JPH0627557A - Silver halide photographic sensitive material for x-ray - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material for X-rays having a wide exposure latitude, satisfactory graininess and sharpness, excellent in the color tone of an image and diagnostic ability and capable of rapid development. CONSTITUTION:This photographic sensitive material has silver halide emulsion layers on both sides of the base and contains a dye which reduces crossover light having >=300nm wavelength to <=16% and can be decolored by dry-to-dry processing in <=60sec. The sensitivity of the emulsion layer on one side is >=1.1 times that of the emulsion layer on the other side. The silver halide particles in the emulsion layers are of apex development type. The total amt. of gelatin applied per one side is <=3.6g/m<2> and 15-80min melting time is attained. This sensitive material contains a dye having lambdamax at 570-700nm and/or a dye having lambdamax at 520-560nm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material for X-rays which has a wide exposure latitude, is excellent in graininess and sharpness and can be rapidly processed.

[0002]

2. Description of the Related Art In recent years, as a silver halide photographic light-sensitive material for medical use, an X-ray light-sensitive material having high sensitivity, wide latitude, good graininess and sharpness, and rapid processability is required. For these requirements, for example, US Pat.
No. 994,355; No. 4,997,750; No. 5,0.
No. 21,327; No. 5,108,881; European Patent Publication No. 0449,101A1 etc., in which crossover light having a wavelength of 300 nm or more is reduced to 10% or less, and both surfaces of the support (A surface and B surface, respectively). The sensitivity of the emulsion layer
Silver halide light-sensitive materials having different gradations are disclosed.
However, in the range described in the above patent,
Dry to Dry It was difficult to satisfy the photographic property, the dry property and the image color tone by the treatment for 60 seconds or less.

[0003]

The object of the present invention is to provide a wide exposure latitude, good graininess and sharpness, good image color tone, excellent diagnostic ability to accurately detect fine lesions, and rapid processing. It is possible to provide a silver halide photographic light-sensitive material for X-rays.

[0004]

The above object has been achieved by the following constitution. It comprises first and second silver halide emulsion layers coated on both sides of a transparent support, and the sensitivity of the first emulsion layer is at least 1.1 times that of the second emulsion layer. Can contribute to latent image formation 300
A silver halide photographic light-sensitive material for X-rays, which contains a dye that reduces crossover light having a wavelength of nm or more to 16% or less and is decolorized in a processing step of 60 seconds or less, and further has the following features. (I) At least 50% of the projected area of the silver halide grains constituting the silver halide emulsion layer is the apex of the ridge of the grain and / or
Alternatively, the silver halide grains are controlled so that development is started in the vicinity thereof. (ii) The total gelatin coating amount on one side of the support is 3.6 g /
m ² or less, and the melting time of the light-sensitive material is 15 minutes or more and 80 minutes or less. (iii) At least one of the layers constituting the photosensitive material
The layer contains a dye having a maximum absorption wavelength between 570 and 700 nm and / or a dye having a maximum absorption wavelength between 520 and 560 nm.

Specific examples of dyes that are decolorized during the processing process useful in the present invention include Japanese Patent Application No. 03-99678 and International Publication WO88.
/ 04794, U.S. Pat. No. 4,900,652 and the like. A method of preparing silver halide grains useful in the present invention is disclosed in U.S. Pat. No. 4,968,595, which is controlled to initiate development at or near the ridges of the silver halide grains and / or in the vicinity thereof. Have been described. Further, regarding the ridges, the vertices of the ridges, the definition of their vicinity and the method of observing the development start point, the above-mentioned US Pat.
No. The sensitive material of the present invention is Dry to Dry 60
In order to obtain good drying with no residual color and no drying unevenness in a treatment of seconds or less, the total gelatin coating amount on one side is 3.6 g / m ² or less and the melting time is 15 minutes or more and 80 minutes or less.
Here, the melting time means that when the light-sensitive material of the present invention cut into 1 cm × 2 cm is immersed in a 1.5 wt% aqueous solution of sodium hydroxide at 50 ° C., at least one coating layer constituting the light-sensitive material is It is the time until it begins to melt. In the light-sensitive material of the present invention, the sensitivity of the first emulsion layer (A side) is higher than that of the second emulsion layer (B side). Generally, the covering power of the first emulsion layer is smaller than that of the second emulsion layer, but it is desirable to make the covering power as large as possible. Therefore, it is desirable that the silver halide grains constituting the first emulsion layer have a larger aspect ratio than that of the silver halide grains constituting the second emulsion layer. The aspect ratio of the tabular silver halide grains according to the present invention is preferably 3 or more, more preferably 5 or more. The definition of aspect ratio and the method for preparing a tabular emulsion are described in JP-B-4-23769.
It is described in.

In the light-sensitive material of the present invention, the sensitivity of the first emulsion layer is preferably 1.1 times or more that of the second emulsion layer. Here, the sensitivity is defined as the reciprocal of the exposure amount required to obtain a base density + fog density + 1.0 density by preparing a sample in which the first emulsion layer is applied on both sides and a sample in which the second emulsion layer is applied on both sides. To be done. Further, in the light-sensitive material according to the present invention, the gradation of the first emulsion layer and the gradation of the second emulsion layer are independent. However, in comparison of the same sample prepared for sensitivity measurement, it is desirable that the gradation of the first emulsion layer be softer than that of the second emulsion layer. As described in US Pat. No. 5,108,881, the gradation of the first emulsion layer is 0.5 compared to the gradation of the second emulsion layer.
It is desirable that it is smaller than the above. The light-sensitive material according to the present invention preferably contains a compound selected from 3-pyrazolidones, hydroquinones, quinones and aminophenols in its constituent layers as described in JP-A-4-102843. The film swelling rate of the light-sensitive material of the present invention is 2
It is preferably 70% or less. The method for measuring the swelling ratio is in accordance with the method disclosed in JP-A-58-111933. The water content of side A containing the first emulsion layer after washing with water and the water content of side B containing the second emulsion layer after washing may be the same or different. In the light-sensitive material of the present invention, a red-infrared absorbing solid disperse dye as described in JP-A-4-138449 is contained in an emulsion layer containing a silver halide emulsion and a protective layer for the purpose of improving the safelight fog property. be able to.

Cyan and / or magenta dyes used in the present invention for adjusting image color tone are disclosed in Japanese Patent Application No. 3-35285.
7 and 4-90658 are useful. The dye for controlling the image color tone can be contained in the protective layer, the emulsion layer, the undercoat layer of the support and the base support. In general, both dope dyeing on the support and addition to the light-sensitive material layer are carried out. It is desirable that the cyan and magenta dyes be added to the light-sensitive material layer in an R concentration and a G concentration of 0.12 or less, respectively.

Various additives and the like used in the photographic light-sensitive material of the present invention are not particularly limited and, for example, those described in the following relevant parts can be used. Item Applicable place 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, bottom 6 to its manufacturing line, page 10 upper right column, line 12, 3-2453 37, second Page 10, lower right column, line 10 to page 6, upper right column, line 1; page 10, upper left column, line 16 to page 11 lower left column, line 19; Japanese Patent Application No. 2-225637. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. 3) Antifoggants and Stabilizers JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column . 4) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 5) Surfactant JP-A-2-68539, page 11, upper left column, line 14 Antistatic agent to page 12, upper left column, line 9 6) Matting agent, slipping agent JP-A-2-68539, page 12, upper left column, line 10 plasticizer, from page 10 to upper right column, line 10, from page 14, lower left column, line 10 to lower right column, line 1 7) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 8) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 9) Support, JP-A-2-68539, page 13, upper right column, line 7 to line 20. 10) Crossover JP-A-2-264944, page 4, upper right column, line 20: From cut method, page 14 upper right column. 11) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9 No. 3-24537, page 14, lower left column to page 16, lower right column. 12) Polyhydroxy JP-A-3-39948, page 11, upper left column to benzenes, page 12, lower left column, EP Patent No. 452772A. 13) Layer structure JP-A-3-198041. 14) Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, left lower column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 Page 6, upper right column, line 10

[0009]

【Example】

Example 1 Preparation of Emulsion-A 5 g of potassium bromide and 0.05 g of potassium iodide in 1 liter of water,
Gelatin 10 g, thioether _{HO (CH 2) 2 S (} CH 2) 2 S (CH 2) 2
Add 3.5 cc of 5% aqueous solution of OH, and while stirring, add an aqueous solution of 8.33 g of silver nitrate and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide while stirring. It was added by the jet method in 45 seconds. Subsequently, 2.5 g of potassium bromide was added, and then an aqueous solution containing 8.33 g of silver nitrate was added over 26 minutes so that the flow rate at the end of the addition was twice that at the start of the addition. After that, 20 cc of 25% ammonia solution and 10 cc of 50% NH ₄ NO ₃ were added to 20 cc.
After physically aging for 15 minutes, 15 cc of glacial acetic acid was added to neutralize. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added by the control double jet method for 40 minutes while keeping the potential at pAg 8.2. The flow rate at this time was accelerated so that the flow rate at the start of addition was 9 times the flow rate at the start of addition. At the end of the addition, 15 cc of 2N potassium thiocyanate solution was added, and further 25 cc of 1% potassium iodide aqueous solution was added over 30 seconds. After this the temperature is set to 35
After removing the soluble salts by the precipitation method,
The temperature was raised to 0 ° C, 40 g of gelatin and 2 g of phenol were added, and the pH was adjusted to 6.40 with sodium hydroxide and potassium bromide.
Adjusted to 8.50. After the temperature was raised to 56 ° C., 520 mg of sensitizing dye A having the following structure and 150 mg of stabilizer A were added. After 10 minutes, sodium thiosulfate pentahydrate 2.
4 mg, potassium thiocyanate 140 mg, chloroauric acid 2.1
Each mg was added, and after 80 minutes, it was rapidly cooled and solidified to obtain an emulsion. In the obtained emulsion, 98% of the total projected area of all grains was composed of grains having an aspect ratio of 3 or more, and the average projected area of all grains having an aspect ratio of 3 or more was 1.6 μm.
m, standard deviation 18%, average thickness was 0.2 μm, and aspect ratio was 8.0.

[0010]

[Chemical 1]

Preparation of Emulsion-B In the preparation of Emulsion-A, thioether HO (CH ₂ ) ₂ S (CH ₂ )
Emulsion-A exactly the same as Emulsion-A except that the addition amount of 5% aqueous solution of ₂ S (CH ₂ ) ₂ OH was 2.4 cc and the preparation temperature was 69 ° C.
B was obtained. The average projected area diameter is 1.2 μm and the standard deviation is 15 for all particles with an aspect ratio of 3 or more.
%, And the aspect ratio was 7.4. Preparation of Emulsion-C In preparation of Emulsion-A, thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S
(CH ₂ ) ₂ OH 5% aqueous solution added amount 2.0cc Charge temperature 6
9 ° C, 25% ammonia solution 15cc, glacial acetic acid 11.5c
Emulsion-C was prepared in the same manner as in Emulsion-A except that the amount of sensitizing dye A was 600 mg, sodium thiosulfate pentahydrate was 2.9 mg, and chloroauric acid was 2.8 mg. The average projected area diameter for all particles with an aspect ratio of 3 or more is 1.1μ.
m, the standard deviation was 15%, and the aspect ratio was 7.0. The above emulsions A, B and C were prepared according to US Pat. No. 4,968,59.
The sample was coated and developed by the method of EXAMPLE 1 of No. 5, and the starting point of development was observed. The ratio at which development was started at the ridge or the apex of the ridge and / or in the vicinity thereof was 65% or more in terms of projected area.

Preparation of Dye Emulsion Dispersion Preparation of Cyan Emulsion 60 g of Dye A and the following high boiling point organic solvent A62.8
g, 62.8 g of B and 333 g of ethyl acetate were dissolved at 60 ° C. Next, 65 cc of 5% aqueous solution of sodium dodecylbenzene sulfonate, 94 g of gelatin and 581 cc of water.
Was added and emulsified and dispersed by a dissolver at 60 ° C. for 30 minutes. Then, 2 g of the following compound C and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, using Asahi Kasei's ultrafiltration laboratory module ACP1050, the total amount was concentrated to 2 kg, and 1 g of the compound C was added to give a cyan dye emulsion. Dye A

[0013]

[Chemical 2]

High boiling organic solvent

[0015]

[Chemical 3]

Compound C

[0017]

[Chemical 4]

Preparation of Magenta Emulsion A mixture of 2.5 g of color tone dye B and 10 g of a 1: 1 copolymer of styrene and methyl methacrylate dissolved in 50 cc of ethyl acetate was used as sodium dodecylbenzenesulfonate 1.
5 g and 0.18 g of 2-phenoxyethanol 8
% Gelatin aqueous solution (90 g) was mixed at 60 ° C., and the mixture was stirred at high speed with a homogenizer. After completion of high-speed stirring, pressure reduction treatment was carried out at 60 ° C. using an evaporator to obtain 92 wt% of ethyl acetate.
Removed. As a result, a dye dispersion having an average particle size of 0.2 μ was obtained. Color dye B

[0019]

[Chemical 5]

Preparation of coating liquid Emulsion layer coating liquid-Emulsion-A and -C were mixed in 1/1 (equal amount) to prepare a coating liquid by adding the following chemicals to 1 mol of silver halide.・ Gelatin Ag / gelatin Adjust the amount added to 0.8 (weight ratio) ・ Polymer latex [poly (ethyl acrylate / methacrylic acid) = 97/3] 25.0 g ・ 1,2-bis (vinylsulfonylacetamide) Add an amount such that the ethane melting time is 45 minutes ・ Potassium hydroquinone monosulfonate 12g ・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 80mg ・ Sodium polyacrylate (average molecular weight 41,000) 4.0 g-Potassium polystyrene sulfonate (average molecular weight 600,000) 1.0 g-Cyan emulsion Cyan dye A 2 x 10 ^-4 mol / mol Ag-Magenta emulsion Magenta dye B 4 x 10 ^-5 Mol / mole Ag emulsion layer coating liquid-emulsion B-using emulsion B instead of A and -C Ku coating solution in the same manner - was prepared.

Preparation of Photosensitive Material [Support] Corona discharge treatment was carried out on a biaxially stretched blue dyed polyethylene terephthalate film having a thickness of 175 μm, and a wire bar coater was applied so that the coating amount per one side would be the following coating amount. Apply on both sides by 185 ℃
And dried for 1 minute. Subbing lower layer Butadiene - Styrene copolymer latex of butadiene / styrene weight ratio ^{/ 31/69 0.322g / m 2} · 2,4- dichloro-6-hydroxy -s- triazine sodium salt 8.4 mg / m ²

[0022]

[Chemical 6]

Undercoat upper layer ・ Gelatin 300 mg / m ²・ Polyethylene acrylate 20 mg / m ²・ C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 4 mg / m ²

[0024]

[Chemical 7]

The dye used here had a magenta color, and the dispersion in the microcrystalline state (0.2 μm) was added to the gelatin solution by the following preparation method. 20 g of the dye, 200 g of a 1% aqueous solution of carboxymethyl cellulose, and 287 g of H ₂ O were mixed, and the mixture was treated with an Eiger mill (Eiger Japan Co., Ltd.) using beads of zirconium oxide (ZrO ₂ ) having a diameter of 2 mm under conditions of 5000 rpm for 8 hours. .

Surface Protective Layer The surface protective layer is the same on both the A side and the B side. The composition and coating amount are described below.

Contents of the surface protective layer: Gelatin 1.15 g / m ²・ Polyacrylamide (average molecular weight 45,000) 0.25 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.02 g / m ²・ Sodium salt of pt-octylphenoxydiglyceryl butyl sulfone compound 0.02 g / m ²・ Poly (degree of polymerization 10) oxyethylene-poly (degree of polymerization 3) oxy glyceryl-p-octylphenoxy ether 0.01 g / m ²・ C ₈ F ₁₇ SO ₃ K 0.003 g / m ²

[0028]

[Chemical 8]

Polymethylmethacrylate (average particle size 3.5 μm) 0.025 g / m ² Poly (methylmethacrylate / methacrylate) (molar ratio 7: 3, average particle size 2.5 μm) 0.020 g / m ²

Light-Sensitive Material-1 (Invention) An emulsion layer coating solution and a surface protective layer are coated on the A side of a support having an undercoat underlayer and an undercoat upper layer coated thereon, and an emulsion layer coating solution and a surface protective layer are coated on the B side. Then, a light-sensitive material-1 was prepared. The coated silver amount is 1.7 g / m ² for both the A side and the B side. Photosensitive Material-2 (Comparative) A light sensitive material-2 was prepared by coating an emulsion layer coating solution on both A and B and a surface protective layer. Photosensitive Material-3 (Comparative) A light sensitive material-3 was prepared by coating an emulsion layer coating solution on both A and B and a surface protective layer.

Results Exposure Conditions HR-4 screens manufactured by Fuji Photo Film Co., Ltd., which emit green light, were used for exposing the emulsion layers A and B of the light-sensitive materials-1 to -3, respectively. X-ray irradiation conditions are: tube voltage: 70KV, grid unused, tube current: 80mA, time: 0.1sec, distance: 2.2m, wedge: using aluminum wedge Processing developer and fixer CE-D-F1 (Fuji Photo Film ( Development temperature 35 ° C., fixing temperature 32 ° C. Development machine CEPROS M (Fuji Photo Film Co., Ltd.)
Processing time Dry to Dry 35 sec (CEPROS M was modified to enable processing in 35 seconds) Sensitivity and gradation change Relative sensitivity of photosensitive material-2 is 1.3 of sensitivity of photosensitive material-3.
Double (base density + fog density + reciprocal of exposure required to obtain density of 1.0), gradation is (characteristic curve on orthogonal coordinates with equal optical axis and logarithm of exposure (log E) coordinate axis unit length) (Defined by the average gradation produced by base density + fog density + 0.3 and base density + fog density + 1.3), photosensitive material-2 was 1.6 and photosensitive material-3 was 2.8. Measurement of Crossover Light Crossover light was measured according to the method described in US Pat. No. 4,425,425. The crossover light of the photosensitive material-1 was 12%. Chest Phantom Practical Technique Fuji Photo Film Co., Ltd. HR as a front screen with a tube voltage of 120 KV for each of the photosensitive materials-1, -2 and -3.
-4 on the B side of the photosensitive material, HR as a back screen
8 is used to overlap the side A of the light-sensitive material (light-sensitive material-2, -3
He performed the chest phantom practice. The light-sensitive material-1 of the present invention provided a chest phantom photograph having a wider latitude and excellent graininess and sharpness as compared with the comparative materials-2 and -3. The image color tone was a cool black color which was preferable for all the samples.

Claims (1)

[Claims] 1. A transparent support comprising first and second silver halide emulsion layers coated on both sides, wherein the sensitivity of the first emulsion layer is at least 1.1 times that of the second emulsion layer. The photosensitive material further contains a dye that reduces the crossover light having a wavelength of 300 nm or more that can contribute to latent image formation to 16% or less and is decolorized in a processing step of 60 seconds or less, and further has the following features. A silver halide photographic light-sensitive material for X-rays. (I) Silver halide in which at least 50% of the projected area of the silver halide grains constituting the silver halide emulsion layer is controlled so that development is started at the ridges of the grains or at the vertices of the ridges and / or in the vicinity thereof. It is a particle. (ii) The total gelatin coating amount on one side of the support is 3.6 g /
m ² or less, and the melting time of the light-sensitive material is 15 minutes or more and 80 minutes or less. (iii) At least one of the layers constituting the photosensitive material
The layer contains a dye having a maximum absorption wavelength between 570 and 700 nm and / or a dye having a maximum absorption wavelength between 520 and 560 nm.