JPH07301874A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE:To provide the photosensitive material restrained from processing fluctuation and occurrence of residual silver in the case of processing in a low replenishing rate and small in residual dye stains after processing and superior in sharpness of an image. CONSTITUTION:(1) The photosensitive material containing flat silver halide grains comprising silver bromide or silver iodobromide and having an aspect ratio of >=3 and occupying >=50% of the projection areas of the total silver halide grains in at least one silver halide emulsion layer and containing flat silver chloride grains in a hydrophilic colloidal layer located farthest apart from a support, and (2) the photosensitive material described in (1) further containing at least one kind of silver halide solvent in this emulsion layer and/or a hydrophilic colloidal layer, and (3) the method for processing the photosensitive material described in (1) and (2) in an automatic developing-machine regulating a replenishing rate for a developing solution to 50-300ml per 1m<2> of the photosensitive material.

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 having high sensitivity, excellent sharpness, little residual color contamination and little variability in running processing, and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials have been reduced in silver in order to reduce cost or processing dependence, but it is high to maintain the conventional high performance with a small amount of silver. Covering power and excellent spectral sensitization are required.

Tabular silver halide grains (hereinafter referred to as tabular grains) are known as emulsions for improving covering power. The particles have a large surface area to volume ratio and can adsorb a large amount of the spectral sensitizing dye. Therefore, a light-sensitive material having a spectral sensitivity that is relatively high with respect to the intrinsic sensitivity can be obtained. When used in an X-ray photographic system, the absorption coefficient of the dye can be increased, which is useful in that the crossover light can be significantly reduced and the sharpness can be improved.

Other means for reducing crossover light include, for example, including a dye in the emulsion layer, providing a dye layer between the emulsion layer and the subbing layer, and forming fine grain silver layers above and below the emulsion layer. It is known to provide such an element, but it has a defect that not only the effect of improving sharpness is insufficient, but also residual color contamination and desensitization are caused.

On the other hand, the processing of the light-sensitive material is, in the case of medical X-ray light-sensitive material, developed-fixed-washed-dried by an automatic processor, but in the sense of replenishing the components consumed by running, a developer is used. , The fixer is replenished with replenisher.
However, fluctuations in the developing components in the developing solution due to running are not only consumed, but also process fluctuations are likely to occur due to additives that elute from the running film and halide ions that are released during the development reaction. ,
In addition, components brought in from the developer (eg K ⁺ ions)
However, there is a problem that the fixing property is deteriorated due to the accumulation of

In order to eliminate such processing fluctuations, the amount of the replenisher solution is increased, the replenisher solution component is devised, or the kind of the additive of the light-sensitive material,
There have been reports of devising binders, but none of them are effective means. In particular, recently, due to strict environmental regulations, low replenishment with a reduced amount of waste liquid has been promoted, but in the low replenishment treatment, accumulated substances are concentrated, resulting in further increase in process fluctuation and performance deterioration.

[0007]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, excellent sharpness and no residual color contamination. It is a second object of the present invention to provide a silver halide photographic light-sensitive material and a processing method thereof, which have less variability in running processing, and in particular, suppress processing fluctuation and generation of residual silver during low replenishment processing.

[0008]

The objects of the present invention have been solved by the following items.

In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a hydrophilic colloid layer on at least one side of a support, at least one of the silver halide emulsion layers comprises Of the sum of all projected areas
A tabular hydrophilic colloid layer containing tabular silver halide grains of which 50% or more is composed of silver bromide or silver iodobromide having an aspect ratio of 3 or more, and which is placed farthest from the support, is tabular. A silver halide photographic light-sensitive material comprising silver chloride grains.

A silver halide photographic light-sensitive material as described in the above item, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer contains at least one silver halide solvent.

In the method of processing the silver halide photographic light-sensitive material described in the above item or paragraph with an automatic processor, the replenishment amount of the developing solution is 50 ml to 300 ml per 1 m ^{2 of the} light-sensitive material. Method of processing photosensitive material.

The present invention will be described in detail below.

In the present invention, by using tabular silver halide grains composed of silver bromide or silver iodobromide having an aspect ratio of 3 or more, high covering power and high sensitivity and sharpness can be obtained. . Further, by incorporating tabular silver chloride grains in the hydrophilic colloid layer formed at the position farthest from the support, it is possible to further sharpen by absorbing extra radiation and light which are factors of a blurred image. It is also excellent in terms of improving the property and reducing the load of fixing or the inhibition of development by halide ions. Further effects of halide ions in the developer for silver chloride composition Br ^-,
The influence of developer accumulation can be improved in that Cl ⁻ is much smaller than I ⁻ . Moreover, it is excellent in falling out in the fixer.

Further, according to the present invention, it was initially unexpected that stable photographic characteristics could be obtained with very little processing fluctuation in running processing for a long period of time.

Although the reason for this is not clear, the Br ⁻ and I ⁻ accumulated during running are formed of tabular silver chloride grains in the hydrophilic colloid layer in the processing solution or the photosensitive material film.
Cl ^- and cause conversions, greater Cl solubility product ^- is eluted, Br ^-, I ^- it is believed that the developing property is improved by being brought to form a silver halide.

By using a conventionally known silver halide solvent in the constituent layer of the silver halide photographic light-sensitive material of the present invention, a larger running fluctuation can be improved and the fixing property can be improved. I found a thing.

The light-sensitive silver halide emulsion used in the present invention is preferably tabular silver halide grains in which 50% or more of the total projected area is silver bromide or silver iodobromide having an aspect ratio of 3 or more. Good. Particularly, tabular silver halide grains in which 50% or more, and more preferably 70% or more of the total projected area are silver bromide or silver iodobromide having an aspect ratio of 3 or more are preferable. Further, the silver iodobromide emulsion may contain 0.01 to 10 mol% of silver iodide, and the aspect ratio is 3 or more, preferably 0.1 to
Especially preferred is 5.0. In the present invention, the hydrophilic colloid layer contains silver chloride. For this silver chloride grain, 50% or more of the total of the total projected areas has an aspect ratio of 5 or more, and more preferably 8 or more. Also preferred are particles having a thickness of less than 0.35 μm. The silver chloride grains may have photosensitivity or may be non-photosensitive grains having substantially no sensitivity.

The hydrophilic colloid layer containing the silver chloride grains may be any layer, but more preferably, the hydrophilic colloid layer is provided at the farthest position from the support, for example, the uppermost layer. It may be a protective layer, an antistatic layer, a filter layer, a silver halide emulsion layer or the like. It is preferably a protective layer. The amount of silver chloride contained is 15
It may be mg / dm ² or less.

Examples of the silver halide solvent used in the silver halide emulsion layer and / or the hydrophilic colloid layer of the present invention include thioethers, polyalkylene oxides and mercapto compounds, which have a strong affinity with silver halide. . Specific compound examples of the silver halide solvent preferably used in the present invention are shown below.

[0020]

[Chemical 1]

The above compounds are known compounds, and can be easily synthesized by, for example, the synthesis methods described in JP-B-47-11116 and British Patent 942,865, or a method analogous thereto.

The amount of the silver halide solvent used may be 10 ^-7 mol to 10 ^-2 mol, and particularly preferably 10 ^-5 mol to 10 ^-3 mol, per 1 mol of silver halide.

The photosensitive silver halide emulsion of the silver halide photographic light-sensitive material of the present invention may be silver bromide, silver iodobromide or a silver iodochlorobromide emulsion containing a small amount of silver chloride. The halogenated grain may be of any crystal type as long as it has the constitution of the present invention, for example, a single crystal such as a cube, an octahedron or a tetrahedron, and may have various shapes. It may be twin crystal grains.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No.17643 (December 1978), 22
Can be prepared by the method described in "Emulsion Preparation and Types" on page 23 or the method described in (RD) No. 18716 (November 1979), page 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is, for example, "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Published by Paul Montel (1967) or VL Zelikman et al. “Makin
g And Coating Photographic Emulsion "can be prepared by the method described in Focal Press (1964).

That is, the mixing conditions such as the forward mixing method, the reverse mixing method, the double jet method and the control double jet method under the solution conditions such as the acidic method, the ammonia method and the neutral method,
It can be produced using a particle preparation condition such as a conversion method, a core / shell method, or a combination thereof.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. The monodisperse referred to here, when measuring the average particle diameter by a conventional method,
At least 95% by number or weight of grains are silver halide grains having an average grain size within ± 40%, preferably within ± 30%.

The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may be composed of different silver halide compositions inside and outside,
For example, a core / shell type monodisperse emulsion having a clear two-layer structure in which a high silver iodide core portion is covered with a low silver iodide shell layer may be used.

The method for producing the above monodisperse emulsion is known, and for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like.

For the emulsion used in the silver halide photographic light-sensitive material of the present invention, for example, a seed crystal is used as a method for obtaining the above monodisperse emulsion, and the seed crystal is used as a growth nucleus to supply silver ions and halide ions. A grown emulsion may be used.

A method for producing the above-mentioned core / shell type emulsion is known, for example, J. Phot. Sci, 24.198. (1976), US Pat.
The methods described in 250, 3,505,068, 4,210,450, 4,444,877 or JP-A-60-143331 can be referred to.

The emulsion used in the silver halide photographic light-sensitive material of the present invention has an aspect ratio (ratio of grain size / grain thickness).
Is 3 or more tabular grains. As an advantage of such tabular grains, for example, it is possible to obtain an improvement in spectral sensitization efficiency and an improvement in image graininess and sharpness. For example, British Patent 2,11
2,157, U.S. Pat. Nos. 4,414,310, 4,434,226, etc., and the emulsion can be prepared by referring to the methods described in these publications. The above-mentioned emulsion is either a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on both the surface and inside. May be.

These emulsions are used at the stage of physical ripening or grain preparation, for example, using cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt. May be.

The emulsion may be subjected to a Nudel water washing method, a flocculation sedimentation method or the like in order to remove soluble salts, and a preferable water washing method is, for example, an aromatic hydrocarbon containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin, and a desalting method using a polymer flocculant such as Exemplified G-3 and G-8 described in JP-A-2-7037.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include (RD) No. 1 described above.
Various compounds described in 7643, (RD) No. 18716 and (RD) No. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV A Desensitizing dye 23 IV 998 IV B 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 Hardener 26 X 651 Left 1004-5 X Interface Activator 26-27 XI 650 Right 1005-6 XI 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 XVII 1009 XVII Examples of the support used for the silver halide photographic light-sensitive material include those described in the above RD,
A suitable support is a polyethylene terephthalate film or the like, and the surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

In the method of processing a silver halide photographic light-sensitive material of the present invention with an automatic processor, the replenishing amount of the developing solution is 50 to 300 ml per 1 m ² of the light-sensitive material. When the amount is 300 ml or more, the merit of reducing the amount of waste liquid becomes poor and the effect of the present invention is reduced. Also, if it is less than 50 ml, the amount of accumulation increases during running, resulting in deterioration of photographic performance.

The development processing method of a silver halide light-sensitive material according to the present invention includes steps from development to drying when processed by an automatic processor including the steps of development, fixing, washing and drying.
It is preferable to complete the process within 45 seconds.

That is, the time from the time when the tip of the photosensitive material begins to be dipped in the developing solution to the time when the tip comes out of the drying zone through the processing steps (so-called Dry to Dry time).
Within 90 seconds, more preferably this Dry to Dry
The time is within 45 seconds. More preferably
Within 30 seconds.

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

The developing time with the developer of the present invention is 5 to 45 seconds, preferably 6 to 20 seconds. Development temperature is 25-50 ° C
Is preferable, and 30-40 degreeC is more preferable.

The drying time is usually 35 to 100 ° C., preferably 40.
The automatic developing machine may be provided with a drying zone in which a hot air of -80 ° C. is blown or a heating means by far infrared rays is provided.

Further, the automatic developing machine is provided with a mechanism for applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive material during the respective steps of developing, fixing and washing with water (special feature: Kaihei 3-264953) may be used. Further, the automatic developing machine may have a built-in device capable of preparing a developing solution and a fixing solution.

The developing solution of the present invention is based on the fact that it contains 1,4-dihydroxybenzenes or, if necessary, p-aminophenol compounds and / or pyrazolidone compounds as a developer.

Examples of 1,4-dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2, There are 5-dimethylhydroquinone, hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. P-aminophenol-based developing agents include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl)-
There are p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable.

Examples of the pyrazolidone compound that can be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone. 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4- Dihydroxymethyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxy Phenyl-4,4-
Dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl) -3-
Examples thereof include pyrazolidone compounds such as pyrazolidone and 3-acetoxy-1-phenyl-3-pyrazolidone.

The amount of 1,4-dihydroxybenzene added may be 0.01 mol to 0.7 mol, preferably 0.1 to 0.5 mol, per liter of the developing solution.

The amount of p-aminophenol compound and pyrazolidone compound added is 0.0005 per liter of the developing solution.
It is a mole to 0.2 mole, preferably 0.001 to 0.1 mole.

Examples of the sulfite used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metasulfite and the like.

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

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

Specific examples of these include ethylenediaminedioltohydroxyphenylacetic 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, glycoletheraminetetraacetic 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-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, tetrapolyline Examples thereof include sodium acid salt and sodium hexametaphosphate.

The developing solution of the present invention may contain a hardening agent which strengthens the physical properties of the film by undergoing a hardening reaction with gelatin in the light-sensitive material during the development processing. Examples of the hardener include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde,
α, α-dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butylmaleindialdehyde, or a bisulfite adduct thereof is used.

As additives used in addition to the above components, development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, Antifoggants such as organic solvents such as methanol or mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, and benztriazole compounds such as 5-methylbenztriazole May be contained, and if necessary, a toning agent, a surfactant, an antifoaming agent, etc. may be contained.

The pH of the developing solution may be 9.0 to 12, preferably 9.0 to 11.5. The alkaline agent or buffer used for setting the pH is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, boric acid, sodium triphosphate or potassium triphosphate.
Contains regulators.

In the present invention, a fixing solution containing a fixing agent such as sodium thiosulfate or ammonium thiosulfate can be used as the fixing solution. Of these, ammonium thiosulfate is preferable from the viewpoint of fixing speed. These fixing agents are generally used in an amount of about 0.1 mol 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.

As the fixing solution, malic acid, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination. It is effective that these compounds are contained in an amount of 0.001 mol or more per liter of the fixing solution.
0.03 mol is particularly effective.

The fixing solution has a pH of 3.8 or more, preferably 4.2.
Those having .about.7.0 are preferred. Considering the fixing dura or odor of sulfite, 4.3 to 4.8 is more preferable.

The rate of increase of the fixing solution according to the present invention due to running is preferably 0.21 or less, more preferably 0.21 to 0.05.

In the processing method according to the present invention, it is preferable to use a starter for the developing solution or the developing replenishing solution. The decrease in pH during running due to the decrease in aperture ratio is improved by keeping the pH of the replenisher solution higher than that of the mother liquor. As a method for preparing a mother liquor having a low pH, a method of lowering the pH by adding a starter to a replenisher to obtain a mother liquor is preferable.

The starter used in the present invention is an acidic additive and may be an organic acid, an inorganic acid or a mixture thereof.
The starter may be solid or solution as long as it is soluble in the developing solution, and the solution state is preferably easy to use. Specific components of the starter include, for example, acetic acid, citric acid, boric acid,
There are sulfuric acid, salicylic acid, etc., and their salts may be used.

These acids may be used alone or in combination of two or more. The amount of the starter added is 0.1 to 100 g, preferably 0.5 to 50 g, per liter of the developing solution. The range in which the developer pH is lowered by the addition of the starter is preferably 0.2 or more, more preferably 0.2 to 1.0.

In the present invention, the starter may contain a component other than an acid, and in particular, can contain a component such as halogen which increases in the development reaction and hydroquinone monosulfonate. As halogen, KBr, KCl, etc. are preferably added in an amount of 0.1 to 10 g per liter of the developing solution.

The light-sensitive material that has been developed and fixed is subsequently washed with water or stabilized. Washing or stabilizing treatment,
Not only does water saving become possible with a replenishment amount of 3 liters or less per 1 m ^{2 of} silver halide photographic light-sensitive material (including 0. That is, it can be carried out by washing with water with a reservoir), and piping for installing an automatic processor is unnecessary. can do.

When the washing with water is carried out with a small amount of water, JP-A-63-1 is used.
It is more preferable to provide a squeeze roller cleaning tank as described in No. 8350 and No. 62-287252. Further, in order to reduce the pollution load which becomes a problem when washing with a small amount of water, various oxidizing agents may be added and filter filtration may be combined. Further, a part or all of the overflow liquid from the washing or stabilizing bath, which is produced by supplementing the washing or stabilizing bath with antifungal-treated water, 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 a processing step before that.

In addition, the treatment agent component that prevents unevenness of water bubbles and / or adheres to the squeeze roller, which is likely to occur when washing with a small amount of water,
A water-soluble surfactant or an antifoaming agent may be added to prevent transfer to the treated film. Also, to prevent contamination by dyes eluted from the light-sensitive material, see Japanese Patent Laid-Open No. 63-16345.
The dye adsorbent described in No. 6 may be installed in the washing tank. or,
In some cases, a stabilizing treatment may be carried out following the water washing treatment, and examples thereof include JP-A-2-201357, JP-A-2-132435, and JP-A-1-102553.
A bath containing the compound described in JP-A-46-44446 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines and surface active agents. Agents can be added.

As the water used in the washing step or the stabilizing step, tap water, deionized water, halogen, ultraviolet germicidal lamp, various oxidizing agents (ozone, hydrogen peroxide,
It is possible to use water that has been sterilized by chlorate, etc.).

[0069]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 <Preparation of silver halide photographic light-sensitive material> Preparation of seed emulsion 1 Silver iodide 2 having an average grain size of 0.3 μm by the double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0. Monodisperse cubic grains of silver iodobromide containing mol% were prepared.

The obtained reaction solution was desalted at 40 ° C. using Kao Atlas Co., Ltd. Demol N aqueous solution and magnesium sulfate aqueous solution, and then redispersed by adding an aqueous gelatin solution to obtain a seed emulsion.

Growth from Seed Emulsion 1 Grains were grown as follows using the above seed emulsion. First
The seed emulsion was dispersed in a gelatin aqueous solution kept at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid.
An aqueous ammoniacal silver nitrate solution and an aqueous solution of potassium bromide and potassium iodide were added to this solution by the double jet method.
During the addition, pAg = 7.3 and pH were controlled to 9.7 to form a layer having a silver iodide content of 35 mol%. Next, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method. The pAg was maintained at 9.0 up to 95% of the target particle size, and the pH was continuously changed from 9.0 to 8.0. Then adjust pAg to 11.0
The grain size was grown to the target grain size while maintaining the value of 8.0. Subsequently, the pH was lowered to 6.0 with acetic acid and then 5,5'-dichloro-9-ethyl-
400 mg of anhydrous 3,3′-di- (3-sulfopropyl) -oxacarbocyanine sodium salt per mol of silver halide
After the addition, desalting was performed using the demole N aqueous solution and the magnesium sulfate aqueous solution, and then a gelatin solution was added and redispersed.

By this method, the average grain size was 0.40 μm and the average grain size was 0.40 μm in a tetrahedron having a rounded vertex with an average silver iodide content of 2.0 mol%.
65 μm, 1.00 μm, coefficient of variation (δ / r) of 0.17,
0.16, 0.16 monodisperse silver iodobromide emulsions (A), (B) and (C) were prepared.

Preparation of Seed Emulsion 2 0.2% containing hydrogen peroxide treated gelatin vigorously stirred at 40 ° C.
To the 05N potassium bromide aqueous solution, an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin was added by the double jet method, and after 25 minutes, it took 25 minutes.
After the liquid temperature was lowered to ℃, 80 ml of ammonia water (28%) was added per 1 mol of silver nitrate, and stirring was continued for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous demol N solution and an aqueous magnesium sulfate solution, and then an aqueous gelatin solution was added for redispersion. The resulting seed emulsion was spherical grains having an average grain size of 0.23 μm and a coefficient of variation of 0.28.

Growth from Seed Emulsion 2 Grains were grown as follows using the above seed emulsion. 75 ° C
A double jet method was used to add an aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate to an aqueous solution containing ossein gelatin and propyleneoxy-polyethyleneoxy-disuccinate-disodium salt vigorously stirred at.

During this period, the pH was kept at 5.8 and the pAg was kept at 9.0. After the addition was completed, the pH was adjusted to 6.0, and 5,5'-dichloro-9-ethyl-3,
Anhydrous of 3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt was added in an amount of 400 mg per mol of silver halide. Further, the mixture was desalted at 40 ° C. with an aqueous solution of Demol N, and then an aqueous gelatin solution was added to re-disperse.

By this method, a tabular silver iodobromide emulsion (D-1) having an average silver iodide content of 1.5 mol% and a projected area diameter of 0.96 μm, a coefficient of variation of 0.25 and aspect ratios of 2.0, 4.0 and 6.0,
(D-2) and (D-3) were prepared.

Preparation of Samples Obtained Emulsions (A), (B), (C) and (D-1)-
For each of (D-3), at 55 ° C, 5,5'-dichloro-9-
Ethyl-3,3'-di- (3-sulfopropyl) -oxacarbocyanine sodium anhydride and 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) -benzimidazolocarbocyanine sodium salt anhydrous
975 (A) per mol of silver halide at a weight ratio of 200: 1
mg, (B) 600 mg, (C) 390 mg, (D-1) to (D
-3) was added at 500 mg.

After 10 minutes, appropriate amounts of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added for chemical ripening. 15 minutes before the end of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added 3 × 10 per mol of silver halide. ^-2 mol was added and dispersed in an aqueous solution containing 70 g of gelatin.

Of the four ripened emulsions (A),
(B) and (C) are mixed at a weight ratio of 15:65:20 to form an emulsion (R-1), and (D-1), (D-2), (D-
3) was used alone.

For each of the emulsions, JP-A-2-301744,
Additives as shown on page 95, line 16 to page 96, line 20 were added.
Also, a silver halide solvent was added as shown in Table 2.

Further, 1.2 g of the dye emulsion dispersion shown below was added per mol of silver halide to prepare an emulsion coating solution.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 l of tricresylphosphite and 85 l of ethyl acetate. This is called an oil solvent. On the other hand, the following anionic activator (AS)
Prepare a 9.3% gelatin aqueous solution containing 1.35 kg, and then put the oil-based solvent and the gelatin aqueous solution in a dispersion pot and adjust the liquid temperature to 40
Dispersion was performed while maintaining the temperature at ℃. To the resulting dispersion, appropriate amounts of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane were added, and the mixture was made up to 240 kg with water.

[0085]

[Chemical 2]

Preparation of Silver Chloride Emulsion Preparation of Emulsion No. A (AgCl _1.00 tabular grains) In a reactor equipped with a stirrer, 6000 g of distilled water containing 90 g of high methionine gelatin (containing 59.7 mM methionine per 1 g of gelatin) was added. 0.5M CaCl ₂ .2H ₂ O was charged. At 40 ° C
The pH was adjusted to 5.1 and the value of the whole precipitate was kept unchanged by addition of NaOH or HNO ₃ . 1.6% of the total Ag used
The 0.5M AgNO ₃ solution was added over a 4 minute consumption rate. Next, the addition speed was linearly accelerated over another 55 minutes (9.32 times from the start to the end), during which the remaining Ag
It consumed 98.4%. 37 mM at 4, 16 and 36 minutes after the start of precipitation
30 cc of adenine solution of was added. 10 minutes 3M CaCl ₂
3.78 g of solution was added to the precipitate. During the addition of the adenine and CaCl ₂ solution, the silver flow was stopped for 1 minute and the additives were mixed evenly. A total of 1.44M Ag was precipitated.

Preparation of Emulsion No. B (AgBr _0.10 , Cl _0.90 tabular grains) In a reactor equipped with a stirrer, the above high methionine gelatin was added.
6000 g distilled water containing 30 g, 0.7 M NaCl, 20 mM 4,
100 g of 5,6-triaminopyrimidine and 14.0 g of NaBr were charged. The pH was adjusted to 5.6 at 40 ° C. and the total precipitation value was kept unchanged by addition of NaOH or HNO ₃ . 0.5M AgN
O ₃ solution was added over 1 minute at a rate consuming 0.3% of the total Ag used to. Next, the addition speed is linearly accelerated over another 55 minutes (9.8 times from the start to the end),
During that time, the remaining 99.7% of Ag was consumed. After the start of precipitation 1,
At 5 and 18 minutes, 120 cc of gelatin solution was added. 4M NaC
400 g of solution and 100 g of 20 mM 4,5,6-triaminopyrimidine solution were added 5 and 18 minutes after the start of precipitation. After the addition of the above materials, the silver flow was stopped for 1 minute and the additives were mixed uniformly. A total of 1.5M Ag was precipitated.

Preparation of Emulsion No. C (AgBr _0.50 , Cl _0.50 tabular grains) The same procedure as Emulsion B was carried out except that 60 g of NaBr was added to the reactor. The tabular grain emulsion obtained by preparing in the presence of high methionine gelatin and 4,5,6-triaminopyrimidine at pH 5.6 had an average size (diameter) of 1.8 μm, a thickness of less than 0.35 μm and an aspect ratio of Included 10 grains greater than 80% of total grain projected area.

Preparation of Emulsion No. D (AgCl _1.00 tabular grain) 5 g of high methionine gelatin was placed in a reactor maintained at pH of 5.6.
Was prepared in the same manner as Emulsion No. A except that The silver solution was introduced so that 0.3% of the total silver was consumed within 1 minute. The addition of the adenine solution is 1, 16,
I went to the 36th minute. Furthermore, 10% gelatin solution during the above period
120 g was added. The AgCl _1.00 emulsion obtained by preparing in the presence of high methionine gelatin and adenine at pH 5.6 has an average size (diameter) of 2.0 μm, a thickness of less than 0.35 μm, and an aspect ratio of 15 with a total grain projected area. Included more than 80% of.

The tabular emulsion thus obtained is shown below. In the table
TGPA indicates the percentage of total grain projected area occupied by tabular grains having a thickness of less than 0.35 µm.

[0091]

[Table 1]

The additives used in the protective layer liquid are as follows. The addition amount is the amount per liter of the coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 5 μm) 1.1 g Silicon dioxide (area average particle size of 3 μm) Matting agent) 0.5g Ludox AM (DuPont colloidal silica) 30mg Glyoxal 40% aqueous solution 1.5ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 500mg Silver halide solvent Amount shown in Table 2

[0094]

[Chemical 3]

The coating solution thus obtained was uniformly applied onto a blue-colored polyethylene terephthalate film base which had a thickness of 175 μm and which had been undercoated, and dried.

The coating amount was such that the emulsion layer per one surface was 2.25 g / m ² in terms of silver equivalent, the gelatin coating amount was 2.5 g / m ² , and the protective layer coating amount was 0.99 g / m ^2. A sample was obtained by simultaneously coating both sides of the emulsion layer and the protective layer with two slide hopper type coaters at a speed of 90 m / min.

The compositions of the developing solution and fixing solution used in the present invention are shown below.

Developer composition Part-A (for 12 liter finish) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g Boric acid 40 g 5-Methylbenzotriazole 1.4 g 5-Nitro Benzimidazole 0.4 g 1-Phenyl-5-mercaptotetrazole 0.25 g 4-Hydroxymethyl-4-methyl-1-phenylpyrazolidone 102 g Hydroquinone 390 g Diethylene glycol 550 g Add water to make up to 6000 ml Part-B (12l finish) Ice Acetic acid 70 g 5-Nitroindazole 0.6 g Glutaraldehyde (50% solution) 8.0 g N-acetyl-DL-penicillamine 1.2 g Starter glacial acetic acid 120 g HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH 1 g finish 1.0l potassium bromide _{225g CH 3 N (C 3 H} 6 NHCONHC 2 HSC 2 H 5) 2 1.0g 5- methylbenzotriazole 1.5g deionized water Landing formulation Part-A (18.3l for finishing) Ammonium thiosulfate (70wt / vol%) 4500g Sodium sulfite 450g Sodium acetate 450g Boric acid 110g Tartaric acid 60g Sodium citrate 10g Gluconic acid 70g 1- (N, N-Dimethylamino)- Ethyl-5-mercaptotetrazole 18g Glacial acetic acid 330g Aluminum sulphate 62g Finish with pure water to 7200ml To prepare a developer, add Part A and Part B to about 5l of water at the same time, add water while stirring and dissolve, and add 12l to finish pH. .
Adjusted to 53. This is used as a development replenisher.

20 ml / l of the above-mentioned starter was added to 1 liter of this development replenisher to adjust the pH to 10.30 to prepare a working solution.

The fixing solution was prepared by adding Part A to about 5 liters of water and adding water while stirring and dissolving to make 18.3 liters.
The pH was adjusted to 4.6 using NH ₄ OH. This is the fixing replenisher.

Evaluation <Sensitometry> The obtained sample was used as a fluorescent intensifying screen KO-250.
It was sandwiched between (Konica Corporation), irradiated with X-ray for 0.05 seconds at a tube voltage of 90 KVP and 20 mA, and a sensitometric curve was created by the distance method to determine sensitivity and gamma. Sensitivity is fog +1.0
Calculated as the reciprocal of the X-ray required to obtain the concentration of
The relative sensitivity is shown when the sensitivity of 1 is 100. When gamma is the slope of the straight line connecting the densities 1.0 and 2.0,
tan θ was defined as gamma (γ). The larger the value, the higher the gamma. Note that the development was performed using the automatic processor SRX-503 (manufactured by Konica Co., Ltd.) in the following steps by Dry to Dry (all processing steps).
Was processed in 45 seconds mode. The replenishment amounts of the developing solution and the fixing solution are shown in Table 2.

Treatment process Treatment temperature (° C) Treatment time (sec) Development + crossover 35 14.6 Fixing + crossover 33 8.2 Washing + crossover 18 7.2 (Supply water 7 liters / min) squeeze 40 5.7 Drying 50 8.1 Total − −45.0 <Evaluation of running stability> The sample film prepared above was uniformly exposed to a density of 1.0, and 70 sheets of quadrant size film were processed for 1 day, and the sensitivity after 20 days, 60 days,
The change in gamma photographic properties was investigated.

<Evaluation of Remaining Coloring Property> Among the samples for evaluating running stability, the unexposed light-sensitive material was developed at the time of 20 days running, and the remaining color was visually evaluated according to the following evaluation criteria.

Evaluation Criteria 5: No Contamination of Residual Color 4: Slight Contamination of Residual Color 3: Slight Contamination of Residual Color but No Practical Problems 2: Slight Contamination of Residual Color but Limit of Practical Range 1: Contamination of Residual Color It is not practically possible. <Evaluation of residual silver>
An unexposed film sample at the time of day was used as a sample for evaluating residual silver. The residual silver evaluation liquid (sodium sulfide 2.6 × 10
^-3 mol / liter aqueous solution) is added drop by drop to five points on the evaluation film. After leaving it for 3 minutes, wipe off the liquid well and leave it for 15 hours at room temperature and normal humidity. Then use a densitometer PDA-65 (manufactured by Konica Corp.) with an interference filter of 436 ± 10 nm to remove the residual silver evaluation droplet lower part. The blue light transmission density of the portion not dropped was measured, and the difference was used as a guide for the amount of residual silver. The larger the value, the higher the residual silver concentration in the film after processing, which is not preferable.

<Evaluation of Sharpness> A rectangular wave chart of the obtained sample was photographed and the MTF was determined by the contrast method. The MTF was set to a value with a spatial frequency of 2.0 lines / mm. The larger the value, the better the sharpness. The results obtained are shown in Tables 3 and 4 below.

[0106]

[Table 3]

[0107]

[Table 4]

As is clear from the table, the samples of the present invention show stable photographic performance with little fluctuation in sensitivity and gamma during running. Furthermore, the sample of the present invention has less residual color contamination after processing than the comparative sample even when the processing solution is replenished at a low level, and has less desilvering property in the fixing process, resulting in less residual silver and image sharpness. Is also excellent.

[0109]

According to the present invention, a silver halide photographic light-sensitive material having stable photographic performance with little fluctuation in sensitivity and gamma during running even with a low replenishment of the developing solution can be obtained. Further, according to the present invention, a silver halide photographic light-sensitive material having less residual color stain after processing and less desilvering property in fixing processing, less residual silver and excellent image sharpness and its processing I was able to provide a method.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a hydrophilic colloid layer on at least one surface of a support, and at least one silver halide emulsion layer. Is the sum of all projected areas
A tabular hydrophilic colloid layer containing tabular silver halide grains of which 50% or more is composed of silver bromide or silver iodobromide having an aspect ratio of 3 or more, and which is placed farthest from the support, is tabular. A silver halide photographic light-sensitive material comprising silver chloride grains. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer contains at least one silver halide solvent. 3. A method of processing the silver halide photographic light-sensitive material according to claim 1 or 2 by an automatic processor.
A method of processing a silver halide photographic light-sensitive material, characterized in that the replenishing amount of the developing solution is 50 to 300 ml per 1 m ^{2 of the} light-sensitive material.