JPH0996887A - Silver halide photographic emulsion, its production, silver halide photosensitive material and processing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure higher sensitivity and to improve image quality such as fog. SOLUTION: In this silver halide photographic emulsion having 20-100mol% Cl content, flat platy silver halide particles each having an aspect ratio (diameter/thickness) of 2-30 which amounts to >=50% of the total projection area of all silver halide particles. This emulsion has been sensitized with gold- chalcogen and the rate of distribution of gold to the silver halide particle side is 10 to <40%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silver halide photographic emulsion, a method for producing the same, a silver halide photographic light-sensitive material and a method for processing the same.

[0002]

2. Description of the Related Art Recently, photographic light-sensitive materials are required to have various performances, but the performances required for photographic light-sensitive materials, print light-sensitive materials, etc. are improved sensitivity, improved storability, and pressure resistance. Improving is always a demanding task. On the other hand, in recent years, there has been a strong demand for simplifying and speeding up development processing, and for low replenishment of processing solutions. For such requirements, it is advantageous to use silver halide grains having high solubility and high silver chloride content. On the other hand, in order to reduce waste liquid, it is desirable to increase the image density with a small amount of silver, and from the viewpoint of sensitivity, graininess, sharpness, color sensitization efficiency, etc., tabular grains are suitable for those skilled in the art. well known. Regarding tabular grains having a high silver chloride content, {1
Examples of tabular grains having the 11} plane in the main plane include, for example, JP-B-64-8326 and JP-B-64-8325,
64-8324, JP-A-1-250943, JP-B-3-14328, JP-B-4-81782, JP-B-5-40298, JP-A-5-39459, and JP-A-5-126.
96 and Japanese Patent Laid-Open Nos. 63-213836 and 63-218.
No. 938, No. 63-281149, No. 62-2189.
No. 59 is mentioned. Further, regarding the tabular grains having the {100} plane as the principal plane, JP-A-5-204073 can be used.
JP-A-51-88017, JP-A-63-2423
No. 8 etc. are mentioned. In particular, JP-A-6-059360 describes a silver chloride-containing {100} plate.

However, in general, the sensitization of a photographic material, the improvement of the storability of the photographic material, the low replenishment of the processing liquid and the speeding up of the processing speed are often in conflict with each other. That is, excessive chemical sensitization to achieve high sensitivity results in increased fog and significantly deteriorated storability of the photosensitive material. Particularly in the region of a large grain size, in order to achieve the increase in sensitivity commensurate with the increase in surface area, it is necessary to carry out chemical sensitization until the increase in fog occurs. Good sensitivity / fogging ratio, development progress and storage stability cannot be obtained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide emulsion containing silver chloride and having improved image quality such as higher sensitivity and lower fog, a method for producing the same, and a silver halide using the same. It is to provide a photographic light-sensitive material and a processing method thereof. A further object of the present invention is a silver halide photographic emulsion which has a low development and fixing load and is effective for reducing pollution of the processing solution, low replenishment and low waste liquid, a method for producing the same, and a silver halide photographic light-sensitive emulsion using the same. It is to provide a material and a processing method thereof.

[0005]

As a result of earnest studies, the inventors have paid attention to the distribution ratio of gold to the silver halide grain side in a high silver chloride emulsion, and found that the distribution ratio of gold to the silver halide grain side was Low sensitivity means good sensitivity / fog ratio, development progress,
It has been found to have storability. In particular, the chemical sensitization of gold, selenium, and sulfur was performed to increase the distribution ratio of gold to the silver halide grain side, and then partly desorbed by a compound that forms a stable complex with gold, and then the gold halogen was removed. It was discovered that good photographic performance and storability can be obtained by reducing the distribution rate to the silver halide grain side. That is, the object of the present invention was achieved by the following.

(1) Cl content of 20 mol% or more and 100
A silver halide photographic emulsion having a mol% of not more than 50% of the total projected area of silver halide grains in the emulsion,
In a silver halide photographic emulsion which is a tabular grain having an aspect ratio (diameter / thickness) of 2 or more and 30 or less, the silver halide emulsion is gold chalcogen sensitized, and gold is distributed on the silver halide grain side. A silver halide photographic emulsion characterized by a ratio of 10% to less than 40%.

(2) The silver halide photographic emulsion as described in (1), wherein the tabular grains are tabular grains having a {100} plane as a main plane.

(3) The silver halide photographic emulsion according to (1) or (2), wherein the gold chalcogen sensitization is gold selenium sensitization.

(4) Cl content of 20 mol% or more and 100
A silver halide photographic emulsion having a mol% of not more than 50% of the total projected area of silver halide grains in the emulsion,
In the method for producing a silver halide photographic emulsion, which is a tabular grain having an aspect ratio (diameter / thickness) of 2 or more and 30 or less,
When the silver halide grains have a distribution ratio of gold on the silver halide grain side of 50% or more in the chemical sensitization step and then a compound which forms a complex with gold is added, the distribution of gold on the silver halide grain side is achieved. A method for producing a silver halide photographic emulsion, characterized in that the ratio is 10% or more and less than 40%.

(5) Production of a silver halide photographic emulsion as described in (4), wherein the compound that forms a complex with gold is a compound having a stability constant of a complex salt with gold of 28 or more and 39 or less. Method.

(6) The method for producing a silver halide photographic emulsion according to (4), wherein the compound that forms a complex with gold is a sulfite.

(7) On the support, a layer of the silver halide photographic emulsion described in (1) to (3) or the silver halide photographic emulsion manufactured by the manufacturing method described in (4) to (6) is provided. A silver halide photographic light-sensitive material having at least one layer.

(8) Layers of the silver halide photographic emulsion described in (1) to (3) or the silver halide photographic emulsion manufactured by the manufacturing method described in (4) to (6) on both sides of the support. A silver halide photographic light-sensitive material comprising at least one layer of

(9) The silver halide photographic light-sensitive material according to (8), which is used in combination with a fluorescent intensifying screen that emits light having a peak at 400 nm or less when exposed to X-rays.

(10) (a) a developing agent, (b) the following chemical formula 6
A halogenated compound according to (7) or (8), which is a developer containing a compound represented by the formula (c) and (c) at least one selected from the compounds represented by the following formulas 7, 8, 9 and 10. A method of processing a silver halide photographic light-sensitive material, which comprises developing the silver halide photographic material.

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

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[0019]

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[0020]

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In Chemical Formula 6, R ₁ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aminoalkyl group, a dialkylaminoalkyl group or a carboxyalkyl group each having an alkyl moiety having 1 to 6 carbon atoms. In chemical formula 7, R ₂
And R ₃ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. However, R ₂ and R ₃ do not become hydrogen atoms at the same time. R ₄ and R ₅ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₆ represents a hydroxyl group, an amino group or an alkyl group having 1 to 3 carbon atoms. R ₇ and R
Each ₈ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 18 or less carbon atoms, or a —COOM ₁₀ group. here,
M ₁₀ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group or an alkyl group having 15 or less carbon atoms. However, R ₇ and R ₈ are not hydrogen atoms at the same time. M ₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. k is 0, 1 or 2. Chemical formula 8
In the above, X represents a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group. M ₂ and M ₃ may be the same or different and each represents a hydrogen atom, an alkali metal atom or an ammonium group. In Formula 9, D ₁ and B ₁ each independently represent an alkylene group. E ₂ and A ₂ are each independently -COOM, -SO ₂ M, -OM, -SZ,-.
It represents SO ₂ N (X ₁ ) (Y ₁ ) or —CO (X ₁ ) (Y ₁ ). Here, M represents a monovalent cation. X ₁ and Y ₁ each represent a hydrogen atom, a hydroxy group, an alkyl group or a phenyl group which may be substituted by a sulfonic acid or a carboxylic acid, or a sulfonyl group which may be substituted by an alkyl group or a phenyl group. Z has the same meaning as X ₁ and Y ₁ , but is not a hydrogen atom. p is 1-2, m and n are each an integer of 1-3. In chemical formula 10, R ₉ and R
₁₀ is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, a mercapto group, a carboxy group, a sulfo group, a phosphono group, an amino group, a nitro group, a cyano group,
It represents a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group or a heterocyclic group. Also R ₉ and R ₁₀
And may combine with each other to form a ring. )

Regarding the technique of desorbing gold from a silver halide emulsion with sodium sulfite, see L. Dupain-Kle.
rkx and P. Faelens; The Journal of Photographic Scie
nce 35, 136-144 (1987). However, the technique described therein is not the addition of sodium sulfite to the silver halide emulsion in the chemical sensitization step, but the bashing of the silver halide emulsion coated after the chemical sensitization to the sodium sulfite aqueous solution. It is a technique. Therefore, the gold in the binder phase is desorbed from the coated silver halide emulsion, but the gold on the silver halide grains is not desorbed, and 80% or more of the gold is satisfactorily sensitized with gold and sulfur. It is stated that it is distributed to. This point is a point different from the present invention. Further, it is not suggested at all in this known example that an emulsion having high sensitivity and excellent storage stability can be obtained by desorbing gold. Further, although only gold sulfur sensitization is performed in this known example, the present inventors have found that the maximum effect of the present invention can be obtained particularly in gold selenium sensitization.

Further, Japanese Patent Laid-Open No. 62-240951 discloses that
After the gold sensitization of the silver halide emulsion was completed, the gold sensitizer remaining in the binder phase was removed to obtain a high distribution ratio of gold to the silver halide grain side of the resulting emulsion. It is disclosed that it is advantageous in sex. However, in this known example, only the gold in the binder phase is removed, and it is not intended to later desorb the gold once distributed to the silver halide grain side.

Further, in US Pat. No. 3,442,653, sulfite is used in gold selenium sensitization for the purpose of activating the stable selenium sensitizer during the chemical sensitization process. It is disclosed that it is added at the same time as the sensitizer. Japanese Patent Publication No. 2-7445 discloses sulfite as a silver halide solvent added before a chemical sensitizer is added in a chemical sensitization step. Further, JP-A-2-235043 discloses that sodium sulfite is added as a reducing substance added before gold / sulfur sensitization in the chemical sensitization step. However, any of the known examples is completely insufficient for the purpose of desorbing the gold that has once reacted on the silver halide grains later, as in the present invention.

[0025]

Next, the present invention will be described in more detail. The Cl ⁻ content of the silver halide emulsion of the present invention is 20
Mol% to 100 mol%, preferably 50 mol% to 100 mol%, more preferably 75 mol% to 1
00 mol% or less, more preferably 90 mol% or more and 100
It is not more than mol%. The main plane of the tabular silver halide grains in the silver halide emulsion of the present invention may be the {111} plane or the {100} plane, but the {100} plane is preferable. Here, the principal plane refers to the maximum surface of tabular grains.

The average thickness of the tabular grains of the present invention is 0.05.
It is preferably at least .mu.m and not more than 0.35 .mu.m, and 0.05 to 0.
30 μm is more preferable, and 0.05 to 0.25 μm is still more preferable.

The average aspect ratio (diameter / thickness) of the tabular grains of the present invention is 2 or more and 30 or less, preferably 2 or less.
The above is 25 or less, more preferably 4 or more and 20 or less.
Here, the diameter refers to the diameter of a circle having an area equal to the projected area of the tabular grains, and the thickness refers to the distance between two principal planes. The average aspect ratio is the average aspect ratio of all tabular grains.

The variation coefficient of the diameter distribution of the tabular grains of the present invention is preferably 5% or more and 25% or less, preferably 5% or less, based on the definition of the method described in JP-A-59-745481.
It is more preferably 20% or less. Particularly when used for a sensitive material having a high contrast, it is preferably 5% or more and 15% or less. Also,
The tabular grains of the present invention have an average grain diameter of 0.2 to 10 μm.
Is preferable and 0.3-5 micrometers is more preferable.

Among the emulsions of the present invention, the nucleation of the emulsion having the {111} plane as the principal plane is described in JP-B-64-8326.
Nos. 64-8325, 64-8324, JP-A-1-250943, JP-B-3-14328, JP-B-4-81782, JP-B-5-40298, and 5-3
No. 9459, No. 5-12696 and JP-A-63-213.
No. 836, No. 63-218938, No. 63-2811
49, JP-A-62-218959, and the formation of tabular grain nuclei having a {100} plane in the principal plane thereof is described in JP-A-5-204073.
JP-A-51-88017, JP-A-63-24238
Japanese Patent Application Laid-Open No. 7-146522, Japanese Patent Application No. 6-26259.
No. 0 etc. In the present invention, the nucleation method described in these patent documents can be arbitrarily used.

As a method of growing the silver halide grains of the present invention, any method known so far can be used. That is, the silver salt aqueous solution and the halogen salt aqueous solution are added to the reaction vessel under efficient stirring. The specific method is Chemie et Phisique by P. Glafkides.
Photographique (Paul Montel, 1967), GF
Photographic Emulsion Chemistry (The Foca by Duffin
L Press, 1966), by VL Zelikman et al Maki
ng and Coating Photographic Emulsion (TheFocal Pre
ss, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used. Good.

As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase where silver halide is produced, that is, a so-called controlled double jet method can be used. Further, British Patent No. 1535016, Japanese Patent Publication Nos. 48-36890 and 52-1636.
No. 4, etc., a method of changing the addition rate of silver nitrate or an alkali halide aqueous solution according to the particle growth rate, US Pat. No. 4,242,445,
It is also preferable to use the method of changing the concentration of the aqueous solution as described in JP-A-55-158124 and the like to rapidly grow in a range not exceeding the critical supersaturation degree.

When the grains of the present invention have the {100} plane as the principal plane, the growth of the tabular grains is such that new nuclei are generated and the new nuclei do not grow to the critical fine particles at an addition rate of Ag ⁺ salt and halogen. It is preferable to add salt. The new nucleus is {1
The number of grains is preferably 2 times or more, more preferably 5 times or more, and particularly preferably 10 times or more with respect to the number of tabular grains. Here, the generation of new nuclei is preferable because dissolution of tabular grains does not occur due to the generation of new nuclei and anisotropic growth of grains can be maintained. In addition, the decrease in supersaturation of the system due to the generation of new nuclei is also a factor for maintaining the anisotropic growth of particles. The generation of new nuclei, the number of new nuclei, and the fact that no particles larger than the critical particle size have been generated can be confirmed by the direct method TEM of the sample without centrifugation at the time of sample preparation. The generation rate of the new nuclei and the addition rate at which the new nuclei do not grow up to the critical particle size are as follows:
pAg, gelatin type, gelatin concentration, temperature, AgX solvent concentration, {100} tabular grain size, etc. Therefore, it is necessary to determine by the trial and error method at various timings of growth. Generally, the addition rate that satisfies the condition is p
The larger the Cl value, the wider the rate of addition can be achieved. The generation of new nuclei is preferably always occurring, but it is sufficient that new nuclei are generated only when the amount of grown silver is preferably 5% or more, more preferably 10% or more. . However, also in this case, the nuclei formed by the new nuclei must always be present when the Ag salt is added.

When the grains of the present invention have the {100} plane as the principal plane, the growth of the tabular grains is carried out by physical ripening (fine grains are dissolved and substrate grains are grown) in the presence of fine silver halide grains. Crystal growth is also preferably performed. In the fine grain emulsion addition method, the diameter is 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.06 to 0.00.
A 6 μm diameter AgX fine grain emulsion is added, and the tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added either continuously or continuously. The fine grain emulsion can be continuously prepared by supplying the AgNO ₃ solution and the X ⁻ salt solution by a mixer provided near the reaction vessel, and can be immediately added to the reaction vessel immediately or in another vessel in advance. Can be added continuously or continuously after preparation in a batch system. The fine grain emulsion can be added in a liquid form or as a dry powder. The dry powder may be mixed with water immediately before addition, liquefied and added. The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes. If the disappearance time becomes long, ripening occurs between the fine particles and the particle size becomes large, which is not preferable. Therefore, it is preferable not to add the entire amount at once. It is preferable that the fine particles are substantially free of twinned grains. Here, the multiple twin particles refer to particles having two or more twin planes per particle. "Substantially not contained" means that the ratio of the number of multiple twin grains is 5% or less, preferably 1% or less, more preferably 0.1% or less. Further, it is preferable that substantially no single twin particles are contained. Further, it is preferable that the composition does not substantially include a screw dislocation. Here, "substantially not included" complies with the above-mentioned rules.

The halogen composition of the fine particles is AgCl, Ag
Br and AgBrI (I ^- content is preferably 10 mol% or less, more preferably 5 mol% or less) and a mixed crystal of two or more thereof. For other details, see JP-A-6-5936.
The description in No. 0 can be referred to. The total amount of fine grains added must be 20% or more of the total amount of silver halide,
It is preferably at least 40%, more preferably at least 50% and at most 98%. The Cl content of the fine particles is preferably 10 mol% or more, more preferably 50 mol% or more 10
0 mol% or less is preferable.

As the dispersion medium for nucleation, ripening and growth, conventionally known dispersion mediums for AgX emulsions can be used. In particular, the methionine content is preferably 0 to 50 μmol / g, more preferably 0 to 50 μmol / g. Gelatin of ３０30 μmol / g can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are preferably formed. In addition, Tokiko Sho 52
-16365, The Photographic Society of Japan, 29 (1), 1
7, 22 (1966), same 30 volumes (1), 10, 19
(1967), Volume 30 (2), 17 (1967)
), 33 (3), 24 (1967) can be preferably used as a dispersion medium. The pH at the time of growth by adding fine particles needs to be 2.0 or more, but is preferably 6 or more and 10 or less. More preferably, p
H6 or more and 9 or less. Also, pCl needs to be 1.0 or more, but is preferably 1.6 or more. More preferably, it is 2.0 or more and 3.0 or less. These growth conditions are particularly preferable for tabular grains having a {100} plane as a main plane. Here, pCl is defined as pCl = −log [Cl ⁻ ] with respect to the activity [Cl ⁻ ] of Cl ions in the solution. TH James by THE THEORY OF THE RHO
It is described in detail in Chapter 1 of the 4th edition of TOGRAPHIC PROCESS.

When the pH becomes 2.0 or less, for example, in the case of tabular grains having a {100} plane as a main plane, the lateral growth is suppressed, the aspect ratio is reduced, and the covering power of the emulsion is reduced. Tends to be low and the sensitivity is low. When the pH is 2.0 or higher, an emulsion having a high lateral growth rate and a high aspect ratio and a high covering power can be obtained, but the fog is high and the sensitivity is easily lowered. p
When Cl is 1.0 or less, for example, in the case of tabular grains having a {100} plane as a main plane, growth in the vertical direction is promoted, the aspect ratio is lowered, the covering power of the emulsion is low, and It makes you less sensitive. When the pCl is 1.6 or more, the aspect ratio is increased to increase the covering power, but the fog is high and the sensitivity is easily reduced. At this time, when the substrate grains are grown with fine silver halide grains, the pH is 6.
Fog is low even if 0 or more and / or pCl is 1.6 or more,
It has a high feeling and a high aspect ratio, and high covering power.

The tabular grains of the present invention are preferably silver halide grains having dislocation lines. Dislocation lines of tabular grains are, for example, JF Hamilton, Phot. Sci. Eng., 1
1, 57, (1967) and T. Shiozawa, J. Soc. Pho
t. Sci. Japan, 35, 213, (1972) can be observed by a direct method using a low-temperature transmission electron microscope. That is, silver halide grains taken out with care not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope,
Observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (eg, printout) due to an electron beam. At this time, the thicker the particle, the more difficult it is for an electron beam to pass. Therefore, a clearer observation can be obtained by using a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). From the photograph of the particles obtained by such a method, the position and number of dislocations for each particle when viewed from the direction perpendicular to the main plane can be determined. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof may be present together.

The present invention can be achieved by desorbing a part of gold distributed to the chemically sensitized silver halide grain side after the addition of the chemical sensitizer.

The distribution ratio of gold on the silver halide grain side of the present invention is preferably 10% or more and less than 40%, more preferably 12% or more and less than 35%, most preferably 15% or more and 3%.
It is less than 0%.

The distribution ratio of gold on the silver halide grain side depends on the amount of gold in the silver halide grain phase and the total amount of gold present in the silver halide emulsion phase, which is determined by the method described below. It is defined as follows. That is, (distribution rate of gold on silver halide grain side) = (amount of gold in silver halide grain phase) / (amount of all gold in silver halide emulsion phase) gold in silver halide grain phase And the total amount of gold present in the silver halide emulsion phase are determined by, for example, colorimetric analysis, atomic absorption spectrometry, ICP emission spectroscopy, neutron activation,
Mass spectrometry or the like may be used. More specifically, the following methods (i), (ii) and (iii) can be used for analysis. The amount of all the gold present in the silver halide emulsion phase may be the sum of the amount of gold in the silver halide grain phase and the amount of gold in the binder phase, but the silver halide emulsion can be obtained without the following separation operation. It may be a quantitative value of gold analyzed as a whole, or may be the total amount of gold added to the silver halide emulsion. (I) In a silver halide emulsion dispersion before being coated on a support, it is divided into a silver halide grain solid phase and a binder phase by a centrifugal separation method, and each of them is separated by a gold sensitizer by the above-mentioned analysis method. Quantify the amount. (Ii) In the coating material coated on the support, the silver halide emulsion is peeled from the support by swelling with water and enzymatic or acid decomposition, and then the solid phase of the silver halide grains and the binder are separated by centrifugation. Separated into phases, each is analyzed for the amount of gold sensitizer by the analytical method described above. (iii) In the case of a coating material applied on a support, the coating material itself should be treated with a dilute aqueous solution of sodium thiosulfate or potassium thiocyanate (for example, 0.01% aqueous solution) with care so that the silver halide is not fixed. It is known that almost all the gold sensitizer in the binder phase is washed away by washing with water.Therefore, determine the amount of total gold sensitizer in the coating before and after sodium thiosulfate or potassium thiocyanate bath treatment. The amount of gold sensitizer in the solid phase of silver halide grains and the binder phase is found. For details on this method (iii), see P.A.
Falens), Photographische Korrespondenz, 104, 13
7-146 (1968).

The silver halide grains of the present invention are prepared by adding a compound which forms a complex with gold after the distribution ratio of gold on the silver halide grain side becomes high in the chemical sensitization step. It is preferable to lower the distribution rate on the side. Immediately before the addition of the compound that forms a complex with gold, the distribution ratio of gold on the silver halide grain side is preferably 50% or more, more preferably 55% or more, and most preferably 60% or more. After the chemical sensitization, the distribution ratio of gold on the silver halide grain side is preferably 10% or more and less than 40%, more preferably 12% or more and less than 35%, and most preferably 15% or more 3
It is less than 0%. As the compound which forms a complex with gold, a compound having a stability constant of a complex salt with gold of 28 or more and 39 or less is preferable. Specific examples thereof include thiosulfates, sulfites, cyanides and the like, and sulfites are particularly preferable. The amount of the compound that forms a complex with gold used in the present invention varies depending on the stability constant of the complex salt with gold, the silver halide grains used, the chemical sensitization conditions, etc., but is 10 ⁻⁸ per mol of silver halide. 10 ⁻² mol, preferably 10 ^{−7 to} 5 × 10
^Use about ^-3 mol.

As the chemical sensitization in the present invention, chalcogen sensitization such as sulfur sensitization, selenium sensitization and tellurium sensitization is used in combination with gold sensitization.

In sulfur sensitization, unstable sulfur compounds were used, and P. Grafkides, Chimie et Physique Photograph was used.
ique (Paul Momtel, 1987, 5th edition), Research
Unstable sulfur compounds described in Disclosure magazine 307, volume 307105 and the like can be used. Specifically, thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-
Ethyl-N '-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (for example, thioacetamide), rhodanines (for example, diethylrhodanine, 5-benzylidene-N-ethyl-). Rhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg,
Known sulfur compounds such as dimorpholine disulfide, cystine, lenthionine), mercapto compounds (eg, cystine), polythionates, elemental sulfur, and active gelatin can also be used.

In the selenium sensitization, an unstable selenium compound is used, and Japanese Patent Publication Nos. 43-13489 and 44-157 are used.
48, JP-A-4-25832 and 4-109240.
JP-A-4-271341, JP-A-5-4032
Unstable selenium compounds described in No. 4 can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenamides (eg, selenoacetamide, N, N-diethylphenyl selenamide), phosphine selenides (for example, triphenylphosphine selenide, pentafluorophenyltriphenylphosphine selenide), selenophosphates (for example, tri-p-tolyl selenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids,
Selenoesters and diacyl selenides may be used. Furthermore, Japanese Patent Publications Nos. 46-4553 and 52-3.
The non-unstable selenium compounds described in Japanese Patent No. 4492, such as selenious acid, potassium selenocyanide, selenazoles, and selenides, can also be used.

In tellurium sensitization, an unstable tellurium compound is used, and Canadian Patent No. 800958, British Patent No. 1,
Nos. 295,462 and 1,396,696, JP-A-4-204640 and 4-271341.
The unstable tellurium compounds described in JP-A Nos. 4-333043 and 5-303157 can be used. Specifically, telluroureas (for example, tetramethyl tellurourea, N, N'-dimethylethylene tellurourea, N, N'-diphenylethylene tellurourea), phosphine tellurides (for example, butyl-diisopropylphosphine). Telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-
Diphenylphosphine telluride), diacyl (di) tellurides (for example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (Ethoxycarbonyl) telluride), isotellocyanates, telluroamides, tellurohydrazides, telluroesters (for example, butylhexyl telluroester), telluroketones (for example,
(Telloacetophenone), colloidal tellurium, (di) tellurides, and other tellurium compounds (potassium telluride, telluropentathionate sodium salt) and the like may be used.

Regarding the gold sensitization, the above-mentioned P. Grafkides
By Chimie et Physique Photographique (Paul Momtel
(Published in 1987, 5th edition), Research Disclosure magazine 30
Gold salts described in Vol. 7, No. 307105, etc. can be used. Specifically, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
US Patent 2,642,361 in addition to gold selenide
No. 5,049,484, No. 5,049,485, etc. can also be used. Further, a noble metal salt such as platinum, palladium or iridium may be added.

The chalcogen sensitization may be used alone or in combination of two or more, and may be combined with gold sensitization, but selenium sensitization and gold sensitization are most preferable, and a combination of sulfur sensitization, selenium sensitization and gold sensitization is also preferable. Further, reduction sensitization may be combined.

The amount of the chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, the chemical sensitization conditions and the like, but it is 10 ^-8 to 10 per mol of silver halide.
^-2 mol, preferably about 10 ^{-7 to} 5 × 10 ^-3 mol is used.

The amount of the gold sensitizer and the noble metal sensitizer used in the present invention is 10 ^-7 to 1 per mol of silver halide.
Use about 0 ^-2 mol. The conditions of the chemical sensitization in the present invention are not particularly limited, but pAg is preferably 6 to 11, more preferably 7 to 10, and pH is 4 to 4.
10 is preferable, and the temperature is preferably 40 to 95 ° C, more preferably 45 to 85 ° C. The time from the addition of the gold sensitizer and the chalcogen sensitizer to the addition of the compound that forms a complex with gold, which is necessary for making the distribution ratio of gold on the silver halide grain side 50% or more, is particularly It depends strongly on the pAg, the silver halide grains used, the temperature of chemical sensitization, the chalcogen sensitizer used, and there is no particular limitation, but it is preferably 20 minutes or more. The distribution ratio of gold on the silver halide grain side is 10%
The time from the addition of the compound that forms a complex with gold to the end of the chemical sensitization, which is necessary for adjusting the content to 40% or less, is especially the pAg of the emulsion, the silver halide grains used, the temperature of the chemical sensitization, It depends strongly on the chalcogen sensitizer used and is not particularly limited, but it is 3 minutes or more, preferably 5 minutes or more, and most preferably 10 minutes or more and 100 minutes or less.

Regarding reduction sensitization, the above-mentioned P. Grafkides
By Chimie et Physique Photographique (Paul Momtel
(Published in 1987, 5th edition), Research Disclosure magazine 30
Known reducing compounds described in Volume 7, No. 307105 and the like can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compound (eg, dimethylamineborane), hydrazine compound (eg, hydrazine, p-tolylhydrazine), polyamine compound (eg, diethylenetriamine, triethylene). Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas and the like may be used. Further, reduction sensitization may be carried out in an atmosphere of high pH or silver ion excess (so-called silver ripening).

In the silver halide emulsion of the present invention, the grain surface or a part thereof may be halogen-converted in the chemical sensitization step. As a method of applying halogen conversion,
Water-soluble bromide salts such as potassium bromide and sodium bromide, water-soluble iodide salts such as potassium iodide and the like can be used alone or in combination, and they are added as solids or as an aqueous solution or gelatin dispersion. can do. Further, it is also preferable to add silver bromide, silver iodobromide, and silver halide fine grains of silver iodide, and these can be used alone or in combination. When added in the form of fine particles, the average equivalent spherical diameter of the fine particles is preferably 0.1 μm or less, more preferably 0.05 μm or less. Further, the fine particles can be continuously adjusted by supplying an aqueous solution of silver nitrate and an aqueous solution of an alkali halide having an arbitrary composition with a mixer provided in the vicinity of the reaction vessel, and can be immediately added to the reaction vessel, or separately. It can also be added after adjusting it in a container in a batch manner. If necessary, the fine silver halide grains may contain ions or compounds of heavy metals such as iridium, rhodium and platinum.

The emulsion of the present invention is usually spectrally sensitized. Examples of dyes used for this purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Examples include styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. As these dyes, any of nuclei usually used for cyanine dyes can be applied as basic heterocyclic nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a selenazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, a tellurazole nucleus and the like; Condensed nuclei; and nuclei in which aromatic hydrocarbon rings are condensed to these nuclei, that is, indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzimidazole nuclei, naphthimidazole nuclei, A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a quinoline nucleus, a benzoterrazole nucleus and the like can be applied. These heterocyclic nuclei may be substituted on carbon atoms.

For the merocyanine dye or the composite merocyanine dye, as the nucleus having a ketomethylene structure, any nucleus generally used for merocyanine dyes can be applied. Particularly useful nuclei include pyrazolin-5-one nuclei, thiohydantoin nuclei, and 2-thiooxazolidine-2,4-
Applying 5-membered and 6-membered heterocyclic nuclei such as dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus and 2-thioselenazolidine-2,4-dione nucleus You can

These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,977,229,
No. 3397060, No. 3522052, No. 3527
No. 641, No. 3617293, No. 3628964,
No. 3666480, No. 3672898, No. 3679
No. 428, No. 3703377, No. 3769301,
3614609, 3838762, 4026
No. 707, British Patent Nos. 1344281 and 150780.
No. 3, each specification, Japanese Patent Publication Nos. 43-4936 and 53-12
No. 375, JP-A Nos. 52-110618 and 52-10.
No. 9925, etc.

Furthermore, these sensitizing dyes are dyes that do not exhibit a spectral sensitizing action by themselves, or substances that do not substantially absorb visible light and are combined with a sensitizing dye to achieve remarkable spectral sensitization. It may be used in combination with any compound known to be called a so-called supersensitizer which exhibits an increase. Typical examples of the supersensitizer include bispyridinium salt compounds described in JP-A-59-142541 and stilbene derivatives described in JP-B-59-18691, and JP-B-49-46932. Water-soluble bromides such as potassium bromide and potassium iodide, water-soluble iodides, condensates of aromatic compounds and formaldehyde described in US Pat. No. 3,743,510, cadmium salts, azaindene compounds, etc. Is mentioned.

The sensitizing dye is added after chemical ripening or before chemical ripening. For the silver halide grains of the present invention,
Most preferably, the sensitizing dye is added during chemical ripening or before chemical ripening (for example, during grain formation or physical ripening).

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, azoles, for example, benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds), heterocyclic mercapto compounds, for example, mercaptothiazoles, mercapto Benzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto having a water-soluble group such as a carboxyl group or a sulfone group. Compounds; Thioketo compounds such as oxazoline thione; Azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); Benzes Thiosulfonic acids; benzenesulfinic acid; can be added to many compounds known as antifoggants or stabilizers, such as.

The emulsion layer of the present invention contains 1.
0 × 10 ⁻³ mol or more and less than 2.0 × 10 ⁻² mol may be contained. The thiocyanic acid compound may be added in any process of grain formation, physical ripening, grain growth, chemical sensitization and coating, but is preferably added before chemical sensitization. As the thiocyanate compound used during the preparation of the silver halide emulsion in the present invention, a water-soluble salt such as a metal thiocyanate or an ammonium salt can be generally used. Care should be taken to use a metal element that does not affect, and potassium and sodium salts are preferred. Further, a sparingly soluble salt such as AgSCN may be added in the form of fine particles. The timing of addition of these antifoggants or stabilizers is usually carried out after chemical sensitization, but more preferably it can be selected during chemical ripening or before the start of chemical ripening.

In the present invention, it is also preferable to coexist with the nucleic acid or a decomposition product thereof before the chemical sensitization for chemical sensitization. Regarding nucleic acids or their degradation products,
No. 67541 can be used. The nucleic acid used in the present invention includes deoxyribonucleic acid (DN)
A) and ribonucleic acid (RNA), and examples of the nucleic acid degradation products include those undergoing degradation and simple substances such as adenine, guanine, uracil, cytosine, and thymine.
In particular, adenine is a preferred nucleolytic product. These can be used alone or in combination. In this case, it goes without saying that the nucleic acid and the nucleic acid degradation product may be used in combination. The amount of the nucleic acid or the decomposition product thereof varies depending on the type of the nucleic acid decomposition product, but is in the range of 20 mg or more, preferably 100 mg to 1 g per mol of silver halide. As described above, when these nucleic acids or nucleic acid degradation products are used alone or in combination of two or more, the total amount of additions described above is sufficient.

The developer of the present invention and the developer prepared from the developer preferably contain the compound represented by Chemical formula 6 and at least one of the compounds represented by Chemical formulas 7 to 10.

The chemical formula 6 will be explained. In the chemical formula 6,
R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl), an aminoalkyl group having an alkyl moiety having 1 to 6 carbon atoms (eg, aminomethyl, aminoethyl), a dialkylaminoalkyl group (eg, Dimethylaminomethyl, dimethylaminoethyl) and an optionally substituted carboxyalkyl group (eg, carboxymethyl, carboxyethyl, 1,2-dicarboxyethyl).

Specific examples of the compound of Chemical formula 6 are shown below. Among them, 11-1 is the most preferable.

[0063]

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The compounds of formula 6 may be used alone or in combination of two or more. The content of this compound in the developing solution is 0.01 to 10 mmol / liter, more preferably 0.1 to 10 mmol / liter.
It is preferably 2.0 mmol / liter.

The chemical formula 7 will be explained. In the chemical formula 7, R
₂ , R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (eg, methyl, ethyl, propyl). However, R ₂ and R ₃
Are not hydrogen atoms at the same time, and both are preferably alkyl groups. R ₄ and R ₅ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, propyl), and R ₆ is a hydroxyl group (including metal salt), an amino group, or an alkyl group having 1 to 3 carbon atoms. Groups (eg methyl,
Ethyl, propyl). R ₇ and R ₈ are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, propyl), an acyl group having 18 or less carbon atoms, usually 2 to 18 (eg, acetyl, propionyl), or a —COOM ₁₀ group. Represent Here, M ₁₀ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group, a carbon number of 15 or less,
Usually, it represents an alkyl group of 7 to 15. However, R ₇ and R ₈ are not hydrogen atoms at the same time. M ₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. k represents 0, 1 or 2.

Specific examples of the compound of Chemical formula 7 are shown below.

[0067]

[Chemical 12]

The chemical formula 8 will be explained. In the chemical formula 8, X
Is a hydrogen atom, a hydroxy group, a lower group (preferably having 1 carbon atom)
To 4) alkyl group, lower (preferably having 1 to 4 carbon atoms) alkoxy group, halogen atom, carboxyl group or sulfo group. M ₂ and M ₃ may be the same or different and each represents a hydrogen atom, an alkali metal atom or an ammonium group.

Specific examples of the compound of Chemical formula 8 are shown below. Among them, 13-1 is the most preferable.

[0070]

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The chemical formula 9 will be explained. In the chemical formula 9,
D ₁ and B ₁ are independently of each other an alkylene group which may have a substituent (for example, methylene, ethylene,
Dimethylmethylene, dimethylethylene, phenylethylene, methylphenylmethylene). E ₂ and A ₂
Each independently of one _{another, -COOM, -SO 2 M, -OM} , -SZ,
_{-SO 2 N (X 1) (} Y 1), - CO (X 1) representing the (Y _1). Where M is 1
Represents a valent cation (eg, H ⁺ ). X ₁ and Y ₁ each represent a hydrogen atom, a hydroxy group, an alkyl group or a phenyl group which may substitute a sulfonic acid or a carboxylic acid, or a sulfonyl group which may substitute an alkyl group or a phenyl group. Z has the same meaning as X ₁ and Y ₁ , but is not a hydrogen atom. p is 1 to
2, m and n are integers of 1 to 3.

A concrete example of the chemical formula 9 is shown below.

[0073]

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The chemical formula 10 will be explained. In the chemical formula ₁₀ , R ₉ and R ₁₀ are each a hydrogen atom, an alkyl group (which may have a substituent, for example, methyl, ethyl, propyl, morpholinomethyl, 4-methylpiperazyl). Methyl, diaminomethyl), aryl groups (eg phenyl), aralkyl groups, hydroxy groups, mercapto groups, carboxy groups, sulfo groups, phosphono groups, amino groups, nitro groups, cyano groups, halogen atoms, alkoxy groups, alkoxycarbonyl groups,
It represents an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, or a heterocyclic group. R ₉ and R ₁₀ may combine with each other to form a ring (for example, cyclohexene).

Specific examples of the compound of Chemical formula 10 are shown below.

[0076]

[Chemical 15]

The compounds of Chemical formulas 7 to 10 may be used alone or in combination of two or more kinds. The content in the developer is 0.01 to 10 mmol / liter, and further 0.1 to
It is preferably 2.0 mmol / liter.

The developing agent preferably used in the developer or developing solution of the present invention is an ascorbic acid type developing agent or a dihydroxybenzene type developing agent. Of these, ascorbic acid-based developing agents are preferred.

As the ascorbic acid type developing agent, compounds represented by the following chemical formula 16 are preferable.

[0080]

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In Chemical formula 16, R ¹ and R ² each represent a hydroxy group, an amino group, a mercapto group or an alkylthio group. P and Q each represent a hydroxy group, a carboxy group, an alkoxy group, an alkyl group, a sulfo group, an amino group or an aryl group, or P and Q are bonded to each other and substituted by R ¹ and R ² . It represents an atomic group forming a 5- to 8-membered ring together with a vinyl carbon atom and a carbon atom substituted by Y ¹ . Y ¹ represents ＯO or ＮN—R ³ . Where R ³
Represents a hydrogen atom, a hydroxy group, an alkyl group, or an acyl group.

The compound of Chemical formula 16 will be described in detail.

In Chemical formula 16, R ¹ and R ² are each a hydroxy group, an amino group, a mercapto group or an alkylthio group (eg methylthio, ethylthio), and the amino group may have a substituent. Is an alkyl-substituted amino group having 1 to 10 carbon atoms (for example, methylamino, ethylamino, n-butylamino, hydroxyethylamino), an acylamino group (for example, acetylamino,
Examples thereof include benzoylamino), alkylsulfonylamino groups (eg methanesulfonylamino), arylsulfonylamino groups (eg benzenesulfonylamino, p-toluenesulfonylamino) and alkoxycarbonylamino groups (eg methoxycarbonylamino). R
Preferred examples of ¹ and R ² include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonyl group.

P and Q are respectively a hydroxy group, a carboxy group, an alkoxy group, an alkyl group, a sulfo group, an amino group,
Represents an aryl group, or P and Q are linked together to form R
^1, R ² represents an atomic group forming a 5- to 8-membered ring together with the carbon atom to which the two vinyl carbon atoms and Y ¹ which is substituted is substituted. The alkoxy group, alkyl group, amino group and aryl group may be substituted. Specific examples of the ring structure ^{-O -, - C (R 9} ) (R 10) -, - C (R 11)
=, - C (= O) -, - N (R 12) -, - formed by combining the N = like. Here, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 10 and may have a substituent. As a substituent, a hydroxy group, a carboxy group, a sulfo group Group, etc.), a hydroxy group or a carboxy group.
Further, a saturated or unsaturated condensed ring may be formed on the 5- to 8-membered ring.

Examples of the 5- to 8-membered ring include dihydrofuranone ring, dihydropyrroline ring, pyranone ring, cyclopentenone ring, cyclohexenone ring, pyrrolinone ring, pyrazolinone ring, pyridone ring, azacyclohexenone ring, uracil ring. Examples of preferred 5- to 8-membered rings include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

Y ¹ represents ═O or ═N—R ³ . R
³ represents a hydrogen atom, a hydroxy group, an alkyl group (eg methyl, ethyl) or an acyl group (eg acetyl). The alkyl group and the acyl group may be substituted. Examples of the substituted alkyl group include a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl), and a carboxyalkyl group (eg, carboxymethyl, carboxyethyl).

Specific examples of the ascorbic acid type developing agent of the present invention are shown below, but the present invention is not limited thereto.

[0088]

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[0089]

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[0090]

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[0091]

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Of these, ascorbic acid or erythorbic acid represented by I-1 (diastereomer of ascorbic acid) and alkali metal salts such as lithium salt, sodium salt and potassium salt thereof are preferable. These ascorbic acid and its derivative-based developing agents are preferably used in an amount of 1 to 100 g, preferably 5 to 80 g per liter of the developing solution.

On the other hand, as the dihydroxybenzene type developing agent, hydroquinone, hydroquinone monosulfonic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone,
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,
Although there are 5-dimethylhydroquinone and the like, hydroquinone is particularly preferred.

When an ascorbic acid type developing agent is used, it is preferable that the developer or developer of the present invention does not substantially contain a polyhydroxybenzene compound represented by dihydroxybenzene such as hydroquinone. . That is, the content of the polyhydroxybenzene compound in the developer is desirably 0.0001 mol / liter or less, and most preferably, it is not contained at all. The pH of the developer is preferably 8.5 to 12, and 9 to 1
1.5 is particularly preferred.

As various additives and the like used in the photographic light-sensitive material of the present invention, for example, those described in the following relevant parts can be used. Item Applicable place 1) Antifoggant, JP-A-2-68539, page 10, lower left column 17, stabilizer Stabilizer line to page 11, upper left column, line 7 and page 3, left lower column, line 2 to same Page 4, lower left column. 2) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, left lower column, line 20; JP-A-3-94249, page 6, lower left column, line 15 to 1 Page 1, upper right column, line 19 3) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 4) Surfactant, JP-A-2-68539, page 11, upper left column 14, antistatic agent line to page 12, upper left column, line 9 thereof. 5) Matting agent, slipping agent, JP-A-2-68539, page 12, upper left column 10, plasticizer line to same upper right column, line 10; page 14, lower left column 10, line 10 to lower right column 1, line 1 . 6) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 7) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 8) Support, JP-A-2-68539, page 13, upper right column, line 7 to line 20. 9) Crossover JP-A-2-264944, page 4, upper right column, 20th cutting method, line 14 to upper right column. 10) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, left lower column, line 9; JP-A 3-24537, page 14, lower left column, page 16 lower right Column. 11) Polyhydroxy JP-A-3-39948, page 11, upper left column, benzenes, page 12, lower left column, EP Patent No. 452772A. 12) Layer structure JP-A-3-198041. 13) Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, left lower column, line 15, and JP-A-2-115837, page 3, lower right column, line 5 Page 6, upper right column, line 10

The AgX emulsion grains of the present invention and the AgX emulsion produced by the production method can be used in all photographic light-sensitive materials. For example, black-and-white silver halide photographic light-sensitive material [for example, X-ray sensitive material, printing sensitive material, photographic paper, negative film, microfilm, direct positive sensitive material, ultrafine particle dry plate sensitive material (for LSI photomask, shadow mask) , For liquid crystal masks)], and color photographic light-sensitive materials (for example, negative films, photographic papers, reversal films, direct positive color photographic materials, silver dye bleaching photography, etc.). Further, a diffusion transfer type photosensitive material (eg, color diffusion transfer element, silver salt diffusion transfer element), photothermographic material (black and white, color), high density
Examples include digital recording materials and holographic materials.

As a method of forming an image using the light-sensitive material of the present invention, a method of forming an image in combination with a phosphor having a main peak at 400 nm or less by X-ray exposure can be mentioned.

A screen having a main emission peak at 400 nm or less is disclosed in JP-A-6-11804, WO93 / 0152.
The screen described in No. 1 is used, but not limited to this. The emission wavelength of the phosphor preferably used in the present invention is 400 nm or less, more preferably 370 nm or less.

A typical phosphor is M ′ phase YTaO.
₄ alone or Gd, Bi, Pb, Ce, Se, Al,
Compounds to which Rb, Ca, Cr, Cd, Nb, etc. are added,
A compound obtained by adding Gd, Tm, Gd and Tm, Gd and Ce, Tb to LaOBr, a compound obtained by adding an oxide of HfZr alone or an alkali metal such as Ge and Ti,
A compound containing Y ₂ O ₃ alone or containing Gd and Eu,
_There are a compound in which Gd is added to ₂ O ₂ S, a compound in which Gd, Tl, and Ce are used as an activator in a host of various phosphors. Particularly preferred compounds include M′-phase YTaO ₄ alone or a compound obtained by adding Gd and Sr, LaOBr to which Gd, Tm, Gd and Tm are added, HfZ
An oxide of r or a compound to which an alkali metal such as Ge or Ti is added.

The particle size of the phosphor is preferably 1 μm or more and 20 μm or less, but can be changed depending on the required sensitivity and manufacturing problems. The coating amount is preferably 400 g / mm ² or more and 2000 g / mm ² or less, but it cannot be unequivocally determined depending on the required sensitivity and image quality. A single intensifying screen may be used to provide a particle size distribution from the vicinity of the support to the surface. In this case, it is generally known that particles on the surface are enlarged. The space filling rate of the phosphor is 40% or more, preferably 6
It is 0% or more.

When the phosphor layers are provided on both sides of the light-sensitive material for photographing, the phosphor coating amount on the X-ray incident side and the opposite side can be changed. In general, it is known to reduce the coating amount of the intensifying screen on the X-ray incident side, especially when a high-sensitivity system is required for shielding by the intensifying screen on the X-ray incident side.

The support used in the screen used in the present invention may be paper, metal plate, polymer sheet or the like, but a flexible sheet such as polyethylene terephthalate is generally used. The support may be added with a reflecting agent or a light absorbing agent, if necessary, or may be provided as a separate layer on the surface.

If necessary, the surface of the support may be slightly uneven, or an adhesive layer for increasing the adhesion to the phosphor layer or a conductive layer may be provided as an undercoat. Examples of the reflecting agent include zinc oxide, titanium oxide, barium sulfate, etc., but titanium oxide and barium sulfate are preferable because the phosphor has a short emission wavelength. The reflecting agent may be present not only in the support or between the support and the phosphor layer, but also in the phosphor layer. When it is present in the phosphor layer, it is preferred that it is localized near the support.

As the binder used in the screen of the present invention, proteins such as gelatin, polysaccharides such as dextran and corn starch, natural polymer substances such as gum arabic; polyvinyl butyral, polyvinyl acetate, polyurethane, polyalkyl acrylate, chloride Examples thereof include synthetic polymer substances such as vinylidene, nitrocellulose, fluorine-containing polymers and polyesters, and mixtures and copolymers thereof. Preferred binders include:
The basic performance is high transmittance for the light emitted from the phosphor. In this respect, gelatin, corn starch, an acrylic polymer, a fluorine-containing olefin polymer, a polymer containing a fluorine-containing olefin as a copolymer component, a styrene / acrylonitrile copolymer and the like can be mentioned. These binders may have functional groups that are crosslinked by the crosslinking agent. Further, depending on the required image quality performance, an absorber for light emission from the phosphor may be added to the binder, or a binder having a low transmittance may be used. Examples of the absorbent include a pigment, a dye, and an ultraviolet absorbing compound. The ratio of phosphor to binder is generally 1: 5 to 50: 1 by volume, preferably 1: 1 to 1: 5: 1. The ratio between the phosphor and the binder may be uniform or non-uniform in the thickness direction.

The phosphor layer is usually formed by a coating method using a coating liquid in which the phosphor is dispersed in a binder solution.
Examples of the solvent for the coating liquid include water or alcohols, chlorine-containing hydrocarbons, organic solvents such as ketones, esters and ether aromatic compounds, and mixtures thereof.
Phosphoric acid, stearic acid,
A dispersion stabilizer such as caproic acid and a surfactant, and a plasticizer such as a phosphate, a phthalate, a glycolate, a polyester, and a polyethylene glycol may be added.

In the screen used in the present invention, a protective layer can be provided on the phosphor layer. As the protective layer, a method of coating on the phosphor layer or a method of separately forming a protective layer film and laminating is used. In the coating method, the coating may be performed simultaneously with the phosphor layer, or may be performed after the phosphor layer is coated and dried. The protective layer may be the same substance as the binder of the phosphor layer or a different substance. Examples of the substance used for the protective layer include the substances listed as the binder for the phosphor layer, as well as cellulose derivatives, polyvinyl chloride, melamine, phenol resins and epoxy resins.
Preferred materials include gelatin, corn starch, acrylic polymers, fluorine-containing olefin polymers, polymers containing fluorine-containing olefins as copolymer components, and styrene / acrylonitrile copolymers. The thickness of the protective layer is generally 1 μm or more and 2 μm or more.
0 μm or less, preferably 2 μm or more and 10 μm or less,
It is more preferably from 6 μm to 6 μm. It is preferable to emboss the surface of the protective layer of the present invention. Further, a matting agent may be present in the protective layer, or a substance having a light-scattering property for light emission depending on the image to be obtained, such as titanium oxide may be present.

A surface slipperiness may be imparted to the protective layer of the screen used in the present invention. Examples of preferable slip agents include polysiloxane skeleton-containing oligomers and perfluoroalkyl group-containing oligomers. You may give electroconductivity to the protective layer of this invention. Examples of the conductivity imparting agent include white and transparent inorganic conductive substances and organic antistatic agents. As a preferable inorganic conductive substance, Z
Examples thereof include nO powder, whiskers, SnO ₂ and ITO.

[0108]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 "Preparation of {100} high AgCl tabular emulsion A-1" In a reaction vessel, 1582 ml of an aqueous gelatin solution (gelatin-1 (deionized alkali-treated bone gelatin having a methionine content of about 40 µmol / g) 19.5 g, HNO). ₃ 7.8 ml of 1N solution, pH 4.3, NaCl-1 solution (N in 100 ml)
13 ml of aCl (containing 10 g) was added, and while maintaining the temperature at 40 ° C., Ag-1 solution (AgNO ₃ 20 in 100 ml) was added.
g) and solution X-1 (NaCl 7.0 in 100 ml).
(Including 5 g) was simultaneously mixed and added at 62.4 ml / min in 15.6 ml portions. After stirring for 3 minutes, Ag-2 solution (100
AgNO ₃ containing 2g) and X-2 solution in ml (100 ml
Containing 1.4 g of KBr) at 80.6 ml / min 2
8.2 ml was mixed simultaneously. After stirring for 3 minutes, Ag-
Solution 1 and solution X-1 were simultaneously mixed and added at a rate of 62.4 ml / min in 46.8 ml portions. After stirring for 2 minutes, aqueous gelatin solution 20
3 ml (oxidized gelatin 11.3 g, NaCl 1.
3 g, including NaOH 1N solution to adjust pH to 5.5) and pCl to 1.8, and then the temperature to 75
The temperature was raised to 0 ° C., the pCl was adjusted to 1.8, and aging was performed for 10 minutes. Thereafter, 1 × 10 ^-4 mol of disulfide compound A was added per 1 mol of silver halide, and an AgCl fine grain emulsion (average grain diameter: 0.1 μm) was further added at an addition rate of 2.68 × 10 ⁻² mol / min of AgCl. Added for 20 minutes. After aging for 10 minutes after the addition, a precipitant was added, the temperature was lowered to 35 ° C., and the precipitate was washed by settling. Add an aqueous gelatin solution and p
H was adjusted to 6.0.

[0109]

[Chemical 21]

A transmission electron microscope photographic image (hereinafter referred to as TEM) of a replica of the particles was observed. The emulsion obtained is
It was a silver chlorobromide {100} tabular grain containing 0.44 mol% of AgBr based on silver. The shape characteristic values of the particles were as follows. (Total projected area of tabular grains having an aspect ratio of 2 or more and 30 or less / sum of projected areas of all AgX grains) × 100 = a ₁ = 90
% (Average aspect ratio of tabular grains (average diameter / average thickness)) = a ₂ = 9.3 (Average diameter of tabular grains) = a ₃ = 1.67 μm (Average thickness) = a ₄ = 0 .18 μm

"Preparation of {111} AgCl Tabular Emulsion B-1" Silver chloride tabular grains were prepared as follows.

[0112]

Embedded image

[0113]

Solution (2) and solution (3) were simultaneously added to solution (1) kept at 35 ° C. with stirring at a constant addition rate over 1 minute, and the temperature of the solution was raised to 70 ° C. over 15 minutes. Let At this point, grains corresponding to about 5.7% of the total silver were formed. Next, the solution (4) and the solution (5) were
The solution (6) and the solution (7) were simultaneously added over a period of 40 minutes at a constant addition rate,
A silver chloride tabular emulsion was obtained. Wash the emulsion with water by sedimentation
After desalting, 30 g of gelatin and H ₂ O were added, 2.0 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the mixture was redispersed with caustic soda to a pH of 6.0. The emulsion thus obtained had a ₁ = 90%, a ₃ = 1.55 μm, a ₄ =
This is a silver chloride tabular emulsion having a {111} plane as the principal plane of 0.18 μm, a ₂ = 8.6, and a coefficient of variation of projected area diameter corresponding to a circle of 19%.

"{100} plane AgBrCl tabular emulsion C-
Preparation of 1 "1582 ml of an aqueous gelatin solution (gelatin-1 (deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 19.5 g, HNO ₃
1N solution (7.8 ml, pH 4.3), NaCl-1 solution (100 ml contains 10 g NaCl) 13 ml,
While maintaining the temperature at 40 ° C., Ag-1 solution (containing 100 g of AgNO ₃ 20 g) and solution X-1 (containing 100 ml of 7.05 g of NaCl) at 62.4 ml / min.
5.6 ml were added simultaneously. After stirring for 3 minutes, A
g-2 solution (containing 2 g of AgNO _{3 in} 100 ml) and X
-Part 2 (containing 1.4 g of KBr in 100 ml) 8
28.2 ml were mixed simultaneously at 0.6 ml / min. After stirring for 3 minutes, Ag-1 solution and X-1 solution were mixed at 62.4 ml / min for 4 minutes.
6.8 ml were added simultaneously. After stirring for 2 minutes, 203 ml of gelatin aqueous solution (gelatin-1 13 g, NaC
l 1.3 g, NaOH to adjust pH to 5.5
1N solution was added) to adjust the pCl to 1.8, the temperature was raised to 75 ° C., the pCl was adjusted to 1.8, and the mixture was aged for 10 minutes. After this, Ag-3 solution (100 mL of AgNO ₃
25 g), solution X-3 (KBr 8.75 in 100 ml)
g, the NaCl 4.30 g), were grown in pCl 1.8 20 minutes by a controlled double jet method at an addition rate of 2.68 × 10 ^-2 mol / min. After aging for 10 minutes after the addition, a precipitant was added, the temperature was lowered to 35 ° C., and the precipitate was washed by settling. An aqueous gelatin solution was added, and pH 6.0 at 60 ° C.
Adjusted to. A TEM image of a replica of the particles was observed.
The obtained emulsion was silver chlorobromide {100} plane tabular grains containing about 50 mol% of AgBr based on silver. The shape characteristic values of the particles were as follows. (Total projected area of tabular grains having an aspect ratio of 2 or more and 30 or less / sum of projected areas of all AgX grains) × 100 = a ₁ = 90
% (Average aspect ratio of tabular grains (average diameter / average thickness)) = a ₂ = 9.3 (Average diameter of tabular grains) = a ₃ = 1.67 μm (Average thickness) = a ₄ = 0 .18 μm

"{111} AgBrCl tabular grains D-
Preparation of 1 ”6.0 g of potassium bromide and 7.0 g of low molecular weight gelatin having an average molecular weight of 15,000 were added to 1 liter of water, and the mixture was stirred into a container kept at 55 ° C., and an aqueous solution of silver nitrate 3 was added.
38 cc of an aqueous solution containing 7 cc (4.00 g of silver nitrate) and 5.9 g of potassium bromide was added over 37 seconds by the double jet method. Next, after adding 18.6 g of gelatin, 70 ° C
The temperature was raised to 89 ° C. and 89 cc of an aqueous silver nitrate solution (9.80 g of silver nitrate) was added over 22 minutes. Here, 7 cc of a 25% aqueous ammonia solution was added, the mixture was physically aged at the same temperature for 10 minutes, and then 6.5 cc of a 100% acetic acid solution was added. Subsequently, an aqueous solution of 153 g of silver nitrate and a mixed aqueous solution of potassium bromide and potassium chloride were added over 35 minutes by the control double jet method while keeping the pAg at 8.5. Next 2N
15 cc of potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. a ₁ = 95%, average projected area diameter a ₃ = 1.50 μ
m, thickness a ₄ = 0.185 μm, average aspect ratio a ₂
= 8.1, the variation coefficient of diameter was 18.5%, and a monodisperse silver chlorobromide tabular emulsion D-1 having a {111} plane as the main plane and having a silver chloride content of 17% was prepared. After this, the soluble salts were removed by the sedimentation method. The temperature was raised again to 40 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and pH was adjusted to 5.90 with caustic soda and silver nitrate solution, pAg.
Adjusted to 8.00.

"Preparation of Monodisperse Cubic Silver Halide Emulsion E" 32 g of gelatin was dissolved in 1 liter of water, and 0.3 g of potassium bromide, 5 g of sodium chloride and compound [I] were placed in a container heated at 53 ° C.

[0118]

Embedded image

After adding 46 mg, 444 ml of an aqueous solution containing 80 g of silver nitrate and 452 ml of an aqueous solution containing 45 g of potassium bromide and 5.5 g of sodium chloride were added by the double jet method over about 20 minutes, and then 80 g of silver nitrate was added. 400 ml of aqueous solution, 46.4 g of potassium bromide, 5.7 g of sodium chloride and hexachloroiridium (III)
Aqueous solution 415 containing potassium salt (10 ^-7 mol / mol silver)
ml and a double jet method for about 25 minutes to add cubic monodispersed silver chlorobromide grains having an average grain size (projected area diameter) of 0.34 μm (variation coefficient of projected area diameter: 10
%).

This emulsion was desalted by the coagulation method, and then 62 g of gelatin and 1.75 g of phenoxyethanol were added.
Adjusted to pH 6.5 and pAg 8.5.

[Chemical Sensitization] Next, emulsion A-1 was optimally chemically sensitized while being kept at 56 ° C. with stirring. First, thiosulphonic acid compound-1 was added in an amount of 6 × 10 ^-5 mol equivalent per mol of silver halide, and then AgBr fine particles having an average spherical phase equal diameter of 0.05 μm were added at 1.0 mol% per mol of silver halide. A corresponding amount was added and ripening was carried out for about 5 minutes, and a 1% KI aqueous solution corresponding to 0.2 mol% per mol of silver halide was further added. After 3 minutes, 1 × 10 ⁻⁶ mol / mol Ag of thiourea dioxide was added, and the mixture was kept for 22 minutes for reduction sensitization. Next, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added in an amount of 1.5 × 10 ^-4 mol per mol of silver halide, and sensitizing dyes A-1 and A- were added. 2 and 1 × 10 ⁻³ mol and 1.2 × 10 ⁻⁵ mol per mol of silver halide were simultaneously added. Subsequently, sodium thiosulfate was added in an amount of 5 × 10 ^-6 mol per mol of silver halide and selenium compound-1 was added in an amount of 1 × 10 ^-6 mol per mol of silver halide, and then chloroauric acid was added to 1 mol of silver halide. 2.7 × 10 ^-6 mol per mol of potassium thiocyanate and 1.8 × 10 ^-3 mol per mol of silver halide were added. Nucleic acid (made by Sanyo Kokusaku Pulp Co., Ltd .: trade name RNA
-F) was added in an amount of 67 mg per mol of silver halide. Then, 20 minutes after the addition of chloroauric acid, sodium sulfite was added at 3.2 × 10 ⁻⁴ per mol of silver halide.
80 minutes after adding chloroauric acid, add water-soluble mercapto compound-1 and add at a temperature of 35 ° C.
And cooled. Thus, the preparation (chemical ripening) of emulsion A-1 was completed.

[0122]

Embedded image

Emulsion A-2 was prepared in the same manner except that the addition amount of sodium sulfite and the time from the addition of gold to the addition of sodium sulfite were changed as shown in Table 1.
.About.3, B-1 to 3, C-1 to 3, D-1, and E-1 were chemically sensitized. Emulsion A-4 was prepared in exactly the same manner as emulsion A-1, except that sodium thiosulfate and a selenium sensitizer were not added. Emulsion A-1 was prepared in the same manner except that equimolar amounts of potassium thiocyanate (stability constant of complex salt with gold 20) and KBr (stability constant of complex salt with gold 15) were added in place of sodium sulfite. To prepare emulsions A-5 and A-6, respectively.

The obtained emulsion and the emulsion immediately before the addition of sodium sulfite (prepared separately with the same formulation) were centrifuged to separate into a binder phase and a silver halide grain phase. For the silver halide grain phase, the silver halide grains are dissolved in an ammonium thiosulfite aqueous solution, and then gold is quantified by atomic absorption spectrometry. I asked for the rate. Emulsions A-1 to A-6, B-1 to B-3, C prepared in Table 1
The distribution rates of -1 to C-3, D-1, and E-1 of gold on the silver halide grain side are shown.

[0125]

[Table 1]

"Preparation of coating sample" Emulsions A-1 to A-6,
The following chemicals were added to B-1 to B-3, C-1 to C-3, D-1 and E-1 per mol of silver halide to prepare emulsion coating solutions. -Gelatin (including gelatin in emulsion) 111 g-Dextran (average molecular weight 39,000) 21.5 g-Sodium polyacrylate (average molecular weight 400,000) 5.1 g-Sodium polystyrene sulfonate (average molecular weight 600,000) 1.2 g Hardener 1,2-bis (vinylsulfonylacetamido) ethane Addition amount is adjusted so that the swelling ratio becomes 230%. Compound-I 42.1 mg Compound-II 10.3 g Compound-III 0.11 g Compound-IV 8.5 mg Compound-V 0.43 g Compound-VI 0.004 g Compound-VII 0.1 g Compound-VIII 0.1 g Adjusted to pH 6.1 with NaOH

[0127]

Embedded image

[0128]

[Chemical formula 26]

Dye Emulsion A was added to the above coating solution so that each of Dye-I to III was 10 mg / m ² .

[0130]

Embedded image

(Preparation of Dye Emulsion A) The above Dyes-I to II
20 g each, and 62.degree.
8 g, 62.8 g of high boiling organic solvent-II and 333 g of ethyl acetate were dissolved at 60 ° C. Next, 65 cc of a 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin and 581 cc of water were added, and the mixture was emulsified and dispersed at 60 ° C. for 30 minutes with a dissolver. Next, 2 g of the following compound-VI and 6
One liter was added and the temperature was lowered to 40 ° C. Next, using Asahi Kasei's ultrafiltration laboratory module ACP1050, the total amount was concentrated to 2 kg, and 1 g of the compound-VI was added to obtain a dye emulsion A.

[0132]

Embedded image

(Preparation of Coating Solution for Surface Protective Layer) The coating solution for surface protective layer was prepared so that each component had the following coating amount. Gelatin 0.780 g / m ² · Sodium polyacrylate (average molecular weight 400,000) 0.035 g / m ² · Sodium polystyrenesulfonate (average molecular weight 600,000) 0.0012 g / m ² · polymethylmethacrylate (average particle size 3.7μm ) 0.072g / m ² · coating aids -I 0.020g / m ² · coating aids -II 0.037g / m ² · coating aids -III 0.0080 g / m ² · coating aids -IV 0.0032 g / m ²・ Coating aid-V 0.0025 g / m ²・ Compound-VII 0.0022 g / m ²・ Proxel (manufactured by ICI) 0.0010 g / m ² (pH adjusted to 6.8 with NaOH)

[0134]

[Chemical 29]

(Preparation of Support A) (1) Preparation of Dye Dispersion B for Undercoat Layer Dyes IV and V below were ball-milled by the method described in JP-A-63-197943.

[0136]

Embedded image

434 ml of water and Triton X-200 (Ro
791 ml of a 6.7% aqueous solution of Om and Haas Company) was placed in a 2 liter ball mill. 20 g of the dye were added to this solution. 400 ml of zirconium oxide (ZrO ₂ ) beads (2 mm diameter) were added and the contents were crushed for 4 days. Thereafter, 160 g of 12.5% gelatin was added.
After defoaming, the ZrO ₂ beads were removed by filtration.
Observing the obtained dye dispersion, the particle size of the crushed dye has a wide range of diameters from 0.05 to 1.15 μm, and the average particle size was 0.37 μm. Furthermore, dye particles having a size of 0.9 μm or more were removed by centrifugation. Thus, a dye dispersion B was obtained.

(2) Preparation of support Corona discharge was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and the coating amount of the first undercoating liquid having the following composition was 4.9 cc / m ^2. Thus, it was applied by a wire converter and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used is a dye-
The one containing 0.06 wt% of IV and 0.06 wt% of Dye-V was used.

* Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 cc * 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41 cc・ Distilled water 801 cc * The latex solution contains the following compounds as an emulsifying dispersant in an amount of 0.4 wt% of the latex solids.

[0140]

[Chemical 31]

(3) Coating of Undercoat Layer On the above-mentioned first undercoat layer on both sides, a second undercoat layer having the following composition is applied on each side so that the coating amount is as described below. To the wire bar coder method,
It was dried at 155 ° C.・ Gelatin 80 mg / m ²・ Dye dispersion B (as dye solid content) 8 mg / m ²・ Coating aid-VI 1.8 mg / m ²・ Compound-VIII 0.27 mg / m ²・ Mat agent Average particle size 2.5 μm polymethylmethacrylate 2.5 mg / m ²

[0142]

Embedded image

(Preparation of photographic material) The above-prepared support was combined with the above emulsion layer and surface protective layer and coated on both sides by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . In this way, coated samples 1 to 1
4 was produced.

(Evaluation of Photographic Performance) The photographic material was brought into close contact with both sides by using X Ray Orthoscreen HR-4 manufactured by Fuji Film Co., Ltd., and exposed for 0.05 seconds from both sides, and X Line sensitometry was performed. The adjustment of the exposure amount was performed by changing the distance between the X-ray tube and the cassette. After the exposure, the film was subjected to automatic developing machine processing using the following developing solution and fixing solution.

(Processing) Automatic developing machine: CEPROS manufactured by FUJIFILM Corporation
-30 Preparation of concentrated solution <Developer> Part agent A Potassium hydroxide 330 g Potassium sulfite 630 g Sodium sulfite 255 g Potassium carbonate 90 g Boric acid 45 g Diethylene glycol 180 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamine ) Ethyl-5-mercaptotetrazole 0.75 g Hydroquinone 450 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 60 g Water was added and 4125 ml

Part Agent B Diethylene glycol 525 g 3,3 ′ Dithiobishydrocinnamic acid 3 g Glacial acetic acid 102.6 g 2-Nitroindazole 3.75 g 1-Phenyl-3-pyrazolidone 34.5 g Water 750 ml

Parts agent C Glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 105 g Water 750 ml

<Fixer> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid / disodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N-diethylamine) -ethyl-5 -Mercaptotetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulfate 150 g Water 6000 ml pH 4.68

(Preparation of Treatment Solution) The above developer solution was filled in the following containers for each parts agent. In this container, the respective partial containers of the parts agents A, B, and C are connected together by the container itself. Further, the above fixing solution concentration was filled in the same kind of container. First, as a starter in the developing tank,
Aqueous solution 30 containing 54 g of acetic acid and 55.5 g of potassium bromide
0 ml was added. Insert the processing agent container upside down and insert it into the perforation blade of the processing liquid stock tank mounted on the side of the automatic processing machine, break the sealing film of the cap, and transfer each processing agent in the container to the stock tank. Filled. These processing agents were filled in the developing tank and fixing tank of the developing machine at the following ratios by operating the pumps installed in the developing machine. Also,
Every time the photosensitive material was processed into 8 pieces in terms of 4 slices, the processing solution stock solution and water were mixed at this ratio and replenished to the processing tank of the automatic processing machine.

Developer solution Part solution A 51 ml Part solution B 10 ml Part solution C 10 ml Water 125 ml pH 10.50 Fixer concentrate 80 ml Water 120 ml pH 4.62 The wash tank was filled with tap water.

As a water stain inhibitor, 0.4 g of actinomycetes supported on perlite having an average particle size of 100 μm and an average pore size of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300-mesh nylon cloth. Prepare three pieces filled with water and fungi from the cloth), two of them at the bottom of the washing tank, and one at the bottom of the stock tank for washing water (liquid volume 0.2 liters). I sunk each.

(Evaluation of natural aging) 50 ° C. 68% inside
The coated sample was placed in a closed container kept at 10 ° C. for 5 days (forced aging). This sample and a sample for comparison (stored in a light-shielding container at room temperature) were subjected to the same treatment as used for evaluation of photographic properties, and the density of the fog portion was measured. The natural aging property was evaluated as a fogging rate. (Increased fog rate) = [(Increased fog over time) /
{(Maximum density)-(support density)} × 100 The lower the fog rate, the better the natural aging property.

(Evaluation of Fixability) The photographic materials 1 to 14 were processed in the size of 4 pieces without exposure using the above processing liquid and an automatic developing machine. Whether or not the film could be fixed was evaluated by visually observing the processed film. The results are shown in Table 2.

[0154]

[Table 2]

The sensitivity is represented by the reciprocal of the exposure amount giving a density of Fog + 1.0, and the sensitivity of the photographic material 1 is 100. As shown in Table 2, it is understood that only the emulsion of the present invention is excellent in fog and sensitivity, stability with time, and fixability at the same time.

Example 2 The photographic materials 1 to 14 prepared in Example 1 were used as Du Pont.
Ultra Vision First Detail (UV)
X-ray sensitometry was carried out by making the film adhere to both sides using the above, exposing from both sides for 0.05 seconds. The adjustment of the exposure amount was performed by changing the distance between the X-ray tube and the cassette. After the exposure, automatic developing machine processing was performed with the following developing solution.

Preparation of Developer A Developer A Sodium sulfite 10.0 g Potassium carbonate 55.2 g Diethylene glycol 25.0 g Diethylenetriaminepentaacetic acid 2.0 g Sodium bromide 1.0 g 5-Methyl-benzotriazole 0.1 g 4-hydroxymethyl- 4-methyl-1-phenyl 6.6 g-3-pyrazolidone L-ascorbic acid 30.0 g

Water is added to make 1 liter, and the pH is adjusted to 10.3.

Developer solutions A, to which the respective compounds were added, were prepared as mother solution developers B, C, D, E, F, G, H, and
As J and K, the developing solutions shown in Table 3 were prepared. Further, as a starter, there were prepared those in which 7.4 g of potassium bromide and 7.2 g of acetic acid were added in correspondence with the developers A to K, respectively.

[0160]

[Table 3]

Using Fuji Medical Film Processor CEPROS-S, the film was processed for 10 m ² per day and each developer was run at a rate of 200 ml / m ² for 2 months while replenishing with the developer without starter added. I did a test. The development at this time was performed at 35 ° C. for 29 seconds, and the total processing time (Dry to Dry) was 100 seconds. The obtained results are shown in Table 4.

The sensitivities in the table are shown as relative values with the reciprocal of the exposure amount required to obtain a blackening density of 1.0 for the developer of the coated sample 1 being 100. The sensitivities for other developers were omitted because the relative relationship between the coated samples did not change. The silver stain was visually evaluated on the processed film and the developing tank of the automatic processor by running for 2 months. In this case, "1"
Indicates that a part of silver stains adheres to the film and corresponds to a failure. “3” indicates that there is no silver stain on the film, but there is silver stain on the bottom of the developing tank of the automatic processor, wall rack, etc. There is a risk of silver stains on the film when running for a period of time, and at this point it is necessary to wash the development tank and rack. "5" indicates that there is no silver stain on the bottom wall rack of the development tank and automatic development Machine cleaning tank, rack, etc. need not be washed
Visual evaluation was performed on a scale of 5 on a scale between "1" and "3" with "2" and "3" with "5".

[0163]

[Table 4]

As shown in the results of Table 4, compounds 11-1, 12-1, 13- of the conventionally known silver stain inhibitors were used.
Developers B, C, D, E containing 1, 14-1, 15-1
Although F improved the silver stain with respect to the developer A, it was insufficient. Among them, the developing solution B is a combination of the compound of Chemical formula 6 and a benzotriazole compound as in JP-A-58-169147, but the effect of preventing silver stain is insufficient. Surprisingly, in the case of the developers G, H, J, and K of the present invention in which the coating sample of the present invention was used in combination with the compound represented by the chemical formula 6 and any one of the compounds of the chemical formulas 7 to 10, silver stains were removed. It has improved significantly. By the way, developer G,
Since H, J, and K use two types of compounds together, the total is
Although the added amount is 1.0 mM, such an effect of preventing silver stain cannot be obtained even if the added amount is 1.0 mM alone as in the case of the developing solutions B, C, D, E and F. It is considered that the combined use of the compound of Chemical formula 6 and the compounds of Chemical formulas 7 to 10 effectively acted on the silver stain preventing effect which has not been conceivable until now by combining the coated sample of the present invention.

Although the liquid developer used is used in the above, similar results were obtained even when diluted with a compact concentrated liquid developer.

[0166]

According to the present invention, high sensitivity, low fog and excellent stability can be obtained, and fixing property and silver stain resistance can be improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 1/06 502 G03C 1/06 502 5/17 5/17 5/305 5/305 G21K 4 / 00 G21K 4/00 A

Claims (10)

[Claims] 1. A silver halide photographic emulsion having a Cl content of 20 mol% or more and 100 mol% or less, wherein 50% or more of the total projected area of silver halide grains in the emulsion has an aspect ratio (diameter). / Thickness) is a tabular grain having a grain size of 2 or more and 30 or less, and the silver halide emulsion is sensitized with gold chalcogen, and the distribution ratio of gold on the silver halide grain side is 10%. A silver halide photographic emulsion characterized in that it is at least 40%. 2. The silver halide photographic emulsion according to claim 1, wherein the tabular grains are tabular grains having a {100} plane as a main plane. 3. The silver halide photographic emulsion according to claim 1, wherein the gold chalcogen sensitization is gold selenium sensitization. 4. A silver halide photographic emulsion having a Cl content of 20 mol% or more and 100 mol% or less, wherein 50% or more of the total projected area of silver halide grains in the emulsion has an aspect ratio (diameter). / Thickness) is a tabular grain having a grain size of 2 or more and 30 or less. In the method for producing a silver halide photographic emulsion, the silver halide grain has a distribution ratio of 50% of gold on the silver halide grain side in the chemical sensitization step. A method for producing a silver halide photographic emulsion, characterized in that the distribution ratio of gold on the silver halide grain side is made 10% or more and less than 40% by adding a compound which forms a complex with gold after the above. 5. The method for producing a silver halide photographic emulsion according to claim 4, wherein the compound that forms a complex with gold is a compound having a stability constant of a complex salt with gold of 28 or more and 39 or less. . 6. The method for producing a silver halide photographic emulsion according to claim 4, wherein the compound that forms a complex with gold is a sulfite. 7. A silver halide photographic emulsion according to any one of claims 1 to 3 or a silver halide photographic emulsion manufactured by the method according to any one of claims 4 to 6 on a support. A silver halide photographic light-sensitive material having at least one layer of 8. The support according to claim 1, which is provided on both sides of the support.
7. A silver halide photographic emulsion according to claim 4 or 6.
A silver halide photographic light-sensitive material comprising at least one layer of a silver halide photographic emulsion produced by the production method described in any one of the above. 9. The silver halide photographic light-sensitive material according to claim 8, which is used in combination with a fluorescent intensifying screen that emits light having a peak at 400 nm or less by X-ray exposure. 10. (a) a developing agent, (b) represented by the following chemical formula 1.
Compound and (c) the following chemical formula 2, chemical formula 3, chemical formula 4 and chemical formula 5
Containing at least one compound selected from
A silver halide photograph according to claim 7 or 8 with a developing solution
Silver halide photography characterized by developing material
Method of processing photosensitive material. [Chemical 1][Chemical 2][Chemical 3]Embedded imageEmbedded image(In chemical formula 1, R₁Is hydrogen atom, alkyl having 1 to 6 carbon atoms
A group or an alkyl group having 1 to 6 carbon atoms.
Minoalkyl group, dialkylaminoalkyl group or
Represents a carboxyalkyl group. R in chemical formula 2₂And R
_ThreeEach represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
You. Where R₂And R_ThreeDoes not become a hydrogen atom at the same time
Yes. R_FourAnd R_FiveAre each a hydrogen atom or 1 to 3 carbon atoms
Represents an alkyl group of₆Is hydroxyl group, amino group or charcoal
It represents an alkyl group having a prime number of 1 to 3. R₇And R₈Are each
Hydrogen atom, C1-C5 alkyl group, C18 or less
Acyl group or --COOM_TenRepresents a group. Where M_TenIs water
Elementary atoms, alkyl groups having 1 to 4 carbon atoms, alkali metal raw materials
Child, aryl group or alkyl group having 15 or less carbon atoms
You. Where R₇And R₈Cannot become hydrogen atoms at the same time
Yes. M₁Is a hydrogen atom, an alkali metal atom or ammonium
Represents an um group. k is 0, 1 or 2. X in chemical formula 3
Is a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkyl
Coxy group, halogen atom, carboxyl group or sulfo group
Represents a group. M₂And M_ThreeAre the same or different
Also, hydrogen atom, alkali metal atom or ammonium
Represents a group. D4₁And B₁Are independent of each other
And each represents an alkylene group. E₂And A₂Are each other
Independently, -COOM, -SO₂M, -OM, -SZ, -SO₂N
(X₁) (Y ₁) Or −CO (X₁) (Y₁). Where M is 1
Represents the cation of. X₁And Y₁Is a hydrogen atom,
Substituted by droxy group, sulfonic acid or carboxylic acid
Alkyl group or phenyl group which may be
Sulfo which may be substituted by a kill group or phenyl group
Represents a nyl group. Z is X₁, Y₁Has the same meaning as, but hydrogen
It cannot be an atom. p is 1-2, m and n are each
It is an integer of 1 to 3. R in chemical formula 5₉And R_TenEach is water
Elementary atom, alkyl group, aryl group, aralkyl group, hydr
Roxy group, mercapto group, carboxy group, sulfo group,
Suphono group, amino group, nitro group, cyano group, halogen source
Child, alkoxy group, alkoxycarbonyl group, aryl
Oxycarbonyl group, carbamoyl group, sulfamoyl
Represents a group or a heterocyclic group. Also R₉And R_TenAre connected to each other
They may be joined to form a ring. )