JPH11305370A - Silver halide particle, silver halide emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain silver halide particles having excellent storage stability and adaptability for rapid treatment by preparing the particles in such a manner that in each planer silver halide particle, the silver chloride content in the top part of the particle is lower than the average silver chloride content in the particle. SOLUTION: The emulsion contains planer silver halide particles having (111) principal planes parallel to each other, and in each particle, the silver chloride content in at least one top part of the particle is lower than the average silver chloride content of the particle. The silver chloride content at the top is preferably >=0.1 mol.% and <=99.9 mol.%. The silver chloride content in the inner part of the top has only to be higher than in the top. In the silver halide emulsion, planer particles having >=2 aspect ratio possess >=50%, preferably >=60%, and more preferably >=70% of the whole projected area of particles. It is preferable that the proportion of hexagonal planer particles in the planer particles is higher and that the ratio of the length of adjacent side lines of the hexagon is preferably <=1/2. The coefft. of variation in the particle size distribution is preferably <=20%, and especially <15%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide grain, a silver halide emulsion and a silver halide photographic material. More particularly, the present invention relates to a silver halide photographic material having high storage stability and suitable for rapid processing.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material for photography,
Silver iodobromide is usually used in terms of sensitivity / granularity. In recent years, quickness has also been required in the field of photography, and minilabs have been installed in major spots. On the other hand, silver chloride photographic emulsions have been put to practical use in photographic light-sensitive materials for appreciation from the viewpoint of speed. Hitherto, it has been known that the iodine content suppresses the development, whereby the graininess is improved, and it has been considered that the graininess and the quickness are contradictory. Silver chloride is known to promote development, but is not preferred in terms of sensitivity / granularity, and has not been put to practical use in photographic light-sensitive materials for photography.

Further, from the viewpoint of resource saving, there is a demand for a reduction in silver, and development of an emulsion having a high developed silver amount / coated silver amount ratio has been desired. Silver chloride-containing silver halide emulsions are known to have a high developed silver amount / coated silver amount ratio, but are not preferred in terms of sensitivity / granularity ratio. JP-A-9-3190
No. 17 shows that these problems are solved by grains whose silver chloride content near the apex is higher than the average silver chloride content of the grains. However, storage stability (sensitivity fluctuation, increase in fog) was a problem because silver chloride was contained near the top.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide tabular silver halide grains, silver halide emulsions and silver halide photographic materials having excellent storage stability and rapid processing suitability. .

[0005]

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

(1) In a tabular silver halide grain having a (111) major plane and containing silver chloride, the silver chloride content of at least one apex is determined by the average silver chloride of the tabular silver halide grain. Tabular silver halide grains characterized by having a content lower than the content.

(2) The tabular silver halide grains as described in (1) above, wherein the tabular silver halide grains are hexagonal tabular silver halide grains.

(3) In each of the tabular silver halide grains, at least half or more of the apex portions have a silver chloride content lower than the average silver chloride content of the tabular silver halide grains. Or tabular silver halide grains according to 2.

(4) In the individual tabular silver halide grains, the silver chloride content at all apexes is lower than the average silver chloride content of the tabular silver halide grains. The tabular silver halide grains described in the above.

(5) A silver halide emulsion characterized in that at least 50% (number) or more of the silver halide grains are tabular silver halide grains as described in any one of the above (1) to (4).

(6) All the silver halide grains have the above-mentioned 1
5. A silver halide emulsion comprising the tabular silver halide grains according to any one of items 1 to 4.

(7) A silver halide photographic light-sensitive material comprising a support having at least one silver halide emulsion layer containing the silver halide emulsion described in 5 or 6 above.

Hereinafter, the present invention will be described in detail. The silver halide emulsion of the present invention is a silver halide emulsion containing tabular silver halide grains whose parallel principal planes are (111) planes. Preferred is a silver halide emulsion in which 50% or more of the total projected area is occupied by tabular silver halide grains having an aspect ratio of 2 or more. Here, the tabular silver halide grains (hereinafter also referred to as tabular grains) are opposed in parallel (1).
11) Consists of a main plane and side faces connecting the main planes.

At least one twin plane is present between the (111) main planes, and usually two twin planes are observed. The distance between the two twin planes is described in US Pat.
As described in JP-A-9,720, the distance can be made smaller than 0.012 μm. Further, as described in JP-A-5-249585, the distance between the (111) main planes is divided by the twin plane spacing. It is also possible to set the value to 15 or more. The silver halide emulsion of the present invention is composed of tabular grains having an aspect ratio of 2 or more, 50% or more, preferably 60% or more of the total projected area.
Above, particularly preferably 70% or more. Here, the projected area and the aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method shadowed with a latex sphere for reference.
When viewed from above, tabular grains usually have a hexagonal, triangular or circular shape, and the aspect ratio is the value obtained by dividing the equivalent diameter of a circle having an area equal to the projected area by the thickness. The shape of the tabular grains is preferably as high as the ratio of hexagons, and the ratio of the lengths of adjacent sides of the hexagons is preferably 1: 2 or less. The effects of the present invention can be obtained regardless of the aspect ratio if the aspect ratio is 2 or more. Therefore, the tabular grain emulsion preferably has an aspect ratio of 2% or more, more preferably 50% or more of the total projected area. Is too large, the variation coefficient of the particle size distribution tends to increase, so that the aspect ratio is usually preferably 20 or less.

The coefficient of variation of the particle size distribution is preferably at most 20%, particularly preferably at most 15%. The silver halide emulsion of the present invention preferably comprises silver chloroiodobromide grains. The silver iodide content is at most 15 mol%, more preferably at most 10 mol%. The average silver chloride content is preferably from 0.1 mol% to 50 mol%. The variation coefficient of the distribution of the silver chloride content between grains is preferably 20% or less, particularly preferably 10% or less.

In the present invention, the vertices are defined as six triangular regions formed outside the hexagon formed by connecting the midpoints of the sides of the final hexagonal tabular grain. The silver chloride content at the top is preferably from 0.1 mol% to 99.9 mol%. On the other hand, the silver chloride content inside the peak should be higher than the peak. That is, 0.2 mol% or more and 100 mol%
The following may be sufficient. According to Japanese Patent Application Laid-Open No. 9-319017, if the silver chloride content near the apex is higher than the average silver chloride content of the whole grains, a sufficient development promoting effect can be obtained. Therefore, even if the silver chloride content is high only at the top, a sufficient development promoting effect cannot be obtained unless the inside is developed. In the grains of the present invention, not only the apex but also the whole grains are improved in developability, and a large development promoting effect can be expected. Furthermore, the apex originally has a large specific surface area per unit volume and is easily dissolved. Therefore, when the silver chloride content at the top is extremely high, the grain shape itself becomes unstable and the storage stability deteriorates. In the present invention, an effect of preventing deterioration of storage stability while maintaining the effect of improving developability can be expected.

The individual tabular silver halide grains of the present invention preferably have at least half or more of the peaks having a silver chloride content lower than the average silver chloride content of the tabular silver halide grains. It is more preferred that the silver chloride content of the silver halide grains be lower than the average silver chloride content of the tabular silver halide grains.

The silver halide grains having a low silver chloride content at the apexes of the hexagonal tabular grains of the present invention are prepared by dissolving silver chloride-containing hexagonal tabular grains as a host to form disc-shaped grains, It can be realized by growing the contained phase. Methods for dissolving the hexagonal tabular grains of the host in a disk shape include a method of ripening in a low pBr atmosphere and a method of ripening in a silver halide solvent described later.

In the present invention, the silver chloride content at the top of each grain can be measured at a low temperature using a transmission electron microscope equipped with an elemental analyzer. On the other hand, the average silver chloride content can be measured by X-ray diffraction by a conventional method.

The silver halide emulsion of the present invention can be prepared, for example, by the method described in "Theory and Practice of Photography" by Cleeve (Cleve, Phot).
OGRAPHY Theory and Practi
ce (1930)), p. 131; Gatov, Photography Science and Engineering (Gu
toff, Photographic Science
and Engineering), Vol. 14, 24
8-257 (1970); U.S. Pat.
No. 226, No. 4,414,310, No. 4,43
No. 3,048, 4,439,520 and British Patent No. 2,112,157.

Preparation of host particles basically consists of a combination of three steps of nucleation, ripening and growth. The methods described in U.S. Pat. No. 4,797,354 and JP-A-2-838 are extremely effective in preparing the host of the present invention.

In the nucleation step, US Pat.
Use of gelatin having a low methionine content described in US Pat. Nos. 13,320 and 4,942,120, nucleation at a high pBr described in U.S. Pat. Performing nucleation in a short time described in 222,940 is extremely effective in the core nucleation step of the present invention. The ripening step performed in the presence of a low-concentration base described in US Pat. No. 5,254,453, and performed at a high pH described in US Pat. It may be effective in the ripening step of the grain emulsion.

US Pat. Nos. 5,147,771, 5,147,772, 5,147,773, 5,171,659, 5,210,013 and 5,210,013; The method of forming tabular grains using the polyalkylene oxide compound described in No. 5,252,453 is preferably used for preparing the host particles of the present invention.

A silver chloride-containing portion is grown on the host tabular grains at the apex by the method described above. Basically, the shell is grown by adding a silver nitrate aqueous solution and a halogen aqueous solution containing chloride and bromide by a double jet method. The temperature and pH of the system, the type and concentration of the protective colloid agent such as gelatin, the presence / absence of the silver halide solvent, the type, and the concentration can vary widely.

Preferably, the pCl at the time of growing the apex is 3 or less. More preferably, it is 2 or less. Here, pCl means the logarithm of the reciprocal of the chloride ion concentration in the unreacted system when bromine ions react 100% with silver ions and the remaining silver ions react with chloride ions.
Instead of adding the aqueous silver nitrate solution and the aqueous halogen solution containing chloride and bromide by the double jet method, it is also effective to simultaneously add the aqueous silver nitrate solution, the aqueous halogen solution containing chloride and bromide, and the silver iodide fine grain emulsion. Further, the first shell can be formed by adding and ripening a silver iodobromide fine grain emulsion. In this case, it is particularly preferable to use a silver halide solvent.

Examples of the silver halide solvent usable in the present invention include US Pat. Nos. 3,271,157, 3,531,286 and 3,574,628; (A) Organic thioethers described in JP-A Nos. 1019 and 54-158917;
(B) thiourea derivatives described in JP-A Nos. 408, 55-77737 and 55-2982;
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, (d) imidazoles described in JP-A-54-100717, e) sulfite, (f) ammonia, (g) thiocyanate and the like.

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

In the present invention, the tabular grains may have dislocation lines. Dislocation lines of tabular grains are described, for example, in J. Am.
F. Hamilton, Photo. Sci. Eng. ,
11, 57, (1967); Shiozawa,
J. Soc. Photo. Sci. Japan, 35, 2
13, (1972) can be observed by a direct method using a transmission electron microscope at a low temperature.
That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate.
The use of an electron microscope (200 kV or more for particles having a thickness of m) enables more clear observation. From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

Gelatin is advantageously used as a protective colloid used in preparing the silver halide emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids may also be used. Can be.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives A variety of synthetic hydrophilic polymer substances such as homo- or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Ph
oto. Japan. No. 16, P30 (1966)
Enzyme-treated gelatin as described in may be used,
In addition, a hydrolyzate or enzymatic decomposition product of gelatin can also be used.

The silver halide emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The washing temperature can be selected according to the purpose,
It is preferable to select in the range of 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. P at the time of washing
Ag can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

In preparing the silver halide emulsion of the present invention, for example, at the time of grain formation, at the desalting step, at the time of chemical sensitization, or before coating, it is preferable to use a salt of a metal ion depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the whole grain and a method of doping only the core part or the shell part of the grain can be selected. Mg, Ca, Sr, Ba, A
1, Sc, Y, La, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b, Bi, etc. can be used. These metals can be added as long as they can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, hexacoordinate complex salts, and tetracoordinate complex salts. For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (N
O ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (C
N) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrC
l _6, etc. _{(NH 4) 3 RhCl 6,} K 4 Ru (CN) 6 and the like. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

The metal compound is preferably added by dissolving a suitable solvent such as water or methanol or acetone in a solvent.
To stabilize the solution, an aqueous solution of hydrogen halide (eg, HCl, HBr, etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.)
Can be used. If necessary, an acid or alkali may be added. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. In addition, a water-soluble silver salt (eg, AgNO ₃ ) or an alkali halide (eg, NaCl, KB)
(r, KI) can be added continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogenide compound during the preparation of a silver halide emulsion as described in US Pat. No. 3,772,031 is sometimes useful. S, S
In addition to e and Te, cyanide, thiocyanate, selenocyanate, carbonate, phosphate and acetate may be present.

The silver halide grains of the present invention may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization in any step of the production process of a silver halide emulsion. Can be applied. It is preferable to combine two or more sensitization methods. Various types of silver halide emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the silver halide emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

One of the chemical sensitizations that can be preferably carried out in the present invention is a chalcogenide sensitization and a noble metal sensitization alone or in combination, and is described in TH James, The Photographic Process, No. 4. Edition, Macmillan, 1977, (TH James, The Th
eory of the PhotographicP
process, 4th ed, Macmillan, 1
977) pages 67-76, and can be carried out using active gelatin, and can also be performed by Research Disclosure 120, April 1974, 12008; Research Disclosure 34, 1975 June.
Moon, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, and 3,772,031,
No. 3,857,711, No. 3,901,714
Nos. 4,266,018 and 3,90
No. 4,415 and pAg 5-10, pH 5-8 and temperature 30-80 ° C. as described in GB 1,315,755, sulfur, selenium, tellurium, gold,
It can be platinum, palladium, iridium or a combination of several of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. Palladium compound is palladium 2
A valent salt or a tetravalent salt is meant.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
Nos. 711, 4,266,018 and 4,0
No. 54,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine,
Compounds known to suppress fog and increase sensitivity during the process of chemical sensitization are used. Examples of the chemical sensitization aid modifier are described in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526 and the above-mentioned duffin. "Photographic emulsion chemistry", pp. 138-143.

The silver halide emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mol, per mol of silver halide. A preferred range of the palladium compound is 1 × 10 ⁻³ to
It is 5 × 10 ^-7 mol. The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 1.
0 ^-6 mol.

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mole of silver halide.
10 ^-4 to 1 × 10 ^-7 mol, more preferably 1
It is from × 10 ^{-5 to} 5 × 10 ^-7 mol.

Selenium sensitization is a preferable sensitizing method for the silver halide emulsion of the present invention. In selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium and selenoureas (for example, N,
Selenium compounds such as N-dimethylselenourea, N, N-diethylselenourea), selenoketones, and selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, reduction sensitization means a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing in a pAg1 to 7 low pAg atmosphere called silver ripening or a method of ripening, and a method of high pH ripening called pH 8 to 11. Growth or ripening in a high pH atmosphere.
Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted. As reduction sensitizers, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. Alkynylamine compounds described in US Pat. No. 5,389,510 are also effective compounds. The addition amount of the reduction sensitizer depends on the silver halide emulsion production conditions, so it is necessary to select the addition amount. However, the addition amount is 10 ^-7 to 1 mol per mol of silver halide.
A range of 10 ^-3 mol is suitable.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the silver halide emulsion of the present invention. The oxidizing agent for silver refers to a compound having an action of converting metallic silver into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water, such as silver halide, silver sulfide, and silver selenide,
Further, a silver salt easily soluble in water such as silver nitrate may be formed. The oxidizing agent for silver may be inorganic or organic. Inorganic oxidizing agents include ozone, hydrogen peroxide and its adducts, peroxy acid salts, peroxy complex compounds, oxyacid salts such as permanganate and chromate, halogen elements such as iodine and bromine, and perhalic acid Salts, salts of high valent metals and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T). , Chloramine B).

Preferred oxidants of the present invention are inorganic oxidants such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates and organic oxidants such as quinones.
The disulfide compounds described in EP 0 627 657 A2 are also preferred compounds. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic silver halide emulsion used in the present invention contains various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; For example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes Known as antifoggants or stabilizers such as Den acids, it can be added to many compounds. For example, those described in U.S. Pat. Nos. 3,954,474 and 3,982,947 and JP-B-52-28660 can be used. One of the preferred compounds is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects when added during the preparation of silver halide emulsions, it also controls grain habit, reduces grain size, reduces grain solubility, and enhances chemical sensitization. It can be used for various purposes such as controlling and controlling the arrangement of dyes.

The photographic silver halide emulsion used in the present invention is preferably spectrally sensitized by a methine dye or the like to exhibit the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used as basic heterocyclic nuclei in cyanine dyes can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole A nucleus and a quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, nuclei having a ketomethylene structure include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, and a thiazolidine-2,4-nucleus.
A 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
No. 7,229, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527,641, No. 3,
Nos. 617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
7,803, JP-B-43-4936, 53-12
No. 375, JP-A-52-110618, JP-A-52-10
No. 9925.

Along with the sensitizing dye, a silver halide emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. . The sensitizing dye may be added to the silver halide emulsion at any stage in the preparation of the silver halide emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but as described in U.S. Pat. Nos. 3,628,969 and 4,225,666, chemical sensitizers are used. At the same time as the above, spectral sensitization can be performed at the same time as chemical sensitization, or can be performed prior to chemical sensitization as described in JP-A-58-113928. It can be added before the completion of the formation to start spectral sensitization. No. 4,225,6.
It is also possible to add these compounds separately as taught in No. 66, i.e. to add some of these compounds prior to chemical sensitization and the remainder after chemical sensitization. At any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount of addition was 4 × / mol of silver halide.
It can be used in an amount of from 10 ^-6 to 8 × 10 ^-3 mol. In the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is more effective. It is.

In the silver halide emulsion according to the present invention, the above-mentioned various additives are used, but other various additives can be used according to the purpose. These additives are described in more detail in Research Disclosure (RD) Item 17643 (December 1978), Item 18716 (November 1979) and It
em 308119 (December 1989), and the relevant locations are summarized below.

Additive type RD17643 RD18716 RD308119 1. Chemical sensitizer page 23 page 648 right column page 996 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizer, page 23-24 page 648 right column-996 right-998 right supersensitizer 649 page right column Brightener page 24 998 right 5. 5. Antifoggant pages 24 to 25 page 649 right column 998 right to 1000 right and stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to 1003, left to 1003 right, filter dye, page 650, left column, ultraviolet absorber 7. Stain inhibitor 25 pages right column 650 left to right column 1002 right 8. Dye image stabilizer page 25 1002 right Hardener page 26 page 651 left column 1004 right to 1005 left 10. 10. Binder page 26 page 651 left column 1003 right to 1004 right Plasticizers and lubricants 27 pages 650 pages right column 1006 left to 1006 right 12. 12. Coating aid, pages 26 to 27, page 650, right column, 1005 left to 1006 left, surfactant 13. Static 27 page 650 right column 1006 right to 1007 left Inhibitor Matting agent 1008 left to 1009 left Silver halide emulsion of the present invention and techniques such as layer arrangement that can be used in a photographic light-sensitive material using the silver halide emulsion, silver halide emulsion, dye-forming coupler, DI
Functional couplers such as R couplers, various additives, and development processing are described in European Patent No. 0565096A1 (published on October 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding places.

1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14 2. Intermediate layer: page 61, lines 36 to 40 3. Multilayer effect imparting layer: page 62, lines 15 to 18 4. Silver halide composition: page 62, lines 21 to 25 5. Silver halide grain habit: page 62, lines 26 to 30 6. Silver halide grain size: page 62, lines 31 to 34 7. Method for producing silver halide emulsion: page 62, lines 35 to 40 8. Silver halide grain size distribution: page 62, lines 41 to 42; 9. Tabular grains: page 62, lines 43 to 46 10. Internal structure of particle: page 62, line 47 to line 53 Latent image formation type of silver halide emulsion: 62 pages 54
Line to page 63, 5 lines 12. Physical ripening and chemical ripening of silver halide emulsion: page 63, lines 6-9. Mixed use of silver halide emulsion: page 63, 10-13
Row 14. 14. Fogged emulsion: page 63, lines 14 to 31 Non-light-sensitive emulsion: page 63, lines 32 to 43 16. Silver coating amount: page 63, lines 49 to 50 18. Photographic additives: RD as described above. Formaldehyde scavenger: page 64, 54-
57 lines 19. 20. Mercapto antifoggant: page 65, lines 1-2 Release agent such as fogging agent: page 65, lines 3-7 21. Dye: page 65, lines 7 to 10 General color couplers: p. 65, lines 11 to 13 23. Yellow, magenta and cyan couplers: page 65, lines 14 to 25 Polymer coupler: page 65, lines 26-28 25. Diffusible dye-forming coupler: page 65, lines 29-31 26. Colored coupler: page 65, lines 32 to 38 27. General functional couplers: p. 65, lines 39 to 44 Bleach accelerator releasing coupler: page 65, lines 45 to 48 29. Development accelerator releasing coupler: page 65, lines 49 to 53 30. Other DIR couplers: page 65, line 54 to page 66, line 4 31. Coupler dispersion method: page 66, lines 5-28 32. Preservatives / fungicides: page 66, lines 29-33 33. Type of photosensitive material: page 66, lines 34-36 34. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, 1
Row 35. Back layer: page 67, lines 3 to 8 36. General development processing: page 67, lines 9 to 11 37. Developer and developer: page 67, lines 12 to 30 38. Developer additive: page 67, lines 31 to 44 39. Inversion processing: page 67, lines 45 to 56 40. Processing solution opening ratio: page 67, line 57 to page 68, line 12 Developing time: page 68, lines 13 to 15 42. Bleaching and fixing, bleaching and fixing: page 68, line 16 to page 69, 3
1 line 43. Automatic developing machine: page 69, lines 32 to 40 Rinsing, rinsing, stabilization: page 69, line 41 to page 70, 1
8 rows 45. Processing solution replenishment, reuse: page 70, lines 19-23 46. Built-in developer sensitive material: page 70, lines 24 to 33 47. Development processing temperature: page 70, lines 34 to 38 Utilization for a film with a lens: p. 70, lines 39 to 41 Also, a ferric salt such as 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid and ferric nitrate described in EP-A-602600. And a bleaching solution containing a persulfate can also be preferably used. In the use of this bleaching solution, it is preferable to interpose a stopping step and a washing step between the color developing step and the bleaching step, and use an organic acid such as acetic acid, succinic acid, or maleic acid as the stopping liquid. Is preferred. Further, the bleaching solution may contain an organic acid such as acetic acid, succinic acid, maleic acid, glutaric acid and adipic acid in the range of 0.1 to 2 mol / liter for the purpose of pH adjustment and bleaching fog. preferable.

[0057]

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

Example 1 Preparation of Silver Halide Emulsion 1 (Comparative Example 1) (Step A) An aqueous gelatin solution (1350 ml of distilled water, 1.14 g of low molecular weight gelatin having an average molecular weight of 15,000, KBr1) was placed in a reaction vessel equipped with a stirrer. .01 g, pBr2.
2, pH 6.0) and the temperature of the solution was maintained at 45 ° C. 52.0 ml of an aqueous AgNO ₃ solution (Ag
NO ₃ containing 2.60 g) and an aqueous KBr solution 52.0ml
(Including 1.82 g of KBr) was simultaneously added at a constant flow rate over 45 seconds to form nuclei, and the mixture was left for 5 minutes. 70
° C and an aqueous gelatin solution (inert gelatin 24.1).
g, containing 217 ml of distilled water).

(Step B) Subsequently, an AgNO ₃ aqueous solution 5
21 ml (including 155.8 g of AgNO ₃ ) and 2.56
A mixed aqueous solution containing mol / liter of KBr and 0.29 mol / liter of NaCl was added at a constant flow rate so as to maintain pBr of 2.33.

(Step C) Further, pBr was adjusted to 1.3.
After stirring for 10 minutes, the AgNO ₃ aqueous solution 1
77 ml (including 52.8 g of AgNO ₃ ) and 2.56 m
ol / liter of KBr and a mixed aqueous solution containing 0.29 mol / liter of NaCl were added at a constant flow rate so as to be equimolar.

(Step D) The resulting silver halide emulsion was subjected to desalting and washing with a usual flocculation method, redispersed, and adjusted to pH 5.5 and pBr 3.1 at 40 ° C. The obtained particles had a circle equivalent diameter of 0.70 μm, a thickness of 0.13 μm, and an average AgCl content of 10 mol%.
And a hexagonal flat plate having a uniform halogen composition with the (111) plane as the main plane.

Preparation of Silver Halide Emulsion 2 (Comparative Example 2) Step B and Step C in the preparation of silver halide emulsion 1
Was changed to the following step B2 and step C2 to prepare a silver halide emulsion 2.

(Step B2) 521 ml of an aqueous AgNO ₃ solution
(Including 155.8 g of AgNO ₃ ) and 2.85 mol /
One liter of aqueous KBr was added at a constant flow rate to maintain pBr 2.33.

(Step C2) Subsequently, the pBr was increased to 1.31.
After stirring for 10 minutes, the aqueous AgNO ₃ solution 17
7ml (including 52.8g of AgNO ₃ ) and 1.71mo
1 / liter of KBr and 1.14 mol / liter of an aqueous NaCl solution were added at a constant flow rate so as to be equimolar.

The silver halide grains obtained by changing as described above have an equivalent circle diameter of 0.69 μm and a thickness of 0.14.
μm, average AgCl content: 10 mol%, and a hexagonal flat plate with a (111) plane having a high AgCl content at the top as a main plane.

Preparation of Silver Halide Emulsion 3 (Invention) Step B and Step C in the preparation of silver halide emulsion 1
Was changed to the following steps B3 and C3 to prepare a silver halide emulsion 3.

(Step B3) 521 ml of an AgNO ₃ aqueous solution
(Including 155.8 g of AgNO ₃ ) and 2.54 mol /
Liter of KBr and 0.31 mol / liter of N
The aCl aqueous solution was added at a constant flow rate to maintain pBr 2.33.

(Step C3) Subsequently, the pBr was increased to 1.31.
After stirring for 10 minutes, the aqueous AgNO ₃ solution 17
7ml (including 52.8g of AgNO ₃ ) and 2.65mo
1 / liter of KBr and 0.20 mol / liter of an aqueous solution of NaCl were added at a constant flow rate so as to be equimolar.

The silver halide grains obtained by changing as described above have a circle equivalent diameter of 0.70 μm and a thickness of 0.13.
μm, average AgCl content: 10 mol%, and a hexagonal flat plate having a (111) plane having a low AgCl content (7%) at the apex as a main plane.

The obtained silver halide emulsions 1, 2, and 3
Each was heated and dissolved at 55 ° C., and 4 × 10 ⁻⁴ mol of sensitizing dye SD-1 and 8 × 8 of SD-2 per mol of silver halide.
× 10 ^-5 mol, the SD-3 5 × 10 ^-5 mol was added, 55
After 20 minutes while maintaining the temperature at 5.5 ° C., 5.5 × 10 ⁻⁶ mol of sodium thiosulfate pentahydrate, 2.5 × 10 ⁻⁶ mol of pentafluorophenyl-diphenyl-phosphine selenide, 3.2 × of chloroauric acid 10 ^-6 mol and potassium thiocyanate 3.5
A mixture of × 10 ^-4 mol was successively added at an interval of 2 minutes, and the mixture was aged so as to optimize the sensitivity. Stabilizer ST- at the end of aging
1 and the antifoggant AF-1 were added, and Em
-1, Em-2 and Em-3 were obtained.

To each of the obtained emulsions, ethyl acetate and magenta coupler M-1 dissolved in tricresyl phosphate (OIL-1) were added and emulsified and dispersed in an aqueous solution containing a dispersing aid (SU-1) and gelatin. Dispersion, spreading agent (SU-
2) and a hardener (H-1, H-2) were added to prepare a coating solution, each of which was coated on a subbed cellulose triacetate support by a conventional method, and dried to obtain samples 11, 12, and 13. 13 was produced.

Hereinafter, a method for preparing a sample coated with a single emulsion layer will be described. Each weight indicates the amount applied per m ² .

<Coating prescription> In order from the support side, first layer: green-sensitive silver halide emulsion layer Emulsion (described in Table 1) Silver coating amount 1.5 g Magenta coupler (M-1) 0.33 g tricresylphos Fate (OIL-1) 0.50 g Gelatin 3.5 g Second layer: Surface protective layer PM-1 0.15 g PM-2 0.04 g Gelatin 0.65 g

[0074]

Embedded image

[0075]

Embedded image

These samples were stored under high temperature and high humidity (50
A similar exposure for sensitometry (1/100 second) was performed before and after one week at 50 ° C. and 50% humidity, and the following color development processing was performed.

Processing method Step Processing time Processing temperature * Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ° C. 25 ml 10 liter Bleaching 45 seconds 38 ° C. 5 ml 4 liter Bleaching and fixing (1) 45 seconds 38 ° C. -4 liter Bleaching Fixing (2) 45 seconds 38 ° C 30 ml 4 liters Washing with water (1) 20 seconds 38 ° C-2 liters Washing with water (2) 20 seconds 38 ° C 30 ml 2 liters Stabilizing 20 seconds 38 ° C 20 ml 2 liters Drying 1 minute 55 ° C * The amount of replenishment is the amount per 35 m width and 1 m length. The bleach-fixing and washing steps are (2) to (1) respectively.
The overflow solution of the bleaching solution was all introduced into the bleach-fix (2).

The amount of the bleach-fix solution brought into the washing step in the above process was 2 m per 1 m of the photosensitive material having a width of 35 mm.
l.

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 3.0. 5 Potassium iodide 1.2 mg-hydroxylamine sulfate 2.0 3.6 4- [N-ethyl-N-β-hydroxy 4.7 7.2 ethylamino] -2-methylaniline sulfate 1.0 liter 1.0 liter pH 10.00 10.15 (Bleaching solution) Mother liquor (g) Replenisher (g) Ferric 1,3-diaminopropanetetraacetate 144.0 206.0 Ammonium monohydrate 1 , 3-Diaminopropanetetraacetic acid 2.8 4.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Aqueous ammonia (27%) 10.0 1.8 Acetic acid ( 51.1 73.0 Add water 1.0 liter 1.0 liter pH 4.3 3.4 (Bleaching / fixing solution) Mother liquor (g) Replenisher (g) Ferric ammonium ethylenediaminetetraacetate 50 2.0-dium dihydrate disodium ethylenediaminetetraacetate 5.0 25.0 ammonium sulfite 12.0 20.0 aqueous solution of ammonium thiosulfate 290.0 ml 320.0 ml (700 g / l) ammonia water (27%) 6.0 ml 15.0 ml Add water 1.0 liter 1.0 liter pH 6.8 8.0 (wash water) Common for mother liquor and replenisher Tap water is replaced with H-type strongly acidic cation exchange resin (Amber manufactured by Rohm and Haas Co.) Light IR-120B) and OH
Type strongly basic anion exchange resin (Amberlite IRA)
-400) is passed through a mixed-bed column packed with water to treat the calcium and magnesium ion concentrations to 3 mg / l or less, followed by sodium diisocyanurate 2
0 mg / L and 150 mg / L of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to mother liquor and replenisher (unit: g) Formalin (37%) 1.2 ml Surfactant [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] 0.4 ethylene Glycol 1.0 Water was added, and 1.0 liter of the sample, which had been treated with pH 5.0-7.0, was subjected to concentration measurement with a green filter. The sensitivity was defined as the reciprocal of the exposure amount giving a density 0.2 higher than the fog density, and expressed as a relative value with the value of sample 11 before storage being 100. Fog was expressed as an absolute value of optical density.

[0081]

[Table 1]

As described above, in the present invention, it was found that the change in sensitivity was small and the rise in fog was suppressed.

Example 2 Emulsions Em-1, Em-2 and Em-3 prepared in Example 1
Each layer having the composition shown below was sequentially formed on the triacetyl cellulose film support provided with an undercoat layer from the support side by using
2, 23 were produced. (Emulsions in the tenth layer were changed to Emulsions Em-1, Em-2, and Em-3 prepared in Example 1, respectively, to obtain Samples 21, 22, and 23, respectively.) The added amount was grams in 1 m ² . Expressed by However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by S) were expressed in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.123 CC-1 0.044 OIL-1 0.167 Gelatin 1.33 Second Layer (Intermediate) Layer) AS-1 0.160 OIL-1 0.20 Gelatin 0.69 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 S-12 .37 × 10 ^-5 S-2 1.2 × 10 ^-4 S-3 2.4 × 10 ^-4 S-4 2.4 × 10 ^-6 C-1 0.32 CC-1 0.038 OIL- 2 0.28 AS-2 0.002 Gelatin 0.73 Fourth layer (Medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 S-1 4.5 × 10 ^-5 S-2 2.3 × 10 ^-4 S-3 4.5 × 10 ^-4 C-2 0.52 CC-1 0.06 DI-1 0.047 OIL-2 0.4 6 AS-2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 S-1 3.0 × 10 ^-5 S -2 1.5 × 10 ^-4 S-3 3.0 × 10 ^-4 C-2 0.047 C-3 0.09 CC-1 0.036 DI-1 0.024 OIL-2 0.27 AS -2 0.006 Gelatin 1.28 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 Gelatin 1.00 7th layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0 .19 silver iodobromide b 0.062 S-4 3.6 × 10 ^-4 S-5 3.6 × 10 ^-4 M-1 0.18 CM-1 0.033 OIL-1 0.22 AS- 2 0.002 AS-3 0.05 gelatin 0.61 8th layer (intermediate layer) OIL-1 0.26 AS-1 0.054 gelatin 0.80 9th layer (medium Green-sensitive layer) Silver iodobromide e 0.54 iodobromide f 0.54 S-6 3.7 × 10 -4 S-7 7.4 × 10 -5 S-8 5.0 × 10 ^-5 M-1 0.17 M-2 0.33 CM-1 0.024 CM-2 0.029 DI-2 0.024 DI-3 0.005 OIL-1 0.73 AS-3 0.035 AS-2 0.003 Gelatin 1.80 Tenth layer (highly sensitive green color-sensitive layer) Emulsion Em-1, Em-2 or Em-3 prepared in Example 1 1.19 M-1 0.065 CM -2 0.026 CM-1 0.022 DI-3 0.003 DI-2 0.003 OIL-1 0.19 OIL-2 0.43 AS-3 0.017 AS-2 0.014 Gelatin 1. 23 11th layer (yellow filter layer) Yellow colloidal silver 0.05 OIL-1 0.18 AS-10 6 Gelatin 1.00 12th layer (low sensitivity blue-sensitive layer) Silver iodobromide b 0.22 Silver iodobromide a 0.08 Silver iodobromide h 0.09 S-9 6.5 × 10 - ⁴ S-10 2.5 × 10 ^-4 Y-1 0.77 DI-4 0.017 OIL-1 0.31 AS-2 0.002 Gelatin 1.29 13th layer (high-sensitivity blue-sensitive layer ) Silver iodobromide h 0.41 Silver iodobromide i 0.61 S-9 4.4 × 10 ^-4 S-10 1.5 × 10 ^-4 Y-1 0.23 OIL-1 0.10 AS -2 0.004 Gelatin 1.20 14th layer (first protective layer) Silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.30 Gelatin 1.32 15th Layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Gelatin 0.55 The above silver iodobromide Show light of the following (one side length of a cube having the same volume as the average particle diameter).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 c 0.60 7.0 3.0. 1 d 0.74 7.0 5.0 e 0.60 7.0 4.1 f 0.65 8.7 6.5 h 0.65 8.0 1.4 i 1.00 8.0 2.0. 0 j 0.05 2.0 1.0 As typical examples of forming silver halide grains of the present invention, JP-A-1-183417 and JP-A-1-183644.
Nos. 1-183645 and 2-166442.

In addition to the above composition, a dispersing aid SU-
1, coating aid SU-2, SU-3, SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-11, two kinds of polyvinylpyrrolidone (AF-12) having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000, inhibitors AF-13, AF-1, and A
F-15, hardeners H-1, H-2 and preservative Ase-1
Was added.

The structure of the compound used in the above sample is shown below.

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

These samples 21, 22 and 23 were exposed to sensitometry (1/100 second) and processed by the method described below.

Processing method Step Processing time Processing temperature * Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ° C 25 ml 10 liters Bleaching 45 seconds 38 ° C 5 ml 4 liters Bleaching and fixing (1) 45 seconds 38 ° C -4 liters Bleaching Fixing (2) 45 seconds 38 ° C 30 ml 4 liters Washing with water (1) 20 seconds 38 ° C-2 liters Washing with water (2) 20 seconds 38 ° C 30 ml 2 liters Stabilizing 20 seconds 38 ° C 20 ml 2 liters Drying 1 minute 55 ° C * The amount of replenishment is the amount per 35 m width and 1 m length. The bleach-fixing and washing steps are (2) to (1) respectively.
The overflow solution of the bleaching solution was all introduced into the bleach-fix (2). The amount of the bleach-fixing solution brought into the washing step in the above processing was 2 ml per 1 m of the photosensitive material having a width of 35 mm.

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 3.0. 5 Potassium iodide 1.2 mg-hydroxylamine sulfate 2.0 3.6 4- [N-ethyl-N-β-hydroxy 4.7 7.2 ethylamino] -2-methylaniline sulfate 1.0 liter 1.0 liter pH 10.00 10.15 (bleach) Mother liquor (g) Replenisher (g) Ferric 1,3-diaminopropanetetraacetate 144.0 206.0 Ammonium monohydrate 1 , 3-Diaminopropanetetraacetic acid 2.8 4.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Aqueous ammonia (27%) 10.0 1.8 Acetic acid ( 51.1 73.0 Add water 1.0 liter 1.0 liter pH 4.3 3.4 (Bleaching and fixing solution) Mother liquor (g) Replenisher (g) Ferric ammonium ethylenediaminetetraacetate 50 2.0-ium dihydrate disodium ethylenediaminetetraacetate 5.0 25.0 ammonium sulfite 12.0 20.0 aqueous solution of ammonium thiosulfate 290.0 ml 320.0 ml (700 g / l) ammonia water (27%) 6.0 ml 15.0 ml Add water 1.0 liter 1.0 liter pH 6.8 8.0 (Washing solution) Common for mother liquor and replenisher Tap water is replaced with H-type strongly acidic cation exchange resin (Amber manufactured by Rohm and Haas Co.) Light IR-120B) and OH
Type strongly basic anion exchange resin (Amberlite IRA)
-400) to reduce the calcium and magnesium ion concentration to 3 mg / L or less by passing water through a mixed bed column packed with sodium diisocyanurate 2
0 mg / liter and 150 mg / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Common to mother liquor and replenisher (unit: g) Formalin (37%) 1.2 ml Surfactant [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] 0.4 Ethylene Glycol 1.0 Water was added, and 1.0 liter of the sample, which had been treated with pH 5.0-7.0, was subjected to concentration measurement with a green filter. The samples 21, 22, and 23 were compared with respect to the sensitivity in the same manner as in Example 1, and it was confirmed that this multilayer coated sample had the same effect as the single layer coated sample.

[0101]

The silver halide photographic light-sensitive material using the silver halide emulsion of the present invention exhibits excellent storage stability.

Claims (7)

[Claims] 1. In a tabular silver halide grain having a (111) major plane and containing silver chloride, the silver chloride content of at least one apex portion is determined by the average silver chloride content of the tabular silver halide grain. Tabular silver halide grains, characterized in that the ratio is lower than the ratio. 2. The tabular silver halide grains according to claim 1, wherein the tabular silver halide grains are hexagonal tabular silver halide grains. 3. The individual tabular silver halide grains according to claim 1, wherein the silver chloride content of at least half or more of the apexes is lower than the average silver chloride content of said tabular silver halide grains. Or tabular silver halide grains according to 2. 4. The tabular silver halide grains according to claim 1 or 2, wherein the silver chloride content at all apexes is lower than the average silver chloride content of said tabular silver halide grains. The tabular silver halide grains described in the above. 5. A silver halide emulsion characterized in that at least 50% (number) or more of the silver halide grains are tabular silver halide grains according to any one of claims 1 to 4. 6. The method according to claim 1, wherein all silver halide grains are present.
5. A silver halide emulsion comprising the tabular silver halide grains according to any one of the above. 7. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing the silver halide emulsion according to claim 5 on a support.