JPH08272019A - Silver halide photographic sensitive material and method for processing the material - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material and its processing method superior in sharpness, good in processing stability and freed of defective fixation even at the time of processing small in a replenishing amount. CONSTITUTION: At least one of silver halide emulsion layers comprises silver halide grains having an aspect ratio of >=3, and a silver chloride content of >=50mol%, and a layer formed between a support and a photosensitive silver halide emulsion layer on at least one side of a support contains zinc oxide particles having an average particle diameter of <=0.05μm. This photosensitive material is processed each in an replenishing amount of 15ml per a quarter for each of a developing solution and fixing solution.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material and a method for processing a silver halide photographic light-sensitive material. The present invention particularly relates to a silver halide photographic light-sensitive material having excellent sharpness, good processing stability, high sensitivity even in low replenishment processing, and fixing failure, and a processing method thereof.

[0002]

In the field of silver halide photographic light-sensitive materials,
Various technological improvements are required. For example, in the field of medical photography, further technical improvements are desired with the following background.

That is, in medical radiography, for example, an image of a tissue of a patient uses a silver halide photographic light-sensitive material containing at least one light-sensitive silver halide emulsion layer coated on a transparent support, It is generally made by recording an X-ray transmission pattern on the silver halide photographic light-sensitive material. The X-ray transmission pattern can be recorded by using the silver halide photographic light-sensitive material alone. However, since it is not desirable for the human body to be exposed to a large amount of X-ray exposure, a radiographic intensifying screen is usually combined with a silver halide photographic light-sensitive material for X-ray photography. The radiographic intensifying screen has a phosphor on the surface of a support, and the phosphor absorbs X-rays and converts them into wavelengths having high photosensitivity for the light-sensitive material. The sensitivity of the system can be significantly improved.

As a method for further improving the sensitivity of an X-ray photography system, a silver halide photographic light-sensitive material having light-sensitive silver halide emulsion layers on both sides (front side and back side) of a support is used, and both sides thereof are used. A method for X-ray photography with a radiographic intensifying screen sandwiched between
Such an imaging method is used in many X-ray imaging.

However, in this method, the light emitted from one side of the radiographic intensifying screen not only exposes the adjacent silver halide emulsion layer, but also diffuses through the support (this passage). Light is referred to as crossover light) The phenomenon of exposing the silver halide emulsion layer on the opposite side of the support (referred to as crossover effect) occurs, and sharpness is reduced.

One of the methods for improving the deterioration of the sharpness of an image due to crossover light is a means for cutting the crossover light by using an organic compound such as an ultraviolet absorber or a dye. However, in this method, the compound itself absorbs ultraviolet rays and deteriorates, and the effect decreases with time, or the absorption edge extends to a long wavelength by simply adding it to the silver halide emulsion, and the reduction due to the absorption. It cannot be used in a sufficient amount because it may cause a sensation and may cause a yellow or brown stain due to the added ultraviolet absorber or dye.

On the other hand, there is a means of using an inorganic compound such as titanium oxide or a metal oxide.
Since it has insufficient ultraviolet absorption ability and strong absorption and irregular reflection, it has low transparency and has a drawback that it affects photographic performance such as sensitivity and fog.

Further, Japanese Patent Laid-Open No. 5-323497 discloses a method of improving sharpness by using zinc oxide which is a substantially transparent metal oxide without affecting stain and fog sensitivity. However, it lacks processing stability and is not suitable for low replenishment and rapid processing.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having excellent sharpness, good processing stability, high sensitivity even in low replenishment processing and free from fixing defects, and a processing method thereof. To provide.

[0010]

The silver halide photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on each surface of a support. At least one of the silver halide emulsion layers is composed of silver halide grains having an aspect ratio of 3 or more, and is formed of a silver halide emulsion having a silver chloride content of 50 mol% or more. A silver halide photographic light-sensitive material characterized in that it contains zinc oxide having an average grain size of 0.05 μm or less between the silver halide emulsion layer and the silver halide emulsion layer.

The processing method of the silver halide photographic light-sensitive material in the present invention is such that at least 1 is formed on each side of the support.
Layer having a photosensitive silver halide emulsion layer, at least one of the silver halide emulsion layers is composed of silver halide grains having an aspect ratio of 3 or more, and the silver chloride content is 50 mol% or more. A silver halide photographic light-sensitive material containing zinc oxide having an average grain size of 0.05 μm or less between a support and a light-sensitive silver halide emulsion layer on at least one side. In the method of processing a silver halide photographic light-sensitive material, the replenishment amounts of the developing solution and the fixing solution are each divided into four.
A processing method of a silver halide photographic light-sensitive material, characterized in that the processing is carried out at 15 ml or less per sheet, by which the above object is achieved.

The silver halide photographic light-sensitive material and the method for processing the silver halide photographic light-sensitive material of the present invention will be described in detail below.

The silver halide emulsion used in the present invention comprises silver halide grains having an aspect ratio of 3 or more and has a silver chloride content of 50 mol% or more (hereinafter referred to as "emulsion of the present invention", etc.). However, it is preferably a silver halide emulsion having an aspect ratio of 3 to 15 and a silver chloride content of 90 mol% or more.

The silver halide emulsion used in the present invention is
Any halide composition such as silver chloride emulsion, silver chlorobromide emulsion, and silver chloroiodobromide emulsion can be used.

The silver halide emulsion used in the present invention may have any degree of dispersion, but it is preferably a monodisperse emulsion, and it is also preferable to use two or more kinds of monodisperse emulsions in combination.

In the present invention, the aspect ratio means a (grain diameter / grain thickness) ratio of silver halide grains. The grain diameter in the present invention refers to a diameter when a projected image of the grain is converted into a circular image having the same area. For example, a silver halide grain is magnified and photographed with an electron microscope at a magnification of 10,000 to 50,000, and a print thereof. It can be obtained by measuring the particle diameter above or the area at the time of projection (the number of measurements is indiscriminately 1000
And more).

The grain thickness in the present invention means a distance between two principal planes of a tabular grain which face each other, that is, a minimum length of a diameter passing through the center of gravity of the grain. The thickness of the particles can be obtained by observing the sample obliquely with an electron microscope.

The projected area of a grain can be obtained from the sum of the grain areas. The total projected area and the projected area for determining the grain diameter can be obtained by observing the silver halide crystal sample distributed on the sample stage with an electron microscope so that the grains do not overlap each other.

In the silver halide photographic light-sensitive material of the present invention, the above-mentioned grain thickness is preferably 0.5 μm or less on average, and more preferably 0.3 μm or less.

A preferable monodisperse emulsion in the practice of the present invention is a distribution width (%) = (particle size standard deviation / average particle diameter) × 100, which is less than 30%, It is preferably a silver halide emulsion of 20% or less. Here, the method for measuring the particle size is as described above, and the average particle size is a simple average.

The average particle size = Σd _i n _i / n _i where, n _i in the formula represents the number of particles having a particle diameter of d _i.

As a method for obtaining the above emulsion according to the present invention, a known method may be used. For example, when a water-soluble halide solution is mixed with a gelatin aqueous solution containing seed particles by a double jet method, the pAg value The particle size, thickness and its particle distribution, aspect ratio, photographic characteristics and the like can be appropriately changed by controlling, changing the amount of seed particles, or changing the halide composition. As a method for obtaining this emulsion as a monodisperse emulsion, a known method may be used. For example, an aqueous gelatin solution containing seed particles is mixed with a water-soluble silver salt solution and a water-soluble halide solution under double jet under the control of pAg and pH. In order to determine the addition rate of these, reference can be made to JP-A-54-48521, JP-A-58-49938 and the like.

In the present invention, it is preferable to use twin grains as the tabular grains used. As used herein, the term "twin crystal" means a silver halide crystal having one or more twin crystal planes in one grain. The twin morphology is classified into Photographi by Klein and Moiser.
sche Korrespodenz 99, 99, 100, 57.

Two or more twin planes of a twin may or may not be parallel to each other. The twin plane can be directly observed with an electron microscope, but it can also be observed from the cross section as an ultrathin section sample by dispersing silver halide in a resin and hardening it.

When the above-mentioned silver halide twin grains constitute the emulsion used in the light-sensitive material of the present invention, the grains are mainly 2 grains.
It is preferable to have one or more parallel twin planes, more preferably an even number, and particularly preferably two twin planes.

As used herein, "mainly having two or more parallel twin planes" means that the number of twin grains having two or more parallel twin planes is the number when counted from the large grain size particles. 50%
Above, preferably 60% or more, particularly preferably 70% or more.

The halogen distribution in the grains may be a uniform composition or a halogen composition having different internal and external halogen compositions, and may have a layered structure (core / shell structure).

The emulsion used in the light-sensitive material of the present invention may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B No. 35-16086, or an aggregating polymer agent described in JP-A-2-7037, eg G-3, G A particularly preferable desalting method is a method using -8 or the like.

A chemical sensitization method can be used for the emulsion to be used. As the chemical sensitization method, so-called sulfur sensitization, sensitization with a selenium compound, sensitization with a tellurium compound, gold sensitization, periodic table VIII is used. Group noble metals (eg Pd, Pt,
Sensitization with Ir, etc., and a combination of these can be used. Above all, a combination of gold sensitization and sulfur sensitization, or a combination of gold sensitization and a selenium compound is preferable. Further, it is also preferable to use it in combination with reduction sensitization.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of chemical sensitization from the viewpoint of sensitivity and dye adsorption. In particular, the method of adding silver iodide in the form of fine particles is preferable.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. As the compound, azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, particularly, compounds having a mercapto group and compounds having a benzene ring are preferable.

The emulsion used in the silver halide photographic light-sensitive material can be subjected to reduction treatment, so-called reduction sensitization method. As such reduction sensitization method, a method of adding a reducing compound,
A method of passing a silver ion excess state of pAg = 1 to 7 called silver ripening, pH = 8 to 11 called high pH ripening
There is also a method of allowing the high pH state of the above to pass, and even if these are applied to the silver halide emulsion used in the present invention. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferable because the degree of reduction sensitization can be finely adjusted. The reducing compound may be an inorganic or organic compound, such as thiourea dioxide, stannous salt, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives, sulfite. Examples thereof include salts, and particularly preferable examples include thiourea dioxide, stannous chloride and dimethylamine borane. The addition amount of the reducing compound is reducible and the type of silver halide of the compound varies depending emulsion preparation conditions such as dissolving conditions, preferably per mole of silver halide ^{1 × 10 - 8 ~1 × 10} - A range of ² moles is suitable. These reducing compounds are preferably dissolved in, for example, water or an organic solvent such as alcohols and added during the growth of silver halide grains.

The silver halide photographic light-sensitive material can be spectrally sensitized by using a known spectral sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

The sensitizing dye can be used in the same concentration as that used in a normal negative type silver halide emulsion. In particular, it is advantageous to use a dye concentration that does not substantially reduce the intrinsic sensitivity of the silver halide emulsion. Generally, about 1.0 × silver halide sensitization per mole of sensitizing dye 10 ^{- 5} mol to about 5 × 10 ^{- 4} mol are preferred, particularly about 4 × 10 halogen per mole sensitizing dye ^{- 5} mol to 2 × 10 ^- it is preferred to use ⁴ molar.

Next, regarding the zinc oxide contained between the support and the silver halide emulsion layer on at least one side (preferably the emulsion layer on the most support side) in the silver halide photographic light-sensitive material of the present invention. Describe.

The zinc oxide used in the present invention is fine particles having an average particle size of 0.05 μm or less. If the average particle size is larger than this, not only the light scattering increases, but also the transparency decreases, and silver halide photography It affects the sensitometric performance of the light-sensitive material, especially sharpness and residual color. By setting the average particle size of the zinc oxide particles to be 0.05 μm or less, it is possible to obtain a substantially transparent silver halide photographic light-sensitive material having a good crossover light cut performance.

The zinc oxide used in the present invention contains different metal atoms and has no oxygen deficiency, and is clearly distinguished from zinc oxide used as a conductive metal oxide. Preferably there is.

The content of the above zinc oxide fine particles is preferably 0.1 g to 1.0 g per 1 m ² of one side of the light-sensitive material, and within this range, the original effect is mainly obtained.
Light of 00 nm or less can be absorbed, and sharpness can be improved. If the addition amount is 0.1 g / m ² or less, the sharpness is not improved, and if it is 1.0 g / m ² or more, the sharpness is improved, but the transparency and fog (base) are improved.
The concentration becomes high, which is not preferable.

The zinc oxide fine particles used in the present invention are disclosed in JP-A-3-779, JP-A-2-169673 and JP-A-3-13.
It can be obtained by the method described in No. 4069, No. 3-143965 and the like.

The silver halide photographic light-sensitive material of the present invention is constituted by mixing fine particles of zinc oxide used in gelatin as an aqueous dispersion containing a surfactant and coating the mixture as an undercoat layer of the silver halide photographic light-sensitive material. can do.

A protective layer can be used in the silver halide photographic light-sensitive material of the present invention. The protective layer is generally a layer composed of a hydrophilic colloid layer, and as the hydrophilic colloid to be used, various gelatin and the like are used. Further, the protective layer may be a single layer or multiple layers.

A matting agent and / or a leveling agent may be added to the emulsion layer or protective layer of the silver halide photographic light-sensitive material of the present invention, preferably to the protective layer.

As an example of the matting agent, it is preferable that the matting agent has a suitable particle size (particle size of 0.3 to 5 μm, or one having a thickness of 2 times or more the thickness of the protective layer, and more preferably 4 times or more). An organic compound such as a water-dispersible vinyl polymer such as methyl methacrylate, or an inorganic compound such as silver halide or strontium barium sulfate is preferably used. Similar to the matting agent, the smoothing agent is useful for preventing adhesion failure, and is also effective for improving the friction characteristics related to the adhesion and peeling compatibility in the transport mechanism of the automatic image capturing device and the auto cassette. Is liquid paraffin,
Waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or derivatives thereof, polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or silicones such as alkylene oxide addition derivatives thereof It is preferably used.

The silver halide photographic light-sensitive material of the present invention comprises
In addition, an anti-halation layer, an intermediate layer, a filter layer and the like can be provided if necessary.

In the production process of the silver halide photographic light-sensitive material of the present invention, the pH of the coating solution is preferably in the range of 5.8 to 7.5. In the case of multi-layer coating, the pH of the coating liquid obtained by mixing the coating liquid of each layer in the ratio of the coating layer.
Is preferably in the above range of 5.8 to 7.5.
If the pH is lower than 5.8, the hardening progresses slowly, which is not preferable, and if the pH is higher than 7.5, photographic performance may be adversely affected.

The emulsion used in the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, RD N
o. 17643 (December 1978), the same No. 187
16 (November 1979) and No. 16 of the same. 308119
(December 1989). The types of compounds shown in these three Lisaly Disclosures and the locations where they are listed are listed below.

Additive RD-17643 RD-18716 RD-08119 Page classification Page classification Page classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-679 996-8 IVA Desensitizing dye 23 IV 998 IVB dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic Agent 27 XII 650 Right 1006-7 XII Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 28 XVII 100 XVII

As the support which can be used in the light-sensitive material of the present invention, for example, those described on page 28 of RD-17643 and page 1009 of RD-308119 can be used.

The processing method of the silver halide photographic light-sensitive material of the present invention is preferably processed by an automatic processor including the steps of developing, fixing, washing (or stabilizing) and drying.

In the processing method of the present invention, the replenishment amount of the developing solution and the fixing solution is 15 ml or less per quadrant size of the light-sensitive material. It is more preferably 10 ml or less. Further, the replenishment amounts of the developing solution and the fixing solution may be the same or different.

The development processing in the processing method of the present invention is carried out from the time when the tip of the photosensitive material begins to be dipped in the developing solution.
The time (Dry to Dry) until the tip exits the drying zone after the treatment step is preferably 30 seconds or less, and particularly preferably 10 seconds to 25 seconds.

[0053]

EXAMPLES Examples of the present invention will be described below. The present invention is not limited to the examples below.

Example 1 In this example, the present invention is embodied in a silver halide photographic light-sensitive material which can be used as an X-ray photographic light-sensitive material. First, the following emulsions EM-1 to 8 were prepared.

Preparation of Emulsion EM-1 (AgBr _0.10 Cl _0.90 tabular grains) [Solution A] High methionine gelatin (methionine 59.7 mM per 1 g of gelatin) 30 g 4,5,6-triaminopyrimidine 100 g NaCl 1054 g NaBr 68. 7 g Distilled water up to 6000 ml. [Solution B] Silver nitrate 1135 g Distilled water up to 2000 ml.

At 40 ° C., Japanese Examined Patent Publication No. 58-58288
No. 58-58289, the pH of solution A in the mixing stirrer was adjusted to 5.6, and solution B was added over 6 ml of minutes. Then add 55 more
Linear acceleration over minutes (9.8 from start to finish)
And the total amount of Solution B was added in the meantime. Gelatin solution 12 was added 1 minute, 5 minutes, and 18 minutes after the addition of solution B was started.
0 ml was added. After 5 and 18 minutes, 400 g of 4M NaCl solution and 100 g of 20 mM 4,5,6-triaminopyrimidine solution were added. During the addition of the above materials, the silver flow was stopped for 1 minute and the additives were mixed uniformly.

During this period, the pH was controlled to be constant by adding NaOH or HNO ₃ .

After the addition is completed, in order to remove excess salts,
Precipitation desalting was performed. This gave Emulsion EM-1.

Approximately 3,000 grains of the emulsion EM-1 were observed and measured by an electron microscope to analyze the shape, and they were tabular grains having an average equivalent circle diameter of 1.80 μm and an average thickness of 0.12 μm.

Emulsions EM-2 to 3 (AgBr _0.10 Cl _0.90
Preparation of tabular grains) In the method for preparing emulsion EM-1, the temperature of solution A, p
By changing the silver ion potential during addition of H and solution B,
Emulsions EM-2 to 3 comprising AgBr _0.10 Cl _0.90 tabular grains having different grain diameters and grain thicknesses were prepared. Table 1 shows the grain shape of the obtained emulsion as observed by an electron microscope.
It shows in Table 2.

Preparation of emulsion EM-4 (AgBr _0.50 Cl _0.50 tabular grains) In solution A, 586 g of NaCl and 34 of NaBr were added.
It was prepared in the same manner as Emulsion EM-1 except that the amount was 3.7 g.

About 3,000 grains of Emulsion EM-4 were observed and measured by an electron microscope, and the shape was analyzed. As a result, they were tabular grains having an average equivalent circle diameter of 1.95 μm and an average thickness of 0.13 μm.

Emulsions EM-5 to 6 (AgBr _0.50 Cl _0.50
Preparation of tabular grains) In the method for preparing emulsion EM-4, the temperature of solution A, p
By changing the silver ion potential during addition of H and solution B,
Emulsions EM-5 to 6 composed of AgBr _0.50 Cl _0.50 tabular grains having different grain diameters and grain thicknesses were prepared. Table 2 shows the grain shape of the obtained emulsion as observed by an electron microscope.

Preparation of emulsion EM-7 (AgBr _0.70 Cl _0.70 tabular grains) In solution A, 351 g of NaCl and 48 of NaBr were added.
It was prepared in the same manner as Emulsion EM-1 except that the amount was 1.2 g.

About 3,000 grains of Emulsion EM-7 were observed and measured by an electron microscope, and the shape was analyzed. As a result, they were tabular grains having an average equivalent circle diameter of 1.90 μm and an average thickness of 0.13 μm.

Preparation of emulsion EM-8 (AgBr _0.70 Cl _0.30 tabular grains) In the preparation method of emulsion EM-7, the temperature of solution A, p
By changing the silver ion potential during addition of H and solution B,
An emulsion EM-8 composed of AgBr _0.70 Cl _0.30 tabular grains having different grain diameters and grain thicknesses was prepared. Table 1 shows the grain shape of the obtained emulsion as observed by an electron microscope.

The following sensitizing dye A was added to each of the obtained emulsions EM-1 to EM-8 per mol of silver halide, the emulsion EM-1 was 400 mg, and the emulsions EM-2 to EM-8 were grains. An appropriate amount was added according to the surface area ratio of.

Sensitizing dye A

Embedded image

After 10 minutes, appropriate amounts of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added for chemical ripening. 40 minutes before the end of aging, the average particle size is 0.06 μm
6 × 10 −4 mol / Ag mol of the silver iodide fine grain emulsion ( ⁴ ) was added, and then 4-hydroxy-6-methyl 1,3,3a,
3 × 1 of 7-tetrazitene per mol of silver halide
0 ^{- 2} mol, and the mixture was dispersed in an aqueous solution containing gelatin 70 g.

For this emulsion, JP-A-2-301744
No., page 95, line 16 to page 96, line 20, the additives were added to prepare emulsion coating solutions (1) to (8), respectively.

The additives used for the protective layer are as follows. The added amount is shown as an amount per 1 liter of the coating liquid.

Coating liquid for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Polymethylmethacrylate (matting agent having an area average particle size of 6.0 μm) 1.1 g Silicon dioxide particles (matting agent having an area average particle diameter of 3.0 μm) 0.5 g Glyoxal 40% aqueous solution (hardener) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 500 mg C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0073]

Embedded image

As the support, a coating solution prepared so that the coating amount per one surface would be the following composition was applied to both surfaces of a 175 μm thick polyerylene terephthalate support colored blue with a concentration of 0.15. The undercoat layer was used.

Gelatin 0.7 g / m ² nonylphenoxy polyethylene oxide (degree of polymerization = 10) 6 mg / m ² ZnO (average particle size 0.03 μm) 50 mg / m ² 1-morpholinocarbonyl-3- (pyridinio) methanesulfonate 80 mg / M ² Polymethylmethacrylate (matting agent with an average particle size of 2.5 μm) 2 mg / m ²

On the undercoated support, the emulsion coating solution (1) was applied in an amount of 1.5 g / m ^{2 in} terms of silver per side, the amount of gelatin attached was 1.8 g / m ² , the amount of gelatin for the protective layer attached. The emulsion layer and the surface protective layer were simultaneously extruded so as to be 0.9 g / m ² and coated at a speed of 90 m / min by a coating method and dried for 2 minutes and 30 seconds to produce a silver halide photographic light-sensitive material A. .

Similarly, silver halide photographic light-sensitive materials B to Q were produced using the emulsions shown in Table 1 and zinc oxide or other compounds (average grain sizes and addition amounts are shown in Tables 1 and 2). .

Silver halide photographic light-sensitive materials R and S were prepared by adding zinc oxide to the undercoat layer of the support without adding zinc oxide to the coating emulsion.

The obtained sample was subjected to a dry to dry treatment for 25 seconds by modifying the automatic developing machine SRX503 manufactured by Konica Corp. using the developing solution and fixing solution shown below.

Developer formulation Part-A (for finishing 10.8 liters) Potassium hydroxide 340 g Potassium sulfite (50% solution) 2150 g Diethylenetetraamine pentaacetic acid 32.3 g Sodium hydrogencarbonate 108 g 5-Methylbenzetriazole 150 mg 1-phenyl -5-Mercaptotetrazole 15 mg Hydroquinone 320 g Water is added to make 3600 ml.

Part-B (for finishing 10.8 liters) Glacial acetic acid 158 g Triethylene glycol 144 g 1-Phenyl-pyrazolidone 19.5 g 5-Nitroindazole 0.32 g n-Acetyl-D, L-benicillamine 0.11 g Part -A and B were mixed and made up to 10.8 liters with water.

Starter formulation (for 1.0 liter finishing) Glacial acetic acid 138 g Potassium bromide 325 g 5-Methylbenzotriazole 1.5 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 20 mg Water was added. To 1.0 liter. 20 ml of the starter was added per 1.0 liter of the developing solution.

Developer Formulation Part-A (for finishing 16.4 liters) Ammonium thiosulfate (70 wt / vol%) 3100 g Sodium sulfite 150 g Sodium acetate / trihydrate 350 g Sodium citrate 43 g Boric acid 26 g Glacial acetic acid 120 g Part-B ( For finishing 16.4 liters) Aluminum sulphate 56 g Sulfuric acid (50 wt /%) 91 g Part-A and B were mixed, and water was made up to 10.8 liters.

Processing Steps Processing Temperature (° C.) Processing Time (sec) Insertion ── 0.7 Development + Crossover 35 8.1 Fixing + Crossover 33 4.5 Washing + Crossover 18 4.0 Squeeze 40 3.2 Drying 50 4.5 Total ── 25.0

The capacity of each tank of the automatic processor used was 16 liters for the developing tank, 10 liters for the fixing tank, and 10 for the washing tank.
Clinker 205 (manufactured and sold by Nitban Kenkyusho Co., Ltd., main component SiO _2, Al ₂ O ₃ , Ag ⁺ ion ceramics particle size 1.0 to 1.5 mm, specific gravity 2.5.
˜2.6) 200 g was filled in a bag sewn with a 20-mesh polyethylene woven cloth, and immersed in the vicinity of the washing water supply section of the washing tank. For drying, an infrared heater (heater temperature 220 ° C) and warm air (60 ° C) were used in combination.

An infrared sensor was used to detect the insertion of the film. The film area for one sheet of four sheets was detected, and the replenishment amount for one sheet of four sheets (developing solution 10 ml, fixing solution 15 ml) was replenished.

(Evaluation of Sensitivity) The above coated sample was sandwiched with an intensifying screen for X-ray photography NR-160 (manufactured by Konica), placed at a distance of 2 m from the X-ray tube, and an aluminum wedge was used.
After the X-ray irradiation at 90 KVP and 50 mA for 0.08 seconds, the above development processing was performed. To measure the X-ray sensitivity of each surface, the fog +0.
The reciprocal of the exposed X-ray at the concentration of 1 was determined, and the relative value was determined with the sensitivity of the high sensitivity surface of Sample 1 being 100.

(Evaluation of Sharpness) The above coated sample was sandwiched with an intensifying screen for X-ray photography, NR-160 (manufactured by Konica Corporation), and a phantom for the chest placed at a distance of 2 m from the X-ray tube. I took a picture. The imaging conditions were 90 KVP and 50 mA, but the irradiation time was adjusted so that the concentration in the lung field was 1.8. Then, the development processing described above was performed, and the sharpness of the lung field and the depiction system of the mediastinum of the film processed on Schaukasten were evaluated. In each case, the evaluation was performed on a scale of 5. 5 is the highest level, 3 is the diagnostically acceptable limit level, and levels less than 3 are levels that cannot be practically used for diagnosis.

(Evaluation of devitrification property) After the unexposed film was subjected to the above treatment, the devitrification property was visually evaluated. Rank 5 is a level with no devitrification. Rank 3 indicates the lower limit acceptable in the market. Rank 1 shows the level of devitrification in pure white.

(Evaluation of Residual Color) The sample was cut into a size of four, and the above treatment was performed as it was without exposing. The treated film was applied to Schaukasten, and the color tone of the base was visually evaluated. Rank 5 represents a level in which no color remains, and 3 represents a lower limit that can be used in the market although color remains. Ranks less than 3 are levels that are not suitable for practical use due to severe residual color.

(Evaluation of Residual Silver) A sample film of four-cut size was developed 23 under the above-mentioned conditions without being exposed to light, and then 23
Conditioning was carried out for 1 hour under conditions of ℃ and RH55%. Then, under the same conditions, one drop of a 1 wt% sodium sulfide aqueous solution was dropped on the center of the sample film, and after 30 seconds, it was wiped with a paper towel and naturally dried.

The concentrations of the portion of the obtained sample where sodium sulfide was dropped and the portion where it was not dropped were measured with a densitometer PDA-65.
It was measured with blue light (manufactured by Konica Corp.) to obtain the density difference ΔD. The smaller the value in the table, the less residual silver and the less yellowing of developed silver.

The results obtained by the above evaluations are shown in Tables 3 and 4.

As can be seen from Tables 3 and 4, when the samples according to the present invention were used (Samples A to C, F, G, M,
Regarding N), the sharpness, devitrification, residual color, and residual silver were all evaluated excellently, and the sensitivity was satisfactory.
On the other hand, sample D using zinc oxide having a large particle size,
In H and I, the devitrification property was particularly poor, and in Sample E which did not use zinc oxide, the sharpness was remarkably deteriorated. Further, the content of silver chloride is low (Samples P and Q), the aspect ratio is small (Samples L and O), materials other than zinc oxide are used (Samples J and K), and zinc oxide is used in the emulsion layer. No sufficient effect was obtained with those using (Samples R and S).

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

Comparative compound

Embedded image

[0100]

As described above, according to the present invention, a silver halide photographic light-sensitive material excellent in sharpness, good in processing stability, high in sensitivity even in low replenishment processing and free from fixing defects, and a processing method thereof. Could be provided.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 5/31 G03C 5/31 5/395 5/395

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on each side of a support, wherein at least one of the silver halide emulsion layers has an aspect ratio of 3 or more. Of silver halide grains having a silver chloride content of 50 mol% or more, and an average grain size of 0. 0 between the support and the photosensitive silver halide emulsion layer on at least one side. A silver halide photographic light-sensitive material characterized by containing zinc oxide of not more than 05 μm. 2. A support having at least one photosensitive silver halide emulsion layer on each side, and at least one of the silver halide emulsion layers comprises silver halide grains having an aspect ratio of 3 or more. Formed from a silver halide emulsion having a silver chloride content of 50 mol% or more, and containing zinc oxide having an average particle size of 0.05 μm or less between a support and a photosensitive silver halide emulsion layer on at least one side. A method of processing a silver halide photographic light-sensitive material, which comprises processing a silver halide photographic light-sensitive material with at least a developing solution and a fixing solution. A method of processing a silver halide photographic light-sensitive material, which comprises processing.