JP2002148395A - Radiation emission panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an edge bonded layer of a radiation emission panel being quick to harden and having high strength, moisture resistance and dirt resistance. SOLUTION: The radiation emission panel comprises a support layer 11, a phosphor layer 12 and a protective layer 13 stacked one on top of another in that order. The edge bonded layer 14 containing an ultraviolet- or electron- ray-cutting resin and a silicone macromonomer having a functional group capable of reacting with the resin is provided at the end of phosphor layer 12. The edge bonded layer 14 is irradiated with an ultraviolet ray or an electron ray to cure the layer 14.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation image conversion panel used in a radiation image conversion method using a stimulable phosphor, and a method for converting transmitted radiation into visible light and / or ultraviolet radiation by the phosphor. The present invention relates to a radiation emitting panel such as an intensifying screen for X-ray photography.

[0002]

2. Description of the Related Art As an alternative to the conventional radiographic method, there is known a radiation image conversion method using a stimulable phosphor as described in, for example, JP-A-55-12145. This method uses a radiation image conversion panel (a stimulable phosphor sheet) containing a stimulable phosphor, and transmits radiation transmitted through a subject or emitted from a subject to the stimulable phosphor of the panel. And then stimulating the stimulable phosphor with electromagnetic waves (excitation light) such as visible light and infrared light in a time-series manner, so that the radiation energy accumulated in the stimulable phosphor is (Stimulated emission light), and the fluorescence is photoelectrically read to obtain an electric signal.
Then, a radiation image of the subject or the subject is reproduced as a visible image based on the obtained electric signal. The panel after reading is prepared for the next photographing after the remaining image is erased. That is, the radiation image conversion panel is used repeatedly.

According to this radiographic image conversion method, a radiographic image with a large amount of information can be obtained with a much smaller exposure dose than the radiographic method using a combination of a conventional radiographic film and an intensifying screen. There is an advantage that it can be obtained. Furthermore, in contrast to the conventional radiographic method, which consumes radiographic film for each photographing operation, this radiographic image conversion method uses a radiographic image conversion panel repeatedly, which is advantageous in terms of resource conservation and economic efficiency. It is.

The radiation image conversion panel used in the radiation image conversion method has, as a basic structure, a support and a phosphor layer and a protective layer provided on the surface of the support. The phosphor layer is composed of a phosphor and a binder containing and supporting the phosphor in a dispersed state, and an aggregate or a crystal of the phosphor without a binder formed by an evaporation method or a sintering method. Is known. There is also known a radiation image conversion panel having a phosphor layer in which a polymer substance is impregnated in a gap between phosphor aggregates or crystals. In any of these phosphor layers, the phosphor has the property of emitting light when irradiated with excitation light after absorbing radiation such as X-rays, so that radiation transmitted through the subject or emitted from the subject is used. Emits light instantaneously in proportion to the radiation dose or is absorbed by the emitting phosphor layer and stored as an accumulated image. When the phosphor is stimulable, this accumulated image can be emitted as stimulating light by irradiating with excitation light, and this light is converted into an electric signal by a photoelectric element to accumulate radiation energy. Images can be imaged.

In order to prevent the phosphor layer from being deteriorated due to moisture absorption or the like,
Alternatively, in order to increase the mechanical strength of the panel, the edge of each layer of the radiation image conversion panel, that is, the edge of the radiation image conversion panel is generally sealed with a thermosetting resin or the like to seal the phosphor layer. Conventionally, isocyanates, melamines, and the like have been used as curing agents. JP-A-5-119198 describes the use of an ultraviolet-curable (electron-beam-curable) resin for the edge application layer.

[0006]

However, it is difficult to obtain the strength and antifouling properties required for the current repetitive use with the above-mentioned curing agents and resins as conventionally known. In addition, there is a problem in productivity and quality design because the curing reaction takes time or the curing reaction progresses with time to change the physical properties of the binder. In addition, a large amount of an organic solvent has to be used to apply these resins, which is not so preferable from an environmental point of view.

The present invention has been made in view of the above circumstances, has a short curing reaction time, can easily control physical properties, and has an edge adhesive layer having good strength, moisture resistance, and stain resistance. It is an object of the present invention to provide a radiation-emitting panel with improved performance.

[0008]

According to the present invention, there is provided a radiation-emitting panel comprising a support layer, a phosphor layer, and a protective layer laminated in this order. Or an electron beam curable resin, and a border layer containing a silicone macromonomer having a functional group capable of reacting with the ultraviolet or electron beam curable resin is provided, and the border layer is cured by irradiation with ultraviolet rays or electron beams. It is characterized by having.

A radiation-emitting panel is a radiation image conversion panel containing a stimulable phosphor or an X-ray for converting transmitted radiation into visible light and / or ultraviolet radiation using a non-stimulable phosphor. This is a broad concept including intensifying screens for photographs.

[0010] The provision of the border layer at the end of the phosphor layer means that the border layer is provided so that the end of the phosphor layer is not exposed to the outside air. This includes not only the case where the edge sticking layer is provided only at the end but also the case where it is provided so as to cover the entire end of the protective layer, the phosphor layer and the support.

Preferably, the functional group capable of reacting with the ultraviolet or electron beam curable resin is at one end of the molecule of the silicone macromonomer. Further, the functional group of the silicone macromonomer is preferably a methacryloxy group. The number average molecular weight of the silicone macromonomer is preferably from 5,000 to 20,000, more preferably from 10,000 to 15,000.

The curable functional group of the ultraviolet or electron beam curable resin is preferably a vinyl group or an acrylate group.

Preferably, the thickness of the border layer at the end face of the phosphor layer is 5 μm or more and 1000 μm or less,
More preferably, it is 10 μm to 500 μm. The thickness of the rim layer here means the thickness of the rim layer in a direction perpendicular to the end face of the phosphor layer at a portion in contact with the end face of the phosphor layer, and the width of the thickness of this part is If there is
The thinnest part is more than 5μm, the thickest part is 1000μm
It means the following.

[0014]

The radiation-emitting panel according to the present invention comprises, at the end of the phosphor layer, an ultraviolet or electron beam curable resin and a silicone macromonomer having a functional group capable of reacting with the ultraviolet or electron beam curable resin. An edge adhesive layer is provided, and since this edge adhesive layer is cured by irradiation with ultraviolet rays or electron beams, the radiation having improved strength and durability having an edge adhesive layer having good strength, moisture resistance, and stain resistance. A light-emitting panel can be obtained.

That is, in the case of the conventional adhesive layer made of a curing agent, there is a problem in productivity such that the curing reaction takes a long time, and the curing reaction progresses with time, so that it takes time in the manufacturing process. However, the edge application layer of the present invention contains an ultraviolet or electron beam curable resin, and a silicone macromonomer having a functional group capable of reacting with the ultraviolet or electron beam curable resin, which is cured by irradiation with ultraviolet light or electron beam. Therefore, the curing time is short, and thus the productivity can be improved.

Further, since it contains an ultraviolet or electron beam curable resin and a silicone macromonomer having a functional group capable of reacting with this resin, it can be compared with a conventional edge adhesive layer consisting of only an ultraviolet or electron beam curable resin. As a result, it is possible to remarkably improve the strength, and it is possible to obtain a radiation-emitting panel that has sufficient strength and antifouling property that can sufficiently cope with the current repeated use.

When a functional group capable of reacting with an ultraviolet or electron beam curable resin is present at one end of a silicone macromonomer molecule, when a silicone macromonomer is a methacryloxy group, or when an ultraviolet or electron beam curable resin is used. When the curable functional group of the resin is a vinyl group or an acrylate group, the curing time of the border patch layer can be shortened, and the strength and stain resistance of the border patch layer can be further improved.

Further, in the case of the conventional adhesive layer made of ultraviolet or electron beam curable resin, a large amount of organic solvent had to be used for coating the resin. Since it contains a silicone macromonomer, it can be applied without any trouble without using an organic solvent, and even when it is used, its usage can be reduced.

Further, since the silicone macromonomer has a high antifouling property, the edge adhesive layer containing the silicone macromonomer can obtain a high antifouling property, and when the number average molecular weight of the silicone macromonomer is 5,000 to 20,000, In addition, the antifouling property can be further improved.

When the thickness of the border layer at the end face of the phosphor layer is 5 μm or more and 1000 μm or less, a radiation-emitting panel having high productivity is obtained while effectively preventing the phosphor layer from absorbing moisture. be able to.

The present invention relates to a panel for converting transmitted radiation into visible light and / or ultraviolet radiation using a phosphor which is not stimulable, for example, the strength of a phosphor layer such as an intensifying screen for X-ray photography. Although useful for improving the durability, it is extremely useful for a radiation image conversion panel using a stimulable phosphor.

[0022]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view of a radiation-emitting panel showing a first embodiment of the present invention, FIG. 2 is a cross-sectional view of a radiation-emitting panel showing a second embodiment of the present invention,
FIG. 3 is a sectional view of a radiation-emitting panel according to a third embodiment of the present invention.

As shown in FIG. 1, a radiation-emitting panel 10 according to the first embodiment of the present invention has a phosphor layer 12 laminated on a support 11 and further protected on the phosphor layer 12. The layer 13 is laminated, and the end of the phosphor layer 12 is sealed by the edge sticking layer 14. As described above, if the edge sticking layer 14 seals the phosphor layer 12, as shown in FIG. 1, the support 11, the phosphor layer 12, and the protective layer 13 are entirely wrapped around the phosphor layer 12 to form the phosphor layer 12. It may be sealed.

As shown in FIG. 2, when the phosphor layer 22 is a radiation-emitting panel 20 in a state smaller than the support 21, the edge sticking layer 24 is placed on the edge of the support 21 and the fluorescent layer 22 is placed on the edge of the support 21. Body layer
22 may be sealed. However, in this case, if the side surface portion of the phosphor layer 22 is exposed, moisture is absorbed from a slightly exposed portion. Therefore, it is necessary to provide the edge adhesive layer 24 to the side surface portion of the protective layer 23. It is more preferable to seal up to the upper surface portion of the protective layer 23 as shown in FIG.

As shown in FIG. 3, in the case of a radiation-emitting panel 30 in which the phosphor layer 32 is smaller than the support 31 and smaller than the protective layer 33, for example, the phosphor layer 32 is not exposed so that the phosphor layer 32 is not exposed. As shown in the figure, it is preferable to provide an edge sticking layer 34 so as to cap the phosphor layer 32.

The thickness of the border layer at the end face of the phosphor layer means a thickness of a portion of the border layer in contact with the end face of the phosphor layer in a direction perpendicular to the end face of the phosphor layer,
1 is d1, FIG. 2 is d2, and FIG. 3 is d3. The thickness of the border layer is preferably from 5 to 1000 μm, more preferably from 10 to 500 μm. If the thickness is less than 5 μm, sufficient effects cannot be obtained in terms of moisture proof and strength for the phosphor layer,
When the thickness is larger than 00 μm, improvement in productivity cannot be expected.

Next, each layer of the radiation-emitting panel of the present invention will be described in more detail in the order of the phosphor layer, the support, the protective layer, and the border layer. First, the case where the phosphor of the phosphor layer of the radiation-emitting panel of the present invention is a stimulable phosphor will be described. The stimulable phosphor is a phosphor that emits stimulable light when irradiated with radiation and then irradiated with excitation light as described above, but the wavelength is in the range of 400 to 900 nm from a practical viewpoint. It is desirable that the phosphor be a phosphor that shows stimulated emission in a wavelength range of 300 to 500 nm by the excitation light. Examples of the stimulable phosphor used in the radiation image storage panel of the present invention include JP-B-7-84.
No. 588, etc.

General formula (M _{1 -f} · M _f ^I ) X · bM ^III X3 ″: cA (I)
The stimulable phosphor represented by From the viewpoint of the stimulated emission luminance, M ^I in the general formula (I) is preferably Na and K containing Rb, Cs and / or Cs, and particularly preferably at least one alkali metal selected from Rb and Cs. M ^III is preferably at least one trivalent metal selected from Y, La, Lu, Al, Ga and In. X "
Is preferably at least one halogen selected from F, Cl and Br. The b value representing the content of M ^III X3 ″ is preferably selected from the range of 0 ≦ b ≦ 10 ⁻² .

In the general formula (I), the activator A is
At least one metal selected from the group consisting of Eu, Tb, Ce, Tm, Dy, Ho, Gd, Sm, Tl and Na is preferable, and especially Eu, Ce, S
At least one metal selected from m, Tl and Na is preferred. The C value representing the amount of the activator is 10 ⁻⁶ <C <0.1.
It is preferable from the viewpoint of photostimulated light emission luminance.

Further, the following stimulable phosphors can also be used. U.S. patents listed in the 3,859,527 Pat SrS: Ce, Sm, SrS: Eu, Sm, ThO 2: Er, and La ₂ O ₂
S: Eu, Sm,

ZnS: C described in JP-A-55-12142
u, Pb, BaO.xAl ₂ O ₃ : Eu (0.8 ≦ x ≦ 10) and M ^II O.xSiO ₂ : A (where M ^II is Mg, Ca, Sr, Zn, C
d or Ba, and A is Ce, Tb, Eu, Tm, Pb, Tl, Bi
Or Mn, and x is 0.5 ≦ x ≦ 2.5),

(Ba) described in JP-A-55-12143
_1-Xy , Mg _X , Ca _y ) FX: aEu ²⁺ (where X is at least one of Cl and Br, and x and y are 0 <x + y
≦ 0.6 and xy ≠ 0, and a is 10 ⁻⁶ ≦ a ≦ 5 × 10 ⁻² ),

LnOX described in JP-A-55-12144:
xA (where Ln is at least one of La, Y, Gd, and Lu, X is at least one of Cl and Br, and A is
At least one of Ce and Tb, and x is 0
<X <0.1),

It is described in JP-A-55-12145 (B
a _1-X , M ²⁺ _X ) FX: yA (where M ²⁺ is at least one of Mg, Ca, Sr, Zn and Cd, X is at least one of Cl, Br and I, A Are Eu, Tb, Ce, Tm, Dy, Pr, H
at least one of o, Nd, Yb and Er, and x
Is 0 ≦ x ≦ 0.6, y is 0 ≦ y ≦ 0.2),

M ^II FX described in JP-A-55-160078
· XA: yLn (However, M ^II is Ba, Ca, Sr, Mg, Zn and Cd
A is BeO, MgO, CaO, SrO, Ba
O, ZnO, Al ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , In ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO
₂ , GeO ₂ , SnO ₂ , Nb ₂ O ₅ , at least one of Ta ₂ O ₅ and ThO ₂ , Ln is Eu, Tb, Ce, Tm, Dy, Pr, Ho, Nd, Y
X is Cl, B at least one of b, Er, Sm and Gd
at least one of r and I, wherein x and y are respectively 5 × 10 ⁻⁵ ≦ x ≦ 0.5 and 0 <y ≦ 0.2)
A phosphor represented by the composition formula:

JP-A-56-116777 describes (Ba
_1-X , M ^II _X ) F ₂ · aBaX ₂ : yEu, zA (where M ^II is at least one of beryllium, magnesium, calcium, strontium, zinc and cadmium, X is chlorine,
At least one of bromine and iodine, A is at least one of zirconium and scandium, and a, x, y, and z are each 0.5 ≦ a ≦ 1.25,
0 ≦ x ≦ 1, 10 ⁻⁶ ≦ y ≦ 2 × 10 ⁻¹ , and 0 <z ≦ 10 ⁻²
Is a phosphor represented by the composition formula:

It is described in JP-A-57-23673 (B
a_1-X, M^II _X) F_Two・ ABaX_Two: yEu, zB (where M ^IIIs Belliriu
, Magnesium, calcium, strontium, zinc
And at least one of cadmium and X is chlorine,
At least one of bromine and iodine, a,
x, y, and z are respectively 0.5 ≦ a ≦ 1.25, 0 ≦ x ≦
1, 10^-6≦ y ≦ 2 × 10^-1, And 0 <z ≦ 10^-2Is)
A phosphor represented by a composition formula of

As described in JP-A-57-23675 (B
a _1-X , M ^II _X ) F ₂ aBaX ₂ : yEu, zA (where M ^II is at least one of beryllium, magnesium, calcium, strontium, zinc and cadmium, X is chlorine,
A is at least one of bromine and iodine, A is at least one of arsenic and silicon, and a, x, y,
And z are respectively 0.5 ≦ a ≦ 1.25, 0 ≦ x ≦ 1, 10 ⁻⁶
≦ y ≦ 2 × 10 ⁻¹ , and 0 <z ≦ 5 × 10 ⁻¹ ).

M ^III O described in JP-A-58-69281
X: xCe (where M ^III is Pr, Nd, Pm, Sm, Eu, Tb, Dy, H
at least one trivalent metal selected from the group consisting of o, Er, Tm, Yb and Bi, X is one or both of Cl and Br, and x is 0 <x <0.1
Is a phosphor represented by the composition formula:

Ba _1-X described in JP-A-58-206678
M _{X / 2} L _{X / 2} FX: yEu ²⁺ (where M represents at least one alkali metal selected from the group consisting of Li, Na, K, Rb and Cs; L represents Sc, Y, La, Ce, Pr, Nd, Pm, S
represents at least one trivalent metal selected from the group consisting of m, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Ga, In and Tl; X is Cl, Br and I Represents at least one halogen selected from the group; and x is 10
^-2 ≦ x ≦ 0.5, and y is 0 <y ≦ 0.1).

BaFX.xA: yEu ²⁺ described in JP-A-59-27980
(Where X is at least one halogen selected from the group consisting of Cl, Br and I; A is a calcined product of a tetrafluoroborate compound; and x is 10 ⁻⁶ ≦
x ≦ 0.1, y is 0 <y ≦ 0.1) phosphor represented by the composition formula:

BaFX · x described in JP-A-59-47289
A: yEu ²⁺ (where X is at least one halogen selected from the group consisting of Cl, Br and I; A is monovalent or hexafluorosilicic acid, hexafluorotitanic acid and hexafluorozirconic acid) X is a calcined product of at least one compound selected from the group of hexafluoro compounds consisting of salts of divalent metals; and x is 10 ⁻⁶ ≦ x
≦ 0.1, y is 0 <y ≦ 0.1) phosphor represented by the composition formula:

BaFX · x described in JP-A-59-56479
NaX ′: aEu ²⁺ (where X and X ′ are Cl, B
r and at least one of I, wherein x and a are respectively 0 <x ≦ 2 and 0 <a ≦ 0.2)
A phosphor represented by the composition formula:

M ^II FX described in JP-A-59-56480
XNaX ': yEu ²⁺ : zA (where M ^II is at least one alkaline earth metal selected from the group consisting of Ba, Sr and Ca; X and X' are each selected from Cl, Br and I A is at least one halogen selected from the group consisting of; A is at least one transition metal selected from V, Cr, Mn, Fe, Co and Ni; and x is 0 <x ≦
2, y is 0 <y ≦ 0.2, and z is 0 <z ≦ 10 ⁻² ), a phosphor represented by a composition formula:

M ^II FX described in JP-A-59-75200
・ AM ^I X ′ ・ bM ′ ^II X ″ ₂・ cM ^III X ₃・ xA: yEu ²⁺ (However, M ^II
Is at least one alkaline earth metal selected from the group consisting of Ba, Sr and Ca; M ^I is at least one alkali metal selected from the group consisting of Li, Na, K, Rb and Cs; ^II is at least one divalent metal selected from the group consisting of Be and Mg; M ^III is Al, Ga, In
Is at least one trivalent metal selected from the group consisting of and Tl; A is a metal oxide; X is Cl, Br and I
X ′, X ″ and X are at least one halogen selected from the group consisting of F, Cl, Br and I; and a is 0 ≦ a ≦ 2, b is 0 ≦ b ≦ 10 ⁻² , c is 0 ≦ c ≦
10 ⁻² and a + b + c ≧ 10 ⁻⁶ ; x is 0 <x ≦ 0.5, y
Is 0 <y ≦ 0.2), a phosphor represented by a composition formula:

M ^II X described in JP-A-60-84381
₂ · aM ^II X ' ₂ : xEu ²⁺ (where M ^II is at least one alkaline earth metal selected from the group consisting of Ba, Sr and Ca; X and X' are composed of Cl, Br and I At least one halogen selected from the group and X ≠
X '; and a is 0.1≤a≤10.0, x is 0 <x≤0.
2, a stimulable phosphor represented by the composition formula:

M ^II FX described in JP-A-60-101173
AM ^I X ': xEu ²⁺ (where M ^{II is} at least one kind of alkaline earth metal selected from the group consisting ^of Ba, Sr and Ca; M ^I is at least one kind selected from the group consisting of Rb and Cs) X is at least one halogen selected from the group consisting of Cl, Br and I; X 'is at least one halogen selected from the group consisting of F, Cl, Br and I; a and x are respectively 0 ≦ a ≦ 4.0 and 0 <x ≦ 0.2), a stimulable phosphor represented by a composition formula:

M ^I X: x described in JP-A-62-25189
Bi (however, M ^I is at least one alkali metal selected from the group consisting of Rb and Cs; X is at least one halogen selected from the group consisting of Cl, Br and I; and x is 0 <x A photostimulable phosphor represented by a composition formula of

LnOX: xCe described in JP-A-2-229882 (where Ln is at least one of La, Y, Gd and Lu;
X is at least one of Cl, Br and I, and x is 0 <x
≦ 0.2, and the ratio between Ln and X is 0.500 <X / Ln ≦
0.998, and the maximum wavelength λ of the stimulable excitation spectrum
Cerium-activated rare earth oxyhalide phosphor represented by 550 nm <λ <700 nm).

[0050] Further, the JP 60-84381 No. M ^II X ₂ · aM ^II X described in the _'2: xEu ²⁺ stimulable phosphor, additives such as shown below M ^II X ₂ · aM ^II X ′ ₂ may be contained in the following ratio per 1 mol.

BM described in JP-A-60-166379
^IX "(M^IIs selected from the group consisting of Rb and Cs
X "is at least one alkali metal, and X" is F, Cl, B
at least one member selected from the group consisting of r and I
And b is 0 <b ≦ 10.0);
BKX ″ and cMgX described in Sho 60-221483_Two・ DM
^IIIX ′_Three(However, M^IIIIs Sc, Y, La, Gd and Lu
At least one trivalent metal selected from the group consisting of
X ”, X and X ′ are all F, Cl, Br and I
At least one halogen selected from the group consisting of
And b, c and d are each 0 ≦ b ≦ 2.0,
0 ≦ c ≦ 2.0, 0 ≦ d ≦ 2.0, and 2 × 10^-Five≤b + c
+ d); yB described in JP-A-60-228592
(However, y is 2 × 10^-Four≦ y ≦ 2 × 10^-1JP-A-60
BA (where A is SiO _TwoAnd
And P_TwoO_FiveAt least one oxide selected from the group consisting of
And b is 10^-Four≦ b ≦ 2 × 10^-1);
BSiO described in No. 61-120883 (where b is 0 <b
≦ 3 × 10^-2Is described in JP-A-61-120885.
BSnX ″_Two(However, X ″ is composed of F, Cl, Br and I.
At least one halogen selected from the group consisting of
And b is 0 <b ≦ 10^-3Described in JP-A-61-235486.
BCsX ″ and cSnX listed_Two(However, X ″ and X are
A small number selected from the group consisting of F, Cl, Br and I, respectively.
At least a kind of halogen, and b and c are
0 <b ≦ 10.0 and 10 respectively^-6≦ c ≦ 2 × 10^-2In
BCs described in JP-A-61-235487
X ″ ・ yLn³⁺(However, X ″ consists of F, Cl, Br and I
Ln is at least one halogen selected from the group
Sc, Y, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb
At least one rare earth selected from the group consisting of
And b and y are each 0 <b ≦
10.0 and 10 ^-6≦ y ≦ 1.8 × 10^-1Is).

Among the above-described stimulable phosphors, a divalent europium-activated alkaline earth metal halide-based phosphor and a cerium-activated rare earth oxyhalide phosphor are particularly preferable because they exhibit high-luminance stimulable light emission. However, the stimulable phosphor used in the present invention is not limited to the above-described phosphors, and any phosphor can be used as long as it exhibits stimulable emission when irradiated with radiation and then irradiated with excitation light. There may be.

However, the stimulable phosphor used in the present invention is not limited to the above-mentioned phosphors, and any stimulable phosphor that emits stimulable light when irradiated with radiation and then with excitation light. There is no particular limitation.

The radiation-emitting panel of the present invention is
Transmissive radiation with visible light and
And / or panels for converting to ultraviolet radiation, for example
The phosphor used for radiographic intensifying screens
As a tungstate-based phosphor (CaWO_Four, MgW
O_Four, CaWO_Four: Pb), terbium-activated rare earth oxysulfide
Phosphor (Y_TwoO_TwoS: Tb, Gd_TwoO_TwoS: Tb, La_TwoO_TwoS: Tb, (Y, Gd)_TwoO
_TwoS: Tb, (Y, Gd) O_TwoS: Tb, Tm etc.), Terbium activated rare earth
Phosphate phosphors (YPO_Four: Tb, GdPO_Four: Tb, LaPO_Four: Tb
Terbium-activated rare earth oxyhalide-based fireflies
Optical body (LaOBr: Tb, LaOBr: Tb, Tm, LaOCl: Tb, LaOCl: Tb, T
m, LaOCl: Tb, Tm, LaOBr: Tb, GdOBr: Tb, GdOCl: Tb
Thulium-activated rare earth oxyhalide phosphor
(LaOBr: Tm, LaOCl: Tm, etc.), barium sulfate based phosphor
(BaSO_Four: Pb 、 BaSO_Four:EU²⁺, (Ba, Sr) SO_Four:EU²⁺Such),
Bivalent europium activated alkaline earth metal phosphate-based fireflies
Light body (Ba_Three(PO_Four)_Two:EU²⁺, Ba_Three(PO_Four)_Two:EU²⁺Etc.)
Europium activated alkaline earth metal fluoride halides
Phosphor (BaFCl: EU²⁺, BaFBr: Eu²⁺, BaFCl: EU²⁺, Tb, Ba
FBr: Eu²⁺, Tb, BaF_Two・ BaCl_Two・ KCl: Eu²⁺, (Ba ・ Mg) F_Two・ BaCl
_Two・ KCl: Eu ²⁺Etc.), iodide-based phosphors (CsI: Na, CsI: T
l, NaI, KI: Tl), sulfide-based phosphors (ZnS: Ag, (Zn, C
d) S: Ag, (Zn, Cd) S: Cu, (Zn, Cd) S: Cu, Al, etc.), phosphoric acid
Hafnium-based phosphor (HfP_TwoO₇: Cu etc.), tantalate
Based phosphor (YTaO_Four, YTaO_Four: Tm, YTaO_Four: Nb 、 (Y, Sr) TaO
_4-x: Nb, LuTaO_Four, LuTaO_Four: Nb 、 (Lu, Sr) TaO_4-x: Nb, Gd
TaO_Four: Tm, Gd_TwoO_Three・ Ta_TwoO_Five・ B_TwoO_Three: Tb)
Can be However, the phosphor used in the present invention is
It is not limited to these, but can be
Use any phosphor that emits light in the visible or near ultraviolet region.
Can be

As the binder used for the phosphor layer, a thermoplastic elastomer which has elasticity at room temperature and becomes fluid when heated is suitably used. As the thermoplastic elastomer, polystyrene, polyolefin,
Preferred examples include polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluorine rubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber, and silicone rubber.

As the above thermoplastic elastomer, those having a softening temperature or a melting point of 30 ° C. to 300 ° C. are generally used, and those having a softening temperature or 30 ° C. to 200 ° C. are preferably used.
It is more preferable to use one having a temperature of 30 ° C to 150 ° C.

Further, it is also possible to use an ultraviolet or electron beam curable resin to dry and cure with ultraviolet or electron beams. As the ultraviolet-curable or electron-beam-curable resin, the resin used for the border layer described later can be used. In this case, the same resin as the border layer or a different resin may be used.

The above binder is sufficiently mixed with the phosphor and the solvent to prepare a coating solution in which the stimulable phosphor is uniformly dispersed in the binder solution.

As the solvent, methanol, ethanol,
lower alcohols such as n-propanol, n-butanol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters of lower fatty acids such as methyl acetate, ethyl acetate and butyl acetate with lower alcohols; ethylene Ethers such as glycol monopropyl ether; hydrocarbons such as toluene, xylene and cyclohexane;
And mixtures thereof.

The mixing ratio between the binder and the stimulable phosphor in the coating solution varies depending on the desired characteristics of the radiation image conversion panel, the kind of the phosphor, and the like. Is selected from the range of 1: 1 to 1: 100 (weight ratio), more preferably from the range of 1: 8 to 1:40 (weight ratio).

It is to be noted that the phosphor layer in which the phosphor is dispersed in the binder is most preferable because the image quality such as the amount of light emission and noise is relatively easy to control and the mechanical strength is easy to increase. A phosphor that is often used, but is composed only of aggregates of stimulable phosphor without a binder, or a phosphor in which polymer substances are impregnated in the gaps between aggregates of stimulable phosphor. It may be a layer or the like.

Hereinafter, a method of manufacturing a radiation image conversion panel will be described step by step, taking as an example a case where the phosphor layer is composed of a stimulable phosphor and a binder containing and supporting the stimulable phosphor in a dispersed state. .

The phosphor layer can be formed on a support by the following known method. First, a stimulable phosphor and a binder are added to a solvent and mixed well to prepare a coating solution in which the stimulable phosphor is uniformly dispersed in a binder solution. Next, a coating film is formed by uniformly applying the coating solution on the surface of the support. This coating operation can be performed by using ordinary coating means, for example, a doctor blade, a roll coater, a knife coater, or the like.

The support can be arbitrarily selected from materials known as supports for conventional radiation image storage panels. Further, in order to strengthen the bond between the support and the phosphor layer or to improve the sensitivity or image quality (sharpness, granularity) of the radiation image conversion panel, the surface of the support on which the phosphor layer is provided is provided. Applying a polymer substance such as gelatin to provide an adhesion-imparting layer, or providing a light-reflective layer composed of a light-reflective substance such as titanium dioxide or a light-absorbing layer composed of a light-absorbing substance such as carbon black. However, the support used in the present invention may be provided with these various layers. These configurations can be arbitrarily selected according to the purpose, use, and the like of a desired radiation image conversion panel.

Further, as described in JP-A-58-200200, for the purpose of improving the sharpness of the obtained image,
The surface of the support on the side of the phosphor layer (when the surface of the support on the side of the phosphor layer is provided with an adhesiveness-imparting layer, a light-reflecting layer or a light-absorbing layer, means the surface) Irregularities may be formed.

After forming a coating on the support as described above, the coating is dried to complete the formation of the stimulable phosphor layer on the support. The thickness of the phosphor layer depends on the characteristics of the intended radiation image conversion panel, the type of phosphor, the mixing ratio between the binder and the phosphor, and is generally about 20 μm to 1 mm. It is more preferable that the thickness be 50 μm to 500 μm.

The stimulable phosphor layer does not necessarily need to be formed by directly applying a coating solution on a support as described above. For example, a glass plate, a metal plate, a plastic sheet, or the like may be separately provided. After forming a phosphor layer by applying a coating solution on the sheet and drying, the support is pressed against the support or an adhesive is used to separate the support and the phosphor layer. You may join.

In the radiation-emitting panel, a transparent protective film for physically and chemically protecting the phosphor layer is provided on the surface of the phosphor layer opposite to the side in contact with the support. Is common.

The transparent protective film is made of, for example, cellulose derivatives such as cellulose acetate and nitrocellulose; or polymethyl methacrylate, polyvinyl butyral,
A solution prepared by dissolving a transparent polymer such as a synthetic polymer such as polyvinyl formal, polycarbonate, polyvinyl acetate, and vinyl chloride / vinyl acetate copolymer in a suitable solvent is applied to the surface of the phosphor layer. It can be formed by a method. In addition, polyethylene terephthalate, polyethylene naphthalate, polyethylene,
By forming a plastic sheet made of polypropylene, polyvinylidene chloride, polyamide, etc., and a protective film forming sheet such as a transparent glass plate separately, and bonding them to the surface of the phosphor layer using an appropriate adhesive. Can also be formed.

More preferably, the protective film is formed of a film-forming resin, a reactive silicone having at least one hydroxyl group or amino group at a terminal and having a number average molecular weight of about 5,000 to 20,000, and a cross-linking reaction with a hydroxyl group or an amino group. After coating, drying and curing a coating solution for forming a protective film containing a coating agent on a transparent support such as PET using a coating means such as a doctor blade, dip coater, slide coater or extrusion coater, the adhesive layer is formed. It is formed on the PET surface on the opposite side of the protective film and laminated on the phosphor surface, or by directly applying, drying and curing on the phosphor layer surface. Of course, this protective film may be formed simultaneously with the formation of the phosphor layer by simultaneous multi-layer coating.

As the film-forming resin used for forming the protective film, polyurethane resins, polyacryl resins, cellulose derivatives, polymethyl methacrylate, polyester resins, epoxy resins, etc., which are generally known as film-forming resins, are preferred. In particular, an organic solvent-soluble fluororesin can be preferably used.

The fluorine-based resin is a polymer of a fluorine-containing olefin (fluoroolefin) or a copolymer containing a fluorine-containing olefin as a copolymer component. Examples thereof include polytetrafluoroethylene, polychlorotrifluoroethylene, and polyfluoroethylene. Preferable examples include vinyl chloride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer and fluoroolefin-vinyl ether copolymer. Alternatively, the protective film can be formed by drying and curing with an ultraviolet ray or an electron beam using an ultraviolet ray or an electron beam curable resin. The thickness of the protective film depends on the substance used, but is about 0.1
Preferably it is ~ 20 μm.

Further, for the purpose of improving the sharpness of the obtained image, a coloring layer which absorbs excitation light but does not absorb stimulated emission light may be added to at least one of the above-mentioned layers. No. 59-23400). Further, for the purpose of improving the sharpness of the obtained image, at least one of the layers constituting the radiation image conversion panel of the present invention absorbs excitation light and does not absorb stimulated emission light. It may be colored by an agent (see Japanese Patent Publication No. 54-23400).

Next, the border layer will be described. The edge application layer contains an ultraviolet ray or electron beam curable resin, and a silicone macromonomer having a functional group capable of reacting with the ultraviolet ray or electron beam curable resin, and further contains a colorant, a yellowing inhibitor, and the like as necessary. May be.

As the ultraviolet or electron beam curable resin,
Acrylate monomers, vinyl compound monomers, acrylate oligomers, cationic polymerization monomers, cationic polymerization oligomers, and the like can be preferably used.

In the case of curing by irradiating ultraviolet rays, these resins and a photo-polymerization initiator such as a radical photo-polymerization initiator, a cationic photo-polymerization initiator, a radical-type photo-polymerization accelerator, and a cationic photo-polymerization accelerator are used. A polymerization initiator is used in combination. Also,
When a photopolymerization initiator is used, a polymerization inhibitor such as benzoquinone may be used in combination. In the case of curing by irradiation with an electron beam, a photopolymerization initiator is unnecessary.

The acrylate monomer is a low molecular weight compound having 1 to 6 acrylate groups and having a molecular weight of about 1,000 or less, and a reactive group other than the acrylate group (isocyanate group, epoxy group, acid anhydride group, carboxyl group, etc.). May be provided. Further, the molecule may contain a halogen element such as fluorine and bromine in addition to sulfur.

Specifically, acrylates obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide or ε-caprolactone to an alcohol, N-vinylcaprolactam, N-vinylcaprolactam, N-vinylformamide, imide acrylate,
Alkylene oxide such as 2-methacryloyloxyethyl isocyanate, propylene oxide or ε-
Preferable examples include poly (meth) acrylate obtained by addition reaction of caprolactone with polyhydric alcohol, tricycloidecanedimethylol diacrylate, dipentaerythritol penta and hexaacrylate, and ditrimethylol.

The curable functional group of these monomers and oligomers is more preferably a vinyl group or an acrylate group, and in a cationic polymerization system, more preferably an epoxy group, a vinyl ether group or an oxetane group.

Specific examples of the ultraviolet or electron beam curable resin include RAPI-CU manufactured by ASP Japan Co., Ltd.
RE series, manufactured by Asahi Denka Kogyo Co., Ltd .: Adeka Optomer KRM series, manufactured by Arakawa Chemical Industry Co., Ltd .: beam set series, manufactured by Osaka Organic Chemical Industry Co., Ltd .: various acrylates, manufactured by Kyoei Chemical Co., Ltd. : Light ester, light acrylate, epolite, epoxy ester, urethane acrylate series, manufactured by San Nopco Ltd .: Photomer
Series, manufactured by JSR Corporation: Desolite S series, Opstar JL, JM series, manufactured by Showa Kogyo Co., Ltd .: Lipoxy SP / VR series, manufactured by Shin-Nakamura Chemical Co., Ltd .: NK
Ester, NK Oligo Series, Daiichi Kogyo Pharmaceutical Co., Ltd.
Made: New Frontier Series, Daicel Chemical Industries
Co., Ltd .: each series of Placcel G, Cyclomer P, Eporide D, Eporide PB, Daimac, PUE, Daicel UCB Co., Ltd .: Ebecryl,
Uvecryl, celloside, dimax, Uvac
ure, EB series, Daiso Corporation: Daiso Dapp, Daiso Isodap series, Dainippon Ink & Chemicals, Ltd .: LUMICURE, UNIDEC series, Toagosei Co., Ltd .: Aronix M series ,
Toyobo Co., Ltd .: Virocure Series, Nagase Kasei Co., Ltd .: Denacol Acrylate, Nippon Kayaku Co., Ltd .:
KAYARAD series, manufactured by Nippon Synthetic Chemical Co., Ltd .: Shikko and Coponil series, Nippon SiberHegner
Ltd .: Actylene / Actilane Series, Nippon Soda Co., Ltd .: TE Series, Nippon Yushi Co., Ltd .: Blemmer Series, Negami Kogyo Co., Ltd .: Art Resin UN,
SH series, manufactured by Hitachi Chemical Co., Ltd .: Hitaloid
Series, manufactured by Mitsui Chemicals, Inc .: Orestar RA series,
Mitsubishi Rayon Co., Ltd .: Diamond Beam Series, Union Carbide Japan Co., Ltd .: CYRACURE UVR
・ Series, FS Japan Co., Ltd .: Larom
er, various acrylate series, Morton
International: Ubitane series and the like.

As the photopolymerization initiator, benzophenone,
Methyl orthobenzoylbenzoate, isopropylthioxanthone, diethylthioxanthone, benzyldimethylketal, α-hydroxyalkylphenone, α-amylalkylphenone, acylphosphine oxide,
Alkylphenyl glyoxylate, diethoxyacetophenone and the like can be preferably mentioned.

More specifically, Adeka Optomer SP series manufactured by Asahi Denka Kogyo KK, Sun Aid SI series manufactured by Sanshin Kagaku Kogyo KK, Ciba Specialty Chemicals
Inc .: Irgacure and Darocur series, Nippon Kayaku Co., Ltd .: KAYACURE series, VSF Japan Ltd .: Lucirin series, and the like. The ultraviolet or electron beam curable resin is preferably contained in the edge adhesive layer in the range of 40 to 100% by weight, more preferably in the range of 60 to 100% by weight.

Examples of the silicone macromonomer having a functional group capable of reacting with the ultraviolet or electron beam curable resin include those having a dimethylpolysiloxane skeleton, and at least one or more ultraviolet curable functional groups (for example, , A vinyl group and a methacryloxy group). The number average molecular weight (Mn) of the silicone macromonomer is preferably in the range of 5,000 to 20,000, more preferably in the range of 10,000 to 15,000.

The silicone macromonomer has at least one UV-curable functional group at the terminal, and preferably has at least one UV-curable functional group at one terminal. Further, the silicone macromonomer may include a perfluoroalkyl group.

The silicone macromonomer is commercially available from Chisso Corporation under the trade name: Syraprene FM-07 series, and may be used.
M-07 series (methacryloxypropyl-modified silicone)

Embedded image And the like can be preferably used. (M in the chemical formula is
Represents a number such that Mn is between 5000 and 20000. ) The above silicone macromonomer is 0.1 ~
It is preferably contained in the range of 20% by weight,
More preferably, it is contained within the range of 0% by weight.

The border layer is coated with a border layer-forming coating solution containing an ultraviolet or electron beam curable resin and a silicone macromonomer on the side surface of the phosphor layer using a coating means such as a nozzle, a screen, a dip coater, or the like. When a solvent is contained, the layer is formed by removing the solvent, irradiating ultraviolet rays or an electron beam, and drying and curing. The formation and curing of the rim layer may be performed simultaneously with the formation of the protective layer.

In the case of an ultraviolet curable resin, the output is 50 W / cm to 5
Cured by irradiating with a mercury lamp or metal halide lamp of about 00 W / cm for about 0.01 to 10 seconds.
In the case of an electron beam curable resin, the resin is cured by irradiating with an acceleration voltage of about 100 kV to 1000 kV for about 0.001 to 1 second.

Either the ultraviolet curable resin or the electron beam curable resin may be selected. However, when the ultraviolet curable resin is selected, the irradiation time for curing is longer than when the electron beam curable resin is selected. However, since the ultraviolet irradiation device is small and inexpensive, the burden of new capital investment is reduced.

Examples of the ultraviolet irradiation apparatus are: A-Line Co., Ltd .: Σ-Line, Eye Graphics Co., Ltd .: Eye Grandage, Eye Cure series, Iwasaki Electric Co., Ltd.
Manufactured by: Eye UV Cure System, manufactured by Ushio Inc .: UniCure System Series, manufactured by Chemitec Corporation: UV
C-Series, manufactured by San-A-Tech, Inc .: OPTICUR
E series, manufactured by Toshiba Lighting & Technology Corp .: Toskure series and the like can be preferably used.

As an electron beam irradiation apparatus, Iwasaki Electric Co., Ltd.
Made by: ELECTROCURTAIN, USHIO INC.
Manufactured by Min-EB, manufactured by Sumitomo Heavy Industries, Ltd .: WIPL,
Lyocure manufactured by Toyo Ink Mfg. Co., Ltd., EPS series manufactured by Nissin High Voltage Co., Ltd. can be preferably used.

[0091]

EXAMPLES Example 1 A radiation image storage panel of the present invention was manufactured as follows. First, as a phosphor layer forming coating solution, phosphor: BaFBr _0.8 I _0.2 : 0.001Eu ²⁺ 1000 g,
246 g of a 13% MEK solution of a polyurethane resin (manufactured by Dainippon Ink and Chemicals, Inc .: Pandex T5265H), a bisphenol A type epoxy resin (manufactured by Shell Chemical Co., Ltd .: Epicoat 100)
1) 30 g of a 50% MEK solution, 3 g of a polyisocyanate (manufactured by Nippon Polyurethane Co., Ltd .: Coronate HX), a colorant (ultramarine;
0.02 g of Daiichi Kasei Kogyo Co., Ltd .: SM-1) and 52 g of MEK were dispersed with a disper for 3 hours to prepare a coating solution having a viscosity of 3.5 Pa · s (25 ° C.).

This coating solution was applied on a polyethylene terephthalate sheet (temporary support, thickness: 180 μm) coated with a silicone release agent by an extrusion coater to a dry thickness of 250 μm, dried, and then temporarily dried. Peeled from the support.

Next, the following support having a reflective undercoat layer was prepared. 350 g of gadolinium oxide (Gd ₂ O ₃ ) fine particles (90% by weight of all particles having a particle size in the range of 1 to 5 μm) and a binder (soft acrylic resin; Dainippon Ink and Chemicals, Inc.) ): Chris Coat P-1018GS (20% toluene solution)) 1800g, plasticizer (phthalate ester; Daihachi Chemical)
# 10) 40 g, ZnO whisker (Matsushita Amtech Co., Ltd .: Panatetra A-1-1) 120 g as a conductive agent, and 2 g of ultramarine (Daiichi Kasei Kogyo Co., Ltd .: SM-1) as a colorant in MEK. In addition, a dispersion liquid for the undercoat layer (viscosity 0.5 Pa · s: 20 ° C.) was prepared by dispersing and dissolving using a disper, and this was used as a polyethylene terephthalate sheet (Lumirror s-10 manufactured by Toray Co., Ltd. 250 μm; typical) = 20, carbon black, silica on one side,
On the light-shielding layer (about 18 μm) provided with a binder), using an extrusion coater, apply evenly on the opposite side to the light-shielding layer, then dry the coating,
A reflective undercoat layer having a thickness of 20 μm was formed.

Next, the phosphor sheet and the support having a reflective undercoat layer were superposed on each other, and a calender roll was used.
a, Heat compression was continuously performed at an upper roll temperature of 75 ° C, a lower roll temperature of 75 ° C, and a feed rate of 1.0 m / min. By this heating and compression, the phosphor sheet was completely fused to the support via the reflective undercoat layer to form a phosphor layer (layer thickness: 210 μm).

Next, a protective layer was formed by the following procedure. Fluorine-based copolymer resin solution (Lumiflon LF, manufactured by Asahi Glass Co., Ltd.)
504X (30% xylene solution) 40g, melamine-formaldehyde as organic filler (Nippon Shokubai Co., Ltd .: poster
S6) A mixture of 28.4 g, a dispersant of 0.5 g of an aluminum coupling agent (Ajinomoto Co., Inc .: Plenact AL-M) and 200 g of MEK was subjected to a ball mill using a zirconia ball of 3 mmφ by a ball mill.
After time-dispersion mixing, 360 g of Lumiflon LF504X (30% xylene solution) was added, and the mixture was further dispersed for 8 hours. afterwards,
Hydroxyl group reactive silicone oligomer (Chisso Corporation:
1.4 g of polyaisocyanate (Sumitomo Bayer Urethane Co., Ltd .: Sumidur)
N3300 (solid content: 100%)) of 22.2 g, dibutyltin dilaurate (Kyodo Yakuhin Co., Ltd .: KS1260) of 1.4 mg and MEK of 800 g were additionally mixed as a catalyst to prepare a coating solution for a protective layer.

This protective layer coating solution was lined with a 6 μm-thick PET film (Toray Industries, Inc .: Lumirror 6-CF53) and a heat-resistant removable film (PANAC, Inc .: CT50). After applying with a bar coater,
Heat treatment was performed at 120 ° C. for 20 minutes, followed by drying and thermosetting to provide a protective film having a thickness of 2 μm.

Next, the heat-resistant re-peelable film was peeled off from the 6 μm-thick PET film provided with the protective film.
Polyester resin solution (Toyobo Co., Ltd .: Byron 30SS)
Was applied and dried to form an adhesive layer (adhesive application weight 2 g / m ² ).

[0098] This PET film with a protective film was bonded to the phosphor layer via an adhesive layer using a laminating roll to form a protective layer. Furthermore, Ra0.
A 4 μm roughness emboss was applied.

Subsequently, a 20 μm thick OPP film (Toray Industries, Inc.)
Co., Ltd., Trefan YM-11 # 20), apply an unsaturated polyester resin solution (Toyobo Co., Ltd .: Byron 30SS) and dry to form an adhesive layer (adhesive application weight 9 g / m ² ). This OPP film was adhered to the opposite side (light-shielding layer side) of the support from the side on which the phosphor layer was provided using an adhesive layer using a laminating roll to form a back protective layer.

Further, 70 g of a polyester-based urethane acrylate (Negami Industry Co., Ltd .: Art Resin UN-330), 3 g of a photopolymerization initiator (Nagase Sangyo Co., Ltd .: Irgacure 184), and an epoxy resin (oil oil) as a yellowing inhibitor Shell Epoxy Co., Ltd .:
0.6 g of Epicoat # 1001 (solid), a silicone oligomer having a terminal methacryloxy group reactive (Chisso
Co., Ltd., Cyraprene FM-0725, Mn 10,000) 0.2g of MEK 5g
To prepare a coating solution. After the corona discharge treatment of the protective layer at the end face of the phosphor layer provided with the protective layer prepared above, the coating solution was applied with a syringe so as to cover the end face, and then an air-cooled metal halide lamp manufactured by Eye Graphic Co., Ltd. Using M08-L41, UV light with 80W / cm
The coating was cured by irradiating for 2 seconds to form an edge adhesive layer having a thickness of about 25 μm.

As described above, a radiation image conversion panel with an edge sticking layer in which the end face of the phosphor layer was protected was manufactured.

Example 2 A phosphor layer was prepared in the same manner as in Example 1 except that urethane acrylate UA122P manufactured by Shin-Nakamura Chemical Co., Ltd. was used in place of the art resin UN-330 used for edge bonding. A radiation image conversion panel with an edge-adhering layer having a protected end face was manufactured.

(Example 3) In place of the art resin UN-330 used for the edge application in Example 1, Daicel UCB was used.
A radiation image conversion panel with an edge sticking layer in which the end faces of the phosphor layer were protected was produced in the same manner except that the linear acrylic oligomer EB745 of Co., Ltd. was used.

(Example 4) In place of the art resin UN-330 used for the edge application in Example 1, Daicel UCB was used.
A radiation image conversion panel with an edge sticking layer in which the end face of the phosphor layer was protected was produced in the same manner except that Epoxy Acrylate EB3701 manufactured by KK was used.

(Comparative Example 1) The edge face of the phosphor layer was protected in the same manner as in Example 1 except that the antifouling agent (methacryloxy group-reactive silicone oligomer at the terminal) of the edge patch was not used. A radiation image conversion panel with an edge sticking layer was manufactured.

(Comparative Example 2) A radiation image conversion panel with an edge-attached layer in which the end faces of the phosphor layers were protected was manufactured in the same manner except that the following edge-attached layer was provided instead of the edge-attached layer of Example 1. did.

70 g of a silicone polymer (polyurethane having a polydimethylsiloxane unit; Dainichisei Chemical Co., Ltd., dialomer SP-3023 (15% methyl ethyl ketone / toluene solution)) 70 g, and a polyisocyanate (Dainichi Seika Co., Ltd.) as a crosslinking agent: 3 g of Closnate D-70 (50% solution), 0.6 g of an epoxy resin (Yuika Shell Epoxy Co., Ltd .: Epicoat # 1001 (solid)) as a yellowing inhibitor, and an alcohol-modified silicone (Shin-Etsu Chemical Co., Ltd.) as a slipping agent ): X-22-2809 (66% xylene-containing paste)) 0.2 g was dissolved in 15 g of solvent MEK to prepare a coating solution. This coating solution was applied to each side surface of the phosphor sheet provided with the protective layer prepared above, and dried sufficiently at room temperature to form a side cured film having a thickness of about 25 μm.

(Evaluation Experiment) The radiation image conversion panel obtained above was evaluated for drop strength and stain removal as follows.

1. The radiation image conversion panel having a drop strength of 355 mm square was vertically dropped from a height of 80 cm so as to hit a 20 mm φ SUS rod at a right angle, and then visually inspected for peeling of an edge adhesive layer, and evaluated according to the following four grades. A: None B: Slightly present C: Clearly present D: Remarkably present

[0110] 2. Magic stain removal Marking was performed on the edge application layer with black magic ink, dried, wiped off with a tissue paper, and visually checked for the remaining amount of the magic ink, and evaluated according to the following four grades. A: None B: Slightly present C: Clearly present D: Remarkably present

3. Sliding test The edge layer of the radiation image conversion panel was cut into a rectangle of 5 cm x 15 cm, and a nonwoven fabric (manufactured by Idemitsu Petrochemical Co., Ltd .: Stratec) was cut.
The sheet was cut into 3 cm × 4 cm, and a load of 0.98 N was applied. After sliding, the presence or absence of peeling of the edge application layer was visually checked, and evaluated by the following four grades. A: None B: Slightly present C: Clearly present D: Remarkably present

Further, after sliding, a mark was applied on the edge application layer with black magic ink, and after drying, the mark was wiped off with a tissue paper. The remaining amount of the magic ink was visually checked, and evaluated according to the following four grades. A: None B: Slightly present C: Clearly present D: Remarkably present The results are shown in Table 1.

[0113]

[Table 1] As is evident from the above experimental results, the edge adhesive layer of the radiation image storage panel of the present invention had high strength, and had high antifouling properties even after sliding. On the other hand, in Comparative Example 1 in which no silicone macromonomer was used, the antifouling property was not sufficient even though the strength was high, and in Comparative Example 2 in which no ultraviolet or electron beam curing resin was used, the strength of the edge adhesive layer of the present invention was low. And the antifouling property after sliding was not sufficient.

Although the embodiment using a radiation image conversion panel using a stimulable phosphor has been described here, the bordering layer according to the present invention uses a non-stimulable phosphor to transmit transmitted radiation and / or visible light. Or panels for converting to ultraviolet radiation,
For example, it is extremely useful for improving the strength and antifouling property of the side face of a panel used repeatedly, such as an intensifying screen for X-ray photography.

[Brief description of the drawings]

FIG. 1 is a sectional view of a radiation-emitting panel according to a first embodiment of the present invention.

FIG. 2 is a sectional view of a radiation-emitting panel according to a second embodiment of the present invention.

FIG. 3 is a sectional view of a radiation-emitting panel according to a third embodiment of the present invention.

[Explanation of symbols]

 10 Radiation-emitting panel 11 Support layer 12 Phosphor layer 13 Protective layer 14 Edge application layer

Claims (6)

[Claims] 1. A radiation-emitting panel in which a support layer, a phosphor layer and a protective layer are laminated in this order, an ultraviolet ray or an electron beam curing resin, and an ultraviolet ray or an electron beam at an end of the phosphor layer. A radiation-emitting panel, comprising: a border layer containing a cured resin and a silicone macromonomer having a functional group capable of reacting; and the border layer is cured by irradiation with ultraviolet rays or electron beams. 2. The radiation-emitting panel according to claim 1, wherein the functional group is provided at one end of the silicone macromonomer molecule. 3. The radiation-emitting panel according to claim 1, wherein the functional group of the silicone macromonomer is a methacryloxy group. 4. The radiation-emitting panel according to claim 1, wherein the number average molecular weight of the silicone macromonomer is 5,000 to 20,000. 5. The radiation-emitting panel according to claim 1, wherein the curable functional group of the ultraviolet or electron beam curable resin is a vinyl group or an acrylate group. 6. The radiation-emitting panel according to claim 1, wherein a thickness of the edge sticking layer at an end face of the phosphor layer is 5 μm or more and 1000 μm or less.