JPH08114880A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material having high sensitivity for rapid processing and improved resistance against pressure, and to provide its processing method. CONSTITUTION: (a) The silver halide particles in this silver halide photographic emulsion include plate-like silver halide particles by >50% of the total projection area of particles. The average silver iodide content of the silver halide particles is 0.8-0mol%. In the silver halide particle, the max. point of silver iodide content as 4mol% to 100mol% is present in a certain part. Moreover, silver nuclei are formed in the silver halide particle. (b) The silver halide photographic sensitive material described in (a) is processed with a developer containing ascorbic acid or its deriv.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion comprising tabular silver halide grains and a silver halide photographic light-sensitive material using the same, more specifically, a silver halide photographic light-sensitive material having improved film pressure resistance. The present invention relates to materials, particularly medical light-sensitive materials.

[0002]

2. Description of the Related Art In recent years, with respect to the development processing of silver halide photographic light-sensitive materials, it has been strongly desired to shorten the processing time and reduce the processing waste liquid.

For example, in the medical field, the number of X-ray photographs taken is rapidly increasing due to the spread of regular medical examinations, medical checkups, etc., and the increase in diagnosis and examination in general medical care. Therefore, under the present circumstances, further rapid development processing and further reduction of processing waste liquid are increasing.

In order to speed up the processing of silver halide photographic light-sensitive materials, it is essential to shorten the processing time such as development, fixing, washing with water and drying. However, if the conventional photosensitive material is simply shortened by the developing time, for example, the image density and the sensitivity are greatly lowered and the gradation is deteriorated.

Further, if only the fixing time is shortened, the fixing becomes defective and the image quality is deteriorated. Therefore, it is basically necessary to increase the developing rate, fixing rate, drying rate, etc. of the silver halide photographic light-sensitive material.

It has been conventionally known that the silver iodide content of silver halide grains should be lowered to increase the dissolution rate in order to increase the developing rate and the fixing rate. However, if the silver iodide content is lowered, the inherent sensitivity of silver halide is generally lowered, and the adsorption of the spectral sensitizing dye is weakened, so that sufficient spectral sensitivity cannot be obtained. Further, if the average silver iodide content or the silver iodide content inside the silver halide is lowered, the pressure resistance may deteriorate. It is generally well known that pressure fog or pressure desensitization occurs when pressure is applied to silver halide grains, and improvement of pressure resistance is a very important issue for silver halide photographic light-sensitive materials.

On the other hand, tabular silver halide grains are widely known as a technique for improving the sensitivity and image quality of silver halide photographic light-sensitive materials. The tabular silver halide grains are hexahedrons,
Compared with so-called regular crystal silver halide grains such as octahedron, the surface area is large in the same volume, so it is possible to increase the adsorption amount of the sensitizing dye on the grain surface, and as a result, it is possible to achieve high sensitivity. Have.

On the other hand, however, tabular silver halide grains have the drawback of poor pressure resistance. Generally, silver halide grains are sensitive to pressure, and if the sensitivity is increased, they will become more sensitive to pressure.
In the case of tabular silver halide grains, the degree is remarkable.
This means that even if materials having the same mechanical strength are compared with each other in the same volume, a larger moment is more likely to be applied because the tabular grains have a smaller thickness than the spherical grains, and the mechanical strength of the grains as a whole is large. Interpreted as weak.

The pressure characteristics also differ depending on the chemical sensitization conditions of the silver halide grains in addition to the silver halide shape. Generally, when chemical sensitization is insufficient (chemical ripening is insufficient), pressure desensitization occurs frequently. Conversely, when chemical sensitization is excessive, pressure desensitization decreases, but pressure fog tends to increase.

Although many proposals have been disclosed for the deterioration of the pressure resistance as described above, the conventional technology has not yet achieved a sufficient improvement effect.

Particularly, in ultra-rapid processing of medical silver halide photographic light-sensitive materials by an automatic processor, pressure fog called "roller mark" due to high-speed roller conveyance is apt to occur, and pressure is also applied to avoid misdiagnosis. It was strongly desired to prevent fog.

By the way, in the field of medical X-ray photographic light-sensitive materials, in order to improve patient service and workability, in addition to speeding up development processing and reducing processing waste liquid, simplification over all processing operations is strongly desired. Is requested. However, since the liquid processing agent for diluting the concentrated solution of the development processing agent and replenishing it in the processing tank is heavy and has a large volume, it is difficult to improve work efficiency.

As an alternative to this, in recent years, a solid processing agent has been proposed which is supplied to a processing tank of an automatic processor with a solid component and dilution water. As a result, transportation costs are reduced, storage space is reduced, work efficiency is improved, and the amount of packaging material used can also be reduced, which is preferable from the viewpoint of environmental protection.

However, because of the solubility of the solid components,
In the case of rapid processing, it was difficult to obtain sufficiently stable running performance.

[0015]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material having improved pressure resistance, and particularly, it has rapid processing suitability and high sensitivity with improved pressure resistance. The present invention provides a medical silver halide photographic light-sensitive material and a method for processing the same.

[0016]

The objects of the present invention have been achieved by the following.

(1) 50% or more of the total projected area of silver halide grains contained in the emulsion is tabular silver halide grains,
The tabular silver halide grains have an average silver iodide content of 0.8.
Mol% to 0 mol%, the silver iodide content in any part of the inside of the tabular silver halide grains has a maximum value of 4 mol% to 100 mol%, and the tabular halogen A silver halide photographic emulsion characterized in that silver nuclei are formed inside a silver halide grain.

(2) A silver halide photographic light-sensitive material containing at least one silver halide emulsion layer containing the silver halide grains described in (1) above.

(3) A method of processing a silver halide photographic light-sensitive material for medical use, which comprises processing the silver halide photographic light-sensitive material described in the above item (2) for a total processing time of 15 to 90 seconds.

(4) The method for processing a silver halide photographic light-sensitive material according to item (2), 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.

(5) The method for processing a silver halide photographic light-sensitive material according to the item (1), which comprises processing with a developing solution containing ascorbic acid or a derivative thereof.

The present invention will be described in detail below.

In the silver halide emulsion of the present invention, silver iodobromide, silver iodochloride, silver chloroiodobromide and the like can be used as the silver halide, and particularly silver iodobromide and silver chloroiodobromide. It is preferable. When silver iodobromide is used, the silver iodide content is 0.8 as the average silver iodide content in the entire silver halide grains.
It is at most mol%, preferably at most 0.5 mol%, more preferably at most 0.4 mol%.

In the present invention, the tabular silver halide grains contain silver iodide, but the containing position is inside.

The term "inside" as used herein means a part other than the outermost surface of the particles.

Further, the grains preferably contain silver iodide on the outermost surface / inside thereof. The tabular silver halide grains have a maximum silver iodide content of 4 mol% or more, and preferably 4 mol% or more and 10 mol% or less, at any site inside the grain.

In the present invention, the expression "the silver iodide content has a maximum value in any part inside the tabular grain" means that the silver iodide content in the part is iodide around the part adjacent to the part. It means greater than the silver content. The site may be any site other than the outermost surface, or may be a plurality of sites.

In the present invention, the silver iodide content on the outermost surface of tabular silver halide grains is determined by the XPS method (X-ray P
photoelectron Spectroscop
y: depth of about 50 analyzed by X-ray photoelectron spectroscopy)
It refers to the silver iodide content up to Å and can be determined as follows.

The sample was cooled to -110 ° C. or lower in an ultrahigh vacuum of 1 × 10 ^-8 torr or less, and MgKα was irradiated as an X-ray for a probe with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA to obtain Ag3d5 /. 2, Br3d, I3d 3/2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor (Sensitivity Factor), and the halide composition of the outermost surface is determined from the intensity ratio of these.

The purpose of cooling the sample is to eliminate the measurement error caused by the destruction of the sample (the decomposition of silver halide and the diffusion of halide (particularly iodine)) by the X-ray irradiation at room temperature and to enhance the 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 silver iodide content and the average silver iodide content of individual silver halide grains are determined by the EPMA method (E
electron Probe Micro Analysis
(Zer method). According to this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, and an X-ray analysis by electron beam excitation and electron beam excitation is performed. By this method, the silver halide composition of each grain can be determined by obtaining the characteristic X-ray intensity of silver and iodide emitted from each grain. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content can be determined from the average thereof.

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

The tabular silver halide grain referred to in the present invention means a grain having two parallel main planes facing each other.
Ratio of grain size to grain thickness (hereinafter referred to as aspect ratio)
Is greater than 1.3. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), and a diameter corresponding to a circle of a projected area of the tabular silver halide grains (a diameter of a circle having the same projected area as the silver halide grains). ), And the thickness means the distance between two parallel principal planes forming a tabular silver halide grain.

In the present invention, the grains occupying 50% or more of the total projected area of the silver halide grains contained in the emulsion are preferably tabular silver halide grains, and more preferably 70% or more.

The average aspect ratio of the tabular silver halide grains contained in the silver halide emulsion of the present invention is preferably 2 or more and less than 5, and more preferably 2.2 or more and less than 5.0. The average aspect ratio as used herein refers to the average value of all hexagonal tabular grains of the present invention having an aspect ratio of 1.3 or more that are present in the emulsion. Tabular silver halide grains having an average aspect ratio of 5 or more, or conversely, thick tabular silver halide grains having an average aspect ratio of less than 2.0 or normal crystal grains have poor pressure resistance.

In the present invention, the silver halide emulsion is characterized in that silver nuclei are formed at any site inside the tabular grains.

The formation of silver nuclei in the present invention is carried out by adding a reducing agent to a mixed solution for growing a silver halide emulsion or grains, or mixing for growing a silver halide emulsion or grains. The solution is aged under low pAg of pAg7 or lower or under high pH conditions of pH7 or higher, or by grain growth. A method of combining these methods is a preferred embodiment of the present invention.

Reduction sensitization has long been known as a technique for forming silver nuclei. For example, Journal o
f Photographic Science 25th
Volume 19-27 (1977) and Photogra.
phic Science and Engineer
ng 23, pages 113-117 (1979), the silver nuclei formed by reduction sensitization are Ph.
otographishe Korresponden
z Volume 1, 20 (1957) and Photograph.
hic Science and Engineer
As described by Michelle and Lowe in the report of ng Vol. 19, 49-55 (1975), it has been thought that the reaction is represented by the following formula at the time of exposure and contributes to sensitization.

AgX + hv → e ⁻ + h ⁺ (1) Ag2 + h ⁺ → Ag ⁺ + Ag (2) Ag → Ag ⁺ + e ⁻ (3) where h ⁺ and e ⁻ are free holes and free electrons generated by exposure, and hv Indicates a photon, and Ag2 indicates a silver nucleus formed by reduction sensitization.

However, Photographic Sci
Sense and Engineering Volume 16
35-42 (1971) and Vol. 23, 113-
According to page 117 (1979), silver nuclei not only trap holes but also electrons.
The current situation is that the above theory alone does not always provide a sufficient explanation.

Further, in the spectrally sensitized grains, the behavior of the reduction sensitization is even more complicated and difficult to predict because the sensitization process is different from the light-sensing region peculiar to the silver halide grains. .

On the other hand, many techniques for putting reduction sensitization into practical use have been disclosed. As reduction sensitizers, tin compounds, polyamine compounds, thiourea dioxide, etc. have been proposed.
As conditions for reduction sensitization, aging at high pH and low pAg
A method of ripening in, etc. has been proposed. Further, many techniques for compensating for the drawback of reduction sensitization have been disclosed.

For example, Japanese Patent Laid-Open No. 2-191938 discloses that reduction sensitization and addition of a thiosulfonic acid compound are used in combination to achieve high sensitivity, reduction of fog and improvement of pressure resistance. In the specification, it is preferable that the silver halide grains have a halogen composition which is not uniform and has a distribution, for example, a structure such as a core-shell grain. However, the preferable range of the silver iodide content is Is not listed. In particular, the Examples do not mention that the silver iodide content is 0.8 mol% or less.

Further, Japanese Patent Laid-Open No. 3-194537 shows that the storage stability of a light-sensitive material can be improved by using a light-sensitive material having an equilibrium pAg of 7 to 11 using an emulsion subjected to reduction sensitization. There is no description about the silver content,
There is no description in the region where the silver iodide content is 0.8 mol% or less. It is surprising that the structure of the present invention improves both sensitivity, pressure resistance and rapid processability.

In the present invention, preferred reducing agents include thiourea dioxide, ascorbic acid and its derivatives, and stannous salt. Other suitable reducing agents include borane compounds, hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount of these reducing agents is preferably 10 ^-2 to 10 ^-8 mol per mol of silver halide.

A silver salt may be added for ripening with a low pAg, but a water-soluble silver salt is preferred and a silver nitrate is preferred as the water-soluble silver salt. The pAg during aging is suitably 7 or less, preferably 6 or less, more preferably 1 to 3
(Where pAg = −log [Ag ⁺ ]).

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

As a method of adding the silver salt or the alkaline compound for forming the silver nuclei according to the present invention, rush addition may be performed, or addition may be performed over a certain period of time. In this case, the flow rate may be added at a constant flow rate, or the flow rate may be functionally changed with respect to time.

The required amount may be added in several divided portions. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, they may be present in the reaction vessel, or they may be mixed in the 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.

In the preparation of the silver halide emulsion of the present invention, a method of growing from a seed grain is preferably used.
Specifically, it is obtained by preliminarily allowing an aqueous solution containing a protective colloid and seed particles to exist in a reaction vessel, and optionally supplying silver ions, halogen ions, or silver halide fine particles to cause the seed particles to grow crystals. is there. Here, the seed particles can be prepared by a single jet method, a controlled double jet method or the like well known in the art. The halogen composition of the seed grains is arbitrary, silver bromide,
It may be any of silver iodide, silver chloride, silver iodobromide, silver chloroiodide, silver chlorobromide, and silver chloroiodobromide, with silver bromide and silver iodobromide being preferred, and iodobromide. In the case of silver, the average silver iodide content is 0.
1 mol% to 6 mol% is preferable.

In the form of crystal growth from seed particles,
The low pAg ripening is preferably carried out by adding silver nitrate after the seed emulsion is formed, that is, immediately before the desalting of the seed grains to after the desalting. Particularly, it is preferable to add silver nitrate after the desalting of the seed particles for aging, and the aging temperature is 40 ° C. or higher.
50 ° C to 80 ° C is preferable. Aging time is 30 minutes or more, 5
0 to 150 minutes are preferably used.

In the form of growing from seed particles, high p
When performing H aging, the volume of the grown grains should be 7
It is necessary to grow the particles through an environment of pH 7 or more at least once before the portion corresponding to 0% grows, and to grow the portion corresponding to 50% of the volume of the grown particles to pH 7 or more. It is more preferable to grow the particles through the above environment at least once, and it is necessary to increase the p by the time the part corresponding to 40% of the volume of the grown particles grows.
It is particularly preferable that the particles grow at least once through an environment of H8 or higher.

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

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.

Peroxyacid salt: K ₂ S ₂ O ₃ , K ₂ C ₂ O ₃ ,
_{K 4 P 2 O 3, K} 2 _{[Ti (O 2) C 2 O} 4 ]-3H ₂ O and the like.

Other examples include peracetic acid, ozone, iodine, bromine and thiosulfonic acid compounds.

The amount of these oxidizing agents used in the present invention is
The amount depends on the type of reducing agent, the conditions for silver nucleus formation, the timing of adding the oxidizing agent, and the adding conditions, but 10 ^-2 to 10 ^-5 mol is preferable per 1 mol of the reducing agent used.

The oxidizing agent may be added at any time during the silver halide emulsion manufacturing process. It can also be added prior to the addition of the reducing agent. Further, after adding the oxidizing agent, a reducing substance may be newly added in order to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the above-mentioned oxidizing agents, and include sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazine and hydrazides, p-phenylenediamines, aldehydes, aminophenols, Examples include endiols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives. The amount of these reducing substances added is 10 ⁻³ to 10 ³ per mol of the oxidizing agent used.
Molar is preferred.

The average grain size of the tabular silver halide grains of the present invention is preferably 0.4 to 3.0 μm, more preferably 0.4 to 2.0 μm.

The average thickness of the tabular silver halide grains of the present invention is preferably 0.05 to 1.0 μm, more preferably 0.05 to 0.40 μm, and particularly preferably 0.05 to 0.30 μm. Is.

The grain size and thickness of silver halide grains are sensitivity,
It is preferable to optimize the pressure characteristics and the like. Other factors that affect the sensitivity and pressure characteristics include the thickness of the hydrophilic colloid layer, the degree of hardening, the chemical ripening conditions, the set sensitivity of the light-sensitive material, and the silver coverage.

The tabular silver halide grain of the present invention is preferably a monodisperse emulsion having a narrow grain size distribution, specifically, (standard deviation of grain size / average grain size) × 100 = broadness of grain size distribution (% When the breadth of distribution is defined by (), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

The tabular silver halide grains of the present invention preferably have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width of thickness distribution (%), it is preferably 25% or less, more preferably 20%. It is as follows, particularly preferably 15% or less.

The tabular silver halide grains of the present invention are crystallographically classified as twins. A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified by Klein and Moiser in the article Photographic Correspondents (Photographs).
hise Korrespondenz) Volume 99 99
Pp. 100, 57.

The tabular silver halide grain of the present invention has two or more twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a photosensitive silver halide emulsion is coated so that the main planes of the tabular silver halide grains contained are oriented substantially parallel to the support, and a sample is prepared. This is cut with a diamond cutter to a thickness of 0.
Obtain a thin section of about 1 μm. The presence of twin planes can be confirmed by observing this section with a transmission electron microscope.

In the present invention, the average value of the distance between twin planes is preferably 0.008 μm or more, more preferably 0.010 μm or more and 0.05 μm or less. Here, the distance between twin planes represents the distance between the twin planes when there are two twin planes, and the longest distance among the twin planes when there are three or more twin planes. Say In the present invention, the average value of the distance between twin planes can be obtained as follows.

That is, by observing the section using the transmission electron microscope, 100 or more tabular silver halide grains having a cross section cut substantially perpendicular to the main plane are arbitrarily selected and each grain is selected. About the distance between twin planes,
It can be obtained by the averaging.

In the present invention, in the tabular silver halide grains, the outer wall of the crystal may substantially consist of {111} planes or {100} planes. Further, it may have both the {111} plane and the {100} plane. In this case, 50% or more of the grain surface is the {111} plane, and more preferably 60% to 99%.
% Is the {111} plane, and particularly preferably 70 to 95%
Is the {111} plane. It is preferable that the planes other than the {111} plane are mainly the {100} plane. This surface ratio is measured by T.V., which utilizes the difference in the adsorption dependence between the {111} plane and the {100} plane in the adsorption of the sensitizing dye. Tani, J .; Ima
ging Sci. 29,165 (1985).

In the present invention, the tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains (hereinafter also referred to as hexagonal tabular grains) have {1
The shape of the 11} plane is hexagonal, and the maximum adjacency ratio thereof is 1.0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, the hexagonal tabular grain has a maximum adjacent side ratio of 1.0 to
If it is 2.0, it is also preferable that the corners are rounded. The length of a side when the corner is rounded is represented by the distance between the straight line portion of the side and the intersection with the line obtained by extending the straight line portion of the adjacent side. The corners are sharper,
It is also preferable that the tabular grains are substantially circular.

In the present invention, it is preferable that each side forming the hexagon of the hexagonal tabular grain has a straight line at least ½ of each side. In the present invention, the ratio of adjacent sides is 1.0.
It is more preferable that it is ˜1.5.

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

The silver halide emulsion of the present invention is preferably grown by a method of precipitating silver halide on seed grains. For example, in the method for producing a silver halide photographic emulsion which is carried out by supplying a water-soluble silver salt solution and a water-soluble halide solution to the presence of a protective colloid to obtain the tabular silver halide emulsion of the present invention, the following conditions Is preferred.

(A) The p of the mother liquor is maintained for a period of ½ or more from the initial stage of silver halide precipitation formation having a silver iodide content of 0 to 5 mol%.
Providing a nuclear particle generation step for keeping Br at 2.5 to -0.7,
(B) Subsequent to the step of forming core particles, the mother liquor contains a silver halide solvent in an amount of 10 ^{−5 to} 2.0 mol per mol of silver halide, and is a substantially monodisperse spherical twin crystal. A seed grain forming step of forming a seed grain or providing a seed grain forming step of raising the temperature of the mother liquor to 40 to 80 ° C. to form a silver halide twin seed grain after the seed grain forming step. And (c) a water-soluble silver salt solution and a water-soluble halide solution and / or silver halide fine particles are added to grow a seed grain. Here, the mother liquor is a liquid (including a silver halide emulsion) that is used in the preparation stage of a silver halide emulsion up to a completed photographic emulsion.

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

The seed grain forming step for forming the silver halide seed grains includes pAg during precipitation of the silver halide, pAg during Ostwald ripening, pH, temperature, concentration of silver halide solvent and silver halide composition, silver halide and halogen. It is formed by a process of controlling the addition rate of the compound solution.

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

In order to obtain the tabular silver halide grains of the present invention, the conditions for growing the seed grains are, for example, JP-A No. 5/1985.
1-39027, 55-142329, 58-
113928, 54-48521 and 58-4.
As described in No. 9938, a water-soluble silver salt solution and a water-soluble halide solution are added by a double jet method, and the addition rate is adjusted according to the growth of particles so that new nucleation does not occur and the size distribution by Ostwald ripening There is a method of gradually changing the speed without spread, that is, within a range of 30 to 100% of the speed at which new nuclei are generated. As another condition for growing the seed grains, a method of growing by adding silver halide fine grains and dissolving and recrystallizing the grains is preferably used, as shown in Item 88 of 1983 Annual Meeting of the Photographic Society of Japan. To be As silver halide fine particles, silver iodide fine particles, silver bromide fine particles, and silver iodobromide fine particles are particularly preferably used.

The silver halide grains may be so-called halogen conversion type grains.
The amount of halogen conversion is preferably 0.2 mol% to 0.5 mol% with respect to the amount of silver, and the conversion time may be physical ripening or after physical ripening. As a method for converting halogen, an aqueous solution of halogen or silver halide fine particles having a smaller solubility product with silver than the halogen composition on the surface of the grain before halogen conversion is usually added. The particle size at this time is 0.2μ
m or less is preferable, and more preferably 0.02 to 0.1 μ
m.

As a method of adjusting the silver iodide content on the outermost surface of the silver halide grains of the present invention, a silver nitrate solution and a solution containing iodo ions are simultaneously added to an emulsion containing tabular grains as a base. A method, a method of adding fine silver halide grains such as silver iodide, silver iodobromide or silver chloroiodobromide, a method of adding potassium iodide or a mixture of potassium iodide and potassium bromide, and the like can be applied. Among these, the method of adding fine silver halide grains is preferable. Especially preferred is the addition of fine silver iodide grains.

The time for adjusting the silver iodide content on the outermost surface is from the final step of the silver halide crystal production step to the chemical ripening step, and further until the end of the solution preparation step immediately before the coating of the silver halide emulsion. Although it can be selected in the meantime, it is preferable to adjust it by the end of the chemical ripening step. The term "chemical ripening step" as used herein means from the time when the physical ripening and desalting operations of the silver halide emulsion of the present invention are completed to the time when the chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Points between.

The silver halide fine grains may be added in several times with a time interval, or another chemically ripened emulsion may be added after the addition of the fine grains. The temperature of the emulsion according to the present invention when the fine silver halide grains are added is preferably in the range of 30 to 80 ° C, and more preferably 40 to 65.
The range of ° C. is particularly preferred. Further, the present invention is preferably carried out under the condition that the silver halide fine grains to be added are partially or wholly disappeared after the addition and immediately before coating. More preferable condition is 20% of the added silver halide fine grains.
The above is the disappearance just before coating.

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

The details regarding the above-mentioned supersaturation factor are as follows.
For example, JP-A-63-92942, or JP-A-1-
Reference can be made to the description such as No. 213637.

The silver halide grains contained in the silver halide emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt) in the process of producing and / or growing the grains. ), A rhodium salt (including a complex salt), and an iron salt (including a complex salt), at least one metal ion is added to allow the metal element to be contained inside and / or on the surface of the particle. it can.

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

In the present invention, it is preferable to use gelatin as the dispersion medium for the protective colloid of silver halide grains, and as the gelatin, alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 100,000).
Alternatively, modified gelatin such as phthalated gelatin may be used. Other hydrophilic colloids can also be used. Specifically, Research Disclosure (Resea)
rch Disclosure, hereinafter abbreviated as RD. ) N
o. 17643. Examples thereof include those described in Section IX (December 1978).

In the silver halide emulsion, unnecessary soluble salts may be removed during the growth of silver halide grains, or may be contained therein. When removing the salts,
RD No. 17643.

The silver halide emulsion of the present invention can be chemically sensitized. Chemical sensitization refers to process conditions such as pH,
The pAg, temperature, time, etc. are not particularly limited, and can be performed under the conditions generally used in the art. For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitization method using a selenium compound, a tellurium sensitization method using a tellurium compound, or a reducing substance is used. The reduction sensitization method used, gold or the like, and the noble metal sensitization method using a noble metal can be used alone or in combination, and among them, the selenium sensitization method, the tellurium sensitization method, the reduction sensitization method and the like are preferably used. Particularly, the selenium sensitization method is preferably used.

In the case of selenium sensitization, the selenium sensitizers used include a wide variety of selenium compounds. US Patent 1
No. 574944, No. 1602592, No. 162349
9, JP-A-60-150046 and JP-A-4-258.
No. 32, No. 4-109240, No. 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), 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 and the like), selenoketones (for example, selenoacetone, selenoacetone) Acetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophos Fates (eg, tri-
p-triselenophosphate, etc.) and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, selenium ketones, and selenides.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but generally it is 10 ^-8 mol to 1 mol per mol of silver halide.
About 0 ^-4 mol is used. Depending on the nature of the selenium compound to be used, water may be added alone or dissolved in an organic solvent such as methanol or ethanol or a mixed solvent thereof, or may be added by mixing with a gelatin solution in advance. -140739,
That is, it can be added by a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

The temperature for chemical ripening using a selenium sensitizer is 4
The range of 0 to 90 ° C is preferable. It is more preferably 45 ° C. or higher and 80 ° C. or lower. Moreover, pH is 4-9, pAg is 6-
A range of 9.5 is preferred.

Regarding the tellurium sensitizer and the sensitizing method, US Pat. Nos. 1,623,499, 3,320,069, 3,772,031, 3,531,289 and 3,655 are cited. , 394, British Patent No. 235,211, No. 1,121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958,
It is disclosed in Japanese Patent Application Laid-Open Nos. 4-204640 and 4-3334303.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, N, N'-. Dimethyl-N'phenyl tellurourea), phosphine tellurides (eg tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (eg Telluroacetamide, N, N-dimethyl tellurobenzamide), telluroketones, telluroesters, isotelloocyanates and the like. The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer.

By subjecting the emulsion to a suitable reducing atmosphere, so-called reduction sensitization can be carried out on the grain surface. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and their derivatives. Other preferred reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

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

As conditions for reduction sensitization, the temperature is about 40 to 7
0 ° C, time about 10-200 minutes, pH about 5-11, p
Ag is preferably in the range of about 1-10.

Silver nitrate is preferred as the water-soluble silver salt. So-called silver ripening, which is one of reduction sensitization techniques, is performed by adding a water-soluble silver salt. The pAg during silver ripening is suitably 1 to 6, and preferably 2 to 4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range. As a stabilizer for a silver halide photographic emulsion containing reduction-sensitized silver halide grains, a general stabilizer described below can be used, but it is disclosed, for example, in JP-A-57-82831. Antioxidants and / or V.I. S. Gahle
r's paper [Zeitshift fur wiss
enschaftriche Photographi
e Bd. 63, 133 (1969)] and JP-A-54.
Good results are often obtained in combination with the thiosulphonic acids described in -1019. The addition of these compounds may be carried out at any stage of the emulsion production process from crystal growth to the preparation process immediately before coating.

The silver halide photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material containing the above-described silver halide emulsion of the present invention, and for example, a black-and-white silver halide photographic light-sensitive material (for example, a medical sensitive material, Sensitive materials for printing, negative sensitive materials for general photography, etc., color photographic light-sensitive materials (for example, color negative light-sensitive materials, color reversal light-sensitive materials, color print light-sensitive materials, etc.), diffusion transfer light-sensitive materials, photothermographic materials, etc. However, it is preferably a black and white silver halide photographic light-sensitive material,
Particularly preferred are silver halide photographic light-sensitive materials for medical use.

The silver halide emulsion of the present invention may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in the emulsion layer or other layers.

The hydrophilic colloid of the silver halide emulsion layer and the non-photosensitive layer of the light-sensitive material of the present invention preferably contains 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) methyl ether, N, N′-methylenebis (β- (vinylsulfonyl) propionamide), active halogen compounds ( 2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycyclo acid, etc.), isoxazoles, 2-chloro-6-hydroxytriazinylated gelatin, etc. Others can be used in combination.

Among them, JP-A-53-41221 and JP-A-53-42121.
3-57257, 59-162456, 60-
Active vinyl compounds described in 80846 and the like and active halogen compounds described in US Pat. No. 3,325,287 are preferable. Further, a polymer hardener can be effectively used. For example, dialdehyde starch, polyacrolein, US Pat.
Polymers having aldehyde groups such as the acrolein copolymers described in 396,029, 3,623,878
Having an epoxy group described in No. 3,362,
827, RD magazine No. 17333 (1978) and the like, polymers having a dichlorotriazine group, JP-A-56-66841, polymers having an active ester group, JP-A-56-142524, U.S. Pat.
61,407, JP-A-54-65033, RD magazine N.
o. A polymer having an active vinyl group described in 16725 (1978) or a group serving as a precursor thereof is preferable, and among them, an active vinyl group or a precursor thereof is obtained by a long spacer described in JP-A-56-142524. Particularly preferred are polymers in which the groups are attached to the polymer backbone.

In the photographic light-sensitive material of the present invention, an appropriate amount of a hardener is added in advance in the light-sensitive material coating step so as to be suitable for rapid processing, and the water swelling rate in the developing-fixing-water washing step is adjusted. Therefore, it is preferable to reduce the water content in the light-sensitive material before the start of drying.

The silver halide light-sensitive material of the present invention comprises
The swelling rate during development is preferably 150 to 250%, and the film thickness after expansion is preferably 70 μm or less. Water swelling rate is 25
If it exceeds 0%, poor drying occurs, and, for example, poor handling occurs in automatic processor processing, especially in rapid processing. If the water swelling ratio is less than 150%, uneven development often occurs during development and residual color contamination tends to increase.

Here, the water swelling ratio is obtained by calculating the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, dividing this by the film thickness before processing, and multiplying by 100. To tell.

In the present invention, the automatic developing machine having a mechanism for supplying the solid processing agent to the processing tank is used as a supplying means, for example, when the solid processing agent is a tablet.
No. 83, No. 63-97522, 1-85732
Although there is a known method such as No. No., any method may be used as long as it has at least the function of supplying tablets to the processing tank. Further, when the solid processing agent is granules or powders, JP-A-62-81964, JP-A-63-84151, and JP-A-HEI-1.
-292375, the gravity drop method described in Japanese and Shokai Sho 63-
105159, 63-195345 and the like screw or screw method is a known method,
It is not limited to these.

The solid processing agent of the present invention may be placed in a processing tank, but preferably, it is communicated with a processing section for processing a light-sensitive material, and a processing solution flows between the processing section and the processing section. It is preferable that the structure is a place where the dissolved components are moved to the treatment part because there is a certain amount of circulation of the treatment liquid with the treatment part. The solid processing agent is preferably added to the temperature-controlled processing liquid.

In the developer used in the development processing method of the present invention, as a developing agent, Japanese Patent Application No. 4-286232 (1) is used.
In addition to the dihydroxybenzenes, aminophenols and pyrazolidones described on pages 9 to 20), JP-A-5-1651.
The reductones described in No. 61 are also used. Among the pyrazolidones to be used, those substituted at the 4-position (dimesone, dimeson S, etc.) are particularly preferable because their water solubility and the solid treating agent themselves do not change over time.

As a preservative, an organic reducing agent can be used as a preservative in addition to the sulfite described in Japanese Patent Application No. 4-286232. In addition, Japanese Patent Application No. 4-586323 (20
The chelating agent described in page) and the bisulfite adduct of the hardening agent described in the same (page 21) can be used.

Further, as a silver sludge inhibitor, Japanese Patent Application No. 4-9
No. 2947, Japanese Patent Application No. 5-96118 (general formula [4-
It is also preferable to add the compound described in a] [4-b]). Addition of a cyclodextrin compound is also preferable, and the compounds described in JP-A No. 1-124853 are particularly preferable.

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

It is necessary to use a buffering agent for the developer, and examples of the buffering agent include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate and borohydride. Sodium acid, potassium borate, sodium tetraborate (boric acid),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
2-hydroxybenzoic acid potassium (potassium 5-sulfosalicylate) etc. can be mentioned.

As a development accelerator, JP-B-37-1608
No. 8, No. 37-5987, No. 38-7826, No. 4
Nos. 4-12380 and 45-9019 and U.S. Pat.
No. 81347 and other thioether compounds, JP-A Nos. 52-49829 and 50-15554, p-phenylenediamine compounds, and JP-A-50-
137726, JP-B-44-30074, JP-A-5
Quaternary ammonium salts represented by 6-156826 and 52-43429, p-aminophenols described in U.S. Pat. Nos. 2610122 and 4119462, U.S. Pat.
No. 4,230,796, No. 3,253,919, and Japanese Patent Publication No. 41.
-11431, U.S. Pat. Nos. 2,482,546, 259.
Amine compounds described in 6926 and 3582346, and JP-B-37-16088 and 42-2520.
No. 1, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-114
31, 42-23883, and US Pat. No. 35325.
Polyalkylene oxide represented by No. 01, etc., other 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles,
Etc. can be added as needed.

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

Further, in the developer composition used in the present invention, if necessary, methyl cellosolve, methanol,
Acetone, dimethylformamide, cyclodextrin compound, other Japanese Patent Publication Nos. 47-33378 and 44-9
The compounds described in JP-A No. 509 can be used as an organic solvent for increasing the solubility of the developing agent.

Furthermore, other various additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

A compound known as a fixing agent can be added to the fixing agent used in the present invention. Fixing agents and chelating agents, p
An H buffer, a hardener, a preservative and the like can be added, and these are described in, for example, JP-A-4-242246 (page 4) and JP-A-5-11.
Those described in 3632 (pages 2 to 4) can be used. In addition, as a hardener, a chelating agent described in Japanese Patent Application No. 4-586323 (page 20), a bisulfite adduct of the hardener described in the same (page 21), or a known fixing accelerator can be used.

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

Further, in the processing method of the silver halide photographic light-sensitive material of the present invention, the total processing time is 10 seconds to 45 seconds. More preferably, it is 15 seconds to 30 seconds. The total processing time referred to in the present invention means that the steps from development to drying are completed within 45 seconds with an automatic processor. That is, the time from the time when the tip of the photosensitive material begins to be dipped in the developing solution to the time when the tip comes out of the drying zone after the processing step (so-called Dry to Dry time) is within 45 seconds.

Drying time is usually 35 to 100 ° C., preferably 40 to 80 ° C., or a drying zone provided with a far infrared ray heating means may be installed in the automatic processor. The automatic developing machine is equipped with a mechanism for applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive material during the steps of development, fixing and washing with water (JP-A-3-264953). May be used. Furthermore, a device capable of preparing a developing solution and a fixing solution may be incorporated.

The light-sensitive material of the present invention can be processed by a conventional processing method using no solid processing agent.

The support which can be used in the light-sensitive material of the present invention is, for example, No. RD magazine mentioned above. 17643, p. 28 and ibid. Examples thereof include those described on page 1009 of 308119.

A suitable support is a polyethylene terephthalate film or the like, and the surface of these supports may be provided with an undercoat layer to improve the adhesion of the coating layer, corona discharge or ultraviolet irradiation.

In the silver halide photographic light-sensitive material of the present invention, various additives can be added to the silver halide emulsion according to the purpose. Examples of the additive include RD. No. 17
643 (December 1978), the same No. 18716 (1
997) and the same No. 308119 (1989
December, 2012). The places where they are written are listed below.

Additives RD-17643 RD-18716 RD-308119 Page classification Page page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25 -26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26-27 XI 650 right 1005-6 XI plasticizer 27 XII 650 right 1006 XII slip agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1003-4 IX support 28 XVII 1009 XVII The developing process of the photosensitive material will be described.

In the development processing method of the medical silver halide photographic light-sensitive material of the present invention, it is preferable that the total processing time of Dry to Dry is 15 seconds to 90 seconds, more preferably 15 seconds to 45 seconds. is there.

Next, the ascorbic acid used in the present invention will be described.

In the processing method of the silver halide photographic light-sensitive material of the present invention, the developing solution or the developing replenishing solution used does not substantially contain a dihydroxybenzene compound and contains ascorbic acid represented by the following general formula (A). Is contained.

[0128]

Embedded image

In the formula, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
It represents a substituted or unsubstituted alkylthio group, and R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k is 1, X represents a -CO- or -CS- group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

In the present invention, R ₁ and R ₂ in the above formula are
Compounds represented by the following general formula (A-a) in which are bonded to each other to form a ring are preferable.

[0131]

Embedded image

In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, Amide group, sulfonamide group, Y ₁ represents O or S, Y ₂ represents O, S or NR
Represents ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

The alkyl group in formula (A) or (A-9) is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent. Often, the substitutable group includes a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like as a preferable substituent.

Specific examples of the compound represented by the general formula (A) or the general formula (Aa) according to the present invention are shown below.
The present invention is not limited to these.

[0135]

Embedded image

[0136]

[Chemical 4]

These compounds are typically ascorbic acid or erythorbic acid or derivatives derived from them, and they are available as commercial products or can be easily synthesized by known synthetic methods.

The amount of ascorbic acid or erythorbic acid or a derivative thereof according to the present invention used is preferably 0.005 to 0.5 mol, more preferably 0.02 to 0.4 mol, per liter of the developing solution. .

Sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone and the like may be included, preferably 0.2 to 1 mol / liter, more preferably 0.3 to 1 mol / liter.
It is preferable to use 0.6 mol / liter. In addition, adding a large amount of ascorbic acid also leads to processing stability.

As the alkaline agent, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate are included. Further, the borate described in JP-A-61-282808,
Buffer agents such as saccharose, acetoxime, 5-sulfosalicylic acid, phosphates and carbonates described in JP-A-60-93439 may be used. The content of these chemicals is p
H is selected to be 9.0 to 13, preferably 10 to 12.5.

As the solubilizing agent, polyethylene glycols and their esters can be contained, and as the sensitizing agent, for example, a quaternary ammonium salt, a development accelerator, a surfactant and the like can be contained.

As a silver sludge inhibitor, JP-A-56-1
No. 06244 silver stain inhibitor, JP-A-3-5184
No. 4 sulfide, disulfide compound, Japanese Patent Application No. 4
A cysteine derivative or a triazine compound described in No. 92947 is preferably used.

As an organic inhibitor, an azole antifoggant, for example, an indazole type, an imidazole type, a benzimidazole type, a triazole type, a benztriazo type, a tetrazole type, a thiadiazole type compound or the like is used.

The inorganic inhibitor may contain sodium bromide, potassium bromide, potassium iodide and the like. In addition to this, for example, L. F. A. Menson, Photographic Processing Chemistry, published by Focal Press, Inc. (1966), pages 226-229, US Pat.
93,015, 2,592,364, JP-A-48.
You may use what is described in No. -64933 etc. As the chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate stabilization constant of 8 or more with iron described in JP-A No. 1-193853 is used as an organic chelating agent. It is preferably used. Sodium hexametaphosphate as an inorganic chelating agent,
Examples include calcium hexametaphosphate and polyphosphate.

As the development hardening agent, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used. However, for rapid processing, it is preferable that the hardener is allowed to act in the coating step of the light-sensitive material in advance rather than acting in the developing step.

The processing temperature of the medical silver halide photographic light-sensitive material of the present invention is preferably 25 to 50 ° C, more preferably 30 to 40 ° C. The development time is 3 to 90 seconds, more preferably 5 to 60 seconds. Processing time is Dr
It is 15 to 90 seconds in y to Dry.

In the processing method of the present invention, the developer is replenished with the components corresponding to the fatigue of the processing agent and the oxidation fatigue. Examples of the replenishment method include replenishment by width and feed rate 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. However, the preferred developer replenishment rate is 500 to 150 cc / m ² .

Preferred fixing solutions can include fixing materials commonly used in the art. pH 3.
8 or more, preferably 4.2 to 5.5.

The fixing agent is a thiosulfate such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of the fixing speed. The concentration of ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / liter, more preferably 0.8 to 3 mol / liter. The fixer may be an acid hardening agent. In this case, aluminum ions are preferably used as the hardener. For example, it is preferably added in the form of aluminum sulfate, aluminum chloride, potassium alum, or the like.
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.), hydrochloric acid, etc. may be used in the fixer if desired. Various acids and metal hydroxides (potassium hydroxide, sodium hydroxide)
PH adjusting agents such as the above and chelating agents having the ability to soften water can be included. Examples of fixing accelerators include Japanese Patent Publication No. 45-
No. 35754, No. 58-122535, No. 58-12.
No. 2536, thiourea derivatives, U.S. Pat.
Thioether described in US Pat. No. 6,459.

When the present invention is applied to medical X-ray radiography, for example, a fluorescent intensifying screen whose main component is a phosphor that emits near-ultraviolet light or visible light upon exposure to penetrating radiation is used. It is desirable that the emulsion is adhered to both sides of a light-sensitive material prepared by coating the emulsion of the present invention on both sides and exposed.

The penetrating radiation referred to here is an electromagnetic wave of high energy and means X-rays and gamma rays. Further, the fluorescent intensifying screen means, for example, an intensifying screen mainly containing calcium tungstate as a fluorescent component or a fluorescent intensifying screen mainly containing a rare earth compound activated by terbium. As the fluorescent intensifying screen, one having a fluorescent component uniformly applied on a support or one having a cylindrical shape applied can be used. When using a light-sensitive material having particularly low sensitivity, 9
2 German Karman and Karls presented at RSNA Session 868C
Fluorescent sensitization that enhances the sensitivity of the intensifying screen by increasing the thickness of the fluorescent component and applying it in a conical shape like the intensifying screen of the ruhe Nuclear research microstructure, while at the same time reducing the quantum mottle to improve graininess. Paper can be used.

[0152]

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

Example 1 Preparation of seed emulsion-1 Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 mg polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt 6.78 mg (10% aqueous ethanol solution) potassium bromide 10.8 g 10% nitric acid 114 mg B1 2.5N silver nitrate aqueous solution 6825 mg C1 Potassium bromide 841 g Water 2825 mg D1 1.75N Potassium bromide aqueous solution Silver potential control amount at 42 ° C Japanese Patent Publication Nos. 58-58288 and 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
And 464.3 ml of each of Solution C1 were added by the simultaneous mixing method over 1.5 minutes to perform nucleation.

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

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

Preparation of seed emulsion-2 After seed salt-1 was desalted and washed with water, it was vigorously stirred in a reaction vessel while maintaining the temperature at 60 ° C, and the whole amount of solution E1 was added. Seed emulsion-2 was prepared by adding the total amount of F1.

E1 Silver nitrate 20.64 g Finish with water to 129.8 ml F1 Potassium bromide 14.46 g Finish with water to 192.8 ml Preparation of Em-1 Using the above seed emulsion-1 and the following three solutions. A tabular pure silver bromide emulsion Em-1 was prepared.

A2 ossein gelatin 34.03 g polypropyleneoxy-polyethyleneoxy 2.25 ml-disuccinate sodium salt (10% aqueous ethanol solution) seed emulsion-1 1.218 mol equivalent Boiled to 3150 ml B2 potassium bromide 1747 g water Then, the solution A2 is vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and the total amount of the solution B2 and the solution C2 is added thereto by the simultaneous mixing method over 100 minutes. During this time, the pH was 5.8 and p
Ag was kept at 8.8 throughout. Here, solution B2 and solution C2
The addition rate of was changed in a function-like manner with time so as to match the critical growth rate. That is, the addition was performed at an appropriate addition rate so that small particles were not generated other than the growing seed particles and polydispersion did not occur due to Ostwald ripening.

After the addition is complete, the emulsion is cooled to 40.degree.
As an aggregating polymer agent, 1800 ml of a 13.8% (weight) modified gelatin aqueous solution modified with a phenylcarbamoyl group (substitution rate 90%) was added and stirred for 3 minutes. Thereafter, a 56% (weight) aqueous acetic acid solution was added to adjust the pH of the emulsion to 4.
After adjusting to 6, the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then 40
C. Distilled water 9.0.degree. C. was added, the mixture was left to stir, and the supernatant liquid was drained. Further, 11.25 l of distilled water was added, and the mixture was left standing with stirring, and then the supernatant liquid was drained.

Then, an aqueous gelatin solution and sodium carbonate 1
A 0% (weight) aqueous solution was added to adjust the pH to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C.

Subsequently, after the emulsion was heated to 60 ° C., predetermined amounts of the following spectral sensitizing dyes A and B were added as a solid fine particle dispersion, and then ammonium thiocyanate, chloroauric acid and sodium thiosulfate were mixed. Aqueous solution and N, N'-
A methanol solution of dimethylselenourea was added and aged for a total of 2 hours. At the end of the aging, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

Spectral sensitizing dye (A) 5,5'-dichloro-9-ethyl-3,3'-di- (3
-Sulfopropyl) oxacarbocyanine sodium salt anhydride Spectral sensitizing dye (B) 5,5'-di- (butoxycarbonyl) -1,1'-di-ethyl-3,3'-di- (4- Sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride Additives other than the spectral sensitizing dye and their addition amounts (AgX
(Per mol) is shown below.

Ammonium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Stabilizer (TAI) 1000 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in Japanese Patent Application No. 4- 994
It was prepared by a method similar to that described in No. 37.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature was adjusted to 27 ° C. in advance, and a high-speed stirrer (dissolver) was used to obtain 3.5.
Obtained by stirring at 00 rpm for 30-120 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μm and the average thickness was 0.2.
5 μm, average aspect ratio of about 4.5, width of particle size distribution 1
It was 8.1% of tabular silver halide grains. The average distance between twin planes is 0.020 μm, and 97% (number) of all tabular silver halide grains have a ratio of twin plane distance to thickness of 5 or more. 49% and particles of 15 or more accounted for 17%.

Preparation of Em-2 A tabular silver halide emulsion Em-2 having an average silver iodide content of 1.0 mol% was prepared using seed emulsion-1 and the following four kinds of solutions.

A3 ossein gelatin 34.03 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Water finish to 3150 ml B3 Potassium bromide 1733 g Finish with water to 3641 ml C3 Silver nitrate 2466 g Finish with water to 4145 ml D3 Fine grain emulsion consisting of 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm) (*) 0.136 mol equivalent (*) 0.06 5.0% by weight containing moles of potassium iodide
To 6.64 liters of the above gelatin aqueous solution, 2 liters each of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After the particles were formed, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution.

Solution A3 was vigorously stirred in the reaction vessel while maintaining it at 60 ° C., and 1 part of solution B3 and 1 part of solution C3 were added thereto.
Parts and the total amount of the solution D3 were added by the simultaneous mixing method over 41 minutes, and then the remaining amount of the solution B3 and the solution C3 was 33%.
It was added by the double-sided mixing method over minutes.

During this period, pH was kept at 5.8 and pAg was kept at 8.8 throughout. Here, the addition rates of the solution B3 and the solution C3 were changed in a function-like manner with respect to time so as to match the critical growth rate. That is, the addition was performed at an appropriate addition rate so that small particles were not generated other than the growing seed particles and polydispersion did not occur due to Ostwald ripening. Regarding the addition rate of the solution D3, the rate ratio (molar ratio) with the solution C3 was maintained at 0.06.

Further, the above solution D3 was added to the total silver amount of 0.
Halogen substitution was carried out by adding 15 mol equivalent.

After completion of the addition, soluble salts were removed in the same manner as Em-1. Subsequently, spectral sensitization and chemical sensitization were performed in the same manner as Em-1.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.09 μm and the average thickness was 0.2.
4 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 8.9% of tabular silver halide grains. The average twin plane distance was 0.020 μm.

Preparation of Em-3 B2 and C2 were added to the solution A2 in exactly the same manner as Em-1, and after the addition was completed, the solution D3 was added in an amount of 0.15 mol based on the total amount of silver in the same manner as Em-2. Halogen substitution was carried out by adding a corresponding amount, and soluble salts were removed, spectral sensitization and chemical sensitization were performed in the same manner as Em-1.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μm and the average thickness was 0.2.
5 μm, average aspect ratio of about 4.5, width of particle size distribution 1
It was 8.1% of tabular silver halide grains. The average twin plane distance was 0.020 μm.

Preparation of Em-4 Using A3, B3, C3 used in Em-2 and D4 shown below, a tabular silver halide emulsion Em-4 having an average silver iodide content of 0.7 mol% was prepared. did.

D4 grain emulsion (*) 0. Equivalent to 088 mol (*) 5.0 wt% containing 0.06 mol of potassium iodide
To 6.64 liters of the above gelatin aqueous solution, 2 liters each of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After the particles were formed, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution. Solution A3 60 in the reaction vessel
The mixture was vigorously stirred while maintaining the temperature at 0 ° C., 1 part of the solution B3, 1 part of the solution C3 and the total amount of the solution D4 were added thereto by the simultaneous mixing method over 17 minutes, and then the solution B4 and the solution C4 were continuously added.
Was added by the simultaneous mixing method over 52 minutes. During this period, the pH was kept at 5.8 and the pAg was kept at 8.8 throughout. Here, the addition rates of the solution B3 and the solution C3 were changed in a function-like manner with respect to time so as to match the critical growth rate. That is, the addition was performed at an appropriate addition rate so that small particles were not generated other than the growing seed particles and polydispersion did not occur due to Ostwald ripening. Regarding the addition rate of the solution D4, the rate ratio (molar ratio) with the solution C3 was kept at 0.06.

Thereafter, Em- is performed in the same manner as Em-2.
Got 4.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.10 μm and the average thickness was 0.2.
4 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 8.5% of tabular silver halide grains. The average twin plane distance was 0.020 μm.

Preparation of Em-5 Using seed emulsion-2 and the following four kinds of solutions, silver nuclei were formed inside the grains and the average silver iodide content was 0.7 mol% in the same manner as in Em-4. A tabular silver halide emulsion Em-5 was prepared.

A4 ossein gelatin 34.03 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25 ml seed emulsion-2 1.218 mol equivalent Equal to 3150 ml with water B4 potassium bromide 1733 g water 3641 ml C4 Silver nitrate 2466 g Finished to 4145 ml with water D4 Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm) Equivalent to 0.135 mole Fine grain emulsion (*): 0. To 6.64 liters of a 5.0% by weight gelatin aqueous solution containing 06 mol of potassium iodide,
Two liters each of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After the particles were formed, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution.

Solution A4 was vigorously stirred in the reaction vessel while maintaining it at 60 ° C., and 1 part of solution B4 and 1 part of solution C4 were added thereto.
Parts and the total amount of the solution D4 were added by the simultaneous mixing method over 41 minutes, and then the remaining amount of the solution B4 and the solution C4 was 33%.
It was added by the double-sided mixing method over minutes. During this time, the pH is 5.8.
In addition, pAg was kept at 8.8 throughout. Here, the addition rates of the solution B4 and the solution C4 were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate. That is, the addition was performed at an appropriate addition rate so that small particles were not generated other than the growing seed particles and polydispersion did not occur due to Ostwald ripening. Regarding the addition rate of the solution D4, the rate ratio (molar ratio) with the solution C4 was maintained at 0.06.

Further, the above solution D4 was added to the total silver amount of 0.
Halogen substitution was carried out by adding 15 mol% equivalent.

After completion of the addition, soluble salts were removed in the same manner as Em-1. Subsequently, spectral sensitization and chemical sensitization were performed in exactly the same manner as Em-1.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.10 μm and the average thickness was 0.2.
4 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 8.5% of tabular silver halide grains. The average distance between twin planes was 0.020 μm.

Preparation of Em-6 Except that Solution G1 shown below was rushed into the reaction vessel immediately after Solutions B3 and C3 were added to Solution A3.
-4, a tabular silver halide emulsion Em− having a silver nucleus formed inside the grain and having an average silver iodide content of 0.7 mol%
6 was prepared.

G1 thiourea dioxide 0.035 g Finished with water to 32.5 ml The obtained silver halide emulsion was observed with an electron microscope. The average grain size was 1.10 μm, the average thickness was 0.24 μm, and the average aspect ratio was about 4 It was tabular silver halide grains having a grain size distribution of 18.5%. The average twin plane distance was 0.020 μm.

Preparation of Em-7 Em-4 except that the pH is set to 9.0 while adding half of the added silver amount from the start of addition of the solutions B3 and C3 to the solution A3.
Em-7 was prepared in the same manner as.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.10 μm and the average thickness was 0.2.
4 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 8.5% of tabular silver halide grains. The average distance between twin planes was 0.020 μm.

Preparation of Em-8 E was prepared in the same manner as Em-7 except that the seed emulsion-2 was used.
m-8 was prepared.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.09 μm and the average thickness was 0.2.
4 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 9.0% of tabular silver halide grains. The average twin plane distance was 0.020 μm.

Preparation of Em-9 E-9 was prepared in the same manner as Em-3 except that the seed emulsion-2 was used.
m-9 was prepared.

The obtained silver halide emulsion was observed with an electron microscope to find that the average grain size was 1.10 μm and the average thickness was 0.24.
μm, average aspect ratio about 4.5, particle size distribution width 1
It was 8.5% of tabular silver halide grains. The average twin plane distance was 0.020 μm.

Preparation of Em-10 Tabular silver halide emulsion Em-10 having an average silver iodide content of 0.7 mol% was prepared using seed emulsion-1 and the following three solutions.
Was prepared.

A4 Ocein gelatin 34.03 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25 ml Potassium iodide 14.50 g Seed emulsion-1 1.218 mol equivalent Water finish to 3150 ml B4 Potassium bromide 1747 g Finish with water to 3669 ml C4 Silver nitrate 2493 g Finish with water to 4193 ml Solution A4 was vigorously stirred while maintaining the temperature at 60 ° C., and 1 part of solution B4 and the total amount of solution C4 were added over 100 minutes. Added by simultaneous mixing method. During this time, the pH is 5.8.
In addition, pAg was kept at 8.8 throughout. Here, the addition rates of the solution B4 and the solution C4 were changed in a function-like manner with respect to time so as to match the critical growth rate. That is, it was added at an appropriate addition rate so that small particles were not generated other than the growing seed particles, and polydispersion was not caused by Ostwald ripening.

After that, Em- is performed in the same manner as Em-2.
Got 10.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.10 μm and the average thickness was 0.2.
4 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 8.5% of tabular silver halide grains. The average twin plane distance was 0.020 μm.

Preparation of Em-11 Em-11 was prepared in exactly the same manner as Em-10 except that Seed Emulsion-2 was used.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.10 μm and the average thickness was 0.2.
4 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 9.0% of tabular silver halide grains. The average distance between twin planes was 0.021 μm.

Preparation of Em-12: Em-12 except that G1 was added in the same manner as Em-6.
Em-12 was prepared in exactly the same manner as 10.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.10 μm and the average thickness was 0.2.
4 μm, average aspect ratio about 4.4, width of particle size distribution 1
It was 8.5% of tabular silver halide grains. The average twin plane distance was 0.020 μm.

Preparation of Em-13 Like Em-7, the pH was adjusted from the start of addition to half the amount of added silver.
Em- in the same manner as Em-10 except that is maintained at 9.0.
13 was prepared.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.10 μm and the average thickness was 0.2.
4 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 8.5% of tabular silver halide grains. The average twin plane distance was 0.019 μm.

Preparation of Em-14 Em-14 was prepared in exactly the same manner as Em-13 except that Seed Emulsion-2 was used.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.09 μm and the average thickness was 0.2.
4mμ, average aspect ratio about 4.5, width of particle size distribution 1
It was 9.0% of tabular silver halide grains. The average twin plane distance was 0.019 μm.

Preparation of Em-15 A3, B3, C3 used in Em-2 and D5 shown below.
Was used to prepare a tabular silver halide emulsion Em-15 having an average silver iodide content of 0.4 mol%.

D5: Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) equivalent to 0.040 fine grain emulsion (*): 0.06 mol of potassium iodide 6.64 liters of a 5.0% by weight gelatin aqueous solution containing
Two liters of an aqueous solution each containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

Solution A3 was vigorously stirred in the reaction vessel while maintaining it at 60 ° C., and 1 part of solution B3 and 1 part of solution C3 were added thereto.
Parts and the total amount of the solution D4 were added by the simultaneous mixing method over 17 minutes, and then the remaining amount of the solution B4 and the solution C4 was 5%.
It was added by the double-sided mixing method over 2 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.8 throughout. Where solution B
The addition rates of 3 and solution C3 were changed in a function-like manner with respect to time so as to match the critical growth rate. That is, the addition was performed at an appropriate addition rate so that small particles were not generated other than the growing seed particles and polydispersion did not occur due to Ostwald ripening. Regarding the addition rate of the solution D4, the rate ratio (molar ratio) with the solution C3 was kept at 0.06.

[0209] After that, Em- is performed in the same manner as Em-2.
I got 15.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μm and the average thickness was 0.2.
5 μm, average aspect ratio of about 4.5, width of particle size distribution 1
It was 8.1% of tabular silver halide grains. The average twin plane distance was 0.020 μm.

Preparation of Em-16 Em-16 was prepared in exactly the same manner as Em-15 except that Seed Emulsion-2 was used. When the obtained silver halide emulsion was observed with an electron microscope, a tabular halogen having an average grain size of 1.10 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5, and a wide grain size distribution of 18.5%. It was a silver halide grain. The average twin plane distance was 0.020 μm.

The above-obtained emulsions Em-1 to Em-16
The average silver iodide content, the maximum value of the silver iodide content inside the grains, and the silver iodide content on the outermost surface were measured.

The silver iodide content on the outermost surface was determined as follows.

A 0.05% by weight aqueous solution of proteolytic enzyme (pronase) was added to the emulsion, and the mixture was stirred at 45 ° C. for 30 minutes to decompose gelatin. This is centrifuged to precipitate the emulsion particles, and the supernatant is removed. Distilled water is then added to disperse the emulsion particles in distilled water and centrifuged to remove the supernatant. Further, the emulsion particles are redispersed in water and thinly coated on a mirror-polished silicon wafer to obtain a measurement sample.
Using the sample thus prepared, surface silver iodide measurement by XPS was performed. In order to prevent the destruction of the sample due to X-ray irradiation, the sample is stored in the XPS measurement chamber at -10 to 10
Cooled to -120 ° C.

As probe X-rays, MgKα was irradiated with an X-ray source voltage of 15 kv and an X-ray source current of 40 mA to obtain Ag3d5.
/ 2, Br3d, I3d3 / 2 electrons were measured.
The integrated intensity of the measured peak is determined by the sensitivity factor (Sensit
(ivity Factor), and the halide composition of the outermost surface was determined from the intensity ratio of these.

The resulting emulsions are listed in Table 1 below.

[0219]

[Table 1]

The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution described below was also prepared. Using both coating solutions, the coating amount was 2.
0 g / m ^2, gelatin with the amount of 3.1 g / m ² and so as to 80m per minute using two slide hopper type coaters
Simultaneously coat both sides on the support at the speed of 20 minutes for 2 minutes
Sample No. 1 to No. Got 10. As a support, glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, butyl methacrylate 40 wt%
The copolymer aqueous dispersion obtained by diluting the copolymer consisting of the three monomers described above to a concentration of 10 wt% was blue-colored to a concentration of 0.15 for a 175 μm X-ray film using an undercoat liquid A polyethylene terephthalate film base was used.

The additives used in the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenyl Phosphonium chloride 50 mg 1,3-dihydroxybenzene-4-sulfonic acid ammonium 2 g

[0221]

Embedded image

C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1-phenyl-5-mercaptotetrazole 15 mg Protective Layer Solution Next, the following coating solution for the protective layer was prepared. The additives are shown in the amount per liter of coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particles) Matting agent having a diameter of 1.2 μm) 0.5 g (CH ₂ = CHSO ₂ CH ₂ ) ₂₀ (hardening agent) 500 mg C ₄ F ₉ SO ₃ K 2 mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2 0.0 g

[0224]

[Chemical 6]

Obtained sample No. Photographic properties were evaluated using 1 to 16. First of all, the sample was made into two intensifying screens (KO-2
50), and a tube voltage of 80 kv via an aluminum wedge.
p, tube current 100 mA, X-ray irradiation for 0.05 seconds,
Exposure. Then, using an automatic developing machine (SRX-502), processing was performed with a developing solution and a fixing solution having the following formulations.

Developer Formulation Part-A (for 12 l finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine 5 acetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5 -Mercaptotetrazole 0.2 g Hydroquinone 340 g Add water to finish to 5000 ml Part-B (for 12 l finishing) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter glacial acetic acid 120 g Odor Potassium iodide 225 g Add water to finish to 1.0 l Fixer formulation Part-A (for 18 l finish) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate / trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B Aluminum sulfate 800 g Preparation of developer to approximately 5 liters of water PartA , Part
B was added at the same time, water was added while stirring and dissolving to make 12 liters, and the pH was adjusted to 10.40 with glacial acetic acid. This is used as a development replenisher.

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

The fixing solution was prepared by adding Part to about 5 liters of water.
A and Part B are added at the same time, water is added while stirring and dissolving to make 18 liters, and pH is adjusted with sulfuric acid and NaOH.
Was adjusted to 4.4. This is the fixing replenisher.

The processing temperature is 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing, 50 ° C. for drying, and the processing time is dry.
It is 45 seconds and 25 seconds in to dry.

After the treatment, the sensitivity was measured. Sensitivity is expressed as the reciprocal of the exposure amount that gives a density of fog +0.5
o. The relative sensitivity is shown when the sensitivity in the treatment of No. 1 for 45 seconds is 100. The results obtained are shown in Table 2 below. It can be seen that the sample of the present invention has high sensitivity and does not impair the sensitivity even in rapid processing such as 25 seconds.

Furthermore, the unexposed sample No. A load of 5 g was applied to Nos. 1 to 16 with a scratch hardness meter of a needle having a needle head of 0.3, and then the same development processing as above was performed, and the density of occurrence of pressure fog was measured with a microdensitometer. The degree of fogging is the sample No. It was shown as a relative value when the fog increase of 1 was 100. In addition, the pressure characteristics during development (the degree of pressure marks generated by the rollers of the automatic processor, that is, the degree of roller marks)
Was evaluated as follows.

The sample was processed in an X-ray automatic developing machine having a special facing roller which was unexposed and strongly uneven, with a processing time of 25 seconds. The treatment liquid used was the same as the above treatment liquid.
The roller marks generated at that time were observed, and the evaluation results were classified into the following 5 grades according to their degree.

5: No occurrence of roller mark 4: Very slight occurrence 3: Slight occurrence (within practical tolerance) 2: Large occurrence (outside practical tolerance) 1: Very large occurrence Is shown in Table 2.

[0234]

[Table 2]

As is apparent from the table, the sample of the present invention has no or very little roller mark, and there is no deterioration in sensitivity due to rapid processing, and there is no problem in practical use.

Example 2 Preparation of seed emulsion-3 Seed emulsion-3 was prepared as follows.

A5 Ossein gelatin 24.2 g Water 9657 ml HO- (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5 to 7) ( 10% ethanol aqueous solution) 1.20 ml potassium bromide 10.8 g 10% nitric acid 160 ml B5 2.5N silver nitrate aqueous solution 2825 ml C5 potassium bromide 841 g water 2825 ml D5 ossein gelatin 121 g water 2040 ml HO- (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5 to 7) (10% ethanol aqueous solution) 5.70 ml E5 1.75N potassium bromide aqueous solution The following silver potential control amount 35 Japanese Patent Publication Nos. 58-58288 and 58-5828 at ℃
Solution A5 was added to Solution B5 using the mixing stirrer shown in No. 9.
And 475.0 ml of each of Solution C5 were added by the simultaneous mixing method over 2.0 minutes to perform nucleation.

After stopping the addition of the solutions B5 and C5, it took 60 minutes to raise the temperature of the solution A5 to 60 ° C., add the whole amount of D5, and adjust the pH to 5% with 3% KOH.
5, the solution B5 and the solution C5 were again added by the simultaneous mixing method at a flow rate of 55.4 ml / min for 42 minutes. This temperature rise from 35 ° C. to 60 ° C. and solution B5,
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during re-simultaneous mixing with C5 was measured as a solution D.
5 was used to control to +8 mv and +30 mv, respectively.

After the addition was completed, the pH was adjusted to 6 with 3% KOH.
It was desalted and washed with water immediately after setting to 0. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have an average thickness of 0.090 μm and an average grain size. It was confirmed with an electron microscope that the diameter (converted to a circle diameter) was 0.510 μm.

Preparation of Em-17 Tabular silver iodobromide emulsion Em-17 was prepared using seed emulsion-3 and the following four kinds of solutions.

A6 ossein gelatin 19.04 g HO- (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5 to 7) (10% Aqueous ethanol solution) 2.00 ml Potassium iodide 7.00 g Seed emulsion-3 1.55 mol equivalent Water finish to 2800 ml B6 Potassium bromide 1493 g Water finish to 3585 ml C6 Silver nitrate 2131 g Water finish to 3585 ml D6 3% by weight gelatin Fine grain emulsion (*) consisting of and silver iodide grains (average grain size: 0.05 μm) equivalent to 0.028 mol (*) 5.0 wt% containing 0.06 mol of potassium iodide
To 6.64 liters of the above gelatin aqueous solution, 2 liters each of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After particle formation, the pH is adjusted with an aqueous sodium carbonate solution.
Was adjusted to 6.0.

Solution A6 was vigorously stirred in the reaction vessel while maintaining the temperature at 55 ° C., and half the amounts of solution B6 and solution C6 were added thereto by the simultaneous mixing method over 35 minutes. During this time, pH
Kept at 5.8. After adjusting the pH to 8.8 with a 1% KOH solution, the solution B6 and a part of the solution C6 and the solution B6
And the remaining amount of solution C6 was added by the simultaneous mixing method over 25 minutes.

During this period, pAg was maintained at 8.9. Here, the addition rates of the solution B6 and the solution C6 were changed in a function-like manner with respect to time so as to match the critical growth rate. That is, the addition was performed at an appropriate addition rate so that small particles were not generated other than the growing seed particles and polydispersion did not occur due to Ostwald ripening.

After completion of the addition, desalting, washing with water and redispersion were carried out in the same manner as Em-1. After redispersion, the pH was adjusted to 5.8 at 40 ° C.
0 and pAg were adjusted to 8.2.

Subsequently, after the emulsion was heated to 47 ° C.,
After adding predetermined amounts of the spectral sensitizing dyes A and B as a solid fine particle dispersion, a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate and triphenylphosphine selenide are added as a solid fine particle dispersion.
Aging was performed for a total of 2 hours and 30 minutes. 4-hydroxy-6-methyl-1,3,3a, 7 as a stabilizer at the end of aging
-The appropriate amount of tetrazaindene (TAI) was added.

Spectral sensitizing dyes and other additives and the addition amount (per 1 mol of AgX) are shown below.

Spectral sensitizing dye (A) 5,5′-dichloro-9-ethyl-3,3′-di- (3-sulfopropyl) -oxacarbocyanine sodium salt anhydride 390 mg Spectral sensitizing dye (B ) 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (3-sulfopropyl) -benzimidazolocarbocyanine sodium salt anhydrous 4 mg adenine 10 mg thiosulfate Sodium 3.3 mg Ammonium thiocyanate 50 mg Chloroauric acid 2.0 mg Silver iodide fine particles 5 mmol Triphenylphosphine selenide 4.0 mg Stabilizer (TAI) 1000 mg The silver iodide fine particles used herein were those used during emulsion preparation. The same fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average grain size of 0.05 μm) as described above.

A solid fine particle dispersion of a spectral sensitizing dye was prepared by a method similar to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been adjusted to 27 ° C in advance, and the mixture is mixed with a high-speed agitator (dissolver) for 3,50
Obtained by stirring at 0 rpm for 30-120 minutes.

The dispersion liquid of the above selenium sensitizer was prepared as follows. That is, triphenylphosphine selenide 12
0 g was added to 30 kg of ethyl acetate at 50 ° C. and stirred,
It was completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzene sulfonate was added thereto. Next, these two liquids were mixed and dispersed at 50 ° C. for 30 minutes at a peripheral speed of the dispersing blade of 40 m / sec using a high-speed stirring type disperser having a dissolver having a diameter of 10 cm. afterwards,
Immediately under reduced pressure, the residual concentration of ethyl acetate is 0.3 wt.
Ethyl acetate was removed while stirring until the amount became less than or equal to%. Then, this dispersion was diluted with pure water to obtain 80 kg. A part of the thus obtained dispersion was collected and used in the above experiment.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.91 μm and the average thickness was 0.2.
3 μm, average aspect ratio about 4.0, width of particle size distribution 2
It was 0.5% of tabular silver halide grains.

Preparation of Em-18 A tabular silver bromide emulsion was prepared by the preparation method described in Japanese Patent Application No. 6-9762 and sensitized in the same manner as Em-17. When the obtained silver halide emulsion was observed with an electron microscope, a tabular halogen having an average grain size of 0.65 μm, an average thickness of 0.21 μm, an average aspect ratio of about 3.6 and a grain size distribution of 22.2% was obtained. It was a silver halide grain.

Preparation of Em-19 Em-19 was prepared by mixing Em-17 at a ratio of 70% and Em-18 at a ratio of 30%.

Em-1 prepared in Example 1 and Example 2
The breakdown of the emulsion prepared in 1. is shown below.

[0254]

[Table 3]

Then, the emulsions thus sensitized were added with the additives described below to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution was also prepared.

Next, the above-mentioned emulsion was applied from the bottom to both sides of a support in which the following dye layers were pre-coated on both sides of a polyethylene terephthalate film base for X-rays (thickness: 175 μm) colored blue with a concentration of 0.15. The layer coating solution and the protective layer coating solution were simultaneously layered so as to give the following predetermined coating amounts, and dried.

First layer (dye layer) Solid fine particle dispersion dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² Latex (L) 0.2 g / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² Hardener A 2 mg / m ² Second layer (emulsion layer) The following various additives were added to each emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-5 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer Combined 80 mg / m ² sodium polystyrene sulfonate 80 mg / m ² trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 2-mercaptobenzimidazole-5-sulfonate 5 mg / m ² compound (H) 0.5 mg / m ² n-C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / M ² colloidal silica 0.5 g / m ² latex (L) 0.2 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² compound (P) 0.2 g / m ² compound (Q) 0.2 g / m ² 5-methylbenzotriazole 0.7 g / m ² However, as gelatin It was adjusted to be 1.0 g / m ² .

Third layer (protective layer) Gelatin 0.8 g / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.02 g / m ² Matting agent consisting of polymethylmethacrylate 50 mg / M ² (area average particle size 7.0 μm) Formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² Bis-vinylsulfonylmethyl ether 36 mg / m ² Latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (S1) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound Objects (S-2) 5mg / m 2 C 9 F 19 -O- (CH 2 CH 2 O) 11 -H 3mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2 ^{_{O) 15 -H 2mg / m 2}} C 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2 K-2 71mg / m ^Two

[0260]

[Chemical 7]

[0261]

Embedded image

[0262]

[Chemical 9]

The amount of additive added was for one side, and the coated silver amount was adjusted to be 1.6 g / m ² for one side.

The sample No. 1, N
o. 17, No. 19 was evaluated in the same manner as in Example 1. The results obtained are shown in Table 4.

[0265]

[Table 4]

As can be seen from the graph, the sample of the present invention shows less sensitivity fluctuation due to rapid processing, less pressure blackening, and improved pressure resistance. Further, it can be seen that there is no roller mark, or even if there is, it is very slight and there is no problem in practical use.

Example 3 Sample No. used in Example 2 1, No. 17, No.
19 was developed with the following developing solution, and the sensitivity was the same as in Example 1,
The pressure resistance was evaluated.

A developing tablet was prepared according to the following procedure (A, B).

Operation (A) 13,000 g of sodium elsorbate as a developing agent is ground in a commercially available bandam mill until the average particle size becomes 10 μm. Sodium sulfite (1528 g), phenidone (1105 g) and DTPA (975 g) were added to this fine powder, and the mixture was stirred in a mill for 30
After mixing for 30 minutes and granulating by adding 30 ml of water in a commercial stirred granulator at room temperature for about 10 minutes, the granulated product is dried in a fluid bed dryer at 40 ° C. for 2 hours. The water content of the granulated product is almost completely removed. In this way, 1300 of polyethylene glycol 6000 was added to the prepared granules.
g, 1300 g of mannitol were uniformly mixed for 10 minutes using a mixer in a room whose humidity was controlled at 25 ° C. and 40% RH or less, and the obtained mixture was remodeled as Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho KK The tableting machine described above was used for compression tableting with the filling amount per tablet being 7.683 g.
500 developing tablet A agents were prepared.

Operation (B) 16250 g of potassium carbonate, 65 g of 5-methylbenzotriazole, 32.5 g of 1-phenyl-5-mercaptotetrazole, N-acetyl-D, L-penicillamine 6
5 g, 1625 g of Mannit and 1625 g of polyethylene glycol 6000 are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 30.0 ml, and after granulation, 50 ℃
And dried for 30 minutes to almost completely remove the water content of the granulated product. The mixture thus obtained was compressed into tablets by the above-mentioned tableting machine with the filling amount per tablet being 7.865 g to prepare 2500 developing tablet B agents.

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

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), add 500 m of water.
Granulate with l. After the granulation, the granulated product is dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product. The mixture thus obtained was compressed into tablets by the above-mentioned tableting machine at a filling amount of 8.032 g per tablet.
00 fixing tablets C formulation were prepared.

Operation (D) 5804 g of succinic acid and 11607 g of β-alanine are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 100m
After the granulation, the granulated product is dried at 50 ° C. for 30 minutes to almost completely remove the water content of the granulated product. To the thus-prepared product, 2321 g of polyethylene glycol 6000 was added and mixed for 3 minutes, and then the resulting mixture was compressed into tablets using the tableting machine at a filling amount of 7.429 g per tablet. 2500 fixing tablets D agents were prepared.

Developer solution Starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1 L.

At the start of processing of the developing solution (starting of running), 16.5 liters of the developing solution prepared by diluting the developing tablet with diluting water was added to the developing tank with 330 ml of the starter to fill the developing tank and start the processing did. still,
The pH of the developer containing the starter was 10.45.

The light-sensitive material prepared above was exposed to light so that the optical density after development was 1.0, and was run. For running, an automatic processor SRX-502 (manufactured by Konica Corp.) equipped with a solid processing agent charging member and modified so that the processing speed could be adjusted was used.

During running, the photosensitive material 1.
One each of the above-mentioned agents A and B and 120 ml of water per 00 m ²
Was added. The pH of each of the agents A and B when dissolved in 120 ml of water was 10.70. To the fixing solution were added 4 parts each of the above-mentioned C and D agents and 165 ml of water per 1.00 m ² of the light-sensitive material. The rate of water addition to one treatment agent was started almost at the same time as the addition of the treatment agent, and was added at a constant rate for 10 minutes in proportion to the dissolution rate of the treatment agent.

[0278] (Developer) The composition of the developer per liter of water is shown below. The pH of this developing solution was 10.70.

Potassium carbonate 50.0 g Sodium sorbate 40.0 g Phenidone 3.4 g Diethylenetriamine pentaacetic acid-5Na (DTPA) 3.0 g 5-Methylbenzotriazole 0.2 g 1-Phenyl-5-mercaptotetrazole 0.1 g Sodium sulfite 4.7 g Polyethylene glycol 9.0 g N-acetyl-D, L-penicillamine 0.2 g Mannit 9.0 g Fixing solution The composition of the fixing solution per liter of water is shown below. The pH of this fixer was 4.80.

Sodium thiosulfate 45.0 g Ammonium thiosulfate 105.0 g Sodium sulfite 10.0 g Succinic acid 50.0 g β-Alanine 100.0 g Pine flow 13.0 g Polyethylene glycol 20.0 g The evaluation results are shown below.

[0281]

[Table 5]

As is clear from Table 5, the samples of the present invention did not contain dihydroxybenzenes, and the sensitivity was not impaired even when they were processed with a developing solution containing a solid processing agent.
It can be seen that the pressure resistance is also improved. Furthermore, there is no roller mark, or even if there is, it is very slight, and it can be seen that there is no problem in practical use.

[0283]

According to the present invention, while achieving high sensitivity,
Moreover, a silver halide photographic light-sensitive material excellent in pressure resistance could be obtained. Further, according to the present invention, it is possible to provide a medical silver halide photographic light-sensitive material which does not generate roller marks even when it is rapidly processed with a developer containing no hardener.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shigeaki Takahashi 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company In-house

Claims (5)

[Claims] 1. The tabular silver halide grains account for 50% or more of the total projected area of the silver halide grains contained in the emulsion, and the tabular silver halide grains have an average silver iodide content of 0.8 mol. % To 0 mol%, and the silver iodide content in any portion inside the tabular silver halide grains is 4 mol% to 1
A silver halide photographic emulsion having a maximum value of 00 mol% and having silver nuclei formed inside the tabular silver halide grains. 2. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing the silver halide grains according to claim 1. 3. A method of processing a silver halide photographic light-sensitive material for medical use, which comprises processing the silver halide photographic light-sensitive material according to claim 2 for a total processing time of 15 seconds to 90 seconds. 4. The method of processing a silver halide photographic light-sensitive material according to claim 2, 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. 5. The method of processing a silver halide photographic light-sensitive material according to claim 1, which comprises processing with a developing solution containing ascorbic acid or a derivative thereof.