JP6984515B2 - Manufacturing method of scintillator panel and scintillator panel - Google Patents

Description

The present invention relates to a scintillator panel and a method for manufacturing a scintillator panel.

Conventionally, radiographic images using films have been widely used in medical practice. However, the radiographic image using the film is analog image information. Therefore, in recent years, digital radiation detectors such as a flat panel detector (hereinafter referred to as “FPD”) have been developed. The FPD uses a scintillator panel to convert radiation into visible light. The scintillator panel contains a radiation phosphor. Depending on the emitted radiation, the radiation phosphor emits visible light. The emitted light is converted into an electric signal by a TFT (thin film transistor) or a CCD (charge-coupled device), and radiation information is converted into digital image information. However, the FPD has a problem that when the radiation phosphor emits light, the radiation phosphor itself scatters visible light and the sharpness is lowered.

Therefore, in order to reduce the influence of scattering of emitted light, a method has been proposed in which a phosphor is filled in a space partitioned by a partition wall having a reflective layer on the surface, that is, in a cell. As a material for the reflective layer, a method using a powder of a metal oxide having a high refractive index such as titanium oxide powder (Patent Document 1) and a method using a metal having a high reflectance such as silver (Patent Document 2) are known. There is.

International Publication No. 2016/021540 Japanese Unexamined Patent Publication No. 2011-257339

However, the reflective layer using the metal oxide powder described in Patent Document 1 has a low reflectance and a low luminance. Further, in order to obtain high reflectance, it is essential to increase the thickness of the reflective layer. Therefore, the volume inside the cell is reduced by the reflective layer, and the filling amount of the phosphor is reduced. As a result, the brightness of the scintillator panel is reduced. Further, in the method using silver described in Patent Document 2, the metal reflective layer such as silver corrodes, and the reflectance tends to decrease. Therefore, in this method, the initial brightness, which will be described later, is lowered, and pinhole defects are likely to occur in a high temperature and high humidity environment. Further, Patent Document 2 describes that an acrylic protective layer is formed on the surface of silver. However, even in this case, the effect of suppressing the decrease in brightness and pinhole defects is insufficient.

By the way, polysiloxane is known as a resin having excellent properties such as heat resistance, chemical resistance, and transparency. As a result of the studies by the inventors, it was found that by forming the organic protective layer containing polysiloxane, it is possible to suppress the decrease in the initial brightness and the generation of pinhole defects in a high temperature and high humidity environment. However, when general polysiloxane is used as a protective layer for silver, uneven packing occurs due to the polysiloxane repelling the phosphor layer in the process of forming the phosphor layer, and as a result, uneven brightness occurs when the scintillator panel emits light. ..

Therefore, the present invention has been made in view of such conventional problems, and is a scintillator having high brightness and high sharpness, small brightness unevenness, and suppression of pinhole defect generation in a high temperature and high humidity environment. It is an object of the present invention to provide a method for manufacturing a panel and a scintillator panel.

The present invention that solves the above problems mainly includes the following configurations.

（上記一般式（１）中、Ｒ¹は、エポキシ基および酸無水物基のうち少なくともいずれか一方を有する１価の有機基を表す。Ｒ²およびＲ³は、それぞれ、水素、炭素数１〜６のアルキル基、炭素数２〜６のアシル基または炭素数６〜１６のアリール基を表す。ｍは１〜３の整数を表す。ｎは０〜２の整数を表す。ｍ＋ｎは１〜３である。ｍが２以上の場合、複数のＲ¹は、それぞれ同じでも異なってもよい。また、ｎが２の場合、複数のＲ²は、それぞれ同じでも異なってもよい。また、ｍ＋ｎが２以下の場合、複数のＲ³は、それぞれ同じでも異なってもよい。） (1) The partition wall has a phosphor layer in a partition and a cell partitioned by the partition wall, and the partition wall has a metal reflective layer and an organic protective layer containing polysiloxane as a main component, and the polysiloxane is contained. Is a scintillator panel containing a hydrolyzed / partially condensate of an organosilane containing an organosilane represented by the following general formula (1).

(In the above general formula (1), R ¹ represents a monovalent organic group having at least one of an epoxy group and an acid anhydride group. R ² and R ³ are hydrogen and carbon number 1, respectively. Represents an alkyl group of ~ 6, an acyl group of 2 to 6 carbon atoms or an aryl group of 6 to 16 carbon atoms. M represents an integer of 1 to 3. n represents an integer of 0 to 2. M + n represents 1 to 1. If .m is 2 or more and 3, a plurality of R ¹ each may be the same or different. Further, when n is 2, a plurality of R ² may be the same or different from each other. also, m + n If it is 2 or less, more R ³ may be same or different.)

According to such a configuration, the scintillator panel has high brightness and high sharpness, small brightness unevenness, and it is easy to suppress the occurrence of pinhole defects in a high temperature and high humidity environment.

(2) The organosilane represented by the general formula (1) contains at least one of 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane and 3-trialkoxysilylpropylsuccinate anhydride. , (1) The scintillator panel.

With such a configuration, uneven brightness of the scintillator panel and occurrence of pinhole defects in a high temperature and high humidity environment are more likely to be suppressed.

(3) The scintillator according to (1) or (2), wherein the content of the hydrolyzed / partially condensed product of the organosilane represented by the general formula (1) in the organic protective layer is 5 mol% or more. panel.

According to such a configuration, in the scintillator panel, the repelling of the phosphor layer is remarkably suppressed, and the luminance unevenness is likely to be significantly reduced.

(4) The scintillator panel according to any one of claims 1 to 3, wherein the fluorescent material layer has a fluorescent material and a binder resin, and the binder resin is in contact with the organic protective layer.

According to such a configuration, in the scintillator panel, the repelling of the phosphor layer is remarkably suppressed, and the luminance unevenness is likely to be significantly reduced.

(5) The scintillator panel according to any one of (1) to (4), wherein the binder resin contains at least one of an acrylic resin, an acetal resin and a cellulose derivative.

According to such a configuration, the scintillator panel is less likely to be repelled by the organic protective layer, and the occurrence of luminance unevenness is more likely to be suppressed.

(6) The scintillator panel according to any one of (1) to (5), wherein the metal reflective layer contains silver as a main component.

According to such a configuration, the scintillator panel tends to have higher brightness.

(7) The scintillator panel according to (6), wherein the metal reflective layer contains a silver alloy containing at least one of palladium and copper.

With such a configuration, the scintillator panel is more resistant to discoloration in the atmosphere.

(8) The scintillator panel according to any one of (1) to (7), wherein the partition wall contains 98% by volume or more of low softening point glass having a softening point of 650 ° C. or less.

According to such a configuration, the scintillator panel tends to have a higher initial brightness.

（上記一般式（１）中、Ｒ¹は、エポキシ基および酸無水物基のうち少なくともいずれか一方を有する１価の有機基を表す。Ｒ²およびＲ³は、それぞれ、水素、炭素数１〜６のアルキル基、炭素数２〜６のアシル基または炭素数６〜１６のアリール基を表す。ｍは１〜３の整数を表す。ｎは０〜２の整数を表す。ｍ＋ｎは１〜３である。ｍが２以上の場合、複数のＲ¹は、それぞれ同じでも異なってもよい。また、ｎが２の場合、複数のＲ²は、それぞれ同じでも異なってもよい。また、ｍ＋ｎが２以下の場合、複数のＲ³は、それぞれ同じでも異なってもよい。） (9) A partition wall forming step of forming a partition wall on a substrate to partition cells, a reflective layer forming step of forming a metal reflective layer on the surface of the partition wall, and an organic protective layer on the surface of the reflective layer. The organic protective layer comprises a step of forming an organic protective layer and a step of filling a cell partitioned by the partition wall with a phosphor, wherein the organic protective layer contains polysiloxane as a main component, and the polysiloxane is described below. A method for producing a scintillator panel, which comprises a hydrolyzed / partially condensate of an organosilane containing an organosilane represented by the general formula (1).

(In the above general formula (1), R ¹ represents a monovalent organic group having at least one of an epoxy group and an acid anhydride group. R ² and R ³ are hydrogen and carbon number 1, respectively. Represents an alkyl group of ~ 6, an acyl group of 2 to 6 carbon atoms or an aryl group of 6 to 16 carbon atoms. M represents an integer of 1 to 3. n represents an integer of 0 to 2. M + n represents 1 to 1. If .m is 2 or more and 3, a plurality of R ¹ each may be the same or different. Further, when n is 2, a plurality of R ² may be the same or different from each other. also, m + n If it is 2 or less, more R ³ may be same or different.)

According to such a configuration, the obtained scintillator panel has high luminance and high sharpness, small luminance unevenness, and easy to suppress the occurrence of pinhole defects in a high temperature and high humidity environment.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a scintillator panel and a method for manufacturing a scintillator panel, which have high luminance and high sharpness, small luminance unevenness, and suppressed generation of pinhole defects in a high temperature and high humidity environment. ..

FIG. 1 is a sectional view schematically showing a member for a radiation detector including a scintillator panel according to an embodiment of the present invention. FIG. 2 is a sectional view schematically showing a scintillator panel according to an embodiment of the present invention.

<Scintillator panel>
Hereinafter, a specific configuration of the scintillator panel according to the embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing a radiation detector member 1 including the scintillator panel 2 of the present embodiment. The radiation detector member 1 has a scintillator panel 2 and an output board 3. The scintillator panel 2 has a substrate 4, a partition wall 5, and a phosphor layer 6 in a cell partitioned by the partition wall 5. The output substrate 3 has a substrate 10, an output layer 9 formed on the substrate 10, and a photoelectric conversion layer 8 having a photodiode formed on the output layer 9. A diaphragm layer 7 may be provided on the photoelectric conversion layer 8. It is preferable that the light emitting surface of the scintillator panel 2 and the photoelectric conversion layer 8 of the output substrate 3 are adhered or adhered to each other via the diaphragm layer 7. The light emitted by the phosphor layer 6 reaches the photoelectric conversion layer 8, is photoelectrically converted, and is output. Each will be described below.

(Board 4)
The substrate 4 is a member preferably provided in the scintillator panel 2 of the present embodiment, and is not essential. The material constituting the substrate 4 is preferably a material having radiation permeability. As an example, the materials constituting the substrate 4 are various types of glass, polymer materials, metals and the like. The glass is quartz, borosilicate glass, chemically tempered glass, or the like. The polymer compound is polyester such as cellulose acetate or polyethylene terephthalate, polyamide, polyimide, triacetate, polycarbonate, carbon fiber reinforced resin and the like. The metal is aluminum, iron, copper or the like. This may be used in combination. Among these, the material constituting the substrate 4 is preferably a polymer material having high radiation permeability. Further, the material constituting the substrate 4 is preferably a material having excellent flatness and heat resistance.

From the viewpoint of reducing the weight of the scintillator panel 2, the thickness of the substrate 4 is preferably 2.0 mm or less, more preferably 1.0 mm or less in the case of a glass substrate. Further, the thickness of the substrate 4 is preferably 3.0 mm or less in the case of a substrate made of a polymer material.

(Partition wall 5)
The partition wall 5 is provided to form at least a partitioned space (cell). The partition wall 5 has a metal reflective layer 11 and an organic protective layer 12 containing polysiloxane as a main component. The metal reflective layer 11 and the organic protective layer 12 may be provided on at least a part of the partition wall 5.

-Metal reflective layer 11
The metal reflective layer 11 has a high reflectance even if it is a thin film. Therefore, by providing the metal reflective layer 11 which is a thin film, the filling amount of the phosphor 13 is unlikely to decrease, and the brightness of the scintillator panel 2 tends to be improved. The metal constituting the metal reflective layer 11 is not particularly limited. As an example, the metal reflective layer 11 preferably contains a metal having a high reflectance such as silver or aluminum as a main component, and more preferably contains silver as a main component. The metal reflective layer 11 may be an alloy. The metal reflective layer 11 is particularly preferably a silver alloy containing palladium and copper. The metal reflective layer 11 made of such a silver alloy has excellent discoloration resistance in the atmosphere. In addition, in this embodiment, "containing as a main component" means that a predetermined component is contained in an amount of 50 to 100% by mass.

The thickness of the metal reflective layer 11 is not particularly limited. As an example, the thickness of the metal reflective layer 11 is preferably 10 nm or more, and more preferably 50 nm or more. The thickness of the metal reflective layer 11 is preferably 500 nm or less, more preferably 300 nm or less. When the thickness of the metal reflective layer 11 is 10 nm or more, the scintillator panel 2 can obtain sufficient light shielding properties and further improve the sharpness. When the thickness of the metal reflective layer 11 is 500 nm or less, the unevenness of the surface of the metal reflective layer 11 is less likely to increase, and the reflectance is less likely to decrease.

The arithmetic mean inclination angle of the surface of the metal reflective layer 11 is not particularly limited. As an example, the arithmetic mean tilt angle is preferably 20 ° or less, and more preferably 10 ° or less. When the arithmetic mean inclination angle is 20 ° or less, the flatness of the metal reflective layer 11 is high, so that the scintillator panel 2 has a high reflectance and the brightness is more likely to be improved. In the present embodiment, the arithmetic mean inclination angle is such that the side surface of the partition wall 5 on which the metal reflective layer 11 is formed is exposed by cutting the substrate or the like, and the partition wall 5 is used with a laser microscope (for example, manufactured by KEYENCE CORPORATION). It can be measured by observing the side surface of.

Here, the cell-type scintillator having a metal reflective layer has problems such as a decrease in initial brightness due to corrosion of the metal reflective layer and occurrence of pinhole defects in a high temperature and high humidity environment. The decrease in the initial brightness means that the actual brightness is lower than the brightness of the scintillator panel assumed from the original reflectance of the metal reflective layer. This is because when the metal reflective layer is formed or when the phosphor layer is formed after the metal reflective layer is formed, the components on the partition wall surface and the components in the phosphor layer react with the metal reflective layer, and the metal reflective layer is corroded. It is presumed that this is due to the decrease in reflectance. In addition, pinhole defects in a high temperature and high humidity environment mean that when the scintillator panel after fabrication is exposed to high temperature and high humidity, the brightness of the scintillator panel is extremely reduced in a narrow area of about one cell to several cells. , Refers to the problem of becoming a dark spot during X-ray irradiation. Since the cause of this occurrence tends to occur from a minute unformed region of the metal reflective layer, it is electrochemically generated by direct contact with high-temperature water vapor at the boundary between the formed region and the unformed region of the metal reflective layer. It is presumed that the corrosion reaction is caused by the local concentration. Since the temperature of the X-ray detector rises during use and is affected by the water vapor contained in the atmosphere, pinhole defects that occur in the scintillator in a high temperature and high humidity environment are long-term defects of the X-ray detector. It also occurs with use. Therefore, it is necessary to suppress the occurrence of pinhole defects in a high temperature and high humidity environment. In the scintillator panel 2 of the present embodiment, these problems are solved by forming the organic protective layer 12 described later.

In the scintillator panel 2 of the present embodiment, it is preferable that an inorganic protective layer is formed on the metal reflective layer 11. In a high temperature and high humidity environment, the metal reflective layer may be corroded by the high temperature steam even in a place where the above-mentioned pinhole defect does not occur, and the brightness may decrease on almost the entire surface of the scintillator panel. The inorganic protective layer has low water vapor permeability. Therefore, the scintillator panel 2 provided with such an inorganic protective layer tends to suppress a decrease in brightness in a high temperature and high humidity environment.

The inorganic protective layer can be formed by a known method such as a sputtering method. The material of the inorganic protective layer is not particularly limited. For example, the material of the inorganic protective layer is an oxide such as silicon oxide, indium tin oxide, zinc oxide, a nitride such as silicon nitride, or a fluoride such as magnesium fluoride. Among these, silicon nitride is particularly preferable as the material of the inorganic protective layer because it has low water vapor permeability and the reflectance of silver does not easily decrease in the formation of the inorganic protective layer. When silicon oxide is used, in order to suppress discoloration of the metal reflective layer 11, an inorganic protective layer other than silicon oxide is formed on the metal reflective layer 11, and then an inorganic protective layer of silicon oxide is formed on the inorganic protective layer. It is preferable to form.

The thickness of the inorganic protective layer is not particularly limited. As an example, the thickness of the inorganic protective layer is preferably 2 nm or more, and more preferably 5 nm or more. The thickness of the inorganic protective layer is preferably 200 nm or less, more preferably 100 nm or less. When the thickness is 2 nm or more, the scintillator panel 2 can further increase the effect of suppressing the decrease in brightness in a high temperature and high humidity environment. When the thickness is 200 nm or less, coloring of the inorganic protective layer can be suppressed and the brightness can be further improved. The thickness of the inorganic protective layer can be measured by exposing a cross section perpendicular to the partition wall substrate with a polishing device such as a cross section polisher and observing it with a scanning electron microscope or a transmission electron microscope. The inorganic protective layer formed in the inorganic protective layer forming step described later tends to be thick in the vicinity of the top of the partition wall and thin in the side surface near the bottom. Therefore, when there is such a difference in thickness, the thickness of the inorganic protective layer refers to the thickness on the side surface of the central portion in the height direction of the partition wall.

・ Organic protective layer 12
The organic protective layer 12 contains polysiloxane as a main component. By forming the organic protective layer 12 containing polysiloxane as a main component, the initial brightness of the scintillator panel 2 is improved. Further, in the scintillator panel 2, pinhole defects are remarkably suppressed in a high temperature and high humidity environment, and a decrease in brightness is also suppressed. When polysiloxane is not contained as a main component, the scintillator panel 2 lacks heat resistance, chemical resistance, transparency, flatness, etc., and has an effect of improving initial brightness and pinholes in a high temperature and high humidity environment. Defect suppression effect becomes insufficient.

As shown in FIG. 1, the organic protective layer 12 may be formed on the metal reflective layer 11 or may be formed between the partition wall 5 and the metal reflective layer 11. In either case, the initial brightness of the scintillator panel 2 is improved, and pinhole defects and brightness reduction in a high temperature and high humidity environment are suppressed.

When the organic protective layer 12 is formed on the metal reflective layer 11, the scintillator panel 2 reflects the metal reflective layer 11 by the reaction between the metal reflective layer 11 and the phosphor layer 6 when the scintillator panel 6 is formed. The rate decrease is suppressed and the initial brightness is improved. Further, in the scintillator panel 2, the minute metal reflective layer non-formed region of the metal reflective layer 11 that causes pinhole defects is covered with the organic protective layer 12. As a result, the scintillator panel 2 suppresses direct contact with high-temperature steam, and pinhole defects are suppressed. Further, in the scintillator panel 2, the high temperature water vapor transmitted through the phosphor layer 6 side is suppressed from penetrating to the metal reflective layer 11, the decrease in the reflectance of the entire metal reflective layer 11 is suppressed, and the temperature and humidity are high. The decrease in brightness is suppressed.

When the organic protective layer 12 is formed between the partition wall 5 and the metal reflective layer 11, the scintillator panel 2 suppresses the reaction between the partition wall component and the metal reflective layer 11. Further, in the scintillator panel 2, the surface of the partition wall 5 is flattened, the reflectance of the metal reflective layer 11 is improved, and the initial brightness is improved. Further, the scintillator panel 2 is covered with protrusions and dents on the surface of the partition wall 5, and unformed regions of the metal reflective layer 11 that cause pinhole defects are less likely to occur, and pinhole defects are suppressed. Further, in the scintillator panel 2, the surface area of the metal reflective layer 11 is reduced by flattening, the reaction with high temperature water vapor is suppressed, and the decrease in brightness in a high temperature and high humidity environment is suppressed.

The thickness of the organic protective layer 12 is preferably 0.05 μm or more, and more preferably 0.2 μm or more. The thickness of the organic protective layer 12 is preferably 10 μm or less, and more preferably 5 μm or less. When the thickness of the organic protective layer 12 is 0.05 μm or more, the scintillator panel 2 can further enhance the effects of improving the initial luminance and suppressing pinhole defects. Further, when the thickness of the organic protective layer 12 is 10 μm or less, the scintillator panel 2 can further improve the brightness by increasing the volume in the cell and increasing the filling amount of the phosphor 13. In the present embodiment, the thickness of the organic protective layer 12 can be measured by observation with a scanning electron microscope. The organic protective layer 12 formed in the organic protective layer forming step described later tends to be thin on the side surface near the top of the partition wall and thick on the side surface near the bottom. Therefore, when there is such a difference in thickness, the thickness of the organic protective layer 12 refers to the thickness on the side surface of the central portion in the height direction of the partition wall 5.

（上記一般式（１）中、Ｒ¹は、エポキシ基および酸無水物基のうち少なくともいずれか一方を有する１価の有機基を表す。Ｒ²およびＲ³は、それぞれ、水素、炭素数１〜６のアルキル基、炭素数２〜６のアシル基または炭素数６〜１６のアリール基を表す。ｍは１〜３の整数を表す。ｎは０〜２の整数を表す。ｍ＋ｎは１〜３である。ｍが２以上の場合、複数のＲ¹は、それぞれ同じでも異なってもよい。また、ｎが２の場合、複数のＲ²は、それぞれ同じでも異なってもよい。また、ｍ＋ｎが２以下の場合、複数のＲ³は、それぞれ同じでも異なってもよい。）なお、Ｒ¹におけるエポキシ基および酸無水物基とは、それぞれ下記化学式（２）および化学式（３）の構造を表す。 In the present embodiment, the polysiloxane which is the main component of the organic protective layer 12 contains a hydrolyzed / partially condensate of organosilane including organosilane represented by the following general formula (1).

(In the above general formula (1), R ¹ represents a monovalent organic group having at least one of an epoxy group and an acid anhydride group. R ² and R ³ are hydrogen and carbon number 1, respectively. Represents an alkyl group of ~ 6, an acyl group of 2 to 6 carbon atoms or an aryl group of 6 to 16 carbon atoms. M represents an integer of 1 to 3. n represents an integer of 0 to 2. M + n represents 1 to 1. If .m is 2 or more and 3, a plurality of R ¹ each may be the same or different. Further, when n is 2, a plurality of R ² may be the same or different from each other. also, m + n If is 2 or less, more R ³ are each also different may.) Note that the same, as the epoxy group and acid anhydride groups in R ^1, each following chemical formula (2) and formula the structure of (3) show.

When the scintillator panel 2 does not contain a hydrolyzed / partially condensate of an organosilane containing an organosilane represented by the general formula (1), the scintillator panel 2 is formed by polysiloxane forming the phosphor layer 6 in the step of forming the phosphor layer 6. By repelling, uneven filling occurs, and as a result, uneven brightness occurs. Further, in this case, the scintillator panel 2 also causes uneven brightness even when the organic protective layer 12 is formed between the partition wall 5 and the metal reflective layer 11. It is considered that this is because a part of the components of the organic protective layer 12 passes through the metal reflective layer 11 and moves to the surface of the metal reflective layer 11 to repel the phosphor layer 6. On the other hand, since the scintillator panel 2 of the present embodiment contains a hydrolyzed / partially condensate of organosilane containing the organosilane represented by the above general formula (1), the repelling of the phosphor layer 6 is suppressed and the luminance unevenness is suppressed. Is suppressed.

The organosilane represented by the general formula (1) is not particularly limited. As an example, the organosilane represented by the general formula (1) is 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, 3-trialkoxysilylpropyl succinate anhydride, 3-glycidoxypropyl. Trialkoxysilane, 3-glycidoxypropylmethyldialkoxysilane and the like. Among these, the organosilane represented by the general formula (1) is at least one of 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane and 3-trialkoxysilylpropylsuccinate anhydride. It is preferable to include it. As a result, uneven brightness of the scintillator panel and occurrence of pinhole defects in a high temperature / high humidity environment are more likely to be suppressed.

In the polysiloxane containing the hydrolysis / partial condensation product of the organosilane represented by the general formula (1), the epoxy group and the acid anhydride group are in the hydrolysis / partial condensation reaction of the polysiloxane. Part or all of it may be open.

The content of the hydrolyzed / partially condensate of organosilane represented by the above general formula (1) in the organic protective layer 12 is not particularly limited. Here, the content of the hydrolyzed / partially condensate of the organosilane represented by the general formula (1) is the hydrolysis / partial condensate of the organosilane represented by the general formula (1) and another organosilane. In the case of, it means the content of the structural unit derived from the organosilane represented by the general formula (1). As an example, the content of the hydrolyzed / partially condensate of organosilane represented by the above general formula (1) is preferably 5 mol% or more, and more preferably 10 mol% or more. When the content of the hydrolyzed / partially condensed product of the organosilane represented by the general formula (1) is 5 mol% or more, the repelling of the phosphor layer 6 is remarkably suppressed in the scintillator panel 2, and the brightness is increased. Unevenness is greatly reduced.

Returning to the description of the partition wall 5 as a whole, the partition wall 5 is preferably made of an inorganic substance in order to increase the strength and heat resistance. The inorganic substance refers to a simple partial carbon compound (allotrope of carbon such as graphite or diamond) and a compound composed of elements other than carbon. In addition, "consisting of an inorganic substance" does not exclude the existence of components other than the inorganic substance in a strict sense, but is about impurities contained in the inorganic substance itself as a raw material and impurities mixed in the process of manufacturing the partition wall 5. The presence of non-inorganic components is permissible.

The partition wall 5 preferably contains glass as a main component. Glass refers to an inorganic amorphous solid containing silicate. When the main component of the partition wall 5 is glass, the partition wall 5 has increased strength and heat resistance, and is less likely to be deformed or damaged in the process of forming the metal reflective layer 11 and the step of filling the phosphor 13. In addition, "having glass as a main component" means that 50 to 100% by mass of the material constituting the partition wall 5 is glass.

The partition wall 5 preferably contains 95% by volume or more of low softening point glass having a softening point of 650 ° C. or lower, and more preferably 98% by volume or more. When the content of the low softening point glass is 95% by volume or more, the surface of the partition wall 5 tends to be flattened in the firing step. As a result, in the scintillator panel 2, the arithmetic mean inclination angle of the surface of the metal reflective layer 11 when the metal reflective layer 11 is formed on the surface of the partition wall 5 becomes small, the reflectance becomes high, and the initial brightness tends to be higher. The arithmetic mean inclination angle of the surface of the metal reflective layer 11 can be measured by cutting the partition wall substrate to expose the cross section, imaging the side surface of the partition wall 5 with a laser microscope, and performing image analysis.

The components other than the low softening point glass contained in the partition wall 5 are high softening point glass powder, ceramic powder and the like. These powders make it easy to adjust the shape of the partition wall 5 in the partition wall forming step. In order to increase the content of the low softening point glass, the content of the components other than the low softening point glass is preferably less than 5% by volume.

FIG. 2 is a schematic cross-sectional view of the scintillator panel 2 of the present embodiment. The height L1 of the partition wall 5 is preferably 50 μm or more, and more preferably 70 μm or more. The height of the partition wall 5 is preferably 3000 μm or less, more preferably 1000 μm or less. When L1 is 3000 μm or less, absorption of emitted light by the phosphor 13 itself is unlikely to occur, and the brightness of the scintillator panel 2 is unlikely to decrease. On the other hand, when L1 is 50 μm or more, the amount of the phosphor 13 that can be filled in the scintillator panel 2 becomes appropriate, and the brightness is less likely to decrease.

The distance L2 between the adjacent partition walls 5 is preferably 30 μm or more, and more preferably 50 μm or more. The spacing L2 between the partition walls 5 is preferably 1000 μm or less, and more preferably 500 μm or less. When L2 is 30 μm or more, the scintillator panel 2 can easily fill the cell with the phosphor 13. On the other hand, when L2 is 1000 μm or less, the scintillator panel 2 is more excellent in sharpness.

The bottom width L3 of the partition wall 5 is preferably 5 μm or more, and more preferably 10 μm or more. The bottom width L3 is preferably 150 μm or less, and more preferably 50 μm or less. When L3 is 5 μm or more, the scintillator panel 2 is less likely to have a pattern defect. On the other hand, when L3 is 150 μm or less, the amount of the phosphor 13 that can be filled in the scintillator panel 2 becomes appropriate, and the brightness is less likely to decrease.

The top width L4 of the partition wall 5 is preferably 3 μm or more, and more preferably 5 μm or more. The top width L4 is preferably 80 μm or less, and more preferably 50 μm or less. When L4 is 3 μm or more, the strength of the partition wall 5 of the scintillator panel 2 becomes appropriate, and pattern defects are less likely to occur. On the other hand, when L4 is 80 μm or less, the scintillator panel 2 has an appropriate region from which the emitted light of the phosphor 13 can be taken out, and the brightness is less likely to decrease.

The aspect ratio (L1 / L3) of the height L1 of the partition wall 5 with respect to the bottom width L3 of the partition wall 5 is preferably 1.0 or more, and more preferably 2.0 or more. The aspect ratio (L1 / L3) is preferably 100.0 or less, and more preferably 50.0 or less. When the aspect ratio (L1 / L3) is 1.0 or more, the scintillator panel 2 tends to have an appropriate filling amount of the phosphor 13. Further, when the aspect ratio (L1 / L3) is 100.0 or less, the scintillator panel 2 tends to have appropriate partition wall strength.

The aspect ratio (L1 / L2) of the height L1 of the partition wall 5 with respect to the distance L2 of the partition wall 5 is preferably 0.5 or more, and more preferably 1.0 or more. The aspect ratio (L1 / L2) is preferably 20.0 or less, and more preferably 10.0 or less. Since the aspect ratio (L1 / L2) is 0.5 or more, the scintillator panel 2 is unlikely to have a low X-ray absorption efficiency. Further, when the aspect ratio (L1 / L2) is 20.0 or less, the scintillator panel 2 is less likely to reduce the light extraction efficiency and the brightness.

The height L1 of the partition wall 5 and the distance L2 of the adjacent partition walls 5 shall be cut in a cross section perpendicular to the substrate or exposed by a polishing device such as a cross section polisher, and the cross section shall be observed with a scanning electron microscope. Can be measured by. Here, the width of the partition wall 5 at the contact portion between the partition wall 5 and the substrate is L3. Further, the width of the uppermost portion of the partition wall 5 is L4.

In the scintillator panel 2 of the present embodiment, each cell is partitioned by a partition wall 5. Therefore, in the scintillator panel 2, by matching the size and pitch of the pixels of the photoelectric conversion element arranged in a grid pattern with the size and pitch of the cells of the scintillator panel 2, each pixel of the photoelectric conversion element and the pitch are matched. Each cell of the scintillator panel 2 can be associated with each other. As a result, the scintillator panel 2 can easily obtain high sharpness.

(Fluorescent layer 6)
The phosphor layer 6 is formed in a cell partitioned by a partition wall 5. The phosphor layer 6 absorbs the energy of radiation such as incident X-rays and emits electromagnetic waves having a wavelength in the range of 300 nm to 800 nm, that is, light in the range from ultraviolet light to infrared light centered on visible light. .. The light emitted by the phosphor layer 6 is photoelectrically converted by the photoelectric conversion layer 8 and output as an electric signal through the output layer 9. The fluorescent material layer 6 preferably has the fluorescent material 13 and the binder resin 14.

・ Fluorescent material 13
The phosphor 13 is not particularly limited. As an example, the phosphor 13 has a high conversion rate from radiation to visible light, CsI, Gd ₂ O ₂ S, Lu ₂ O ₂ S, Y ₂ O ₂ S, LaCl ₃ , LaBr ₃ , LaI ₃ , CeBr is _{3, CeI 3, LuSiO 5,} Ba (Br, F) or the like.

An activator may be added to the phosphor 13 in order to increase the luminous efficiency. The activator is not particularly limited. For example, the activators are sodium (Na), indium (In), thallium (Tl), lithium (Li), potassium (K), rubidium (Rb), sodium (Na), terbinium (Tb), cerium. (Ce), europium (Eu), praseodymium (Pr) and the like. Among these, the fluorescent substance 13 is preferably a fluorescent substance (hereinafter, “GOS: Tb”) in which Tb is added to _{Gd 2} O ₂ S from the viewpoint of high chemical stability and high luminous efficiency. ..

-Binder resin 14
The binder resin 14 is not particularly limited. As an example, the binder resin 14 is a thermoplastic resin, a thermosetting resin, a photocurable resin, or the like. More specifically, the binder resin 14 is a polyester resin such as acrylic resin, acetal resin, cellulose derivative, polysiloxane resin, epoxy resin, melamine resin, phenol resin, urea resin, vinyl chloride resin, polyethylene terephthalate and polyethylene naphthalate. , Polypropylene, Polypropylene, Polystyrene, Polyvinyltoluene, Polyphenylbenzene and the like. Among these, the binder resin 14 preferably contains at least one of an acrylic resin, an acetal resin and a cellulose derivative, and more preferably contains 1 to 3 of these as a main component. As a result, the scintillator panel 2 is less likely to be repelled by the organic protective layer 12, and the occurrence of luminance unevenness is likely to be suppressed. In addition, when at least one of the acrylic resin, the acetal resin and the cellulose derivative is used as the main component, the total amount of the acrylic resin, the acetal resin and the cellulose derivative is 50 to 100% by mass of the material constituting the resin. Say that.

The binder resin 14 is preferably in contact with the organic protective layer 12. In this case, the binder resin 14 may be in contact with at least a part of the organic protective layer 12. As a result, in the scintillator panel 2, the phosphor 13 is less likely to fall out of the cell. As shown in FIG. 1, the binder resin 14 may be filled in the cell with almost no voids, or may be filled so as to have voids.

As described above, according to the scintillator panel 2 of the present embodiment, the luminance and sharpness are high, the luminance unevenness is small, and the occurrence of defects in a high temperature and high humidity environment is easily suppressed.

<Manufacturing method of scintillator panel>
The method for manufacturing a scintillator panel according to an embodiment of the present invention includes a partition wall forming step of forming a partition wall on a substrate to partition cells, and a reflective layer forming step of forming a metal reflective layer on the surface of the partition wall. It includes an organic protective layer forming step of forming an organic protective layer on the surface of the reflective layer, and a filling step of filling a cell partitioned by a partition wall with a phosphor. Hereinafter, each step will be described. In the following description, the items common to the items described in the above-described embodiment of the scintillator panel will be omitted as appropriate.

(Partition wall forming process)
The partition wall forming step is a step of forming a partition wall on the base material. The method of forming the partition wall on the substrate is not particularly limited. As a method for forming the partition wall, various known methods can be used, and the photosensitive paste method is preferable because the shape can be easily controlled.

For a partition wall containing glass as a main component, for example, a coating step of applying a photosensitive paste containing glass powder to the surface of a base material to obtain a coating film, and an exposure and development of the coating film are performed to bake the partition wall. It can be formed by a pattern forming step of obtaining a pre-pattern and a firing step of firing the pattern to obtain a partition wall pattern.

-Coating step The coating step is a step of applying the glass powder-containing paste to the surface of the base material on the entire surface or partially to obtain a coating film. As the base material, a highly heat-resistant support such as a glass plate or a ceramic plate can be used. Examples of the method for applying the glass powder-containing paste include a screen printing method, a bar coater, a roll coater, a die coater or a blade coater. The thickness of the obtained coating film can be adjusted by the number of coatings, the mesh size of the screen, the viscosity of the paste, and the like.

In order to produce a partition wall containing glass as a main component, it is necessary that 50 to 100% by mass of the inorganic component contained in the glass powder-containing paste used in the coating step is glass powder.

The glass powder contained in the glass powder-containing paste is preferably glass that softens at the firing temperature, and more preferably low softening point glass having a softening temperature of 650 ° C. or lower. The softening temperature is determined by tangentially determining the endothermic end temperature at the endothermic peak from the DTA curve obtained by measuring the sample using a differential thermal analyzer (for example, differential differential thermal balance TG8120; manufactured by Rigaku Co., Ltd.). It can be obtained by extrapolation. More specifically, first, using a differential thermal analyzer, the temperature is raised from room temperature to 20 ° C./min using an alumina powder as a standard sample, and the inorganic powder as a measurement sample is measured to obtain a DTA curve. Then, the softening point Ts obtained by extrapolating the third inflection point in the obtained DTA curve by the tangential method can be used as the softening temperature.

In order to obtain a low softening point glass, a metal oxide selected from the group consisting of lead oxide, bismuth oxide, zinc oxide and alkali metal oxides, which are effective compounds for reducing the softening point of the glass, is used. be able to. It is preferable to adjust the softening temperature of the glass by using an oxide of an alkali metal. The alkali metal refers to a metal selected from the group consisting of lithium, sodium and potassium.

The proportion of the alkali metal oxide in the low softening point glass is preferably 2% by mass or more, and more preferably 5% by mass or more. The proportion of the alkali metal oxide in the low softening point glass is preferably 20% by mass or less, and more preferably 15% by mass or less. When the proportion of the alkali metal oxide is 2% by mass or more, the softening temperature becomes appropriate, it is less likely that the firing step needs to be performed at a high temperature, and defects are less likely to occur in the partition wall. On the other hand, when the proportion of the alkali metal oxide is 20% by mass or less, the viscosity of the glass is less likely to be excessively lowered in the firing step, and the shape of the obtained lattice-shaped post-firing pattern is less likely to be distorted.

The low softening point glass preferably contains 3 to 10% by mass of zinc oxide in order to appropriately adjust the viscosity at high temperature. Since the proportion of zinc oxide in the low softening point glass is 3% by mass or more, the low softening point glass tends to have an appropriate viscosity at a high temperature. On the other hand, when the zinc oxide content is 10% by mass or less, the manufacturing cost of the low softening point glass tends to be appropriate.

The low softening point glass is at least one selected from the group consisting of oxides of silicon oxide, boron oxide, aluminum oxide and alkaline earth metals for the adjustment of stability, crystallinity, transparency, refraction or thermal expansion properties. It preferably contains a metal oxide of the species. Here, the alkaline earth metal refers to a metal selected from the group consisting of magnesium, calcium, barium and strontium. An example of the composition range of the preferred low softening point glass is shown below.
Alkali metal oxide: 2 to 20% by mass
Zinc oxide: 3-10% by mass
Silicon oxide: 20-40% by mass
Boron oxide: 25-40% by mass
Aluminum oxide: 10 to 30% by mass
Alkaline earth metal oxide: 5 to 15% by mass

The particle size of the inorganic powder including the glass powder can be measured using a particle size distribution measuring device, for example, MT3300 (manufactured by Nikkiso Co., Ltd.). More specifically, the particle size can be measured after the inorganic powder is put into a sample chamber of a particle size distribution measuring device filled with water and ultrasonically treated for 300 seconds.

The 50% volume average particle diameter (hereinafter, “D50”) of the low softening point glass powder is preferably 1.0 μm or more, and more preferably 2.0 μm or more. The D50 is preferably 4.0 μm or less, more preferably 3.0 μm or less. When D50 is 1.0 μm or more, the glass powder is less likely to aggregate, uniform dispersibility can be obtained, and the flow stability of the obtained paste becomes appropriate. On the other hand, when D50 is 4.0 μm or less, the surface unevenness of the post-firing pattern obtained in the firing step is less likely to increase, and it is less likely to cause the partition wall to be destroyed after the fact.

In addition to the low softening point glass, the glass powder-containing paste is a high softening point glass having a softening temperature of more than 700 ° C. Ceramic particles such as silicon oxide, aluminum oxide, titanium oxide or zirconium oxide may be contained as a filler. The ratio of the filler to the total inorganic component is preferably 2% by volume or less in order to improve the flatness of the partition wall. The filler D50 is preferably the same as the low softening point glass powder.

The photosensitive glass powder-containing paste suppresses light scattering during exposure and forms a highly accurate pattern. Therefore, the refractive index n1 of the glass powder and the refractive index n2 of the organic component are -0.1 <n1. It is preferable to satisfy the relationship of −n2 <0.1, more preferably the relationship of −0.01 ≦ n1-n2 ≦ 0.01, and the relationship of −0.005 ≦ n1-n2 ≦ 0.005. It is even more preferable to meet. The refractive index of the glass powder can be appropriately adjusted depending on the composition of the metal oxide contained in the glass powder.

The refractive index of the glass powder can be measured by the Becke line detection method. Further, the refractive index of the organic component can be obtained by measuring the coating film composed of the organic component by ellipsometry. More specifically, the refractive index (ng) of the glass powder or the organic component at a wavelength of 436 nm (g line) at 25 ° C. can be set to n1 or n2, respectively.

The photosensitive organic component contained in the photosensitive glass powder-containing paste is not particularly limited. As an example, the photosensitive organic component is a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer. The photosensitive monomer, the photosensitive oligomer, and the photosensitive polymer refer to a monomer, an oligomer, and a polymer whose chemical structure changes by causing a reaction such as photocrosslinking or photopolymerization by irradiation with active light.

The photosensitive monomer is preferably a compound having an active carbon-carbon unsaturated double bond. Examples of such compounds include compounds having a vinyl group, an acryloyl group, a methacryloyl group or an acrylamide group. The photosensitive monomer is preferably a polyfunctional acrylate compound or a polyfunctional methacrylate compound in order to increase the density of photocrosslinking and form a highly accurate pattern.

The photosensitive oligomer or polymer is preferably an oligomer or polymer having an active carbon-carbon unsaturated double bond and having a carboxyl group. Such oligomers or polymers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate or their acid anhydrides, methacrylic acid esters, acrylic acid esters, styrene. , Acrylonitrile, vinyl acetate or 2-hydroxyacrylate, an oligomer or polymer obtained by copolymerizing. A method of introducing an active carbon-carbon unsaturated double bond into an oligomer or polymer is, for example, for a mercapto group, an amino group, a hydroxyl group or a carboxyl group of the oligomer or polymer, such as acrylic acid chloride, methacrylate chloride or allyl. Examples thereof include a method of reacting a carboxylic acid such as a chloride, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, or maleic acid.

By using a photosensitive monomer or a photosensitive oligomer having a urethane bond, a glass powder-containing paste that can relieve stress at the initial stage of the firing step and is less likely to cause pattern defects in the firing step can be obtained. The photosensitive glass powder-containing paste may contain a photopolymerization initiator, if necessary. The photopolymerization initiator is a compound that generates radicals when irradiated with active light.

The photopolymerization initiator is not particularly limited. For example, the photopolymerization initiators are benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-. Benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2- Isopropylthioxanthone, diethylthioxanthone, benzyl, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butyl anthraquinone, antron, benzanthron, dibenzosverone, methyleneanthron, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 1-phenyl-1,2-butadion-2- (O-methoxycarbonyl) oxime, 1-Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenylpropanthrion-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2 -(O-benzoyl) oxime, Michler ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanol, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Butanon-1, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, benzoin peroxide or photoreducing dyes such as eosin or methylene blue and ascorbic acid or triethanolamine, etc. It is a combination of a reducing agent with and the like.

Since the photosensitive glass powder-containing paste contains a polymer having a carboxyl group as the photosensitive polymer, the photosensitive glass powder-containing paste has improved solubility in an alkaline aqueous solution during development. The acid value of the polymer having a carboxyl group is preferably 50 to 150 mgKOH / g. When the acid value is 150 mgKOH / g or less, the development margin becomes wide. On the other hand, when the acid value is 50 mgKOH / g or more, the photosensitive glass powder-containing paste does not deteriorate in solubility in an alkaline aqueous solution, and a high-definition pattern can be obtained.

The photosensitive glass powder-containing paste can be obtained by blending various components so as to have a predetermined composition and then uniformly mixing and dispersing them with a three-roller or a kneader.

The viscosity of the photosensitive glass powder-containing paste can be appropriately adjusted by the addition ratio of the inorganic powder, the thickener, the organic solvent, the polymerization inhibitor, the plasticizer, the anti-precipitation agent and the like. The viscosity of the photosensitive glass powder-containing paste is preferably 2000 mPa · s or more, and more preferably 5000 mPa · s or more. The viscosity is preferably 200,000 mPa · s or less, and more preferably 100,000 mPa · s or less. For example, when the photosensitive glass powder-containing paste is applied to the substrate by the spin coating method, the viscosity is preferably 2 to 5 Pa · s, and when the paste is applied to the substrate by the blade coater method or the die coater method. It is preferably 10 to 50 Pa · s. When the photosensitive glass powder-containing paste is applied by a single screen printing method to obtain a coating film having a film thickness of 10 to 20 μm, the viscosity is preferably 50 to 200 Pa · s.

-Pattern forming step The pattern forming step is, for example, an exposure step of exposing the coating film obtained in the coating step through a photomask having a predetermined opening, and a solubility in a developing solution in the coating film after exposure. It consists of a developing process that dissolves and removes various parts.

The exposure step is a step of photocuring a necessary part of the coating film by exposure or photodecomposing an unnecessary part of the coating film to make any part of the coating film soluble in a developing solution. .. The developing step is a step of dissolving and removing a portion of the coating film after exposure that is soluble in the developing solution with a developing solution to obtain a grid-like pre-baking pattern in which only the necessary portion remains.

In the exposure step, an arbitrary pattern may be directly drawn with a laser beam or the like without using a photomask. Examples of the exposure apparatus include a proximity exposure machine. Examples of the active light beam irradiated in the exposure step include near infrared rays, visible light rays, and ultraviolet rays, and ultraviolet rays are preferable. Examples of the light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, or a germicidal lamp, and an ultra-high-pressure mercury lamp is preferable.

The exposure conditions differ depending on the thickness of the coating film. Usually, the exposure is performed for 0.01 to 30 minutes using an ultra-high pressure mercury lamp having an output of 1 to ^{100 mW / cm 2.}

Examples of the developing method in the developing step include a dipping method, a spraying method or a brushing method. As the developing solution, a solvent capable of dissolving an unnecessary portion of the coating film after exposure may be appropriately selected. The developer is preferably an aqueous solution containing water as a main component. For example, when the glass powder-containing paste contains a polymer having a carboxyl group, an alkaline aqueous solution can be selected as the developer. Examples of the alkaline aqueous solution include an inorganic alkaline aqueous solution such as sodium hydroxide, sodium carbonate or calcium hydroxide, or an organic alkaline aqueous solution such as tetramethylammonium hydroxide, trimethylbenzylammonium hydroxyside, monoethanolamine or diethanolamine. Among these, the alkaline aqueous solution is preferably an organic alkaline aqueous solution because it can be easily removed in the firing step. The concentration of the alkaline aqueous solution is preferably 0.05% by mass or more, more preferably 0.1% by mass or more. The concentration of the alkaline aqueous solution is preferably 5% by mass or less, and more preferably 1% by mass or less. When the concentration of the alkaline aqueous solution is 0.05% by mass or more, unnecessary portions in the coating film after exposure can be sufficiently easily removed. On the other hand, when the alkali concentration is 5% by mass or less, the grid-like pre-firing pattern is less likely to be peeled off or corroded. The development temperature is preferably 20 to 50 ° C. to facilitate process control.

In order to form a pattern by exposure and development, the glass powder-containing paste applied in the coating step needs to be photosensitive. That is, the glass powder-containing paste needs to contain a photosensitive organic component. The proportion of the organic component in the photosensitive glass powder-containing paste is preferably 30% by mass or more, more preferably 40% by mass or more. The proportion of the organic component in the photosensitive glass powder-containing paste is preferably 80% by mass or less, and more preferably 70% by mass or less. When the proportion of the organic component is 30% by mass or more, the dispersibility of the inorganic component in the paste is lowered, and defects are less likely to occur in the baking step. In addition, the paste has an appropriate viscosity and is excellent in coatability and stability. On the other hand, when the proportion of the organic component is 80% by mass or less, the shrinkage rate of the lattice pattern in the firing step is unlikely to increase, and defects are unlikely to occur.

The glass powder contained in the photosensitive glass powder-containing paste preferably has a softening temperature of 480 ° C. or higher in order to almost completely remove organic components in the firing step and secure the strength of the finally obtained partition wall. ..

-Baking step In the firing step, the lattice-shaped pre-firing pattern obtained in the pattern forming step is fired to decompose and remove the organic components contained in the glass powder-containing paste, and the glass powder is softened and sintered to form a lattice. This is a step of obtaining a post-firing pattern, that is, a partition wall.

The firing conditions differ depending on the composition of the glass powder-containing paste and the type of the base material. For example, firing can be performed in a firing furnace with an air, nitrogen or hydrogen atmosphere. Examples of the firing furnace include a batch type firing furnace and a belt type continuous firing furnace. The firing temperature is preferably 500 ° C. or higher, more preferably 550 ° C. or higher. The firing temperature is preferably 1000 ° C. or lower, more preferably 700 ° C. or lower, and even more preferably 650 ° C. or lower. When the firing temperature is 500 ° C. or higher, the organic component can be sufficiently decomposed and removed. On the other hand, since the firing temperature is 1000 ° C. or lower, the base material used is not limited to the highly heat-resistant ceramic plate or the like. The firing time is preferably 10 to 60 minutes.

In the method for manufacturing a scintillator panel of the present embodiment, the base material at the time of forming the partition wall may be used as the substrate of the scintillator panel, and after the partition wall is peeled from the base material, the peeled partition wall is placed on the substrate and used. May be. As a method of peeling the partition wall from the base material, a known method such as a method of providing a peeling auxiliary layer between the base material and the partition wall can be used.

(Reflective layer forming process)
The method for manufacturing a scintillator panel of the present embodiment includes a reflective layer forming step of forming a metal reflective layer on the surface of a partition wall. The metal reflective layer may be formed on at least a part of the partition wall surface.

The method of forming the metal reflective layer is not particularly limited. As an example, the metal reflective layer can be formed by a vacuum film forming method such as a vacuum vapor deposition method, a sputtering method or a CVD method, a plating method, a paste coating method or a spray injection method. Among these, the metal reflective layer formed by the sputtering method is preferable because it has higher reflectance uniformity and corrosion resistance than the metal reflective layer formed by other methods.

The method for manufacturing the scintillator panel of the present embodiment may include an inorganic protective layer forming step of forming an inorganic protective layer on the surface of the reflective layer. The method for forming the inorganic protective layer is not particularly limited. As an example, the inorganic protective layer can be formed by a vacuum film forming method such as a vacuum vapor deposition method, a sputtering method or a CVD method, a paste coating method or a spray injection method. Among these, the inorganic protective layer formed by the sputtering method is preferable because it has higher uniformity and corrosion resistance than the inorganic protective layer formed by other methods.

(Organic protective layer forming process)
The method for manufacturing a scintillator panel of the present embodiment includes an organic protective layer forming step of forming an organic protective layer on the surface of the reflective layer. The method for forming the organic protective layer is not particularly limited. As an example, the organic protective layer can be formed by applying a solution containing polysiloxane on a partition wall substrate under vacuum and then drying to remove the solvent. Further, it is preferable that the dried substrate is cured at a temperature higher than the drying temperature. By curing the substrate, the condensation of polysiloxane proceeds, the heat resistance and chemical resistance are improved, and the initial brightness of the scintillator panel is likely to be improved.

In the present embodiment, the organic protective layer contains polysiloxane as a main component, and the polysiloxane is hydrolyzed / partially condensed with organosilane containing the organosilane represented by the above general formula (1) in the embodiment of the scintillator panel. Including things.

（上記一般式（１）中、Ｒ¹は、エポキシ基および酸無水物基のうち少なくともいずれか一方を有する１価の有機基を表す。Ｒ²およびＲ³は、それぞれ、水素、炭素数１〜６のアルキル基、炭素数２〜６のアシル基または炭素数６〜１６のアリール基を表す。ｍは１〜３の整数を表す。ｎは０〜２の整数を表す。ｍ＋ｎは１〜３である。ｍが２以上の場合、複数のＲ¹は、それぞれ同じでも異なってもよい。また、ｎが２の場合、複数のＲ²は、それぞれ同じでも異なってもよい。また、ｍ＋ｎが２以下の場合、複数のＲ³は、それぞれ同じでも異なってもよい。）

(In the above general formula (1), R ¹ represents a monovalent organic group having at least one of an epoxy group and an acid anhydride group. R ² and R ³ are hydrogen and carbon number 1, respectively. Represents an alkyl group of ~ 6, an acyl group of 2 to 6 carbon atoms or an aryl group of 6 to 16 carbon atoms. M represents an integer of 1 to 3. n represents an integer of 0 to 2. M + n represents 1 to 1. If .m is 2 or more and 3, a plurality of R ¹ each may be the same or different. Further, when n is 2, a plurality of R ² may be the same or different from each other. also, m + n If it is 2 or less, more R ³ may be same or different.)

(Filling process)
The method for manufacturing a scintillator panel of the present embodiment includes a filling step of filling a cell partitioned by a partition wall with a phosphor. The method of filling the phosphor is not particularly limited. As an example, since the process is simple and uniform phosphor filling into a large area is possible, the filling method is to apply a fluorescent paste in which a fluorescent powder and a binder resin are mixed as a solvent on a partition substrate. A method of applying under vacuum and then drying to remove the solvent is preferable.

As described above, according to the method for manufacturing a scintillator panel of the present embodiment, the obtained scintillator has high luminance and high sharpness, small luminance unevenness, and easily suppresses the occurrence of defects in a high temperature and high humidity environment.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these.

(Synthesis of polysiloxane)
Among the compounds used in the synthesis examples and the examples, those using the abbreviation are shown below.
PGMEA: Propylene Glycol Monomethyl Ether Acetate

The solid content concentration of the polysiloxane solution in the synthetic example was determined by the following method. 1.5 g of the polysiloxane solution was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The weight of the solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration of the polysiloxane solution was determined from the ratio with the weight before heating. The content ratio of each organosilane unit in polysiloxane was ^{measured by 29} Si-NMR, and the ratio of the integrated value of Si derived from a specific organosilane unit to the integrated value of the entire Si derived from organosilane. Was calculated and calculated based on their content ratio. The measurement sample (liquid) was injected into an NMR sample tube manufactured by Teflon (registered trademark) having a diameter of 10 mm. ²⁹ Si-NMR measurement conditions are shown below.
Device: Nuclear magnetic resonance device JNM-GX270 (manufactured by JEOL Ltd.)
Measurement method: Gated decoupling method Measurement nucleus frequency: 53.6693 MHz ( ²⁹ Si nucleus)
Spectral width: 20000Hz
Pulse width: 12 μs (45 ° pulse)
Pulse repetition time: 30.0 seconds Solvent: Acetone-d6
Reference substance: Tetramethylsilane Measurement temperature: 23 ° C
Sample rotation speed: 0.0Hz

The organosilanes used in the synthesis of polysiloxane are as follows.
Organosilane S-1: Methyltrimethoxysilane Organosilane S-2: Phenyltrimethoxysilane Organosilane S-3: 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane Organosilane S-4: 3-Trimethoxy Cyrilpropyl succinic anhydride

(Synthesis Example 1) 16.34 g (0.12 mol) of organosilane S-1 and 29.75 g (0.15 mol) of organosilane S-2 in a three-necked flask containing a 500 ml polysiloxane (A-1) solution. 7.39 g (0.03 mol) of silane S-3 and 45.00 g of PGMEA were charged, and 0.16 g of phosphoric acid (0.30% by weight based on the charged monomer) was dissolved in 16.21 g of water while stirring at room temperature. The aqueous solution of phosphoric acid was added over 30 minutes. Then, the flask was immersed in an oil bath at 70 ° C. and stirred for 90 minutes, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution. During the temperature rise and heating and stirring, 0.05 liter / minute of nitrogen was flowed. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (A-1) solution. ²⁹ The molar ratios of repeating units derived from organosilanes S-1, S-2, and S-3 measured by Si-NMR were 40 mol%, 50 mol%, and 10 mol%, respectively.

(Synthesis Example 2) Polysiloxane (A-2) Solution Organosilane S-1 is 18.39 g (0.135 mol), Organosilane S-2 is 29.75 g (0.15 mol), and Organosilane S-4 is 3. .94 g (0.015 mol), 45.00 g of PGMEA was charged, and 30 phosphoric acid aqueous solution in which 0.16 g of phosphoric acid (0.30% by weight based on the charged monomer) was dissolved in 16.21 g of water while stirring at room temperature was added. A polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that the mixture was added over a minute period. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (A-2) solution. ²⁹ The molar ratios of repeating units derived from organosilanes S-1, S-2 and S-4 measured by Si-NMR were 45 mol%, 50 mol% and 5 mol%, respectively.

(Synthesis Example 3) Polysiloxane (A-3) Solution 20.02 g (0.147 mol) of organosilane S-1, 29.75 g (0.15 mol) of organosilane S-2, and 0 for organosilane S-3. .74 g (0.003 mol), 45.00 g of PGMEA was charged, and 30 phosphoric acid aqueous solution in which 0.15 g of phosphoric acid (0.30% by weight based on the charged monomer) was dissolved in 16.21 g of water while stirring at room temperature was added. A polysiloxane solution was obtained by the same procedure as in Synthesis Example 1 except that the mixture was added over a minute period. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (A-2) solution. ²⁹ The molar ratios of repeating units derived from organosilanes S-1, S-2 and S-3 measured by Si-NMR were 49 mol%, 50 mol% and 1 mol%, respectively.

(Synthesis Example 4) Polysiloxane (A-4) Solution 20.43 g (0.15 mol) of organosilane S-1, 29.75 g (0.15 mol) of organosilane S-2, and 45.00 g of PGMEA were charged. The procedure is the same as that of Synthesis Example 1 except that an aqueous phosphoric acid solution prepared by dissolving 0.15 g of phosphoric acid (0.30% by weight based on the charged monomer) in 17.0 g of water while stirring at room temperature was added over 30 minutes. To obtain a polysiloxane solution. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (A-2) solution. ²⁹ The molar ratios of the repeating units derived from organosilanes S-1 and S-2 measured by Si-NMR were 50 mol% and 50 mol%, respectively.

(Raw material for paste containing glass powder)
The raw materials used to prepare the photosensitive glass powder-containing paste are as follows.
Photosensitive Monomer M-1: Trimethylol Propane Triacrylate Photosensitive Monomer M-2: Tetrapropylene Glycoldimethacrylate Photosensitive Polymer: Copolymer having a mass ratio of methacrylic acid / methyl methacrylate / styrene = 40/40/30 (Weight average molecular weight 43000; acid value 100) obtained by adding 0.4 equivalents of glycidyl methacrylate to the carboxyl group of
Photopolymerization Initiator: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) Butanone-1 (manufactured by BASF)
Polymerization inhibitor: 1,6-hexanediol-bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate])
UV absorber solution: Sudan IV (manufactured by Tokyo Ohka Kogyo Co., Ltd.) γ-butyrolactone 0.3% by mass solution Viscosity adjuster: Fronon EC121 (manufactured by Kyoeisha Chemical Co., Ltd.)
Solvent: γ-Butyrolactone Low softening point Glass powder:
SiO ₂ 27% by mass, B ₂ O ₃ 31% by mass, ZnO 6% by mass, Li ₂ O 7% by mass, MgO 2% by mass, CaO 2% by mass, BaO 2% by mass, Al ₂ O ₃ 23% by mass, refraction Rate (ng) 1.56, glass softening temperature 588 ° C., thermal expansion coefficient 70 × 10 ^-7 (K ^-1 ), average particle size 2.3 μm
High softening point glass powder:
SiO ₂ 30% by mass, B ₂ O ₃ 31% by mass, ZnO 6% by mass, MgO 2% by mass, CaO 2% by mass, BaO 2% by mass, Al ₂ O ₃ 27% by mass, refractive index (ng) 1.55 , Softening temperature 790 ° C., Thermal expansion coefficient 32 × 10 ^-7 (K ^-1 ), Average particle size 2.3 μm

(Preparation of paste containing glass powder)
Glass powder-containing paste P-1:
4 parts by mass of photosensitive monomer M-1, 6 parts by mass of photosensitive monomer M-2, 24 parts by mass of photosensitive polymer, 6 parts by mass of photopolymerization initiator, 0.2 parts by mass of polymerization inhibitor and 12 8.8 parts by mass of the UV absorber solution was heated and dissolved in 38 parts by mass of the solvent at a temperature of 80 ° C. After cooling the obtained solution, 9 parts by mass of a viscosity modifier was added to obtain an organic solution 1. The refractive index (ng) of the organic coating film obtained by applying the obtained organic solution 1 to a glass plate and drying it was 1.555. After adding 50 parts by mass of the low softening point glass powder to 50 parts by mass of the organic solution 1, the mixture was kneaded with a three-roller kneader to obtain a glass powder-containing paste P-1.

Glass powder-containing paste P-2:
Glass powder-containing paste in the same manner as the above glass powder-containing paste P-1 except that 49 parts by mass of low-softening point glass powder and 1 part by mass of high-softening point glass powder were added to 50 parts by mass of organic solution 1. Obtained P-2. The volume ratio of the low softening point glass to the total amount of the low softening point glass and the high softening point glass was 98% by volume.

Glass powder-containing paste P-3:
Glass powder-containing paste in the same manner as the above glass powder-containing paste P-1 except that 40 parts by mass of low-softening point glass powder and 10 parts by mass of high-softening point glass powder were added to 50 parts by mass of organic solution 1. Obtained P-3. The volume ratio of the low softening point glass to the total amount of the low softening point glass and the high softening point glass was 80% by volume.

(Making a bulkhead substrate)
Bulkhead substrate 1:
As a base material, a soda glass plate having a size of 125 mm × 125 mm × 0.7 mm was used. The glass powder-containing paste P-1 was applied to the surface of the base material with a die coater so that the thickness after drying was 220 μm and dried to obtain a coating film of the glass powder-containing paste. Next, a coating film of the glass powder-containing paste was applied to an ultrahigh-pressure mercury lamp via a photomask having openings corresponding to the desired pattern (a chrome mask having a pitch of 127 μm, a line width of 15 μm, and a grid-like openings). It was exposed at an exposure amount of 300 mJ / cm ^2. The coating film after exposure was developed in a 0.5% by mass ethanolamine aqueous solution, and the unexposed portion was removed to obtain a grid-like pre-baking pattern. The obtained lattice-shaped pre-firing pattern was fired in air at 580 ° C. for 15 minutes to form a lattice-shaped partition wall containing glass as a main component. The partition wall cross section was exposed by splitting, and the height of the partition wall L1 was 150 μm, the distance between the partition walls L2 was 127 μm, and the bottom width L3 of the partition wall was 30 μm, which was measured by imaging with a scanning electron microscope S2400 (manufactured by Hitachi, Ltd.). The top width L4 of the partition wall was 10 μm.

Partition board 2:
It was formed in the same manner as the partition wall substrate 1 except that the glass powder-containing paste P-2 was used. The height L1 of the partition wall was 150 μm, the distance L2 of the partition wall was 127 μm, the bottom width L3 of the partition wall was 30 μm, and the top width L4 of the partition wall was 10 μm.

Bulkhead substrate 3:
It was formed in the same manner as the partition wall substrate 1 except that the firing temperature of the partition wall was set to 590 ° C. using the glass powder-containing paste P-3. The height L1 of the partition wall was 150 μm, the distance L2 of the partition wall was 127 μm, the bottom width L3 of the partition wall was 30 μm, and the top width L4 of the partition wall was 10 μm.

(Formation of metal reflective layer)
A commercially available sputtering device and a sputtering target were used. At the time of sputtering, a glass flat plate was placed in the vicinity of the partition wall substrate, and sputtering was carried out under the condition that the metal thickness on the glass flat plate was 300 nm. As the sputtering target, APC (manufactured by Furuya Metal Co., Ltd.), which is a silver alloy containing palladium and copper, or non-alloy silver was used. The partition wall in each partition wall substrate was measured by exposing the partition wall cross section using a triple ion milling device EM TIC 3X (manufactured by LEICA) and imaging with a field emission scanning electron microscope (FE-SEM) Merlin (manufactured by Zeiss). The thickness of the metal reflective layer on the side surface of the central portion in the height direction was 70 nm.

(Raw material for metal oxide reflective layer paste)
The raw materials used to prepare the metal oxide reflective layer paste are as follows.
Metal oxide filler Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.)
Binder solution A mixture of 5% by mass ethyl cellulose (manufactured by Dow Chemical Co., Ltd.) and 95% by mass of tarpineol (manufactured by Nippon Terpen Chemical Co., Ltd.) Monomer 30% by mass dipentaerythritol pentaacrylate and 70% by mass dipentaerythritol hexa A mixture of acrylates (both manufactured by Toa Synthetic Co., Ltd.) Polymerization initiator 1,1'-azobis (cyclohexane-1-carbonitrile) (V-40: manufactured by Wako Pure Chemical Industries, Ltd.)

(Formation of metal oxide reflective layer)
50 parts by mass of metal oxide filler, 45 parts by mass of binder solution, 4.5 parts by mass of monomer and 1.5 parts by mass of polymerization initiator are kneaded with a three-roller kneader to make a metal oxide reflective layer paste. Got The metal oxide reflective layer paste was vacuum-printed on the partition wall, dried at 90 ° C. for 1 h, and further cured at 190 ° C. for 1 hour to form a metal oxide reflective layer.

(Measurement of arithmetic mean tilt angle)
After forming the reflective layer, the partition substrate is cut, and the cross section where the reflective layer on the side surface of the partition is exposed is covered with a laser microscope VK-X200 (manufactured by KEYENCE CORPORATION) at 5 locations on the side surface of the partition with an objective lens with a magnification of 50 times. The photograph was taken, and the length range of 20 μm in the center of the side surface of the partition wall was analyzed by the attached analysis software for line roughness analysis, and the average value of 5 points was obtained and used as the arithmetic mean inclination angle.

(Formation of inorganic protective layer)
A commercially available sputtering device and a sputtering target were used. At the time of sputtering, a glass flat plate was placed in the vicinity of the partition wall substrate, and sputtering was carried out under the condition that the thickness of the inorganic protective layer on the glass flat plate was 100 nm. The thickness of the inorganic protective layer on the side surface of the central portion in the height direction of the partition wall in each partition wall substrate measured in the same manner as the thickness of the metal reflective layer was 20 nm.

(Formation of organic protective layer)
The organic protective layer containing polysiloxane was formed as follows. A diluted solution was prepared by mixing 1 part by mass of a polysiloxane solution with 10 parts by mass of γ-butyrolactone as a solvent on a partition wall substrate. The polysiloxane solution shown in Table 1 was used for each Example and Comparative Example. After vacuum printing this diluted solution on the partition wall substrate, it was dried at 90 ° C. for 1 hour and further cured at 190 ° C. for 1 hour to form an organic protective layer. In Table 1, the sample described as partition wall-reflection layer at the formation position is before the formation of the reflection layer, and the sample whose formation position is on the reflection layer is after the formation of the reflection layer, and the formation position is on the partition wall-reflection layer + reflection layer. The sample formed an organic protective layer twice, before and after forming the reflective layer, by the above method. In addition, in the sample in which the inorganic protective layer was formed and the position where the organic protective layer was formed was on the reflective layer, the reflective layer, the inorganic protective layer, and the organic protective layer were formed in this order. The organic protective layer thickness on the side surface of the central portion in the height direction of the partition wall in each partition wall substrate measured in the same manner as the thickness of the metal reflective layer was 1 μm in both the partition wall-reflection layer and the reflective layer.

The organic protective layer of acrylic was formed as follows. A diluted solution was prepared by dissolving 1 part by mass of Oricox (registered trademark) KC7000 (manufactured by Kyoeisha Chemical Co., Ltd.) in 20 parts by weight of γ-butyrolactone. This diluted solution was vacuum-printed on the partition wall substrate and then dried at 90 ° C. for 1 hour.

The organic protective layer of polyparaxylylene was formed by a known vacuum vapor deposition method.

(Fluorescent material)
Commercially available GOS: Tb (Tb-doped gadolinium sulfide) fluorophore powder was used as it was. The average particle size D50 measured by the particle size distribution measuring device MT3300 (manufactured by Nikkiso Co., Ltd.) was 11 μm.
(Binder resin for fluorescent material layer)
The following resins were used.
Cellulose derivative: Etocell (registered trademark) 7 cp (manufactured by Dow Chemical Co., Ltd.)
Butyral: Eslek (registered trademark) B BL-S (manufactured by Sekisui Chemical Co., Ltd.)
Acrylic: Oricox (registered trademark) KC7000 (manufactured by Kyoeisha Chemical Co., Ltd.)
Polyolefin: ARTON (registered trademark) D4540 (manufactured by JSR Corporation)

(Formation of phosphor layer)
10 parts by mass of the fluorescent substance powder was mixed with 5 parts by mass of a binder resin solution having a concentration of 10 wt% to prepare a fluorescent substance paste. Benzyl alcohol was used as the solvent for the cellulose derivative, butyral, and the acrylic resin solution. In addition, cyclohexanone was used as the solvent for the polyolefin resin solution. This fluorescent paste is vacuum-printed on a partition substrate on which a reflective layer, an inorganic protective layer, an organic protective layer, etc. are formed, filled so that the volume fraction of the fluorescent substance is 65%, and dried at 150 ° C. for 15 minutes. , A phosphor layer was formed.

(Evaluation of initial brightness)
After filling the phosphor layer, each scintillator panel was placed in the center of the sensor surface of the X-ray detector PaxScan 2520V (manufactured by Varian) so that the cells of the scintillator panel had a one-to-one correspondence with the pixels of the sensor. The end of the substrate was fixed with adhesive tape. This detector is irradiated with X-rays from the X-ray radiating device L9181-02 (manufactured by Hamamatsu Photonics Co., Ltd.) under the condition that the tube voltage is 50 kV and the distance between the X-ray tube and the detector is 30 cm to obtain an image. Obtained. The average value of the digital values of 256 × 256 pixels at the center of the light emitting position of the scintillator panel in the obtained image was used as the luminance value, and the relative value with respect to the luminance value of Example 1 was calculated for each sample and used as the initial luminance. If the initial brightness is less than 80, the brightness is low and unsuitable.

(Moisture resistance test)
As an accelerated test for the generation of defects in a high temperature and high humidity environment, the produced scintillator panel was allowed to stand in a constant temperature and humidity chamber having a temperature of 65 ° C. and a humidity of 90% for 300 hours.
-Evaluation of the brightness retention rate after the moisture resistance test For each scintillator panel after the moisture resistance test, the brightness value was measured in the same manner as the initial brightness, and the ratio of each sample to the brightness value before the moisture resistance test was obtained.
-Evaluation of the number of pinholes after the moisture resistance test The number of pinhole-shaped brightness reduction points in the X-ray image of each scintillator panel after the moisture resistance test was counted. When the number of pinhole defects is 10 or more, it is difficult to remove the defects by correcting the X-ray image, which is not suitable for practical use.

(Resistant to discoloration over time)
After the scintillator panel was prepared, the discoloration of the surface of the scintillator panel was visually judged for the sample stored in the air at room temperature for one month. The case where no discoloration was observed was evaluated as ⊚, and the case where discoloration was observed but there was no practical problem was evaluated as Δ.

(Evaluation of uneven brightness)
Visually check the X-ray image of each scintillator panel, ◎ when no unevenness is seen, ○ when unevenness is very slight, △ when unevenness is seen but practically usable, practical use The case where it is unsuitable for is marked with x, and the case where unevenness is extremely remarkable is marked with XX.

(Examples 1 to 14, Comparative Examples 1 to 9)
A metal reflective layer or a metal oxide reflective layer is formed on the partition wall substrate shown in Table 1 by the above-mentioned method using the materials shown in Table 1, and the inorganic protective layer and the organic protective layer shown in Table 1 are formed by the above-mentioned method. Formed. Then, a phosphor layer was formed by the above-mentioned method using the binder resin shown in Table 1. Table 1 shows the configurations of each example and comparative example, and various evaluation results.

As shown in Table 1, Examples 1 to 1 in which an organic protective layer containing a hydrolyzed / partially condensate of an organosilane containing an organosilane represented by the general formula (1) is formed on a metal reflective layer. The scintillator panel of No. 4 had a high initial brightness, a small number of pinhole defects after the moisture resistance test, and no uneven brightness was observed. In the scintillator panel of Example 5 in which polyolefin was used as the binder resin, there was a tendency for some cissing to occur on the partition wall substrate, and uneven brightness was observed, but the range was not a problem. The scintillator panel of Example 6 having an organic protective layer both on the partition-reflecting layer and on the reflective layer had extremely high initial brightness and was good. In addition, the brightness maintenance rate after the moisture resistance test was relatively good. In the scintillator panel of Example 7 having an organic protective layer only between the partition wall and the reflective layer, the initial brightness was slightly lowered, and a small number of pinhole defects were generated after the moisture resistance test, but the range was not a problem. The scintillator panel of Example 8 in which the content of the structural unit derived from the organosilane represented by the general formula (1) was small tended to cause a slight cissing on the partition wall substrate, and uneven brightness was observed. There was no problem. The scintillator panels of Examples 9 to 11 having silicon nitride as an inorganic protective layer on the metal reflective layer had an extremely good brightness retention rate after the moisture resistance test. The scintillator panel of Example 12 in which silver was used as the metal reflective layer material showed some discoloration over time, but was within the range without any problem. In the scintillator panels of Examples 13 to 14 in which the partition wall contains the high softening point glass as the filler, the initial brightness tends to decrease slightly as the filler content increases, but this is within the range where there is no problem. rice field.

On the other hand, the scintillator panels of Comparative Examples 1 and 2 having no siloxane organic protective layer were unsuitable because pinhole defects frequently occurred after the moisture resistance test. The initial brightness of the scintillator panel of Comparative Example 1 was also unsuitable. The scintillator panels of Comparative Examples 3 to 5 having a siloxane organic protective layer but not containing a hydrolyzed / partially condensate of an organosilane containing an organosilane represented by the general formula (1) are unsuitable because of extremely large uneven brightness. Met. The scintillator panels of Comparative Examples 6 to 7 having a metal oxide reflective layer instead of the metal reflective layer had low initial brightness and were unsuitable. The scintillator panels of Comparative Examples 8 to 9 having an organic protective layer other than siloxane had low initial brightness and were unsuitable.

From the above results, it is clear that the scintillator panel of the present invention can provide a scintillator panel having high luminance and high sharpness, small luminance unevenness, and suppressed defect generation in a high temperature and high humidity environment.

1 Radiation detector member 2 Scintillator panel 3 Output board 4 Board 5 Septum 6 Fluorescent layer 7 Septal layer 8 Photoelectric conversion layer 9 Output layer 10 Board 11 Metal reflective layer 12 Organic protective layer 13 Fluorescent material 14 Binder resin L1 Bulkhead height L2 Spacing between adjacent bulkheads L3 Bottom width of bulkhead L4 Top width of bulkhead

Claims (9)

It has a bulkhead and a fluorophore layer in the cell partitioned by the bulkhead.
The partition wall has a metal reflective layer and an organic protective layer containing polysiloxane as a main component.
The polysiloxane is a scintillator panel containing a hydrolyzed / partially condensate of an organosilane containing an organosilane represented by the following general formula (1).

(In the above general formula (1), R ¹ represents a monovalent organic group having at least one of an epoxy group and an acid anhydride group. R ² and R ³ are hydrogen and carbon number 1, respectively. Represents an alkyl group of ~ 6, an acyl group of 2 to 6 carbon atoms or an aryl group of 6 to 16 carbon atoms. M represents an integer of 1 to 3. n represents an integer of 0 to 2. M + n represents 1 to 1. If .m is 2 or more and 3, a plurality of R ¹ each may be the same or different. Further, when n is 2, a plurality of R ² may be the same or different from each other. also, m + n If it is 2 or less, more R ³ may be same or different.) The organosilane represented by the general formula (1) comprises at least one of 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane and 3-trialkoxysilylpropylsuccinic anhydride. 1. The scintillator panel according to 1. The scintillator panel according to claim 1 or 2, wherein the content of the hydrolyzed / partially condensate of organosilane represented by the general formula (1) in the organic protective layer is 5 mol% or more. The fluorescent material layer has a fluorescent material and a binder resin, and has a fluorescent material and a binder resin.
The scintillator panel according to any one of claims 1 to 3, wherein the binder resin is in contact with the organic protective layer. The scintillator panel according to any one of claims 1 to 4, wherein the binder resin contains at least one of an acrylic resin, an acetal resin, and a cellulose derivative. The scintillator panel according to any one of claims 1 to 5, wherein the metal reflective layer contains silver as a main component. The scintillator panel according to claim 6, wherein the metal reflective layer contains a silver alloy containing at least one of palladium and copper. The scintillator panel according to any one of claims 1 to 7, wherein the partition wall contains 98% by volume or more of low softening point glass having a softening point of 650 ° C. or less. A partition wall forming step of forming a partition wall on a substrate and partitioning cells,
A reflective layer forming step of forming a metal reflective layer on the surface of the partition wall,
An organic protective layer forming step of forming an organic protective layer on the surface of the reflective layer,
It comprises a filling step of filling the cells partitioned by the partition with a fluorescent substance.
The organic protective layer contains polysiloxane as a main component and contains polysiloxane as a main component.
The polysiloxane is a method for producing a scintillator panel, which comprises a hydrolyzed / partially condensate of an organosilane containing an organosilane represented by the following general formula (1).

(In the above general formula (1), R ¹ represents a monovalent organic group having at least one of an epoxy group and an acid anhydride group. R ² and R ³ are hydrogen and carbon number 1, respectively. Represents an alkyl group of ~ 6, an acyl group of 2 to 6 carbon atoms or an aryl group of 6 to 16 carbon atoms. M represents an integer of 1 to 3. n represents an integer of 0 to 2. M + n represents 1 to 1. If .m is 2 or more and 3, a plurality of R ¹ each may be the same or different. Further, when n is 2, a plurality of R ² may be the same or different from each other. also, m + n If it is 2 or less, more R ³ may be same or different.)

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