JPH03194538A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having high sensitivity especially in a color sensitization range and hardly causing fog by forming a silver halide emulsion contg. silver halide particles contg. coexistent reduced silver and silver chalcogenide and sensitized with gold, sulfur, etc., on a substrate. CONSTITUTION:Reduced silver is formed during the growth of silver halide particles and a compd. contg. an active chalcogen atom is added during the formation of the particles to allow reduced silver and silver chalcogenide such as AgS or AgSe to coexist with each other in the particles. The particles are then sensitized with gold, sulfur, selenium, a group VIII noble metal of the periodic table or a combination of such elements and a silver halide emulsion contg. the resulting silver halide particles in formed on a substrate. A sensitive material having high sensitivity especially in a color sensitization range and hardly causing fog is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more specifically, reduced silver and a silver chalcogenide compound coexist within the grains to achieve high sensitivity and fogging. The present invention relates to a silver halide photographic material that has a small amount of oxidation, high sensitivity, especially in the color sensitization region, and good storage stability.

(Prior Art) The basic properties required of a silver halide emulsion for photographing are high sensitivity, low fog, and fine grain.

In order to increase the sensitivity of an emulsion, (1) increase the number of photons absorbed by a single grain; (2) increase the efficiency with which photoelectrons generated by light absorption are converted into silver clusters (latent images); and (3) it is necessary to increase the development activity in order to effectively utilize the formed latent image.

Increasing the size increases the number of photons absorbed by one particle, but
Decrease image quality. Increasing the development activity is also an effective means for increasing the sensitivity, but in the case of parallel development such as color development, graininess generally deteriorates. In order to increase sensitivity without causing deterioration of graininess, it is most preferable to increase the efficiency of converting photoelectrons into latent images, that is, to increase quantum sensitivity. In order to increase quantum sensitivity, it is necessary to eliminate inefficient processes such as recombination and latent image dispersion as much as possible.

It is known that a method of creating small silver nuclei without development activity inside or on the surface of silver halide is effective in preventing recombination.

In addition, James et al. have found that when a coated film of a gold-sulfur sensitized emulsion is vacuum degassed and then heat-treated in a hydrogen gas atmosphere, the fog level is lower than that in conventional reduced silver formation. We found that sensitivity can be increased by

This sensitization method is well known as hydrogen sensitization, and is effective as a means of increasing sensitivity on a laboratory scale. Furthermore, hydrogen sensitization is actually used in the field of astrophotography.

Attempts to form reduced silver have been considered for a long time.

Carroll has been awarded U.S. Patent No. 2. 487
．． No. 850, a tin compound, Lowe et al. No. 2,512,925, a polyamine compound, Fallens et al. British Patent No. 789,823, a thiourea dioxide compound. It was disclosed that it is useful as a silver forming agent. Furthermore, Co11ier (Korea) is a Photographer.
icScience and Engineering
23, p. 113 (1979) compares the properties of silver nuclei produced by various reduced silver formation methods. She employed dimethylamine borane, stannous chloride, hydrazine, high pH aging, and low pAg aging.

The method of forming reduced silver is further described in U.S. Pat.
No. 8, No. 3,201,254, No. 3゜411.9
No. 17, No. 3,779,777, No. 3,930,
It is also disclosed in No. 867.

Not only the selection of the reducing silver forming agent but also the method of using the reducing agent are disclosed in Japanese Patent Publications No. 57-33572, No. 58-1410, and Japanese Patent Application Laid-Open No. 57-179835. Furthermore, regarding techniques for improving the storage stability of emulsions containing reduced silver, JP-A-57-82831 and JP-A-60-178445 are also disclosed.
Disclosed in the issue. Despite many studies as described above, the increase in sensitivity has not been sufficient compared to hydrogen sensitization in which photosensitive materials are treated with hydrogen gas under vacuum.

This is reported in the Journal of Imaging 5
Mo1 in science volume 29 page 233 (1985)
It has been reported by Sar (Moyser) et al.

In addition, the above-mentioned literature lists conventionally known reduced silver forming agents, and ascorbic acid is mentioned among them. However, compounds such as thiourea dioxide are preferred, and those shown in the Examples are thiourea dioxide, silver ripening, and hydrazine. Therefore, favorable characteristics of ascorbic acid compounds as reduced silver forming agents have not been found. Regarding further innovations, JP-A-57-1
No. 79835.

However, in order to put reduced silver formation into practical use, it is necessary to overcome the problem of the storage stability of photosensitive materials. Regarding the technology for improving the storage stability of emulsions containing reduced silver, Japanese Patent Application Laid-Open No. 57-8
Although it is disclosed in No. 2831 and No. 60-178445, it has not reached a sufficient level of improvement. At the same time, improvements in the storage stability of light-sensitive materials containing reduced silver-forming emulsions have been awaited.

Furthermore, U.S. Patent No.
, 772,031, but it has a low recombination prevention function and is insufficient as a means for increasing sensitivity.

[Problem that the invention seeks to solve]

Conventional techniques for forming reduced silver have not been sufficient to meet the recent demands for photographic materials with high sensitivity and high image quality. Hydrogen sensitization also has the disadvantage that if the photosensitive material is left in the air after hydrogen sensitization, the sensitizing effect is lost. Therefore, it is difficult to utilize this sensitization method in the case of photographic materials for which special equipment cannot be used.

Further, when color sensitization is performed, there is a problem in that the increase in sensitivity due to the formation of reduced silver is reduced.

(Objective of the Invention) An object of the present invention is to provide a silver halide photographic material which is highly sensitive and has little fog, particularly in the color sensitized region. A second object is to provide a color photographic material that is highly sensitive and has little fog, which is less susceptible to deterioration due to natural radiation.

[Means to solve the problem]

The objects of the present invention have been achieved by silver halide photographic materials described in (1) to 00 below.

(11) A silver halide emulsion layer containing silver halide grains in which reduced silver and a silver chalcogenide compound coexist inside the grains, and which has been subjected to one of gold sensitization, sulfur sensitization, and precious metal sensitization. A silver halide photographic light-sensitive material having a small amount of (or one layer) on a support.

(2) The silver halide photographic material according to claim 11, wherein the coexisting chalcogenide compound is a sulfide.

(3) The amount of silver chalcogenide compounds present inside the particles is 10-9 mol or more per mol of silver l0-5 mo/1,1
1. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic material has the following properties.

(Claim 15 (1) spectrally sensitized with a sensitizing dye whose 41HOMO level is -5.6 eV or higher
) The silver halide photographic material described in ).

(5) The halogenated silver halide grains according to claim 1, wherein the average value of the ratio of projected area diameter to thickness is 3 or more!
Photographic material.

(6) The halogenated tactile photographic material according to claim 11, wherein the coefficient of variation of the grain size distribution of the 10 silver saponide grains is 720% or less.

(n) The silver halide photographic material according to claim 11, which contains silver halide grains whose grain surfaces contain 5 mol % or more of silver iodide.

(8) The silver halide photographic material according to claim (1), which has an emulsion layer containing a nitrogen-containing heterocyclic compound having a mercapto group on the support.

(9) The silver halide photographic material according to claim (1), in which a diffusive DIR coupler coexists.

(10) The silver halide photographic material according to claim (1), which is a color photographic material.

The present invention will be explained in detail below.

In the production of silver halide grains, which is a feature of the present invention, reduced silver is formed during the growth of silver halide grains. Growing means that silver halide grains are undergoing physical ripening, addition of water-soluble silver salt and water-soluble alkali halide (precipitation,
Precipitat 1 on) is also meant to be included during further precipitation steps after the formation of reduced silver with these additions suspended.

The method of forming reduced silver of the present invention is a method of adding a reduced silver forming agent to a silver halide emulsion, and a pAg method called silver ripening.
A method of growing or aging in an atmosphere with a low pAg of 1 to 7, a high pH of 8 to 11 called high pH aging.
Either the method of growing in an H atmosphere or the method of aging can be selected. Moreover, two or more methods can also be used together.

The method of adding a reduced silver forming agent is a preferred method since the level of reduced silver formation can be finely controlled.

As reduced silver forming agents, stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds, borane compounds, ascorbic acids, and the like are known. For forming reduced silver in the present invention, these known reduced silver forming agents can be selected and used, and two or more types of compounds can also be used in combination. Preferred compounds as the reduced silver forming agent are stannous chloride, thiourea dioxide, dimethylamine porane, and ascorbic acids. The amount of reduced silver forming agent added depends on the emulsion manufacturing conditions, so it is necessary to select the amount added, but it is 10-7 to 1 O-1 per mole of silver halide.
A molar range is suitable.

The reduced silver forming agent is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, amides, etc., and added during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle growth. In addition, a reduced silver forming agent is added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide.
Silver halide grains may be precipitated using these aqueous solutions. It is also preferable to add the solution of the reduced silver forming agent in several portions as the grains grow, or to add the solution continuously over a long period of time.

The silver chalcogenide compound of the present invention is A g t S
.

Ag*Se, Ag2TAg2Te1(A, , (Agx
SeL, (AgtTe), (n is an integer), and further 5
2Se'', also referred to as Te2-, and each compound is present alone or in a mixture. Preferred compounds are A
gxS (Ag2S)-, AggSSe and S'-. The amount of silver chalcogenide compound present inside the grains is preferably 101 or more and 10-5 mol or less per mol of silver halide.If the amount is less than this, the sensitivity will not increase, and if it is more than this, it will cause fogging. Desensitization occurs.

The first method for coexisting reduced silver and a silver chalcogenide compound in grains is to add a compound containing an active chalcogen atom during grain formation.

Compounds containing sulfur are preferred. The addition may be made at any stage during particle formation. Preferably, it is allowed to coexist when forming reduced silver, or added after forming reduced silver.

Preferred compounds are represented by the general formulas CI), [■], or CI), and at least one of these is added.

CI) R-3O21M (n) R-3O2S-R (II[] RS Or S L m S S
In the formula O2R2, RSR' and R' may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group,
M represents a cation. L represents a divalent linking group, and m is 0 or l.

The compounds of general formulas [I] to [IIr) may be polymers containing divalent groups derived from the structures represented by [I] to I[[] as repeating units. Furthermore, when possible, R, R', R2, and L may be combined with each other to form a ring.

Another method for coexisting reduced silver and silver chalcogenide in grains is to coexist a chalcogen sensitizer during grain formation. Chalcogen sensitizers include sulfur-containing compounds such as hypo, thiourea compounds, and rhodanine compounds; for example, dimethylselenourea, selenocarbamide, allylselenourea described in U.S. Pat. Selenium-containing compounds, such as colloidal selenium, and e.g.
2031, but is not limited to these compounds. Preferably it is a sulfur-containing compound.

The amount of the compound containing an active chalcogen atom and the chalcogen sensitizer added is 10-7 to 10 per mole of silver halide.
-1 mol is preferred. Furthermore 1O-6 to 1
An amount of O-2, particularly 10-' to 10-' mole to 1 mole of Ag, is preferred. compounds containing active chalcogen atoms,
And the chalcogen sensitizer is water or alcohol,
It is added after being dissolved in a solvent such as ketones, esters, and amides. Although it is possible to add it to the reaction vessel in advance, it is preferable to add it at an appropriate time during particle growth. Although it is preferable to add it in advance to an aqueous solution of a water-soluble alkali halide, it is more preferable to add it from the surface of the reaction vessel at an appropriate time of particle growth.

To explain the compounds of general formulas [I], (II) and (III) in more detail, when R, R' and R2 are aliphatic groups, saturated or unsaturated, linear, branched or cyclic, aliphatic It is a hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an alkynyl group having 2 to 22 carbon atoms, and these may have a substituent.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and naphthyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic groups for R, R' and R2 include monocyclic or condensed ring aromatic groups, preferably those having 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, R' and R2 includes nitrogen, oxygen,
3 to 1 having at least one element selected from sulfur, selenium, and tellurium and having at least one carbon atom
A 5-membered ring, preferably a 3- to 6-membered ring, such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole,
Examples include imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tetrazole, triazole, benzotriazole, tetrazole, oxadiazole, and thiadeazole ring.

Substituents for R, R' and R2 include, for example, alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (e.g. methoxy, ethoxy, octyl), aryl groups (e.g. phenyl, naphthyl, tolyl), hydroxy groups, halogen atoms (fluorine, chlorine, bromine, iodine), aryloxy groups (e.g. phenoxy), alkylthio groups (e.g. methylthio, butylthio), arylthio groups (e.g. phenylthio), acyl groups (e.g. acetyl, propionyl, butyryl) , valeryl), sulfonyl groups (e.g., methylsulfonyl, phenylsulfonyl)
, acylamino group (e.g. acetylamino, benzoylamino), sulfonylamino group (e.g. methanesulfonylamino, benzenesulfonylamino), acyloxy group (e.g. acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, Examples include -8025M group and -3O,R' group.

The divalent linking group represented by is an atom or atomic group containing at least one selected from C, N, S and O. Specifically, alkylene group, alkenylene group, alkynylene group, arylene group, -0--8--NH--
It consists of CO--SO,-, etc. alone or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. L is a divalent aliphatic group, for example +CH, ÷, (
n=1 to 12), CH= CH= CHCH2- -CH2C::CCH,-. Examples of the divalent aromatic group for L include a phenylene group and a naphthylene group.

These substituents may be further substituted with the substituents described above.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Examples of organic cations include ammonium ions (ammonium, tetramethylammonium, tetrabutylammonium, etc.), phosphonium ions (tetraphenylphosphonium), guanidyl groups, and the like.

When general formula (I) to III) is a polymer,
Examples of the repeating unit include the following.

+CH-CH2-)- COt CH! CHt OCHt CH2S Ot
S M025M These polymers may be homopolymers or copolymers with other copolymerizable monomers.

Specific examples of the compounds represented by the general formulas CI], [II], or CI[I) are listed in Table A, but the compounds are not limited thereto.

The compound of general formula CI) is disclosed in JP-A-54-1019; British Patent No. 972. 211; Journal of O
rga-nic Chemistry (Journal of Organic Chemistry) Volume 53, 396
(1988) and Chemical Abstract
ts (Chemical Abstracts) Volume 59, 977
It can be easily synthesized by the method described or cited in 6e.

The compound represented by general formula CI), (II) or [III) is 1O-7 to 1O-1 per mole of silver halide.
Preferably, it is added in moles. Further from 1O-6 to 10-
1. Particularly preferred is an amount of 10-5 to 10-' mol of Ag.

In order to add the compounds represented by general formulas CI) to (III) during the manufacturing process, methods commonly used for adding additives to photographic emulsions can be applied.

For example, for water-soluble compounds, make an aqueous solution of an appropriate concentration,
Compounds that are insoluble or sparingly soluble in water are dissolved in a suitable organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, amides, etc., and does not adversely affect photographic properties. However, it can be added as a solution.

The compound represented by compound [I], [II) or CI) may be present at any stage of reduced silver formation during grain growth. Preferably, the compound is added before or while the reduced silver is being formed. Particularly preferably, it is added so as to coexist with the reduced silver forming agent.

The most preferred general formula of the compound for the present invention is a compound represented by general formula [I].

The presence and amount of silver chalcogenide compounds coexisting with reduced silver inside the silver halide grains of the present invention are determined by radioactive isotope ii
It is detected by an analytical means using a compound labeled with S, +iSe or 12++nTe, but a method using 113 is preferred. It is believed that it is possible to detect less than 1X10-' mole of silver chalcogenide compound per mole of silver halide by this method.

The method for synthesizing labeled compounds is described in Nippon Kagaku Complete Edition, "Labeled Compounds" (New Experimental Chemistry Course 11, published by Maruzen, 1976) and Chemical Abstracts (1958, 17917c1).
It is described or cited in etc.

A method for measuring the presence and amount of silver chalcogenide compounds contained in silver halide grains using a labeling compound is described, for example, in Berichte der Bunsen Gesel.
schaftfjr Physicalische C
hemie vol. 68 (4) pp. 389-399 (1964
), Journal of Imaging Science
nce, Vol. 32, pp. 20-27 (1988). In order to measure the presence and amount of silver chalcogenide compounds present inside the particles, the silver chalcogenide compounds present on the particle surfaces must be removed in advance. This is done by dissolving the silver chalcogenide compound on the particle surface with bromine water and washing with water.

Here, chemical sensitization includes sulfur sensitization, gold sensitization, and selenium sensitization using noble metals of group II of the periodic table (e.g., Pd, Pt, Id).
It is possible to employ sensitization based on the combination of sensitization and sensitization based on combinations of these sensitizations. Among these, gold sensitization or sulfur sensitization is preferred, and gold plus sulfur sensitization (also referred to as "gold/sulfur sensitization") is particularly preferred. Further, it is preferable to carry out gold/sulfur sensitization after reduction sensitization in the present invention.

It is preferable that the surface of the silver halide grains of the present invention contains 5 mol % or more of silver iodide.

Various conventionally known methods can be employed to control the silver iodide content near the surface of the grains. A method in which an aqueous solution of a water-soluble silver salt and an aqueous solution of a halide containing a water-soluble iodide are further added to silver halide grains grown in the presence of a protective colloid; The method can be selected from among a method in which silver iodide is added and a method in which a sparingly soluble iodide such as silver iodide or silver iodobromide is added and ripened. Alternatively, a method may be used in which iodide is distributed near the surface by physically ripening silver halide grains containing iodide.

5 to 30 contained on the surface of the silver halide grains of the present invention.
In the case of cubic or octahedral crystals, it is preferable that the mole % of silver iodide be as uniform as possible on the surface. It is preferable that the grain has a layered structure in which the entire surface is covered with a layer containing silver iodide. However, in grains such as tetradecahedrons in which 111) and (100) planes coexist, or in grains such as tabular grains in which main planes and side surfaces coexist, only specific planes are mainly covered with a layer containing silver iodide. It is also a preferred form of the present invention.

When forming a layer containing 5 mol% or more of silver iodide on the surface, the presence of spectral sensitizing dyes such as cyanine and merocyanine, or antifoggants and stabilizers such as mercapto compounds, azole compounds, and azaindene compounds is recommended. This is the preferred method. Similarly, it may be preferable to include a silver halide solvent such as thiocyanic acid, thioether, or ammonia e.

The silver iodide content on the surface of silver halide grains can be detected by various surface elemental analysis means. It is useful to use methods such as XPS, Auger electron spectroscopy, and TSS.

The simplest and most accurate method is X P S (X-r
ay Photoelectron 5pectr.

5copY), and the surface silver iodide content of the present invention is defined by the measured value by this method.

XPS (X-ray Photoelectro
The depth that can be analyzed using the surface analysis method (n 5 pectroscopy) is said to be about 10 people.

Regarding the principle of the XPS method used to analyze the iodine content near the surface of silver halide grains, please refer to "Electron Spectroscopy" by Atsushi Aihara et al. (Kyoritsu Library 16, published by Kyoritsu Shuppan, 1978). can do.

The standard measurement method for XPS is
This is a method of observing the intensity of photoelectrons of iodine (I) and silver (Ag) (usually I3ds7□, Ag-3ds/l) emitted from silver halide grains in an appropriate sample format. be.

To determine the iodine content, a calibration curve of the photoelectron intensity ratio of iodine (I) and silver (Ag) (intensity (I) 7 intensity (Ag)) is calculated using several types of standard samples with known iodine contents. can be calculated from this calibration curve. In the case of a silver halide emulsion, XPS measurement must be performed after gelatin adsorbed on the surface of silver halide grains is decomposed and removed using a protease or the like.

Silver halide containing 5 mol% or more of silver iodide on the grain surface is defined as silver halide containing 5 mol% or more of silver iodide when the emulsion grains contained in one emulsion are analyzed using surface elemental analysis. refer to something. In this case, if two or more types of emulsions are clearly mixed, it is necessary to perform an appropriate pretreatment such as centrifugation or filtration before analyzing the same type of emulsion.

More preferably, it refers to an emulsion having a silver iodide content of 5 to 30 mol% when measured by standard XPS.

Grains whose surfaces contain silver iodide in an amount of 5 mol % or more are preferred, more preferably 7.5 mol % or more, and more preferably 10-15 mol % on their surfaces.

The surface halogen composition other than silver iodide is preferably silver bromide, but may also contain up to 10 mol % of silver chloride.

The average silver halide composition of the entire grain of the silver halide grains forming the reduced silver of the present invention is silver iodobromide or silver iodochlorobromide containing 1 to 30 mol % of silver iodide. Preferably 7~
It contains 20 mol% of silver iodide and may contain up to 10 mol% of silver chloride.

The silver halide grains used in the present invention may be normal crystals that do not contain twin planes; Select from single twins containing one crystal plane, parallel multiple twins containing two or more parallel twin planes, nonparallel multiple twins containing two or more nonparallel twin planes, etc. depending on the purpose. In the case of normal crystals, it is a cube consisting of (100) planes, an octahedron consisting of (111) planes, and the Japanese Patent Publication No. 55-427.
37, disclosed in Japanese Patent Application Laid-Open No. 60-222842 (1
10) Dodecahedral particles consisting of faces can be used.

In addition, Journal of ImagingScie
nce Vol. 30, p. 247 As reported in 1986, (hl) plane particles with (211) as a representative, (
The (hhl) plane particles represented by (331) planes, the (hko) plane particles which represent (210) planes, and the (hkl) plane particles which represent (321) planes also require some ingenuity in their preparation methods, but they can be prepared depending on the purpose. You can choose and use it. (100) plane and (11
1) A tetradecahedral particle whose faces coexist in one particle, (100
) plane and (110) plane coexisting or (111) plane
Particles in which two planes or a large number of planes coexist, such as particles in which a plane and a (l l O'') plane coexist, can also be selected and used depending on the purpose.

The grain size of the silver halide grains may be fine grains of 0.1 micron or less, large grains with a projected area diameter of up to 10 microns, monodisperse emulsions with a narrow distribution, or polydisperse emulsions with a wide distribution. Although a dispersed emulsion may be used, a monodispersed emulsion is more preferable.

In the present invention, a monodisperse silver halide emulsion is one in which the weight of silver halide contained within a grain size range of ±20% around the average projected area diameter is 80% or more of the weight of all silver halide grains. It is preferably 90% or more. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions may be mixed or layered for use.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimie et Physi
que Photography Paul Mo
Ntel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duf f.
in.

Photographic Emulsion Che
mistry (Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, published by Focal Press (V, L, Zelikma
Net al, Making and Coatin
g Photographic Emulsion, F
ocal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and pH during grain formation. For more information, see Photographic Science and Engineering (Photographic Science and Engineering).
5science and Engineering) Volume 6, pp. 159-165 (1962): Journal of Photographic Science (Journa10
f Photographic 5science),
12, pp. 242-251 (1964), U.S. Patent No. 3. 655. No. 394 and British Patent No. 1,413
, No. 748.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in ``Theory and Practice of Photography'' by Cripe, Phot.

graphy theory and practice
(1930), p. 131; Cutoff, Photographic Science and Engineering (Cutoff, Phot.

graphic 5science and engine
14, pp. 248-257 (197
0); U.S. Patent No. 4゜434.226, U.S. Patent No. 4,41
No. 4,310, No. 4.433,048, No. 4,439
, 520 and British Patent No. 2,112,157. The use of tabular grains has advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in the above-cited U.S. Pat. No. 4,434,226. .

Tabular grains are preferred as emulsions of the present invention.

In particular, tabular grains in which grains with an aspect ratio of 3 or more occupy 50% or more of the total projected area are preferred.

In order to obtain monodisperse tabular grains, a fine grain tabular silver iodobromide emulsion can be obtained by adding equal amounts of an aqueous solution of silver nitrate and an aqueous solution of a mixture of potassium bromide and potassium iodide using a double jet method. can.

Subsequently, grain growth can be carried out in several batches or continuously by adding equal amounts of an aqueous solution of silver nitrate and an aqueous solution of a mixture of potassium bromide and potassium iodide, and increasing the total amount and rate of addition. The pAg being added is controlled so as to maintain a flat plate shape without causing re-nucleation, and pAg of 9 to 7 is preferable.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
No. 46, U.S. Patent No. 3.505.068, U.S. Patent No. 4,44
No. 4,877 and Japanese Patent Application No. 58-248469.

Further, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

The silver halide emulsion of the present invention preferably has a distribution or structure in terms of halogen composition in its grains.

Typical examples are JP-B No. 43-13162 and JP-A No. 6.
These are core-shell type or double-structured particles in which the interior and surface layers of the particles have different halogen compositions, as disclosed in JP-A No. 1-215540, JP-A-60-222845, JP-A-61-75337, and the like. In such particles, the shape of the core portion and the overall shape including the shell may be the same or different. Specifically, the core part has a cubic shape, and the shape of the shelled particle may be cubic or octahedral. Conversely, the core may be octahedral and the shelled particle may be cubic or octahedral. Further, although the core portion is a clearly regular particle, the shape of the shelled particle may be slightly distorted or irregular. In addition, instead of a simple double structure, it is possible to create a triple structure as disclosed in JP-A No. 60-222844, or a multilayer structure with more than that, or a halogen with a different composition on the surface of the core-shell double structure particle. You can apply a thin layer of silver.

In order to give a structure to the inside of a particle, it is possible to create a particle having not only the above-mentioned enveloping structure but also a so-called bonding structure. These examples are disclosed in Japanese Patent Application Laid-Open No. 59-13354.
0, Japanese Patent Publication No. 58-108526 EP199290A
2. Japanese Patent Publication No. 58-24772, Japanese Patent Publication No. 59-16254
etc. are disclosed. The crystal to be bonded can have a composition different from that of the host crystal and can be formed by bonding to an edge, part of a corner, or surface of the host crystal.

Such a bonded crystal can be formed even if the host crystal is uniform in terms of halogen composition or has a core-shell structure.

Of course, a combination of silver halides is possible in the case of a bonding structure, but a bonding structure can be formed by combining silver halide with a silver salt compound that does not have a rock salt structure, such as silver rhodan or silver carbonate. Further, non-silver salt compounds such as PbO may also be used if a bonded structure is possible.

In the case of grains such as silver iodobromide having these structures, for example, in core-shell type grains, the silver iodide content in the core portion is preferably higher than that in the shell portion. Conversely, the grains may have a low silver iodide content in the core part and a high content in the shell part. Similarly, grains having a bonded structure may be grains in which the silver iodide content of the host crystal is high (or grains in which the silver iodide content of the bonded crystal is relatively low), or vice versa.

In addition, the boundaries between particles with these structures with different halogen compositions may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to composition differences, or may be actively continuous boundaries. It may also be one with some structural changes.

The silver halide emulsion used in the present invention is EP-009672.
7BISEP-0064412B1, etc., or DE-2
The surface may be modified as disclosed in JP-A-60-221320, No. 306447C2.

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but an internal latent image type emulsion can also be used by selecting the developer or development conditions, as disclosed in JP-A-59-133542. can. A light latent image type emulsion covered with a thin shell can also be used depending on the purpose.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can also be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the addition of the silver and halide salts, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used.

The silver halide grains of the present invention have at least one of sulfur sensitization, gold sensitization, or noble metal sensitization in addition to the coexistence of reduced silver and a silver chalcogenide compound inside the grains. is applied at any step of particle formation. These chemical sensitizations vary depending on the composition, structure, and shape of the emulsion grains and the intended use of the emulsion, but are typically carried out at a grain growth stage subsequent to the reduced silver formation of the present invention. . There are cases in which chemical sensitizing nuclei are embedded inside particles, in cases where they are embedded at a shallow position from the particle surface, or in cases where chemical sensitizing nuclei are created on the surface. Although the effects of the present invention are effective in any case, it is particularly preferable to create chemically sensitized nuclei near the surface. In other words, surface latent image type emulsions are more effective than internal latent image type emulsions.

In addition to reduced silver formation, chemical sensitizations that may be preferably carried out in the present invention (hereinafter also simply referred to as chemical sensitization) include gold sensitization, sulfur sensitization, or noble metal sensitization, singly or in combination, as described by James ( T. H. James), The Photographic Process, 4th edition, Macmillan Publishing, 1977.
(T.H.James, The Theory of
he Photographic Process,
4th ed, Macmillan.

1977) 6, page 76, or as described in Research Disclosure, Vol. 120, April 1974, 12008.
Research Disclosure, Volume 34, June 1975, 13452. U.S. Patent No. 2,642,361, 3
．． 297. No. 446, No. 3,772,031, No. 3,857゜711, No. 3,901,714, No. 4
, No. 266.018, and No. 3,904,415,
and pAg 5-101 pH 5-8 and temperature 30-80 as described in British Patent No. 1,315,755.
The sensitizers can be sulfur, selenium, chilli, gold, platinum, palladium, iridium or combinations of these sensitizers at 0.degree. These chemical sensitizations are most preferably
In the presence of a gold compound and a thiocyanate compound, sulfur-containing compounds or hypo-thiourea compounds as described in U.S. Pat. , in the presence of sulfur-containing compounds such as rhodanine compounds. Chemical sensitization can also be carried out in the presence of so-called chemical sensitization aids. Useful chemical sensitization aids include azaindene, azapyridazine,
Compounds known to suppress fog and increase sensitivity during chemical sensitization are used, such as azapyrimidines. Examples of chemical sensitization aid modifiers include U.S. Pat.
No. 54,757, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention does not exhibit any drawbacks even when other chemical sensitizations are used in combination with the formation of reduced silver. In particular, conventionally it has been difficult to use both gold sensitization and reduced silver formation because of increased fog, but the emulsion of the present invention shows favorable effects even when gold sensitization is used in combination. The preferred amount of gold sensitizer is lXl0 per mole of silver halide.
-' to lXl0-' moles, more preferably l
Xl0-5 to 5xio-' moles.

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is lXl0-' to lXl0-' per mole of silver halide.
0-7 mol, more preferably lXl0-'~
5×10-' moles.

In gold/sulfur sensitization, it is preferable to use the above conditions in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines: mercaptotriazines; thioketo compounds such as oxadorinthion; niazaindenes, such as triazaine; A number of compounds known as antifoggants or stabilizers such as denes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc. can be added. For example, U.S. Patent 3,954
, No. 474, No. 3,982.947, Special Publication No. 1972-2
8,660 can be used.

In the present invention, the nitrogen-containing heterocyclic compound having a mercapto group may be added at any step of the silver halide emulsion manufacturing process. For example, it may be carried out during nucleation, which is the initial stage of grain formation, during physical ripening, during growth, or may be carried out before or after chemical sensitization. Furthermore, it may be added just before coating. Regarding addition in the coating process, generally when the compound represented by formula (IV) or formula (V) is diffusive, it may be added to the same layer as the emulsion of the present invention, or it may be added in the water permeability relationship. The object of the present invention can be achieved even if it is added to other layers that are coated in a multilayer manner. It is necessary to select a suitable amount of the nitrogen-containing heterocyclic compound having a mercapto group, but silver halide 1
1O-6 to 1O- per mole! A molar range is preferred.

In the present invention, the nitrogen-containing heterocyclic compound is preferably a compound represented by the general formula (IV) described below, particularly a compound represented by the general formula [v], and more preferably a compound represented by the general formula [VI]. The compounds represented by are more preferred.

General formula (IV) ,-2-1・,.

-C-3M In the general formula [I], Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and M represents a hydrogen atom, an alkali metal, quaternary ammonium, or quaternary phosphonium.

General formula [v] In general formula [v], R1 is at least one -CO
It represents an aliphatic group, aromatic group or heterocyclic group substituted with OM or -8O,M, where M has the same meaning as in formula (IV).

Hereinafter, the nitrogen-containing heterocyclic compound represented by general formula (IV) [v] used in the present invention will be explained in detail.

Specifically, the aliphatic group represented by R' in the general formula [■] is a linear or branched alkyl group having 1 to 20 carbon atoms (
Examples of aromatic groups include methyl, propyl, hexyl, dodecyl, isopropyl), cycloalkyl groups having 1 to 20 carbon atoms (e.g. cyclopropyl, cyclohexyl), and aromatic groups such as aryl groups having 6 to 20 carbon atoms (e.g. phenyl). , naphthyl), and the heterocyclic group specifically includes 5 containing one or more nitrogen, oxygen or sulfur atoms, etc.
A membered ring, 6-membered ring, or 7-membered heterocycle (e.g., morpholino, piperidino, pyridine), which further forms a fused ring at an appropriate position (e.g., quinoline ring, pyrimidine ring, isoquinoline ring). ).

Further, the above-mentioned linear or branched alkyl group, cycloalkyl group, aryl group and heterocyclic group may have a substituent in addition to -COOM or -305M. Specifically, these substituents include halogen atoms (F, C
L Br), an alkyl group (e.g. methyl, ethyl),
aryl groups (e.g. phenyl, p-chlorophenyl),
alkoxy groups (e.g. methoxy, methoxyethoxy),
Aryloxy groups (e.g. phenoxy), sulfonyl groups (e.g. methanesulfonyl, p-)luenesulfonyl)
, sulfonamide groups (e.g. methanesulfonamide, benzenesulfonamide), sulfamoyl groups (e.g. diethylsulfamoyl, unsubstituted sulfamoyl), carbamoyl groups (e.g. unsubstituted carbamoyl, diethylcarbamoyl), amide groups (e.g. acetamide, benzamide), Ureido groups (e.g. methylureido, phenylureido), alkoxycarbonylamino groups (e.g. methoxycarbonylamino), aryloxycarbonylamino groups (e.g. phenoxycarbonylamino), alkoxycarbonyl groups (e.g. methoxycarbonyl), aryloxycarbonyl groups (e.g. phenoxy carbonyl), cyan group, hydroxy group, carboxy group, sulfo group, nitro group, amino group (e.g. unsubstituted amino, dimethylamino), alkaline sulfinyl group (e.g. methoxysulfinyl), arylsulfinyl group (e.g. phenylsulfinyl), Examples include an alkylthio group (for example, methylthio) and an arylthio group (for example, phenylthio), and these substituents may be substituted with two or more, and the substituents may be the same or different.

Among the nitrogen-containing heterocyclic compounds represented by the general formulas (IV) and [v], those represented by the general formula (VI) are particularly preferred.

2 R2 in general formula [VI) represents a phenyl group substituted with at least one -COOM or -3O1M, and this phenyl group is substituted with at least one -COOM or -SO,M, and this phenyl group is further substituted with other substituents. May be replaced. Specific examples of other substituents include the same substituents as those for the linear or branched alkyl group, cycloalkyl group, aryl group, and heterocyclic group represented by R1.

Here, when there are two or more -COOM and -305M, they may be the same or different. M means the same as that represented by the general formula [■] [V].

Table 8 below lists preferred specific examples of the nitrogen-containing heterocyclic compound having a mercapto group used in the present invention.

However, the present invention is not limited to these specific examples.

As is generally well known, the above compound can be easily synthesized by using a reaction between isothiocyanate and sodium azide. below,
For reference, literature and patents related to these synthesis methods are listed.

U.S. Patent No. 3,266.897, Japanese Patent Publication No. 42-2184
No. 2, JP-A-56-111,846, British patents 1 and 2
No. 75,701, D. A. Berges
et al., Journal of Heterocyclic Chemistry
cChemistry) Volume 15, Page 981 (197
8), R, G, Dubenko, V, D
, written by Panchenko,
himiia Getero-tsiklichesk
ikh 5oedinenii)'', Part 1, (Azo
leoder Jhaschie Geterotsi
Kly, 1967, pp. 199-201).

This compound may be added to the emulsion in accordance with the usual method for adding photographic emulsion additives. For example, methyl alcohol,
It can be dissolved in ethyl alcohol, methyl cellosolve, acetone, water, or a mixed solvent thereof and added as a solution.

The use of compounds of formula (IV) as defined above in the photographic field is already known. For example, JP-A-62-89952
The specification describes a combination of a nitrogen-containing heterocyclic compound having a mercapto group and a cyanine dye, thereby achieving prevention of fog and high sensitivity. However, by using these techniques, it is also possible to improve the storage stability of silver halide photographic materials formed by reduced silver.

The photographic emulsion used in the present invention is preferably spectrally sensitized with methine dyes or the like in order to exhibit the effects of the present invention. The 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 include cyanine dyes, merocyanine dyes,
and a pigment belonging to complex merocyanine pigments.

Any of the nuclei commonly used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, viroline nucleus, oxazoline nucleus, thiozoline nucleus,
Pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring fused to these nuclei The nucleus, i.e.
Indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

A typical example is U.S. Patent No. 2,688,545, 2.9
No. 77.229, No. 3,397,060, No. 3,52
No. 2,052, No. 3,527,641, No. 3,617
, No. 293, 3.628. No. 964, 3,666
．． No. 480, No. 3,672゜898, No. 3,679,
No. 428, No. 3,703.377, No. 3,769,3
No. 01, No. 3゜814.609, No. 3,837.86
No. 2, No. 4.026,707, British Patent 1. 344
．． No. 281, No. 1,507.803, Special Publication No. 434
No. 936, No. 53-12,375, JP-A No. 52-11
No. 0,618 and No. 52-109,925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The sensitizing dye may be added to the emulsion at any stage of emulsion preparation known to be useful. It is most commonly carried out after the completion of chemical sensitization and before application, but US Patent No. 3,628,969,
It is also described in JP-A-58-113,928 that spectral sensitization can be performed at the same time as chemical sensitization by adding a chemical sensitizer at the same time as described in JP-A No. 4,225.666. It can be carried out prior to chemical sensitization as described above, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, U.S. Patent No. 4
, 225,666, in which a portion of these compounds is added prior to chemical sensitization and the remainder is added after chemical sensitization. It is also possible to do so, as described in U.S. Patent No. 4. 183
．． No. 756, or at any time during silver halide grain formation.

The amount added is 4X10-@~8 per mole of silver halide.
Although the silver halide grain size can be used in an amount of 0.2 to 1. For 2 μm, about 5X10-' to 2XIO-'' moles are more effective.

The highest occupied level of the sensitizing dye used in the present invention is +0. 5eV~-0,3
It is desirable to be in the eV range; outside this range, efficient spectral sensitization cannot be achieved. The highest occupied level is also called the HOMO level, and its role in photographic phenomena is explained by the Photographic Society of Japan line, the basic silver halide photographic line of the photographic industry (Corona Publishing, 1979), p. 9l-93), and Photogra.
phic 5science and engineering
ng Volume 18, No. 5 (1974) p.

475-485, etc.

The method for measuring the highest occupied level of a sensitizing dye is Photo
graphic 5science and engine
eeringl Volume 2, No. 2 (1968) p, 80
~ and Vol. 18, No. 5 (1974), p. 475-48
5.

The various additives mentioned above are used in the photosensitive material related to the present technology, but other various additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978)
and same 1te+++ 18716 (1979, 11
The relevant sections are summarized in the table below.

■Chemical sensitizers 2 Sensitivity enhancers 23 pages 648 pages Right column Same as above 4 Brighteners 24 pages 7 Stain inhibitors 25 pages Right column 65050 pages Right column Dye Image stabilizer Hardener Binder Plasticizer, lubricant 25 pages 26 Page 26 Page 27 Page 651 Left column Same as above 650 Right column Various color couplers can be used in the present invention, and specific examples thereof can be found in the aforementioned Research Disclosure (
RD) Nα17643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4.022,620, No. 4.3
No. 26,024, No. 4,401゜752, Special Publication No. 5
B-10739, British Patent No. 1,425,020,
Same 1st. 476, No. 760 is preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, for example, US Pat.
, 310,619, 4,351.897, European Patent No. 73,636, U.S. Patent No. 3,061,432
No. 3,725゜067, Research Disclosure Nα24220 (June 1984), JP-A-60-33552, Research Disclosure N
α24230 (June 1984), JP-A-60-436
Particularly preferred are those described in US Pat. No. 59, eg, US Pat. No. 4,500,630 and US Pat.

Cyan couplers include phenolic and naphthol couplers, such as those described in U.S. Pat.
No. 212, same No. 4. 146. No. 396, same No. 4;
No. 228,233, No. 4,296.200, No. 2,369,929, No. 2.801,171, No. 2,772,162, No. 2.895.826,
Same 3rd. TT2゜002, TT3,758.308, TT4゜334.011, TT4,327,173
No. 3,329,729, European Patent No. 121,365A, U.S. Pat. No. 3,446.622, U.S. Pat.
No. 4,427.767, European Patent No. 161,6
Those described in No. 26A are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes include, for example, Research Disclosure Nα176.
Section 43 ■-G, U.S. Patent No. 4,163.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,92
No. 9, No. 4,138°258, British Patent No. 1.14
6,368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include, for example, U.S. Patent No. 4.366.237, British Patent No. 2,
125,570, European Patent No. 96.570 and West German Patent Publication No. 3,234°533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820; U.S. Pat.
It is described in No. 173, etc.

Furthermore, in the present invention, the compound that is cleaved after the reaction with the oxidized developing agent reacts with another molecule of the oxidized developing agent, thereby improving development activity and color reproduction. This is particularly preferred for improving sexual sharpness.

Examples of preferred compounds are described in JP-A-1-269935.

Couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No. 2097.14.
No. 0, No. 2,131,188, JP-A-59-157
Those described in No. 638 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include, for example, the competitive couplers described in U.S. Pat. No. 4,130.427 and the like, and U.S. Pat.
No. 4. 338. No. 393, No. 4,310,
Multi-equivalent coupler described in No. 618 etc., JP-A-60-18
DIR redox compounds or DIR coupler-releasing couplers or DIR coupler-releasing couplers or redoxes described in JP-A-62-24252, etc.; couplers that release dyes that fade after separation as described in EP 173.302A, e.g. R,D.

Nα11449, Nα24241. Unexamined Japanese Patent Publication 1986-2012
47, such as the ligand-releasing couplers described in US Pat. No. 4,553,477.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). ), esters of phosphoric or phosphonic acids (e.g. triphenol phosphate, tribrezyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate), benzoic acid esters (e.g. 2-ethylhexyl phosphate), ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone),
Alcohols or phenols (e.g. isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (e.g. bis(
2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate), ani, phosphorus derivatives (e.g. N, N-dibutyl-2-butoxy-5-t)
ert-octylaniline), hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate,
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate,
Examples include dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

When used in the color photographic material of the present invention, it can be applied to light-sensitive materials of various configurations and light-sensitive materials in which color materials with special layer configurations are combined.

A typical example is illustrated below. JP 47-49031, JP 49-3843, JP 50-21248, JP 59-38147, JP 59-60437,
JP-A-60-227256, JP-A-61-4043, JP-A-61. No.-43743, JP-A-61-4265
A combination of the coupling speed and diffusivity of a color coupler and the layer structure, such as No. 7. Special Public Service 1977-1
No. 5495, U.S. Pat. No. 3,843,469, a form in which the same color-sensitive layer is divided into two or more layers, Japanese Patent Publication No. 53-37
No. 017, Japanese Patent Publication No. 53-37018, Japanese Patent Publication No. 51-4
No. 9027, JP-A-52-143016, JP-A-53
-97424, JP-A-53-97831, JP-A-6
Examples include those in which the arrangement of high-sensitivity layers and low-sensitivity layers and the arrangement of layers with different color sensitivities are stipulated, such as in No. 2-200350 and JP-A-59-177551.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643, and the same N (L187
16, from the right column on page 647 to the left column on page 648.

The color photographic material according to the present invention includes the above-mentioned RD, N
α17643, pages 28-29, and Nα1B716
651, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, typical examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3-diethylaniline, and Methyl-4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents such as competing couplers sodium poron hydride, - Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity-imparting agents, various calcinates such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetra Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1,
1 diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 31 per square meter of the light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be reduced to 500 -
You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (II).
Compounds of polyvalent metals such as I), chromium (■), and copper (II), peracids, quinones, and nitro compounds are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1. Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. may be used. I can do it. Among these, aminopolycarboxylic acid iron(III) complexes and persulfates, including ethylenediaminetetraacetic acid iron(I[I) complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions.

The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(III) complexes is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are found in U.S. Pat. No. 3,893.
It is described in the specification in No. 858 and the like. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urna10f the 5ociety of Mo
tion Picture and Televisi
onEngineers Vol. 64, P, 248-253
(May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" written by Hiroshi Horiguchi, "Microbial It is also possible to use the fungicides described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" published by Japan Antibacterial and Antifungal Science.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds - 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds and 5 minutes at 5-40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8,543 and 58-14.83
All known methods described in No. 4 and No. 60-220.345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The oat flow solution accompanying water washing and/or replenishment of the stabilizing solution can also be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated. Typical compounds are described in JP-A Nos. 56-64,339, 57-144.547, and 58115.438.

Various treatment liquids in the present invention are used at 1066-50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can do. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.660A2, and the like.

Examples will be shown and explained below.

(Example 1) Average iodine content is 20 mol%, average projected area diameter is 0.9μ
m, particle size variation coefficient 19%, average aspect ratio 5.0
Using silver iodobromide double grains as seed crystals, shelling was carried out in an aqueous gelatin solution for 30 minutes by a controlled double jet method under conditions such that the silver potential was 140 mV.

The ratio of core to shell should be 1=2 in terms of silver content.
The composition of the halogen solution was controlled so that the iodine content of the shell was 0 to 5.0 mol%.

One minute after the start of shell formation, thiourea dioxide, L-ascorbic acid, thiourea dioxide and thiosulfonic acid compound 1
-2, L-ascorbic acid and thiosulfonic acid compound 1
-2, or L-ascorbic acid and sodium thiosulfate were added. The formulation contents of Emulsions 1 to 8 are summarized in Table 1.

After grain formation, the emulsion was subjected to a normal desalination washing process and then redispersed at 40° C. under the conditions of pAg 8.9 and pH 6.3. Each emulsion was then optimally chemically sensitized using 6X10-' moles of sodium thiosulfate and 2XIO-' moles of auric acid chloride per mole of silver halide. After chemical sensitization, the following nitrogen-containing heterocyclic compound containing a mercapto group was added in an amount of 1X10-' mol per mol of silver halide.

Further, prior to chemical sensitization, emulsions were prepared in which spectral sensitizing dyes having the following structural formulas were added in moles of 2.5XIO-' and 3.0XIO-' per mole of silver halide, respectively.

(CHt)ssOse (CHt)ssOsNa The emulsion and protective layer were coated on a triacetylcellulose film support provided with an undercoat layer in the coating amounts shown in Table 2.

Table 2 (1) Emulsion layer Emulsion... Emulsion shown in Tables 8 and 9 (silver 1.7 x 10-'' mol/l) - Coupler (1.5 x 10-'' mol/l) - Tricresyl phosphate (1 ,10g/rr?) ・Gelatin (2,30g/rr?) (2)
Protective layer・2,4-dichlorotriazine-6-hydroxy-3-
Triazine sodium salt (0.08 g/rr?) Gelatin (1.80 g/rr) These samples were exposed to light for sensitometry as described below, and then subjected to the following color development process.

The concentration of the treated sample was measured using a green filter.

The development process used here was carried out at 38°C under the following conditions.

1. Color development... 2 minutes 45 seconds 2. Drifting
White... 6 minutes 30 seconds 3, wash with water...
・・・ 3 minutes 15 seconds 4, established ・・・ 6 minutes 3
0 seconds 5, wash with water 3 minutes 15 seconds 6, low
3 minutes and 15 seconds The processing composition used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.4g Sodium sulfite 4.0g Sodium carbonate Potassium bromide Hydroxylamine sulfate 4-(N-ethyl-N-β hydroxyethylamino) 2-Methyl-aniline sulfate Add aqueous bleaching solution Ammonium bromide Aqueous ammonia (28% w/w) Ethylenediamine- Sodium ferric tetraacetate trihydrate Add glacial acetic acid water to fix fixing solution Sodium tetrapolyphosphate Sodium sulfite Ammonium thiosulfate (700 g/f) 30.0 g 1.4 g 2,4g 4,5g 1 160.0g 25.01n1 30g 4J 1 2,0g 4,0g 175゜〇- Sodium bisulfite 4.6g Add water 11 Stabilizing liquid formalin 86 〇- Add water 11 Emulsion 1 Table 3 shows the photographic properties of samples chemically sensitized by adding a spectral sensitizing dye to Samples 1 to 8. Exposure is 1/100 through a yellow filter.
It was done in seconds.

Sensitivity was evaluated at a density of fog +0.2. Table 8 shows the photographic properties immediately after coating as well as the photographic properties after the sample was left in an atmosphere of 23° C. and 55% relative humidity for two months.

Table 4 shows the photographic properties of samples chemically sensitized using Emulsions 1, 6 and 8 in Table 1 without using any spectral sensitizing dye and with the addition of spectral sensitizing dye B.

Samples without spectral sensitizing dye were exposed through a blue filter, while samples with dye B were exposed through a yellow filter at 1/100 seconds. Sensitivity is fog+
Evaluation was made at a concentration of 0.2.

From Table 3, when only reduced silver is present in the grains (emulsion-3
, -5) and when only silver sulfide is present in the grains (emulsion-7), the sensitivity is higher when reduced silver and silver sulfide coexist within the grains (emulsions-4, -6, and 8). It turns out that it can be achieved.

Table 4 shows that the emulsions of the present invention can achieve high sensitivity even when there is no spectral sensitizing dye.

From the comparisons of Emulsions 3 and 4, Emulsions 5 and 6, and Emulsions 7 and 8 in Table 3, it is clear that when reduced silver and silver sulfide coexist in the grains, not only high sensitivity is obtained, but also emulsions It can be seen that the film has favorable characteristics in that the increase in fog and the decrease in sensitivity that occur over time are significantly small.

Example 2 A dye was added to the chemically sensitized emulsions 1 and 6.8 prepared in Example 1 to prepare red-sensitive, green-sensitive and blue-sensitive emulsions.

Samples 301 to 30, which are multilayer color light-sensitive materials, were prepared by coating layers having the compositions shown below on a cellulose triacetate film support that was undercoated with these emulsions.
4 was produced.

(Composition of photosensitive layer) The coating amount is a number in g/rd unit. However, for silver halide and colloidal silver, the amounts are expressed in g/rd units of silver, and for sensitizing dyes, the number of moles is expressed per 1 mole of silver halide in the same layer.

1st layer: antihalation layer black colloidal silver Silver coating amount 0.2 gelatin
2.2UV-10,l UV-20,2 cpct-to, osS
olv-10,01 Solv-20,01 Solv-30,08 2nd layer: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin l, 0ExC-
40,03 Cpd-20,2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (Ag 18.5 mol%, internal high AgI type,
Equivalent sphere diameter 0.1μ, coefficient of variation of equivalent sphere diameter 25%, diameter/
Thickness ratio 3.0) Silver coating amount 0.42 Silver iodobromide emulsion (Ag 14.0 mol%, internal high Agl type,
Equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.33 Gelatin 1. 0ExS-1
4,5XlO-'mol ExS-21,5X10-'mol ExS-30,4X10-'mol ExC-10,40 ExC-20,11 ExC-30,009 ExC-40,023 Solv-10,24 4th layer : Second red-sensitive emulsion layer silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type,
Equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0.55 Gelatin 0.7ExS-13
X10 ExS-21XIO-'ExS-30,3X10-' ExC-10,10 ExC-20,55 ExC-40,025 Solv-10,20 Fifth layer/third red-sensitive emulsion layer Silver iodobromide emulsion 1 ( Agll. 3 mol%, internal high Agl
Mold, equivalent sphere diameter 1.4 μ, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 6°0) Silver coating amount 1.29 Gelatin 0.6
ExS-12xlO-'ExS-20,6xlO-'ExS-30,2X10-' ExC-20,08 ExC-40,01 ExC-50,06 Solv-10,12 Solv-20,12 6th layer: Intermediate layer Gelatin 1. OCM-4
0, ■ 5olv-10,1 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type,
Equivalent ball diameter 1. 0 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3.0) Silver coating amount 0.28 Silver iodobromide emulsion (Agl 14.0 mol%, internal high Agl type, equivalent sphere diameter 0) .7 μ, coefficient of variation of equivalent sphere diameter 38%, plate-shaped particles, diameter/thickness ratio 2°0) Silver coating amount
0. 1 Gelatin 1. 2
ExS-55XIO'ExS-62XIO-'ExS-71XIO-' ExM-10,50 ExM-20,10 ExM-50,03 Solv-10,2 Solv-40,03 8th layer: 2nd green-sensitive emulsion layer Silver bromide emulsion (Ag18.5 mol%, internal high iodine type,
Equivalent ball diameter 1. 0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 3.0) Silver coating amount 0.47 Ceratin 0.35ExS-5
3,5X10- ExS-61,4X10-'ExS-70,7xlO-' ExM-10,12 ExM-20,01 ExM-30,01 Solv-10,15 Solv-40,03 9th layer: Intermediate layer gelatin 0.5 10th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion II (AgI l 1.3 mol%, internal high Agl type, equivalent sphere diameter 1.4μ, coefficient of variation of equivalent sphere diameter 28%, plate shaped particles, diameter/thickness ratio 6゜0)
Silver coating amount 1. 3 gelatin
018ExS-52xlO-' ExS-60,8xlO~4 ExS-70,8XIO' ExM-30,01 ExM-40,04 ExC-40,005 Cpd-50,01 Solv-10,2 11th layer: Yellow filter layer Cpd-30,05 Gelatin 0.5Solv-1
0,1 12th layer: Intermediate layer gelatin 0.5Cpd-2o
, 1 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (Aglto mol%, internal high iodine type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%, tetradecahedral grains) Silver coating amount 0. 1 Silver iodobromide emulsion (Ag 14.0 mol%, internal high iodine type,
Equivalent sphere diameter 064 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.05 Gelatin 1. 0ExS-8
3XlO-' ExY-10.60 ExY-20,02 Solv-10,15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Agl 19.0 mol%, internal high AgI type, equivalent sphere diameter 1. 0 μ, coefficient of variation of equivalent sphere diameter 16%, 1
Tetrahedral particles) Silver coating amount 0.19 Gelatin 0.3ExS-82
X10-” ExY-10,22 Solv-10,07 15th layer: Intermediate layer fine grain silver iodobromide (AgI 2 mol%, uniform type, equivalent sphere diameter 0
．． 13μ) Silver coating amount 0.2 gelatin
0.36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion I [I (Agl l 1.3 mol%,
Internal type AgI type, ball equivalent diameter 1. 4μ, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 6゜0)
Silver coating amount 1.35 gelatin
0.5ExS-91,5X10-' ExY-10,2 Solv-10,07 17th layer: 1st protective layer gelatin 1. 8UV-10
, l UV-20,2 Solv-10,01 Solv-20,01 18th layer: 2nd protective layer Fine particle silver chloride (equivalent sphere diameter 0.07μ) Silver coating amount 0.36 Gelatin 0.70 Polymethyl methacrylate The chemical structural formulas of the compounds used to create samples 301 to 304 are shown in Table 0 below. show.

These samples were exposed to light for sensitometry, and then subjected to the following color development process.

The concentration of the treatment agent sample was measured using a red filter, a green filter, and a blue filter. The results obtained are shown in Table IO.

Regarding the results of photographic performance, the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each expressed as relative sensitivities, with the sensitivity of Sample 301 being 100.

Processing method Color development processing was carried out at 38°C according to the following processing steps.

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water washing 2 minutes lO seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 3 minutes 15 seconds Safe, stable, 1 minute, 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1.0gl-Hydroxyethylidene 1. 1-Diphosphonate Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N~ethyl-N-β hydroxyethylamino) = 2-Methylaniline sulfate pH by adding aqueous solution Bleach solution Ethylenediaminetetraacetic acid Ferric Add the ammonium salt ethylenediaminetetraacetic acid disodium salt ammonium bromide ammonium nitrate water and add 4.5g 1, OR I Oo 0 100, 0g 10゜l 50゜10゜l.

pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Add water
1.01 pH 6.6 Stabilizing liquid formalin (40%) 2. Oyt/
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization to) Add 0.3 g of water l, 01 As is clear from Table 5, the emulsion of the present invention has a high sensitivity with almost no increase in fog. It turns out that it is effective.

Samples 301 to 303 were left in an atmosphere of 23° C. and 55% relative humidity for two months, and then subjected to sensitometric exposure and color development. 301 showed a decrease in sensitivity due to increased fog in all of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer, but
There was no change in 302 and 303.

(Effects) Conventionally, emulsions in which reduced silver has been formed have had the disadvantage that when a coated sample is aged, fog increases significantly and sensitivity decreases significantly, resulting in poor storage stability.

The present inventors have discovered that by allowing reduced silver and a silver chalcogenide compound to coexist inside silver halide grains, the storage stability of coated samples is significantly improved.

Hitherto, increasing sensitivity through reduced silver formation has been difficult to achieve with color sensitized emulsions. The present inventor has determined that the silver iodide content on the surface is 5
It has been found that when reduced silver and a silver chalcogenide compound coexist in silver halide grains containing up to 30 mol %, sensitivity in the color sensitization region can be specifically increased. For example, if reduced silver and silver chalcogenide compounds are not formed within the grains of double-structured silver halide grains during grain growth, an increase in the silver iodide content in the shell portion will instead result in a decrease in sensitivity in the color sensitized region. .

Table A (1-1) CHsSO*5Na (1-2) CtHsSOtSNa (1-3)
csHtsotsK (1-4) C, HsSO, SL 1 (1-5)
C, H, *SO, 5Na (1-6) C, H,
,SO,5Na(17) CHs(CHt)scH
cHtsO2s-NH4C, Hl C+ o H! l S Ot S N aC+tHt
sSO! S Na C+5HssSO*5Na (1-8) (1-9) (1-10) (1-12) t-CsHsSOtSNa (1 13) CH=OCH*CHtSOtS-Na (1-15) CH2=CHCH,5OtSNa (1-29) KSSOx (CHs) tsO*sK (1-30) Na S 5Ox (CHzLSOtSNa (2-4) (1-31) Na S Sow (CH2), 5 (CHt), 5OtS
Na(25) C2H,SO,SCH,CH,CNSOtSNaC,H,SO,5CHCH,CN(29)SO2SNa(21)C2H5SO,5-CH.

(2 2) C,H? S Ot S CH2CH5 (2-18) C,H2SO,SCH,CH2CH2CH,0H(2-
13) (2 14) (2-21) CH=SSOxCCHt>4SOtSCH-(2-22
) CHsS 5Ox(CHt)tsO-3CH-(3-3
) (3-4) CxHsSO*5CHtN(CH*CHt)NCHt
SSOtCtHs (2 24) CHICI(IOHCF(ICHIORX: y = 2/1 (molar ratio)) (3-7) C,H,SO,5SSO,C,H.

(3-8) (n) CsHtSOiSSSOtCsHt(n) (3 2) C2H5SO2SCH2CH, SO□CH2CH25S
O, C2H5 Table B C00H UV-2 xC-1 H xC-2 H (n)l; ttHzs COOI (Table 0 x / y -7/ 3 (weight ratio) xC-3 H CH.

xC-4 H xC-5 H OCHtCHxSCHCOOH lIH1S ExM-1 CH.

ExM-2 ExM-2 ExM-3 ExM-4 xS-1 xS-2 xS-3 1 ExS-8 ExS-9 pd-2 pd-3 pd CH CH CH olv-1 olv-2 olv pd-1 (: pcl-Ei CHl -1 CAF l ?5O1NHCH, CH2CH10CH,
CH,N(CH3).

-1 CH,=CH3O,CH,C0NH H2

Claims (3)

[Claims] (1) A silver halide emulsion layer containing silver halide grains in which reduced silver and a silver chalcogenide compound coexist inside the grains, and which has been subjected to at least one of gold sensitization, sulfur sensitization, and noble metal sensitization. A silver halide photographic material having at least one layer on a support. (2) The silver halide photographic material according to claim (1), wherein the coexisting silver chalcogenide compound is a sulfide. (3) The silver halide photographic material according to claim 1, wherein the amount of the silver chalcogenide compound present inside the grains is from 10^-^3 mol to 10^-^5 mol per mole of silver.