JPS6180100A - Manufacture of radiation image converting panel - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing a radiation image conversion panel used in a radiation image conversion method using a stimulable phosphor. More specifically, the present invention is directed to a method for manufacturing a radiation image storage panel having a support, a phosphor layer made of an exhaustible phosphor, and a protective film in this order.

[Technical backstory of 91 A and conventional technology] Radiation image F
! As the iR method (1), a so-called radiographic method has conventionally been used in which a combination of a radiographic film having an emulsion layer made of a silver salt photosensitive material and an intensifying screen is used. Recently, as an alternative method to the above-mentioned radiographic method, a radiation image conversion method using photostimulable 1-photase, as described in Japanese Patent Application Laid-open No. 55-12145, has attracted attention. It became so. This radiation image conversion method uses a radiation image conversion panel (
This method uses a stimulable phosphor (stimulable phosphor), which absorbs the radiation transmitted through the subject or the radiation emitted from the subject into the stimulable phosphor of the panel, and then makes the stimulable phosphor visible. Radiation energy accumulated in the stimulable phosphor by time-series excitation with electromagnetic waves (excitation light) such as light rays and infrared rays? It is emitted as fluorescence (stimulated luminescence), and this fluorescence is read photoelectrically to obtain an electrical signal.
The obtained '#' and Qi signals are visualized.

The above-mentioned radiation image conversion method has the advantage that a radiation image rich in information can be obtained with a much lower radiation dose than conventional radiography. Therefore, this radiation image conversion method has a very high utility value especially in direct medical radiography such as X-ray photography for the purpose of medical diagnosis.

The radiation image conversion panel used in the above radiation image conversion method is:
The basic structure consists of a support and a phosphor layer provided on one side of the support. Generally, a transparent protective film is provided on the surface of this phosphor layer opposite to the support (the surface not facing the support), and the phosphor layer is protected from chemical or physical alteration. Protects from physical impact.

The phosphor layer is composed of a stimulable phosphor and a binder containing and supporting the stimulable phosphor in a dispersed state.
After absorbing radiation such as radiation, it emits light (r4
It has the property of exhibiting (exhaustive luminescence). Therefore, the object was penetrated. Alternatively, the radiation emitted from the subject is absorbed by the phosphor layer of the radiation image conversion panel in proportion to the radiation dose, and the subject or the radiation image of the subject is stored as a stored image of radiation energy on the radiation image conversion panel. is formed as. This savings! Image A can be emitted as stimulated luminescence by exciting the electromagnetic waves in a time-series manner, and by photoelectrically reading this stimulated luminescence and converting it into an electrical signal, an image of accumulated radiation energy can be generated. It becomes possible to convert into

The radiation image conversion method is a very advantageous image forming method as mentioned above, but the radiation image used in this method! Similar to the intensifying screen used in the conventional radiography method, the replacement panel is also desired to have high sensitivity and provide an image with good image quality (sharpness, 1 graininess, etc.). .

Until now, protective films have generally been applied to radiation-electric conversion panels by applying a solution of a transparent polymeric substance dissolved in a suitable solvent to the surface of an already formed phosphor layer, or by forming a protective film separately. This is done by bonding a transparent thin film using an adhesive or the like.

When forming a protective film on the phosphor layer by coating, the type of solvent in the coating solution, the combination of the polymer substance in the coating solution and the binder in the phosphor layer, and the phosphor particles in the phosphor layer are important. Since the adhesion strength between the phosphor layer and the protective film varies greatly depending on the content of was. Furthermore, although radiation image conversion panels are generally used repeatedly, if a protective film is attached to the phosphor layer via an adhesive layer, the adhesive layer may be damaged mechanically or It was prone to thermal deterioration, and as a result, the protective film tended to peel off. That is, there was a problem in that the adhesion strength between the phosphor layer and the protective film was insufficient, and the panel lacked durability when used repeatedly.

In addition, light (excitation light) is generally easily scattered at the interface between each layer, and when a protective film is attached to the phosphor layer via an adhesive layer, the phosphor layer, adhesive layer and protective film Because light scattering occurs at the interfaces between the layers, the quality of the resulting images tends to deteriorate.

Furthermore, the scattering of stimulated luminescence light at each of the above-mentioned interfaces reduces the readout efficiency of light from the panel surface (protected V surface), contributing to a decrease in the sensitivity of the radiation image conversion panel. .

[Summary of the Invention J The present invention provides a radiation image conversion panel with improved mechanical strength! Its purpose is to provide a manufacturing method.

Furthermore, the present invention provides radiation SI that provides images with improved image quality.
It is also an object to provide a method for manufacturing an A-image conversion panel.

A further object of the present invention is to provide a method for manufacturing a radiation image storage panel with improved sensitivity.

That is, 1. (The invention comprises: (1) a binder solution I in which an exhaustible phosphor is dispersed;
The stimulable phosphor is dispersed in a binder solution II which is a binder solution that does not contain the stimulable phosphor and is made of a binder that is incompatible with the binder contained in the binder solution I. A radiation image conversion panel for undetected odor 1, characterized in that a binder solution I formed by ff1) is simultaneously applied to the surface of the support so as to form a phosphor layer and a protective film. Manufacturing method.

and (2) a binder solution I in which a stimulable phosphor is dispersed, and a binder solution containing no stimulable phosphor, the above-mentioned binder solution! A binder solution II consisting of a binder that is incompatible with the binder contained in A method for producing a radiation image storage panel according to the present invention, which comprises separating the panel from the sheet and attaching the panel to a support.

It provides:

[Effects of the Invention] The present invention improves the mechanical strength and sensitivity of a radiation conversion panel by simultaneously forming a phosphor layer and an M retention film on a support by multilayer coating. This is to realize WJ-yf improvements in various characteristics such as improvement in the image quality of images obtained.

Conventionally, in general, a binder solution O1 in which phosphor particles are dispersed is used. A phosphor layer is formed by coating (blood) on a support using a conventional coating method and drying, and then a transparent thin film made of a polymeric substance such as polyethylene terephthalate is bonded to the surface of this phosphor layer using an adhesive. In the present invention, a protective film is attached by applying a coating solution containing dispersed phosphor particles and a binder solution containing no phosphor particles, and the coating solution is placed on the support side. The phosphor N! j8 and the protective film can be formed simultaneously by applying -IPL. Therefore, unlike the conventional method, there is no need to provide a protective film on the phosphor layer, and the manufacturing process of the radiation image conversion panel can be simplified.

Another invention! In the Ii manufacturing method, both p#, ! for forming a phosphor layer and a protective film are used. I'2 dries at the same time,
As a result, the adhesion strength between the protective film and the phosphor layer can be increased compared to the conventional method, and the problem of the protective film peeling off from the phosphor layer due to deterioration of the adhesive layer does not occur.

Furthermore, since the radiation image conversion panel manufactured according to the present invention does not have an interface formed by attaching an adhesive layer, scattering of excitation light can be reduced compared to conventional panels, resulting in improved sharpness and graininess. You can obtain images with improved image quality.

At the same time, since there is no scattering of fluorescence at the interface, it is possible to improve image quality and increase sensitivity.

In addition, in the past, when attaching (laminating) a protective MM, dust tended to adhere to the surface of the phosphor, and care was required during the attaching operation, but with the present invention, such problems do not occur. .

This also makes it easy to obtain high-quality images.

[Structure of the Invention] A radiation image conversion panel having the preferable characteristics as described above can be manufactured by, for example, the manufacturing method of the final Ijl as described in the following.

That is, the formation of the phosphor layer and the protective film, which are the characteristic requirements of the present invention, can be performed, for example, in a first-order manner.

First, in order to form a phosphor layer, a coating liquid (I) in which stimulable phosphor particles are uniformly dispersed in a binder solution is prepared.

As mentioned above, a stimulable phosphor is a phosphor that exhibits stimulated luminescence when irradiated with radiation and then irradiated with excitation light.
From a practical standpoint, it is desirable that the phosphor be a phosphor that exhibits stimulated luminescence in the wavelength range of 300 to 500 nm when excited by excitation light in the wavelength range of 400 to 900 nm. An example of a phosphor is

SrS:Ce, Sm, SrS:Eu as described in U.S. Pat. No. 3,859,527.

Sm, Th02: E r, and I, a202s'
:Eu, Sm.

ZnS described in Japanese Patent Application Laid-Open No. 55-12142
:Cu, Pb, Ba0exA1203:Eu (however,
08≦X≦10), and M”0-XSiO2:A(
However, 1M violet is Mg, Ca, Sr, Zn, Cd, or Ba, and A is Ce, Tb, Eu, Tm, Pb, TQ.
, Bi.

or M n Te, X is 0.5≦X≦2,5), as described in Japanese Patent Application Laid-open No. 12143/1983 (Ba
s-x-y, Mgx, Cay) FX: a E u 9 (
However, X is at least one of C1 and Br, and X and y are O<x+y≦0.6. andxy#
0 and a is 10'≦a≦5XIQ4), LnO described in JP-A-55-12144
X: xA (Ln is La, Y, Gd, and Lu
X is at least one of 0 ships and Br, A is at least one of Ce and Tb, and X is 0<x<0.1), JP It is described in Publication No. 55-12145 (B
& I-x, M"X) FX: 7 A (However, M' is at least one of Mg, Ca, Sr, Zn, and Cd, and A is Eu, Tb, Ce, Tm, Dy
, Pr, Ha, Nd, yb, and Er, and X is O≦X≦o, s, y is 0≦y
≦0,2), M'FX-xA described in JP-A-55-160078: yLn [However, 1
M is at least one of Ba, Ca, Sr, Mg, Zn, and Cd, A is Bed, MgO, CaO,
SrO, Bad, Zr+O, Al2O3, Y2O3, L
a2O3, In2O3, 5i02. TiO2, Z r0
2, GeO2, S n 02, Nb2O5, T a 2
05, and at least one of Th02(7),
Ln is Eu, Tb, Ce, Tm, Dy, Pr, H-o,
At least one of Nd, Yb, Er, Sm, and Gd, or zero.

Br, and at least one of
7≦02].

It is described in Japanese Patent Application Laid-open No. 116777/1983 (B
a+-)(,M”x)F2*aBaX2:yEu,zA
[However, 1M11 is IJ IJ SF /a, at least one of magnesium, calcium, strontium, zinc, and cadmium, X is at least one of chlorine, bromine, and iodine, and A is at least one of zirconium and scandium. It is a kind, a,
x, y, and 2 are each 0.5≦a≦1.25.0
≦X≦1.10-≦y≦2X10-', and 0<z≦
107].

It is described in Japanese Patent Application Laid-open No. 57-23673 (
Ba I-x, M”x) F2 * a
BaX2: yEu, zB [where Ml is at least one of beryllium, magnesium, calcium, strontium, zinc, and cadmium, X is at least one of chlorine, bromine, and iodine, a
, x, y, and 2 are each 0.5≦a≦1.25.
0≦X≦1.10-≦y≦2×10-' and 0<z
A phosphor represented by the composition formula: ≦2XlO-'t'.

It is described in Japanese Unexamined Patent Publication No. 57-23675 (Ba
l-3(,M”x)F2*aBaX2:yEu,zA[
However, 1M is beryllium, magne/rum, calcium, strontium, and zinc.

and Katomiuno, X is)i
! at least one of arsenic, bromine, and iodine; A is at least one of arsenic and silicon;
, y, and 2 are each 0.5≦a≦1.25.0≦
X≦i, to'≦Y≦2×10−1, and O<z≦5
A phosphor represented by the composition formula: XlO-1.

M” described in Japanese Patent Application Laid-Open No. 58-69281r+
OX: xCe [However, M” is Pr, Nd, Pm
, Sm, Eu, 'rb, Dy, Ho, Er.

At least one trivalent metal selected from the group consisting of Tm, Yb, and Bi, X is either one or both of 0 and Br, and X is 0<x<
A phosphor represented by the composition formula of
a+-xMxwLx/2FX: yE u" [where 1M represents at least one alkali metal found in the group consisting of Ll, Na, Rb, and Cs; L represents Sc, Y, La, Ce, Pr, Nd, Pm, S
m, Gd, Tb, Dy, Ho, Er, Tm, Yb,
represents at least one trivalent metal selected from the group consisting of Lu, AM, Ga, In, and one sentence;
represents at least one kind of haloken selected from the group consisting of CQ, Br, and I: and X is 104≦X
≦0.5, y is O x y≦0.1].

BaF described in Japanese Patent Application Laid-Open No. 59-27980
X・xA: yEu2+ [However, X is C1, Er,
and ■; A is a calcined product of a tetrafluoroboric acid compound; and X is lO1≦X≦o, i, y are O<
7≦0.1] A phosphor B described in JP-A-59-47289
aFX-xA: yE u2+ [where X is C
1, Br, and I, and zA is hexafluorosilicic acid,
is a fired product of at least one compound selected from the group of hexafluoro compounds consisting of monovalent or trivalent metal salts of hexafluorotitanic acid and hexafluorozirconic acid; and X is 10'≦X≦0.1; y is O
<7≦0.1];
BaF described in Japanese Patent Application Laid-Open No. 59-56479
X-xNaX': aEu' [where X and X' are
Cff1. A phosphor which is at least one of Br and I, and is represented by the composition formula: X and a are O<x<2 and Ova<0.2, respectively.

M'F described in Japanese Patent Application Laid-open No. 59-56480
XIIxNaX':yEu'': zA [where MW is at least one alkaline earth metal selected from the group consisting of Ba, Sr, and Ca; There is at least one kind of halogen selected from A, V, Cr,
is at least one transition metal selected from Mn, Fe, Co, and Ni; and X is 0<X≦2.7, o<y≦0.2, and 2 is Q<z≦10' ] A phosphor represented by the composition formula M”F described in JP-A-59-75200
Xa aM'X' a bM'"X"2・CM"X"
'39xA: y E u'' [However, M is Ba
, Sr, and Ca, and M X is Li, Na
, is at least one kind of alkali metal selected from the group consisting of Rb and Cs, M'I is at least one divalent metal selected from the group consisting of Be and Mg, M x is A, Ga , In, and TQ
at least one trivalent metal selected from the group consisting of; A is a metal oxide; X is C, Br, and ■
at least one kind of halogen selected from the group consisting of; X', x'', and X''° are at least one kind of halogen selected from the group consisting of is O≦a≦2, b is O≦b≦10
-”, C is O≦C≦104゜h + b + c≧
to4-C' is present, X is O<x≦05, y is 0<7≦0
．． Examples include a phosphor represented by the composition formula 2].

Among the above-mentioned stimulable phosphors, divalent europium-activated alkaline earth metal fluoride halide phosphors and island-earth element-activated island xyhalide phosphors emit high-brightness stimulated luminescence. However, the stimulable phosphors used in the present invention are not limited to the above-mentioned phosphors, but include phosphors that exhibit stimulated luminescence when irradiated with radiation and then irradiated with excitation light. It can be anything.

Examples of binders for the phosphor layer include proteins such as gelatin,
Polysaccharides such as dextran, or natural polymeric substances such as gum arabic; and polyvinylbutyral, polyvinyl acetate, nitrocellulose, ethylcellulose, vinylidene monochloride @ vinyl chloride copolymer, polyalkyl (meth)acrylate, 1! ! Examples of binders include synthetic polymeric substances such as vinyl chloride Φ vinyl acetate copolyurethane, cellulose acetate butyrate, polyvinyl alcohol, and linear polyester. Particularly preferred among such binders are nitrocellulose, linear polyesters, polyalkyl (meth)acrylates, mixtures of nitrocellulose and linear polyesters, and mixtures of nitrocellulose and polyalkyl (meth)acrylates. be.

Note that these binders may be crosslinked with a crosslinking agent.

Examples of solvents for preparing coating solutions include lower alcohols such as methanol, ethanol, n-propanol, and n-phthanol; hydrocarbons containing 111 atoms such as methylene glolite and ethylene chloride; acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones such as; esters of lower fatty acids and lower alcohols such as methyl acetate, ethyl acetate, and butyl acetate; ethers such as dioxane, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether; and mixtures thereof.

The mixing ratio of the binder and the stimulable phosphor in the coating solution will be +A depending on the characteristics of the intended radiation image conversion panel, the type of phosphor, etc., but in general, the mixing ratio of the binder and the stimulable phosphor is: Selected from the range 1:1 to 1:1 OO (East ratio), and especially 1:8 to L: 40 (@, i ratio)
It is preferable to choose from the range.

The coating solution also contains a dispersant to improve the dispersibility of the phosphor in the coating solution, and a dispersant to improve the bonding force between the binder and the phosphor in the phosphor layer after formation. Examples of thickeners used for such purposes include phthalate, stearic acid, caproic acid, lipophilic surfactants, etc. can be mentioned. Examples of plasticizers include phosphate esters such as triphenyl phosphate, tricresyl phosphate, and diphenyl phosphate; phthalate esters such as diethyl phthalate and dimethoxyethyl phthalate; ethyl phthalyl ethyl glycolate, butyl phthalyl glycolate, etc. and polyesters of polyethylene glycol and aliphatic dibasic acids, such as polyesters of triethylene glycol and adipic acid, and polyesters of diethylene glycol and succinic acid.

Furthermore, in order to improve image sharpness, the coating liquid has an average reflectance in the excitation light wavelength region of the stimulable phosphor that is higher than the average reflectance in the stimulated emission wavelength region of the stimulable phosphor. Colorants with reflective properties such as small ones may be included, such as, for example,
JP-A-55-163500 and JP-A-57-9
Colorants such as those disclosed in Japanese Patent No. 6300 may be mentioned. Or turn it from 1 to 1 to improve the sharpness of the image.
A white powder as described in Japanese Patent No. 6447 may be contained.

Next, in order to form a protective film, a coating solution CU) in which only the binder is dissolved in a suitable solvent is prepared.

As a binder, the coating liquid for forming the phosphor layer mentioned above (
In addition to the binder used in I), cellulose derivatives, polyvinyl mide, polyvinylidene chloride, polyvinyl formal, melamine, phenol resin, Evoquin resin, etc. can be mentioned. However, one simultaneous heavy FF of Komei! In order to form a protective film at the same time as a phosphor layer by coating,
The binder used in coating liquid (II) needs to be incompatible with the binder used in coating liquid CI). Further, from the viewpoint of scratch resistance on the surface of the radiation image storage panel, it is preferable that the binder in the coating liquid (II) is relatively hard.

As the solvent, the solvent used in 'Nll1fu (I) in '- can be used, and it may be the same as or different from the solvent of QIT liquid (I). It is desirable to match the drying speed of the coating film formed by the solutions (1) and (I[), and for this purpose it is desirable to use solvents that are compatible with each other.

Furthermore, the coating liquid (n) may contain various dispersants, plasticizers, colorants, etc. used in the coating liquid (I).

Next, the coating liquid (I) and the coating liquid (II) prepared as described above are coated uniformly and simultaneously in layers on the surface of the support by placing the coating liquid (I) on the support side. Forms a coating film of coating liquid.

This coating operation can be performed, for example, by using a dual hopper type coating device.

The coating amounts of coating liquid (l) and coating liquid (I[) are as follows.

The characteristics of the target radiation image conversion panel, the viscosity of the coating liquid,
Although it varies depending on the mixing ratio of binder and phosphor, it is usually selected from the range of 100:l to 1:l (volume ratio),
Preferably it is in the range of 10:1 to 1.1.

After simultaneous multilayer coating, a coating film of coating liquid (r) is formed on the support side and on it,,! The coated film of coating solution (II) is gradually heated and dried to complete the formation of the phosphor layer and the protective film on the support.

In this way, on the support, there is a phosphor layer made of a binder that contains and supports phosphor particles in a dispersed state on the support side, and a protective layer made of a binder that does not contain phosphor particles provided on the support side. A film is formed.

The phosphor layer and the protective film do not necessarily need to be formed by applying a coating liquid on the support as described above, but for example, they may be formed separately on a 1-sided sheet such as a glass plate, a metal plate, or a plastic sheet. A phosphor layer and a protective film are formed by dipping the coating solution in duplicate, and then pressing it onto a support, or The support, the phosphor layer, and the protective film may be bonded to each other by using an adhesive or the like. In this case, the Coating 41 liquid (I) and the coating liquid (ff) are used in accordance with the desired characteristics of the radiation image storage panel. , stuttering +z depending on application conditions etc.
Multilayer coating may be performed by arranging the face sheets unevenly.

The thickness of the phosphor layer varies depending on the characteristics of the intended radiation image conversion panel, the type of phosphor, the mixing ratio of the binder and the phosphor, etc., but is usually 20 ALm to 1 mm. However, the thickness of this layer is preferably 50 to 5004 m, and the thickness of the protective film is preferably about 3 to 20 gm. In general, the thickness of the phosphor layer and the thickness of the protective film are Preferably, the ratio is in the range 100:1 to 5:1.

The support used in the present invention can be arbitrarily selected from various materials used as supports for intensifying screens in conventional radiography methods or materials known as supports for radiation image conversion panels. . Examples of such materials include cellulose acetate, polyester,
Films of plastic materials such as polyethylene terephthalate, polyamide, polyimide, triacetate, polycarbonate, metal sheets such as aluminum foil, aluminum alloy foil, ordinary paper, baryta paper, resin coated paper, pigment paper containing pigments such as titanium dioxide, Examples include paper sized with polyvinyl alcohol or the like. However, in consideration of the characteristics and handling of the radiation image storage panel as an information recording material, a particularly preferred material for the support in the present invention is a plastic film. This plastic film may be kneaded with a light-absorbing substance such as carbon black, or may be kneaded with a light-reflecting substance such as titanium dioxide.

The former is a support suitable for a high sharpness type radiation image conversion panel, and the latter is a support suitable for a high sensitivity type radiation image conversion panel.

In the known radiation image conversion panel, a phosphor layer is added 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. A polymeric substance such as gelatin is coated on the surface of the support on the side where gelatin is provided to form a single layer of adhesive RF, or a light reflective layer made of a light reflective material such as titanium dioxide or a light absorbing material such as carbon black. It has also been practiced to provide a light absorption layer consisting of. These various layers can also be provided on the support used in the present invention.

Furthermore, as described in JP-A-58-200200, in order to improve the sharpness of the obtained image, the surface of the support on the phosphor layer side (the surface of the support on the phosphor layer side) When an adhesion-imparting layer, a light-reflecting layer, a light-absorbing layer, etc. are provided, fine irregularities may be uniformly formed on the surface (meaning the surface thereof).

Next, Examples and Comparative Examples of the present invention will be described.

However, these six examples do not limit the present invention. In the following six examples, "parts" represent "parts by weight" unless otherwise specified.

[Example 1] Polyacrylic resin A (Criscoat P-+018Gs.

Dainippon Inoki Chemical Industry Co., Ltd.) and polyacrylic resin B
(Dianal BR-107, Mitsubishi Rayon Prosthetics) was dissolved in methyl ethyl ketone to prepare a polyacrylic resin solution. Further, a nitrocellulose solution was prepared by dissolving nitrocellulose (R3120, manufactured by Daicel Kagaku Kogyo X: Koji) in methyl ethyl ketone.

After dispersing particles of photostimulable divalent Ni-a-pium-activated barium fluoride bromide phosphor (BaFBr: Eu'') in methyl ethyl ketone, the above polyacrylic resin solution and nitrocellulose solution are added to this dispersion, Further J
VnCa material; PB-100, m-Kaseiko Kogyo Fuso) and tricresyl phosphate were added, and a propeller mixer was used to prepare coating solution 7a (■) in which the phosphor was uniformly dispersed.

Separately, polyuretano resin (Pap-/Cus T-527
55, Large "One-in-one chemical industry support), Vinyl chloride and vinyl acetate combination (υCAR5 solution Vin
yl VYHH, Union Carbide Car
p, M) 8, phosphoric acid trif, and z-nyl were added to methyl ethyl ketone and mixed uniformly using a propeller mixer to prepare a coating solution (ff). The compositions of Liquid I (liquid (1) and coating liquid (ff) are shown below.

/11 Composition of liquid (1) aFBr+Eu2+phosphor 900 parts Polyacrylic tree 1 stone A 67.5 parts Polyacrylic resin B 10.5 parts Nitrocellulose 4.5 parts Tricresyl phosphate 1.5 parts Ultramarine
0.0585 parts methyl ethyl ketone
257 parts, cloth ■ Polyurethane resin 14 parts Vinyl/vinyl acetate copolymer 24.8 parts Triphenyl phosphate 1.2 parts Methyl ethyl ketone 360
Place the coating solution CI) horizontally on a glass plate for 50 river meters).
and Coating Solution (II) were simultaneously coated onto the support using a dual hopper type coating device as shown in Figure i1.

That is, in FIG. 1, the coating liquid (I) was injected into the right side introduction part 2 of the dual hopper type coating device l, and the coating liquid (II) was introduced into the left side introduction part 3. The lengths of the lower open EJ parts of introduction parts 1 and 2 are 0.500 nm and 0, respectively.
．． It was set to 150m+n.

The glass plate 4 on which the support 5 is placed is moved in the direction of the arrow 8 by 1.0
While moving at a speed of m/min, coating liquids (1) and (]II are simultaneously coated in a multilayer manner onto the support 5 from the lower opening to form coating liquids II!26 and ?# fabric liquid of coating liquid (I). (H>
A coating film 7 was formed.

After coating IIj, the support on which the coating film has been formed is placed in a dryer, and the temperature inside the dryer is increased from 25°C to 100°C.
The coating film was allowed to dry for 50 minutes by gradually lowering the temperature to 20°C. In this way, the support, the phosphor layer and the transparency, l
A radiation image storage panel constructed from I film was manufactured.

From the cross-sectional photograph obtained using a scanning electron microscope of the phosphor layer of this radiation image conversion panel, it was found that on the support,
It was clear that the phosphor layer containing phosphor particles at a high density and the transparent protective film were provided with an interface. Also, from the cross-sectional photo, is it Yui? The layer thickness of the light layer is approximately 350
pm, and the film thickness of 1-year A to IIQ was about full m.

[Comparative Example 1] In Example 1, except that only the coating liquid CI of Example 1 was used and only the introduction part 1 (length of the lower opening + 0.500 mm) of the dual hopper 5 coating device was used. teeth,
A layer thickness of approximately 350 mm was deposited on the support in the same manner as in Example 1.
A phosphor layer of 1.0 m was formed.

Next, a transparent film of polyethylene terephthalate (3FF film, thickness = 7 gm, coated with a polyester adhesive) was placed on top of the phosphor layer with the adhesive layer side facing down, and heated to 90 to 100°C. A transparent protective film was attached by pressure bonding using a heating roll, and a radiation image conversion panel consisting of a support, a phosphor layer, and a transparent protective film was manufactured.

Each radiation image conversion panel obtained in Example 1 and Comparative Example 1 was subjected to an image sharpness test, an image graininess test,
Evaluation was carried out by a sensitivity test and an adhesion strength test.

(1) Image sharpness test MT X-rays with a tube voltage of 80 KVp are applied to the radiation image conversion panel.
After irradiating through the F chart, the phosphor particles are excited by scanning with He-Ne laser light (wave i: 632.8 nm), and the stimulated luminescence emitted from the phosphor layer is transferred to a receiver (with a spectral sensitivity of S5). A photomultiplier tube) receives the light and converts it into an electrical signal.
Then, this was generated as a tip using an image reproducing device to obtain an image of the MTF chart on a display device. The modulation transfer function (MTF) was measured from the obtained image and expressed as an MTF value at a spatial frequency of 2 cycles/mm.

(2) Image graininess test The radiation image conversion panel was placed at a tube voltage of 80 KVp and line Iij.
l f) rn After irradiating 1μ of R X-rays, He-N
The phosphor particles are excited by scanning with e laser light (wavelength: 632.8 nm), and the light emitted from the phosphor layer is received by a photomultiplier tube of spectral sensitivity IF S-5. The granularity of the resulting image is determined by photographic density D = 1.2. Spatial frequency 0.4-5 lines/
It is expressed as an RMS value in mm.

(3) Sensitivity test After irradiating the radiation image conversion panel with X-rays with a tube voltage of 80 KVp,
m) and the sensitivity was measured.

(4) Adhesion strength test A radiation image conversion panel was cut into a test piece with a width of 100 mm, and a cut was made at the interface between the phosphor layer and the protective film. Then, the adhesion strength was measured by pulling apart the protective film portion of the test piece thus prepared and the support and phosphor layer portions. The measurement was performed using a Tensilon universal tensile testing machine (UTM-ff-20 manufactured by Toyo Baldwin).
The force F(
The adhesion strength was expressed in g/cm).

The results obtained are shown in Table 1.

Table 1 Example 1 Comparative Example 1 Sharpness 36.8% 35.5% Graininess
0.85X 10-” 0.70X lf
l” Relative sensitivity 127 115 Adhesion strength
130z/cm 70g/am As is clear from Table 1, the radiation image conversion panel according to the present invention (Example 1) has higher sensitivity and sharpness than the conventional radiation image conversion panel (Comparative Example 1). It gave an image with excellent graininess and was also crushed in adhesion strength.

[Example 2] In Example 1, polyester resin A (Vylon 30'O) was used instead of polyacrylic resin as the binder.

Toyobo MnM) and polyester resin B (Vylon 2
00, Toyobo Co., Ltd.) was carried out in the same manner as in Example 1.

Coating II bush (I) was made from A.

In addition, in Example 1, instead of polyurethane resin and vinyl chloride/vinyl acetate copolymer as binders, polyurethane resin was used with Tuboran 5120° Nippon Polyurethane Kogyo-gM) and polyacrylic resin (Alumatex L).
1020, manufactured by Mitsui Toatsu Kagaku Co., Ltd.), and a coating liquid (II) was prepared by carrying out the same treatment as in Example 1, except that tributyl phosphate was used instead of triphenyl phosphate as a plasticizer. . Coating liquid (I) and (I
The composition of I) is shown below.

1 average 1 uni A grooved BaFBr: Eu2+i light body 900 parts Polyester resin A 19.8 parts Polyester resin 8 5.1 parts Nitrocellulose 33 parts Trichloride phosphate
1.8 part group n
0.0585 parts methyl ethyl ketone
233 1l 121 Rishu 11
6 parts polyacrylic resin 28.5 parts tributyl phosphate 1.44 parts methyl ethyl ketone 312 Example 1 except that coating liquids CI) and (II) described in L were used in the evil method.
A radiation-electric conversion panel consisting of a support, a phosphor layer, and a transparent protective film was manufactured by carrying out the same treatment as in the method described above.

Regarding the phosphor layer of this radiation image conversion panel, scanning type il
From the cross-sectional photograph obtained using the I-A microscope, it is clear that on the support there is a phosphor layer containing phosphor particles at a high density and a transparent I-A layer.
51 that the protective film is provided with an interface.
It was clear. Also, from the cross-sectional photograph, the thickness of the phosphor layer is approximately 34811. m, and the film thickness of the protective i1Q was about 7 kawaguchi.

[Comparative Example 2] In Comparative Example 1, a phosphor layer of the same thickness was formed on the support by performing the same treatment as in Comparative Example 1 except for using the coating liquid (r) of Example 2. did.

Next, a protective film was attached by pressure in the same manner as in Comparative Example 1, thereby producing a radiation image storage panel composed of a support, a phosphor layer, and a transparent protective film.

Each of the radiation image conversion panels obtained in Example 2 and Comparative Example 2 was evaluated by the same tests as above.

The results obtained are shown in Table 2.

Table 2 Example 2 Comparative Example 2 Sharpness 34.5% 33.5% Graininess
0.80X 10-0. [15X 10-Relative sensitivity 135 125 Adhesion strength 2
00 g/c Ru 100 g/c As is clear from Table 2, the radiation image conversion panel according to the present invention (Example 2) has a higher sensitivity than the conventional radiation image conversion panel (Comparative Example 2). Gives a crushed image in high a, T theory and graininess +'1, and also in adhesion strength! It was broken.

[Example 3] In Example 1, polyurethane resin (Desmolac 4125) was used instead of polyacrylic resin as the Jll'1 mixture.
(manufactured by Sumitomo Bayer Urethane Hayashi), isopropyl alcohol is used in addition to methyl ethyl ketone as the solvent, and triphenyl phosphate is used instead of tricresyl phosphate as the JQ plasticizer. In this way, a coating liquid (I) was prepared.

In addition, in Example 1, polyacrylic resin (Paraloid A-30, Rohm and
) Iaas Carp, ) and aliphatic polyisocyanate (SumiDur Door 5. Sumitomo Bayer Urethane Co., Ltd. ffi), and the same treatment as in Example 1 except that tricresyl phosphate was used instead of triphenyl phosphate as the plasticizer. A coating solution (In) was prepared by performing the following steps.The compositions of coating solutions (I) and (II) were as described above.

Huff 111's 11'BaFBr:Eu"ii? Photon 900 parts Polyurethane resin 756 parts Nitrocellulose 8.1 parts Triphenyl phosphate 3.0 parts Ultramarine
0.0585 parts methyl ethyl ketone
259 parts isopropyl alcohol
46 parts ■-1 Polyacrylic resin 48.4 parts Aliphatic borysonanate 74 parts Tricresyl phosphate 8.1 parts Methyl ethyl ketone 336 Example 1 except that the above coating liquids CI) and (ff) were used in the evil method. A radiation image conversion panel consisting of a support, a phosphor layer and a transparent protective film was manufactured by carrying out the same treatment as in the method described in .

From the cross-sectional photograph obtained using a scanning electron microscope of the phosphor layer of this radiation image conversion panel, it was found that the support "-" contains a phosphor layer containing phosphor particles in the form of f^ honey melon and a transparent protective layer. 1JI that the membrane is provided with an interface.
It was clear. Further, from the cross-sectional photograph, the thickness of the phosphor layer was about 350 m, and the thickness of the protective film was about 7 m.

[Comparative Example 3] In Comparative VA1, a phosphor layer of the same thickness was formed on the support by performing the same treatment as in Comparative Example 1 except that the coating solution (1) of Example 3 was used.

Then, apply the protective film to fJ using the same method as in Comparative Example 1.
- By depositing the support, the phosphor layer and the r!
! A radiation image storage panel was manufactured comprising light-protected de-η1.

Each radiation image conversion panel obtained in Example 3 and Comparative Example 3 was evaluated by the same test as in Section +iii.

The results obtained are shown in Table 3.

11+Reihaku Table 3 Example 3 Comparative Example 3 Sharpness 36% 35% Graininess
0.75X to-20, 85X 10-” Relative sensitivity 128 120 Adhesion strength 140g
/cm 90g/am As is clear from Table 3, the radiation image conversion panel (Example 3) according to the present invention is:
It has higher sensitivity than the conventional radiation image conversion panel (Comparative Example 3) and provides images with excellent sharpness and graininess.

It was also excellent in adhesion strength.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view of a dual hopper type coating device, which is an example of a coating device used in the method of manufacturing a radiation & l image conversion panel of the present invention. l. Dual hopper type coating device, 2. Right side introduction part [coating liquid (1) 1.3: Left side introduction part [coating liquid (II)], 4:
Crow small, 5: Support, 6, Coating film of Coating 7' IJ Kai (I), Coating film of 7. Coating 41 liquid (It), 8: Arrow

Claims (1)

[Claims] 1. A binder solution I in which a stimulable phosphor is dispersed, and a binder solution that does not contain a stimulable phosphor, and which is a binder solution contained in the binder solution I. A binder solution II consisting of an incompatible binder is simultaneously coated on the surface of the support in a multilayer manner so that the binder solution I containing the stimulable phosphor is on the support side. A method for producing a radiation image storage panel, comprising forming a layer and a protective film. 2. The volume ratio of the coating amount of the binder solution I formed by dispersing the above-mentioned stimulable phosphor to the coating amount of the binder solution II not containing the stimulable phosphor is 100:1 to 1:1. 2. A method for manufacturing a radiation image conversion panel according to claim 1, wherein the radiation image conversion panel is within the range. 3. Claim 1, characterized in that the solvents in the binder solution I in which the stimulable phosphor is dispersed and the binder solution II that does not contain the stimulable phosphor are compatible with each other. 2. Method for manufacturing the radiation image conversion panel described in Section 1. 4. The binder solution I in which the above-mentioned stimulable phosphor is dispersed has an average reflectance in the excitation light wavelength region of the stimulable phosphor and an average reflectance in the stimulated emission wavelength region of the stimulable phosphor. 2. The method for producing a radiation image storage panel according to claim 1, wherein the radiation image storage panel contains a colorant having a coloring ratio smaller than that of the colorant. 5. A binder solution I in which a stimulable phosphor is dispersed, and a binder solution that does not contain a stimulable phosphor and is incompatible with the binder contained in the binder solution I. After forming a phosphor layer and a protective film by simultaneously applying a binder solution II consisting of a binder solution II on a flat sheet, the phosphor layer and protective film are separated from the sheet and attached to a support. A method for manufacturing a radiation image conversion panel characterized by: 6. The volume ratio of the coating amount of the binder solution I formed by dispersing the above-mentioned stimulable phosphor to the coating amount of the binder solution II not containing the stimulable phosphor is 100:1 to 1:1. 6. The method for manufacturing a radiation image conversion panel according to claim 5, wherein the radiation image conversion panel is within the range of 7. Claim 5, characterized in that the solvents in the binder solution I in which the stimulable phosphor is dispersed and the binder solution II that does not contain the stimulable phosphor are compatible with each other. 2. Method for manufacturing the radiation image conversion panel described in Section 1. 8. The binder solution I in which the above-mentioned stimulable phosphor is dispersed has an average reflectance in the excitation light wavelength region of the stimulable phosphor and an average reflectance in the stimulated emission wavelength region of the stimulable phosphor. 6. The method for producing a radiation image storage panel according to claim 5, wherein the radiation image storage panel contains a coloring agent smaller than the colorant.