JPH11194457A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for processing a silver halide photographic sensitive material by which a high-quality image is stably obtained without causing any uneven development and residual dye stains or the like even in the case of processing with a small replenishing amount to a developing solution. SOLUTION: This silver halide photographic sensitive material having at least one silver halide emulsion layer on a support is processed by developing and fixing and rinsing, and this silver halide emulsion layer comprises host flat silver halide grains having sites for forming epitaxial silver halide grains and it is processed with a developing solution and a fixing solution each containing substantially not any boric acid and its salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly, to the occurrence of processing unevenness and residual color even in a system having a rapid processing suitability and a small replenishing amount of a processing solution. And a method for processing a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Since 1995, the disposal of photographic processing wastewater into the ocean has been prohibited, and incineration has been carried out. However, land-based processing of processing wastewater causes an increase in energy and cost, and the amount of replenishment is reduced in order to suppress the processing wastewater. It has been desired to reduce this. However, the reduction of the processing waste liquid increases the stagnation time of the liquid in the processing tank, causes oxidative fatigue of the processing liquid, and lowers or lowers the concentration or gamma of the silver halide photographic light-sensitive material (hereinafter also referred to as light-sensitive material) to be processed. There is a disadvantage that processing unevenness such as unevenness or residual color is generated and processing stability is deteriorated.

[0003] Therefore, as a means for remedying these drawbacks, a method of reducing the average grain size of silver halide grains or using flat silver halide grains having a high aspect ratio and a small grain thickness has been developed. It is known to increase the silver covering power to reduce the amount of silver applied.

[0004]

However, when the average grain size of the silver halide grains is reduced, the sensitivity is lowered. Therefore, sensitization is indispensable to maintain the conventional sensitivity. Until now, various sensitization techniques have been used to reduce the amount of silver in photosensitive materials to shorten processing time and reduce processing waste liquid. At present, the time has not been shortened and the treatment waste liquid has not been reduced.

[0005] The present invention has been proposed in view of the above circumstances, and its object is to have rapid processing suitability.
Another object of the present invention is to provide a processing method for a photosensitive material which does not cause processing unevenness even in a processing system in which the replenishing amount of the processing liquid is small, and which can stably provide a high quality image.

[0006]

The above object of the present invention is achieved by the following constitution.

[0007] 1. Developing a silver halide photographic material having at least one silver halide emulsion layer on a support,
In the processing method of the silver halide photographic light-sensitive material method of fixing and washing, the silver halide emulsion layer contains silver halide grains in which the host grains are tabular silver halide grains and the grains have an epitaxially formed portion. A method for processing a silver halide photographic light-sensitive material, comprising a silver emulsion layer and processed with a developer and a fixer substantially free of boric acid or a salt thereof.

[0008] 2. 2. The method for processing a silver halide photographic light-sensitive material as described in 1 above, wherein the silver halide grains having the epitaxially formed portion are silver halide grains satisfying the following conditions (i) to (iii).

(I) Host grains are tabular silver halide grains having a (111) plane as a main plane, and have a circle equivalent diameter of 0.5 to 5.0 μm and a thickness of 0.07 to 0.3 μm. (Ii) a silver halide projection which is epitaxially attached to a face-centered cubic lattice structure forming an epitaxy junction; and (iii) the silver halide projection is a peripheral portion of a tabular halide grain as a host grain. Located in.

[0010] 3. Developing a silver halide photographic material having at least one silver halide emulsion layer on a support,
In the method for processing a silver halide photographic material to be fixed and washed, the silver halide emulsion layer has a (100) major plane, a silver chloride content of 30 mol% or more, and an average aspect ratio of 2 or more. A silver halide emulsion layer comprising tabular silver halide grains of the formula (I), which is processed with a developing solution and a fixing solution containing substantially no boric acid or a salt thereof. Processing method.

4. Wherein the silver halide emulsion layer is subjected to selenium sensitization and / or reduction sensitization.
4. The method for processing a silver halide photographic light-sensitive material according to any one of items 1 to 3,

5. 5. The method for processing a silver halide photographic light-sensitive material according to any one of the items 1 to 4, wherein the developer contains reductones.

6. Replenishing amount of the developing solution and fixing solution, a halogen according to any one of the 1 to 5, wherein the treatment with the silver halide light-sensitive material 1 m ² per 200ml or less is automatic development processing system for processing Processing method of silver halide photographic light-sensitive material.

Hereinafter, the present invention will be described in detail. Conventionally, tabular silver halide grains contained in a light-sensitive material are commonly used. For example, the tabular silver halide grains are described in US Pat. No. 4,434,226 to Wilgus et al .; U.S. Pat. No. 4,439,520
US Patent No. 4,433,0 to Solver et al.
No. 48; Yamada et al., US Pat.
U.S. Patent No. 4,026,012 to Sugimoto et al .; U.S. Patent No. 4,679,745 to Yamada et al .; U.S. Patent No. 4,713,320 to Maskasky. ; Notor
U.S. Pat. No. 4,722,886 to Sugi;
Moto U.S. Pat. No. 4,755,456; G
oda, US Pat. No. 4,755,617; El.
lis U.S. Pat. No. 4,801,522; Ik
eda et al., U.S. Pat. No. 4,806,461; O
US Pat. No. 4,835,095 to Hashi et al .; US Pat. No. 4,835,322 to Makino et al .; US Pat. No. 4,91 to Daubendiek et al.
No. 4,014; Aida et al., U.S. Pat.
No. 2,015; Ikeda et al., US Pat.
U.S. Patent No. 5,061,609; Piggin et al., U.S. Patent No. 5,061,616; Tsur et al., U.S. Patent No. 5,147,771. U.S. Pat. No. 5,147,772 to Tsur et al .; U.S. Pat. No. 5,147,773 to Tsur et al .; U.S. Pat. No. 5,171,659 to Tsur et al .; Sutto
No. 5,300,413 to Del et al .; Del.
ton, US Patent No. 5,310,644; Ch.
ang et al., US Pat. No. 5,314,793; B
ack et al., US Patent No. 5,334,495;
U.S. Patent No. 5,358,840 to Chaffee et al. And U.S. Patent No. 5,372,927 to Delton.
It is described in the specification and the like.

<Silver Halide Grain According to Claim 1 of the Present Invention> The tabular silver halide grain according to claim 1 of the present invention (hereinafter also referred to as silver halide grain (A)) is described in the above specification. After preparing tabular silver halide grains as described in (1) above as host grains, the tabular silver halide grains (hereinafter also referred to as host tabular grains) as the host grains are obtained by epitaxy growth. The halogen composition of the host tabular grains is preferably any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. When silver iodide is contained, the silver iodide content is preferably 0.1 mol% to 10 mol%, more preferably 0.2 mol% to 6 mol%, and 0.1 mol% to 6 mol%.
4 mol% to 2 mol% is particularly preferred. The host tabular grains can contain a small amount of silver chloride. For example, US Pat. No. 5,372,927 discloses a salty odor having a silver chloride content of 0.4 to 20 mol%. It describes silver halide tabular silver halide grains.

One preferred embodiment of the silver halide grain (A) used in the present invention has two opposing parallel main planes, and the main plane is a (111) plane;
The equivalent circle diameter is 0.5 to 5.0 μm, more preferably 0.5 to 5.0 μm.
5 to 2.0 μm, and the thickness is preferably 0.07 to
0.3 μm, more preferably 0.1 to 0.3 μm
It is. Here, the circle equivalent diameter means an average projected area diameter (hereinafter also referred to as a particle diameter), and is a circle equivalent diameter of the projected area of the silver halide grain (A) (the silver halide grain (A)). Diameter of a circle having the same projected area as
The thickness represents a distance between two parallel main planes forming the silver halide grain (A).

The silver halide grains (A) are preferably obtained from a monodisperse emulsion having a narrow grain size distribution. Specifically, (standard deviation of grain size / average grain size) × 100 = grain size distribution When the area of distribution is defined by the area (%) of
It is preferably at most 5%, more preferably at most 20%, particularly preferably at most 15%. The distribution of the thickness of the host tabular grains is preferably small, specifically, (standard deviation of thickness / average thickness) × 1.
When the width of the distribution is defined by 00 = the width (%) of the thickness distribution, it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

In the silver halide grains (A), the silver halide projections are formed on the main plane (1) of the host tabular grains.
11) It may be formed on the surface or on the peripheral edge, but is preferably formed on the peripheral edge. Here, the peripheral portion means the outer periphery of the main plane of the host tabular grain and a line segment represented by a set of points whose distance from the outer periphery is 10% of the equivalent circle diameter of the host tabular grain. It refers to the enclosed area.

Further, in the silver halide grain (A) of the present invention, the halogen composition of the silver halide projections is selected from silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. Any of them is preferable, and when silver iodide is contained, the silver iodide content is preferably 0.1 to 13 mol%, more preferably 0.1 to 10 mol%. Further, when the silver halide projections are deposited on the host tabular grains, halide ions are introduced.When a plurality of halide ions are introduced, a salt having a high solubility of silver and salts may be added. preferable.

Since the solubility of the silver iodide is lower than that of silver bromide and the solubility of silver bromide is lower than that of silver chloride, when halide ions are added in a preferred order,
Chloride ions are most likely to adhere near the joint. In some cases, the projections form a clear layer and can detect regions with high and low chloride ion concentrations, but sometimes cannot be detected when halides are added in a preferred order. This is because both bromide and iodide ions have the ability to replace the chloride of silver chloride deposited earlier to some extent.

In the present invention, the silver halide epitaxy is formed at a position closest to the periphery of the host tabular grains and less than 50% of the (111) planes of the tabular grains, preferably far from the (111) planes of the host tabular grains. It is preferred to limit the proportion to less than 25%, preferably less than 25%, most preferably less than 10% and optimally less than 5%. When the host tabular grains include a central region having a low iodide concentration and a region disposed on a side portion having a high iodide concentration, silver halide epitaxy, typically at the edge of the host tabular grain, It is preferable to limit to a portion formed by a region arranged on the side including the corner.

In practicing the present invention, a nominal amount of silver halide epitaxy of about 0.05 mol% based on the total silver (including silver in the host and epitaxy) is effective. It is preferred to limit silver halide epitaxy to less than 50% of total silver. Generally, a silver halide epitaxy concentration of 0.3 to 25 mol% is preferred, and a concentration of about 0.5 to 15 mol% is generally optimal for sensitization.

When the halide ions are introduced, the temperature of the emulsion containing host tabular grains is introduced at an arbitrary temperature of 35 to 70 ° C. Moreover, pAg is 6-8.5, pH
Is preferably in the range of 4 to 9.

When silver halide projections are formed on the periphery of the host tabular grains, a compound having an action of limiting the site where the silver halide projections are epitaxially attached before introducing halide ions (hereinafter referred to as a compound) Site director). When the site director is not added, the silver halide projections are precipitated not only on the peripheral portion of the host tabular grain but also on the entire main plane.

The site director preferably used in the present invention may be any compound generally known in the art as a spectral sensitizing dye for silver halide grains, and specific examples thereof include cyanine, merocyanine, complex cyanine, and complex merocyanine. , Holopolar, hemicyanine, styryl, hemioxanol dyes and the like are preferred. In particular, green and red absorbing cyanine dyes are preferred. Further, as a site director of the inorganic compound, iodide, thiocyanide, selenocyanide and the like can also be used.

When the site director is introduced, the temperature of the emulsion containing host tabular grains is introduced at an arbitrary temperature of 35 to 70 ° C. Preferably it is 35-60 degreeC.

When the site director is introduced, the pAg of the emulsion containing the host tabular grains is 6 to 8.5, and the pH of the emulsion is 6 to 8.5.
Is preferably in the range of 4 to 9.

<Silver halide grain according to claim 3 of the present invention> The silver halide grain according to claim 3 of the present invention (hereinafter referred to as "silver halide grain")
In the silver halide grains (B), 50% or more of the total projected area of the silver halide grains contained in the emulsion layer is (1).
It is characterized by tabular silver halide grains having the (00) plane as the main plane, but preferably at least 70%, more preferably at least 90%.

In the present invention, silver halide grains (B)
Is a shape of a right-angled parallelogram or a shape with rounded corners. The adjacent side ratio of the right-angled parallelogram is less than 10, preferably less than 5, and more preferably less than 2. In addition, the length of a side when the corner is rounded is represented by a distance between an intersection of a line extending the straight part of the side and the straight part of the adjacent side.

The average particle size of the silver halide grains (B) is preferably from 0.15 to 5.0 μm, more preferably from 0.4 to 5.0 μm.
It is more preferably 3.0 μm, most preferably 0.4 to 2.0 μm, and the average thickness of the silver halide grains (B) is preferably 0.01 to 1.0 μm. , More preferably 0.02 to 0.40 μm, and still more preferably 0.02 to 0.30 μm. The grain size and thickness of the silver halide grains (B) can be optimized so as to optimize sensitivity and other photographic characteristics. Further, the above-mentioned optimum particle size and optimum thickness are, for example, the thickness of the hydrophilic colloid layer, the hardness, the degree of chemical ripening, the sensitivity of the photosensitive material, the sensitivity setting of the photosensitive material, and the other factors affecting the sensitivity and other photographic characteristics. It depends on the amount.

In the present invention, the silver halide grains (B) are also preferably obtained from a monodisperse emulsion having a narrow particle size distribution. When the breadth of the distribution is defined (in the same manner as in the case of the host tabular grains in (1)), it is preferably 25% or less, more preferably 20% or less,
Especially preferably, it is 15% or less. It is preferable that the thickness distribution is small. Specifically, when the width of the distribution is defined as described above (similar to the case of the host tabular grains of the silver halide grains (A) in claims 1 and 2),
It is preferably at most 25%, more preferably at most 20%, particularly preferably at most 15%.

In the present invention, the silver halide grains (B) are silver halide grains containing silver chloride as a main component, and include silver chloride, silver chlorobromide, silver chloroiodide, silver chloroiodobromide and the like. Can be used. Here, the content of silver iodide is 1.0 mol% as an average silver iodide content in the whole silver halide grains.
The following is preferred, and more preferably 0.5 mol% or less.

Further, the silver halide grains (B) referred to in the present invention are grains having two opposing parallel main planes, and the average of the ratio of the grain size to the grain thickness (hereinafter referred to as aspect ratio). It means that the value is greater than 1.3. Here, the grain size means an average projected area diameter (hereinafter, referred to as a grain size), and is a circle equivalent diameter of the projected area of the silver halide grain (B) (the same projected area as the silver halide grain (B)). The thickness of the silver halide grains (B)
Is defined as the distance between two parallel main planes.

The average aspect ratio of the silver halide grains (B) is preferably 2 or more, more preferably 2.0 to 15.0. Particularly, 4 to 8 is preferable. The tabular grains can have various halogen compositions, but preferably contain 30 mol% or more of silver chloride, more preferably 50 mol% or more.

The silver halide grains (B) can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to form nuclei at a low chloride ion concentration in the presence of iodine ions under conditions that facilitate formation of the (100) plane. After the nucleation, Ostwald ripening and / or
Alternatively, growth can be performed to obtain tabular grains having a desired particle size and distribution.

For example, first, a silver salt solution, a halide solution containing iodide ions, and a protective colloid solution are added to a first container to form nuclei. After the nuclei are formed, the mixed solution is transferred to a second container. Therefore, a method of growing is preferably used.

At this time, the growth may be temporarily stopped in the middle of the process, and this may be used as seed grains, and the seed grains may be grown by depositing silver halide on the seed grains. Specifically, an aqueous solution and seed particles containing a protective colloid are present in the reaction vessel in advance,
If necessary, silver ion, halogen ion or silver halide fine particles can be supplied to grow seed particles.

To prepare the silver halide grains (B) of the present invention, the pCl of the protective colloid solution is 0.5 to 3.5.
It is preferably in the range of 1.0 to 3.0, more preferably 1.0 to 3.0, and most preferably 1.5 to 2.5.

In the preparation of the silver halide grains (B), nucleation is started when the silver salt solution is added to the protective colloid solution. It is preferably added before the silver salt solution, and most preferably, it is added before the silver salt solution.

In the preparation of the silver halide grains (B), iodine can be introduced up to the solid solution limit of silver iodide and silver chloride, but as a pI in the protective colloid solution at the start of nucleation. Is preferably 10 mol% or less, more preferably 0.01 mol% or more and 10 mol% or less, and most preferably 0.05 mol% or more and 10 mol% or less.

Further, the silver halide grains (B)
In the preparation of, the addition time of the silver salt solution during nucleation is preferably 5 seconds or more and less than 1 minute. It is preferable that both a silver salt solution and a halide solution are added during nucleation. In particular, iodine ions are preferably added. Further, bromine ions in the protective colloid solution during nucleation may be present as long as chloride ions are present in an amount of 50 mol% or more.

In the present invention, the nucleus has a silver chloride content of at least 50 mol%, preferably at least 70 mol%.
More preferably, it is 90 mol% or more. Nucleation pH
Is preferably 2 to 8. The temperature is preferably from 30 to 90C, more preferably from 35 to 70C. The amount of silver added during nucleation is preferably 0.1 to 10 mol% of the total silver.

In the preparation of the silver halide grains (B) of the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like can be present. In the production of the silver halide grains (B), a silver salt solution and a halide solution are added by a double jet method at the time of growth, and the addition speed is adjusted according to the growth of the grains so that no new nuclei are formed and Ostwald ripening is performed. Speed, ie, 30 to 1 of the speed at which new nuclei are generated.
Particles having a desired particle diameter and distribution can be obtained by a method of gradually changing the particle diameter in the range of 00%. As another condition for further growth, a method of growing by adding silver halide fine particles, dissolving and recrystallizing as described in the 88th Annual Meeting of the 1983 Annual Meeting of the Photographic Society of Japan is also preferably used. In particular, silver iodide fine grains, silver bromide fine grains,
Silver iodobromide fine grains and silver chloride fine grains are preferably used.

The silver halide grains (A) and (B) of the present invention have a halogen content and an average halogen content of EP
MA method (Electron Probe Micro)
(Analyzer method). In this method, a sample in which emulsion grains are well dispersed so as not to contact each other is prepared, and an electron beam is irradiated thereon.
X-ray analysis by electron beam excitation enables elemental analysis of extremely small parts. By determining the characteristic X-ray intensity of silver and halogen emitted from each grain by this method, the silver halide composition of each grain can be determined. If the halogen content of at least 50 grains is determined by the EPMA method, the halogen content is determined from the average of the halogen content.

Both the host tabular grains of the silver halide grains (A) and the tabular grains of the silver halide grains (B) preferably have a more uniform halogen content between grains. When the distribution of halogen content between grains is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less. The silver halide grains (A) and (B) are also collectively referred to as silver halide grains of the present invention.

<Silver halide grains of the present invention> The silver halide grains of the present invention may have dislocations. Dislocations are described in F. Hamilton, Photo. Sci. En
g, 57 (1967); Shiozawa, J .;
Soc. Photo. Sci. Japan, 35, 213
(1972) can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling.

At this time, since the electron beam becomes more difficult to penetrate as the thickness of the particles is larger, it is more clear to observe using an electron microscope of a high-pressure type (200 kV or more for particles having a thickness of 0.25 μm). can do.

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

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

When silver iodide is contained in the outermost surface of the silver halide grains of the present invention, a method for containing silver nitrate solution and iodide ions in an emulsion containing silver halide grains as a base is used. A method of simultaneously adding a solution, silver iodide,
A method of adding silver halide fine particles such as silver iodobromide or silver chloroiodobromide, a method of adding potassium iodide or a mixture of potassium iodide and potassium bromide, and an organic compound that releases iodine ions are applied. it can.

Of these, the method of adding fine silver halide grains is preferred. Particularly preferred are the addition of silver iodide fine grains and the addition of an organic compound that releases iodine ions. The timing of adjusting the silver iodide content on the outermost surface is selected from the final stage of the silver halide crystal production process to the chemical ripening process and further to the end of the solution preparation process immediately before the application of the silver halide emulsion. However, it is preferable to adjust by the end of the chemical ripening step. The chemical ripening step referred to here is a point in time when physical ripening and desalting of the silver halide emulsion of the present invention are completed, when a chemical sensitizer is added, and thereafter, an operation for stopping chemical ripening is performed. Up to. Further, the addition of silver halide fine particles may be carried out in several times at intervals, or after the addition of the fine particles,
Further chemically ripened emulsions may be added.

The temperature of the silver halide emulsion of the present invention when adding silver halide fine grains is preferably in the range of 30 to 80 ° C., more preferably in the range of 40 to 65 ° C.
Further, the present invention is preferably carried out under the condition that part or all of the silver halide fine grains to be added disappears immediately before coating immediately after the addition, more preferably 20% of the added silver halide fine grains. The above is the disappearance immediately before the application.

<< Production of Silver Halide Grains of the Present Invention >> In producing the silver halide grains of the present invention, stirring conditions during production are extremely important. As a stirring device, see
An apparatus disclosed in Japanese Patent Application Laid-Open No. 2-160128, in which an additive liquid nozzle is installed in a liquid near a mother liquor suction port of a stirrer, is particularly preferably used. At this time, the stirring rotation speed is 100 to 1200.
rpm is preferable.

In the silver halide grains of the present invention, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), and rhodium salts (including complex salts) during the process of forming and / or growing the grains. ) And at least one selected from iron salts (including complex salts), and it is preferable to add metal ions to the inside and / or the surface of the particles to contain these metal elements.

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

In the present invention, gelatin is preferably used as a dispersion medium for the protective colloid of the silver halide particles (A) and the silver halide particles (B). Examples of the gelatin include alkali-treated gelatin, acid-treated gelatin,
Modified gelatin such as low molecular weight gelatin (molecular weight of 20,000 to 100,000) and phthalated gelatin is used. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (Research Disc)
loss. (Hereinafter abbreviated as RD) Vol. 17
643 (December 1978).

In the preparation of the silver halide grains of the present invention, unnecessary soluble salts may be removed during the growth of the silver halide grains, or they may be contained. When removing the salts, see RD Vol. 1
This can be performed based on the method described in 7643, section II.

<< Sensitizer >> The silver halide grains of the present invention are preferably spectrally sensitized with a spectral sensitizing dye. Specific compounds include the following compounds.

[0059]

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[0060]

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[0061]

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Various dispersers are effectively used to mechanically pulverize and disperse these spectral sensitizing dyes in an aqueous solvent to form solid fine particles of 1 μm or less. Specifically, a high-speed stirrer, a ball mill, a sand mill, a colloid mill, an ultrasonic disperser or the like is used. In the present invention, a high-speed stirrer is preferable.

The sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, an aminostilbene compound substituted by a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
Nos. 390 and 3,635,721), formaldehyde condensates of aromatic organic acids (for example, those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene It may contain a compound or the like.

In the case of the epitaxial silver halide grains, the spectral sensitizing dye may be added at the time of spectral sensitization by using a site director added at the time of forming silver halide projections. It may be added at any time after the formation of the silver halide projections and before the preparation of the emulsion coating solution.

The reduction sensitization in the present invention will be described below.

The process for producing a silver halide emulsion is roughly classified into processes such as grain formation, desalting, and chemical sensitization. Particle formation is divided into nucleation, ripening, and growth. These steps are not performed uniformly, the order of the steps is reversed,
The process is performed repeatedly. Applying reduction sensitization during the production process of a silver halide emulsion basically means that it may be performed in any process. Reduction sensitization may be performed during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth, and may be performed prior to chemical sensitization other than reduction sensitization or after this chemical sensitization. . When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog. Most preferred is a method of reduction sensitization during growth of silver halide grains. Here, "growing" refers to a method of performing reduction sensitization in a state where silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. It is also meant to include a method of further growing after performing reduction sensitization in a state.

The reduction sensitization of the present invention is a method in which a known reducing agent is added to a silver halide emulsion, or a pA called silver ripening.
Either a method of growing in a low pAg atmosphere of g1 to 7 or ripening, a method of growing in an atmosphere of high pH of 8 to 11 called high pH ripening, or a method of ripening can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers include stannous salts, amines and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like. In the present invention, these known compounds can be selected for use, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane is a preferred compound. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount. However, the addition amount is 10 ^-7 to 10 ^-7 per mol of silver halide.
A range of ^-3 moles is suitable.

[0070] Ascorbic acid and derivatives can also be used as the reduction sensitizer of the present invention.

Ascorbic acid and its derivatives (hereinafter referred to as
It is called "ascorbic acid compound". The following can be mentioned as specific examples of ()).

(A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3) Potassium L-ascorbate (A-4) DL-ascorbic acid (A-5) D-ascorbic acid Sodium (A-6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid- 5,6-Diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene The ascorbic acid compound used in the present invention is compared with the amount of the conventional reduction sensitizer which is preferably used. It is desirable to use a large amount. The preferable addition amount of the ascorbic acid compound used in the present invention depends on factors such as the grain size of the emulsion, the halogen composition, the temperature for preparing the emulsion, the pH and the pAg, but 5 × 10 ⁻⁵ per mol of silver halide.
It is desirable to select from the range of １1 × 10 ⁻¹ mol. More preferably, it is preferably selected from the range of 5 × 10 ⁻⁴ to 1 × 10 ⁻² mol. Particularly preferred is 1 × 10 ⁻³ to 1 ×.
To choose from a range of 10 ^-2 moles.

In the specification of US Pat. No. 2,487,850, it is described as "1 × 10 ^{-7 to} 44 × 10 ^-6 mol as an addition amount in which a tin compound can be used as a reduction sensitizer". ing. JP-A-57-179835 discloses that the amount of thiourea dioxide added is about 0.01 mg to about 2 mg per mol of silver halide and about 0.0 mg of stannous chloride.
It is stated that it is appropriate to use 1 mg to about 3 mg.

The reduction sensitizer may be water or alcohols,
It can be dissolved in a solvent such as glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. The compound may be added during any step of the emulsion production process, but a particularly preferable method is to add the compound during grain growth. It is good to add to the reaction vessel in advance,
It is preferable to add at an appropriate time during the particle formation. Alternatively, a reduction sensitizer may be added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance, and particles may be formed using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

In the method for chemically ripening silver halide grains according to the present invention, reduction sensitization, gold sensitization, sulfur sensitization, sensitization with a chalcogen compound, and combinations thereof are preferably used.

The chemical sensitization method includes so-called sulfur sensitization,
Gold sensitization, noble metals of group VIII of the periodic table (eg Pd, Pt
And the like, and a sensitization method based on a combination thereof. Among them, a combination of gold sensitization and sulfur sensitization or a combination of gold sensitization and sensitization with a selenium compound is preferable. The addition amount of the selenium compound can be arbitrarily set, but it is preferable to use it together with sodium thiosulfate during chemical sensitization. More preferably, the molar ratio of the selenium compound to sodium thiosulfate is 2: 1 or less, more preferably 1: 1 or less.

In the case of selenium sensitization, a wide variety of conventionally known selenium compounds can be used as the selenium sensitizer. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (e.g., allyl isoselenocyanate, etc.), selenoureas (e.g., N, N-
Dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenyl Carbonyl selenoureas), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids, and selenoesters (eg, 2-seleno) Propionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.) ). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, selenides.

The amount of the selenium sensitizer varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 to 1 ^-8 per mol of silver halide.
About 0 ^-4 mol is used. Depending on the properties of the selenium compound to be used, the addition method may be a method in which water or an organic solvent such as methanol or ethanol is dissolved alone or in a mixed solvent. Further, a method in which the mixture is added in advance with a gelatin solution or a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent according to a method disclosed in JP-A-4-140739 may be used.

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

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of the chemical sensitization in terms of sensitivity and dye adsorption. Particularly, a method of adding silver iodide in the form of fine grains is preferable.

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

US Pat. Nos. 3,615,613 and 3,6
No. 15,641, No. 3,617,295, No. 3,63
The combination described in each specification such as 5,721 is particularly useful.

<Binders and Others> Gelatin is preferably used as the hydrophilic colloid and the binder in the light-sensitive material used in the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, protein hydroxyethylcellulose such as albumin and casein, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate, dextran and starch derivatives, polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic polymer substances such as homopolymers or copolymers of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like can be used. In particular, it is preferable to use dextran or polyacrylamide having an average molecular weight of 5,000 to 100,000 together with gelatin.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Photo, Japan
an. No. 16, 30 (1966), gelatin derivatives (e.g., acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, and maleic acid) Obtained by reacting various compounds such as imide compounds, polyalkylene oxides, and epoxy compounds).

<Dye for Cutting Scattered Light> A dye capable of decoloring and / or flowing out during development processing is contained in at least any one of the silver halide emulsion layer of the present invention and constituent layers other than the emulsion layer. Thus, a photosensitive material having high sensitivity, high sharpness, and rapid processing suitability can be obtained. The dye used in the photosensitive material may be appropriately selected from dyes that can improve sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the photosensitive material. I can do it. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and that the coloring is not visible when the image is completed.

It is also preferred to add the dye as a solid particulate dispersion. As a method for producing a solid particulate dispersion of a dye, specifically, a fine dispersing machine such as a ball mill, a vibration mill, a planetary mill, a sand mill, a roller mill, a jet mill, and a disk impeller mill using a surfactant. Can be prepared. Further, after dissolving the dye in a weakly alkaline aqueous solution, a method of precipitating fine solid particles by lowering the pH and making it weakly acidic or a weakly alkaline solution of the dye and an acidic aqueous solution are simultaneously mixed while adjusting the pH. A dispersion of the dye can be obtained by a method of producing a fine solid. The dyes may be used alone or as a mixture of two or more. 2
When a mixture of more than one species is used, they may be dispersed separately and then mixed, or they may be dispersed simultaneously.

The constituent layer to which the dye is added and contained is preferably a silver halide emulsion layer and / or a layer closer to the support, and more preferably a layer added to the coating layer adjacent to the transparent support. It is effective to do. The concentration of the dye is preferably high on the side close to the support.

The amount of the dye to be added can be changed according to the purpose of sharpness. Preferably, 0.2 to 20 m
g / m ² , more preferably 0.8 to 15 mg / m ² .

When the silver halide emulsion layer is colored in the light-sensitive material of the present invention, a dye is added to the silver halide emulsion before coating, or to the aqueous solution of a hydrophilic colloid.
These liquids may be applied to the support directly or through another hydrophilic colloid layer by various methods.

As described above, it is preferable that the concentration of the dye is higher on the side closer to the support, but a mordanting agent can be used to fix the dye on the side closer to the support. For example, a non-diffusible mordanting agent can be used to bind to at least one of the dyes described above.

The method of binding the non-diffusible mordant to the dye may be carried out by various methods known in the art. In particular, the method of binding in a gelatin binder is preferably applied. In addition, a method of binding in a suitable binder and dispersing in an aqueous gelatin solution by ultrasonic waves or the like can also be applied.

Although the binding ratio is not uniform depending on the compound, usually, 0.1 part to 10 parts of the non-diffusible mordant is bound to 1 part of the water-soluble dye. Since the amount of the water-soluble dye added to the non-diffusible mordant is large, it can be used in a larger amount than when the dye is used alone.

When incorporated in the light-sensitive material, a constituent layer containing a combination of a dye and a non-diffusible mordant may be newly provided as a constituent layer, and the position thereof can be arbitrarily selected. It is effective to use it as a coating layer adjacent to the support.

As the surfactant for preparing the solid particulate dispersion, any of anionic surfactant, nonionic surfactant, cationic surfactant and amphoteric surfactant can be used. Anionics such as alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, and N-acyl-N-alkyl taurines Surfactants and nonionic surfactants such as saponins, alkylene oxide derivatives, alkyl esters of sugars and the like.

The amount of the anionic surfactant and / or the nonionic surfactant is not uniform depending on the kind of the activator or the conditions of the dispersion of the dye, but is usually 0.1 to 2000 mg / g of the dye. And preferably 0.5 to 1000 mg, more preferably 1 to 500 mg. The concentration of the dye in the dispersion is 0.01 to 10% by weight, preferably 0.1 to 5% by weight. The surfactant is preferably added at a position before the start of the dispersion of the dye, and may be further added to the dye dispersion after the completion of the dispersion, if necessary. These anionic surfactants and / or nonionic surfactants may be used alone, respectively, or two or more kinds may be used in combination, or both may be used in combination. .

When the silver halide emulsion according to the present invention is coated on only one side of a support, it is usual to provide an antihalation dye-containing layer. The antihalation dye-containing layer may be located between the emulsion and the support, or on the opposite side of the emulsion layer with the support interposed therebetween. It is preferably provided as a back layer. The transmission density of the dye-containing layer at the wavelength of the exposure light source is 0.4 to 1.5, preferably 0.4 to 1.5.
5 to 1.2. The method of adding the dye includes aqueous solution addition, micelle dispersion addition, solid dispersion addition, and the like, depending on its properties.

<Developing Solution and Fixing Solution> The processing method of the present invention will be described. In developing solutions for black-and-white silver halide photographic materials, dihydroxybenzene compounds represented by hydroquinone have been frequently used as developing agents. However, in recent years, it has been clarified that hydroquinone is unfavorable from an ecological and toxicological point of view, and furthermore, it has been desired to take measures in consideration of the pollution load (high COD and BOD) of a developing waste solution in a laboratory.

On the other hand, enediols such as ascorbic acid have been recently attracting attention because they are known to function as a developing agent, and have no problem from the viewpoint of ecology and toxicology. .

However, a developing solution containing ascorbic acid as a principal agent is more oxidized and decomposed at a higher alkalinity (eg, pH 10.4 to 11.5) than a hydroquinone developing solution.
Due to the large amount of acid generated, there was a disadvantage that the pH was greatly lowered and the stability of developing activity was lacking.

Therefore, as a corresponding technique, for example, a method of suppressing the oxidative decomposition itself by lowering the pH of a developing solution and improving the stability of pH fluctuation, or a method of increasing the carbonate carbonate concentration to 0.5 mol / liter or more. There is disclosed a method of suppressing pH fluctuation by a Bacher function.

These enediols are typically ascorbic acid or erythorbic acid or a derivative derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

The amount of ascorbic acid or erythorbic acid or a derivative thereof used according to the present invention is 0.05 to 120 g, preferably 10 to 60 g per liter of the developer.
g, more preferably 40 to 50 g.

Examples of the auxiliary developing agent having superadditivity with enediols include 3-pyrazolidone derivatives and p-aminophenol derivatives. Hereinafter, specific examples of the auxiliary developer will be described, but the invention is not limited thereto.

1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4, 4'-dimethyl-
3-pyrazolidone, 1-p-tolyl-4,4'-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-
4'-hydroxymethyl-3-pyrazolidone, N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-amino Phenol, p-benzylaminophenol and the like.

In the developer according to the present invention, a dihydroxybenzene-based developer may be used in combination. Specific compounds include, for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone,
Examples thereof include 2,3-dibromohydroquinone and 2,5-dimethylhydroquinone, and the one most commonly used is hydroquinone.

In the processing method using the developing solution and the fixing solution of the present invention, the processing may be performed using both replenishers. The amount of replenishment is not particularly limited, but may be from 6 to 90 cc per one sheet of the photosensitive material, preferably from 10 to 40 cc for both the developing solution and the fixing solution.

Further, as a preservative, a developer is disclosed in
In addition to the sulfite described in JP-A-38591, an organic reducing agent can be used. In addition, a bisulfite adduct of a chelating agent or a hardener described in JP-A-6-138391 can be used. Japanese Patent Application No. 4-92947, 5
It is also preferable to add a silver sludge inhibitor described in the specifications of JP-A-96118, a cyclodextrin compound described in JP-A-1-124852, and an amine compound described in U.S. Pat. No. 4,269,929.

It is necessary to use a buffer for the developer.
Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium borate, o-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

Examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, and hydrazine. , A mesoionic compound, an ionic compound, imidazoles and the like can be added as necessary.

As antifoggants, alkali metal halides such as potassium iodide and benzotriazole;
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole,
Organic antifoggants such as 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be used.

Further, the developer composition includes methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound, JP-B-47-33378,
The compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of a developing agent, and other stain inhibitors, sludge inhibitors, and multilayer effect promoters can also be used.

Known compounds such as a fixing agent, a chelating agent, a pH buffer and a preservative can be used in the fixing solution. For example, JP-A-4-242246 or 5-111363.
No. 2 can be used.

As the fixing agent, thiosulfate, thiocyanate and the like are used, and may further contain a preservative, a pH adjuster, a water softener and the like.

<Processing Method and Apparatus> An advantageous method for processing the photosensitive material of the present invention is to use an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank.

As the processing agent supply means, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No.
JP-A-97-522 and JP-A-1-85732, and in the case of granules and powders, JP-A-62-81964 and JP-A-63-84151;
Reference can be made to the gravity drop method described in each of the publications such as JP-A-292375 and the method using a screw or a screw described in each of the publications such as Japanese Utility Model Application Laid-open No. 63-105159 and 63-195345. The place where the solid processing agent is charged is in the processing tank, but it is preferably in communication with the processing section for processing the photosensitive material, where the processing liquid is flowing between the processing section and the processing section. A preferred structure is one in which there is a constant processing solution circulation amount and the dissolved components move to the processing section. Further, it is preferable that the solid processing agent is introduced into a processing liquid whose temperature is controlled.

When an automatic developing machine is used, the total processing time (D
(ry to Dry) is not particularly limited, but may be 10 to 9
The treatment is preferably performed in 0 seconds, more preferably 15 to 45 seconds, and most preferably 15 to 30 seconds.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0118]

Example 1 <Preparation of Seed Emulsion-1> Seed Emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 841 g of potassium bromide 2825 ml of water D1 1.75N aqueous solution of potassium bromide The following silver potential control amount: 42 ° C, JP-B-58-58288, 58-5828
The solution A1 was prepared using a mixing stirrer described in each publication of No. 9
Then, 464.3 ml of each of the solution B1 and the solution C1 were added by a simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. for 60 minutes, the pH was adjusted to 5.0 with 3% KOH, and then the solution was again added. The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It controlled so that it might be set to 8 mv and +16 mv.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The average thickness of the hexagonal tabular grains is 0.064 μm, and the average grain size is 0.064 μm. Diameter (converted to circle diameter)
Was confirmed to be 0.595 μm by an electron microscope. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

<Preparation of [Em-1]> Using a seed emulsion-1 and the following four kinds of solutions, a tabular silver halide emulsion [E
m-1] was prepared.

A2 Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol solution) 2.25 ml Seed emulsion-1 equivalent to 1.722 mol Equivalent to 3,150 ml with water B2 Potassium bromide 1,734 g water Finished to 3644 ml with C2 2478 g Finished to 4165 ml with water D2 Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average particle size 0.05μ) Equivalent to 0.080 mol Fine grain emulsion (*) Was added to 6.64 liters of a 5.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide, and 2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide in 10 parts each. Over a period of minutes. The pH during the formation of the fine particles was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

In the reaction vessel, the solution A2 was vigorously stirred while keeping it at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by a double jet method over 5 minutes. Thereafter, half of the remaining amount of the solution B2 and the solution C2 are added over a period of 37 minutes, and a part of the solution B2, a part of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. Was added over 33 minutes. During this time, the pH was 5.8 and the pAg was
It was kept at 8.8 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate.

After completion of the addition, the emulsion was cooled to 40 ° C., subjected to ultrafiltration desalting by a known method, and then added with a 10% gelatin solution, stirred at 50 ° C. for 30 minutes, and redispersed. After the redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.984 μm and the average thickness was 0.1 mm.
Tabular silver halide grains having a size of 22 μm, an average aspect ratio of about 4.5, and a particle size distribution of 18.1% were obtained. Also,
The average twin plane distance is 0.020 μm, and grains having a ratio of twin plane distance to thickness of 5 or more account for 97% (number) of all tabular silver halide grains and 49 or more for 10 or more grains. %, 15% or more of the particles accounted for 17%.

<Preparation of [Em-2]> The above [Em-1]
Was melted at 40 ° C., and the pAg was adjusted to 7.5 by simultaneously adding a silver nitrate solution and a potassium iodide solution. At this time, the silver nitrate solution and the potassium iodide solution have a silver iodide content of 12 mol% of silver halide precipitated in a small amount during this preparation.
It was added in such a ratio that

Next, after adding a 2 mol% sodium chloride solution to the first amount of [Em-1], calcium chloride,
Sodium bromide, a silver iodide fine grain emulsion (the same one used in the preparation of [Em-1]), and a silver nitrate solution were added in this order. The amount of silver nitrate added was 6 mol% based on the total silver amount of the silver halide grains. Eventually, the composition ratio (mol%) of the halide added in the preparation of [Em-2] was Cl: Br: I = 42: 42: 16.

When the obtained [Em-2] was observed with an electron microscope, a large number of silver halide projections epitaxially adhered were observed not only on the periphery but also on the entire surface of the main plane (111).

<Preparation of [Em-3]> In the preparation of [Em-2], between the addition of sodium chloride and the addition of calcium chloride, 0.1 mol of the exemplified sensitizing dye D-3 was added per mol of silver.
[Em-2] was prepared in the same manner as in the preparation of [Em-2] except that 6 mmol, and 0.006 mmol of the exemplified sensitizing dye D-4 (in each case, per mol of silver) were added as a dispersion of solid fine particles. Em-3] was prepared.

A dispersion of the spectral sensitizing dye in the form of solid fine particles was prepared by adding a predetermined amount of the spectral sensitizing dye to water previously adjusted to 27 ° C. and using a high-speed stirrer (dissolver) at 3,500 rpm for 30 minutes.
Obtained by stirring for ~ 120 min.

Observation of the obtained [Em-3] with an electron microscope showed that silver halide projections epitaxially adhered to the periphery of the main plane (111) plane.

<Chemical sensitization of [Em-1]>
m-1] is 300 m per mole of silver halide.
l of pure water to 50 ° C., 20 mg of benzyladenine, and 10 minutes later the exemplified sensitizing dye (D
-3) and (D-4) as solid fine particle dispersions were added at 0.6 mol and 0.006 mol, respectively, and after 10 minutes, 3 × 10 ^-3 mol of ammonium thiocyanate was further added. Amounts of chloroauric acid and sodium thiosulfate were added. 60 minutes before the end of the chemical sensitization, 4 g of silver iodide fine particles and 2 g of triphenylphosphine selenide dispersion were added, and then 4-hydroxy-6-methyl-1,3,3a, 7-
An appropriate amount of tetrazaindene (TAI) was added to complete the chemical sensitization.

The above-mentioned dispersion of triphenylphosphine selenide was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to ethyl acetate 3 at 50 ° C.
It was added to 0 kg, stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at a dispersion blade peripheral speed of 40 m / sec at 50 ° C. for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3 wt% or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

In this example, as shown in Table 1, a case where reduction sensitization was performed and a case where reduction sensitization was not performed were included. When the reduction sensitization was performed, the above-mentioned benzyladenine (20 m
Five minutes before the addition of g), the addition of the reduction sensitizer takes place.
In addition, as shown in Table 1, there are cases in which selenium sensitization is performed and cases in which selenium sensitization is not performed. In the case of performing selenium sensitization, the above triphenylphosphine selenide is added. Triphenylphosphine selenide is not added.

<Chemical sensitization of [Em-2]> [Em-1]
[Em-2] was subjected to chemical sensitization in the same manner as in the above.

<Chemical sensitization of [Em-3]> Sensitizing dye D-
3, except that D-4 and D-4 were not added (in [Em-3], the sensitizing dyes D-3 and D-4 were added first).
[Em-3] was chemically sensitized in the same manner as the chemical sensitization of [m-1].

The following emulsion additives were added to the obtained emulsion, and the pH was 6.20 and the silver potential was 80 mV (35 ° C.).
Thus, 17 kinds of emulsion coating solutions were obtained by using sodium carbonate and a potassium bromide solution so as to obtain. Next, these 17 types of emulsion coating solutions are coated on a support so that the metal silver equivalent is 1.8 g / m ² per one side and the amount of gelatin is 1.7 g / m ² per one side. At the same time, the following protective layer liquid additive was coated simultaneously on both sides of the support at a speed of 80 m / min using a slide hopper type coater so that the amount of gelatin applied to one side was 0.7 g / m ^2, and 2 minutes 20 minutes Samples 1 to 17 were obtained after drying in seconds.

(Emulsion Additive) The amount of the additive was shown in terms of the amount per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 10 mg t-butyl-catechol 70 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.0 g nitrophenyl-triphenyl Phosphonium chloride 5.0 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 2.0 g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.5 g 1-phenyl-5-mercaptotetrazole 15 mg methacrylic acid-ethyl acrylate copolymer 18 g

[0141]

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(Additive for Protective Layer Liquid) Lime-treated inert gelatin 58 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1.0 g Polymethyl methacrylate, matting agent having an area average particle size of 3.5 μm 0 0.4 g silicon dioxide particles, matting agent having an area average particle diameter of 1.2 μm 0.7 g Ludox AM (manufactured by DuPont) (colloidal silica) 3.0 g The following surfactants (a), (b), (c) and hard Add film agent

[0143]

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Bis-vinylsulfonyl methyl ether 0.4 g [Preparation of solid developer using reductone as a developing agent] A solid processing agent was prepared as follows.

<Granulated product (A)> 300 g of 1-phenyl-3-pyrazolidone, 10 g of N-acetyl-D, L-penicillamine, and 500 g of sodium glutaraldehyde bisulfite adduct were each averaged in a commercially available bantam mill at an average of 1 g.
Grind to 0 μm. 1500 g of sodium metabisulfite and 400 g of sodium erysorbate
0 g and binder D-Sorbit 600 g were added, mixed in a mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 10 minutes in a commercial stirring granulator. Is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the water content of the granulated product.

<Preparation of Solid Developer A> The granulated product (A) thus obtained was mixed with 80 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less using a mixer. After the mixture was uniformly mixed for 10 minutes, the obtained mixture was used as a tough press collect 152 manufactured by Kikusui Seisakusho Co., Ltd.
7HU modified tableting machine to reduce filling amount per tablet to 10
g and compression tableting was carried out to prepare a reductone-based main developing tablet.

<Granulated product (B)> Potassium carbonate 9000
g and 100 g of sodium bicarbonate are each ground in a commercially available bantam mill to an average of 10 μm. Diethyleneamine pentapentaacetic acid (DTPA · 5H) 2 in each fine powder
50 g, 1- (3-sulfophenyl-sodium) -5
-Mercapto-tetrazole 45 g, 5-mercapto-
10 g of sodium tetrazole-1-acetate, 7 g of KI,
Add 200 g of methyl-β-cyclodextrin, 2000 g of binder mannitol, 700 g of D-sorbitol, mix in a mill for 30 minutes and add 30 ml of water for about 15 minutes at room temperature in a commercial stirred granulator. After granulation, the granulated product is dried at 40 ° C. for 2 hours with a fluidized drier to almost completely remove water from the granulated product.

<Preparation of Solid Developer B> The granulated product (B) thus obtained was mixed with 150 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less using a mixer. After the mixture was uniformly mixed for 10 minutes, the obtained mixture was mixed with Tough Presto Collect 15 manufactured by Kikusui Seisakusho Co., Ltd.
27HU modified tableting machine reduces filling amount per tablet to 1
The tablet was compressed to 0 g and subjected to compression tableting to prepare an alkali-developed tablet.

The solid developers A and B were sealed and packed in 4.0-liter amounts in pillow bags containing aluminum for moisture protection.

[Preparation of Fixing Agent] A solid fixing agent having a volume of 100 l was prepared as the following operation fixing solution.

<Granulated product (C)> Ammonium thiosulfate /
Sodium thiosulfate (90/10 weight ratio) 15000g
Is ground in a commercial bantam mill to an average of 10 μm. 500 g of sodium sulfite, Na ₂ S ₂
750 g of O ₅ and a binder pine flow of 1300 g are added, and the amount of water to be added is 50 ml, and the mixture is stirred and granulated.

<Granulated product (D)> 1200 g of aluminum sulfate octahydrate, 1200 g of succinic acid and 300 g of tartaric acid are ground in a commercially available bantam mill until the average particle size becomes 10 μm.
D-Mannit 250g, D-Sorbit 1
20 g, 160 g of PEG # 4000 and a water addition amount of 30
and agitated granulation.
Dry at ℃ to remove water completely.

<Preparation of solid fixing agent> β-alanine (3,000 g), sodium acetate (4330 g) and sodium 1-octanesulfonate (1.5% of the total weight) were added to the granulated product (C) thus obtained. 750 g of sodium metabisulfite and sodium 1-octanesulfonate are added to the granulated product (D) so that the total weight thereof becomes 1.0% of the total weight. After uniformly mixing for 10 minutes using a mixer in a humidified room, the obtained mixture was filled at a filling amount per tablet (C) using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Then, compression tableting was performed at 10.2 g and (D) at 11.2 g to prepare a cylindrical fixing tablet having a diameter of 30 mm. This was enclosed in a pillow bag containing aluminum for moisture proofing in an amount of 4.0 l each.

<Processing Method> An automatic developing machine TCX was used by combining the following 17 types of samples with and without boric acid (7.5 g / L) in each of the following developing solution and fixing solution.
Using a modified machine of -201 (manufactured by Konica Corporation), 26 kinds of processing tests shown in Table 1 were performed by the method described later. At this time, the processing was carried out at a developing temperature of 35 ° C. and a fixing temperature of 35 ° C., with a processing time of dry to dry of 40 seconds.
The replenisher was replenished at 160 ml / m ² .

The developing solution in the developing tank at the start was prepared by diluting and dissolving the above-mentioned sealed and packaged developing tablet with 4 l of dilution water using a modified chemical mixer described later. The tablets were completely dissolved, and no precipitate was observed. 7.8 liters of the developing solution thus finished was put into TCX-201 (manufactured by Konica Corporation), and the following starter was added thereto to fill a developing tank as a starting solution, and processing was started. The starter addition amount was 35 cc / l. The fixer is prepared by diluting the above-fixed and packed fixer tablet with diluted water 4 with a modified chemical mixer described later.
and diluted with 1. The tablets were completely dissolved, and no precipitate was observed. Fixer 5.6 finished in this way
1 was placed in the fixing tank of TCX-201 to be used as a starting liquid.

(Developer Starter Formulation) KBr 5.5 g HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH 0.05 g N-acetyl-D, L-penicillamine 0.10 g meta-weight Sodium sulfite Amount of the following starting solution to pH 9.90 Water finish 35 cc In addition, a modified chemical mixer inlet is provided so that each solid processing agent can be charged for both development and fixing of TCX-201, and built in for dissolving the solid processing agent The chemical mixer was also modified.

In each of the developing and fixing steps, the packaging bag opened by hand is set at the inlet of each solid agent, and the tablets are dropped into the built-in chemical mixer.
(0 ° C.) and dissolving with stirring for 25 minutes while dissolving with stirring.
Adjust to 0 l. This was used as a developing and fixing replenisher.

The pH at the time of dissolving the developer was finely adjusted with acetic acid and KOH so as to be 10.15. The pH of the dissolution replenisher of the fixing solution was 4.80.

The built-in chemical mixer is divided into a liquid preparation tank and a spare tank tank. The capacity of the liquid preparation tank is 4.0 liters and the capacity of the spare tank is 4.0 liters. A spare tank was provided so that the replenisher was supplied so that the replenisher was not replenished during the stirring and dissolving time (about 25 minutes) even when the solution was exhausted.

The starting developer p when adding the starter
H was 9.90.

<Evaluation of Running Stability><< Evaluation of Density Unevenness >> Each of the prepared samples 1 to 17 was cut into large-sized pieces, and the 17 types of samples and two types of processing solutions (with and without boric acid) (developing solution) were used. , A fixing solution) were used in combination as shown in Table 1, and the entire surface was uniformly exposed so that the optical density after processing was 1.0, and 26 kinds of running processing tests in Table 1 were performed. The running process is 50 sheets per day for each test, the first day (starting liquid state),
When the number of sheets reached 250 on the fifth day and the number of sheets reached 500 on the tenth day, a five-level evaluation was performed based on the following criteria. The results are shown in Table 1.

5: No unevenness in density was observed. 4: Slight density unevenness was observed at the periphery of the film when gazing, but at a level that was not problematic in practical use. 3. Slight density unevenness was observed in the entire film when gazing. However, this is a level that does not cause a problem in practical use 2: Density unevenness clearly occurs at the periphery of the film and there is a problem in practical use 1: Density unevenness occurs strongly on the entire surface of the film, making it impossible to use << Evaluation of residual color In the 26 kinds of processing tests, the 17 kinds of each of the 17 kinds of samples were unexposed for 5 consecutive sheets, the first day of the running processing (the state of the starting solution), and the 5th day was 250 days.
When the number of sheets reaches 500 on day 10, 5
Table 1 shows the average level of the five sheets.

5: No residual color contamination 4: Slight residual color contamination 3: Slight residual color contamination is observed, but at a level that is not problematic for practical use 2: Slightly more residual color contamination occurs, and there is a problem in practical use Yes 1: Pollution of residual color occurs strongly, making it impractical

[0164]

[Table 1]

From Table 1, it can be seen that the sample of the present invention has no density unevenness, no residual color, and the like, and a good quality image can be obtained.

Example 2 <Preparation of Seed Emulsion 2><SolutionA3> Ossein Gelatin 37.5 g KI 0.625 g NaCl 16.5 g Adjust to 7,500 ml with distilled water <Solution B3> 1500 g of silver nitrate Adjust to 2500 ml with distilled water < Solution C3> KI 4 g NaCl 140 g Make up to 684 ml with distilled water <Solution D3> Make up 375 g of NaCl with 1816 ml with distilled water At 40 ° C., add solution B3 to solution A3 in a mixing stirrer described in JP-B-58-58288. Was added over 1 minute. 14 EAg
The pressure was adjusted to 9 mV, and after Ostwald ripening for 20 minutes, the entire remaining amount of solution A3 and the total amount of solution D3 were added over 40 minutes. Meanwhile, EAg was controlled at 149 mV.

Immediately after completion of the addition, desalting and washing were performed to obtain a tabular seed emulsion-2. In the seed emulsion obtained, 60% or more of the total projected area of the silver halide grains consisted of tabular grains having a (1,0,0) plane as a main plane, and an average thickness of 0.07 μm.
Electron microscope observation revealed that the average diameter was 0.5 μm and the coefficient of variation was 25%.

<Preparation of Silver Chloride Tabular Emulsion [Em-4]> A tabular high silver chloride emulsion was prepared using the following four kinds of solutions.

[0169] <solution A4> ossein gelatin _{29.4g HO- (CH 2 CH 2 O} ) n - (CH [CH _{3] CH 2 O) 17 - (CH} 2 CH 2 O) m H (n + m = 5~ 7) 10% methanol aqueous solution 1.45 ml seed emulsion-2 equivalent to 1.05 mol Make up to 3000 ml with distilled water <Solution B4> 3.50 N AgNO ₃ aqueous solution 2240 ml <Solution C4> NaCl 455 g Make up to 2240 ml with distilled water <Solution D4> 1.75 N NaCl aqueous solution At the following silver potential control amount at 40 ° C., using a mixing stirrer described in JP-B-58-58288, the solution B4 and the solution C were added to the solution A4.
The total amount of No. 4 was adjusted by the simultaneous mixing method (double jet method) so that the flow rate at the end of the addition was three times the flow rate at the start of the addition.
It took 10 minutes to perform additional growth.

During this time, the silver potential was +11 using the solution D4.
It controlled so that it might be set to 5 mV. After completion of the addition, precipitation and desalting were performed by the method described below to remove excess salts.

[0171] 1. The temperature of the reaction mixture after completion of mixing is raised to 40 ° C.
Modified with phenylcarbamoyl group (substitution rate 90%)
Add 20g / AgX1mol of modified gelatin, 56wt%
Add acetic acid to lower the pH to 4.30, and allow to stand for decantation 2. Add 1.8 L of pure water at 40 ° C./1 mol of AgX, stir for 10 minutes, then allow to stand and decant 3. 3. Repeat the above step 2 once more. Then, 15 g of post-gelatin / 1 mol of AgX, sodium carbonate and water were added to adjust the pH to 6.0 and dispersed.
Finish to 0 ml / AgX1 mol.

When about 3,000 of the obtained emulsion [Em-4] were observed and measured by an electron microscope to analyze the shape, 80% or more of the total projected area was defined such that the (1,0,0) plane was the main plane. Average diameter 1.09 μm, average thickness 0.21 μm
m and tabular grains having a coefficient of variation of 24%.

The obtained emulsion [Em-4] was prepared as shown in Table 2.
Chemical sensitization was carried out in the same manner as in the case of the emulsion [Em-1] of Example 1, but nine kinds of silver halide emulsions were prepared depending on whether or not the chemical sensitization was performed with or without reduction selenium sensitization. .
These nine types of silver halide emulsions and the emulsion of Example 1 [Em
-1] with and without reduction sensitization and chemical sensitization in Table 2
Each of the three types of silver halide emulsions and a total of 12 types of silver halide emulsions was coated on a support in the same manner as in Example 1 to prepare 12 types of photosensitive materials. These were designated as samples 1 to 3 and 18 to 26. In the same manner as in Example 1 using the obtained 12 kinds of samples 1 to 3 and 18 to 26, and using a combination of two kinds of processing solutions (a developing solution and a fixing solution) with and without boric acid. Using a modified automatic developing machine TCX-201, density unevenness and residual color were evaluated, and the results are shown in Table 2.

[0174]

[Table 2]

From Table 2, it can be seen that the sample of the present invention is free from density unevenness, residual color, and the like, and a good quality image can be obtained.

[0176]

As demonstrated by the examples, according to the method for processing a photosensitive material of the present invention, even in a processing system in which the replenishing amount of the processing solution is small, there is no occurrence of processing unevenness such as density unevenness or residual color and good quality. Has an excellent effect, such as stably obtaining an image.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03C 5/31 G03C 5/31

Claims (6)

[Claims] 1. A method for processing a silver halide photographic material comprising developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer is A host grain is a tabular silver halide grain, and comprises a silver halide emulsion layer containing silver halide grains having an epitaxially formed portion, and a developing solution and a fixing solution containing substantially no boric acid or a salt thereof. A method for processing a silver halide photographic material, which is processed. 2. The silver halide photograph according to claim 1, wherein the silver halide grains having the epitaxially formed portion are silver halide grains satisfying the following conditions (i) to (iii). Processing method of photosensitive material. (I) Host grains are tabular silver halide grains having a (111) plane as a main plane, and have a circle equivalent diameter of 0.5 to 5.0.
(ii) including epitaxially deposited silver halide projections having a face-centered cubic lattice structure forming an epitaxy junction, and (iii) the silver halide projections having a thickness of 0.07 to 0.3 μm. Are located at the periphery of tabular silver halide grains as host grains. 3. A method for processing a silver halide photographic material comprising developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer is It is composed of a silver halide emulsion layer containing tabular silver halide grains having a (100) major plane, a silver chloride content of 30 mol% or more, and an average aspect ratio of 2 or more, and substantially comprises borane. A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed with a developer and a fixer that do not contain an acid or a salt thereof. 4. The method according to claim 1, wherein said silver halide emulsion layer is selenium sensitized and / or reduction sensitized.
4. The method for processing a silver halide photographic light-sensitive material according to any one of items 1 to 3, 5. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the developer contains reductones. 6. The process according to claim 1, wherein the replenishment amounts of the developing solution and the fixing solution are 200 ml or less per 1 m ^{2 of the} silver halide photosensitive material to be processed. 2. The method for processing a silver halide photographic material according to claim 1.