JP3531020B2 - Silver halide photographic material and processing method thereof - Google Patents

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 a processing method thereof, and more particularly to a silver halide photographic light-sensitive material exhibiting more excellent processing variability (stability) and a processing method thereof.

BACKGROUND OF THE INVENTION 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 centered on silver halide emulsions have been developed. Has been considered.

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, the gradation is particularly important for reproducing an image, and it is desired that gradation does not change for each development process.

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, Japanese Patent Laid-Open No. 2-110542 discloses that
It has been disclosed that by mixing a tabular silver halide emulsion and a normal crystal core / shell type silver halide emulsion in the same layer, gradation fluctuation due to processing fluctuation is improved.
The technique is still insufficient, and under the present circumstances, there is a demand for the development of a technique which is superior in processing variability (stability) and is free from gradation variation.

[Object of the Invention] The object of the present invention has been made in view of the above circumstances. The object of the present invention is to improve the processing variability and to prevent the gradation variation of silver halide photographic light-sensitive materials and It is to provide a method of processing the light-sensitive material.

[Configuration of Invention] The above object of the present invention has been achieved by the following configurations.

(1) In a silver halide photographic light-sensitive material having two or more light-sensitive silver halide emulsion layers on only one side on a support, the light-sensitive layer closest to the support has at least the following silver halide. A silver halide photograph containing grains, wherein the average iodine content of the silver halide grains in the photosensitive layer adjacent to the above-mentioned photosensitive layer is 0.1 mol% or more higher than that of the following silver halide grains. Photosensitive material.

(A) The average iodine content is less than 2.0 mol%, and (b) the average iodine content on the outermost surface is 3 mol% or more and 1
5 mol% or less, (c) tabular silver halide grains having an average aspect ratio of 2 or more and less than 10, (d) most sensitive (2) the above silver halide photographic light-sensitive material, and a solid processing agent in a processing tank. A method of processing a silver halide photographic light-sensitive material, which comprises processing with an automatic processor having a supply mechanism.

(3) A method of processing a silver halide photographic light-sensitive material, which comprises processing the above silver halide photographic light-sensitive material with a developer containing substantially no dihydroxybenzenes.

The present invention will be described in more detail below.

In the silver halide photographic light-sensitive material of the present invention, the photosensitive layer closest to the support has at least (a) an average iodine content of less than 2.0 mol% and (b) an average iodine content of the outermost surface. 3 mol% or more and 15 mol% or less, and (c) tabular silver halide grains having an average aspect ratio of 2 or more and less than 10,
(D) The silver halide grains containing the most sensitive silver halide grains and having an average iodine content of the silver halide grains in the photosensitive layer adjacent to the photosensitive layer is 0.1 mol% as compared with the silver halide grains.
It is characterized by the fact that there are many of them.

The light-sensitive layer of the silver halide photographic light-sensitive material of the present invention, particularly the light-sensitive layer closest to the support, contains tabular silver halide grains having tabular twin parallel planes. It is preferable to have two sheets.

The twin plane can be observed by a transmission electron microscope. The specific method is as follows. First, a silver halide photographic emulsion is coated so that the contained silver halide grains 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 tabular silver halide grains, a method of precipitating silver halide on a seed crystal is preferably used.

In order to obtain a tabular silver halide emulsion, 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 nucleus grain forming step of keeping the pBr of the mother liquor at 2.5 to -0.7 for a period of ½ or more from the initial stage of silver halide precipitation formation having a silver iodide content of 0 to 5 mol%; Subsequent to the step of forming the nucleus grains, the mother liquor contains a silver halide solvent in an amount of 10 ^{−5 to} 2.0 mol per mol of the silver halide to form silver halide seed grains which are substantially monodisperse spherical twin crystals. Or a seed particle forming step of forming a silver halide twin seed particle by raising the temperature of the mother liquor to 40 to 80 ° C. following the core particle forming step. c) Then, a water-soluble silver salt solution and a water-soluble halide solution and / or Alternatively, a method of providing a growth step (particle formation step) of enlarging seed particles by adding halogenated fine particles is preferably used. Here, the mother liquor is a liquid (including a silver halide emulsion) that is used in the preparation stage of a silver halide emulsion up to a completed photographic emulsion.

The silver halide grains formed in the core 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. The morphology of twins is classified by Klein and Moiser in the article Photographische Correspondents [PhotographishK
orrespondenz] 99, 99, 100
Volume, page 57.

The tabular silver halide grain means a silver halide grain having two parallel main planes facing 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. In the present invention,
The tabular silver halide grains have an average aspect ratio of 2 or more and less than 10 and preferably 2.0 or more and less than 5.

The photosensitive layer containing tabular silver halide grains, especially the photosensitive layer closest to the support, has a total projected area of 5
0% or more is tabular silver halide grains, preferably 70% or more, more preferably 90% or more.

The average grain size of the tabular silver halide grains is 0.
It is preferably 15 to 5.0 μm, and 0.4 to 3.
It is more preferably 0 μm, most preferably 0.
It is 4 to 2.0 μm.

The average thickness of tabular silver halide grains is 0.
It is preferably from 15 to 0.3 μm, and the particle size and thickness can be optimized to optimize the sensitivity and other photographic characteristics. Other factors that influence the sensitivity and other photographic characteristics of the photosensitive material (thickness of hydrophilic colloid layer, degree of hardening, chemical ripening condition, set sensitivity of photosensitive material, silver coating amount, etc.)
The optimum particle size and thickness differ depending on the type.

The tabular silver halide grains are composed of silver iodochloride, silver chloroiodobromide, silver chlorobromide, silver bromide, silver iodobromide and the like as silver halide. The average iodine content of the tabular silver halide grains contained in the photosensitive layer closest to the support is 2.
Less than 0 mol% but not less than 0.5 mol% and not more than 2.0 mol%
Less than is more preferred.

In the present invention, the iodine content and average iodine content of individual silver halide grains are determined by the EPMA method (E
electron Probe Micro Analysis
(Zer method). In this method, a sample in which emulsion grains are well dispersed so that they do not come into contact with each other is prepared, and then an X-ray analysis is carried out by irradiating with an electron beam and excited by an electron beam. By this method, the silver halide composition of each grain can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each grain. At least 5
If the iodine content is determined by the EPMA method for 0 particles, the average iodine content can be determined from the average thereof.

The tabular silver halide grains contained in the silver halide emulsion preferably have a more uniform iodide content between grains. When the distribution of iodine content between particles is measured by the EPMA method, the relative standard deviation is 35%.
Hereafter, it is preferably 20% or less.

When the tabular silver halide grains contain silver iodide, it is preferred that they be contained at least inside. In the case of the inside, it is more preferable that it exists at least in the center. It is also preferable that it is present on the outermost surface.

The halogen composition distribution inside the silver halide grains can be determined by pretreating the grains into ultrathin sections, and then observing and analyzing with a transmission electron microscope while cooling. Specifically, after taking out silver halide grains from the emulsion, they are embedded in a resin and cut with a diamond knife to prepare a slice having a thickness of 60 nm. 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,
It is obtained by quantitative calculation (Inoue, Nagasawa: Proceedings of the 62nd Annual Meeting of the Photographic Society of Japan, p62).

In the present invention, the iodine content on the outermost surface of silver halide grains means the XPS method (X-ray Pho).
toelectron Spectroscopy: X
It refers to the iodine content in the portion up to a depth of 50 Å 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 irradiated as an X-ray for a probe with an X-ray source voltage of 15 kv and an X-ray source current of 40 mA to obtain Ag3d5 /. 2, Br3d, I3d 3/2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor (Sensitivity Factor), and the halide composition of the outermost surface is determined from the intensity ratio of these.

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 tabular silver halide grains contained in the light-sensitive layer closest to the support is
It is 3 to 15 mol%, and more preferably 4 to 14 mol%.

The tabular silver halide grains may have dislocations. The dislocation is described in, for example, J. F. Hamilton, P
hot. Sci. Eng, 57 (1967) and T.W. S
hiozawa, J .; Soc. Photo. Sci. Ja
It can be observed by a direct method using a transmission electron microscope at low temperature described in Pan, 35, 213 (1972). 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 the electron beam to pass therethrough.
It can be observed more clearly by using an electron microscope of 200 kv or more for particles having a thickness of 25 μm.

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 = width of grain size distribution (%) When the breadth of distribution 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, (standard deviation of thickness / average thickness) × 100 = distributed by the width (%) of the thickness distribution. When the width is defined, it is preferably 25% or less, more preferably 20% or less.

In the present invention, in addition to the tabular silver halide grains described above, other silver halide grains such as monodisperse core / shell type silver halide grains may be contained.

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 above twinned grains, twinned grains having an aspect ratio of less than 2 are preferable. Spherical means the roundness of the radius of curvature corresponding to ⅙L to ½L of the length L when focusing on the surface having the largest area among the polygons forming the outer shape of the silver halide grain before spheroidizing. It is defined as having on the ridge part of the polygon. The roundness of the grains can be determined by observing the silver halide grains with an electron microscope.

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

The average particle diameter d here is the product ni × di ³ of the frequency ni and di ³ particles having a particle size di is defined as the particle size di of when maximized. (3 significant digits, rounding off the least significant digit to 4) The grain size referred to here is the diameter of spherical silver halide grains, or the projected image of grains other than spherical grains. It is the diameter when converted to 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 (measurement). It is assumed that the number of particles is 1000 or more indiscriminately.)

Particularly preferred highly monodisperse grains, such as the monodisperse core / shell type silver halide grains that can be used in the present invention, have a broad distribution of 20% or less, and more preferably. It is less than 15%.

The particle size measuring method is based on the above-mentioned measuring method, and the average particle size is a simple average.

Average grain size = Σdini / Σni The monodisperse core / shell type silver halide grains are composed of silver halide grains having a grain structure composed of two or more layers having different iodine 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. It is preferable that the core and the shell have different iodine contents, and it is particularly preferable that the core is formed with the highest iodine content.

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.

The content of the core is preferably at least 3 mol% or more. 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, but it may have a distribution.

For example, from the center toward the outside,
Even if the concentration is high, the intermediate region may have a maximum or minimum concentration.

The monodisperse core / shell type silver halide grains are prepared by preliminarily allowing an aqueous solution containing a protective colloid and seed grains to be present in a reaction vessel, and supplying silver ions, halogen ions, or silver halide fine grains as needed. What is obtained by crystal growth of seed particles is preferable.

In this case, the central portion of the grain may have a halogen composition region different from that of the core. The halogen composition of the seed grains is arbitrary and may be any of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, silver chloroiodide and silver iodide.

The average iodine content of the silver halide grains in the photosensitive layer adjacent to the support is often higher than the average iodine content of the silver halide grains in the photosensitive layer closest to the support by 0.1 mol% or more. It is more preferably 0.3 mol% or more.

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. It may be gradually changed 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 enlarging by adding silver halide fine particles and dissolving and recrystallizing the grains can be used, as shown in Section 88 of the 1983 Annual Meeting of the Photographic Society of Japan.

For growth, an aqueous solution of silver nitrate and an aqueous solution of halide can be added by double jet, but iodine can also be supplied into the system as silver iodide. The addition rate is preferably such that new nuclei are not generated, and that the size distribution is not broadened by Ostwald ripening, that is, in the range of 30 to 100% of the speed at which new nuclei are generated.

In producing a silver halide emulsion, stirring conditions during production are extremely important.

As a stirring device, Japanese Patent Laid-Open No. 62-16012
The apparatus shown in No. 8 in which the additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer is particularly preferably used.

At this time, the stirring rotation speed is 100 to 120.
It is preferably 0 rpm. In preparing the silver halide emulsion, a known silver halide solvent such as ammonia, thioether, or thiourea can be present during the seed grain formation step and the seed grain growth. During the preparation of silver halide grains, a silver salt solution and a halide solution are added by the double jet method during the growth, the nucleation does not occur depending on the grain growth, and the size distribution is broadened by Ostwald ripening. A particle having a desired particle size and distribution can be obtained by a method in which the particle size is gradually changed within a range from 30% to 100% of the rate 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 completion of physical ripening.

As a method for converting halogen, 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 preferably 0.2 μm or less, and more preferably 0.02 to 0.1 μm.

As a method of incorporating silver iodide on the outermost surface of silver halide grains, a method of simultaneously adding a silver nitrate solution and a solution containing iodide to an emulsion containing a base silver halide grain, iodide A method of adding fine silver halide grains such as silver, silver iodobromide or silver chloroiodobromide, a method of adding potassium iodide or a mixture of potassium iodide and potassium bromide, and the like can be applied. Among these, the method is preferable, and the method of adding fine silver iodide grains is particularly preferable.

The time for adjusting the iodine content on the outermost surface is
It can be selected 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, but it is preferable to adjust by the end of the chemical ripening step. . The term "chemical ripening step" as used herein means a period 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 silver halide grains is preferably in the range of 30 to 80 ° C., and more preferably 40.
The range of to 65 ° C is particularly preferable. Further, the present invention is preferably carried out under the condition that the silver halide fine grains to be added are partially or wholly disappeared after the addition and immediately before coating. More preferable condition is 20% of the added silver halide fine grains. The above is the disappearance 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 a thiocyanic acid compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) in an amount of 1 × 10 ^{−3 to} 3 × 10 ⁻² mol per mol of silver.

Gelatin is preferably used as the dispersion medium for the protective colloid of silver halide grains, and examples of the gelatin include alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 1,000 to 50,000), phthalated gelatin and the like. Modified gelatin is used. Other hydrophilic colloids can also be used. Specifically, Research Disclosure (Research Disclo)
sur. Hereinafter referred to as RD) Volume 176 No. 1764
3 (December 1978).

Further, the silver halide grains are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), in the process of forming grains and / or in the process of growing grains.
At least one metal ion selected from rhodium salts (including complex salts) and iron salts (including complex salts) can be added to allow these metal elements to be contained inside the particles and / or in the surface layer of the particles. By placing in a suitable reducing atmosphere, reduction sensitizing nuclei can be imparted to the inside and / or the surface of the grain.

Further, the action of the reducing agent added at a desired time of grain 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 gold sensitizer in the chemical sensitization step (or when the gold sensitizer is not used, the chemical sensitizer) is added. is there.

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. When removing the salts, RD Vol. 176 No. It can be carried out based on the method described in Item 17643, Item II, and the silver halide grains can be chemically sensitized. There are no particular restrictions on the conditions of the step of chemical ripening, that is, chemical sensitization, such as pH, pAg, temperature, time, etc., and the conditions generally used in the art can be used. 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, gold and other noble metal sensitization methods using a noble metal 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, etc., but is generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide. The addition method may be a method in which water or an organic solvent such as methanol and ethanol is dissolved alone or in a mixed solvent and added depending on the properties of the selenium compound used. Alternatively, the method may be a method in which it is mixed with a gelatin solution in advance and added, or a method disclosed in JP-A-4-140739 and 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
It is preferably in the range of 0 to 90 ° C, more preferably 45 ° C or higher and 80 ° C or lower. Also, pH is 4-9, pAg is 6-
A range of 9.5 is preferred.

The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer.

By placing in a suitable reducing atmosphere,
It is also preferable to perform so-called reduction sensitization on the grain surface.

Preferred examples of the reducing agent include thiourea dioxide and 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 is preferably changed according to the environmental conditions such as the type of reduction sensitizer, the grain size of the silver halide grains, the composition and crystal habit, the temperature of the reaction system, pH and pAg. In the case of urea, 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, it is preferably in the range of about 50 mg to 2 g per mol of silver halide. The conditions for reduction sensitization are a temperature of about 40 to 70 ° C. and a time of about 10 to 2
It is preferable that the range of 00 minutes, pH is about 5 to 11 and pAg is about 1 to 10 (here, the pAg 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 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 those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the commonly used nuclei can be applied to these dyes. 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., and a nucleus in which an aliphatic hydrocarbon ring is fused to these nuclei, that is, India A renin nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole 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.

In the merocyanine dye or the complex merocyanine dye, pyrazoline-containing nuclei having a ketomethine structure are used.
5 to 6 such as 5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazoline-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for the purpose of supersensitization. Further, together with the sensitizing dye, a dye having no spectral sensitizing property or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect may be contained in the emulsion layer. For example, a substituted aminostilbene compound having a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
933,390, 3,635,721), an aromatic organic acid formaldehyde condensate (for example, also described in US Pat. No. 3,743,510), a cadmium salt, an 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 after each step of nucleation, growth, desalting, chemical sensitization, or after chemical sensitization.

In the present invention, in order to be suitable for rapid processing, an appropriate amount of a hardener is added in advance in the step of applying a light-sensitive material, and the water swelling rate in the developing-fixing-washing step is adjusted to start drying. It is preferable to reduce the water content in the preceding light-sensitive material. In the present invention, the swelling ratio during development is preferably 150 to 250%, and the film thickness after swelling is 70 μm.
m or less is preferable. When the water swelling rate exceeds 250%, poor drying occurs, and, for example, poor handling occurs in automatic processor processing, especially 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 here 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, a processing method in which a silver halide photographic light-sensitive material is processed by an automatic processor having a mechanism for supplying a solid processing agent to a processing tank is preferably used.

The solid processing agent in the present invention is a powder processing agent or a solid processing agent such as tablets, pills and granules, which is optionally subjected to moisture-proof treatment.

The powder in the present invention refers to an aggregate of fine crystal grains, and the granule refers to a powder obtained by subjecting the powder to a granulation step, and refers to a granular material having a particle diameter of 50 to 5000 μm. The term "powder or granule" refers to a product obtained by compression-molding the powder or granule into a given shape.

As a cause of fluctuations in photographic performance, it is effective to reduce the opening coefficient of the developer in the automatic processor. Particularly, the aperture coefficient is preferably 80 cm ² / l or less. That is, when the opening coefficient exceeds 80 cm ² / l, the undissolved solid processing agent or the concentrated liquid immediately after dissolution is easily subjected to air oxidation, and as a result, insoluble matter or scum is generated, which is processed by the automatic processing machine or processed. Although problems such as contamination of the photosensitive material occur, these problems can be solved when the aperture coefficient is 80 m ² / l or less. The opening coefficient referred to here is represented by the contact area with the air per unit volume of the processing liquid, and the unit is (cm ² / l). In the present invention, the aperture coefficient is preferably 80 cm ² / l or less, more preferably 50 to ³ cm ² / l, and further preferably 35 to 10 cm ² / l.

The opening coefficient can be generally reduced by using a resin or the like for blocking the air as a floating pig, or disclosed in JP-A-63-1.
No. 31138, No. 63-216050, No. 63-23
The size can be reduced by the slit type developing device described in No. 5940.

Further, in the automatic developing machine, even after the development processing of the photosensitive material is completed and the driving of the photosensitive material conveying means is stopped, a predetermined time required for the processing agent to be dissolved from the time of the stop. It is preferable that the pump is continuously driven to circulate the processing liquid.

The time for which the pump is driven after the completion of the development process is preferably within 2 hours, particularly preferably within the range of 10 minutes to 70 minutes, and further within this range, 1
The range of 5 minutes to 50 minutes is preferable. If this time is too long, it is not preferable from various viewpoints such as usability, energy saving, deterioration of the processing liquid, and clogging of the filter. On the contrary, if it is too short, the dissolution of the solid processing agent becomes insufficient.

To solidify the photographic processing agent, a concentrated solution or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is mixed with a water-soluble binder. Arbitrary means, such as forming a coating layer by spraying with, can be employed (JP-A-4-29236 and 4-85).
No. 533, No. 4-85534, No. 4-85535,
4-85536 and 4-172341).

A preferred method for producing tablets is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed. There is an advantage that the solubility and the storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting step by simply mixing the solid processing agent components.

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation are used. Can be done.
In order to form tablets, the average particle size of the obtained granules is 100 to 800 μm in that when the granules are mixed and compressed under pressure, nonuniformity of the components, so-called segregation does not easily occur.
It is preferable to use the above-mentioned one, and more preferably 200
˜750 μm. Furthermore, the particle size distribution is 60 for granulated particles.
% Or more is preferably within a deviation of ± 100 to 150 μm. When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a preketching machine can be used. The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity, handleability, or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

The method for producing the tablet treating agent is described in, for example, JP-A-51-61837, JP-A-54-155038 and JP-A-52-51838.
-88025, British Patent No. 1,213,808 and the like can be produced by a general method, further granule treating agent,
For example, JP-A Nos. 2-109042 and 2-10904.
It can be produced by a general method described in No. 3, No. 3-39735 and No. 3-39739. Further, the powder processing agent can be prepared by a general method as described in JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. Can be manufactured.

[0091] The bulk density of the solid processing agent, and in view of its solubility, the object of the present invention, from the viewpoint of the effect, is when a tablet is 1.0g / cm ³ ~2.5g / cm ³ Preferably
When it is larger than 1.0 g / cm ³ , the strength of the obtained solid matter is more preferable, and when it is smaller than 2.5 g / cm ³ , the solubility of the obtained solid matter is more preferable. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

The solid processing agent used in the present invention is a developer,
Although it is used as a photographic processing agent such as a fixing agent and a rinsing agent, it is the developer that has a great effect of the present invention, particularly the effect of stabilizing photographic performance.

It is within the scope of the present invention to solidify only one part of a certain treating agent in the solid treating agent used in the present invention, but preferably all the components of the treating agent are solidified. is there. It is desirable that each component be molded as a separate solid processing agent and packaged in the same manner. It is also desirable that the individual components are packaged in the order in which they are periodically added repeatedly in a package.

It is preferable to add all the processing agents to be replenished to the respective processing tanks as solid processing agents according to the processing amount information.
When replenishment water is required, it is replenished based on the throughput information or other replenishment water control information. In this case, the liquid to be replenished in the processing tank can be only replenishing water. That is, when there are two or more types of processing tanks that need to be replenished, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the automatic developing machine can be made compact. The replenishing water tank may be placed outside or may be built in the automatic developing machine, and it is preferable to install the replenishing water tank from the viewpoint of space saving.

When the developer is solidified, all of the alkaline agent and the reducing agent are solidified, and in the case of tablets, at least 3 agents or less, most preferably 1 agent is used. It is a preferred embodiment of the agent. When two or more agents are divided into solid processing agents, it is preferable that the plurality of tablets and granules be packed in the same package.

The following materials can be used for the package of the solid processing agent.

As the synthetic resin material, polyethylene (either high pressure method or low pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched or unstretched), polychlorinated Vinylidene, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PET), other polyesters, hydrochloric acid rubber, acrylonitrile butadiene copolymer, epoxy-phosphoric acid resin (JP-A-63-6)
No. 3037, the polymer described in JP-A-57-32952.
Of the polymers described in No. 1). Alternatively, pulp may be used.

Although these are preferably made of a single material, when they are used as a film, the films are laminated and adhered, but they may be used as a coating layer or a single layer.

Furthermore, for example, by using aluminum foil or aluminum vapor-deposited synthetic resin between the above synthetic resin films,
It is more preferable to use various gas barrier films.

Further, in order to maintain the solid processing agent and prevent stains from being generated, the oxygen permeability of these packaging materials is 50 ml /
m224hr ・ atm or less (at 20 ° C, 65% RH),
It is more preferably 30 ml / m 224 hr · atm or less.

The total thickness of these laminated films or single layers is 1 to 3000 μm, more preferably 10 to 2000.
μm, and more preferably 50 to 1000 μm.

The above synthetic resin film may be a single layer (polymer) resin film, or a laminate of two or more (polymer)
It may be a resin film.

Examples of the one-layer polymer resin film satisfying the conditions of the present invention include (1) polyethylene terephthalate (PET) having a thickness of 0.1 mm or more, and (2) a thickness of 0.3 mm.
The acrylonitrile butadiene copolymers described above and (3) hydrochloric acid rubber having a thickness of 0.1 mm or more can be mentioned. Among them, polyethylene terephthalate is excellent in alkali resistance and acid resistance, and thus can be suitably used in the present invention.

Next, as the laminated polymer resin film which meets the conditions of the present invention, for example, (4) PET / polyvinyl alcohol / ethylene copolymer (Eval) / polyethylene (PE), (5) stretched polypropylene ( OPP) / Eval / PE, (6) unstretched polypropylene (CPP) /
EVAL / PE, (7) Nylon (N) / Aluminum foil (A
l) / PE, (8) PET / Al / PE, (9) cellophane / PE / Al / PE, (10) Al / paper / PE,
(11) PET / PE / Al / PE, (12) N / PE
/ Al / PE, (13) Paper / PE / Al / PE, (1
4) PET / Al / PET / polypropylene (PP),
(15) PET / Al / PET / high density polyethylene (HDPE), (16) PET / Al / PE / low density polyethylene (LDPE), (17) Eval / PP,
(18) PET / Al / PP, (19) paper / Al / P
E, (20) PE / polyvinylidene chloride (PVDC) coated nylon / PE / ethyl vinyl acetate / polyethylene condensate (EVA), (21) PE / PVDC coated N / PE, (22) EVA / PE / aluminum deposited nylon / PE / EVA (23) Aluminum vapor deposition nylon / N / PE / EVA (24) OPP / PVDC coat N / PE, (25) P
E / PVDC coated N / PE, (26) OPP / Eval / LDPE, (27) OPP / Eval / CPP,
(28) PET / EVAL / LDPE, (29) ON
(Stretched nylon) / Eval / LDPE, (30) CN
(Unstretched nylon) / Eval / LDPE and the like, among which (20) to (30) are preferably used.

As a more specific configuration of the packaging material, if the side in contact with the treating agent is the inner surface, PE / mainly paperboard / PE / Al / epoxy-phosphoric acid resin layer / polyester resin in this order from the inner surface. Layer / PE PE / K-nylon / PE or adhesive / Al / PE /
Paperboard / PE, PE / vinylon / PE or adhesive / Al /
PE / paperboard / PE PE / vinylidene chloride / PE or adhesive / Al / PE /
Paperboard / PE PE / Polyester / PE or Adhesive / Al / PE / Paperboard / PE Polypropylene / K-Nylon / Polypropylene / Al
/ Polypropylene / paperboard / polypropylene etc.

As a method for moisture-proof packaging of tablets and granules, 4-way seal 3-way seal Stick (pillow packaging, gusset packaging) PTP cartridge There is.

The four-way seal, three-way seal, and stick (pillow, gusset) packaging have different forms, and the above materials are used, but when used in the peel-open system, a sealant agent is laminated to give the peel-open suitability. .

The peel-open method generally includes a cohesive failure method, an interfacial peeling method, and an interlayer peeling method.

The cohesive failure method is an adhesive called hot melt, which is used as a sealant in a heat-seal lacquer, and peels off due to internal cohesive failure of the sealant layer at the time of opening.

The surface-active peeling method is a method of peeling at the interface between films, in which the sealing film (sealant) and the adherend are not completely fused and can be peeled with an appropriate strength. The sealant is a film in which an adhesive resin is mixed, and polyethylene, polypropylene or a copolymer thereof, a polyester type, or the like can be selected depending on the material of the adherend.

Further, the delamination method is one in which the sealant is peeled between the layers of the laminate film by using a multilayer coextrusion film such as a laminate film.

In the peel-open method using a film, the interlayer peeling method or the interface peeling method is preferable.

Further, since such a sealant is thin, other films such as polyethylene, polypropylene,
It is used by laminating polystyrene, polycarbonate, polyester (polyethylene terephthalate), polyvinyl chloride, nylon, eval, aluminum, etc., but polyethylene, polypropylene, polyester, considering moisture resistance, environmental friendliness and matching with contents,
Eval and the like are preferable. Considering printability, the outermost surface is preferably unstretched polypropylene polyester, paper or the like.

Examples of the sealant film include CMPS film manufactured by Tohcello, Diffran PP-100 and PS-300 manufactured by Dainippon Ink and LTS film manufactured by Toppan Printing, Sunseal FR manufactured by San-A Chemical, and Sunseal M.
There are S etc., and as a type already laminated with polyester, Declan C-1600T, C-16
02T and so on.

PTP is a packaging form in which a solid processing agent is put into a sheet of PVC, CPP or the like which is molded as a kind of blister packaging and heat sealed with an aluminum sealing material.

Environmentally, PVC is not used as a forming material, and recently A-PET and highly moisture-proof PP (for example, TAS) are used.
-1130, TAS-2230, TAS-3230: Taisei Kako Co., Ltd. are preferably used.

When the treating agent is packaged or bound or coated with a water-soluble film or a binder, the water-soluble film or the binder may be a polyvinyl alcohol type, a methyl cellulose type, a polyethylene oxide type, a starch type, a polyvinyl pyrrolidone type, Hydroxypropyl cellulose system,
Film or binder consisting of pullulan-based, dextran-based, gum arabic-based, polyvinyl acetate-based, hydroxyethyl cellulose-based, carboxyethyl cellulose-based, carboxymethyl hydroxyethyl cellulose sodium salt-based, poly (alkyl) oxazoline-based, polyethylene glycol-based substrates Agents are preferably used, and among these, polyvinyl alcohol-based and pullulan-based agents are more preferably used from the viewpoint of the effect of coating or binding.

The preferred polyvinyl alcohol is a very good film-forming material and has good strength and flexibility under most conditions. Commercially available polyvinyl alcohol compositions cast as films vary in molecular weight and degree of hydrolysis, but preferably have a molecular weight of about 10,000 to about 100,000. The degree of hydrolysis is the rate at which the acetic acid ester group of polyvinyl alcohol is replaced with a hydroxyl group. To apply to film,
The range of hydrolysis is usually up to about 70-100%. Thus, the term polyvinyl alcohol usually includes polyvinyl acetate compounds.

The method for producing these water-soluble films is described in, for example, JP-A-2-124945 and JP-A-61-17343.
No. 8, 60-158245, and JP-A-2-86638.
JP-A-57-117867 and JP-A-2-7565.
No. 0, JP-A-59-226018, 63-2187.
No. 41 and No. 54-13565, etc., but it is produced by a general method.

Further, as these water-soluble films, those commercially available under the names of Solbron (manufactured by Aicello Chemical Co., Ltd.), Hi-Selon (manufactured by Nigo Film Co., Ltd.) or Pullulan (manufactured by Hayashibara Co., Ltd.) can be used. Also, Chris Craft Industries
stories) Inc. The 7-000 series polyvinyl alcohol films available from the MONO-SOL Division of the Company dissolve in water temperatures of about 34 ° F. to about 200 ° F., are harmless and exhibit a high degree of chemical resistance, and are particularly preferred. Used.

The thickness of the water-soluble film is preferably 10 to 120 μm, more preferably 15 to 80 μm, from the viewpoints of storage stability of the solid processing agent, dissolution time of the water-soluble film and crystal precipitation in an automatic processor. Those having a thickness of 20 to 60 μm are particularly preferably used.

The water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellently achieved.

Further, the tensile strength of the water-soluble film is 0.
5 × 10 ⁶ to 50 × 10 ⁶ kg / m ² is preferable, and especially 1
× 10 ^{6 to} 25 × 10 ⁶ kg / m ² is preferable, and 1.5 × 10 ⁶ to 10 × 10 ⁶ kg / m ² is particularly preferable. These tensile strengths are measured by the method described in JISZ-1521.

Further, the photographic processing agent packaged or bound or coated with a water-soluble film or a binding agent is used in storage, transportation, and handling during storage, transportation, and handling, such as high humidity, atmospheric humidity such as rain and fog, and water. In order to prevent damage from sudden contact with water due to splashing or wet hands, it is preferable to be packaged in a moisture-proof packaging material, and the moisture-proof packaging material has a film thickness of 10 to 150.
A film having a thickness of μm is preferable, and a moisture-proof packaging material is a polyolefin film such as polyethylene terephthalate, polyethylene, or polypropylene, kraft paper, wax paper, moisture-resistant cellophane, glassine, polyester, polystyrene, or polyvinyl chloride, which can have a moisture resistance effect with polyethylene.
Polyvinylidene chloride, polyamide, polycarbonate,
At least one selected from acrylonitrile-based and metal foils such as aluminum and metallized polymer films is preferable, and a composite material using these may be used.

In the practice of the present invention, it is also preferable to use a moisture-proof packaging material made of degradable plastic, particularly biodegradable or photodegradable plastic.

Examples of the biodegradable plastic include natural polymers, polymers produced by microorganisms, synthetic polymers having good biodegradability, blending of biodegradable natural polymers with plastics, and photodegradable plastics are ,
Examples thereof include a group that is excited by ultraviolet rays and has a group that is linked to cleavage in the main chain. Further, in addition to the above polymers, those having two functions of photodegradability and biodegradability at the same time can be favorably used.

The specific representative examples are as follows.

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof such as microorganism-derived polymers PHB-PHV (3-hydroxybutyrate and 3-hydroxyvalerate). (Copolymer with rate) as a component
pol ", a biodegradable synthetic polymer such as cellulose produced by microorganisms, polyvinyl alcohol, polycaprolactone, or the like, or a copolymer or a mixture thereof, with a biodegradable natural polymer as a biodegradable natural polymer. , Starch, and cellulose, which have shape-disintegrating properties in addition to plastic.

Examples of the photodegradability include the introduction of a carbonyl group for photodisintegration and the addition of an ultraviolet absorber to accelerate the disintegration.

Regarding such degradable plastic,
"Science and Industry" Vol. 64, No. 10, pp. 478-484 (1990), "Functional Materials", July 1990, No. 23
What is generally described on page-34 etc. can be used.
Also, Biopol (manufactured by ICI), E
co (Eco) (made by Union Carbide), E
colite (Eco Plastic)
Co., Ltd., Ecostar (St. Law)
Commercially available disassembled plastics such as Rence Starch) and Knuckle P (Nihon Unicar) can be used. The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hr or less, more preferably 5 g · mm / m ² 24 hr.
It is as follows.

In the present invention, as a means for supplying the solid processing agent to the processing tank, for example, in the case where the solid processing agent is a tablet, JP-B-63-137783 and 63-975 are used.
There are known methods such as those described in No. 22 and Jikkaihei 1-85732. However, any method may be used as long as it has at least the function of supplying tablets to the processing tank. Further, when the solid processing agent is granules or powders, it is used in the actual product of Shokai 62-8196.
No. 4, 63-84151, JP-A-1-292375.
Gravity drop method described in No. 63-105159
Nos. 63-195345 and the like include methods using screws or screws as known methods, but the invention is not limited thereto.

However, a preferable method is, for example, a method in which a predetermined amount of a solid processing agent which is previously weighed and divided and packaged is opened and taken out of the package according to the processing amount of the photosensitive material. Specifically, the solid processing agent is sandwiched and housed in a package composed of at least two packaging materials by a predetermined amount, preferably a replenishment amount for one time, and the package is separated in two directions or the package A part of it is opened so that it can be taken out. The solid processing agent that can be taken out can be easily supplied to the processing tank having the filtering means by spontaneous dropping. A predetermined amount of the solid processing agent is housed in a package that is divided and sealed so that air permeability between the solid processing agent and the adjacent solid processing agent is blocked. Therefore, moisture resistance is guaranteed unless the package is opened.

As an embodiment, a configuration is conceivable in which a package composed of at least two packaging materials sandwiching the solid processing agent is adhered or adhered to each other at their contact surfaces so that the periphery of the solid processing agent can be separated. . By pulling the respective packaging materials sandwiching the solid processing agent in different directions, the closely contacted or bonded contact surfaces are separated, and the solid processing agent can be taken out.

As another embodiment, it is conceivable that at least one of the packages made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term "opening" as used herein means a cut or break that leaves a part of the packaging material. As the unsealing method, the solid processing agent is forcibly extruded by applying a compressive force from the packaging body on the non-opening side toward the packaging body that can be opened through the solid processing agent, or on the packaging body on the unsealable side. It is considered that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting the processing amount information. The supply stop signal is obtained by detecting the information that the supply of the predetermined amount is completed. Further, when the treatment agent is packaged and needs to be opened, the driving means for separating or unsealing operates based on the obtained supply start signal, and the driving means for separating or unsealing based on the supply stop signal operates. It can be controlled to stop.

The above-mentioned solid processing agent supplying means has a control means for charging a fixed amount of the solid processing agent according to the processing amount information of the photosensitive material, which is an important requirement in the present invention.
That is, in an automatic processor, it is necessary to keep the concentration of components in each processing tank constant and to stabilize photographic performance.
The processing amount information of the silver halide photographic light-sensitive material is the processing amount of the silver halide photographic light-sensitive material processed by the processing liquid, or
It is a value proportional to the treatment amount of the processed silver halide photographic light-sensitive material or the treatment amount of the silver halide photographic light-sensitive material under treatment, and indirectly or directly indicates the reduction amount of the processing agent in the processing liquid.

It may be detected before or after the silver halide photographic light-sensitive material is carried into the processing solution, or at any timing during the immersion in the processing solution. Further, it may be a physical parameter such as the concentration of the composition in the treatment liquid or a change in the concentration, pH and specific gravity. Further, it may be the amount of the treatment liquid which is discharged to the outside after drying.

The place where the solid processing agent is charged may be in the processing tank, but is preferably a place where the processing solution is in communication with the processing section for processing the photographic material and the processing solution is flowing between the processing section and the processing section. In addition, a structure in which a fixed amount of the processing liquid is circulated between the treatment unit and the dissolved components moves to the treatment unit is preferable. The solid processing agent is preferably added to the temperature-controlled processing liquid.

Generally, since the temperature of an automatic developing machine is controlled, the temperature of the processing liquid is controlled by an electric heater.

As a general method, a heat exchange section is provided in an auxiliary tank connected to the processing layer, a heater is installed, and a liquid is sent from the processing tank in a constant circulation amount to this replenishment tank, and a pump is provided to keep the temperature constant. It is arranged.

Usually, a filter is arranged for the purpose of removing the crystalline foreign matter that is mixed in the processing liquid or is generated by crystallization, and plays a role of removing the foreign matter.

The most preferable method is to put the solid processing agent in a place, such as this auxiliary tank, which communicates with the processing section and in which the temperature is adjusted. This is because the insoluble components in the processing agent that has been added are blocked from the processing section by the filter section, and it is possible to prevent solids from flowing into the processing section and adhering to photosensitive materials, and the solubility of the solid processing agent is also very high. It will be good.

Further, when the treatment agent input portion is provided together with the treatment portion in the treatment tank, it is preferable to devise a shield or the like so that the insoluble portion does not come into direct contact with the film or the like.

As the material of the filter, the filter, and the like, all those used in general automatic processors can be used, and the special structure and material do not influence the effect of the present invention.

The number of times of circulation of the treatment liquid circulated by the circulation means in the present invention is preferably 0.5 to 2.0 times / min, particularly 0.8 to 2.0 times / min, and more preferably 1.0 to 2.0 times / min.
2.0 times / min is preferable. As a result, the dissolution of the solid processing agent is promoted, the solidification of the high-concentration liquid can be prevented, the unevenness of the density of the processed photosensitive material can be prevented, and the insufficiently processed photosensitive material is generated. It can be prevented. Here, the number of circulations indicates the flow rate of the liquid to be circulated, and it is defined as once when the liquid amount corresponding to the total liquid amount in the processing tank flows.

The solid treating agent according to the present invention is added to the treatment tank separately from the replenishing water, and the replenishing water is supplied from the replenishing water tank.

The anti-mold means of the refill water tank will be described. When the replacement rate in the replenishing water tank is reduced and the residence time of water becomes long, water scales are generated, and there is a problem in that the water rots for 2-3 weeks and a bad odor is generated. In addition, if the generated water scale is replenished as it is, it will adhere to the surface of the photographic light-sensitive material or the solid processing agent, resulting in uneven development in the case of a developing tank and poor fixing in the case of a fixing tank, resulting in a significant decrease in commercial value. There is. Therefore, in order to remove this water stain, it has to be washed regularly, which is very troublesome. Therefore, this water supply tank has a fungicide. This antifungal means can be achieved by at least one means selected from the following group.

(Group) 1. Chelating agent addition means, 2. Antifungal agent addition means, 3. Deionization treatment means, 4. UV irradiation means, 5. Magnetic processing means, 6. Ultrasonic processing means, 7. Electrolytic sterilization means, 8. Silver ion releasing means, 9. Air bubbling means, 10. Active oxygen releasing means, 11. Means by contact with porous material, 12. Means to prevent the growth of harmful bacteria by adding harmless other fungi.

These means will be specifically described. The chelating agent and bactericide used as the antifungal means in the present invention are described in L. E. West “Water Quality”
Criteria "Photo Sci. And En
g. , Vol. 9, No. 6, p. 398 (1965),
M. E. Eachch ”. Microbiologicala
lGrowth in Motion-Pictur
e Processing "SMPTE Journal
l, vol. 85. mar. (1976), R.S. O. D
eegan, “Photoprocessingu W
ash Water Biocides "J.Imag
ing Tech. vol. 10, No. 6, 239 Dec (1984), JP-A-57-8542, 58.
-105145, 57-157244, 62-
The compounds described in 220951 and the like can be used.

Preferred chelating agents are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
1-hydroxyethylidene-1,1-diosphonic acid, ethylenediaminetetra (methylenephosphonic acid), 2-hydroxy-4-sulfophenol, 2-hydroxy-
3,5-Disulfophenol is preferable, and as the bactericide, phenol compounds, thiazole compounds and benztriazole compounds are used. Specifically, 1,2-benzisothiazolin-3-one, 2-methyl-4-osothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin 3 -One, 0-phenylphenol sodium, and benztriazole are mentioned as preferable compounds.
It is preferable that these compounds are in the form of tablets if they are packaged in a package, and if they are divided and weighed in advance, they are individually packaged in an amount to be added at one time. Means for adding these may be added by hand by the pharmacist, but it is preferable to install a solid processing agent supply device, and to add by this, more preferably a tank with a detector attached to the rehydration tank From the viewpoint of maintenance-free, it is preferable to add water automatically when water is replenished to a certain fixed amount.

The means for modifying water with the ion exchange resin of the present invention can be implemented based on the means described in JP-A-61-131632.

As the ion exchange resin, various publicly known cation exchange resins described in published technical report, official technique number 90-473, etc. (strongly acidic cation exchange resin, weakly acid cation exchange resin)
And various anion exchange resins (strongly basic anion exchange resins)
And these can be used alone or in combination. Usually, it is preferable to use a strongly acidic H type cation exchange resin and a weakly basic OH type anion exchange resin. It may be attached to the water replenishment tank or the water may be improved elsewhere.

Preferred ion exchange resins for strong acid are DIAION SK1B SK102 and SK10.
4, SK106, SK110, SK112, SK116
(Mitsubishi Kasei Co., Ltd.), and preferred OH type strongly basic anion exchange resins are DIAION PA406 and P.
There are A408, PA412, PA416, PA418 (Mitsubishi Kasei Co., Ltd.).

The means for irradiating with ultraviolet rays is disclosed in JP-A-60-2.
It can be carried out by the means described in 63939. As the ultraviolet irradiation device, a product manufactured by Kindai Bio Research Institute (headquarters Kobe City) is small and can be preferably used. The means for applying the magnetic field of the present invention can be implemented by the means described in JP-A-60-263939. The means for applying ultrasonic waves of the present invention can be implemented by the means described in JP-A-60-263940. Means for applying this electrolysis is disclosed in JP-A-3-2246.
It can be carried out by the means described in No. 8. The means for releasing Ag ions include a means for putting a silver foil or a silver plate in a water replenishing tank, a means for coating the inner wall with silver, and a means for putting a silver ion releasing compound.

The air bubbling means may be a very simple means for blowing bubbles into the refill water tank, and is appropriately selected according to the size of the refill water tank. The means for preventing the generation of these scales and microorganisms are compact and economical in terms of 1.
2, 3, 7 and 8 are preferable, and 1, 3 and 8 are more preferably selected.

The silver ion-releasing compound of means 8 is an organic material such as silver chloride, silver bromide, silver iodide, silver oxide, silver sulfate, silver nitrate, silver acetate, silver oxalate, silver behenate, and silver maleate. Specific examples include silver oxide.

These silver compounds include those having a SiO ₂ —Na ₂ O type glass body having a network structure as a base structure component, a methane type SiO ₄ tetrahedron and an Al compound.
In the present invention, a zeolite body having a three-dimensional skeleton structure in which O ₄ tetrahedra have one oxygen atom in common with each other and the silver compound is contained therein is preferably used in the present invention.

These silver compounds, and the zeolite bodies and glass bodies containing the compounds can be obtained as commercial products, for example, Bio-Sure SG manufactured by Kinki Pipe Giken Co., Ltd., Opa Pharma (Switzerland) Opagent Tablets (Opargent
Tablets and Zeomic (Ze manufactured by Sinanen Zeomic Co., Ltd.)
mic) and the like.

Further, the silver compound and the zeolite body and glass body containing the compound can be used in various shapes. For example, it may be in the form of powder, spheres, pellets, fibers or filters, or these may be used by kneading into fibers such as cotton, wool, polyester and the like. Specific examples thereof include Saniter 30 manufactured by Kuraray Co., Ltd. and the like.

Of these, a filter-like or spherical one is one of the preferred embodiments in the present invention.

Further, the silver compound or the zeolite body or glass body containing the silver compound may be put in a plastic case or a tea pack-like water permeable container for use.
This is one of the preferred embodiments. In addition to these, Clinker 205 manufactured by Nichiban Kenkyusho Co., Ltd. and Pacific Chemical's rackin can also be preferably used.

In the developer, as a developing agent, JP-A-6-
In addition to the dihydroxybenzenes, aminophenols and pyrazolidones described in No. 138591 (pages 19 to 20), the reductones described in JP-A No. 5-165161 are also preferably used. Among the pyrazolidones to be used, those substituted at the 4-position (dimesone, dimeson S, etc.) are particularly preferable because their water solubility and the solid treating agent themselves do not change over time.

As a preservative, the above-mentioned JP-A-6-1385 can be used.
In addition to the sulfite described in No. 91, an organic reducing agent can be used as a preservative. Other known chelating agents and bisulfite adducts of hardening agents can be used. It is also preferable to add the compounds described in JP-A-5-289255 and JP-A-6-308680 (general formulas [4-a] [4-b]) as silver sludge inhibitors. Addition of a cyclodextrin compound is also preferable, and JP-A-1-124485
The compounds described in No. 3 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 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), etc. Can be mentioned.

As a development accelerator, Japanese Patent Publication No. 37-160
88, 37-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247, and the like. 49829 and 50-1555.
P-phenylenediamine compounds represented by No. 4, JP-A-50-137726, JP-B-44-30074,
Quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, US Pat.
P- of 10,122 and 4,119,462
Aminophenols, US Pat. No. 2,494,903
No. 3,128,182, 4,230,796
No. 3,253,919, Japanese Patent Publication No. 41-11431
No. 2,482,546 and 2,596, US Pat.
Amine compounds described in JP-A Nos. 926 and 3,582,346 and the like, JP-B-37-16088 and JP-A-42-252.
No. 01, US Pat. No. 3,128,183, Japanese Patent Publication No. 41
No. 11431, No. 42-23883, and polyalkylene oxides represented by US Pat. No. 3,532,501 and the like, other 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazole Etc. can be added as required.

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

Further, the developer composition may, if necessary,
Methyl cellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, and other compounds described in JP-B Nos. 47-33378 and 44-9509 can be used as the organic solvent for increasing the solubility of the developing agent.

Further, various additives such as stain inhibitors, sludge inhibitors, and multi-layer effect accelerators can be used.

As the fixing agent, known compounds can be added. A fixing agent, a chelating agent, a pH buffering agent, a hardener, a preservative and the like can be added, and these are described, for example, in JP-A-4-242246 (page 4) and JP-A-5-113632 (pages 2-4). Can be used. In addition, known chelating agents, bisulfite adducts of hardening agents, and fixing accelerators can also be used.

Prior to the treatment, it is also preferable to add a starter, and it is also preferable to solidify the starter and add the starter. As the starter, in addition to organic acids such as polycarboxylic acid compounds, halides of alkaline earth metals such as KBr, organic inhibitors, and development accelerators 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 light-sensitive material.

The silver halide photographic light-sensitive material of the present invention is preferably treated with a developer containing substantially no dihydroxybenzenes (hydroquinones).

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 working safety and environmental protection. Substantially free of hydroquinones from the standpoint of US Pat. No. 5,236,81
It is preferable to use a developing solution using ascorbic acid described in No. 6.

The development time of the black-and-white photographic light-sensitive material is 3 to 90 seconds, more preferably 5 to 60 seconds, and the processing time is Dr.
y to Dry is 15 to 210 seconds, 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 Agents 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 silver halide photographic light-sensitive material of the present invention The support can have, for example, 2 of the aforementioned RD-17643
8 and pages 1009 of RD-308119. A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer to improve the adhesion of the coating layer, corona discharge, ultraviolet irradiation or the like.

[0178]

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

Example 1 (Preparation of tabular seed emulsion) Seed emulsion A was prepared as follows.

A ₁ ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous solution of ethanol) 6.78 ml KBr 10.8 g 10% nitric acid 114 ml B ₁ AgNO ₃ (aqueous solution 2.5N) ) 2825 ml C ₁ KBr 824 g KI 23.5 g Make up to 2825 ml with water.

D ₁ KBr Aqueous Solution (1.75N) The following silver potential control amount at 35 ° C. was used, as shown in Japanese Examined Patent Publication Nos. 58-58288 and 58-5828.
Using the mixing stirrer shown in No. 9, 464.3 ml of each of solution B ₁ and solution C ₁ was added to solution A ₁ by the double mixing method.
Nucleation was performed by adding in minutes. After the addition of the solution B ₁ and the solution C ₁ was stopped, it took 60 minutes to complete the solution A ₁
Temperature to 60 ° C and pH to 5.0 with 3% KOH
After that, the solution B ₁ and the solution C ₁ were again added by the simultaneous mixing method at a flow rate of 55.4 ml / min for 42 minutes. Silver potential during re simultaneous mixing by heating, and the solution B _1, C ₁ from the 35 ° C. to 60 ° C. - a solution D ₁ a (saturated silver measured with a silver ion selection electrode as a comparative electrode silver chloride electrode) Were controlled to be +8 mV and +16 mV, respectively. After the addition was completed, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. This seed emulsion has a maximum adjacent side ratio of 1.0 to 90% or more of the total projected area of silver halide grains.
The hexagonal tabular grains have an average thickness of 0.065 μm and an average diameter (converted to a circle diameter) of 0.5.
It was found to be 2 μm by an electron microscope.

<Preparation of Em-1> (Preparation of fine grain silver iodide emulsion) 5000 ml of 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 grain size of the obtained silver iodide fine grains was 0.05 μm.

Using seed emulsion A and the following three kinds of solutions,
A tabular silver halide emulsion Em-1 was prepared.

[0184] A ₂ 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 Equivalent to 1.624 mol of seed emulsion A Make up to 4200 ml with water.

B ₂ ossein gelatin 24.0 g potassium bromide 2285 g Water to make 4800 ml.

C ₂ Silver nitrate 3260 g Water to make 5484 ml.

D ₂ Fine Grain Silver Iodide Emulsion Equivalent to 0.37 mol E ₂ 2.0N potassium bromide solution A ₂ solution was vigorously stirred at 60 ° C., and then B ₂ solution, C ₂ solution and D ₂ solution were doubled in 90 minutes. It was added by the jet method. Where B
The addition rates of the _2nd solution and the _2nd solution are changed in a function-like manner with respect to time so as to correspond to the critical growth rate so that polydispersion does not occur due to generation of small particles other than the growing seed crystal and Ostwald ripening. It was added at an appropriate addition rate.

[0188] The supply of D ₂ solution i.e. fine silver iodide emulsion, the speed of the C ₂ solution (molar ratio) is changed with respect to grain size (addition time) as 0.2, the total of C ₂ solution 10% of usage
The addition was completed at the time of addition. Further, the pAg of grain growth was kept at 9.15 by using the E ₂ solution. 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 Co.) and an aqueous solution of magnesium sulfate, and gelatin was added and redispersed at 40 ° C.
An emulsion having a pAg of 8.1 and a pH of 5.85 was obtained. Observation of the obtained emulsion by an electron microscope showed an average diameter of 1.0.
The tabular silver halide grains had a distribution of 4 μm, a distribution of 20%, an average silver iodide content of 2 mol%, and an average aspect ratio of 4.3.

<Preparation of Em-2> In the preparation of emulsion Em-1, the addition amount of the fine grain silver iodide emulsion of D ₂ was set to 0.11 mol, and the C ₂ solution was added by the amount corresponding to the reduction of the D ₂ solution. A tabular silver halide emulsion Em-2 was prepared in the same manner as the emulsion Em-1, except that the amount of the D ₂ solution was increased and the addition was completed when 3% of the total amount of the C ₂ solution was added.

When the obtained emulsion was observed with an electron microscope, a tabular halogen having an average diameter of 1.06 μm, a distribution width of 20%, an average silver iodide content of 0.6 mol% and an average aspect ratio of 4.5. It was a silver halide grain.

<Preparation of Em-3> In the preparation of emulsion Em-1, the seed emulsion A was set to 3.21 mol, the addition amount of the fine grain silver iodide emulsion D ₂ was set to 0.20 mol, and D _{2 was set.} The addition of the solution was terminated when the amount of the C ₂ solution used was 5.9% of the total amount used. The C ₂ solution was added in such an amount that the amount of silver halide at the end of the addition was the same as that of the emulsion Em-1.

A tabular silver halide emulsion Em-3 was prepared in the same manner as Em-1 except that the pAg of grain growth was kept at 8.55 by using the E ₂ solution.

Observation of the obtained emulsion by an electron microscope revealed that tabular halogen having an average diameter of 0.77 μm, a distribution width of 23%, an average silver iodide content of 1.3 mol% and an average aspect ratio of 3.5. It was a silver halide grain.

<Preparation of Em-4> In the preparation of Emulsion Em-3, the addition amount of the fine grain silver iodide emulsion of D ₂ was set to 0.06 mol, and the C ₂ solution was added by the amount corresponding to the reduction of the D ₂ solution. A tabular silver halide emulsion Em-4 was prepared in the same manner as Em-3, except that the amount of the D ₂ solution was increased and the addition of C ₂ solution was stopped at the time of 1.8% of the total amount used.

When the obtained emulsion was observed by an electron microscope, a tabular halogen having an average diameter of 0.79 μm, a distribution width of 20%, an average silver iodide content of 0.6 mol% and an average aspect ratio of 3.6. It was a silver halide grain.

(Preparation of Normal Crystal Seed Emulsion) Seed emulsion B was prepared as follows.

A ₃ Ossein gelatin 100 g Potassium bromide 2.05 g Water to 11.5 l.

B ₃ ossein gelatin 55 g Potassium bromide 65 g Potassium iodide 1.8 g Sulfuric acid (0.2N) 38.5 ml Water to make 2.6 l.

C ₃ ossein gelatin 75 g Potassium bromide 950 g Potassium iodide 27 g Water to make 3.0 l.

D ₃ Silver nitrate 95 g Water to make 2.7 l.

E ₃ Silver nitrate 1410 g Water to 3.2 l.

The solution B _{3 and the} solution D ₃ were added to the solution A _{3 which} was kept at 60 ° C. in the reaction kettle by the control double jet method.
The mixture was added over 1 minute, and then the C ₃ and E ₃ solutions were added over 105 minutes by the control double jet method. The stirring was performed at 500 rpm.

The flow rate was such that no new nuclei were generated 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 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 desalting was carried out by the method described in JP-B-35-16086 in order to remove excess salts. 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-5> A monodisperse core / shell type emulsion was prepared by using the seed emulsion B and the following seven kinds of solutions.

A ₄ ossein gelatin 10.4 g Ammonia water (28%) 28.3 ml 56% acetic acid aqueous solution 4.2 ml Seed emulsion B 0.216 mol Equivalent to 700 ml with water.

B ₄ Ossein gelatin 0.5 g Potassium bromide 2.8 g Potassium iodide 1.44 g Water to make 76 ml.

C ₄ ossein gelatin 1.9 g potassium bromide 81 g made up to 165 ml with water.

D ₄ Silver nitrate 17.1 g Ammonia water (28%) 13.9 ml Make up to 191 ml with water.

E ₄ Silver nitrate 116.1 g Ammonia water (28%) 94.3 ml Make up to 217 ml with water.

Liquid A ₄ was kept warm at 40 ° C and stirred for 800 r
Stirring was done at pm. The pH of the A ₄ solution was 9.9 using acetic acid.
Adjust to 0, collect seed emulsion B, disperse and suspend, then D
Solution ₄ was added at a constant rate over 7 minutes to adjust the pAg to 7.3. Further, solution B _{4 and} solution D ₄ were simultaneously added over 20 minutes. At this time, pAg was kept constant at 7.3. PH = 8. Using potassium bromide solution and acetic acid over a further 10 minutes.
83, was adjusted to pAg = 9.0, C ₄ solution was added over E ₄ solution simultaneously for 50 minutes. Meanwhile, the 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 is adjusted to 8.8 in proportion to the flow rate ratio.
It was reduced from 3 to 8.00. Add acetic acid and add p
The H was adjusted to 6.0. 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 Co.) and an aqueous solution of magnesium sulfate, gelatin was added and redispersed, and pAg 8.5, p at 40 ° C was obtained.
An emulsion of H5.85 was obtained. When the obtained emulsion was observed with an electron microscope, the average diameter was 0.45 μm and the distribution was 15
%, The average silver iodide content was 1.3 mol%, and a cube-shaped tetradecahedral monodisperse core / shell type emulsion with slightly broken corners was obtained.

Obtained Silver Halide Emulsion (Em-1)
After each of (Em-5) (however, only (Em-2) was divided into two) was brought to 55 ° C., 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene (TA
I) and a predetermined amount of the spectral sensitizing dyes A and B shown below (A: B
= 100: 1 (weight ratio) as a solid fine particle dispersion, and after 10 minutes, an appropriate amount of ammonium thiocyanate, chloroauric acid and sodium thiosulfate is added to start chemical ripening, and 40 minutes after that, fine particles are added. The silver iodide emulsion was added in an amount corresponding to 0.1 mol% per mol of silver halide for optimum chemical ripening, and then as a stabilizer (T
AI) was added and stabilized. Further, one of the remaining (Em-2) obtained by dividing into two was added with an amount of fine grain silver iodide emulsion 70 minutes before the completion of chemical ripening of 0.
Chemical aging was performed in the same manner except that the amount was equivalent to 02 mol% to prepare stable (Em-6). The solid fine particle dispersion of the 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 is added to water whose temperature has been adjusted to 27 ° C. in advance, and a high-speed stirrer (dissolver) is used for 30 to 1 at 3.500 rpm.
Obtained by stirring for 20 minutes.

[0212]

[Chemical 1]

Additives described below were added to the obtained silver halide emulsion to prepare a photosensitive layer coating solution. The addition amount is represented by the amount per mol of silver halide.

(Composition of Photosensitive Layer Coating Liquid) 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 1.0g nitrophenyl - triphenyl - phosphonium chloride 5 mg 2-anilino-4,6-ammonium dimercaptotriazine 10 mg 1,3-dihydroxybenzene-4-sulfonic acid _{2.0g n-C 4 H 9 OCH} 2 CH (OH ) CH ₂ N (CH ₂ COOH) ₂ 1.0 g 1-phenyl-5-mercaptotetrazole 15 mg 2-mercaptobenzimidazole-5-sodium sulfonate 8 mg

[0215]

[Chemical 2]

At the same time, a protective layer coating solution was also prepared. The additives used in the protective layer coating liquid are as follows. The amount of addition is represented by the amount per liter of coating liquid.

(Protective Layer Coating Liquid Composition) Lime-treated gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-decylsulfosuccinate 1 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide ( Matting agent having an area average particle diameter of 1.2 μm) 0.5 g C ₄ F ₉ SO ₃ K 2 mg (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) 500 mg Glyoxal 40% aqueous solution (hardening agent) 5 ml

[0218]

[Chemical 3]

The resulting photosensitive layer coating solution and protective layer coating solution were applied to the following supports, and silver halide emulsions were formed into two photosensitive layers as shown in Table 1. The coating amount was one side. The amount of silver is 4.2 g / m ² (the upper and lower layers are 2.1 g / m ² each),
The coating amount of gelatin in the photosensitive layer coating solution is 3.5 g / m ² ,
80m / min using two slide hopper type coaters so that the amount of gelatin in the protective layer is 1.15g / m ^2.
Simultaneous coating was performed on both sides at the speed of 1 to obtain samples 1 to 5.

(Support) The following back layer was applied to a blue-colored, subbed polyethylene terephthalate film base (thickness: 175 μm) on the side opposite to the coated side of the photosensitive layer.

The additives used for the back layer are as follows. The amount of addition is represented by the amount per liter of coating liquid. The coating amount of gelatin in the back layer was 5 g / m ² .

[0222]   Lime treated inert gelatin 68g

[0223]

[Chemical 4]

[0224]

[Chemical 5]

Polymethylmethacrylate particles (matting agent having an average particle size of 5 μm) 1.1 g Formalin aqueous solution (37%) 0.8 ml Glyoxal aqueous solution 0.9 ml Sodium chloride 0.1 g Photographic properties using the obtained samples 1 to 5 Was evaluated. First, a sample was made to pass through an acrylic wedge at a tube voltage of 28 kVp, a tube current of 100 mA, and a duration of 0.5 seconds using an X-ray generator MGU-10 manufactured by Toshiba Corp., and X-rays were emitted through a Konica M-100 screen. Irradiated. Then, using an automatic developing machine (Konica Corp. SRX-502), a developer having the following formulation,
Treated with fixer.

(Developer formulation) Part-A (for 12l finish) 450 g potassium hydroxide Potassium sulfite (50% solution) 2280g Diethylenetriamine pentaacetic acid 120g Sodium bicarbonate 132g 5-methylbenzotriazole 1.2 g 1-phenyl-5-mercaptotetrazole 0.2 g Hydroquinone 340g Add water to make 5000 ml Part-B (for 12l finish) Glacial acetic acid 170g Triethylene glycol 185g 1-phenyl-3-pyrazolidone 22 g 5-nitroindazole 0.4g starter Glacial acetic acid 120g 225g potassium bromide Add water to make 1.0 l.

[0227] Part-B (for 18 l finishing) Aluminum sulfate 800 g To prepare a developing solution, Part A and Part B were simultaneously added to about 5 l of water, water was added while stirring and dissolved to 12 l, and the pH was adjusted to 10.40 with glacial acetic acid. This is used as a development replenisher. 20 ml / l of the above-mentioned starter was added to 1 liter of this development replenisher to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part A and P to about 5 liters of water.
ArtB is added simultaneously, and water is added while stirring and dissolving.
The pH was adjusted to 4.4 with sulfuric acid and NaOH. This is the fixing replenisher. The processing temperature is 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing, and 50% for drying.
C., the processing time is 90 seconds in dry to dry.
In another embodiment, the developer temperature is 32 ° C.
It was processed for 3 minutes and 30 seconds to dry.

<Evaluation> The processing variability was evaluated by comparing the performance of the samples processed at the developing solution temperatures of 35 ° C. and 32 ° C. The sensitivity and contrast of each sample obtained by the development treatment were evaluated.

(Sensitivity) Sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog + 1.0, and is shown as relative sensitivity when the sensitivity of Sample 1 processed at a developer temperature of 35 ° C. is 100.

(Contrast) Contrast represents the slope from the minimum density +0.25 to the minimum density +2.0 in the characteristic curve.

Table 1 also shows the obtained results and the main characteristic values of each silver halide emulsion.

[0233]

[Table 1]

As is clear from Table 1, the samples 4 and 5 of the present invention have higher contrast and less variation in sensitivity and contrast even if the processing temperature changes (less gradation variation), as compared with the comparative example. It can be seen that the processing variability is excellent.

Example 2 Next, an automatic developing machine (manufactured by Konica Corporation, modified from SRX-502) was used to perform processing with a developing solution and a fixing solution having the following formulations.
Operation (A) in which a developer replenishing tablet was produced according to the following operations (A, B): 3000 g of hydroquinone as a developing agent was ground in a commercially available bandam mill until the average particle size became 10 μm. 3000g of sodium sulfite and 2 of potassium sulfite are added to this fine powder.
000 g and Dimezone S1000 g were added and mixed in a mill for 30 minutes, and then in a commercial stirred granulator at room temperature for about 10 minutes,
After granulating by adding 30 ml of water, the granulated product is dried in a fluidized bed dryer at 40 ° C. for 2 hours to remove almost completely the water content of the granulated product. In this way, 100 g of polyethylene glycol 6000 was added to the granules thus prepared.
After uniformly mixing for 10 minutes in a room controlled at 5 ° C and 40% RH or less, the obtained mixture was mixed with a tableting machine which was modified from Tuffpress Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Tablet compression was performed by setting the filling amount per tablet to 3.84 g to prepare 2,500 developer-supplementing tablet A agents.

Procedure (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, 10 g of N-acetyl-D, L-penicillamine. Pulverize and granulate as in the operation (A).
The amount of water added was 30.0 ml, and after granulation, 30 at 50 ° C
Dry for a minute to almost completely remove the water content of the granulated product. The mixture thus obtained was compressed into tablets by the above-mentioned tableting machine at a filling amount of 1.73 g per tablet, and compressed to 250
0 developer replenishing tablet B agents were prepared.

Next, a fixing supplemental tablet was prepared by the following procedure.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in the operation (A), the amount of water added is adjusted to 500 ml and granulation is performed. After granulation, granulate at 60 ℃
And dried for 30 minutes to almost completely remove the water content of the granulated product. In this way, 4 g of sodium N-lauroylalanine was added to the adjusted granules, and the mixture was added at 25 ° C. and 40% RH.
Mix for 3 minutes using a mixer in a conditioned room below. Next, the obtained mixture was compressed into tablets by the above-mentioned tableting machine at a filling amount of 6.202 g per tablet, and compressed to 250
0 fixing replenishing tablet A preparations were prepared.

Operation (D) Boric acid 1000 g, aluminum sulfate.18 hydrate 150
0 g, sodium hydrogen acetate (dried by mixing glacial acetic acid and sodium acetate in equal moles) 3000 g, tartaric acid 200
Then, g is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 100 ml, and after granulation, the granules are dried for 30 minutes to almost completely remove the water content. In this way, 4 g of sodium N-lauroylalanine was added to the thus-prepared mixture and mixed for 3 minutes, and then the obtained mixture was compressed into tablets by the above-mentioned tableting machine at a filling amount of 4.562 g. After that, 1250 fixing supplement tablet D agents were prepared.

Developer starter 2.98 g of glacial acetic acid KBr 4.0g Water was added to make 1 liter.

At the start of processing of the developing solution (start of running), 16.5 l of developing solution prepared by diluting the developing tablet with diluting water
On the other hand, the developing tank was filled with the solution obtained by adding 330 ml of the starter as the starting solution to start the processing. The pH of the developer containing the starter was 10.45. Samples 1 to 5 were exposed to light so that the optical density after development was 1.0 and run. For running, an automatic processor SRX-502 equipped with a solid processing agent charging member was used.

During running, the developing solution contained 0.6% light-sensitive material.
It was carried out by adding 2 each of the above-mentioned agents A and B and 76 ml of water per 2 m ² . The pH when each of the agents A and B was dissolved in 38 ml of water was 10.70. To the fixing solution, ² parts of the above C agent, 1 part of D agent and 74 ml of water were added per 0.62 m ² of the light-sensitive material. The rate of water addition to each treatment agent was started almost at the same time as the addition of the treatment agent, and was added at a constant rate for 10 minutes in proportion to the dissolution rate of the treatment agent.

[0243] Dissolve these in 300 ml of water and finally add 400 m of pure water.
finished to 1. This concentrate was diluted to 1 liter with water to prepare a replenisher. The pH of this replenisher was 10.70.

(Fixer) Sodium thiosulfate 42.0 g Potassium thiosulfate 98.0 g Sodium sulfite 15.0 g Boric acid 10.0 g Sodium hydrogen acetate 30.0 g Glacial acetic acid 17.3 g Sodium acetate 12.7 g Tartaric acid 2.0 g Is dissolved in 400 ml of water and finally 500 m with pure water
finished to 1. This concentrate was diluted to 1 liter with water to prepare a replenisher. The pH of this replenisher was 4.50.

In the same manner as in Example 1, the developer temperature is 35 ° C.,
The processing variability was evaluated by comparing the performance of a sample processed for 90 seconds with dry to dry and a sample processed for 3 minutes and 30 seconds with a developer temperature of 32 ° C. and dry to dry.

The results are shown in Table 2. In addition, Table 2 shows the processing variability by the ratio (%) of the sensitivity and the contrast of the 32 ° C. treatment to the 35 ° C. treatment of each sample.

[0247]

[Table 2]

As is clear from Table 2, the samples of the present invention have small sensitivity ratio (%) and contrast differences and are excellent in processing variability.

Example 3 Samples 1 to 5 were treated and evaluated in the same manner as in Example 2 except that the operation (A, B) was changed to the following operation (A ₂ ) and operation (B ₂ ).

Operation (A ₂ ) 12,500 g of sodium erythorbate as a developing agent is ground in a commercial Van Dam mill until the average particle size becomes 10 μm. To this fine powder, 2000 g of sodium sulfite, 2700 g of dimezone S, 1250 g of DTPA, 12.5 g of 5-methylbenzotriazole, 4 g of 1-phenyl-5-mercaptotetrazole, 4 g of N-acetyl-D, L-penicillamine were added and mixed in a mill for 30 minutes. After granulating by adding 30 ml of water in a commercially available stirred granulator at room temperature for about 10 minutes, the granulated product is dried at 40 ° C. in a fluidized bed dryer.
And dried for 2 hours to almost completely remove the water content of the granulated product.

1670 g of polyethylene glycol 6000 was added to the granules thus prepared,
670 g of the mixture was uniformly mixed for 10 minutes by using a mixer in a room whose humidity was adjusted to 25 ° C. and 40% RH or less, and then the obtained mixture was packed at a loading amount of 8.77 per tablet by the tableting machine.
Then, the mixture was compressed to g and compressed to give 2500 developing supplement tablets A ₂ .

Operation (B ₂ ) 4000 g of potassium carbonate, 2100 g of mannitol, and 2100 g of polyethylene glycol 6000 were pulverized and granulated in the same manner as in the operation (A ₂ ). The amount of water added is 30.
After granulating to 0 ml, the granulated product is dried at 50 ° C. for 30 minutes to almost completely remove the water content of the granulated product. The mixture thus obtained was loaded in a tableting machine having a filling amount of 3.2 per tablet.
Performs compression tablet in the 8 g, to prepare a 2500 developer replenisher tablets B ₂ agent.

The results obtained are shown in Table 3 below.

[0254]

[Table 3]

As is clear from Table 3, the samples of the present invention have small differences in sensitivity ratio (%) and contrast, and are excellent in processing variability.

[0256]

EFFECTS OF THE INVENTION According to the present invention, the processing variability is remarkably excellent such that the sensitivity and the contrast are very little changed despite the processing temperature and the processing time.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI G03C 5/29 G03C 5/29 5/30 5/30 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1 / 035 G03C 1/00

Claims (5)

(57) [Claims] 1. A silver halide photographic light-sensitive material having two or more light-sensitive silver halide emulsion layers on only one side of a support, wherein the light-sensitive layer closest to the support has at least the following silver halide grains. And a silver halide grain in the photosensitive layer adjacent to the above-mentioned photosensitive layer has an average iodine content of 0.1 mol% or more higher than that of the following silver halide grain. material. (A) Average iodine content is less than 2.0 mol% (b) Average iodine content on the outermost surface is 3 mol% or more and 15 mol% or less (c) Tabular silver halide having an average aspect ratio of 2 or more and less than 10 Particle (d) Highest sensitivity 2. The silver halide grains contained in the photosensitive layer closest to the support have (a) an average iodine content of 0.5 mol% or more and less than 2.0 mol%, and (b) an outermost surface. The average iodine content of 4 mol% or more and 14 mol% or less, (C)
The silver halide photographic light-sensitive material according to claim 1, which is a tabular silver halide grain having an average aspect ratio of 2 or more and less than 5. 3. The silver halide grain contained in the uppermost photosensitive 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. The silver halide photographic light-sensitive material according to claim 1 or 2. 4. A silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 1 is processed by an automatic processor having a mechanism for supplying a solid processing agent to a processing tank. Processing method. 5. A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to claim 1 with a developer containing substantially no dihydroxybenzenes.