JPH0980662A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material improved in processing fluctuating property. SOLUTION: In a silver halide photographic sensitive material having two or more photosensitive silver halide emulsion layers only on one side of a base, the silver halide grain of the photosensitive layer farthest from the base is formed of a monodispersing core/shell type grain having an average iodide content ratio on the top surface of 0.2 mole % or more and 7 mole % or less which is smaller than that of the silver halide grain in the adjacent lower layer, and this silver halide grain is less sensitive than the silver halide grain in the adjacent lower layer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, demands for higher sensitivity, higher image quality and stability of photographic performance over time for silver halide photographic light-sensitive materials have become more and more strict, and various improved techniques have been investigated centering on silver halide emulsions. Came.

Further, in the development process of silver halide photographic light-sensitive materials, high temperature processing has rapidly spread, and the processing time has been shortened even in the automatic development processing of various light-sensitive materials.
In terms of stability of photographic performance in a silver halide photographic light-sensitive material with high contrast, gradation is important for reproducing an image, and stability against processing fluctuations such as no gradation fluctuation during each development processing. Is desired.

With respect to such processing fluctuation, improvement of the processing liquid has been conventionally studied in order to improve the processing stability, but it cannot be said to be 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. However, the improvement is still inadequate, and there has been a demand for the development of a better technique that does not cause gradation fluctuation due to processing fluctuation.

[0005]

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

[0006]

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 have an average of the outermost surface. Monodisperse core / shell type grains having an iodine content lower than that of the adjacent lower silver halide grains and having an average iodine content of the outermost surface of 0.2 mol% or more and 7 mol% or less, A silver halide photographic light-sensitive material characterized in that the silver halide grains have lower sensitivity than the adjacent lower silver halide grains.

2) The silver halide grain of the uppermost layer is a monodisperse core / shell type grain having a core portion having an average iodine content of 5 mol% or more inside the grain. Silver halide photographic light-sensitive material.

3) 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 of 2 mol%. And the silver halide grains have the highest sensitivity.

The present invention will be described in more detail below.

The monodisperse core / shell type silver halide grains in the present invention may be cubic grains, tetradecahedral grains and octahedral grains, or may be spherical grains or twin grains. Among the twinned grains, twinned grains having an aspect ratio of less than 2 are preferable.

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

In the present invention, the monodisperse silver halide grains mean that the weight of silver halide contained within a grain size range of ± 20% around the average grain size d is 60% of the total weight of silver halide.
The above is mentioned, and preferably 70% or more, more preferably 80% or more.

Here, the average particle size d is defined as the particle size di when the product ni × di ³ of the frequency ni and di ^{3 of} particles having the particle size di becomes maximum. (3 significant digits, rounding down to the least significant digit 4) The grain size referred to here is the diameter of spherical silver halide grains, and the projection of grains having a shape other than spherical. It is the diameter when the image is converted into a circular image of the same area.

The particle size can be obtained, for example, by magnifying the particles with an electron microscope from 10,000 times to 50,000 times, and measuring the particle diameter on the print or the area at the time of photographing. (It is assumed that the number of measured grains is 1000 or more indiscriminately.) Particularly preferred highly monodispersed grains such as monodispersed core / shell type silver halide grains which can be used in the present invention have a broad distribution. Is not more than 20%, and more preferably not more than 15%.

The monodisperse core / shell type silver halide grain used in the present invention comprises a silver halide grain having a grain structure composed of two or more layers having different silver iodide contents. , A particle composed of a core (inner layer) and a shell covering the core, and the shell is formed by one or more layers. The iodine content of the core and the shell are preferably different from each other, and it is particularly preferable that the iodine content of the core is maximized.

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

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

The iodine distribution of the core is usually uniform,
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 of the present invention are prepared by allowing a reaction vessel to contain an aqueous solution containing a protective colloid and seed grains in advance and, if necessary, silver ions, halogen ions or silver halide fine grains. Is preferably supplied to cause the seed particles to grow crystals. 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,
Any of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, silver chloroiodide, and silver iodide may be used.

In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (E
Electron Probe Micro Analysis
zer method). According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, an electron beam is irradiated, and X-ray analysis by electron beam excitation is performed. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the silver halide composition of each grain can be determined. If the silver iodide content of at least 50 grains is determined by the EPMA method,
From these averages, the average silver iodide content is determined.

In the present invention, the halogen composition distribution inside the silver halide grain is obtained by pretreating the grain into an ultrathin section and then observing and analyzing with a transmission electron microscope while cooling. Specifically, silver halide grains are taken out of the emulsion, embedded in a resin, and cut with a diamond knife to produce a 60-nm-thick section. This section can be obtained by observation and point analysis with a transmission electron microscope equipped with an energy dispersive X-ray analyzer while cooling the section with liquid nitrogen, and by quantitative calculation (Inoue, Nagasawa: Photographic Society of Japan, 1987) Conference Abstracts p. 62).

In the present invention, the silver iodide content on the outermost surface of silver halide grains means the XPS method (X-ray Pho).
toelectron Spectroscopy: X
It refers to the silver iodide content of a portion up to a depth of 50Å analyzed by line photoelectron spectroscopy, and can be determined as follows.

The sample was cooled to -110 ° C. or lower in an ultrahigh vacuum of 1 × 10 ^-8 torr or less, and MgKα was used as an X-ray for a probe, an X-ray source voltage of 15 kv and an X-ray source current of 40 mA.
And the Ag3d5 / 2, Br3d, and I3d3 / 2 electrons are measured. 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 the destruction of the sample (the decomposition of silver halide and the diffusion of halide (particularly iodine)) by the X-ray irradiation at room temperature, and to improve the measurement accuracy. By cooling to −110 ° C., sample destruction can be suppressed to a level that does not hinder measurement.

The average iodine content of the outermost surface of the monodisperse core / shell type silver halide grains used in the uppermost layer of the present invention is at least more than the average iodine content of the outermost surface of the adjacent lower silver halide grains. The amount is preferably 0.5 mol% or less, more preferably 0.2 mol% or more and 7 mol% or less, and further preferably 0.5 mol% or more and 7 mol% or less.

The average iodine content of the monodisperse core / shell type silver halide grains used in the uppermost layer of the present invention is 0.1 mol% based on the average iodine content of the adjacent silver halide grains in the lower layer. The amount is preferably more than the above, and more preferably 0.3 mol% or more.

The tabular silver halide grains preferably used in the photosensitive layer closest to the support of the present invention preferably have two twin planes parallel to each other.

The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide photographic emulsion is applied so that the silver halide grains contained therein are oriented on a support to prepare a sample.
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 the tabular silver halide emulsion of the present invention, a method of precipitating silver halide on a seed crystal is preferably used.

A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified by Klein and Moiser in the article Photographiesche Correspondents. [Photographishe
Korespondenz] Vol. 99, pp. 99, pp. 100
Vol., P. 57.

The tabular silver halide grain of the present invention 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), and a diameter corresponding to a circle of a projected area of the tabular silver halide grains (a diameter of a circle having the same projected area as the silver halide grains). ), And the thickness means the distance between two parallel principal planes forming a tabular silver halide grain.

The average aspect ratio of the tabular silver halide grains of the present invention is 2 or more and less than 10, but preferably 2.0 or more and 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. .

The average grain size of the tabular silver halide grains of the present invention is preferably 0.15 to 5.0 μm,
The thickness is more preferably from 4 to 3.0 μm, most preferably from 0.4 to 2.0 μm.

The tabular silver halide grains of the present invention preferably have an average thickness of 0.15 to 0.3 μm, and the grain size and the thickness are optimized to optimize the sensitivity and other photographic characteristics. can do. Optimum particle size and optimum depending on other factors constituting the photosensitive material (sensitivity of hydrophilic colloid layer, hardness, chemical ripening conditions, sensitivity of photosensitive material, amount of silver coating, etc.) that affect sensitivity and other photographic characteristics The thickness is different.

In the tabular silver halide grains of the present invention, 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 preferably less than 2 mol% and more preferably 0.5 mol% or more and less than 2 mol% as the average silver iodide content in the entire silver halide grains.

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 iodine content between grains was measured by the EPMA method, the relative standard deviation was 3
It is preferably at most 5%, more preferably at most 20%.

In the present invention, the tabular silver halide grains 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. It is also preferred that it be present on the outermost surface.

The average iodine content of the outermost surface of the tabular silver halide used in the present invention is 2 mol% or more and 15 mol% or more.
Or less, more preferably 3 mol% or more and 12 mol% or less.

The tabular silver halide grains of the present invention may have dislocations. Dislocations are described in F. Hamilt
on, Photo. Sci. Eng, 57 (1967)
And T. Shiozawa, J .; Soc. Photo. S
ci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time,
The thicker the particles, the more difficult it is for the electron beam to pass,
High-pressure type (200 kv for particles of 0.25 μm thickness)
It is possible to observe more clearly by using the above electron microscope.

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

The tabular silver halide grains of the present invention 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, it is preferably 25% or less, more preferably 20%. These are:

To obtain the tabular silver halide grains and monodisperse core / shell type silver halide grains of the present invention, the conditions under which the produced seed grains are enlarged are as follows:
-39027, 55-142329, 58-1
Nos. 13928, 54-48521 and 58-49
As also seen in No. 938, a water-soluble silver salt solution and a water-soluble halide solution are added by the double jet method, and the addition rate is within a range where new nucleation does not occur according to the enlargement of particles and Ostwald ripening does not occur. It is possible to change gradually. 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.

For growth, an aqueous solution of silver nitrate and an aqueous solution of halide can be added by double jet, but the iodide can be supplied to the system as silver iodide. The addition rate is preferably such that no new nuclei are generated and at a rate such that the size distribution does not spread due to Ostwald ripening, that is, 30 to 100% of the rate at which new nuclei are generated.

In producing the silver halide emulsion of the present invention, stirring conditions during production are extremely important. As the stirrer, an apparatus described in JP-A-62-160128, in which an additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer, is particularly preferably used. In this case, the rotation speed of the stirring is preferably set to 100 to 1200 rpm.

In preparing the emulsion of the present invention, 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.

The silver halide grains of the present invention may be so-called halogen conversion type grains. The halogen conversion amount is from 0.2 mol% to the silver amount.
It is preferably 0.5 mol%, and the conversion may be performed during physical ripening or after completion of physical ripening.

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

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 to the end of the solution preparation step immediately before the coating of the silver halide emulsion. Although it can be selected in the meantime, it is preferable to adjust it by the end of the chemical ripening step. The chemical ripening step referred to here is a point in time when physical ripening and desalting of the silver halide emulsion of the present invention are completed, when a chemical sensitizer is added, and thereafter, an operation for stopping chemical ripening is performed. Up 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 of the present invention at the time of adding fine silver halide grains is preferably in the range of 30 to 80 ° C, and particularly preferably in the range of 40 to 65 ° C. Further, the present invention is preferably carried out under the condition that part or all of the silver halide fine grains to be added disappears immediately before coating immediately after the addition, more preferably 20% of the added silver halide fine grains. The above is the disappearance immediately before the application.

In the present invention, it is also preferable to add a silver halide solvent before the desalting step in order to accelerate the developing rate. For example, a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is added in an amount of 1 × 10 ⁻³ mol or more and 3 × 10 ³ mol / mol of silver.
It is preferable to add ^-2 mol or less.

In the present invention, it is preferable to use gelatin as the dispersion medium for the protective colloid of silver halide grains, and as the gelatin, alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (having a molecular weight of 1,000 to 5) is used.
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used. Specifically, Research Disclosure (Resea)
rc Disclosure. RD)
76 volume No. 17643 (December 1978).

In the production of the silver halide grains of the present invention, unnecessary soluble salts may be removed during the growth of the silver halide grains, or they may remain contained. When removing the salts, see RD Vol. 17643
The method can be carried out based on the method described in section II.

Further, the silver halide grains of the present invention are provided with a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (a complex salt) in the process of forming and / or growing the grain. At least one metal ion selected from the group consisting of a metal salt) and an iron salt (including a complex salt) can be added to allow these metal elements to be contained inside the particle and / or in the surface layer of the particle. By placing in an atmosphere, reduction sensitizing nuclei can be provided inside the grain and / or on the grain surface.

Further, the action of the reducing agent added at a desired time of particle formation is to add an oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxo acid salt, ozone and I ₂ at a desired time. It is preferable to deactivate the reducing agent and suppress or stop the reducing agent.

The oxidizing agent may be added at any time from when the silver halide grains are formed until before the addition of the gold sensitizer in the chemical sensitization step (or when the gold sensitizer is not used, the chemical sensitizer). is there.

In the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may remain contained. In the case of removing the salts, the above-mentioned RD Vol. 1
It can be performed based on the method described in Section II of 7643.

The silver halide grains of the present invention can be chemically sensitized. Chemical ripening or chemical sensitization process conditions,
For example, the pH, pAg, temperature, time and the like are not particularly limited, and the reaction can be performed under conditions generally performed in the art. For chemical sensitization, sulfur sensitization using a compound containing sulfur that can react with silver ions or active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, using a reducing substance A reduction sensitization method, a gold or other noble metal sensitization method using a noble metal, or the like can be used alone or in combination.

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

The temperature of chemical ripening using a selenium sensitizer is 4
The range is preferably from 0 to 90 ° C, more preferably from 45 ° C to 80 ° C. The pH is 4-9 and the pAg is 6
The range of -9.5 is preferable.

The technique for using the tellurium sensitizer is similar to that for 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 and ascorbic acid and their derivatives. Other preferred 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,
It is preferable to change the pH according to environmental conditions such as pH and pAg, but in the case of thiourea dioxide, for example, as a rough guide, about 0.01 to 2 mg per mol of silver halide is used.
Is used with good results. 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 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 (here, pAg
The value is the reciprocal of Ag + ion concentration).

Silver nitrate is preferred as the water-soluble silver salt. So-called silver ripening, which is one of reduction sensitization techniques, is performed by adding a water-soluble silver salt. 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 in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

As these dyes, any of the nuclei usually used can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenin nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye includes pyrazoline- as a nucleus having a ketomethine structure.
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, a substituted aminostilbene compound which is a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
33,390, 3,635,721), aromatic organic acid formaldehyde condensate (for example, also described in US Pat. No. 3,743,510), cadmium salt, azaindene compound, etc. Good.

US Pat. Nos. 3,615,613 and 3,6
No. 15,641, No. 3,617,295, No. 3,63
The combinations described in No. 5,721 and the like are particularly useful. The sensitizing dye may be added during or during each step of nucleation, growth, desalting, and chemical sensitization, or after chemical sensitization.

In order to make the photographic light-sensitive material of the present invention suitable for rapid processing, an appropriate amount of a hardener is added in advance in the step of applying the light-sensitive material to adjust the water swelling rate in the developing-fixing-washing step. By doing so, it is preferable to reduce the water content in the light-sensitive material before the start of drying.

The silver halide light-sensitive material of the present invention preferably has a swelling ratio of 150 to 250% during the development processing and a film thickness after expansion of 70 μm or less. Water swelling rate is 250%
If it exceeds the above range, poor drying occurs, and, for example, defective transport occurs in automatic processor processing, especially in rapid processing.

If the water swelling ratio is less than 150%, uneven development or residual color tends to increase during development. The water swelling ratio as referred to herein means the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, and this is divided by the film thickness before processing and multiplied by 100. .

In the present invention, powder processing agents, tablets, pills,
Solid processing agents such as granules may be used, and those subjected to moisture-proof treatment as needed may be used. .

The powder used in the present invention refers to an aggregate of fine crystal grains. The term “granules” as used in the present invention refers to granules having a particle diameter of 50 to 5000 μm, which are obtained by adding a granulation step to powder. The tablet referred to in the present invention refers to a tablet obtained by compressing powder or granules into a certain shape.

The solid processing agent is used as a photographic processing agent such as a developing agent, a fixing agent and a rinsing agent, and it is the developing agent that is particularly effective in stabilizing photographic performance.

In addition to the dihydroxybenzenes, aminophenols and pyrazolidones, reductones are preferably used as the developing agent in the developer. Of the pyrazolidones used, those substituted at the 4-position (dimesone, dimeson S, etc.) are particularly preferable because they have low water solubility and little change with time.

As a preservative, an organic reducing agent can be used as a preservative in addition to sulfite. In addition, a chelating agent or a bisulfite adduct of a hardening agent can be used. It is also preferable to add a silver sludge inhibitor. It is also preferable to add a cyclodextrin compound.
The compounds described in No. 4853 are particularly preferred.

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 for 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 (borate), potassium tetraborate, o-hydroxybenzoic acid Sodium (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like. Can be mentioned.

As the development accelerator, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrozine If desired, compounds, mesoionic compounds, ionic compounds, imidazoles, etc. can be added.

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, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be exemplified by 1-phenyl-5-mercaptotetrazole as a typical example.

Further, in the developer composition, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, and other compounds described in JP-B-47-33378 and 44-95009 are used as a developing agent. Can be used as an organic solvent for increasing the solubility of

Further, various additives such as stain inhibitors, sludge inhibitors, and stacking 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-
Those described in page 4) can be used.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

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

Generally, in a developing solution used for developing a black-and-white photographic light-sensitive material, hydroquinones are used as a developing agent in many cases. However, the present invention improves work safety and protects the environment. From this viewpoint, 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 photographic light-sensitive material of the present invention is 3
~ 90 seconds, more preferably 5 to 60 seconds, and the processing time is 15 to 210 seconds in terms of Dry to Dry, and more preferably 15 to 90 seconds.

In the silver halide photographic light-sensitive material of the present invention, various additives can be further added to the silver halide emulsion according to the purpose. Examples of additives and the like used include RD-17643 (December 1978) and RD 1871.
6 (November 1979) and 308119 (1989).
December, 2012). The places where they are written are listed below.

Additives RD-17643 RD-18716 RD-308119 Page classification Page classification Page classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic Agent 27 XII 650 Right 1006-7 XIII 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 For use in the silver halide photographic light-sensitive material of the present invention The Kill support, for example 2 of the aforementioned RD-17643
8 and RD-308119, 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.

[0097]

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 l B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml water 2.6 l C1 ossein gelatin 75 g Potassium bromide 950 g Potassium iodide 27 g Water 3.0 l D1 Silver nitrate 95 g Water 2.7 l E1 Silver nitrate 1410 g Water 3.2 l To liquid A1 kept at 60 ° C in the reaction kettle, control liquid B1 and liquid D1 Method, the solution was added over 30 minutes, and then the C1 and E1 solutions were added by the control double jet method over 105 minutes. Stirring is 5
It was carried out at 00 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 was not widened. At the time of adding the silver ion solution and the halide ion solution, the pAg was adjusted to 8.3 ± 0.05 using a potassium bromide solution, and the pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the completion of the addition, the pH was adjusted to 6.0, and then in order to remove 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 distribution of 17% with slightly rounded corners.

Preparation of Em-1 Monodisperse core / shell type emulsions were prepared using seed emulsion-A and the following 5 solutions.

A2 ossein gelatin 10.4 g Ammonia water (28%) 28.3 ml 56% Acetic acid aqueous 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 potassium iodide 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 ammonia water (28%) 13.9 ml water 191 ml E2 silver nitrate 120.1 g ammonia water (28 %) The 217 ml A2 solution was kept warm at 40 ° C. with 94.3 ml water and stirred at 800 rpm with a stirrer. The pH of the A2 solution was adjusted to 9.90 with acetic acid,
Seed emulsion-A was collected and dispersed and suspended, and then D2 solution was added at a constant rate for 7 minutes to adjust pAg to 7.3. Further, B
Solution 2 and solution D2 were added simultaneously over 20 minutes. At this time, the pAg was kept constant at 7.3. PH = 8.83, pAg using potassium bromide solution and acetic acid over 10 minutes
After adjusting to = 9.0, the C2 solution and the E2 solution were simultaneously added over 50 minutes.

At this time, the flow rate ratio at the start of addition and at 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 completion of the addition, in order to remove excess salts, precipitation desalting was carried out using an aqueous solution of demole (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate, gelatin was added and redispersed, and pAg 8.5 at 40 ° C. was obtained. , PH 5.8
An emulsion of 5 was obtained.

When the obtained emulsion was observed with an electron microscope, it had a cubic shape with an average diameter of 0.45 μm, a distribution width of 15%, and an average iodine content of 2.3 mol%, which had a slightly rounded corner.
A tetrahedral monodisperse core / shell emulsion was obtained.

Preparation of Em-2 A monodisperse emulsion having a uniform iodine composition was prepared by using seed emulsion-A and the following three kinds of solutions.

A3 ossein gelatin 10.4 g ammonia water (28%) 28.3 ml 56% acetic acid aqueous solution 4.2 ml Seed emulsion-A 0.216 mol equivalent Water 700 ml B3 ossein gelatin 3.7 g potassium bromide 90. 9 g potassium iodide 3.09 g water 184 ml C3 silver nitrate 133.2 g ammonia water (28%) 104.3 ml water 224 ml A3 solution was kept at 40 ° C. and stirred at 800 rpm with a stirrer. The pH of the A3 solution was adjusted to 9.0 with acetic acid, the seed emulsion-A was collected and dispersed and suspended, and then the pAg = 9.0 was adjusted using a potassium bromide solution, and then the B3 solution and the C solution were used.
Solution 3 was added simultaneously over 50 minutes. Meanwhile, pAg was maintained at 9.0 with a potassium bromide solution.

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 9.0 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 8.5 was obtained at 40 ° C. , PH 5.8
An emulsion of 5 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 of 15%, a uniform iodine composition and an average iodine content of 2.3 mol%, and a slightly rounded corner. A monohedral monodisperse emulsion was obtained.

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

A4 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml KBr 10.8 g 10% nitric acid 114 ml B4 2.5N AgNO3 aqueous solution 2825 ml C4 KBr 824 g KI 23.5 g with water 2825 ml D4 1.75N KBr aqueous solution The following silver potential control amount at 35 ° C. Japanese Patent Publication Nos. 58-58288 and 58-5828
Nucleation was performed by adding 464.3 ml of each of solution B4 and solution C4 to solution A4 by the simultaneous mixing method over 2 minutes using a mixing stirrer shown in No. 9 specification.

After stopping the addition of the solutions B4 and C4, it took 60 minutes to raise the temperature of the solution A4 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then re-solution. B4 and solution C4 were each mixed at 55.4 by simultaneous mixing method.
It was added at a flow rate of 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 the temperature increase from 35 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B4 and C4 was + performed using the solution D4.
It was controlled to be 8 mv and +16 mv.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The average thickness of the hexagonal tabular grains is 0.065 μm, and the average diameter is 0.065 μm. (Circle diameter conversion)
Was found to be 0.52 μm by an electron microscope.

Preparation of Em-3 (Preparation of fine grain silver iodide emulsion) 5000 ml of a 5.0% by weight gelatin solution containing 0.128 mol of potassium iodide.
1,500 ml of an aqueous solution containing 5.24 mol of silver nitrate and 5.24 mol of potassium iodide were 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 seed emulsion B and the following four solutions,
A tabular silver halide emulsion Em-3 was prepared.

[0121] A5 ossein gelatin _{45.37g 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) (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 A5 solution stirred vigorously at 60 ° C., B5 solution, C5 solution and D solution
Solution 5 was added by the double jet method in 90 minutes.

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 be commensurate with the critical growth rate, and a large number of small particles other than the growing seed crystal were generated and Ostwald ripening was used to increase the rate. It was added at an appropriate addition rate so as not to disperse. The D5 solution, that is, the fine grain silver iodide emulsion was supplied at a rate (molar ratio) of 0.2 with respect to the C5 solution, which was changed with respect to the particle size (addition time), so that the total amount of the C5 solution used was 4.6. The addition was completed at the time of addition.

By using the E5 solution, the pAg of grain growth was kept at 9.15.

After the addition was completed, in order to remove excess salts, precipitation desalting was carried out using an aqueous solution of demole (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate, gelatin was added and redispersed, and pAg of 8.1 at 40 ° C was obtained. , PH 5.8
An emulsion of 5 was obtained.

The obtained emulsion was observed by an electron microscope to find tabular silver halide grains having an average diameter of 1.04 μm, a distribution width of 20%, an average iodine content of 1 mol% and an average aspect ratio of 4.3. there were.

Example 2 The silver halide emulsions (Em-1) obtained in Example 1 to
After each of (Em-3) was heated to 55 ° C., an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 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 are added to start chemical ripening, and 40 minutes after that. After changing the fine grain silver iodide emulsion to be added later as shown in Table 1 and performing optimum chemical ripening,
4-hydroxy-6-methyl-1,3,3 at the end of aging
Stabilization was performed by adding an appropriate amount of a, 7-tetrazaindene.

[0127]

Embedded image

A solid fine particle dispersion of a spectral sensitizing dye was prepared by a method according to the method described in JP-A-5-297496.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature was adjusted to 27 ° C. in advance, and a high-speed stirrer (dissolver) was used for 3500.
Obtained by stirring at rpm for 30-120 minutes.

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 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 15 mg 2-Mercaptobenzimidazole-5-sodium sulfonate 8 mg

[0132]

Embedded image

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

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

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide (area average particle size) Matting agent of 1.2 μm) 0.5 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) 250 mg C ₄ F ₉ SO ₃ K 2 mg Glyoxal 40% aqueous solution (hardening agent) 5.0 ml

[0136]

Embedded image

The obtained emulsion coating solution and protective layer coating solution were
The following back layer was previously coated on the opposite side of the emulsion layer, and a blue-colored 175 μm-thick undercoated polyethylene terephthalate film base was used. In the emulsion 2 layers shown in Table 1, the silver amount was 4.0 g / m ² (Upper and lower layers are 2.0 g each
/ M ² ), and the amount of gelatin in the emulsion coating solution is 3.8.
g / m ² , using a slide hopper type coater so that the gelatin of the protective film is 1.15 g / m ² , 8 per minute
Simultaneous coating was performed on the support at a speed of 0 m to prepare samples 1 to 5 shown in Table 1.

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

68 g of lime-treated inert gelatin

[0140]

Embedded image

[0141]

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 (hardener) 0.9 ml sodium chloride 0.1 g Obtained sample No. 1 to 5 using an X-ray generator MGU-10C manufactured by Toshiba Corp., tube voltage 28 KV, 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 Corporation).

Next, an automatic processor (manufactured by Konica Corporation. SR
X-502) was used to treat with a developer and a fixer having the following formulations.

Developer Formulation Part-A (for 12 l finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriamine pentaacetic acid 120 g Sodium bicarbonate 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 12 l finishing) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter glacial acetic acid 120 g Potassium bromide Add 225 g water to make 1.0 l.

Fixer Formulation Part-A (for 18 l finishing) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethylamino) -Ethyl-5-mercaptotetrazole 18g Part-B (for 18l finishing) Aluminum sulphate 800g To prepare the developer, add Part A and Part B simultaneously to about 5l of water, add water while stirring and dissolve, and add 12l to finish pH with glacial acetic acid. Was adjusted to 10.40. This is used as a development replenisher.

20 ml / l of the aforesaid starter was added to 1 liter of this development replenisher to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part A and P to about 5 liters of water.
artB was added at the same time, and water was added while stirring and dissolving.
and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This is used as a fixing replenisher.

The processing temperature is 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing, 50 ° C. for drying, and the processing time is dry.
90 seconds for to dry.

Further, the development processing temperature is set to 32 ° C., and the dry
The processing variability was evaluated by comparing the performance with a sample processed at a development processing temperature of 35 ° C. after processing for 3 minutes and 30 seconds with to dry.

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

Sensitivity is expressed as the reciprocal of the amount of light exposure that gives a density of fog +1.0, and the sensitivity of sample N processed at a developer temperature of 35 ° C.
o. The relative sensitivity is shown when the sensitivity of 1 is 100.

The contrast represents the slope from the minimum density +0.25 to the minimum density +2.0 in the characteristic curve.

The results are shown in Table 1. The main characteristic values of the obtained emulsions are also shown in Table 1.

[0154]

[Table 1]

As is clear from Table 1, the samples of the present invention are:
Even if the processing temperature changes despite the high contrast,
It can be seen that there is little variation in sensitivity and contrast, and processing variability is excellent.

[0156]

According to the present invention, a silver halide photographic light-sensitive material having improved processing variability is obtained.

Claims (3)

[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 have an average of the outermost surface. Monodisperse core / shell type grains having an iodine content lower than that of the adjacent lower silver halide grains and having an average iodine content of the outermost surface of 0.2 mol% or more and 7 mol% or less, A silver halide photographic light-sensitive material characterized in that the silver halide grains have lower sensitivity than the adjacent lower silver halide grains. 2. The silver halide grain of the uppermost layer is a monodisperse core / shell type grain having a core portion having an average iodine content of 5 mol% or more inside the grain. Silver halide photographic light-sensitive material. 3. 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 of 2 mol%. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide grain is less than 1, and the silver halide grain has the highest sensitivity.