JP2017114719A - X ray absorbing glass and photosensitive paste containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an X ray absorbing glass which is transparent to visible lights, contains a large amount of Ba as an element absorbing X ray, and is suitable for a partition material of a scintillator panel using a photosensitive paste low in refractive index, and a photosensitive paste containing the X ray absorbing glass.SOLUTION: There is provided an X ray absorbing glass, containing, by cation %, Siof 18 to 40%, Bof 18 to 46%, Alof 8 to 20%, Baof 5 to 25%, as cation components, and, by anion %, Oof 52 to 90% and Fof 10 to 48%, as anion components. Refractive index by g ray is preferably 1.52 to 1.62, further preferably 1.55 to 1.60 and absorption index to X ray of 100 keV is 1.0 cmor more, preferably 1.3 cmor more. There is provided a photosensitive glass paste containing photopolymerizable polyfunctional monomer or oligomer, a photopolymerization initiator, and the X ray absorbing glass with 50% particle diameter in a particle size distribution based on volume of 0.1 to 10 μm.SELECTED DRAWING: None

Description

  The present invention relates to an X-ray absorbing glass and a photosensitive paste.

  Conventionally, X-ray transmission images have been used for medical applications, inspection applications, and the like. As this X-ray transmission image, an analog image obtained by developing a film exposed to X-rays is mainly used. On the other hand, in recent years, flat panel type radiation detectors (radiation detection devices) have been developed as digital image systems.

  In a flat panel type radiation detector, a scintillator panel is used to convert radiation into visible light. The scintillator panel includes an X linear alternation part (scintillator layer) such as cesium iodide. The X-ray phosphor emits visible light according to the irradiated X-ray, and the visible light is electrically converted by a TFT or CCD. It is converted into a signal and obtained as digital image information.

  As such a radiation detector, in order to obtain a higher-definition image, a structure in which barrier ribs are formed with a photosensitive paste containing glass powder in a structure in which phosphors are filled in cells partitioned by barrier ribs is proposed. (Patent Document 1).

  When using a photosensitive paste, 1) a filler containing a low melting glass powder and a photosensitive organic component, optionally adjusting the shape of the partition wall and adjusting the thermal expansion coefficient (even a crystal is a high melting glass. And a photosensitive paste containing film may be applied on a glass substrate to form a photosensitive paste coating film, and 2) the obtained photosensitive paste coating film may be passed through a photomask having a predetermined opening. 3) Development process for dissolving and removing the portion of the photosensitive paste coating film after exposure that is soluble in the developer, 4) Organic component by heating the photosensitive paste coating film pattern after development to high temperature The partition wall is formed by a process of removing the glass and softening and sintering the low melting point glass to form the partition wall.

  Further, it is known that in an X-ray imaging apparatus, when X-rays are directly incident on a CCD element, the destruction of the CCD element and the generation of noise on the image may occur (Patent Document 2).

  Further, data published by NIST is known for the mass absorption coefficient of X-rays by various elements (Non-patent Document 1).

International Publication WO2012 / 161304 JP 2000-329898 A

JH Hubbell and SM Seltzer, Tables of X-Ray Mass Attenuation Coefficients and Mass Energy-Absorption Coefficients from 1 keV to 20 MeV for Elements Z = 1 to 92 and 48 Additional Substances of Dosimetric Interest, [online], Last updated: May 19 , 2015, Radiation Physics Division, PML, NIST, [Search on December 21, 2015], Internet <URL: http://www.nist.gov/pml/data/xraycoef/#>

  The barrier rib material in the scintillator panel is not a phosphor, so it does not emit visible light, but does not absorb X-rays at the same time. Then, the X-rays that have passed through the partition wall directly affect the TFT and the CCD, causing noise in the signal, which may cause a reduction in image contrast. In particular, the photosensitive paste method requires a glass having a low refractive index and a high transmittance in accordance with the organic component, so that it is inevitably a glass having a low heavy element content, and a glass that is easy to transmit X-rays. Yes.

  Accordingly, an object of the present invention is to provide a glass having both a low refractive index suitable for use in a photosensitive paste and a high heavy element content suitable for X-ray absorption.

  The present inventor can obtain a transparent glass by suppressing devitrification and phase separation of the glass by controlling to a specific composition range in the glass containing Si, B, Al, Ba, O, F, The inventors have found that the content of the heavy element Ba can be increased and the refractive index can be decreased, and further studies have been made to complete the present invention. That is, the X-ray absorption glass and photosensitive paste of the present invention are configured as follows.

(1) The X-ray absorption glass according to the present invention contains Si ⁴⁺ , B ³⁺ , Al ³⁺ and Ba ²⁺ as cation components, and is cation%, Si ⁴⁺ 18 to 40%, B ³⁺ 18 to 46%, Al ^{3+ is 8 to} 20%, Ba ^{2+ is} 5 to 25%, O ²⁻ and F ⁻ are contained as anion components, and an anion% is O ² −52 to 90% and F ⁻ 10 to 48%.

  (2) The X-ray absorbing glass according to the present invention preferably has a refractive index of 1.52 to 1.62 at g-ray.

(3) The X-ray absorption glass according to the present invention preferably has a linear absorption coefficient with respect to 100 keV X-ray of 1.0 cm ⁻¹ or more.

(4) X-ray absorption glass according to the present invention is cation%, Si ⁴⁺ 21-36%, B ³⁺ 21-43%, Al ³⁺ 11-17%, Ba ²⁺ 13-22%, anion% ^in, O 2- ^58~86%, F - is 14 to 42%, X-ray absorption coefficient is not less 1.3 cm ^-1 or more, the refractive index at the g-line is to be 1.55 to 1.60 preferable.

(5) The X-ray absorption glass according to the present invention preferably has a thermal expansion coefficient at 50 to 400 ° C. of 60 to 100 × 10 ⁻⁷ / K.

  (6) The X-ray absorption glass according to the present invention contains alkali metal ions as a cation component, the total content of alkali metal ions is 3 to 21% in terms of cation%, and the softening point is 500 to 500%. It is preferable that it is 700 degreeC.

(7) The X-ray absorption glass according to the present invention preferably contains Li ⁺ as a cation component, is cation%, Li ^{+ is 3 to} 21%, and has a softening point of 500 to 700 ° C.

  (8) In the X-ray absorption glass according to the present invention, the total content of alkali metal ions as the cation component is preferably 0 to 5% in cation%, and the softening point is preferably 650 to 850 ° C. .

(9) It is preferable that the X-ray absorption glass according to the present invention does not substantially contain Pb ²⁺ .

  (10) The X-ray absorption glass according to the present invention has a 50% particle size in a volume-based particle size distribution of 0.1 to 10 μm, and is preferably used for a photosensitive glass paste.

  (11) The photosensitive paste according to the present invention includes a photopolymerizable polyfunctional monomer or oligomer, a photopolymerization initiator, and the X-ray absorbing glass of (10).

  The X-ray absorbing glass of the present invention is transparent to visible light, contains a large amount of Ba as an element that absorbs X-rays, and has a low refractive index, so that it can be used as a partition material for a scintillator panel using a photosensitive paste method. Is suitable.

It is the schematic of the radiation detection apparatus which used the X-ray absorption glass of this invention for the partition for scintillators.

The X-ray absorption glass according to the present invention contains Si ⁴⁺ , B ³⁺ , Al ³⁺ , Ba ²⁺ as cation components, and is cation%, Si ⁴⁺ 18-40%, B ³⁺ 18-46%, Al ³⁺ 8. ^20%, a ^{Ba 2+ 5~25%, O 2-,} F as an anion component ^- containing, ^anionic%, O 2-from 52 to ^90%, F - is 10 to 48%.

  Hereinafter, each component of the glass composition of this invention and its content are demonstrated. In the present specification, unless otherwise specified, the content of each component is expressed in terms of cation% or anion% based on the molar ratio. Here, “cation%” and “anion%” are contained in the glass by separating the glass component of the optical glass of the present invention into a cation component and an anion component, and the total ratio is 100 mol% in each. It is the composition which described each component.

Si ⁴⁺ is an essential component. Si ⁴⁺ is a glass network former, and is a component that increases the stability of the glass and lowers the refractive index. On the other hand, when the content increases, the viscosity increases and it becomes difficult to melt the glass. Therefore, Si ⁴⁺ is 18 to 40% in terms of cation%, preferably 20 to 37%, and more preferably 21 to 36%.

B ³⁺ is an essential component. B ³⁺ is a glass network former, and is a component that increases the stability of the glass, lowers the softening point, and increases the coefficient of thermal expansion. On the other hand, when the content is increased, water resistance is deteriorated. Therefore, ^{B3 +} is 18 to 46% in terms of cation%, preferably 20 to 44%, and more preferably 21 to 43%.

Al ³⁺ is an essential component. Al ³⁺ functions as a glass network former. In addition, SiO ₂ , B ₂ O ₃ , and BaO have properties that are difficult to mix with each other, and glass containing these three types is likely to cause phase separation. When phase separation occurs, the glass becomes cloudy and scatters light, which makes the glass unsuitable for a photosensitive paste. The phase separation can be suppressed by adding a certain amount of Al ³⁺ or more. On the other hand, when the content of Al ³⁺ increases, devitrification tends to occur, the melting point becomes high, and it becomes difficult to melt the glass. Therefore, Al ³⁺ is 8 to 20% in terms of cation%, preferably 10 to 18%, and more preferably 11 to 17%.

Ba ²⁺ is an essential component. Ba ²⁺ is a component that absorbs X-rays and is a component that increases the refractive index. On the other hand, when the content of Ba ²⁺ increases, devitrification is likely to occur, the melting point increases, and it becomes difficult to melt the glass. Therefore, Ba < ²⁺ > is 5-25% in cation%, Preferably it is 8-23%, More preferably, it is 13-22%.

O ²⁻ is an essential component. It is responsible for combining glass network formers. On the other hand, when the content of O ²⁻ increases, the refractive index increases, the melting point increases, and melting becomes difficult. Therefore, O ²⁻ is 52 to 90% in anion%, preferably 56 to 88%, and more preferably 58 to 86%.

F ^- is an essential component. F ⁻ is a component that lowers the refractive index and increases the thermal expansion coefficient. On the other hand, when the content of F ⁻ increases, devitrification easily occurs. The thermal expansion coefficient becomes high. Therefore, F ⁻ is 10 to 48% in anionic%, preferably 12 to 44%, more preferably 14 to 42%.

Alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ ) are optional components. It is a component that lowers the softening point of glass and increases the coefficient of thermal expansion. When a low melting point glass softening at low temperature is desired, the total amount of alkali metal ions is 3 to 21% cation%, preferably 5 to 19%, and more preferably 6 to 18%. On the other hand, when filler glass that does not soften at low temperatures is desired, the total amount of alkali metal ions is 5% or less, preferably 3% or less, more preferably 1% or less in terms of cation%.

Among the alkali metal ions, Li ⁺ is an ion that has a relatively weak effect of increasing the thermal expansion coefficient. Therefore, when it is desired to achieve both a low softening point and a low thermal expansion coefficient, it is preferable to include Li ⁺ . When a low melting point glass that softens at a low temperature is desired, Li ⁺ is 3 to 21% cation%, preferably 5 to 19%, and more preferably 6 to 18%. On the other hand, when a filler glass that does not soften at a low temperature is desired, Li ⁺ is 6% or less in cation%, preferably 4% or less, and more preferably 2% or less.

Mg ²⁺ , Ca ²⁺ and Sr ²⁺ are optional components. It is a component that stabilizes the glass and increases the refractive index. On the other hand, if these contents increase, it will become easy to devitrify, melting | fusing point will also become high, and it will become difficult to fuse | melt glass. Therefore, the total of Mg ²⁺ , Ca ²⁺ and Sr ²⁺ is cation%, preferably 15% or less, more preferably 10% or less, and further preferably 5% or less.

La ³⁺ , Gd ³⁺ , Yb ³⁺ , Hf ⁴⁺ and Ta ⁵⁺ are optional components. These are heavy element ions that absorb X-rays and do not color the glass. On the other hand, when these contents increase, the refractive index increases, the glass tends to devitrify, the melting point increases, and it becomes difficult to melt the glass. Therefore, the total of La ³⁺ , Gd ³⁺ , Yb ³⁺ , Hf ⁴⁺ , Ta ⁵⁺ is cation%, preferably 15% or less, more preferably 10% or less, and further preferably 5% or less.

Other elements can be added as long as the characteristics of the glass of the present invention are not impaired. Transition metal ions of Group 5 to Group 11 (excluding Ta ⁵⁺ ) may cause coloration and impair transparency. Pb ²⁺ is an environmentally harmful component and is preferably not substantially contained. Here, “substantially does not contain” means that it is less than 1000 ppm in terms of mass concentration even if it is inevitably contained as an impurity. More preferably Pb ²⁺ is less than 100 ppm.

Therefore, Si ⁴⁺ , B ³⁺ , Al ³⁺ , Ba ²⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , La ³⁺ , Gd ³⁺ , Yb ³⁺ , Hf ⁴⁺ , The total of Ta ⁵⁺ is cation%, preferably 90% or more, more preferably 97% or more, and further preferably 99% or more.

Anions such as Cl ⁻ , Br ⁻ and I ⁻ may impair chemical durability.
Therefore, the total of O ²⁻ and F ⁻ is preferably 90% or more, more preferably 97% or more, and further preferably 99% or more in terms of anion%.

The X-ray absorption capacity of the glass of the present invention is represented by the linear absorption coefficient μ (cm ⁻¹ ) calculated by Equation 1. Here, ρ _glass is the glass density (g / cm ³ ), w _i is the mass fraction of element i in the glass, and (μ _en / ρ) _i is the mass absorption coefficient (cm ² / g) of element i. .

As the mass absorption coefficient, data published by NIST (Non-Patent Document 1) can be used. For example, Table 1 shows the mass absorption coefficient when the energy of X-rays is 100 keV.

The linear absorption coefficient μ (cm ⁻¹ ) at 100 keV of the glass of the present invention is preferably 1.0 or more, and more preferably 1.3 or more.

  The refractive index at g-line (about 436 nm) of the glass of the present invention is preferably the same value as the organic component used in the photosensitive paste in order to suppress light scattering when the photosensitive paste is exposed. Therefore, the value of the refractive index is preferably 1.520 to 1.620, more preferably 1.530 to 1.610, and still more preferably 1.540 to 1.600.

  The softening point of the glass of the present invention (DTA softening point under the measurement conditions described later) is 500 to 700 ° C. when it is a low-melting glass that softens at low temperatures. By doing in this way, it becomes the thing excellent as low melting glass used for a partition. In order to perform the partition wall manufacturing process at a low temperature, the softening point is preferably 650 ° C. or lower. The softening point can be appropriately adjusted based on the characteristics of each component described above.

  On the other hand, the softening point suitable for the filler glass is determined by the softening point of the low melting point glass combined therewith. The softening point of filler glass should just be 50 degreeC or more higher than low melting glass. A preferred softening point for filler glass compatible with many low melting glass is 650-850 ° C. By doing in this way, since it does not soften at low temperature, it is excellent as glass for fillers combined with low melting glass.

The thermal expansion coefficient of the glass of the present invention is not particularly limited. This is because the thermal expansion coefficient of the substrate material of the scintillator panel has various values, and the thermal expansion coefficient as a result of mixing the low melting point glass and the filler may be a thermal expansion coefficient close to the substrate material of the scintillator panel. . For example, the soda lime glass substrate has a thermal expansion coefficient of about 90 × 10 ⁻⁷ / K, and the alumina substrate has a thermal expansion coefficient of about 70 × 10 ⁻⁷ / K. The preferred coefficient of thermal expansion for glass compatible with many substrate materials is (60-100) × 10 ⁻⁷ / K.

The glass in the present invention can be produced by a conventional method. As a material, a compound serving as a supply source of each component of the glass in the present invention may be used as a starting material. For example _B 2 _H 3 _BO 3 for _{O 3,} B 2 _{O 3} or the like can be used. Also it is possible to use _{Al (OH) 3, Al 2} O 3, AlF 3 , etc. For example _Al 2 _{O 3.} As for other components, it is possible to employ starting materials usually used in the production of glass, such as various oxides, hydroxides, carbonates, nitrates, etc., such as SiO ₂ , BaCO ₃ , Li ₂ CO _3. it can. And a mixture containing these in a predetermined ratio is used as a starting material, and the mixture is melted.

  The glass of the present invention can be produced, for example, by a conventional production method including a first step of obtaining a mixture by mixing raw material compounds and a second step of obtaining a melt by melting the obtained mixture.

  In the first step, the starting material is weighed so as to have the intended composition and ratio of the glass and mixed to prepare a mixture. In this case, the order of mixing the raw materials of each component is not particularly limited, and may be blended at the same time or may be blended in a specific compound order. The raw material is usually supplied to the glass melting furnace in the form of powder. The raw material powder for that purpose can be obtained by pulverizing, mixing, etc., the raw material containing each component by a conventional method.

  In the second step, a melt is obtained by melting the above mixture. At the time of melting, the glass melting temperature may be set according to the composition of the raw material, but usually it may be about 1300 to 1600 ° C. The obtained melt may be subjected to a process for producing a powder as it is from the melt as necessary. For example, a flaky powder can be obtained while cooling the melt with a cooling roll. Moreover, after cooling a melt, a powder can also be obtained by processes, such as a grinding | pulverization and a classification, as needed. Thus, the glass of the present invention can be suitably provided as a powder.

  In the present invention, the “X% particle size” refers to a particle size that is cumulative X% counted from the small particle size side in a volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution meter. In the present invention, the term “maximum particle diameter” refers to a 99.9% particle diameter.

In the present invention, when the glass is powdered, the 50% particle size (D ₅₀ ) is not limited, but can be appropriately adjusted in accordance with the use form, application, etc., usually within a range of 50 μm or less. For example, when a paste is prepared using glass powder, the particle size may be adjusted as described below.

  A photosensitive paste can be prepared using the glass powder in the present invention. That is, using at least one binder, a solvent, and glass powder, the glass powder is uniformly distributed in a vehicle mainly composed of a binder polymer, a photopolymerizable polyfunctional monomer (or oligomer), a photopolymerization initiator, and other additives. What is necessary is just to disperse.

In the present invention, the 50% particle diameter (D ₅₀ ) of the glass powder is not particularly limited, but is usually 0.1 to 10 μm, and particularly preferably 0.5 to 5 μm. When the 50% particle size is less than 0.1 μm, a large amount of resin is required when preparing the paste, the degree of volume shrinkage before and after firing is increased, and the particles are strongly agglomerated in the paste. The dispersibility of the material may deteriorate. When the 50% particle diameter is 10 μm or more, it becomes difficult to produce a pattern having a narrow line width.

  The maximum particle size of the powder is not limited, but is usually 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less.

  Although the density | concentration in the paste of the said glass powder is not restrict | limited in particular, Usually, it can set suitably within the range of about 60 to 90 weight% in a paste.

  As the binder polymer, a copolymer of methyl methacrylate as a main component and various acrylates, methacrylate, acrylamide, styrene, acrylonitrile, etc. and acrylic acid, methacrylic acid, etc., and various unsaturated groups were further added thereto. And the like. Examples of the photopolymerizable polyfunctional monomer (or oligomer) include trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, (Di) pentaerythritol (tri-hexa) acrylate and the like. Since these photopolymerizable polyfunctional monomers (or oligomers) may be difficult to balance the characteristics (sensitivity, resolution, adhesiveness, patterning property, developability, etc.) with only one kind, mix two or more kinds. It is preferable to use it.

  Examples of the photopolymerization initiator include benzophenone series, thioxanthone series, anthraquinone series, acetophenone series, and benzoin ether series.

  In addition, in the preparation of the photosensitive glass paste, a thermal polymerization inhibitor, a plasticizer, a thickener, a sensitizer, a dispersant, a solvent, and the like can be added as additives as necessary.

  In addition, in the preparation of the glass paste, a plasticizer, a thickener, a dispersant, a solvent, and the like can be appropriately added as an additive by a conventional method as necessary.

  The use of the X-ray absorbing glass of the present invention is not limited, but it is preferably used for forming a structure by a photosensitive paste method. In the present invention, among these, the X-ray absorption glass of the present invention can be preferably used in order to form a partition for housing (storing) a phosphor in a scintillator panel of a radiation detection apparatus.

  FIG. 1 shows a schematic diagram of the structure of the radiation detection apparatus. In this radiation detection apparatus 10, a partition wall 13 is formed on a radiation transmissive substrate 11 via a buffer layer 16, and a phosphor (scintillator) 12 is accommodated in a region (cell) surrounded by the partition wall. An output substrate 15 having a photoelectric conversion layer (not shown) is provided thereon. As shown in FIG. 1, the scintillator panel 14 includes a radiation transmissive substrate 11, a phosphor 12, and a partition wall 13. In FIG. 1, the buffer layer 16 for forming the partition wall more effectively is provided, but a structure in which the buffer layer 16 is omitted may be used. In FIG. 1, the partition walls are formed only on the side surfaces of each cell. However, the bottom surfaces of each cell can also be configured by the partition walls as necessary.

  In the partition wall shown in FIG. 1, the configuration / structure itself other than the material constituting the partition wall can be the same as that of a known or commercially available radiation detector (or scintillator panel).

Hereinafter, the features of the present invention will be described more specifically with reference to examples. However, the present invention is not intended to be limited to these examples.
[Starting materials]
The starting materials used to make the glass compositions of Examples and Comparative Examples are as _{follows: SiO 2, H 3 BO 3} , Al (OH) 3, AlF 3, BaCO 3, BaF 2, Li _{2 CO 3, K 2 CO 3} , and _Yb 2 _O 3.

[Production of glass]
The above starting materials were prepared and mixed so as to obtain 100 g of glass in mol% based on oxide and fluoride, respectively, and 1300 g using a 500 cc platinum crucible. It melted at a temperature of 1400 ° C. for 1-2 hours. The melt was quenched with a stainless steel cooling roll to produce glass flakes having a thickness of 0.3 to 0.6 mm. Next, the glass flakes were pulverized, and powder glass having an average particle diameter (D ₅₀ ) of 1 to 4 μm and a maximum particle diameter of 20 μm or less was obtained by air classification. In addition, the particle size of the powder glass was measured using a laser scattering type particle size distribution measuring machine, thereby obtaining the air classification conditions.

  Similarly, the melt melt was poured into a carbon mold, slowly cooled, cut into a predetermined shape, and used as a test piece for refractive index measurement or thermal expansion coefficient measurement.

  Table 2 also shows values obtained by converting mol% on the oxide and fluoride basis into cation% and anion%.

[Preparation of each evaluation sample]
1. Refractive index: The glass obtained by melting was processed into a rectangular parallelepiped shape of 7 mm or more × 7 mm or more × 7 mm or more to obtain a sample for refractive index measurement.
2. Differential thermal analysis of glass: The powdered glass obtained by airflow classification was used as a sample for differential thermal analysis (DTA).
3. Measurement of thermal expansion coefficient of glass: The glass obtained by melting was processed into a rod shape having a diameter of 5 mm and a length of 15 mm to obtain a sample for measuring a thermal expansion coefficient.

[Evaluation methods for each physical property]
1. Refractive Index The refractive index of each glass at the helium g line was measured by a V-block method using a precision refractometer (model name “KPR200”, manufactured by Shimadzu Corporation).

2. Density The density of each glass was measured by the Archimedes method using their bulk.

3. Glass transition point, yield point, softening point Approximately 50 mg of each glass powder sample is put in a platinum cell, and alumina powder is used as a standard sample in a differential thermal analyzer (model name “TG-8120”, ( DTA curve was obtained from room temperature at a heating rate of 20 K / min. The starting point (extrapolated point) of the first endothermic peak was defined as the glass transition point, and the temperature at the apex (extrapolated point) of the endothermic peak was defined as the yield point. The starting point (extrapolated point) of the second endothermic peak was taken as the softening point.

4). Thermal expansion coefficient (α)
Using the thermomechanical measuring device (model name “TMA8310”, manufactured by Rigaku Co., Ltd.), the rod-shaped samples of Examples and Comparative Examples of each glass and glass fired product and a standard sample formed of quartz glass were used at room temperature. Then, the temperature was increased at 10 K / min and the thermal expansion curve was measured, and the thermal expansion coefficient values observed from 50 ° C. to 400 ° C. were averaged to obtain the thermal expansion coefficient of each sample.

5. Linear absorption coefficient (μ)
The composition of each glass was converted into a mass fraction and calculated using the measured density value and the literature value of the mass absorption coefficient at 100 keV.

[Evaluation of physical properties]
Each physical property was measured using the samples obtained in each Example and Comparative Example. The results are shown in Table 2.

  As shown in Table 2, the glass of the example of the present invention is transparent, has a refractive index in the range of 1.52 to 1.62, and is suitable for the photosensitive paste method. Further, Examples 1 to 10 have low softening points and are suitable as low melting point glasses. Examples 11 to 13 have high softening points and are suitable for filler glass. On the other hand, the glasses of Comparative Examples 1 and 2 are cloudy due to phase separation and are not suitable for the photosensitive paste method. The glass of Comparative Example 3 is not suitable for X-ray absorption because it has a small linear absorption coefficient. The glass of Comparative Example 4 is not suitable for the photosensitive paste method because of its high refractive index.

The X-ray absorption glass of the present invention can be used for a photosensitive paste method, and is particularly useful for the production of a scintillator panel.

10 radiation detector 11 radiation transmissive substrate 12 scintillator (phosphor)
13 Bulkhead
14 Scintillator panel 15 Output board 16 Buffer layer

Claims (11)

Containing Si ⁴⁺ , B ³⁺ , Al ³⁺ , Ba ²⁺ as a cation component,
% Cation,
Si ⁴⁺ 18-40%,
B ³⁺ 18-46%,
Al ³⁺ 8-20%,
Ba ²⁺ 5-25%,
And
Containing O ²⁻ and F ⁻ as anionic components,
Anion%
O ^2- 52-90%,
F ⁻ X-ray absorbing glass that is 10% to 48%.   The X-ray absorption glass of Claim 1 whose refractive index in g line | wire is 1.52-1.62. The X-ray absorption glass according to claim 1 or 2, wherein a linear absorption coefficient for 100 keV X-rays is 1.0 cm ^-1 or more. % Cation,
Si ⁴⁺ 21-36%,
B ³⁺ 21-43%,
Al ³⁺ 11-17%,
Ba ²⁺ 13-22%,
And
Anion%
O ² 58-86%,
F ^- 14-42%,
The X-ray absorption coefficient is 1.3 cm ⁻¹ or more,
X-ray absorption glass of any one of Claim 1- Claim 3 whose refractive index in g line | wire is 1.55-1.60. The X-ray absorption glass according to any one of claims 1 to 4, wherein a thermal expansion coefficient at 50 ° C to 400 ° C is 60 to 100 × 10 ^-7 / K.   The alkali metal ion is contained as a cation component, the total content of alkali metal ions is 3 to 21% in terms of cation%, and the softening point is 500 to 700 ° C. The X-ray absorption glass of any one of Claims. Containing Li ⁺ as a cationic component, in cation ^percent, Li + 3 to 21%, a softening point of 500 to 700 ° C., X-ray according to any one of claims 1 to 6 Absorption glass.   The total content of alkali metal ions as a cation component is 0 to 5% in terms of cation%, and the softening point is 650 to 850 ° C, according to any one of claims 1 to 7. X-ray absorption glass. X-ray absorption glass of any one of Claim 1- Claim 8 which does not contain Pb2 ⁺ substantially.   The X-ray absorption glass according to any one of claims 1 to 9, wherein a 50% particle diameter in a volume-based particle size distribution is from 0.1 to 10 µm, and is used for a photosensitive glass paste. A photosensitive paste comprising a photopolymerizable polyfunctional monomer or oligomer, a photopolymerization initiator, and the X-ray absorbing glass according to claim 10.

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