JP2002107495A - Radioluminescent panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provided a radioluminescent panel excellent in moisture proofness and an antifouling property, and reduced in deterioration of image quality. SOLUTION: In this panel composed by laminating a phosphor layer 1, a protection layer 2 and an antifouling layer 3 on a support body 4 in this order, the protection layer 2 comprises a resin film 2a laminated on the phosphor layer 1, and a vapor deposition layer 2b of an inorganic substance vapor- deposited on the resin film 2a, having no photo-absorption in a wavelength range of 300 nm-1,000 nm, and having a gas barrier property, and the antifouling layer 3 contains a film forming resin, a reactive silicone, a crosslinker and white powder.

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 panel 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 a 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, an inorganic or organic support and a stimulable phosphor layer provided on the surface thereof. Since the stimulable phosphor of the phosphor layer has a property of exhibiting stimulable emission when irradiated with excitation light after absorbing radiation such as X-rays, the stimulable phosphor is transmitted through the subject or emitted from the subject. Radiation is absorbed by the stimulable phosphor layer of the radiation image conversion panel in proportion to the radiation dose, and a radiation image of a subject or a subject is formed on the panel as a radiation energy accumulation image. This accumulated image can be emitted as stimulated emission light by irradiating the excitation light, and the accumulated image of radiation energy is imaged by photoelectrically reading the stimulated emission light and converting it into an electric signal. It is possible to do.

[0005] A protective film is usually provided on the surface of the stimulable phosphor layer (the surface not facing the support), and the phosphor layer is chemically modified by moisture absorption or the like. Protects from pollution. The protective film is formed by applying a solution prepared by dissolving a transparent organic polymer substance in an appropriate solvent onto the phosphor layer, or an organic polymer film such as polyethylene terephthalate or a transparent polymer film. Known are those in which a protective film forming sheet such as a glass plate is separately formed and provided on the surface of the phosphor layer using an appropriate adhesive, or those in which an inorganic compound is formed on the phosphor layer by vapor deposition or the like. Have been. These are, in addition to Patent 2715189, JP-A-62-15498, JP-A-62-209400, JP-A-62-245200.
No., JP-A-8-043598, JP-A-8-201598, JP-B-4-76
No. 440 and Tokuhei 7-13680.

In carrying out the radiation image conversion method, the radiation image conversion panel includes radiation irradiation (recording of a radiation image), irradiation of excitation light (reading of a recorded radiation image), irradiation of erasing light (remaining radiation image). Erasure). The transition of the radiation image conversion panel to each step is performed by a conveying means such as a belt or a roller. After one cycle, the panels are usually stacked and stored. However, when the radiation image conversion panel having the protective film formed by the above-described coating is repeatedly used or stored for a long period of time, the sensitivity is reduced due to the moisture absorption of the phosphor layer, and the image quality is reduced. May deteriorate. In particular, the phosphor layer provided by the vapor deposition method easily absorbs moisture because the phosphor is not covered with a binder or the like.

[0007]

As a protective film capable of preventing the sensitivity of the radiation image storage panel from lowering due to moisture absorption, glass is most preferable from the viewpoint of moisture permeability, but in the case of glass, the strength during the panel manufacturing process is reduced. Thickness from the surface
400 μm or more is required. For this reason, in the case of a glass protective film, the image quality may be deteriorated (blurred) due to the diffusion of light, which is not always satisfactory.

On the other hand, a transparent resin film has a thickness of 100 μm.
There is no problem in the strength during the manufacturing process even if the thickness is reduced to the following, and it is preferable in terms of the initial image quality because it is a thin layer. It was easy to deteriorate. For this reason, it has been proposed in Japanese Patent Application Laid-Open No. H11-344598 to deposit a metal oxide on the surface of the resin film.However, there is a case where the hygroscopic property is deteriorated due to the metal oxide being scraped or cracked by running the panel. In some cases, the image quality may be deteriorated due to the presence of dirt or scratches on the surface of the protective layer.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a radiation-emitting panel which has good moisture-proof and antifouling properties and has little image quality deterioration.

[0010]

According to the present invention, there is provided a radiation-emitting panel in which a phosphor layer, a protective layer, and an antifouling layer are laminated on a support in this order. A resin film laminated on the body layer, and a vapor-deposited layer of an inorganic substance having no gas absorption and a gas barrier property at a wavelength of 300 nm to 1000 nm deposited on the resin film, wherein the antifouling layer is a film-forming resin. And a reactive silicone, a cross-linking agent, and a white powder.

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 wide concept including photographic intensifying panels.

No light absorption at a wavelength of 300 nm to 1000 nm means that the light transmittance is 90% at a wavelength of 300 nm to 1000 nm.
It means above.

[0013] The A gas barrier, 1 atm, 20 ° C. moisture permeability 6g / m ² / 24h or less in oxygen permeability 5cc / m ^2/24
means that h is less, moisture permeability 1g / m ² / 24h or less, and more preferably less oxygen permeability 1cc / m ² / 24h.

Preferably, the inorganic substance is aluminum oxide and / or silicon oxide. Although aluminum oxide and silicon oxide may be used alone, it is more preferable to use both aluminum oxide and silicon oxide together to form a protective layer.

The thickness of the protective layer is preferably 100 μm or less, more preferably 50 μm, and further preferably 20 μm or less. The thickness of the antifouling layer is preferably 1 μm or more and less than 5 μm, and more preferably 1 μm or more and less than 2.5 μm.

It is preferable that the reactive silicone has at least one hydroxyl group or amino group at the terminal and has a number average molecular weight of 5,000 to 20,000. The crosslinking agent is preferably a polyisocyanate or an amino resin. The white powder has a particle size of 0.3 μm to 1.5 μm.
Preferably, it is an organic or inorganic powder of μm.

The phosphor of the phosphor layer is preferably a stimulable phosphor, and the phosphor is preferably provided by a vapor deposition method.

It is preferable that the phosphor has a columnar shape. The columnar shape means that the short axis surface of the phosphor is in contact with the protective layer surface and the phosphor is standing in a columnar shape on the protective layer surface.

[0019]

The radiation-emitting panel of the present invention has a resin film in which a protective layer is laminated on a phosphor layer, and has no gas absorption and a gas barrier property at a wavelength of 300 nm to 1000 nm deposited on the resin film. Since the radiation-emitting panel is composed of the inorganic substance deposited layer, the moisture-proof property of the radiation-emitting panel can be improved.

Further, since the antifouling layer contains the film-forming resin, the reactive silicone, the crosslinking agent and the white powder, the antifouling property of the radiation-emitting panel can be improved.
Further, by containing a white powder, it is possible to prevent unevenness of an image due to unevenness of a coating film, to increase haze of the coating film, and to obtain a radiation-emitting panel with less deterioration in image quality.

Further, since the radiation-emitting panel of the present invention is provided with the protective layer having high moisture resistance and the antifouling layer having high antifouling property, the image quality is deteriorated due to the moisture absorption of the phosphor layer and the contamination of the panel. Can be effectively prevented.

When the reactive silicone has at least one hydroxyl group or amino group at the terminal and has a number average molecular weight of 5,000 to 20,000, higher antifouling property can be realized. .

When the crosslinking agent is a polyisocyanate or an amino resin, the durability of the antifouling layer can be further improved. In addition, white powder, particle size 0.
In the case of an organic or inorganic powder of 3 μm to 1.5 μm,
Image unevenness due to coating film unevenness can be further suppressed.

In order to read an X-ray image, a laser beam is irradiated from the surface of the protective layer. However, when the phosphor is in a columnar form, light enters from the end of the columnar phosphor and the phosphor layer enters the phosphor layer. And the light is hardly spread, so that a clearer X-ray image can be taken out.

It is to be noted that the present invention provides a panel for converting transmitted radiation into visible light and / or ultraviolet radiation using a non-stimulable phosphor, for example, improving the image quality of a phosphor layer such as an intensifying panel for X-ray photography. However, it is extremely useful in a radiation image conversion panel using a stimulable phosphor.

[0026]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a sectional view of a radiation-emitting panel according to a first embodiment of the present invention.

As shown in FIG. 1, the radiation-emitting panel of the present invention comprises a support 4 on which a phosphor layer 1, a protective layer 2, and an antifouling layer 3 are laminated in this order. Are a resin film 2a laminated on the phosphor layer 1 and a resin film 2a
A vapor-deposited layer 2b containing an inorganic substance that has no light absorption at a wavelength of 300 nm to 1000 nm and has a gas barrier property.
The protective layer 2 is adhered on the support 4 via the adhesive layer 5. The antifouling layer 3 contains a film-forming resin, a reactive silicone, a cross-linking agent, and a white powder, and as shown in FIG. It is formed so as to surround body layer 1.

FIG. 2 is a cross-sectional view schematically showing a phosphor layer composed of a columnar phosphor and a support. In this manner, the phosphor layer is formed such that the short-axis surface of the phosphor 11 is a support. 4 on top,
It is preferable that the phosphor 11 has a columnar shape and forms a phosphor layer. When the phosphor is a phosphor layer of spherical particles,
The X-ray image may be blurred due to the diffusion of the laser light in the phosphor layer, but in the case of a columnar phosphor, light enters from the end of the columnar phosphor and diffuses in the phosphor layer. , It is possible to extract a clearer X-ray image.

The radiation emitting panel of the present invention will be described in more detail.

First, the stimulable phosphor constituting the phosphor layer of the radiation image storage panel of the present invention 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. By the excitation light
It is desirable that the phosphor exhibit stimulable emission in the wavelength range of 300 to 500 nm. Examples of the stimulable phosphor used in the radiation image storage panel of the present invention are described in JP-B-7-84588 and the like.

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.

As described in US Pat. No. 3,859,527,
SrS: Ce, Sm, SrS: Eu, Sm, ThO_Two: Er, and La_TwoO_TwoS:
Eu, Sm, ZnS: Cu, P described in JP-A-55-12142
b, BaO xAl_TwoO_Three: Eu (where 0.8 ≦ x ≦ 10) and M
^IIOxSiO_Two: A (but M^IIIs Mg, Ca, Sr, Zn, Cd, or
Or A is Ce, Tb, Eu, Tm, Pb, Tl, Bi or
Mn, and x satisfies 0.5 ≦ x ≦ 2.5).
(Ba_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^-2And JP-A-55-1214
LnOX: xA described in No. 4 (where Ln is La, Y, G
at least one of d and Lu; X is Cl and Br
At least one of them, A is at least one of Ce and Tb
And x is 0 <x <0.1).
No. 55-12145 (Ba_1-X, M²⁺ _X) FX: yA (ta
But M²⁺Is the lesser of Mg, Ca, Sr, Zn, and Cd
X is at least one of Cl, Br and I
Species, A is Eu, Tb, Ce, Tm, Dy, Pr, Ho, Nd, Yb and Er
X is 0 ≦ x ≦ 0.6, y
Is 0 ≦ y ≦ 0.2) described in JP-A-55-160078.
M^IIFX xA: yLn (however, M^IIIs Ba, Ca, Sr, Mg,
At least one of Zn and Cd, A is BeO, MgO, Ca
O, SrO, BaO, ZnO, Al_TwoO_Three, Y_TwoO_Three, La_TwoO_Three, In_TwoO_Three, Si
O_Two, TiO_Two, ZrO_Two, GeO_Two, SnO_Two, Nb_TwoO_Five, Ta_TwoO_FiveAnd ThO
_TwoLn is Eu, Tb, Ce, Tm, Dy,
At least one of Pr, Ho, Nd, Yb, Er, Sm and Gd
The species X is at least one of Cl, Br and I
Where x and y are each 5 × 10^-Five≤x≤0.5, and 0 <
y ≦ 0.2), a phosphor represented by a composition formula:
-116777 (Ba_1-X, M^II _X) F_Two・ ABaX_Two: yEu,
zA (however, M^IIIs beryllium, magnesium, calcium
Of chromium, strontium, zinc and cadmium
X is at least one of chlorine, bromine and iodine
At least one, A is zirconium and scandium
A, x, y, and z
Are 0.5 ≦ a ≦ 1.25, 0 ≦ x ≦ 1, 10^-6≦ y ≦ 2
× 10^-1, And 0 <z ≦ 10^-2Is represented by the composition formula
Phosphor, 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)
Phosphor represented by the composition formula of JP-A-57-23675
(Ba_1-X, M^II _X) F_Two・ ABaX_Two: yEu, zA (where M
^IIIs beryllium, magnesium, calcium, stron
At least one of titanium, zinc and cadmium
Species, X is at least one of chlorine, bromine and iodine
Species A is at least one of arsenic and silicon
A, x, y, and z are each 0.5 ≦ a ≦ 1.25,
0 ≦ x ≦ 1,10^-6≦ y ≦ 2 × 10^-1, And 0 <z ≦ 5 × 10
^-1A phosphor represented by the composition formula:
M listed in Issue 81^IIIOX: xCe (where M^IIIIs P
r, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb and Bi
At least one trivalent metal selected from the group consisting of
X is either Cl or Br or its
X is 0 <x <0.1).
Phosphor, Ba described in JP-A-58-206678
_1-XM_{X / 2}L_{X / 2}FX: yEu²⁺(However, M is Li, Na, K, Rb
At least one kind of alka selected from the group consisting of
L represents Sc, Y, La, Ce, Pr, Nd, Pm, S
m, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Ga, In and
At least one trivalent metal selected from the group consisting of
X is selected from the group consisting of Cl, Br and I
Represents at least one halogen; and x is 10
^-2≦ x ≦ 0.5, y is 0 <y ≦ 0.1)
Phosphor, BaFXxA: yEu described in JP-A-59-27980
²⁺(Where X is selected from the group consisting of Cl, Br and I)
Is at least one halogen; A is tetrafur
A calcined product of an oroboric acid compound; and x is 10^-6
≦ x ≦ 0.1, y is 0 <y ≦ 0.1)
Phosphor, BaFX described in JP-A-59-47289
・ XA: yEu²⁺(Where X is a group consisting of Cl, Br and I
At least one halogen selected from
Xafluorosilicic acid, hexafluorotitanic acid and
Xafluorozirconate monovalent or divalent metal
Less selected from the group of hexafluoro compounds consisting of salts
Are calcined products of a compound; and x is 10^-6≤
x ≦ 0.1, y is 0 <y ≦ 0.1)
Phosphor, BaFXx described in JP-A-59-56479
NaX ′: aEu²⁺(However, X and X 'are Cl, B
r and at least one of I, x and
a is 0 <x ≦ 2 and 0 <a ≦ 0.2, respectively.
Phosphor represented by the composition formula of JP-A-59-56480
M^IIFX ・ xNaX ′: yEu²⁺: zA (where M^IIIs B
at least one selected from the group consisting of a, Sr and Ca
X and X 'are each C
at least one selected from the group consisting of l, Br and I
A is V, Cr, Mn, Fe, Co and Ni
At least one transition metal selected; and
x is 0 <x ≦ 2, y is 0 <y ≦ 0.2, and z is 0 <z
≦ 10^-2A phosphor represented by the composition formula:
M described in -75200^IIFX ・ aM^IX ′ ・ bM ′^IIX ″_Two・
cm^IIIX_Three・ XA: yEu²⁺(However, M^IIIs from Ba, Sr and Ca
At least one alkaline earth metal selected from the group consisting of
And M^IIs from the group consisting of Li, Na, K, Rb and Cs
At least one alkali metal selected; M ′^IIIs
At least one member selected from the group consisting of Be and Mg
Is a valent metal; M^IIIIs a group consisting of Al, Ga, In and Tl
Is at least one trivalent metal selected; A is a metal
X is selected from the group consisting of Cl, Br and I
At least one halogen; X ', X "and
 X is a small number selected from the group consisting of F, Cl, Br and I
At least a halogen; and a is 0 ≦ a ≦
2, b is 0 ≦ b ≦ 10^-2, C is 0 ≦ c ≦ 10^-2, And a + b + c
≧ 10^-6X is 0 <x ≦ 0.5, y is 0 <y ≦ 0.2
A phosphor represented by the composition formula of JP-A-60-84381
M listed in the issue^IIX_Two・ AM^IIX ′_Two: xEu²⁺(However
Then M^IIIs a small number selected from the group consisting of Ba, Sr and Ca
At least a kind of alkaline earth metal; X and X 'are C
at least one selected from the group consisting of l, Br and I
And X ≠ X ′; and a is
0.1 ≦ a ≦ 10.0, x is 0 <x ≦ 0.2)
Stimulable phosphor described in JP-A-60-101173
M^IIFX ・ aM^IX ′: xEu²⁺(However, M^{II Is}Ba 、 Sr
At least one type of al selected from the group consisting of
Potassium earth metal; M^IIs from the group consisting of Rb and Cs
At least one alkali metal selected; X is Cl,
At least one member selected from the group consisting of Br and I
X 'is a group consisting of F, Cl, Br and I
At least one selected halogen; and a
And x are 0 ≦ a ≦ 4.0 and 0 <x ≦ 0.2, respectively.
Stimulable phosphor represented by the following formula:
M described in No. 89^IX: xBi (where M^IAre Rb and
At least one alkali selected from the group consisting of
X is selected from the group consisting of Cl, Br and I
X is at least one halogen; and x is 0 <x ≦
Photostimulability represented by a composition formula of 0.2)
Phosphor, LnOX: xCe described in JP-A-2-229882 (however, Ln
Is at least one of La, Y, Gd and Lu, and X is C
at least one of l, Br and I, x is 0 <x ≦ 0.2
And the ratio between Ln and X is 0.500 <X / Ln ≦ 0.998 in atomic ratio.
And the maximum wavelength λ of the stimulable excitation spectrum is 550n
Cerium-activated rare earth oxy represented by m <λ <700 nm)
Halide phosphor, and the like.

Further, the JP 60-84381 No. M ^II X ₂ · aM ^II X described in the _'2: xEu ²⁺ stimulable phosphor, is added, such as the following 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
Described in -228593 (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).

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

Further, 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

Next, a radiation image conversion panel using a stimulable phosphor among radiation emission panels will be described as an example. The stimulable phosphor layer is formed by applying a coating solution comprising a stimulable phosphor and a binder containing the stimulable phosphor in a dispersed state on a support, and a vapor-phase deposition without a binder. Although it can be provided by a known method such as a method of forming by a method, here, the case of providing by a vapor deposition method will be described.

The support is preferably made of an inorganic film from the viewpoint of moisture resistance. However, if the thickness is large, a plastic plate can also be used since the moisture permeability can be substantially ignored. Specifically, metal plates such as aluminum plates and stainless steel plates, glass plates, ceramic plates, PVC plates, melamine phenol resin plates, PET plates, FRP
Plate, GFRP plate and the like can be preferably used. The thickness of the support is preferably about 500 μm to 10 mm.
These supports may be opaque in the case of single-sided excitation / light collection, or may be used by providing a light-shielding layer or a reflective layer on a transparent support. On the other hand, when exciting or condensing light from both sides of the panel, it is preferable to use a transparent material.

The phosphor layer can be formed on a support by a known vapor deposition method such as an evaporation method or a sputtering method.
In the vapor deposition method, first, a support is placed in a vapor deposition apparatus, and then the inside of the apparatus is evacuated to a degree of vacuum of about 10 ⁻⁴ Pa. Next, at least one of the stimulable phosphors is heated and evaporated by a method such as a resistance heating method or an electron beam method to deposit the stimulable phosphor on the surface of the support to a desired thickness. Thereby, a stimulable phosphor layer containing no binder can be formed. It is also possible to form the stimulable phosphor layer by performing the vapor deposition step a plurality of times. In the vapor deposition step, a plurality of resistance heaters or electron beams are used for co-evaporation to synthesize a desired stimulable phosphor on a support and simultaneously form a stimulable phosphor layer. After the deposition, a radiation image conversion panel is manufactured by providing a protective layer on the opposite side of the stimulable phosphor layer from the support as described later. Further, at the time of vapor deposition, the object to be deposited (protective layer) may be cooled or heated as necessary. After the deposition, the stimulable phosphor layer may be subjected to a heat treatment.

In the sputtering method, as in the case of the vapor deposition method, a support is placed in a sputtering apparatus, and then the inside of the apparatus is once evacuated to a degree of vacuum of about 10 ^-4 Pa, and then Ar, Ne or the like is used as a sputtering gas. Is introduced into the sputtering apparatus to a gas pressure of about 10 ^-1 Pa.

Next, using a stimulable phosphor as a target,
By sputtering, the stimulable phosphor is deposited to a desired thickness on the surface of the protective layer. In the sputtering step, similarly to the vapor deposition method, it is also possible to form the stimulable phosphor layer in a plurality of times, or, using a plurality of targets made of different stimulable phosphors, Simultaneously or sequentially, it is also possible to form a stimulable phosphor layer by sputtering a target. In the sputtering method, reactive sputtering may be performed by introducing a gas such as O ₂ , H _2, or halogen as needed. After the end of the sputtering, a radiation image conversion panel is manufactured by providing a protective layer on the side opposite to the support side of the stimulable phosphor layer as in the vapor deposition method. In the sputtering method, as in the case of the vapor deposition method, the object to be vapor-deposited (primary protective layer) may be cooled or heated as needed during the sputtering. After the end of the sputtering, the stimulable phosphor layer may be subjected to a heat treatment.

The protective layer is composed of a resin film laminated on the phosphor layer and a wavelength of 300 nm to 1000 nm on the resin film.
Is formed by vapor-depositing an inorganic substance having no gas absorption and having a gas barrier property. Inorganic substances having a wavelength of 300 nm to 1000 nm and having no light absorption include, for example, silicon oxide, aluminum oxide, zirconium oxide, tin oxide, etc. Among them, aluminum oxide (Al ₂ O ₃ ) and silicon oxide (SiO _x , X:
1-2) are particularly preferred because they have high light transmittance and high gas barrier properties, that is, can form a dense film with few cracks and micropores. Aluminum oxide and silicon oxide may be deposited alone, but if both are deposited together, the gas barrier properties can be further improved, so it is more preferable to deposit both aluminum oxide and silicon oxide.

As the resin film, it is preferable to use a transparent resin film having heat resistance and relatively small moisture permeability. In particular, polyethylene terephthalate (PE
T) is preferable because it is inexpensive and has sufficient heat resistance. The thickness of the film is preferably about 1 to 50 μm,
More preferably, it is about 6 μm. The thickness of the entire protective layer is preferably 100 μm or less, more preferably 50 μm.
It is more preferably at most 20 μm, more preferably at most 20 μm.

The deposition of the inorganic substance on the resin film is performed by PVD.
Method (Physical Vapor Deposition, physical vapor deposition) or CVD method (Chemical Vapor Deposition, chemical vapor deposition)
Alternatively, a method such as PE-CVD (Plasma enhanced CVD) can be used. The transparency and barrier properties of the protective layer are not significantly changed by any of the methods, and can be appropriately selected. The vapor deposition may be performed after the resin film is bonded to the phosphor layer, or may be performed before the resin film is bonded to the phosphor layer. The deposition thickness is preferably about 0.01 μm to 1 μm.

The PET film on which an inorganic substance having a gas barrier property is deposited is manufactured by Toppan Printing Co., Ltd. from GL-AU, AE,
BARRIALOX from Toyo Metallizing Co., Ltd., Tech Barrier from Mitsubishi Kojin Co., Ltd., MOS from Oike Kogyo Co., Ltd., Fine Barrier from Reiko Co., Ltd., and Dai Nippon Printing Co., Ltd.
Since they are commercially available under the trade name of IB-PET, these may be used.

The antifouling layer is provided by coating or by laminating or bonding a separately formed antifouling film in the form of a film. The antifouling layer contains a film-forming resin, a reactive silicone, a cross-linking agent, and a white powder.
A yellowing inhibitor and the like may be further contained.

As the film-forming resin, for example, a soluble fluororesin can be preferably mentioned. 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, such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, or the like. Preferable examples include polyvinylidene fluoride, a tetrafluoroethylene-hexafluoropropylene copolymer and a fluoroolefin-vinyl ether copolymer.

The fluororesin is generally insoluble in an organic solvent, but a copolymer containing a fluoroolefin as a copolymer component may be soluble in an organic solvent depending on other structural units (other than the fluoroolefin) to be copolymerized. Therefore, a solution prepared by dissolving the resin in an appropriate solvent is applied to the phosphor layer and dried to easily form the protective film. As such a copolymer, a fluoroolefin-vinyl ether copolymer can be preferably mentioned. Further, polytetrafluoroethylene and its modified product are also soluble in a suitable fluorinated organic solvent such as a perfluoro solvent, and therefore, like the copolymer containing the above-mentioned fluoroolefin as a copolymer component, the coating is performed. Thus, a protective film can be formed.

Specific examples of the fluorine-based resin soluble in these organic solvents include: Opstar JN7212 and JN720 manufactured by JSR Corporation.
5, JN7220, manufactured by Daikin Industries, Ltd .: Zeffle LC-930, GK5
10, Sumitomo 3M Co., Ltd .: Dionin THV220, Asahi Glass Co., Ltd .:
Lumiflon LF100, LF200, LF216T, LF400, LF504, LF60
0, LF810, LF916, LF924, LF946, LF976, LF9010 and the like can be preferably mentioned.

The reactive silicone (silicone macromonomer) has, for example, a dimethylpolysiloxane skeleton and has at least one or more functional groups (for example, hydroxyl group, amino group, etc.) and has a number average molecular weight. It is preferably in the range of 5000 to 20000, and 10
More preferably, it is in the range of 000 to 15,000.

The reactive silicone has at least one hydroxyl group or amino group at its terminal, and preferably has at least one hydroxyl group or amino group at both terminals, or has at least two hydroxyl groups at one terminal. More preferably, the reactive silicone has two or more hydroxyl groups or amino groups at one terminal, and more preferably, a silicone having two or more hydroxyl groups at one terminal. Further, the reactive silicone may include a perfluoroalkyl group.
Reactive silicones are also commercially available from Chisso Corporation under the trade name Cyraprene Series.

The reactive silicone is contained in the protective film in an amount of 0.1 to 20.
It is preferably contained in an amount within the range of 0.1% by weight.
More preferably, it is contained in an amount in the range of 5 to 10% by weight.

The white powder can prevent the unevenness of the image due to the unevenness of the coating film, and can increase the haze of the coating film. The white powder is preferably an organic or inorganic white fine powder, the average particle size is in the range of 0.1 to 5 μm, particularly, the average particle size is 0.3 to 1.5.
Those in the range of μm are preferred. These fine powders are contained in the range of 0.5 to 120% by weight based on the weight of the film-forming resin of the protective film, 5 to 40% by weight for the organic fine powder, and 10 to 100% by weight for the inorganic fine powder. Is preferred.

Preferred examples of the white organic powder include benzoguanamine resin powder, melamine formaldehyde resin powder, cured acrylic resin powder, silicone resin powder, fluorine resin powder, polyester resin powder, and the like. MS, M30, S, S6, S12, Eposter MA series, Eposter MA series, MR-2G, MR-7G, MP series, manufactured by Soken Chemical Co., Ltd., Lubron L, manufactured by Daikin Industries, Ltd. -2, L-5, LD-1, LD-100, Tospearl XC99-A8808, Tospearl 1 manufactured by Toshiba Silicone Co., Ltd.
20, 130, 145, 240, and PETEBEADS series manufactured by Toyobo.

As the white inorganic powder, alumina, silica,
Calcium carbonate, magnesium oxide, zinc oxide, lead oxide, tin oxide, gadolinium oxide, mica, zeolite,
Barium sulfate, diamond and the like are preferable. Specific examples of these inorganic powders include silica powder manufactured by Nippon Shokubai Co., Ltd .: Seahoster KE series P50, P100, P150, and alumina fine powder manufactured by Sumitomo Chemical Co., Ltd. Preferable examples are Sumicorundum series AA05, AA07, AA1, AA1.5, AA2, AA3 and AKP10, AKP20, AKP30, AKP50, HIT-55, HIT-100 and the like.

The crosslinking agent can increase the durability of the antifouling layer by increasing the strength of the resin and reacting with the reactive silicone. It is preferable to use a polyisocyanate or an amino resin as the crosslinking agent. In the case of a polyisocyanate, it is more preferable to use a non-yellowing type polyisocyanate which does not easily yellow over time.

Specific examples of the non-yellowing polyisocyanate include Nippon Polyurethane Co., Ltd .: Coronate HL, Coronate HX, Sumitomo Bayer Urethane Co., Ltd .: Sumidur N75, N
3200, HT, death module N3300, Z4470, E3265, E428
0, Takenate D-120N, 127N, 140N, 170N, 172N, 190N
And the like.

As the amino resin, melamine such as hexamethoxymethylol melamine, benzoguanamine and the like can be preferably used. Specific examples of hexamethoxymelamine include Mitsui Cytec Co., Ltd .: 300 series such as Cymel 303, Cymel 200 series, Cymel 700 series, Cymel 1100 series, Mycoat 1
Preferred examples include the 00 series, the Mycoat 500 series, and the Cymel 1100 series.

The thickness of the antifouling layer is preferably from 1 μm to less than 5 μm, more preferably from 1 μm to less than 2.5 μm. By adding the white powder, even if the thickness of the antifouling layer is less than 2.5 μm, the occurrence of image unevenness can be suppressed.

In some cases, moisture absorption from the side surface of the phosphor layer cannot be sufficiently prevented only by the gas-barrier vapor deposition protective layer. Therefore, the phosphor layer is sealed with an epoxy resin, a UV curing resin, a metal (solder), or the like. Is preferred. Also,
In order to prevent performance degradation due to moisture absorption of the phosphor layer, it is preferable to perform the process from removal from the vapor deposition tank (vaporizer) to sealing of the end face in vacuum or dry air or an inert gas or a hydrophobic inert gas. .

Hereinafter, the present invention will be described more specifically with reference to examples.

EXAMPLES (Example 1) A 1 mm thick quartz glass plate (UFF0.40 manufactured by Nippon Sheet Glass Co., Ltd.) was placed in a vapor deposition device as a support. Next, the alkali halide stimulable phosphors (Cs.Br) and (Eu) were placed in two platinum boats, and the inside of the evaporator was evacuated to a vacuum of 2 × 10 ⁻⁴ Pa. Thereafter, the stimulable phosphor in the platinum boat is irradiated with an electron beam having an accelerating voltage of 2.3 kV for 30 minutes from an electron gun, and the stimulable phosphor (Cs · Br: 0.01Eu) was deposited in a columnar shape. After the deposition of the phosphor, the irradiation of the electron beam was stopped, and the inside of the evaporator was returned to a dried atmospheric pressure, and the quartz glass plate on which the phosphor layer was formed was taken out. 20 μm thick, 90 length on quartz glass plate
The columnar stimulable phosphor of 0 μm was densely deposited.

Next, PET with ALO _X deposited as a protective film
An antifouling layer was applied on the deposited layer (GL-AU, 12 μm, manufactured by Toppan Printing Co., Ltd.). First, 40 g of a fluorine-based copolymer solution (Lumiflon LF504X (30% xylene solution), manufactured by Asahi Glass Co., Ltd.), and melamine-formaldehyde (Nippon Shokubai Co., Ltd., S6) 28.4 as an organic filler g, aluminum coupling agent as a dispersant (Ajinomoto Co.,
AL-M) 0.5 g and methyl ethyl ketone (MEK) 200 g are dispersed and mixed in a ball mill using zirconia balls of 3 mmφ for 20 hours, and then Lumiflon LF504X (30% xylene solution) 360 g
Was added and dispersed for an additional 4 hours. Then, a silicone macromonomer (manufactured by Chisso Corporation: Cylaprene FM-DA2)
6) 5.6 g, polyisocyanate (Sumitomo Bayer Urethane Co., Ltd., Sumidur N3500 (solid content 100%)) as a crosslinking agent 2
2.2g, dibutyltin dilaurate as catalyst (Kyodo
(KS1260) 1.4 mg and MEK 800 g were additionally mixed to prepare an antifouling film coating solution. This was applied, dried and cured to form a 2 μm thick antifouling layer.

A polyester resin solution (Toyobo Co., Ltd., Byron 30SS) was applied to the surface of the protective film on which the antifouling layer was not provided, and dried to form an adhesive layer (adhesive application weight 2 g / m ² ). . This is covered with the phosphor layer with the side on which the adhesive layer is not provided outside, and thermally bonded with a pressure of 10 mm in the peripheral portion of the support while decompressing to form a radiation image conversion panel having a protective film with an antifouling film. Obtained.

Example 2 Instead of providing the protective film with an antifouling layer in Example 1 while reducing the pressure, a protective film with an antifouling film was provided by sealing with dry nitrogen gas and thermocompression bonding. Except for the above, a radiation-emitting panel in which the phosphor layer was kept with dry nitrogen gas was obtained in the same manner as in Example 1.

[0067] was obtained (Comparative Example 1) The radiation image conversion panel in the same manner as in Example 1, except for not forming the antifouling layer on PET with a deposit of ALO _x.

(Comparative Example 2) Instead of PET deposited with ALO _x
A radiation image storage panel was obtained in the same manner as in Example 1, except that a PET film having a thickness of 12 μm was used.

Comparative Example 3 A radiation image storage panel was obtained in the same manner as in Comparative Example 2 except that the antifouling layer was not provided.

(Evaluation Experiments) The radiation image conversion panels obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were subjected to the following evaluation experiments. Table 1 shows the results.

1. Emission intensity After irradiating the radiation image conversion panel with X-rays at a tube voltage of 80 kVp, the phosphor is excited by scanning with He-Ne laser light (632.8 nm), and the stimulus emitted from the phosphor layer is emitted. The emitted light was received and converted into an electric signal, and the amount of stimulated emission was measured. The luminescence amount was expressed as a relative value when Example 1 was set to 100%.

2. Humidity Resistance The obtained panel was placed in a high-temperature, high-humidity room at 60 ° C. and 80% RH for one week, and the change in stimulable luminescence was examined.

A: Reduction of less than 5% B: Reduction of 5% or more and less than 10% C: Reduction of 10% or more

3. Magic (registered trademark) antifouling property A line was drawn with black magic on the surface of the protective layer, dried and wiped with a Kimwipe, and the degree of erasure of the magic line was observed.

A: No remaining line B: About half remaining C: All remaining

[0076]

[Table 1] As is clear from the above experimental results, the radiation image conversion panel according to the present invention was excellent in moisture resistance and stain resistance, and was able to obtain a radiation image conversion panel with little image quality deterioration.

Although the embodiment describes only the radiation image conversion panel, the protective layer of the present invention can be similarly used for an intensifying panel 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 cross-sectional view schematically showing a phosphor layer composed of a phosphor in a columnar form and a support.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Phosphor layer 2 Protective layer 2a Resin film 2b Vapor deposition layer 3 Antifouling layer 4 Support 5 Adhesive layer

Claims (12)

[Claims] 1. A radiation-emitting panel comprising a support, on which a phosphor layer, a protective layer, and an antifouling layer are laminated in this order, wherein: a resin film in which the protective layer is laminated on the phosphor layer; Wavelength 300nm to 1000n deposited on resin film
m, wherein the antifouling layer comprises a film-forming resin, a reactive silicone, a cross-linking agent, and a white powder. panel. Wherein said gas barrier moisture permeability 1 g / m ^2/24
2. The radiation-emitting panel according to claim 1, wherein an oxygen permeability is 1 cc / m 2/24 h or less. 3. The radiation-emitting panel according to claim 1, wherein the inorganic substance is aluminum oxide and / or silicon oxide. 4. The radiation-emitting panel according to claim 1, wherein the thickness of the protective layer is 100 μm or less. 5. The radiation-emitting panel according to claim 1, wherein the thickness of the protective layer is 20 μm or less. 6. The radiation-emitting panel according to claim 1, wherein the thickness of the antifouling layer is 1 μm or more and less than 5 μm. 7. The reactive silicone according to claim 1, wherein the reactive silicone has at least one hydroxyl group or amino group at the terminal, and has a number average molecular weight of 5,000 to 20,000. Radiation panel. 8. The radiation-emitting panel according to claim 1, wherein the crosslinking agent is a polyisocyanate or an amino resin. 9. The method according to claim 9, wherein the white powder has a particle size of 0.3 μm.
The radiation emitting panel according to any one of claims 1 to 8, wherein the radiation emitting panel is an organic or inorganic powder of 1.5 µm. 10. The radiation-emitting panel according to claim 1, wherein the phosphor of the phosphor layer is a stimulable phosphor. 11. The radiation-emitting panel according to claim 10, wherein the phosphor is provided by a vapor deposition method. 12. The radiation-emitting panel according to claim 11, wherein the phosphor has a columnar shape.