JPH112879A - Silver halide photographic sensitive material and its processing method and image forming method by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance sensitivity and storage stability with the lapse of time and to reduce fog and fluctuation due to processing even in the case of ultrahigh-speed low-replenishing processing by incorporating at least one of the 2 kinds of specified compounds in the photosensitive material and specified flat silver halide grains in at least one of photographic silver halide emulsion layers. SOLUTION: The photosensitive material contains flat silver halide grains occupying >=50% of the projection areas of the total silver halide grains and having a silver chloride content of 20-100 mol.% and an aspect ratio of >=2 in at least one of silver halide photographic emulsion layers, and the photosensitive material contains at least one of the compounds represented by formulae I and II in which each of R<1> and R<2> is a hydroxy group or the like; each of P and Q is a hydroxy group or the like; Y is a =O or =N-R3 group; R3 is an H atom or a substituent; each of R4 -R8 in formula II is an H atom or a group substitutable on the benzene ring; and Z is an H atom or a protective group releasable in an alkaline condition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has environmental suitability,
The present invention relates to a silver halide photographic material suitable for rapid processing and low replenishment processing, a processing method thereof, and an image forming method using the same. More specifically, the present invention relates to a silver halide photographic material containing an emulsion containing tabular silver halide grains and a developing agent, a processing method thereof, and an image forming method using the same.

[0002]

2. Description of the Related Art In recent years, with regard to the development processing of a silver halide photographic light-sensitive material, it has been increasingly desired to shorten the processing time.

For example, in the medical field, the number of X-ray films taken has increased due to the spread of periodic medical examinations, medical checkups, etc., and the increase in examinations including diagnosis in general medical care. Need to be notified. In recent years, angiographic imaging, intraoperative imaging, and the like have been increasing, but these essentially require the photograph to be viewed in a short time. To meet these demands, it is necessary to promote the automation of diagnosis (imaging, transportation, etc.) and to process X-ray films more quickly.

[0004] Low replenishment of the developing solution is also strongly demanded. From the viewpoint of environmental protection, there has been a demand for a reduction in the amount of development processing waste liquid. However, since the ban on the dumping of industrial waste into the ocean at the end of 1995 has been increasingly demanded.

It is necessary to address these demands for rapid processing and low replenishment processing as a whole system including a photosensitive material, a processing solution, and a processor. Particularly, the development of a photosensitive material to be processed is important. Many studies have been made so far.

For a photographic material, for example, by changing the silver halide photographic emulsion from silver iodobromide to silver bromide, silver chlorobromide, or silver chloride emulsion, the development processing time can be greatly reduced. And low replenishment suitability.

However, the use of silver chloride-containing emulsions causes a great deal of desensitization and fogging, and the fluctuations in sensitivity and gradation during the development processing are extremely difficult, so that practical use has been extremely difficult.

It is also advantageous from the viewpoint of low replenishment processing to reduce the amount of silver applied to the light-sensitive material. For this purpose, a tabular silver halide having a large projected area and a high image density can be obtained with a small amount of silver. Preferably, particles are used. Further, tabular silver halide grains are preferred from the viewpoint of color sensitization efficiency, that is, from the viewpoint of sensitivity.

Therefore, in order to obtain a high-sensitivity silver halide photographic light-sensitive material having suitability for rapid processing and low replenishment processing, it is desired to develop tabular silver halide grains containing silver chloride.

Many studies have been made on tabular grains containing silver chloride and having the (111) plane as the main plane. However, all of these studies have been made to form the (111) plane with additives. And the essential problems caused by the instability of the (111) surface of silver chloride, such as the fact that the additive has a large adverse effect on the photographic performance and the formed (111) surface is unstable. It was expected that the transformation would be difficult.

On the other hand, many studies have been made on tabular grains containing silver chloride and having a (100) plane as a main plane. JP-A-5-204073 discloses an emulsion comprising high silver chloride tabular grains having a (100) main plane using silver iodide during nucleation. JP-A-7-234470 discloses an emulsion comprising silver halide tabular grains having a halogen composition gap plane in the center of the grains and having a (100) main plane. However, these emulsions were not practical because of insufficient sensitivity and low γ.

Japanese Patent Application Laid-Open No. 8-76306 discloses that high sensitivity and low sensitivity can be attained by continuously changing the halogen composition of the shell portion in a core / shell type silver chlorobromide having a (100) main plane. Fog, high covering power,
It is said that the resistance to pressure blackening has been improved, but the feature is that the halogen composition of the shell portion is changed, and that the composition of the core portion has a small effect on the performance.
The photographic performance achieved has been far from practical use.

Japanese Patent Application Laid-Open No. 8-1222953 discloses that a seed crystal containing silver chloride is used to form (1)
Tabular silver halide grains having the (00) plane as the main plane,
Although the monodispersity, sensitivity, and granularity of the particles are said to be improved, the volume of the seed crystal used is as small as 0.001 μm ³ or less, which is not practical.

As described above, the tabular silver halide grains containing silver chloride having the (100) plane as the main plane provide sensitivity, fog,
Basic photographic performances such as γ and covering power are not yet satisfactory, and further improvement is required for practical use.

JP-A-8-184935 states that tabular grains containing silver chloride and a silver halide photosensitive material containing a developing agent provide good sensitivity and fog even when the processing solution is reduced in replenishment amount. However, these samples showed remarkable rise in fog during storage over time, especially under high humidity conditions, and were not practically usable. Furthermore, development unevenness occurs in ultra-rapid processing with a development time of 7 seconds or less, and processing fluctuation is large under ultra-low replenishment (developer replenishment amount ≦ 100 ml / m ² ), so that it can be put to practical use. It was not.

[0016]

In view of the above-mentioned problems, the object of the present invention is, firstly, to provide high sensitivity, low fog, excellent storage stability with time, even in ultra-rapid and low replenishment processing,
Another object of the present invention is to provide a silver halide photographic emulsion and a light-sensitive material having small processing variability.

A second object of the present invention is to provide a method for producing a silver halide photographic emulsion having such performance.

A third object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having such performance in a quick, safe and environmentally friendly manner.

A fourth object of the present invention is to provide an image forming method using a silver halide photosensitive material having such performance.

[0020]

The above objects of the present invention have been attained by the following constitutions.

(1) In a silver halide photographic material having at least one silver halide photographic emulsion layer on a support, the photographic material is represented by the following formula (1) or (2): The silver halide grains contained in at least one of the silver halide photographic emulsion layers and at least 50% of the total projected area have a silver chloride content of 20 to 100 mol%. And tabular silver halide grains having an aspect ratio of 2 or more, and the silver halide grains satisfy at least one of the following (A), (B), (C), (D) or (E). A silver halide photographic material comprising tabular silver halide grains.

(A) A tabular silver halide grain containing silver iodide therein, in which silver salt is added in the absence of iodide to start nucleation, and Silver halide grains produced through two processes of adding a silver salt in the presence of a halide to cause nucleation and / or crystal growth (B). Silver grains (C) Tabular silver halide grains containing a nucleus composed of silver bromide or silver iodobromide (D) Tabular silver halide grains grown with normal crystals as seed crystals (E) Inside grains Tabular silver halide grains containing cations other than silver ions

[0023]

Embedded image

Wherein R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P and Q are a hydroxy group, a carboxy group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group,
Represents a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a methylcapto group, an alkyl group or an aryl group, or represents two vinyl carbons substituted by R ₁ and R ₂ by combining P and Q. Represents an atom group that forms a 5- to 8-membered ring together with the atom and the carbon atom substituted by Y. Y =
O, or = NR ₃ . R ₃ represents a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group,
Represents a sulfoalkyl group or a carboxyalkyl group. ]

[0025]

Embedded image

Wherein R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are
A hydrogen atom or a group capable of being substituted on a benzene ring, which may be the same or different. However, the total number of carbon atoms of R ₄ to R ₈ is 8 or more, and at least one of R ₄ and R ₆ is a hydroxy group, a sulfonamide group or a carbonamide group. Z is a hydrogen atom or a protecting group which can be removed under alkaline conditions. R ₄ to R ₈ and OZ may form a ring together. (2) The main plane of the tabular silver halide grains is (100)
2. The silver halide photographic light-sensitive material as described in 1 above, which is a surface.

(3) The silver halide photographic light-sensitive material as described in (1) or (2) above, wherein the compound of the general formula (1) or (2) and the silver halide photographic emulsion are contained in the same layer.

(4) The silver halide photographic material as described in (1) or (2) above, wherein the compound of the formula (1) or (2) and the silver halide photographic emulsion are contained in separate layers.

(5) A method for processing a silver halide photographic light-sensitive material, comprising subjecting the silver halide photographic light-sensitive material according to any one of the above items 1 to 4 to photographic processing including development processing.

(6) The processing method according to the above (5), wherein the development processing time is from 1 second to 7 seconds.

(7) The photographic processing is a method in which processing is performed while continuously replenishing a processing solution according to the photosensitive material to be processed. The replenishment amount of the developing solution is per 1 m ^{2 of the} photosensitive material to be processed. 7. The method for processing a silver halide photographic material according to the above item 5 or 6, wherein the amount is 1 cc or more and less than 100 cc.

(8) The above-mentioned item (5), wherein a developer and / or a development replenisher containing no developing agent is used.
8. A method for processing a silver halide photographic light-sensitive material according to any one of claims 1 to 7.

(9) The method for processing a silver halide photographic material as described in any one of (5) to (8) above, wherein the fixing time is from 1 second to 7 seconds.

[0034] (10) the photographic process is a method of processing while continuously replenishing the processing solution in accordance with the light-sensitive material being processed, the photosensitive material 1 m ² per the replenishing amount of the fixing solution to be processed 10. The method for processing a silver halide photographic light-sensitive material according to any one of the above items 5 to 9, wherein the amount is 1 cc or more and less than 100 cc.

(11) The developing solution and / or the developing replenishing solution contains a fixing agent.
10. The method for processing a silver halide photographic light-sensitive material according to any one of 10 above.

(12) The method according to any one of the above items 5 to 11, wherein development and fixing are carried out in substantially the same solution.
The method for processing a silver halide photographic light-sensitive material described in the above item.

(13) The silver halide photographic material as described in any one of (5) to (12) above, wherein the material is processed by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank of the automatic developing machine. Processing method.

(14) The silver halide photographic material as described in any one of (1) to (4) above, sandwiched with a radiographic intensifying screen,
14. An image forming method, wherein an X-ray image is taken and processed by the processing method according to any one of the items 5 to 13.

Hereinafter, the present invention will be described in more detail. In the silver halide photographic emulsion contained in the silver halide photographic light-sensitive material of the present invention, 50% or more of the total projected area of the silver halide grains in the emulsion is composed of tabular silver halide grains having an aspect ratio of 2 or more. Preferably, 70% or more, more preferably 80% or more and 100% or less, and still more preferably 90% or more and 100% or less comprise tabular silver halide grains.

In the present invention, the tabular silver halide grains are grains having two opposing parallel main planes and having a grain size ratio to grain thickness (aspect ratio) of more than 2. . Here, the grain size means an average projected area diameter (hereinafter, referred to as a grain size), and is a circle equivalent diameter of a projected area of the tabular silver halide grains (of a circle having the same projected area as the silver halide grains). Diameter), and thickness refers to the distance between two parallel major planes forming tabular silver halide grains.

In the present invention, the tabular silver halide grains are characterized in that the main plane is the (100) plane. The average aspect ratio of the tabular silver halide grains (hereinafter, also referred to as silver halide grains of the present invention) is 2 or more, preferably 2 or more and less than 20, more preferably 2 or more and 15 or less. Is less than.

The shape of the main plane of the tabular silver halide grains of the present invention is a right-angled parallelogram or a shape in which the corners of a right-angled parallelogram are rounded. The adjacent side ratio of the right-angled parallelogram is 10
It is preferably less than 5, more preferably less than 5, and even more preferably less than 2. In addition, the length of the side when the corner is rounded is represented by the length up to the intersection with the line obtained by extending the straight part of the side of the right-angled parallelogram and extending the straight part of the adjacent side.

In the present invention, the method for measuring the crystal plane of tabular silver halide grains is described in Journal of
Imaging Science, vol. 29, N
o. 5, Sept. 1985, (SPRINGFIEL
D US) P. 165-171, the method reported by Tani et al.

The silver halide grains of the present invention may have dislocations. Dislocations are described in F. Hamilton,
Photo. Sci. Eng, 57 (1967),
T. Shiozawa, J .; Soc. Photo. Sc
i. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a sharper observation can be obtained by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). it can.

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

The average thickness of the tabular silver halide grains of the present invention is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.40 μm, even more preferably from 0.02 to 0.4 μm. 30 μm.

In the present invention, the tabular silver halide grains are preferably monodisperse grains having a narrow particle size distribution.

Specifically, when the distribution width is defined by (standard deviation of particle size / average particle size) × 100 = width (%) of particle size distribution, it is preferably 30% or less, and 25% or less. The following is more preferable, 20% or less is still more preferable, and 17% or less is the most preferable.

The tabular silver halide grains of the present invention preferably have a narrow thickness distribution. Specifically, when the width of distribution is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is preferably 30% or less, and more preferably 25%. The content is particularly preferably 20% or less.

Particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Optimum particle size and optimum depending on other factors constituting the photosensitive material (sensitivity of hydrophilic colloid layer, hardness, chemical ripening conditions, sensitivity of photosensitive material, amount of silver coating, etc.) that affect sensitivity and other photographic characteristics The thickness is different.

The tabular silver halide grains of the present invention have a silver chloride content of 20 to 100 mol%, preferably 2 to 100 mol%.
5 mol% or more and 100 mol% or less.

In the tabular silver halide grains of the present invention, silver iodobromochloride, silver bromochloride, silver iodochloride and the like can be used as silver halide. In the case of silver iodobromochloride or silver iodochloride, the content of silver iodide is preferably 0.01 mol% or more and 1.0 mol% or less as an average silver iodide content of the whole silver halide grains. The content is more preferably from 0.01% to 0.5% by mole.

In the case of silver bromochloride or silver iodobromochloride, the content of silver bromide is not particularly limited. If the contents of silver chloride and silver iodide are within the range of the present invention, the effects of the present invention can be obtained. Can be presented.

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

The tabular silver halide grains contained in the silver halide photographic emulsion of the present invention preferably have a more uniform halogen composition between grains. When the distribution of the halogen composition between the grains was measured by the EPMA method, the relative standard deviation of the composition between the grains of iodine was particularly 35% or less, more preferably 20% or less.
The following is preferred.

In the tabular silver halide grains of the present invention, the halogen composition inside and / or on the surface of the grains may be uniform or may have a distribution depending on the position, but has a distribution depending on the position. Is preferred.

In one embodiment of the tabular silver halide grains of the present invention, it is preferable that the nucleus portion is composed of silver bromide or silver iodobromide, that is, it does not contain silver chloride. here,
The nucleus portion is a central portion of the silver halide grains, and means a first portion where the grains are precipitated from the liquid continuous phase as silver halide microcrystals, that is, a portion formed during so-called nucleation. The nucleus portion preferably contains silver iodide, that is, silver iodobromide. In the case of silver iodobromide, the silver iodide content of the core portion is preferably 0.1 mol% or more and 5 mol% or less.

The distribution of the halogen composition inside the silver halide grains can be determined by pretreating the grains into ultrathin sections, and then observing and analyzing them with a transmission electron microscope while cooling. Specifically, silver halide grains are taken out of the emulsion, embedded in a resin, and cut with a diamond knife to produce a 60-nm-thick section. 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 can be obtained by quantitative calculation (Inoue, Nagasawa: Abstracts of the 62nd Annual Meeting of the Photographic Society of Japan, 1987 p62).

In the present invention, the tabular silver halide grains preferably have silver bromide and / or silver iodide on the outermost surface of the grains. Silver bromide content on the outermost surface is 20 mol%
Or more, more preferably 50 mol% or more. The silver iodide content is preferably at most 10 mol%, more preferably at most 5 mol%, most preferably at most 1.0 mol%.

Here, the silver halide composition on the outermost surface of the tabular silver halide grains is defined by the XPS method (X-ray Ph
otoelectron Spectroscopy:
X-ray photoelectron spectroscopy) refers to the silver halide composition up to a depth of 50 °, which can be determined as follows.

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

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

In the present invention, the tabular silver halide grains preferably have a silver bromide and / or silver iodide localized phase near the surface and / or near the apex. The term "near the surface" as used in the present invention means that the particle size is 1 particle,
Within / 5, preferably within 1/7. Further, the vicinity of the vertex in the present invention means about ３ of the diameter of a circle having the same area as the area of the projected silver halide grain in the present invention.
Is defined as an area of a tabular grain having the length of one side as one side and the vertex of the grain as one corner.

The silver bromide content of the silver bromide localized phase near the surface and / or near the apex is preferably at least 20 mol%.
0 mol% or more is more preferable. Further, the silver iodide content of the silver iodide localized phase is preferably 5 mol% or less, more preferably 1.0 mol%.
The following are more preferred.

As one embodiment of the tabular silver halide grains of the present invention, 1) a process of adding a silver salt in the absence of iodide to start nucleation, and 2) a silver salt in the presence of iodide Is preferably produced through two processes of adding nucleus and performing nucleation and / or crystal growth.

Specifically, (a) nucleation is started in the absence of iodide, and nucleation is continued in the presence of iodide. (B) nucleation is started in the absence of iodide. Crystal growth in the presence of iodide (c) a production method having any of the steps of starting nucleation in the absence of iodide, and subsequently growing crystals simultaneously with nucleation in the presence of iodide. Is characterized in that iodide does not exist at the start of nucleation, but iodide immediately follows. Hereinafter, each process will be described in detail.

(1) Step of Initiating Nucleation Nucleation is performed by adding a silver salt and / or halide salt solution to a dispersion medium solution containing at least a dispersion medium and water while stirring. The pCl at the start of nucleation is adjusted to a value that easily forms the (100) plane, that is, 0.5 to 3.5, preferably 1.0 to 3.0, and more preferably 1.5 to 2.5. The pH is preferably at least 1.0, more preferably at least 1.5, and even more preferably from 2.0 to 7.0. Gelatin and gelatin derivatives are preferably used as the dispersion medium, and gelatin from which impurities have been removed is more preferable.
In particular, it is preferable to use a so-called low methionine gelatin having a methionine content of less than 30 μmol / g of gelatin, preferably less than 15 μmol / g of gelatin. Further, it is preferable to use so-called low molecular weight gelatin having a molecular weight of 1,000 to 10 × 10 ⁴ , preferably 2000 to 6 × 10 ⁴ . These gelatins may be used alone or as a mixture of two or more. The concentration of the dispersion medium is preferably 0.1 to 10% by weight, and 0.3 to 5% by weight.
% By weight is more preferred.

The nucleation is started from the moment when the silver salt is added to the dispersion medium solution. Therefore, in the present invention,
"Initiating nucleation in the absence of iodide" means that iodide is not contained in the dispersion medium solution at the start of nucleation, ie, at the start of silver salt addition. Here, the start of the addition of the silver salt means the moment when the addition of the silver salt to the dispersion medium solution is started. The silver salt addition period in the absence of iodide is preferably 1 second to 2 minutes including this instant, and more preferably 5 seconds to 30 seconds. During this time, other halide salts may or may not be added. That is, a so-called single jet method in which only a silver salt is added or a double jet method in which a silver salt and a halide salt solution is added may be used.

(2) A process of subsequently adding a silver salt in the presence of iodide to cause nucleation and / or crystal growth In the present invention, the silver salt is added to the dispersion medium solution in the absence of iodide as described above. Immediately after the addition, a silver salt is continuously added in the presence of iodide to perform nucleation and / or crystal growth. At this time, the iodide ion concentration in the dispersion medium solution can be introduced up to the solid solution limit of silver iodide and silver chloride.
It is preferably set to 10 to 10 mol%, and more preferably 0.01 to 8 mol%. Further, the chloride ion concentration is preferably at least 50 mol%. The bromine ions in the dispersion medium solution at the time of nucleation consisted of 50 mol% of chloride ions.
As long as it exists, it may be present.

As a method for causing iodide to be present in the dispersion medium solution, for example, a method in which an iodide salt is contained in a halide salt solution and added thereto can be used. At this time, any method such as a double jet method in which a silver salt solution is added at the same time and a method in which only a halide solution is added and then a silver salt solution is added can be used. The silver salt addition period in the presence of iodide is preferably 1 second to 5 minutes, and more preferably 5 seconds to 5 seconds.
2 minutes is more preferable, and 10 seconds to 1 minute is most preferable.

In the above-mentioned production method, the temperature in the step of initiating the nucleation and the step of subsequently adding a silver salt in the presence of iodide to cause nucleation and / or crystal growth are preferably 10 ° C. or higher, 20-70 ° C is particularly preferred.

In the method for producing tabular silver halide grains according to the present invention, the amount of silver added during nucleation is preferably 0.1 mol% to 10 mol% of the total silver amount.

In the method for producing tabular silver halide grains according to the present invention, the step of initiating the nucleation and the step of subsequently adding a silver salt in the presence of iodide to perform nucleation and / or crystal growth. It is preferable to have a ripening step following the ripening step. In the ripening process, tabular grains generated during nucleation by Ostwald ripening can be further grown and other grains can be eliminated. Aging temperature is 20-90
C. is preferred, 30 to 85C is more preferred, and most preferably 40 to 80C. The temperature during ripening may be constant or changed, but when a crystal growth process described below is further provided, a method of changing the ripening temperature is advantageously used.
The pCl at the time of aging is preferably 0.5 to 3.5, more preferably 1.0 to 3.5.
3.0 is more preferred. Further, the pH is preferably 1 to 12, more preferably 2 to 8, and most preferably 2 to 6. The ripening is preferably carried out in the absence of a so-called silver halide solvent such as ammonia.

The tabular silver halide grains according to the present invention 1
As an embodiment, it is preferable that a chalcogen compound is contained in the inside, preferably in the core portion.

Here, the inside of the silver halide grain is a portion from the center of the grain to 50% of the total volume, preferably a portion to 30% of the total volume. The nucleus portion is a portion from the center of the particle to 10% of the total volume, preferably 5%, and most preferably 1%.

The chalcogen compound is a general term for inorganic or organic compounds containing at least one element of sulfur, selenium, and tellurium.

Specific examples of chalcogen compounds preferably used in the present invention include sulfur compounds such as thiosulfates (eg, sodium thiosulfate, p-toluenethiosulfonate), sulfides (eg, sodium sulfide), and the like.
Thioureas (for example, thiourea, monomethylthiourea,
Dimethylthiourea, diethylthiourea, trimethylthiourea, tetramethylthiourea, allylthiourea, dioctylthiourea, etc., thioamides (eg, thioacetamide), thiocyanates (eg, potassium thiocyanate, ammonium thiocyanate, methyl thiocyanate, etc.) ), Disulfides (eg, dimorpholino disulfide, etc.), thiosulfonic acids (eg, sodium benzenethiosulfonate, etc.), mercapto compounds (eg, 5-mercapto-1-phenyltetrazole, cysteine, etc.), elemental sulfur, etc. Can be mentioned.

Examples of selenium compounds include colloidal selenium metal, selenocyanic acids, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N, N-dimethylselenourea, N, N,
N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-
Trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides ( For example, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophos) And selenides (such as triphenylphosphine selenide, diethyl selenide, and diethyl diselenide).

Examples of tellurium compounds include telluroureas (for example, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'-dimethyl-N ' Phenyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (eg, telluroacetamide) , N, N-dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates and the like.

Of these, preferred are thiosulfates,
Thioureas, thioamides, thiocyanic acids, disulfides, thiosulfonic acids, selenocyanic acids, selenoureas, selenoamides, selenoketones, and selenides.

In the present invention, the amount of the chalcogen compound contained in the tabular silver halide grains varies depending on the kind of the compound, silver halide grains, chemical ripening conditions, etc., but is 10 ⁻ per mol of silver halide. ^{It is from 9} to 10 ^-1 mol, preferably from 10 ^-8 to 10 ^-2 mol.

As another embodiment of the tabular silver halide grains of the present invention, it is preferable that the tabular silver halide grains contain a cation of a typical element other than silver ions, and more preferably, a cation of a group I to group V of the periodic table. It is a cation of a typical element. It has not been expected that the introduction of the cation of a typical element will improve the performance of the present invention, such as high sensitivity and low fog.

The ion radius is preferably a cation less than 0.95 or 1.05 times the silver ion, and more preferably 0.5 to less than 0.9 or 1.1 to 1.1. The cation is less than 0.5-fold, more preferably 0.5-0.85 or 1.15-1.5, most preferably 1.15-1.5. Here, the ion radius is a value that indicates the size of the ion.
The values described in Tables 15 and 24 (pages II-725 to 726) can be referred to. In the present invention, the radius of a silver ion represents a value in the case of hexacoordination of a monovalent silver ion. According to Tables 15 and 24, it is 1.29 ° (angstrom).

A tabular silver halide grain having a (100) plane as a main plane is formed when the (100) plane having defects such as dislocations is formed because the growth rate is increased and consequently anisotropic growth occurs. Conceivable. In the present invention, it is considered that the problem is achieved by forming defects for the anisotropic growth with cations of typical elements other than silver ions.

In the case of a cation having an ionic radius of less than 0.5 times that of a silver ion, the cation is hardly incorporated into the silver halide crystal, or even if incorporated, the cation disturbs the lattice of the silver halide crystal. Therefore, it is considered that it is difficult to promote anisotropic growth. Also, cations having an ionic radius substantially equal to 0.95 times to 1.05 times that of silver ions are not likely to disturb the silver halide crystal lattice even when incorporated, and thus it is considered difficult to promote anisotropic growth. . Conversely, cations having an ionic radius that is 1.5 times or more as large as silver ions are less likely to be taken into silver halide crystals, and therefore it is considered that it is difficult to promote anisotropic growth.

In the present invention, the cation contained in the tabular silver halide grains is a typical element, and the greatest effect can be obtained when the ionic radius is in the above preferred range. Even in this case, sufficient effects can be obtained if they can be successfully incorporated into the crystal lattice.Also, if they are not typical elements, the ionic radius is within the above preferred range, and if they can be successfully incorporated into the crystal lattice, the effect is sufficient. is there.

The silver halide grains described above are characterized in that they contain a cation of a typical element other than the silver ion in the inside thereof, but preferably contain them in the core.

Here, the inside of a silver halide grain is a portion from the center of the grain to 50% of the total volume, preferably a portion to 30% of the total volume. The nucleus portion is a portion from the center of the particle to 10% of the total volume, preferably 5%, and most preferably 2%.

In the present invention, the amount of cations of typical elements other than silver ions contained in the tabular silver halide grains varies depending on the type of cations, silver halide grains, chemical ripening conditions and the like. It is 10 ^-9 to 10 ^-1 mol, preferably 10 ^-8 to 10 ^-2 per mol of silver.
Is a mole.

In one embodiment of the tabular silver halide grains of the present invention, it is preferable that a seed crystal part is present and the part is a normal crystal. The seed crystal portion refers to a portion from the nucleation to the Ostwald ripening process and / or the crystal growth process in the grain formation process until the grain size becomes uniform and the grains are stably present. Preferably, the volume is 0.0012 μm ^{3 to} 0.
It is a portion of 50 μm ³ and 0.1% to 33% of the total volume of the finally formed particles, more preferably 1% to 25%. In addition, that the seed crystal portion is a normal crystal means that the portion does not have dislocations, twin planes, or the like and does not grow anisotropically.

The tabular silver halide grains of the present invention are preferably formed by using normal seed crystals. By using a seed crystal of a normal crystal, it is possible to reduce the variation in the size and shape between the particles after growth, and as a result, fog,
It is considered that sensitivity, γ, etc. can be improved. The seed crystals preferably have a volume of 0.0012 μm ^{3 to} 0.50 μm ³ , and preferably 0.1% to 33% of the total volume of the particles finally formed, and more preferably 1% to 33%. % To 25%. The habit of the seed crystal is not particularly limited, but preferably has a (100) plane.
More preferably, the surface area of the (100) plane occupies 50% or more of the total surface area of the seed crystal.
%. Seed crystal size distribution is 30
% Or less, and more preferably 20% or less.

In the tabular silver halide grains described above, the halogen composition of the seed crystal portion is not particularly limited, but silver chloride, silver bromide and silver chlorobromide are preferred. The seed crystal may contain silver iodide as long as it is a normal crystal, and silver iodochloride, silver iodobromide, and silver iodochlorobromide are also preferably used.

Although the halogen composition of the seed crystal may be uniform or have a distribution depending on the position, it is preferable that the halogen composition has a distribution depending on the position. Further, it is preferable that the seed crystal surface is converted by a different kind of halogen.

In the above-described method for producing a silver halide photographic emulsion, it is preferable to form tabular silver halide grains having a (100) plane as a main plane and an aspect ratio of 2 or more, using a normal crystal as a seed crystal.

That is, a silver halide photographic emulsion produces seed crystals composed of normal crystals through Ostwald ripening and / or crystal growth after nucleation, and is anisotropically grown on the surface of the seed crystals or during the subsequent growth process. It is preferable to introduce defects that promote the formation of tabular grains.

The method for producing a seed crystal is not particularly limited as long as a normal crystal is formed, and a conventionally known method for producing a normal crystal can be used.

For example, a nucleus is formed under conditions that easily form the (100) plane, and then Ostwald ripening and / or crystal growth is carried out to form a (100) plane having a desired grain size and distribution as a seed crystal. It is preferred to obtain cubic silver halide grains. Also, octahedral particles may be formed under conditions that facilitate formation of the (111) plane, or tetrahedral particles may be formed.

In this case, first, a silver salt solution, a halide solution, and a protective colloid solution are added to the first container to form nuclei.
After the nucleation, a method of transferring the mixed solution to a second container and growing there is preferably used. A method in which nucleation and growth are performed in the same vessel is also preferable.

The grain size of the seed crystal is 0.11 μm to 0.80 μm.
Is preferred, and the particle size distribution is preferably 30% or less, and 20% or less.
The following is more preferred. Therefore, it is necessary to adjust the temperature, pH, pAg, addition concentration of the addition solution, addition speed, and the like so that such seed crystals are formed.

In the method for producing a silver halide photographic emulsion according to the present invention, the surface of the seed crystal thus produced is
Crystal growth is performed to finally form tabular silver halide grains having a (100) plane as a main plane.

More specifically, an aqueous solution and a seed crystal containing a protective colloid are previously present in a reaction vessel, and silver ions, halide ions or silver halide fine particles are supplied as needed to grow the seed crystal. it can.

The growth from the seed crystal includes a ripening process and / or a crystal growing process.

In the method for producing tabular silver halide grains according to the present invention, anisotropic growth is carried out on the surface of the seed crystal or in the course of subsequent growth in order to grow normal crystals and obtain tabular grains. It is necessary to introduce flaws that promote it. The defect is preferably a linear defect such as a screw dislocation or an edge dislocation. In order to introduce the defect, for example, addition of different kinds of halogens or impurities is preferably used. As a different kind of halogen, iodine is preferable. As the impurity, an anion that forms an insoluble salt with silver is preferable. For example, SCN ⁻ ,
SeCN ^-, thioureas, and the like. Further, metal ions incorporated into silver halide grains are also preferably used as impurities.

In the method for producing a silver halide photographic emulsion of the present invention, a known silver halide solvent such as ammonia, thioether, thiourea and the like can be present.

In the method for producing a silver halide photographic emulsion of the present invention, a silver salt solution and a halide solution are added by a double jet method at the time of growth, and a new nucleation does not occur according to the rate of addition according to the growth of grains. Particles having a desired particle size and distribution can be obtained by a method in which the size distribution is not spread due to Ostwald ripening, that is, a method in which the size is gradually changed within the range of 30 to 100% of the rate at which new nuclei are generated. 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. Especially silver iodide fine grains,
Silver bromide fine grains, silver iodobromide fine grains, silver bromochloride fine grains, and silver chloride fine grains are preferably used.

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

As a halogen conversion method, usually, an aqueous halogen solution or silver halide fine particles having a smaller solubility product with silver than the halogen composition on the grain surface before the halogen conversion is added. The particle size at this time is 0.2 μm
The following is preferable, and more preferably 0.02 to 0.1 μm
When silver iodide and / or silver bromide on the outermost surface of the tabular silver halide grains of the present invention is contained, the method is as follows.
A method of simultaneously adding a silver nitrate solution and a solution containing iodide ion and / or bromide ion to an emulsion containing tabular grains as a base, silver iodide, silver bromide, silver iodobromide or silver chloroiodobromide, etc. Of silver halide fine particles, potassium iodide or a mixture of potassium iodide and potassium bromide. Of these, the method of adding fine silver halide grains is preferable. Particularly preferred is a method of adding silver iodide fine grains, silver bromide fine grains, and silver iodobromide fine grains.

The time for adjusting the silver iodide and / or silver bromide content on the outermost surface is from the final stage of the silver halide crystal production process to the chemical ripening process, and immediately before the application of the silver halide photographic emulsion. Can be selected until the completion of the liquid preparation step, but it is preferable to adjust the pH by the end of the chemical ripening step. The term "chemical ripening step" as used herein means a step of adding a chemical sensitizer and then stopping the chemical ripening from the time when the physical ripening and desalting operations of the silver halide photographic emulsion of the present invention are completed. Point to the time. The addition of silver halide fine grains may be carried out several times at intervals, or another chemically-ripened emulsion may be added after the addition of the fine grains.

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

In producing the silver halide photographic emulsion of the present invention, stirring conditions during production are extremely important. As the stirring device, a device in which an additive liquid nozzle disclosed in JP-A-62-160128 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 preferably set to 100 to 1200 rpm.

In the silver halide grains of the present invention, silver nuclei may be formed during grain formation. Silver nucleation is carried out by adding a reducing agent to a silver halide photographic emulsion or a mixed solution for grain growth, or a silver halide photographic emulsion or a mixed solution for grain growth is reduced to a low pAg of pAg7 or less. It is carried out by ripening or growing the particles under high pH conditions of pH 7 or higher. A method performed by combining these methods is a preferred embodiment of the present invention.

Preferred reducing agents include, for example, thiourea dioxide, ascorbic acid and its derivatives,
And tin salts. Other suitable reducing agents include
Examples include borane compounds, hydrazine derivatives, formamidine sulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount of these reducing agents is preferably from 10 ^-2 to 10 ^-8 mol per mol of silver halide.

For low pAg ripening, a silver salt can be added, but a water-soluble silver salt is preferable and silver nitrate is preferable as the water-soluble silver salt. The pAg at the time of aging is suitably 7 or less, preferably 6 or less, and more preferably 1 to 1.
3 (where pAg = -log [Ag ⁺ ]).

The high pH ripening is carried out, for example, by adding an alkaline compound to a silver halide photographic emulsion or a mixed solution for grain growth. As the alkaline compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. In the method of adding ammoniacal silver nitrate to silver halide formation, an alkaline compound other than ammonia is preferably used because the effect of ammonia is reduced.

As a method of adding a silver salt and an alkaline compound for forming silver nuclei, rush addition or addition over a certain period of time may be used. In this case, the addition may be performed at a constant flow rate, or may be performed while changing the flow rate with respect to time.

The required amount may be added in several portions. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed in a soluble halide solution and added together with the halide. Furthermore,
The addition may be performed separately from the soluble silver salt and the soluble halide.

An oxidizing agent can be used in the silver halide photographic emulsion of the present invention. The following oxidizing agents can be used.

Hydrogen peroxide (water) and its adduct: H
₂ O ₂ , NaBO ₂ , H ₂ O ₂ -3H ₂ O ₂ , Na ₄ P ₂ O ₇ -2
Such as _{H 2 O 2, 2Na 2 SO} 4 -H 2 O 2 -2H 2 O. Peroxy acid salts: K ₂ S ₂ O ₃ , K ₂ C ₂ O ₃ , K ₄ P ₂ O ₃ , K ₂ [T
_{i (O 2) C 2 O} 4 ]-3H ₂ O and the like.

Besides, peracetic acid, ozone, iodine, bromine,
Thiosulfonic acid compounds, chloramine T and the like.

The amount of the oxidizing agent used in the present invention is affected by the type of the reducing agent, the conditions for forming silver nuclei, the timing of adding the oxidizing agent, and the adding conditions. ^-2 to ^10-5 mol is preferred.

The oxidizing agent may be added at any time during the silver halide photographic emulsion manufacturing process. It can be added prior to the addition of the reducing agent. Further, after the oxidizing agent is added, a reducing substance may be newly added to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the oxidizing agent, and include sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazines and hydrazides, p-phenylenediamines,
Aldehydes, aminophenols, enediols,
There are oximes, reducing sugars, phenidones, sulfites, ascorbic acid derivatives and the like. The amount of these reducing substances to be added is 10 ⁻³ to 10 per mol of the oxidizing agent used.
³ moles are preferred.

The silver halide photographic emulsion of the present invention can use heavy metal ions. As heavy metal ions,
Periodic table of iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, etc.
Group VIII metal, cadmium, zinc, mercury, etc.
Group II transition metals, lead, rhenium, molybdenum, tungsten, chromium, thallium and other ions,
Among them, transition metal ions of iron, iridium, platinum, ruthenium, and osmium are preferable.

These heavy metal ions can be added to a silver halide photographic emulsion in the form of a salt or a complex salt. Among them, those added to the emulsion in the form of a complex salt are preferred because they can be easily incorporated into a silver halide photographic emulsion.

When the heavy metal ion forms a complex,
Examples of the ligand include cyanide, thiocyanic acid, isothiocyanic acid, cyanic acid, chloride, bromide, iodide, carbonyl, and ammonia.
Among them, thiocyanic acid, isothiocyanic acid and cyanate ion are preferred.

In order to incorporate a heavy metal ion into a silver halide photographic emulsion, the heavy metal compound is subjected to various steps during the formation of silver halide grains, during formation of silver halide grains, and during physical ripening after formation of silver halide grains. May be added at any location. For this purpose, for example, a heavy metal compound may be added as an aqueous solution at a desired timing. Alternatively, they may be dissolved together with the silver halide and added continuously during the grain formation step.

The amount of heavy metal ion added to a silver halide photographic emulsion is from 1 × 10 ^-9 to 1 / mol of silver halide.
× 10 ^-2 mol is preferred, and in particular 1 × 10 ^-8 to 1 × 10 ^-3.
Molar is preferred.

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 grains.
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (Resea
rc Disclosure. RD)
76 volume No. 17643 (December 1978).

In the production of the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed during the growth of silver halide grains, or they may be contained. When removing the salts, see RD Vol. 1764
The method can be carried out based on the method described in 3 II. When seed particles are used, desalination is preferably performed once seed particle formation is completed.

The tabular silver halide grains of the present invention are preferably spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holoboralar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

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

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

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, a substituted aminostilbene compound which is a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
Nos. 933,390 and 3,635,721), formaldehyde condensates of aromatic organic acids (for example, those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like. Is also good.

US Pat. Nos. 3,615,613;
615,641, 3,617,295, 3,6
The combinations described in JP-A-35,721 and the like are particularly useful. The sensitizing dye may be added during or during each step of nucleation, growth, desalting, and chemical sensitization, or after chemical sensitization.

The tabular silver halide grains of the present invention are preferably selenium and / or tellurium sensitized.

In the case of selenium sensitization, a wide variety of selenium compounds can be used as the selenium sensitizer.
Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylselenourea) , N,
N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenyl Carbonylselenourea, etc.), 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 (for example, tri-
p-triselenophosphate, etc.), and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenoketones, selenides.

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

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

With respect to tellurium sensitizers and sensitization methods, examples of useful tellurium sensitizers include telluroureas (eg,
N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (for example, tributylphosphine) Telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (eg, telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro Esters, isotellocyanates and the like.

The technique for using the tellurium sensitizer is the same as the technique for using the selenium sensitizer.

The tabular silver halide grains of the present invention are preferably used in combination with chemical sensitization other than selenium and / or tellurium sensitization. Chemical sensitization process conditions such as pH, pA
There are no particular restrictions on g, temperature, time, and the like, and the reaction can be performed under conditions generally performed in the art. As a preferable chemical sensitization method when used in combination, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin,
Examples thereof include a reduction sensitization method using a reducing substance, gold and other noble metal sensitization methods using a noble metal. Above all,
Sulfur sensitization, gold sensitization, reduction sensitization and the like are preferred.

Specific examples of the sulfur sensitizer applicable to the present invention include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl, 3- (2-thiazolyl) thiourea, and the like. Preferable examples include rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and simple sulfur. still,
As the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Examples of the gold sensitizer include chloroauric acid, gold thiosulfate, gold thiocyanate, and gold complexes of thioureas, rhodanines, and other various compounds.

The amounts of the sulfur sensitizer and the gold sensitizer to be used are not uniform depending on the type of silver halide grains, the type of compound used, the ripening conditions and the like.
It is preferably from 1 × 10 ^-4 mol to 1 × 10 ^-9 mol per mol. Further, preferably 1 × 10 ⁻⁵ mol to 1 ×
10 ^-8 mol.

In the present invention, the sulfur sensitizer and the gold sensitizer may be added by dissolving them in water or alcohols or other inorganic or organic solvents and adding them in the form of a solution. Alternatively, it may be added in the form of a dispersion obtained by emulsifying and dispersing using a medium such as gelatin.

In the present invention, selenium and / or tellurium sensitization, sulfur sensitization, and gold sensitization may be performed simultaneously, or separately and stepwise.

It is also preferable to perform so-called reduction sensitization on the surface of the grains by placing the grains in an appropriate reducing atmosphere.

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

The amount of the reducing agent added depends on the type of reduction sensitizer, the particle size of silver halide grains, the composition and crystal habit, the temperature of the reaction system,
It is preferable to change the pH depending on environmental conditions such as pH and pAg. For example, in the case of thiourea dioxide, approximately 0.01 to 2 mg per mole of silver halide is used as a rough guide.
Is preferable. In the case of ascorbic acid, the range is preferably about 50 mg to 2 g per mol of silver halide.

The conditions for reduction sensitization are as follows:
0 ° C., time is about 10 to 200 minutes, pH is about 5 to 11, p
Ag is preferably in the range of about 1 to 10 (here, pAg
The value is the reciprocal of the Ag ⁺ ion concentration).

As the water-soluble silver salt, silver nitrate is preferable. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably from 1 to 6, and preferably from 2 to 4. Conditions such as temperature, pH, and time are preferably in the above-described reduction sensitization condition range. As a stabilizer for a silver halide photographic emulsion containing silver halide grains subjected to reduction sensitization, the following general stabilizers can be used, but the antioxidant disclosed in JP-A-57-82831 can be used. Agent and / or V.I. S. Gahler's paper [Zeithshift fur wissensc]
haftliche Photographie B
d. 63, 133 (1969)] and JP-A-54-133.
Good results are often obtained when thiosulfonic acids described in No. 1019 are used in combination. These compounds may be added at any stage of the emulsion production process from the crystal growth to the preparation process immediately before coating.

The silver halide photographic light-sensitive material of the present invention is characterized in that at least one compound of the formula (1) or (2) is contained in a layer having an emulsion layer or other layers.

In particular, the silver halide photographic light-sensitive material of the present invention preferably contains the compound represented by formula (2).

In the compound of the present invention represented by the general formula (1), R ₁ and R ₂ each represent a hydroxy group or an amino group (substituents are alkyl groups having 1 to 10 carbon atoms, for example, methyl , Ethyl, hydroxyethyl, etc. as substituents), acylamino group (acetylamino, benzoylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino, p-toluenesulfonylamino group, etc.), alkoxysulfonyl Amino (methoxycarbonylamino group, etc.), mercapto group, alkylthio group (methylthio, ethylthio group, etc.)
Represents

Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group.

In the formula, P and Q represent an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, and a mercapto group. P and Q are bonded to each other and two vinyl carbon atoms substituted by R ₁ R ₂ and Y are substituted with 5 carbon atoms.
Represents an atom group necessary for forming a to 8-membered ring.

Specific examples of the ring structure include dihydrofuranone, dihydropyrone, pyranone, cyclopentenone, cyclohexenone, pyrrolinone, pyrazolinone, pyridone, azacyclohexenone, uracil ring, and the like. Pentenone, cyclohexenone, pyrrolinone, azacyclohexenone, uracil ring and the like can be mentioned.

Specific examples of the compound represented by formula (1) are shown below, but the invention is not limited thereto.

[0159]

Embedded image

[0160]

Embedded image

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

The above-mentioned compounds are typically ascorbic acid or erythorbic acid or derivatives thereof, and are commercially available or can be synthesized by a known synthesis method.

The general formula (2) according to the present invention will be described in more detail. Preferred examples of the substituent represented by R ₄ to R ₈ in the general formula (2) include a halogen atom (for example, chlorine and bromine), a hydroxy group, a sulfo group, a carboxyl group, a cyano group, and an alkyl group (having 1 carbon atom). To 30 linear, branched or cyclic ones such as methyl, se
c-octyl, t-octyl, hexadecyl, cyclohexyl), alkenyl group (having 2 to 30 carbon atoms, for example, allyl, 1-octenyl), alkynyl group (having 2 to 30 carbon atoms, for example, propargyl), aralkyl Groups (with 7 to 30 carbon atoms such as 1,1-dimethyl-1-phenylmethyl, 3,5-
Di-t-butyl-2-hydroxyphenylmethyl), an aryl group (having 6 to 30 carbon atoms, for example, phenyl or naphthyl), or a heterocyclic group (oxygen, nitrogen, sulfur, phosphorus, selenium, or tellurium) A 3- to 12-membered ring containing, for example, furfuryl, 2-pyridyl, morpholino, 1-tetrazolyl, 2-selenazolyl), an alkoxy group (having 1 to 30 carbon atoms, for example, methoxy, ethoxyethoxy, hexadecyloxy) , Isopropoxy, allyloxy), aryloxy group (having 6 to 30 carbon atoms such as phenoxy, 4
-Nonylphenoxy), an alkylthio group (having 1 to 30 carbon atoms, for example, butylthio, dodecylthio,
-Hexyldecylthio, benzylthio), an arylthio group (having 6 to 30 carbon atoms, for example, phenylthio), a carbonamido group (having 1 to 30 carbon atoms, for example, acetamide, 2- (2,4-di-t) -Pentylphenoxy) butanamide, benzamide, 3,5-
Bis (2-hexyldecaneamide) benzamide), a sulfonamide group (having 1 to 30 carbon atoms such as methanesulfonamide, 4- (2,4-di-t-pentylphenoxy) butanesulfonamide, benzenesulfonamide, 4-dodecyloxybenzenesulfonamide), ureido group (having 1 to 30 carbon atoms, for example, N'-octadecylureido, N '-[3- (2,4
-Di-t-pentylphenoxy) propyl] ureido,
N '-(4-cyanophenyl) ureido, N'-(2-
Tetradecyloxyphenyl) ureido), alkoxycarbonylamino group (having 2 to 30 carbon atoms, for example, benzyloxycarbonylamino, ethoxycarbonylamino) aryloxycarbonylamino group (having 7 to 30 carbon atoms, for example, phenoxycarbonyl Amino), an acyloxy group (having 1 to 30 carbon atoms, for example, acetoxy, dichloroacetoxy, 4-oxopentanoyloxy, 2- (2,4-di-t-pentylphenoxy) hexanoyloxy, benzoyloxy, Nicotinoyloxy), a sulfamoylamino group (having 30 or less carbon atoms, for example, N'-benzyl-N'-methylsulfamoylamino, N'phenylsulfamoylamino), a sulfonyloxy group (having 1 carbon atom) Thirty to thirty, such as meta Sulfonyloxy, benzenesulfonyloxy), to a carbamoyl group (C 1 -C 30
For example, N-dodecylcarbamoyl, N- [3
-(2,4-di-t-pentylphenoxy) propyl]
Carbamoyl, N- [2-chloro-5- (1-dodecyloxycarbonylethyloxycarbonyl) phenyl] carbamoyl), sulfamoyl group (having 30 or less carbon atoms, for example, ethylsulfamoyl, hexadecylsulfamoyl, 4- (2,4-di-t-pentylphenoxy) butylsulfamoyl, phenylsulfamoyl), an acyl group (having 1 to 30 carbon atoms, for example, acetyl, octadecalyl, benzoyl), a sulfonyl group (having a carbon number of 1 to 30) 1 to 30, for example, methanesulfonyl, octadecanesulfonyl, benzenesulfonyl, 4-dodecylbenzenesulfonyl), alkoxycarbonyl group (2 to 30 carbon atoms, for example, ethoxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl) , Alilo Aryloxycarbonyl group (7 carbon atoms
To 30; for example, phenoxycarbonyl). These groups may be further substituted with the groups mentioned above.

Next, Z in the general formula (2) will be described.
Z is a hydrogen atom or a protecting group which can be removed under alkaline conditions. Examples of the protecting group for Z include an acyl group (for example, acetyl, chloroacetyl, dichloroacetyl, benzoyl, 4-cyanobenzoyl, 4-oxopentanoyl), an oxycarbonyl group (for example, ethoxycarbonyl, phenoxycarbonyl, 4-methoxybenzyl) Oxycarbonyl), a carbamoyl group (for example, N-methylcarbamoyl, N- (4-nitrophenyl) carbamoyl, N (2-pyridyl) carbamoyl, N- (1-imidazolyl) carbamoyl), and JP-A-59-197.
Nos. 037, 59-201057, 59-1087
No. 76 and U.S. Pat. No. 4,473,537. When OZ and R ₄ to R ₈ together form a ring, preferably OZ and R ₄ , R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ or R ₈ And OZ combine to form a saturated or unsaturated 4- to 8-membered carbocyclic or heterocyclic ring. In this case, for example, the following may be mentioned. Here, the symbol * indicates a position where the compound is bonded to the benzene ring in the general formula (2).

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The compound represented by the general formula (2) may form a bis-form, a tris-form, an oligomer or a polymer. The total number of carbon atoms of R ₄ to R _{8 in} the general formula (2) is preferably 8 or more.

Of the general formula (2), the following general formulas (3) to (6) are preferred.

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In the general formula (3), X is a hydroxy group or a sulfonamide group, and R ₄ , R ₅ , R ₇ and R ₈ have the same meanings as those in the general formula (2).

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In the general formula (4), X represents a hydroxy group or a sulfonamide group, and R ₄ to R ₇ have the same meaning as in the general formula (2).

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In the general formula (5), X is a hydroxy group or a sulfonamide group, Y is a carbamoyl group, an oxycarbonyl group, an acyl group or a sulfonyl group.
₅ and R ₇ have the same meanings as those in formula (2).

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In the general formula (6), R ₁₁ to R ₁₈ have the same meaning as R _{4 in the} general formula (2), and R ₁₉ to R ₂₂ are a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;
Is an integer of 0 to 50.

In the general formula (3), R ₄ , R ₅ , R ₇ ,
R ₈ is preferably a hydrogen atom, a halogen atom, a sulfo group, an alkyl group, an ether group, a thioether group, a carbonamide group, a sulfonamide group, a ureido group, a sulfonyl group, a carbamoyl group, an acyl group, more preferably a hydrogen atom, halogen atom, a sulfo group, an alkyl group, a carbonamido group, a sulfonamido group, a sulfonyl group, and most preferably either an alkyl group of R ₄ and R _7, carbonamido group, the other is a hydrogen atom at the sulfonamide group , A halogen atom, a sulfo group, a sulfonyl group, and an alkyl group. X is preferably a hydroxy group.

In formula (4), R ₄ to R ₇ are preferably a hydrogen atom, an alkyl group, an ether group, a thioether group, a carbonamide group, a sulfonamide group, a ureido group, a sulfonyl group, a carbamoyl group, an oxycarbonyl group. , An acyl group, more preferably a hydrogen atom,
An alkyl group, an ether group, a thioether group, a carbonamide group, and a sulfonamide group, most preferably a hydrogen atom, an alkyl group, and an ether group. R ₅ , R ₆
Are preferably a hydrogen atom, an alkyl group, a halogen atom, and an ether group, more preferably a hydrogen atom and an alkyl group, and most preferably a hydrogen atom. X is preferably a hydroxy group.

In the general formula (5), X is preferably a hydroxyl group, and Y is preferably a carbamoyl group or an oxycarbonyl group.

In formula (6), R ₁₁ to R ₁₈ are preferably a hydrogen atom, a halogen atom, an alkyl group,
Ether group, thioether group, carbonamide group, sulfonamide group, sulfonyl group, acyl group, carbamoyl group, more preferably hydrogen atom, halogen atom, alkyl group, carbonamide group, sulfonamide group, ether group, thioether group And most preferably a hydrogen atom, a halogen atom, an alkyl group, and a carbonamido group. When n = 0, R ₁₂ and R ₁₄ are preferably an alkyl group, a carbonamide group, or a sulfonamide group. n is 0
In other cases, R ₁₂ and R ₁₄ are preferably hydrogen atoms. n is 0
Or an integer of 20 to 50 is preferred.

Specific examples of the compound represented by formula (2) according to the present invention are shown below, but it should not be construed that the invention is limited thereto.

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The compound represented by the general formula (2) according to the present invention can be synthesized by the methods described in the following patents and the patents cited therein, and methods analogous thereto.

Among the compounds represented by the general formula (3), monoalkyl-substituted hydroquinone is described in US Pat.
0,290, 2,419,613, 2,40
3,721, 3,960,570, 3,70
No. 0,453, JP-A-49-106329 and JP-A-49-106329.
No. 156438, a dialkyl-substituted hydroquinone is
U.S. Pat. Nos. 2,728,659 and 2,732,30
0, 3,243,294, 3,700,453
No., JP-A-50-156438 and JP-A-53-9528.
Nos. 53-55121, 54-29637 and 60-55339, hydroquinone sulfonates are disclosed in U.S. Pat. No. 2,701,197, and JP-A-60-1.
No. 72040, No. 61-48855, No. 61-488
No. 56 discloses amide hydroquinones in U.S. Pat.
Nos. 98,239 and 4,732,845;
JP-A-150346 and JP-A-63-309949 disclose hydroquinones having an electron-withdrawing group.
No. 521, No. 56-109344, No. 57-2223
No. 7, 58-21249.

Compounds represented by formula (4) are described in US Pat. Nos. 4,447,523 and 4,525,451;
JP-A-4,530,899, JP-A-4,584,264, JP-A-4,717,651, JP-A-59-220733,
Nos. 61-169845, JP-B-62-1386, and German Patent No. 2,732,971 disclose the compound represented by the general formula (5) in U.S. Pat.
476,219 and JP-A-59-133544 disclose a compound represented by the general formula (6) in U.S. Pat.
0,801, 2,816,028, 4,71
No. 7,651, JP-A-57-17949, JP-A-61-1
69844, JP-A-1-134448, 1-13
No. 4449, No. 1-206337, No. 2-64631
And No. 2-90153.

The alkali precursors of hydroquinone are described in US Pat. No. 4,443,537 and JP-A-59-108776.

In the light-sensitive material of the present invention, the compound represented by the general formula (1) or (2) may be an emulsion layer of the light-sensitive material or an intermediate layer thereof, a protective layer, an antihalation layer,
Although it can be contained in the crossover cut layer and other non-photosensitive layers, it is preferably contained in the emulsion layer or a layer adjacent to the emulsion layer. It is also preferred that the layer to be contained be a plurality of layers such as an emulsion layer and an adjacent layer.

In the light-sensitive material of the present invention, the content of the compound represented by formula (1) or (2) is 0.005 to 8 mol per mol of silver halide contained in the emulsion layer. Is preferably, more preferably 0.05 to 2 mol, even more preferably 0.1 to 1.3 mol.

In the light-sensitive material of the present invention, the compound represented by the general formula (1)
Or it is also preferable to contain two or more types of the compounds represented by (2). At that time, the content is preferably in the above range in total.

It is also preferable that the light-sensitive material of the present invention contains a compound represented by the general formula (1) or (2) and hydroquinone. In this case, the content is preferably in the above range in total including hydroquinone.

As a method of adding the compounds of the general formulas (1) and (2) of the present invention, it is preferable to add the compound as a solution in an organic solvent, an emulsion of gelatin or a solid dispersion of fine particles to a coating solution for a photosensitive material.

As a method for producing a gelatin emulsion, the compounds of the general formulas (1) and (2), a melting point depressant and a high-boiling organic solvent or / and a polymer are insoluble in water (the solubility in water is 30% or less). )) And dissolving in a low boiling point organic solvent and emulsifying and dispersing in an aqueous phase (at this time, if necessary, an emulsifying aid such as a surfactant and gelatin may be used). After the compound and the melting point depressant are contained in the polymer fine particles, it is preferable in view of storage stability to remove an unnecessary organic solvent. Further, the emulsion may be emulsified and dispersed without using a high boiling point organic solvent or polymer. The emulsified dispersion of the present invention is prepared as follows. After completely dissolving the compounds of the general formulas (1) and (2) and the high boiling point organic solvent in the low boiling point organic solvent, the solution is dissolved in water, preferably in a hydrophilic colloid aqueous solution, more preferably in gelatin aqueous solution. In addition, if necessary, using a dispersing aid such as a surfactant,
It is dispersed in fine particles by ultrasonic waves, a colloid mill, a dissolver or the like, and is contained in the coating solution. It is preferable from the viewpoint of the stability of the dispersion to remove the low boiling point organic solvent from the prepared dispersion. Examples of the method for removing the low boiling point organic solvent include distillation under reduced pressure with heating, distillation under normal pressure with heating under a gas atmosphere such as nitrogen or argon, washing with noodle, or ultrafiltration. As used herein, the high boiling organic solvent includes phosphoric acid (such as tricresyl phosphate and triphenyl phosphate), phthalic acid (such as dibutyl phthalate, dioctyl phthalate, and dicyclohexyl phthalate), and higher saturated / unsaturated fatty acid ester (such as olein Organic solvents such as ethyl acid), higher alcohols, and phenols, which are substantially insoluble in water and do not evaporate during the coating and drying steps of the photosensitive material. In the present invention,
Two or more high boiling organic solvents may be used in combination.

The low-boiling organic solvent as used herein is an organic solvent useful at the time of emulsification and dispersion, which is finally removed from the ordinary photosensitive material by a drying step at the time of coating or the above-mentioned method. And a solvent having a low boiling point, or a solvent having a certain degree of solubility in water and being removable by washing with water. Examples of the low boiling point organic solvent include ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, and the like. Further, if necessary, an organic solvent which is completely mixed with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran or the like can be partially used. These organic solvents can be used in combination of two or more kinds. The average particle size of the particles in the emulsion thus obtained is
It is preferably from 0.02 μm to 2 μm, more preferably 0.02 μm.
4 μ to 0.4 μ. The particle size of the particles in the emulsion can be measured, for example, with a measuring device such as a Naicizer manufactured by Coulter, USA. In the present invention, the high-boiling organic solvent and the polymer are used in an amount of 10 to 400% by weight, especially 20 to 300% by weight, based on the compounds of the general formulas (1) and (2).
It is preferable to use in the range of. In the present invention, when the compound of the general formula (1) or (2) is contained in the polymer particles to be added, it is extremely preferable to use a melting point depressant. The melting point depressant used in the present invention is substantially diffusion-resistant and has a function of lowering the melting point when mixed with the compounds of the general formulas (1) and (2). Means an organic compound which is not a solvent in water.

Fine (crystal) of general formulas (1) and (2)
A solid dispersion of particles can be prepared by using a suitable solvent (water, alcohol, or the like), if necessary, in the presence of a dispersing agent in the presence of a known micronizing means (for example, ball mill, vibrating ball mill, planetary ball mill, sand mill, colloid mill, jet mill, (Roller mill). Further, fine (crystal) particles of the compound are prepared by dissolving the compound in an appropriate solvent using a surfactant for dispersion, and then adding the compound to a poor solvent for the compound to precipitate microcrystals. By controlling the pH, the compound can be first dissolved, and then the pH can be changed to obtain microcrystals. The layer containing the fine powder of the compound is prepared as a solid dispersion of substantially uniform particles by dispersing the fine (crystal) particles thus obtained in a suitable binder, and then forming the desired dispersion. Can be provided by coating on the support of the above. Alternatively, it can also be provided by a method in which the compound in a dissociated state is applied in the form of a salt, and then an acidic gelatin is overcoated to obtain dispersion fixation at the time of application. The binder is not particularly limited as long as it is a hydrophilic colloid that can be used for the photosensitive emulsion layer and the non-photosensitive layer, and usually gelatin or a synthetic polymer is used. As the surfactant for dispersion, a known surfactant can be used, and an anionic, nonionic, or amphoteric surfactant is preferable.
In particular, use of an anionic and / or nonionic surfactant is preferred. Fine particles of the compound in the solid dispersion have an average particle diameter of 0.005 μm to 10 μm, preferably 0.01 μm to 10 μm.
μm to 1 μm, more preferably 0.01 μm to 0.5 μm
m is preferable.

The light-sensitive material of the present invention preferably has an emulsion layer containing the emulsion of the present invention on both sides or one side of a support. When a silver halide photographic emulsion layer is provided on both sides of the support, the amount of silver per side is 1.8 g / m ² or less, and when a silver halide photographic emulsion layer is provided on one side, the amount of silver is 3.6 g / m ^2.
m ² or less, more preferably 0.5 to 1.5 g / m ² and 1.0 to 3.0 g / m ² , respectively.

When at least one of the constituent layers of the silver halide light-sensitive material of the present invention contains a dye capable of decoloring and / or flowing out during the development, high sensitivity, high sharpness and rapidity can be achieved. A photosensitive material having processability is obtained, which is preferable. 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.

The dye is a dye which is substantially insoluble in water at a pH of 7 or less and substantially water-soluble at a pH of 8 or more.

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

The amount of the dye added is preferably 0.2
-20 mg / m ² , more preferably 0.8-15 mg
/ M ² .

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

In the surface layer of the silver halide photographic light-sensitive material of the present invention, a silicon compound described in US Pat. Nos. 3,489,576 and 4,047,958 as a slipping agent, described in JP-B-56-23139. In addition to colloidal silica, paraffin wax, higher fatty acid ester, starch derivative and the like can be used.

To the constituent layers of the silver halide photographic light-sensitive material of the present invention, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be added as plasticizers.

Further, in the present invention, a polymer latex can be contained in at least any one of the silver halide photographic emulsion layers and the constituent layers other than the emulsion layers for the purpose of improving pressure resistance. As the polymer latex, a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid or styrene, styrene-
A butadiene copolymer, a polymer or copolymer comprising a monomer having an active methylene group, a water-soluble group or a crosslinkable group with gelatin can be preferably used.

Particularly, in order to increase the affinity with gelatin as a binder, a copolymer with a water-soluble group mainly composed of a hydrophobic monomer such as an alkyl ester of acrylic acid or styrene or a monomer having a crosslinkable group with gelatin is most preferable. It is preferably used. Preferred examples of the monomer having a water-soluble group include acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, and styrenesulfonic acid. Desirable examples of the monomer having a crosslinking property with gelatin are provided. Examples thereof include glycidyl acrylate, glycidyl methacrylate, N-methylol acrylamide, and the like.

In the present invention, as a matting agent, for example, US Pat. Nos. 2,992,101 and 2,701,245
Nos. 4,142,894, 4,396,706 and the like, homopolymers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid, organic compounds such as starch, silica, titanium dioxide, Fine particles of an inorganic compound such as strontium sulfate and barium sulfate can be used in combination. The particle size is preferably 0.6 to 10 μm, particularly preferably 1 to 5 μm.

In the present invention, organic matter aggregated particles can be used as the matting agent. The term “organic matter aggregated particles” refers to a substance having a particle diameter of 0.1 mm.
It refers to aggregated particles having a particle diameter of 1.0 to 20 μm in which a plurality of temporary particles having a small particle diameter of 0.5 to 0.50 μm are aggregated. The shape of the aggregated particles may be spherical or amorphous. The component as an organic substance is arbitrarily selected from alkyl methacrylate, alkyl acrylate, methacrylate in which an alkyl group is substituted with fluorine or silicon, acrylate and styrene, and may be a homopolymer or a copolymer, but polymethyl methacrylate is preferred. Specific examples include GR-5 and GR-5P manufactured by Soken Chemical Co., Ltd. A preferable addition amount for obtaining the effect without deteriorating the haze is 10 to 200 mg / m ² .

In the present invention, for the purpose of improving the pressure resistance, it is preferred that the silver halide photographic emulsion layer contains inorganic fine particles and / or a composite latex.

As the inorganic fine particles, the main components are silicon, aluminum, titanium, indium, yttrium, tin,
Oxide selected from antimony, zinc, nickel, copper, iron, cobalt, manganese, molybdenum, niobium, zirconium, vanadium, alkali metals, alkaline earth metals, etc. Among them, silicon oxide in terms of transparency and hardness (Colloidal silica), aluminum oxide, tin oxide,
Vanadium oxide and yttrium oxide are preferred. When these inorganic oxides are dispersed in water to form a sol,
The surface may be treated with alumina, yttrium, cerium, or the like in order to enhance the stability of its own water dispersion. In order to increase the affinity with gelatin, shelling may be performed with gelatin which has been crosslinked in advance. The preferred use amount of the inorganic fine particles used in the present invention is 0.05 to 1.0 in terms of a dry weight ratio to gelatin used as a binder of a layer to be added, preferably 0.1
~ 0.7. The above-mentioned inorganic fine particles may be used in combination. The preferred particle size of the inorganic fine particles is 1 to 300 nm.

The hydrophilic colloid layer used in the light-sensitive material of the present invention preferably contains a composite latex. The amount of the composite latex is 0.3-1.
It is contained in a weight ratio of 1.

In the present invention, the composite latex is a dispersion of composite polymer fine particles composed of inorganic fine particles and a hydrophobic polymer, or a composite latex formed by polymerizing a composition having a hydrophobic monomer in the presence of inorganic fine particles. Refers to a dispersion of molecular fine particles.

In the present invention, examples of the inorganic fine particles used in the composite latex include inorganic oxides, nitrides, sulfides, etc., and preferably, oxides. Specifically, Si, Na, K, Ca, Ba, Al, Zn, Fe,
Cu, Sn, In, W, Y, Sb, Mn, Ga, V, N
b, Tu, Ag, Bi, B, Mo, Ce, Cd, Mg,
Single or composite oxides such as Be and Pb are preferable, and in particular, Si, Y, Sn, Ti, Al, V, Sb, In, Mn,
Single or multiple oxides of Ce and B are preferred from the viewpoint of miscibility with the emulsion.

These may be crystalline or amorphous, but are preferably amorphous. The average particle diameter of the inorganic fine particles is about 0.5 to 3000 nm, preferably 3 to 500 nm. The inorganic fine particles are preferably used by dispersing in water and / or a solvent soluble in water. The addition amount of the inorganic fine particles is 1 to 200 with respect to the hydrophobic polymer compound.
It is about 0% by weight, preferably 30 to 1000% by weight.

In the present invention, the hydrophobic polymer means a polymer which does not substantially elute in an aqueous solution such as a developing solution.
As the hydrophobic monomer forming the hydrophobic polymer compound,
Vinyl esters, acrylic esters, methacrylic esters, olefins, styrenes, crotonic esters, itaconic diesters, maleic diesters, fumaric diesters, allyl compounds, vinyl ethers, vinyl ketones, vinyl Heterocyclic compounds,
Glycidyl esters, unsaturated nitriles, various unsaturated acids and the like can be mentioned, but those forming the composite latex used in the present invention are preferably selected from vinyl esters, acrylic esters and methacrylic esters. At least one kind or styrenes,
As the former, it is particularly preferred that the ester group has 6 or more carbon atoms. It is preferable to use a hydrophobic monomer having a glycidyl group in combination with these hydrophobic monomers, and to use at least 1% by weight, more preferably 20% by weight or more.

Examples of the polymerization method of the composite latex include an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a radiation polymerization method.

The silver halide photographic light-sensitive material of the present invention preferably contains a water-soluble polymer. As the water-soluble polymer, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and the like as described in US Pat. No. 3,271,158 can be effectively used. Polysaccharides such as dextrin, dextran, saccharose and pullulan are also effective. Among them, polyacrylamide, dextran and dextrin are preferable, and dextrin is particularly preferable. The average molecular weight of these substances is preferably 20,000 or less, more preferably 1 to 20,000.
Less than 10,000.

In the present invention, the amount of the hydrophilic binder in the silver halide photographic emulsion layer is preferably not more than 3.0 g / m ² per one side of the support when the emulsion layer is on both sides of the support.
More preferably, it is 1.0 g or more and 2.0 g / m ² or less. When it is on one side of the support, the weight is preferably 6.0 g / m ² or less, more preferably 4.0 g / m ² or less.

The silver halide photographic light-sensitive material of the present invention includes black-and-white silver halide photographic light-sensitive materials (for example, medical light-sensitive material, printing light-sensitive material, negative film for general photography, etc.) and color photographic light-sensitive materials (for example, color negative light-sensitive material). Photographic materials, color reversal photographic materials, color printing photographic materials), diffusion transfer photographic materials, heat-developable photographic materials, etc., preferably black-and-white silver halide photographic materials, and particularly preferably medical photographic materials. It is.

The silver halide photographic emulsion layer and the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention preferably contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl))
Active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine) such as methyl ether, N, N'-methylenebis (β- (vinylsulfonyl) propionamide), and mucohalic acids (mucochloric acid, mucophenoxy) Chloric acid, etc.), isoxazoles, 2-
Chlor-6-hydroxytriazinylated gelatin or the like can be used alone or in combination. Among them, active vinyl compounds described in JP-A-53-41221, JP-A-53-57257, JP-A-59-162456 and JP-A-60-80846, and U.S. Pat. No. 3,325,28
The active halogen compounds described in No. 7 are preferred.

As the hardener of the present invention, a polymer hardener can also be effectively used. Polymers having aldehyde groups, such as dialdehyde starch, polyacrolein, acrolein copolymers described in US Pat. No. 3,396,029,
U.S. Pat. No. 3,623,878, polymers having epoxy groups, U.S. Pat. No. 3,362,827, RD
And polymers having a dichlorotriazine group described in JP-A--17333 (1978).
No. 41, a polymer having an active ester group, JP-A-56-142524, U.S. Pat.
No. 1,407, JP-A-54-65033, RD-16
725 (1978) and the like, or a polymer having a group which is a precursor thereof, and the like. Among them, an active vinyl group, a polymer having a long spacer as described in JP-A-56-142524,
Alternatively, a polymer in which a precursor group is bonded to the polymer main chain is particularly preferable.

In the photographic light-sensitive material of the present invention, an appropriate amount of a hardener is added in advance in the coating step of the light-sensitive material so as to adjust the water swelling ratio in the development-fixing-washing step so as to be suitable for rapid processing. By doing so, it is preferable to reduce the water content in the photosensitive material before the start of drying.

The silver halide light-sensitive material of the present invention preferably has a swelling ratio of 150 to 250% during the development processing, and a film thickness after expansion of 70 μm or less. 250% water swelling
If the temperature exceeds the limit, drying failure occurs, and for example, conveyance failure also occurs in automatic developing machine processing, particularly in rapid processing.

When the water swelling ratio is less than 150%, development unevenness and residual color tend to increase when developed. The water swelling ratio as referred to herein means the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, and this is divided by the film thickness before processing and multiplied by 100. .

Examples of the support which can be used in the silver halide photographic light-sensitive material of the present invention include, for example, the aforementioned RD-1
7643 and RD-308119, page 1009.

As a suitable support, a plastic film or the like may be used. The surface of the support may be provided with an undercoat layer to improve the adhesion of the coating layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like.

In the silver halide photographic light-sensitive material of the present invention, various additives can be further added to the silver halide photographic emulsion depending on the purpose. Examples of additives and the like used are RD-17643 (December 1978),
716 (November 1979) and 308119 (19
Dec. 1989). The locations of those descriptions 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 Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surface activity 26 to 7 XI 650 right 1005 to 6 XI Antistatic agent 27 XII 650 right 1006 to 7 XIII Plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008 to 9 XVI binder 26 XXII 1003 to 4 IX Support 28 XVII 1009 XVII Next, a preferred photographic processing method of the silver halide photographic light-sensitive material of the present invention (hereinafter sometimes referred to as a processing method) will be described.

In the processing method of the silver halide photographic light-sensitive material of the present invention, the silver halide photographic light-sensitive material of the present invention is preferably processed with a development processing time of 1 second to 7 seconds. Here, the development processing time refers to the time during which the photosensitive material is immersed in the developing solution. More specifically, for example, when the photosensitive material is processed by a roller-conveying type automatic developing machine, the moment when the tip of the photosensitive material enters the developing solution. From the moment when it enters the fixing solution.
The temperature of the development treatment is preferably 25 to 50 ° C, more preferably 30 to 40 ° C. The fixing processing time is 1
The time is preferably from 7 seconds to 7 seconds. Fixing temperature is 20 ° C ~ 5
0 ° C is preferable, and 30 ° C to 40 ° C is more preferable. The temperature and time of the water washing treatment are preferably 2 to 15 seconds at 0 to 50 ° C, more preferably 2 to 8 seconds at 15 to 40 ° C.

The light-sensitive material which has been developed, fixed and washed (or stabilized) is dried through a squeeze roller for squeezing the washing water. Drying is performed at 40 ° C. to 100 ° C., and the drying time can be appropriately changed depending on the environmental temperature. Usually, it may be 3 seconds to 12 seconds, particularly preferably 40 ° C. to 80 ° C. for 3 seconds to 8 seconds. More preferably, a far infrared heater is used. Furthermore, the total processing time (DRY TO
DRY) is preferably from 10 seconds to 30 seconds, more preferably from 10 seconds to 25 seconds.

As the developing solution for developing the silver halide photographic light-sensitive material of the present invention, a developing agent such as dihydroxybenzene described in JP-A-4-15641 or JP-A-4-16841, such as hydroquinone, may be used.
Examples of 3-pyrazolidones such as para-aminophenols such as p-aminophenol, N-methyl-p-aminophenol and 2,4-diamiphenol include 1-phenyl-3-pyrazolidones and 1-phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like, and further ascorbic acids. Used in combination depending on the situation.

The preferred use amount of the above-mentioned paraaminophenols and 3-aminopyrazolidones is 0.004 mol / l, more preferably 0.04 to 0.12 mol / l.

The dihydroxybenzenes, paraaminophenols, 3
The total molar number of pyrazolidones and ascorbic acids is 0.
It is preferably at most 1 mol / liter.

In particular, in the method for processing a silver halide photographic light-sensitive material of the present invention, the developing solution and / or the replenisher containing the compound represented by the formula (1) is used. The silver photographic light-sensitive material is preferably processed by an automatic processor.

In the processing method of the light-sensitive material of the present invention, the compound represented by the above general formula (1) is preferably used in an amount of 0.005 to 0.8 mol, more preferably 0.02 to 0.8 mol per liter of a developing solution. 0.6 mol.

Specific examples of the compound represented by the general formula (1) are the compounds (1-1) to (1-22), but the present invention is not limited thereto.

The developer used in the present invention preferably contains a 1-phenyl-3-pyrazolindone-based or p-aminophenol-based developing agent as an auxiliary developing agent of the above compound.

In the processing method of the light-sensitive material of the present invention, it is preferable that the developing solution and the developing replenisher do not contain a developing agent because the preservability of the processing solution can be improved and the processing variability can be reduced. In this case, the development proceeds according to the general formula (1) or the general formula (2) contained in the photosensitive material.

The developer may contain, as a preservative, sulfites, for example, potassium sulfite, sodium sulfite, and reductones, for example, piperidinohexose reductone, preferably 0.2 to 1 mol / l. Liter, more preferably 0.3 to 0.6 mol / liter. Also, the addition of a large amount of ascorbic acids leads to processing stability.

In the developing solution, alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate may be used.
Contains regulators.

Further, borate described in JP-A-61-28708, saccharose described in JP-A-60-93439,
Buffers such as acetoxime, 5-sulfosalicylic acid, phosphates and carbonates may be used. The content of these chemicals increases the pH of the developer from 9.0 to 13, preferably from pH 10 to 10.
Choose to be 12.5.

As a solubilizing agent, polyethylene glycols and esters thereof can be contained, and as a sensitizer, for example, a development accelerator, a surfactant and the like such as quaternary ammonium salts can be contained.

Examples of the silver sludge inhibitor in the developing solution include silver stain inhibitors described in JP-A-56-106244, sulfides and disulfide compounds described in JP-A-3-51844, and cysteine derivatives described in JP-A-5-289255. Alternatively, a triazine compound is preferably used.

An organic or inorganic inhibitor may be used in the developer.

As organic inhibitors, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benzotriazo, tetrazole and thiadiazole compounds are used.

The inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition,
L. F. A. Menson, "Photographic Processing Chemistry," Focal Press (19
66), pages 226-229, U.S. Pat.
No. 15,2,592,364, JP-A-48-649
No. 33 may be used.

As a chelating agent for masking calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate stabilizing constant with iron of 8 or more described in JP-A-1-193853 as an organic chelating agent is used. Is preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the developing hardener, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used. However, for rapid processing, it is preferable that the hardening agent be incorporated in the coating step of the photosensitive material in advance as described above, rather than being applied in the developing step.

In the present invention, the replenishment of the developer replenishes the processing agent fatigue and the oxidative fatigue. Examples of the replenishment method include replenishment by width and feed speed described in JP-A-55-126243, area replenishment described in JP-A-60-104946, and area replenishment controlled by the number of continuously processed sheets described in JP-A-1-149156. May be.

When the processing method of the silver halide photographic light-sensitive material of the present invention is a method in which processing is performed while continuously replenishing a processing solution according to the light-sensitive material to be processed, the replenishment amount of the developing solution is processed. It is preferable that the replenisher is replenished at 1 to 100 cc per 1 m ^{2 of the} photosensitive material, and more preferably 15 to 100 cc.

In the present invention, preferable fixing solutions may include fixing materials generally used in the art. The pH is at least 3.8, preferably 4.2-5.5.

Examples of the fixing agent include thiosulfates such as ammonium thiosulfate and sodium thiosulfate. Ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The concentration of the ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably in the range of 0.8 to 3 mol / l. The fixing solution may be one that forms an acidic hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like. Other fixatives include preservatives such as sulfites and bisulfites, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid, nitric acid), organic acids (citric acid, oxalic acid, malic acid, etc.), and hydrochloric acid, if desired. PH adjusting agents such as various acids, metal hydroxides (potassium hydroxide and sodium hydroxide), and chelating agents having water softening ability. Examples of the fixing accelerator include JP-B-45-35754 and 58-122535.
And the thiourea derivatives described in U.S. Pat. No. 4,126,459.

In the present invention, the replenishment method of the fixing solution includes replenishment by width and feed speed described in JP-A-55-126243, area replenishment described in JP-A-60-104946, and replenishment described in JP-A-1-149156. Area replenishment controlled by the number of sheets continuously processed may be used.

When the processing method of the silver halide photographic light-sensitive material of the present invention is a method in which the processing solution is continuously replenished in accordance with the light-sensitive material to be processed, the replenishment amount of the fixing solution is processed. It is preferable that the replenisher is replenished at 15 to 250 cc per m ^{2 of the} photosensitive material, and more preferably 15 to 100 cc.

In the present invention, it is preferable that the developing solution and the developing replenisher contain a fixing agent. In this case, the content of the fixing agent is preferably in the range of 0.01 to 5 mol / l, more preferably in the range of 0.05 to 3 mol / l.

In the present invention, the photosensitive material is substantially reduced to 1 by using a developer containing a fixing agent and a development replenisher.
It is preferable to carry out the treatment with a liquid.

That is, it is preferable to carry out development and fixing with the same liquid, followed by washing with water and drying.

Further, a method of supplying a developer and / or a fixing agent as a solid processing agent to a processing tank of an automatic developing machine is also preferably used.

Here, the solid processing agents are powder processing agents, solid processing agents such as tablets, pills and granules, etc., which have been subjected to moisture proof processing as required.

The powder refers to an aggregate of fine crystals. Granules are obtained by adding a granulation process to powder, and have a particle size of 5
It refers to a granular material of 0 to 5000 μm. Tablets are obtained by compressing powder or granules into a certain shape.

To solidify the photographic processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily molded photographic processing agent. Any means can be adopted such as forming a coating layer by spraying.

A preferred tablet production method is a method of granulating a powdery solid processing agent and then performing a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

As the granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pre-ketting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handleability, or the problem of dust when used on the user side, a cylindrical, 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 a tablet processing agent is described in, for example, JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
No. 88025, British Patent No. 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-10942 and 2-9042.
Nos. 109043, 3-39735 and 3-397
It can be produced by a general method described in the specification such as No. 39. Furthermore, powder processing agents are described, for example, in JP-A-54-13.
3332, British Patent Nos. 725,892 and 729,
No. 862 and German Patent No. 3,733,861 and the like.

The bulk density of the above solid processing agent is 1.0 g /
Preferably ^{cm 3 ~2.5g / cm 3, 1.0g} / cm 3
If it is larger, the strength of the obtained solid is 2.5 g /
When the diameter is smaller than ³ cm ³ , the solubility of the obtained solid is more preferable. When the solid processing agent is a granule or powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

Solid processing agents are used in photographic processing agents such as a developer, a fixing agent, and a rinsing agent, but the developer has a great effect of stabilizing photographic performance.

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

It is preferable that all the processing agents to be replenished into each processing tank according to the processing amount information are charged as solid processing agents.
When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishing water. That is, when two or more types of processing tanks need replenishment, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the size of the automatic developing machine can be reduced. The replenishing water tank may be provided outside or externally, or may be built in an automatic developing machine.

In the case of solidifying the developer, it is preferable that all of the alkali agent and the reducing agent are converted into solid processing agents, and in the case of tablets, at least three agents are used, and most preferably one agent is used. It is. When the solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged in the same manner.

It is preferable to photograph using the light-sensitive material of the present invention and a radiographic intensifying screen. The filling rate of the phosphor in the phosphor layer of the radiation intensifying screen is preferably 68% or more, more preferably 70% or more, and most preferably 72% or more.

The thickness of the phosphor layer is at least 150 μm,
250 μm or less is preferred. The thickness of the phosphor layer is 150μ
This is because if it is less than m, sharpness rapidly deteriorates.

It is preferable that the radiographic intensifying screen is filled with a phosphor in a gradient particle size structure. In particular, it is preferable to apply large-sized phosphor particles to the surface protective layer side and to apply small-sized phosphor particles to the support side.
In the case of 0 μm and those having a large particle diameter, the range of 10 to 30 μm is preferable.

The radiographic intensifying screens used in the combination are prepared by increasing the filling rate of the phosphor particles to increase the X-ray intensity of each intensifying screen.
Preferably, the X-ray absorptivity is 30% or more per 100 μm thickness of the phosphor layer. The amount of X-ray absorption was determined as follows. In other words, with a three-phase power supply, the inherent filtration is 80 mm from an X-ray generator equivalent to 2.2 mm
X-rays generated from a tungsten target operated at kVp are transmitted through a 3 mm thick aluminum plate having a purity of 99% or more and reach a radiographic intensifying screen fixed at a position 200 cm from the tungsten anode of the target tube.
Next, measurement was performed using an ionizing dosimeter at a position 50 cm after the phosphor layer of the radiation intensifying screen to determine the amount of X-ray absorption.
As a reference, the X-ray dose at the above measurement position measured without passing through the intensifying screen was used.

Preferred binders used for the radiographic intensifying screen include thermoplastic elastomers. Specifically, it is selected from the group consisting of polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluorine rubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber. At least one thermoplastic elastomer is included.

Preferred phosphors used for the radiographic intensifying screen include the following.

A tungstate-based phosphor (CaWO ₄ ,
MgWO ₄ , CaWO ₄ : Pb, etc.), terbium-activated rare earth oxysulfide-based phosphor [Y ₂ O ₂ S: Tb, Gd ₂ O ₂ S:
Tb, La ₂ O ₂ S: Tb, (Y, Gd) ₂ O ₂ S: Tb,
Tm etc.), terbium-activated rare earth phosphate-based phosphor (YP
O ₄ : Tb, GdPO ₄ : Tb, LaPO ₄ : Tb, etc.),
Terbium-activated rare earth oxyhalide phosphor La
OBr: Tb, LaOBr: Tb. Tm, LaOCl:
Tb, LaOCl: Tb. TmGdOBr: Tb, Gd
OCr: Tb, etc.), thulium-activated rare earth oxyhalide phosphor (LaOBr: Tm, LaOCl: Tm)
Etc.), barium sulfate-based phosphor [BaSO ₄ : Pb, Ba
SO ₄ : Eu ²⁺ , (Ba.Sr) SO ₄ : Eu ²⁺ etc.], 2
-Valent eurobium-activated alkaline earth metal phosphate-based phosphor [Ba ₃ (PO ₄ ) ₂ : Eu ²⁺ , (Ba, Sr) ₃ (P
O ₄ ) ₂ : Eu ² etc.] divalent eurobium-activated alkaline earth metal fluorohalide-based phosphor [BaFCl: Eu
²⁺ , BaFBr: Eu ²⁺ , BaFCl: Eu ²⁺ . Tb,
BaFBr: Eu ²⁺ . Tb, BaF ₂ . BaCl ₂ . XB
aSO ₄ . KCl: Eu ²⁺ , (Ba.Mg) F ₂ . BaC
l ₂ . KCl: Eu ²⁺ etc.], iodide-based phosphor (CSI:
Na, CSI: Tl, NaI. KI: Tl, etc.) Sulfide-based phosphor [ZnS: Ag, (Zn.Cd) S: Ag, (Z
n. Cd) S: Cu, (Zn. Cd) S: Cu. Al
Etc.), a hafnium phosphate-based phosphor (HfP ₂ O ₇ : Cu
Etc.) However, the phosphor used is not limited to these, and any phosphor that emits light in the visible or near ultraviolet region upon irradiation with radiation can be used.

[0281]

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

Example 1 Preparation of Em-1 (Comparative Emulsion) A tabular silver iodochloride emulsion Em was prepared using the following five kinds of solutions.
-1 was prepared.

A1 Low methionine gelatin 35.53 g Sodium chloride 1.306 g Potassium iodide 49.87 mg Make up to 2030 ml with water B1 Sodium chloride 1.737 g Potassium iodide 49.80 mg Make up to 30 ml with water C1 Silver nitrate 5.096 g with water Finish to 30 ml D1 Sodium chloride 46.80 g Finish to 800 ml with water E1 Silver nitrate 135.90 g Finish to 800 ml with water While keeping solution A1 at 40 ° C. in a reaction vessel, vigorously stir and add the total amount of solution B1 and solution C1 there. The mixture was added at a flow rate of 30 ml per minute over 1 minute by the double-mixing method. During this time, p
Cl was kept at 1.95 throughout. The obtained core particles contained 2 mol% of iodine.

Next, after keeping this mixed solution at 40 ° C. for 10 minutes, the total amount of the solution D1 and the solution E1 was added at a flow rate of 2 ml / min over 40 minutes by a double jet method. During this time, pC
l was kept at 1.95 throughout. Immediately after addition, desalting,
Washing was performed.

When the obtained silver halide emulsion was observed with an electron microscope, it was found that 50% or more of the total projected area had an adjacent side ratio of 1
It consists of rectangular parallelepiped tabular grains of less than 0, and the average particle diameter (in terms of circular diameter) of the rectangular parallelepiped tabular grains is 0.84 μm.
m, average thickness 0.037 μm, average aspect ratio 2
3. Tabular silver halide grains having a particle size distribution of 18.1%.

Preparation of Em-2 (Emulsion of the Invention) A tabular silver iodochloride emulsion Em was prepared using the following six kinds of solutions.
-2 was prepared.

A2 Low methionine gelatin 35.53 g Sodium chloride 1.324 g Make up to 2030 ml with water B2 Sodium chloride 0.869 g Make up to 15 ml with water B22 Sodium chloride 0.869 g Potassium iodide 49.80 mg Make up to 15 ml with water C2 Silver nitrate 5.096 g Finished with water to 30 ml D2 Sodium chloride 46.80 g Finished with 800 ml with water E2 Silver nitrate 135.90 g Finished with 800 ml with water While maintaining solution A2 at 40 ° C. in a reaction vessel, vigorously stir the solution B2. The total amount and 15 ml of the solution C2 were added at a flow rate of 30 ml per minute over 30 seconds by a double jet method,
Subsequently, the entire amount of the solution B22 and 15 ml of the solution C2 were added at a flow rate of 30 ml per minute over 30 seconds by a double jet method. During this time, pCl was kept at 1.95 throughout. The obtained core particles contained 2 mol% of iodine.

Next, after keeping this mixed solution at 40 ° C. for 10 minutes, the total amount of the solution D2 and the solution E2 was added at a flow rate of 2 ml / min over 40 minutes by a double jet method. During this time, pC
l was kept at 1.95 throughout. Immediately after addition, desalting,
Washing was performed.

When the obtained silver halide emulsion was observed with an electron microscope, it was found that 50% or more of the total projected area had an adjacent side ratio of 1
It consists of rectangular parallelepiped tabular grains of less than 0, and the average particle diameter (in terms of circular diameter) of the rectangular parallelepiped tabular grains is 0.84 µ
m, average thickness 0.037 μm, average aspect ratio 1
5. Tabular silver halide grains having a particle size distribution of 17.2%.

Preparation of Em-3 A tabular silver iodochloride emulsion Em-3 was prepared in exactly the same manner as Em-2 except that the amount of potassium iodide in solution B22 was changed to 24.90 mg. did.

When the obtained silver halide emulsion was observed with an electron microscope, it was found that 50% or more of the total projected area had an adjacent side ratio of 1
It consists of rectangular parallelepiped tabular grains of less than 0, and the average particle diameter (in terms of circular diameter) of the rectangular parallelepiped tabular grains is 0.585 μm.
m, average thickness is 0.078 μm, and average aspect ratio is 7.
5. Tabular silver halide grains having a particle size distribution of 17.0%.

Table 1 shows the emulsions obtained as described above.

[0293]

[Table 1]

Subsequently, the prepared emulsions Em-1 to Em-
Sample No. 3 was heated to 55 ° C, and subjected to spectral sensitization and chemical sensitization by the following method [sensitization-1].

[Sensitization-1] As compounds adsorbed on silver halide, 4-hydroxy-6-methyl-1,3,3a,
After addition of 7-tetrazaindene (TAI), predetermined amounts of the following spectral sensitizing dyes, a mixed aqueous solution of ammonium thiocyanate and chloroauric acid, 1-ethyl-3- (2-thiazolyl) thiourea, triphenyl A solid fine particle dispersion of phosphine selenide and butyl diisopropylphosphine telluride was added, and the mixture was stirred for 20 minutes. Thereafter, 0.1 mol% of a silver bromide fine particle emulsion was added, and ripening was performed for a total of 2 hours. At the end of ripening, 1-phenyl-5-
Mercaptotetrazole (PMT) and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) were added.

The amounts of the compounds added (per mole of silver halide) are shown below.

Spectral sensitizing dye (D-1) 350 mg Spectral sensitizing dye (D-2) 25 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 50 mg Ammonium thiocyanate 145 mg Chloroauric acid (gold sensitizer) 25.5 mg 1-ethyl-3- (2-thiazolyl) thiourea (sulfur sensitizer) 5.0 mg triphenylphosphine selenide (selenium sensitizer) 3.0 mg butyl- Diisopropylphosphine telluride (tellurium sensitizer) 0.5 mg Silver bromide fine particles 0.1 mol% PMT (as a stabilizer at the end of chemical ripening) 10 mg TAI (as a stabilizer at the end of chemical ripening) 100 mg The solid particulate dispersion is prepared by adding a predetermined amount of the spectral sensitizing dye to water whose temperature has been previously adjusted to 27 ° C., and mixing with a high-speed stirrer (dissolver). 30 to 120 at 500rpm
Obtained by stirring for minutes.

[0298]

Embedded image

Next, the obtained emulsions (Em-1 to Em-
The additives described in the second layer (emulsion layer) described below were added to 3) to obtain an emulsion layer coating solution. At the same time, the first layer (dye layer) and the third layer
Using the additives described in the layer (protective layer), a coating solution for the dye layer and a coating solution for the protective layer are prepared, and using these three types of coating solutions,
Using two slide hopper coaters at a speed of 80 m / min. On both sides of the support simultaneously so that the amount of silver applied per side is 1.6 g / m ² and the amount of gelatin applied is 2.5 g / m ^2. The sample was applied and dried for 2 minutes and 20 seconds.
1 to 3 (Sample No. 1 using Em-1;
m-2 was 2 and Em-3 was 3). As a support, an aqueous copolymer dispersion and a colloid obtained by diluting a copolymer composed of three monomers of 50 wt% of glycidyl methacrylate, 10 wt% of methyl acrylate, and 40 wt% of butyl methacrylate so as to have a concentration of 10 wt% A polyethylene terephthalate film base which was colored blue to a concentration of 0.15 for a 175 μm X-ray film using a mixture of a tin oxide dispersion (see Japanese Patent Application No. 7-231445) as an undercoating liquid was used.

The additives used for each layer are as follows.
The amount of addition is shown in an amount per 1 m ² .

First Layer (Dye Layer) Solid Fine Particle Dispersion Dye (AH) 20 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-dichloro-6-hydroxy-1,3,5- Triazine sodium salt 5 mg Colloidal silica (average particle size 0.014 μm) 10 mg Latex (L) 0.2 g Potassium polystyrene sulfonate 50 mg Second layer (emulsion layer) Potassium tetrachloropalladium (2) 100 mg Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg t-butyl-catechol 5 mg polyvinylpyrrolidone (molecular weight 10,000) 20 mg styrene-maleic anhydride copolymer 80 mg sodium polystyrene sulfonate 0 mg Trimethylolpropane 350 mg Diethylene glycol 50 mg Nitrophenyl-triphenyl-phosphonium chloride 1 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 50 mg 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg Compound (H) 0.5 mg n- _{C 4 H 9 OCH 2 CH (} OH) CH 2 N (CH 2 COOH) 2 20mg compound (M) 5 mg compound (N) 5 mg developer dispersion (DE-1) see below complex latex (L-1) 1. 0 g dextrin (average molecular weight: about 1000) 0.2 g dextran (average molecular weight: about 40,000) 0.2 g sodium styrenesulfonate (molecular weight: about 500,000) 7 mg The amount of gelatin to be applied is 0.8 g / m ^2. It was adjusted.

Third layer (lower layer of protective layer) Gelatin 0.2 g Tricresyl phosphate 0.2 g Latex (L) 0.2 g Sodium polyacrylate (average molecular weight: 50,000) 30 mg Sodium styrene sulfonate (molecular weight: about 500,000) 7 mg 4th layer (protective layer upper layer) Gelatin 0.28 g Matting agent composed of polymethyl methacrylate 27 mg (area average particle size 7.0 μm) 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg Latex (L) 0.2 g Colloidal silica (average particle size 0.014 μm) 50 mg Polyacrylamide (average molecular weight 10,000) 0.1 g Sodium polyacrylate 30 mg Polysiloxane (SI) 50 mg Compound (I) 30 mg Compound (J) 2 mg Compound (S-1) 7 mg Compound (K) 15 mg Compound (O) 50 mg Compound (S-2) 5 mg Compound (F-1) 3 mg Compound (F-2) 2 mg Compound (F-3) 1 mg Compound (F-4) 10 mg Compound (P) 50mg

[0303]

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[0304]

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[0305]

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A developing agent dispersion (DE-1) was prepared as follows.

A solution of 3.1 g of the compound (2-29) in 4.8 g of tricresyl phosphate, 2 g of dibutyl phthalate and 20 cc of ethyl acetate was prepared.
g at 65 ° C., and dispersed at high speed with a homogenizer. After completion of the high-speed stirring, the mixture was subjected to a reduced pressure treatment at 60 ° C. using an evaporator to remove 90 wt% of ethyl acetate. Thereby, a developing agent dispersion having an average particle size of 0.1 μm (DE-
1) was obtained. The amount of the dispersion added was 1 × per 1 m ^2.
10 ^-2 mol.

The composite latex L-1 was produced as follows.

A stirrer was placed in a 1000 ml four-necked flask,
A thermometer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser were installed, and nitrogen gas was introduced to perform deoxygenation.
126 g of 0 cc, 30% by weight colloidal silica dispersion
And heated until the internal temperature reached 80 ° C., and 4.5 g of hydroxypropylcellulose and 1 g of dodecylbenzenesulfonic acid were added. 0.023 g of ammonium persulfate are added as initiator and then 12.6 g of vinyl acetate
g was added and reacted for 4 hours. After cooling, the pH was adjusted to 6 with a sodium hydroxide solution, and the composite latex L
-1 was obtained.

<Sensitometric evaluation> Sample N obtained
o. The photographic characteristics were evaluated using Nos. 1 to 3. First, sample 2
Sandwiched between intensifying screens (KO-250, manufactured by Konica Corporation)
Tube voltage 80 kVp, tube current 10 via aluminum wedge
Exposure was performed by irradiating with 0-ray X-rays for 0.05 second, and processing-1.
Was subjected to photographic processing.

After the treatment, fog and sensitivity were measured. The fog is represented by the lowest density, the sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog + 1.0, and the sample No. The relative sensitivities when the sensitivities in the processing of No. 1 were set to 100 were shown. Table 2 shows the obtained results.

<Evaluation of storage stability over time> Next, each sample was stored for 7 days under the following two conditions.

Condition A: 55% RH at 23 ° C. Condition B: 80% RH at 40 ° C. After exposure, the same exposure and development processing as described above was performed, and after processing, the sensitivity was measured. The sensitivity difference between Condition A and Condition B was determined for each sample, and Sample No. The values are shown as relative values when the sensitivity difference of 1 is 100. The smaller the value, the smaller the change and the better. Table 2 shows the obtained results.
Shown in

<Evaluation of process variability> The obtained sample no. 1
~ 3 in processing-1 instead of pH of developer
Processing was performed using the developing solution changed by 0.1, and the impression fluctuation when the pH was changed from -0.1 to +0.1 was obtained. Sample No. It was expressed as a relative value when the sensitivity variation of 1 was taken as 100. Table 2 shows the obtained results.

[Processing-1] Adjustment of 100 liter amount as developer.

[Granulated product (A)] 3000 g of hydroquinone as a developing agent, 400 g of phenidone, 1000 g of boric acid
g, 10 g of N-acetyl-D, L-penicillamine and 500 g of glutaraldehyde sodium bisulfite are each ground in a commercially available bantam mill until the average particle size becomes 10 μm. 700 g of sodium sulfite, binder D
-200 g of sorbit were added and mixed in the mill for 30 minutes. 30ml for about 5 minutes at room temperature in a commercially available stirring granulator
After granulation by adding water, the granulated product was dried at 40 ° C. for 2 hours with a fluidized bed drier to remove water completely from the granulated product.

[Preparation of Solid Developer A] The granulated product (A) thus obtained was mixed with 100 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 compression tableting was performed to prepare a hydroquinone-based developer tablet into a cylindrical shape having a diameter of 30 mm.

[Granulated product (B)] Potassium carbonate was prepared so as to have the buffer capacity shown in Table 1. 1000 g of sodium bicarbonate and 200 g of KBr are each ground in a commercially available bantam mill until the average particle size becomes 10 μm. 200 g of LiOH.H ₂ O, DTPA.5H for each fine powder
250 g, 1-phenyl-5-mercaptotetrazole, 5 g of sodium sulfite, 40 g of the compound (M) described above, 8 g of the compound (N), and 1000 g of a binder mannitol were added, and the mixture was mixed in a mill for 30 minutes. After granulating by adding 30 ml of water for about 15 minutes at room temperature in a room, the granulated material is dried at 40 ° C. for 2 hours with a fluidized drier to almost completely remove the moisture of the granulated material. .

[Preparation of Solid Developer B] The granulated product (B) thus obtained was mixed with 200 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.

Both developers A and B were sealed and packaged in 4.0 liter quantities in pillow bags containing aluminum for moisture protection.

The following procedure was used to prepare a solid fixing agent having a fixing liquid amount of 100 liters.

[Granulated product (C)] Ammonium thiosulfate /
Sodium thiosulfate (90/10 weight ratio) 15000g
Is ground to a mean particle size of 10 μm in a commercially available bantam mill. 500 g of sodium sulfite, Na
750 g of ₂ S ₂ O _{5 and} 1300 g of a binder pine flow were added, and the mixture was stirred and granulated with an addition amount of water of 50 ml. The granulated product was dried at 40 ° C. in a fluidized bed drier to remove water almost completely.

[Granulated product (D)] 400 g of boric acid, 1200 g of aluminum sulfate octahydrate, 1200 g of succinic acid, tartaric acid 3
00 g is ground in a commercially available bantam mill to an average particle size of 10 μm. 250 g of D-mannite in this fine powder,
120 g of D-sorbit and 400 g of PEG # 400160 are added, and the mixture is stirred for 30 ml with water, and the granulated product is dried at 40 ° C. in a fluidized bed drier to completely remove water.

[Solid Fixing Agent] The thus obtained granulated product (C) was prepared by adding 3000 g of β-alanine, 4330 g of sodium acetate and 1.5% of sodium 1-octanesulfonate to the total weight. Further, 750 g of sodium sodium metabisulfite and sodium 1-octanesulfonate were added to the granulated product (D) so as to be 1.0% of the total weight, and each was humidified at 25 ° C. and 40% RH or less. After the mixture was uniformly mixed for 10 minutes using a mixer in the prepared room, the obtained mixture was charged with a tableting machine obtained by modifying a Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., and the filling amount per tablet (C) was 10%. 0.2 g and (D) 11.2 g, and compression tableting was performed to prepare a cylindrical fixing tablet having a diameter of 30 mm. Each of these was sealed in a pillow bag containing aluminum for moisture proofing in a quantity of 40 liters.

<Treatment method> The automatic processing machine was a modified SRX-201 (manufactured by Konica Corporation). The developer in the developing tank at the start is prepared by mixing the solid developers A and B, and then diluting and dissolving with a dilution water with a modified chemical mixer.
The tablets were completely dissolved, and no precipitate was observed. 7.8 liters of this developing solution was put into SRX-201, and a starter described later was added to fill the developing tank as a starting solution to start processing. The starter addition amount was 33 cc / liter. The fixing agent is prepared by diluting the solid fixing agents (C) and (D) with dilution water using a chemical mixer. The tablets were completely dissolved, and no precipitate was observed. 5.6 liters of the adjusted fixing solution was put into an SRX-201 fixing processing tank to be used as a start solution.

Starter formulation KBr 5.5 g HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH) ₂ OH 0.05 g N-acetyl-D, L-penicillamine 0.10 g Sodium metabisulfite Starting solution pH In addition, a modified chemical mixer inlet was provided so that each solid agent could be charged for both development and fixing of the SRX-201, and a built-in chemical mixer for dissolving the solid agent was modified.

In each of the developing and fixing steps, each of the packaging bags was opened by hand at the inlet of each solid agent, and the tablets were dropped into the built-in chemical mixer.
(0 ° C.) and stirring and dissolving with a dissolution time of 25 minutes.
Adjust to 0 liters. This was used as a developing and fixing replenisher. The replenisher thus prepared is supplied to a developing tank and a fixing tank to satisfy the above-mentioned amount.

The pH at the time of dissolving the development was finely adjusted with acetic acid and potassium hydroxide so as to become 10.55. The pH of the dissolution replenisher for the fixer 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 3.0 liters, and the capacity of the spare tank is 3.0 liters. Even if the replenisher runs out,
A spare tank was provided so that the replenisher was supplied so as not to be in a non-replenished state during the stirring and dissolving time (about 25 minutes). The pH of the developer when the starter was added was 10.45.

The sample prepared above was exposed to light so that the optical density after development processing was 1.0, and the sample was run. During the running in developer and the photosensitive material 1 m ² per developer replenisher was added 90 ml. 1m of photosensitive material in fixer
90 ml of the fixing replenisher was added per ^two .

(Processing conditions) Developing 35 ° C. 8.2 seconds Fixing 33 ° C. 5 seconds Washing at room temperature 4.5 seconds Squeeze 1.6 seconds Drying 40 ° C. 5.7 seconds Total 25 seconds After reaching running equilibrium, The evaluation of metrology, evaluation of storage stability over time, and evaluation of processing variability were performed.

[0332]

[Table 2]

According to the sample No. of the present invention, It can be seen that the samples Nos. 2 and 3 have low fog and high sensitivity, and have little fluctuation over time and processing.

Example 2 Preparation of Em-4 (Comparative Emulsion) A4 Ossein Gelatin 75.0 g KI 1.25 g NaCl 33.0 g Make up to 15000 ml with distilled water B4 Silver nitrate 410 g Make up to 684 ml with distilled water C4 Silver nitrate 11590 g distilled water D4 KI 4.0 g NaCl 140 g Distilled water to 684 ml E4 NaCl 2272 g KBr 3277 g Distilled water to 19274 ml at 40 ° C. at 40 ° C., JP-B-58-58288, 58-58
No. 58289, solution A4 in a mixing stirrer
, The total amount of Solution B4 and Solution D4 was added over 1 minute. The EAg was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the total amount of Solution C4 and Solution E4 was added over 320 minutes. Meanwhile, EAg was controlled at 100 mV.

Immediately after the addition was completed, desalting and washing were performed. Em-4 thus prepared is composed of tabular grains having a (100) plane as the main plane, with 65% of the total projected area of the silver halide grains having an average thickness of 0.14 µm and an average grain size of 1. 0
μm, the coefficient of variation was found to be 25% by electron microscope observation. Of the tabular silver halide grains, 90% or more of the end faces were composed of (100) planes and accounted for 95% of the total projected area.

Preparation of Em-5 (Comparative Emulsion) At the stage when 60% of the total silver content was added to Em-4, the addition of the solution C4 and the solution E4 was interrupted, and the following solution F5 was added to 2
Added over minutes. Thereafter, the remaining C4 solution and E4 solution were added. After completion of the addition, desalting and washing were performed in the same manner as in Em-4.

F5 KSCN 3.4 g Make up to 200 ml with distilled water Em-5 prepared in this way is composed of tabular grains having 65% of the total projected area of silver halide grains having the (100) plane as the main plane. , Average thickness 0.14 μm, average particle size 1.
It was found by electron microscope observation that the coefficient of variation was 0 μm and the coefficient of variation was 25%. In addition, of the tabular grains, 9
Particles in which 0% or more consist of (100) planes account for 9 of the total projected area.
Accounting for 2%.

Preparation of Em-6 (Emulsion of the Invention) In Em-4, except that Solution A4 was changed to Solution A6,
Em-6 was prepared in the same manner as Em-4.

A6 Ossein gelatin 75.0 g KI 1.25 g KSCN 3.4 g NaCl 33.0 g Make up to 15000 ml with distilled water Em-6 thus produced has 65% of the total projected area of silver halide grains. It is composed of tabular grains having a (100) plane as the main plane, and has an average thickness of 0.14 μm and an average grain size of 1.
It was found by electron microscope observation that the coefficient of variation was 0 μm and the coefficient of variation was 25%. In addition, of the tabular grains, 9
Particles in which 0% or more consist of (100) planes account for 9 of the total projected area.
Accounting for 6%.

Subsequently, in the same manner as in Example 1, the above emulsions Em-4 to Em-6 were spectrally sensitized and chemically sensitized. 4 to 6 were prepared.

The obtained sample no. Example 1 was repeated except that the processing was changed from processing-1 to processing-2 below for processing 4 to 6.
In the same manner as in the above, sensitometry evaluation, storage stability evaluation with time, and processing variability evaluation were performed. The sensitivity, storage stability over time, and processing variability are as shown in Sample No. It was expressed as a relative value when 4 was taken as 100. Table 3 shows the obtained results.

[Processing-2] Adjustment of 100 liter amount as developer.

[Granulated product (A1)] 300 g of 1-phenyl-3-pyrazolidone, 10 g of N-acetyl-D, L-penicillamine, and 500 g of sodium glutaraldehyde bisulfite were each placed on a commercially available bantam mill at an average of 10 μm.
pulverize to m. To this fine powder, 1500 g of sodium metabisulfite, 6000 g of the compound 1-1 of the present invention,
600 g of binder D-Sorbit was added and mixed in a mill for 30 minutes, and then stirred at room temperature for about 10 minutes in a commercial stirring granulator.
After granulation by adding ml of water, the granules are dried in a fluid bed dryer at 40 ° C. for 2 hours to remove almost completely the moisture of the granules.

[Preparation of Solid Developer A1] The granulated product (A1) 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 mixed uniformly for 10 minutes, the resulting mixture was used in a Kikusui Seisakusho Co., Ltd. Tough Presto Collect 1
527HU was subjected to compression tableting using a modified tableting machine with a filling amount of 10 g per tablet to produce a solid developer A1.

[Granulated product (B1)] Potassium carbonate was prepared to have the buffer capacity shown in Table 1. 100 g of sodium bicarbonate are each ground in a commercially available bantam mill until the average particle size is 10 μm. DTPA for each fine powder,
250 g of 5H, 40 g of compound (M), compound (N) 8
g, KI 10 g, methyl-β-cyclodextrin 200 g, binder mannitol 2000 g, D-sorbit 700 g, and mix in a mill for 30 minutes. After granulating by adding water, the granulated material is heated at 40 ° C. in a fluidized drier.
For 2 hours to remove the moisture of the granules almost completely.

[Preparation of Solid Developer B1] The granulated product (B1) 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 subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being 10 g, and alkali-developed tablets. Was prepared.

Both the developers A1 and B1 were sealed and packaged in 4.0 liter quantities in a pillow bag containing aluminum for moisture protection.

The solid fixing agent and the starter used in Example 1 were used.

<Processing Method> As in the first embodiment, the automatic processing machine
Example 1 was carried out in the same manner as in Example 1 except that RX-201 (manufactured by Konica Corporation) was modified and used, and solid developers A and B were changed to solid developers A1 and B1. However, the pH when the developer was dissolved was finely adjusted with acetic acid and potassium hydroxide so as to be 10.15. The pH of the developer when the starter was added was 9.90.

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material was run. During the running, 40 ml of a developing replenisher was added to the developing solution per 1 m ² of the photosensitive material. 70 ml of replenisher was added to the fixing solution per 1 m ² of the light-sensitive material.

Processing conditions Current image 39 ° C. 5.0 sec. Fixing 36 ° C. 3.5 sec. Rinse at room temperature 2.5 sec. Squeeze 1.5 sec. Drying 50 ° C. 2.5 sec. (15 sec. In total) After reaching, the sensitometry evaluation, the storage stability evaluation with time, and the processing variability evaluation were performed.

[0352]

[Table 3]

According to the sample No. of the present invention, No. 6 has low fog and high sensitivity, and it can be seen that variation with time and processing variation are small.

Example 3 Preparation of Em-7 (Comparative Emulsion) A7 Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Make up to 15000 ml with distilled water B7 Silver nitrate 410 g Make up to 684 ml with distilled water C7 Silver nitrate 11590 g Distilled water D7 KI 4.0 g NaCl 140 g Distilled water to 684 ml E7 NaCl 3980 g Distilled water to 19274 ml At 40 ° C., JP-B-58-58288 and 58-58
Solution A7 in a mixing stirrer as described in US Pat.
, The total amount of the solution B7 and the solution D7 was added over 1 minute. The EAg was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the total amount of Solution C7 and Solution E7 was added over 320 minutes. Meanwhile, EAg was controlled at 149 mV.

Immediately after the addition was completed, desalting and washing were performed. Em-7 thus prepared is composed of tabular grains having a (100) plane as the main plane, with 65% of the total projected area of the silver halide grains having an average thickness of 0.15 μm and an average grain size of 0.1 mm. 9
It was found by electron microscopy that the coefficient of variation was 9 μm and the coefficient of variation was 26%. Of the tabular silver halide grains, 90% or more of the end faces were composed of (100) planes and accounted for 95% of the total projected area.

Preparation of Em-8 (Emulsion of the Invention) In Em-7, except that Solution A7 was changed to Solution A8,
Em-8 was prepared in the same manner as Em-7.

A8 Ossein gelatin 75.0 g KI 1.25 g KSCN 3.4 g NaCl 33.0 g Make up to 15000 ml with distilled water Em-8 thus produced has 65% of the total projected area of silver halide grains. It is composed of tabular grains having a (100) plane as a main plane, and has an average thickness of 0.15 μm and an average grain size of 0.1 μm.
Electron microscope observation revealed that the particle diameter was 99 μm and the coefficient of variation was 26%. Further, among the tabular grains, grains having (100) planes accounted for 90% or more of the end faces occupied 96% of the total projected area.

Preparation of Em-9 (Emulsion of the Present Invention) In Em-8, the solution E7 was changed to the solution E9.
9 except that the EAg at the time of addition of 9 was changed to 143 mV.
In a similar manner to 8, Em-9 was prepared.

E9 3772 g of NaCl, 423 g of KBr, and 19274 ml of distilled water Em-9 prepared in this way is composed of tabular grains having 65% of the total projected area of silver halide grains having a (100) plane as a main plane. , Average thickness 0.15 µm, average particle size 0.
Electron microscope observation revealed that the particle diameter was 99 μm and the coefficient of variation was 26%. Further, among the tabular grains, grains having (100) planes accounted for 90% or more of the end faces occupied 96% of the total projected area.

Preparation of Em-10 (Emulsion of the Present Invention) In Em-9, the solution E9 was changed to the solution E10,
0 except that the EAg at the time of addition of 0 was changed to 138 mV.
In the same manner as in No. 9, Em-10 was prepared.

E10 3357 g of NaCl 1268 g of KBr Make 19274 ml with distilled water Em-10 thus produced is composed of tabular grains having 65% of the total projected area of silver halide grains having a (100) plane as a main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 26%. Further, among the tabular grains, grains having (100) planes accounted for 90% or more of the end faces occupied 96% of the total projected area.

Preparation of Em-11 (Emulsion of the Present Invention) In Em-9, the solution E9 was changed to the solution E11,
1 except that the EAg at the time of addition 1 was changed to 133 mV.
In the same manner as in No. 9, Em-11 was prepared.

E11 NaCl 2942 g KBr 2114 g Make up to 19274 ml with distilled water Em-11 made in this way is composed of tabular grains having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 26%. Further, among the tabular grains, grains having (100) planes accounted for 90% or more of the end faces occupied 96% of the total projected area.

Preparation of Em-12 (Emulsion of the Present Invention) In Em-9, the solution E9 was changed to the solution E12,
2 except that the EAg at the time of addition 2 was changed to 129 mV.
In the same manner as in No. 9, Em-12 was prepared.

E12 NaCl 2526 g KBr 2959 g Make up to 19274 ml with distilled water Em-12 produced in this way is composed of tabular grains having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 26%. Further, among the tabular grains, grains having (100) planes accounted for 90% or more of the end faces occupied 96% of the total projected area.

Preparation of Em-13 (Emulsion of the Present Invention) In Em-9, the solution E9 was changed to the solution E13,
3 except that EAg at the time of addition was changed to 124 mV.
In a similar manner to 9, Em-13 was prepared.

E13 NaCl 2111 g KBr 3805 g Make up to 19274 ml with distilled water Em-13 prepared in this manner is composed of tabular grains having 65% of the total projected area of silver halide grains having a (100) plane as a main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 26%. Further, among the tabular grains, grains having (100) planes accounted for 90% or more of the end faces occupied 96% of the total projected area.

Preparation of Em-14 (Emulsion of the Present Invention) In Em-9, the solution E9 was changed to the solution E14,
4 except that the EAg at the time of addition was changed to 118 mV.
In the same manner as in No. 9, Em-14 was prepared.

E14 1696 g of NaCl, 4651 g of KBr, and 19274 ml of distilled water Em-14 thus produced is composed of tabular grains having 65% of the total projected area of silver halide grains having a (100) plane as a main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 26%. Further, among the tabular grains, grains having (100) planes accounted for 90% or more of the end faces occupied 96% of the total projected area.

Preparation of Em-15 (Emulsion of the Present Invention) In Em-9, the solution E9 was changed to the solution E15,
5 except that the EAg at the time of addition was changed to 114 mV.
In the same manner as in No. 9, Em-15 was prepared.

E15 NaCl 1281 g KBr 5496 g Make up to 19274 ml with distilled water Em-15 produced in this way is composed of tabular grains having 65% of the total projected area of silver halide grains having a (100) plane as a main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 26%. Further, among the tabular grains, grains having (100) planes accounted for 90% or more of the end faces occupied 96% of the total projected area.

Preparation of Em-16 (Emulsion of the Present Invention) In Em-9, the solution E9 was changed to the solution E16,
6 except that the EAg at the time of addition was changed to 108 mV.
In a similar manner to 9, Em-16 was prepared.

E16 865 g of NaCl, 6342 g of KBr, and 19274 ml of distilled water Em-16 prepared in this manner is composed of tabular grains in which 65% of the total projected area of silver halide grains has a (100) plane as a main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 26%. Further, among the tabular grains, grains having (100) planes accounted for 90% or more of the end faces occupied 96% of the total projected area.

Preparation of Em-17 (Comparative emulsion) In Em-9, the solution E9 was changed to the solution E17, and E1
7 except that the EAg at the time of addition of 7 was changed to 102 mV.
In a similar manner to 9, Em-17 was prepared.

E16 450 g of NaCl, 7187 g of KBr, and 19274 ml of distilled water Em-17 prepared in this way is composed of tabular grains having 65% of the total projected area of silver halide grains having a (100) plane as a main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 26%. Further, among the tabular grains, grains having (100) planes accounted for 90% or more of the end faces occupied 96% of the total projected area.

The halogen compositions of the emulsions Em-7 to 17 are shown in Table 4 below.

[0377]

[Table 4]

Subsequently, the emulsions Em-7 to Em-17 were spectrally and chemically sensitized in the same manner as in Example 2.
Using these emulsions, coating sample Nos. 7-1
7 was created. However, the developer dispersion of the second layer 2-29
Was replaced with Compound 2-31, and sensitometric evaluation, storage stability evaluation with time, and processing variability evaluation were performed. The sensitivity, storage stability over time, and processing variability are as shown in Sample No. 7 is represented by a relative value when 100 is taken. Table 5 shows the results.

[0379]

[Table 5]

According to the sample No. of the present invention, Nos. 8 to 16 have low fog and high sensitivity, and show little change over time and processing variation.

Example 4 Preparation of Em-18 (Comparative Emulsion) A18 Ossein Gelatin 75.0 g KI 1.25 g NaCl 33.0 g Make up to 15000 ml with distilled water B18 Silver nitrate 410 g Make up to 684 ml with distilled water C18 Silver nitrate 11590 g distilled water D18 KI 4.0 g NaCl 140 g Distilled water to 684 ml E18 NaCl 2272 g KBr 3477 g Distilled water to 19274 ml At 40 ° C., JP-B-58-58288, 58-58
No. 58289, solution A1 in a mixing stirrer
8, the total amount of Solution B18 and Solution D18 was added over 1 minute. After adjusting the EAg to 149 mV, 0.5 g / min.
The temperature was raised at a rate of 60 ° C. to 60 ° C. Thereafter, the total amount of the solution C18 and the solution E18 was added over 320 minutes.
Meanwhile, EAg was controlled at 100 mV. After the addition,
Immediately, desalting and washing were performed.

Emulsion Em-18 thus prepared
Means that 60% of the total projected area of the silver halide grains is (10
Electron microscopic observation revealed that the particles consisted of tabular grains having the 0) plane as the main plane, and had an average thickness of 0.158 μm, an average particle diameter of 0.950 μm, and a coefficient of variation of 29%.

Preparation of Em-19 (Emulsion of the Present Invention) Em-19 was prepared in the same manner as in Em-18, except that solution B18 was changed to solution B19.

B19 Silver nitrate 410 g Thallium nitrate 18.8 g Make up to 684 ml with distilled water Emulsion Em-19 prepared in this way has 77% of the total projected area of silver halide grains with (100) plane as the main plane. Electron microscopy revealed that the particles were composed of tabular grains, had an average thickness of 0.158 μm, an average particle diameter of 0.950 μm, and a coefficient of variation of 22.0%.

Subsequently, the emulsions Em-18 to Em-19 were spectrally sensitized and chemically sensitized in the same manner as in Example 2, and these emulsions were used. 1
Nos. 8 to 19 were prepared, and sensitometry evaluation, storage stability evaluation with time, and processing variability evaluation were performed. The sensitivity, storage stability over time, and processing variability are as shown in Sample No. It was expressed as a relative value when 18 was taken as 100. Table 6 shows the results.

[0386]

[Table 6]

According to the sample No. of the present invention, 19 is low fog and high sensitivity, and it can be seen that the variation over time and the variation in processing are small.

Example 5 Preparation of Em-20 (Comparative emulsion) A20 Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Make up to 15000 ml with distilled water B20 Silver nitrate 410 g Make up to 684 ml with distilled water C20 Silver nitrate 11590 g Distilled water D20 KI 4.0 g NaCl 140 g Distilled water to 684 ml E20 NaCl 3358 g KBr 1265 g Distilled water to 19274 ml At 40 ° C., JP-B-58-58288 and 58-58
No. 58289, solution A2 in a mixing stirrer
To 0, the total amount of Solution B20 and Solution D20 was added over 1 minute. The EAg was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the total amount of solution C20 and solution E20 was reduced to 3%.
Added over 20 minutes. Meanwhile, EAg was controlled at 138 mV.

Immediately after the addition was completed, desalting and washing were performed.
In Em-20 thus prepared, 66% of the total projected area of the silver halide grains is composed of tabular grains having a (100) plane as a main plane, the average thickness is 0.158 μm, and the average grain size is 0.1 mm. It was found by electron microscope observation that the coefficient of variation was 950 μm and the coefficient of variation was 26%.

Preparation of Em-21 (Emulsion of the Present Invention) Em-21 was prepared in the same manner as Em-20, except that solution A20 was changed to solution A21.

A21 Ossein Gelatin 75.0 g KI 1.25 g NaCl 33.0 g Ca (NO ₃ ) ₂ .4H ₂ O 16.7 g Make up to 15000 ml with distilled water Emulsion Em-21 prepared in this way is halogen 79% of the total projected area of the silver halide grains is composed of tabular grains having a (100) plane as a main plane, the average thickness is 0.158 μm, the average grain size is 0.950 μm, and the variation coefficient is 23%. It was found by electron microscope observation.

Preparation of Em-22 (Emulsion of the Present Invention) Em-22 was prepared in the same manner as Em-20, except that solution A20 was changed to solution A22.

A22 Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Hg ₂ Cl ₂ 3.33 g Make up to 15000 ml with distilled water Emulsion Em-22 thus prepared was obtained by total projection of silver halide grains. Electron microscopy revealed that 80% of the area was composed of tabular grains having the (100) plane as the main plane, the average thickness was 0.158 μm, the average particle diameter was 0.950 μm, and the coefficient of variation was 23%. .

Preparation of Em-23 (Emulsion of the Present Invention) Em-23 was prepared in the same manner as Em-20, except that solution A20 was changed to solution A23.

A23 Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Pb (NO ₃ ) ₂ 2.34 g Make up to 15000 ml with distilled water Emulsion Em-23 prepared in this manner was made of silver halide grains. According to electron microscopic observation, 80% of the total projected area is composed of tabular grains having a (100) plane as a main plane, the average thickness is 0.158 μm, the average particle diameter is 0.950 μm, and the coefficient of variation is 24%. found.

Subsequently, the emulsions Em-20 to Em-23 were spectrally sensitized and chemically sensitized in the same manner as in Example 2. Coating sample Nos. 2
0 to 23 were prepared, and sensitometry evaluation, storage stability evaluation with time, and processing variability evaluation were performed. The sensitivity, storage stability over time, and processing variability are as shown in Sample No. It was expressed as a relative value when 20 was taken as 100. Table 7 shows the results.

[0397]

[Table 7]

According to the sample No. of the present invention, 21 to 23 show low fog and high sensitivity, and small variations over time and processing.

Example 6 Preparation of Em-24 (Comparative Emulsion) A24 Ossein Gelatin 75.0 g KI 1.00 g NaCl 33.0 g Make up to 15000 ml with distilled water B24 Silver nitrate 410 g Make up to 684 ml with distilled water C24 Silver nitrate 590 g distilled water D24 KI 4.0 g NaCl 140 g Distilled water to 684 ml E24 NaCl 2272 g KBr 3277 g Distilled water to 19274 ml at 40 ° C. At 40 ° C., JP-B-58-58288, 58-58
To the solution A24 in the mixing stirrer described in No. 58289, the entire amount of the solution B24 and the solution D24 was added over 50 seconds.
The EAg was adjusted to 149 mV, and after Ostwald ripening for 22 minutes, the total amount of Solution C24 and Solution E24 was added over 320 minutes. Meanwhile, EAg was controlled at 100 mV. Immediately after the addition was completed, desalting and washing were performed.

Emulsion Em-24 thus prepared
Means that 65% of the total projected area of the silver halide grains is (10
Electron microscopic observation revealed that the particles were composed of tabular grains having the 0) plane as the main plane, the average thickness was 0.140 μm, the average particle diameter was 1.00 μm, and the coefficient of variation was 25%.

Preparation of Em-25 (Emulsion of the Invention) Em-25 was prepared by changing the solution A24 to the solution A25, the solution D24 to the solution D25, and the solution E24 to the solution E25 in the above Em-24.

A25 Ossein gelatin 75.0 g KI 1.00 g KBr 67.2 g Make up 15000 ml with distilled water D25 KI 4.0 g KBr 285 g Make up 684 ml with distilled water E25 NaCl 2445 g KBr 3125 g Make up 19274 ml with distilled water Emulsion Em-25 prepared in this manner comprises tabular grains having 79% of the total projected area of silver halide grains having the (100) plane as the main plane, and has an average thickness of 0.142 μm, an average grain size of 1.00 μm, Electron microscope observation revealed that the coefficient of variation was 22%.

Preparation of Em-26 (Comparative Emulsion) In Em-24, Solution A24 was replaced with Solution A26, and Solution D was replaced with Solution D.
Em-26 was prepared by changing Solution 24 to Solution D26 and Solution E24 to Solution E26.

A26 Ossein gelatin 75.0 g NaCl 33.0 g Distilled water to 15000 ml D26 NaCl 140 g Distilled water to 684 ml E26 NaCl 2274 g KBr 3377 g Distilled water to 19274 ml Emulsion Em-26 prepared in this way Is that tabular grains having 60% of the total projected area of the silver halide grains having the (100) plane as a main plane, having an average thickness of 0.154 μm, an average grain size of 0.96 μm, and a variation coefficient of 26%. Was found by electron microscope observation.

Preparation of Em-27 (Emulsion of the Invention) In Em-24, Solution A24 was replaced with Solution A27, and Solution D was replaced with Solution D.
Em-27 was prepared by changing solution 24 to solution D27 and solution E24 to solution E27.

A27 Ossein gelatin 75.0 g KBr 67.2 g Distilled water to 15000 ml D27 KBr 285 g distilled water to 684 ml E27 NaCl 2447 g KBr 3125 g distilled water to 19274 ml Emulsion Em-27 prepared in this way Means that 75% of the total projected area of the silver halide grains is composed of tabular grains having a (100) plane as a main plane, the average thickness is 0.159 μm, the average grain size is 0.94 μm, and the variation coefficient is 23%. Was found by electron microscope observation.

Preparation of Em-28 (Comparative Emulsion) Em-28 was prepared in the same manner as Em-24, except that the addition time of solution C24 and solution E24 was changed to 275 minutes.

Emulsion Em-28 thus prepared was composed of tabular grains having a (100) plane as the main plane and 65% of the total projected area of silver halide grains, and an average thickness of 0.19.
Electron microscope observation revealed that the average particle diameter was 1 μm, the average particle diameter was 0.86 μm, and the coefficient of variation was 25%.

Preparation of Em-29 (Emulsion of the Present Invention) Em-29 was prepared in the same manner as Em-25 except that the addition time of solution C25 and solution E25 was changed to 275 minutes. .

Emulsion Em-29 thus prepared was composed of tabular grains having 80% of the total projected area of silver halide grains having (100) plane as a main plane, and an average thickness of 0.19.
Electron microscope observation revealed that the average particle diameter was 1 μm, the average particle diameter was 0.86 μm, and the coefficient of variation was 21%.

Subsequently, in the same manner as in Example 2, the above emulsions Em-24 to Em-29 were subjected to spectral sensitization and chemical sensitization. 2
Nos. 4 to 29 were prepared, and sensitometry evaluation, storage stability evaluation with time, and processing variability evaluation were performed. The sensitivity, storage stability over time, and processing variability are as shown in Sample No. It was expressed as a relative value when 24 was taken as 100. Table 8 shows the results.

[0412]

[Table 8]

The sample No. of the present invention. 25, 27, and 29 show low fog and high sensitivity, and small variations over time and processing.

Example 7 Preparation of Em-30 (Comparative Emulsion) A30 Ossein Gelatin 75.0 g KI 1.25 g NaCl 33.0 g Make up to 15000 ml with distilled water B30 Silver nitrate 144.4 g Make up 240 ml with distilled water C30 Silver nitrate 11855 D30 KI 4.0 g NaCl 49.9 g Distilled water 240 ml E30 NaCl 2362 g KBr 3477 g Distilled water 19274 ml At 40 ° C., at 40 ° C., Japanese Patent Publication Nos. 58-58288 and 58-58.
No. 58289, solution A3 in a mixing stirrer
To 0, the total amount of Solution B30 and Solution D30 was added over 21 seconds. After adjusting the EAg to 149 mV, 0.1 g / min.
The temperature was increased at a rate of 5 ° C. to 60 ° C. Thereafter, the total amount of the solution C30 and the solution E30 was added over 320 minutes.
Meanwhile, EAg was controlled at 100 mV. After the addition,
Immediately, desalting and washing were performed.

Emulsion Em-30 thus prepared
Means that 65% of the total projected area of the silver halide grains is (10
Electron microscopic observation revealed that the particles consisted of tabular grains having the 0) plane as the main plane, and had an average thickness of 0.120 μm, an average particle diameter of 1.08 μm, and a coefficient of variation of 25%.

Preparation of Em-31 (Emulsion of the Present Invention) <Preparation of Seed Crystal> A31 Ossein Gelatin 75.0 g NaCl 33.0 g Make up to 15000 ml with distilled water B31 Silver Nitrate 144.4 g Make up 240 ml with distilled water D31 NaCl 49.9 g Make up to 240 ml with distilled water. At 40 ° C, JP-B-58-58288, 58-58288
No. 58289, solution A3 in a mixing stirrer
To 1, the total amount of Solution B31 and Solution D31 was added over 21 seconds. After adjusting the EAg to 149 mV, 0.1 g / min.
The temperature was increased at a rate of 5 ° C. to 60 ° C. After the temperature rise,
Immediately, desalting and washing were performed to obtain a seed crystal emulsion A. Seed emulsion A was composed of cubic grains having a (100) plane, and the average grain size was found to be 0.110 μm by electron microscopic observation.

<Preparation of Em-31> G31 Ossein gelatin 75.0 g NaCl 33.0 g Seed crystal emulsion A Total amount Make up to 15000 ml with distilled water C31 Silver nitrate 11855.6 g Make up to 19316 ml with distilled water E31 NaCl 2362 g KBr 3377 g Distilled water 5.31 g of F31 KI made up to 100 ml with distilled water. At 60 ° C., JP-B-58-58288 and JP-B-58-58288.
Solution G3 in a mixing stirrer as described in US Pat.
Solution 1 was added to 1 over 5 seconds and then held for 5 minutes. Subsequently, the total amount of the solution C31 and the solution E31 was changed to 32
Added over 0 minutes. Meanwhile, EAg was controlled at 100 mV.

Emulsion Em-31 thus prepared
Means that 79% of the total projected area of the silver halide grains is (10
Electron microscopic observation revealed that the sample was composed of tabular grains having a 0) plane as a main plane, and had an average thickness of 0.120 μm, an average grain size of 1.08 μm, and a coefficient of variation of 22.1%.

Subsequently, the emulsions Em-30 to Em-31 were spectrally sensitized and chemically sensitized in the same manner as in Example 2, and these emulsions were used. 3
0 to 31 were prepared, and sensitometry evaluation, storage stability evaluation with time, and processing variability evaluation were performed. The sensitivity, storage stability over time, and processing variability are as shown in Sample No. It was expressed as a relative value when 30 was taken as 100. Table 9 shows the results.

[0420]

[Table 9]

The sample No. of the present invention. It can be seen that No. 31 has low fog and high sensitivity, and fluctuations with time and processing fluctuations are small.

Example 8 Sample No. 1 prepared in Example 1 was used. The same evaluation as in Example 1 was performed by changing the processing method to [Processing-3] using Nos. 1-3. Table 10 shows the results.

[Treatment-3] The granulated product (A) obtained in [Treatment-1]
Except for excluding hydroquinone as a developing agent in the preparation of

[0424]

[Table 10]

The sample No. of the present invention Samples Nos. 2 and 3 were treated with a developer containing no developing agent. It can be seen that the fog is low in sensitivity and high in sensitivity, and the variation over time and the variation in processing are smaller than those of Comparative Example 1.

Example 9 The sample no. Using Nos. 4 to 6, the exposure method and processing method were changed as follows. Exposure is in Example 2.
From the intensifying screen used in the above, the following high-sensitivity radiation intensifying screen S
Changed to 1. The processing method was changed to [Processing-4]. Table 11 shows the results.

[Production of high-sensitivity radiation intensifying screen S1] Phosphor Gd ₂ O ₂ S: Tb (average particle size: 1.8 μm) 200 g Binder Polyurethane-based thermoplastic elastomer Demolac TPKL-5-2525 <solid content: 40% > 20 g of nitrocellulose (manufactured by Sumitomo Bayer Urethane Co., Ltd.) is added to 2 g of nitrocellulose (digestion degree: 11.5%) in a methyl ethyl ketone solvent, and dispersed with a propeller mixer to give a coating solution for forming a phosphor layer having a viscosity of 25 PS (25 ° C.) Prepared (binder / phosphor ratio = 1/22).

[0428] Separately, 90 g of soft acrylic resin solids and 50 g of nitrocellulose were used as a coating solution for forming an undercoat layer.
Is added to methyl ethyl ketone, dispersed and mixed to obtain a viscosity of 3 to
A 6PS (25 ° C.) dispersion was prepared.

A thickness of 250 μm into which titanium dioxide has been kneaded.
Of polyethylene terephthalate (support) is placed horizontally on a glass plate, and the above-mentioned coating solution for forming an undercoat layer is uniformly applied on the support using a doctor blade, and then gradually raised from 25 ° C to 100 ° C. The coating film was dried by drying to form an undercoat layer on the support (thickness of the coating film: 15 μm).

The above-mentioned coating solution for forming a phosphor layer was uniformly coated thereon with a doctor blade to a thickness of 240 μm, dried, and then compressed. Compression was performed using a calender roll at a pressure of 300 kg / cm ² and a temperature of 80 ° C. After this compression, a transparent protective film having a thickness of 3 μm was formed by the method described in Example 1 of JP-A-6-75097.

The characteristics of the obtained screen are as follows.
60 μm, phosphor filling rate 68%, sharpness (CTF) 48
%Met.

[Treatment-4] After the running was completed in [Treatment-2], 50 g / L of sodium thiosulfate was added as a fixing agent to the developer. Otherwise, the same processing method as in [Processing-2].

[0433]

[Table 11]

The sample No. of the present invention was used. In No. 6, when exposed with a high-sensitivity radiographic intensifying screen and processed with a developer containing a fixing agent, the fogging and the sensitivity are further lower than those of the comparative sample, and the fluctuations with time and processing are reduced.

[0435]

The silver halide photographic light-sensitive material according to the present invention, the processing method thereof and the image forming method using the same have low fog, high sensitivity, excellent storage stability over time, and low processing variability. The effect is a treatment with a developing solution containing no developing agent,
This is remarkable in processing with a developer containing a fixing agent.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/09 G03C 1/09 1/42 1/42 5/17 5/17 5/26 5/26 520 520 5/31 5 / 31 5/395 5/395 G21K 4/00 G21K 4/00 A

Claims (14)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein the light-sensitive material is represented by the following formula (1) or (2): The silver halide grains containing at least one compound and contained in at least one of the silver halide photographic emulsion layers have a silver chloride content of 20 to 100 mol% at least 50% of the total projected area, Tabular silver halide grains having an aspect ratio of 2 or more, and the silver halide grains satisfy at least one of the following (A), (B), (C), (D) or (E): Silver halide photographic light-sensitive material, characterized by being silver halide grains. (A) a tabular silver halide grain containing silver iodide therein, in which a silver salt is added in the absence of iodide to start nucleation, and then in the presence of iodide Tabular silver halide grains containing a chalcogen compound inside the tabular silver halide grains (B) produced through two processes of adding a silver salt and causing nucleation and / or crystal growth in (B). C) Tabular silver halide grains containing a nucleus portion composed of silver bromide or silver iodobromide. (D) Tabular silver halide grains grown using normal crystals as seed crystals. Tabular silver halide grains containing the following cations: [Wherein, R ₁ and R ₂ each represent a hydroxy group, an amino group,
Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P, Q
Represents a hydroxy group, a carboxy group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a methylcapto group, an alkyl group or an aryl group, or P and Q are And 5 to 5 carbon atoms together with the two vinyl carbon atoms substituted by R ₁ and R ₂ and the carbon atom substituted by Y
Represents an atom group forming an 8-membered ring. Y is = O or = N
It represents the -R _3. R ₃ represents a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. [Chemical formula 2] [Wherein, R ₄ , R ₅ , R ₆ , R ₇ and R ₈ represent a hydrogen atom or a group capable of being substituted on a benzene ring, and may be the same or different. However, the total number of carbon atoms of R ₄ to R ₈ is 8 or more, and at least one of R ₄ and R ₆
One is a hydroxy group, a sulfonamide group or a carbonamide group. Z is a hydrogen atom or a protecting group which can be removed under alkaline conditions. R ₄ to R ₈ and OZ may form a ring together. ] 2. The main plane of the tabular silver halide grains is (1)
2. The silver halide photographic material according to claim 1, wherein the photographic material is a (00) plane. 3. A silver halide photographic light-sensitive material according to claim 1, wherein the compound of the formula (1) or (2) and the silver halide photographic emulsion are contained in the same layer. 4. The silver halide photographic material according to claim 1, wherein the compound of the formula (1) or (2) and the silver halide photographic emulsion are contained in separate layers. 5. A method for processing a silver halide photographic light-sensitive material, comprising subjecting the silver halide photographic light-sensitive material according to claim 1 to photographic processing including development processing. 6. The processing method according to claim 5, wherein the development processing time is from 1 second to 7 seconds. 7. The photographic processing is a method in which processing is performed while continuously replenishing a processing solution according to the photosensitive material to be processed, and the replenishment amount of the developing solution is 1 m ^{2 of the} photosensitive material to be processed.
7. The method for processing a silver halide photographic light-sensitive material according to claim 5, wherein the amount is 1 cc or more and less than 100 cc. 8. A developing solution containing no developing agent and / or a developing replenisher is used.
A method for processing a silver halide photographic material according to any one of the above. 9. The method for processing a silver halide photographic light-sensitive material according to claim 5, wherein the fixing time is 1 second or more and 7 seconds or less. 10. The photographic processing is a method in which processing is performed while continuously replenishing a processing solution in accordance with the photosensitive material to be processed.
^The method for processing a silver halide photographic light-sensitive material according to any one of claims 5 to 9, wherein the amount of the silver halide photographic material is 1 cc or more and less than 100 cc. 11. A developing solution and / or a developing replenisher containing a fixing agent.
A method for processing a silver halide photographic light-sensitive material according to any one of the preceding claims. 12. The method for processing a silver halide photographic material according to claim 5, wherein development and fixing are performed in substantially the same solution. 13. A silver halide photographic light-sensitive material according to claim 5, wherein the processing is carried out by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank of the automatic developing machine. Processing method. 14. The processing method according to claim 5, wherein the silver halide photographic light-sensitive material according to claim 1 is sandwiched between radiographic intensifying screens and X-rays are taken. An image forming method characterized in that the method is performed by: