JPH06175260A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photographic sensitive material which deals with rapid processability, has excellent stability with lapse of time in spite of gold sensitization processing and features a high sensitivity and low fogging by adding silver halide particulates added with a gold compd. into the photographic sensitive material before the end of a chemical maturation stage. CONSTITUTION:The silver halide particulates added with the gold compd. are added to the photographic sensitive material before the end of the chemical maturation stage. The silver halide particles in the silver halide emulsion may be normal crystal particles, i.e., cubes, octahedrons and 14-faced bodies which are all isotropically grown or a polyhedral crystal type, such as spherical shape or particles consisting of twins having face defects or a mixed type or composite type thereof. Flat planar silver halide particles are more preferably used. While the timing for addition of the silver halide particulates may be any stage from the chemical maturation stage to just before the application and the addition in the chemical maturation stage is more preferable. Chalcogen sensitization and gold sensitization are preferably used in combination for the silver halide emulsion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which has been subjected to a gold sensitization treatment and has high sensitivity, low fog and excellent stability over time.

[0002]

2. Description of the Related Art In recent years, rapid processing has been rapidly progressing in silver halide photographic light-sensitive materials, and therefore, rapid processing has been improved by reducing the amount of silver and resource saving has been attempted. At present, there is a demand for higher sensitivity of silver halide photographic light-sensitive materials.

As one method of increasing the sensitivity of a silver halide photographic light-sensitive material, a method of adding a gold salt during chemical ripening of an emulsion is well known and is called a gold sensitization method.

Usually, sulfur sensitization is required to increase the sensitivity and contrast of silver halide photographic light-sensitive materials.
It is common to carry out reduction sensitization and the above-mentioned noble metal sensitization method using gold or the like. Of these, the noble metal sensitization method alone has low sensitization and is apt to cause fog, but it is well known that when sulfur sensitization is used together, fog is reduced and a superadditive increase in sensitivity is obtained.

On the other hand, it is known that gold ions interact with gelatin, which is the main protective colloid of silver halide emulsions, and they form a gold-gelatin complex to suppress the sensitizing effect and are the main cause of fog. It is said to be one of the causes.
Further, when the gold sensitization, the sulfur sensitization, and the reduction sensitization are performed in combination due to the effect of the gold ion (or gold atom) as described above, the sensitivity becomes extremely high, but fog occurs over time. It has a drawback that it is easy and its stability with time is significantly deteriorated.

As for the halogen composition of the silver halide photographic light-sensitive material, when the content of silver chloride is increased, the water solubility of the silver halide grains is increased, and as a result, the development and fixing processes can be accomplished in a shorter time. A photographic light-sensitive material suitable for rapid processing can be obtained by using a silver halide emulsion consisting of solid solution particles with silver.

However, for example, in the case of a high-sensitivity silver iodochlorobromide emulsion having a relatively high silver chloride content, although the developing speed becomes fast, fog is apt to occur in general, and the gold sensitization method is particularly applied. In this case, the silver iodochlorobromide emulsion has a problem that it is difficult to perform the gold sensitization treatment. Further, a core provided with a shell layer having a relatively high silver chloride content /
Even when the shell type silver iodochlorobromide emulsion was subjected to the gold sensitization treatment, fog frequently occurred over time, and there was a problem in storage stability.

For this reason, various additives have been tried to suppress fog, but they have impaired the performance of the light-sensitive material such as a decrease in sensitivity and a deterioration in developability.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a photographic light-sensitive material capable of rapid processing, which has excellent stability over time even when subjected to a gold sensitization treatment, and has high sensitivity and low fog. A silver halide photographic light-sensitive material is provided.

[0010]

The above objects of the present invention are as follows.
It has been solved by the present invention described below. That is, the silver halide photographic light-sensitive material is characterized in that fine silver halide grains to which a gold compound is added are added before the end of the chemical ripening step.

The present invention will be described in detail below.

The silver halide grains in the silver halide emulsion according to the present invention are regular crystal grains, that is, all isotropically grown grains such as cubes, octahedrons and tetrahedrons, or polyhedral grains such as spheres. Although it may be a conventional crystal type, a twin crystal having a plane defect, or a mixed type or a complex type thereof, tabular silver halide grains are preferably used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No.17643 (December 1978), 22
Can be prepared by the method described in "Emulsion Preparation and Types" on page 23 or the method described in (RD) No. 18716 (November 1979), page 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is, for example, "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Published by Paul Montel (1967) or VL Zelikman et al. “Makin
g And Coting Photographic Emulsion "Focal Press, Inc. (1964).

That is, the mixing conditions such as the forward mixing method, the reverse mixing method, the double jet method and the control double jet method under the solution conditions such as the acidic method, the ammonia method and the neutral method,
It can be produced using a particle preparation condition such as a conversion method, a core / shell method, or a combination thereof.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

The silver halide emulsions preferably used in the present invention are, for example, JP-A-59-177535 and 61-802237.
No. 61-132943, No. 63-49751, and the like, high internal iodine type monodisperse particles are disclosed. Crystal habits are cubic, octahedron, tetrahedron and {111} faces and {10} in the middle.
The 0} planes may be mixed arbitrarily.

The term "monodisperse" as used herein means that when the average particle diameter is measured by a conventional method, the number of particles or the weight is at least 95.
% Particles are within ± 40% of average particle size, preferably ± 30%
It is within the range of silver halide grains. The monodispersity referred to here is defined in JP-A-60-162244, and the coefficient of variation with respect to particle diameter is 0.20 or less.

The crystal structure of silver halide may be composed of different silver halide compositions inside and outside. That is, it has a core / shell structure composed of a core and at least one shell having different halogen compositions. The silver iodide content in the high iodine portion is 20 to 40 mol%, particularly preferably 20 to 30 mol%.

A method for producing such a monodisperse emulsion is well known, for example, J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890.
Nos. 52-16364, 55-142329, 58-49938, British Patent 1,413,748, U.S. Patents 3,574,628, 3,655,39.
It is described in detail in No. 4 etc.

As a method for obtaining the above monodisperse emulsion, an emulsion obtained by using, for example, a seed crystal and supplying silver ions and halide ions as growth nuclei to grow the seed crystal is particularly preferable.

A method for producing a core / shell type emulsion is well known, for example, British Patent No. 1,027,146 and US Pat. No. 3,505,068.
No. 4,444,877 or JP-A-60-143331 can be referred to.

The silver halide photographic light-sensitive material of the present invention comprises
Tabular grains having an aspect ratio (ratio of grain size / grain thickness) of 2 or more are preferably used.

The average grain size of tabular silver halide grains is 0.3
˜3.0 μm is preferable, and 0.5 to 1.5 μm is particularly preferable.

The tabular silver halide emulsion according to the present invention comprises
The average value of particle diameter / thickness (called aspect ratio) (called average aspect ratio) is 2.0 or more, preferably 2.0
˜20.0, particularly preferably 2.0 to 10.0.

The average thickness of the tabular silver halide emulsion according to the present invention is preferably 1.0 μm or less, particularly preferably 0.5 μm.
Or less, and more preferably 0.3 μm or less.

The advantages of such tabular silver halide grains are:
As an improvement in spectral sensitization efficiency, improvement of image graininess and sharpness, etc. are obtained, for example, British Patent 2,112,157, U.S. Patents 4,439,520, 4,433,048, 4,414,310,
No. 4,434,226 and the like, and the emulsion can be prepared by the methods described in these specifications.

In the present invention, the diameter of a tabular silver halide grain is defined as the diameter of a circle having an area equal to the projected area of the grain from the observation of an electron micrograph of the silver halide grain.

In the present invention, the thickness of the tabular silver halide grain is defined as the minimum distance between the two parallel planes constituting the tabular silver halide grain.

The thickness of tabular silver halide grains can be determined from electron micrographs of silver halide grains with shadows or electron micrographs of sample slices obtained by coating a support with a silver halide emulsion and drying. .

To obtain the average aspect ratio, the minimum
Measure 100 samples.

In the silver halide emulsion of the present invention, the proportion of tabular silver halide grains in all silver halide grains is 50% or more, preferably 60% or more, particularly preferably 70% or more.

The tabular silver halide emulsion according to the present invention is preferably monodisperse, and the fact that it is monodisperse means that the variation coefficient of grain size (standard deviation of grain size / average grain size × 10 6).
0) is 25% or less, preferably 20% or less, particularly preferably 15% or less.

The silver halide emulsion according to the present invention may have any halogen composition such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide, but has high sensitivity. From this point of view, silver iodobromide is preferred, and the average silver iodide content is 0.1 to 4.0 mol%, particularly preferably 0.5 to 3.0 mol%. Further, silver chloroiodobromide is preferable from the viewpoint of rapid processability.

The silver chloride may be contained at any site in the grain, but it is particularly preferred that the silver chloride is unevenly distributed in the shell of the outermost layer. The average silver chloride content of the shell of the outermost layer is 0.3 mol% or more, preferably 1 to 60 mol%, particularly preferably 5 to 40 mol%.

In the tabular silver halide emulsion according to the present invention, the halogen composition may be uniform within the grain, or silver iodide may be localized, but it is localized in the central portion. The existing one is preferably used. A method for producing a tabular silver halide emulsion is described in JP-A Nos. 58-113926 and 58-113927.
No. 58-113934, No. 62-1855, European Patent 219,
You can also refer to 849 and 219,850. or,
As a method for producing a monodisperse tabular silver halide emulsion,
Reference can be made to JP-A-61-6643.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, a silver nitrate aqueous solution is added to a gelatin aqueous solution whose pBr is kept at 2 or less, or a silver nitrate aqueous solution and a halide aqueous solution are simultaneously added. To generate twin seed particles and then grow by the double jet method. The size of tabular silver halide grains can be controlled by the temperature at the time of grain formation and the addition rate of silver salt and halide aqueous solution.

The average silver iodide content and average silver chloride content of the silver halide emulsion according to the present invention (hereinafter referred to as parent grain emulsion) are the compositions of the aqueous halide solution to be added, that is, bromide, iodide and chloride. It can be controlled by changing the ratio of. In addition, a silver halide solvent such as ammonia, thioether or thiourea can be used, if necessary, during the production of the parent grains.

The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts (desalting treatment step). As a preferable washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or aggregating polymer agent exemplified G3, G8 described in JP-A-63-158644, etc. The method used is mentioned as a particularly preferable desalting method.

The parent grain emulsion of the present invention is chemically ripened.

The chemical ripening temperature of the parent grain emulsion according to the present invention is arbitrarily determined, but is preferably in the range of 20 ° C to 90 ° C, preferably 30 ° C to 80 ° C, more preferably 35 ° C to 70 ° C.
℃.

The silver halide emulsion of the present invention is preferably combined with chalcogen sensitization and gold sensitization as sensitizing methods.
Particularly, the combined use of gold sensitization and sulfur sensitization is preferable because not only the sensitizing effect is remarkable but also the fog suppressing effect is obtained.

For sulfur sensitization, examples of sensitizers include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like. Other U.S. Patents 1,574,944
No. 3,656,955, German Patent 1,422,869, Japanese Patent Sho 56
The sulfur sensitizers described in JP-A-24937 and JP-A-55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount can be varied over a wide range under various conditions such as pH, temperature and size of silver halide grains, but as a standard, it is 5 × 10 ^-8 per mol of silver halide of the parent grain emulsion according to the present invention.
~ 5 x 10 ^-5 mol is preferred.

For gold sensitization, gold sensitizers such as chloroauric acid salt, gold thiourea complex, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauramide, ammonium auro are used. Examples thereof include thiocyanate and pyridyl trichlorogold. The addition amount of these gold sensitizers can be varied over a wide range under various conditions, but as a guide, it is preferably 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol per mol of the silver halide of the parent grain emulsion of the present invention, 2 x 10 ^-6 ~
4 × 10 ⁻⁴ mol is more preferable.

For sulfur sensitization, sensitizers such as thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine can be used. Other U.S. Patents 1,574,944
No. 3,656,955, German Patent 1,422,869, Japanese Patent Sho 56
The sulfur sensitizers described in JP-A-24937 and JP-A-55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount can be varied over a wide range under various conditions such as pH, temperature, size of silver halide grains, and as a guide, it is 5 × 10 ^-8 per mol of silver halide in the parent grain emulsion according to the present invention.
~ 5 x 10 ^-5 mol is preferred.

For gold sensitization, gold sensitizers such as chloroauric acid salts, gold thiourea complex salts, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric amide, ammonium auro are used. Examples thereof include thiocyanate and pyridyl trichlorogold. The addition amount of these gold sensitizers can be varied over a wide range under various conditions, but as a guide, it is preferably 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol per mol of silver halide in the parent grain emulsion of the present invention. 2 x 10 ^-6
More preferably, it is 4 × 10 ^-4 mol.

In the present invention, gold sensitization is performed by adding a gold compound, that is, a silver halide fine grain emulsion to which a gold sensitizer has been added, before the chemical ripening step of the parent grain emulsion according to the present invention. preferable.

When the gold compound is added to the silver halide fine grains, the temperature at the time of addition depends on the kind of the gold compound and is 20 ° C to
80 ° C is preferable, and 30 ° C to 50 ° C is particularly preferable. pH is 2.0
〜 11.2 is preferable, and 4.0 to 9.0 is particularly preferable. pAg is 5.
0 to 11.0 is preferable, and 7.0 to 9.5 is particularly preferable.

When the gold compound is added, it is preferable that the fine grain emulsion is kept under stirring for a certain period of time (for example, 1 minute to 120 minutes) depending on the kind of the gold compound to be added.

The gold compound may have a valence of +1 or +3, but a gold compound having +1 valence gold is preferable. Further, the addition of the gold compound to the halogenated fine particles is preferably performed in the presence of a silver halide solvent.

The silver halide solvent that can be used in the present invention includes US Pat. Nos. 3,271,157 and 3,531,289,
No. 3,574,628, organic thioethers described in JP-A-54-1019, 54-158917, etc., JP-A-53-82408,
Nos. 55-77737 and 55-2982, thiourea derivatives, and halogenated compounds having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. Examples thereof include silver solvents, imidazoles described in JP-A-54-100717, sulfites, thiocyanates and the like.

Particularly preferred solvents include thiocyanate and tetramethylthiourea. The amount of the solvent added to the fine silver halide grains depends on the kind of the solvent, but is preferably 5 × 10 ^{−7 to} 5 × 10 ⁻² mol per mol of silver.

In the present invention, gold sensitization is carried out by a method of adding a gold compound to the silver halide fine grain emulsion of the present invention and adding it to a parent grain emulsion, and a conventional gold sensitization method, for example, an aqueous solution of a gold sensitizer. May be used in combination with the method of directly adding to the emulsion.

Examples of the silver halide fine grains according to the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodochloride, silver iodobromide and silver chloroiodobromide. Of these, silver bromide and silver iodide are preferred. The grain size of these silver halide fine grains is preferably 0.12 μm or less, more preferably 0.09 μm or less, and particularly preferably 0.06 μm or less.

When silver iodide fine grains are used in the present invention, cubic silver γ-AgI and hexagonal β-type AgI are generally known for silver iodide. It may be present or a mixture thereof.

In the present invention, when fine particles such as AgBr ₉₀ I ₁₀ containing silver bromide, silver chloride or a solid solution mainly containing these rock salt structures are used, these fine particles have substantially no twin planes. A so-called normal crystal or a single twin crystal having one twin plane is preferable. The silver halide fine grains used in the present invention preferably have good monodispersibility and are preferably adjusted by the double jet method while suppressing temperature, pH and pAg.

The addition amount of fine silver halide grains is preferably 1/100 dmol or less per 1 mol of the parent grain emulsion, and more preferably 1 mol of the parent grain emulsion, when the average grain size of the parent grain emulsion is d (μm). It is preferably in the range of 1 / 20,000 d to 1/300 d mol, and most preferably 1/5000 d to 1/500 d mol per 1 mol of the parent grain emulsion.

The silver halide fine grains in the present invention may be added at any step from the chemical ripening step to immediately before coating, but it is preferably added in the chemical ripening step. The term "chemical ripening step" as used herein means a period from after the grain formation of the parent grain emulsion and from the time when the desalting operation is completed to the time when the chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Point to. As a method of ending the chemical ripening step, a method of lowering the temperature, a method of lowering the pH, a method of using a chemical ripening stopper, etc. are known, but a chemical ripening stopper is used in consideration of the stability of the emulsion. The method is preferred. Examples of the chemical aging inhibitor include halides (eg potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (eg 4-hydroxy-6-methyl-1,3,3a, 7-Tetrazaindene, etc.) is known. These are used alone or in combination of a plurality of compounds.

Further, as described above, the addition of silver halide fine grains may be carried out in several times at intervals, or after the addition of silver halide fine grains, another chemically ripened emulsion is added. May be.

The temperature of the parent grain emulsion when adding the silver halide grains is preferably in the range of 30 to 80 ° C., more preferably 40 ° C.
A range of up to 65 ° C is particularly preferred.

Further, the present invention is preferably carried out under the condition that after the addition of the silver halide fine grains to be added and immediately before the coating, a part or all of the fine silver halide fine grains are added, and more preferable conditions are the added silver halide fine grains. 20% or more of the above has disappeared just before coating.

The amount of disappearance is quantified by centrifuging the emulsion or coating solution after the addition of silver halide fine particles under appropriate conditions, and then measuring the absorption spectrum of the supernatant to obtain silver halide fine particles of known concentration. It can be performed by comparing with the absorption spectrum of. In the present invention, reduction sensitization and hydrogen sensitization methods can be used. As the reduction sensitizer, stannous salt, amines, formamine disulfinic acid, silane compound, borane compound, ascorbic acid and its derivatives can be used.

The addition amount of the reduction sensitizer depends on the reducing property of the compound,
Although not uniform depending on the type of silver halide and the dissolution conditions, the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol per mol of silver halide is suitable. The reduction sensitizer is added after being dissolved in water or a solvent such as alcohol, glycol, ketone, ester, amide and the like. The reduction sensitization is preferably performed at the time of silver halide grain formation. The term "during grain formation" means any one of a nucleation step, a ripening step, and a growth step.

As a method of performing reduction sensitization at the time of grain formation, a method of forming a silver halide grain by adding a water-soluble silver salt and an aqueous halide solution, and adding a reduction sensitizer to the aqueous halide solution in advance. Or a method in which the reduction sensitizer is added in a state where the growth is temporarily stopped and then further grown, and a method in which the reduction sensitizer is added in several times as the particles grow. . In addition to the known method of using a reduction sensitizer, a method of growing or aging in an atmosphere of pH so-called silver ripening, a method of growing or aging in an atmosphere of high pH, for example, pH 8 to 11, should be selected. It is also possible to use these in combination.

Further, selenium sensitization is preferably used in the present invention. In particular, it is preferable to use it in combination with the above-mentioned other sensitizing method.

Here, the selenium sensitization is carried out by a conventionally known method. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is carried out by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Selenium sensitization using the unstable selenium sensitizer described in JP-B-44-15748 is preferably used.
Specific examples of unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, and selenophosphates. Particularly preferred unstable selenium compounds are shown below.

Colloidal Metal Selenium Organic Selenium Compound (Selenium Atom Double Bonded to Carbon Atom of Organic Compound by Covalent Bond) a. Isoselenocyanates Aliphatic isoselenocyanates such as allyl isoselenocyanates b. Selenoureas (including enol type) For example, selenoureas, and methyl, ethyl, propyl,
Isopropyl, butyl, hexyl, octyl, dioctyl, tetramethyl, N- (βcarboxyethyl) -N, N'-
Aliphatic selenoureas such as dimethyl, N, N-dimethyl, diethyl, dimethyl, etc .; Aromatic selenoureas having one or more aromatic groups such as phenyl, tolyl, etc .; Heterocycles having heterocyclic groups such as pyridyl, benzothiazolyl, etc. Cyclic selenoureas.

Particularly preferred selenoureas are N, N′-
It is a 4-substituted selenourea. Preferred substituents are R, RC
O-, ArCO-, R is an alkyl group or a perfluoroalkyl group (C number of 1 to 7 is preferable),
Ar is halogen or a phenyl group which may be substituted with a lower alkoxy group.

C. Selenoketones, for example, selenoacetone, selenoacetophenone, selenoketone having an alkyl group bonded to = C = Se, selenobenzophenone, d. Selenoamides For example, selenoamide e. Selenocarboxylic acids and esters For example, 2-selenopropionic acid, 3-selenobutyric acid, methyl
-3-Selenobutyrate Other a. Selenides For example, diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide b. Selenophosphates For example, preferred types of tri-p-triselenophosphate, tri-n-butylselenophosphate labile selenium compounds are mentioned above, but these are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, such a broad concept of unstable selenium compounds is advantageously used.

Selenium sensitization using the non-labile selenium sensitizers described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491 can also be used. Examples of the non-labile selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles,
Diaryl selenide, diaryl diselenide, 2-thioselenazolidinedione, 2-selenooxazolidinedione and derivatives thereof are included.

The non-labile selenium sensitizer and thioselenazolidinedione compound described in JP-B-52-38408 are also effective.

These selenium sensitizers are dissolved in water or an organic solvent such as methanol and ethanol alone or in a mixed solvent and added at the time of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. A combination of an unstable selenium compound and a non-unstable selenium compound is preferred.

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, etc.
The amount is preferably 1 × 10 ⁻⁸ mol or more per mol of the parent grain emulsion. It is more preferably 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁵ mol or less.

Selenium sensitization is more effective when carried out in the presence of the same silver halide solvent as described above.

Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 × per mol of silver halide.
It is 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less.

The chemical ripening temperature of the emulsion according to the present invention is arbitrarily determined, but it is preferably in the range of 20 to 90 ° C, preferably 30 to 80 ° C, and more preferably 35 to 70 ° C.

Especially when a selenium sensitizer is used, the temperature is preferably 45 ° C. or higher.

The parent particle of the present invention may contain a Group VIII metal of the periodic table.

In order to contain the Group VIII metal of the Periodic Table in the parent particle, it is usually sufficient that it is present as the metal compound at the time of forming the parent particle, and it is added by rush addition, continuous addition or divided addition in several times. May be.

Further, a method is preferred in which it is added to a water-soluble silver salt and / or a water-soluble halide solution in advance and the silver halide grains are precipitated using these aqueous solutions.

Compounds of Group VIII metals of the Periodic Table are iron,
Iridium, platinum, palladium, nickel, rhodium,
Refers to metal compounds derived from osmium, ruthenium and cobalt. Of course, not only these metal compounds but also metal ions and metal atoms thereof may be contained in the parent particle according to the present invention. One example of the Group VIII metal compound of the periodic table is shown below.

Ferrous arsenate, ferrous bromide, ferrous carbonate, ferrous chloride, ferrous citrate, ferrous fluoride, ferrous formate, ferrous gluconate, water Ferrous oxide, ferrous iodide, ferrous lactate, ferrous oxalate, ferrous phosphate, ferrous succinate, ferrous sulfate, ferrous thiocyanate, ferrous nitrate,
Ferrous ammonium nitrate, basic ferric acetate, ferric albuminate, ferric ammonium acetate, ferric bromide, ferric chloride, ferric chromate, ferric citrate, fluorinated Ferric iron, ferric formate, glycero-ferric phosphate, ferric hydroxide, ferric acid phosphate, ferric nitrate, ferric phosphate,
Ferric pyrophosphate, sodium ferric pyrophosphate, ferric thiocyanate, ferric sulfate, ferric ammonium sulfate, ferric guanidine sulfate, ferric ammonium citrate, hexacyanoferrate (II) Sodium, potassium hexacyanoferrate (II), potassium pentacyanoammine ferrous, sodium ferric ethylenedinitrilotetraacetate, potassium hexacyanoferrate (III), ferric tris (dipyridyl) chloride, pentacyanonitrosyl ferric Iron potassium,
Ferric hexaurea chloride, ferric iridium chloride (II
I), first iridium (III) bromide, second iridium chloride (IV), sodium hexachloroiridium (III), hexaammineiridium (III) salt, hexaammineiridium (IV) salt, trioxalatoiridium (III) ) Salt, trioxalatoiridium (IV) salt, platinum (IV) chloride, potassium hexachloroplatinate (IV), sodium hexachloroplatinate (IV), ammonium hexachloroplatinate (IV), tetrachloroplatinate (II) acid, Tetrabromoplatinum (II) acid, sodium tetrakis (thiocyanato) platinum (VI), hexaammineplatinum (I
V) chloride, sodium tetrachloropalladium (II) acid, sodium tetrachloropalladium (IV) acid,
Hexachloropalladium (IV) acid potassium, tetraamminepalladium (II) chloride, potassium tetracyanopalladium (II) acid, nickel chloride, nickel bromide,
Potassium tetrachloronickel (II), hexaamminenickel (II) chloride, sodium tetracyanonickel (II), potassium hexachlororhodate, sodium hexachlororhodate, sodium hexabromorhodate, ammonium hexachlororhodate, etc. .

These compounds are preferably dissolved in water or a suitable solvent and added at the time of silver halide grain formation or after the completion of the formation process and before the desalting step. Alkali (KCI, NaCI, KBr, NaBr
Etc.) may be added to the aqueous solution.

The addition amount of the compound of Group VIII metal of the periodic table is 1 × 10 ⁻¹⁰ per mol of the finally formed parent particles.
It may be in the range of 1 × 10 ⁻² mol, preferably 1 × 10 ⁻⁸ to 1
× 10 ⁻⁵ mol.

The parent grain emulsion of the present invention is preferably spectrally sensitized before use.

As the spectral sensitizing dye used in the present invention, a methine dye is usually used.
It includes merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Examples thereof include oxacarbocyanine, benzimidazolocarbocyanine, and benzimidazolo-oxacarbocyanine as described in Japanese Patent Application No. 3-95310. In addition, JP-A-59-119344 and JP-A-4-2
A dye having a sensitizing effect in the blue light range described in No. 34031 is also preferably used. These spectral sensitizing dyes
Each can be used alone or in combination.

The spectral sensitizing dye is preferably added as a solution dissolved in an organic solvent such as methanol.

The amount of the spectral sensitizing dye added is not uniform depending on the type of dye and the emulsion conditions, but is preferably 10 mg to 900 mg, and particularly preferably 60 mg to 400 mg per mol of silver in the parent grain emulsion.

The spectral sensitizing dye is preferably added before the end of the chemical ripening step, and may be added in several batches before the end of the chemical ripening step. More preferably, after the completion of the parent grain growth step and before the completion of the chemical ripening step, the chemical ripening is preferably started.

In the emulsion according to the present invention, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978),
No. 18716 (November 1979) and No. 308119 (December 1989)
Month). The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Examples of the support that can be used in the light-sensitive material of the present invention include RD-17643, page 28 and RD-308119, 100.
Examples include those described on page 9.

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

[0094]

EXAMPLES Examples of the present invention will be described below. However, as a matter of course, the present invention is not limited to the examples described below.

Example 1 (Preparation of silver iodide fine particles (a)) 5000 ml of a 5.2% by weight gelatin solution containing 0.008 mol of potassium iodide, and 1500 ml of an aqueous solution containing 1.06 mol of silver nitrate and potassium iodide were constantly distributed. Over 35 minutes. Temperature during particle preparation is 40
Kept at ℃. When the obtained silver iodide fine grains were confirmed by an electron micrograph at a magnification of 60,000, the average grain size was 0.05 μm.
It was a mixture of β-AgI and γ-AgI at m.

(Preparation of silver iodide fine particles (b)) While maintaining 1 mol of silver iodide fine particles (a) at 40 ° C., the silver potential was adjusted to −80 mV with an aqueous solution of silver nitrate, and then ammonium thiocyanate was added. 42.1 g and 830 mg of chloroauric acid were added, and the mixture was stirred for a certain period of time to prepare silver iodide fine particles (b).

(Preparation of silver iodide fine particles (c)) Silver iodide fine particles (b) except that a gold thiourea complex (Au (NH ₂ CSNH ₂ ) ₂ ⁺ ) was added in an equivalent mole instead of chloroauric acid. Fine silver iodide grains (c) were prepared in the same manner as in (1).

(Preparation of silver bromide fine particles (d)) 9664 ml of a 11.0% by weight gelatin solution containing 0.12 mol of potassium bromide was added.
The pH was adjusted to 3.2 while stirring at 30 ° C, and then 4036 ml of 3.5 N silver nitrate aqueous solution and 4000 ml of potassium bromide aqueous solution were constantly flowed by the double jet method, and the silver solution was 28 minutes later than the KBr solution. Add to completion (silver solution for 12 minutes). After the addition was completed, the pH was adjusted to 5.8 and the pH was adjusted to 8.9, and the mixture was cooled.
Fine silver bromide particles (d) were obtained. The average particle size of these fine particles is 0.
It was 07 μm.

(Preparation of silver bromide fine particles (e)) After preparing silver bromide fine particles (d) at 41 ° C. while stirring, ammonium thiocyanate (40.0 g) and chloroauric acid (800 mg) were added, and the mixture was stirred for about 20 minutes. After cooling, silver bromide fine particles (e) were obtained.

(Preparation of silver bromide fine particles (f)) Silver bromide fine particles (e) except that gold thiourea complex (Au (NH ₂ CSNH ₂ ) ₂ ⁺ ) was added in an equivalent mole instead of chloroauric acid. ), And silver bromide fine particles (f) were obtained.

(Preparation of seed emulsion) The following solutions were prepared.

A ₁ liquid Water 11.5l Potassium bromide 2.05g Ocein gelatin 100g B ₁ liquid Water 2.6l Potassium bromide 65g Potassium iodide 1.8g Ocein gelatin 55g 0.2N sulfuric acid 38.5cc C ₁ liquid Water 3.0l Bromide and kept at 60 ° C. put a ₁ solution of potassium 950g potassium iodide 27g ossein gelatin 75 g D ₁ liquid water 2.7l silver nitrate 95 g E ₁ solution water 3.2l silver nitrate 1410g kettle, other liquid was added at 19 ° C. . At this time, solution B _{1 and} solution D ₁ were added by the control double jet method over 30 minutes, and then C
Solution _{1 and} solution E ₁ are controlled by the control double jet method.
Add over 5 minutes. The stirring was performed at 500 rpm. The flow velocity is increased in proportion to the total surface area of the silver halide grains as the grains grow, new growth nuclei do not occur when the additive liquid flows in, and so-called Ostwald ripening occurs, resulting in a grain size distribution. Was added at a flow rate that did not spread. When the silver ionic liquid and the halide ionic liquid were added, the pAg was adjusted to 8.3 ± 0.05 using potassium bromide liquid, and the pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the completion of the addition, the pH was adjusted to 6.0, and then desalting treatment was carried out by the method described in JP-B-35-16086 in order to remove excess salts.

The resulting emulsion had a grain size of 0.27 μm, {111}
The tetrahedral monodisperse grains were in the shape of a cube having 5% of the plane and the other of which were composed of {100} planes and the corners were slightly chipped and the silver iodide content was 2 mol%. This seed emulsion is designated as Em-1.

(Preparation of Parent Particle Emulsion EM-1) First, the following solutions were prepared. All amounts are given per mol of silver halide.

F ₁ solution (reaction mother liquor) Gelatin 10 g Concentrated ammonia water 28 ml Glacial acetic acid 3 ml Water 600 ml G ₁ solution Potassium bromide 5 g Potassium iodide 3 g Gelatin 0.8 g Water 110 ml H ₁ solution Potassium bromide 72 g Sodium chloride 8.84 g Gelatin 2.0g Water 240ml I ₁ solution (0.75N) AgNO ₃ 9.9g NH ₄ OH 7.0ml Water 110ml J ₁ solution AgNO ₃ 130g NH ₄ OH 100ml Water 240ml K ₁ solution Potassium bromide 94g Water 165ml L ₁ Liquid AgNo ₃ 9.9 g NH ₄ OH 7.0 ml Water 110 ml M ₁ liquid Sodium chloride 6.2 g Water 40.0 ml F ₁ liquid was kept at 42 ° C and stirred at 800 rpm with a stirrer.
The pH of the F ₁ solution was adjusted to 9.90 with acetic acid, and the seed emulsion was added to this.
Em-1 was sampled in an amount of 0.119 mol per mol of silver halide and dispersed and suspended. Then, the L ₁ solution was added at a constant rate over 7 minutes to adjust the pAg to 7.3. Further, solution G _{1 and} solution I ₁ were simultaneously added over 20 minutes. At this time, pAg was fixed at 7.30. Furthermore, after adjusting the pH to 8.83 and the pH to 8.8 with potassium bromide solution and acetic acid over 10 minutes, M ₁ solution was added to 2
The solution was added over a period of 30 minutes, and the H ₁ solution and the J ₁ solution were simultaneously added over 30 minutes. At this time, the inflow rate ratio at the start of addition and the end of addition was 1:10, and the flow rate was increased with time. Moreover, the pH was decreased from 8.83 to 8.00 in proportion to the inflow. When the H ₁ solution and the J ₁ solution were added by 2/3 of the total amount, the K ₁ solution was additionally injected and added at a constant rate over 8 minutes. At this time, pAg rose from 9.0 to 11.0.
Further, acetic acid was added to adjust the pH to 6.0. Then, by the same desalting method as for the seed emulsion, excess salt was removed to obtain the parent grain emulsion EM.
-1 was obtained. The grains were rounded tetrahedral monodisperse emulsions having an average grain size of 0.66 μm and a grain size variation coefficient of 18%.

<Chemical Ripening> (Preparation of EM-A) 1 mol of silver of the obtained emulsion EM-1 was sampled and chemically sensitized while maintaining it at 51 ° C. Ammonium thiocyanate 52 mg, silver chloride 1.2 mg,
Sodium thiosulfate pentahydrate 12.0mg was added, 32
After a minute, 1.6 × 10 ⁻³ mol of silver iodide fine grain emulsion (a) was added. After a certain time, 4-hydroxy-6-methyl-
2.34 g of 1,3,3a, 7-tetrazaindene was added to stabilize and optimally perform chemical sensitization.

Spectral sensitization was carried out 10 minutes before the start of chemical sensitization by adding 210 mg and 1.5 mg of the following spectral sensitizing dyes (A) and (B) to 1 mol of silver halide, respectively.

Spectral sensitizing dye (A) 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydrous Spectral sensitizing dye (B) 5 , 5'-di- (butoxycarbonyl) -1,1'-diethyl-3,
Anhydrous of 3'-di- (4-sulfobutyl) bernzoimidazolocarbocyanine sodium salt The obtained chemically sensitized emulsion was designated as EM-A.

(Preparation of EM-B) At the start of chemical sensitization, 17 mg of ammonium thiocyanate and 12.0 mg of sodium thiosulfate pentahydrate were added without adding chloroauric acid, and 32 minutes after that, 35 mg of ammonium thiocyanate was added. Chemical sensitization was performed in exactly the same manner as in EM-A, except that 1.2 mg of chloroauric acid, and silver iodide fine particles (a) were added in an amount of 1.6 × 10 ^-3 mol, and the resulting emulsion was designated as EM-B. did.

(Preparation of EM-C) Chloroauric acid was not added, and 52 mg of ammonium thiocyanate and 12 mg of sodium thiosulfate were added.
Add mg, and 32 minutes after that, add 1.6 × 1 of silver iodide fine particles (b).
Chemical sensitization was performed in exactly the same manner as in EM-A except that 0 to ³ mol was added, and the obtained emulsion was designated as EM-C.

(Preparation of EM-D) As silver iodide fine particles,
The emulsion thus obtained was chemically sensitized in the same manner as in EM-C except that (c) was added instead of (b).
-D.

(Preparation of EM-E) EM-E was prepared in exactly the same manner as EM-B except that silver bromide fine particles (d) were used instead of silver iodide fine particles (a).

(Preparation of EM-F) EM-F was prepared in the same manner as in EM-C except that silver bromide fine particles (e) were used instead of silver iodide fine particles (b).

(Preparation of EM-G) EM-G was prepared in the same manner as in EM-D except that silver bromide fine particles (f) were used instead of silver iodide fine particles (c).

The emulsions EM-A to EM-G thus obtained were added with the additives described below to prepare emulsion layer coating solutions. At the same time, a protective layer coating solution described below was also prepared. In addition, the coating amount was 1.7 g / m ² per side and the amount with gelatin was 2.9 g / m ² using two slide hopper type coaters at the speed of 80 m / min on both sides simultaneously on the support. Coating was performed and drying was performed for 2 minutes and 20 seconds to obtain coating samples No. 1 to No. 7, respectively. As the support, a copolymer aqueous dispersion obtained by diluting the copolymer consisting of three kinds of monomers of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt% and butyl methacrylate 40 wt% to 10 wt% is used. A blue-colored polyethylene terephthalate film base having a density of 0.15 for a 175 μm X-ray film was used as the drawing liquid.

The additives used in the emulsion are as follows.
The addition amount is indicated by the amount per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butyl-catechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1 Ammonium 3,3-dihydroxybenzene-4-sulfonate 4g 2-Sodium mercaptobenzimidazole-5-sulfonate 1.5g

[0119]

[Chemical 1]

C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1-phenyl-5-mercaptotetrazole 15 mg diethylene glycol 7 g dextran (average molecular weight 60,000) 600 mg sodium polyacrylate (average molecular weight 3.6 2.5 g Next, the following was prepared as a protective layer coating liquid. The additive is shown in the amount per liter of coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decyl sulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particle size) Matte agent of 1.2 μm) 0.5 g Ludox AM (DuPont) (colloidal silica) 30 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 7 mg Glyoxal 40% aqueous solution (hardener) 2.0 ml

[0122]

[Chemical 2]

For each of the obtained coated samples, 23
The samples were stored in the dark at 1 ° C and 55% RH for 1 day and 7 days, 40 ° C and 78% RH for 7 days, and evaluated by sensitometry.

Sensitometry (evaluation of photographic performance) In sensitometry, a sample was sandwiched between two intensifying screens (KO-250 Konica Corporation), and a tube voltage of 80 kv was applied through an aluminum wedge.
p, tube current 100 mA, X-ray irradiation for 0.05 seconds. Next, using a roller-conveying type automatic developing machine, development and fixing were performed with the developing solution and fixing solution shown below. Shown below.

The processing time was dry to dry for 45 seconds, and the sensitivity was obtained. The temperature during processing is 35 ℃ for development and 33 for fixing.
℃, washed with water at 20 ℃, and dried at 50 ℃. Sensitivity is fog +
Expressed as the reciprocal of the exposure dose that gives a density of 0.5, 23 of sample No. 1
The relative sensitivity is shown with the sensitivity of 100 ° C., 55% RH, and one day storage as 100. The results are shown in Table 1.

[0126]

[Table 1]

The compositions of the developing solution and fixing solution used in the present invention are shown below.

Developer Formulation Part-A (for 12 liter finish) Potassium hydroxide 450g Potassium sulfite (50% solution) 2280g Diethylenetetraamine pentaacetic acid 120g Sodium bicarbonate 132g 5-Methylbenzotriazole 1.2g 1-phenyl-5- Mercaptotetrazole 0.2g Hydroquinone 340g Add water to make 5000ml.

Part-B (for 12 l finishing) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g N-Acetyl-DL-penicillamine 1.2 g Starter glacial acetic acid 120 g Potassium bromide 225 g Water Add to make 1.0 liter.

Fixer formulation Part-A (for 18l finish) Ammonium thiosulfate (70wt / vol%) 6000g Sodium sulfite
110 g sodium acetate trihydrate
450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B Aluminum sulphate 800 g To prepare a developer, add Part A and Part B to approximately 5 liters of water and stir at the same time. While dissolving, add water to make 12 liters and p with glacial acetic acid.
The H was adjusted to 10.40. This is used as a developing solution.

20 ml / l of the aforesaid starter was added to 1 liter of this developing solution to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part A and Part B to approximately 5 liters of water.
Was added at the same time, water was added while dissolving with stirring to make 18 l, and the pH was adjusted to 4.6 using sulfuric acid and NaOH. This is the fixer.

Example 2 (Preparation of Twin Crystal Seed Emulsion) A monodisperse spherical seed emulsion was prepared by the method described in JP-A-61-6643.

A ₂ Hydrogen peroxide-treated gelatin 150 g Potassium bromide 53.1 g Potassium iodide 24 g Water 7.2 l B ₂ Silver nitrate 1500 g Water 6 l C ₂ Potassium bromide 1327 g Water 3 l D ₂ Ammonia water (28%) 705 ml 40 Nucleation was performed by adding the B ₂ solution and the C ₂ solution, which were kept at a constant temperature of 15 ° C., to the A ₂ solution vigorously stirred at 30 ° C. for 30 seconds by the double jet method. The pBr at this time was 1.09 to 1.15.

After 1 minute and 30 seconds, the D ₂ solution was added in 20 seconds and aging was carried out for 5 minutes. The KBr concentration during aging was 0.071 mol / l, and the ammonia concentration was 0.63 mol / l.

After that, the pH was adjusted to 6.0, and desalting and washing with water were immediately performed. When this seed emulsion was observed with an electron microscope, it was a monodisperse spherical emulsion having an average grain size of 0.22 μm and a grain size variation coefficient of 15%. This twinned seed emulsion was designated as Em-2.

[Preparation of Tabular Emulsion] The Twin Crystal Emulsion Em-
Using tabular solution No. 2 and the following six solutions, tabular silver halide parent grain emulsions mainly composed of tabular twin grains were prepared.

E ₂ ossein gelatin 45.8 g propyleneoxy polyethyleneoxy disuccinate disodium salt (10% methanol solution) 8.0 ml Twin seed emulsion Em-2 0.214 mol equivalent Water equivalent 4132 ml F ₂ ossein gelatin 11.9 g Odor Potassium iodide 757.4g Potassium iodide 16.2g Water 2172ml G ₂ Silver nitrate 1108.6g Water 2172ml H ₂ Sodium chloride 41.3g Water 266.6ml I ₂ Silver nitrate 62.3g Water 333.2ml J ₂ Sodium chloride 4.3g Potassium bromide 34.5g To the E ₂ solution which was vigorously stirred with 333.2 ml of water at 65 ° C., the F ₂ solution and the G ₂ solution were added by the double jet method in 40 minutes. During this time, pH is 5.9 and p
Ag kept at 9.0 throughout. The addition rates of the F ₂ solution and the G ₂ solution were linearly increased to 2.3 times in the initial and final stages.

Next, the H ₂ solution was added for 2 minutes and 24 seconds, and 2 minutes after the addition, the I ₂ solution and the J ₂ solution were added for 6 minutes and 15 seconds by the double jet method.

After the addition was completed, the pH was adjusted to 6.0, and then desalting treatment was carried out by the method described in JP-B-35-16086 in order to remove excess salts.

The obtained parent grain emulsion had an average grain size of 1.35 μm,
This is a tabular silver halide emulsion having an average thickness of 0.28, an average aspect ratio of 4.82, and a grain size variation coefficient of 18%.
It was set to M-2.

<Chemical Ripening> (Preparation of EM-H) 1 mole of silver of the obtained emulsion EM-2 was sampled and chemically sensitized while maintaining it at 51 ° C. Ammonium thiocyanate 52 mg, chloroauric acid 1.56 mg,
Sodium thiosulfate pentahydrate 14.0mg added, 32
After a minute, 1.72 × 10 ^-3 mol of silver iodide fine grain emulsion (a) was added. After a certain time, 4-hydroxy-6-methyl-
Add 2.34 g of 1,3,3a, 7-tetrazaindene, stabilize,
Optimally chemically sensitized.

Spectral sensitization was carried out 10 minutes before the start of chemical sensitization by adding 220 mg and 1.8 mg of the spectral sensitizing dyes (A) and (B) of Example 1 per mol of silver halide, respectively.

The obtained chemically sensitized emulsion was designated as EM-H.

(Preparation of EM-I) Chloroauric acid was not added at the start of chemical sensitization, 17 mg of ammonium thiocyanate and 14 mg of sodium thiosulfate pentahydrate were added, and 32 minutes later, 35 mg of ammonium thiocyanate was added. Chemical sensitization was performed in exactly the same manner as EM-H except that 1.56 mg of chloroauric acid and 1.72 × 10 ^-3 mol of silver iodide fine particles (a) were added, and the obtained emulsion was designated as EM-I. .

(Preparation of EM-J) Silver chloride was not added,
Ammonium thiocyanate 52mg, sodium thiosulfate 14
32 minutes after that, 1.72 × of silver iodide fine particles (b) was added.
Chemical sensitization was performed in exactly the same manner as in EM-H except that the addition of 10 ^-3 mol equivalent was carried out, and the obtained emulsion was designated as EM-J.

(Preparation of EM-K) EM-K was prepared in the same manner as EM-J except that silver iodide fine particles (b) were added instead of (c).

(Preparation of EM-L) EM-I except that silver bromide fine particles (d) were added instead of silver iodide fine particles (a).
Chemical sensitization was performed in exactly the same way
ML was prepared.

(Preparation of EM-M) EM-J except that silver bromide fine particles (e) were added instead of silver iodide fine particles (b).
EM-M was prepared in exactly the same manner as in.

(Preparation of EM-N) EM-K except that silver bromide fine particles (f) were added instead of silver iodide fine particles (c).
EM-N was prepared in exactly the same manner as in.

(Preparation of Internal Reduction Sensitized Emulsion EM-3) E ₂
After the seed emulsion Em-2 was dispersed and suspended in the solution, thiourea dioxide was added thereto in an amount of 0.25 mg per mol of the finally formed parent grain emulsion.
EM-3 was prepared in exactly the same manner as EM-2 except that the addition of the F ₂ solution and the G ₂ solution was started 12 minutes after the addition.

(Preparation of EM-O) The obtained EM-3 was
Chemical sensitization was performed in the same manner as in EM-I, and the obtained emulsion was designated as EM-O.

(Preparation of EM-P) Next, EM-3 and EM
Chemical sensitization was performed in the same manner as in -J, and the obtained emulsion was designated as EM-P.

(Preparation of EM-Q) Furthermore, EM-3 was chemically sensitized in the same manner as in EM-K, and the obtained emulsion was designated as EM-Q.

(Preparation of EM-R) EM-3 was chemically sensitized in the same manner as in EM-L, and the obtained emulsion was EM.
-R.

(Preparation of EM-S) EM-3 was chemically sensitized in the same manner as in EM-M, and the resulting emulsion was subjected to EM.
-S.

(Preparation of EM-T) EM-3 was chemically sensitized in the same manner as in EM-N, and the obtained emulsion was EM.
-T.

The obtained emulsions EM-H to EM-T were coated in the same manner as in Example 1 to obtain coated sample Nos. 8 to 20, respectively.
Got

Further, sensitometry was evaluated in the same manner as in Example 1. The results are shown in Tables 2-3.

The sensitivities in the table are for sample No. 8 at 23 ° C., 55
% RH The relative sensitivity was shown with the sensitivity of 1-day storage as 100.

[0161]

[Table 2]

[0162]

[Table 3]

Example 3 (Preparation of hexagonal tabular twin seed emulsion) A hexagonal tabular seed emulsion was prepared by the following method.

A ₃ ossein gelatin 24.2 g distilled water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml KBr 10.8 g 10% nitric acid 114 ml B ₃ 2.5N AgNO ₃ aqueous solution 2825 ml C ₃ KBr 824g KI 23.5g Distilled water to 2825ml D ₃ 1.75N KBr Aqueous solution Solution A ₃ using the mixing stirrer shown in Japanese Patent Publication Nos. 58-58288 and 58-58289 at the following silver potential control amount of 35 ° C. 464.3 ml of each of solution B ₃ and solution C ₃ was added to the above by the double mixing method over 2 minutes,
Nucleation was performed.

After stopping the addition of solution B ₃ and solution C ₃ ,
It takes 60 minutes to raise the temperature of solution A ₃ to 60 ° C,
After adjusting the pH to 5.0 with 3% KOH, the solution B ₃ and the solution C were again adjusted.
₃ was added by the double-sided mixing method at a flow rate of 55.4 ml / min for 42 minutes. This temperature rise from 35 ° C. to 60 ° C. and solution B ₃ , C ₃
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the re-simultaneous mixing was controlled to +8 mv and +16 mv, respectively, using solution D ₃ .

After the completion of the addition, the pH was adjusted to 6 with 3% KOH, and the mixture was immediately desalted and washed with water. This seed emulsion has a maximum adjacent side ratio of 1.0 to 90% of the total projected area of silver halide grains.
It was confirmed by an electron microscope that the hexagonal tabular grains had an average thickness of 0.06 μm and an average diameter (circle diameter conversion) of 0.59 μm.

(Preparation of Growth Emulsion) The obtained hexagonal tabular seed emulsion was taken in an amount of 0.11 mol per mol of silver of the growth emulsion, and gelatin containing polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt at a liquid temperature of 60 ° C. After being dissolved and dispersed in an aqueous solution, subsequently, a silver nitrate solution and a halide solution of potassium bromide and potassium iodide, which were finally adjusted to have an average silver iodide content of 1.55 mol%, were mixed.
pH = 5.8, pH = 8.8, keeping at 60 ℃ for the whole time, add by the controlled double jet method in 107 minutes,
Average particle size 1.03 μm, average thickness 0.21 μm, aspect ratio 4.83
To obtain tabular silver iodobromide emulsion EM-4.

<Chemical Ripening> (Preparation of EM-U) 1 mol of silver of the obtained emulsion EM-4 was sampled and subjected to chemical sensitization while maintaining it at 50 ° C. Ammonium thiocyanate 52 mg, chloroauric acid 1.4 m
g, and 15.0 mg of sodium thiosulfate pentahydrate were added, and 32 minutes after that, 1.80 × 10 ⁻³ mol of silver iodide fine grain emulsion (a) was added. After that, after a certain period of time, 2.34 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to stabilize and optimally perform chemical sensitization.

Spectral sensitization was carried out 10 minutes before the start of chemical sensitization by adding 240 mg and 1.5 mg of the spectral sensitizing dyes (A) and (B) of Example 1 per mol of silver halide, respectively.

The obtained emulsion after chemical sensitization was designated as EM-U.

(Preparation of EM-V) At the start of chemical sensitization, 17 mg of ammonium thiocyanate and 15 mg of sodium thiosulfate pentahydrate were added without adding chloroauric acid, and 32 minutes after that, 35 mg of ammonium thiocyanate was added. Chemical emulsion was sensitized in the same manner as in EM-U except that 1.4 mg of chloroauric acid and 1.8 × 10 ^-3 mol of silver iodide fine particles (a) were added, and the obtained emulsion was designated as EM-V. .

(Preparation of EM-W) Chloroauric acid was not added and ammonium thiocyanate 52 mg and sodium thiosulfate 15 mg
32 minutes after that, 1.80 × 10 of silver iodide fine particles (b) was added.
Chemical sensitization was performed in exactly the same manner as in EM-V except that ^-3 mol equivalent was added, and the obtained emulsion was designated as EM-W.

(Preparation of EM-X) As silver iodide fine particles,
The emulsion obtained was chemically sensitized in the same manner as in EM-W except that (c) was added instead of (b).
-X.

(Preparation of EM-Y) EM-Y was prepared in exactly the same manner as EM-V except that silver bromide fine particles (d) were used instead of silver iodide fine particles (a).

(Preparation of EM-Z) EM-Z was prepared in the same manner as EM-W except that silver bromide fine particles (e) were used instead of silver iodide fine particles (b).

(Preparation of EM-AZ) Fine silver iodide particles (c)
Instead of using silver bromide fine particles (f), EM-X
EM-AZ was prepared in exactly the same manner as in.

The resulting emulsions EM-U to EM-AZ were coated in the same manner as in Example 1, and coated sample Nos. 21 to 2 respectively.
Got 7.

Further, sensitometry was evaluated by the same method as in Example 1.

The results are shown in Table 4.

The relative sensitivity is shown with sample No. 21 being stored at 23 ° C. and 55% RH for 1 day as 100.

[0181]

[Table 4]

As is clear from Tables 1 to 4, the light-sensitive material of the present invention has high sensitivity, and the sample in which the gold compound is added to the silver halide fine particles is excellent in stability over time.

Especially when reduction sensitization is applied to the inside of the grain,
The effect was great.

[0184]

According to the present invention, it is possible to cope with rapid processability and improve the temporal stability of a silver halide photographic light-sensitive material which has been subjected to gold sensitization.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material, characterized in that fine silver halide grains containing a gold compound are added before the completion of the chemical ripening step of the silver halide emulsion.