solid content of the transfer layer.
  • the transfer layer (protective layer) according to the present invention preferably has a thickness of 2Z3 to 3Z3 colored blue to green. That is, from the viewpoint of preferably obtaining the effects of the present invention, in the present invention, it is preferable to provide the transfer layer with the ability to absorb excitation light. It is preferable that it is colored so as to absorb in the range. For this purpose, for example, an excitation light absorbing function can be provided by coating a layer containing a colorant that selectively absorbs excitation light. In the present invention, as a means for imparting an excitation light absorption function, it is preferable to color the transfer layer itself with a colorant or the like. The degree of absorption is such that the light transmittance at the excitation light wavelength is 50 to 97%.
  • the colorant used for imparting the excitation light absorption function to the transfer layer according to the present invention is determined depending on the type of stimulable phosphor used in the radiation image conversion panel.
  • the stimulable phosphor a phosphor exhibiting a stimulated emission in the wavelength range of 300 to 500 nm by excitation light having a wavelength in the range of 400 to 900 nm is usually used. Therefore, the colorant is usually blue to green. Organic or inorganic colorants are preferably used.
  • Examples of the above organic colorants include Zavon First Blue 3G (produced by Hoechst), Estrol Brill Blue N_3RL (produced by Sumitomo Chemical Co., Ltd.), Sumiacryl Blue F_GSL (Sumitomo Chemical Co., Ltd.) ), D & C Blue Nol (manufactured by National Anilin), Spirit Blue (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue No603 (manufactured by Orient Co., Ltd.), Kitton Blue A (manufactured by Chiba Gaigi Co., Ltd.), Aizen Cachiron Blue GLH (Hodogaya Chemical Co., Ltd.), Lake Blue A, F, H (Kyowa Sangyo Co., Ltd.), Rhodaline Blue 6GX (Kyowa Sangyo Co., Ltd.), Primosyanin 6 GX (Inabata Sangyo) Co., Ltd.), Brill Acid Green
  • the colorant is preferably a pigment rather than a dye.
  • the transfer layer comprises at least a low refractive index layer and a high refractive index layer, the difference in refractive index between 0.2 and 0.7, and the low refractive index layer is photostimulable. It is preferably on the phosphor layer side.
  • the low refractive index layer according to the present invention preferably contains silica fine particles and the following silane coupling agent in addition to the resin.
  • silane coupling agent examples include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, etyltrimethoxysilane, etyltriethoxysilane, Butyltrimethoxysilane, butyltriethoxysilane, vinyltriacetoxysilane, butyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, Methoxysilane, ⁇ -black propyltriethoxysilane, ⁇
  • silane coupling agents having a di-substituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyljetoxysilane, phenylmethyljetoxysilane , ⁇ — Glycidyloxypropylmethyl jetoxysilane
  • bitrimethoxysilane, vinyltriethoxysilane, butyltriacetoxysilane, vinyltrimethoxyethoxysilane, ⁇ -atariroylan having a double bond in the molecule and a disubstituted alkyl group for silicon.
  • ⁇ -Atalylyloxypropylmethyldimethoxysilane ⁇ -Atalylyloxypropylmethyljetoxysilane
  • y-methacryloyloxypropylmethyldimethoxysilane ⁇ -methacryloyloxypropyl pirmethyljetoxysilane
  • ⁇ -Ataryloxypropyl trimethoxy silane and ⁇ — Meta oxy silane ⁇ — Ataryl oxypropyl methyl methoxy silane, ⁇ - Methacryloyl silane Xylpropylmethyldimethoxysilane and ⁇ -methacryloyloxypropylmethyljetoxysilane are particularly preferred.
  • silane coupling agents include Shin-Etsu Chemical Co., Ltd. ⁇ -303, ⁇ ⁇ -403, ⁇ -402, ⁇ -403, ⁇ -1403, ⁇ -502, ⁇ -50 3, ⁇ — 502, ⁇ —503, ⁇ —603, ⁇ —603, ⁇ —903, ⁇ —903, ⁇ _9103, ⁇ _802, ⁇ —803, etc.
  • Two or more coupling agents may be used in combination.
  • other silane coupling agents may be used.
  • Other silane coupling agents include alkyl esters of orthokeys (eg, methyl orthokeate, ethyl orthokete, orthoketate ⁇ _propyl, orthokeate i_propyl, orthokeate n-butyl, orthokete sec-butyl, T-butyl orthokeate) and hydrolysates thereof.
  • alkyl esters of orthokeys eg, methyl orthokeate, ethyl orthokete, orthoketate ⁇ _propyl, orthokeate i_propyl, orthokeate n-butyl, orthokete sec-butyl, T-butyl orthokeate
  • a specific method of surface treatment with a coupling agent is shown below.
  • silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance.
  • the silane coupling agent is hydrolyzed, the surface of the silica-based fine particles and the silica-based fine particles having an organic group can be easily reacted to form a stronger film.
  • a hydrolyzed silane coupling agent may be added in advance to the coating solution.
  • a small amount of polymer for example, polybutyl alcohol, polyoxyethylene, polymethyl metatalylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, Alkyd resin
  • polymer for example, polybutyl alcohol, polyoxyethylene, polymethyl metatalylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, Alkyd resin
  • the low refractive index layer according to the present invention is a low refractive index layer formed by cross-linking of a fluorinated resin cross-linked by heat or ionizing radiation (hereinafter also referred to as "fluorinated resin before cross-linking"). It's okay.
  • fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group.
  • fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2- Dimethyl-1,3-dioxole), partially (meth) acrylic acid or fully fluorinated alkyl ester derivatives (eg, Biscote 6FM (Osaka Organic Chemical) or M-2020 (Daikin)), complete or Examples thereof include partially fluorinated butyl ethers.
  • a crosslinkable functional group is previously added in the molecule such as glycidyl methacrylate, butyltrimethoxysilane , ⁇ -methacryloyloxyprovir trimethoxysilane, bululglycidyl ether, or the like.
  • crosslinkable group examples include taliloyl, metatalilolenole, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group.
  • fluorine-containing copolymer is crosslinked by heating by a crosslinking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator, or an epoxy group and a thermal acid generator, etc.
  • ionizing radiation curable type In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, etc., ionizing radiation curable type is there.
  • light preferably ultraviolet rays, electron beams, etc.
  • a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing bull monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. Good.
  • the monomers that can be used in combination are not particularly limited, for example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylates (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl tolylene, ⁇ -methylstyrene, etc.), vinyl ethers (Such as methyl vinyl ether), butyl esters (such as butyl acetate, butyl propionate and cinnamate), acrylamides (such as tert-butyl acrylamide, N-cyclohexyl acrylate), methacrylamides, Ronitorir
  • a polyonoreganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties.
  • Use percentage of each monomer used to form the fluorine containing copolymers prior to coating it is preferably a fluorine-containing Biel monomer 20-70 mol 0/0, more preferably 40 to 70 Mo Le%, monomers preferably 1 to 20 mol% for imparting a crosslinking group, more preferably 5-20 Monore 0/0, preferably other monomers to be used in combination 10 to 70 mole 0/0, more preferably is the ratio of 10 to 50 mole 0/0.
  • the fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means of solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or the like.
  • the fluorine-containing resin before crosslinking is commercially available and can be used.
  • Examples of commercially available fluorine-containing resins in front of the bridge include Cytop (Asahi Glass), Teflon (registered trademark) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opster CJSR), etc. Can be mentioned.
  • the low refractive index layer containing a cross-linked fluorine-containing resin as a constituent component has a dynamic friction coefficient of 0.03 to 0.00.
  • the contact angle to water is in the range of 15 to 15 degrees.
  • the organic solvent for dilution used in the present invention is preferably a water-miscible organic solvent.
  • water-miscible organic solvents include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl).
  • polyhydric alcohols for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, Glycerin, hexanetriol, thiodiglycol, etc.
  • polyhydric alcohol ethers eg, ethylene glycol monomethyl ether, ethylene glycol) -Nole Monotechno Reethenole, Ethylene Glyco Nore Mono Butino Rete Noetre, Diethylene Glyco Nore Mono Methino Rete Nore, Diethylene Glyco Nore Monomethino Rete Nore, Diethylene Glyco Nore Monobutino Rete Nore, Propylene Glycol Nore Monomethy Nore Tenoré, Propylene Glycol Nole Monobutenoleate Nore, Ethylene Glycol Monomet
  • the dilution rate is appropriately selected because it acts as a factor that determines the degree of uneven distribution of the silica-based fine particles in the low refractive index layer by the action of controlling the viscosity of the coating solution.
  • the coating method of the low refractive index layer includes dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and etatrusion coating (US Patent No. 2, 681, No. 294). Two or more layers may be applied simultaneously.
  • U.S. Pat.Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki coating Engineering, page 253, Asakura Shoten (1973).
  • each low refractive index layer according to the present invention is preferably 50 to 200 nm, more preferably 60 to 150 nm.
  • the refractive index of the high refractive index layer is preferably 1.55-2.30, more preferably 1.57-2.20.
  • the refractive index of the medium refractive index layer is adjusted to be an intermediate value between the refractive index of the support and the refractive index of the high refractive index layer.
  • the refractive index of the middle refractive index layer is preferably from 1.55 to 1.80.
  • the thickness of the high refractive index layer and the medium refractive index layer is preferably 5 nm to lxm, and is preferably 10 nm to 0.0. Force S Further preferably 30 nm to 0.1 ⁇ m is most preferable. .
  • High refractive index layer and medium bending The haze of the refractive index layer is preferably 5% or less3. / 0 or less is more preferable, and 1% or less is most preferable.
  • the strength of the high refractive index layer and the medium refractive index layer is preferably H or higher at a pencil hardness of 1 kg load, more preferably 2H or higher, and most preferably 3H or higher.
  • the high refractive index layer comprises a coating liquid containing a monomer, oligomer or hydrolyzate thereof of an organic titanium compound represented by the following general formula (1) in addition to the above resin.
  • a layer having a refractive index of 1.55 to 2.5 formed by coating and drying is preferably used.
  • R is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably 1 carbon atom.
  • the monomer, oligomer or hydrolyzate of the organotitanium compound undergoes hydrolysis of the alkoxide group and reacts like Ti 2 O—Ti to form a crosslinked structure, thereby forming a cured layer.
  • a preferred example is a dimer to demer of 3 7 4 3 7 4 4 9. These can be used alone or in combinations of two or more
  • the body is particularly preferred.
  • the organotitanium compound to a solution in which water and an organic solvent described later are sequentially added. If water is added later, hydrolysis / polymerization does not proceed uniformly, resulting in white turbidity or reduced film strength. After the water and the organic solvent are added, it is preferable that they are mixed and dissolved by stirring in order to mix well.
  • an organic titanium compound and an organic solvent are mixed, and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.
  • the amount of water is preferably in the range of 0.25 to 3 mol with respect to 1 mol of the organic titanium compound. If it is less than 0.25 mol, hydrolysis and polymerization will not proceed sufficiently and the film strength will be low. descend. If the amount exceeds 3 moles, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse cocoon particles.
  • the water content is preferably less than 10% by mass relative to the total amount of the coating solution. If the water content is 10% by mass or more based on the total amount of the coating solution, it is not preferable because the coating solution is not stable over time and may become cloudy.
  • the organic solvent used for the high refractive index layer is preferably a water-miscible organic solvent.
  • the amount of these organic solvents to be used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.
  • the monomer, oligomer or hydrolyzate of the organotitanium compound used in the present invention preferably occupies 50.0 to 98.0 mass% of the solid content contained in the coating solution.
  • the solid content ratio is more preferably 50 to 90% by mass, and further preferably 55 to 90% by mass.
  • an organic titanium compound polymer which has been previously crosslinked by hydrolysis of an organic titanium compound
  • titanium oxide fine particles to the coating composition.
  • the high refractive index layer and the medium refractive index layer used in the present invention preferably contain metal oxide particles.
  • the metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, more preferably 1.90-2.80. I like it.
  • the weight average diameter of the primary particles of the metal oxide particles is preferably: ⁇ 150 nm, 1 ⁇ : more preferably OOnm:! ⁇ 80 nm is the most preferred, .
  • the weight average particle diameter of the metal oxide particles in the layer is: power of S to 200 nm, preferably 5 to: power of 150 nm, more preferably 10 to 100 nm, more preferably 10 to 100 nm. Most preferably, it is 80 nm.
  • the average particle diameter of the metal oxide particles is 20 to 30 nm or more, 20 to 3 If it is less than Onm, it is measured by an electron micrograph.
  • metal oxide particles are selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S
  • titanium oxide eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure
  • tin oxide indium oxide, zinc oxide, and zirconium oxide.
  • Tium titanium oxide, tin oxide and indium oxide are particularly preferred.
  • the metal oxide particles can contain such metal oxide as a main component and further contain other elements.
  • the main component means the component having the largest content (mass%) among the components constituting the particles.
  • other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.
  • the metal oxide particles are preferably surface-treated.
  • the surface treatment can be performed using an inorganic compound or an organic compound.
  • inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferred.
  • organic compound used for the surface treatment include polyol, alkanolamine, stearic acid, silane coupling agent and titanate coupling agent. Among these, the silane coupling agent is most preferable.
  • silane coupling agent two or more coupling agents may be used in combination, and other silane coupling agents may be used.
  • Other silane coupling agents include alkyl esters of orthokeys (eg, methyl orthokeate, ethyl orthokelate, n-propyl orthokeate, i_propyl orthokeate, n-butyl orthokeate, sec-butyl orthokete, orthokeate). Acid t-butyl) and hydrolysates thereof.
  • Surface treatment with a coupling agent can be carried out by adding a coupling agent to a dispersion of fine particles and allowing the dispersion to stand for several hours to 10 days at a temperature of room temperature up to 60 ° C.
  • inorganic acids for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthokeyic acid, phosphoric acid, carbonic acid
  • organic acids for example, acetic acid, polyacrylic acid, Benzene sulfonic acid, phenol, polyglutamic acid
  • salts thereof eg gold (Genus salts, ammonium salts) may be added to the dispersion.
  • silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance.
  • the silane coupling agent is hydrolyzed, the surface of the organic titanium compound and the metal oxide particles react with each other, and a stronger film is formed immediately. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance.
  • the water used for the hydrolysis can also be used for the hydrolysis Z polymerization of the organic titanium compound.
  • the shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in combination in the high refractive index layer and the middle refractive index layer.
  • the ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume in the layer, more preferably 10 to 60% by volume, and still more preferably. Is 20-55% by volume.
  • the metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium.
  • a dispersion medium for the metal oxide particles it is preferable to use a liquid having a boiling point of 60 to 170 ° C.
  • dispersion solvent examples include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl oxalate, ethyl formate, propyl oxalate, butyl oxalate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons ( Eg, methylene chloride, chlorophenol, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylethanolamide, dimethylacetamide, n_methylpyr
  • the metal oxide particles can be dispersed in the medium using a disperser.
  • dispersers include sand grinder mills (eg, bead mills with pins), high-speed impeller minoles. , Pebble mill, roller mill, attritor and colloid mill.
  • a sand grinder mill and a high-speed impeller mill are particularly preferred.
  • Examples of a dispersing machine used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a feeder and an etastruder.
  • a polymer having a relatively high refractive index examples include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenolic resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate with polyol. Is mentioned. Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups, and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.
  • each layer of the antireflective layer or the coating liquid thereof includes a polymerization inhibitor, a leveling agent, Thickeners, anti-coloring agents, UV absorbers, silane coupling agents, antistatic agents and adhesion promoters may be added.
  • the active energy ray is irradiated every time each layer is coated.
  • the active energy ray to be used in the present invention ultraviolet rays, electron beams, in ⁇ rays, can be used without limitation as long as the energy source for activity of the compound, ultraviolet, electron beam is preferable device in particular handling Ultraviolet light is preferred because it is simple and high energy can be easily obtained.
  • the ultraviolet light source for photopolymerizing the ultraviolet reactive compound any light source that generates ultraviolet light can be used.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • an ArF excimer laser, KrF excimer laser, excimer lamp, synchrotron radiation, or the like can also be used.
  • Different forces irradiation light amount irradiation conditions by each lamp 20 preferably the 10000 mJ / cm 2 is preferred gesture et a 100 ⁇ 200 Omj / cm 2, particularly preferably is 400 ⁇ 2000mj / cm 2 .
  • the multilayer antireflection layer may be irradiated one by one, or may be irradiated after lamination. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.
  • an electron beam can be used in the same manner.
  • an electron beam it is emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. 50 to 1000 keV, preferably An electron beam having an energy of 100 to 300 keV can be mentioned.
  • each refractive index layer constituting the antireflection layer is preferably selected in accordance with the refractive index of each layer.
  • a resin whose outermost surface layer of the transfer layer (protective layer) is cured by heat or light can also be used.
  • Thermosetting resins include phenolic resins, melamine resins, epoxy resins, acrylate resins, epoxy acrylate resins, unsaturated polyester resins, polyester acrylate resins, urethane acrylate resins. And spirane resin and diallyl phthalate resin.
  • the inorganic resin include colloidal silica and those obtained by polymerizing a silicone monomer after hydrolysis. One or more components selected from these are mixed and used, but it is effective to add various curing agents, coupling agents and the like as necessary.
  • the photocurable resin is made of a material having addition polymerization property or ring-opening polymerization property
  • the addition polysynthetic compound is a radical polymerizable compound such as JP-A-7-159983.
  • It may be a photo-curable material using a photo-polymerization (including thermal polymerization) composition described in each publication such as No. 31399.
  • a cationic polymerization type photo-curing material is known, and a photo-power thione polymerization type photo-curing material sensitized to a long wavelength region longer than visible light is also disclosed in, for example, 6-43633 and other publications. Either may be used for the purposes of the present invention.
  • radical polymerization initiators include tridian derivatives described in JP-B-59-1281, JP-B-61-9621, JP-A-60-60104, JP-A-59-1504, and the like.
  • the polymerization initiator is preferably contained in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the compound having an ethylenically unsaturated bond capable of radical polymerization. More preferably, the range is:! To 5% by mass.
  • the photosensitive composition containing the radically polymerizable compound contains, as a thermal polymerization initiator for the radically polymerizable monomer, a known radical polymerization initiator that is generally used for polymer synthesis reaction by radical polymerization without any particular limitation. Can be made.
  • the thermal polymerization initiator is a compound capable of generating a polymerizable radical by applying thermal energy.
  • Examples of such compounds include 2,2'-azobisisobutyronitrile, azobisnitrile compounds such as 2,2'-azobispropionitrile, benzoyl peroxide, lauroyl peroxide, Acetyl peroxide, t-butyl perbenzoate, a cumyl hydroperoxide, Organic peroxides such as di-t-butyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, peracids, alkylperoxylrubamates, nitrosoaryl acyloleamines Inorganic peroxides such as potassium persulfate, ammonium persulfate, potassium perchlorate, diazoaminobenzene, p_nitrobenzenediazonium, azobis-substituted alkanes, diazothioethers, allylazosulfol Examples include azo or diazo compounds such as phon
  • thermal polymerization initiators can be used alone or in combination. Further, the thermal polymerization initiator is usually preferably in the range of 0.5 to 10% by mass in the thermally polymerizable composition: more preferably in the range of 5 to 5% by mass.
  • UV-curable prepolymers and monomers of the epoxy type that are polymerized by cationic polymerization (mainly epoxy type) and monomers that contain two or more epoxy groups in one molecule.
  • prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, and polyglycidyls of aromatic polyols. Mention may be made of ethers, hydrogenated compounds of liglycidyl ethers of aromatic polyols, urethane polyepoxy compounds and epoxy-polybutadienes.
  • prepolymers can be used alone or in combination of two or more.
  • the content of the prepolymer having two or more epoxy groups in one molecule in the UV curable protective layer-forming coating agent is preferably 70% by mass or more.
  • Other cationic polymerizable compounds contained in the cationic polymerizable composition include, for example, the following (1) styrene derivatives, (2) bullaphthalene derivatives, (3) bull ethers, and (4) N-Bulu ⁇ . Compounds can be mentioned. In the present invention, a radical polymerization system is preferred.
  • the surface roughness of the outermost surface layer of the transfer layer (protective layer) is preferably 0.:! To l z m.
  • the surface roughness Ra average surface roughness defined by the surface roughness and the IS-B-060K2001) in the present invention.
  • it can be measured by a known surface roughness measuring method such as a stylus method or laser interferometry.
  • the transfer layer preferably contains fine particles.
  • fine particles include resin fine particles such as melamine and PMMA as organic compounds, and examples of inorganic compounds include titanium oxide, zinc oxide, calcium carbonate, aluminum oxide, kaolin, clay, silica, talc, and mica. From the viewpoint of dispersibility, silica is preferred, and the larger the oil absorption (specific surface area, bulk specific gravity) is particularly preferred.
  • the smoothness of the support of the transfer foil is high, a good surface can be obtained by adjusting the amount of these fine particles added.
  • the average particle size of the fine particles is from 0.1 ⁇ m to ⁇ , the addition amount is usually from 0.1 to 40% by mass, preferably from 1 to 30% by mass, based on the total solid content of the transfer layer.
  • Another method for obtaining this surface roughness is to use an uneven support.
  • An uneven support is commercially available.
  • the transfer layer when a resin having no thermal adhesiveness (geet sealability) is used for the transfer layer, it is preferable to use an adhesive layer made of a thermal adhesive resin.
  • the adhesive layer made of a heat-adhesive resin is prepared in advance with a heat-resistant support, for example, a transparent layer ribbon or transparent foil formed by coating on a polyethylene terephthalate resin film, This can be formed, for example, by thermal transfer using a thermal head or a thermal transfer roll.
  • Examples of the heat-adhesive resin include a vinyl chloride resin, a polyester resin, an acrylic resin, a polyvurecetal resin, a polybutyral resin, a polyvinyl alcohol, a polycarbonate, a cellulose resin, Examples include styrene resins, urethane resins, amide resins, urea resins, epoxy resins, phenoxy resins, polystrength resins, polyacrylonitrile resins, SEBS resins, SEPS resins, and modified products thereof.
  • the salt-based resin preferred are the polyester resin, the acrylic resin, the polybutyl plastic resin, the styrene resin, the epoxy resin, and the urethane resin for the purpose of the present invention.
  • Resin, urethane acrylate resin, SEBS resin, SEPS resin. These resins can be used alone or in combination of two or more.
  • the transfer layer is brought into contact with the surface of the photostimulable phosphor layer existing on another support, and after the heating and pressurization, the support holding the transfer layer is peeled off to release the photostimulable phosphor. Transferred to protect the surface of the layer.
  • the heating and pressing conditions are preferably heating and pressure bonding at a temperature equal to or higher than the soft point of the resin of the transfer layer.
  • the upper limit of the heating temperature is preferably the softening point + 100 ° C.
  • the heating and pressurizing means for forming the protective layer can be used without particular limitation as long as it has excellent adhesion and can be pressurized or heated and pressurized without mixing bubbles or the like.
  • a pressure roll or stamper can be used, and in the case of heating / pressurizing treatment, a thermal head, heat roll, hot stamp or the like can be used.
  • the pressure is usually 1 to 200 NZcm 2 , preferably 5 to 100 NZcm 2 , and the conveyance speed is usually 0.:! To 200 mm / second, preferably 0.5 to 100 mm / second.
  • the pressure is usually 0.5 to: 100 N / cm 2 , preferably 5 to 50 NZcm 2 , and the caloric pressure time is normal. .:! ⁇ Five. Seconds, preferably. 5 to 20 seconds.
  • the calorie temperature when using a heat roll is usually 60-200.
  • the pressure is usually 1 to 200 NZcm 2 , preferably 5 to 100 N / cm 2
  • the conveying speed is usually 0.:! To 200 mm / sec, preferably Is 0.5 to 100 mm / sec.
  • a release plate As a method of peeling off the support of the transfer foil after pressurization or heating'pressure, a release plate, As long as it does not affect the photostimulable phosphor layer, such as the peel angle fixing method using a peeling roll, and the hand peeling method in which the stimulable phosphor layer existing on the transfer foil and the support is peeled off without being fixed by hand.
  • Various peeling methods can be used.
  • the phosphor layer forming material 427 g of the europium-activated barium fluoroiodide phosphor obtained above, polyurethane resin (Desmolac 4125, manufactured by Sumitomo Bayer Urethane Co., Ltd.) 15.8 g, bisphenol A type epoxy resin 2. Og methyl Ethyl ketone Toluene (1: 1) was added to a mixed solvent and dispersed with a propeller mixer to prepare a coating solution having a viscosity of 2.5 to 3. OPa's. This coating solution was applied on a black PET support having a thickness of 100 ⁇ m using a doctor blade, and then dried at 100 ° C. for 15 minutes to form a phosphor layer having a thickness of 270 / im. [0170] (Preparation of protective layer)
  • TPE Thermoplastic Elastomer shown in Table 2 E-1 to E5 was made to have a solid concentration of 15%, and X-22-22809 made by Shin-Etsu Chemical Co., Ltd. was used as a slip agent to a solid content concentration of 0.1%. Soaked in MEK and applied with a silicone release agent at a thickness of 10 am using a doctor blade.Applied to a PET temporary support so that the dry film thickness is 10 zm. Transfer foil for protective layer Formed.
  • the obtained transfer foil was laminated so that the protective layer surface and the phosphor layer were in contact with each other, and heat-pressed with a heating roll of 60 to 70 ° C to prepare a phosphor sheet. .
  • TPE Thermoplastic Elastomer shown in Table 2 E-1 to E7 is made to have a solid content of 15%, and X-22-22809 made by Shin-Etsu Chemical Co., Ltd. as a slipping agent has a solid content of 0.1%. As shown in Table 3, it was applied to the entire periphery of the end of the phosphor sheet and dried at 60 ° C. for 30 minutes to obtain radiation image conversion panels 11 to 119.
  • NPG Neobench ⁇ Dariko-le
  • the prepared radiation image conversion panel was allowed to stand for 1 week at 80 ° C and 90% RH, and the moisture resistance was evaluated by measuring the mass change (mass increase rate%) of the radiation image conversion panel before and after being left.
  • the Ipanema SaC-200 type transport tester manufactured by Seika Sangyo Co., Ltd. was repeatedly transported until the coating on the radiation image conversion panel was damaged, and the number was used as an index of strength.
  • the radiation image conversion panel of the present invention in which the difference between the softening points of the protective layer and the covering portion is 30 ° C or less has a larger difference in softening point. It can be seen that it is superior in moisture resistance and strength.
  • any radiation image conversion panel was good in sensitivity and image quality.
  • a radiation image conversion panel was obtained in the same manner as in Example 1 except that the protective layer and the covering portion were produced by the following method.
  • TPE Thermoplastic Elastomer shown in Table 2 of Example 1 E-1 to E5 were used as a slipping agent so that the solid content concentration was 15%.
  • X-22-22809 manufactured by Shin-Etsu Chemical Co., Ltd. had a solid content concentration of 0. Dissolved in MEK to 1% and applied onto a 5 ⁇ m thick PET support with a doctor blade to a dry film thickness of 10 ⁇ m.
  • an unsaturated polyester resin Toyobo Co., Ltd .: Byron 30SS
  • the adhesive layer of the protective layer with an adhesive layer was laminated so that the phosphor layer prepared in Example 1 was in contact with each other, and thermocompression bonded with a heating roll at 60 to 70 ° C. A phosphor sheet was prepared.
  • TPE Thermoplastic Elastomer shown in Table 2 of Example 1 E-1 to E7 was used as a slipping agent so that the solid content concentration was 15%, and X-22-22809 made by Shin-Etsu Chemical Co., Ltd. had a solid content concentration of 0. ⁇ Dissolved in MEK to 1%, and coated on the entire periphery of the phosphor sheet as shown in Table 4, dried at 60 ° C for 30 minutes, and then the radiation image conversion panel 2—:! 2-19 was obtained.
  • the produced radiation image conversion panel was evaluated in the same manner as in Example 1.
  • Table 4 shows the evaluation results.
  • the radiation image conversion panel of the present invention in which the difference between the softening points of the outermost layer of the protective layer and the covering portion is 30 ° C or less has a larger difference in softening point. It can be seen that it is superior to the conversion panel in moisture resistance and strength.
  • any radiation image conversion panel was good in sensitivity and image quality.

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Abstract

A radiation image transformation panel which is protected against a physical impact at the peripheral portion of the radiation image transformation panel and prevented from panel deterioration due to moisture absorption or the like by a stimulable phosphor layer. The radiation image transformation panel has on a support member at least a stimulable phosphor layer and a protection layer having a softening point, characterized in that the panel has a covering portion having a softening point and sealing at least the end portion of the stimulable phosphor layer along with the protection layer, and the difference in softening point between at least one layer of the protection layer and the covering portion is 0-30°C.

Description

明 細 書  Specification
放射線像変換パネル  Radiation image conversion panel
技術分野  Technical field
[0001] 本発明は、放射線像変換パネルに関し、詳しくは、放射線像変換パネル周辺部に おける物理的衝撃から放射線像変換パネルを保護し、輝尽性蛍光体層の吸湿等に よるパネルの劣化が防止された放射線像変換パネルに関する。  TECHNICAL FIELD [0001] The present invention relates to a radiation image conversion panel, and more specifically, the radiation image conversion panel is protected from physical impact in the periphery of the radiation image conversion panel, and the panel is deteriorated due to moisture absorption of the photostimulable phosphor layer. The present invention relates to a radiation image conversion panel in which the above is prevented.
背景技術  Background art
[0002] X線画像のような放射線画像は病気診断用等に多く用いられている。この X線画像 を得るために被写体を通過した X線を蛍光体 (蛍光スクリーン）に照射し、これにより 可視光を生じさせてこの可視光を通常の写真を撮るときと同じように銀塩を使用した フィルムに照射して現像した、いわゆる放射線写真が従来、広範囲に利用されている  [0002] Radiation images such as X-ray images are often used for disease diagnosis and the like. To obtain this X-ray image, the phosphor (fluorescent screen) is irradiated with X-rays that have passed through the subject, thereby generating visible light, and this visible light is applied to silver salt in the same way as when taking a normal picture. So-called radiographs developed by irradiating and developing the used film have been widely used in the past.
[0003] しかし、近年、従来の放射線写真法に代わる方法として、例えば、特許文献 1、 2に 記載されているような輝尽性蛍光体を用いる放射線像変換方法が知られている。こ の方法は、輝尽性蛍光体を含有する放射線像変換パネル (蓄積性蛍光体シート）を 利用するもので、被写体を透過した、あるいは被検体から発せられた放射線を該パ ネルの輝尽性蛍光体に吸収させ、その後、輝尽性蛍光体を可視光線、赤外線等の 電磁波 (励起光)で時系列的に励起することにより、該輝尽性蛍光体中に蓄積されて レ、る放射線エネルギーを蛍光 (輝尽発光光）として放出させ、この蛍光を光電的に読 み取って電気信号を得、次いで得られた電気信号に基づいて被写体あるいは被検 体の放射線画像を可視像として再生するものである。読み取りを終えた該パネルは、 残存する画像の消去が行なわれた後、次の撮影のために備えられる。すなわち、放 射線像変換パネルは繰り返し使用される。 However, in recent years, a radiation image conversion method using a stimulable phosphor as described in Patent Documents 1 and 2, for example, is known as an alternative to the conventional radiographic method. This method uses a radiation image conversion panel (accumulative phosphor sheet) containing a stimulable phosphor. The panel transmits the radiation transmitted through the subject or emitted from the subject. The stimulable phosphor is then absorbed and then accumulated in the stimulable phosphor by exciting the stimulable phosphor in a time series with electromagnetic waves (excitation light) such as visible light and infrared light. Radiation energy is emitted as fluorescence (stimulated luminescence light), this fluorescence is photoelectrically read to obtain an electrical signal, and then a radiographic image of the subject or subject is visualized based on the obtained electrical signal. As something to play. The panel which has been read is prepared for the next photographing after the remaining image is erased. That is, the radiation image conversion panel is used repeatedly.
[0004] この放射線像変換方法によれば、従来の放射線写真フィルムと增感紙との組合せ を用いる放射線写真法による場合に比較して、はるかに少ない被曝線量で情報量の 豊富な放射線画像を得ることができるという利点がある。さらに、従来の放射線写真 法では一回の撮影ごとに放射線写真フィルムを消費するのに対して、この放射線像 変換方法では放射線像変換パネルをくり返し使用するので資源保護、経済効率の 面からも有利である。 [0004] According to this radiographic image conversion method, a radiographic image having a large amount of information can be obtained with a much smaller exposure dose than in the case of radiography using a combination of a conventional radiographic film and an intensifying screen. There is an advantage that can be obtained. In addition, conventional radiography consumes radiographic film for each shot, whereas this radiographic image is used. The conversion method uses a radiation image conversion panel repeatedly, which is advantageous in terms of resource protection and economic efficiency.
[0005] このような輝尽性蛍光体は、放射線を照射した後、励起光を照射すると輝尽発光を 示す輝尽性蛍光体である力 実用上では、波長が 400〜900nmの範囲にある励起 光によって 300〜500nmの波長範囲の輝尽発光を示す輝尽性蛍光体が一般的に 利用される。  [0005] Such a stimulable phosphor is a stimulable phosphor that exhibits stimulating luminescence when irradiated with radiation and then irradiated with excitation light. In practice, the wavelength is in the range of 400 to 900 nm. Stimulable phosphors that exhibit stimulated emission in the wavelength range of 300 to 500 nm by excitation light are generally used.
[0006] そして、輝尽性蛍光体層の表面（支持体に面していない側の表面）には通常、保護 層が設けられていて、蛍光体層を化学的な変質あるいは物理的な衝撃から保護して いる。保護層には、セルロース誘導体やポリメチルメタタリレート等のような透明な有 機高分子物質を適当な溶媒に溶解して調製した溶液を蛍光体層の上に塗布するこ とで形成されたもの、あるいはポリエチレンテレフタレート等の有機高分子フィルムや 透明なガラス板等の保護層形成用シートを別に形成して蛍光体層の表面に適当な 接着剤を介して固着したもの、あるいは無機化合物を蒸着等によって蛍光体層上に 成膜したもの等が知られている。  [0006] Then, a protective layer is usually provided on the surface of the photostimulable phosphor layer (the surface not facing the support), and the phosphor layer is subjected to chemical alteration or physical impact. It protects from. The protective layer was formed by applying a solution prepared by dissolving a transparent organic polymer substance such as cellulose derivative or polymethylmetatalylate in an appropriate solvent on the phosphor layer. , Or an organic polymer film such as polyethylene terephthalate, or a sheet for forming a protective layer such as a transparent glass plate, which is fixed to the surface of the phosphor layer with an appropriate adhesive, or an inorganic compound is deposited. For example, a film formed on a phosphor layer is known.
[0007] 放射線像変換方法の実施にぉレ、て、放射線像変換パネルは、放射線の照射 (放 射線像の記録） ·励起光の照射 (記録された放射線像の読出し） '消去光の照射 (残 存する放射線像の消去）というサイクルで繰り返し使用される。そして放射線像変換 パネルの各ステップへの移行はベルト、ローラー等の搬送手段により行なわれ、ーサ イタル終了後パネルは通常積層して保存される。ところ力 上記のような、塗布によつ て形成された保護層を有する放射線像変換パネルを、このように繰返し使用してレ、る と、例えば保護層表面に汚れや擦り傷が発生する等の理由により、当該放射線像変 換パネルが形成する放射線画像の画質が徐々に低下する傾向がある。  [0007] When implementing the radiation image conversion method, the radiation image conversion panel is used to irradiate radiation (record radiation images), irradiate excitation light (read out recorded radiation images), and then apply erasing light. It is used repeatedly in a cycle of (erasing the remaining radiation image). The transition to each step of the radiation image conversion panel is performed by a conveying means such as a belt and a roller, and after completion of the site, the panels are usually laminated and stored. However, if the radiation image conversion panel having the protective layer formed by coating as described above is repeatedly used in this manner, for example, the surface of the protective layer may be contaminated or scratched. For the reason, the image quality of the radiation image formed by the radiation image conversion panel tends to be gradually lowered.
[0008] 放射線像変換パネルも従来の放射線写真法と同様に、高感度であってかつ画質（ 鮮鋭度、粒状性等）の良好な画像を与えるものであることが望まれるから、上記のよう な汚れや擦り傷の発生を防止することは重要な課題である。  Since the radiographic image conversion panel is also desired to provide an image with high sensitivity and good image quality (sharpness, graininess, etc.) as in the conventional radiographic method, as described above. It is an important issue to prevent the occurrence of various stains and scratches.
[0009] 特許文献 3には、架橋性フッ素系樹脂を含む樹脂組成物層を設けた保護層を輝尽 性蛍光体層の表面に積層（ラミネート）して、防汚性、防傷性及び耐久性に優れる放 射線像変換パネルを得る方法が開示されている。この方法は防汚性、防傷性はある ものの、薄膜ィ匕が困難であり、保護層に用いられる PETの延伸ムラ防止に表面に散 乱層が必要である、厚膜のため鮮鋭性、コントラストが低下するといつた問題がある。 [0009] In Patent Document 3, a protective layer provided with a resin composition layer containing a crosslinkable fluororesin is laminated (laminated) on the surface of the photostimulable phosphor layer to obtain antifouling property, scratch resistance and A method for obtaining a radiation image conversion panel having excellent durability is disclosed. This method is antifouling and scratchproof However, a thin film is difficult, and a scattering layer is necessary on the surface to prevent stretching unevenness of the PET used for the protective layer. Due to the thick film, there is a problem that sharpness and contrast are lowered.
[0010] 特許文献 4には、支持体上に輝尽性蛍光体層を有する蛍光体シートと、該蛍光体 シートの上下に配置され、該蛍光体シートの全表面を被覆するように設けられた保護 フィルム（レ、わゆる封止フィルム）を有する放射線像変換パネルが開示されている。こ の方法は防汚性、防傷性はあるものの、生産性が悪いという問題がある。  [0010] In Patent Document 4, a phosphor sheet having a stimulable phosphor layer on a support, and a phosphor sheet that is disposed above and below the phosphor sheet and covers the entire surface of the phosphor sheet are provided. Further, a radiation image conversion panel having a protective film (la, so-called sealing film) is disclosed. Although this method is antifouling and scratch resistant, it has the problem of poor productivity.
[0011] また、放射線像変換パネルの周辺部には縁部被膜を設け、パネル周辺部における 物理的衝撃からパネルを保護し、また蛍光体層の吸湿等によるパネルの劣化を防止 する方法が特許文献 5、 6に開示されている。し力しながら、さらなる強度'バリア性が 要求されている。  [0011] Further, there is a patent on a method for providing an edge coating on the periphery of the radiation image conversion panel, protecting the panel from physical impact at the periphery of the panel, and preventing deterioration of the panel due to moisture absorption of the phosphor layer. It is disclosed in References 5 and 6. However, further strength and barrier properties are required.
特許文献 1 :米国特許第 3， 859, 527明細書  Patent Document 1: US Pat. No. 3,859,527
特許文献 2 :特開昭 55— 12144号公報  Patent Document 2: JP-A-55-12144
特許文献 3：特開 2001— 13298号公幸艮  Patent Document 3: Japanese Patent Publication No. 2001-13298
特許文献 4 :特開 2002— 131498号公報  Patent Document 4: Japanese Patent Laid-Open No. 2002-131498
特許文献 5：特開 2002— 148395号公報  Patent Document 5: Japanese Patent Laid-Open No. 2002-148395
特許文献 6 :特開 2002— 174698号公報  Patent Document 6: Japanese Unexamined Patent Application Publication No. 2002-174698
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0012] 本発明は、上記課題に鑑みなされたものであり、その目的は、放射線像変換パネ ル周辺部における物理的衝撃から放射線像変換パネルを保護し、また輝尽性蛍光 体層の吸湿等によるパネルの劣化が防止された放射線像変換パネルを提供すること である。 [0012] The present invention has been made in view of the above problems, and its purpose is to protect the radiation image conversion panel from physical impact at the periphery of the radiation image conversion panel and to absorb moisture from the stimulable phosphor layer. It is an object of the present invention to provide a radiation image conversion panel in which deterioration of the panel due to, for example, is prevented.
課題を解決するための手段  Means for solving the problem
[0013] 本発明の上記課題は、以下の構成により達成される。 [0013] The above object of the present invention is achieved by the following configurations.
[0014] (1)支持体上に少なくとも輝尽性蛍光体層及び軟化点を有する保護層を有する放 射線像変換パネルにおいて、該放射線像変換パネルは、該輝尽性蛍光体層の少な くとも端部を該保護層と共に封止する、軟化点を有する被覆部を有し、且つ、該保護 層の少なくとも 1層と該被覆部の軟化点の差が 0〜30°Cであることを特徴とする放射 線像変換パネル。 [0014] (1) In a radiation image conversion panel having at least a stimulable phosphor layer and a protective layer having a softening point on a support, the radiation image conversion panel has a small amount of the stimulable phosphor layer. Both have a covering portion having a softening point that seals the end portion together with the protective layer, and the difference between the softening point of at least one of the protective layer and the covering portion is 0 to 30 ° C. Characteristic radiation Line image conversion panel.
[0015] (2)前記保護層の少なくとも 1層と前記被覆部はそれぞれ熱可塑性エラストマ一を 含有し、それぞれの熱可塑性エラストマ一は、同一のモノマーユニットを含有してなり 、該同一のモノマーユニットの含有率は、該保護層に含有される熱可塑性エラストマ 一を基準として 30〜： 100%であることを特徴とする上記（1)に記載の放射線像変換 パネル。  [0015] (2) At least one of the protective layers and the covering portion each contain a thermoplastic elastomer, and each thermoplastic elastomer contains the same monomer unit, and the same monomer unit. The radiation image conversion panel according to (1) above, wherein the content of is 30 to 100% based on the thermoplastic elastomer contained in the protective layer.
[0016] (3)前記保護層の少なくとも 1層が前記保護層の最外層であることを特徴とする上 記（2)に記載の放射線像変換パネル。  [0016] (3) The radiation image conversion panel according to (2), wherein at least one of the protective layers is an outermost layer of the protective layer.
[0017] (4)前記輝尽性蛍光体層が下記一般式（1)で表される輝尽性蛍光体を含有するこ とを特徴とする上記（1)〜（3)のいずれ力 1項に記載の放射線像変換パネル。 [0017] (4) Any one of the above-mentioned (1) to (3), wherein the photostimulable phosphor layer contains a photostimulable phosphor represented by the following general formula (1): The radiation image conversion panel according to item.
[0018] 一般式（1) [0018] General formula (1)
Ba M2 FBr I ： aM1, bLn, c〇 Ba M 2 FBr I: aM 1 , bLn, c〇
1 - x x y 1 y  1-x x y 1 y
(式中、 M1は Li、 Na、 K、 Rb及び Csから選ばれる少なくとも一種のアルカリ金属原子 、 M2は Be、 Mg、 Sr及び Caから選ばれる少なくとも一種のアルカリ土類金属原子、 L ηίま Ce、 Pr、 Sm、 Eu、 Gd、 Tb、 Tm、 Dy、 Ho、 Nd、 Er及び Yb力ら選 ίまれる少なく とも一種の希土類元素、 x、 y、 a、 b及び cは、それぞれ 0≤x≤0. 3、 0≤y≤l . 0、 0 ≤a≤0. 05、 0<b≤0. 2、 0< c≤0. 1を表す。） (Wherein M 1 is at least one alkali metal atom selected from Li, Na, K, Rb and Cs, M 2 is at least one alkali earth metal atom selected from Be, Mg, Sr and Ca, L ηί Ce, Pr, Sm, Eu, Gd, Tb, Tm, Dy, Ho, Nd, Er, and Yb force are selected from at least one rare earth element, x, y, a, b, and c, respectively. ≤x≤0. 3, 0≤y≤l. 0, 0 ≤a≤0. 05, 0 <b≤0. 2, 0 <c≤0.
(5)前記保護層が転写箔で形成されることを特徴とする上記（1)〜（4)のレ、ずれか 1項に記載の放射線像変換パネル。  (5) The radiation image conversion panel according to (1), wherein the protective layer is formed of a transfer foil.
発明の効果  The invention's effect
[0019] 本発明によれば、放射線像変換パネル周辺部における物理的衝撃から放射線像 変換パネルを保護し、また輝尽性蛍光体層の吸湿等によるパネルの劣化が防止され た放射線像変換パネルを提供することができる。  According to the present invention, a radiation image conversion panel that protects the radiation image conversion panel from physical impact at the periphery of the radiation image conversion panel and prevents deterioration of the panel due to moisture absorption or the like of the stimulable phosphor layer. Can be provided.
図面の簡単な説明  Brief Description of Drawings
[0020] [図 1]本発明の第一の実施形態を示す放射線像変換パネルの断面図である。  FIG. 1 is a cross-sectional view of a radiation image conversion panel showing a first embodiment of the present invention.
[図 2]本発明の第二の実施形態を示す放射線像変換パネルの断面図である。  FIG. 2 is a cross-sectional view of a radiation image conversion panel showing a second embodiment of the present invention.
[図 3]本発明の第三の実施形態を示す放射線像変換パネルの断面図である。  FIG. 3 is a cross-sectional view of a radiation image conversion panel showing a third embodiment of the present invention.
符号の説明 [0021] 10 放射線像変換パネル Explanation of symbols [0021] 10 Radiation image conversion panel
11 支持体層  11 Support layer
12 輝尽性蛍光体層  12 photostimulable phosphor layer
13 保護層  13 Protective layer
14 被覆部  14 Covering part
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0022] 本発明者は鋭意検討の結果、支持体上に少なくとも輝尽性蛍光体層及び軟化点 を有する保護層を有する放射線像変換パネルにぉレ、て、該放射線像変換パネルは 、該輝尽性蛍光体層の少なくとも端部を該保護層と共に封止する、軟化点を有する 被覆部を有し、且つ、該保護層の少なくとも 1層と該被覆部の軟化点の差が 0〜30°C であることを特徴とする放射線像変換パネルにより、感度、画質の低下がなぐ放射 線像変換パネル周辺部における物理的衝撃から放射線像変換パネルを保護し、ま た輝尽性蛍光体層の吸湿等によるパネルの劣化が防止された放射線像変換パネル が得られるとの本願発明の効果を見出した。  [0022] As a result of intensive studies, the inventor has found that the radiation image conversion panel has at least a stimulable phosphor layer and a protective layer having a softening point on the support. A coating portion having a softening point that seals at least an end of the photostimulable phosphor layer together with the protective layer, and a difference in softening point between at least one layer of the protective layer and the coating portion is 0 to The radiation image conversion panel, which is characterized by 30 ° C, protects the radiation image conversion panel from physical impacts at the periphery of the radiation image conversion panel, which does not deteriorate the sensitivity and image quality. The inventors have found the effect of the present invention that a radiation image conversion panel in which deterioration of the panel due to moisture absorption of the layer is prevented can be obtained.
[0023] また、上記する輝尽性蛍光体層の封止は、被覆部と保護層と支持体により封止され ることが好ましぐこの場合も、上記保護層の少なくとも 1層と該被覆部の軟化点の差 力 S0〜30°Cであることにより本願発明の効果が奏される。  [0023] It is preferable that the photostimulable phosphor layer is sealed by a covering portion, a protective layer, and a support. In this case, at least one of the protective layer and the coating are also used. The effect of the present invention is achieved by the difference in the softening point of the part between S0 and 30 ° C.
[0024] 以下、図面を参照して本発明の実施の形態について説明する。図 1は本発明の第 一の実施形態を示す放射線像変換パネルの断面図、図 2は本発明の第二の実施形 態を示す放射線像変換パネルの断面図、図 3は本発明の第三の実施形態を示す放 射線像変換パネルの断面図である。  Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a sectional view of a radiation image conversion panel showing a first embodiment of the present invention, FIG. 2 is a sectional view of a radiation image conversion panel showing a second embodiment of the present invention, and FIG. It is sectional drawing of the radiation image conversion panel which shows three embodiment.
[0025] 図 1に示すように、本発明の第一の実施形態を示す放射線像変換パネル 10は、支 持体 11の上に輝尽性蛍光体層 12が積層され、輝尽性蛍光体層 12の上にさらに保 護層 13が積層されており、輝尽性蛍光体層 12の端部が被覆部 14により封止されて いるものである。このように被覆部 14は、輝尽性蛍光体層 12を封止するものであれ ばよく、図 1に示すように支持体 11、輝尽性蛍光体層 12、保護層 13の全体を包み込 んで輝尽性蛍光体層 12を封止するものが好ましい。  As shown in FIG. 1, in the radiation image conversion panel 10 showing the first embodiment of the present invention, a photostimulable phosphor layer 12 is laminated on a support 11, and the photostimulable phosphor is displayed. A protective layer 13 is further laminated on the layer 12, and the end portion of the stimulable phosphor layer 12 is sealed with the covering portion 14. Thus, the covering portion 14 only needs to seal the photostimulable phosphor layer 12, and wraps the entire support 11, the photostimulable phosphor layer 12, and the protective layer 13 as shown in FIG. It is preferable to encapsulate the photostimulable phosphor layer 12.
[0026] また、図 2に示すように、輝尽性蛍光体層 22が支持体 21よりも小さい状態の放射線 像変換パネル 20である場合には、被覆部 24が支持体 21の縁部分に載って輝尽性 蛍光体層 22を封止するものであってもよレ、。ただし、この場合、輝尽性蛍光体層 22 の側面部分が露出していると、わずかな露出部分から吸湿が起こるため、保護層 23 の側面部分まで被覆部 24を設けることが必要であり、図 2に示すように、保護層 23の 上面部分まで封止することがより好ましい。 In addition, as shown in FIG. 2, radiation in a state where the photostimulable phosphor layer 22 is smaller than the support 21. In the case of the image conversion panel 20, the covering portion 24 may be placed on the edge portion of the support 21 to seal the stimulable phosphor layer 22. However, in this case, if the side portion of the photostimulable phosphor layer 22 is exposed, moisture absorption occurs from a slightly exposed portion, so it is necessary to provide the covering portion 24 up to the side portion of the protective layer 23. As shown in FIG. 2, it is more preferable to seal up to the upper surface portion of the protective layer 23.
[0027] また、図 3に示すように、輝尽性蛍光体層 32が支持体 31よりも小さぐ保護層 33よ りも小さい放射線像変換パネル 30の場合には、輝尽性蛍光体層 32が露出しないよ うに例えば、図 3に示すように輝尽性蛍光体層 32にキャップをするように被覆部 34を 設けることが好ましい。 In addition, as shown in FIG. 3, in the case of the radiation image conversion panel 30 in which the stimulable phosphor layer 32 is smaller than the support 31 and smaller than the protective layer 33, the stimulable phosphor layer For example, a covering portion 34 is preferably provided so as to cap the photostimulable phosphor layer 32 as shown in FIG.
[0028] 被覆部の輝尽性蛍光体層の端面における厚みは、被覆部の、輝尽性蛍光体層の 端面に接触してレ、る部分における輝尽性蛍光体層の端面に対して垂直方向の厚み を意味し、図 1では dl、図 2では d2、図 3では d3である。この被覆部の厚みは輝尽性 蛍光体層に対する防湿や強度の面及び生産性の面から 5〜： 1000 μ mが好ましぐ 1 0〜500 μ mであることがより好ましレ、。  [0028] The thickness of the end face of the photostimulable phosphor layer of the covering portion is in contact with the end face of the stimulable phosphor layer of the covering portion with respect to the end face of the stimulable phosphor layer. Thickness in the vertical direction, which is dl in Fig. 1, d2 in Fig. 2, and d3 in Fig. 3. The thickness of the coating portion is preferably 5 to 1000 μm, more preferably 10 to 500 μm, from the viewpoint of moisture resistance and strength with respect to the stimulable phosphor layer and productivity.
[0029] 以下、本発明の放射線像変換パネルの各層について、輝尽性蛍光体層、支持体、 保護層、被覆部の順に説明する。  Hereinafter, each layer of the radiation image conversion panel of the present invention will be described in the order of a stimulable phosphor layer, a support, a protective layer, and a covering portion.
[0030] 《輝尽性蛍光体層》  [0030] <Stimulable phosphor layer>
本発明に係る輝尽性蛍光体層について説明する。  The photostimulable phosphor layer according to the present invention will be described.
[0031] 輝尽性蛍光体層は、少なくともバインダと輝尽性蛍光体粒子とを含有してレ、る。輝 尽性蛍光体とは、最初の光または高エネルギー放射線が照射された後に、光的、熱 的、機械的、科学的または電気的等の刺激 (輝尽励起）により、最初の光または高工 ネルギー放射線の照射量に対応した輝尽発光を示す蛍光体をいうが、実用的な面 からは、光刺激 (輝尽励起）により輝尽発光を示す蛍光体が好ましぐ波長が 500nm 〜1 μ mの輝尽励起光によって輝尽発光を示す蛍光体が好ましい。  [0031] The photostimulable phosphor layer contains at least a binder and photostimulable phosphor particles. A photostimulable phosphor is a material that is exposed to the initial light or high energy radiation by stimulating (stimulated excitation) such as optical, thermal, mechanical, scientific or electrical after the initial light or high-energy radiation. Phosphors exhibiting stimulated emission corresponding to the irradiation dose of engineering radiation. From a practical standpoint, phosphors that exhibit stimulated emission by light stimulation (stimulated excitation) have a preferred wavelength of 500 nm ~ A phosphor exhibiting stimulated emission by 1 μm stimulated excitation light is preferred.
[0032] (輝尽性蛍光体）  [0032] (Stimulable phosphor)
以下に本発明に用いられる輝尽性蛍光体の具体例を挙げるが、本発明はこれらに 限定されない。  Specific examples of the stimulable phosphor used in the present invention are given below, but the present invention is not limited thereto.
[0033] 1.特開平 2— 58593号に記載の一般式 aBaX · (1— a) BaY： bEu + (式中、 X、 Yは、各々 F、 Cl、 Br、 Iの少なくとも 1種を表し、 X≠Yであり、 a、 bは、 0< aく 1、 10— 5<b< 10— 1を満たす数を表す。）で表される輝尽性蛍光体。 [0033] 1. General formula aBaX · (1– a) BaY: bEu + described in JP-A-2-58593 (Wherein, X, Y are each represents F, Cl, Br, at least one I, a X ≠ Y, a, b is 0 <a rather 1, 10- 5 <b <10- 1 A stimulable phosphor represented by the following formula:
[0034] 2.特開昭 61— 72087号に記載の一般式 M X' aM X' -bM X/r ： cA (ただし、 [0034] 2. General formula MX ′ aM X ′ -bM X / r described in JP-A-61-72087: cA (provided that
I II 2 III 3  I II 2 III 3
Mは、 Li、 Na、 K、 Rb、 Csの少なくとも 1種のアルカリ金属を表し、 Mは、 Be、 Mg、 M represents at least one alkali metal of Li, Na, K, Rb, and Cs, and M represents Be, Mg,
I II I II
Ca、 Sr、 Ba、 Zn、 Cd、 Cu、 Niの少なくとも 1種の 2価の金属を表し M は、 Sc、 Y、  Represents at least one divalent metal of Ca, Sr, Ba, Zn, Cd, Cu, and Ni, and M is Sc, Y,
III  III
La、 Ce、 Pr、 Nd、 Pm、 Sm、 Eu、 Gd、 Tb、 Dy、 Ho、 Er、 Tm、 Yb、 Lu、 Al、 Ga、 I nの少なくとも 1種の 3価の金属を表し、 X、 X' 、X〃 は、 F、 Cl、 Br、 Iの少なくとも 1種 の/ヽロゲンを表し、 Αίま、 Eu、 Tbゝ Ce、 Tm、 Dyゝ Prゝ Ho、 Nd、 Yb、 Erゝ Gd、 Lu, S m、 Y、 Tl、 Na、 Ag、 Cu、 Mgの少なくとも 1種の金属を表し、 a、 b、 cは、 0≤a< 0. 5 、 0≤b< 0. 5、 0≤c< 0. 2を満たす数を表す。）で表されるアルカリハライド輝尽性 蛍光体。  Represents at least one trivalent metal of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Ga, In, X, X 'and X〃 represent at least one of F, Cl, Br, and I / ヽ, and Eu, Tb ゝ Ce, Tm, Dy ゝ Pr ゝ Ho, Nd, Yb, Er ゝ Gd, Represents at least one metal of Lu, S m, Y, Tl, Na, Ag, Cu, Mg, a, b, c are 0≤a <0.5, 0≤b <0.5, 0≤ Represents a number that satisfies c <0.2. ) An alkali halide photostimulable phosphor represented by
[0035] 3·特開昭 55— 12145号に記載の一般式（Ba (M ) ) FX: vA (ただし、 Mは、 M  [0035] 3 · General formula (Ba (M)) FX: vA (where M is M
l-x I X I g、 Ca、 Sr、 Zn、 Cdの少なくとも 1種を表し、 Xは、 Cl、 Br、 Iの少なくとも 1種を表し、 Aは、 Eu、 Tb、 Ce、 Tm、 Dy、 Pr、 Ho, Nd、 Yb、 Erの少なくとも 1種を表し、 x、 yは 、 0≤x< 0. 6、 0≤y< 0. 2を満たす数を表す。）で表される輝尽性蛍光体。  lx IXI represents at least one of g, Ca, Sr, Zn, and Cd, X represents at least one of Cl, Br, and I, A represents Eu, Tb, Ce, Tm, Dy, Pr, Ho, It represents at least one of Nd, Yb and Er, and x and y represent numbers satisfying 0≤x <0.6 and 0≤y <0.2. Stimulable phosphor represented by
[0036] 4.特開昭 55— 160078号に記載の一般式 M FX'xA :yLn (ただし、 Mは、 Mg、 Ca、 Ba、 Sr、 Zn、 Cdの少なくとも 1種を表し、 Aは Be〇、 MgO、 Ca〇、 SrO、 Ba〇、 ZnO、 Al O、 Y O、 La O、 In〇、 SiO、 TiO、 Zr〇、 GeO、 Sn〇、 Nb O、 Ta [0036] 4. General formula M FX'xA: yLn described in JP-A-55-160078 (where M represents at least one of Mg, Ca, Ba, Sr, Zn, Cd, and A represents Be Yes, MgO, CaO, SrO, BaO, ZnO, AlO, YO, La O, InO, SiO, TiO, ZrO, GeO, SnO, NbO, Ta
2 3 2 3 2 3 2 3 2 2 2 2 2 2 5 2 2 3 2 3 2 3 2 3 2 2 2 2 2 2 5 2
〇、 ThOの少なくとも 1種を表し、： Lnは、 Eu、 Tb、 Ce、 Tm、 Dy、 Pr、 Ho, Nd、 Yb〇, represents at least one of ThO, Ln is Eu, Tb, Ce, Tm, Dy, Pr, Ho, Nd, Yb
5 2 5 2
、 Er、 Sm、 Gdの少なくとも 1種を表し、 Xは Cl、 Br、 Iの少なくとも 1種を表し、 x、 yは、 5 X 10— 5≤x≤0. 5、 0<y≤0. 2を満たす数を表す。）で表される輝尽性蛍光体。 , Er, Sm, Gd, X is at least one of Cl, Br, I, x, y are 5 X 10— 5 ≤x≤0. 5, 0 <y≤0. Represents a number satisfying 2. Stimulable phosphor represented by
[0037] 〈一般式（1)で表される輝尽性蛍光体〉  <Stimulable phosphor represented by the general formula (1)>
中でも、下記一般式（1)で表される輝尽性蛍光体が好ましい。  Among these, stimulable phosphors represented by the following general formula (1) are preferable.
[0038] 一般式（1) Ba M2 FBr I ： aM1, bLn, cO [0038] General formula (1) Ba M 2 FBr I: aM 1 , bLn, cO
丄- x x y 1-y  丄-x x y 1-y
式中、 M1は Li、 Na、 K、 Rb及び Csから選ばれる少なくとも一種のアルカリ金属原 子、 M2は Be、 Mg、 Sr及び Caから選ばれる少なくとも一種のアルカリ土類金属原子、 Lnは Ce、 Pr、 Sm、 Eu、 Gd、 Tb、 Tm、 Dy、 Ho、 Nd、 Er及び Ybから選ばれる少な くとも一種の希土類元素、 x、 y、 a、 b及び cは、それぞれ 0≤χ≤0· 3, 0≤y≤l . 0、 0≤a≤0. 05、 0<b≤0. 2、 0< c≤0. 1を表す。 Wherein M 1 is at least one alkali metal atom selected from Li, Na, K, Rb and Cs, M 2 is at least one alkali earth metal atom selected from Be, Mg, Sr and Ca, and Ln is At least one rare earth element selected from Ce, Pr, Sm, Eu, Gd, Tb, Tm, Dy, Ho, Nd, Er, and Yb, x, y, a, b, and c is 0≤χ≤ 0 · 3, 0≤y≤l. 0, 0≤a≤0. 05, 0 <b≤0. 2, 0 <c≤0.1.
[0039] 液相法による輝尽性蛍光体前駆体製造については、特開平 10— 140148号に記 載された前駆体製造方法、特開平 10— 147778号に記載された前駆体製造装置が 好ましく利用できる。ここで輝尽性蛍光体前駆体とは、前記一般式（1)で示される物 質が 600°C以上の高温を経ていない状態を示し、輝尽性蛍光体前駆体は、輝尽発 光性や瞬時発光性をほとんど示さなレ、。本発明では以下の液相合成法により前駆体 を得ることが好ましい。 [0039] For the production of stimulable phosphor precursors by the liquid phase method, a precursor production method described in JP-A-10-140148 and a precursor production apparatus described in JP-A-10-147778 are preferred. Available. Here, the photostimulable phosphor precursor refers to a state in which the substance represented by the general formula (1) has not been subjected to a high temperature of 600 ° C. or higher. , Which shows almost no sexual activity or instantaneous luminescence. In the present invention, the precursor is preferably obtained by the following liquid phase synthesis method.
[0040] 上記一般式（1)からなる輝尽性蛍光体の製造は、粒子形状の制御が難しい固相法 ではなぐ粒径の制御が容易である液相法により行なうことが好ましい。特に、下記の 液相合成法により輝尽性蛍光体を得ることが好ましい。  [0040] The photostimulable phosphor composed of the general formula (1) is preferably produced by a liquid phase method in which the particle size is easily controlled as compared with the solid phase method in which the particle shape is difficult to control. In particular, it is preferable to obtain a photostimulable phosphor by the following liquid phase synthesis method.
[0041] 製造法： Balと Lnのハロゲン化物を含み、一般式（1)の xが 0でない場合にはさら に、 M2のハロゲン化物を、 yが 0でない場合は BaBrを、そして M1のハロゲン化物を 含み、それらが溶解したのち、 Bal濃度が 3. 3mol/L以上、好ましくは 3. 5mol/L 以上の溶液を調製する工程；上記の溶液を 50°C以上、好ましくは 80°C以上の温度 に維持しながら、これに濃度 5mol/L以上、好ましくは 8mol/L以上の無機弗化物[0041] Production method: It contains a halide of Bal and Ln, and if x in the general formula (1) is not 0, it further contains a halide of M 2 , if y is not 0, BaBr, and M 1 A step of preparing a solution having a Bal concentration of 3.3 mol / L or more, preferably 3.5 mol / L or more after dissolving them, and the above solution is 50 ° C or more, preferably 80 ° C. Inorganic fluoride with a concentration of 5 mol / L or more, preferably 8 mol / L or more, while maintaining a temperature of C or more
(弗化アンモニゥムもしくはアルカリ金属の弗化物）の溶液を添加して輝尽性蛍光体 前駆体結晶の沈澱物を得る工程；上記の無機弗化物を添加しつつ、反応液から溶 媒を除去する工程上記の前駆体結晶沈澱物を反応液から分離する工程;そして、分 離した前駆体結晶沈澱物を焼結を避けながら焼成する工程を含む製造方法である。 A step of obtaining a stimulable phosphor precursor crystal precipitate by adding a solution of (ammonium fluoride or alkali metal fluoride); removing the solvent from the reaction solution while adding the above inorganic fluoride Process A process comprising: separating the precursor crystal precipitate from the reaction solution; and firing the separated precursor crystal precipitate while avoiding sintering.
[0042] なお、本発明では粒子（結晶）は平均粒径が 1〜： 10 μ mで、かつ単分散性のものが 好ましぐ平均粒径が l〜5 x m、平均粒径の分布が 20%以下のものが好まし 特 に平均粒径が:!〜 3 μ m、平均粒径の分布が 15%以下のものが好ましい。  In the present invention, the particles (crystals) have an average particle size of 1 to 10 μm, and monodisperse particles preferably have an average particle size of 1 to 5 xm and an average particle size distribution of Those having a particle size of 20% or less are preferred. Particularly, those having an average particle size of: ~ 3 μm and a distribution of average particle size of 15% or less are preferable.
[0043] 本発明における平均粒径とは、粒子 (結晶）の電子顕微鏡写真より無作為に粒子 2 00個を選び、球換算の体積粒子径で平均を求めたものである。  [0043] The average particle diameter in the present invention is obtained by randomly selecting 200 particles from an electron micrograph of particles (crystals) and calculating the average with a volume particle diameter in terms of a sphere.
[0044] 以下に輝尽性蛍光体の製造法の好ましい例について詳細について説明する。  [0044] Hereinafter, preferred examples of the method for producing a photostimulable phosphor will be described in detail.
[0045] 最初に、水系媒体中を用いて弗素化合物以外の原料化合物を溶解させる。すなわ ち、 Balと Lnのハロゲン化物、そして必要によりさらに M2のハロゲン化物、そしてさら に M1のハロゲン化物を水系媒体中に入れ充分に混合し、溶解させて、それらが溶解 した水溶液を調製する。ただし、 Bal濃度が 3. 3molZL以上、好ましくは 3. 5molFirst, a raw material compound other than a fluorine compound is dissolved in an aqueous medium. That is, the halides of Bal and Ln, and if necessary, further M 2 halides, and further M 1 halides are placed in an aqueous medium and mixed thoroughly to dissolve them. Prepare an aqueous solution. However, Bal concentration is 3.3molZL or more, preferably 3.5mol
ZL以上となるように、 Bal濃度と水系溶媒との量比を調整しておく。 The amount ratio between the Bal concentration and the aqueous solvent is adjusted so as to be equal to or higher than ZL.
[0046] このときバリウム濃度が低いと所望の組成の前駆体が得られなレ、か、得られても粒 子が肥大化する。よって、バリウム濃度は適切に選択する必要があり、本発明者らの 検討の結果、 3. 3molZL以上で微細な前駆体粒子を形成することができることが分 かった。  [0046] At this time, if the barium concentration is low, a precursor having a desired composition cannot be obtained, or even if obtained, the particles are enlarged. Therefore, it is necessary to select the barium concentration appropriately, and as a result of the study by the present inventors, it was found that fine precursor particles can be formed at 3.3 molZL or more.
[0047] このとき、所望により、少量の酸、アンモニア、アルコール、水溶性高分子ポリマー、 水不溶性金属酸化物微粒子粉体等を添加してもよい。 Balの溶解度が著しく低下し ない範囲で低級アルコール (メタノール、エタノール）を適当量添加しておくのも好ま しい態様である。この水溶液 (反応母液）は 80°Cに維持される。  [0047] At this time, if desired, a small amount of acid, ammonia, alcohol, water-soluble polymer, water-insoluble metal oxide fine particle powder or the like may be added. It is also preferable to add an appropriate amount of lower alcohol (methanol or ethanol) within a range where the solubility of Bal does not significantly decrease. This aqueous solution (reaction mother liquor) is maintained at 80 ° C.
[0048] 次に、この 80°Cに維持され、撹拌されている水溶液に、無機弗化物（弗化アンモニ ゥム、アルカリ金属の弗化物等）の水溶液を注入する。この注入は、撹拌が特に激し く実施されている領域部分に行なうのが好ましい。この無機弗化物水溶液の反応母 液への注入によって、前記一般式（1)に該当する蛍光体前駆体結晶が析出する。  [0048] Next, an aqueous solution of an inorganic fluoride (ammonium fluoride, alkali metal fluoride, etc.) is poured into the aqueous solution maintained at 80 ° C and stirred. This injection is preferably carried out in the region where stirring is particularly intense. By injecting the inorganic fluoride aqueous solution into the reaction mother liquor, the phosphor precursor crystal corresponding to the general formula (1) is precipitated.
[0049] 本発明においては、無機弗化物水溶液の添加時に反応液から溶媒を除去すること が好ましい。溶媒を除去する時期は添カ卩中であれば、特に問わない。溶媒の除去後 の全質量が除去前の質量 (反応母液の質量と添加した水溶液の質量の和）に対する 比率（以下、除去比率という）が 0. 97以下であることが好ましい。 0. 97を超えると結 晶が BaFIになりきらない場合がある。そのため除去比率は 0. 97以下であることが好 ましぐ 0. 95以下がより好ましい。また、除去しすぎても反応溶液の粘度が過剰に上 昇する等、ハンドリングの面で不都合が生じる場合がある。  [0049] In the present invention, it is preferable to remove the solvent from the reaction solution when adding the inorganic fluoride aqueous solution. The timing for removing the solvent is not particularly limited as long as it is in the additive. The ratio (hereinafter referred to as the removal ratio) of the total mass after removal of the solvent to the mass before removal (the sum of the mass of the reaction mother liquor and the mass of the added aqueous solution) is preferably 0.97 or less. If it exceeds 0.9, the crystal may not be BaFI. Therefore, the removal ratio is preferably 0.97 or less, more preferably 0.95 or less. Moreover, even if it is removed too much, the viscosity of the reaction solution may increase excessively, which may cause inconvenience in handling.
[0050] そのため溶媒の除去比率は 0. 5まで（0. 50以上）が好ましい。溶媒の除去に要す る時間は生産性に大きく影響するば力りでな 粒子の形状、粒径分布も溶媒の除 去方法に影響されるので、除去方法は適切に選択する必要がある。一般的に溶媒の 除去に際しては溶液を加熱し、溶媒を蒸発する方法が選択される。本発明において もこの方法は有用である。溶媒の除去により、意図した組成の前駆体を得ることがで きる。さらに、生産性を挙げるため、また、粒子形状を適切に保っため、他の溶媒除 去方法を併用することが好ましい。併用する溶媒の除去方法は特に問わない。逆浸 透膜等の分離膜を用レ、る方法を選択することも可能である。本発明では生産性の面 から、以下の除去方法を選択することが好ましい。 [0050] Therefore, the solvent removal ratio is preferably up to 0.5 (0.50 or more). The time required to remove the solvent is not a force that greatly affects the productivity. The shape and particle size distribution of the particles are also affected by the method of removing the solvent, so the removal method must be selected appropriately. Generally, when removing the solvent, 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. Furthermore, in order to increase productivity and to maintain the particle shape appropriately, it is preferable to use other solvent removal methods in combination. The method for removing the solvent used in combination is not particularly limited. Reverse immersion It is also possible to select a method using a separation membrane such as a permeable membrane. In the present invention, it is preferable to select the following removal method from the viewpoint of productivity.
[0051] 1.乾燥気体を通気する反応容器を密閉型とし、少なくとも 2箇所以上の気体が通 過できる孔を設け、そこから乾燥気体を通気する。気体の種類は任意に選ぶことがで きる。安全性の面から、空気、窒素が好ましい。通気する気体の飽和水蒸気量に依 存し、溶媒が気体に同伴され、除去される。反応容器の空隙部分に通気する方法の 他、液相中に気体を気泡として噴出させ、気泡中に溶媒を吸収させる方法もまた有 効である。  [0051] 1. The reaction vessel through which dry gas is vented is sealed, and at least two or more holes through which gas can pass are provided, and dry gas is vented from there. The type of gas can be selected arbitrarily. Air and nitrogen are preferable from the viewpoint of safety. Depending on the amount of saturated water vapor in the gas being aerated, the solvent is entrained in the gas and removed. In addition to the method of venting the void portion of the reaction vessel, a method of jetting gas as bubbles in the liquid phase and absorbing the solvent in the bubbles is also effective.
[0052] 2.よく知られるように減圧にすることにより、溶媒の蒸気圧は低下する。蒸気圧降下 により効率的に溶媒を除去することができる。減圧度としては溶媒の種類により適宜 選択することができる。溶媒が水の場合 86kPa以下が好ましい。  [0052] 2. As is well known, by reducing the pressure, the vapor pressure of the solvent decreases. The solvent can be efficiently removed by the vapor pressure drop. The degree of reduced pressure can be appropriately selected depending on the type of solvent. When the solvent is water, 86 kPa or less is preferable.
[0053] 3.液膜蒸発面積を拡大することにより溶媒の除去を効率的に行うことができる。一 定容積の反応容器を用いて加熱、攪拌し、反応を行わせる場合、加熱方法しては、 加熱手段を液体中に浸潰するか、容器の外側に加熱手段を装着する方法が一般的 である。該方法によると、伝熱面積は液体と加熱手段が接触する部分に限定され、溶 媒除去に伴い、伝熱面積が減少し、よって、溶媒除去に要する時間が長くなる。これ を防ぐため、ポンプ、あるいは攪拌機を用いて反応容器の壁面に散布し、伝熱面積 を増大させる方法が有効である。このように反応容器壁面に液体を散布し、液膜を形 成する方法は"濡れ壁"として知られている。濡れ壁の形成方法としては、ポンプを用 いる方法のほか、特開平 6— 335627号、同 11— 235522号に記載の攪拌機を用い る方法が挙げられる。  [0053] 3. The solvent can be efficiently removed by enlarging the liquid film evaporation area. When heating and stirring with a fixed volume reaction vessel to cause the reaction to take place, the heating method is generally either by immersing the heating means in a liquid or by attaching the heating means outside the container. It is. 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 solvent removal increases. In order to prevent this, it is effective to spread the heat transfer area by spraying it on the wall of the reaction vessel using a pump or a stirrer. This method of spraying a liquid on the reaction vessel wall to form a liquid film is known as a “wetting wall”. As a method for forming the wetting wall, in addition to a method using a pump, a method using a stirrer described in JP-A Nos. 6-335627 and 11-235522 can be mentioned.
[0054] これらの方法は単独のみならず、組み合わせて用いてもかまわない。液膜を形成す る方法と容器内を減圧にする方法の組み合わせ、液膜を形成する方法と乾燥気体を 通気する方法の組み合わせ等が有効である。特に前者が好ましぐ特開平 6— 3356 27号、特開 2003— 236303号に記載の方法が好ましく用いられる。  [0054] These methods may be used not only alone but also in combination. A combination of a method of forming a liquid film and a method of reducing the pressure inside the container, a combination of a method of forming a liquid film and a method of ventilating dry gas, and the like are effective. In particular, the methods described in JP-A-6-335627 and JP-A-2003-236303, which are preferred by the former, are preferably used.
[0055] 次に、上記の蛍光体前駆体結晶を、濾過、遠心分離等によって溶液から分離し、メ タノール等によって充分に洗浄し、乾燥する。この乾燥蛍光体前駆体結晶に、アルミ ナ微粉末、シリカ微粉末等の焼結防止剤を添加、混合し、結晶表面に焼結防止剤微 粉末を均一に付着させる。なお、焼成条件を選ぶことによって焼結防止剤の添加を 省略することも可能である。 [0055] Next, the phosphor precursor crystal is separated from the solution by filtration, centrifugation, or the like, sufficiently washed with methanol or the like, and dried. A sintering inhibitor such as alumina fine powder or silica fine powder is added to and mixed with the dried phosphor precursor crystal, and the sintering inhibitor fine powder is added to the crystal surface. Apply the powder uniformly. It is also possible to omit the addition of the sintering inhibitor by selecting the firing conditions.
[0056] 次に、蛍光体前駆体の結晶を、石英ポート、アルミナ坩堝、石英坩堝等の耐熱性 容器に充填し、電気炉の炉心に入れて焼結を避けながら焼成を行う。焼成温度は 40 0〜： 1， 300°Cの範囲が適当であり、 500〜1， 000°Cの範囲が好ましレ、。焼成時間は 、蛍光体原料混合物の充填量、焼成温度及び炉からの取出し温度等によっても異な るが、一般には 0. 5〜： 12時間が適当である。  [0056] Next, the phosphor precursor crystals are filled in a heat-resistant container such as a quartz port, an alumina crucible, a quartz crucible, and the like, and placed in an electric furnace core to be sintered while avoiding sintering. The firing temperature is suitably from 400 to 1,300 ° C, and preferably from 500 to 1,000 ° C. The firing time varies depending on the filling amount of the phosphor raw material mixture, the firing temperature, the removal temperature from the furnace, etc., but generally 0.5 to 12 hours is appropriate.
[0057] 焼成雰囲気としては、窒素ガス雰囲気、アルゴンガス雰囲気等の中性雰囲気、ある いは少量の水素ガスを含有する窒素ガス雰囲気、一酸化炭素を含有する二酸化炭 素雰囲気等の弱還元性雰囲気、あるいは微量酸素導入雰囲気が利用される。焼成 方法については、特開 2000— 8034号に記載の方法が好ましく用いられる。上記の 焼成によって目的の輝尽性蛍光体が得られ、これを用いて形成された蛍光体層を有 する放射線像変換パネルが作製される。  [0057] 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, or the like. An atmosphere or a trace oxygen introduction atmosphere is used. Regarding the firing method, the method described in JP-A-2000-8034 is preferably used. The target photostimulable phosphor is obtained by the above firing, and a radiation image conversion panel having a phosphor layer formed using the phosphor is produced.
[0058] (バインダ）  [0058] (Binder)
本発明に係る輝尽性蛍光体層に用レ、られるバインダ (結合剤ともいう）について説 明する。  The binder (also referred to as binder) used in the photostimulable phosphor layer according to the present invention will be described.
[0059] 本発明に用いられるバインダの例としては、ゼラチン等の蛋白質、デキストラン等の ポリサッカライド、またはアラビアゴムのような天然高分子物質;及び、ポリビュルプチ ラール、ポリ酢酸ビュル、ニトロセルロース、ェチルセルロース、塩化ビニリデン'塩化 ビュルコポリマー、ポリアルキル（メタ）アタリレート、塩化ビュル'酢酸ビュルコポリマー 、ポリウレタン、セルロースアセテートブチレート、ポリビュルアルコール、線状ポリエス テル等のような合成高分子物質等により代表されるバインダを挙げることができるが、 ノインダが熱可塑性エラストマ一を主成分とする樹脂であることが好ましレ、。熱可塑 性エラストマ一としては、例えば、ポリスチレン系熱可塑性エラストマ一、ポリオレフィ ン系熱可塑性エラストマ一、ポリウレタン系熱可塑性エラストマ一、ポリエステル系熱 可塑性エラストマ一、ポリアミド系熱可塑性エラストマ一、ポリブタジエン系熱可塑性ェ ラストマー、エチレン酢酸ビュル系熱可塑性エラストマ一、ポリ塩化ビュル系熱可塑 性エラストマ一、天然ゴム系熱可塑性エラストマ一、フッ素ゴム系熱可塑性エラストマ 一、ポリイソプレン系熱可塑性エラストマ一、塩素化ポリエチレン系熱可塑性エラスト マー、スチレン一ブタジエンゴム及びシリコンゴム系熱可塑性エラストマ一等が挙げら れる。これらのうち、ポリウレタン系熱可塑性エラストマ一及びポリエステル系熱可塑 性エラストマ一は、蛍光体との結合力が強いため分散性が良好であり、また延性にも 富み、放射線増感スクリーンの対屈曲性が良好となるので好ましい。なお、これらの ノ インダは、架橋剤により架橋されたものでもよい。 [0059] Examples of the binder used in the present invention include proteins such as gelatin, polysaccharides such as dextran, or natural high molecular substances such as gum arabic; and polybuleptyl, polyacetic acid bule, nitrocellulose, ethyl Represented by synthetic polymer materials such as cellulose, vinylidene chloride 'butyl chloride copolymer, polyalkyl (meth) acrylate, butyl chloride' acetic acid butyl copolymer, polyurethane, cellulose acetate butyrate, polybutyl alcohol, linear polyester, etc. The binder is preferably a resin whose main component is a thermoplastic elastomer. Examples of thermoplastic elastomers include polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polybutadiene-based thermoplastics. Elastomer, ethylene acetate butyl thermoplastic elastomer, polychlorinated butyl thermoplastic elastomer, natural rubber thermoplastic elastomer, fluororubber thermoplastic elastomer 1, polyisoprene-based thermoplastic elastomers, chlorinated polyethylene-based thermoplastic elastomers, styrene-butadiene rubber, silicone rubber-based thermoplastic elastomers, and the like. Of these, polyurethane-based thermoplastic elastomers and polyester-based thermoplastic elastomers have good dispersibility due to their strong bonding strength with phosphors, and are also highly ductile, and are flexible against radiation intensifying screens. Is preferable. These nodes may be crosslinked with a crosslinking agent.
[0060] 塗布液におけるバインダと輝尽性蛍光体との混合比は、 目的とする放射線像変換 パネルのヘイズ率の設定値によって異なる力 蛍光体に対し 1〜20質量部が好まし ぐさらには 2〜： 10質量部がより好ましい。  [0060] The mixing ratio of the binder and the photostimulable phosphor in the coating solution varies depending on the target haze ratio setting value of the radiation image conversion panel. 1 to 20 parts by mass is preferable with respect to the phosphor. 2 to: 10 parts by mass are more preferable.
[0061] (輝尽性蛍光体層の形成）  [0061] (Formation of photostimulable phosphor layer)
輝尽性蛍光体層塗布液の調製に用いられる有機溶剤としては、例えば、メタノーノレ 、エタノール、イソプロパノール、 n—ブタノール等の低級アルコール、アセトン、メチ ルェチルケトン、メチルイソブチルケトン、シクロへキサノン等のケトン、酢酸メチル、 酢酸ェチル、酢酸 n—ブチル等の低級脂肪酸と低級アルコールとのエステル、ジォ キサン、エチレングリコールモノェチルエーテル、エチレングリコールモノメチルエー テル等のエーテル、トリオール、キシロール等の芳香族化合物、メチレンクロライド、 エチレンクロライド等のハロゲンィ匕炭化水素及びそれらの混合物等が挙げられる。  Examples of the organic solvent used for the preparation of the stimulable phosphor layer coating solution include lower alcohols such as methanol, ethanol, isopropanol and n-butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, Esters of lower fatty acids and lower alcohols such as methyl acetate, ethyl acetate and n-butyl acetate; ethers such as dioxane, ethylene glycol monoethyl ether and ethylene glycol monomethyl ether; aromatic compounds such as triol and xylol; And halogenated hydrocarbons such as methylene chloride and ethylene chloride, and mixtures thereof.
[0062] なお、塗布液には、該塗布液中における蛍光体の分散性を向上させるための分散 剤、また、形成後の輝尽性蛍光体層中におけるバインダと蛍光体との間の結合力を 向上させるための可塑剤等の種々の添加剤が混合されていてもよい。そのような目 的に用いられる分散剤の例としては、フタル酸、ステアリン酸、カブロン酸、親油性界 面活性剤等を挙げることができる。また、可塑剤の例としては、燐酸トリフエニル、燐 酸トリクレジル、燐酸ジフヱニル等の燐酸エステル；フタル酸ジェチル、フタル酸ジメト キシェチル等のフタル酸エステノレ；グリコール酸ェチルフタリルェチル、グリコール酸 ブチルフタリルブチル等のグリコール酸エステル；そして、トリエチレングリコールとァ ジピン酸とのポリエステル、ジエチレングリコールとコハク酸とのポリエステル等のポリ エチレングリコールと脂肪族二塩基酸とのポリエステル等を挙げることができる。また 、輝尽性蛍光体層塗布液中に、輝尽性蛍光体粒子の分散性を向上させる目的で、 ステアリン酸、フタル酸、カブロン酸、親油性界面活性剤等の分散剤を混合してもよ レ、。 [0062] The coating liquid contains a dispersant for improving the dispersibility of the phosphor in the coating liquid, and a bond between the binder and the phosphor in the photostimulable phosphor layer after formation. Various additives such as a plasticizer for improving the strength may be mixed. Examples of the dispersant used for such purpose include phthalic acid, stearic acid, cabronic acid, lipophilic surfactant and the like. Examples of plasticizers include phosphoric esters such as triphenyl phosphate, tricresyl phosphate and diphenyl phosphate; phthalate esters such as jetyl phthalate and dimethochetyl phthalate; ethyl phthalyl glycolate, butylphthalyl 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. In addition, in order to improve the dispersibility of stimulable phosphor particles in the stimulable phosphor layer coating solution, Dispersants such as stearic acid, phthalic acid, cabronic acid, and lipophilic surfactants may be mixed.
[0063] 輝尽性蛍光体層用塗布液の調製は、例えば、ボールミル、ビーズミル、サンドミル、 アトライター、三本ロールミル、高速インペラ一分散機、 Kadyミル、あるいは超音波分 散機等の分散装置を用いて行なわれる。  [0063] Preparation of the stimulable phosphor layer coating liquid is performed by, for example, a dispersing device such as a ball mill, a bead mill, a sand mill, an attritor, a three-roll mill, a high-speed impeller-dispersing machine, a Kady mill, or an ultrasonic dispersing machine. It is performed using.
[0064] 上記のようにして調製された塗布液を、後述する支持体表面に均一に塗布すること により塗膜を形成する。用いることのできる塗布方法としては、通常の塗布手段、例え ば、ドクターブレード、ロールコーター、ナイフコーター、コンマコーター、リップコータ 一等を用いることができる。  [0064] A coating film is formed by uniformly coating the coating solution prepared as described above on the surface of a support described later. As a coating method that can be used, a usual coating means such as a doctor blade, a roll coater, a knife coater, a comma coater, a lip coater or the like can be used.
[0065] 上記の手段により形成された塗膜を、その後加熱、乾燥して、支持体上への輝尽 性蛍光体層の形成を完了する。輝尽性蛍光体層の膜厚は、 目的とする放射線像変 換パネルの特性、輝尽性蛍光体の種類、バインダと蛍光体との混合比等によって異 なる力 10〜： 1000 /i m力 S好ましく、さらに好ましくは、 10〜500 /i mである。  [0065] The coating film formed by the above means is then heated and dried to complete the formation of the photostimulable phosphor layer on the support. The film 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 binder and phosphor, etc. 10 to 1000 / im force S is preferable, and more preferably 10 to 500 / im.
[0066] 《支持体》  [0066] << Support >>
本発明に係る放射線像変換パネルの支持体としては、例えば、ガラス、ウール、コッ トン、紙、金属等の種々の素材から作られたものが使用することができる力 情報記 録材料としての取り扱い上、可撓性のあるシートあるいはロールに加工できるものが 好ましい。この点から、例えば、セルロースアセテートフィルム、ポリエステルフィルム、 ポリエチレンテレフタレートフィルム、ポリアミドフイノレム、ポリイミドフィルム、トリァセテ 一トフイルム、ポリカーボネートフィルム等のプラスティックフィルム、アルミニウム箔、ァ ルミ二ゥム合金箔等の金属シート、一般紙及び例えば写真用原紙、コート紙、もしく はアート紙のような印刷用原紙、バライタ紙、レジンコート紙、ベルギー特許第 784， 615号明細書に記載されているようなポリサッカライド等でサイジングされた紙、二酸 化チタン等の顔料を含むピグメント紙、ポリビニールアルコールでサイジングした紙等 の加工紙が特に好ましい。これら支持体の膜厚は、用いる支持体の材質等によって 異なるが、一般的には 80〜： 1000 z mであり、取り扱い上の観点から、さらに好ましく は 80〜500 z mである。これらの支持体の表面は滑面でもよいし、下引き層との接着 力を向上させる目的でマット面としてもよい。 [0067] 《保護層、被覆部》 As the support of the radiation image conversion panel according to the present invention, for example, a material made from various materials such as glass, wool, cotton, paper, metal, etc. can be used as a force information recording material. In addition, a material that can be processed into a flexible sheet or roll is preferable. From this point, metal sheets such as cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, triacetate film, polycarbonate film, etc., aluminum foil, aluminum alloy foil, etc. General paper and printing paper such as photographic paper, coated paper, or art paper, baryta paper, resin coated paper, polysaccharides as described in Belgian Patent No. 784,615, etc. Particularly preferred are processed papers such as paper sized with, pigment paper containing pigments such as titanium dioxide, and paper sized with polyvinyl alcohol. The film thickness of these supports varies depending on the material of the support to be used, but is generally 80 to 1000 zm, and more preferably 80 to 500 zm from the viewpoint of handling. The surface of these supports may be a smooth surface, or a mat surface for the purpose of improving the adhesive strength with the undercoat layer. [0067] << Protective layer, covering part >>
輝尽性蛍光体層の吸湿等による劣化を防ぎ、放射線像変換パネルの機械的強度 を高めるために、放射線像変換パネルの各層の端部、すなわち放射線像変換パネ ル稜部は、樹脂等で被覆して輝尽性蛍光体層を封止することが行われる。  In order to prevent deterioration of the photostimulable phosphor layer due to moisture absorption and increase the mechanical strength of the radiation image conversion panel, the edge of each layer of the radiation image conversion panel, that is, the edge of the radiation image conversion panel is made of resin or the like. Covering and sealing the photostimulable phosphor layer is performed.
[0068] 本発明は、支持体上に少なくとも輝尽性蛍光体層及び軟化点を有する保護層を有 する放射線像変換パネルにおいて、該放射線像変換パネルは、該輝尽性蛍光体層 の少なくとも端部を該保護層と共に封止する、軟ィ匕点を有する被覆部を有し、且つ、 該保護層の少なくとも 1層と該被覆部の軟化点の差が 0〜30°Cであることが特徴であ る。保護層の少なくとも 1層と被覆部の軟ィ匕点の差はより好ましくは 0〜： 15°Cである。 軟化点は TMA (熱機械分析)の針入測定や DSC (示差走査熱量測定)を用いての 測定により得られる。  [0068] The present invention provides a radiation image conversion panel having at least a stimulable phosphor layer and a protective layer having a softening point on a support, the radiation image conversion panel comprising at least the stimulable phosphor layer. It has a covering portion having a soft saddle point that seals the end portion together with the protective layer, and the difference between the softening point of at least one layer of the protective layer and the covering portion is 0 to 30 ° C. Is a feature. The difference between the soft spot of at least one of the protective layers and the covering is more preferably 0 to: 15 ° C. The softening point can be obtained by TMA (thermomechanical analysis) penetration measurement or DSC (differential scanning calorimetry) measurement.
[0069] 具体的には、「プラスチック加工技術ハンドブック」（高分子学会編)、日刊工業新聞 社発行、第 1版、第 1437頁に記載する TMAを用いる方法により求めることができる。  [0069] Specifically, it can be determined by the method using TMA described in "Plastic Processing Technology Handbook" (edited by Polymer Society), published by Nikkan Kogyo Shimbun, 1st edition, page 1437.
[0070] このような保護層及び被覆部を形成する材料としては、熱可塑性エラストマ一（以下 、 TPEともいう）を用いることが好ましレ、。  [0070] It is preferable to use a thermoplastic elastomer (hereinafter also referred to as TPE) as a material for forming such a protective layer and a covering portion.
[0071] 本発明で言う熱可塑性エラストマ一とは、常温では加硫ゴムの性質 (エラストマ一と しての性質）を示すが、高温では塑性変形が可能となってプラスチックの加工機等で 成形が可能となる高分子材料のことを言う。 TPEはゴム成分 (ソフトセグメント）と樹脂 成分 (ノヽードセグメント）から形成されており、本発明で言う熱可塑性エラストマ一のモ ノマーユニットとは上記ソフトセグメント及びハードセグメントを表す。本発明で用いら れる TPEとしては、ハードセグメントとしてポリスチレン、ソフトセグメントとしてポリジェ ンを用いたポリスチレン系 TPEや、ハードセグメントにポリプロピレン等のポリオレフィ ン、ソフトセグメントにエチレン.プロピレンのようなゴムを用いたポリオレフイン系 TPE 、ハードセグメントとして結晶性ポリブタジエン、ソフトセグメントとして無定形ポリブタ ジェン等を用いたポリジェン系 TPE、ハードセグメントとしてポリ塩化ビュル、ソフトセ グメントとして部分架橋型 NBR等のゴムを用いてァロイ化したポリ塩化ビュル系 TPE 、ハードセグメントとして短鎖グリコールとイソシァネートの反応で得られるポリウレタン と、ソフトセグメントとして長鎖グリコールとイソシァネートの反応で得られるポリウレタン との直鎖状のマルチブロックコポリマーであるポリウレタン系 TPE、ハードセグメントと してポリエステルを、ソフトセグメントとしてガラス転移温度 (Tg)の低いポリエーテルあ るいはポリエステルを用いたマルチブロックコポリマーであるポリエステル系 TPE、ノヽ ードセグメントとしてポリアミドを、ソフトセグメントとしてガラス転移温度 (Tg)の低レヽポ リエーテルあるいはポリエステルを用いたマルチブロックコポリマーであるポリアミド系[0071] The thermoplastic elastomer referred to in the present invention indicates the properties of vulcanized rubber (properties as an elastomer) at room temperature, but can be plastically deformed at high temperatures and molded with a plastic processing machine or the like. It refers to a polymer material that can be used. TPE is formed from a rubber component (soft segment) and a resin component (node segment), and the monomer unit of the thermoplastic elastomer referred to in the present invention represents the soft segment and the hard segment. As TPE used in the present invention, polystyrene-based TPE using polystyrene as a hard segment and polyethylene as a soft segment, polyolefin such as polypropylene as a hard segment, and rubber such as ethylene and propylene as a soft segment are used. Polyolefin TPE, crystalline polybutadiene as a hard segment, polygen TPE using amorphous polybutadiene as a soft segment, polychlorinated butyl as a hard segment, and polyalloyed using rubber such as partially crosslinked NBR as a soft segment Bure chloride TPE, polyurethane obtained by reaction of short chain glycol and isocyanate as hard segment, and polyurethane obtained by reaction of long chain glycol and isocyanate as soft segment Polyurethane TPE, which is a linear multi-block copolymer, and polyester, which is a multi-block copolymer using polyester or hard segment as a hard segment and polyether or polyester having a low glass transition temperature (Tg) as a soft segment Polyamide, which is a multiblock copolymer using TPE, polyamide as the node segment, and low-polyether or polyester with a low glass transition temperature (Tg) as the soft segment
TPE、ハードセグメントとしてフッ素樹脂を、ソフトセグメントとしてフッ素ゴムからなるフ ッ素系 TPE等、例えば「熱可塑性エラストマ 基礎 ·応用 '巿場'将来展望一」 ( 日刊工業新聞社)や「プラスチック成形材料商取引便覧 2005年版」（化学工業日報 社）に記載の TPEが挙げられる。なお、ポリウレタン系 TPEのソフトセグメントやハード セグメントを形成するポリオールと、ポリエステル系 TPEやポリアミド系 TPEのソフトセ グメントゃハードセグメントを形成するポリエステル ·ポリエーテルが同一構造であれ ばモノマーユニットとして同一としてみなすことができる。 TPE, fluorine-based TPE made of fluororesin as hard segment and fluoro-rubber as soft segment, etc., such as `` Thermoplastic Elastomer Basics & Applications 'Kiba' Future Prospects '' (Nikkan Kogyo Shimbun) or `` Plastic molding materials Examples include TPE described in “Handbook of Commercial Transactions 2005” (Chemical Industry Daily). In addition, if the polyol that forms the soft segment or hard segment of polyurethane-based TPE and the polyester-polyether that forms the hard segment of polyester-based TPE or polyamide-based TPE have the same structure, they are regarded as the same monomer unit. Can do.
[0072] 本発明の放射線像変換パネルの保護層や被覆部に用いられる TPEは、ソフトセグ メントとハードセグメントの比率としてソフトセグメントの量が 10質量％以上が軟質性の 点で好ましぐエラストマ一としての物性も好ましい。また、この量が 90質量％以下の 場合、ハードセグメントの平均連鎖長が短くなり過ぎず、物理的架橋点であるハード ブロックが外力に対して抵抗でき機械強度も良好でエラストマ一材料として機能でき 好ましレ、。より好ましいソフトセグメントの量は 25〜75質量％である。このハード Zソ フトセグメントの比率は1 H— NMRを用いて正確に定量することが可能である。 [0072] The TPE used in the protective layer and covering portion of the radiation image conversion panel of the present invention is preferably an elastomer that is preferred in terms of softness when the soft segment amount is 10% by mass or more as the ratio of the soft segment to the hard segment. The physical properties are also preferable. If this amount is 90% by mass or less, the average chain length of the hard segments will not be too short, and the hard blocks, which are physical crosslink points, can resist external forces and have good mechanical strength and function as an elastomer material. I like it. The amount of the soft segment is more preferably 25 to 75% by mass. This hard Z soft segment ratio can be accurately quantified using 1 H-NMR.
[0073] また、本発明の放射線像変換パネルの保護層や被覆部の軟化点の調整について は、用レ、る TPEのソフトセグメントやハードセグメントの分子量による調整方法（ポリオ ール成分とポリイソシァネート成分とのモル比、高分子量ポリオールの使用、高分子 ポリマーの使用等）、ポリエステルポリオールのエチレン鎖の結晶による調整方法、ポ リオール成分やポリイソシァネート成分の芳香族環の構造による調整方法、ウレタン 結合の量による調整方法等が挙げられる。  [0073] Further, regarding the adjustment of the softening point of the protective layer and the covering portion of the radiation image conversion panel of the present invention, an adjustment method (polyol component and polyisotope based on the molecular weight of the soft segment or hard segment of the TPE is used. (Molar ratio with cyanate component, use of high molecular weight polyol, use of high molecular weight polymer, etc.), adjustment method by crystal of ethylene chain of polyester polyol, adjustment by structure of aromatic ring of polyol component or polyisocyanate component Examples thereof include a method and an adjustment method depending on the amount of urethane bonds.
[0074] 本発明に好ましく用いられる熱可塑性エラストマ一を表 1に示す。 [0074] Table 1 shows thermoplastic elastomers preferably used in the present invention.
[0075] [表 1]
Figure imgf000017_0001
[0075] [Table 1]
Figure imgf000017_0001
TPA： テレフタ 酸  TPA: terephthalic acid
フタル酸  Phthalic acid
[0076] 吸湿等による劣化を防ぎ、かつ放射線像変換パネルの機械的強度を高めるために は、保護層と被覆部を構成する材料の物性、化学構造は似ていることが好ましぐ本 発明においては、保護層の少なくとも 1層と被覆部は熱可塑性エラストマ一を含有し[0076] In order to prevent deterioration due to moisture absorption and increase the mechanical strength of the radiation image conversion panel, it is preferable that the physical properties and chemical structures of the materials constituting the protective layer and the covering portion are similar. In this case, at least one of the protective layers and the covering portion contain a thermoplastic elastomer.
、保護層の少なくとも 1層を構成する熱可塑性エラストマ一のモノマーユニットと被覆 部を構成する熱可塑性エラストマ一のモノマーユニットが 30〜 100%同一であること が好ましレ、。なお、ここで言う「30〜： 100%同一である」とは、後述の様に、保護層の 熱可塑性エラストマ一を基準にしてのモノマーユニット 30〜100%が同一であること を言う。さらに、多層保護層では最外層の保護層の熱可塑性エラストマ一のモノマー ユニットと被覆部を構成する熱可塑性エラストマ一のモノマーユニットが 30〜： 100% 同一であることが好ましい。 Preferably, the monomer unit of the thermoplastic elastomer constituting at least one layer of the protective layer and the monomer unit of the thermoplastic elastomer constituting the covering portion are 30 to 100% identical. As used herein, “30 to 100% identical” means that 30 to 100% of the monomer units are the same based on the thermoplastic elastomer of the protective layer. Further, in the multilayer protective layer, it is preferable that the monomer unit of the thermoplastic elastomer in the outermost protective layer and the monomer unit of the thermoplastic elastomer constituting the covering portion are 30 to 100% identical.
[0077] 本発明に係る熱可塑性エラストマ一のモノマーユニットの同一性について説明する 。例えば、保護層の熱可塑性エラストマ一 A力 互いに化学式が異なる Al、 A2、 A3 の 3種のモノマーユニットからなり、 Al、 A2、 A3の質量分率がそれぞれ 30。/。、 30% 、 40%であり、被覆部の熱可塑性エラストマ一 B力 互いに化学式が異なる Bl、 B2 の 2種のモノマーユニットからなり、 A1 =B1で他のモノマーユニットが全て異なる時 は、 Bl、 B2の質量分率に係わらず、 30%同一であるという。 A1 =B1、 A2 = B2で 他のモノマーユニットが全て異なる時は、 60%同一であるという。 [0077] The identity of the monomer units of the thermoplastic elastomer according to the present invention will be described. For example, the thermoplastic elastomer of the protective layer A force A different chemical formula Al, A2, A3 It consists of three types of monomer units, and the mass fractions of Al, A2 and A3 are 30, respectively. /. , 30%, 40%, thermoplastic elastomer of the coating part B force Consists of two types of monomer units, Bl and B2, with different chemical formulas. When A1 = B1 and all other monomer units are different, Bl, Regardless of the mass fraction of B2, it is said to be 30% identical. When A1 = B1 and A2 = B2 and all other monomer units are different, they are said to be 60% identical.
[0078] 〔保護層〕 [Protective layer]
本発明の放射線像変換パネルの保護層としては、上記被覆部の軟化点との関係を 保持することの他に、光学的に透明度の非常に高いものが求められる。 ASTMD- 1003に記載の方法により測定したヘイズ率は画像ムラや線状ノイズの解消効果及 び鮮鋭性の向上効果の点から 5%以上 60%未満が好ましぐより好ましくは 10%以 上 50%未満である。  The protective layer of the radiation image conversion panel of the present invention is required to have a very high optical transparency in addition to maintaining the relationship with the softening point of the covering portion. The haze ratio measured by the method described in ASTMD-1003 is preferably 5% or more and less than 60%, more preferably 10% or more, from the viewpoint of the effect of eliminating image unevenness and linear noise and the effect of improving sharpness. Less than%.
[0079] また、保護層としては輝尽性蛍光体の吸湿劣化防止を考慮して、防湿性が求めら れる。透湿度は少なくとも 5. 0g/m2' day以下であることが好ましい。保護層を多層 とし、樹脂フィルムや樹脂フィルムに金属酸化物、窒化珪素等の薄膜を蒸着した蒸着 フィルムを複数枚積層することで最適な防湿性とすることができる。樹脂フィルムの積 層方法としては、特に制限はなぐ公知のいずれの方法を用いてもよい。 [0079] Further, the protective layer is required to have moisture resistance in consideration of prevention of moisture absorption deterioration of the stimulable phosphor. The moisture permeability is preferably at least 5.0 g / m 2 'day or less. Optimum moisture resistance can be achieved by laminating a plurality of vapor-deposited films obtained by vapor-depositing a thin film such as a metal oxide or silicon nitride on the resin film or resin film. As a method for stacking the resin film, any known method with no particular limitation may be used.
[0080] また、画質向上の面から保護層に励起光吸収層を設けることが好ましいが、積層さ れた樹脂フィルム間に励起光吸収層を設けることによって、励起光吸収層が物理的 な衝撃や化学的な変質から保護され安定したプレート性能が長期間維持でき好まし レ、。また、励起光吸収層は複数設けてもよいし、積層するための接着剤層に色材を 含有して、励起光吸収層としてもよい。  [0080] In addition, it is preferable to provide an excitation light absorption layer in the protective layer from the viewpoint of improving the image quality. However, by providing an excitation light absorption layer between the laminated resin films, the excitation light absorption layer is physically impacted. It is preferable to maintain stable plate performance for a long time, protected from chemical alteration. Further, a plurality of excitation light absorption layers may be provided, or an excitation light absorption layer may be formed by containing a coloring material in an adhesive layer for lamination.
[0081] 保護層の形成方法は、一般に樹脂組成物層を設けた PETフィルム等の保護層 (保 護フィルム）を輝尽性蛍光体層の表面に積層する方法 (ラミネート法）、支持体上に輝 尽性蛍光体層を有する蛍光体シートと、該蛍光体シートの上下に配置され、該蛍光 体シートの全表面を被覆するように設けられた保護フィルム（レ、わゆる封止フィルム） を用いる方法 (封止法)、輝尽性蛍光体層の上に、保護層塗布液を塗布、乾燥するこ とにより保護層を形成する方法 (塗布法)等がある。 [0081] The method for forming the protective layer is generally a method of laminating a protective layer (protective film) such as a PET film provided with a resin composition layer on the surface of the stimulable phosphor layer (laminating method), on the support. A phosphor sheet having a stimulable phosphor layer, and a protective film (la, a so-called sealing film) disposed on and under the phosphor sheet so as to cover the entire surface of the phosphor sheet. And a method of forming a protective layer by applying and drying a protective layer coating solution on the stimulable phosphor layer (coating method).
[0082] しかしながら、ラミネート法は防汚性、防傷性はあるものの、薄膜ィ匕が困難であり、 厚膜のため鮮鋭性、コントラストが低下しやすいといった問題がある。封止法は、防汚 性、防傷性はあるものの、生産性が悪いという問題がある。また、塗布法は一般に輝 尽性蛍光体層との接着強度が強ぐまた比較的簡単な工程で製造できるという利点 を持っているが、保護層を塗布によって形成する場合、塗布ムラや塗布欠陥を生じる 場合があり、得られる放射線像変換パネルの画像上のムラの原因となり、微妙な診断 を妨げる可能性があり、従来から低減させることが望まれていた。 [0082] However, although the laminate method has antifouling properties and scratch resistance, it is difficult to form a thin film. Due to the thick film, there is a problem that sharpness and contrast tend to decrease. Although the sealing method has antifouling property and scratch resistance, there is a problem that productivity is poor. In addition, the coating method generally has the advantage that the adhesive strength with the stimulable phosphor layer is strong and can be manufactured by a relatively simple process. However, when the protective layer is formed by coating, coating unevenness and coating defects This may cause unevenness on the image of the obtained radiation image conversion panel and may interfere with subtle diagnosis, and it has been desired to reduce it conventionally.
[0083] このような問題を解決するため、転写箔を用いて保護層を形成することが好ましい。  [0083] In order to solve such a problem, it is preferable to form a protective layer using a transfer foil.
[0084] 《転写箔保護層》  [0084] << Transfer foil protective layer >>
(転写箔の層構成）  (Layer structure of transfer foil)
転写箔の層構成の例としては下記のような例が挙げられる。  Examples of the layer configuration of the transfer foil include the following examples.
[0085] (1)支持体一樹脂層 1層型 [0085] (1) Support-resin layer 1-layer type
(2)支持体一樹脂層 接着層 2層型  (2) Support / resin layer Adhesive layer 2-layer type
(3)支持体一樹脂層 (低屈折率層）一樹脂層（高屈折率層） 接着層 3層型 (支持体、仮支持体）  (3) Support 1 resin layer (low refractive index layer) 1 resin layer (high refractive index layer) Adhesive layer 3 layer type (support, temporary support)
上記する転写箔の支持体 (輝尽性蛍光体層の下に設けられた支持体とは別の支 持体であり、放射線像変換パネルの使用時までに剥離、除去されるため仮支持体と もいう）としては、アクリル酸エステル、メタクリル酸エステル、ポリエチレンテレフタレー ト、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、ポリアリ レート、ポリ塩化ビュル、ポリエチレン、ポリプロピレン、ポリスチレン、ナイロン、芳香 族ポリアミド、ポリエーテルエーテルケトン、ポリスルホン、ポリエーテルスルホン、ポリ イミド、ポリエーテルイミド等の各樹脂フィルム、さらには上記樹脂を 2層以上積層して 成る樹脂フィルム等を挙げることができる。中でもポリエチレンテレフタレート（PET) が好ましレ、。支持体の厚みは通常 5〜： 100 z m程度、好ましくは 10〜50 x mである。  The transfer foil support described above (a support separate from the support provided under the stimulable phosphor layer, which is peeled off and removed before the radiation image conversion panel is used) Acrylates, methacrylates, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polychlorinated butyl, polyethylene, polypropylene, polystyrene, nylon, aromatic polyamide, poly Examples of the resin film include ether ether ketone, polysulfone, polyether sulfone, polyimide, and polyetherimide, and a resin film formed by laminating two or more layers of the above resins. Of these, polyethylene terephthalate (PET) is preferred. The thickness of the support is usually about 5 to about 100 zm, preferably 10 to 50 xm.
[0086] 本発明に係る転写箔は、上記の様に、仮支持体上に転写層（保護層）を有してレ、る The transfer foil according to the present invention has a transfer layer (protective layer) on the temporary support as described above.
[0087] (樹脂層、転写層） [0087] (Resin layer, transfer layer)
転写箔の転写層は樹脂層からなることが好ましい。樹脂層は樹脂ェマルジヨンを塗 ェして形成することが好ましい。樹脂ェマルジヨンとは、溶媒中に完全に溶解せず、 ある一定の粒径分布を有する樹脂微粒子が必要に応じて界面活性剤等の分散助剤 を用いて分散された分散液の状態のものを意味する。溶媒中に完全に溶解する樹脂 を用いた場合、塗布乾燥後の塗膜が均一かつ平坦になるため、転写箔支持体との 密着性が高まることにより輝尽性蛍光体層上に加熱加圧する際の転写性が低下し、 そのために転写後の接着性が不十分になる。 The transfer layer of the transfer foil is preferably made of a resin layer. The resin layer is preferably formed by coating a resin emulsion. Resin emulsion does not dissolve completely in the solvent, It means a dispersion in which resin fine particles having a certain particle size distribution are dispersed using a dispersion aid such as a surfactant as necessary. When a resin that completely dissolves in the solvent is used, the coating film after coating and drying becomes uniform and flat, so that the adhesiveness to the support for the transfer foil is increased, so that the photostimulable phosphor layer is heated and pressurized. The transferability at the time is reduced, so that the adhesiveness after transfer becomes insufficient.
[0088] 〈樹脂〉 [0088] <Resin>
樹脂ェマルジヨンに用いる樹脂としては、前記熱可塑性エラストマ一を主成分に用 レ、、他に、ポリエステル系樹脂、ウレタン系樹脂、スチレン ブタジエン共重合体ゃス チレン イソブイレン共重合体等のスチレン ゴム共重合体樹脂；アクリル系樹脂、 酢酸ビニル系樹脂、エチレン 酢酸ビニル共重合体、エチレン ェチルアタリレート 共重合体等のエチレン系樹脂；ポリビニルブチラール等のポリビュルァセタール系樹 脂、塩化ビニルー酢酸ビニル共重合体等の塩ビ系樹脂等が挙げられる。これらの中 でも、特にポリエステル系樹脂が接着性や耐久性の点で好ましレ、。  As the resin used in the resin emulsion, the thermoplastic elastomer is used as a main component. In addition, polyester resins, urethane resins, styrene butadiene copolymers, styrene rubber copolymers such as styrene isobutylene copolymers, etc. Polymer resins: Acrylic resins, vinyl acetate resins, ethylene vinyl acetate copolymers, ethylene ethyl acrylate copolymers, and other ethylene resins; Polybutylacetal resins such as polyvinyl butyral, vinyl chloride-vinyl acetate Examples thereof include a vinyl chloride resin such as a polymer. Of these, polyester resins are particularly preferred in terms of adhesion and durability.
[0089] 本発明においては、この樹脂のガラス転移温度（Tg)が 20〜70°Cであり、かつ、そ の含有量が転写層全固形分の 50質量％以上が好ましい。これにより、装置内での放 射線像変換パネルの搬送時における滑りが低減され、さらに輝尽性蛍光体層との接 着性 (密着性)が高くなる。  In the present invention, the glass transition temperature (Tg) of this resin is preferably 20 to 70 ° C., and the content thereof is preferably 50% by mass or more based on the total solid content of the transfer layer. As a result, slippage during transport of the radiation image conversion panel in the apparatus is reduced, and adhesion (adhesion) with the photostimulable phosphor layer is further increased.
[0090] 〈溶媒〉  [0090] <Solvent>
上記樹脂ェマルジヨンは、分散溶媒中に樹脂を微粒子分散物の状態で存在させる ものであり、この様な状態とさせるためには、樹脂溶解性の乏しい分散溶媒を単独ま たは 2種以上の混合して用いることが好ましい。  The above resin emulsion is one in which a resin is present in the form of a fine particle dispersion in a dispersion solvent. In order to achieve such a state, a dispersion solvent having poor resin solubility or a mixture of two or more of them is used. And preferably used.
[0091] 好ましく用いられる樹脂ェマルジヨンの分散溶媒としては、水またはメタノール、エタ ノール、直鎖もしくは分岐のプロパノール、ブタノール等のアルコール類が好ましい。 これら以外にも、分散性を損ねない範囲で他の有機溶媒を混合して用いてもよい。  [0091] The resin emulsion dispersion solvent that is preferably used is preferably water or alcohols such as methanol, ethanol, linear or branched propanol, and butanol. In addition to these, other organic solvents may be mixed and used as long as the dispersibility is not impaired.
[0092] 本発明に用いられる転写箔の転写層の厚みは 2〜： 15 z mが好ましい。これより薄 い場合は十分な耐久性が確保できず、これよりも厚い場合は転写箔を密着させて加 熱'加圧後、支持体を剥離する際に、十分な接着性が得られない場合がある。  [0092] The thickness of the transfer layer of the transfer foil used in the present invention is preferably 2 to 15 zm. If it is thinner than this, sufficient durability cannot be secured, and if it is thicker than this, sufficient adhesion will not be obtained when the support is peeled off after the transfer foil is adhered and heated and pressed. There is a case.
[0093] 転写箔の転写層の転写後の耐久性を向上させる目的で、シリコーンィヒ合物ゃヮッ タス類、固形のモリブデン化合物、テフロン (登録商標）パウダー等の滑剤を添加する ことが好ましい。これら滑剤の添加量は通常、転写層の全固形分に対し 0.：!〜 50質 量％、好ましくは 1〜： 10質量％である。 [0093] For the purpose of improving the durability after transfer of the transfer layer of the transfer foil, the silicone resin compound is used. It is preferable to add lubricants such as tass, solid molybdenum compounds, and Teflon (registered trademark) powder. The addition amount of these lubricants is usually from 0.:! To 50 mass%, preferably from 1 to: 10 mass%, based on the total solid content of the transfer layer.
[0094] 〈着色剤〉 [0094] <Colorant>
本発明に係る転写層（保護層）は膜厚の 2Z3〜3Z3が青色〜緑色に着色されて レ、ることが好ましい。すなわち、本発明の効果を好ましく得る観点から、本発明におい ては転写層に励起光吸収能を付与することが好まし好ましぐ従って、下記する様に 転写層が吸収波長域 600nm〜700nmの範囲において吸収する様に着色されてい ること力 S好ましい。そのためには、例えば、励起光を選択的に吸収する着色剤を含有 する層を塗設すること等により励起光吸収機能を付与することができる。本発明にお いては励起光吸収機能を付与する手段としては、転写層自体を着色剤等により着色 することが好ましい。吸収の程度は、励起光波長における光透過率が 50〜97%であ ること力 S好ましレ、。  The transfer layer (protective layer) according to the present invention preferably has a thickness of 2Z3 to 3Z3 colored blue to green. That is, from the viewpoint of preferably obtaining the effects of the present invention, in the present invention, it is preferable to provide the transfer layer with the ability to absorb excitation light. It is preferable that it is colored so as to absorb in the range. For this purpose, for example, an excitation light absorbing function can be provided by coating a layer containing a colorant that selectively absorbs excitation light. In the present invention, as a means for imparting an excitation light absorption function, it is preferable to color the transfer layer itself with a colorant or the like. The degree of absorption is such that the light transmittance at the excitation light wavelength is 50 to 97%.
[0095] 本発明に係る転写層に励起光吸収機能を付与するために用いられる着色剤として は、放射線像変換パネルに用いる輝尽性蛍光体の種類によって決まるが、放射線像 変換パネル用の輝尽性蛍光体としては、通常、波長が 400〜900nmの範囲にある 励起光によって 300〜500nmの波長範囲の輝尽発光を示す蛍光体が用いられるた め、着色剤としては通常、青色〜緑色の有機系もしくは無機系の着色剤が好ましく用 いられる。  [0095] The colorant used for imparting the excitation light absorption function to the transfer layer according to the present invention is determined depending on the type of stimulable phosphor used in the radiation image conversion panel. As the stimulable phosphor, a phosphor exhibiting a stimulated emission in the wavelength range of 300 to 500 nm by excitation light having a wavelength in the range of 400 to 900 nm is usually used. Therefore, the colorant is usually blue to green. Organic or inorganic colorants are preferably used.
[0096] 上記の有機系着色剤としては、ザボンファーストブルー 3G (へキスト社製）、エストロ ールブリルブルー N _ 3RL (住友化学（株）製）、スミアクリルブルー F _ GSL (住友化 学 (株)製）、 D&Cブルー Nol (ナショナル.ァニリン社製）、スピリットブルー（保土谷 化学 (株)製）、オイルブルー No603 (オリエント（株)製）、キトンブルー A (チバ 'ガイ ギ一社製）、アイゼンカチロンブルー GLH (保土谷化学 (株）製）、レイクブルー A、 F 、 H (協和産業 (株)製)、ローダリンブルー 6GX (協和産業 (株)製）、プリモシァニン 6 GX (稲畑産業 (株)製）、ブリルアシッドグリーン 6BH (保土谷化学 (株)製）、シァニン ブルー BNRS (東洋インキ (株)製）、ライォノルブルー SL (東洋インキ (株)製）が挙 げられる。青色〜緑色の無機系着色剤の例としては、群青、コバルトブルー、セルリ アンブル一、酸化クロム、 TiO _Zn〇_CoO_NiO系顔料が挙げられる。本発明に [0096] Examples of the above organic colorants include Zavon First Blue 3G (produced by Hoechst), Estrol Brill Blue N_3RL (produced by Sumitomo Chemical Co., Ltd.), Sumiacryl Blue F_GSL (Sumitomo Chemical Co., Ltd.) ), D & C Blue Nol (manufactured by National Anilin), Spirit Blue (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue No603 (manufactured by Orient Co., Ltd.), Kitton Blue A (manufactured by Chiba Gaigi Co., Ltd.), Aizen Cachiron Blue GLH (Hodogaya Chemical Co., Ltd.), Lake Blue A, F, H (Kyowa Sangyo Co., Ltd.), Rhodaline Blue 6GX (Kyowa Sangyo Co., Ltd.), Primosyanin 6 GX (Inabata Sangyo) Co., Ltd.), Brill Acid Green 6BH (Hodogaya Chemical Co., Ltd.), Shean Blue BNRS (Toyo Ink Co., Ltd.), and Rionol Blue SL (Toyo Ink Co., Ltd.). Examples of blue to green inorganic colorants include ultramarine, cobalt blue, celery Amble, chromium oxide, TiO_ZnO_CoO_NiO pigments. In the present invention
2  2
おいては着色剤としては染料より顔料が好ましい。  In this case, the colorant is preferably a pigment rather than a dye.
[0097] 〈低屈折率層及び高屈折率層〉  <Low Refractive Index Layer and High Refractive Index Layer>
本発明においては、転写層は、少なくとも低屈折率層及び高屈折率層からなり、そ の屈折率の差が 0. 2〜0. 7であり、かつ、前記低屈折率層が輝尽性蛍光体層側に あることが好ましい。  In the present invention, the transfer layer comprises at least a low refractive index layer and a high refractive index layer, the difference in refractive index between 0.2 and 0.7, and the low refractive index layer is photostimulable. It is preferably on the phosphor layer side.
[0098] 〈低屈折率層〉  [0098] <Low refractive index layer>
本発明に係る低屈折率層は、上記樹脂に加えて、シリカ系微粒子と下記シランカツ プリング剤を含むことが好ましい。  The low refractive index layer according to the present invention preferably contains silica fine particles and the following silane coupling agent in addition to the resin.
[0099] 具体的なシランカップリング剤の例としては、メチルトリメトキシシラン、メチルトリエト キシシラン、メチルトリメトキシエトキシシラン、メチルトリァセトキシシラン、メチルトリブト キシシラン、ェチルトリメトキシシラン、ェチルトリエトキシシラン、ビュルトリメトキシシラ ン、ビュルトリエトキシシラン、ビニルトリァセトキシシラン、ビュルトリメトキシエトキシシ ラン、フエニルトリメトキシシラン、フエニルトリエトキシシラン、フエニルトリァセトキシシ ラン、 Ί—クロ口プロビルトリメトキシシラン、 γ—クロ口プロピルトリエトキシシラン、 γ  [0099] Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, etyltrimethoxysilane, etyltriethoxysilane, Butyltrimethoxysilane, butyltriethoxysilane, vinyltriacetoxysilane, butyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, Methoxysilane, γ-black propyltriethoxysilane, γ
、 yーグリシジルォキシプロビルトリメトキシシラン、 γ—グリシジルォキシプロピルトリ エトキシシラン、 γ _ ( /3—グリシジルォキシエトキシ）プロピルトリメトキシシラン、 β - (3， 4—ェポシシシクロへキシノレ）ェチノレトリメトキシシラン、 j3 _ (3， 4_エポキシシク 口へキシル）ェチルトリエトキシシラン、 γ—アタリロイルォキシプロピルトリメトキシシラ シラン、 γ—ァミノプロピルトリエトキシシラン、 γ—メルカプトプロピルトリメトキシシラ ン、 Ί—メルカプトプロピルトリエトキシシラン、 Ν— /3 _ (アミノエチル） - y—アミノプ 口ピルトリメトキシシラン及び β—シァノエチルトリエトキシシランが挙げられる。 , Y-glycidyloxypropyl trimethoxysilane, γ-glycidyloxypropyltriethoxysilane, γ _ (/ 3-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexenole) Tinoletrimethoxysilane, j3 _ (3,4-epoxy hexyl) ethyltriethoxysilane, γ-ataryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxy Examples include silane, Ί -mercaptopropyltriethoxysilane, Ν- / 3_ (aminoethyl) -y-aminopropyl pyrroltrimethoxysilane, and β-cyanoethyltriethoxysilane.
[0100] また、珪素に対して 2置換のアルキル基を持つシランカップリング剤の例として、ジメ チルジメトキシシラン、フエ二ルメチルジメトキシシラン、ジメチルジェトキシシラン、フ ェニルメチルジェトキシシラン、 Ί—グリシジルォキシプロピルメチルジェトキシシラン[0100] Examples of silane coupling agents having a di-substituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyljetoxysilane, phenylmethyljetoxysilane , Ί — Glycidyloxypropylmethyl jetoxysilane
、 yーグリシジルォキシプロピルメチルジメトキシシラン、 γ—グリシジルォキシプロピ ノレフエ二ルジェトキシシラン、 γ—クロ口プロピルメチルジェトキシシラン、ジメチルジ ァセトキシシラン、 γ—アタリロイルォキシプロピルメチルジメトキシシラン、 Ί—アタリ ロイルォキシプロピルメチルジェトキシシラン、 γ—メタクリロイルォキシプロピルメチ ルジメトキシシラン、 γ—メタクリロイルォキシプロピルメチルジェトキシシラン、 Ί—メ , Y-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropyl Norefue two Rougier butoxy silane, .gamma. black port propyl methyl jet silane, dimethyldi Asetokishishiran, .gamma. Atari Roy Ruo propyl methyl dimethoxy silane, I - Atari Roy Ruo carboxypropyl methyl jet silane, .gamma.-methacryloyloxy Ruo propyl methylation Dimethoxysilane, γ-methacryloyloxypropylmethyljetoxysilane, Ί -me
ラン、メチルビ二ルジメトキシシラン及びメチルビ二ルジェトキシシランが挙げられる。 Orchid, methylvinyldimethoxysilane and methylvinyljetoxysilane.
[0101] これらのうち、分子内に二重結合を有するビエルトリメトキシシラン、ビニルトリェトキ シシラン、ビュルトリァセトキシシラン、ビニルトリメトキシエトキシシラン、 γ—アタリロイ ラン、珪素に対して 2置換のアルキル基を持つものとして γ —アタリロイルォキシプロ ピルメチルジメトキシシラン、 γ —アタリロイルォキシプロピルメチルジェトキシシラン、 yーメタクリロイルォキシプロピルメチルジメトキシシラン、 γ—メタクリロイルォキシプ 口ピルメチルジェトキシシラン、メチルビ二ルジメトキシシラン及びメチルビ二ルジェト キシシランが好ましぐ γ—アタリロイルォキシプロピルトリメトキシシラン及び γ —メタ トキシシラン、 γ —アタリロイルォキシプロピルメチルジェトキシシラン、 γ—メタクリロ ィルォキシプロピルメチルジメトキシシラン及び γ—メタクリロイルォキシプロピルメチ ルジェトキシシランが特に好ましい。 [0101] Of these, bitrimethoxysilane, vinyltriethoxysilane, butyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-atariroylan having a double bond in the molecule, and a disubstituted alkyl group for silicon. Γ-Atalylyloxypropylmethyldimethoxysilane, γ-Atalylyloxypropylmethyljetoxysilane, y-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyl pirmethyljetoxysilane, Methyl vinyl dimethoxy silane and methyl vinyl methoxy silane are preferred. Γ-Ataryloxypropyl trimethoxy silane and γ — Meta oxy silane, γ — Ataryl oxypropyl methyl methoxy silane, γ- Methacryloyl silane Xylpropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyljetoxysilane are particularly preferred.
[0102] シランカップリング剤の具体例としては、信越化学工業株式会社製 ΚΒΜ— 303、 Κ ΒΜ— 403、 ΚΒΜ— 402、 ΚΒΜ— 403、 ΚΒΜ— 1403、 ΚΒΜ— 502、 ΚΒΜ- 50 3、 ΚΒΕ— 502、 ΚΒΕ— 503、 ΚΒΜ— 603、 ΚΒΕ— 603、 ΚΒΜ— 903、 ΚΒΕ— 9 03、 ΚΒΕ_ 9103、 ΚΒΜ_ 802、 ΚΒΜ— 803等カ挙げられる。  [0102] Specific examples of silane coupling agents include Shin-Etsu Chemical Co., Ltd. 、 -303, Κ ΒΜ-403, ΚΒΜ-402, ΚΒΜ-403, ΚΒΜ-1403, ΚΒΜ-502, ΚΒΜ-50 3, ΚΒΕ — 502, ΚΒΕ—503, ΚΒΜ—603, ΚΒΕ—603, ΚΒΜ—903, ΚΒΕ—903, ΚΒΕ_9103, ΚΒΜ_802, ΚΒΜ—803, etc.
[0103] 2種類以上のカップリング剤を併用してもよい。上記に示されるシランカップリング剤 に加えて、他のシランカップリング剤を用いてもよレ、。他のシランカップリング剤には、 オルトケィ酸のアルキルエステル（例えば、オルトケィ酸メチル、オルトケィ酸ェチル、 オルトケィ酸 η_プロピル、オルトケィ酸 i_プロピル、オルトケィ酸 n—ブチル、オルト ケィ酸 sec—ブチル、オルトケィ酸 tーブチル）及びその加水分解物が挙げられる。 [0104] カップリング剤による表面処理の具体的方法は、下記に示す。 [0103] Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthokeys (eg, methyl orthokeate, ethyl orthokete, orthoketate η_propyl, orthokeate i_propyl, orthokeate n-butyl, orthokete sec-butyl, T-butyl orthokeate) and hydrolysates thereof. [0104] A specific method of surface treatment with a coupling agent is shown below.
[0105] これらシランカップリング剤は予め必要量の水で加水分解されていることが好ましい 。シランカップリング剤が加水分解されていると、シリカ系微粒子及び有機基を有する シリカ系微粒子の表面が反応しやす より強固な膜が形成される。また、加水分解 されたシランカップリング剤を予め塗布液中に加えてもよい。 [0105] These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surface of the silica-based fine particles and the silica-based fine particles having an organic group can be easily reacted to form a stronger film. Further, a hydrolyzed silane coupling agent may be added in advance to the coating solution.
[0106] 低屈折率層の塗布液に、少量のポリマー（例えば、ポリビュルアルコール、ポリオキ シエチレン、ポリメチルメタタリレート、ポリメチルアタリレート、ジァセチルセルロース、 トリァセチルセルロース、ニトロセルロース、ポリエステル、アルキド樹脂）を添加しても よい。 [0106] A small amount of polymer (for example, polybutyl alcohol, polyoxyethylene, polymethyl metatalylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, Alkyd resin) may be added.
[0107] また、本発明に係る低屈折率層が、熱または電離放射線により架橋する含フッ素榭 脂（以下、「架橋前の含フッ素樹脂」ともいう）の架橋からなる低屈折率層であってもよ い。  [0107] Further, the low refractive index layer according to the present invention is a low refractive index layer formed by cross-linking of a fluorinated resin cross-linked by heat or ionizing radiation (hereinafter also referred to as "fluorinated resin before cross-linking"). It's okay.
[0108] 上記架橋前の含フッ素樹脂としては、含フッ素ビニルモノマーと架橋性基付与のた めのモノマーから形成される含フッ素共重合体を好ましく挙げることができる。上記含 フッ素ビニルモノマー単位の具体例としては、例えばフルォロォレフイン類（例えば、 フルォロエチレン、ビニリデンフルオライド、テトラフルォロエチレン、へキサフルォロ エチレン、へキサフルォロプロピレン、パーフルオロー 2, 2—ジメチルー 1 , 3—ジォ キソール等）、（メタ）アクリル酸の部分または完全フッ素化アルキルエステル誘導体 類 (例えば、ビスコート 6FM (大阪有機化学製)や M— 2020 (ダイキン製)等）、完全 または部分フッ素化ビュルエーテル類等が挙げられる。架橋性基付与のためのモノ マーとしては、グリシジルメタタリレートや、ビュルトリメトキシシラン、 Ί—メタクリロイノレ ォキシプロビルトリメトキシシラン、ビュルグリシジルエーテル等のように分子内に予め 架橋性官能基を有するビュルモノマーの他、カルボキシル基ゃヒドロキシル基、ァミノ 基、スルホン酸基等を有するビュルモノマー（例えば、 （メタ）アクリル酸、メチローノレ（ メタ）アタリレート、ヒドロキシアルキル（メタ）アタリレート、ァリノレアタリレート、ヒドロキシ アルキルビュルエーテル、ヒドロキシアルキルァリルエーテル等）が挙げられる。後者 は共重合の後、ポリマー中の官能基と反応する基ともう 1つ以上の反応性基を持つ 化合物を加えることにより、架橋構造を導入できることが特開平 10— 25388号、同 1 0— 147739号に記載されている。架橋性基の例には、アタリロイル、メタタリロイノレ、 イソシアナート、エポキシ、アジリジン、ォキサゾリン、ァノレデヒド、カルボニル、ヒドラジ ン、カルボキシル、メチロール及び活性メチレン基等が挙げられる。含フッ素共重合 体が、加熱により反応する架橋基、若しくは、エチレン性不飽和基と熱ラジカル発生 剤若しくはエポキシ基と熱酸発生剤等の相み合わせにより、加熱により架橋する場合 、熱硬化型であり、エチレン性不飽和基と光ラジカル発生剤若しくは、エポキシ基と 光酸発生剤等の組み合わせにより、光（好ましくは紫外線、電子ビーム等）の照射に より架橋する場合、電離放射線硬化型である。 [0108] Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2- Dimethyl-1,3-dioxole), partially (meth) acrylic acid or fully fluorinated alkyl ester derivatives (eg, Biscote 6FM (Osaka Organic Chemical) or M-2020 (Daikin)), complete or Examples thereof include partially fluorinated butyl ethers. As a monomer for imparting a crosslinkable group, a crosslinkable functional group is previously added in the molecule such as glycidyl methacrylate, butyltrimethoxysilane , Ί -methacryloyloxyprovir trimethoxysilane, bululglycidyl ether, or the like. In addition to the butyl monomer, a butyl monomer having a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. (for example, (meth) acrylic acid, methylone (meth) acrylate, hydroxyalkyl (meth) acrylate, aldehyde) Attalylate, hydroxyalkyl butyl ether, hydroxyalkyl allyl ether, etc.). In the latter case, it is possible to introduce a crosslinked structure after copolymerization by adding a compound that reacts with a functional group in the polymer and one or more reactive groups. 0—It is described in No. 147739. Examples of the crosslinkable group include taliloyl, metatalilolenole, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is crosslinked by heating by a crosslinking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator, or an epoxy group and a thermal acid generator, etc. In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, etc., ionizing radiation curable type is there.
[0109] また上記モノマーに加えて、含フッ素ビュルモノマー及び架橋性基付与のための モノマー以外のモノマーを併用して形成された含フッ素共重合体を架橋前の含フッ 素樹脂として用いてもよい。併用可能なモノマーには特に限定はなぐ例えばォレフ イン類（エチレン、プロピレン、イソプレン、塩化ビニル、塩化ビニリデン等）、アクリル 酸エステル類（アクリル酸メチル、アクリル酸メチル、アクリル酸ェチル、アクリル酸 2— ェチルへキシル）、メタクリル酸エステル類（メタクリル酸メチル、メタクリル酸ェチル、メ タクリル酸ブチル、エチレングリコールジメタタリレート等）、スチレン誘導体（スチレン、 ジビニルベンゼン、ビニルトノレェン、 α—メチルスチレン等）、ビニルエーテル類（メチ ルビニルエーテル等）、ビュルエステル類（酢酸ビュル、プロピオン酸ビュル、桂皮酸 ビュル等）、アクリルアミド類（Ν— tertブチルアクリルアミド、 N—シクロへキシルアタリ ルアミド等）、メタクリルアミド類、アクリロニトリル誘導体等を挙げることができる。また、 含フッ素共重合体中に、滑り性、防汚性付与のため、ポリオノレガノシロキサン骨格や 、パーフルォロポリエーテル骨格を導入することも好ましい。これは、例えば末端にァ クリル基、メタクリノレ基、ビュルエーテル基、スチリル基等を持つポリオルガノシロキサ ンゃパーフルォロポリエーテルと上記のモノマーとの重合、末端にラジカル発生基を 持つポリオルガノシロキサンやパーフルォロポリエーテルによる上記モノマーの重合 、官能基を持つポリオルガノシロキサンやパーフルォロポリエーテルと、含フッ素共重 合体との反応等によって得られる。 [0109] Further, in addition to the above-mentioned monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing bull monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. Good. The monomers that can be used in combination are not particularly limited, for example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylates (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl tolylene, α -methylstyrene, etc.), vinyl ethers (Such as methyl vinyl ether), butyl esters (such as butyl acetate, butyl propionate and cinnamate), acrylamides (such as tert-butyl acrylamide, N-cyclohexyl acrylate), methacrylamides, Ronitoriru derivatives and the like can be mentioned. It is also preferable to introduce a polyonoreganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. This is because, for example, polymerization of a polyorganosiloxane siloxane perfluoropolyether having an acryl group, a methacrylol group, a butyl ether group, a styryl group, or the like at a terminal and the above-mentioned monomer, or a polymer having a radical generating group at a terminal. It can be obtained by polymerization of the above monomers with organosiloxane or perfluoropolyether, reaction of polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.
[0110] 架橋前の含フッ素共重合体を形成するために用いられる上記各モノマーの使用割 合は、含フッ素ビエルモノマーが好ましくは 20〜70モル0 /0、より好ましくは 40〜70モ ル％、架橋性基付与のためのモノマーが好ましくは 1〜20モル％、より好ましくは 5〜 20モノレ0 /0、併用されるその他のモノマーが好ましくは 10〜70モル0 /0、より好ましくは 10〜50モル0 /0の割合である。 [0110] Use percentage of each monomer used to form the fluorine containing copolymers prior to coating, it is preferably a fluorine-containing Biel monomer 20-70 mol 0/0, more preferably 40 to 70 Mo Le%, monomers preferably 1 to 20 mol% for imparting a crosslinking group, more preferably 5-20 Monore 0/0, preferably other monomers to be used in combination 10 to 70 mole 0/0, more preferably is the ratio of 10 to 50 mole 0/0.
[0111] 含フッ素共重合体は、これらモノマーをラジカル重合開始剤の存在下で、溶液重合 、塊状重合、乳化重合、懸濁重合法等の手段により重合することにより得ることができ る。 [0111] The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means of solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or the like.
[0112] 架橋前の含フッ素樹脂は、市販されており使用することができる。市販されている架 橋前の含フッ素樹脂の例としては、サイトップ (旭硝子製）、テフロン (登録商標) AF ( デュポン製）、ポリフッ化ビニリデン、ルミフロン (旭硝子製）、ォプスター CJSR製）等が 挙げられる。  [0112] The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins in front of the bridge include Cytop (Asahi Glass), Teflon (registered trademark) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opster CJSR), etc. Can be mentioned.
[0113] 架橋した含フッ素樹脂を構成成分とする低屈折率層は、動摩擦係数が 0. 03〜0.  [0113] The low refractive index layer containing a cross-linked fluorine-containing resin as a constituent component has a dynamic friction coefficient of 0.03 to 0.00.
15の範囲、水に対する接触角が 90〜120度の範囲にあることが好ましい。  It is preferable that the contact angle to water is in the range of 15 to 15 degrees.
[0114] 本発明に用いられる希釈用の有機溶媒としては、水混和性の有機溶媒であること が好ましい。水混和性の有機溶媒としては、例えば、アルコール類（例えば、メタノー ル、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、セカン ダリーブタノール、ターシャリーブタノール、ペンタノール、へキサノール、シクロへキ サノール、ベンジルアルコール等）、多価アルコール類（例えば、エチレングリコール 、ジエチレングリコーノレ、トリエチレングリコーノレ、ポリエチレングリコーノレ、プロピレン グリコーノレ、ジプロピレングリコーノレ、ポリプロピレングリコーノレ、ブチレングリコーノレ、 へキサンジオール、ペンタンジオール、グリセリン、へキサントリオール、チォジグリコ ール等）、多価アルコールエーテル類（例えば、エチレングリコールモノメチルエーテ ノレ、エチレングリコーノレモノェチノレエーテノレ、エチレングリコーノレモノブチノレエーテノレ 、ジエチレングリコーノレモノメチノレエーテノレ、ジエチレングリコーノレモノメチノレエーテ ノレ、ジエチレングリコーノレモノブチノレエーテノレ、プロピレングリコーノレモノメチノレエー テノレ、プロピレングリコーノレモノブチノレエーテノレ、エチレングリコ一ノレモノメチノレエー テノレアセテート、トリエチレングリコーノレモノメチノレエーテノレ、トリエチレングリコーノレモ ノエチノレエーテノレ、エチレングリコーノレモノフエニノレエーテノレ、プロピレングリコーノレ モノフエニルエーテル等）、アミン類（例えば、エタノールァミン、ジエタノールァミン、ト リエタノーノレアミン、 N—メチルジェタノールァミン、 N—ェチルジェタノールァミン、モ ノレホリン、 N_ェチルモルホリン、エチレンジァミン、ジエチレンジァミン、トリエチレン テトラミン、テトラエチレンペンタミン、ポリエチレンィミン、ペンタメチルジェチレントリア ミン、テトラメチルプロピレンジァミン等）、アミド類（例えば、ホルムアミド、 N, N—ジメ チルホルムアミド、 N, N—ジメチルァセトアミド等）、複素環類（例えば、 2_ピロリドン 、 N—メチル _ 2_ピロリドン、シクロへキシルピロリドン、 2_ォキサゾリドン、 1， 3—ジ メチル _ 2_イミダゾリジノン等）、スルホキシド類（例えば、ジメチルスルホキシド等）、 スルホン類（例えば、スルホラン等）、尿素、ァセトニトリル、アセトン等が挙げられるが 、特に、アルコール類、多価アルコール類、多価アルコールエーテル類が好ましい。 [0114] The organic solvent for dilution used in the present invention is preferably a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl). Alcohol), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, Glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol) -Nole Monotechno Reethenole, Ethylene Glyco Nore Mono Butino Rete Noetre, Diethylene Glyco Nore Mono Methino Rete Nore, Diethylene Glyco Nore Monomethino Rete Nore, Diethylene Glyco Nore Monobutino Rete Nore, Propylene Glycol Nore Monomethy Nore Tenoré, Propylene Glycol Nole Monobutenoleate Nore, Ethylene Glycol Monore Monomethinoreate Tenole Acetate, Triethylene Glycol Nore Monomethinoreate Nore, Triethylene Glyco Nore Noetino Noetino Rete Nore, Ethylene Glycol Nore Monophe Ninore etherol, propylene glycol monophenyl ether, etc.), amines (eg ethanolamine, diethanolamine, Lietananolamine, N-methyljetanolamine, N-ethyljetanolamine, monoreforin, N_ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine ), Amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2 _Pyrrolidone, N-methyl _2 pyrrolidone, cyclohexyl pyrrolidone, 2_oxazolidone, 1,3-dimethyl _2 imidazolidinone, etc.), sulfoxides (eg dimethyl sulfoxide etc.), sulfones (eg Sulfolane, etc.), urea, acetonitrile, acetone, etc. , Alcohols, polyhydric alcohols, polyhydric alcohol ethers are preferable.
[0115] 希釈率は、塗布液の粘度を制御する作用により、前記シリカ系微粒子の低屈折率 層内での偏在化の程度を決定する因子となるため、適宜選択される。  [0115] The dilution rate is appropriately selected because it acts as a factor that determines the degree of uneven distribution of the silica-based fine particles in the low refractive index layer by the action of controlling the viscosity of the coating solution.
[0116] 低屈折率層の塗布方法は、ディップコート法、エアーナイフコート法、カーテンコー ト法、ローラーコート法、ワイヤーバーコート法、グラビアコート法やエタストルージョン コート法 (米国特許第 2， 681 , 294号）により、塗布により形成することができる。また 、 2以上の層を同時に塗布してもよい。同時塗布の方法については、米国特許第 2, 761, 791号、同第 2, 941, 898号、同第 3, 508, 947号、同第 3, 526, 528号及 び原崎勇次著、塗布工学、 253頁、朝倉書店（1973)に記載がある。  [0116] The coating method of the low refractive index layer includes dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and etatrusion coating (US Patent No. 2, 681, No. 294). Two or more layers may be applied simultaneously. For the simultaneous application method, U.S. Pat.Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, coating Engineering, page 253, Asakura Shoten (1973).
[0117] 本発明に係る低屈折率層の各膜厚は 50〜200nmであることが好ましぐ 60-150 nmであることがより好ましい。  [0117] The thickness of each low refractive index layer according to the present invention is preferably 50 to 200 nm, more preferably 60 to 150 nm.
[0118] 〈高屈折率層〉  [0118] <High refractive index layer>
本発明においては、反射率の低減のために、前記低屈折率層の上に、高屈折率 層を設けることが好ましい。また、支持体と低屈折率層との間に中屈折率層を設ける ことは、反射率の低減のためにさらに好ましい。高屈折率層の屈折率は、 1. 55〜2. 30であることが好ましぐ 1. 57-2. 20であることがさらに好ましレ、。中屈折率層の屈 折率は、支持体の屈折率と高屈折率層の屈折率との中間の値となるように調整する 。中屈折率層の屈折率は、 1. 55〜： 1. 80であることが好ましい。高屈折率層及び中 屈折率層の厚さは、 5nm〜l x mであることが好ましぐ 10nm〜0. であること 力 Sさらに好ましぐ 30nm〜0. 1 μ mであることが最も好ましい。高屈折率層及び中屈 折率層のヘイズは、 5%以下であることが好ましぐ 3。/0以下であることがさらに好まし ぐ 1%以下であることが最も好ましい。高屈折率層及び中屈折率層の強度は、 lkg 荷重の鉛筆硬度で H以上であることが好ましぐ 2H以上であることがさらに好まし 3H以上であることが最も好ましレ、。 In the present invention, it is preferable to provide a high refractive index layer on the low refractive index layer in order to reduce reflectance. In addition, it is more preferable to provide a middle refractive index layer between the support and the low refractive index layer in order to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55-2.30, more preferably 1.57-2.20. The refractive index of the medium refractive index layer is adjusted to be an intermediate value between the refractive index of the support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably from 1.55 to 1.80. The thickness of the high refractive index layer and the medium refractive index layer is preferably 5 nm to lxm, and is preferably 10 nm to 0.0. Force S Further preferably 30 nm to 0.1 μm is most preferable. . High refractive index layer and medium bending The haze of the refractive index layer is preferably 5% or less3. / 0 or less is more preferable, and 1% or less is most preferable. The strength of the high refractive index layer and the medium refractive index layer is preferably H or higher at a pencil hardness of 1 kg load, more preferably 2H or higher, and most preferably 3H or higher.
[0119] 本発明に係る中、高屈折率層は、上記樹脂に加えて、下記一般式（1)で表される 有機チタン化合物のモノマー、オリゴマーまたはそれらの加水分解物を含有する塗 布液を塗布し乾燥させて形成させた屈折率 1.55〜2.5の層であることが好ましい。  [0119] In the present invention, the high refractive index layer comprises a coating liquid containing a monomer, oligomer or hydrolyzate thereof of an organic titanium compound represented by the following general formula (1) in addition to the above resin. A layer having a refractive index of 1.55 to 2.5 formed by coating and drying is preferably used.
[0120] —般式（1) Ti(OR)  [0120] — General formula (1) Ti (OR)
1 4  14
式中、 Rとしては炭素数 1〜8の脂肪族炭化水素基がよいが、好ましくは炭素数 1  In the formula, R is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably 1 carbon atom.
1  1
〜4の脂肪族炭化水素基である。また、有機チタン化合物のモノマー、オリゴマーま たはそれらの加水分解物は、アルコキシド基が加水分解を受けて Ti O— Ti一の ように反応して架橋構造を作り、硬化した層を形成する。  ~ 4 aliphatic hydrocarbon groups. In addition, the monomer, oligomer or hydrolyzate of the organotitanium compound undergoes hydrolysis of the alkoxide group and reacts like Ti 2 O—Ti to form a crosslinked structure, thereby forming a cured layer.
[0121] 本発明に用いられる有機チタン化合物のモノマー、オリゴマーとしては、 Ti(〇CH [0121] As the monomer and oligomer of the organotitanium compound used in the present invention, Ti (〇CH
3 Three
) 、Ti(〇CH) , Ti(O-n-CH) , Ti(O-i-CH) , Ti(O-n-CH) 、Ti(), Ti (〇CH), Ti (O-n-CH), Ti (O-i-CH), Ti (O-n-CH), Ti (
4 2 5 4 3 7 4 3 7 4 4 9 44 2 5 4 3 7 4 3 7 4 4 9 4
O-n-C H ) の 2〜10量体、 Ti(0-i-C H ) の 2〜10量体、 Ti(0—n—C H ) O-n-C H) 2-10 mer, Ti (0-i-C H) 2-10 mer, Ti (0—n—C H)
3 7 4 3 7 4 4 9 の 2〜10量体等が好ましい例として挙げられる。これらは単独で、または 2種以上組 A preferred example is a dimer to demer of 3 7 4 3 7 4 4 9. These can be used alone or in combinations of two or more
4 Four
み合わせて用いることができる。中でも Ti(〇一 n— CH) 、Ti(0— i— CH) 、Ti(  They can be used together. Among them, Ti (〇1 n— CH), Ti (0— i— CH), Ti (
3 7 4 3 7 4  3 7 4 3 7 4
O-n-C H ) 、Ti(〇一 n— CH) の 2〜10量体、 Ti(〇一 n— C H ) の 2〜10量  O-n-C H), Ti (〇1 n— CH) 2-10 mer, Ti (〇1 n— C H) 2-10 mer
4 9 4 3 7 4 4 9 4  4 9 4 3 7 4 4 9 4
体が特に好ましい。  The body is particularly preferred.
[0122] 本発明に用いられる中、高屈折率層用塗布液は、水と後述する有機溶媒が順次添 加された溶液中に上記有機チタン化合物を添加することが好ましい。水を後から添 加した場合は、加水分解/重合が均一に進行せず、白濁が発生したり、膜強度が低 下する。水と有機溶媒は添加された後、よく混合させるために攪拌し混合溶解されて いることが好ましい。  [0122] Among the coating solutions for the high refractive index layer used in the present invention, it is preferable to add the organotitanium compound to a solution in which water and an organic solvent described later are sequentially added. If water is added later, hydrolysis / polymerization does not proceed uniformly, resulting in white turbidity or reduced film strength. After the water and the organic solvent are added, it is preferable that they are mixed and dissolved by stirring in order to mix well.
[0123] また、別法として有機チタン化合物と有機溶媒を混合させておき、この混合溶液を、 上記水と有機溶媒の混合攪拌された溶液中に添加することも好ましい態様である。  [0123] As another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed, and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.
[0124] また、水の量は有機チタン化合物 1モルに対して、 0.25〜3モルの範囲であること が好ましい。 0.25モル未満であると、加水分解、重合の進行が不十分で膜強度が 低下する。 3モルを超えると加水分解、重合が進行し過ぎて、 ΤΪΟの粗大粒子が発 [0124] The amount of water is preferably in the range of 0.25 to 3 mol with respect to 1 mol of the organic titanium compound. If it is less than 0.25 mol, hydrolysis and polymerization will not proceed sufficiently and the film strength will be low. descend. If the amount exceeds 3 moles, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse cocoon particles.
2  2
生し白濁するため好ましくない。従って水の量は上記範囲で調整する必要がある。  It is not preferable because it becomes cloudy. Therefore, the amount of water needs to be adjusted within the above range.
[0125] また、水の含有率は塗布液総量に対して 10質量％未満であることが好ましい。水 の含有率を塗布液総量に対して 10質量％以上にすると、塗布液の経時安定が劣り 白濁を生じたりするため好ましくない。 [0125] The water content is preferably less than 10% by mass relative to the total amount of the coating solution. If the water content is 10% by mass or more based on the total amount of the coating solution, it is not preferable because the coating solution is not stable over time and may become cloudy.
[0126] 中、高屈折率層に用いられる有機溶媒としては、水混和性の有機溶媒であることが 好ましい。これらの有機溶媒の使用量は、前述したように、水の含有率が塗布液総量 に対して 10質量％未満であるように、水と有機溶媒のトータルの使用量を調整すれ ばよい。 [0126] Among them, the organic solvent used for the high refractive index layer is preferably a water-miscible organic solvent. The amount of these organic solvents to be used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.
[0127] 本発明に用いられる有機チタン化合物のモノマー、オリゴマーまたはそれらの加水 分解物は、塗布液に含まれる固形分中の 50. 0〜98. 0質量％を占めていることが 望ましい。固形分比率は 50〜90質量％がより好ましぐ 55〜90質量％がさらに好ま しい。この他、塗布組成物には有機チタン化合物のポリマー（予め有機チタンィ匕合物 の加水分解を行って架橋したもの）または酸化チタン微粒子を添加することも好まし い。  [0127] The monomer, oligomer or hydrolyzate of the organotitanium compound used in the present invention preferably occupies 50.0 to 98.0 mass% of the solid content contained in the coating solution. The solid content ratio is more preferably 50 to 90% by mass, and further preferably 55 to 90% by mass. In addition, it is also preferable to add an organic titanium compound polymer (which has been previously crosslinked by hydrolysis of an organic titanium compound) or titanium oxide fine particles to the coating composition.
[0128] 本発明に用いられる高屈折率層及び中屈折率層は、金属酸化物粒子を含むこと が好ましい。  [0128] The high refractive index layer and the medium refractive index layer used in the present invention preferably contain metal oxide particles.
[0129] 上記塗布液調製法で加水分解 Z重合した有機チタン化合物（上記有機チタン化 合物の重合物またはその加水分解物）と金属酸化物粒子を組み合わせると、金属酸 化物粒子と加水分解 Z重合した有機チタン化合物とが強固に接着し、粒子のもつ硬 さと均一膜の柔軟性を兼ね備えた強い塗膜を得ることができる。  [0129] Hydrolysis Z-polymerized organotitanium compound (polymer of organotitanium compound or hydrolyzate thereof) and metal oxide particles combined with the above-mentioned coating solution preparation method yields metal oxide particles and hydrolyzed Z. The polymerized organic titanium compound adheres firmly, and a strong coating film having both the hardness of the particles and the flexibility of the uniform film can be obtained.
[0130] 高屈折率層及び中屈折率層に用いる金属酸化物粒子は、屈折率が 1. 80〜2. 8 0であることが好ましぐ 1. 90-2. 80であることがさらに好ましレ、。金属酸化物粒子 の 1次粒子の重量平均径は、：!〜 150nmであることが好まし 1〜： !OOnmであるこ とがさらに好ましぐ：!〜 80nmであることが最も好ましレ、。層中での金属酸化物粒子 の重量平均径は、：!〜 200nmであること力 S好ましく、 5〜： 150nmであること力 Sより好ま しぐ 10〜100nmであることがさらに好まし 10〜80nmであることが最も好ましい 。金属酸化物粒子の平均粒径は、 20〜30nm以上であれば光散乱法により、 20〜3 Onm以下であれば電子顕微鏡写真により測定される。金属酸化物粒子の比表面積 は、 BET法で測定された値として、 10〜400m2Zgであることが好ましぐ 20-200 m2/gであることがさらに好ましく、 30〜： 150m2/gであることが最も好ましレ、。 [0130] The metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, more preferably 1.90-2.80. I like it. The weight average diameter of the primary particles of the metal oxide particles is preferably: ~~ 150 nm, 1 ~: more preferably OOnm:! ~ 80 nm is the most preferred, . The weight average particle diameter of the metal oxide particles in the layer is: power of S to 200 nm, preferably 5 to: power of 150 nm, more preferably 10 to 100 nm, more preferably 10 to 100 nm. Most preferably, it is 80 nm. If the average particle diameter of the metal oxide particles is 20 to 30 nm or more, 20 to 3 If it is less than Onm, it is measured by an electron micrograph. The specific surface area of metal oxide particles, as measured values by the BET method, more preferably it is 10 to 400 m 2 Zg is preferred instrument 20-200 m 2 / g, 30~: 150m 2 / Les, most preferred to be g.
[0131] 金属酸化物粒子の例としては、 Ti、 Zr、 Sn、 Sb、 Cu、 Fe、 Mn、 Pb、 Cd、 As、 Cr、 Hg、 Zn、 Al、 Mg、 Si、 P及び Sから選択される少なくとも一種の元素を有する金属酸 化物であり、具体的には二酸化チタン (例、ルチル、ルチル /アナターゼの混晶、ァ ナターゼ、アモルファス構造）、酸化錫、酸化インジウム、酸化亜鉛、及び酸化ジルコ 二ゥムが挙げられる。中でも、酸化チタン、酸化錫及び酸化インジウムが特に好まし い。金属酸化物粒子は、これらの金属の酸化物を主成分とし、さらに他の元素を含む こと力 Sできる。主成分とは、粒子を構成する成分の中で最も含有量 (質量％)が多い 成分を意味する。他の元素の例としては、 Ti、 Zr、 Sn、 Sb、 Cu、 Fe、 Mn、 Pb、 Cd、 As、 Cr、 Hg、 Zn、 Al、 Mg、 Si、 P及び S等が挙げられる。  [0131] Examples of metal oxide particles are selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S In particular, titanium oxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Nium. Of these, titanium oxide, tin oxide and indium oxide are particularly preferred. The metal oxide particles can contain such metal oxide as a main component and further contain other elements. The main component means the component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.
[0132] 金属酸化物粒子は表面処理されていることが好ましい。表面処理は、無機化合物 または有機化合物を用いて実施することができる。表面処理に用いる無機化合物の 例としては、アルミナ、シリカ、酸化ジルコニウム及び酸化鉄が挙げられる。中でもァ ルミナ及びシリカが好ましい。表面処理に用いる有機化合物の例としては、ポリオ一 ル、アルカノールァミン、ステアリン酸、シランカップリング剤及びチタネートカップリン グ剤が挙げられる。中でも、前記シランカップリング剤が最も好ましい。  [0132] The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferred. Examples of the organic compound used for the surface treatment include polyol, alkanolamine, stearic acid, silane coupling agent and titanate coupling agent. Among these, the silane coupling agent is most preferable.
[0133] 2種類以上のカップリング剤を併用してもよぐ前記シランカップリング剤に加えて、 他のシランカップリング剤を用いてもよレ、。他のシランカップリング剤には、オルトケィ 酸のアルキルエステル（例えば、オルトケィ酸メチル、オルトケィ酸ェチル、オルトケィ 酸 n_プロピル、オルトケィ酸 i_プロピル、オルトケィ酸 n—ブチル、オルトケィ酸 sec —ブチル、オルトケィ酸 t—ブチル）及びその加水分解物が挙げられる。  [0133] In addition to the silane coupling agent, two or more coupling agents may be used in combination, and other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthokeys (eg, methyl orthokeate, ethyl orthokelate, n-propyl orthokeate, i_propyl orthokeate, n-butyl orthokeate, sec-butyl orthokete, orthokeate). Acid t-butyl) and hydrolysates thereof.
[0134] カップリング剤による表面処理は、微粒子の分散物に、カップリング剤をカ卩え、室温 力も 60°Cまでの温度で、数時間から 10日間分散物を放置することにより実施できる。 表面処理反応を促進するため、無機酸 (例えば、硫酸、塩酸、硝酸、クロム酸、次亜 塩素酸、ホウ酸、オルトケィ酸、リン酸、炭酸）、有機酸 (例えば、酢酸、ポリアクリル酸 、ベンゼンスルホン酸、フエノール、ポリグルタミン酸）、またはこれらの塩（例えば、金 属塩、アンモニゥム塩）を、分散物に添加してもよい。 [0134] Surface treatment with a coupling agent can be carried out by adding a coupling agent to a dispersion of fine particles and allowing the dispersion to stand for several hours to 10 days at a temperature of room temperature up to 60 ° C. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthokeyic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzene sulfonic acid, phenol, polyglutamic acid) or salts thereof (eg gold (Genus salts, ammonium salts) may be added to the dispersion.
[0135] これらシランカップリング剤は予め必要量の水で加水分解されていることが好ましい 。シランカップリング剤が加水分解されていると、前述の有機チタン化合物及び金属 酸化物粒子の表面が反応しやすぐより強固な膜が形成される。また、加水分解され たシランカップリング剤を予め塗布液中に加えることも好ましい。この加水分解に用い た水も有機チタン化合物の加水分解 Z重合に用いることができる。  [0135] These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surface of the organic titanium compound and the metal oxide particles react with each other, and a stronger film is formed immediately. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance. The water used for the hydrolysis can also be used for the hydrolysis Z polymerization of the organic titanium compound.
[0136] 本発明では 2種類以上の表面処理を組み合わせて処理されていても構わない。金 属酸化物粒子の形状は、米粒状、球形状、立方体状、紡錘形状または不定形状で あることが好ましい。 2種類以上の金属酸化物粒子を高屈折率層及び中屈折率層に 併用してもよい。  [0136] In the present invention, two or more kinds of surface treatments may be combined. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in combination in the high refractive index layer and the middle refractive index layer.
[0137] 高屈折率層及び中屈折率層中の金属酸化物粒子の割合は、該層において 5〜65 体積％であることが好ましぐより好ましくは 10〜60体積％であり、さらに好ましくは 2 0〜55体積％である。  [0137] The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume in the layer, more preferably 10 to 60% by volume, and still more preferably. Is 20-55% by volume.
[0138] 上記金属酸化物粒子は、媒体に分散した分散体の状態で、高屈折率層及び中屈 折率層を形成するための塗布液に供される。金属酸化物粒子の分散媒体としては、 沸点が 60〜： 170°Cの液体を用いることが好ましい。分散溶媒の具体例としては、水、 アルコール（例、メタノール、エタノール、イソプロパノール、ブタノール、ベンジルアル コール）、ケトン（例、アセトン、メチルェチルケトン、メチルイソブチルケトン、シクロへ キサノン）、エステル（例、酢酸メチル、酢酸ェチル、酢酸プロピル、酢酸ブチル、蟮 酸メチル、蟻酸ェチル、蟮酸プロピル、蟮酸ブチル)、脂肪族炭化水素 (例、へキサ ン、シクロへキサン）、ハロゲン化炭化水素（例、メチレンクロライド、クロロホノレム、四 塩化炭素）、芳香族炭化水素（例、ベンゼン、トルエン、キシレン）、アミド (例、ジメチ ノレホノレムアミド、ジメチルァセトアミド、 n_メチルピロリドン）、エーテル（例、ジェチノレ エーテル、ジォキサン、テトラハイド口フラン）、エーテルアルコール（例、 1—メトキシ _ 2_プロパノーノレ）が挙げられる。中でも、トルエン、キシレン、メチルェチルケトン、 メチルイソブチルケトン、シクロへキサノン及びブタノールが特に好ましレ、。  [0138] The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for the metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl oxalate, ethyl formate, propyl oxalate, butyl oxalate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons ( Eg, methylene chloride, chlorophenol, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylethanolamide, dimethylacetamide, n_methylpyrrolidone), ethers (eg, , Jetinore ether, dioxane, tetrahydrate furan), ether alcohol (E.g., 1-methoxy_2_propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred.
[0139] また金属酸化物粒子は、分散機を用いて媒体中に分散することができる。分散機 の例としては、サンドグラインダーミル (例、ピン付きビーズミル）、高速インペラーミノレ 、ぺッブルミル、ローラーミル、アトライター及びコロイドミルが挙げられる。サンドグライ ンダーミル及び高速インペラ一ミルが特に好ましい。また、予備分散処理を実施して もよレ、。予備分散処理に用いる分散機の例としては、ボールミル、三本ロールミル、二 ーダー及びエタストルーダーが挙げられる。 [0139] The metal oxide particles can be dispersed in the medium using a disperser. Examples of dispersers include sand grinder mills (eg, bead mills with pins), high-speed impeller minoles. , Pebble mill, roller mill, attritor and colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. You can also perform preliminary distributed processing. Examples of a dispersing machine used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a feeder and an etastruder.
[0140] 中屈折率層及び高屈折率層には、比較的屈折率が高いポリマーを用いることが好 ましレ、。屈折率が高いポリマーの例としては、ポリスチレン、スチレン共重合体、ポリ力 ーボネート、メラミン樹脂、フヱノール樹脂、エポキシ樹脂及び環状 (脂環式または芳 香族）イソシァネートとポリオールとの反応で得られるポリウレタンが挙げられる。その 他の環状（芳香族、複素環式、脂環式)基を有するポリマーや、フッ素以外のハロゲ ン原子を置換基として有するポリマーも、屈折率が高く用いることができる。  [0140] For the medium refractive index layer and the high refractive index layer, it is preferable to use a polymer having a relatively high refractive index. Examples of polymers having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenolic resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate with polyol. Is mentioned. Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups, and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.
[0141] 反射防止層の各層またはその塗布液には、前述した成分 (金属酸化物粒子、ポリ マー、分散媒体、重合開始剤、重合促進剤)以外に、重合禁止剤、レべリング剤、増 粘剤、着色防止剤、紫外線吸収剤、シランカップリング剤、帯電防止剤や接着付与 剤を添加してもよい。  [0141] In addition to the above-described components (metal oxide particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator), each layer of the antireflective layer or the coating liquid thereof includes a polymerization inhibitor, a leveling agent, Thickeners, anti-coloring agents, UV absorbers, silane coupling agents, antistatic agents and adhesion promoters may be added.
[0142] 本発明に係る中〜高屈折率層及び低屈折率層の塗設後、金属アルコキシドを含 む組成物の加水分解または硬化を促進するため、活性エネルギー線を照射すること が好ましい。より好ましくは、各層を塗設するごとに活性エネルギー線を照射すること である。  [0142] After application of the middle to high refractive index layer and the low refractive index layer according to the present invention, it is preferable to irradiate active energy rays in order to promote hydrolysis or curing of the composition containing the metal alkoxide. More preferably, the active energy ray is irradiated every time each layer is coated.
[0143] 本発明に使用する活性エネルギー線は、紫外線、電子線、 Ί線等で、化合物を活 性させるエネルギー源であれば制限なく使用できるが、紫外線、電子線が好ましぐ 特に取り扱いが簡便で高エネルギーが容易に得られるという点で紫外線が好ましレ、 。紫外線反応性化合物を光重合させる紫外線の光源としては、紫外線を発生する光 源であれば何れも使用できる。例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超 高圧水銀灯、カーボンアーク灯、メタルハライドランプ、キセノンランプ等を用いること ができる。また、 ArFエキシマレーザ、 KrFエキシマレーザ、エキシマランプまたはシ ンクロトロン放射光等も用いることができる。照射条件はそれぞれのランプによって異 なる力 照射光量は 20〜： 10000mj/cm2が好ましぐさらに好ましくは、 100〜200 Omj/cm2であり、特に好ましくは、 400〜2000mj/cm2である。 [0144] 紫外線を用いる場合、多層の反射防止層を 1層ずつ照射してもよいし、積層後照 射してもよレ、。生産性の点から、多層を積層後、紫外線を照射することが好ましい。 [0143] The active energy ray to be used in the present invention, ultraviolet rays, electron beams, in Ί rays, can be used without limitation as long as the energy source for activity of the compound, ultraviolet, electron beam is preferable device in particular handling Ultraviolet light is preferred because it is simple and high energy can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, KrF excimer laser, excimer lamp, synchrotron radiation, or the like can also be used. Different forces irradiation light amount irradiation conditions by each lamp 20: preferably the 10000 mJ / cm 2 is preferred gesture et a 100~200 Omj / cm 2, particularly preferably is 400~2000mj / cm 2 . [0144] When ultraviolet rays are used, the multilayer antireflection layer may be irradiated one by one, or may be irradiated after lamination. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.
[0145] また、電子線も同様に使用できる。電子線としては、コックロフトワルトン型、バンデ グラフ型、共振変圧型、絶縁コア変圧器型、直線型、ダイナミトロン型、高周波型等の 各種電子線加速器から放出される 50〜： 1000keV、好ましくは 100〜300keVのェ ネルギーを有する電子線を挙げることができる。  [0145] Also, an electron beam can be used in the same manner. As an electron beam, it is emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. 50 to 1000 keV, preferably An electron beam having an energy of 100 to 300 keV can be mentioned.
[0146] 反射防止層を構成する各屈折率層の膜厚は、各層の屈折率に応じて各々適切な 膜厚を選択することが好ましレヽ。  [0146] The thickness of each refractive index layer constituting the antireflection layer is preferably selected in accordance with the refractive index of each layer.
[0147] 〈熱硬化性樹脂、光硬化性樹脂〉  <Thermosetting resin, photocurable resin>
本発明においては、転写層（保護層）の最表面層が、熱または光により硬化された 樹脂を用いることもできる。  In the present invention, a resin whose outermost surface layer of the transfer layer (protective layer) is cured by heat or light can also be used.
[0148] 熱硬化性樹脂としては、フエノール樹脂系、メラミン樹脂系、エポキシ樹脂系、アタリ ル樹脂系、エポキシアタリレート樹脂系、不飽和ポリエステル樹脂系、ポリエステルァ タリレート樹脂系、ウレタンアタリレート樹脂系、スピラン樹脂系、ジァリルフタレート榭 脂系等が挙げられる。また無機系樹脂の例として、コロイダルシリカ、シリコーンモノマ 一を加水分解してから重合させるもの等が挙げられる。これらの中から選ばれた 1種 類以上の成分を混合して使用するが、必要に応じて各種硬化剤、カップリング剤等を 適量添加して用いると効果的である。  [0148] Thermosetting resins include phenolic resins, melamine resins, epoxy resins, acrylate resins, epoxy acrylate resins, unsaturated polyester resins, polyester acrylate resins, urethane acrylate resins. And spirane resin and diallyl phthalate resin. Examples of the inorganic resin include colloidal silica and those obtained by polymerizing a silicone monomer after hydrolysis. One or more components selected from these are mixed and used, but it is effective to add various curing agents, coupling agents and the like as necessary.
[0149] 光硬化性樹脂としては、付加重合性または開環重合性を有する素材からなるもの であり、付加重合成化合物とは、ラジカル重合性化合物、例えば特開平 7— 159983 号、特公平 7— 31399号等の各号公報に記載されている光重合成 (熱重合性も含む )組成物を用いた光硬化型材料であってもよい。付加重合成化合物とは、カチオン重 合系の光硬化型材料が知られており、最近では可視光以上の長波長域に増感され た光力チオン重合系の光硬化材料も例えば、特開平 6— 43633号公報等に公開さ れている。本発明の目的においてはどちらを用いても構わない。  [0149] The photocurable resin is made of a material having addition polymerization property or ring-opening polymerization property, and the addition polysynthetic compound is a radical polymerizable compound such as JP-A-7-159983. — It may be a photo-curable material using a photo-polymerization (including thermal polymerization) composition described in each publication such as No. 31399. As the addition polysynthetic compound, a cationic polymerization type photo-curing material is known, and a photo-power thione polymerization type photo-curing material sensitized to a long wavelength region longer than visible light is also disclosed in, for example, 6-43633 and other publications. Either may be used for the purposes of the present invention.
[0150] ラジカル重合開始剤としては、特公昭 59— 1281号、特公昭 61— 9621号、及び 特開昭 60— 60104号等の各公報記載のトリジアン誘導体、特開昭 59— 1504号及 び特開昭 61 - 243807号等の各公報に記載の有機過酸化物、特公昭 43 - 23684 号、特公昭 44— 6413号、特公昭 44— 6413号及び特公昭 47— 1604号等の各公 報並びに米国特許第 3, 567, 453号明細書に記載のジァゾニゥム化合物、米国特 許第 2， 848 , 328号、同第 2， 852, 379号及び同 2, 940， 853号明糸田書に記載の 有機アジド'ィ匕合物、特公昭 36— 22062号、特公昭 37— 13109号、特公昭 38— 18 015号、特公昭 45— 9610号等の各公報に記載のオルト—キノンジアジド類、特公 昭 55— 39162号、特開昭 59— 14023号等の各公報及びマクロモレキュルス（Mac romolecules)、第 10卷、第 1307頁（1977年）に記載の各種ォニゥム化合物、特開 昭 59— 142205号公報に記載のァゾ化合物、特開平 1— 54440号公報、ヨーロッパ 特許第 109、 851号、ヨーロッパ特許第 126、 712号等の各明細書、ジャーナル'ォ ブ 'イメージング'サイエンス J. Imag. Sci. )、第 30卷、第 174頁（1986年）に記載 の金属アレン錯体、特開平 5— 213861号公報及び特開平 5— 255347号公報に記 載の（ォキソ)スルホニゥム有機ホウ素錯体、特開昭 61 - 151 197号公報に記載のチ タノセン類、コーディネーション 'ケミストリー 'レビュー（Coordination Chemistry Review)、第 84卷、第 85〜第 277頁（1988年）及び特開平 2— 182701号公報に 記載のルテニウム等の遷移金属を含有する遷移金属錯体、特開平 3— 209477号 公報に記載の 2, 4, 5 トリアリールイミダゾール二重体、四臭化炭素や特開昭 59— 107344号公報記載の有機ハロゲン化合物等が挙げられる。本発明において重合 開始剤はラジカル重合可能なエチレン不飽和結合を有する化合物 100質量部に対 して 0. 5〜5質量部の範囲で含有されるのが好ましい。さらに好ましくは、：!〜 5質量 %の範囲が好ましい。 [0150] Examples of radical polymerization initiators include tridian derivatives described in JP-B-59-1281, JP-B-61-9621, JP-A-60-60104, JP-A-59-1504, and the like. Organic peroxides described in JP-A 61-243807, JP-B 43-23684 No. 4, JP-B 44-6413, JP-B 44-6413, JP-B 47-1604, etc., as well as diazonium compounds described in US Pat. No. 3,567,453, US Pat. , 848, 328, No. 2, 852, 379 and No. 2, 940, 853, Organic azide compounds described in Meito, Shoko 36-22062, Shoko 37-13109, Ortho-quinonediazides described in JP-B-38-18015, JP-B-45-9610, etc., JP-B 55-39162, JP-A-59-14023, etc., and macromolecules. (Macromolecules), Vol. 10, pp. 1307 (1977), various onium compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent 109 , 851, European Patent Nos. 126 and 712, etc., Journal 'Ob' Imaging 'Science J. Imag. Sci.), Pp. 30, 174 1986), (oxo) sulfonium organoboron complexes described in JP-A-5-213861 and JP-A-5-255347, and compounds described in JP-A-61-151197. Tanocenes, transition metal complexes containing transition metals such as ruthenium described in Coordination Chemistry Review, No. 84, 85-277 (1988) and JP-A-2-182701 And 2,4,5 triarylimidazole duplexes described in JP-A-3-209477, carbon tetrabromide, and organic halogen compounds described in JP-A-59-107344. In the present invention, the polymerization initiator is preferably contained in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the compound having an ethylenically unsaturated bond capable of radical polymerization. More preferably, the range is:! To 5% by mass.
[0151] ラジカル重合性化合物を含有する感光性組成物には、ラジカル重合性モノマーの 熱重合開始剤として、一般にラジカル重合による高分子合成反応に用いられる公知 のラジカル重合開始剤を特に制限なく含有させることができる。ここで、熱重合開始 剤とは、熱エネルギーを与えることにより重合性のラジカルを発生することが可能な化 合物である。  [0151] The photosensitive composition containing the radically polymerizable compound contains, as a thermal polymerization initiator for the radically polymerizable monomer, a known radical polymerization initiator that is generally used for polymer synthesis reaction by radical polymerization without any particular limitation. Can be made. Here, the thermal polymerization initiator is a compound capable of generating a polymerizable radical by applying thermal energy.
[0152] このような化合物としては、例えば、 2, 2' —ァゾビスイソブチロニトリル、 2, 2' - ァゾビスプロピオ二トリル等のァゾビス二トリル系化合物、過酸化べンゾィル、過酸化 ラヮロイル、過酸化ァセチル、過安息酸 tーブチル、 a クミルヒドロパーオキサイド、 ジ— t—ブチルバ—オキサイド、ジイソプロピルパ―ォキシジカーボネート、 t—ブチ ルパ—ォキシイソプロピルカーボネート、過酸類、アルキルパーォキシ力ルバメート類 、ニトロソァリールアシノレアミン類等の有機過酸化物、過硫酸カリウム、過硫酸アンモ 二ゥム、過塩素酸カリウム等の無機過酸化物、ジァゾァミノベンゼン、 p_ニトロべンゼ ンジァゾニゥム、ァゾビス置換アルカン類、ジァゾチォエーテル類、ァリールァゾスル フォン類等のァゾまたはジァゾ系化合物、ニトロソフエ二ル尿素、テトラメチルチウラム ジスノレフイド、ジァリキルキサントゲン酸ジスルフイド類、ァリールスルフィン酸類、ァリ ールアルキルスルフォン類、 1 アルカンスルフィン酸類等を挙げることができる。こ れらの中で特に好ましいものは、常温での安定性に優れ、加熱時の分解速度が速く 、かつ分解時に無色となる化合物であり、このようなものとしては、過酸化べンゾィル、 2, 2' —ァゾビスイソプチロニトリル等を挙げることができる。また、本発明では、これ らの熱重合開始剤を 1種または 2種以上混合して用いることができる。さらに、熱重合 開始剤は、熱重合性の組成物中通常 0. 5〜： 10質量％が好ましぐ：!〜 5質量％の範 囲がより好ましい。 [0152] Examples of such compounds include 2,2'-azobisisobutyronitrile, azobisnitrile compounds such as 2,2'-azobispropionitrile, benzoyl peroxide, lauroyl peroxide, Acetyl peroxide, t-butyl perbenzoate, a cumyl hydroperoxide, Organic peroxides such as di-t-butyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, peracids, alkylperoxylrubamates, nitrosoaryl acyloleamines Inorganic peroxides such as potassium persulfate, ammonium persulfate, potassium perchlorate, diazoaminobenzene, p_nitrobenzenediazonium, azobis-substituted alkanes, diazothioethers, allylazosulfol Examples include azo or diazo compounds such as phonones, nitrosodiurea, tetramethylthiuram disunolide, dialkylxanthate disulfides, allylsulfinic acids, arylalkylsulfones, 1 alkanesulfinic acids, etc. Can do. Particularly preferred among these are compounds that have excellent stability at room temperature, have a high decomposition rate when heated, and become colorless upon decomposition. Examples of such compounds include benzoyl peroxide, 2 , 2'-azobisisoptyronitrile and the like. In the present invention, these thermal polymerization initiators can be used alone or in combination. Further, the thermal polymerization initiator is usually preferably in the range of 0.5 to 10% by mass in the thermally polymerizable composition: more preferably in the range of 5 to 5% by mass.
カチオン重合により高分子化の起こるタイプ（主にエポキシタイプ）のエポキシタイプ の紫外線硬化性プレボリマー、モノマーは、 1分子内にエポキシ基を 2個以上含有す るプレボリマーを挙げることができる。このようなプレボリマーとしては、例えば、脂環 式ポリエポキシド類、多塩基酸のポリグリシジルエステル類、多価アルコールのポリグ リシジルエーテル類、ポリオキシアルキレングリコールのポリグリシジルエーテル類、 芳香族ポリオールのポリグリシジルエーテル類、芳香族ポリオールのリグリシジルエー テル類の水素添加化合物類、ウレタンポリエポキシ化合物類及びエポキシィ匕ポリブタ ジェン類等を挙げることができる。これらのプレボリマーは、その一種を単独で使用す ることもできるし、また、その二種以上を混合して使用することもできる。前記紫外線 硬化保護層形成用コーティング剤中の、エポキシ基を 1分子内に 2個以上有するプ レポリマーの含有量は 70質量％以上であることが好ましい。カチオン重合性組成物 中に含有されるカチオン重合性化合物としては、他に例えば下記の（1)スチレン誘 導体、（2)ビュルナフタレン誘導体、（3)ビュルエーテル類及び (4) N—ビュルィ匕合 物類を挙げることができる。 [0154] 本発明においてはラジカル重合系が好ましい。 Examples of UV-curable prepolymers and monomers of the epoxy type that are polymerized by cationic polymerization (mainly epoxy type) and monomers that contain two or more epoxy groups in one molecule. Examples of such prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, and polyglycidyls of aromatic polyols. Mention may be made of ethers, hydrogenated compounds of liglycidyl ethers of aromatic polyols, urethane polyepoxy compounds and epoxy-polybutadienes. These prepolymers can be used alone or in combination of two or more. The content of the prepolymer having two or more epoxy groups in one molecule in the UV curable protective layer-forming coating agent is preferably 70% by mass or more. Other cationic polymerizable compounds contained in the cationic polymerizable composition include, for example, the following (1) styrene derivatives, (2) bullaphthalene derivatives, (3) bull ethers, and (4) N-Bulu 匕. Compounds can be mentioned. In the present invention, a radical polymerization system is preferred.
[0155] 〈転写層の表面粗さ〉  <Surface roughness of transfer layer>
転写層（保護層）の最表面層の表面粗さは 0.：!〜 l z mであることが好ましい。本発 明で表面粗さと ίお IS -B-060K2001)により定義される表面粗さ Ra (平均表面粗 さ）をいう。測定装置としては、例えば、触針法やレーザ干渉測長法といった周知の 表面粗さ測定法で測定することができる。  The surface roughness of the outermost surface layer of the transfer layer (protective layer) is preferably 0.:! To l z m. The surface roughness Ra (average surface roughness) defined by the surface roughness and the IS-B-060K2001) in the present invention. As a measuring device, for example, it can be measured by a known surface roughness measuring method such as a stylus method or laser interferometry.
[0156] この表面粗さを得るためには転写層に微粒子を含有させることが好ましい。このよう な微粒子としては、有機化合物ではメラミン、 PMMA等の樹脂微粒子、無機化合物 としては酸化チタン、酸化亜鉛、炭酸カルシウム、酸化アルミニウム、カオリン、クレー 、シリカ、タルク、雲母等が挙げられる。分散性の点からシリカが好ましぐ特に吸油量 (比表面積、嵩比重）が大きいものほど好ましい。転写箔の支持体の平滑性が高い場 合は、これらの微粒子の添加量を調節して良好な面を得ることができる。添加量は微 粒子の平均粒径が 0. l x m〜： ίθ μ ΐηの場合、通常、転写層の全固形分に対し 0. 1 〜40質量％、好ましくは 1〜30質量％である。  [0156] In order to obtain this surface roughness, the transfer layer preferably contains fine particles. Examples of such fine particles include resin fine particles such as melamine and PMMA as organic compounds, and examples of inorganic compounds include titanium oxide, zinc oxide, calcium carbonate, aluminum oxide, kaolin, clay, silica, talc, and mica. From the viewpoint of dispersibility, silica is preferred, and the larger the oil absorption (specific surface area, bulk specific gravity) is particularly preferred. When the smoothness of the support of the transfer foil is high, a good surface can be obtained by adjusting the amount of these fine particles added. When the average particle size of the fine particles is from 0.1 × m to ίθμΐη, the addition amount is usually from 0.1 to 40% by mass, preferably from 1 to 30% by mass, based on the total solid content of the transfer layer.
[0157] また、この表面粗さを得るための別方としては、凹凸のある支持体を用いることであ る。凹凸のある支持体は市販されている。  [0157] Another method for obtaining this surface roughness is to use an uneven support. An uneven support is commercially available.
[0158] (接着層）  [0158] (Adhesive layer)
本発明で転写層に熱接着性 (ジートシール性）のない樹脂を用いる場合には、熱接 着性樹脂からなる接着層を用いることが好ましい。  In the present invention, when a resin having no thermal adhesiveness (geet sealability) is used for the transfer layer, it is preferable to use an adhesive layer made of a thermal adhesive resin.
[0159] 熱接着性樹脂からなる接着層は、耐熱性の支持体、例えばポリエチレンテレフタレ ート樹脂フィルム上に塗工によって形成された透明層リボンまたは透明箔をあらかじ め用意しておき、これを、例えば、サーマルヘッドや熱転写ロールを用いて、熱転写 することによって形成することができる。  [0159] The adhesive layer made of a heat-adhesive resin is prepared in advance with a heat-resistant support, for example, a transparent layer ribbon or transparent foil formed by coating on a polyethylene terephthalate resin film, This can be formed, for example, by thermal transfer using a thermal head or a thermal transfer roll.
[0160] 前記熱接着性樹脂としては、例えば塩化ビニル系樹脂、ポリエステル系樹脂、ァク リル系樹脂、ポリビュルァセタール系樹脂、ポリビュルプチラール系樹脂、ポリビニノレ アルコール、ポリカーボネート、セルロース系樹脂、スチレン系樹脂、ウレタン系樹脂 、アミド系樹脂、尿素系樹脂、エポキシ樹脂、フエノキシ樹脂、ポリ力プロラ外ン樹脂 、ポリアクリロニトリル樹脂、 SEBS樹脂、 SEPS樹脂、及びそれらの変性物等を挙げ ること力 Sできる。 [0160] Examples of the heat-adhesive resin include a vinyl chloride resin, a polyester resin, an acrylic resin, a polyvurecetal resin, a polybutyral resin, a polyvinyl alcohol, a polycarbonate, a cellulose resin, Examples include styrene resins, urethane resins, amide resins, urea resins, epoxy resins, phenoxy resins, polystrength resins, polyacrylonitrile resins, SEBS resins, SEPS resins, and modified products thereof. Ability to do S.
[0161] 上述した樹脂の中でも本発明の目的に好ましいのは、塩ィ匕ビュル系樹脂、ポリエス テル系樹脂、アクリル系樹脂、ポリビュルプチラール系樹脂、スチレン系樹脂、ェポキ シ樹脂、ウレタン系樹脂、ウレタンアタリレート樹脂、 SEBS樹脂、 SEPS樹脂である。 これらの樹脂は一種を単独に用いることもできるし、二種以上を組み合わせて用いる こともできる。  [0161] Among the above-described resins, preferred are the salt-based resin, the polyester resin, the acrylic resin, the polybutyl plastic resin, the styrene resin, the epoxy resin, and the urethane resin for the purpose of the present invention. Resin, urethane acrylate resin, SEBS resin, SEPS resin. These resins can be used alone or in combination of two or more.
[0162] (保護層の形成）  [0162] (Formation of protective layer)
転写層は、別の支持体上に存在する輝尽性蛍光体層の面に対面接触させ、加熱' 加圧後、転写層を保持していた支持体を剥離することにより輝尽性蛍光体層の表面 を保護するように転写される。加熱'加圧条件は、転写層の樹脂の軟ィヒ点以上の温 度で加熱 ·圧着することが好ましい。加熱する温度の上限は、軟化点 + 100°Cが好ま しい。  The transfer layer is brought into contact with the surface of the photostimulable phosphor layer existing on another support, and after the heating and pressurization, the support holding the transfer layer is peeled off to release the photostimulable phosphor. Transferred to protect the surface of the layer. The heating and pressing conditions are preferably heating and pressure bonding at a temperature equal to or higher than the soft point of the resin of the transfer layer. The upper limit of the heating temperature is preferably the softening point + 100 ° C.
[0163] 転写層のみを輝尽性蛍光体層上に転写することにより保護層を形成することが普 通であるが、本発明においては、放射線像変換パネルの使用時までの製造や輸送 工程の搬送等による傷を防止するため、転写箔の支持体を剥離することなく保持し、 使用直前に剥離することが好ましい。  [0163] It is common to form a protective layer by transferring only the transfer layer onto the photostimulable phosphor layer. In the present invention, however, the manufacturing and transportation steps until the use of the radiation image conversion panel are performed. In order to prevent scratches due to the conveyance of the film, it is preferable to hold the transfer foil support without peeling and peel it immediately before use.
[0164] 保護層を形成するための加熱'加圧手段には、密着性に優れ、気泡等が混入せず に加圧または加熱 ·加圧処理できるものであれば特に制限なく用いることができ、カロ 圧する場合には、圧力ロールやスタンパー等を、加熱 ·加圧処理する場合には、サー マルヘッド、ヒートロール、ホットスタンプ等を用いることができる。  [0164] The heating and pressurizing means for forming the protective layer can be used without particular limitation as long as it has excellent adhesion and can be pressurized or heated and pressurized without mixing bubbles or the like. In the case of caloric pressure, a pressure roll or stamper can be used, and in the case of heating / pressurizing treatment, a thermal head, heat roll, hot stamp or the like can be used.
[0165] 圧力ロールを用いる場合の圧力は通常 l〜200NZcm2、好ましくは 5〜100NZc m2であり、また、搬送速度は通常 0. ：!〜 200mm/秒、好ましくは 0. 5~ 100mm/ 秒であり、スタンパーを用いる場合の圧力としては通常 0. 5〜： 100N/cm2、好ましく は 5〜50NZcm2、また、カロ圧時間は通常。.：!〜 5。秒、好ましくは。. 5〜20秒であ る。ヒートローノレを用レヽる場合のカロ熱温度は通常 60〜200。C、好ましくは 150〜190 °Cの範囲であり、圧力は通常 l〜200NZcm2、好ましくは 5〜100N/cm2であり、ま た、搬送速度は通常 0.：!〜 200mm/秒、好ましくは 0. 5〜： 100mm/秒である。 [0165] When a pressure roll is used, the pressure is usually 1 to 200 NZcm 2 , preferably 5 to 100 NZcm 2 , and the conveyance speed is usually 0.:! To 200 mm / second, preferably 0.5 to 100 mm / second. When the stamper is used, the pressure is usually 0.5 to: 100 N / cm 2 , preferably 5 to 50 NZcm 2 , and the caloric pressure time is normal. .:!~ Five. Seconds, preferably. 5 to 20 seconds. The calorie temperature when using a heat roll is usually 60-200. C, preferably in the range of 150 to 190 ° C, the pressure is usually 1 to 200 NZcm 2 , preferably 5 to 100 N / cm 2 , and the conveying speed is usually 0.:! To 200 mm / sec, preferably Is 0.5 to 100 mm / sec.
[0166] 加圧または加熱'加圧後に転写箔の支持体を引き剥がす方法としては、剥離板、 剥離ロールによる剥離角度固定方法、手で転写箔と支持体上に存在する輝尽性蛍 光体層を固定せずに引き剥がす手剥離方法等、輝尽性蛍光体層に影響を与えない 限り、種々の剥離方法を用いることができる。 [0166] As a method of peeling off the support of the transfer foil after pressurization or heating'pressure, a release plate, As long as it does not affect the photostimulable phosphor layer, such as the peel angle fixing method using a peeling roll, and the hand peeling method in which the stimulable phosphor layer existing on the transfer foil and the support is peeled off without being fixed by hand. Various peeling methods can be used.
実施例  Example
[0167] 以下、実施例を挙げて本発明を詳細に説明するが、本発明はこれらに限定されな い。なお、特に断りない限り、実施例中の「％」は「質量％」を表す。  [0167] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “%” in the examples represents “mass%”.
[0168] 実施例 1 [0168] Example 1
《放射線像変換パネルの作製》  <Production of radiation image conversion panel>
(輝尽性蛍光体粒子の作製）  (Production of photostimulable phosphor particles)
ユーロピウム賦活弗化ヨウ化バリウムの輝尽性蛍光体前駆体を合成するために、 Ba I水溶液（3. 6mol/U 2780mlと Eul水溶液（0. 2mol/U 27mlを反応器に入れ た。この反応器中の反応母液を撹拌しながら 83°Cで保温した。弗化アンモニゥム水 溶液（8molZU 322mlを反応母液中にローラーポンプを用いて注入し、沈澱物を 生成させた。注入終了後も保温と撹拌を 2時間続けて沈澱物の熟成を行なった。次 に沈澱物をろ別後、エタノールにより洗浄した後真空乾燥させてユーロピウム賦活弗 ィ匕ヨウ化バリウムの結晶を得た。焼成時の焼結により粒子形状の変化、粒子間融着 による粒子サイズ分布の変化を防止するために、アルミナの超微粒子粉体を 0. 2% 添加し、ミキサーで充分撹拌して、結晶表面にアルミナの超微粒子粉体を均一に付 着させた。これを石英ボートに充填して、チューブ炉を用いて水素ガス雰囲気中、 85 0°Cで 2時間焼成してユーロピウム賦活弗化ヨウ化バリウム蛍光体粒子を得た。次に 上記蛍光体粒子を分級することにより平均粒径 7 μ mの粒子を得た。  In order to synthesize a stimulable phosphor precursor of europium-activated barium fluoroiodide, Ba I aqueous solution (3.6 mol / U 2780 ml and Eul aqueous solution (0.2 mol / U 27 ml were placed in the reactor). The reaction mother liquor in the vessel was stirred and kept at 83 ° C. Ammonium fluoride aqueous solution (322 ml of 8 molZU was poured into the reaction mother liquor using a roller pump to form a precipitate. Stirring was continued for 2 hours to ripen the precipitate, and then the precipitate was filtered, washed with ethanol, and dried in vacuo to obtain europium-activated barium fluoroiodide crystals. In order to prevent changes in particle shape due to crystallization, and changes in particle size distribution due to interparticle fusion, 0.2% of ultrafine alumina powder was added and stirred thoroughly with a mixer. The fine particle powder was evenly attached. Filled in a boat and fired at 850 ° C for 2 hours in a hydrogen gas atmosphere using a tube furnace to obtain europium-activated barium fluoroiodide phosphor particles, and then classifying the phosphor particles Thus, particles having an average particle diameter of 7 μm were obtained.
[0169] (蛍光体層を有するシートの作製） [0169] (Production of sheet having phosphor layer)
蛍光体層形成材料として、上記で得たユーロピウム賦活弗化ヨウ化バリウム蛍光体 427g、ポリウレタン樹脂（住友バイエルウレタン社製、デスモラック 4125) 15. 8g、ビ スフエノール A型エポキシ樹脂 2. Ogをメチルェチルケトン トルエン（1： 1)混合溶媒 に添加し、プロペラミキサーによって分散し、粘度 2. 5〜3. OPa' sの塗布液を調製し た。この塗布液をドクターブレードを用いて厚さ 100 μ mの黒色 PET支持体上に塗 布した後、 100°Cで 15分間乾燥させて、 270 /i mの厚さの蛍光体層を形成した。 [0170] (保護層の作製） As the phosphor layer forming material, 427 g of the europium-activated barium fluoroiodide phosphor obtained above, polyurethane resin (Desmolac 4125, manufactured by Sumitomo Bayer Urethane Co., Ltd.) 15.8 g, bisphenol A type epoxy resin 2. Og methyl Ethyl ketone Toluene (1: 1) was added to a mixed solvent and dispersed with a propeller mixer to prepare a coating solution having a viscosity of 2.5 to 3. OPa's. This coating solution was applied on a black PET support having a thickness of 100 μm using a doctor blade, and then dried at 100 ° C. for 15 minutes to form a phosphor layer having a thickness of 270 / im. [0170] (Preparation of protective layer)
表 2に示す TPE (熱可塑性エラストマ一） E1〜E5を固形分濃度が 15%になるよう に、すべり剤として信越化学 (株)製 X— 22— 2809を固形分濃度が 0. 1%になるよう に MEKに溶解しドクターブレードを用いて厚さ 10 a mでシリコーン系離形剤が塗布 されている PET仮支持体上にドライ膜厚が 10 z mになるように塗布し保護層の転写 箔を形成した。  TPE (Thermoplastic Elastomer) shown in Table 2 E-1 to E5 was made to have a solid concentration of 15%, and X-22-22809 made by Shin-Etsu Chemical Co., Ltd. was used as a slip agent to a solid content concentration of 0.1%. Soaked in MEK and applied with a silicone release agent at a thickness of 10 am using a doctor blade.Applied to a PET temporary support so that the dry film thickness is 10 zm. Transfer foil for protective layer Formed.
[0171] 続いて、表 3に示す様に、得られた転写箔を保護層面と前記蛍光体層が接するよう に重ねあわせ 60〜70°Cの加熱ロールで加熱圧着し蛍光体シートを作製した。  [0171] Subsequently, as shown in Table 3, the obtained transfer foil was laminated so that the protective layer surface and the phosphor layer were in contact with each other, and heat-pressed with a heating roll of 60 to 70 ° C to prepare a phosphor sheet. .
[0172] (被覆部の作製）  [0172] (Preparation of coating)
表 2に示す TPE (熱可塑性エラストマ一） E1〜E7を固形分濃度が 15%になるよう に、すべり剤として信越化学 (株)製 X— 22— 2809を固形分濃度が 0. 1%になるよう に MEKに溶解させ、表 3に示す様に、前記蛍光体シートの端部全周に塗布し 60°C で 30分間乾燥させて放射線像変換パネル 1 1〜 1 19を得た。  TPE (Thermoplastic Elastomer) shown in Table 2 E-1 to E7 is made to have a solid content of 15%, and X-22-22809 made by Shin-Etsu Chemical Co., Ltd. as a slipping agent has a solid content of 0.1%. As shown in Table 3, it was applied to the entire periphery of the end of the phosphor sheet and dried at 60 ° C. for 30 minutes to obtain radiation image conversion panels 11 to 119.
[0173] [表 2]  [0173] [Table 2]
Figure imgf000039_0001
Figure imgf000039_0001
101 Iジフエ二 メタン ·'；?イソシァネ一ト  101 I Diphenyl methane · ； Isocyanate
t oi ： フエ二 イソプ αピレンジイソシァネ一  t oi ： Hueni Isop α-Pyrene Diisocyanate
NPG： ネオベンチ Λダリコ- ·ル  NPG: Neobench Λ Dariko-le
Ηδ: 1, δ—へキサンジ才一ル  Ηδ: 1, δ—Hexaneji
EG：ェチレングリコ一ル  EG: Ethylene glycol
CHDM： シク £3 キサンジメタメ一ル  CHDM: Siku £ 3
PCL： # s—カブ Oラタタム  PCL: # s—Cub O Ratata Tam
： アジピン酸  : Adipic acid
I イソフタル酸  I Isophthalic acid
IPA：チレフタル酸 ·  IPA: Tirephthalic acid ·
PA フタル酸 ·  PA Phthalic acid ·
[0174] 《放射線像変換パネルの評価》 [0174] << Evaluation of Radiation Image Conversion Panel >>
(耐湿性） 作製した放射線像変換パネルについて、 80°C、 90%RHの条件で 1週間放置して 放置前後の放射線像変換パネルの質量変化 (質量増加率％)を測定することにより 耐湿性を評価した。 (Moisture resistance) The prepared radiation image conversion panel was allowed to stand for 1 week at 80 ° C and 90% RH, and the moisture resistance was evaluated by measuring the mass change (mass increase rate%) of the radiation image conversion panel before and after being left.
[0175] (強度） [0175] (Strength)
西華産業社製 Ipanema SaC— 200タイプの搬送試験機で放射線像変換パネル の被覆部の破損が生じるまで搬送繰り返し、その数を強度の指標とした。  The Ipanema SaC-200 type transport tester manufactured by Seika Sangyo Co., Ltd. was repeatedly transported until the coating on the radiation image conversion panel was damaged, and the number was used as an index of strength.
[0176] 評価の結果を表 3に示す。 [0176] The results of the evaluation are shown in Table 3.
[0177] [表 3] [0177] [Table 3]
Figure imgf000040_0001
Figure imgf000040_0001
[0178] 表 3から、保護層と被覆部の軟化点の差が 30°C以下の本発明の放射線像変換パ ネルは、軟化点の差がこれより大きレ、比較例の放射線像変換パネルに比べ、耐湿性 及び強度に優れていることが分かる。 [0178] From Table 3, the radiation image conversion panel of the present invention in which the difference between the softening points of the protective layer and the covering portion is 30 ° C or less has a larger difference in softening point. It can be seen that it is superior in moisture resistance and strength.
[0179] なお、感度及び画質については何れの放射線像変換パネルも良好であった。  [0179] It should be noted that any radiation image conversion panel was good in sensitivity and image quality.
[0180] 実施例 2  [0180] Example 2
《放射線像変換パネルの作製》 保護層と被覆部を下記の方法で作製した以外は実施例 1と同様にして放射線像変 換パネルを得た。 <Production of radiation image conversion panel> A radiation image conversion panel was obtained in the same manner as in Example 1 except that the protective layer and the covering portion were produced by the following method.
[0181] (保護層の作製）  [0181] (Preparation of protective layer)
実施例 1の表 2に示す TPE (熱可塑性エラストマ一） E1〜E5を固形分濃度が 15% になるように、すべり剤として信越化学 (株)製 X— 22— 2809を固形分濃度が 0. 1% になるように MEKに溶解しドクターブレードを用いて厚さ 5 μ mの PET支持体上にド ライ膜厚が 10 μ mになるように塗布した。この反対側に不飽和ポリエステル樹脂（東 洋紡 (株）：バイロン 30SS)溶液をドライ膜厚 5 μ mになるように塗布し接着層を形成 し、接着層付き保護層 (保護層が 2層で最外層に熱可塑性エラストマ一を含有)を作 製した。  TPE (Thermoplastic Elastomer) shown in Table 2 of Example 1 E-1 to E5 were used as a slipping agent so that the solid content concentration was 15%. X-22-22809 manufactured by Shin-Etsu Chemical Co., Ltd. had a solid content concentration of 0. Dissolved in MEK to 1% and applied onto a 5 μm thick PET support with a doctor blade to a dry film thickness of 10 μm. On the opposite side, an unsaturated polyester resin (Toyobo Co., Ltd .: Byron 30SS) solution was applied to a dry film thickness of 5 μm to form an adhesive layer, and a protective layer with an adhesive layer (two protective layers) And the outermost layer contains a thermoplastic elastomer).
[0182] 次いで、表 4に示す様に、この接着層付き保護層の接着層と実施例 1で作製した蛍 光体層が接するように重ね合わせ、 60〜70°Cの加熱ロールで加熱圧着し蛍光体シ ートを作製した。  [0182] Next, as shown in Table 4, the adhesive layer of the protective layer with an adhesive layer was laminated so that the phosphor layer prepared in Example 1 was in contact with each other, and thermocompression bonded with a heating roll at 60 to 70 ° C. A phosphor sheet was prepared.
[0183] (被覆部の作製）  [0183] (Preparation of coating)
実施例 1の表 2に示す TPE (熱可塑性エラストマ一） E1〜E7を固形分濃度が 15% になるように、すべり剤として信越化学 (株)製 X— 22— 2809を固形分濃度が 0· 1% になるように MEKに溶解させ、表 4に示す様に、前記蛍光体シートの端部全周に塗 布し 60°Cで 30分間乾燥させて放射線像変換パネル 2— :!〜 2— 19を得た。  TPE (Thermoplastic Elastomer) shown in Table 2 of Example 1 E-1 to E7 was used as a slipping agent so that the solid content concentration was 15%, and X-22-22809 made by Shin-Etsu Chemical Co., Ltd. had a solid content concentration of 0. · Dissolved in MEK to 1%, and coated on the entire periphery of the phosphor sheet as shown in Table 4, dried at 60 ° C for 30 minutes, and then the radiation image conversion panel 2—:! 2-19 was obtained.
[0184] 《放射線像変換パネルの評価》  [0184] << Evaluation of Radiation Image Conversion Panel >>
作製した放射線像変換パネルについて実施例 1と同様に評価した。評価の結果を 表 4に示す。  The produced radiation image conversion panel was evaluated in the same manner as in Example 1. Table 4 shows the evaluation results.
[0185] [表 4]
Figure imgf000042_0001
[0185] [Table 4]
Figure imgf000042_0001
[0186] 表 4から、保護層の最外層と被覆部の軟化点の差が 30°C以下の本発明の放射線 像変換パネルは、軟化点の差がこれより大きレ、比較例の放射線像変換パネルに比 ベ、耐湿性及び強度に優れていることが分かる。 [0186] From Table 4, the radiation image conversion panel of the present invention in which the difference between the softening points of the outermost layer of the protective layer and the covering portion is 30 ° C or less has a larger difference in softening point. It can be seen that it is superior to the conversion panel in moisture resistance and strength.
[0187] なお、感度及び画質については何れの放射線像変換パネルも良好であった。  [0187] It should be noted that any radiation image conversion panel was good in sensitivity and image quality.

Claims

請求の範囲 The scope of the claims
[1] 支持体上に少なくとも輝尽性蛍光体層及び軟化点を有する保護層を有する放射線 像変換パネルにおいて、該放射線像変換パネルは、該輝尽性蛍光体層の少なくとも 端部を該保護層と共に封止する、軟化点を有する被覆部を有し、且つ、該保護層の 少なくとも 1層と該被覆部の軟ィ匕点の差が 0〜30°Cであることを特徴とする放射線像 変換パネル。  [1] A radiation image conversion panel having at least a stimulable phosphor layer and a protective layer having a softening point on a support, wherein the radiation image conversion panel protects at least an end of the stimulable phosphor layer. Radiation having a covering portion having a softening point sealed together with a layer, and a difference in soft point between at least one layer of the protective layer and the covering portion is 0 to 30 ° C Image conversion panel.
[2] 前記保護層の少なくとも 1層と前記被覆部はそれぞれ熱可塑性エラストマ一を含有 し、それぞれの熱可塑性エラストマ一は、同一のモノマーユニットを含有してなり、該 同一のモノマーユニットの含有率は、該保護層に含有される熱可塑性エラストマ一を 基準として 30〜100%であることを特徴とする請求の範囲第 1項に記載の放射線像 変換パネル。  [2] At least one layer of the protective layer and the covering portion each contain a thermoplastic elastomer, and each thermoplastic elastomer contains the same monomer unit, and the content of the same monomer unit 2. The radiation image conversion panel according to claim 1, wherein the content is 30 to 100% based on the thermoplastic elastomer contained in the protective layer.
[3] 前記保護層の少なくとも 1層が前記保護層の最外層であることを特徴とする請求の 範囲第 2項に記載の放射線像変換パネル。  [3] The radiation image conversion panel according to claim 2, wherein at least one of the protective layers is an outermost layer of the protective layer.
[4] 前記輝尽性蛍光体層が下記一般式（1)で表される輝尽性蛍光体を含有することを 特徴とする請求の範囲第 1項〜第 3項のいずれ力 1項に記載の放射線像変換パネル 一般式（1) Ba M2 FBr I ： aM1, bLn, cO [4] The stimulating phosphor according to any one of claims 1 to 3, wherein the stimulable phosphor layer contains a stimulable phosphor represented by the following general formula (1): Radiation image conversion panel as described General formula (1) Ba M 2 FBr I: aM 1 , bLn, cO
丄- x x y 1-y  丄-x x y 1-y
(式中、 M1は Li、 Na、 K、 Rb及び Csから選ばれる少なくとも一種のアルカリ金属原子 、 M2は Be、 Mg、 Sr及び Caから選ばれる少なくとも一種のアルカリ土類金属原子、 L nfま Ce、 Pr、 Sm、 Eu、 Gd、 Tb、 Tm、 Dy、 Ho, Nd、 Er及び Yb力ら選 ίま'れる少なく とも一種の希土類元素、 x、 y、 a、 b及び cは、それぞれ 0≤x≤0. 3、 0≤y≤l . 0、 0 ≤a≤0. 05、 0<b≤0. 2、 0< c≤0. 1を表す。） (Wherein M 1 is at least one alkali metal atom selected from Li, Na, K, Rb and Cs, M 2 is at least one alkali earth metal atom selected from Be, Mg, Sr and Ca, L nf also Ce, Pr, Sm, Eu, Gd, Tb, Tm, D y, Ho, Nd, Er and Yb Chikararasen ί or 'at least one rare earth element, x, y, a, b and c, 0≤x≤0. 3, 0≤y≤l. 0, 0 ≤a≤0. 05, 0 <b≤0. 2, 0 <c≤0.1.)
[5] 前記保護層が転写箔で形成されることを特徴とする請求の範囲第 1項〜第 4項の レ、ずれか 1項に記載の放射線像変換パネル。 [5] The radiation image conversion panel according to any one of [1] to [4], wherein the protective layer is formed of a transfer foil.
PCT/JP2006/316447 2005-09-05 2006-08-23 Radiation image transformation panel WO2007029492A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009031159A (en) * 2007-07-27 2009-02-12 Fujifilm Corp Radiation detector
WO2009144982A1 (en) * 2008-05-29 2009-12-03 コニカミノルタエムジー株式会社 Scintillator panel
WO2014128957A1 (en) * 2013-02-25 2014-08-28 株式会社日立製作所 Scintillator and radiation detector
JP2016133346A (en) * 2015-01-16 2016-07-25 浜松ホトニクス株式会社 Radiographic image conversion panel

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002131500A (en) * 2000-10-27 2002-05-09 Konica Corp Radiation image conversion plate and radiation image conversion panel
JP2002148395A (en) * 2000-11-14 2002-05-22 Fuji Photo Film Co Ltd Radiation emission panel
JP2004244447A (en) * 2003-02-12 2004-09-02 Konica Minolta Holdings Inc Stimulable phosphor, method for producing the same and radiological image-converting panel
JP2005114397A (en) * 2003-10-03 2005-04-28 Konica Minolta Medical & Graphic Inc Radiographic image transformation panel, and manufacturing method therefor
JP2005201752A (en) * 2004-01-15 2005-07-28 Konica Minolta Medical & Graphic Inc Stimulable phosphor sheet seal, method for preparing it and sealing bag used for it and such method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002131500A (en) * 2000-10-27 2002-05-09 Konica Corp Radiation image conversion plate and radiation image conversion panel
JP2002148395A (en) * 2000-11-14 2002-05-22 Fuji Photo Film Co Ltd Radiation emission panel
JP2004244447A (en) * 2003-02-12 2004-09-02 Konica Minolta Holdings Inc Stimulable phosphor, method for producing the same and radiological image-converting panel
JP2005114397A (en) * 2003-10-03 2005-04-28 Konica Minolta Medical & Graphic Inc Radiographic image transformation panel, and manufacturing method therefor
JP2005201752A (en) * 2004-01-15 2005-07-28 Konica Minolta Medical & Graphic Inc Stimulable phosphor sheet seal, method for preparing it and sealing bag used for it and such method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009031159A (en) * 2007-07-27 2009-02-12 Fujifilm Corp Radiation detector
WO2009144982A1 (en) * 2008-05-29 2009-12-03 コニカミノルタエムジー株式会社 Scintillator panel
WO2014128957A1 (en) * 2013-02-25 2014-08-28 株式会社日立製作所 Scintillator and radiation detector
JPWO2014128957A1 (en) * 2013-02-25 2017-02-02 株式会社日立製作所 Scintillator and radiation detector
JP2016133346A (en) * 2015-01-16 2016-07-25 浜松ホトニクス株式会社 Radiographic image conversion panel

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