JPH11295829A - Radiograph forming assembly - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiograph forming assembly having a wide latitude and capable of obtaining a radiograph of excellent sharpness. SOLUTION: As for the radiograph forming assembly, at least one of radiation sensitizing screens is provided with the absorption of >=45% with reference to an X ray whose X-ray energy is 80 kV, and silver halide photographic sensitive material is provided with the radiation sensitizing screen having a contrast transmission function(CTF) >=0.79 with a spatial frequency one piece/mm, and >=0.36 with a spatial frequency three pieces/mm and at least single-layered silver halide emulsion layers on both sides of a support, and the silver halide photographic sensitive material is provided with such a characteristic curve that a point gamma in all points of 1.5 to 2.0 is controlled to be 1.0 to 1.8, as for the optical density in development of the halide photographic sensitive material by using specified developer at a developing temperature of 35 deg.C for 25 seconds as a developing time, fixing, washing and drying after exposing the silver halide photographic sensitive material with monochromatic light whose wavelength is the same as the light emission wavelength of the radiation sensitizing screen, and also whose half value width is 20±5 nm through a step wedge, and also, a crossover in fixing, washing and drying the silver halide photographic sensitive material is controlled to be <=15% with reference to light emitted by the radiation sensitizing screen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation image forming assembly (hereinafter, also simply referred to as "assembly").
The present invention relates to an image forming assembly comprising a low gamma silver halide photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material) and a radiation intensifying screen (hereinafter, also simply referred to as a screen).

[0002]

2. Description of the Related Art Radiation images used for radiation diagnosis are:
In general, a photosensitive material containing at least one silver halide emulsion layer on a transparent support is closely adhered to a screen having a phosphor that absorbs and emits radiation and converts it into visible light, and is irradiated with the radiation. Is obtained.

A radiation image can be obtained by directly irradiating the radiation to a photosensitive material (direct X-ray method), but it is not preferable because the radiation dose to the human body increases, and the imaging method using the screen (screen-screen) is not preferable. Film method) is generally used because high sensitivity can be obtained.

[0004] A radiographic image can be obtained with high image quality by photographing using a screen having low light emission intensity and a photosensitive material having low sensitivity. However, such a combination increases the exposure dose to the human body. With a combination of a screen having a high emission intensity and a photosensitive material having high sensitivity, the exposure dose is reduced, but a high quality image cannot be obtained. Therefore, a radiation image of high image quality without deterioration in sensitivity has been desired.

On the other hand, in the radiographic diagnosis of the upper gastrointestinal tract (stomach), the radiographic image forming methods developed so far have not been sufficient. In particular, in the gastric radiation diagnosis, the structure of the stomach wall and the accumulation of the contrast medium in the double contrast gastric method were insufficient to provide a diagnosis as a still image.
That is, in the double contrast method of the stomach, the observation of the fine structure of the stomach wall to which the contrast agent is attached and the observation of the portion filled with gas are performed with one image. The contrast and sharpness required to observe the microstructure were needed. JP-A-7-2820
In No. 3, point gammas 1.8 to 3.0 and optical densities 2,0 to 2,0 at all points having an optical density of 0.7 to 1.5.
No. 8, a radiation imaging method having a characteristic curve with a point gamma in the range of 1.2 to 2.0 is disclosed, but the latitude is obtained but not satisfactory, and a wider latitude is required. There has been a demand for a photosensitive material and a radiation image forming method.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation image forming assembly capable of obtaining a radiation image with a wide latitude and excellent sharpness.

[0007]

The above-mentioned problems are achieved by the following constitutions.

[0008] 1. At least one of the radiographic intensifying screens has 45% of the X-ray energy of 80 kVp.
Above absorption, contrast transfer function (CTF)
Is 0.79 or more at a spatial frequency of 1 line / mm and a spatial frequency of 3
A silver halide photographic material having at least one silver halide emulsion layer on both sides of a support and a radiation intensifying screen of 0.36 or more / mm, the same wavelength as the emission wavelength of the radiation intensifying screen. And the half width is 20
After exposing the silver halide photographic light-sensitive material through a step wedge with monochromatic light of ± 5 nm, development and fixing were performed using a developer (1) described below at a development temperature of 35 ° C. and a development time of 25 seconds.
The characteristic curve shown on the orthogonal coordinates having the same unit length of the exposure amount (X-axis) and the optical density (Y-axis) obtained by washing and drying treatments is obtained at all points where the optical density is 1.5 to 2.0. A characteristic curve having a point gamma of 1.0 to 1.8,
A radiation image forming assembly wherein the crossover of the silver halide photographic light-sensitive material is not more than 15% of the light emitted from the radiation intensifying screen.

Developer (1) Composition Potassium hydroxide 21 g Potassium sulfite 63 g Boric acid 10 g Hydroquinone 26 g Triethylene glycol 16 g 5-Nitroindazole 0.2 g 5-Methylbenzotriazole 0.06 g 1-Phenyl-3-mercaptotetrazole 0.01 g Glacial acetic acid 12 g 1-phenyl-3-pyrazolidone 1.2 g glutaraldehyde 5 g potassium bromide 4 g After adding water to 1 liter, the pH is adjusted to 10.0.

[0010] 2. The optical density of the characteristic curve is 0.7 to 1.
5 is 1.3 to 2.
2. The radiation imaging assembly according to claim 1, wherein the point gamma at all points in the range of 0 and the optical density of 2.0 to 2.5 is in the range of 0.5 to 1.3.

3. The silver halide photographic material has a silver halide emulsion layer on both sides of the support, at least one of which has the same wavelength as the main emission peak wavelength of the radiographic intensifying screen, and has a half-width. The silver halide photographic light-sensitive material is exposed to monochromatic light of 20 ± 5 nm, and is developed, fixed, washed with water, and dried at a developing temperature of 35 ° C. for a developing time of 25 seconds using the developing solution (1). After the opposite emulsion layer was peeled off, the exposure required for the optical density obtained by measurement to reach a value obtained by adding 0.5 to the minimum density was 0.01%.
3. The radiation image forming assembly according to 1 or 2, having a sensitivity of 0 to 0.035 lux-second.

Hereinafter, the present invention will be described in detail.

The radiographic intensifying screen used in the radiographic image forming assembly of the present invention has high sensitivity, and has a characteristic that a contrast transfer function (CTF) is 0.79 or more at a spatial frequency of 1 line / mm, 0.3 at 3 wires / mm
6 or more. The screen used in the radiation image forming assembly of the present invention has a spatial frequency (1 lines / mm) of 0.79 or more and a spatial frequency (3 lines / m).
m) to be 0.36 or more.

Books / mm CTF 0.00 1.000 0.25 0.950 0.50 0.905 0.75 0.840 1.00 0.790 1.50 0.720 1.75 0.655 2 .00 0.535 2.50 0.430 3.00 0.360 3.50 0.300 4.00 0.255 5.00 0.180 6.00 0.130 From radiation intensifying screen to photosensitive material For measurement and calculation of the contrast transfer function, a square wave chart (a sample printed on an MRE single-sided material manufactured by Eastman Kodak Company)
Can be performed.

The screen phosphor preferably used in the radiation image forming assembly of the present invention has an average particle diameter of 0.3 to 7
μm is preferable to prevent diffusion of light in the phosphor layer which causes a decrease in sharpness, and more preferably 0.5 to 4 μm
It is. Here, the average particle diameter means a number average.

In the screen, the weight ratio of the binder to the phosphor in the phosphor layer is set to 0.1 to 3.0%, and the dispersibility of the binder in the phosphor is improved. In this case, the binder is thinly and uniformly present, so that the phosphor particles can come close to each other, so that the packing ratio is improved. That is, a phosphor layer with a high filling rate can be obtained without using any means such as compression.

The weight ratio of the binder to the phosphor in the phosphor layer is 0.1 to 3.0%, and the filling ratio of the phosphor is 6%.
It is preferably at least 5%.

In general, the phosphor layer is composed of phosphor particles, a binder and voids free of these. Here, the void refers to a space in the phosphor layer in which the phosphor particles and the binder are not substantially present.

Therefore, the volume ratio of the voids in the phosphor layer increases as the amount of the binder decreases. Since this gap acts as a light scattering factor, diffusion of light emission from the phosphor can be prevented and sharpness can be improved.

The weight ratio of binder to phosphor is 3.0%
When the ratio exceeds 1, the scattering of the light emission is reduced due to the decrease in the gap in the layer, and the light emission is easily diffused, so that the sharpness of the image is deteriorated.

The weight ratio of binder to phosphor is 0.1%
When the value is less than the above range, it is difficult for the binder to widely cover the surface of the phosphor, and it is difficult to perform the intrinsic function of the binder, which binds the phosphors, and it is not possible to obtain a high phosphor filling rate. In addition, the binder is hard to be uniform throughout the entire layer, so that the fluorescent substance is hard to be uniformly present, and the light emission becomes non-uniform, thereby deteriorating the granularity of the image. Further, it is not preferable in that the phosphor layer is fragile and easily damaged.

In order to measure the filling factor of the phosphor in the phosphor layer, the protective layer of the screen is removed, the entire phosphor layer is eluted with an organic solvent, filtered, dried, and dried in an electric furnace.
The weight of the phosphor obtained by baking at 1 ° C. for 1 hour to remove the resin on the surface was Og, the thickness of the phosphor layer before elution was Pcm, the screen area used for elution was Qcm ² , and the specific gravity of the phosphor was Rg / cm ³ . At this time, the phosphor filling rate = [O ÷ (P × Q × R)] × 100.

Examples of the binder usable in the present invention include polyurethane, polyester, vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer and vinyl chloride-acrylonitrile copolymer. , Butadiene-acrylonitrile copolymer, polyamide resin, polyvinyl butyral, cellulose derivative (such as nitrocellulose), styrene-butadiene copolymer, various synthetic rubber resins, phenolic resin, epoxy resin, urea resin, melamine resin, phenoxy resin , A silicone resin, an acrylic resin, a urea formamide resin, and the like. Among them, polyurethane, polyester,
It is preferable to use a vinyl chloride copolymer, polyvinyl butyral, or nitrocellulose.

The weight average molecular weight of the binder is 5,000 to 2
00,000 is particularly preferred.

In particular, the binder preferably used according to the present invention contains a resin having a hydrophilic polar group. The hydrophilic polar group is adsorbed on the phosphor surface to improve the dispersibility of the phosphor particles and prevent the aggregation of the phosphor particles, thereby improving the coating stability, sharpness, and granularity.

Among the resins having a hydrophilic polar group preferably used in the present invention, particularly preferred are -SO ₃ M,-
_{OSO 3 M, -COOM, -PO (} OM ') 2 and -OP
O (OM ') ₂ (where M and M' are hydrogen atoms or L
It is a resin having at least one hydrophilic polar group (negative functional group) composed of an alkali metal atom such as i, K, and Na).

The thickness of the phosphor layer used in the screen of the present invention is preferably from 20 to 150 μm, more preferably from 50 to 120 μm.

Further, in order to prevent the sharpness from lowering due to the diffusion of light, the phosphor may be colored with a dye (red, yellow) having an absorption at the emission wavelength of the phosphor.

Preferred phosphors for use in the screen of the present invention include the following.

Terbium-activated rare earth oxysulfide-based phosphor [Y ₂ O ₂ S: Tb, Gd ₂ O ₂ S: Tb, La ₂ O ₂ S: T
b, (Y, Gd) ₂ O ₂ S: Tb, (Y, Gd) O ₂ S:
Tb, Tm, etc.], terbium-activated rare earth phosphate-based phosphors (YPO ₄ : Tb, GdPO ₄ : Tb, LaPO ₄ : Tb
Terbium-activated rare earth oxyhalide phosphors (LaOBr: Tb, LaOBr: Tb, Tm, La)
OCl: Tb, LaOCl: Tb, Tm, LaOCl:
Tb, Tm, LaOBr: Tb, GdOBr: Tb, G
dOCl: Tb, etc.), thulium-activated rare earth oxyhalide-based phosphors (LaOBr: Tm, LaOCl: Tm)
Etc.), barium sulfate-based phosphor [BaSO ₄ : Pb, Ba
SO ₄ : Eu ²⁺ , (Ba, Sr) SO ₄ : Eu ²⁺ etc.), 2
-Valent europium-activated alkaline earth metal phosphate-based phosphor [Ba ₃ (PO ₄ ) ₂ : Eu ²⁺ , Ba ₃ (PO ₄ ) ₂ : Eu ²⁺
Etc.], divalent europium-activated alkaline earth metal fluorohalide-based phosphor [BaFCl: Eu ²⁺ , BaFB
r: Eu ²⁺ , BaFCl: Eu ²⁺ , Tb, BaFBr:
Eu ²⁺ , Tb, BaF ₂ .BaCl ₂ .KCl: Eu ²⁺ ,
(Ba, Mg) F ₂ .BaCl ₂ .KCl: Eu ²⁺ etc.],
Iodide phosphors (CsI: Na, CsI: Tl, Na
I, KI: Tl, etc.), sulfide-based phosphors [ZnS: Ag,
(Zn, Cd) S: Ag, (Zn, Cd) S: Cu,
(Zn, Cd) S: Cu, Al, etc.), hafnium phosphate-based phosphor (HfP ₂ O ₇ : Cu, etc.), tantalate-based phosphor [YTaO ₄ , YTaO ₄ : Tm, YTaO ₄ : Nb,
(Y, Sr) TaO _4-x : Nb, LuTaO ₄ , LuTa
O ₄ : Nb, (Lu, Sr) TaO _4-x : Nb, GdTa
O ₄ : Tm, Gd ₂ O ₃ .Ta ₂ O ₅ .B ₂ O ₃ : Tb, etc.],
However, the phosphor used in the present invention is not limited to these, and any phosphor that emits light in the visible or near ultraviolet region upon irradiation with radiation can be used.

As a first method for producing a screen, a phosphor coating solution comprising a binder and a phosphor (hereinafter referred to as a phosphor paint) is applied on a support to form a phosphor layer.

As a second production method, a phosphor coating sheet comprising a binder and a phosphor is formed, placed on a support, and applied to the support at a temperature equal to or higher than the softening temperature or the melting point of the binder. It is manufactured in the process of bonding.

As a method for forming the phosphor layer on the support,
The above two types are conceivable, but any method may be used as long as it is a method for uniformly forming the phosphor layer on the support, and a method such as spraying may be used.

The phosphor layer of the first production method can be produced by applying a phosphor coating material in which a phosphor is uniformly dispersed in a binder solution on a support and drying it.

The sheet to be used as the phosphor layer in the second production method is prepared by applying a phosphor paint on a temporary support for forming a phosphor sheet or on a protective film applied on the temporary support, and then drying. Thereafter, it can be manufactured by peeling from the temporary support.

That is, first, a binder and phosphor particles are added to an appropriate organic solvent, and stirred and mixed using a disperser or a ball mill to prepare a phosphor coating material in which the phosphor is uniformly dispersed in the binder. I do.

Solvents for preparing the phosphor coating include lower alcohols such as methanol, ethanol, n-propanol and n-butanol, hydrocarbons containing chlorine atoms such as methylene chloride and ethylene chloride, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Ketones, aromatic compounds such as toluene, benzene, cyclohexane, cyclohexanone, and xylene; esters of lower fatty acids such as methyl acetate, ethyl acetate, and butyl acetate with lower alcohols; dioxane; ethylene glycol monoethyl ester; ethylene glycol monomethyl ester; And mixtures thereof.

In the phosphor coating, a dispersant for improving the dispersibility of the phosphor in the coating or a binding force between the binder and the phosphor in the phosphor layer after formation is used. Various additives such as a plasticizer may be mixed.

Examples of dispersants include phthalic acid, stearic acid, caproic acid, lipophilic surfactants and the like.

Examples of the plasticizer include phosphoric esters such as triphenyl phosphate, tricresyl phosphate and diphenyl phosphate; phthalic esters such as diethyl phthalate and dimethoxyethyl phthalate; ethyl phthalyl ethyl glycolate; and butyl butyl butyl glycolate. And polyesters of polyethylene glycol and aliphatic dibasic acid, such as polyesters of triethylene glycol and adipic acid, and polyesters of diethylene glycol and succinic acid.

The phosphor coating containing the phosphor and the binder prepared as described above is uniformly applied to the surface of a support or a temporary support for sheet formation to form a coating film of the paint. I do.

As the coating means, for example, a doctor blade, a roll coater, a knife coater, an extrusion coater or the like can be used.

As the support and the temporary support, those made of various materials such as glass, wool, cotton, paper and metal can be used, but they are flexible in handling as information recording materials. What can be processed into a sheet or a roll is preferred. From this point, for example, cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, triacetate film, plastic film such as polycarbonate film, metal sheet such as aluminum foil and aluminum alloy foil, general paper and photographic base paper Base paper for printing such as coated paper or art paper, baryta paper, resin coated paper, paper sized with polysaccharides as described in Belgian Patent 784,615, pigments such as titanium dioxide Pigment paper containing, and processed paper such as paper sized with polyvinyl alcohol are preferred, but those having a high absorption rate of the luminescence of the phosphor, for example, black PET (black polyethylene te containing carbon black) Phthalate) can prevent reflection of light at the support, especially preferred prevent a decrease in sharpness.

In the second production method, a phosphor paint is applied on a temporary support or a protective film applied on the temporary support, dried, and then peeled off from the temporary support to be applied on a screen support. By bonding, the phosphor layer is attached to the support.

Therefore, it is preferable that a release agent is applied to the surface of the temporary support in advance so that the formed phosphor sheet is easily released from the temporary support.

In order to strengthen the bond between the support and the phosphor layer, an undercoat layer is provided on the surface of the support by applying a high molecular substance such as polyester or gelatin to impart adhesiveness, and sensitivity, image quality (sharpness, granularity, etc.) In order to improve the property, a light reflecting layer made of a light reflecting substance such as titanium dioxide or a light absorbing layer made of a light absorbing substance such as carbon black may be provided. These configurations can be arbitrarily selected according to the purpose, use, and the like.

The phosphor layer preferably used in the image forming method of the present invention may be compressed. By compressing the phosphor layer, the packing density of the phosphor can be further improved, and the sharpness and granularity can be further improved. As a compression method, a press machine, a calender roll, or the like can be used.

In the case of the first production method, the phosphor layer and the support are compressed as they are.

In the case of the second production method, the phosphor sheet obtained as described above is placed on a support, and the sheet is bonded to the support while being compressed at a temperature not lower than the softening temperature or the melting point of the binder.

In this way, the sheet can be spread thinly by utilizing the method of pressing the phosphor sheet without fixing the phosphor sheet on the support in advance.

Usually, the screen is provided with a protective layer for physically and chemically protecting the surface of the phosphor layer on the side opposite to the side in contact with the support described above. Such a protective layer is preferably provided also for a screen used in the image forming method of the present invention. The thickness of the protective layer is generally in the range from 2 to 20 μm.

The protective layer is made of, for example, a cellulose derivative such as cellulose acetate or nitrocellulose, or a synthetic polymer such as polymethyl methacrylate, polyethylene terephthalate, polyvinyl butyral, polyvinyl formal, polycarbonate, polyvinyl acetate, or vinyl chloride / vinyl acetate copolymer. It can be formed by a method in which a solution prepared by dissolving in a suitable solvent is applied to the surface of the phosphor layer. These polymer substances can be used alone or in combination. When the protective layer is formed by coating, it is desirable to add a crosslinking agent immediately before coating.

Alternatively, it can be formed by a method such as bonding a plastic sheet made of polyethylene terephthalate, polyethylene naphthalate, polyethylene, polyvinylidene chloride, polyamide or the like using an adhesive.

The protective layer is preferably formed of a coating film containing a fluorine resin soluble in an organic solvent. The fluororesin refers to a polymer of an olefin containing fluorine (fluoroolefin) or a copolymer containing an olefin containing fluorine as a copolymer component. The protective layer formed by the fluororesin coating film may be crosslinked. The protective layer made of a fluororesin can easily remove dirt such as fats and plasticizers coming out of the photosensitive material by contact with tentacles or photosensitive materials. There are advantages that can be done. Further, for the purpose of improving the film strength, etc., a fluorine-based resin and another polymer substance may be mixed.

The protective layer is preferably a synthetic resin layer having a thickness of 10 μm or less formed on the phosphor layer. By using such a thin protective layer, the distance from the phosphor to the silver halide emulsion is reduced, which contributes to the improvement of the sharpness of the obtained radiographic image.

The preferred sensitivity range of the photosensitive material used in the radiation image forming assembly of the present invention is that the photosensitive material has the same wavelength as the main emission peak wavelength of the screen and has a half width of 20 ± 5.
exposure with a monochromatic light of nm, development processing using the above-described developer (1) at a development temperature of 35 ° C. and a development time of 25 seconds, and peeling off the emulsion layer on the side opposite to the exposed surface. The sensitivity is such that the exposure required for the resulting density to be 0.5 plus the minimum density is 0.010 to 0.035 lux seconds, preferably 0.012 to 0.030 lux seconds. Things. The sensitivity in this range is equivalent to that of commercially available X-ray film SR.
-G (manufactured by Konica Corporation). In the method for measuring the sensitivity of a photosensitive material, the exposure light source used must match or almost match the wavelength of the main emission peak of the screen used in combination. For example, when the phosphor of the screen is terbium-activated gadolinium oxysulfide, since the main emission peak wavelength is 545 nm, the exposure light source used when measuring the sensitivity of the photosensitive material is light having a wavelength of 545 nm as the center. .

As a method for obtaining monochromatic light, a method using a filter system combining an interference filter can be used. According to this method, although it depends on the combination of the interference filters, usually, monochromatic light having a necessary exposure amount and a half width of 20 ± 5 nm can be easily obtained.

It should be noted that the spectral sensitization spectrum of the photosensitive material is continuous irrespective of whether or not spectral sensitization has been performed, and the sensitivity does not substantially change in the wavelength range of 20 ± 5 nm. it can.

As an example of the exposure light source, when the phosphor of the screen used in combination is terbium-activated gadolinium oxysulfide, a tungsten light source (color temperature: 2856K) and a transmission peak wavelength of 545 nm are used.
And a system combined with a filter having a half-value width of 20 nm and a transmittance.

In the radiation image forming assembly of the present invention, the optical density of the characteristic curve shown on a rectangular coordinate having the same unit length of the common logarithm of radiation exposure (X axis) and the optical density (Y axis) is 1.5 to 1.5. A light-sensitive material having a point gamma of 1.0 to 1.8 at all points of 2.0 provides an image in which the structure of the stomach wall in gastric double contrast imaging can be easily diagnosed as a still image. If the point gamma at all points of the optical density of 1.5 to 2.0 is less than 1.0, the contrast is low and the reading is hardly affected, and if it exceeds 1.8, the fine structure of the stomach wall becomes slightly difficult to see. Preferably, the point gamma at all points having an optical density of 0.7 to 1.5 is in the range of 1.3 to 2.0 and the point gamma at all points having the optical density of 2.0 to 2.5 is 0.5. ~ 1.3. That is, in the double stomach contrast imaging method, an image is obtained in which there is no blackened portion in one screen, and the fine structure of the stomach wall is clear and easy to diagnose.

The point gamma in the present invention is defined as follows. This is a gradient when a tangent to the characteristic curve is drawn in a characteristic curve shown on orthogonal coordinates having the same unit length represented by a common logarithmic value (X axis) and an optical density (Y axis) of the radiation exposure amount. That is, assuming that the angle between the tangent and the X axis is θ, it is indicated by tan θ.

The term "crossover" as used in the present invention means that in a light-sensitive material having a transparent support coated with a photosensitive emulsion on both sides, light from one direction passes through the first emulsion layer and the support, and Light to expose the photosensitive layer.

The crossover (%) is Abbott e
It is measured by the method described in US Pat. No. 4,425,425 to tal. That is, in a photosensitive material having substantially the same photosensitive layer on both sides of a support, black paper, a photosensitive material, and then a screen are arranged in the order of an X-ray source, packed in an X-ray cassette, and stepped into an X-ray cassette. Line exposure. After the development, an image of only the photosensitive layer in contact with the screen is divided into two and an image of only the photosensitive layer on the opposite side is separated, and respective characteristic curves are obtained. When the curve sensitivity difference is ΔlogE, crossover (%) = 100 / (anti log
(ΔlogE) +1).

The smaller the crossover, the sharper the image. Although there are various methods for reducing crossover, the most preferable method is to fix a dye capable of being decolorized by a development process between the support and the photosensitive layer.

As a means for reducing the crossover to 15% or less in the present invention, the dye layer is provided with a solid disperse dye as dense as possible, the amount of gelatin used as a binder is reduced, and the thickness of the dye layer is reduced. 0.5 μm or less, most preferably 0.05 to 0.3 μm
It is.

The solid disperse dye preferably used in the present invention is a compound represented by the following general formula (1).

[0067]

Embedded image

In the formula, R ₁ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group. Group, acylamino group, ureido group, amino group, acyl, alkoxy group, aryloxy group, hydroxy group, carboxy group, cyano group, sulfamoyl group or sulfonamide group, and B is a 5- or 6-membered oxygen-containing heterocyclic ring Represents a group or a 6-membered nitrogen-containing heterocyclic group, L _{1 to} L ₃ represent a methine group, and n represents 0 or 1.

However, the compound of the general formula (1) has at least one of a carboxy group, a sulfonamide group and a sulfamoyl group.

In the general formula (1), examples of the alkyl group represented by R ₁ and R ₂ include a methyl group, an ethyl group,
n-propyl group, i-propyl group, t-butyl group, n-
Examples include a pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-dodecyl group, n-pentadecyl group, and eicosyl group. These alkyl groups include those having a substituent. Examples of the substituent include a halogen atom (for example, each atom such as chlorine, bromine, iodine, and fluorine), an aryl group (for example, a phenyl group and a naphthyl group), and a cycloalkyl group. (Eg, cyclopentyl group, cyclohexyl group, etc.), heterocyclic group (eg, pyrrolidyl group, pyridyl group, furyl group, thienyl group, etc.), sulfinic acid group, carboxyl group, nitro group, hydroxyl group, mercapto group, amino group (eg, amino group , Diethylamino group, etc.), alkyloxy group (eg, methyloxy group, ethyloxy group, n-butyloxy group, i-propyloxy group, etc.), aryloxy group (phenyloxy group, naphthyloxy group, etc.), carbamoyl group (eg, amino Carbamoyl group, methylcarbamoyl group, n-pentylcarbamoyl group Phenylcarbamoyl group, etc.), amide group (eg, methylamide group, benzamide group, n-octylamide group, etc.), aminosulfonylamino group (eg, aminosulfonylamino group, methylaminosulfonylamino group, anilinosulfonylamino group, etc.), sulfamoyl Group (eg, sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, n-butylsulfamoyl group, etc.), sulfonamide group (eg, methanesulfonamide group, n-heptanesulfonamide group, benzenesulfonamide group, etc.) ), A sulfinyl group (eg, an alkylsulfinyl group such as a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, an octylsulfinyl group, an arylsulfinyl group such as a phenylsulfinyl group), an alkyloxy group Carbonyl group (e.g., methyl group, an ethyloxycarbonyl group,
2-hydroxyethyloxycarbonyl group, n-octyloxycarbonyl group, etc., aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylthio group (eg, methylthio group, ethylthio group, n-hexylthio group, etc.) ), An arylthio group (eg, phenylthio group, naphthylthio group, etc.), an alkylcarbonyl group (eg, acetyl group, ethylcarbonyl group, n-butylcarbonyl group, n-octylcarbonyl group, etc.), an arylcarbonyl group (eg, benzoyl group, p- Methanesulfonamidobenzoyl group,
p-carboxybenzoyl group, naphthoyl group, etc.), cyano group, ureido group (eg, methylureide group, phenylureide group, etc.), and thioureide group (eg, methylthioureide group, phenylthioureide group, etc.).

The aryl group represented by R ₁ and R ₂ includes, for example, a phenyl group and a naphthyl group. The aryl group includes those having a substituent, and examples of the substituent include the above-described groups described as the substituent of the alkyl group or the alkyl group.

The heterocyclic group represented by R ₁ and R ₂ includes, for example, a pyridyl group (for example, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 5-carboxy-2-pyridyl group, 3,5 -Dichloro-2-pyridyl group, 4,6-
Dimethyl-2-pyridyl group, 6-hydroxy-2-pyridyl group, 2,3,5,6-tetrafluoro-4-pyridyl group, 3-nitro-2-pyridyl group, etc.), oxazolyl group (5-carboxy- 2-benzoxazoline group, 2-
Benzoxazoline group, 2-oxazoline group, etc.), thiazolyl group (5-sulfamoyl-2-benzthiazolyl group, 2-benzothiazolyl group, 2-thiazolyl group, etc.),
Imidazolyl group (1-methyl-2-imidazolyl group, 1
-Methyl-5-carboxy-2-benzimidazolyl group, etc.), furyl group (3-furyl group, etc.), pyrrolyl group (3-
Pyrrolyl group), thienyl group (2-thienyl group, etc.), pyrazinyl group (2-pyrazinyl group, etc.), pyrimidinyl group (2-pyrimidinyl group, 4-chloro-2-pyrimidinyl group, etc.), pyridazinyl group (2-pyridazinyl) Group), a purinyl group (such as an 8-purinyl group), an isoxazolyl group (such as a 3-isoxazolyl group), a selenazolyl group (such as a 5-
A carboxy-2-selenazolyl group, a sulfolanyl group (a 3-sulfolanyl group, etc.), a piperidinyl group (a 1-methyl-3-piperidinyl group, etc.), a pyrazolyl group (a 3-pyrazolyl group, etc.), a tetrazolyl group (1-methyl- And the heterocyclic group includes those having a substituent. Examples of the substituent include those exemplified as the alkyl group and the substituent of the alkyl group.

The alkoxycarbonyl group represented by R ₂ includes, for example, methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, dodecyloxycarbonyl group and the like.

The aryloxycarbonyl group represented by R ₂ includes, for example, a phenyloxycarbonyl group and a naphthyloxycarbonyl group.

The carbamoyl group represented by R ₂ includes
For example, aminocarbamoyl group, methylcarbamoyl group,
An ethylcarbamoyl group, an i-propylcarbamoyl group,
t-butylcarbamoyl group, dodecylcarbamoyl group,
Examples include a phenylcarbamoyl group, a 2-pyridylcarbamoyl group, a 4-pyridylcarbamoyl group, a benzylcarbamoyl group, a morpholinocarbamoyl group, and a piperazinocarbamoyl group. Examples of the acylamino group represented by R ₂ include a methylcarbonylamino group, an ethylcarbonylamino group, an i-propylcarbonylamino group,
Examples include a t-butylcarbonylamino group, a dodecylcarbonylamino group, a phenylcarbonylamino group, a naphthylcarbonylamino group, and the like.

Examples of the ureide group represented by R ₂ include a methylureide group, an ethylureide group, an i-propylureide group, a t-butylureide group, a dodecylureide group, a phenylureide group, a 2-pyridylureide group, and a thialide group. Zolylureido group and the like.

Examples of the amino group represented by R ₂ include an amino group, a methylamino group, an ethylamino group, an i-propylamino group, a t-butylamino group, an octylamino group, a dodecylamino group, a dimethylamino group, Examples include an anilino group, a naphthylamino group, a morpholino group, and a piperazino group.

Examples of the acyl group represented by R ₂ include a methylcarbonyl group, an ethylcarbonyl group, an i-propylcarbonyl group, a t-butylcarbonyl group, an octylcarbonyl group, a dodecylcarbonyl group, a phenylcarbonyl group and a naphthylcarbonyl group. And the like.

Examples of the alkoxy group represented by R ₂ include a methoxy group, an ethoxy group, an i-propoxy group and a t-
Examples thereof include a butyloxy group and a dodecyloxy group.

The aryloxy group represented by R ₂ includes, for example, a phenoxy group and a naphthyloxy group.

Examples of the sulfamoyl group represented by R ₂ include aminosulfamoyl, methylsulfamoyl, i-propylsulfamoyl, t-butylsulfamoyl, dodecylsulfamoyl, phenyl Sulfamoyl group, 2-pyridylsulfamoyl group, 4
-A pyridylsulfamoyl group, a morpholinosulfamoyl group, a piperazinosulfamoyl group and the like.

Examples of the sulfonamide group represented by R ₂ include a methylsulfonamide group, an ethylsulfonamide group, an i-propylsulfonamide group, a t-butylsulfonamide group, a dodecylsulfonamide group, a phenylsulfonamide group, And a naphthyl sulfonamide group.

[0083] Each of these groups include those having a substituent, examples of the substituent, exemplified as substituents for the alkyl group shown as the alkyl group and R ₁ and R ₂ shown as R ₁ and R ₂ above What was done.

In the general formula (1), the 5-membered or 6-membered oxygen-containing heterocyclic group represented by B and the 6-membered nitrogen-containing heterocyclic group may be a furyl group (2-furyl group, 3-furyl group). Group, 2-benzofuranyl group, 3-benzofuranyl group, 1
-Isobenzofuranyl group), pyranyl group (2-tetrahydropyranyl group, 3-2H-pyranyl group, 4-2H-
Pyranyl group, 5-2H-pyranyl group, 6-2H-pyranyl group, 2-4H-pyranyl group, 3-4H-pyranyl group,
2-chromanyl group, 3-chromanyl group, 4-2H-chromenyl group, 2-4H-chromenyl group, pyronyl group (2-
4H-pyronyl group, 3-4H-pyronyl group, 2-chromonyl group, 3-coumarinyl group, 3-chromonyl group, etc., pyridyl group (2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolyl) Group, 3-quinolyl group, 4-quinolyl group, 9-acridyl group, 3-thienopyridyl group, etc.),
Examples include a pyrazinyl group (such as a 2-pyrazyl group), a pyrimidinyl group (such as a 2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, and a 2-quinazolinyl group), and a piperidinyl group (such as a 3-piperidinyl group). The Heteri ring group include those having a substituent, examples of the substituent include include those exemplified as substituents for the alkyl group and alkyl group of R ₁ and R _2, further, the amino group of R _2, Examples thereof include those exemplified as the alkoxy group and the aryloxy group.

In the general formula (1), the methine groups represented by L _{1 to} L ₃ include those having a substituent, and the substituent includes an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a t-group). -Butyl group, 3-hydroxypropyl group,
A benzyl group), an aryl group (eg, a phenyl group), a halogen atom (eg, chlorine, bromine, iodine, fluorine, etc.),
Examples include an alkoxy group (eg, a methoxy group, an ethoxy group, etc.), an acyloxy group (eg, a methylcarbonyloxy group, a phenylcarbonyloxy group, etc.).

Hereinafter, specific examples of these compounds according to the present invention will be described, but the present invention is not limited thereto.

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

In addition to the compounds represented by the above general formula (1), for example, the compounds represented by the formula (I) described in JP-A-5-216143
Compounds 1 to 1-2, II-1 to II-10, and III-1 to III-72 can be preferably used.

As silver halide grains used in the silver halide photographic light-sensitive material of the present invention, tabular silver halide grains (hereinafter, also simply referred to as tabular grains) are preferably used in order to obtain high sensitivity. A as silver halide composition
gBr, AgCl, AgClBr, AgClBrI, A
Although it can be used arbitrarily, such as gBrI, AgBrI rich in AgBr composition is preferable.

Tabular grains are disclosed in US Pat. No. 4,439,520.
No. 4,425,425, and No. 4,414,304, and the desired tabular grains can be easily obtained. In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled on specific surface portions. In order to control the photosensitive nucleus, a transition line may be provided on the surface or inside of the tabular grain.

The tabular grains are preferably tabular grains having an aspect ratio of at least 50% of the total projected area of all grains in the emulsion layer in which the tabular grains are used. Particularly, as the proportion of tabular grains increases from 60% to 70%, and more preferably to 80%, more favorable results are obtained.

The term “aspect ratio” as used herein refers to the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes. In the present invention, the aspect ratio is 2
It is preferably at least 20 and less than 3 and at least 3 and less than 16.

The thickness of the tabular grains is preferably 0.5 μm or less, more preferably 0.3 μm or less. In addition, the distribution of tabular grains can be calculated by using a coefficient of variation (a value S obtained by dividing a standard deviation S when the projected area is approximated by a circle) by a diameter D.
/ 100) is preferably 30% or less, particularly 20% or less. Further, two or more tabular grains and non-tabular grains of normal crystals may be mixed.

For controlling the growth of grains during the formation of tabular grains, for example, ammonia, a thioether compound, a thione compound or the like can be used as a silver halide solvent. In addition, metal salts such as zinc, lead, thallium, iridium, and rhodium can coexist during physical ripening or chemical ripening.

In the case of chemical sensitization, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, noble metal sensitization and a combination thereof are used.

Examples of the sulfur sensitizer applicable in the present invention include US Pat. Nos. 1,574,944 and 2,41.
No. 0,689, 2,278,947, 2,72
8,668, 3,501,313, 3,65
No. 6,955, West German Application Publication (OLS) 1,422,8
No. 69, JP-A-56-24937, and JP-A-55-4501.
No. 6, etc., can be used. Specific examples include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur alone. And the like are preferred examples. still,
As the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Selenium sensitizers used for chemical sensitization include a wide variety of selenium compounds. For example, US Pat. Nos. 1,574,944 and 1,602,5
Nos. 92 and 1,623,499, JP-A-60-150
No. 046, JP-A-4-25832 and JP-A-4-10924.
No. 0, 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). Urea, N,
N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenyl Carbonylselenourea, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids, and selenoesters (eg, 2-seleno) Propionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (for example, tri-
p-triselenophosphate, etc.) and selenides (diethyl selenide, diethyl diselenide, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenoketones.

Specific examples of techniques for using these selenium sensitizers are described in H.S. E. FIG. Journal of the author by Spencer et al.
Photographic Science, 31
Vol. 158-169 (1983).

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. In addition, the addition method may be a method in which water or an organic solvent such as methanol, ethanol, ethyl acetate or the like is dissolved alone or in a mixed solvent depending on the properties of the selenium compound to be used, or may be preliminarily mixed with a gelatin solution. The method of addition may be the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

The temperature of chemical ripening using a selenium sensitizer is as follows:
A range from 40 to 90C is preferred. More preferably 45 ° C
Not less than 80 ° C. The pH is 4-9 and the pAg is 6
The range of -9.5 is preferred.

The tellurium sensitizers and sensitization methods used for chemical sensitization are described in US Pat. Nos. 1,623,499, 3,320,069, 3,772,031, and 3,531. No. 289, No. 3,655,394; British Patent Nos. 235,211; 1,121,496; 1,295,462; 1,396,696; and Canadian Patent 800,958. No., JP-A-4-204640
And No. 4-333430. Examples of useful tellurium sensitizers include telluroureas (eg,
N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (for example, tributylphosphine) Telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (eg, telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro Esters, isotellocyanates and the like.

The technique for using the tellurium sensitizer is the same as the technique for using the selenium sensitizer.

In the present invention, it is also preferable to use reduction sensitization in combination. The reduction sensitization is preferably performed during the growth of silver halide grains. As a method of applying during the growth, not only a method of performing reduction sensitization in a state where silver halide grains are growing, but also a method of performing reduction sensitization in a state where growth of silver halide grains is interrupted, and then performing reduction sensitization. Includes a method of growing the perceived silver halide grains.

The gold sensitizer used in the present invention includes, in addition to chloroauric acid, gold thiosulfate and gold thiocyanate, gold complexes of thioureas, rhodanines and other various compounds. .

The amount of the sulfur sensitizer, selenium sensitizer, tellurium sensitizer, reduction sensitizer and gold sensitizer to be used depends on the type of silver halide emulsion, the type of compound used and the ripening conditions. Usually, it is preferably 1 × 10 ^-4 to 1 × 10 ^-9 mol per mol of silver halide. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

In the present invention, the method of adding a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, a reduction sensitizer, and a gold sensitizer is as follows. Or in the form of a dispersion obtained by emulsifying and dispersing using a solvent insoluble in water or a medium such as gelatin.

The sensitizing dye used in the present invention may be added at the time of silver halide grain formation or at any time after the formation until coating, but is preferably before the end of the desalting step.

The pH of the reaction solution (usually in a reaction vessel) at the time of addition is preferably in the range of 4 to 10. More preferably, the pH is in the range of 6 to 9. The pAg in the reaction solution (reaction vessel) is preferably 5 to 11.

The spectral sensitizing dye used in the present invention is optional. For example, a cyanine dye can be preferably used. In that case, S-1 to S-12 represented by the general formulas (I) to (III) described in JP-A-1-100533.
4 compounds can be preferably used.

When the above-mentioned spectral sensitizing dye is added, two or more kinds thereof may be used in combination. In this case, two or more kinds of spectral sensitizing dyes may be mixed and added simultaneously, or may be added separately at different times. The amount of addition is 1 to 1000 mg per mole of silver, preferably 5 to 1000 mg.
500 mg is good. Further, it is preferable to add potassium iodide before adding these spectral sensitizing dyes and then add them.

The spectral sensitizing dye can be directly dispersed in the emulsion. They can also be dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and added in the form of a solution. Also, ultrasonic waves can be used for dissolution. Further, the water-insoluble spectral sensitizing dye may be added as a fine particle dispersion by high-speed impeller dispersion without dissolving in water.

In the present invention, as matting agents, US Pat. Nos. 2,992,101 and 2,701,245
No. 4,142,894, No. 4,396,70
No. 6, homopolymers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid, organic compounds such as starch, fine particles of inorganic compounds such as silica, titanium dioxide, strontium sulfate, and barium sulfate can be used. . The particle size is preferably 0.6 to 10 μm, particularly preferably 1 to 5 μm.

In the surface layer of the light-sensitive material of the present invention, US Pat. Nos. 3,489,576 and 4,047, US Pat.
No. 958, etc .;
In addition to the colloidal silica described in JP-A-3139, paraffin wax, higher fatty acid esters, starch derivatives and the like can be used.

To the constituent layers of the light-sensitive material, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be added as plasticizers.

Further, a polymer latex can be contained for the purpose of improving pressure resistance. As the polymer, a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid or styrene, a styrene-butadiene copolymer, a polymer or copolymer comprising a monomer having an active methylene group, a water-soluble group or a crosslinkable group with gelatin is preferred. Can be used. In particular, in order to increase the affinity with gelatin as a binder, an alkyl ester of acrylic acid, a copolymer with a monomer having a water-soluble group having a hydrophobic monomer such as styrene as a main component or a crosslinkable group with gelatin is most preferable. Used. Preferred examples of the monomer having a water-soluble group include acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, and styrenesulfonic acid, and preferred examples of the monomer having a crosslinkable group with gelatin. Examples thereof include glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, and the like.

Various additives can be added to the light-sensitive material of the present invention depending on the purpose. Other additives used include, for example, Research Disclosure (RD) No. 17643 (December 1978
No.), and No. 18716 (November 1979) and the same No. 308119 (December 1989). The places to be described are listed below.

[0120]

[Table 1]

The processing method of the light-sensitive material used in the assembly of the present invention is such that when processing is performed by an automatic developing machine including development, fixing, washing and drying steps, the processing steps from development to drying are performed within 45 seconds. Yes, preferably within 30 seconds. That is, the time from when the leading end of the photosensitive material starts to be immersed in the developing solution to when the leading end comes out of the drying zone through a processing step (so-called Dry to Dry time) is 4 times.
It is within 5 seconds, more preferably within 30 seconds.

The development time is from 6 seconds to 20 seconds. The development temperature is preferably from 25 to 50C, more preferably from 30 to 40C.

The fixing temperature and time are about 20 to 50 ° C. and 6 to
20 seconds is preferable, and 6 to 15 seconds at 30 to 40 ° C is more preferable.

Drying is usually performed at 35 to 100 ° C., preferably at 4 to 100 ° C.
A drying zone in which hot air of 0 to 80 ° C. is blown or heating means by far infrared rays is provided may be provided in the automatic developing machine.

The automatic developing machine is provided with a mechanism for applying water or a rinsing liquid of an acidic solution having no fixing ability to the photosensitive material during each of the developing, fixing and washing steps. Kaihei 3-264953) may be used. Further, the automatic developing machine may have a built-in device for preparing a developing solution and a fixing solution.

As developing agents, dihydroxybenzenes (for example, hydroquinone), 1-phenyl-3-pyrazolidones (for example, phenidone), aminophenols (for example, metol), azole organic antifoggants (for example, indazole and imidazole, Benzimidazole-based, triazole-based, benztriazole-based, tetrazole-based, thiadiazole-based) and alkaline agents, preservatives and sodium hexametaphosphate, a concealing agent for concealing calcium ions mixed in tap water used for treatment liquid,
There are calcium hexametaphosphate, polyphosphate and the like.

Examples of the developing agent include hydroquinones, combinations of hydroquinones with 1-phenyl-3-pyrazolidone and hydroquinones with p-aminophenols, as well as reductones (eg, asicorbic acid, erythorbic acid or derivatives thereof). Etc.) are also preferably used.

Examples of the sulfite used as a preservative include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite,
Potassium metasulfite and the like can be mentioned.

The developer may contain a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the iron ion means ferric iron (Fe ³⁺ ).

Examples of the chelating agent having a chelating stability constant for iron of 8 or more include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent and a polyhydroxy compound.

Specific examples of these are, for example, ethylenediaminediorthohydroxyphenylacetic acid, triethylenetetramineacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid,
Ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etheraminetetraacetic acid, ethylenediamine-N , N, N ', N'-tetrakismethylenephosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-
Phosphonobtan-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, hexametaphosphoric acid Sodium and the like.

The developing solution may contain a hardening agent which hardens and reacts with the gelatin in the light-sensitive material during the development processing to enhance the film properties. Examples of the hardening agent include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maledialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde,
α, α-Dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butylmaledialdehyde, or a bisulfite adduct thereof are used.

In addition to the above components, additives used include development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, and the like. Organic solvents such as methanol or 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-
Mercapto compounds such as 5-sulfonic acid sodium salt,
It may contain an antifoggant such as a benztriazole-based compound such as 5-methylbenztriazole, and may further contain a color tone agent, a surfactant, an antifoaming agent, and the like, if necessary.

The pH of the developing solution may be 9.0 to 12, preferably in the range of 9.0 to 11.5. Examples of the alkaline agent or buffer used for setting the pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, boric acid, sodium tribasic phosphate and potassium tribasic phosphate.

As the fixing solution according to the present invention, a fixing solution containing a fixing agent such as sodium thiosulfate and ammonium thiosulfate can be used. Of these, ammonium thiosulfate is preferable in terms of fixing speed. These fixing agents are generally used in an amount of about 0.1 to 6 mol / l.

The fixing solution may contain an aqueous solution aluminum salt as a hardening agent, and further includes aluminum chloride, aluminum sulfate, potassium alum and the like.

For the fixing solution, malic acid, tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination. It is effective to contain these compounds in an amount of 0.001 mol or more per liter of the fixing solution.
0.005 to 0.03 mol is particularly effective.

The pH of the fixing solution is preferably 3.8 or more, and more preferably 4.2 to 7.0. In consideration of the fixed hardening film or the odor of sulfurous acid, 4.3 to 4.8 is more preferable.

At the time of development, it is preferable to use a starter as a developer. The starter is an acidic additive and may be either an organic acid or an inorganic acid, or may be a mixture.

The starter may be a solid or a solution as long as it is soluble in a developing solution, and is preferably used in a solution state. Specific components of the starter include, for example, acetic acid, citric acid, boric acid, sulfuric acid and salicylic acid, and salts thereof.

These acids can be used alone or in combination of two or more. The addition amount of the starter is 0.1 to 100 g, preferably 0.5 to 50 g per liter of the developer. The width of the decrease in developer pH due to the addition of the starter is preferably 0.2 or more, more preferably 0.2 to 1.0.

Further, the starter may contain components other than the acid, and in particular, may contain components such as halogen and hydroquinone monosulfonate which increase in the development reaction. Halogen such as KBr or KCl is preferably added in an amount of 0.1 to 10 g per liter of the developing solution.

The photosensitive material which has been developed and fixed is subsequently washed or stabilized. Washing or stabilizing treatment
Not only is it possible to save water with a replenishment amount of 3 liters or less per 1 m ^{2 of} silver halide photographic material (including 0, that is, it can be carried out by pooled water washing), and the piping for installing an automatic developing machine is unnecessary. can do.

When the washing is performed with a small amount of water, see Japanese Unexamined Patent Publication No.
It is more preferable to provide a squeeze roller washing tank described in -18350 and 62-287252. In addition, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Furthermore, by replenishing the washing or stabilizing bath with water subjected to a fungicide according to the treatment, part or all of the overflow liquid generated from the washing or stabilizing bath is described in JP-A-60-235133. As described above, it can also be used for a processing solution having a fixing ability, which is the preceding processing step.

In addition, the treatment agent component which prevents water bubble unevenness which tends to occur when washing with a small amount of water and / or adheres to the squeeze roller is
A water-soluble surfactant or an antifoaming agent may be added to prevent transfer to the treated film. Japanese Patent Application Laid-Open No. 63-1 / 1988 describes prevention of contamination by dyes eluted from a photosensitive material.
The dye adsorbent described in No. 63456 may be installed in a washing tank. In some cases, a stabilization treatment may be performed after the water washing treatment. For example, Japanese Patent Application Laid-Open Nos. 2-201357 and 2-1
No. 32435, No. 1-125553, JP-A-46-4
A bath containing the compound described in No. 4446 may be used as the final bath of the light-sensitive material. If necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, various chelating agents, a film pH regulator, a hardening agent, a bactericide, an antifungal agent, an alkanolamine, or a surfactant may be used in this stabilizing bath. Agents can be added.

The water used in the washing step or the stabilizing step includes tap water, deionized water, halogen, an ultraviolet germicidal lamp, and various oxidizing agents (ozone, hydrogen peroxide,
For example, water sterilized by chlorate or the like can be used.

[0147]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of Em-1) A tabular silver iodobromide grain emulsion was prepared as follows.

[0149] A ₁ ossein gelatin 24.2g Water _{9657ml HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~ 7) (10% methanol solution) 1.20 ml potassium bromide 10.8 g 10% nitric acid 160 ml B ₁ 2.5 N aqueous silver nitrate solution 5651ml C ₁ 5651ml potassium bromide 1682g water D ₁ ossein gelatin 121g water 2040ml HO- (CH _{2 CH 2 O) n - [} CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~7) (10% aqueous solution of methanol) 5.70ml E ₁ 1.75N odor aqueous solution of potassium following silver potential control amount 35 ° C. in using the mixing stirrer shown in Japanese Patent Publication No. 58-58288 solution a ₁ in solution B ₁ and each of the solutions C ₁ 47
5.0 ml was added by the simultaneous mixing method over 2.0 minutes to form nuclei.

After stopping the addition of the solution B ₁ and the solution C ₁ ,
By taking 60 minutes to raise the temperature of the solution A ₁ to 60 ° C., was added the total amount of D _1, after adjusting the pH to 5.5 with 3% KOH, the solution B ₁ again and the solution C ₁ Was added by a double jet method over 90 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 35 ° C. to 60 ° C. and the re-mixing with the solutions B ₁ and C ₁ was measured using the solution D ₁ . +8 mV and +30 respectively
It controlled so that it might be set to mV.

After completion of the addition, the pH was adjusted to 6 with 3% KOH.
It was desalted and washed immediately with 0. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.18 μm. It was confirmed with an electron microscope that the diameter (in terms of circular diameter) was 0.590 μm.

Subsequently, after this emulsion was heated to 53 ° C.,
After adding a predetermined amount of the spectral sensitizing dyes A and B as a dispersion in the form of solid fine particles, 4-hydroxy-6-methyl-1,
A mixed aqueous solution of 3,3a, 7-tetrazaindene (TAI), adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate, and a methanol solution of triphenylphosphine selenide were added, and aging was performed for a total of 2 hours and 30 minutes. did. At the end of aging, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was further added as a stabilizer.

The spectral sensitizing dyes and other additives and the amounts of the additives (per mole of AgX) are shown below.

Spectral sensitizing dye (A) 5,5′-Dichloro-9-ethyl-3,3′-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydrous 450 mg Spectral sensitizing dye (B) 5,5'-Di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium anhydride 8 mg 4-hydroxy-6-methyl-1 , 3,3a, 7-tetrazaindene 60 mg adenine 15 mg sodium thiosulfate 5.0 mg ammonium thiocyanate 50 mg chloroauric acid 2.5 mg silver iodide fine grain emulsion (average particle size 0.05 μm) 5 mmol min triphenylphosphine selenide 6 0.0 mg Stabilizer (TAI) 750 mg (Preparation of solid particulate dispersion of spectral sensitizing dye) A predetermined amount of the sensitizing dye (A) and the spectral sensitizing dye (B)
The dispersion was added to water previously adjusted to 27 ° C. and stirred with a high-speed stirrer (dissolver) at 3.500 rpm for 30 to 120 minutes to obtain a solid fine particle dispersion of the spectral sensitizing dye.

The dispersion of the selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at a dispersion blade peripheral speed of 40 m / sec at 50 ° C. for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above experiment.

[0156] The (Em-2 of Preparation) seed emulsion preparation A ₂ ossein gelatin 24.2g Water _{9657ml HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 _{CH 2 O) m H (n} + m = 5~7) (10% methanol solution) 1.20 ml potassium bromide 10.8 g 10% nitric acid 160 ml B ₂ 2.5 n aqueous silver nitrate solution 2825ml C ₂ potassium bromide 841g water at 2825Ml D ₂ ossein gelatin 121g water _{2040ml HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~7) (10% methanol solution) 5.70ml E ₂ 1.75N solution of potassium bromide aqueous solution following silver potential control amount 35 ° C. to a solution a ₂ with a mixing and stirring machine shown in Japanese Patent Publication No. 58-58288 B ₂ and soluble Each of the C ₂ 47
5.0 ml was added by the simultaneous mixing method over 2.0 minutes to form nuclei.

After stopping the addition of the solution B ₂ and the solution C ₂ ,
By taking 60 minutes to raise the temperature of the solution A ₂ in 60 ° C., was added the total amount of D _2, after adjusting the pH to 5.5 with 3% KOH, again solution B ₂ and Solution C ₂ Was added at a flow rate of 55.4 ml / min for 42 minutes by the double jet method. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 35 ° C. to 60 ° C. and re-mixing with the solutions B ₂ and C ₂ was measured using the solution D ₂ . To control to +8 mV and +30 mV, respectively.

After completion of the addition, the pH was adjusted to 6 with 3% KOH.
It was desalted and washed immediately with 0. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.090 μm. It was confirmed with an electron microscope that the diameter (in terms of circular diameter) was 0.510 μm.

A tabular silver iodobromide grain emulsion Em-2 was prepared using the seed emulsion and the following four kinds of solutions.

[0160] A ₃ ossein gelatin _{19.04g HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~7) (10% aqueous methanol solution) 2.00 ml Potassium iodide 7.00 g Seed emulsion 1.55 mol equivalent Equivalent to 2800 ml with water.

[0161] finish to 3585ml in B ₃ potassium bromide 1493g water.

Finish up to 3585 ml with 2131 g of C ₃ silver nitrate water.

D ₃ Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) (*) Equivalent to 0.028 mol (*) Containing 0.06 mol of potassium iodide 5 0.0% by weight
2 liters of an aqueous solution containing 7.06 moles of silver nitrate and 7.06 moles of potassium iodide were added to 6.64 liters of the gelatin aqueous solution over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles have been formed, p
H was adjusted to 6.0.

The solution A ₃ was vigorously stirred in the reaction vessel while maintaining the temperature at 55 ° C., and half the amount of the solution B ₃ and the solution C ₃ were added thereto over 35 minutes by the simultaneous mixing method. .
It was kept at 8. After adjusting to pH 8.8 with 1% KOH solution, and a part of the solution B ₃ and solution C _3, it was added the total amount of solution D ₃ by simultaneous mixing method. After adjusting the pH to 6.0 with 0.5% citric acid, the remaining amount of solution B ₃ and solution C ₃ was reduced to 25.
Over a period of minutes, the mixture was added by the simultaneous mixing method. During this time, the pAg was 8.
I kept it at 9. Here, the addition rates of the solution B ₃ and the solution C ₃ were changed as a function of time with respect to the critical growth rate. That is, they were added at an appropriate addition rate so as to prevent generation of small particles other than the growing seed particles and to prevent polydispersion by Ostwald ripening.

After completion of the addition, desalting, washing with water,
After re-dispersion, the pH was adjusted to 5.80 and p at 40 ° C.
Ag was adjusted to 8.2.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.91 μm and the average thickness was 0.2.
3μ, average aspect ratio about 4.0, width of particle size distribution 2
The tabular silver halide grains were 0.5%.

Subsequently, after this emulsion was heated to 47 ° C.,
After adding predetermined amounts of the following spectral sensitizing dyes A and B as a solid fine particle dispersion, a mixed aqueous solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a methanol solution of triphenylphosphine selenide were added. Aging for a total of 2 hours and 30 minutes. At the end of ripening, 4-hydroxy-6-methyl-1,3,3 is used as a stabilizer.
An appropriate amount of 3a, 7-tetrazaindene (TAI) was added.

The spectral sensitizing dyes and other additives, and their amounts (per mole of AgX) are shown below.

Spectral sensitizing dye (A) 5,5′-Dichloro-9-ethyl-3,3′-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride 390 mg Spectral sensitizing dye (B) 2. 5,5'-di- (butoxycarbonyl) -1,1'-di-ethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium anhydride 4 mg adenine 10 mg sodium thiosulfate 3 mg ammonium thiocyanate 50 mg chloroauric acid 2.0 mg silver iodide fine grain emulsion 5 mmol min triphenylphosphine selenide 4.0 mg stabilizer (TAI) 750 mg The silver iodide fine grains used herein were used during the emulsion growth. % Gelatin and silver iodide grains (average grain size 0.05 μ
m).

The preparation of the solid fine particle dispersion of the spectral sensitizing dye and the dispersion of the selenium sensitizer was carried out in the same manner as in the preparation of Em-1. Was prepared in the same manner as in the preparation of A portion of the dispersion thus obtained was taken out and used for the experiments.

Next, the emulsion Em sensitized as described above was used.
Emulsions 1 to 5 containing -1 and Em-2 in the proportions shown in Table 2 were prepared.

[0172]

[Table 2]

The following coating solutions were simultaneously coated and dried in order from the bottom in the order of a transverse light-shielding layer, an emulsion layer and an emulsion protective layer on both sides of a 175 μm thick polyethylene terephthalate support which had been subjected to an undercoating treatment in blue. .

(Preparation of Sample) First Layer (Transverse Light Shielding Layer) Solid Fine Particle Dispersion Dye Illustrative 1-11 50 mg / m ² Gelatin 0.4 g / m ² Sodium-di- (2-ethylhexyl) succinate 5 mg / m ² Compound (I) 5 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² Latex (L) 0.2 g / m ² Compound AD-1 8 mg / m ² Potassium polystyrene sulfonate 50 mg / m ² Second layer (emulsion layer) The following various additives were added to each emulsion obtained in Table 2.

Potassium tetrachloropalladium (II) 100 mg / m ² Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² sodium polystyrene sulfonate 80 mg / m ² trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / M ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² Sodium ² -mercaptobenzimidazole-5-sulfonate 5 mg / m ² Compound (H) 0. _{^{mg / m 2 n-C 4}} H 9 OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 350mg / m 2 Compound (M) 5mg / m ² Compound (N) 5mg / m ² Colloidal silica (average particle 5 mg / m ² latex (L) 0.4 g / m ² However, the gelatin was adjusted to 1.2 g / m ² .

Third layer (protective layer) Gelatin 0.8 g / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 50 mg / m ² Matting agent comprising polymethyl methacrylate (area average particle diameter 7.0μm) 50mg / m ² colloidal silica (average particle diameter 0.014μm) 10mg / m ² formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonyl methyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² Sodium - di - (2-ethylhexyl Le) succinate 50 mg / m ² Compound (K) 15mg / m ² Compound (O) 50mg / m ² It is noted that the amount with the material is one-sided partial silver coverage becomes 1.6 g / m ² as a one-sided partial Was adjusted as follows.

[0177]

Embedded image

[0178]

Embedded image

(Production of Screen 1) Phosphor Gd2O2S: Tb (average particle size: 1.8 μm) 200 g Bound polyurethane-based thermoplastic elastomer Demolac TPKL-5-2625 40% solid content (manufactured by Sumitomo Bayer Urethane Co., Ltd.) 20 g Nitrocellulose (digestion degree: 11.5%) 2 g A methyl ethyl ketone solvent was added to the above, and the mixture was dispersed with a propeller type mixer to prepare a coating solution for forming a phosphor layer having a viscosity of 25 ps (25 ° C.). (Binder / Phosphor ratio = 1/2)
2) Separately, 90 g of a soft acrylic resin solid content and 50 g of nitrocellulose were added and dispersed and mixed as a coating liquid for forming an undercoat layer with methyl ethyl ketone to obtain a viscosity of 3 to 6 ps (25 g).
C).

A thickness of 250 μm into which titanium dioxide has been kneaded.
Polyethylene terephthalate base (support) is placed horizontally on a glass plate, and the above-mentioned coating solution for forming an undercoat layer is uniformly coated on the support using a doctor blade.
The coating film was dried by gradually raising the temperature from 100 ° C. to 100 ° C. to form an undercoat layer on the support. The thickness of the coating film is 15μ
m.

The above-mentioned coating solution for forming a phosphor layer was uniformly coated thereon with a doctor blade to a thickness of 240 μm and dried, and then compressed. Compression was performed using a calender roll at a pressure of 800 kgw / cm ² and a temperature of 80 ° C. After this compression, Example 1 of JP-A-6-75097 was used.
A transparent protective film having a thickness of 3 μm was formed by the method described above.

As described above, a fluorescent intensifying screen 1 comprising a support, an undercoat layer, a phosphor layer and a transparent protective film was produced.

(Manufacture of Screen 2) In the manufacture of screen 1, a support, an undercoat layer, and a coating liquid were formed in the same manner as in screen 1 except that a coating solution for forming a phosphor layer was applied at a thickness of 150 μm and compression was not performed at all. A screen 2 comprising a phosphor layer and a transparent protective film was manufactured.

(Evaluation of Screen) (Amount of X-ray Absorption)
A voltage of 0 kVp is applied, a 3 mm aluminum equivalent material is transmitted through a tungsten target using a tungsten target, and reaches a sample screen fixed at a position 200 cm from the tungsten anode of the target tube. The X-ray transmitted through the screen is used as the phosphor surface of the screen. Using an ionizing dosimeter at a position 50 cm away from the specimen, the amount of X-ray absorption was determined. As a reference, a value measured without passing through a screen was used as a reference value.

(Sensitivity) The green-sensitized MRE single-sided photosensitive material manufactured by Eastman Kodak Co., Ltd. was combined with a sample screen, and the X-ray exposure was varied by the distance method. logE =
Step exposure was performed with a width of 0.15. After exposure, the film was treated with the following developer (1) and fixed with a fixing solution XF-SR to obtain a measurement sample. The obtained sample was measured for density with a densitometer PDA-65 (manufactured by Konica Corporation), and the reciprocal of the amount of X-ray exposure required to obtain a density of 1.8 from the characteristic curve was used as a sensitivity, and a comparative screen XG-M ( (Konica Corporation) as 100.

Developer (1) Developer Composition Potassium hydroxide 21 g Potassium sulfite 63 g Boric acid 10 g Hydroquinone 26 g Triethylene glycol 16 g 5-Nitroindazole 0.2 g 5-Methylbenzotriazole 0.06 g 1-Phenyl-3-mercaptotetrazole 0 0.01 g Glacial acetic acid 12 g 1-Phenyl-3-pyrazolidone 1.2 g Glutaraldehyde 5 g Potassium bromide 4 g After adding water to 1 liter, adjust the pH to 10.0.

(Measurement of CTF) The photosensitive material prepared above was placed in a cassette in close contact with the screen prepared above, and a rectangle for MTF measurement was placed at a position 2 cm from the X-ray source. (Thickness: 80 μm, spatial frequency: 0 lines / mm to 10 lines / mm). X-ray source,
The processing conditions were such that the X-ray exposure time was adjusted in the same manner as in the sensitometry, so that the density of the portion not covered with molybdenum was 1.2.

The obtained sample was placed on a microdensitometer P
Scanning was performed with DM-5 (manufactured by Konica Corporation). At this time, a 30 × 500 μm slit was used as the aperture, and the density was repeatedly averaged 20 times at a sampling interval of 30 μm to obtain a density profile. From this concentration profile, CTF was calculated by an ordinary method to obtain 1 / mm and 3 /
Table 3 shows the CTF value in mm.

[0189]

[Table 3]

Evaluation of assembly (Measurement of photosensitive material and absolute sensitivity) Transmission peak wavelength 545 ±
Using a filter exhibiting a transmittance of 20 nm, a color temperature of 28
Using a 5K tungsten light source, 545
nm-light (light centered on the main emission wavelength of the screen used together later) was selected and used as irradiation light, and SG-R (manufactured by Konica Corporation) was used as the obtained sample and the comparative sample. It was exposed and its sensitivity was measured. That is, the sample light-sensitive material was irradiated with the above-mentioned illumination light for 1/25 second to perform exposure.

After the exposure, the photosensitive material of the sample was converted into an automatic developing machine FP
M-5000 (manufactured by Fuji Photo Film Co., Ltd.) with the developer described above at 35 ° C. for 25 seconds (total processing time 90 seconds)
A development process was performed. After peeling off the photosensitive layer on the side opposite to the exposed side, the density was measured to obtain a characteristic curve. From the characteristic curve, the amount of exposure required to reach the minimum density + 0.5 was calculated, and the sensitivity was shown in Table 4 in lux seconds.

In calculating the amount of exposure, the illuminance of light emitted from a tungsten light source and transmitted through the above-described filter was measured with an IM-3 type illuminometer (manufactured by Topcon Corporation).

(Sensitometry) The photosensitive material prepared above was placed in a cassette in close contact with the screen prepared above, and the X-ray exposure was changed by the distance method.
Step exposure was performed with a width of ogE = 1.5. The X-ray apparatus used was Toshiba DRX-3724HD, using a tungsten target, and the focal spot size was 0.6 × 0.6.
mm, including Shibori, through a 3 mm aluminum equivalent material, apply a voltage of 80 kV with a three-phase pulse generator, and take an image through a water 7 cm filter having absorption almost equivalent to a human body.

For development, an automatic developing machine was used to perform development processing using SRX-501 (manufactured by Konica Corporation) using developer (1), and a sample was prepared using XF-SR as a fixer.

For the measurement sample, a densitometer PDA-65 was used.
The density was measured by Konica Corporation to obtain a characteristic curve represented by orthogonal coordinates in which the unit length of the radiation exposure amount (X axis) and the optical density (Y axis) were equal.

Point Gamma Further, the characteristic curve is differentiated to obtain gamma vs. log E. From this gamma curve, the point gamma (B ') at all points having an optical density of 0.7 to 1.5 obtained by irradiation. ), Point gamma (A ') at all points 1.5 to 2.0, and point gamma (C') at all points 2.0 to 2.8.

(Measurement of CTF) The photosensitive material prepared above was placed in a cassette in close contact with the screen prepared as described above, and was loaded into a cassette at a position 2 cm from the X-ray source. (Thickness: 80 μm, spatial frequency: 0 lines / mm to 10 lines / mm). X-ray source,
The processing conditions were such that the X-ray exposure time was adjusted in the same manner as in the sensitometry, so that the density of the portion not covered with molybdenum was 1.2.

[0198] The obtained sample was placed on a microdensitometer P.
Scanning was performed with DM-5 (manufactured by Konica Corporation). At this time, a 30 × 500 μm slit was used as the aperture, and the density was repeatedly averaged 20 times at a sampling interval of 30 μm to obtain a density profile. From this concentration profile, CTF was calculated by an ordinary method to obtain 1 / mm and 3 /
It was shown by CTF value of mm.

(Measurement of Crossover) The above-prepared photosensitive material was placed in a cassette in close contact with the above-prepared screen and black paper, and was irradiated with X-rays from the black paper side. The X-ray source used was the same as that used in sensitometry, and the irradiation amount was changed by the distance method to irradiate X-rays. After the irradiation, the light-sensitive material was subjected to the same processing as in the measurement of the sensitivity. The processed light-sensitive material was divided into two parts, and each emulsion layer was peeled off.
The density of the emulsion layer on the side that was in contact with the screen was higher than the density of the emulsion layer on the opposite side, and a characteristic curve was prepared for each emulsion layer. Sensitivity difference (Δlog)
The average value of E) was obtained, and the crossover was calculated from the average value by the following equation.

Crossover (%) = 100 / (ant)
ilkog (ΔlogE) +1) (Evaluation by gastric phantom) A sample film was inserted between screens and loaded into a cassette as an assembly, and a gastric phantom (manufactured by Kyoto Kagaku Co., Ltd.) was supplied with a three-phase 12 pulse power supply. 55 kVp (focus spot size 0.6 × 0.6 m using 3 mm thick aluminum equivalent filter)
Photographs were taken using a conventional method at a distance of 1.2 m from the X-ray source and a grid ratio of 8: 1 using m X-rays. The automatic developing machine is S
It was treated with RX-501 (manufactured by Konica Corporation) under the following treatment solution and under the following treatment conditions, and the following evaluation criteria were used to comprehensively evaluate the gastric wall fine structure, the accumulation of the contrast agent, the cissing, and the depiction of the gastric capsule. .

Evaluation Criteria A: Very good description of both gastric wall fine structure and gastric capsule B: Good description of both gastric wall fine structure and gastric capsule C: Level that can be diagnosed due to good description of gastric wall fine structure and gastric capsule D: The level that cannot be used for diagnosis due to poor description of the gastric wall ultrastructure and gastric capsule.

Tables 4 and 5 summarize the above results.

The processing conditions are as follows.

Developing Conditions Developing 35 ° C. 14 seconds Fixing 34 ° C. 9.7 seconds Washing 26 ° C. 9.0 seconds Squeeze 2.4 seconds Drying 55 ° C. 8.3 seconds Total (Dry to Dry) 43.4 seconds Developer Formulation Part -A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraaminepentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5-mercaptotetrazole 0.2 g Hydroquinone 340 g Add water to make up to 5000 ml Part-B (for finishing 12 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 22 Add 5 g of water to finish to 1.0 liter Fixer formulation Part-A (for finishing 18 liters) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1 -(N, N-dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B Aluminum sulfate 800 g The developer was prepared by adding Part A, Part A to about 5 liters of water.
B was added at the same time, water was added while stirring and dissolving, and the pH was adjusted to 10.40 with glacial acetic acid after finishing to 12 liters. This is used as a development replenisher.

To 1 liter of this replenisher, 20 ml / liter of the above starter was added to adjust the pH to 10.2.
Adjust to 6 and use as working solution.

The fixer was prepared by adding Part 5 to about 5 liters of water.
-A and Part-B were added at the same time, and water was added while stirring and dissolving to make up to 18 liters, and the pH was adjusted to 4.4 with sulfuric acid and NaOH. This is used as a fixing replenisher.

[0207]

[Table 4]

[0208]

[Table 5]

From Tables 4 and 5, it was found that the samples irradiated with X-rays through the screen had photographic characteristics completely equal to those of the characteristic curves using the light sources having the same emission peak wavelength. In addition, the radiation image forming assembly of the present invention is a radiation image forming assembly that is excellent in sharpness without lowering sensitivity, has a wide latitude, and has a gastric wall fine structure in double contrast imaging of the stomach, and extremely excellent description of both gastric capsules. You can see that there is.

[0210]

According to the present invention, a radiation image forming assembly having a wide latitude and excellent sharpness and suitable for gastric radiation diagnosis can be obtained.

Claims (3)

[Claims] At least one of the radiographic intensifying screens has an absorption of 45% or more with respect to X-rays having an X-ray energy of 80 kVp, and has a contrast transfer function (CTF) of 0.79 at a spatial frequency of 1 line / mm. As described above, a radiation intensifying screen having a spatial frequency of 3 lines / mm and 0.36 or more and a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on both sides of a support, It has the same wavelength as the emission wavelength and has a half width of 20 ±
After exposing the silver halide photographic light-sensitive material through a step wedge with monochromatic light of 5 nm, it was developed, fixed, washed with water and dried at a developing temperature of 35 ° C. for a developing time of 25 seconds using the following developer (1). The point gamma of all the points where the optical density is 1.5 to 2.0 in the characteristic curve shown on the orthogonal coordinates having the same unit length of the exposure amount (X axis) and the optical density (Y axis) obtained in the above is 1. A characteristic curve that is between 0 and 1.8,
A radiation image forming assembly wherein the crossover of the silver halide photographic light-sensitive material is not more than 15% of the light emitted from the radiation intensifying screen. Developer (1) Composition Potassium hydroxide 21 g Potassium sulfite 63 g Boric acid 10 g Hydroquinone 26 g Triethylene glycol 16 g 5-Nitroindazole 0.2 g 5-Methylbenzotriazole 0.06 g 1-Phenyl-3-mercaptotetrazole 0.01 g Glacial acetic acid 12 g 1-Phenyl-3-pyrazolidone 1.2 g Glutaraldehyde 5 g Potassium bromide 4 g After adding water to 1 liter, adjust the pH to 10.0. 2. An optical density of the characteristic curve of 0.7 to 1.5.
Point gamma at all points of 1.3 to 2.0
2. The radiation image forming assembly according to claim 1, wherein the point gamma at all points having the optical density of 2.0 to 2.5 is in the range of 0.5 to 1.3. 3. A silver halide photographic material has a silver halide emulsion layer on both sides of a support, at least one of which has the same wavelength as the main emission peak wavelength of a radiation intensifying screen. The silver halide photographic light-sensitive material is exposed to monochromatic light having a half-value width of 20 ± 5 nm, and is developed, fixed, washed with water and dried at a developing temperature of 35 ° C. for a developing time of 25 seconds using the developing solution (1). After the emulsion layer on the side opposite to the exposed surface is peeled off, the exposure required for the optical density obtained by measurement to reach a value obtained by adding 0.5 to the minimum density is 0.010.
The radiation image forming assembly according to claim 1, having a sensitivity of about 0.035 lux-second.