JPH09146199A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve pressure resistance and fluctuation characteristic in processing. SOLUTION: The silver halide particles of the photosensitive layer furthest from the base of the silver halide photographic sensitive material having >=2 layers of photosensitive silver halide emulsion layers only on one side of the base are the silver halide particles formed by using an aq. ammonia silver nitrate soln. and growing the particles at pH7.5 to 2.0. The sensitivity of these silver halide particles is lower than the sensitivity of the silver halide particles of the lower layer adjacent to the particles described above. The average iodide content of the silver halide particles of the photosensitive layer furthest from the base is preferably higher by >=0.1mol% than the average iodide content of the silver halide particles of the photosensitive layer of the adjacent lower layer and is 3 to 0.5mol%. The silver halide particles of the photosensitive layer furthest from the base are preferably the monodisperse core/shell type particles having core parts of the average iodide content of >=5mol% within the particles.

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, and particularly to a silver halide photographic light-sensitive material suitable as an X-ray light-sensitive material.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials (hereinafter also simply referred to as "light-sensitive materials") are required not only to have high sensitivity and high image quality but also to have stable photographic performance. Various improved techniques have been investigated, focusing on emulsions.

For example, in handling a light-sensitive material in photographing, developing, etc., improvement in resistance to various pressures that are accidentally or inevitably applied is desired in terms of stability of photographic performance.

High temperature processing has rapidly spread in the developing process of photosensitive materials, and even in the automatic developing processing of various photosensitive materials,
The processing time has been shortened. In terms of stability of photographic performance, especially in high-contrast photosensitive materials, gradation is important for reproducing images, and stability against processing fluctuations such as no gradation fluctuation between development processes is desired. There is.

Conventionally, as means for improving pressure resistance, for example, US Pat. No. 2,628,167 and Japanese Patent Laid-Open No. 50-11.
No. 6025 and No. 51-107129 describe a method of adding an iridium salt or a thallium salt at the time of forming silver halide grains. However, these methods have a problem that the sensitivity is lowered.

Further, in JP-A-63-220238 and JP-A-1-201649, a technique for improving graininess, pressure resistance and exposure illuminance dependency with high sensitivity by introducing dislocations in silver halide grains. Is disclosed.

On the other hand, regarding the processing fluctuation, improvement of the processing liquid has been conventionally studied in order to improve its stability, but it is hard to say that it is sufficient in terms of gradation fluctuation stability. For example, JP-A-2-110542 discloses that gradation fluctuation due to processing fluctuation is improved by mixing a tabular silver halide emulsion and a normal crystal core / shell type silver halide emulsion in the same layer. Has been done, but it is still insufficient.

As described above, in these conventional techniques, the improvement of the pressure resistance and the processing stability is still insufficient, and it has been desired to develop a technique which is superior in the pressure resistance and the gradation variation due to the processing variation. .

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having excellent pressure resistance and improved processing variability.

[0010]

The above object of the present invention has been attained by the following constitutions.

(1) In a silver halide photographic light-sensitive material having two or more light-sensitive silver halide emulsion layers on only one side of a support, the silver halide grains in the light-sensitive layer farthest from the support are ammonia. PH using a neutral silver nitrate aqueous solution
Silver halide grains grown from 7.5 to 2.0,
A silver halide photographic light-sensitive material having a lower sensitivity than the silver halide grains contained in the lower layer adjacent to the silver halide grains.

(2) The average iodide content of the silver halide grains in the photosensitive layer farthest from the support is at least 0.1 than the average iodide content of the silver halide grains in the adjacent lower photosensitive layer. The silver halide photographic light-sensitive material according to (1), wherein the content is at least 3 mol% and at most 3 to 0.5 mol%.

(3) The silver halide grains in the photosensitive layer farthest from the support are monodisperse core / shell type grains having a core portion having an average iodine content of 5 mol% or more inside the grain ( The silver halide photographic light-sensitive material as described in 1) or (2).

(4) The silver halide grains in the photosensitive layer closest to the support are tabular silver halide grains having an average aspect ratio of 2 or more and less than 10, and the silver halide grains have an average iodine content. The silver halide photographic light-sensitive material according to any one of (1) to (3), wherein the ratio is less than 2 mol% and the silver halide grains have the highest sensitivity.

The present invention will be described in more detail below.

The silver halide grains used in the photosensitive layer (uppermost layer) farthest from the support of the present invention are silver halide grains grown at pH 7.5 to 2.0 using an aqueous ammoniacal silver nitrate solution. is there. More preferably, the pH is 7.3.
It is a silver halide grain grown at .about.4.0. This p
By growing in the H region, it is possible to grow grains in the core portion having a uniform iodine content.

In the present invention, low sensitivity means logE =
0.02 to 0.5 means low sensitivity, preferably l
ogE = 0.05 to 0.4.

The average iodide content of the silver halide grains used in the uppermost layer is 0.1 mol% or more higher than the average iodide content of the silver halide grains in the adjacent lower layer, and 3
It is preferably about 0.5 mol%.

Further, the silver halide grains used in the uppermost layer are preferably monodisperse core / shell type silver halide grains. The monodisperse core / shell type silver halide grains may be regular crystal grains such as cubic grains, tetradecahedral grains and octahedral grains, and may be spherical grains or twin grains. Among the twinned grains, twinned grains having an aspect ratio of less than 2 are preferable.

When the grain is spherical, it means that the radius of curvature corresponding to 1 / 6L to 1 / 2L of the length L of the polygon having the largest area among the polygons forming the outer shape of the silver halide grain. Is defined as having a roundness at the edge of the polygon before spheroidization. Grain roundness can be determined by observing silver halide grains with an electron microscope.

The monodisperse silver halide grains are those in which the weight of silver halide contained in the grain size range of ± 20% around the average grain size d is 60% or more of the total weight of silver halide. , Preferably 70% or more, more preferably 80% or more.

The average particle size d herein is defined as the particle size d _i of when the product n _i × d _i ³ of the frequency n _i and d _i ³ of particles having a particle size d _i is maximum (effective Numbers are 3 digits, minimum digits are rounded to 4).

The term "particle size" as used herein means the diameter of spherical silver halide grains, and, in the case of grains having a shape other than spherical, the projected image thereof when converted into a circular image of the same area. Is the diameter. The particle size is, for example, 10,000 to 5 with an electron microscope.
It can be obtained by enlarging the image by a factor of 10,000 and measuring the particle diameter on the print or the area at the time of image capturing (the number of measured particles is indiscriminately 1000 or more).

Among the monodisperse core / shell type silver halide grains which can be used, particularly preferred highly monodisperse grains have a broad distribution of 20% or less, more preferably 15% or less. .

The particle size measuring method is based on the above-mentioned measuring method, and the average particle size is a simple average. That is, average grain size = Σd _i n _i / Σn _i The monodisperse core / shell type silver halide grain used in the present invention has a grain structure composed of two or more layers having different silver iodide contents. Is a silver halide grain, and is a grain composed of a core (inner layer) and a shell (outer shell) covering the core, and the shell is formed by one or more layers. It is preferable that the core and the shell have different iodide contents, and it is particularly preferable that the core portion is formed with the highest iodide content.

The iodine content of the core is preferably 5 mol% or more and the solid solution limit or less, and more preferably 7 mol% or more and the solid solution limit or less.

The content of the core is preferably at least 3 mol% or more.

Further, the iodide content of the core is preferably at least 3 mol% or more than the iodide content of the shell.

The iodine distribution of the core is usually uniform, but it may have a distribution. For example, as the concentration goes from the center to the outside, the concentration may become higher, or the intermediate region may have a maximum or minimum concentration.

The monodisperse core / shell type silver halide grains used in the present invention are prepared by allowing an aqueous solution containing a protective colloid and seed grains to be present in a reaction vessel in advance, and if necessary silver ion,
What is obtained by supplying halogen ions or fine silver halide grains to crystallize and grow seed grains is preferable. In this case, the grain center can have a halogen composition region different from that of the core.

The halogen composition of the seed particles is arbitrary,
It may be any of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, silver chloroiodide and silver iodide.

The silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (Electron method).
It is calculated by the Probe Micro Analyzer). In this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, an X-ray analysis is performed by irradiating with an electron beam, and electron beam excitation is performed, and elemental analysis of an extremely minute portion can be performed. That is, by obtaining the characteristic X-ray intensity of silver and iodide emitted from each grain,
The silver halide composition of individual grains can be determined. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content is determined from the average thereof.

The halogen composition distribution inside the silver halide grain can be obtained by pretreating the grain into ultrathin slices and then observing and analyzing with a transmission electron microscope while cooling. Specifically, after taking out the silver halide grains from the emulsion,
A 60 nm-thick section is prepared by embedding in resin and cutting it with a diamond knife. While cooling this section with liquid nitrogen, observation and point analysis were performed with a transmission electron microscope equipped with an energy dispersive X-ray analyzer, and quantitatively calculated (Inoue, Nagasawa:
(Proceedings of the 62nd Annual Meeting of the Photographic Society of Japan, 1987).

The silver iodide content on the outermost surface of tabular silver halide grains means the XPS method (X-ray Photoelec).
Tron Spectroscopy: X-ray photoelectron spectroscopy) is a silver iodide content in a portion up to a depth of 50 Å, which can be determined as follows.

The sample was cooled to -110 ° C. or less in an ultrahigh vacuum of 1 × 10 ^-8 torr or less, and M was used as an X-ray for a probe.
Irradiate gKα with an X-ray source voltage of 15 kv and an X-ray source current of 40 mA, and measure for Ag3d5 / 2, Br3d, and I3d3 / 2 electrons. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the outermost surface is determined from these intensity ratios.

The purpose of cooling the sample is to eliminate the measurement error caused by destruction of the sample (decomposition of silver halide and diffusion of halide (particularly iodine)) due to X-ray irradiation at room temperature, and to enhance the measurement accuracy. By cooling to -110 ° C, sample destruction can be suppressed to a level that does not hinder measurement.

The average iodide content of the outermost surface of the monodisperse core / shell type silver halide grains used in the uppermost layer is at least 0 than the average iodide content of the outermost surface of the adjacent lower silver halide grains. It is preferably 0.5 mol% or less, more preferably 0.2 to 7 mol%, still more preferably 0.5 to 7 mol%.

The tabular silver halide grains preferably have two twin planes parallel to each other. This twin plane can be observed with a transmission electron microscope. The specific method is as follows.

First, a sample is prepared by coating a silver halide emulsion so that the contained silver halide grains are oriented on a support. This is cut with a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. The presence of twin planes can be confirmed by observing this section with a transmission electron microscope. As a method of obtaining a tabular silver halide emulsion, a method of precipitating silver halide on a seed crystal is preferably used.

In order to obtain the tabular silver halide emulsion of the present invention, a method for producing a silver halide photographic emulsion comprising supplying a water-soluble silver salt solution and a water-soluble halide solution to the presence of a protective colloid, A) Silver iodide content of 0 to 5 mol%
From the beginning of the formation of silver halide precipitate in
A core particle forming step of keeping pBr of the mother liquor at 2.5 to -0.7 is provided, and (b) subsequent to the core particle forming step, a silver halide solvent is added to the mother liquor at 10 ^-5 to 10 ^-5 per mol of silver halide. 2.
A seed grain forming step of forming a silver halide seed grain containing 0 mol of substantially monodisperse spherical twin crystals is provided, or the temperature of the mother liquor is raised to 40 to 80 ° C. following the core grain forming step. A seed grain forming step of forming a silver halide twin seed grain by heating is provided, and then (c) a water-soluble silver salt solution and a water-soluble halide solution and / or silver halide fine particles are added to enlarge the seed grain. A method of providing a growing step (particle forming step) for performing is preferably used.

Here, the mother liquor is a liquid (including a silver halide emulsion) that is used in the preparation of silver halide emulsions up to the completed photographic emulsion.

The silver halide grains formed in the nucleus grain forming step are twinned grains composed of 0 to 5 mol% silver iodide.

A twin is a silver halide crystal having one or more twin planes in one grain, and the morphology of twins is classified by Klein and Moiser in the article Photographiesche Correspondents. (Photographish
Korrespondenz) 99, 99, 10
0, page 57.

The tabular silver halide grain is a grain having two parallel main planes opposed to each other, and the aspect ratio is represented by the ratio of grain size to grain thickness. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), which is a circle equivalent diameter of a projected area of the tabular silver halide grains (of a circle having the same projected area as the silver halide grains). Diameter) and thickness refers to the distance between two parallel major planes forming a tabular silver halide grain.

The average aspect ratio of the tabular silver halide grains of the present invention is from 2 to less than 10, preferably from 2 to less than 5.

In the present invention, 50% or more of the total projected area of the emulsion layer containing tabular silver halide grains consists of tabular silver halide grains, preferably 70% or more, more preferably 90% or more. is there.

The tabular silver halide grains have an average grain size of 0.
It is preferably from 15 to 5.0 μm, and from 0.4 to 3.0 μm.
More preferably, it is 0 μm, most preferably 0.1 μm.
4 to 2.0 μm. Further, the average thickness of the tabular silver halide grains is preferably 0.15 to 0.3 μm, and the grain size and thickness can be optimized so as to optimize the sensitivity and other photographic characteristics. .

Optimum grain depending on sensitivity and other factors constituting the photographic material (thickness of hydrophilic colloid layer, hardness, chemical ripening condition, preset sensitivity of photographic material, silver coating amount, etc.) Diameter and optimum thickness are different.

In the tabular silver halide grains, silver iodochloride, silver chloroiodobromide, silver chlorobromide, silver bromide, silver iodobromide and the like can be used as the silver halide. The silver iodide content is 2 mol% as the average silver iodide content in the entire silver halide grains.
It is preferably less than 0.5 mol%, more preferably 0.5 mol% or more and less than 2 mol%.

The tabular silver halide grains contained in the silver halide emulsion of the present invention preferably have a more uniform iodide content between grains. When the distribution of the iodide content between the grains was measured by the EPMA method, the relative standard deviation was 35.
%, More preferably 20% or less.

The tabular silver halide grains of the present invention contain silver iodide, but it is preferable that the tabular silver halide grains are contained at least inside. In the case of the inside, it is more preferable that it exists at least in the central portion. Further, it is also preferable that it is present on the outermost surface.

The average iodide content on the outermost surface of the tabular silver halide is preferably 2 to 15 mol%, more preferably 3
~ 12 mol%.

The tabular silver halide grains may have dislocations. The dislocation is described in, for example, J. F. Hamilton;
Photo. Sci. Eng., 57 (1967);
Shiozawa; J. Soc. Photo. Sci. J
Apan, 35, 213 (1972), and can be observed by a direct method using a transmission electron microscope at low temperature. That is, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion, are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beam In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, a high voltage type (200 kV or more for particles having a thickness of 0.25 μm)
Can be observed more clearly using an electron microscope.

The tabular silver halide grains are preferably monodisperse emulsions having a narrow grain size distribution, specifically, (standard deviation of grain size / average grain size) × 100 = distributed by width (%) of grain size distribution. When the width of the is defined, it is preferably 25% or less, more preferably 20% or less.

The tabular silver halide grains preferably have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width of thickness distribution (%), 25% or less is preferable, and 20% is more preferable. It is as follows.

In order to obtain tabular silver halide grains and monodisperse core / shell type silver halide grains, the conditions under which the produced seed grains are enlarged are described in JP-A-51-390.
No. 27, No. 55-142329, No. 58-11392.
No. 8, No. 54-48521 and No. 58-49938, a water-soluble silver salt solution and a water-soluble halide solution are added by the double jet method, and the addition rate is adjusted according to the enlargement of the particles. There is a method of gradually changing it within a range in which no formation occurs and Ostwald ripening does not occur. As another condition for enlarging the seed grains, a method of adding silver halide fine grains, dissolving and recrystallizing the grains, as shown in the 88th Annual Meeting of the Photographic Society of Japan, 1988, may be used.

In growing the grains, an aqueous solution of silver nitrate and an aqueous solution of halide can be added by double jet, but the iodine can also be supplied to the system as silver iodide. The rate of addition is such that no new nuclei are generated,
In addition, it is preferable to add at a rate at which the size distribution does not spread due to Ostwald ripening, that is, in the range of 30 to 100% of the rate at which new nuclei are generated.

In producing a silver halide emulsion, stirring conditions during production are extremely important. As the stirring device, the device shown in JP-A-62-160128, in which the additive liquid nozzle is installed in the liquid near the mother liquid suction port of the stirrer, is particularly preferably used. At this time, the stirring rotation speed is 100
It is preferably set to ~ 1200 rpm.

In preparing the emulsion, a known silver halide solvent such as ammonia, thioether or thiourea can be present during the seed grain forming step and the seed grain growth.

In the preparation of the silver halide grains of the present invention, a silver salt solution and a halide solution are added by the double jet method during the growth, and the addition rate is adjusted according to the growth of the grains so that new nucleation does not occur and Ostwald Particles having a desired particle size and distribution can be obtained by a method in which the size distribution does not spread due to aging, that is, a method of gradually changing it within a range of 30 to 100% of the speed at which new nuclei are generated.

The silver halide grains may be so-called halogen conversion type (conversion type) grains. The amount of halogen conversion is preferably 0.2 to 0.5 mol% with respect to the amount of silver, and the conversion time may be physical ripening or after physical ripening.

As a method for halogen conversion, an aqueous halide solution or silver halide fine particles having a smaller solubility product with silver than the halogen composition on the grain surface before halogen conversion is usually added. The particle size at this time is 0.2μ
m or less, more preferably 0.02 to 0.1 μm
m.

When silver iodide is added to the outermost surface of the silver halide grains of the present invention, the method is to simultaneously add a silver nitrate solution and a solution containing iodide to the emulsion containing the base silver halide grains. A method of adding, a method of adding fine silver halide grains such as silver iodide, silver iodobromide or silver chloroiodobromide, a method of adding potassium iodide or a mixture of potassium iodide and potassium bromide, etc. can be applied. . Of these, the method of adding fine silver halide grains is preferable. Especially preferred is the addition of fine silver iodide grains.

The time for adjusting the silver iodide content on the outermost surface is from the final step of the silver halide crystal production step to the chemical ripening step, and further until the end of the solution preparation step immediately before the coating of the silver halide emulsion. Although it can be selected in a timely manner, it is preferable to adjust it by the end of the chemical ripening step. The term "chemical ripening step" as used herein means from the time when the physical ripening and desalting operations of the silver halide emulsion are completed to the time when the chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Refers to. Further, the addition of silver halide fine grains may be carried out in several times with a time interval, or another chemically ripened emulsion may be added after the addition of the fine grains.

The temperature of the emulsion when adding fine silver halide grains is preferably in the range of 30 to 80 ° C., more preferably 40 to 40 ° C.
The range of 65 ° C. is particularly preferred. Further, in the present invention, it is preferable that the silver halide fine particles to be added be carried out under the condition that a part or all of them disappears after the addition and immediately before coating. More preferable condition is that of the added silver halide fine particles. It means that 20% or more disappears just before coating.

It is also preferable to add a silver halide solvent before the desalting step in order to accelerate the developing rate. For example, it is preferable to add 1 × 10 ^{−3 to} 3 × 10 ⁻² mol of a thiocyanic acid compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) per mol of silver.

Gelatin is preferably used as the dispersion medium for the protective colloid of silver halide grains, and the gelatin is modified with alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 1,000 to 50,000), phthalated gelatin and the like. Gelatin or the like is used. Also, hydrophilic colloids other than gelatin can be used. Specifically, research
Disclosure Magazine (Research Disclo)
Sure, hereinafter abbreviated as RD) Volume 176, Item 17643 (December 1978).

In the preparation of tabular silver halide grains,
Unnecessary soluble salts may be removed during the growth of silver halide grains, or they may be contained. The removal of the salts can be carried out according to the method described in Item II of RD 176, 17643.

Further, the silver halide grains include cadmium salt, zinc salt, and
At least one metal ion selected from a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (including a complex salt) and an iron salt (including a complex salt) is added to the inside and / or the surface of the particle. These layers can contain these metal elements, and by placing them in a suitable reducing atmosphere, reduction sensitizing nuclei can be imparted to the inside and / or the surface of the grains.

The action of the reducing agent added at the desired time of grain formation is the addition of oxidizing agents such as hydrogen peroxide (water) and its adducts, peroxo acid salts, ozone and I ₂ at the desired time. Therefore, it is preferable to inactivate the reducing agent to suppress or stop the reducing agent. The oxidizing agent may be added at any time from the time of silver halide grain formation to the chemical sensitization step and before the addition of the gold sensitizer (or the chemical sensitizer when the gold sensitizer is not used).

In the silver halide photographic emulsion, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may be contained. The removal of the salts can be carried out based on the method described in RD17643, item II.

The silver halide grains can be chemically sensitized. Chemical ripening or chemical sensitization process conditions, eg p
There are no particular restrictions on H, pAg, temperature, time, etc.
Conditions generally used in the industry can be applied. For chemical sensitization, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitizing method using a selenium compound, a tellurium sensitizing method using a tellurium compound, and a reducing substance are used. The reduction sensitization method used, the noble metal sensitization method using gold or other noble metal, and the like can be used alone or in combination.

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 10 ^-8 to 10 ^-4 per mol of silver halide.
Use about moles. The addition method may be a method of adding by dissolving it in a single or mixed solvent of water or an organic solvent such as methanol or ethanol depending on the properties of the selenium compound used, or a method of adding by mixing with a gelatin solution in advance,
Alternatively, a method of adding in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent disclosed in JP-A-4-140739 may be used.

The temperature of chemical ripening using a selenium sensitizer is 4
The range of 0 to 90 ° C. is preferable, and more preferably 45 to 8
0 ° C. The pH is preferably 4 to 9, and the pAg is preferably 6 to 9.5.

The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer. It is also preferable to carry out so-called reduction sensitization on the grain surface by placing it in an appropriate reducing atmosphere.

Preferred examples of the reducing agent include thiourea dioxide, ascorbic acid and their derivatives. Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The amount of the reducing agent added depends on the type of reduction sensitizer, the grain size of the silver halide grains, the composition and crystal habit, the temperature of the reaction system,
Although it is preferable to change it depending on environmental conditions such as pH and pAg, for example, in the case of thiourea dioxide, a preferable result is obtained by using about 0.01 to 2 mg per mol of silver halide as a rough guide. In the case of ascorbic acid, the range is preferably about 50 mg to 2 g per mol of silver halide.

The conditions for reduction sensitization are a temperature of about 40 to 7
0 ° C., time is about 10 to 200 minutes, pH is about 5 to 11, p
Ag is preferably in the range of about 1 to 10 (where pAg value =
Reciprocal of Ag + ion concentration).

Silver nitrate is preferred as the water-soluble silver salt. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably 1 to 6, and preferably 2 to 4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range.

The silver halide grains may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobola cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are cyanine, merocyanine and complex merocyanine dyes.

Any of commonly used nuclei can be applied to these dyes. That is, pyrroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, imidazole, tetrazole, pyridine nucleus, and the like, a nucleus in which an aliphatic hydrocarbon ring is fused to these nuclei, that is, indolenine, benzindolenine, indole, benzine. Oxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

The merocyanine-based or complex merocyanine-based dye has a pyrazoline-containing nucleus as a core having a ketomethine structure.
5- to 6-membered heterocyclic nuclei such as 5-one, thiohydantoin, 2-thiooxazolidine-2,4-dione, thiazoline-2,4-dione, rhodanine and thiobarbituric acid nucleus can be applied.

The sensitizing dyes may be used alone or in combination, and the combination is often used particularly for the purpose of supersensitization.
Further, together with a sensitizing dye, a dye that does not have spectral sensitizing property or a substance that does not substantially absorb visible light,
A substance exhibiting a supersensitizing effect may be contained in the emulsion layer.
For example, a substituted aminostilbene compound having a nitrogen-containing heterocyclic nucleus group (described in U.S. Pat. Nos. 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde condensate ( US Patent 3,743,510
No. 1), a cadmium salt, an azaindene compound, and the like. US Patent 3,615,613
No. 3,615,641, No. 3,617,295
No. 3,635,721 and the like are particularly useful. The sensitizing dye may be added during or during each step of nucleation, growth, desalting, chemical sensitization, or after chemical sensitization.

The photosensitive material of the present invention is prepared by adding an appropriate amount of a hardening agent in advance in the coating step of the photosensitive material so as to be suitable for rapid processing, and adjusting the water swelling rate in the developing-fixing-washing step. Therefore, it is preferable to keep the water content in the light-sensitive material before the start of drying.

The photosensitive material has a swelling ratio of 15 during development.
It is preferably 0 to 250%, and the film thickness after swelling is 70
μm or less is preferred. If the water swelling rate exceeds 250%,
Poor drying occurs, for example, in the automatic processor processing, especially in rapid processing, conveyance failure also occurs. Also, the water swelling rate is 150%
If it is less than 1, there is a bad tendency that uneven development and residual color increase when developed.

The water swelling rate referred to here is the difference between the film thickness after swelling in each processing solution and the film thickness before the development processing, which is divided by the film thickness before processing and multiplied by 100. Say something.

In the present invention, powder processing agents, solid processing agents such as tablets, pills, granules, etc. may be used, and if necessary, those which have been subjected to moisture-proof processing may be used.
The powder in the present invention refers to an aggregate of fine crystal grains.
Granules are powders that have undergone a granulation process and have a particle size of 50 to 5
It means a granular material of 000 μm. Further, the tablet refers to a powder or granules compression-molded into a certain shape.

As a cause of fluctuations in photographic performance, it is effective to reduce the opening coefficient of the developer in the automatic processor. In particular, the opening coefficient is preferably 80 cm ² / liter or less. That is, when the opening coefficient exceeds 80 cm ² / liter, the undissolved solid processing agent or the concentrated liquid immediately after dissolution is susceptible to air oxidation, resulting in insoluble matter or scum, which may be processed by the automatic processing machine or processed. However, when the aperture coefficient is 80 cm ² / liter or less, these problems can be solved. The opening coefficient referred to here is represented by the area of contact with air per unit volume of the processing solution, and the unit is (cm ²
/ Liter). In the present invention, the aperture coefficient is 8
0 cm ² / liter or less, more preferably 5 cm ² / liter or less.
0 to ³ cm ² / liter, more preferably 35 to
It is 10 cm ² / liter.

The opening coefficient can be generally reduced by using a resin or the like for blocking the air as a floating lid, or in Japanese Patent Laid-Open No. 63-13.
No. 1138, No. 63-216050, No. 63-235.
The size can be reduced by the slit type developing device described in No. 940 or the like.

The solid processing agent is used for a photographic processing agent such as a developing agent, a fixing agent, a rinsing agent, etc., and the solid developing agent has a great effect of the present invention, particularly the effect of stabilizing photographic performance.

The solid processing agent may be solidified by only a part of the components of a certain processing agent, but it is preferable that all the components of the processing agent are solidified. It is desirable that each component be molded as a separate solid processing agent and packaged in the same package. It is also desirable that the separate components are packaged in the order in which they are periodically charged repeatedly.

As the supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, the actual method is 6
3-137873, 63-97522, Actual Kaihei 1
Although there are known methods such as No. -85732, any method may be used as long as it has at least the function of supplying tablets to the processing tank. When the solid processing agent is a granule or a powder, it is used in JP-A-62-81964 and 63-84.
151, the gravity drop method described in JP-A-1-292375, etc., and JP-A-63-105159 and 63-19.
Although there is a method using a screw or a screw described in No. 5345, the invention is not limited thereto.

The solid processing agent may be put in any place in the processing tank, but preferably, it is communicated with the processing section for processing the light-sensitive material, and the processing solution flows between the processing section and the processing section. It is preferable that the structure is a place where the solution is present, a certain amount of the processing solution is circulated between the processing section and the dissolved components, and the dissolved components move to the processing section. The solid processing agent is preferably added to the temperature-controlled processing liquid.

In addition to the dihydroxybenzenes, aminophenols, and pyrazolidones described in Japanese Patent Application No. 4-286232, pages 19 to 20 as a developing agent, they are described in JP-A-5-165161. The reductones of are also preferably used. Of the pyrazolidones, those in which the 4-position is substituted (trade names: dimezone, dimezone S, etc.) are water-soluble and the solid treatment agent itself hardly changes with time, and are particularly preferable.

As the preservative, in addition to the sulfite described in Japanese Patent Application No. 4-286232, an organic reducing agent can be used as the preservative. In addition, Japanese Patent Application No. 4-586323, 20
The chelating agent described on page 21 and the bisulfite adduct of the hardener described on page 21 can be used. Moreover, as silver sludge preventive agents, Japanese Patent Application Nos. 4-92947 and 5-9611.
Compounds described in No. 8 (general formulas [4-a], [4-b])
It is also preferable to add. Addition of a cyclodextrin compound is also preferable, and compounds described in JP-A-1-124852 are particularly preferable.

An amine compound may be added to the developer, and the compounds described in US Pat. No. 4,269,929 are particularly preferable.

It is necessary to use a buffering agent in the developer. As the buffering agent, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate,
Tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (= sodium salicylate), potassium o-hydroxybenzoate, 5-
Examples thereof include sodium sulfo-2-hydroxybenzoate (= sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (= potassium 5-sulfosalicylate), and the like.

As a development accelerator, Japanese Examined Patent Publication No. 37-160
Nos. 88, 37-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247; No. 50-15554
Quaternary ammonium salts represented by JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429. US Patent 2,61
P-aminophenols described in U.S. Pat. Nos. 0,122 and 4,119,462; U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796 and 3,253. No. 919, JP-B-41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and the like. 42-25201
No. 3,128,183, JP-B-41-11
Nos. 431 and 42-23883 and U.S. Pat.
No. 2,501 and other polyalkylene oxides,
In addition, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be added as necessary.

As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
1-phenyl-5-mercaptotetrazole can be given as a representative example of a nitrogen-containing heterocyclic compound such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

If necessary, the developer composition may further include methyl cellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, and other Japanese Patent Publication No.
The compounds described in 7-33378 and 44-9509 can be used as an organic solvent for increasing the solubility of the developing agent. In addition, various additives such as anti-stain agents, anti-sludge agents, and multi-layer effect accelerators can be used.

As the fixing agent, a compound known as a fixing agent can be added. Fixing agent, chelating agent, pH buffering agent, hardening agent,
Preservatives and the like can be added.
2246, page 4, and JP-A-5-113632, 2-4.
Those described on the page can be used. In addition, as a hardener,
A chelating agent described in Japanese Patent Application No. 4-586323, page 20, a bisulfite addition product of a hardening agent described on page 21, and a known fixing accelerator can also be used.

Prior to the treatment, it is also preferable to add a starter, and it is also preferable to solidify and add the starter. As the starter, in addition to organic acids such as polycarboxylic acid compounds, halides of alkaline earth metals such as potassium bromide, organic inhibitors, and development accelerators are used.

The present invention comprises a black and white silver halide photographic light-sensitive material (for example, a negative light-sensitive material for medical use, printing, general photography),
It can be applied to a color photographic light-sensitive material (for example, a color negative, a color reversal, a light-sensitive material for color printing), a diffusion transfer light-sensitive material, a photothermographic material, and the like, and more preferably a black-and-white silver halide photographic light-sensitive material.

In many cases, a hydroquinone is used as a developing agent in a developing solution used for developing a black-and-white light-sensitive material. However, in the present invention, from the viewpoint of work safety improvement and environmental protection, A developer containing substantially no hydroquinone, for example, ascorbic acid described in US Pat. No. 5,236,816 may be used.

The development time of the black-and-white light-sensitive material is 3 to 90 seconds, more preferably 5 to 60 seconds, and the processing time is Dry t.
15 to 210 seconds in o Dry, more preferably 15 to 9 seconds
0 seconds.

Various additives may be further added to the light-sensitive material of the present invention depending on the purpose. Additives and the like used are, for example, RD17643, page 23, item III to 2
Page 9, Section XXI (Dec. 1978), id 18716, 64
8 to 651 (November 1979) and 30811
9,996, page III to page 1009, section XVII (1989, 1
(February).

Further, as the support which can be used for the light-sensitive material, the above-mentioned RD17643, page 28 and RD30 can be used.
8119, page 1009.
A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer for improving the adhesion of the coating layer, corona discharge, ultraviolet irradiation or the like.

[0108]

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

Example 1 (Preparation of Normal Crystal Seed Emulsion) Seed Emulsion-A was prepared as follows.

A1 ossein gelatin 100 g potassium bromide 2.05 g with water 11.5 liters B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml water 2.6 liters C1 ose In-gelatin 75 g Potassium bromide 950 g Potassium iodide 27 g Water 3.0 liters D1 Silver nitrate 95 g Water 2.7 liters E1 Silver nitrate 1410 g Water 3.2 liters A1 solution kept at 60 ° C. in a reaction vessel, B1 solution And D1 solution were added by the control double jet method over 30 minutes, and then C1 and E1 solution were added by the control double jet method over 105 minutes. Stirring was performed at 500 rpm.

The flow rate was such that new nuclei did not occur with the growth of particles, and so-called Ostwald ripening occurred, and the particle size distribution did not broaden. At the time of adding the silver ionic liquid and the halide ionic liquid, pAg was adjusted to 8.3 ± 0.05 using potassium bromide liquid, and pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the addition was completed, the pH was adjusted to 6.0, and then in order to remove the excess salts, JP-B-35-1608 was used.
A desalting treatment was performed by the method described in No. 6.

When the seed emulsion was observed with an electron microscope, it was a cubic tetradecahedral monodisperse emulsion having an average grain size of 0.27 μm and a width of 17% with a slight lack of corners.

(Preparation of Em-1) A monodisperse core / shell type emulsion was prepared using the above seed emulsion-A and the following solution.

A2 ossein gelatin 10.4 g 28% aqueous ammonia solution 28.3 ml 56% aqueous acetic acid solution 4.2 ml Seed emulsion-A equivalent to 0.216 mol of water 700 ml B2 ossein gelatin 2.5 g potassium bromide 3.68 g iodine Potassium bromide 3.09 g Water 124 ml C2 ossein gelatin 1.9 g Potassium bromide 86 g Water 169 ml D2 Silver nitrate 13.1 g 28% aqueous ammonia solution 13.9 ml Water 191 ml E2 Silver nitrate 120.1 g 28% aqueous ammonia solution 94.3 ml Water The 217 ml A2 solution was kept warm at 40 ° C. and stirred at 800 rpm with a stirrer. The pH of solution A2 was adjusted to 9.90 with acetic acid, seed emulsion-A was collected and dispersed and suspended, and then solution D2 was added at a constant rate over 7 minutes to adjust pAg to 7.3. Further, solution B2 and solution D2 were added simultaneously over 20 minutes. The pAg at this time was kept constant at 7.3. Further, pH = 8.8 with potassium bromide solution and acetic acid over 10 minutes.
3. After adjusting pAg to 9.0, solution C2 and solution E2 were simultaneously added over 50 minutes.

At this time, the flow rate ratio at the start of addition and the end of addition was 1:10, and the flow rate was increased with time.
Also, the pH was lowered from 8.83 to 8.00 in proportion to the flow rate ratio. Further, acetic acid was added to adjust the pH to 6.0.

After the completion of the addition, in order to remove excess salts, precipitation desalting was carried out using a demole (manufactured by Kao Atlas) aqueous solution and an aqueous magnesium sulfate solution, gelatin was added and redispersed, and pAg of 8. 55, pH
An emulsion of 5.85 was obtained.

The obtained emulsion was observed with an electron microscope. As a result, a cubic tetradecahedral single-sided monohedron having an average diameter of 0.45 μm, a distribution width of 16% and an average iodine content of 2.3 mol% was used. It was a dispersible core / shell emulsion. This is designated as Em-1.

(Preparation of Em-2) A monodisperse core / shell type emulsion was prepared using the seed emulsion-A and the solution shown below.

A3 ossein gelatin 95.40 g SA-1 (10% methanol solution) 3 ml 28% aqueous ammonia solution 897.6 ml 56% acetic acid aqueous solution 1356 ml Seed emulsion-A 4.577 mol Equivalent water 10200 ml B3 ossein gelatin 52. 8 g potassium bromide 109.8 g potassium iodide 65.4 g water 2640 ml C3 ossein gelatin 72 g potassium bromide 1821 g water 3600 ml D3 silver nitrate 224.4 g 28% ammonia solution 183 ml water 2640 ml E3 silver nitrate 2598 g 28% ammonia water (28 %) 2119 ml with water 4369.2 ml F3 1.75N aqueous potassium bromide solution G3 56% aqueous acetic acid solution SA-1: HO (CH ₂ CH ₂ ) _m (CH (CH ₃ ) CH ₂
O) ₁₇ (CH ₂ CH ₂ O) _n H (m + n≈5.7, molecular weight 1700) A2 solution stirred at a temperature of 60 ° C and stirred with a stirrer, B3 solution and D3 solution in a double jet method in 22 minutes Added.

After the addition of solutions B3 and D3 was completed, C3 was further added.
Solution and E3 solution were added by the double jet method in 42 minutes.

Here, solution B3 and solution D3 and solution C3 and solution E3
The addition rate of the liquid is changed in a function-like manner with respect to time so as to match the critical growth rate, and at an appropriate addition rate so as not to cause polydispersion due to generation of small particles other than growing seed crystals and Ostwald ripening. Was added.

Further, by using F3 liquid and G3 liquid,
The particle growth pAg was kept at 7.8 and the pH was kept at 7.

After the addition was completed, acetic acid was further added to adjust the pH to 6.
Adjusted to zero.

In order to remove excess salts, precipitation desalting was carried out using an aqueous solution of demole (described above) and an aqueous solution of magnesium sulfate, gelatin was added and redispersed, and pAg of 8.55 and pH of 5.85 were obtained at 40 ° C. An emulsion was obtained.

The obtained emulsion was observed under an electron microscope to find that it had a cubic shape with an average diameter of 0.45 μm, a distribution width of 15% and an average iodide content of 2.3 mol% and a slightly lacking corner.
It was a monohedral monodisperse core / shell type emulsion. This is Em
-2.

(Preparation of Em-3) In the preparation of Em-2, except that the amount of potassium iodide in the B3 solution was reduced, E
By the same preparation method as m-2, a cubic tetrahedral monodisperse core with an average diameter of 0.45 μm, a distribution width of 15%, and an average iodine content of 1.3 mol% with a slightly lacking corner is used. A shell type emulsion Em-3 was prepared.

(Preparation of Em-4) In the preparation of Em-2, Em- was used except that the amount of potassium iodide in the B3 solution was increased.
By the same preparation method as in 2, a cubic tetrahedral monodisperse core / shell type having an average diameter of 0.45 μm, a distribution width of 15%, and an average iodine content of 3.5 mol% with a slight lack of corners. Emulsion Em-4 was prepared.

(Preparation of tabular seed emulsion) Seed emulsion-B was prepared as follows.

A4 ossein gelatin 24.2 g water 9657 ml SA-2 (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B4 2.5N silver nitrate aqueous solution 2825 ml C4 potassium bromide 824 g potassium iodide 23 2.5 g with water 2825 ml D4 1.75N potassium bromide aqueous solution The following silver potential control amount at 35 ° C. Japanese Patent Publication Nos. 58-58288 and 58-5828.
Solution A4 was mixed with Solution B using the mixing stirrer shown in No. 9.
464.3 ml of each of 4 and solution C4 were added by the simultaneous mixing method over 2 minutes to perform nucleation.

After stopping the addition of solution B4 and solution C4, it took 60 minutes to raise the temperature of solution A4 to 60 ° C. and adjust the pH to 5.0 with a 3% aqueous potassium hydroxide solution. The solution B4 and the solution C4 were added again by the simultaneous mixing method at a flow rate of 55.4 ml / min for 42 minutes.
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during this temperature increase from 35 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B4 and C4 was measured using a solution D4. Controls were made to be +8 mV and +16 mV, respectively.

After the addition was completed, the pH was adjusted to 6 with a 3% aqueous solution of potassium hydroxide, and the mixture was immediately desalted and washed with water. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have an average thickness of 0.065 μm and an average diameter. It was found by an electron microscope that the (circle diameter conversion) was 0.52 μm.

SA-2: Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (Preparation of Em-5) (Preparation of fine grain silver iodide emulsion) 5.0% by weight containing 0.128 mol of potassium iodide. 5000 ml of gelatin solution
To the above, 1500 ml of an aqueous solution containing 5.24 mol of silver nitrate and 5.24 mol of potassium iodide, respectively, was added over 35 minutes. During this time, the temperature was kept at 40 ° C. The average particle size of the obtained silver iodide fine particles was 0.05 μm.

Using the seed emulsion-B and the following solution,
A tabular silver halide emulsion Em-5 was prepared.

A5 ossein gelatin 45.37 g SA-1 (10% methanol solution) 3 ml Seed emulsion-B 1.624 mol equivalent water 4200 ml B5 ossein gelatin 24.3 g potassium bromide 2309 g water 4850 ml C5 silver nitrate 3293 g water 5538 ml D5 fine grain silver iodide emulsion 0.18 mol equivalent E5 2.0N potassium bromide aqueous solution To solution A5 vigorously stirred at 60 ° C., solution B5, solution C5 and solution D5 were added over 90 minutes by the double jet method. .

Here, the addition rates of the B5 solution and the C5 solution were changed in a function-like manner with respect to time so as to correspond to the critical growth rate, and polydispersion was caused by the generation of small particles other than the growing seed crystal and Ostwald ripening. It was added at an appropriate addition rate so as not to become solid. The D5 solution, that is, the fine grain silver iodide emulsion was supplied at a rate (molar ratio) of C5 solution of 0. The particle size (addition time) was changed to 2, and the addition was completed when 4.6% of the total amount of the C5 liquid was added.

Further, by using the E5 solution, the pA for grain growth was increased.
g was kept at 9.15 throughout.

After completion of the addition, in order to remove excess salts, precipitation desalting was carried out using an aqueous solution of demole (described above) and an aqueous solution of magnesium sulfate, gelatin was added and redispersed, and pAg of 8.1 at 40 ° C. An emulsion having a pH of 5.85 was obtained.

When the obtained emulsion was observed with an electron microscope, a tabular silver halide having an average diameter of 1.04 μm, a distribution width of 20% and an average iodine content of 1 mol% and an average aspect ratio of 4.3. It was a particle. This is designated as Em-5.

(Preparation of Em-6) In the preparation of Em-5, Em- was used except that the amount of fine grain silver iodide emulsion B of D5 was increased.
5, a tabular silver halide emulsion Em-6 having an average diameter of 1.04 μm, a distribution width of 20%, an average iodine content of 1.5 mol% and an average aspect ratio of 4.1. Was prepared.

Example 2 The silver halide emulsions (Em-1) obtained in Example 1 to
After each of (Em-6) was brought to 55 ° C., stabilizer S
An appropriate amount of T-1 and a predetermined amount of spectral sensitizing dyes A and B (A:
(B = 100: 1 weight ratio) as a solid fine particle dispersion, and after 10 minutes, appropriate amounts of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added to start chemical ripening, and 40 minutes after that. The fine grain silver iodide emulsion to be added is (Em-1) to (Em-4) in an amount of 0.05 mol% per mol of silver halide, (Em-5) and (Em-6).
Was added for optimum chemical ripening, and then at the end of ripening, an appropriate amount of ST-1 was added for stabilization.

A solid fine particle dispersion of the spectral sensitizing dye was prepared by a method similar to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of the spectral sensitizing dye was previously
In addition to the temperature-controlled water, add 3 to the water with a high-speed stirrer (dissolver).
Obtained by stirring at 500 rpm for 30-120 minutes.

ST-1: 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene

[0144]

Embedded image

Next, the following additives were added to each chemically sensitized emulsion to prepare a photosensitive silver halide emulsion coating solution.

Additives are as follows, and the addition amount is shown as an amount per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butyl-catechol 70 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.0 g Nitrophenyl-triphenyl Phosphonium chloride 5 mg 2-anilino-4,6-dimercaptotriazine 10 mg 1,3-dihydroxybenzene-4-sulfonic acid ammonium 2 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1- Phenyl-5-mercaptotetrazole 8 mg 2-Mercaptobenzimidazole-5-sodium sulfonate 8 mg

[0148]

Embedded image

At the same time, a protective layer coating solution was also prepared.

The additives used in the protective layer liquid are as follows, and the amount of addition is shown per 1 liter of coating liquid.

Protective layer coating liquid Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g SA-3 1 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide (matting having an area average particle size of 1.2 μm) Agent) 0.5 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 250 mg C ₄ F ₉ SO ₃ K 2 mg Glyoxal 40% aqueous solution (hardener) 5.0 ml SA-3: Sodium-i- Amyl-decyl sulfosuccinate

[0152]

Embedded image

The obtained emulsion coating solution and protective layer coating solution were
Emulsion 2 shown in Table 1 was applied to a blue-tinted undercoated polyethylene terephthalate film base having a thickness of 175 μm, which was previously coated with the following back layer on the side opposite to the emulsion layer.
Amount of silver 4.2 g / m ² in the layer (upper layer 2.1 g / m ^2, the lower layer is ^{2.1g / m 2), 3.8g /} m 2 as the amount with gelatin emulsion coating solution, the protective film 1.15 for gelatin
Using a slide hopper type coater so as to obtain g / m ² , simultaneous coating was performed on the support at a speed of 80 m / min to prepare samples 1 to 4 shown in Table 1.

The additives used in the back layer are as follows, and the additives are shown in the amount per liter of the coating liquid. The gelatin content of the back layer was 5 g / m ² .

68 g of lime-processed inert gelatin

[0156]

Embedded image

[0157]

Embedded image

Polymethylmethacrylate (matting agent having an area average particle size of 5 μm) 1.1 g Silicon dioxide (matting agent having an area average particle size of 1.2 μm) 0.5 g Formalin 37% aqueous solution (hardening agent) 0.9 ml Glyoxal 40 % Aqueous solution (hardening agent) 0.9 ml sodium chloride 0.1 mg In the obtained samples 1 to 5, the X-ray generator MGU-10C was used.
(Toshiba), tube voltage 28kVp, tube current 100
mA, 0.5 seconds through acrylic wedge, M-100
Exposure was performed by irradiating X-rays through a screen (manufactured by Konica).

Next, an automatic processor (manufactured by Konica Corporation: SRX)
-502) was used and processed with the developer and fixer having the following formulations.

Developer formulation Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriaminepentaacetic acid 120 g Sodium hydrogen carbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5-mercapto Tetrazole 0.2 g Hydroquinone 340 g Add water to finish to 5000 ml Part-B (for finishing 12 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter glacial acetic acid 120 g Bromide added potassium 225g water finish 1 liter fixer formulation Part-a (for 18 l finish) ammonium thiosulfate (70wt / vol%) 6000g sulfite isocyanatomethyl Um 110 g Sodium acetate trihydrate 450 g Sodium oxalate 50 g Gluconic acid 70 g 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B (for 18 liter finish) Aluminum sulfate 800 g Developer solution Preparation is Part A, Par in about 5 liters of water
tB was added at the same time, water was added while stirring and dissolved to make 12 liters, and the pH was adjusted to 10.40 with glacial acetic acid.
This is used as a development replenisher. To 1 liter of this development replenisher, 20 ml / liter of the starter was added, and p
The H is adjusted to 10.26 and used.

The fixing solution was prepared by adding Part A to about 5 liters of water.
Part B is added simultaneously, and water is added while stirring and dissolving 1
Finish to 8 liters, adjust the pH to 4.4 with sulfuric acid and sodium hydroxide, and use this as the fixing replenisher.

The processing temperature is 35 ° C. for development and 33 for fixing.
℃, water wash 20 ℃, dry 50 ℃, treatment time is dry t
o dry is 90 seconds.

32 ° C., dry to dry 3 minutes 3
The treatment variability was evaluated by comparing the performance with the sample treated at 0 seconds and treated at 35 ° C.

The sensitivity and contrast of each sample obtained by the development processing were evaluated.

Sensitivity is expressed as the reciprocal of the amount of exposure that gives a density of fog +1.0. Sample 1 processed at a developer temperature of 35.degree.
The sensitivity is shown as relative sensitivity when the sensitivity is set to 100. Further, the contrast represents a slope from the minimum density +0.25 to the minimum density +2.0 in the characteristic curve.

Further, the pressure mark (roller mark) by the roller of the automatic processor was also evaluated. The evaluation was carried out by the same processing method as in the case of the sensitivity evaluation (sensitometry), except that uniform exposure was performed so that the blackened density after processing was 0.8 to 1.2. At that time, the generated roller marks were visually classified into the following five grades and evaluated.

5: No generation of roller marks 4: Very slight occurrence 3: Some occurrence (practical possible) 2: Many occurrences (impractical) 1: Very many occurrences The results are shown in Table 1. . The main characteristic values of each emulsion are also shown in Table 1.

[0168]

[Table 1]

As is clear from Table 1, the samples of the present invention are excellent in pressure resistance in spite of the high contrast and show little fluctuation in sensitivity and contrast even when the processing temperature changes.
It can be seen that the processing variability is also reduced.

Example 3 Upper emulsion Em-2 of the photosensitive layer of Sample 3 in Example 2
(Average iodide content 2.3 mol%) was chemically sensitized in Example 2 to Em-3 (average iodide content 1.3 mol%).
Sample 5 was prepared in the same manner as Sample 3 except that the sample was replaced with.

Using Samples 3 and 5, the process variability and pressure mark were evaluated in the same manner as in Example 2. The results are shown in Table 2.

The sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog + 1.0, and is represented by the relative sensitivity when the sensitivity of Sample 3 processed at a developer temperature of 35 ° C. is 100.

[0173]

[Table 2]

As is clear from Table 2, Sample 3 in which the average iodide content of the upper emulsion was higher than the average iodide content of the lower emulsion of the photosensitive layer, the sample 3 was superior in pressure resistance despite the high contrast. It can be seen that even if the processing temperature changes, the fluctuation of the contrast is small and the processing fluctuation is also small.

[0175]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material for X-ray, which is excellent in pressure resistance and has improved processing variability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 1/46 G03C 1/46

Claims (4)

[Claims] 1. In a silver halide photographic light-sensitive material having two or more light-sensitive silver halide emulsion layers on only one side of a support, the silver halide grains in the light-sensitive layer farthest from the support are ammoniacal. PH 7.5 using silver nitrate aqueous solution
A silver halide photographic light-sensitive material, which is a silver halide grain grown by ˜2.0, and has lower sensitivity than silver halide grains contained in an adjacent lower layer. 2. The average iodide content of silver halide grains in the photosensitive layer farthest from the support is at least 0.1 mol more than the average iodide content of silver halide grains in the adjacent lower photosensitive layer. % Or more and 3 to 0.5 mol%, and the silver halide photographic light-sensitive material according to claim 1. 3. The silver halide grain of the photosensitive layer farthest from the support is a monodisperse core / shell type grain having a core portion having an average iodine content of 5 mol% or more inside the grain. A silver halide photographic light-sensitive material according to claim 1 or 2. 4. The silver halide grain in the photosensitive layer closest to the support is a tabular silver halide grain having an average aspect ratio of 2 or more and less than 10, and the silver halide grain has an average iodide content. Is less than 2 mol% and the silver halide grains have the highest sensitivity.
4. The silver halide photographic light-sensitive material according to any one of items 3.