JP3045624B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material.

More specifically, the present invention relates to a silver halide photographic material having low fog, improved sensitivity and improved pressure characteristics.

[0003]

2. Description of the Related Art In recent years, demands for photographic silver halide emulsions have become more and more severe, and in addition to photographic properties such as high sensitivity and excellent granularity, demands for toughness such as pressure properties have been further increased. .

[0004] With respect to tabular grains, US Pat.
4,226, 4,439,520, 4,414,
No. 310, No. 4,433,048, No. 4,414,3
Nos. 06, 4,459, 353 and the like disclose their production methods and techniques for use, including improvements in sensitivity including an improvement in color sensitization efficiency by sensitizing dyes, an improvement in the relationship between sensitivity / granularity, and tabular grains. Sharpness improvement due to the unique optical properties of
Advantages such as an improvement in covering power are known. JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains into which dislocation lines are intentionally introduced. It has been shown that tabular grains having dislocation lines are superior to photographic properties such as sensitivity and reciprocity in comparison with tabular grains having no dislocation lines, and that they are excellent in sharpness and graininess when used in a photosensitive material. . In order to further enhance the sensitivity of silver halide grains, it is necessary to introduce dislocation lines uniformly and densely in individual grains and between grains in a limited position to achieve uniformity and efficient chemical sensitization of each grain. It is considered preferable in terms of centralizing latent image forming sites.

The present invention relates to a technique for controlling and introducing dislocation lines into silver halide tabular grains, particularly to the fringe portion of the grains. In Japanese Patent Application No. 1-322931,
High sensitivity and granularity by tabular silver halide grains having 10 or more dislocation lines per grain in the grain fringe portion,
It is shown that a silver halide emulsion having improved gradation and fog can be obtained. However, in the conventional dislocation line introduction technology as shown in this patent, the density of dislocation lines and the limitation of the position are contradictory. That is, when trying to introduce dislocation lines into the fringe portion of the tabular grains at a higher density, unintended dislocation lines are generated also in the main plane portion of the tabular grains, and uniform high-density dislocation lines inside the grains and between the grains are formed. Could not be introduced. The present inventors have substantially mixed particles other than particles having dislocation lines only in the fringe portion, that is, particles having a large number of dislocation lines in the main plane portion,
Impair the photographic performance of the emulsion (increased fog, reduced sensitivity,
(Deterioration of pressure) There was a possibility, so we tried to eliminate it. The present invention keeps the dislocation dose high,
Substantially limited only to the fringe portion of the particles, the dislocation lines are intended to be introduced homogeneously and at a high density within the particles and between the particles, and could not be reached in Japanese Patent Application No. 1-329231. It is intended to form particles.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having low fog, high sensitivity and improved pressure characteristics.

[0007]

The above object is achieved by the following (1).
(5). (1) Silver halide tabular grains (fringe dislocation type tabular grains) having an aspect ratio of 2 to 40 and having dislocation lines localized substantially only in the fringe portion are 10% of the projected area of all grains.
A silver halide photographic material having a silver halide emulsion layer containing a silver halide emulsion occupying 0 to 80% on a support. Here, the “fringe portion” means “in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide content at a point starting from the side is the average silver iodide content of the whole grain. Outside the point beyond or below the point ". Further, "substantially dislocation lines are localized substantially only in the fringe portion" means "three or more dislocation lines are not included in the main plane portion".

(2) The fringe dislocation type tabular grains are such that 100 to 50% of the iodide ion releasing agent present in the reaction vessel completes the release of iodide ion within 180 consecutive seconds. The silver halide photographic material as described in the above item (1), wherein the particles are formed while rapidly generating ions.

(3) The fringe dislocation type tabular grains are grains formed while rapidly generating iodide ions, and the reaction for rapidly generating iodide ions substantially reduces the iodide ion releasing agent concentration. The halogenation according to the above (1), wherein the secondary reaction is a secondary reaction proportional to the concentration of the iodide ion release controlling agent, and the secondary reaction rate constant is 1000 to 5 × 10 ⁻³ (M ⁻¹ · sec ⁻¹ ). Silver photographic photosensitive material.

(4) The silver halide photographic material as described in (2) or (3) above, wherein iodide ions are rapidly produced using an iodide ion releasing agent and an iodide ion releasing regulator.

(5) The silver halide photographic material as described in (4) above, wherein iodide ions are rapidly generated from an iodide ion releasing agent represented by the following formula (I).

[0012]

[0013]

Embedded image In the formula (I), R represents a monovalent organic residue which releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile.

In the silver halide photographic light-sensitive material of the present invention, at least one silver halide grain (fringe dislocation type tabular grain) having an aspect ratio of 2 to 40 and having dislocation lines localized substantially only in the fringe portion is provided. Occupy 100 to 80% of the total projected area of the silver halide grains in the silver halide emulsion layer of the layer. In the present invention, tabular silver halide grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 2 to 40 are at least 100 to 8 of all silver halide grains in the silver halide emulsion layer.
Preferably, it is present at 0% (area).

More preferably, the aspect ratio is 4 to 3.
0 to 100 to 80% (area), particularly preferably particles having an aspect ratio of 8 to 30 are 100 to 80%.
% (Area). If the aspect ratio is less than 2, the advantages of tabular grains cannot be fully utilized, which is not preferable.
If it is larger than 40, the pressure property is undesirably deteriorated.
When the ratio of tabular grains having an aspect ratio of 2 to 40 is less than 80% (area), it is not preferable in terms of homogeneity between grains. The tabular grains of the present invention are silver halide grains having two opposing parallel main planes. The tabular grains of the present invention have one twin plane or two or more parallel twin planes.

A twin plane is defined as (111) when ions at all lattice points are mirror images on both sides of the (111) plane.
Surface. When the tabular grains are viewed from above, the tabular grains have a triangular shape, a hexagonal shape, or a rounded shape obtained by rounding them, and have outer surfaces parallel to each other.

The aspect ratio is a value obtained by dividing a circle equivalent diameter of a projected area of a silver halide grain by a grain thickness. As an example of a method of measuring the aspect ratio, there is a method of obtaining a circle equivalent diameter and a thickness of a projected area of each particle by taking a transmission electron microscope photograph by a replica method. In this case, the thickness is calculated from the length of the shadow of the replica. The equivalent circle diameter of the tabular grains of the present invention is preferably 0.3 to 10 μm, more preferably 0.4 to 5 μm, and particularly preferably 0.5 to 4 μm.

If the thickness is less than 0.3 μm, the advantages of tabular grains cannot be fully utilized, which is not preferable. When the thickness exceeds 10 μm, the pressure property deteriorates, which is not preferable. The thickness of the tabular grains of the present invention is preferably 0.05 to 1.0 μm, more preferably 0.08 to 0.5 μm, and particularly preferably 0.08 to 0.3 μm. If the thickness is less than 0.05 μm, the pressure property is undesirably deteriorated. If it exceeds 1.0 μm, the advantages of tabular grains cannot be fully utilized, which is not preferable. In the present invention, hexagonal tabular grains having a ratio of the length of the side having the maximum length to the length of the side having the minimum length of 2 to 1 are 1% of the projected area of all the grains in the emulsion.
It preferably occupies 00 to 50%, more preferably 100 to 70%, particularly preferably 100 to 90%.

The emulsion of the present invention is preferably monodisperse. The coefficient of variation of the particle size distribution of all silver halide grains of the present invention is preferably 20% to 3%, more preferably 15% to 3%, and particularly preferably 10%.
Or 3%. It is a value obtained by dividing the variation coefficient of the particle size distribution and the standard deviation of the particle size distribution of the particles by the average particle size.

Further, the tabular grains of the present invention have dislocation lines. A dislocation line is a linear lattice defect on the slip plane of a crystal at the boundary between an already slipped region and a region that has not yet slipped. Regarding dislocation lines of silver halide crystals 1)
C. R. Berry, J.M. Appl. Phys. , 2
7, 636 (1956), 2) C.I. R. Berry,
D. C. Skilman. J. Appl. Phys. ,
35, 2165 (1964), 3) J.I. F. Hamil
ton, Photo. Sci. Eng. , 11,57 (1
967), 4) T.I. Shiozawa, J .; Soc. P
hot. Sci. Jap. , 34, 16 (1971),
5) T. Shiozawa, J .; Soc. Photo. S
ci. Jap. , 35, 213 (1972), which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope. When directly observing dislocation lines using a transmission electron microscope, place the silver halide grains taken out of the emulsion on a mesh for electron microscope observation, taking care not to apply enough pressure to generate dislocation lines on the grains, Observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (for example, printout) by an electron beam. In this case, the thicker the particle, the more difficult it is for an electron beam to pass.
The use of an electron microscope (at 200 kV or more) enables more clear observation. In the case of tabular grains, the position and the number of dislocation lines for each grain as viewed from the direction perpendicular to the main plane can be determined from the photograph of the grain taken using an electron microscope as described above. Note that dislocation lines may be visible or invisible depending on the tilt angle of the sample with respect to the electron beam.Therefore, to observe dislocation lines without omission, observe the particle images of the same particle at as many sample tilt angles as possible and observe the dislocation lines. It is necessary to find the location.

In the present invention, it is preferable to determine the position and number of dislocation lines by changing the inclination angle of the same particle in 5 ° steps using a high-voltage electron microscope and photographing five types of particle photographs. The fringe dislocation type tabular grains of the present invention preferably have 30 or more dislocation lines per grain in the fringe portion of the grains, more preferably 50 or more, and particularly preferably 100 or more. If the number is less than 30, the effect of the present invention is hardly obtained, which is not preferable. When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted.

However, even in these cases,
It can be counted as about 10, 20, or 30. Particularly, the fringe dislocation type tabular grains referred to in the present invention are high density fringe dislocation grains having preferably 30 or more dislocation lines per grain as described above. The fringe portion referred to in the present invention refers to the outer periphery of a tabular grain. Specifically, in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide content at a certain point for the first time when viewed from the side is the grain. Outside the point where the average silver iodide content exceeds or falls below the total.

The grains of the present invention having dislocation lines substantially only in the fringe portion, ie, fringe dislocation type tabular grains, are grains which do not contain three or more dislocation lines in the other than the fringe portion of the tabular grains, ie, the main plane portion. Means Among the high-density fringe dislocation grains, grains having three or more dislocation lines in the principal plane portion (hereinafter, referred to as “principal plane dislocation type tabular grains”) are distinguished from fringe dislocation grains. The proportion of each of the fringe dislocation type tabular grains and the main plane dislocation type tabular grains in the emulsion grains is preferably at least 20%.
It can be determined by directly observing the dislocation line for the 0 grain. In the present invention, fringe dislocation type tabular grains having an aspect ratio of 2 to 40 are 100 to 80 of all grains.
%, More preferably 100 to 85%, particularly preferably 100 to 90%.

The present invention has a particularly remarkable effect when particles are formed while rapidly generating iodide ions using an iodide ion releasing agent represented by the formula (I).
The iodide ion-releasing agent represented by the formula (I) of the present invention is used in JP-A-2-68538 described above to make the halogen composition uniform within and between individual silver halide grains. Partial overlap with compound. However, silver halide grains are formed by rapidly generating iodide ions in the presence of an iodide ion releasing agent represented by the formula (I), thereby obtaining a silver halide emulsion having low fog and high sensitivity. It was unexpected that the present inventors found that such a phenomenon could occur. The iodide ion releasing agent represented by the following formula (I) shown in Chemical formula 3 of the present invention will be described in detail.

[0025]

Embedded image In the formula (I), R represents a monovalent organic residue which releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile. When the compound represented by the formula (I) is described in more detail, R is, for example, 1 to 30 carbon atoms.
An alkyl group, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 3 carbon atoms, an aryl group having 6 to 30 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, a carbamoyl group, an alkyl or aryloxycarbonyl group having 2 to 30 carbon atoms, Alkyl or arylsulfonyl groups and sulfamoyl groups are preferred. R is preferably the above group having 20 or less carbon atoms, and particularly preferably the above group having 12 or less carbon atoms. The number of carbon atoms is preferably in the above range from the viewpoint of solubility and addition amount. Further, R is preferably substituted, and preferred substituents include the following. The substituent may be further substituted with another substituent.

For example, a halogen atom (eg, fluorine, chlorine, bromine, iodine), an alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl), an alkenyl group ( For example, allyl, 2-butenyl, 3-pentenyl), alkynyl group (for example, propargyl, 3-pentynyl), aralkyl group (for example, benzyl, phenethyl), aryl group (for example, phenyl, naphthyl, 4-methylphenyl), complex Ring groups (eg, pyridyl, furyl, imidazolyl, piperidyl, morpholyl), alkoxy groups (eg, methoxy, ethoxy, butoxy), aryloxy groups (eg, phenoxy, naphthoxy),
An amino group (eg, unsubstituted amino, dimethylamino, ethylamino, anilino), an acylamino group (eg, acetylamino, benzoylamino), a ureido group (eg, unsubstituted ureido, N-methylureido, N-phenylureido), Urethane group (eg, methoxycarbonylamino, phenoxycarbonylamino), sulfonylamino group (eg, methylsulfonylamino, phenylsulfonylamino), sulfamoyl group (eg, sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl) , Carbamoyl group (eg, carbamoyl, diethylcarbamoyl, phenylcarbamoyl), sulfonyl group

(Eg, methylsulfonyl, benzenesulfonyl), sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), Acyl groups (eg, acetyl, benzoyl, formyl, pivaloyl), acyloxy groups (eg, acetoxy, benzoyloxy), phosphoric amide groups (eg, N, N-diethylphosphoramide), alkylthio groups (eg, methylthio, ethylthio) ), An arylthio group (for example, a phenylthio group), a cyano group, a sulfo group, a carboxyl group, a hydroxy group, a phosphono group, and a nitro group. More preferred substituents for R include a halogen atom, an alkyl group, an aryl group, a 5- or 6-membered heterocyclic group containing at least one O, N or S, an alkoxy group, an aryloxy group, an acylamino group, a sulfamoyl group, A carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryloxycarbonyl group, an acyl group, a sulfo group, a carboxyl group, a hydroxy group and a nitro group. Particularly preferred substituents for R are a hydroxy group, a carbamoyl group, a lower alkylsulfonyl group or a sulfo group (including its salt) when substituted with an alkylene group, and a sulfo group (including its salt) when substituted with a phenylene group. Including).

The compound of the formula (I) of the present invention is preferably a compound of the formula (II) or the formula (II)
It is a compound represented by I). The compound represented by the formula (II) shown in Chemical Formula 4 of the present invention will be described.

[0029]

Embedded image In the formula (II), R21 represents an electron withdrawing group, and R22 represents a hydrogen atom or a substitutable group. n2 represents an integer of 1 to 6, and n2 is preferably an integer of 1 to 3,
1 or 2 is particularly preferred. The electron-withdrawing group represented by R 21 is preferably Hammett's σ _p or σ _m or σ _I
Is an organic group having a value of greater than 0. Hammett's σ _p value or σ _m value is “Structure-Activity Relationship of Drugs” (Nankodo) 96
Page (1979) and the σ _I value are described on page 105, and can be selected based on this table. R21 is preferably, for example, a halogen atom (eg, fluorine, chlorine, bromine, etc.), a trichloromethyl group, a cyano group, a formyl group, a carboxylic acid group, a sulfonic acid group, a carbamoyl group (eg, unsubstituted carbamoyl, diethylcarbamoyl) ), An acyl group (eg, acetyl group, benzoyl group), an oxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group), a sulfonyl group (eg, methanesulfonyl group, benzenesulfonyl group, etc.), a sulfonyloxy group (eg, methane Sulfonyl group), carbonyloxy group (for example, acetoxy group), sulfamoyl group (for example, unsubstituted sulfamoyl group, dimethylsulfamoyl group), heterocyclic group (for example, 2-thienyl group, 2-benzoxazolyl group, 2-
Benzothiazolyl group, 1-methyl-2-benzimidazolyl group, 1-tetrazolyl group, 2-quinolyl group). The carbon-containing group of R21 is preferably 1 to 20
Containing carbon. As examples of the substitutable group represented by R22, those listed as the substituent of R can be applied as they are. It is preferable that at least half of R22 contained in the compound of the formula (II) is a hydrogen atom. Multiple R22s in the molecule
May be the same or different. R21 and R22 may be further substituted, and preferred substituents include R21 and R22.
Examples of the substituent include those listed above. Also, R21
And R22, or two or more R22 combine to form 3 to 6
It may form a member ring. Next, the compound represented by the formula (III) represented by Chemical Formula 5 of the present invention will be described.

[0030]

Embedded image In the formula (III), R31 is an R33O-group, an R33S-group, (R3
3) ₂ N-group, (R33) ₂ P- group, or a phenyl, R33 is hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 3 carbon atoms , An aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and a heterocyclic group having 4 to 30 carbon atoms. The number of carbon atoms is preferably in the above range from the viewpoint of solubility and addition amount. R31 is (R33) ₂ N-group, when representing the (R33) ₂ P- group, each two R33 groups may be the same or different. R31 is preferably an R33O- group. R
32 and n3 have the same meanings as R22 in formula (II),
May be the same or different. As examples of the substitutable group represented by R32, those listed as the substituent of R can be applied as they are. R32 is preferably a hydrogen atom. n3 is preferably 1, 2, 4 or 5, and particularly preferably 2. R31 and R32 may be further substituted, and preferred substituents include those enumerated as R substituents. Further, R31 and R32, or two or more R32s may combine to form a ring.

Specific examples of the compounds represented by formulas (I), (II) and (III) of the present invention are shown below, but the compounds of the present invention are not limited to these.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

Embedded image The iodide ion releasing agent of the present invention can be synthesized according to the following synthesis method.

J. Am. Chem. Soc. , 76 , 3
227-8 (1954); Org. Chem. , 1
6 , 798 (1951), Chem. Ber. , 97 ,
390 (1964), Org. Synth. , V, 47
8 (1973); Chem. Soc. , 1951 ,
1851, J.A. Org. Chem. , 19 , 1571
(1954); Chem. Soc. , 1952 , 1
42, J.I. Chem. Soc. , 1955 , 1383,
Angew, Chem. , Int. Ed. , 11, 22
9 (1972), Chem. Commu. , 1971 ,
1112.

The iodide ion releasing agent of the present invention releases iodide ions by reacting with an iodide ion releasing regulator (base and / or nucleophile). The nucleophile used in this case is preferably used. The following chemical species may be mentioned. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates, ammonia, amines, Examples include alcohols, ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines, and sulfides. In the present invention, the release rate and timing of iodide ions can be controlled by controlling the concentrations of bases and nucleophiles, the method of addition, and the temperature of the reaction solution. The base is preferably an alkali hydroxide. The preferred concentration range of the iodide ion releasing agent and the iodide ion release controlling agent used to rapidly generate iodide ions is 1 × 10 ^{−7 to} 20 M, more preferably 1 × 10 ^{−5 to} 10 M, Preferably 1 × 10 ^{-4 to} 5
M, particularly preferably 1 × 10 ^{−3 to} 2M. Concentration 2
If it exceeds 0M, the amount of the iodide ion releasing agent having a large molecular weight and the amount of the iodide ion releasing agent to be added become too large with respect to the capacity of the particle forming container.

If it is less than 1 × 10 ^-7 , the reaction rate of releasing iodide ions will be slow, and it will be difficult to rapidly generate an iodide ion releasing agent, which is not preferable.

A preferred temperature range is 30 to 80 ° C.,
More preferably 35 to 75 ° C, particularly preferably 35 to 6 ° C.
0 ° C. At a high temperature exceeding 80 ° C., the reaction rate of iodide ion release generally becomes extremely high.
When the temperature is lower than the above, the reaction rate of iodide ion release generally becomes extremely slow, and the use conditions are respectively limited, which is not preferable.

In the present invention, when a base is used for releasing iodide ions, a change in the pH of the solution may be used. At this time, the preferable range of pH for controlling the release rate and timing of iodide ions is 2 to 12 after pH adjustment, more preferably 3 to 11, particularly preferably 5 to 10, and most preferably. 7.5 to 10.0. Even under neutral conditions at pH 7, hydroxide ions determined by the ionic product of water act as regulators.

A nucleophile and a base may be used in combination.
Also at this time, the release rate and timing of iodide ions may be controlled by controlling the pH within the above range.

The preferred range of the amount of iodide ion released from the iodide ion releasing agent is 0.1 to 20 mol%, more preferably 0.3 to 20 mol%, based on the total amount of silver halide.
15 mol%, particularly preferably 1 to 10 mol%,
You can choose according to your purpose. If it exceeds 20 mol%, the developing speed is generally slow, which is not preferable.

When iodine atoms are released from the iodide ion releasing agent in the form of iodide ions, all iodine atoms may be released, or some of them may remain without being decomposed. The iodide ion release rate from the iodide ion releasing agent will be specifically described.

In the present invention, for example, the formation of a silver halide phase containing silver iodide at the edges of tabular grains while rapidly generating iodide ions during the process of introducing dislocation lines into normal crystal grains is as follows: This is preferable for introducing dislocation lines at high density. If the supply rate of iodide ions is too slow, that is, if the time for forming a silver halide phase containing silver iodide is too long, the silver halide phase containing silver iodide is redissolved during that time, and the dislocation linear density Will decrease. on the other hand,
Supplying iodide ions slowly does not cause locality (non-uniform distribution) of iodide ions. In other words, this is preferable for uniformly introducing dislocation lines within and between grains.
Therefore, it is important to generate iodide ions rapidly and without locality (non-uniform distribution). The region where the locality of iodide ions is large is formed when an iodide ion releasing agent or an iodide ion release controlling agent used in combination with the iodide ion releasing agent is added to the reaction solution in the particle forming container. This is because the iodide ion release reaction is too fast for the resulting uneven concentration distribution of the additive. The time for the released iodide ions to deposit on the host grains is extremely fast, and the grains grow in a region near the addition port where the iodide ions have a high locality, so that uneven grain growth occurs between grains. Therefore, it is necessary to select an iodide ion release rate that does not cause locality of iodide ions. In the conventional method (for example, by adding an aqueous solution of potassium iodide), even if the aqueous solution of potassium iodide is diluted and added, the iodide ions are added in a free state. There is a limit to trying to reduce it. That is, it was difficult to form particles without unevenness in the particles and between the particles by the conventional method. However, according to the present invention in which the iodide ion release rate can be controlled, the locality of iodide ions can be reduced as compared with the conventional method. The present inventors have attempted to introduce dislocations in tabular grains by using a conventional iodide ion supply method having a large locality of iodide ions. Considering that it is not possible to introduce the ions uniformly between the grains, an attempt was made to introduce dislocations into the tabular grains by using a method of rapidly generating iodide ions having low locality of iodide ions. As a result, the present inventors have found that dislocation lines can be introduced homogeneously within grains and between grains by substantially limiting the dislocation lines to only the fringe portions of tabular grains while maintaining the density at a high density.

In the present invention, the iodide ion release rate can be determined by controlling the temperature, the concentration of the iodide ion releasing agent and the concentration of the iodide ion release regulator as described above, and may be selected according to the purpose. In the present invention, the preferred iodide ion release rate is such that 100 to 50% of the total weight of the iodide ion releasing agent present in the reaction solution in the particle forming vessel releases iodide ions within one second or more within 180 seconds. The rate at which the release of iodide ions is completed, more preferably within 120 seconds, particularly preferably within 60 seconds. In the present invention, “within 180 consecutive seconds”
Means 180 while the iodide ion release reaction is continuous.
Within seconds, the iodide ion release time may be measured from any point in the continuous reaction.

When the iodide ion release reaction period is divided into two or more times, it is calculated from any time point of the first iodide ion release reaction period or any time point of the second or later iodide ion release reaction period. Then, the iodide ion release rate from the iodide ion releasing agent present in the reaction solution may be obtained.

If the time exceeds 180 seconds, the release rate is generally low, and if it is less than 1 second, the release rate is too high, and the use conditions are limited. The same applies to less than 50%. The rate at which 100 to 70% of the iodide ion releasing agent present in the reaction solution in the particle forming vessel completes the release of iodide ions within 180 consecutive seconds is more preferable, and more preferably 100 to 80%. Particularly preferably, 100 to 90% is the rate at which iodide ion release is completed within 180 consecutive seconds. In the case where the reaction for rapidly producing iodide ions is represented by a secondary reaction which is substantially proportional to the concentration of the iodide ion releasing agent and the concentration of the iodide ion releasing regulator (40 ° C. in water), the present invention is preferred. Is 2
The next reaction rate constant is 1000 to 5 × 10 ⁻³ (M ⁻¹ · s
ec ^-1 ), more preferably 100 to 5 × 10
⁻² (M ⁻¹ · sec ⁻¹ ), particularly preferably 10 to 0.1 (M ⁻¹ · sec ⁻¹ ). Substantially a second-order reaction means that the correlation coefficient is 1.0 to 0.8. When the concentration of the iodide ion releasing agent is 10 ^-4 to 10
^-5 M, the concentration of the iodide ion release regulator is 10 ^-1 to 1
A typical second-order reaction rate constant k (M ⁻¹ · sec ⁻¹ ) measured in a range of 0 ⁻⁴ M under a condition that can be regarded as a pseudo first-order reaction in water at 40 ° C. is as follows. It is as follows. Compound No. Iodide ion release regulator k 11 hydroxide ion 1.3 1 sulfite ion 1 × 10 ⁻³ or less 2 same as above 0.29 58 same as above 0.49 63 same as above 1.5 22 hydroxide ion 720 k is 1000 If it exceeds 3, the release is too early to control, and if it is less than 5 × 10 ^-3, it is too late to obtain the effect of the present invention.

The control of the release of iodide ions in the present invention is preferably carried out by the following method. That is, by changing the pH, the concentration of the nucleophilic substance, the temperature, etc. from the already uniformly distributed iodide ion releasing agent added to the reaction solution in the particle forming container, the pH is usually changed from low pH to high pH. In this method, iodide ions are released while controlling the reaction solution uniformly throughout the reaction solution. It is preferable that the alkali for raising the pH at the time of releasing the iodide ion and the nucleophilic substance used together are added in a state where the iodide ion releasing agent is uniformly distributed throughout.

Here, the method of introducing dislocation lines into tabular grains of the present invention will be described.

The tabular grains of the present invention are silver halides containing silver iodide. The tabular grains of the present invention contain at least one of a silver iodide phase, a silver iodobromide phase, a silver chloroiodobromide phase, and a silver chloroiodide phase. Other silver salts, for example, rodin silver, silver sulfide,
Silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as part of silver halide grains.

The preferred range of the silver iodide content of the tabular grains of the present invention is 0.1 to 20 mol%, more preferably 0.3 to 15 mol%, and particularly preferably 1 to 10 mol%. In the present invention, it is preferable to introduce dislocation lines into tabular grains as follows.

That is, a tabular grain serving as a base is prepared, and a silver halide phase containing silver iodide is formed at the edge of the base grain.

At this time, the effect of the present invention was remarkable when the compound of the present invention represented by the formula (I) was used as an iodide ion source.

The halogen composition of the silver halide phase containing silver iodide is optional, but the higher the silver iodide content, the more preferable.

The silver iodide content of the base grains is from 0 to 15 mol%.
Is more preferably 0 to 12 mol%, particularly preferably 0 to 10 mol%.

The amount of halogen added to form the high silver iodide content phase on the base grains is 2% of the silver amount of the base grains.
It is preferably from 15 to 15 mol%, more preferably from 2 to 10 mol%, particularly preferably from 2 to 5 mol%.

At this time, the high silver iodide content phase is preferably present in the range of 5 to 80 mol%, more preferably 10 to 70 mol%, particularly preferably 20 to 80 mol% in terms of silver of the whole grains. In the range of 60 mol%.

After a high silver iodide content phase is formed at the edge of the base grain, dislocation lines can be introduced by forming a silver halide shell outside the high silver iodide content phase.

The composition of the silver halide shell is silver bromide,
Either silver iodobromide or silver chloroiodobromide may be used, but silver bromide or silver iodobromide is preferred.

The preferred silver iodide content of silver iodobromide is 0.1 to 12 mol%, more preferably 0.1 to 12 mol%.
-10 mol%, most preferably 0.1-3 mol%. The preferred temperature in the above dislocation line introduction process is 30.
To 80 ° C, more preferably 35 to 75 ° C, particularly preferably 35 to 60 ° C.

The preferred pAg is 6.4 to 10.5.
It is.

It is preferable that the outermost shell in the vicinity of the surface of the silver halide grains is formed uniformly within the grains and between the grains by using the iodide ion releasing method of the present invention.

The formation of a silver halide phase containing silver iodide in the vicinity of the grain surface is important in terms of enhancing the dye adsorbing power and controlling the developing speed.

In the present invention, the particle surface is defined as 5 particles from the surface.
A region up to a depth of about 0 Å.

The halogen composition in such a region is represented by XPS
It can be measured by a surface analysis method such as (X-ray photoelectron spectroscopy) method or ISS (ion scattering spectroscopy) method.

In the present invention, silver halide grains having a silver iodide content of 0.1 to 15 mol% in the silver halide phase on the grain surface of the emulsion grains measured by these surface analysis methods are preferred, and more preferably 0%. 0.3 to 12 mol%, particularly preferably 1 to
It is 10 mol%, most preferably 3 to 8 mol%.

Further, in the present invention, it is preferable that the halogen composition in the emulsion grains and between the grains is uniform.

In the emulsion of the present invention, the coefficient of variation of the silver iodide content distribution of each grain is preferably 20% to 3%. More preferably 15% to 3%, particularly preferably 1%
0% to 3%.

The silver iodide content of each grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer.

The variation coefficient of the silver iodide content distribution is a value obtained by dividing the variation (standard deviation) of the silver iodide content of each grain by the average silver iodide content.

The following is a description of the emulsion of the present invention and the emulsions other than the present invention used in combination. The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. Other silver salts such as silver rhodan, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. The silver halide emulsion of the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. A typical example is Japanese Patent Publication No. 43-13162,
Core-shell having a halogen composition in which the inside and the surface of the grains are different from each other as disclosed in JP-A 1-215540, JP-A-60-222845, JP-A-60-143331 and JP-A-61-75337. Type or double structure type particles. Also, it is not a simple double structure.
A triple structure as disclosed in U.S. Pat.
Alternatively, a silver halide having a different composition can be thinly applied to the surface of a core-shell double-structured grain having a multilayer structure of more layers. In order to give a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonding structure can be produced. Examples of these are disclosed in JP-A-59-133540, JP-A-58-108526, and EP 199,290A2.
No., JP-B-58-24772, JP-A-59-1625.
No. 4, etc. The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure. In the case of a joint structure, a combination of silver halides is naturally possible, but a silver salt compound having no rock salt structure such as silver rhodanate or silver carbonate can be combined with silver halide to form a joint structure. Further, a non-silver salt compound such as lead oxide may be used as long as the bonding structure is possible. In the case of grains such as silver iodobromide having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core and a high shell are sometimes preferred. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. Further, the boundary portions having different halogen compositions of the grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment. In the case of silver halide grains in which two or more silver halides exist as mixed crystals or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable. Another preferred form is an emulsion having a correlation between the grain size and the halogen composition. As an example, there is a correlation such that the iodine content is higher for larger size particles, while the iodine content is lower for smaller size particles. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the surface of the grains. Increase the silver iodide content near the surface,
Alternatively, increasing the silver chloride content can be selected according to the purpose because the adsorption property of the dye and the developing speed are changed.
When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, (100) plane and (1)
11) The case where the halogen composition is changed only on one side of a tetrahedral grain composed of planes, or the halogen composition on one of the main plane and the side face of the tabular grain is changed.

The silver halide grains used in the emulsions of the present invention and the emulsions other than the present invention used in combination with the emulsions can be either normal crystals containing no twin planes, edited by the Photographic Society of Japan, the basics of the photography industry, edited by silver salt photography ( Corona), p. 163, such as a single twin with one twin plane, a parallel multiple twin with two or more parallel twin planes, a non-parallel with two or more non-parallel twin planes It can be selected from multiple twins or the like depending on the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube consisting of (100) planes, an octahedron consisting of (111) planes, Japanese Patent Publication No. 55-42737,
A dodecahedral particle having a (110) plane disclosed in JP-A-222842 can be used. In addition, Jou
rnal of ImagingScience 30
Volume 247 (h11) plane particles represented by (211) as reported in 1986, (331)
(Hh1) plane particles representing (210) plane, (hk0) plane particles representing (210) plane, and (hk) plane representing (321) plane.
1) The surface particles also need to be devised in the preparation method, but can be selected and used according to the purpose. A tetrahedral particle in which (100) plane and (111) plane coexist in one particle, a particle in which (100) plane and (110) plane coexist, or a particle in which (111) plane and (110) plane coexist, Particles in which two faces or many faces coexist can be selected and used according to the purpose.

The value obtained by dividing the circle equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described in Cleeve, "Theory and Practice of Photography" (Cleve, Photography Theo).
ry and Practice (1930)), 13
1st page; Gatov, Photographic Science and Engineering (Gutoff, Photogr)
aphic Science and Engineer
ring, Vol. 14, pp. 248-257 (1970)
U.S. Pat. Nos. 4,434,226 and 4,41.
No. 4,310, No. 4,433,048, No. 4,4
39,520 and British Patent No. 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, which is described in detail in U.S. Pat. No. 4,434,226 cited above. The average aspect ratio of 80% or more of the total projected area of the grains is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 30 and particularly preferably 3 or more and less than 25. The shape of the tabular grains can be selected from triangles, hexagons, and circles. U.S. Pat. No. 4,797,35
No. 4, a regular hexagon having substantially equal lengths of six sides is a preferable form.

The equivalent circle diameter of the tabular grains is 0.15 to 5.0.
μm is preferred. The thickness of the tabular grains is preferably from 0.05 to 1.0 μm. 0.05
If it is less than μm, the pressure property is undesirably deteriorated. 1.0 μm
If it exceeds 90, it is not preferable because the advantages of tabular grains cannot be fully utilized.

The proportion occupied by tabular grains is preferably tabular grains having an aspect ratio of 3 or more, more preferably 50% or more, more preferably 80%, particularly preferably 90% of the total projected area.
% Or more. When monodisperse tabular grains are used, more preferable results may be obtained. The structure and production method of monodisperse tabular grains are described, for example, in JP-A-63-15161.
According to the description of No. 8, etc., if its shape is briefly described,
70% or more of the total projected area of the silver halide grains is a hexagon in which the ratio of the length of the side having the maximum length to the length of the side having the minimum length is 2 or less, and The hexagonal tabular silver halide grains are occupied by tabular silver halide grains having two parallel surfaces as outer surfaces, and the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains (the grain size represented by the circle-converted diameter of the projected area thereof). Variation (standard deviation)
(Value divided by the average particle size) is 20% or less. Further, it is preferable to use particles having dislocation lines. In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. It is also possible to select a dislocation or a dislocation that is introduced linearly with respect to a specific direction of the crystal orientation of the grain, or to introduce the entire grain, or to introduce only a specific portion of the grain, for example. The dislocation can be introduced only in the fringe portion of the particle. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of normal grains or irregular grains typified by potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle. The silver halide emulsion used in the present invention is disclosed in European Patent Nos. 96,727B1 and 64,4.
No. 12,306,447C, for example, a treatment for rounding particles as disclosed in US Pat.
2, the surface may be modified as disclosed in JP-A-60-221320. Although a structure having a flat particle surface is generally used, it is sometimes preferable to form irregularities intentionally. JP-A-58-106532 and JP-A-60-221320 disclose a method of forming a hole in a part of a crystal, for example, a vertex or a center of a plane, or a method described in US Pat. No. 4,643,966. Raffle particles are an example.

The grain size of the emulsion used in the present invention is determined by a circle equivalent diameter of a projected area using an electron microscope, a sphere equivalent diameter of a particle volume calculated from the projected area and the grain thickness, or a sphere equivalent diameter of a volume by the Coulter counter method. Can be evaluated. It can be used by selecting from ultrafine particles having a sphere equivalent diameter of 0.05 μm or less and coarse particles exceeding 10 μm. Preferably, grains having a size of 0.1 μm or more and 3 μm or less are used as photosensitive silver halide grains. Emulsions of normal crystals used in the present invention may be selected according to the purpose, either so-called polydisperse emulsions having a wide grain size distribution or monodisperse emulsions having a narrow size distribution. As a scale representing the size distribution, a variation coefficient of a circle equivalent diameter of a projected area of a particle or a spherical equivalent diameter of a volume may be used. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% to 3%, more preferably 20% to 3%, and still more preferably 15% to 3%. A monodisperse emulsion may be defined as having a grain size distribution such that 80% to 100% of all grains fall within ± 30% of the average grain size by number or weight of grains. In order to satisfy the target gradation of the light-sensitive material, two or more monodispersed silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture. The emulsion of the present invention and photographic emulsions other than the present invention used in combination therewith are described in Grafkid.

"Physics and Chemistry of Photography", published by Paul Montell (P. Glafkids, Chemie et P.)
hisique Photographique, Pa
ulMontel, 1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GF Duffi).
n, Photographic Emulsion C
hemistry (Focal Press, 196)
6)), "Manufacture and Coating of Photographic Emulsion", by Zerikman et al., Focal Press (VL Zelikmanet).
al. , Making and Coating Ph
autographic Emulsion, Focal
Press, 1964) and the like. That is, acid method, neutral method,
Any method such as an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide is a one-sided mixing method,
Any of the simultaneous mixing method and a combination thereof may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one form of the double jet method, the silver halide
A method for keeping pAg constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion, US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is optionally preferred. These can be used as seed crystals,
It is also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from the method of adding the whole amount at a time, adding in a plurality of times or adding continuously. It is also effective in some cases to add particles of various halogen compositions to modify the surface. A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in U.S. Pat. Nos. 3,477,852 and 4,1.
No. 42,900, European Patent 273,429, No. 27
No. 3,430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously. As a method of grain growth, British Patent No. 1,469,4 discloses a method other than adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate.
No. 80, U.S. Pat. Nos. 3,650,757 and 4,2
The particle formation method of changing the concentration or changing the flow rate as described in No. 42,445 is a preferred method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is. A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in U.S. Pat.
No. 6,287, No. 3,342,605, No. 3,4
No. 15,650, 3,785,777, West German Patent Publication 2,556,885, and 2,555,364. Silver halide solvents are useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and the halide salt, or can be added together with the halide salt, the silver salt or the deflocculant. Can also be introduced. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps. As the ripening agent, for example, ammonia, thiocyanate (for example, rhodankali, rhodan ammonium), organic thioether compound (for example, US Pat. Nos. 3,574,628 and 3,021,215)
No. 3,057,724 and 3,038,80
No. 5, No. 4,276,374, No. 4,297,4
No. 39, No. 3,704, 130, No. 4,782
No. 013 and JP-A-57-104926. ), Thione compounds (for example, JP-A-53-8240)
No. 8, No. 55-77737, U.S. Pat.
No. 863, compounds described in JP-A-53-144319) and the growth of silver halide grains described in JP-A-57-202531. Mercapto compounds and amine compounds (for example, JP-A-54-100717). Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. 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 polyvinyl alcohol, a partial acetal of polyvinyl alcohol,
Various kinds of synthetic hydrophilic high molecular substances such as homopolymers or copolymers such as poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo
o. Japan. No. 16. Enzyme-treated gelatin as described in P30 (1966) may be used.
A hydrolyzate or enzymatic hydrolyzate of gelatin can also be used. The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose.
It is preferable to select between 10 and 10. More preferably, 3
-8. The pAg at the time of washing 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.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable 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 entire grain and a method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the base grain of the grain can be selected. For example, Mg, Ca, Sr, Ba,
Al, Sc, Y, La, Cr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Tl, In, S
n, Pb, and Bi 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 , P
b (NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe
(CN) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃
IrCl ₆ , (NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (C
N) ₆ . 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 after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding an aqueous solution of hydrogen halide (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) 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. Further, a water-soluble silver salt (for example, AgNO ₃ ) or an aqueous alkali halide solution (for example, NaCl, K
(Br, 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.

In some cases, a method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is also useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present. The silver halide grains of the present invention are 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 a silver halide emulsion production step. be able to. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. A type in which a chemical sensitizing nucleus is embedded in the interior of a particle,
Alternatively, there is a type that forms a chemical sensitization nucleus on the surface. In the 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 which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination.
es), The Photographic Process, 4th
Edition, Macmillan, 1977, (TH James)
s, The Theory of the Photo
graphic Process, 4th ed, Ma
Cilllan, 1977) pp. 67-76, and can be performed using active gelatin, and is also described in Research Disclosure, Vol. 120, April 1974, 12008; Research Disclosure, 3
4, June 1975, 13452, U.S. Pat.
No. 42,361, No. 3,297,446, No. 3,
No. 772,031, No. 3,857,711, No. 3,
Nos. 901 714, 4,266,018 and 3,904,415, and British Patent 1,31.
No. 5,755, pAg 5-10, pH 5
At 8 and a temperature of 30-80 ° C, it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality 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. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are R ₂ PdX ₆ or R ₂ PdX ₄
Is represented by Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate. As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat.
The sulfur-containing compounds described in Nos. 57,711, 4,266,018 and 4,054,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog in the course of chemical sensitization and increase sensitivity, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in US Pat. No. 2,131,038.
No. 3,411,914, No. 3,554,75
No. 7, JP-A-58-126526 and the aforementioned "Emulsion Chemistry" by Duffin, pp. 138-143. The emulsion of the present invention is preferably used in combination with gold sensitization.
The preferred amount of the gold sensitizer is 1 per mole of silver halide.
It is from × 10 ^-4 to 1 × 10 ^-7 mol, more preferably from 1 × 10 ^{-5 to} 5 × 10 ^-7 mol. The preferred range of the palladium compound is from 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ . The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is from 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably from 1 × 10 ^-5 to 1 × 10 ^-7 mol per mol of silver halide. It is 5 × 10 ^-7 mol. Selenium sensitization is a preferred sensitization method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea), selenoketones And selenium compounds such as selenoamides. 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 refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing in a pAg 1 to 7 low pAg atmosphere called silver ripening, or a method of ripening, and a method of high pH ripening called pH ripening of 8 to 8. Either the method of growing in a high pH atmosphere of 11 or the method of ripening can be selected. 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. Known reduction sensitizers include, for example, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, and borane compounds. 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. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide. The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. It may be added to the reaction vessel in advance, but a method of adding at an appropriate time during the particle growth is preferable. Alternatively, a reduction sensitizer may be added in advance to the water solubility 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 emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it 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 ion generated here may form a water-insoluble silver salt such as silver halide, silver sulfide or silver selenide, or a water-soluble silver salt such as silver nitrate. May be formed. The oxidizing agent for silver may be inorganic or organic. As the inorganic oxidizing agent, for example, ozone, hydrogen peroxide and its adduct (eg, NaBO ₂
・ H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , N
_{a 4 P 2 O 7 · 2H} 2 O 2, 2Na 2 SO 4 · H 2 O 2
2H ₂ O), peroxy acid salts (eg, K ₂ S)
₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] · 3
_{H 2 O, 4K 2 SO 4} · Ti (O 2) OH · SO 4 · 2
H ₂ O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ ] · 6H
Oxyacids such as ₂ O), permanganates (eg, KMnO ₄ ), chromates (eg, K ₂ Cr ₂ O ₇ ),
There are halogens such as iodine and bromine, perhalates (eg, potassium periodate), salts of high valent metals (eg, potassium hexacyanoferric acid) 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 (for example, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example.

Preferred oxidizing agents of the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates, and organic oxidizing agents such as quinones.
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 emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) known as antifoggants or stabilizers, such as titraazaindenes and pentaazaindenes;
Many compounds can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,947,
Those described in JP-B-52-28660 can be used. One of preferred compounds is disclosed in JP-A-63-21.
2932. 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 by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic 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, for example, a pyrroline nucleus, an oxazoline nucleus,
Thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and aromatic hydrocarbon rings in these nuclei Fused nuclei, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus it can. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or composite merocyanine dye has a ketomethylene structure as a nucleus.
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5- or 6-membered heterocyclic nucleus such as a 2,4-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.

In addition to the sensitizing dye, the emulsion may contain a dye having no spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, this is done after completion of chemical sensitization but before coating, but US Pat. No. 3,628,969.
As described in JP-A-58-113928, addition of a chemical sensitizer and simultaneous addition of a chemical sensitizer and spectral sensitization as described in JP-A-58-113928 can also be used. As described above, it can be carried out prior to chemical sensitization, or it can be added before completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add after the feeling, US Pat.
It may be at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 3,756.

The amount of addition was 4 × / mol of silver halide.
Although it can be used in an amount of 10 ^-6 to 8 × 10 ^-3 mol, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is effective when the silver halide grain size is more preferably 0.2 to 1.2 μm. is there.

The light-sensitive material produced by using the silver halide emulsion obtained in the present invention comprises a support, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer. It is sufficient that at least one layer is provided, and there is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one color-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, a unit light-sensitive layer is generally used. Of the red-sensitive layer in order from the support side,
A green color sensitive layer and a blue color sensitive layer are provided in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748.
No. 59-113438, No. 59-113440
Couplers and DIR compounds as described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer constitution of an emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A-62-206541 and JP-A-62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
For example, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / a high-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL) or BH / BL / GL / GH / R
H / RL, or BH / BL / GH / GL / RL /
They can be installed in the order of RH.

As described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of Japanese Patent No. 6, the blue-sensitive layer / GL / RL / GH / RH can be provided in this order from the farthest side from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a lower sensitivity than the middle layer. Further, there is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer / They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order.

Also, in the case of four or more layers, the arrangement may be changed as described above.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The above-mentioned various additives are used in the light-sensitive material according to the present invention, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (1978).
Item 18716 (January 1979)
Jan.) and Item 308119 (December 1989), and the relevant portions are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Super strong Sensitizer 649 right column 4 Brightener 4 page 647 right column 998 right 5 Antifoggant, 24-25 page 649 right column 998 right-1000 right and stabilizer 6 light absorber, 25-26 649 Page right column to 1003 left to 1003 right Filter dye, page 650 Left column UV absorber 7 Stain inhibitor page 25 right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardener 26 page 651 Page left column 1004 right to 1005 left 10 Binder page 26 Same as above 1003 right to 1004 right 11 Plasticizer, lubricant 27 page 650 Page right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 left 1006 left Surfactant 13 Static Page 27 Same as above 1006 right to 1007 left Inhibitor 14 matting agent 1008 left to 1009 left Also to prevent deterioration of photographic performance due to formaldehyde gas For this purpose, it is preferable to add a compound which can react with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503 and can be fixed to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG and N
o. 307105, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
No. 5,951, U.S. Pat. Nos. 4,500,630, 4,540,654 and 4,556,630, and WO 88/04795 are particularly preferred.

Examples of the cyan coupler include phenol type and naphthol type couplers.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,690, 8
No. 89, No. 4,254,212, No. 4,296,
199 and JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137 and European Patent 341,188A.
No.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No.
No. 17643, section VII-G; VII of 307105-
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, British Patent 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in U.S. Pat. No. 4,777,120 as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, VII-F and the same No. 307105, VII-
Patent described in section F, JP-A-57-151944,
Preferred are those described in JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, U.S. Pat. Nos. 4,248,962 and 4,782,012.

Examples of couplers which release a nucleating agent or a development accelerator imagewise during development are described in British Patent No. 2,093.
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds usable in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950, Japanese Patent Application Laid-Open No. 62-24252, and the like.
R redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, couplers capable of releasing dyes which discolor after release as described in EP 173,302A and EP 313,308A , RD. No. 1
Bleaching accelerator releasing couplers described in US Pat. Nos. 4,5, 1449, 24241, and JP-A-61-201247.
55,477 and the like; couplers releasing leuco dyes described in JP-A-63-75747; and couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181. .

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Specific examples of the high boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-tert-amylphenyl)
Phthalates, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); phosphoric acid or phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate); benzoic acid esters (for example, 2-ethylhexyl benzoate) , Dodecyl benzoate, 2-
Ethylhexyl-p-hydroxybenzoate); amides (for example, N, N-diethyldodecaneamide, N,
N-diethyl laurylamide, N-tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol); aliphatic carboxylic acid esters (eg, bis (2- Ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N-dibutyl-2-butoxy-)
5-tert-octylaniline); and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, the boiling point is about 30 ° C. or more, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C. or less can be used. Typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described, for example, in US Pat.
9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-63-257747, may be used.
272248 and JP-A-1-80941, for example, 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, −
It is preferable to add various preservatives or fungicides such as phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. For example, color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers can be mentioned as typical examples. The present invention can be particularly preferably used for a color duplication film.

Suitable supports that can be used in the present invention are described, for example, in RD. No. No. 17643, page 28;
No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. Here, the film thickness means a film thickness measured under humidity control at 25 ° C. and 55% relative humidity (2 days). Further, the film swelling rate T _1/2 can be measured according to a method known in the art, and is described, for example, by A. Green et al. In Photographic Science and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129 can be used for measurement. In addition, T _1/2 is 30 in the color developing solution.
℃, the maximum swelling film thickness of 9 reached when treated for 3 minutes 15 seconds
0% is defined as the saturated film thickness, and defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging conditions after coating.

In the light-sensitive material of the present invention, a hydrophilic colloid layer having a total dry film thickness of 2 to 20 μm (referred to as a back layer) is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains, for example, the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. . The swelling ratio of the back layer is preferably from 150 to 500%.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. No. 17643, pages 28 to 29;
No. 18716, page 651, left column to right column; 30
The development can be carried out by a usual method described on pages 880 to 881 of No. 7105.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, in particular, 3-methyl-4-
Sulfates of amino-N-ethyl-N-β-hydroxyethylaniline are preferred. These compounds are used depending on the purpose.
More than one species may be used in combination.

The color developing solution may be, for example, a pH buffer such as an alkali metal carbonate, borate or phosphate,
It generally contains a development inhibitor or an antifoggant such as chloride, bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid; ethylene glycol; Organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines; dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos Various chelating agents such as carboxylic acids can be used. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and 1-hydroxyethylidene-1,1-
Representative examples include diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. be able to.

When the reversal process is performed, color development is usually performed after black-and-white development. The black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, for example, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-
Known black and white developing agents of aminophenols such as p-aminophenol can be used alone or in combination. The p of these color developing solutions and black-and-white developing solutions
H is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material. You can also When the replenishment amount is reduced, it is preferable to prevent the treatment liquid from evaporating and air oxidizing by reducing the contact area of the processing liquid with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment solution and air (cm ² )] ÷ [capacity of treatment solution (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.1% or less. 001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to a method of providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a movable lid described in JP-A-1-82033 is used. And a slit developing method described in JP-A-63-216050. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the subsequent steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing and stabilization. Further, by using means for suppressing the accumulation of bromide ions in the developer, the replenishing amount can be reduced.

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

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Furthermore, processing in two continuous bleach-fix baths, fixing before bleach-fix processing,
Alternatively, bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids (particularly, sodium persulfate is suitable for a color negative film for movies), quinones, and nitro compounds are used. Representative bleaching agents include organic complex salts of iron (III), for example, ethylenediaminetetraacetic acid,
Complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycoletherdiaminetetraacetic acid, or, for example, citric acid, tartaric acid, malic acid Can be used. Among these, iron (III) aminopolycarboxylate complex salts such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate complex salt are:
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
The aminoboric acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: for example, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95731, No. 53-
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-18426, Research Disclosure No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A-51-140129; thiazolidine derivatives described in JP-A-51-140129; JP-B-45-8506, JP-A-52-20
Nos. 832 and 53-32735, U.S. Pat.
No. 6,561, the thiourea derivative described in West German Patent 1,
127,715; JP-A-58-16235; West German Patent Nos. 966,410 and 2,741
8,430; polyamine compounds described in JP-B-45-8836; and JP-A-49-40943 and JP-A-49-59644;
Nos. 53-94927, 54-35727, 55
Compounds described in -26506 and 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat.
No. 58, West German Patent No. 1,290,812,
Compounds described in -95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,884 are also preferable. These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specific examples include acetic acid, propionic acid, and hydroxyacetic acid.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. Of these, use of thiosulfates is common, and in particular, ammonium thiosulfate can be used most widely. Also, thiosulfate and, for example, thiocyanate,
A combination use of a thioether compound and thiourea is also preferable. Examples of the preservatives of the fixing solution and the bleach-fixing solution include sulfites, bisulfites, carbonyl bisulfite adducts and European Patent No. 2
Sulfinic acid compounds described in No. 94,769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methyl for adjusting pH. It is preferable to add imidazoles such as imidazole in an amount of 0.1 to 10 mol / l.

The total time of the desilvering step is preferably as short as possible without desilvering failure. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on an emulsion surface of a photosensitive material, or a method described in JP-A-62-183461, using a rotating means. There is a method to improve the effect. In addition, the photosensitive material is moved while the emulsion surface is in contact with the wiper blade provided in the solution, and the turbulence of the emulsion surface is used to improve the stirring effect, and the circulation flow rate of the entire processing solution is increased. There is a method to make it. Such a stirring improving means is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement in the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibition effect by the bleaching accelerator.

The automatic developing machine used for developing the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and JP-A-60-19.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 1258 and 60-191259. Japanese Patent Laid-Open No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a transport means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective in shortening the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of water to be washed in the water washing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use,
Further, for example, the washing water temperature, the number of washing tanks (the number of stages),
It can be set in a wide range according to a replenishment method such as countercurrent or forward flow, and other various conditions. Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is shown in Journal of
the Society of Motion Pi
cure and Television Engi
neers, vol. 64, p. 248-253 (1955)
May issue).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, there is a problem that bacteria increase due to an increase in the residence time of the water in the tank, and the generated suspended matter adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also described in JP-A-57-8542, for example, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and others, such as benzotriazole, written by Hiroshi Horiguchi "The Chemistry of Bactericidal and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Techniques" (1982) Industrial Technology Association A fungicide described in "A fungus encyclopedia" (1986) can also be used.

The washing water p in the processing of the light-sensitive material of the present invention.
H is 4-9, preferably 5-8. The washing water temperature and washing time can also be variously set depending on, for example, the characteristics and use of the photosensitive material, but are generally at 15 to 45 ° C. for 20 seconds to 1 hour.
A range of 0 minutes, preferably 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Patent Application Laid-Open No. 57-8543
, 58-14834 and 60-220345 can all be used.

Further, following the water washing treatment, a stabilization treatment may be further performed. An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

For example, in processing using an automatic developing machine,
When each of the above-mentioned treatment liquids is concentrated by evaporation, it is preferable to add water to correct the concentration.

In the silver halide color photographic light-sensitive material of the present invention, a color developing agent may be incorporated for the purpose of simplifying and speeding up the processing. In order to incorporate them, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, for example, U.S. Pat. No. 3,342,599, Research Disclosure No. 14, 850 and the same No.
Nos. 15, 15 and 159; 1
Aldol compounds described in U.S. Pat.
No. 719,492, a metal salt complex disclosed in JP-A-53-1
The urethane compounds described in JP-A-35628 can be exemplified.

The silver halide color light-sensitive material of the present invention comprises:
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described, for example, in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

The various processing solutions in the present invention may be used at a temperature of 10 ° C. to 5
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention comprises
U.S. Pat. No. 4,500,626, JP-A-60-133
No. 449, No. 59-218443, No. 61-2380
No. 56, EP 210,660 A2 and the like.

The silver halide color photographic light-sensitive material of the present invention is disclosed in JP-B-2-32615 and JP-B-3-397.
In the case where the invention is applied to a film unit with a lens described in No. 84 or the like, the effect is more easily exhibited and is effective.

[0153]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Example 1 Tabular silver iodobromide emulsion (1) Preparation of emulsion Tabular silver bromide core emulsion 1-A An aqueous solution 12 containing 6.2 g of gelatin and 6.4 g of KBr
Stirring while maintaining 00 cc at 60 ° C., 1.9M Ag
8cc of NO ₃ aqueous solution and 9.6c of 1.7M KBr aqueous solution
c and double jet for 45 seconds. Gelatin 38
g was added and the temperature was raised to 75 ° C. in the presence of NH _3.
Aged for minutes. After neutralization with HNO ₃ , 1.9 M AgNO
₍₃₎ 405 cc of an aqueous solution and an aqueous KBr solution with a pAg of 8.22
The mixture was added for 87 minutes while accelerating the flow rate while keeping the flow rate (the flow rate at the end was 10 times that at the start). Thereafter, the emulsion was cooled to 35 ° C.
And desalted by a conventional flocculation method. The resulting silver bromide emulsion was tabular grains having an average equivalent circle diameter of 2.0 μm, an average thickness of 0.25 μm, and an average aspect ratio of 8. Tabular silver iodobromide emulsion 1-B (comparative emulsion) Emulsion 1 containing silver bromide equivalent to 164 g of AgNO ₃
A was added to 1950 cc of water, the temperature was kept at 55 ° C., the pAg was kept at 8.9, and the pH was kept at 5.0. Thereafter, 126 cc of a 0.32 M KI aqueous solution was added in a fixed amount for 5 minutes, and subsequently, 206 cc of a 1.9 M AgNO ₃ aqueous solution and a KBr aqueous solution were added over 36 minutes so as to maintain the pAg at 8.9.
Thereafter, desalting was carried out by conventional flocculation. The resulting silver iodobromide emulsion was tabular grains having an average equivalent circle diameter of 2.1 μm, an average thickness of 0.30 μm, and an average aspect ratio of 7. The grains having an aspect ratio of 4 or more occupy 80% or more of the total projected area, and the following tabular emulsions 1-C to 1-H
But it was the same. Tabular silver iodobromide emulsion 1-C (comparative emulsion) Except for the following, emulsion emulsion 1-B was prepared in the same manner as emulsion 1-B.

Instead of adding the KI aqueous solution, a silver iodide fine grain emulsion having an average grain size of 0.02 μm corresponding to AgNO ₃ (6.8 g) separately prepared in advance was added and completely dissolved in 10 minutes. Tabular silver iodobromide emulsion 1-D (comparative emulsion) Except for the following, it was prepared in the same manner as emulsion 1-B.

Instead of adding the KI aqueous solution, an aqueous solution of iodoacetic acid (7.5 g) was added, and then an aqueous solution of NaOH was added, the pH was raised to 10.5, and the mixture was kept for 15 minutes to release iodide ions gradually. Later, it was returned to 5.0. The time for 50% of the iodoacetic acid added to complete the release of iodide ions was more than 30 minutes (starting from the moment the pH was raised to 10.5). The iodide ion release rate was determined as follows. That is, the emulsion grains were separated by centrifugation, and the amount of the unreacted iodide ion-releasing agent contained in the supernatant was quantified by ICP (inductively coupled plasma emission) analysis, and the change over time was determined. The same applies to the following emulsions. Tabular silver iodobromide emulsion 1-E (emulsion of the present invention) Except for the following, it was prepared in the same manner as emulsion 1-B.

Instead of adding the KI aqueous solution, add 2-iodoethanol (3.1 cc), then add an NaOH aqueous solution, raise the pH to 10.5, hold for 4 minutes,
After rapidly producing iodide ions, the value was returned to 5.0. The time for 50% of the added 2-iodoethanol to complete the release of iodide ions was 30 seconds (pH 1
It was counted from the moment when it was raised by 0.5. ). Tabular silver iodobromide emulsion 1-F (emulsion of the present invention) Except for the following, emulsion emulsion 1-F was prepared in the same manner as emulsion 1-B.

Instead of adding the aqueous KI solution, an aqueous solution of 2-iodoacetamide (7.4 g) was added.
An 80 M aqueous sodium sulfite solution (75 cc) was added, an aqueous NaOH solution was added, the pH was raised to 9.0, and maintained for 8 minutes to rapidly generate iodide ions.
Returned to 0. 50% of the added 2-iodoacetamide
The time to complete the release of iodide ions was 10 seconds (calculated from the moment the pH was raised to 9.0). Tabular silver iodobromide emulsion 1-G (emulsion of the invention) Except for the following, emulsion emulsion 1-G was prepared in the same manner as emulsion 1-B.

Instead of adding the KI aqueous solution, sodium p-iodoacetamidobenzenesulfonate (15.
3g) After adding an aqueous solution, an aqueous 0.80 M sodium sulfite solution (60 cc) was added, an aqueous NaOH solution was added, the pH was raised to 9.0, and maintained for 8 minutes to rapidly generate iodide ions. , Back to 5.0. P added
The time for 50% of the sodium iodoacetamidobenzenesulfonate to release iodide ions was 10 seconds (calculated from the moment the pH was raised to 9.0). Tabular silver iodobromide emulsion 1-H (emulsion of the present invention) Except for the following, it was prepared in the same manner as emulsion 1-B.

Instead of adding the KI aqueous solution, sodium N-iodoacetylaminoethanesulfonate (12.
6g) After the aqueous solution was added, 0.80 M sodium sulfite (100 cc) was added, the NaOH aqueous solution was added, the pH was raised to 9.5, and maintained for 8 minutes to rapidly generate iodide ions. Returned to 5.0. N- added
5 of sodium iodoacetylaminoethanesulfonate
The time for 0% to complete the release of iodide ions was 10 seconds (calculated from the moment the pH was raised to 9.5). Tabular silver bromide core emulsion 2-A Except for the following, it was prepared in the same manner as emulsion 1-A.

Keeping the temperature at 30 ° C. instead of 60 ° C.
8cc of 1.9M AgNO ₃ aqueous solution and 1.7M of kBr
Instead of adding 9.6 cc of the aqueous solution in 45 seconds, 0.1 cc is added.
The kBr aqueous 25cc of aqueous AgNO ₃ solution 48cc and 0.2M of 1M were added at 10 seconds, instead of performing the aging in the presence of NH _3, was physical ripening without NH ₃ 20 min. The resulting silver bromide emulsion had an average circle equivalent diameter of 2.6 μm.
m, tabular grains having an average thickness of 0.14 μm and an average aspect ratio of 19. Tabular silver iodobromide emulsion 2-B (comparative emulsion) Except for the following, the same preparation was made as in emulsion 1-B.

Core Emulsion 2-A instead of Core Emulsion 1-A
Was used. The resulting silver iodobromide emulsion had an average circle equivalent diameter of 2.
7 μm, average thickness 0.18 μm, average aspect ratio 15
Were tabular grains. The grains having an aspect ratio of 10 or more occupy 90% or more of the total projected area.
The same was true for -C. Tabular silver iodobromide emulsion 2-C (emulsion of the present invention) Except for the following, emulsion emulsion was prepared in the same manner as emulsion 1-G.

Core emulsion 2-A instead of core emulsion 1-A
Was used. (2) Chemical sensitization The emulsions 1-B to 1-H and 2-B, 2-C were subjected to gold-sulfur sensitization as follows.

[0163] The emulsion was heated to 64 ° C., the sensitizing dyes ExS-1 described in Example 2 given later 2.6 × 10 ^-4 mol / mol Ag, ExS-2 and 1.1 × 10 ^{- 5} mol / mol Ag, E
xS-3 was added at 3.6 × 10 ^-4 mol / mol Ag,
Thereafter, potassium thiocyanate, chloroauric acid, and sodium thiosulfate were added, and each was optimally subjected to chemical sensitization.

Here, “optimal chemical sensitization” means 1 /
This is chemical sensitization in which the sensitivity upon exposure for 100 seconds is the highest. (3) Preparation of coating sample and its evaluation On a cellulose triacetate film support provided with an undercoat layer, each of the emulsions and protective layers shown in Table 1 were coated at the coating amounts shown in Table A below. And coating samples 1 to 9 were prepared. Table A Emulsion coating conditions (1) Emulsion layer · Emulsion ... various emulsion (silver 3.6 × 10 ^-2 mol / m ²⁾ · Coupler (1.5 × 10 ^-3 mol /
m ² )

[0165]

Embedded image - tricresyl phosphate (1.10g / m ²⁾ · Gelatin ^{(2.30g / m 2) (2} ) protective layer, 2,4-dichloro-6-hydroxy -s- triazine sodium salt (0.08 g / m ² ) · gelatin (1.80 g / m ² )
After leaving for a period of time, exposure was performed for 1/100 second through a continuous wedge, and color development shown in the following Table B was performed.

The concentration of the treated sample was measured with a green filter. Table B Process Processing time Processing temperature Color development 2.00 seconds 40 ° C. Bleaching and fixing 3 minutes 00 seconds 40 ° C. Rinse with water (1) 20 seconds 35 ° C. Rinse with water (2) 20 seconds 35 ° C. Stable 20 seconds 35 ° C. Dry Next, the composition of the processing solution is described. (Color developing solution) (Unit g) Diethylenetriaminepentaacetic acid 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 5 mg of hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethyl 4.5 amino) -2-methylaniline sulfate 1.0 liter of water and pH 10.05 (bleach-fixing solution) (Unit g) ferric ethylenediaminetetraacetate 90.0 ammonium dihydrate sodium ethylenediaminetetraacetate 5.0 sodium sulfite 12.0 aqueous solution of ammonium thiosulfate (70%) 260.0 ml acetic acid (98%) 5.0 ml bleaching accelerator 0.01 mol

[0167]

Embedded image Water was added and 1.0 liter pH 6.0 (washing solution) tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas)
And OH type anion exchange resin (Amberlite IR-
400) to treat the calcium and magnesium ion concentrations to 3 mg / L or less, followed by 20 mg of sodium diisocyanurate dichloride.
/ L and 1.5 g / L of sodium sulfate were added.

The pH of this solution is in the range of 6.5 to 7.5. (Stabilizing solution) (Unit g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl 0.3 ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 0 liters pH 5.0-8.0 Sensitivity was expressed as the logarithm of the reciprocal of the exposure, expressed in lux-seconds giving a density of 0.2 on fog.

With respect to the pressure characteristics, a test of the pressure characteristics was performed by the following test method A. Thereafter, sensitometric exposure was performed, and the color development shown in Table B was performed. Test Method A After placing in an atmosphere with a relative humidity of 55% for 3 hours or more, apply a load of 4 g with a needle having a diameter of 0.1 mm in the same atmosphere, and scratch the emulsion surface at a speed of 1 cm / sec. .

The developed sample was measured with a measuring slit of 5 μm × 1 mm to measure the density of the portion where pressure was applied and the portion where no pressure was applied.

The increase in fog due to pressure is defined as ΔFog. Further, in an exposure region equal to or less than 100 times the exposure amount E ₀ that gives a density of fog + 0.2, a certain exposure amount E
_{When the} concentration decreases by 0.01 or more due to pressure between ₁ and E ₂ , pressure desensitization region = ((log E ₂ −log E ₁ ) / 2) ×
100 (%). Table 1 shows the obtained results.

[0172]

[Table 1] In Table 1, the sensitivities of Samples 2 to 9 were 10 deg.
Each value was expressed as a relative value as 0.

The proportions of the fringe dislocation type tabular grains and the main plane dislocation type tabular grains were obtained by observing 200 emulsion grains of each emulsion with a high-pressure electron microscope. (Sample tilt angle -10 °,-
(Each grain is observed at 5 °, 0 °, + 5 °, and + 10 °.) As is clear from Table 1, 80% or more of the silver halide grains are substantially only in the fringe portion and 30 or more per grain. According to the present invention having a dislocation line of?, An emulsion having low fog, high sensitivity, small increase in pressure fog, and small pressure desensitization could be obtained. Example 2 On a subbed cellulose triacetate film support,
Each layer having the composition shown below is applied in a multilayer manner, and the emulsions 1-B, 1-G, 2-B and 2-C described in Example 1 are applied to the fifth layer (red-sensitive emulsion layer) of the multilayer color light-sensitive material. Sample 101 containing each
To 104 were produced. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. (Samples 101 to 104) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20 Second Layer (Intermediate layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS- 1 0.10 HBS-2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.4 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 BS-1 0.10 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion D silver ^{0.70 ExS-1 3.5 × 10 -4} ExS-2 1.6 × 10 -5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd -2 0.023 HBS-1 0.10 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion (any of 1-B, 1-F, 2-B, 2-C silver 1.40) ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20 6th layer (Intermediate layer) Cpd-1 0.10 HBS-1 0.5 Gelatin 1.10 7th layer (low sensitivity green-sensitive emulsion layer) Emulsion C silver ^{0.35 ExS-4 3.0 × 10 -5} ExS-5 2.1 × 10 -4 ExS-6 8.0 × 10 - ⁴ ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 8th layer (medium speed green-sensitive emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.4 × 10 ^-3 gelatin 0.90 Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM -1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44 10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60 Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10 12th layer (Medium-speed blue-sensitive emulsion layer) Emulsion D silver 0.40 ExS- 7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78 13th layer (high-sensitivity blue-sensitive emulsion layer) ) Emulsion F silver 1.00 E ^{S-7 4.0 × 10 -4 ExY} -2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86 14th layer (first protective layer) Emulsion G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Further, each layer may be appropriately preserved, processed, pressure-resistant, and mold-proof.
W-1 for improving antibacterial properties, antistatic properties and coatability
To W-3, B-4 to B-6, F-1 to F-
17 and iron salts, lead salts, gold salts, platinum salts, iridium salts,
Contains a rhodium salt. Hereinafter, the emulsions represented by the above-mentioned abbreviations are shown in Table 2 below, and the compounds are shown below in Chemical Formulas 15 to 29.
Are shown below.

[0174]

[Table 2] In Table 2, (1) Emulsions A to F were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Have been. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-23740 have been observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope. (5) Emulsions A to G are silver iodobromide.

[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

Embedded image After exposing the thus obtained samples 101 to 104, they were processed by the methods described in Table C below. Table C Processing method Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 1 minute 00 seconds 38 ° C Bleaching and fixing 3 minutes 15 seconds 38 ° C. Rinse (1) 40 seconds 35 ° C. Rinse (2) 1 minute 00 seconds 35 ° C. Stability 40 seconds 38 ° C. Drying 1 minute 15 seconds 55 ° C. Next, the composition of the processing solution will be described. (Color developing solution) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 5 mg hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethyl 4.5 amino) -2-methylaniline sulfate Water was added to add 1.0 liter pH 10.05 (bleach solution) ( unit g) ethylenediaminetetraacetic acid ferric 120.0 ammonium dihydrate sodium ethylenediaminetetraacetate 10.0 ammonium bromide 100.0 ammonium nitrate 10.0 bleaching accelerator 0.005 mole _{((CH 3) 2 N-} CH 2 -CH ₂ -S-) ₂ · 2HCl aqueous ammonia (27%) was added to 15.0ml water 1.0 l H 6.3 (Bleaching / fixing solution) (unit g) Ferric ethylenediaminetetraacetate 50.0 Ammonium dihydrate 5.0 Disodium ethylenediaminetetraacetate 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Aqueous ammonia (27%) 6.0 ml Add water 1.0 liter pH 7.2 (Wash solution) Tap water is replaced with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas)
And OH type anion exchange resin (Amberlite IR-
400) to treat the calcium and magnesium ion concentrations at 3 mg / L or less, followed by 20 mg of sodium diisocyanurate dichloride.
/ L and 0.15 g / L of sodium sulfate were added. The pH of this solution is in the range of 6.5-7.5. (Stabilizing solution) (Unit g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water and add 1. The sensitivity was indicated by the relative value of the fog density and the reciprocal of the exposure amount giving a density 0.2 higher than the fog density with respect to the characteristic curve of 0 liter pH 5.0-8.0 cyan dye.

For the pressure characteristics, a test was conducted using the test method A in the same manner as in Example 1, and after exposure and development, the density of the magenta dye characteristic curve was measured at the pressure-applied portion and at the non-pressure-applied portion. In addition, an increase in fog due to pressure ΔFog and a pressure desensitization region were shown.

Table 3 shows the obtained results.

[0192]

[Table 3] In Table 3, the sensitivity of Samples 102 to 104 is
The sensitivity was expressed as a relative value with respect to 100.

As in Example 1, the emulsion of the present invention had low fog, high sensitivity, improved pressure properties, and the effect of the present invention was remarkable. Example 3 The compound (2), (14), (15), (16), (19), or (63) was used in place of the compound (58) used in Example 1, except that an equimolar amount was used. A tabular silver iodobromide emulsion was prepared in the same manner. High sensitivity, low fog and good pressure characteristics were almost the same as those of Sample 3 (Emulsion 1-D).
Compound (58) was replaced with compound (22), and the pH was changed to 5.
Tabular emulsions prepared in exactly the same manner except that the value was increased from 6 to 7.0 also showed good results.

[0194]

According to the present invention, a silver halide emulsion having high sensitivity, low fog and improved pressure can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 1/035 G03C 1/015 G03C 1/07

Claims (5)

(57) [Claims] 1. A silver halide tabular grain (fringe dislocation type tabular grain) having an aspect ratio of 2 to 40 and having dislocation lines localized substantially only in the fringe portion accounts for 100 to 80% of the projected area of all grains. A silver halide photographic material having a silver halide emulsion layer containing a silver halide emulsion on a support. Here, the “fringe portion” means “in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide content at a certain point when viewed from the side is the average silver iodide content of the whole grain. Outside the point beyond or below the point ". Further, "substantially dislocation lines are localized substantially only in the fringe portion" means "three or more dislocation lines are not included in the main plane portion". 2. The silver halide tabular grains (fringe dislocation type tabular grains), wherein 100 to 50% of the iodide ion releasing agent present in the reaction vessel release iodide ions within a continuous 180 seconds. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the grains are formed while rapidly generating iodide ions to the extent that they are completed. 3. The silver halide tabular grains (fringe dislocation type tabular grains) are grains formed while rapidly generating iodide ions, and the reaction for rapidly generating iodide ions is substantially iodine. Secondary reaction proportional to the concentration of the iodide ion releasing agent and the concentration of the iodide ion releasing agent, and the secondary reaction rate constant is 1000 to 5 × 10 ⁻³ (M
^-1 · sec ^-1 ). 4. The silver halide photographic light-sensitive material according to claim 2, wherein iodide ions are rapidly generated by using an iodide ion releasing agent and an iodide ion release controlling agent. 5. The silver halide photographic material according to claim 4, wherein iodide ions are rapidly generated from an iodide ion releasing agent represented by the following formula (I). Embedded image In the formula (I), R represents a monovalent organic residue which releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile.