JP3529764B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material. More specifically, the present invention relates to a silver halide photographic material having high sensitivity and low fog.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material mainly contains a dispersion medium containing photosensitive silver halide grains on a support. A great deal of research has been conducted to increase the sensitivity of silver halide photosensitive materials. It is very important to increase the sensitivity inherent in silver halide grains in order to increase the sensitivity of the silver halide photosensitive material, and various methods are used to enhance the sensitivity inherent in silver halide grains. Has been. For example, sulfur, gold and chemical sensitizers such as group VIII metal sensitizers, sulfur, gold and
Higher sensitivity by combining chemical sensitizers such as Group VIII metal compounds with additives that promote their sensitizing effect, and higher sensitivity by adding additives having a sensitizing effect depending on the type of silver halide emulsion Has been done. These are discussed, for example, in Research Disclosure, 120
Vol. 34, April 1974, 12008; Research Disclosure, Vol. 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361 and 3,297,44.
No. 6, No. 3,772,031, No. 3,857,7
No. 11, No. 3,901,714, No. 4,266,0
18 and 3,904,415 and British Patent 1,315,755. Further, a method of reducing and increasing silver halide grains is also used as a means for increasing sensitivity. Regarding reduction sensitization of silver halide grains, see, for example, US Pat. No. 2,518,698.
No. 3,201,254, No. 3,411,91
No. 7, No. 3,779,777, No. 3,930,8
No. 67, and the method of using the reducing agent is described, for example, in JP-B-57-33572 and JP-B-58-141.
0, JP-A-57-179835. Also, recently, US Pat.
7236, European Patent Nos. 786,692 A1 and 89,373.
1A1, 893732A1, and WO99 / 055
No. 70, a sensitization technique using an organic electron donating compound comprising an electron donating group and a leaving group has been reported. This method is an unprecedented new sensitization technique and is effective for increasing the sensitivity. However, when this compound is used, the sensitivity is increased, but at the same time, the fogging (Dmin) is increased, so that improvement has been strongly demanded.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a silver halide photographic material having high sensitivity and low fogging.

[0004]

The object of the present invention has been achieved by the following means. (1) A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, comprising a compound of the following formula (I), and substantially after coupling with an oxidized developing agent. A silver halide photographic light-sensitive material containing at least one photographically useful group-releasing compound represented by the following general formula (II) or (III), which produces a compound which does not contribute to a dye.

Formula (I) (X) k- (L) m- (AB) n wherein X is at least one atom selected from the group consisting of N, S, P, Se and Te. Represents a silver halide adsorption group or a light absorption group. L is C, N, S and O
Represents a divalent linking group having at least one atom selected from the group consisting of A represents an electron donating group, B represents a leaving group or a hydrogen atom, and after oxidization, is eliminated or deprotonated to form a radical A. k and m each independently represent an integer of 0 to 3, and n represents 1 or 2.

Formula (II) COUP1-D1 In the formula, COUP1 represents a coupler residue that releases D1 by a coupling reaction with an oxidized developing agent and generates a water-soluble or alkali-soluble compound. D1
Represents a photographically useful group linked at the coupling position of COUP1 or a precursor thereof.

In the formula, COUP2 represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and C represents
In the coupling product of COUP2 and oxidized developing agent, an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and an electrophilic site E results in 4
Represents a divalent linking group or a single bond capable of releasing D2 with ring formation of up to 8 members, and may be bonded to COUP2 at the coupling position of COUP2,
It may bind to COUP2 at a position other than the coupling position of 2. D2 represents a photographically useful group or a precursor thereof.

[0008]

[0009]

[0010]

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

(2) When D1 in the general formula ( II ) is-(T
IME ) _m -PUG or-(TIME ) _i -RED -PU
G (where TIME is COUP by a coupling reaction)
Cleavage of PUG or RED-PUG after leaving from 1
RED represents COUP1 or TI
Reacts with oxidized developing agent after release from ME
Represents a group that cleaves, and PUG is a development inhibitor and bleaching accelerator
Represents a photographically useful group selected from the group consisting of
Represents an integer, and i represents 0 or 1. When m is 2
Two TIMEs represent the same or different. )
Wherein D2 in the general formula ( III ) is- ( T ) _k - PUG
(T can release PUG after being released from E
K represents an integer of 0 to 2;
UG is a photographic property selected from development inhibitors and bleach accelerators
Represents a useful group. ) Is described in (1).
Silver halide photographic light-sensitive material. (3) at least one layer of the silver halide photographic material
Containing the emulsified dispersion in the photosensitive silver halide emulsion layer, and
The emulsion has a critical micelle concentration of 4.0 × 10 ⁻³ mol / mol.
L or less of 0.01% by mass of the photosensitive layer.
It is characterized in that it is contained in the above item (1) or (2).
The silver halide photographic light-sensitive material described in the above. (4) The above emulsified dispersion has a high boiling point having a dielectric constant of 7.0 or less.
Item (3) is characterized by containing a point organic solvent.
Silver halide photosensitive material. (5) Any one of (1) to ( 4 ), wherein 50% or more of the total projected area of the silver halide grains contained in the photosensitive layer satisfies the following (a) to (d). 1
6. The silver halide photographic light-sensitive material according to item 1. (A) a parallel main plane having a (111) plane; (b) an aspect ratio of 2 or more; (c) containing at least 10 or more dislocation lines per grain; and (d) iodobromide having a silver chloride content of less than 10 mol%. Tabular silver halide grains composed of silver or silver chloroiodobromide

( 6 ) At least 50% of the total projected area of the silver halide grains contained in the photosensitive layer is as follows:
The silver halide photographic material according to any one of (1) to ( 4 ), which satisfies (d) and (e). (A) parallel main planes are (111) planes (d) tabular silver halide grains composed of silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol% (e) hexagonal halide At least one epitaxial junction per grain at the top and / or side and / or major plane of the silver grain

( 7 ) At least 50% of the total projected area of the silver halide grains contained in the photosensitive layer is as follows:
The silver halide photographic material according to any one of (1) to ( 4 ), which satisfies (f) and (g). (D) Tabular silver halide grains composed of silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol% (f) Parallel main planes are (100) planes (g) Aspect ratio is 2 that's all

( 8 ) At least 50% of the total projected area of the silver halide grains contained in the photosensitive layer satisfies (g), (h) and (i). 4 ) The silver halide photographic light-sensitive material according to any one of the above items. (G) Aspect ratio of 2 or more (h) Parallel main plane is (111) plane or (100)
Surface (i) Tabular grains containing at least 80 mol% or more of silver chloride

[0022] (9) at least 50% of the total projected area of the silver halide grains contained in the light-sensitive layer further below (j), and satisfies the (k) and (m) (5) Or the silver halide photographic light-sensitive material according to any one of ( 8 ) to ( 9 ). (J) The projected area diameter of silver halide grains is 2 μm or more (k) The aspect ratio is 10 or more (m) The average AgI content of each grain is 5 mol% or more

[0023] (1 0) the filling of the 50% or more further below of the total projected area of the silver halide grains contained in the light-sensitive layer (j), the silver halide grains contained in the photosensitive layer of the characterized in that more than 80% of the total projected area of particles having no dislocation lines within 50% from the center of the particle projected section (5) or (6) the silver halide photographic material as claimed in claim. (J) The projected area diameter of silver halide grains is 2 μm or more

[0024] (1 1) forming the at least 50% of the total projected area of the silver halide grains contained in the light-sensitive layer, while allowed rapidly generate iodide ions with iodide ion-releasing agent during the formation of particles The silver halide photographic light-sensitive material according to the item ( 8 ), which is prepared by a production method including a step of:

[0025] (1 2) a step of said at least 50% of the total projected area of the silver halide grains contained in the light-sensitive layer, the addition of silver iodide fine particles in a container that is formed during the formation of particles is carried out The silver halide photographic light-sensitive material according to item ( 5 ), which is prepared by a production method containing:

[0026] (1 3) forming the silver iodide fine particles being formed in reaction vessel being made of a silver halide grain formation (1 2) The silver halide photographic according to claim material.

[0027] (1 4) at least 50% of the total projected area of the silver halide grains contained in the light-sensitive layer, during grain formation,
( 5 ) The grain formation of at least 30% of the total silver is carried out by adding silver halide fine grains formed in a separate vessel to a vessel in which the silver halide grains are present. Or the silver halide photographic light-sensitive material according to any one of ( 8 ) to ( 9 ).

[0028] (1 5) any to the 50% or more of the total projected area of the silver halide grains contained in the light-sensitive layer (5) free, characterized in that emulsions that are sensitized reduction of (1-4) 2. The silver halide photographic light-sensitive material according to item 1.

( 16 ) The silver halide emulsion contained in the photosensitive layer contains gelatin containing 20% or more of a component having a molecular weight of 280,000 or more ( 5 ) to (1).
(5 ) The silver halide photographic material as described in any one of (1) and (2) above.

( 17 ) The photosensitive layer has the following general formula (V)
I), (VII), (VIII-1), (VIII-2), (IX-
(1) The composition according to any one of (1) to ( 16 ), which contains at least one of the compounds represented by (IX-2), (X), and (XI). Silver halide photographic material.

General formula (VI)

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In the formula, Rb1, Rb2, Rb3 and Rb4 each independently represent a hydrogen atom, an aryl group, a chain or cyclic alkyl group, a chain or cyclic alkenyl group, or an alkynyl group; Or a cyclic alkyl group, a chain or cyclic alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

Formula (VII)

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In the formula, Het is an adsorptive group to silver halide. M represents a divalent linking group consisting of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Hy represents a group having a hydrazine structure represented by Rb6Rb7N-NRb8Rb9. Rb6, Rb7, Rb8
And Rb are each independently an alkyl group, an alkenyl group,
Represents an alkynyl group, an aryl group or a heterocyclic group, Rb6
And Rb7, Rb8 and Rb9, Rb6 and Rb8, or Rb7 and Rb9 may be bonded to each other to form a ring. However, Rb6, Rb7, Rb8
And at least one of Rb9 is-in general formula (VII).
(M) an alkylene group for substitution by k2 (Het) k1,
It is an alkenylene group, an alkynylene group, an arylene group or a divalent heterocyclic residue. k1 and k3 are each independently 1,
Represents 2, 3, or 4, and k2 represents 0 or 1.

Formulas (VIII-1) and (VIII-2)

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In the formula (VIII-1), Rb10, Rb11, Rb12 and Rb13 each independently represent a hydrogen atom or a substituent. However, when Rb10 and Rb13 or Rb11 and Rb12 are each an alkyl group, they do not take substituents having exactly the same carbon number. Expression (VI
In II-2), Rb14, Rb15 and Rb16 each independently represent a hydrogen atom or a substituent. Z represents a non-metallic atomic group forming a 4- to 6-membered ring.

Formula (IX-1)

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In the formula (IX-1), Rc1 represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group;
Rc2 represents a hydrogen atom or a group represented by Rc1. Rc3 represents a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group having 1 to 10 carbon atoms. Rc1 and Rc2, Rc1 and Rc3
Alternatively, Rc2 and Rc3 may be bonded to each other to form a 5- to 7-membered ring.

General formula (IX-2)

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In the formula, G 1 and G 2 each represent a hydrogen atom or a monovalent substituent. Further, they may combine with each other to form a ring.

Formula (X)

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In the formula, Rb17, Rb18 and Rb19 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and Rb20 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. , a heterocyclic group or an NRb21Rb22,, J represents -CO- or -SO ₂ -
And n represents 0 or 1. Rb21 represents a hydrogen atom, a hydroxy group, an amino group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and Rb22 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Represent. Rb17 and Rb18, Rb17 and Rb
19, Rb19 and Rb20 or Rb20 and Rb18 may be linked to form a ring.

Formula (XI)

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In the formula, X ² and Y ² each independently represent a hydroxyl group, —NRi23Ri24 or —NHSO ₂ Ri25. Ri21 and
Ri22 independently represents a hydrogen atom or an optional substituent. Ri21 and Ri22 may combine with each other to form a carbocyclic or heterocyclic ring. Ri23 and Ri24 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic ring. Ri23 and Ri24 may combine with each other to form a heterocyclic ring. Ri25 represents an alkyl group, an aryl group, an amino group or a heterocyclic ring.

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The silver halide emulsion in the invention is preferably silver bromide, silver chloride, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodobromide, or the like. The form of the silver halide grains may be a normal crystal such as octahedron, cubic, or tetradecahedron, but tabular grains are more preferred.

First, the first emulsion according to the present invention is prepared from silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol% in which the main plane parallel to silver halide grains is a (111) plane. The tabular silver halide grains will be described.

This emulsion is composed of a (111) main plane which faces each other and side faces connecting the main planes. The tabular grain emulsion comprises silver iodobromide or silver chloroiodobromide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. The silver iodide content is from 0.5 mol% to 40 mol%, preferably from 1.0 mol% to 20 mol%. Regardless of the silver iodide content, the variation coefficient of the distribution of the silver iodide content between grains is preferably 20% or less, particularly preferably 10% or less.

The silver iodide distribution preferably has a structure in the grains. In this case, the structure of the silver iodide distribution is 2
There can be double, triple, quadruple or even more structures. Further, the silver iodide content may be continuously changed inside the grains.

At least 50% of the total projected area has an aspect ratio of 2
Occupied by more particles. Here, the projected area and the aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method shadowed with a latex sphere for reference. When viewed from above, the tabular grains usually have a hexagonal, triangular or circular shape, and the value obtained by dividing the diameter of a circle having an area equal to the projected area by the thickness is the aspect ratio. The shape of the tabular grains is preferably as high as the ratio of hexagons, and the ratio of the lengths of adjacent sides of the hexagons is preferably 1: 2 or less.

The tabular grains preferably have a projected area diameter of 0.1 μm or more and 20.0 μm or less, and 0.2 μm or more and 10.0 μm or less.
μm or less is more preferable. The projected area diameter is the diameter of a circle having an area equal to the projected area of the silver halide grains. Further, the thickness of the tabular grains is preferably from 0.01 μm to 0.5 μm, more preferably from 0.02 μm to 0.4 μm. The thickness of a tabular grain is the distance between two principal planes.
The equivalent sphere diameter is preferably from 0.1 μm to 5.0 μm, more preferably from 0.2 μm to 3 μm. The equivalent sphere diameter is the diameter of a sphere having a volume equal to the volume of an individual particle. Further, the aspect ratio is preferably from 1 to 100, more preferably from 2 to 50. The aspect ratio is a value obtained by dividing the projected area diameter of a particle by the thickness of the particle.

The silver halide grains contained in the first and second emulsions according to the present invention are preferably monodisperse. The variation coefficient of the equivalent spherical diameter of all silver halide grains contained in the first and second emulsions according to the present invention is 30% or less;
Preferably it is 25% or less. In the case of tabular grains, the variation coefficient of the projected area diameter is also important, and the variation coefficient of the projected area diameter of all the silver halide grains of the present invention is preferably 30% or less, more preferably 25% or less. And
It is more preferably at most 20%. Further, the coefficient of variation of the thickness of the tabular grains is preferably 30% or less, more preferably 25% or less, and further preferably 20% or less. The coefficient of variation is a value obtained by dividing the standard deviation of the distribution of the projected area diameters of individual silver halide grains by the average projected area diameter, or the standard deviation of the distribution of the thicknesses of individual silver halide tabular grains is represented by the average thickness. It is the divided value.

The twin plane spacing of tabular grains contained in the first and second emulsions according to the present invention is described in US Pat. No. 5,219,7.
As described in JP-A No. 20, 0.012 μm or less, or as described in JP-A-5-249585, the ratio of (111) distance between main planes / twin plane spacing may be 15 or more. Is good.

The higher the aspect ratio, the more remarkable the effect can be obtained. Therefore, the tabular grain emulsion preferably accounts for 50% or more of the total projected area, preferably 5 or more of the aspect ratio. More preferably, the aspect ratio is 8 or more. If the aspect ratio is too large, the variation coefficient of the particle size distribution described above tends to increase, so that the aspect ratio is usually preferably 100 or less.

The dislocation lines of tabular grains are described, for example, in J. Am. F. Ha
Milton, Photo. Sci. Eng. , 11,5
7, (1967); Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
(1972) can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method in a state where is cooled. At this time, the thicker the particles, the more difficult it is for an electron beam to pass through. Therefore, a clearer image can be observed with a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). . From the photographs of the particles obtained by such a method, the position and number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be determined.

The number of dislocation lines is preferably 10 or more per grain on average. More preferably, an average of 20 per particle
More than a book. 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 is possible to count about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where there are only a few pieces. The average number of dislocation lines per grain is 1
The number of dislocation lines is counted for 00 particles or more, and the number is determined as a number average.

Dislocation lines can be introduced, for example, near the side surfaces of tabular grains. In this case, the dislocation is almost perpendicular to the side surface, and a dislocation line is generated from the position of x% of the distance from the center of the tabular grain to the side (side surface) to reach the side surface. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the start positions of the dislocation lines is similar to the particle shape, but may not be a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The dislocation lines are crystallographically approximately (211), but often meander and may intersect each other.

The tabular grains may have dislocation lines almost uniformly over the entire area near the side surfaces, or may have dislocation lines at local positions near the side surfaces. That is, in the case of hexagonal tabular silver halide grains, dislocation lines may be limited only to the vicinity of six vertices, or dislocation lines may be limited to only one of the vertices. Conversely, it is also possible that the dislocation lines are limited to only the sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the centers of two parallel main planes of the tabular grains. When dislocation lines are formed over the entire area of the main plane, the direction of the dislocation lines may be approximately (211) crystallographically when viewed from a direction perpendicular to the main plane. In some cases, the dislocation lines are formed randomly, and the length of each dislocation line is also random. In some cases, the dislocation lines are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer periphery). is there. Dislocation lines are sometimes straight or meandering. They also often intersect with each other.

As described above, the position of the dislocation line may be limited to the outer periphery, the main plane, or a local position, or may be formed by combining these.
That is, they may be present simultaneously on the outer periphery and on the main plane.

The silver iodide content on the grain surface of the tabular grain emulsion is preferably at most 10 mol%, particularly preferably at most 5 mol%. The silver iodide content on the surface of the grains of the present invention is determined by XPS (X-ray Photoelectron).
(Spectroscopy). Regarding the principle of the XPS method used for analyzing the silver iodide content near the surface of silver halide grains, see Aihara et al., “Electron Spectroscopy” (Kyoritsu Library-16, published by Kyoritsu Shuppan, Showa 53)
Year) can be referred to. The standard measurement method of XPS uses Mg-Kα as an excited X-ray, and photoelectrons (usually I-3d5) of iodine (I) and silver (Ag) emitted from silver halide in an appropriate sample form. / 2, Ag-3d
5/2). To determine the iodine content, a calibration curve of the intensity ratio of photoelectrons of iodine (I) and silver (Ag) (intensity (I) / intensity (Ag)) using several types of standard samples whose iodine content is known. And can be determined from this calibration curve. In a silver halide emulsion, XPS must be measured after gelatin adsorbed on the surface of silver halide grains is decomposed and removed by a protease or the like. The silver iodide content on the grain surface is 10 mol%
The following tabular grain emulsions refer to emulsion grains contained in one emulsion having a silver iodide content of 10 mol% or less when analyzed by XPS. In this case, when two or more kinds of emulsions are clearly mixed, it is necessary to perform an appropriate pretreatment such as a centrifugal separation method or a filtration method and then analyze the same kind of emulsion.

The structure of the tabular grain emulsion of the present invention is preferably a triple structure grain composed of, for example, silver bromide / silver iodobromide / silver bromide or a higher order structure. The boundary of the silver iodide content between the structures may be clear or may be continuously and gradually changing. Usually, the measurement of the silver iodide content using the powder X-ray diffraction method does not show two distinct peaks having different silver iodide contents, and the skirt is drawn in the direction of the high silver iodide content. Such an X-ray diffraction profile is shown.

The silver iodide content of the layer inside the surface is preferably high, and the silver iodide content of the layer inside the surface is preferably at least 3 mol%, more preferably 5 mol%.
More expensive.

Next, the parallel principal plane which is the second emulsion according to the present invention is the (111) plane, and the ratio of the length of the side having the maximum length to the length of the side having the minimum length. Is 2
The following apexes of hexagonal silver halide grains, and / or
Alternatively, a particle having at least one or more epitaxial junctions per particle in the side surface portion and / or the main plane portion will be described. An epitaxially bonded grain is a grain having a crystal part (ie, an epitaxial part) bonded to the silver halide grain in addition to the silver halide grain main body, and the bonded crystal part usually protrudes from the silver halide grain main body. The ratio of the bonded crystal part (epitaxial part) to the total silver content of the grains is preferably 1% or more and 30% or less, more preferably 2% or more and 15% or less. The epitaxial portion may be present at any portion of the grain body, but is preferably a grain main plane portion, a grain side surface portion, or a grain apex portion. The number of epitaxial layers is preferably at least one. The composition of the epitaxial part is AgBr, AgCl, AgBrC.
1, AgBrClI, AgBrI, AgI, AgSCN
Are preferred. When an epitaxial portion exists, dislocation lines may or may not exist inside the grain. In addition, dislocation lines may not be present in the epitaxial portion, the junction between the silver halide grain main body and the epitaxial portion, and the epitaxial portion, but it is preferable that dislocation lines be present.

Next, a method for preparing the first emulsion and the second emulsion silver halide grains according to the present invention will be described. The preparation step of the present invention comprises (a) a base particle forming step and a subsequent particle forming step ((b) step). Basically, it is more preferable to perform the step (b) subsequent to the step (a), but only the step (a) may be performed.
The step (b) may be any one of (b1) a dislocation introduction step, (b2) a top dislocation limitation introduction step, and (b3) an epitaxial junction step, and may be at least one or a combination of two or more. .

First, the step (a) of forming the base particles will be described. The base portion is preferably at least 50% or more, more preferably 6% or more, of the total silver used for grain formation.
0% or more. In addition, the average iodine content relative to the silver content of the base portion is preferably from 0 mol% to 30 mol%, more preferably from 0 mol% to 15 mol%. The base may have a core-shell structure as needed. At this time, the core portion of the base portion is preferably 50% to 70% based on the total silver content of the base portion, and the average iodine composition of the core portion is preferably 0% to 30% by mole, and 0% to 15% by mole. % Is more preferable. The iodine composition of the shell part is 0mol% or more and 3mo
1% or less is preferable.

As a method for preparing a silver halide emulsion, a method of forming silver halide nuclei and then growing silver halide grains to obtain grains of a desired size is generally used. There is no difference. The formation of tabular grains includes at least the steps of nucleation, ripening, and growth. This process is described in U.S. Pat. No. 4,945,03.
It is described in detail in No. 7. Below, nucleation, aging,
The growth and each step will be described.

1. Nucleation step The nucleation of tabular grains is generally performed by adding a silver salt aqueous solution and an alkali halide aqueous solution to a reaction vessel holding an aqueous solution of a protective colloid, or a double jet method, or a protective colloid solution containing an alkali halide. A single jet method in which a silver salt aqueous solution is added to the mixture is used. Also,
If necessary, a method of adding an aqueous alkali halide solution to a protective colloid solution containing a silver salt can also be used.
Further, if necessary, a protective colloid solution, a silver salt solution and an aqueous alkali halide solution are added to a mixer disclosed in JP-A-2-44335, and the resulting mixture is immediately transferred to a reaction vessel to prepare a nucleus of tabular grains. Formation can also be performed. Also, as disclosed in U.S. Pat. No. 5,104,786, nucleation can be performed by passing an aqueous solution containing an alkali halide and a protective colloid solution through a pipe and adding an aqueous silver salt solution thereto. .

Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin are also used. Examples of the types of gelatin include alkali-treated gelatin and oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide (methionine content of 40 μm
l / g or less), the amino group-modified gelatin of the present invention (for example,
Phthalated gelatin, trimellited gelatin, succinated gelatin, maleated gelatin, esterified gelatin) and low molecular weight gelatin (molecular weight: 3000-4)
10,000) is used. For oxidized gelatin, reference can be made to JP-B-5-12696, and for amino group-modified gelatin, reference can be made to JP-A-8-82883 and JP-A-11-143002. Also, if necessary, refer to
In the molecular weight distribution measured by the Paggy method described in JP-A-237704, lime-processed bone gelatin containing 20% or more, preferably 30% or more of a component having a molecular weight of 280,000 or more may be used. Also, for example, European Patent No. 75
Starch described in US Patent No. 8758 and US Patent No. 5,733,718 may be used. Other natural polymers are described in JP-B-7-111550, Research Disclosure, Vol. 176, No. 17643, December 1978, section IX.

In nucleation, the excess halogen salt is
l ^-, Br ^-, I ^- are preferable, they may alone, may be present in multiple. Total halogen salt concentration is 3 × 1
0 ^-5 mol / L or more and 0.1 mol / L or less, preferably 3 × 10 ^-4 mol / L
L and 0.01 mol / L or less.

[0070] The halogen composition of the halide solution added during ^{nucleation, Br -, Cl -, I} - are preferable, they may alone, may be present in multiple. JP-A-10-2
May be used nucleation such that 10 mole% or more relative to the amount of silver is chlorine content as described was used in the nucleation No. 93372, this time Cl ^- concentration of the halogen salt of Total The concentration is preferably from 10 mol% to 100 mol%, more preferably from 20 mol% to 80 mol%. The protective colloid may be dissolved in a halide solution added at the time of nucleation, or the gelatin solution may be added simultaneously with the nucleation, separately from the halide solution.

The temperature at the time of nucleation is preferably 5 to 60 ° C., and more preferably 5 to 48 ° C. in the case of preparing fine tabular grains having an average particle size of 0.5 μm or less. The pH of the dispersion medium is preferably from 4 to 8 when amino group-modified gelatin is used, but is preferably from 2 to 8 when other gelatin is used.
The following is preferred.

2. Aging process In the nucleation in the above, fine particles other than tabular grains (particularly, octahedral and single twin grains) are formed. Before the growth process described below, it is necessary to eliminate grains other than tabular grains to obtain nuclei having a shape to be tabular grains and having good monodispersity. To make this possible, it is well known to carry out Ostwald ripening following nucleation.

Immediately after the nucleation, pBr is adjusted, and the temperature is increased to ripen until the hexagonal tabular grain ratio becomes maximum. At this time, a protective colloid solution may be additionally added.
At this time, the concentration of the protective colloid with respect to the dispersion medium solution is 1
It is preferably 0% by mass or less. The additional protective colloid used at this time is the alkali-treated gelatin described above,
The amino group-modified gelatin, oxidized gelatin, low molecular weight gelatin, natural polymer or synthetic polymer of the present invention is used. Also, if necessary, refer to JP-A-11-237704.
Lime-processed bone gelatin containing 30% or more of a component having a molecular weight of 280,000 or more may be used in the molecular weight distribution measured by the Paggy method described in the above publication. Also, for example, EP 758758 and US Pat.
Starch described in No. 33718 may be used.

The aging temperature is 40 to 80 ° C., preferably 50 to 80 ° C., and the pBr is 1.2 to 3.0.
The pH is 4 when amino-modified gelatin is present.
It is preferably at least 8 and at most 8, but in the case of other gelatins, at least 2 and at most 8 are preferred.

At this time, a silver halide solvent may be added to quickly eliminate grains other than tabular grains. In this case, the concentration of the silver halide solvent is set to 0.
It is preferably at most 3 mol / liter, more preferably at most 0.2 mol / liter (hereinafter, liter is also referred to as “L”). The ripening is carried out in this way to obtain almost 100% tabular grains only. After ripening, if the silver halide solvent is unnecessary in the next growth process, the silver halide solvent is removed as follows.

In the case of an alkaline silver halide solvent such as NH ₃ , an acid having a large solubility product with Ag ⁺ such as HNO ₃ is added to nullify the solvent. In the case of a thioether-based silver halide solvent,
As described in No. 60-136736, the reaction is nullified by adding an oxidizing agent such as H ₂ O ₂ .

In the method for producing an emulsion of the present invention, the term “ripening step” means that grains other than grains having a major plane of hexagonal or triangular tabular grains and having at least two twin planes (regular and regular grains) are used. (Single twin particles). The disappearance of particles other than those having a hexagonal or triangular main plane and having at least two twin planes can be confirmed by observing a TEM image of a particle replica.

In the aging step, if necessary,
An overripening step described in 1-174606 may be provided.
The overripening step is a step of ripening until the hexagonal tabular grain ratio becomes the highest (ripening step) and then further aging the tabular grains themselves by Ostwald ripening to eliminate tabular grains having a low anisotropic growth speed. . When the number of tabular grains obtained in the aging step is set to 100, the number of tabular grains is preferably reduced to 90 or less by the over-ripening step,
More preferably, it is reduced to 60 or more and 80 or less.

In the method for producing an emulsion of the present invention, conditions such as pBr and temperature in the overripening step can be set the same as in the ripening step. In the overripening step, a silver halide solvent can be added in the same manner as in the ripening step, and its kind, concentration, etc. can be set the same as those in the ripening step.

3. The pBr during the crystal growth period following the growth step ripening step is preferably kept at 1.4 to 3.5. When the concentration of the protective colloid in the dispersion medium solution before the growth step is low (1% by mass or less), the protective colloid may be additionally added. Further, a protective colloid may be additionally added during the growth step. The additional addition may be made at any time during the growth process. The protective colloid concentration in the dispersion medium solution is preferably set to 1 to 10% by mass. As the protective colloid used at this time, the above-mentioned alkali-treated gelatin, the amino group-modified gelatin of the present invention, the oxidized gelatin, a natural polymer, or a synthetic polymer is used. If necessary, a lime-processed bone gelatin containing a component having a molecular weight of 280,000 or more, preferably 20% or more, preferably 30% or more, in a molecular weight distribution measured by the Paggy method described in JP-A-11-237704 is used. May be. Further, for example, starch described in European Patent No. 758758 and US Patent No. 5,733,718 may be used. The pH during growth is preferably 4 to 8 or less when amino group-modified gelatin is present.
To 8 are preferred. The addition rate of Ag ⁺ and halogen ions during the crystal growth period is 20 to the critical crystal growth rate.
It is preferable that the crystal growth rate is 100%, preferably 30 to 100%. In this case, the addition rate of silver ions and halogen ions is increased along with the crystal growth, in which case, Japanese Patent Publication Nos. 48-36890 and 52-16364.
As described in the above paragraph, the addition rate of the aqueous solution of the silver salt and the halogen salt may be increased, and the concentration of the aqueous solution may be increased.

In the double jet method in which a silver salt aqueous solution and a halogen salt aqueous solution are simultaneously added, in order to prevent the introduction of growth dislocation due to non-uniform iodine, the stirring of the reaction vessel is improved, and the concentration of the added solution is reduced. Is preferred.

It is more preferable to add the AgI fine grain emulsion prepared outside the reaction vessel simultaneously with the addition of the silver salt aqueous solution and the halogen salt aqueous solution. At this time, the growth temperature is preferably from 50 ° C to 90 ° C, more preferably from 60 ° C to 85 ° C. The AgI fine grain emulsion to be added may be prepared in advance or may be added while being continuously prepared. The preparation method at this time is described in JP-A-10-4357.
No. 0 can be referred to.

The average grain size of the AgI emulsion to be added is 0.
The thickness is from 01 μm to 0.1 μm, preferably from 0.02 μm to 0.08 μm. The iodine composition of the base particles is
It can be changed by the amount of the AgI emulsion to be added.

Further, fine silver iodobromide may be added instead of adding the aqueous silver salt solution and the aqueous halogen salt solution. At this time, by making the iodine amount of the fine particles equal to the iodine amount of the desired base particles, base particles having a desired iodine composition can be obtained. The silver iodobromide fine particles may be prepared in advance, but it is preferable to add them while continuously preparing them. The silver iodobromide fine particle size to be added is 0.005μ.
m to 0.05 μm, preferably 0.01 μm to 0.03 μm. Temperature during growth is 60 ° C or higher 9
The temperature is 0 ° C or lower, preferably 70 ° C or higher and 85 ° C or lower. Further, the above-described ion addition method, AgI fine particle addition method, and AgBrI fine particle addition method may be combined.

In the present invention, the tabular grains preferably have dislocation lines, but it is preferable that no dislocation lines exist in the base portion in order to reduce pressure desensitization. The dislocation lines of tabular grains are
For example, JF Hamilton, Phot.Sci. Eng., 11, 57 (19
67), T. Shiozawa, J. Soc. Phot. Sci. Japan, 35, 213
(1972) can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method in a state where is cooled. At this time, the thicker the particles, the more difficult it is for an electron beam to pass. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). . From the photographs of the particles obtained by such a method, the position and number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be determined.

Next, the step (b) will be described. First, the step (b1) will be described. Step (b1) includes a first shell step and a second shell step. A first shell is provided on the base described above. The ratio of the first shell is preferably 1% or more and 30% or less based on the total silver amount, and the average silver iodide content is 20% by mol or more and 100% by mol or less.
More preferably, the ratio of the first shell is 1% based on the total silver.
And the average silver iodide content is 25 mol% or more and 100 mol% or less. The growth of the first shell on the substrate is basically performed by adding a silver nitrate aqueous solution and an aqueous halogen solution containing iodide and bromide by a double jet method. Alternatively, a silver nitrate aqueous solution and a halogen aqueous solution containing iodide are added by a double jet method. Alternatively, an aqueous halogen solution containing iodide is added by a single jet method.

Any of the above methods may be used, or a combination thereof. As is apparent from the average silver iodide content of the first shell, silver iodide can be precipitated in addition to the silver iodobromide mixed crystal during the formation of the first shell. In any case, the silver iodide usually disappears during the next formation of the second shell, and all of the silver iodide is changed to a silver iodobromide mixed crystal.

As a preferred method for forming the first shell, there is a method in which silver iodobromide or silver iodide fine grain emulsion is added, ripened and dissolved. Further, as a preferable method, there is a method of adding a silver iodide fine grain emulsion and then adding an aqueous solution of silver nitrate or an aqueous solution of silver nitrate and an aqueous solution of halogen. In this case, the dissolution of the silver iodide fine grain emulsion is promoted by the addition of an aqueous solution of silver nitrate.
Mol%. The calculation is made as the second shell using the silver amount of the added silver nitrate aqueous solution. The silver iodide fine grain emulsion is preferably added rapidly.

The rapid addition of the silver iodide fine grain emulsion means that:
It means that the silver iodide fine grain emulsion is preferably added within 10 minutes. More preferably, it is added within 7 minutes. These conditions can vary depending on the temperature of the system to be added, pBr, pH, the type and concentration of the protective colloid agent such as gelatin, the presence or absence of the silver halide solvent, the type and the concentration, but the shorter is preferable as described above. When adding, it is preferable not to substantially add an aqueous solution of silver salt such as silver nitrate.
The temperature of the system at the time of addition is preferably from 40 ° C to 90 ° C,
The temperature is particularly preferably from 50 ° C to 80 ° C.

The silver iodide fine grain emulsion only needs to be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. Preferably 100%
It is silver iodide. Silver iodide has β-form and γ-form in its crystal structure.
And α-isomer or α-isomer-like structures as described in US Pat. No. 4,672,026. In the present invention, the crystal structure is not particularly limited,
A mixture of β-form and γ-form, more preferably β-form is used. A silver iodide fine grain emulsion is disclosed in U.S. Pat. No. 5,004,679.
May be formed immediately before the addition described in the number, etc.,
Any of those which have undergone a normal washing step may be used, but those which have undergone a normal washing step are preferably used in the present invention. A silver iodide fine grain emulsion is disclosed in U.S. Pat.
It can be easily formed by the method described in US Pat. A double jet addition method of an aqueous silver salt solution and an aqueous iodide salt solution is preferred, in which the particles are formed with a constant pI during the formation of the particles. Here, pI is the logarithm of the reciprocal of the I ^- ion concentration of the system. There are no particular restrictions on the temperature, pI, pH, type and concentration of protective colloid such as gelatin, the presence / absence, type and concentration of a silver halide solvent, but the size of the grains is 0.1 μm or less, more preferably 0.07 μm. The following are convenient for the present invention.
Although the particle shape cannot be completely specified because of the fine particles, the variation coefficient of the particle size distribution is preferably 25% or less.
In particular, when the content is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are determined by placing silver iodide fine grains on a mesh for observation with an electron microscope and observing them directly by a transmission method instead of a carbon replica method. This is because the measurement error increases in observation by the carbon replica method due to the small particle size. The grain size is defined as the diameter of a circle having a projected area equal to the observed grain. The particle size distribution is also determined using the same projected area circle diameter. The most effective silver iodide fine grains in the present invention have a grain size of 0.0
6 μm or less and 0.02 μm or more, and the coefficient of variation of the particle size distribution is 18% or less.

The silver iodide fine grain emulsion is preferably formed by the above-mentioned grain formation, followed by usual washing with water as described in US Pat. No. 2,614,929 and the like, adjustment of the concentration of protective colloid such as pH, pI, gelatin and the like. The concentration of silver halide is adjusted. The pH is preferably 5 or more and 7 or less. The pI value is the pI value at which the solubility of silver iodide is minimized or the pI value higher than that value.
It is preferable to set the I value. As the protective colloid agent, ordinary gelatin having an average molecular weight of about 100,000 is preferably used. Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. It is sometimes convenient to use a mixture of gelatins having different molecular weights. Emulsion 1k
The amount of gelatin per g is preferably 10 g or more and 100 g or more.
It is as follows. More preferably, it is 20 g or more and 80 g or less. The silver amount in terms of silver atoms per kg of the emulsion is preferably from 10 g to 100 g. More preferably 20g
Not less than 80 g. The amount of gelatin and / or silver is preferably selected to a value suitable for rapidly adding a silver iodide fine grain emulsion.

The silver iodide fine grain emulsion is usually dissolved and added in advance, but it is necessary to sufficiently increase the stirring efficiency of the system at the time of addition. Preferably, the stirring speed is set higher than usual. Addition of an antifoaming agent is effective to prevent the generation of foam during stirring. Specifically, U.S. Pat.
The antifoaming agents described in the examples of 275,929 and the like are used.

As a more preferable method of forming the first shell, US Pat. No. 5,496,6 replaces the conventional iodide ion supply method (a method of adding free iodide ions).
No. 94, a silver halide phase containing silver iodide can be formed while rapidly generating iodide ions.

The iodide ion-releasing agent releases iodide ions by reacting with an iodide ion-releasing regulator (base and / or nucleophile). Seeds. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates, ammonia, amines, alcohols , Ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines, and sulfides.

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 for rapidly generating iodide ions is 1 × 10 ^{-7 to} 20M, more preferably 1 × 10 ^-5 to 10M, more preferably 1 × 1
It is 0 ^{-4 to} 5M, particularly preferably 1 × 10 ^{-3 to} 2M.
If the concentration exceeds 20 M, 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, which is not preferable. On the other hand, when the concentration is less than 1 × 10 ⁻⁷ M, the reaction rate of releasing iodide ions becomes slow, which makes it difficult to rapidly generate an iodide ion releasing agent, which is not preferable.

The preferred temperature range is 30 to 80 ° C.
More preferably 35 to 75C, particularly preferably 35 to 6C.
0 ° C. If the temperature is higher than 80 ° C., the reaction rate of iodide ion release generally becomes extremely high, and if the temperature is lower than 30 ° C., the reaction rate of iodide ion release generally becomes extremely slow.

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 pH range for controlling the release rate and timing of iodide ions is 2 to 12, more preferably 3 to 12.
11, particularly preferably 5 to 10, and most preferably the adjusted pH is 7.5 to 10.0. Even under neutral conditions at pH 7, hydroxide ions determined by the ionic product of water act as regulators. Further, a nucleophile and a base may be used in combination. At this time, the pH may be controlled within the above range, and the release rate and timing of iodide ions may be controlled.

When iodine atoms are released from the iodide ion releasing agent in the form of iodide ions, all iodine atoms may be released, or a part of the iodine atoms may remain without being decomposed. A second shell is provided on the tabular grain having the above-described base and the first shell. The ratio of the second shell is preferably from 10 mol% to 40 mol% with respect to the total silver amount, and the average silver iodide content is from 0 mol% to 5 mol%. More preferably, the ratio of the second shell is from 15 mol% to 30 mol% based on the total silver amount, and the average silver iodide content is from 0 mol% to 3 mol%. The growth of the second shell on the tabular grains having the base and the first shell may be in a direction of increasing or decreasing the aspect ratio of the tabular grains. Basically, the second shell is grown by adding a silver nitrate aqueous solution and a bromide-containing halogen aqueous solution by a double jet method. Alternatively, an aqueous silver nitrate solution may be added by a single jet method after an aqueous halogen solution containing bromide is added. System temperature, pH, type and concentration of protective colloid agent such as gelatin, presence or absence of silver halide solvent,
Types, concentrations, etc. can vary widely. For pBr,
In the present invention, it is preferable that pBr at the end of the formation of the layer be higher than pBr at the beginning of the formation of the layer. Preferably, pBr at the beginning of the formation of the layer is 2.9 or less, and pBr at the end of the formation of the layer is 1.7 or more. More preferably, pBr at the beginning of the formation of the layer is 2.5 or less, and pBr at the end of the formation of the layer is 1.9 or more. Most preferably, pBr in the initial stage of the formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is 2.1 or more and 4.5 or less.

It is preferable that dislocation lines exist in the step (b1). It is preferable that the dislocation lines exist near the side surfaces of the tabular grains. The term "near the side surface portion" means the side surface portions of the six sides of the tabular grain and the inner portion thereof, that is, the portion grown in the step (b1). The number of dislocation lines on the side is 1
The average is preferably 10 or more per particle. More preferably 1
The average is 20 or more per particle. 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 is possible to count about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where only a few pieces exist. The average number of dislocation lines per particle is determined as the number average by counting the number of dislocation lines for 100 particles or more.

The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% of all grains, more preferably 100 to 70%, particularly preferably 10 to 70%.
It accounts for 0 to 90%. If it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when calculating the ratio of the particles containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

Next, the step (b2) will be described.

The first mode is a method of dissolving only the vicinity of the top with iodide ions, the second mode is a method of simultaneously adding a silver salt solution and an iodide salt solution,
As a third embodiment, there is a method of substantially dissolving only the vicinity of the vertex using a silver halide solvent, and as a fourth embodiment, there is a method via halogen conversion.

The method of dissolving with iodide ions, which is the first embodiment, will be described. By adding iodide ions to the base particles, the vicinity of each apex of the base particles is melted and rounded. Subsequently, when a silver nitrate solution and a bromide solution, or a mixed solution of a silver nitrate solution, a bromide solution, and an iodide solution are simultaneously added, the grains grow further and dislocations are introduced near the apex. This method is disclosed in Japanese Patent Application Laid-Open No. 4-149.
541 and JP-A-9-189974 can be referred to.

The total amount of iodide ions to be added in this embodiment is calculated by dividing the total number of moles of the iodide ions by the total number of moles of silver in the base grains and multiplying 100 by I ₂ (mol%). In this case, it is preferable that (I ₂ −I ₁ ) satisfy 0 to 8 with respect to the silver iodide content I ₁ (mol%) of the base grains in order to obtain effective dissolution according to the present invention, More preferably, it is 0 or more and 4 or less.

In this embodiment, the concentration of the iodide ion added is preferably low, specifically, 0.2 mol / L.
The concentration is preferably not more than 0.1, and more preferably 0.
1 mol / L. Further, the pAg at the time of adding iodide ions is preferably 8.0 or more, more preferably 8.5 or more.

Following the dissolution of the apex portion of the base particles by adding iodide ions to the base particles, a silver nitrate solution alone is added, or a silver nitrate solution and a bromide solution, or a silver nitrate solution, a bromide solution, and a iodide solution are mixed. The liquid is added simultaneously to further grow the particles and introduce dislocations near the vertices.

The second embodiment, a method of simultaneous addition of a silver salt solution and an iodide salt solution, will be described. By rapidly adding a silver salt solution and an iodide salt solution to the base grains, silver iodide or silver halide having a high silver iodide content can be epitaxially generated at the top of the grains. In this case, the addition rate of the silver salt solution and the iodide salt solution is preferably 0.2 to 0.5 minutes, more preferably 0.5 to 2 minutes. This method is described in detail in JP-A-4-149541 and can be referred to.

Following the dissolution of the apex portion of the base particles by adding iodide ions to the base particles, a silver nitrate solution is added alone, or a silver nitrate solution and a bromide solution, or a silver nitrate solution, a bromide solution, and a iodide solution are mixed. The liquid is added simultaneously to further grow the particles and introduce dislocations near the vertices.

A third embodiment, a method using a silver halide solvent will be described. After the silver halide solvent is added to the dispersion medium containing the base grains and then the silver salt solution and the iodide salt solution are added at the same time, silver iodide or silver iodide is contained at the top of the base grains dissolved by the silver halide solvent. Silver halide with a high rate of growth grows preferentially. On this occasion,
The silver salt solution and the iodide salt solution need not be added rapidly. This method is described in detail in JP-A-4-149541, which can be referred to.

Following the dissolution of the apex of the base particles by adding iodide ions to the base particles, a silver nitrate solution is added alone, or a silver nitrate solution and a bromide solution, or a silver nitrate solution, a bromide solution, and a iodide solution are mixed. The liquid is added simultaneously to further grow the particles and introduce dislocations near the vertices.

Next, a method of halogen conversion, which is the fourth embodiment, will be described. By adding an epitaxial growth site indicator (hereinafter, referred to as a site director) to the base grains, for example, a sensitizing dye described in JP-A-58-108526 or a water-soluble iodide, silver chloride is added to the top of the base grains. This is a method in which silver chloride is converted into silver iodide or silver halide having a high silver iodide content by adding iodide ions after forming epitaxial. As the site director, a sensitizing dye, a water-soluble thiocyanate ion and a water-soluble iodide ion can be used, and an iodide ion is preferable. The iodide ion is 0.0005 to 1 mol%, preferably 0.0
It is preferably from 0.01 to 0.5 mol%. When an optimal amount of iodide ion is added and then a silver salt solution and a chloride salt solution are simultaneously added, an epitaxial silver chloride can be formed at the top of the base grains.

The halogen conversion of silver chloride by iodide ions will be described. Highly soluble silver halide is converted to less soluble silver halide by adding halide ions that can form less soluble silver halide. This process is called halogen conversion and is described, for example, in US Pat. No. 4,142,900. A silver iodide phase is formed at the apex portion of the base grain by selectively performing halogen conversion of silver chloride epitaxially grown at the apex portion of the base material by iodide ions. Details are described in JP-A-4-149541.

The silver chloride epitaxially grown at the apex of the base grains was converted into a silver iodide phase by adding iodide ions, followed by the addition of a silver nitrate solution alone, or a silver nitrate solution and a bromide solution, or a silver nitrate solution. A mixture of a bromide solution and an iodide solution is simultaneously added to further grow the grains and introduce dislocations near the apex.

It is preferable that dislocation lines exist in the step (b2). The dislocation lines are preferably present near the vertices of the tabular grains. The vicinity of the vertex is a three-dimensional area surrounded by the perpendicular and the side where the vertex is drawn from the point at x% from the center of the line connecting the center of the particle and each vertex. Part. The value of x is preferably 50 or more and less than 100, more preferably 75 or more and 100
Is less than. The average number of dislocation lines present on the side surface is preferably 10 or more per grain. More preferably, the average is 20 or more per particle. 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 is possible to count about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where only a few pieces exist. The average number of dislocation lines per particle is determined as the number average by counting the number of dislocation lines for 100 particles or more.

The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% of all grains, more preferably 100 to 70%, particularly preferably 10 to 70%.
It accounts for 0 to 90%. If it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when determining the ratio of the particles containing dislocation lines and the number of dislocation lines, it is preferable to directly obtain the dislocation lines for at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

Next, the step (b3) will be described. Regarding the epitaxial formation of silver halide on the base grains, as described in US Pat. No. 4,435,501, an iodide ion, aminoazaindene or a spectral sensitizing dye adsorbed on the surface of the base grains is used. It is shown that the silver salt epitaxial can be formed at a selected site, for example, a vertex portion or a side surface portion of the base particle by the site director of No. 1. Also, JP-A-8-69069
In No. 1, silver halide epitaxial is formed at a selected site on the base of ultrathin tabular grains, and the epitaxial phase is optimally chemically sensitized to achieve high sensitization.

Also in the present invention, it is very preferable to sensitize the base particles of the present invention by using these methods.
As the site director, aminoazaindene or a spectral sensitizing dye may be used, iodide ion or thiocyanate ion may be used, and they may be used properly or may be combined according to the purpose.

By changing the amounts of the sensitizing dye, iodide ion and thiocyanate ion, the formation site of silver salt epitaxial is limited only to the main plane portion, side surface portion or top portion of the base grain. And combinations of them. The addition amount of aminoazaindene, iodide ion, thiocyanate ion, and spectral sensitizing dye to be used in the site director should be appropriately selected according to the silver amount, surface area, and epitaxial limited site of the silver halide base grains to be used. Is preferred. The temperature at which silver salt epitaxial is formed is preferably 40 to 70 ° C, more preferably 45 to 60 ° C. In this case, pA
g is preferably 9.0 or less, more preferably 8.0 or less. As described above, by appropriately selecting the type of the site director, the amount of addition, and the conditions for epitaxial deposition (temperature, pAg, etc.), the epitaxial growth of the silver salt can be selectively performed on the main plane portion, side surface portion, or apex portion of the base particles. Can be formed. The emulsion thus obtained may be selectively sensitized by subjecting the epitaxial phase to chemical sensitization as disclosed in JP-A-8-69069, but the silver salt solution and the halogen salt solution are successively formed after the silver salt epitaxial formation. It may be added simultaneously to further grow. At this time, the added aqueous solution of the halogen salt is
A bromide salt solution or a mixture of a bromide salt solution and an iodide salt solution is preferred. Also, the temperature at this time is 40 ~
80 ° C is preferred, and 45-70 ° C is more preferred. In this case, the pAg is preferably 5.5 or more and 9.5 or less, and more preferably 6.0 or more and 9.0 or less. Further, a halogen solution different from the epitaxial composition may be added to perform epitaxial halogen conversion. Epitaxial formation and subsequent growth, or halogen conversion, may be performed subsequently to the formation of the silver halide base grains, may be performed once after washing / redispersion after formation of the base grains, or may be performed before chemical sensitization. Epitaxial formation and subsequent growth or halogen conversion may be separated before and after washing / redispersion.

The epitaxial formed in the step (b3) is characterized in that it is formed so as to protrude outside the base particles formed in the step (a). The composition of the epitaxial is AgBr, AgCl, AgBrCl, AgB
rClI, AgBrI, AgI, AgSCN and the like are preferred. It is further preferable to introduce a "dopant (metal complex)" into the epitaxial layer as described in JP-A-8-69069. The position of the epitaxial growth may be at least a part of the top part, the side part, or the main plane part of the base particle, or may be over a plurality of places. The apex portion refers to each apex of a triangle or hexagonal tabular grain (six in a hexagonal shape, three in a triangular shape), and it is preferable that at least one of the vertices has an epitaxial layer. In the case of hexagonal tabular grains, the side surface means a surface on six sides and a surface connecting two main planes, that is, a side surface. Epitaxial exists on the six sides and in any part of the side surface. Or at least one or more of them may be present. The same applies to triangular tabular grains.
The main plane portion refers to two main planes referred to as tabular grains, and the epitaxial may be present at any position on the main plane, and at least one epitaxial plane may be present. Regarding the epitaxial shape, the {100} plane, the {111} plane, and the {110} plane may appear alone or a plurality of them may appear. Further, it may have an irregular shape in which a higher-order surface appears.

It is not necessary that dislocation lines exist in the step (b3), but it is more preferable that dislocation lines exist. The dislocation lines are preferably present at the junction between the base grains and the epitaxially grown portion or at the epitaxial portion. The average number of dislocation lines present in the junction or the epitaxial portion is preferably 10 or more per grain. More preferably, the average is 20 or more per particle. 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 is possible to count about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where only a few pieces exist. The average number of dislocation lines per particle is determined as the number average by counting the number of dislocation lines for 100 particles or more.

It is preferable that the 6 cyano metal complex is doped when the epitaxial portion is formed. Of the six cyano metal complexes, those containing iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium are preferred. The addition amount of the metal complex is 1 per mole of silver halide.
It is preferably in the range of 0 ^{-9 to} 10 ^-2 mol, more preferably 10 ^{-8 to} 10 ^-4 mol per mol of silver halide. The metal complex can be added after being dissolved in water or an organic solvent. The organic solvent preferably has miscibility with water. Examples of organic solvents include alcohols, ethers, glycols, ketones, esters, and amides.

The tabular grains of the present invention preferably have a uniform dislocation dose distribution between the grains. In the emulsion of the present invention, silver halide grains containing 5 or more dislocation lines per grain preferably occupy 100 to 50% of all grains, more preferably 100 to 70%, particularly preferably 100 to 70%.
Or 90%. If it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when calculating the ratio of the particles containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

It is advantageous to use gelatin as a protective colloid used in the preparation of 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 macromolecules, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives ;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, and various kinds of synthetic hydrophilic polymer materials such as polyvinylpyrazole Can be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid.
Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin are also used. As the type of gelatin, alkali-treated gelatin,
Oxidized gelatin (methionine content of 40 μmol / g or less) obtained by oxidizing a methionine group in a gelatin molecule with hydrogen peroxide or the like, amino group-modified gelatin of the present invention (for example, phthalated gelatin, trimellitated gelatin, succinated gelatin, maleic Gelatinized or esterified gelatin). Also, if necessary, refer to JP-A-11-237704.
In the molecular weight distribution measured by the puggy method described in No. 2, components having a molecular weight of at least 280,000
Lime-processed bone gelatin preferably containing 30% or more may be used. Further, for example, starch described in European Patent No. 758758 and US Patent No. 5,733,718 may be used. In addition, the natural polymer is Japanese Patent Publication 7-11
No. 1550, Research Disclosure Magazine No. 176
Volume, No. 17643 (December 1978), Section IX.
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, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 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 of washing with water can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugation, coagulation sedimentation, ion exchange, and ultrafiltration. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

In forming the particles of the present invention, for example, JP-A-5-173268, JP-A-5-173269, and JP-A-5-173269
No. 173270, No. 5-173271, No. 6-20
The polyalkylene oxide block copolymer described in Nos. 2258 and 7-175147, or the polyalkylene oxide copolymer described in, for example, Japanese Patent No. 3089578 may be present. The compound may be present at any time during the preparation of the particles, but when used at an early stage of particle formation, the effect is large.

In the third emulsion according to the present invention, the main plane parallel to the silver halide grains has a (100) plane having a silver chloride content of 10%.
The tabular silver halide grains comprising less than mol% of silver iodobromide or silver chloroiodobromide will be described below.

The {100} tabular grains of the present invention comprise 50 to 100%, preferably 70 to 100%, more preferably 90 to 100% of the total projected area.
Up to 100% are tabular grains having an average aspect ratio of 2 or more in which the main plane is a {100} plane. Particle thickness is 0.01-0.10
μm, preferably 0.02 to 0.08 μm, more preferably 0.03 to
0.07 μm, and the aspect ratio is 2 to 100, preferably 3 to
50, more preferably 5 to 30. Coefficient of variation of particle thickness (percentage of “standard deviation of distribution / average particle thickness”, below C
OV.) Is 30% or less, preferably 25% or less, more preferably 20% or less. The smaller this COV is, the higher the monodispersity of the particle thickness is.

The projected area diameter and thickness of the tabular grains are as follows:
A transmission electron microscope (TEM) photograph is taken by a replica method to determine the projected area diameter and thickness of each particle. in this case,
The thickness is calculated from the length of the shadow of the replica.
The measurement of COV in the present invention is a result of measurement of at least 600 or more particles.

The composition of the {100} tabular grains of the present invention is silver chloroiodobromide or silver iodobromide having a silver chloride content of less than 10 mol%. In addition, other silver salts such as silver rhodan, silver sulfide, silver selenide, silver telluride, silver carbonate, silver phosphate, and organic acid silver are contained as separate grains or as part of silver halide grains. Is also good.

As a method for examining the halogen composition in the AgX crystal, an X-ray diffraction method is known. The X-ray diffraction method is described in detail in Basic Analysis Chemistry Course 24 “X-ray diffraction” and the like. As a standard, AgX
The diffraction angle of the (420) plane is determined by a powder method.

Once the diffraction nucleus 2θ is determined, the lattice constant a is determined from the Bragg equation as follows. 2 d sin θ = λ d = a / (h ² + k ² + l ² ) ^1/2 where 2θ is the diffraction angle of the (hkl) plane, λ is the wavelength of the X-ray, and d is the plane of the (hkl) plane. The interval. The relationship between the halogen composition and the lattice constant a of a silver halide solid solution is already known (for example, see “The Theory of Phot” edited by TH James).
4th Ed, Macmillian New York) and knowing the lattice constant allows the halogen composition to be determined.

The halogen composition structure of the {100} tabular grains of the present invention may be any. For example, a particle having a (core / shell) 2 structure in which the halogen composition of the core and the shell is different or a particle having a multi-structure having the core and two or more shells are exemplified. The composition of the core is preferably silver bromide, but is not limited thereto. The composition of the shell preferably has a higher silver iodide content than the core.

The {100} tabular grains of the present invention preferably have an average silver iodide content of 2.3 mol or more and a surface average silver iodide content of 8 mol% or more. More preferably, the coefficient of variation of the silver iodide content between grains is less than 20%. The surface silver iodide content can be measured using the XPS described above.

When the {100} tabular grains of the present invention are classified by shape, the following six can be mentioned. (1) Particles whose main plane is a right-angled parallelogram. (2) Particles in which one or more, preferably 1 to 4 of the four corners of the right-angled parallelogram are non-equivalently missing. That is, [(area of the largest missing part)
/ Minimum missing area = particles with K1 of 2-∞), (3) 4
Particles in which two corners are equivalently missing (particles in which K1 is smaller than 2), (4) particles in which 5 to 100%, preferably 20 to 100% of the area of the side surface of the missing portion is a {111} plane . (5) a particle in which at least two opposing sides of the four sides constituting the main plane are outwardly convex curves, (6) one or more of the four corners of the right-angled parallelogram, preferably Is particles whose 1-4 are missing in the shape of a right-angled parallelogram. These can be confirmed by observation using an electron microscope.

The ratio of the {100} plane to the crystal habit of the surface of the {100} tabular grains of the present invention is 80% or more, preferably 9%.
Although it is 0% or more, it can be estimated statistically using an electron micrograph of particles. Ag in emulsion
In the case where the {100} tabular ratio of the X particles is almost close to 100%, the above estimation can be confirmed by the following method. The method is described in The Chemical Society of Japan, 1984, No. 6, 942p.
The benzothiocyanine dye was added to a certain amount of the {100} tabular grains at a temperature of 40 ° C.
The total surface area (S) of all grains per unit emulsion (S) and the total area of {100} planes (S1) are determined from the light absorption at 625 nm, and the formula: S1 / S ×
This is a method of calculating the {100} plane ratio using 100 (%).

The average equivalent sphere diameter of the {100} tabular grains of the present invention is preferably less than 0.35 μm. Estimation of the particle size can be obtained by measuring the projected area and thickness by the replica method.

In the fourth emulsion according to the present invention, the main plane parallel to the silver halide grains is the (111) plane or the (100) plane.
Surface and the aspect ratio is 2 or more and at least 8
The tabular grains containing 0 mol% or more of silver chloride are described below.

Special measures are required to produce (111) grains with high silver chloride. Wey U.S. Pat.
No. 399,215, a method for producing high silver chloride tabular grains using ammonia may be used. Maskasky U.S. Pat. No. 5,061,617 may use the method of producing high silver chloride tabular grains using thiocyanate. In order to form grains having the (111) plane as the outer surface in the high silver chloride grains described below, a method of adding an additive (crystal phase controlling agent) during grain formation may be used. It is shown below.

[0143]   Patent number Crystal phase control agent   U.S. Patent No. 4,400,463 Azaindenes + Mascasky                               Thioether peptizer   U.S. Pat. No. 4,783,398 2-4-Dithiazolidinone Mifune et al.   U.S. Pat. No. 4,713,323 Aminopyrazolopyrimidine Mascasky   US Patent No. 4,983,508 Bispyridinium salt Ishiguro etc.   U.S. Pat. No. 5,185,239 Triaminopyrimidine Mascasky   U.S. Pat. No. 5,178,997 7-Azaindole-based compound Masukasky   U.S. Patent No. 5,178,998 Xanthine Mascasky   JP-A-64-70741 Dye Nishikawa et al.   JP-A-3-212639 Aminothioether Ishiguro   JP-A-4-283742 Thiourea derivative Ishiguro   JP-A-4-335632 Triazolium salt Ishiguro   JP-A-2-32 Bispyridinium salt Ishiguro etc.   JP-A-8-227117 Monopyridinium salt Ozeki et al.

As for the formation of (111) tabular grains, a method using various crystal habit controlling agents as described in the above table is known. Compound examples 1 to 42) are preferred.
Crystal phase control agents 1 to 29 described in No. 27117 are particularly preferred. However, the present invention is not limited to these.

The (111) tabular grains are obtained by forming two parallel twin planes. Since the formation of the twin plane depends on the temperature, the dispersion medium (gelatin), the halogen concentration, and the like, these appropriate conditions must be set. When a crystal habit controlling agent is present during nucleation, the gelatin concentration is preferably 0.1% to 10%. The chloride concentration is at least 0.01 mol / L, preferably at least 0.03 mol / L.

It is disclosed in JP-A-8-184931 that it is preferable not to use a crystal habit-controlling agent for nucleation in order to monodisperse the particles. When the crystal habit controlling agent is not used at the time of nucleation, the gelatin concentration is 0.03.
% To 10%, preferably 0.05% to 1.0%.
The chloride concentration is 0.001 mol / L to 1 mol / L, preferably 0.003 mol / L to 0.1 mol / L. The nucleation temperature can be selected from 2 ° C to 90 ° C.
80 ° C is preferable, and particularly preferably 5 ° C to 40 ° C.

The nuclei of tabular grains are formed in the first nucleation stage, but immediately after the nucleation, the reaction vessel contains many nuclei other than tabular grains. Therefore, after nucleation, aging is performed,
A technique for leaving only tabular grains and extinguishing others is required. When ordinary Ostwald ripening is performed, the tabular grain nuclei also dissolve and disappear, so that the tabular grain nuclei decrease and the size of the resulting tabular grains increases. In order to prevent this, a crystal habit controlling agent is added. In particular, by using phthalated gelatin in combination, the effect of the crystal habit controlling agent can be enhanced and the dissolution of tabular grains can be prevented. The pAg during ripening is particularly important, and is preferably 60 to 130 mV with respect to the silver-silver chloride electrode.

Next, the formed nuclei are grown in the presence of a crystal habit controlling agent by physical ripening and addition of a silver salt and a halide. In this case, the chloride concentration is 5 mol / L or less, preferably 0.05 to 1 mol / L. The temperature at the time of grain growth can be selected in the range of 10 ° C to 90 ° C.
Is preferable.

The total amount of the crystal habit controlling agent used is at least 6 × 10 ^-5 mol, especially 3 × 10 ^-5 mol, per mol of silver halide in the finished emulsion.
It is preferably from 10 ⁻⁴ mol to 6 × 10 ⁻² mol. The phase control agent may be added at any time during the nucleation of silver halide grains, physical ripening, and during grain growth. After the addition, the (111) plane starts to form. The crystal habit controlling agent may be added to the reaction vessel in advance, but in the case of forming small-sized tabular grains, it is preferable to add the crystal phase controlling agent to the reaction vessel along with the growth of the grains to increase the concentration.

When the amount of the dispersion medium used at the time of nucleation is insufficient for growth, it is necessary to supplement the amount by addition. Preferably, 10 g / L to 100 g / L of gelatin is present for growth. As the complementary gelatin, phthalated gelatin or trimellit gelatin is preferable. PH during particle formation
Is optional, but is preferably in a neutral to acidic region.

Next, the (100) tabular grains will be described. (100) tabular grains are tabular grains having a (100) plane as a main plane. The shape of the main plane may be a right-angled parallelogram or a triangular to pentagonal shape in which one corner of the right-angled parallelogram is missing. A right-angled triangular portion formed by
To an octagonal shape. If the right-angled parallelogram shape supplementing the missing part is a supplementary quadrilateral, the adjacent side ratio (long side length / short side length) of the right-angled parallelogram and the supplementary quadrangle is 1 to 6 , Preferably 1-4, more preferably 1-2.

The (100) tabular silver halide emulsion grains having a main plane can be formed by adding and mixing an aqueous silver salt solution and an aqueous halide salt solution with stirring in a dispersion medium such as an aqueous gelatin solution. At this time, for example, JP-A-6-301129 and JP-A-6-347929.
In JP-A-9-34045 and JP-A-9-96881, silver iodide or iodide ions or silver bromide or bromide ions are allowed to be present, and nuclei are formed due to the difference in crystal lattice size from silver chloride. A method for introducing a crystal defect which causes distortion and imparts anisotropic growth such as screw dislocation is disclosed. When the screw dislocations are introduced, the formation of two-dimensional nuclei on the surface is not rate-determining under low supersaturation conditions, so crystallization proceeds on this surface, and tabular grains are formed by introducing the screw dislocations. Is done. Here, the low supersaturation condition is preferably 35% or less at the time of critical addition, and more preferably 2% or less.
Indicates 20%. Although it is not determined that the crystal defect is a screw dislocation, it is considered that there is a high possibility that the crystal defect is a screw dislocation because the direction in which the dislocation is introduced or anisotropic growth is imparted to grains. In order to make tabular grains thinner, it is preferable that the introduced dislocations be retained.
122954 and 9-189977.

In Japanese Patent Application Laid-Open No. Hei 6-347928, imidazoles and 3,5-diaminotriazoles are used, and in Japanese Patent Application Laid-Open No. Hei 8-339404, polyvinyl alcohols are used. A method of forming (100) tabular grains by addition is disclosed. However, the present invention is not limited to these.

The term "high silver chloride grains" means grains having a silver chloride content of 80 mol% or more, and preferably 95 mol% or more is silver chloride. The particles of the present invention preferably have a so-called core / shell structure comprising a core and a shell surrounding the core. It is preferable that 90 mol% or more of the core portion is silver chloride. The core portion may further include two or more portions having different halogen compositions. The shell portion is preferably 50% or less of the total particle volume,
It is particularly preferred that it is 20% or less. The shell part is preferably silver iodochloride or silver iodobromochloride. The shell part preferably contains 0.5 to 13 mol% of iodine, and particularly preferably 1 to 13 mol%. The content of silver iodide in all grains is preferably at most 5 mol%, particularly preferably at most 1 mol%.

The silver bromide content is preferably higher in the shell part than in the core part. The silver bromide content is preferably at most 20 mol%, particularly preferably at most 5 mol%. The average grain size (equivalent sphere equivalent diameter) of the silver halide grains is not particularly limited, but is preferably 0.1 μm to 0.8 μm, and particularly preferably 0.1 μm to 0.6 μm.

The tabular grains of silver halide have a projected area diameter of preferably 0.2 to 1.0 μm. Here, the projected area diameter of a silver halide grain refers to the diameter of a circle having an area equal to the projected area of the grain in an electron micrograph. The thickness is 0.2 μm or less, preferably 0.1 μm or less, and particularly preferably 0.06 μm or less. In the present invention, 50% or more of the projected area of all silver halide grains has an average aspect ratio (diameter / thickness ratio) of 2 or more, preferably 5 or more and 20 or less.

In general, tabular grains are tabular having two parallel planes. Therefore, the "thickness" in the present invention is represented by the distance between two parallel planes constituting the tabular grains. The grain size distribution of the silver halide grains of the present invention,
It may be polydisperse or monodisperse, but more preferably monodisperse. In particular, the variation coefficient of the projected area diameter of tabular grains occupying 50% or more of the total projected area is preferably 20% or less. Ideally, it is 0%.

If the crystal habit controlling agent is present on the surface of the grains even after the formation of the grains, it affects the adsorption of the sensitizing dye and the development. Therefore, it is preferable to remove the crystal habit controlling agent after forming the particles. However, when the crystal habit controlling agent is removed, high silver chloride (1
11) It is difficult for tabular grains to maintain the (111) plane under ordinary conditions. Therefore, it is preferable to retain the particle form by substituting with a photographically useful compound such as a sensitizing dye. Regarding this method, JP-A-9-80656,
JP-A-9-106026, U.S. Pat. No. 5,221,6
No. 02, No. 5,286,452, No. 5,2
No. 98,387, No. 5,298,388, No. 5,
176,992.

Although the crystal habit controlling agent is desorbed from the grains by the above method, it is preferable to remove the desorbed crystal habit controlling agent out of the emulsion by washing with water. The washing temperature can be set at a temperature at which gelatin usually used as a protective colloid does not coagulate. As the water washing method, various known techniques such as a flocculation method and an ultrafiltration method can be used. The washing temperature is preferably 40 ° C. or higher. The desorption of the crystal habit controlling agent is promoted from the particles at a low pH. Therefore, the pH in the water washing step is preferably low as long as the particles are not excessively aggregated.

The silver halide emulsion may be further characterized by the layer in which the emulsion is used. Particularly when used in a blue-sensitive layer, the silver halide grains contained in the silver halide emulsion preferably have a silver iodide content of at least 3 mol%, more preferably at least 5 mol%. When used for a high-sensitivity layer, the projected area diameter is 1 μm.
m or more, preferably 2 μm or more.

The silver halide emulsion may have the following characteristics in order to impart pressure resistance to the photographic material. The silver halide grains contained in the silver halide emulsion are:
Within 50%, preferably 80% in area from the center of the main plane
It is preferable that particles having no dislocation lines when observed by a transmission electron microscope occupy 80% or more of all the particles, and more preferably 90% or more. The center of the main plane refers to the position of the center of gravity in the area of the main plane.

The contents relating to the emulsion of the present invention in general will be described below. The reduction sensitization preferably used in the present invention includes a method of adding a reduction sensitizer to silver halide, and a method of growing or ripening silver halide grains in a low pAg atmosphere of pAg 1 to 7 called silver ripening. Alternatively, any method of growing or ripening in a high pH atmosphere of pH 8 to 11, which is called high pH ripening, may be selected. Further, two or more of these methods can be used in combination. In particular, the method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, stannous salts, ascorbic acid and its derivatives, hydroquinone and its derivatives, catechol and its derivatives, hydroxylamine and its derivatives, amines and polyamines, hydrazine and its derivatives, paraphenylenediamine and its derivatives Derivatives, formamidinesulfinic acid (thiourea dioxide), silane compounds and borane compounds can be mentioned. These reduction sensitizers can be selected for use in the reduction sensitization of the present invention, and two or more compounds can be used in combination. Regarding the method of reduction sensitization, U.S. Pat.
Nos. 518,698, 3,201,254, 3,411,917, 3,779,777, and 3,930,867. The method of use is described in JP-B-57-33572 and JP-B-58
-1410 and the method disclosed in JP-A-57-179835 can be used. Catechol and its derivatives, hydroxylamine and its derivatives, formamidinesulfinic acid (thiourea dioxide) are preferred compounds as reduction sensitizers. Further, the following general formulas (3) and (4) are also preferable reduction sensitizers.

[0164]

Embedded image

In the general formulas (3) and (4),
W ₅₁ and W ₅₂ represent a sulfo group or a hydrogen atom. Where W
_At least one of ₅₁ and W ₅₂ represents a sulfo group. The sulfo group is generally an alkali metal salt such as sodium or potassium, or a water-soluble salt such as an ammonium salt. Specific examples of preferred compounds include 3,5-disulfocatechol disodium salt, 4-sulfocatechol ammonium salt, 2,3-dihydroxy-7-sulfonaphthalene sodium salt, and 2,3-dihydroxy-6,7-di-sodium salt. And sulfonaphthalene potassium salt.

The addition amount of the reduction sensitizer depends on the emulsion production conditions and must be selected, but is suitably in the range of 10 ^-7 to 10 ^-1 mol per mol of silver halide. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth.

Examples of the silver halide solvent usable in the present invention include US Pat. Nos. 3,271,157, 3,531,289 and 3,574,628, and JP-A-54-1019. (A) organic thioethers described in JP-A Nos. 54-158917 and 54-158917;
(B) thiourea derivatives described in JP-A Nos. 08-55-77737 and 55-2982;
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-4319, (d) imidazoles described in JP-A-54-100717, e) ammonia and (f) thiocyanate. Particularly preferred solvents include thiocyanate, ammonia and tetramethylthiourea. The amount of the solvent to be used varies depending on the kind, for example, in the case of thiocyanate, a preferred amount is per mol of silver halide 1 × 10 ^-4 mol to 1 × 10
^-2 mol or less.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, it is preferable that a metal ion salt is present before coating according to 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. As described above, the case of doping the whole grain and the method of doping only the core portion, only the shell portion, or only the epitaxial portion of the grain can be selected. For example, Mg, Ca, Sr, Ba, Al, S
c, Y, La, Cr, Mn, Fe, Co, Ni, Cu,
Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Can be used. These metals can be added in the form of salts which can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, and six-coordinate complex salts and four-coordinate complex salts. For example, CdB
r ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , P
b (CH ₃ COO) ₂ , K ₄ [Fe (CN) ₆ ], (N
H ₄ ) ₄ [Fe (CN) ₆ ], K ₂ IrCl ₆ , (NH ₄ ) ₃
RhCl ₆ and K ₄ Ru (CN) ₆ are mentioned. Halo, aquo, cyano, cyanate, ligands for coordination compounds
It can be selected from thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may use only one type of metal compound, but may use two or three types.
More than one species may be used in combination.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. 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. A water-soluble silver salt (eg, AgNO ₃ ) or an aqueous alkali halide solution (eg, NaCl, K)
(Br, KI) and continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogen compound during the preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes 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 can be used for chalcogen sensitization such as sulfur sensitization, selenium sensitization and tellurium sensitization, noble metal sensitization such as gold sensitization and palladium sensitization, and reduction sensitization. At least one of them can be applied in any step of the production process of the silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a shallow position from the grain surface, and a type in which a chemical sensitizing nucleus is formed 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 kind 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 a chalcogen sensitization and a noble metal sensitization alone or in combination, and is described in TH James, The Photographic Process, No. 4 Edition, published by Macmillan, 1
977, (TH James, The Theor)
y of the Photographic Pro
cess, 4th ed, Macmillan, 197
7) can be performed using active gelatin as described on pages 67-76, and can also be performed by Research Disclosure, Volume 120, April 1974, 12008; Research Disclosure, Volume 34, June 1975,
13452; U.S. Patent Nos. 2,642,361; 3,297,446; 3,772,031; 3,857,711; 3,901,714; No. 3,266,018 and No. 3,904,41.
5 and pAg 5-10, pH 5-8 and temperature 30-8 as described in GB 1,315,755.
At 0 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In precious metal sensitization, gold, platinum,
Noble metal salts such as palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable.

In gold sensitization, P.I. Grafkide
s, Chimie et Physique Pho
tographique (Paul Momtel, 1987, 5th edition), Research Diss
Gold salts described in Closure, Vol. 307, No. 307105, and the like can be used.

More specifically, in addition to chloroauric acid, potassium chloroaurate and potassium aurithiocyanate,
U.S. Pat. Nos. 2,642,361 (such as gold sulfide and gold selenide), and 3,503,749 (such as thiolate gold having a water-soluble group) and 5,049,484 (including bis (methylhydantoin) Nat) gold complex, etc.) and 5,049,4
No. 85 (a mesoionic thiolate gold complex such as 1,
4,5-trimethyl-1,2,4-triazolium-3
-Thiolate gold complex), the macrocyclic heterocyclic gold complexes of JP-A-5,252,455 and JP-A-5,391,727;
620,841, 5,700,631, 5,7
Nos. 59,760, 5,759,761, 5,91
2,111, 5,912,112, 5,93
9,245, JP-A-1-147537, 8-690
No. 74, No. 8-69075, No. 9-269554,
JP-B-45-29274, German Patent DD-2645
24A, 264525A, 265474A, 29
8321A, JP-A-2001-75214, 2001
-75215, 2001-75216, 200
Gold compounds described in JP-A Nos. 1-75217 and 2001-75218 can also be used.

The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are
It is represented by R ₂ PdX ₆ or R ₂ PdX ₄ . 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 P
dCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl 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.

In sulfur sensitization, an unstable sulfur compound is used. Grafkides, Chimie et
Physique Photographique
(Paul Momtel, 1987, 5th
Edition), Research Disclosure Magazine 30
Unstable sulfur compounds described in Vol. 7, No. 307105, etc. can be used.

Specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, N-ethyl-N ′-(4-methyl-2
-Thiazolyl) thiourea, dicarboxymethyl-dimethylthiourea, carboxymethyl-trimethylthiourea), thioamides (e.g., thioacetamide), rhodanines (e.g., diethyl rhodanine, 5-benzylidene-N-ethyl rhodanine), Phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxooxazolidine-2-thiones, disulfides or polysulfides (eg, dimorpholine disulfide, cystine, hexathiocanthion), mercapto Known compounds such as compounds (eg, cysteine), polythionates, elemental sulfur, active gelatin, and the like can also be used. Particularly preferred are thiosulfates, thioureas, phosphine sulfides and rhodanines.

In the selenium sensitization, an unstable selenium compound was used, and JP-B-43-13489 and JP-B-44-157.
No. 48, JP-A-4-25832, JP-A-4-109340
Nos. 4-271341, 5-40324, and 5
-11385, 6-51415, 6-1804
No. 78, No. 6-180478, No. 6-208186
No. 6-208184, No. 6-317867, No. 7-92599, No. 7-98483, No. 7-140
No. 539 can be used.

More specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg, selenoamide, N, N-diethylphenylselenoamide), phosphine selenides (eg, triphenylphosphine selenide, pentafluorophenyl-)
Triphenylphosphine selenide), selenophosphates (eg, tri-p-tolylselenophosphate, tri-n-butylselenophosphate), selenoketones (eg, selenobenzophenone), isoselenocyanocyanates, selenocarbon Acids, selenoesters (for example, methoxyphenylselenocarboxy-
2,2-dimethoxycyclohexane ester), diacyl selenides and the like may be used. Further, non-labile selenium compounds described in JP-B-46-4553 and JP-B-52-34492, such as selenous acid, selenocyanic acids (eg, potassium selenocyanate), selenazoles, selenides, and the like may be used. I can do it. Particularly, phosphine selenides, selenoureas, selenoesters and selenocyanic acids are preferred.

In tellurium sensitization, an unstable tellurium compound is used and disclosed in JP-A-4-224595 and JP-A-4-27713.
No. 41, No. 4-330430, No. 5-303157
No. 6-27573, No. 6-180478, No. 6
-208186, 6-208184, 6-31
Unstable tellurium compounds described in Nos. 7867 and 7-140539 can be used.

Specifically, phosphine tellurides (for example, butyl-diisopropylphosphine telluride,
Tributylphosphine telluride, tributoxyphosphine telluride, ethoxydiphenylphosphine telluride, diacyl (di) tellurides (for example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride , Bis (N-phenyl-N-methylcarbamoyl) telluride,
Bis (N-phenyl-N-benzylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride, telluroreas (eg, N, N′-dimethylethylenetellurourea, N, N′-diphenylethylenetellurourea) telluroamides, Telluro esters may be used.

Useful chemical sensitizing aids include azaindene,
Compounds known to suppress fog in the course of chemical sensitization and increase sensitivity, such as azapyridazine and azapyrimidine, are used. Examples of chemical sensitization aid modifiers are described in U.S. Pat. Nos. 2,131,038 and 3,41.
Nos. 1,914 and 3,554,757;
No.-126526 and the aforementioned "Emulsion Chemistry" by Duffin, pp. 138-143.

Gold sensitizers and chalcogens used in the present invention
The amount of sensitizer used depends on the silver halide grains used and the chemical sensitizer.
Depending on the sensitivity conditions, etc., per mole of silver halide
10 ^-8-10^-2Mole, preferably 10^-7-10^-3About a mole
Degrees can be used.

The conditions for chemical sensitization in the present invention include:
Although there is no particular limitation, the pAg is 6 to 11, preferably 7 to 10, and the pH is 4 to 10, preferably 5 to 5.
8. The temperature is 40 ° C to 95 ° C, preferably 45 ° C to
85 ° C.

During the production process of the emulsion of the present invention, an acid for silver is used.
It is preferable to use an agent. The oxidizing agent for silver is
Acts on metallic silver to convert it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Extremely small silver particles by-produced during chemical sensitization
Is a compound that can be converted into a silver ion. here
The silver ions generated by, for example, silver halide, sulfide
It may form silver salts that are hardly soluble in water such as silver and silver selenide.
And may form a silver salt easily soluble in water such as silver nitrate.
No. The oxidizing agent for silver can be either inorganic or organic.
There may be. As the inorganic oxidizing agent, for example, Ozo
Hydrogen peroxide and its adducts (eg, NaBO)_Two
・ H_TwoO_Two・ 3H_TwoO, 2NaCO_Three・ 3H_TwoO_Two, Na_FourP_Two
O₇・ 2H_TwoO_Two, 2Na_TwoSO_Four・ H_TwoO_Two・ 2H_TwoO), pe
Leuoxy acid salt (for example, K_TwoS_TwoO₈, K_TwoC_TwoO₆, K_TwoP_Two
O₈), Peroxy complex compounds (eg, K_Two[Ti (O
_Two) C_TwoO _Four] ・ 3H_TwoO, 4K_TwoSO_Four・ Ti (O_Two) OH
・ SO_Four・ 2H_TwoO, Na_Three[VO (O_Two) (C_TwoH_Four)_Two]
・ 6H_TwoO), permanganate (eg, KMnO)_Four),
Chromate (eg, K_TwoCr_TwoO₇Oxygen acid like)
Salts, halogen elements such as iodine and bromine, perhalates
(Eg, potassium periodate), high valent metal salts
(Eg, potassium hexacyanoferrate) and thio
There are sulfonates. In addition, as an organic oxidizing agent,
Quinones such as p-quinone, peracetic acid and perbenzoic acid
Organic peroxides, compounds that release active halogens (eg
For example, N-bromosuccinimide, chloramine T,
Lamin B) is mentioned by way of 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-mentioned reduction sensitization and an oxidizing agent for silver together. The method can be used by selecting from a method of using an oxidizing agent and then performing reduction sensitization, a reverse method, or a method of coexisting both. 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 may contain various compounds for the purpose of preventing fogging 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, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; for example, thioketo compounds such as oxadolinthione; azaindenes, for example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) known as antifoggants or stabilizers such as citrazazaindenes 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 the preferred compounds is described in JP-A-63-21.
2932. Antifoggants and stabilizers can be used at various times before, during, or after particle formation, during the washing step, during dispersion after 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, control the crystal wall of the grains, reduce the grain size, reduce the solubility of the grains, control 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 the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus,
A thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring 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 includes, as a nucleus having a ketomethylene structure, for example,
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 and JP-A-52-10.
No. 9925. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-8-969 and JP-A-4225666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 928, or can be added before the 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 may be chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains are formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.
The addition amount is from 4 × 10 ⁻⁶ to 8 × per mol of silver halide.
It can be used at 10 ^-3 mole.

Next, the compounds used in the light-sensitive material of the present invention will be described. First, the compound represented by formula (I) of the present invention will be described. The compound of the present invention represented by the general formula (I) may be used at any time during the preparation of an emulsion or during the production of a light-sensitive material. For example, at the time of grain formation, at the desalination step, at the time of chemical sensitization, before coating, and the like. Also, it can be added in a plurality of times during these steps. The compound of the present invention is preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. In the case of dissolving in water, a compound whose solubility increases when the pH is increased or decreased may be dissolved by increasing or decreasing the pH, and then added.

The compound of the present invention represented by the general formula (I)
It is preferably used in an emulsion layer, but it may be added to a protective layer or an intermediate layer together with the emulsion layer and diffused during coating. The compound of the present invention may be added at any time before or after the sensitizing dye, and is preferably 1 × per mol of silver halide.
10 ^{-9 to} 5 × 10 ^-2 mol, more preferably 1 × 10 ^-8 to
It is contained in the silver halide emulsion layer at a ratio of 2 × 10 ⁻³ mol.

In the general formula (I), the silver halide adsorbing group represented by X has at least one selected from the group consisting of N, S, P, Se and Te, and is preferably a silver ion It has a ligand structure. If k is 2 or more,
A plurality of Xs may be the same or different. Examples of the silver ion ligand structure include the following.

In the formula (X-1) -G ₁ -Z ₁ -R ₁ , G ₁ is a divalent linking group, which is substituted with a divalent heterocyclic group or a divalent heterocyclic group or Unsubstituted alkylene group, alkenylene group, alkynylene group, arylene group,
Represents a divalent group bonded to any of the SO ₂ groups. Z
₁ represents an S, Se or Te atom. R ₁ represents a hydrogen atom or a sodium ion, a potassium ion, a lithium ion and an ammonium ion as a counter ion required in the case of dissociation of Z ₁ .

Formulas (X-2a) and (X-2b)

Embedded image

Formulas (X-2a) and (X-2b) are ring-formed, and are in the form of a 5- to 7-membered saturated heterocyclic ring, heterounsaturated ring or unsaturated carbocyclic ring. Z _a is, O, N,
Represents an S, Se or Te atom, and n1 represents an integer of 0 to 3. R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. When n1 is 2 or more, a plurality of Z _a may be the same or different.

[0199] Formula _{(X-3) -R 3 -} (Z 2) in _n2 -R ₄ Formula, Z ₂ is S, Se or Te atom, n2 is 1
Represents an integer of 3. R ₃ is a divalent linking group, and includes an alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, or divalent heterocyclic group and alkylene group, alkenylene group, alkynylene group, arylene group, Represents a divalent group bonded to any of the SO ₂ groups.
R ₄ represents an alkyl group, an aryl group or a heterocyclic group.
When n2 is 2 or more, a plurality of Z ₂ may be the same or different.

Formula (X-4)

Embedded image

In the formula, R ₅ and R ₆ each independently represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

Formulas (X-5a) and (X-5b)

Embedded image

In the formula, Z ₃ represents an S, Se or Te atom, and E ₁ is a hydrogen atom, NH ₂ , NHR ₁₀ , N
It represents the _{(R 10) 2, NHN (} R 10) 2, OR 10 or SR _10. E ₂ is a divalent linking group, NH, NR ₁₀ , NHN
Represents R ₁₀ , O or S. R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R ₈ and R ₉ may combine with each other to form a ring. R ₁₀ is a hydrogen atom, an alkyl group,
Represents an alkenyl group, an aryl group or a heterocyclic group.

Formulas (X-6a) and (X-6b)

Embedded image

In the formula, R ₁₁ is a divalent linking group, and represents an alkylene group, alkenylene group, alkynylene group, arylene group or divalent heterocyclic group. G ₂ and J are each independently COOR ₁₂ , SO ₂ R ₁₂ , COR ₁₂ , SO
Represents R ₁₂ , CN, CHO or NO ₂ . R ₁₂ represents an alkyl group, an alkenyl group or an aryl group.

The general formula (X-1) will be described in detail. In the formula, the linking group represented by G ₁ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, 3
-Oxapentylene, 2-hydroxytrimethylene),
A substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (eg, cyclopropylene, cyclopentylene, cyclohexylene), a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (eg, ethene, 2-butenylene),
Examples thereof include an alkynylene group having 2 to 10 carbon atoms (eg, ethyne) and a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene, unsubstituted 2,5-naphthylene).

In the formula, the SO ₂ group represented by G ₁ includes-
In addition to the SO ₂ — group, a substituted or unsubstituted linear or branched alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cyclic alkylene group having 3 to 6 carbon atoms, or a carbon atom having 2 carbon atoms
-SO ₂ bound to an alkenylene group of 10 - group.

Further, as the divalent linking group represented by G ₁ , a divalent heterocyclic group, or a divalent heterocyclic group and an alkylene group, alkenylene group, alkynylene group, arylene group or SO ₂ group A divalent group bonded to any of them, or a group obtained by subjecting a heterocyclic portion of these groups to benzo- or naphtho-condensation (for example, 2,3-tetrazolediyl,
1,3-triazoldiyl, 1,2-imidazolediyl, 3,5-oxadiazolediyl, 2,4-thiazoledyl, 1,5-benzimidazolediyl, 2,
5-benzothiazoldiyl, 2,5-benzoxazoldiyl, 2,5-pyrimidindiyl, 3-phenyl-2,5-tetrazolediyl, 2,5-pyridinediyl, 2,4-furandyl, 1,3- Piperidinediyl, 2,4-morpholinediyl).

In the above formula, G ₁ may have a substituent as much as possible. The substituents are shown below, and these substituents are referred to herein as substituents Y.

Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom), an alkyl group (for example, methyl, ethyl, isopropyl, n-propyl, t-butyl) and an alkenyl group (for example, allyl, 2-
Butenyl), alkynyl group (eg, propargyl), aralkyl group (eg, benzyl), aryl group (eg, phenyl, naphthyl, 4-methylphenyl), heterocyclic group (eg, pyridyl, furyl, imidazolyl, piperidinyl, morpholyl), alkoxy group ( For example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy), aryloxy group (for example, phenoxy, 2-naphthyloxy), amino group (for example, unsubstituted amino, dimethylamino, diethylamino, dipropylamino, dibutyl) Amino, ethylamino, anilino), acylamino group (eg, acetylamino, benzoylamino), ureido group (eg, unsubstituted ureido, N-methylureido), urethane group (eg, methoxycarbonylamino) Phenoxycarbonylamino), a sulfonylamino group (eg, methylsulfonylamino, phenylsulfonylamino), a sulfamoyl group (eg, unsubstituted sulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), a carbamoyl group (eg, unsubstituted) Carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl), sulfonyl group (eg, mesyl, tosyl), sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxy Carbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, benzoyl, formyl, pivaloyl), acyloxy groups (eg, acetoxy, benzoy) Oxy), phosphoric amide group (for example, N, N-diethyl phosphoric amide), cyano group, sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, phosphono group, nitro group, ammonium group, phosphonio group Hydrazino group and thiazolino group. When there are two or more substituents, they may be the same or different, and the substituent may further have a substituent.

Preferred examples of the formula (X-1) are shown below. As a preferable general formula (X-1), G ₁ has 6 to ₁ carbon atoms.
5-7 substituted or unsubstituted arylene group, substituted or unsubstituted alkylene group or arylene group, or benzo- or naphtho-condensed
And a heterocyclic group forming a membered ring. Examples of Z ₁ include S and Se, and examples of R ₁ include a hydrogen atom, a sodium ion, and a potassium ion.

More preferably, G ₁ has 6 to 8 carbon atoms.
Is a heterocyclic group bonded to a substituted or unsubstituted arylene group or forms a 5- to 6-membered ring which is benzo-fused, most preferably a 5- or 5-benzo-fused heterocyclic group bonded to an arylene group. It is a heterocyclic group forming a 6-membered ring. More preferred Z ₁ is S, and R ₁ is a hydrogen atom or a sodium ion.

The formulas (X-2a) and (X-2b) will be described in detail. In the formula, the alkyl group, alkenyl group, and alkynyl group represented by R _{2 have} 1 to 1 carbon atoms.
10 substituted or unsubstituted linear or branched alkyl groups (e.g., methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, n-butoxypropyl, methoxymethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (eg, cyclopropyl, cyclopentyl, cyclohexyl), An alkenyl group having 2 to 10 carbon atoms (e.g., allyl, 2-butenyl, 3-pentenyl);
And alkynyl groups (e.g., propargyl and 3-pentynyl) and aralkyl groups having 6 to 12 carbon atoms (e.g., benzyl). The aryl group has 6 carbon atoms.
To 12 substituted or unsubstituted aryl groups (eg, unsubstituted phenyl, 4-methylphenyl) and the like. R ₂ may further have a substituent Y or the like.

Preferred examples of formulas (X-2a) and (X-2b) are shown below. In the formula, preferably, R ₂ is a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms,
Z _a is O, N or S, n1 is an integer of 1 to 3.

[0215] More preferably, R ₂ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Z _a is N or S, n1 is 2 or 3.

Next, general formula (X-3) will be described in detail. In the formula, as the linking group represented by R ₃ , a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (eg, methylene, ethylene, trimethylene, isopropylene, tetramethylene, hexamethylene, 3-oxapentylene, 2-hydroxytrimethylene), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (for example, cyclopropylene, cyclopentynylene, cyclohexylene), substituted or unsubstituted having 2 to 20 carbon atoms Substituted alkenylene groups (eg, ethene, 2-butenylene), alkynylene groups having 2 to 10 carbon atoms (eg, ethyne), substituted or unsubstituted arylene groups having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene, unsubstituted 2) , 5-naphthylene), and the heterocyclic group includes a substituted or unsubstituted heterocyclic group, Fine alkylene group, an alkenylene group, an arylene group, or even those heterocyclic groups are attached (e.g., 2,5-pyridinediyl, 3-phenyl -
2,5-pyridinediyl, 1,3-piperidindiyl,
2,4-morpholinediyl).

In the formula, as the alkyl group represented by R ₄ , a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, isopropyl, n-propyl, n-propyl) Butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl,
2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, methoxymethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (eg, cyclopropyl, cyclopentyl) , Cyclohexyl)
And examples of the aryl group include a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, unsubstituted phenyl and 2-methylphenyl).

Examples of the heterocyclic group include an unsubstituted or an alkyl group, an alkenyl group, an aryl group, or a group further substituted with a heterocyclic group (eg, pyridyl, 3-phenylpyridyl, piperidyl, morpholyl). R ₄ may further have a substituent Y or the like.

Preferred examples of the formula (X-3) are shown below. In the formula, preferably, R ₃ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and R ₄ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms. An unsubstituted alkyl group or 6-1 carbon atoms
0 is a substituted or unsubstituted aryl group, and Z ₂ is S
Or Se, and n2 is 1-2.

More preferably, R ₃ is an alkylene group having 1 to ₄ carbon atoms, R ₄ is an alkyl group having 1 to ₄ carbon atoms, Z ₂ is S, and n 2 is 1.

Next, the formula (X-4) will be described in detail. In the formula, as the alkyl group or alkenyl group represented by R ₅ and R ₆ , a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, isopropyl, n-propyl) , N-butyl, t-
Butyl, 2-pentyl, n-hexyl, n-octyl,
t-octyl, 2-ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, n-butoxypropyl, methoxymethyl), substitution with 3 to 6 carbon atoms or Examples include an unsubstituted cyclic alkyl group (eg, cyclopropyl, cyclopentyl, cyclohexyl) and an alkenyl group having 2 to 10 carbon atoms (eg, allyl, 2-butenyl, 3-pentenyl).
Examples of the aryl group include a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, unsubstituted phenyl and 4-methylphenyl). Examples of the heterocyclic group include an unsubstituted or alkylene group, an alkenylene group, an arylene group, Or those further substituted with a heterocyclic group (eg, pyridyl, 3
-Phenylpyridyl, furyl, piperidyl, morpholyl). In the above formula, R ₅ and R ₆ may further have a substituent Y or the like.

Preferred examples of the formula (X-4) are shown below. In the formula, R ₅ and R ₆ are preferably a substituted or unsubstituted alkyl group having 1 to ₆ carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. More preferably, R ₅ and R ₆ are an aryl group having 6 to 8 carbon atoms.

Next, formulas (X-5a) and (X-5)
b) will be described in detail. In the formula, the group represented by E ₁ includes NH ₂ , NHCH ₃ , NHC ₂ H ₅ , NHPh, N
(CH ₃ ) ₂ , N (Ph) ₂ , NHNHC ₃ H ₇ , NHNH
Ph, OC ₄ H ₉ , OPh, SCH ₃ , etc., and E ₂
Are NH, NCH ₃ , NC ₂ H ₅ , NPh, NHN
C ₃ H _7, NHNPh etc. (here, Ph = phenyl group (hereinafter, the same.)).

Formulas (X-5a) and (X-5b)
Wherein the alkyl group and alkenyl group represented by R ₇ , R ₈ and R ₉ include a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-
Butyl, 2-pentyl, n-hexyl, n-octyl,
t-octyl, 2-ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, n-butoxypropyl, methoxymethyl), substitution with 3 to 6 carbon atoms or Examples include an unsubstituted cyclic alkyl group (eg, cyclopropyl, cyclopentyl, cyclohexyl) and an alkenyl group having 2 to 10 carbon atoms (eg, allyl, 2-butenyl, 3-pentenyl). As the aryl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, unsubstituted phenyl,
-Methylphenyl), and examples of the heterocyclic group include an unsubstituted or alkylene group, an alkenylene group, an arylene group, or a group further substituted with a heterocyclic group (for example,
Pyridyl, 3-phenylpyridyl, furyl, piperidyl, morpholyl). R ₇ , R ₈ and R ₉ may further have a substituent Y or the like.

Preferred examples of formulas (X-5a) and (X-5b) are shown below. In the formula, E ₁ is preferably an alkyl-substituted or unsubstituted amino group or an alkoxy group, E ₂ is an alkyl-substituted or unsubstituted amino linking group, and R ₇ , R ₈ and R _{9 each} have 1 to 1 carbon atoms. 6 is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and Z ₃ is S or S
e.

More preferably, E ₁ is an alkyl-substituted or unsubstituted amino group, E ₂ is an alkyl-substituted or unsubstituted amino linking group, and R ₇ , R ₈ and R
₉ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and Z ₃ is S.

Next, formulas (X-6a) and (X-6)
b) will be described in detail. Where G_TwoAnd represented by J
COOCH_Three, COOC_ThreeH₇, COOC ₆
H₁₃, COOPh, SO_TwoCH_Three, SO_TwoC_FourH₉, COC_Two
H_Five, COPh, SOCH_Three, SOPh, CN, CHO,
NO_TwoAnd the like.

In the formula, as the linking group represented by R ₁₁ , a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene) Methylene, 3-oxapentylene, 2-hydroxytrimethylene), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (eg, cyclopropylene, cyclopentylene, cyclohexylene), substituted with 2 to 20 carbon atoms Alternatively, an unsubstituted alkenylene group (eg, ethene, 2-butenylene), an alkynylene group having 2 to 10 carbon atoms (eg, ethyne), a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene, Substituted 2,5-naphthylene).

Further, the divalent linking group represented by R ₁₁ includes a divalent heterocyclic group, or a divalent heterocyclic group and an alkylene group, alkenylene group, alkynylene group, arylene group, or SO ₂ group. A divalent group bonded to any of them (for example, 2,5-pyridinediyl, 3-phenyl-2,5-pyridinediyl, 2,4-furandiyl, 1,3-piperidinediyl, 2,4-morpholinediyl) Is mentioned.
In the formula, R ₁₁ may further have a substituent Y or the like.

Preferred examples of formulas (X-6a) and (X-6b) are shown below. In the formula, preferably, G ₂ and J are carboxylic esters or carbonyls having 2 to 6 carbon atoms, and R ₁₁ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms or substituted with 6 to 10 carbon atoms. Alternatively, it is an unsubstituted arylene group.

More preferably, G ₂ and J are carboxylic acid esters having 2 to 4 carbon atoms, and R ₁₁ is a carboxylic acid ester having 1 carbon atom.
A substituted or unsubstituted alkylene group having 4 to 4 carbon atoms or a substituted or unsubstituted arylene group having 6 to 8 carbon atoms.

The preferred general formula of the silver halide adsorbing group represented by X is (X-1)>(X-2a)> (X-2
b)>(X-3)>(X-5a)>(X-5b)> (X
-4)>(X-6a)> (X-6b).

Next, the light absorbing group represented by X in the general formula (I) will be described in detail. In the general formula (I), examples of the light absorbing group represented by X include the following. General formula (X-7)

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In the formula, Z ₄ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and L ₂ , L ₃ , L ₄
And L ₅ represents a methine group. p1 represents 0 or 1,
n3 represents an integer of 0 to 3. M ₁ represents a charge-balancing counter ion, and m 2 represents 0 to 10 required to neutralize the charge of the molecule.
Represents an integer. An unsaturated carbocycle such as a benzene ring may be condensed with the nitrogen-containing heterocyclic ring formed by Z ₄ .

In the formula, the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₄ includes a thiazolidine nucleus, a thiazole nucleus, a benzothiazole nucleus, an oxazoline nucleus, an oxazole nucleus,
Benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine),
Imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxalin nucleus , Oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus and the like. The 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₄ may have the substituent Y described above.

In the formula, L ₂ , L ₃ , L ₄ and L ₅ each represent an independent methine group. The methine groups represented by L ₂ , L ₃ , L ₄ and L ₅ may have a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms (for example, methyl , Ethyl, 2-carboxyethyl), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms (eg, phenyl, o-carboxyphenyl), and a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms (eg, N, A monovalent group obtained by removing one hydrogen atom from N-diethylbarbituric acid), a halogen atom (eg, chlorine, bromine, fluorine, iodine), an alkoxy group having 1 to 15 carbon atoms (eg, methoxy, ethoxy) An alkylthio group having 1 to 15 carbon atoms (eg, methylthio, ethylthio), an arylthio group having 6 to 20 carbon atoms (eg, phenylthio), an amino group having 0 to 15 carbon atoms (eg, N, N -Diphenylamino, N-methyl-N-phenylamino, N-
Methylpiperazino) and the like. Further, a ring may be formed with another methine group. Alternatively, a ring can be formed with other parts.

In the formula, M ₁ is included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the light absorbing group. Typical cations include hydrogen ions (H ⁺ ), inorganic cations such as alkali metal ions (eg, sodium ion, potassium ion, lithium ion), and ammonium ions (eg, ammonium ion, tetraalkylammonium ion, pyridinium ion). , Ethylpyridinium ion). The anion may be any of an inorganic anion or an organic anion, and may be a halogen anion (for example, a fluorine ion, a chloride ion, an iodine ion), a substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p-toluene ion, -Chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion,
1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picric acid Ions, acetate ions, and trifluoromethanesulfonate ions. Further, an ionic polymer or a light absorbing group having a reverse charge may be used.

In the present invention, for example, a sulfo group is represented by SO ₃ ⁻ and a carboxy group is represented by CO ₂ ⁻ . However, when a counter ion is a hydrogen ion, they may be represented by SO ₃ H and CO ₂ H, respectively. it can. In the formula, m2 represents a number required to balance the charges, and is 0 when a salt is formed in the molecule.

Preferred examples of the formula (X-7) are shown below. In a preferred general formula (X-7), Z ₄ is a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus or a quinoline nucleus, and L ₂ , L ₃ , L ₄ and L ₅ are unsubstituted methine groups. , P1 is 0, and n3 is 1 or 2. More preferably, Z ₄ is a benzoxazole nucleus or a benzothiazole nucleus, and n 3 is 1.
Particularly preferred Z ₄ is a benzothiazole nucleus. In the general formula (I), preferred k is 0 or 1, and more preferably 1.

Specific examples of the X group used in the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0241]

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[0242]

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[0243]

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[0244]

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[0245]

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[0246]

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Next, the linking group represented by L in formula (I) will be described in detail. In the general formula (I), examples of the linking group represented by L include a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, Hexamethylene, 3-oxapentylene, 2-
Hydroxytrimethylene), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (eg, cyclopropylene, cyclopentylene, cyclohexylene), a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (eg, Ethene, 2-butenylene), an alkynylene group having 2 to 10 carbon atoms (eg, ethyne), a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene, unsubstituted 2,5-naphthylene) ), A heterocyclic linking group (eg, 2,6-pyridinediyl), a carbonyl group,
Thiocarbonyl group, imide group, sulfonyl group, divalent sulfonic acid group, ester group, thioester group, divalent amide group, ether group, thioether group, divalent amino group,
Examples include a divalent ureido group, a divalent thioureido group, and a thiosulfonyl group. Further, these linking groups may be linked to each other to form a new linking group. When m is 2 or more, a plurality of Ls may be the same or different.

L may further have the aforementioned substituent Y or the like. Preferable examples of the linking group L include an alkylene group having 1 to 10 carbon atoms linked to an unsubstituted alkylene group having 1 to 10 carbon atoms and an amino group, an amide group, a thioether group, a ureido group or a sulfonyl group. Is an alkylene group having 1 to 6 carbon atoms linked to an unsubstituted alkylene group having 1 to 6 carbon atoms and an amino group, an amide group or a thioether group. In the general formula (I), preferred m
Is 0 or 1, and more preferably 1.

Next, the electron donating group A will be described in detail. A reaction process in which the AB portion is oxidized and fragmented to generate electrons to generate radicals A. The radical A. is further oxidized to generate electrons to increase the sensitivity is described below.

[0250]

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Since A is an electron donating group, the substituent on the aromatic group in any structure is preferably selected so that A has an excess of electrons. For example, when the aromatic ring is not excessive in electrons, an electron-donating group is introduced, and when the aromatic ring is very rich in electrons such as anthracene, an electron-withdrawing group is introduced to increase the oxidation potential. Adjustment is preferred.

Preferred A groups are those having the following general formula: General formulas (A-1), (A-2), (A-3)

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In the general formulas (A-1) and (A-2), R
₁₂ and R ₁₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkylene group or an arylene group, and R ₁₄ represents an alkyl group, COOH, halogen, N (R ₁₅ ) ₂ , OR _{1 5,} SR _15, CHO, CO
R ₁₅ , COOR ₁₅ , CONHR ₁₅ , CON (R ₁₅ ) ₂ ,
SO ₃ R ₁₅ , SO ₂ NHR ₁₅ , SO ₂ NR ₁₅ , SO ₂ R ₁₅ ,
Represents SOR ₁₅ and CSR ₁₅ . Ar ₁ represents an arylene group or a heterocyclic linking group. R ₁₂ and R ₁₃ and R ₁₂ and Ar ₁ may combine to form a ring. Q ₂ represents O, S, Se or Te; m 3 and m 4 represent 0 or 1;
4 represents an integer of 1 to 3. L ₂ is N—R (where R is
Represents a substituted or unsubstituted alkyl group. ), NA
represents r, O, S, Se. The cyclic form formed by the bonding of R ₁₂ and R ₁₃ and the bonding of R ₁₂ and Ar ₁ each represents a 5- to 7-membered heterocyclic group or unsaturated ring. R ₁₅ represents a hydrogen atom, an alkyl group or an aryl group. The cyclic form of formula (A-3) represents a substituted or unsubstituted 5- to 7-membered unsaturated ring or heterocyclic group.

Formulas (A-1), (A-2) and (A
-3) will be described in detail. Wherein R ₁₂ and R ₁₃
The substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-
Butyl, t-butyl, 2-pentyl, n-hexyl, n
-Octyl, t-octyl, 2-ethylhexyl, 2-
Hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, methoxymethyl), and a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (eg, cyclopropyl, cyclopentyl, cyclohexyl). Examples of the aryl group include a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, unsubstituted phenyl and 2-methylphenyl).

Examples of the alkylene group include a substituted or unsubstituted linear or branched alkylene group having 1 to 10 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, methoxyethylene). Examples include substituted or unsubstituted arylene groups represented by Formulas 6 to 12 (for example, unsubstituted phenylene, 2-methylphenylene, and naphthylene).

In the general formulas (A-1) and (A-2), R
_{As the} group represented by ₁₄ , an alkyl group (for example, methyl,
Ethyl, isopropyl, n-propyl, n-butyl, 2
-Pentyl, n-hexyl, n-octyl, 2-ethylhexyl, 2-hydroxyethyl, n-butoxymethyl), a COOH group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom), OH, N (CH ₃ ) ₂ , NP
_{h 2, OCH 3, OPh,} SCH 3, SPh, CHO, C
OCH ₃ , COPh, COOC ₄ H ₉ , COOCH ₃ , CO
NHC ₂ H ₅ , CON (CH ₃ ) ₂ , SO ₃ CH ₃ , SO ₃ C ₃
H ₇ , SO ₂ NHCH ₃ , SO ₂ N (CH ₃ ) ₂ , SO ₂ C ₂ H
₅ , SOCH ₃ , CSPh, and CSCH ₃ .

As Ar ₁ represented by the general formulas (A-1) and (A-2), a substituted or unsubstituted arylene group having 6 to 12 carbon atoms (for example, phenylene, 2-methylphenylene, naphthylene) And a divalent or trivalent group in which one or two hydrogen atoms have been removed from a substituted or unsubstituted heterocyclic group (eg, pyridyl, 3-phenylpyridyl, piperidyl, morpholyl).

As L ₂ represented by the general formula (A-1), NH, NCH ₃ , NC ₄ H ₉ , NC ₃ H ₇ (i), NP
_{h, NPh-CH 3, O} , S, Se, Te and the like.

Examples of the cyclic form of formula (A-3) include an unsaturated 5- to 7-membered carbocyclic ring and a saturated or unsaturated 5- to 7-membered heterocyclic ring (for example, furyl, piperidyl, morpholyl).

R in the general formulas (A-1) and (A-2)
₁₂ , R ₁₃ , R ₁₄ , Ar ₁ , L ₂ and the general formula (A-3)
The above-mentioned substituent Y and the like may further be present on the inner ring.

Formulas (A-1), (A-2) and (A
Preferred examples of -3) are shown below. In the general formulas (A-1) and (A-2), preferably, R ₁₂ and R ₁₃ are a substituted or unsubstituted alkyl group or alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkyl group having 6 to 10 carbon atoms. A substituted aryl group, wherein R ₁₄ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an amino group mono- or disubstituted with an alkyl group having 1 to 4 carbon atoms, a carboxylic acid, a halogen or a carbon atom; A carboxylic acid ester of 1-4, wherein Ar ₁ is a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
Q ₂ is O, S or Se, m3 and m4 is 0 or 1, n4 is 1 to 3, L ₂ is a carbon number 0-3
Is an alkyl-substituted amino group of General formula (A-
In 3), a preferred cyclic form is a 5- to 7-membered saturated or unsaturated heterocyclic ring.

In the general formulas (A-1) and (A-2), more preferably, R ₁₂ and R ₁₃ are a substituted or unsubstituted alkyl or alkylene group having 1 to 4 carbon atoms;
₁₄ is an unsubstituted alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
Is a monoamino-substituted or diamino-substituted alkyl group, Ar ₁ is a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, Q ₂ is O or S, and m 3
And m4 is 0, n4 is 1, L ₂ carbon atoms 0
3 alkyl-substituted amino groups.

In formula (A-3), a more preferred cyclic form is a 5- to 6-membered heterocyclic ring. A group is L group (m = 0
In the case of the group (X)), the moiety bonded to Ar ₁ and R ₁₂ or R ₁₃ .

Specific examples of the group A used in the present invention are shown below, but the compounds used in the present invention are not limited to these.

[0265]

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[0266]

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[0267]

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[0268]

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[0269]

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[0270]

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Next, the group B will be described in detail. When B is a hydrogen atom, it is deprotonated by an intramolecular base after oxidation to generate a radical A.

Preferred groups B are those having a hydrogen atom and the following general formula: General formulas (B-1), (B-2), (B-3)

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The formulas (B-1), (B-2) and (B
In -3), W represents Si, Sn or Ge, R ₁₆ each independently represents an alkyl group, and Ar ₂ each independently represents an aryl group. General formulas (B-2) and (B-3) can be bonded to an adsorptive group X.

The formulas (B-1), (B-2) and (B
-3) will be described in detail. In the formula, as the alkyl group represented by R ₁₆ , a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms (for example, methyl,
Ethyl, isopropyl, n-propyl, n-butyl, t
-Butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, n-butoxyethyl, methoxymethyl), substitution of 6 to 12 carbon atoms or An unsubstituted aryl group (for example, phenyl, 2-methylphenyl) is exemplified.

R in formulas (B-2) and (B-3)
₁₆ and Ar ₂ may further have the aforementioned substituent Y or the like.

Formulas (B-1), (B-2) and (B
Preferred examples of -3) are shown below. In Formulas (B-2) and (B-3), preferably, R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and Ar ₂ is a substituted or unsubstituted alkyl group having 6 to 10 carbon atoms. Is an aryl group of
W is Si or Sn.

In formulas (B-2) and (B-3), more preferably, R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and Ar ₂ is a group having 6 to 8 carbon atoms. It is a substituted or unsubstituted aryl group, and W is Si.
Among the general formulas (B-1), (B-2) and (B-3), the most preferred are COO ⁻ of the general formula (B-1) and Si— (R ₁₆ ) in the general formula (B-2). ₃ ).

In the general formula (I), preferred n is 1. In addition, in general formula (I), when n is 2, two (A-
B) may be the same or different. Examples of the AB group used in the present invention are shown below, but the present invention is not limited thereto.

[0279]

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[0280]

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[0281]

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[0282]

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[0283]

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[0284]

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The counter ions necessary for the charge balance of the compounds AB are sodium ion, potassium ion, triethylammonium ion, diisopropylammonium ion, tetrabutylammonium ion,
And tetramethylguanidinium ion.

A preferred oxidation potential of AB is 0 to 1.5 V
, More preferably 0 to 1.0 V, and still more preferably 0.3 to 1.0 V. The preferred oxidation potential of the radical A. (E2) resulting from the bond cleavage reaction is -0.6 to -2.5 V, more preferably -0.9.
To -2 V, and more preferably -0.9 to -1.6.
V range.

The method for measuring the oxidation potential is as follows. E
1 can be performed by cyclic voltammetry. The electron donor A is dissolved in a solution of acetonitrile / 0.1M or 80% / 20% (vol%) of water containing lithium chlorate. A glassy carbon disk is used for the working electrode, a platinum wire is used for the counter electrode, and a saturated calomel electrode (SCE) is used for the reference electrode. 0.1 V /
Measure at a potential scan rate of seconds. The oxidation potential versus SCE is taken at the peak potential of the cyclic voltammetry wave.
The E1 values of these AB compounds are described in EP 93,731.
A1.

The measurement of the oxidation potential of radicals is carried out by excessive electrochemical and pulse radiolysis methods. These are described in J.A. Am. Chem. Soc. , 1988, 110,
132, 1974, 96, 1287, 1974, 9
6,1295.

Specific examples of the compound represented by formula (I) are shown below, but the compounds used in the present invention are not limited to these.

[0290]

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[0291]

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[0292]

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[0293]

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[0294]

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[0295]

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[0296]

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[0297]

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[0298]

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Next, the photographically useful group releasing compound represented by formula (II) will be described in detail. Formula (II) COUP1-D1 (wherein COUP1 represents a coupler residue that releases D1 by a coupling reaction with an oxidized developing agent and generates a water-soluble or alkali-soluble compound.
D1 represents a photographically useful group linked at the coupling position of COUP1 or a precursor thereof. ).

The photographically useful group releasing compound represented by the formula (II) will be described. Specifically, the photographically useful group releasing compound represented by the general formula (II) is represented by the following general formula (IIa) or (IIb). Formula (IIa) COUP1- (TIME) _m -PUG Formula (IIb) COUP1- (TIME) _i -RED-
PUG In the formula, COUP1 reacts with (TIME) _m -PUG or (TIME) _i by a coupling reaction with an oxidized form of the developing agent.
Represents a coupler residue that releases a RED-PUG and generates a water-soluble or alkali-soluble compound, and TIME represents a timing group that cleaves the PUG or RED-PUG after leaving from COUP1 by a coupling reaction; Represents a group capable of cleaving PUG by reacting with an oxidized developing agent after release from COUP1 or TIME, PUG represents a photographically useful group, m represents an integer of 0 to 2, and i represents 0 or 1. . When m is 2, the two TIMEs represent the same or different.

When COUP1 represents a yellow coupler residue, for example, pivaloylacetanilide type, benzoylacetanilide type, malon diester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malonester monoamide type, Benzoxazolylacetamide type, benzimidazolylacetamide type, quinazolin-4-one-2-ylacetoanilide type or cycloalkanoylacetamide type coupler residue.

When COUP1 represents a magenta coupler residue, for example, 5-pyrazolone, pyrazolo [1,5-
a] Benzimidazole type, pyrazolo [1,5-b]
[1,2,4] triazole type, pyrazolo [5,1-
c] [1,2,4] triazole type, imidazo [1,2
-B] pyrazole type, pyrrolo [1, 2-b] [1, 2,
4] Triazole-type, pyrazolo [1,5-b] pyrazole-type or cyanoacetophenone-type coupler residues.

When COUP1 represents a cyan coupler residue, for example, phenol type, naphthol type, pyrrolo [1,
2-b] [1,2,4] triazole type, pyrrolo [2,
1-c] [1,2,4] triazole type or 2,4-
And diphenylimidazole type.

Further, COUP1 may be a coupler residue which does not substantially leave a color image. Examples of this type of coupler residue include indanone type and acetophenone type coupler residues.

A preferred example of COUP1 is represented by the following formula (Cp-
1), (Cp-2), (Cp-3), (Cp-4),
(Cp-5), (Cp-6), (Cp-7), (Cp-
8), (Cp-9), (Cp-10), (Cp-11)
Or a coupler residue represented by (Cp-12). These couplers are preferable because of their high coupling speed.

[0306]

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[0307]

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[0308]

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In the above formula, derived from the coupling position
Free bond indicates the bond position of the coupling-off group.
I forgot. In the above formula, R₅₁, R₅₂, R₅₃, R₅₄, R₅₅,
R₅₆, R₅₇, R₅₈, R₅₉, R ₆₀, R₆₁, R₆₂, R₆₃, R
₆₄, R₆₅And R₆₆Is preferably 10 or less.
Good.

The coupler residue represented by COUP1 is represented by R ₇₁
OCO- group, HOSO ₂ - group, HO- group, R ₇₂ NHCO
- group, or R ₇₂ NHSO ₂ - It is preferred to have at least one substituent group. That is, the formula (Cp-1)
In at least one of R _{51 and} R ₅₂ is a group represented by the formula (C)
In p-2), at least one of R ₅₁ , R ₅₂ or R ₅₃ , and in the formula (Cp-3), at least one of R ₅₄ or R ₅₅ has the formula (Cp-4) or (Cp-5) )), At least one of R _{56 and} R ₅₇ has the formula (Cp
In -6), at least one of R _{58 and} R ₅₉ is
In the formula (Cp-7), at least one of R ₅₉ or R ₆₀ , and in the formula (Cp-8), at least one of R ₆₁ or R ₆₂ is a group represented by the formulas (Cp-9) and (Cp-10)
In formula (Cp-11), at least one R ₆₃ represents a group represented by the formula (Cp-11)
And (Cp-12), R ₆₄ , R ₆₅ or R ₆₆
At least one of R ₇₁ OCO—, HOSO ₂ —,
The substituent preferably has at least one of a HO- group, an R ₇₂ NHCO- group or an R ₇₂ NHSO ₂ -group. R
₇₁ is a hydrogen atom, an alkyl group having 6 or less carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, t-
Butyl) or a phenyl group, and R ₇₂ represents a group represented by R ₇₁ , an R ₇₄ CO— group, an R ₇₄ N (R ₇₅ ) CO— group, an R ₇₃ S
Represents an O ₂ — group or an R ₇₄ N (R ₇₅ ) SO ₂ — group, wherein R ₇₃ is an alkyl group having 6 or less carbon atoms (eg, methyl, ethyl,
Propyl, isopropyl, butyl, t-butyl) or a phenyl group, and R ₇₄ and R ₇₅ each represent a group represented by R _71, which may further have a substituent.

Hereinafter, R _{51 to} R ₆₆ , a, b, d, e, and f will be described in detail. Hereinafter, R ₄₁ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, R ₄₂ represents an aryl group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic hydrocarbon group, Represents an aryl group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . a represents 0 or 1. R ₅₂ and R ₅₃ each have the same meaning as R ₄₃ . In formula (Cp-2), when R ₅₂ is not a hydrogen atom, R ₅₂ and R ₅₁ may combine to form a 5- to 7-membered ring. b represents 0 or 1.

[0313] R ₅₄ is the same meaning as R ₄₁ group, R ₄₁ CON
(R ₄₃ ) -group, R ₄₁ SO ₂ N (R ₄₃ ) -group, R ₄₁ N (R
₄₃ )-, R ₄₁ S-, R ₄₃ O- or R ₄₅ N
(R ₄₃ ) represents a CON (R ₄₄ )-group. R ₅₅ represents a group having the same meaning as R ₄₁ .

R ₅₆ and R ₅₇ are each independently a group having the same meaning as the R ₄₃ group, an R ₄₁ S-group, an R ₄₃ O-group, an R ₄₁ CON (R
₄₃ ) -group, R ₄₁ OCON (R ₄₃ ) -group or R ₄₁ SO ₂
Represents an N (R ₄₃ )-group.

R ₅₈ represents a group having the same meaning as R ₄₃ . And R ₅₉ groups of the same meaning as _{R 41, R 41 CON (R} 43) - group, R ₄₁ O
CON (R ₄₃ ) — group, R ₄₁ SO ₂ N (R ₄₃ ) — group, R _{43
N (R 44) CON (R} 45) - group, R ₄₁ O-group, R ₄₁ S-
Represents a group, a halogen atom or an R ₄₁ N (R ₄₃ ) — group.
d represents 0 to 3. When d is plural, plural R _59s represent the same substituent or different substituents. R ₆₀ represents a group having the same meaning as R ₄₃ .

R₆₁Is R₄₃A group having the same meaning as₄₃OSO_Two
-Group, R₄₃N (R₄₄) SO_Two-Group, R ₄₃OCO- group, R
₄₃N (R₄₄) CO—, cyano, R₄₁SO_TwoN
(R₄₃) CO-group, R₄₃CON (R₄₄) CO-group, R₄₃
N (R₄₄) SO_TwoN (R₄₅) CO-group, R₄₃N (R₄₄)
CON (R₄₅) CO-group, R₄₃N (R₄₄) SO_TwoN (R
₄₅) SO_Two-Group, R₄₃N (R₄₄) CON (R₄₅) SO_Two−
Represents a group.

[0317] R₆₂Is R₄₁A group having the same meaning as₄₁CONH
-Group, R₄₁OCONH- group, R₄₁SO_TwoNH- group, R₄₃
N (R₄₄) CONH- group, R₄₃N (R₄₄) SO_TwoNH-
Group, R ₄₃O-group, R₄₁S-group, halogen atom or R₄₁
N (R₄₃)-Represents a group. In the formula (Cp-8), e is 0
And e is an integer of 4 or more, and when e is 2 or more, a plurality of R
₆₂Represents the same or different.

R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃ CON
(R ₄₄₎ - _{group, R 43 N (R 44)} CO- group, R ₄₁ SO ₂ N
(R ₄₃ ) —, R ₄₁ N (R ₄₃ ) SO ₂ —, R ₄₁ SO ₂ —
Represents group, a halogen atom, a nitro group, a cyano group, or R ₄₃ CO- group - group, R _{4 3} OCO- group, R ₄₃ OSO _2.
In the formula (Cp-9), e represents an integer of 0 to 4,
When e is 2 or more, each of a plurality of R ₆₃ represents the same or different. In the formula (Cp-10), f is 0
Represents an integer of 3 to 3, and when f is 2 or more, a plurality of R
₆₃ represents the same or different.

[0319] R₆₄, R₆₅And R₆₆Are each independently R₄₃
A group having the same meaning as the group₄₁S-group, R ₄₃O-group, R₄₁CO
N (R₄₃) -Group, R₄₁SO_TwoN (R₄₃) -Group, R₄₁OC
O-group, R₄₁OSO_Two-Group, R₄₁SO_Two-Group, R₄₁N (R
₄₃) CO-group, R₄₁N (R₄₃) SO_TwoGroup, nitro group
Or a cyano group.

In the above, R ₄₁ , R ₄₃ , R ₄₄ or R ₄₅
Is a saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 10, preferably 1 to 6 carbon atoms. Representative examples include methyl, cyclopropyl, isopropyl, n-butyl, t-butyl, i-butyl, t-butyl.
-Amyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n-decyl, allyl.

The aryl group represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ or R ₄₅ is an aryl group having 6 to 10 carbon atoms, preferably substituted or unsubstituted phenyl, or substituted or unsubstituted phenyl. Naphthyl.

The heterocyclic group represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ or R ₄₅ is a heteroatom having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, which is a nitrogen atom, oxygen atom or sulfur atom. It is a selected, preferably a 3- to 8-membered, substituted or unsubstituted heterocyclic group. Representative examples of the heterocyclic group include 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3,4-thiadiazol-2-yl, 1,2,2
A 4-triazol-2-yl group or 1-indolinyl is exemplified.

The above-mentioned aliphatic hydrocarbon group, aryl group and
When the heterocyclic group has a substituent, a typical substituent
Is a halogen atom, R₄₃O-group, R₄₁S-group, R₄₃CO
N (R ₄₄) -Group, R₄₃N (R₄₄) CO-group, R₄₁OCO
N (R₄₃) -Group, R₄₁SO_TwoN (R₄₃) -Group, R₄₃N
(R₄₄) SO_Two-Group, R₄₁SO_Two-Group, R₄₃An OCO- group,
R ₄₁SO_TwoO-group, R₄₁A group having the same meaning as₄₃N
(R₄₄) -Group, R₄₁CO2- group, R ₄₁OSO_Two-Group, shea
And a nitro group.

Next, R _{51 to} R ₆₆ , a, b, d, e and f
The preferred range will be described. R ₅₁ is preferably an aliphatic hydrocarbon group or an aryl group. a is particularly preferably 1. R ₅₂ and R ₅₅ are preferably an aryl group. R ₅₃ is b
Is preferably an aryl group when b is 0, and a heterocyclic group when b is 0. R ₅₄ is an R ₄₁ CON (R ₄₃ ) — group or R ₄₁ N
(R ₄₃ ) — groups are preferred. R ₅₆ and R ₅₇ are preferably an aliphatic hydrocarbon group, an aryl group, an R ₄₁ O-group or an R ₄₁ S-group. R ₅₈ is preferably an aliphatic hydrocarbon group or an aryl group.

In the formula (Cp-6), R ₅₉ is preferably a chlor atom, an aliphatic hydrocarbon group or an R ₄₁ CON (R ₄₃ ) — group, and d is preferably 1 or 2. R ₆₀ is preferably an aryl group. In the formula (Cp-7), R ₅₉ is R ₄₁ CO
An N (R ₄₃ )-group is preferred, and d is preferably 1.

R₆₁Is R₄₃OSO_Two-Group, R₄₃N (R₄₄)
SO_Two-Group, R₄₃OCO- group, R₄₃N (R₄₄) CO-
Group, cyano group, R₄₁SO_TwoN (R₄₃) CO-group, R₄₃C
ON (R_{Four Four}) CO-group, R₄₃N (R₄₄) SO_TwoN
(R₄₅) CO-group, R₄₃N (R₄₄) CON (R₄₅) CO
-Groups are preferred. In the formula (Cp-8), e is 0 or
1 is preferred, and R₆₂As R₄₁OCON (R₄₃)-
Group, R₄₁CON (R₄₃) -Group or R ₄₁SO_TwoN
(R₄₃)-Group is preferred, and these substitution positions are naphtho.
Position 5 of the ring is preferred.

In formula (Cp-9), R ₆₃ is R ₄₁
CON (R ₄₃ ) -group, R ₄₁ SO ₂ N (R ₄₃ ) -group, R ₄₁
N (R ₄₃ ) SO ₂ — group, R ₄₁ SO ₂ — group, R ₄₁ N (R ₄₃ )
CO-, nitro or cyano groups are preferred. e is 1
Or 2 is preferred.

In the formula (Cp-10), R ₆₃ is R ₄₃ N
(R ₄₄₎ CO- group, R ₄₃ OCO- group or R ₄₃ CO- group. f is preferably 1 or 2.

In the formulas (Cp-11) and (Cp-12), R ₆₄ and R ₆₅ are R ₄₁ OCO— groups, R ₄₁ OSO
_2- , R ₄₁ SO ₂ —, R ₄₄ N (R ₄₃ ) CO—, R ₄₄
N (R ₄₃₎ SO ₂ - is preferably a group or cyano group, R ₄₁
An OCO- group, an R ₄₄ N (R ₄₃ ) CO- group or a cyano group are particularly preferred. R ₆₆ is preferably a group having the same meaning as R ₄₁ .
Each of R _{51 to} R ₆₆ preferably has a total carbon number of 18 or less including a substituent, and more preferably 10 or less.

Next, the photographically useful group represented by PUG will be described. The photographically useful group represented by PUG may be any PUG known in the art.

Examples thereof include a development inhibitor, a bleaching accelerator, a development accelerator, a dye, a bleaching inhibitor, a coupler, a developing agent, a developing auxiliary, a reducing agent, a silver halide solvent, a silver complex forming agent, and a fixing agent. Agents, image toners, stabilizers, hardeners, tanning agents, fogging agents, ultraviolet absorbers, antifoggants, nucleating agents, chemical or spectral sensitizers, desensitizers, and fluorescent brighteners But are not limited to these.

Preferably, PUG is a development inhibitor (eg, US Pat. Nos. 3,227,554 and 3,38).
No. 4,657, No. 3,615,506, No. 3,6
No. 17,291, No. 3,733,201, No. 5,
No. 200,306 and British Patent No. 1450479), bleaching accelerators (e.g. Research D).
isclosure 1973 Item No. 11449 and European Patent No. 1
No. 93389, a bleaching accelerator described in JP-A-61-201.
247, JP-A-4-350848 and JP-A-4-35084
9, 4-350853), development aids (for example, U.S. Pat. No. 4,585,578 and JP-A-10-4).
8787), a development accelerator (for example, a development accelerator described in U.S. Pat. No. 4,390,618 or JP-A-2-56543), a reducing agent (for example, JP-A-63-1094).
39 and 63-128342) and fluorescent color enhancers (for example, U.S. Pat. Nos. 4,774,181 and 5,23).
6,804), and the pKa of the conjugate acid of PUG is preferably 13 or less, more preferably 11 or less.

PUG is more preferably a development inhibitor or a bleaching accelerator. Preferred development inhibitors are mercaptotetrazole derivatives, mercaptotriazole derivatives, mercaptothiadiazole derivatives, mercaptooxadiazole derivatives, mercaptoimidazole derivatives,
Mercaptobenzimidazole derivatives, mercaptobenzthiazole derivatives, mercaptobenzoxazole derivatives, tetrazole derivatives, 1,2,3-triazole derivatives, 1,2,4-triazole derivatives or benzotriazole derivatives. More preferred development inhibitors are represented by the following general formulas DI-1 to DI-6.

[0334]

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In the formula, R ₃₁ is a halogen atom, an R ₄₆ O— group,
R ₄₆ S-group, R ₄₇ CON (R ₄₈ ) -group, R ₄₇ N (R ₄₈ )
CO— group, R ₄₆ OCON (R ₄₇ ) — group, R ₄₆ O
₂ (R ₄₇₎ - _{group, R 47 N (R 48)} SO 2 group, R ₄₆ SO ₂ -
Group, R ₄₇ OCO— group, R ₄₇ N (R ₄₈ ) CON (R ₄₉ ) —
Group, R ₄₇ CON (R ₄₈ ) SO ₂ — group, R ₄₇ N (R ₄₈ ) C
An ON (R ₄₉ ) SO ₂ — group, a group having the same meaning as R ₄₆ , R ₄₇ N
(R ₄₈₎ - group, R ₄₆ CO ₂ - group, R ₄₇ OSO ₂ - group, a cyano group or a nitro group.

R ₄₆ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, and R ₄₇ , R ₄₈ and R ₄₉ each represent an aliphatic hydrocarbon group, an aryl group, a heterocyclic group or a hydrogen atom. The aliphatic hydrocarbon group represented by R ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ is a saturated or unsaturated, linear or cyclic, linear or branched, having 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms.
It is a substituted or unsubstituted aliphatic hydrocarbon group. Representative examples include methyl, cyclopropyl, isopropyl,
n-butyl, t-butyl, i-butyl, t-amyl, n
-Hexyl, cyclohexyl, 2-ethylhexyl, n
Octyl, 1,1,3,3-tetramethylbutyl, n
-Decyl, allyl, ethynyl.

The aryl group represented by R ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ is an aryl group having 6 to 32 carbon atoms, preferably substituted or unsubstituted phenyl or substituted or unsubstituted naphthyl. .

The heterocyclic group represented by R ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ is a heteroatom having 1 to 32, preferably 1 to 20 carbon atoms selected from a nitrogen atom, an oxygen atom or a sulfur atom. Preferred is a substituted or unsubstituted 3- to 8-membered heterocyclic group. Representative examples of the heterocyclic group include 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl,
1,3,4-thiadiazol-2-yl, 1,2,4-
Examples include a triazol-2-yl group or 1-indolinyl.

R ₃₂ represents a group having the same meaning as R ₄₆ . k is 1
G represents 0 or 1, and h represents 1 or 2. V represents an oxygen atom, a sulfur atom or -N ( _R46 )-. R ₃₁ and R ₃₂ may further have a substituent.

Preferred bleaching accelerators are shown below.

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Next, the group represented by TIME will be described. The group represented by TIME may be any linking group capable of cleaving PUG or RED-PUG after cleavage from COUP1 during development processing. For example, U.S. Pat.Nos. 4,146,396, 4,652,516 or 4,698,29
Group utilizing the cleavage reaction of hemiacetal described in No. 7, U.S. Patent Nos. 4,248,962, 4,847,185 or 4,
No. 857,440, a timing group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction described in U.S. Pat.
No. 323 or 4,421,845, a timing group that causes a cleavage reaction using an electron transfer reaction described in No. 4,421,845, etc., a group that causes a cleavage reaction using a hydrolysis reaction of an imino ketal described in U.S. Pat.No.4,546,073, And groups capable of inducing a cleavage reaction by utilizing an ester hydrolysis reaction described in West German Patent Publication No. 2626317. TI
ME has a heteroatom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom, having the general formula (II
Binds to COUP1 in a) or (IIb). Preferred TIMEs include the following general formulas (T-1) and (T-
2) or (T-3).

General formula (T-1) * -W- (X = Y) j-C (R ₂₁ )
R ₂₂ -** General formula (T-2) * -W-CO-** General formula (T-3) * -W-LINK-E1-** In the formula, * represents the general formula (IIa) or (IIb) COU)
Represents the position that binds to P1, where ** is PUG, TIME
(When m is plural) or RED (in the case of general formula (IIa))
W represents an oxygen atom, a sulfur atom or> NR ₂₃ , X and Y each represent a methine or nitrogen atom, j represents 0, 1 or 2, R ₂₁ , R ₂₂
And R ₂₃ each represent a hydrogen atom or a substituent. Here, when X and Y represent substituted methine, the substituent, R
_21, any two substituents linked cyclic structure each of R ₂₂ and R ₂₃ (such as a benzene ring, a pyrazole ring) when forming a or may be any of the case is not formed. In the general formula (T-3), E1 represents an electrophilic group;
LINK represents a linking group that sterically links W and E1 so that they can undergo an intramolecular nucleophilic substitution reaction.

Specific examples of the TIME represented by the general formula (T-1) include the following.

[0344]

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Specific examples of the TIME represented by the general formula (T-2) include the following.

[0346]

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Specific examples of the TIME represented by the general formula (T-3) include the following.

[0348]

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In the general formula (IIa), when m is 2, (T
IME) Specific examples of _m include, for example, the following.

[0350]

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The group represented by RED in formula (IIb) will be described below. RED is COUP1 or TI
It is a group which can be cross-oxidized by an oxidizing substance existing at the time of development, such as an oxidized developing agent, by being cleaved from ME to form RED-PUG. When RED-PUG is oxidized, it becomes P
Any substance that can cleave UG may be used. Examples of RED include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamidophenols,
Hydrazides or sulfonamide naphthols are included. These groups are specifically described in, for example, JP-A-61-2.
No. 30135, No. 62-251746, No. 61-27
No. 8852, U.S. Pat. Nos. 3,364,022 and 3,
379,529, 4,618,571, 3,6
39,417, 4,684,604 or J.Or
g. Chem., vol. 29, p. 588 (1964).

Preferred RED among the above are hydroquinones, 1,4-naphthohydroquinones,
(Or 4) -sulfonamidophenols, pyrogallols or hydrazides. Among them, the redox group having a phenolic hydroxyl group binds to COUP1 or TIME at the oxygen atom of the phenol group.

The compound represented by the general formula (IIa) or (IIb) was added until the silver halide photographic material containing the compound represented by the general formula (IIa) or (IIb) was developed. For the purpose of fixing to a photosensitive layer or a non-photosensitive layer, the compound represented by formula (IIa) or (IIb) preferably has a diffusion-resistant group, and the diffusion-resistant group is preferably TIME or RED. Is particularly preferred.
In this case, the preferred non-diffusible group has 8 to 40 carbon atoms.
Preferably an alkyl group of 12 to 32 or an alkyl group (3 to 20 carbon atoms), an alkoxy group (3 to 20 carbon atoms)
Alternatively, at least one aryl group (C6-20)
Or more carbon atoms having 8 to 40, preferably 12 to 32
Aryl group.

The method for synthesizing the compound represented by formula (IIa) or (IIb) is described in TIME, RED and PUG.
Publicly known patents or literatures cited for the description of JP-A-61-156127 and 58-16095.
No. 4, No. 58-162949, No. 61-249052
No. 63-37350, U.S. Pat. No. 5,026,6
No. 28, European Patent Nos. 443530A2 and 444501A2.

Next, the photographically useful group releasing compound represented by formula (III) will be described. General formula (III) COUP2-CED2 wherein COUP2 represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and C represents C
In a coupling product of OUP2 and an oxidized developing agent, an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and the electrophilic site E results in a 4- to 8-membered ring formation. Represents a divalent linking group or a single bond capable of releasing D2, and may be bonded to COUP2 at the coupling position of COUP2;
It may be bonded to COUP2 at a position other than the coupling position of OUP2. D2 represents a photographically useful group or a precursor thereof.

The coupler residue represented by COUP2 includes yellow coupler residues generally known as photographic couplers (for example, open-chain ketomethine-type coupler residues such as acylacetanilide and malondianilide) and magenta coupler residues. (Eg, coupler residues such as 5-pyrazolone type or pyrazolotriazole type), cyan coupler residues (eg, phenol type, naphthol type or pyrrolotriazole type coupler residues), and US Pat. No. 5,68.
No. 1,689, JP-A-7-128824, JP-A-7-128823, JP-A-6-22252
6, 9-258400, 9-258401, 9-269573, 6
And a coupler residue for forming a yellow, magenta or cyan dye having a novel skeleton described in JP-A-27612 and the like, and other coupler residues (for example, US Pat. Nos. 3,632,345 and 3,928,041 etc.) And a coupler residue that forms a colorless substance by reacting with an oxidized aromatic amine-based developing agent described in U.S. Patent Nos. 1,939,231 and 2,181,944
And the like, a coupler residue which reacts with an oxidized aromatic amine-based developing agent described in the above-mentioned publication to form a black or neutral-colored substance.

The coupler residue represented by COUP2 may be a monomer or a part of a dimer coupler, an oligomer or a polymer coupler, in which case more than one PUG is contained in the coupler. It may be. Preferred examples of COUP2 of the present invention are shown below, but are not limited thereto.

[0358]

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[0359]

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In the formula, * represents the bonding position with C. X ′ is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chloro atom, a bromine atom, an iodine atom), R ₁₃₁ —, R ₁₃₁ O—, and R ₁₃₁ S
-, R _{13 1} OCOO-, R ₁₃₂ COO-, R ₁₃₂ (R ₁₃₃ ) NCOO-, R ₁₃₂ CON (R
₁₃₃ )-, and Y 'represents an oxygen atom, a sulfur atom, R ₁₃₂ N = or R ₁₃₂ ON =. Here, R ₁₃₁ is an aliphatic hydrocarbon group (the term “aliphatic hydrocarbon group” means a saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group, hereinafter synonymous). An aliphatic hydrocarbon group), an aryl group or a heterocyclic group.

The aliphatic hydrocarbon group represented by R ₁₃₁ is preferably an aliphatic hydrocarbon group having 1 to 32 carbon atoms, more preferably 1 to 22 carbon atoms, and specific examples include methyl, ethyl, vinyl, and ethynyl. , Propyl, isopropyl, 2-propenyl, 2-propynyl, butyl, isobutyl, t-butyl,
Examples include t-amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl and octadecyl. Here, the “carbon number”, when the aliphatic hydrocarbon group is a substituted aliphatic hydrocarbon group, refers to the total carbon number including the carbon number of the substituent. Similarly, the group other than the aliphatic hydrocarbon group means the total carbon number including the carbon number of the substituent.

The aryl group represented by R ₁₃₁ is preferably a substituted or unsubstituted aryl group having 6 to 32 carbon atoms, more preferably 6 to 22 carbon atoms, and specific examples include phenyl, tolyl and naphthyl. .

The heterocyclic group represented by R ₁₃₁ is preferably a substituted or unsubstituted heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 22 carbon atoms. Specific examples thereof include 2-furyl and 2-furyl. Pyrrolyl, 2-thienyl, 3-tetrahydrofuranyl, 4-pyridyl, 2-pyrimidinyl, 2- (1,3,4-thiadiazolyl), 2-benzothiazolyl, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzoselena Zolyl, 2-quinolyl, 2-oxazolyl, 2-thiazolyl, 2-selenazolyl, 5-tetrazolyl and 2- (1,3,4 oxadiazolyl), 2-imidazolyl and the like.

Each of R ₁₃₂ and R ₁₃₃ independently represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. The aliphatic hydrocarbon group, aryl group and heterocyclic group represented by R ₁₃₂ and R ₁₃₃ have the same meaning as R ₁₃₁ .

Preferably, X ′ represents a hydrogen atom, an aliphatic hydrocarbon group, an aliphatic hydrocarbonoxy group, an aliphatic hydrocarbon thio group or R ₁₃₂ CON (R ₁₃₃ ) —, and Y ′ represents an oxygen atom. .

Examples of the substituent suitable for the groups described above and below and the “substituent” described below include, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom,
Iodine atom), hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, alkyl group (eg, methyl, ethyl, hexyl), fluoroalkyl group (eg, trifluoromethyl), aryl group (eg, phenyl, tolyl) , Naphthyl), a heterocyclic group (for example, the heterocyclic group described for R ₁₃₁ ), an alkoxy group (for example, methoxy,
Ethoxy, octyloxy), aryloxy groups (eg, phenoxy, naphthyloxy), alkylthio groups (eg, methylthio, butylthio), arylthio groups (eg, phenylthio), amino groups (eg, amino, N-methylamino, N, N-dimethylamino, N-phenylamino), acyl groups (eg, acetyl, propionyl, benzoyl), alkyl or arylsulfonyl groups (eg, methylsulfonyl, phenylsulfonyl), acylamino groups (eg, acetylamino, benzoylamino), Alkyl or arylsulfonylamino group (for example, methanesulfonylamino, benzenesulfonylamino), carbamoyl group (for example, carbamoyl, N-methylaminocarbonyl, N, N-dimethylaminocarbonyl, N-phenylaminocarbyl) Bonyl), sulfamoyl group (eg, sulfamoyl, N-methylaminosulfonyl, N, N-dimethylaminosulfonyl, N-phenylaminosulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, octyloxycarbonyl), aryloxy Carbonyl groups (eg, phenoxycarbonyl, naphthyloxycarbonyl), acyloxy groups (eg, acetyloxy,
Benzoyloxy), an alkoxycarbonyloxy group (for example, methoxycarbonyloxy, ethoxycarbonyloxy), an aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), an alkoxycarbonylamino group (for example, methoxycarbonylamino,
Butoxycarbonylamino), an aryloxycarbonylamino group (eg, phenoxycarbonylamino),
Examples include an aminocarbonyloxy group (eg, N-methylaminocarbonyloxy, N-phenylaminocarbonyloxy) and an aminocarbonylamino group (eg, N-methylaminocarbonylamino, N-phenylaminocarbonylamino).

R ₁₁₁ and R ₁₁₂ are each independently R ₁₃₂ CO-, R
₁₃₁ OCO-, R ₁₃₂ (R ₁₃₃ ) NCO-, R ₁₃₁ SOn-, R ₁₃₂ (R ₁₃₃ ) NSO _2-
Or represents a cyano group. Where R ₁₃₁ , R ₁₃₂ and R ₁₃₃
Has the same meaning as described above, and n represents 1 or 2.

R ₁₁₃ represents the same group as R ₁₃₁ described above. R ₁₁₄
Is R _132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₂ (R ₁₃₃ ) N-, R ₁₃₁ SO ₂ N (R
₁₃₂ )-, R ₁₃₁ S-, R _{1 31} O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ )
NCON (R ₁₃₄ )-, R ₁₃₁ OCO-, R ₁₃₂ (R ₁₃₃ ) NCO- or a cyano group. Here, R ₁₃₁ , R ₁₃₂ and R ₁₃₃ have the same _meanings as described above, and R ₁₃₄ represents the same group as R ₁₃₂ .

R ₁₁₅ and R ₁₁₆ each independently represent a substituent, preferably R _132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ SO ₂ N
(R ₁₃₂ )-, R ₁₃₁ S-, R ₁₃₁ O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R
_{133) NCON (R 134) -} , R 131 OCO-, R 132 (R 133) NCO-, a halogen atom or a cyano group, more preferably a group represented by R _131. Where R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R
₁₃₄ is as defined above.

R ₁₁₇ represents a substituent, p represents an integer of 0 to 4, and q represents an integer of 0 to 3. Preferred substituents of _{R 117, R 131 -, R} 132 CON (R 133) -, R 131 OCON
(R ₁₃₂ )-, R _{1 31} SO ₂ N (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R
_{And 131} S-, R ₁₃₁ O-, and a halogen atom. Where R
₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above. When p and q are 2 or more, each R ₁₁₇ may be the same or different, or adjacent R ₁₁₇ may be bonded to each other to form a ring. Formulas (III-1E), (III-
In a preferred embodiment of 2E), at least one of the ortho positions of the hydroxyl group is R ₁₃₂ CONH-, R ₁₃₁ OCONH- or R ₁₃₂ (R ₁₃₃ ) NCONH-
Is replaced by

R ₁₁₈ represents a substituent, r represents an integer of 0 to 6, and s represents an integer of 0 to 5. Preferred substituents for R ₁₁₈ include R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ OCON (R ₁₃₂ )-, R
₁₃₁ SO ₂ N (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R ₁₃₁ S-, R
_{131 O-, R 132 (R 133} ) NCO-, R 132 (R 133) NSO2-, R 131 OCO-,
Examples include a cyano group or a halogen atom. Where R
₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above. When r and s are 2 or more, each R ₁₁₈ may be the same or different, or adjacent R ₁₁₈ may be combined with each other to form a ring. Formulas (III-1F), (III-2F),
In a preferred embodiment of (III-3F), the ortho position of the hydroxyl group is R ₁₃₂
CONH-, R ₁₃₂ HNCONH-, R ₁₃₂ (R ₁₃₃ ) NSO ₂ -or R ₁₃₂ NHCO-
Is replaced by

R ₁₁₉ represents a substituent.
_132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ SO ₂ N (R ₁₃₂ )-, R ₁₃₁ S-, R
₁₃₁ O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R
₁₃₁ OCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , R ₁₃₂ (R ₁₃₃ ) NCO-, a halogen atom or a cyano group, more preferably a group represented by R ₁₃₁ . Where R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄
Is as defined above.

R ₁₂₀ and R ₁₂₁ each independently represent a substituent, preferably R _132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ SO ₂ N
(R ₁₃₂ )-, R ₁₃₁ S-, R ₁₃₁ O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R
_{133) NCON (R 134) -} , R 132 (R 133) NCO-, R 132 (R 133) NSO 2 -,
R ₁₃₁ OCO-, a halogen atom and a cyano group, more preferably R ₁₃₂ (R ₁₃₃ ) NCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , a trifluoromethyl group, R ₁₃₁ OCO- and a cyano group . Here, R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above.

E is -CO-, -CS-, -COCO-, -SO-, -SO _2- , -P
_{(= O) (R 151)} -, - P (= S) (R 151) - {R 1 51 is an aliphatic hydrocarbon group, an aryl group, an aliphatic hydrocarbon oxy group, an aryloxy group, an aliphatic hydrocarbon Represents a thio group or an arylthio group. Electrophilic group or -C a} such _{(R 15 2) (R 153} ) - {R 152, R 153 are each a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group. Each of the aliphatic hydrocarbon group, aryl group and heterocyclic group has the same _meaning as described for R131. ｝
And preferably -CO-.

C is obtained by an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent in the coupling product of COUP2 and an oxidized developing agent and directly bonded to the coupling position with the electrophilic site E (preferably 4 Represents a divalent linking group or a single bond capable of releasing D2 with ring formation of from 2 to 8 members, more preferably 5 to 7 members, and still more preferably 6 members.

Examples of the linking group represented by C include the following. × − (CO) _n1 − (Y ′) _n2 − {C (R ₁₄₁ ) (R ₁₄₂ )}
_n4 − ×× × − (CO) _n1 − ｛N (R ₁₄₃ )｝ _n3 − ｛C (R ₁₄₁ ) (R
₁₄₂ ) { _n4 − ××× − (Y ′) _n2 − (CO) _n1 − {C (R ₁₄₁ ) (R ₁₄₂ )}
_n4 − ×× × − {N (R ₁₄₃ )} _n3 − (CO) _{n1 −ΔC} (R ₁₄₁ ) (R
₁₄₂ )｝ _n4 − ×× × − (CO) _n1 − {C (R ₁₄₁ ) (R ₁₄₂ )} _n4 − (Y ′)
_n2 − ×× × − (CO) _n1 − ｛C (R ₁₄₁ ) (R ₁₄₂ )｝ _n4 − ｛N (R
₁₄₃ )｝ _n3 − ×× × − (Y ′) _n2 − ××, × − {N (R ₁₄₃ )} _n3 − ××

In the formula, × represents a site binding to COUP2, xx represents a site binding to E, Y ′ represents an oxygen atom or a sulfur atom, and R ₁₄₁ , R ₁₄₂ and R ₁₄₃ are each hydrogen. An atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group (each of the aliphatic hydrocarbon group, aryl group, and heterocyclic group has the same _meaning as described for R ₁₃₁ );
Each of R ₁₄₁ , R ₁₄₂ and R ₁₄₃ may be bonded to each other or to COUP2 to form a ring.

Each of R ₁₄₁ and R ₁₄₂ is preferably a hydrogen atom or an aliphatic hydrocarbon group, more preferably a hydrogen atom. R ₁₄₃ is preferably a hydrogen atom or an aliphatic hydrocarbon group.

N1 and n3 each represent an integer of 0 to 2;
n2 represents 0 or 1; n4 represents an integer of 1 to 5 (when n3 and n4 represent an integer of 2 or more, each of N (R ₁₄₃ ) and C (R ₁₄₁ ) (R ₁₄₂ ) is the same And a coupling product of COUP2 and an oxidized developing agent, and an intramolecular nucleophilic reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and an electrophilic site E. N1 + n2 + n4, n1 + n3 + n4, and n1 + n2 + n4 to form a 4- to 8-membered ring by the substitution reaction.
n2 and n3 are chosen. However, -N ( _R143 )-
When R is directly bonded to E, R ₁₄₃ is preferably not a hydrogen atom. When the linking group C is linked at the coupling position of COUP2, the portion directly linked to COUP2 is-
It cannot be Y'-.

The coupling position between COUP2 and the linking group C was determined after the coupling reaction between the coupler and the oxidized developing agent.
By an intramolecular nucleophilic substitution reaction between the developing agent-derived nitrogen atom and the electrophilic site E in the coupling product (preferably 4 to 8 members, more preferably 5 to 7 members, and still more preferably 6 members) Any method can be used as long as D2 can be released with ring formation, but C2 is preferably used.
OUP2 is at or near the coupling position (the atom next to the coupling position or the atom next to it).

The present invention when the linking group C is bonded to 1) the coupling position, 2) the atom adjacent to the coupling position and 3) the adjacent atom adjacent to the coupling position of the coupler residue represented by COUP2. And the coupler of the present invention and A
The reaction of an aromatic amine-based developing agent represented by rNH ₂ with an oxidized form (Ar ′ = NH) can be represented by the following formula.

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Formula (III-1) wherein COUP2 is preferably (III-1A), (III-1B), (III
-1C), (III-1D), (III-1E), (III-1
F) or (III-1G). Preferred examples of C for｝ include the following: × —CO—C (R ₁₄₁ ) (R ₁₄₂ ) —C (R ₁₄₁ ) (R ₁₄₂ ) —
XX, X-C ( _R141 ) ( _R142 ) -C ( _R141 ) ( _R142 ) -XX, X-C ( _R141 ) ( _R142 ) -C ( _R141 ) ( _R142 )- C (R
₁₄₁ ) ( _R142 ) -xx, x-C ( _R141 ) ( _R142 ) -N ( _R143 ) -xx, x-C ( _R141 ) ( _R142 ) -C ( _R141 ) (R ₁₄₂ ) -O-x
×, × −C (R ₁₄₁ ) (R ₁₄₂ ) −C (R ₁₄₁ ) (R ₁₄₂ ) −S− ×
×, × -C (R ₁₄₁ ) (R ₁₄₂ ) -C (R ₁₄₁ ) (R ₁₄₂ ) -N (R
₁₄₃ ) -xx, more preferably, -C ( _R141 ) ( _R142 ) -N ( _R143 ) -xx, -C ( _R141 ) ( _R142 ) -C ( _R141 ) (R ₁₄₂ ) -O-x
×, × -C (R ₁₄₁ ) (R ₁₄₂ ) -C (R ₁₄₁ ) (R ₁₄₂ ) -N (R
₁₄₃ ) -xx.

In the formula, X, XX, R ₁₄₁ , R ₁₄₂ and R ₁₄₃ have the same _meanings as described above (two or more -C in one linking group)
_{(R 141) (R 142)} - or each of R ₁₄₁ and R _{1 42} be different even in the same time it is present. ).

Formula (III-2) wherein COUP2 is preferably (III-2A), (III-2B),
(III-2C), (III-2D), (III-2E), (III
-2F) or (III-2G). Preferred examples of C for｝ include the following: x-C (R ₁₄₁ ) (R ₁₄₂ ) -xx, x-C (R ₁₄₁ ) (R ₁₄₂ ) -C (R ₁₄₁ ) ( _R142 ) -xx, x-O-xx, x-S-xx, x-N ( _R143 ) -x
×, × -C (R ₁₄₁ ) (R ₁₄₂ ) -O-xx, × -C (R ₁₄₁ ) (R ₁₄₂ ) -S-xx, × -C (R ₁₄₁ ) (R ₁₄₂ ) -N ( _R143 ) -xx, more preferably, -O-xx, -N ( _R143 ) -xx, -C ( _R141 ) ( _R142 ) -O-xx, -C (R ₁₄₁ ) ( _R142 ) -N ( _R143 ) -xx.

In the formula, X, XX, R ₁₄₁ , R ₁₄₂ and R ₁₄₃ have the same _meanings as described above (two or more -C in one linking group)
_{(R 141) (R 142)} - or each of R ₁₄₁ and R _{1 42} be different even in the same time it is present. ).

Formula (III-3) Here, preferably, COUP2 is represented by (III-3F). For｝, preferred C is x-C (R ₁₄₁ ) (R ₁₄₂ ) -xx, x-O-xx, x-S
-Xx, x-N ( _R143 ) -xx, more preferably x-O
-Xx, x-N ( _R143 ) -xx, x-N
( _R143 ) -xx is particularly preferred. Where x, xx, R
₁₄₁ , R ₁₄₂ and R ₁₄₃ are as defined above.

D2 represents a photographically useful group or a precursor thereof. A preferred embodiment of D2 is represented by the following general formula (III-B). #-(T) _k -PUG (III-B) wherein # represents a site linked to E, T represents a timing group capable of releasing PUG after being released from E, and k represents 0 to The integer of 2 preferably represents 0 or 1, and PUG represents a photographically useful group.

As the timing group represented by T, for example, US Pat. Nos. 4,146,396, 4,652,516 and 4,698,29
Utilizing the hemiacetal cleavage reaction described in No. 7
UG releasing group, JP-A-9-114058, U.S. Pat.
No. 962, 5,719,017 or 5,709,987, etc., a group which releases PUG using an intramolecular ring closure reaction described in
39727, JP-A-57-136640, JP-A-57-154234, JP-A-4
-261530, 4-2-1246, 6-324439, 9-114058
No. 4,409,323 or U.S. Pat.No.4,421,845, which releases a PUG by electron transfer via π electrons, JP-A-57-179842, JP-A-4-61530, JP-A-5-31332.
No. 2, etc., which generates carbon dioxide and releases PUG, U.S. Pat. Examples of the group include a group that releases PUG by a reaction, and a group that releases PUG by utilizing a reaction with sulfite ion described in European Patent No. 5,720,843.

Preferred examples of the timing group represented by T in the present invention include, but are not limited to, the following timing groups.

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In the formula, # represents a site binding to the electrophilic site E or ##, and ## represents a position binding to PUG or #. Z represents an oxygen atom or a sulfur atom, preferably an oxygen atom. R ₁₆₁ represents a substituent, preferably R
_131- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ SO ₂ N (R ₁₃₂ )-, R ₁₃₁ S-, R
₁₃₁ O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R
₁₃₂ (R ₁₃₃ ) NCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , R ₁₃₁ OCO-, a halogen atom, a nitro group and a cyano group. Where R ₁₃₁ ,
R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above. R ₁₆₁
It may combine with any of R ₁₆₂ , R ₁₆₃ and R ₁₆₄ to form a ring. n1 represents the integer of 0-4. When n1 represents an integer of 2 or more, each R ₁₆₁ may be the same or different, and R ₁₆₁ may combine with each other to form a ring.

R ₁₆₂ , R ₁₆₃ and R ₁₆₄ represent the same groups as R _132, and n2 represents 0 or 1. R ₁₆₂ and R ₁₆₃ may combine to form a spiro ring. R ₁₆₂ and R ₁₆₃ are preferably a hydrogen atom or (C 1-20, preferably 1-10)
It is an aliphatic hydrocarbon group, more preferably a hydrogen atom. R ₁₆₄ is preferably (C 1-20, preferably 1-C
10) aliphatic hydrocarbon groups or aryl groups (of 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms). R ₁₆₅ is R _132- , R ₁₃₂ (R
₁₃₃ ) NCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , R ₁₃₁ OCO-, and R ₁₃₂ CO-. Here, R ₁₃₁ , R ₁₃₂ and R ₁₃₃ are as defined above. R ₁₆₅ preferably represents R ₁₃₂ , and more preferably represents an aryl group having 6 to 20 carbon atoms. The photographically useful group represented by PUG has the same meaning as described above.

A preferred embodiment of the coupler of the present invention is represented by the above formula (III-2) or (III-3),
(III-3) is more preferable (in the general formulas (III-2) and (III-3), C, E, D2 and their preferred ranges are the same as those described above).

A more preferred embodiment of the formula (III-3) is represented by the following formula (III-3a), more preferably the following formula (III-3b), and particularly preferably the formula (III-3b)
-3c). The structure of the cyclized compound obtained by the reaction of the general formula (III-3c) with the oxidized form of the developing agent represented by ArNH ₂ (Ar ′ = NH) can be represented by the general formula (III-C). it can.

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In the formula, Q ₁ and Q ₂ are each a non-metallic atomic group necessary to form a 5- or 6-membered ring and to cause a coupling reaction with an oxidized developing agent at the base atom of X ′. X ′, T, k, PUG, R ₁₁₈ , s, and R ₁₃₂ are as defined above. R ₁₄₄ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, preferably represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, more preferably represents an aliphatic hydrocarbon group (each And the aliphatic hydrocarbon group, aryl group and heterocyclic group are the same as those described for R _131. ). In the present invention, at least the following groups are not D1 and D2.

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In the formula, *** represents the electrophile represented by E
Indicates the site or the site linked to the timing group represented by T
Then R₇₁Represents a substituted or unsubstituted aliphatic hydrocarbon group.
Then R ₇₂Represents an unsubstituted aliphatic hydrocarbon group.

Specific examples of the coupler used in the light-sensitive material of the present invention are shown below, but it should not be construed that the invention is limited thereto.

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The method of synthesizing the compound represented by the general formula (II) is described, for example, in JP-A-58-162949, JP-A-63-37350, and JP-A-4-35604.
2, JP-A-5-61160, JP-A-6-130594, and US5234800.

An example of the synthesis of the compound represented by the general formula (III) is shown below.

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In a solution of compound 62a (50 g) and o-tetradecyloxyaniline (51.1 g) in N, N-dimethylacetamide (250 ml (hereinafter referred to as “mL”)) was added dicyclohexylcarbodiimide (41.3 g) at 30 ° C. ) Was added dropwise, and the reaction solution was stirred at 50 ° C. for 1 hour, and ethyl acetate (250 mL) was added, and the mixture was cooled to 20 ° C. The reaction solution was filtered by suction. 1N hydrochloric acid solution (250
mL) was added and the mixture was separated. Hexane (100 mL) was added to the organic layer, and the precipitated crystals were collected by filtration, washed with acetonitrile, and dried to obtain Compound 62b (71 g).

Synthesis of Compound 62c A solution of sodium hydroxide (30 g) (150 mL) was added dropwise to a solution of Compound 62b (71 g) in methanol (350 mL) / tetrahydrofuran (70 mL), and the mixture was stirred at 60 ° C. for 1 hour under a nitrogen atmosphere. . After cooling the reaction solution to 20 ° C., concentrated hydrochloric acid was added dropwise until the system became acidic. The precipitated crystals were collected by filtration, washed with water, washed with acetonitrile, and dried to obtain Compound 62c (63 g).

Synthesis of Compound 62d A compound 62c (20 g), a succinimide (5.25 g) and a 37% formalin aqueous solution (4.3 mL) in ethanol (150 mL) were stirred and refluxed for 5 hours. After cooling to 20 ° C, the precipitated crystals were filtered,
Drying yielded compound 62d (16 g).

Synthesis of Compound 62e 60% of a solution of Compound 62d (7 g) in dimethyl sulfoxide (70 mL) was added.
After sodium borohydride (1.32 g) was slowly added at 70 ° C so as not to exceed 70 ° C, the mixture was stirred at that temperature for 15 minutes. The reaction solution was slowly added to 1N aqueous hydrochloric acid (100 mL), and then extracted with ethyl acetate (100 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The origin component was removed with a short path column (developing solvent: ethyl acetate / hexane = 2/1), and then recrystallized from an ethyl acetate / hexane system to obtain compound 62e (3.3 g).

Synthesis of Compound (62) To a solution of bis (trichloromethyl) carbonate (1.98 g) in dichloromethane (80 mL) was added phenoxycarbonylbenzotriazole (4.78 g) and N, N-dimethylaniline (2.42 g) in dichloromethane (100 mL). / Ethyl acetate (200 mL) solution dropwise, 20
Stirred at C for 2 hours (Solution S).

Compound 62e (2.0 g) and dimethylaniline
(0.60 g) tetrahydrofuran (20 mL) / ethyl acetate (20 mL)
After 120 mL of the above solution S was added dropwise to the solution at 10 ° C, the solution was stirred at 20 ° C for 2 hours. The reaction solution was slowly added to 1N aqueous hydrochloric acid (200 mL), and then extracted with ethyl acetate (200 mL). Wash the organic layer with water,
After drying over magnesium sulfate, the mixture was concentrated under reduced pressure. After purifying the column (developing solvent: ethyl acetate / hexane = 1/5), 1.3 g (m.
p. = 138-140 ° C.) was obtained (the compound was identified by elemental analysis, NMR and Mass spectrum).

The surfactant that can be used in the present invention may be any surfactant as long as the critical micelle concentration is 4.0 × 10 ⁻³ mol / L or less, but a surfactant that functions as a dispersant for a high-boiling organic solvent is preferable. . More preferred surfactants used in the present invention are anionic surfactants such as sulfoalkyl or sulfoaryl, nonionic surfactants such as alkyl polyethylene oxide, and betaine surfactants such as sulfoalkylammonium. Further, a polymer surfactant having a functional group bonded to a polymer can also be used. Here, the critical micelle concentration refers to a solution in which the concentration of the surfactant is changed, and SURFACE TENSIOMETER A manufactured by Kyowa Kagaku Co., Ltd.
The surface tension value at each concentration measured using 3 was plotted with the logarithm of the concentration taken as an axis to obtain a concentration-surface tension curve. The concentration that reached the minimum surface tension of this curve was defined as the critical micelle concentration. The critical micelle concentration is the minimum concentration at which the surfactant forms micelles, and the lower this value is, the better the surfactant activity is.

In the present invention, the content of the surfactant in the light-sensitive material is preferably at least 0.01% by mass based on all components contained in the emulsion layer containing the surfactant. Preferably it is 0.02 mass% or more. The content of the surfactant in the light-sensitive material is preferably 5% by mass or less. Only specific examples of the surfactant used in the present invention are shown below. Of course, the present invention is not limited to these.

[0452]

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The high-boiling organic solvent usable in the present invention is preferably a high-boiling organic solvent having a dielectric constant of 7.0 or less, and a high-boiling organic solvent having a boiling point of about 175 ° C. or more at normal pressure, such as phthalic acid esters. Phosphate esters, phosphonate esters, benzoate esters, fatty acid esters, amides, phenols, alcohols, ethers, carboxylic acids, N, N-dialkylanilines, trialkylamines, hydrocarbons , Oligomers or polymers. However, when two or more kinds of high-boiling organic solvents are used as a mixture, if the dielectric constant after mixing is 7.0 or less, this corresponds to the high-boiling organic solvent having a dielectric constant of 7.0 or less.

It is also possible to use these high-boiling organic solvents having a dielectric constant of 7.0 or less in combination with a high-boiling organic solvent having a dielectric constant of more than 7.0. If the dielectric constant is 7.0 or less, it corresponds to a high-boiling organic solvent having a dielectric constant of 7.0 or less. Here, the permittivity refers to a measurement temperature of 25 ° C. and a measurement frequency of 10 k using a transformer bridge method using a TRS-10T type permittivity measurement device manufactured by Ando Electric
It is a relative dielectric constant with respect to vacuum measured in Hz.
The dielectric constant of an organic solvent is related to the square of the dipole moment of the organic solvent molecule, that is, it indicates the magnitude of the polarity of the molecule. Generally, a molecule having a high dielectric constant has a high polarity.

The high boiling organic solvent preferably used in the present invention is a high boiling organic solvent having a dielectric constant of 7.0 or less and represented by the following general formulas [S-1] to [S-8].

[0456]

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[0457]

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[0458]

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[0459]

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[0460]

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In the formula [S-1], R ₁ , R ₂ and R ₃
Each independently represents an aliphatic hydrocarbon group, a cycloaliphatic hydrocarbon group or an aryl group. In the formula [S-2], R ₄ and R ₅ each independently represent an aliphatic hydrocarbon group, a cycloaliphatic hydrocarbon group, or an aryl group, and R ₆ represents a halogen atom (F, Cl, Br, I and the same hereinafter). ), An aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aryloxy group or an aliphatic hydrocarbon oxycarbonyl group,
a represents an integer of 0 to 3. When a is plural, plural R ₆ may be the same or different.

In the formula [S-3], Ar represents an aryl group
And b represents an integer of 1 to 6;₇Is b-valent hydrocarbon
A hydrocarbon group linked to each other by an
Express. In the formula [S-4], R₈Is an aliphatic hydrocarbon
Represents a group or a cyclic aliphatic hydrocarbon group, and c represents 1 to 6
Represents an integer, R₉Is a c-valent hydrocarbon group or ether
Represents a hydrocarbon group linked to each other by a bond. The formula [S−
5], d represents an integer of 2 to 6,_TenIs d-valent
Represents a hydrocarbon group (excluding an aryl group),₁₁
Is an aliphatic hydrocarbon group, cycloaliphatic hydrocarbon group or
Represents a hydroxyl group. In the formula [S-6], R₁₂, R₁₃And
And R₁₄Are each independently an aliphatic hydrocarbon group, a cycloaliphatic
Represents a hydrocarbon group or an aryl group. R₁₂And R₁₃Also
Is R₁₃And R ₁₄May combine with each other to form a ring.

In the formula [S-7], R ₁₅ is an aliphatic hydrocarbon group, a cycloaliphatic hydrocarbon group, an aliphatic hydrocarbon oxycarbonyl group, an aliphatic hydrocarbon sulfonyl group, an arylsulfonyl group, an aryl group or a cyano group. And R ₁₆
Represents a halogen atom, an aliphatic hydrocarbon group, a cycloaliphatic hydrocarbon group, an aryl group, an alkoxy group, or an aryloxy group, and e represents an integer of 0 to 3. When e is plural, plural R ₁₆ may be the same or different.

In the formula [S-8], R ₁₇ and R ₁₈ each independently represent an aliphatic hydrocarbon group, a cycloaliphatic hydrocarbon group or an aryl group, and R ₁₉ represents a halogen atom, an aliphatic hydrocarbon group, a cyclic Represents an aliphatic hydrocarbon group, an aryloxy group, or an aliphatic hydrocarbonoxy group, and f represents an integer of 0 to 4. When f is plural, plural R ₁₉ may be the same or different. In the formulas [S-1] to [S-8], R
_{When 1} to R ₆ , R ₈ , R _{11 to} R ₁₉ are an aliphatic hydrocarbon group or a group containing an aliphatic hydrocarbon group, the alkyl group may be linear or branched, Moreover, even if it contains an unsaturated bond, it may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group,
Examples include an aryloxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, and an epoxy group.

In the formulas [S-1] to [S-8], when R ₁ to R ₆ , R ₈ and R _{11 to} R ₁₉ are a cyclic aliphatic hydrocarbon group or a group containing a cyclic aliphatic hydrocarbon group. The cyclic aliphatic hydrocarbon group may contain an unsaturated bond in the 3- to 8-membered ring, and may have a substituent or a crosslinking group. Examples of the substituent include a halogen atom, a hydroxyl group, an acyl group, an aryl group, an alkoxy group, an epoxy group, and an alkyl group. Examples of the cross-linking group include methylene, ethylene, and isopropylidene.

In formulas [S-1] to [S-8], when R ₁ to R ₆ , R ₈ , R _{11 to} R ₁₉ are an aryl group or a group containing an aryl group, the aryl group is a halogen atom, an alkyl It may be substituted with a substituent such as a group, an aryl group, an alkoxy group, an aryloxy group, or an alkoxycarbonyl group.

In the formulas [S-3], [S-4] and [S-5], when R ₇ , R ₉ or R ₁₀ is a hydrocarbon group, the hydrocarbon group has a cyclic structure (for example, benzene ring, cyclopentane (A cyclohexane ring) or an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyloxy group, an aryl group, an alkoxy group, an aryloxy group, and an epoxy group.

In the formula [S-1], R ₁ , R ₂ and R ₃
Include the total number of carbon atoms (hereinafter abbreviated as C number) 1 to 24
(Preferably 4 to 18) aliphatic hydrocarbon groups (for example, n
-Butyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, n-dodecyl, n-octadecyl, benzyl, 2-chloroethyl, 2,3-dichloropropyl,
-Butoxyethyl, 2-phenoxyethyl), C number 5
24 (preferably 6 to 18) cycloaliphatic hydrocarbon groups (for example, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 4-methylcyclohexyl) or an aryl group having 6 to 24 (preferably 6 to 18) C atoms ( For example, phenyl, cresyl, p-nonylphenyl, xylyl, cumenyl, p-methoxyphenyl, p-methoxycarbonylphenyl) are included.

In the formula [S-2], examples of R ₄ and R ₅ include an aliphatic hydrocarbon group having 1 to 24 (preferably 4 to 18) C (for example, the aliphatic hydrocarbon group mentioned for R ₁ ). The same group as above, ethoxycarbonylmethyl, 1,1-diethylpropyl group, 2-ethyl-1-methylhexyl, cyclohexylmethyl, 1-ethyl-1,5-dimethylhexyl), C number 5 to 24 (preferably 6 to 18) cycloaliphatic hydrocarbon groups (for example, the cycloaliphatic hydrocarbon groups mentioned for R ₁ above, 3,3,5-trimethylcyclohexyl, menthyl, bornyl, 1-methylcyclohexyl)
Or an aryl group having a C number of 6 to 24 (preferably 6 to 18) (for example, the aryl group described above for R ₁ , 4-t
-Butylphenyl, 4-t-octylphenyl, 1,
3,5-trimethylphenyl, 2,4-di-t-butylphenyl, 2,4-di-t-pentylphenyl), and examples of R ₆ include a halogen atom (preferably Cl),
A C 1-18 aliphatic hydrocarbon group (eg, methyl, isopropyl, t-butyl, n-dodecyl); a C 1-18 aliphatic hydrocarbon oxy group (eg, methoxy, n-butoxy, n-octyloxy; Methoxyethoxy, benzyloxy), an aryloxy group having 6 to 18 carbon atoms (for example, phenoxy, p-tolyloxy, 4-methoxyphenoxy 4-tert-butylphenoxy) or an aliphatic hydrocarbonoxycarbonyl group having 2 to 19 carbon atoms (E.g., methoxycarbonyl, n-butoxycarbonyl, 2-ethylhexyloxycarbonyl), and a is 0 to 3 (preferably 0 or 1).

In the formula [S-3], the example of Ar is C number 6
To 24 (preferably 6 to 18) aryl groups (e.g., phenyl, 4-chlorophenyl, 4-methoxyphenyl,
1-naphthyl, 4-n-butoxyphenyl, 1,3,5
-Trimethylphenyl), b is an integer of 1 to 6 (preferably 1 to 3), and examples of R ₇ include a b-valent C number of 2
24 (preferably 2 to 18) of the hydrocarbon group [for example the aliphatic hydrocarbon group mentioned for R _4, cyclic aliphatic hydrocarbon group, an aryl group, - (CH _{2) 2} -,

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[0471]

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[0472]

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[0473]

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[0474]

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Or a b-valent hydrocarbon group bonded to each other by an ether bond having 4 to 24 (preferably 4 to 18) carbon atoms [for example, -CH ₂ CH ₂ OCH ₂ CH _2- , -C
_{H 2 CH 2 (OCH 2 CH} 2) 3 -, - CH 2 CH 2 CH 2 OC
H ₂ CH ₂ CH ₂ -,

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[0476] is included.

In the formula [S-4], examples of R ₈ include an aliphatic hydrocarbon group having 1 to 24 (preferably 1 to 17) C (for example, methyl, n-propyl, 1-hydroxyethyl, 1-hydroxyethyl). Ethylpentyl, n-undecyl, pentadecyl, 8,9-epoxyheptadecyl) or a cyclic aliphatic hydrocarbon group having a C number of 3 to 24 (preferably 6 to 18) (for example, cyclopropyl, cyclohexyl, 4-methylcyclohexyl). And c is 1 to 6 (preferably 1
-3), and examples of R ₉ include a C-valent C number of 2-24.
(Preferably 2 to 18) hydrocarbon groups or c-valent C 4 to C 24 (preferably 4 to 18) hydrocarbon groups bonded to each other by an ether bond (for example, the groups described for R ₇ above). It is.

In the formula [S-5], d is 2 to 6 (preferably 2 or 3), and examples of R ₁₀ include a d-valent hydrocarbon group [for example,

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[0479]

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[0480]

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[0479] Examples of R ₁₁ include C numbers 1 to 24
(Preferably 4 to 18) aliphatic hydrocarbon group, having 5 to 5 carbon atoms
A cycloaliphatic hydrocarbon group having 24 (preferably 6 to 18) or an aryl group having 6 to 24 (preferably 6 to 18) C (for example, the alkyl group, cycloalkyl group, and aryl group described above for R ₄ ); included.

In the formula [S-6], R₁₂Is C number 1
To 24 (preferably 3 to 20) aliphatic hydrocarbon groups [eg
For example, n-propyl, 1-ethylpentyl, n-undesi
, N-pentadecyl, 2,4-di-t-pentylfe
Nonoxymethyl, 4-t-octylphenoxymethyl, 3
-(2,4-di-t-butylphenoxy) propyl, 1
-(2,4-di-t-butylphenoxy) propyl],
Cycloaliphatic carbonization having 5 to 24 (preferably 6 to 18) C atoms
Hydrogen group (for example, cyclohexyl, 4-methylcyclohexyl)
A) having a C number of 6 to 24 (preferably 6 to 18).
Reel group (for example, the aryl group mentioned above for Ar)
And R₁₃And R₁₄Examples of C numbers 1 to 24 (preferably
Or 1 to 18) aliphatic hydrocarbon groups (e.g., methyl,
Ethyl, isopropyl, n-butyl, n-hexyl, 2
-Ethylhexyl, n-dodecyl), C number 5-18 (preferably
And preferably 6 to 15) cycloaliphatic hydrocarbon groups (for example,
Clopentyl, cyclopropyl) or 6 to 18 carbon atoms
(Preferably 6 to 15) aryl groups (for example, phenyl
, 1-naphthyl, p-tolyl). R₁₃And R
₁₄Are bonded to each other, and together with N, a pyrrolidine ring,
A gin ring or a morpholine ring;₁₂And R₁₃When
May combine with each other to form a pyrrolidone ring.

In the formula [S-7], examples of R ₁₅ include C number 1
To 24 (preferably 1 to 18) aliphatic hydrocarbon groups (e.g., methyl, isopropyl, t-butyl, t-pentyl, t-hexyl, t-octyl, 2-butyl, 2-hexyl, 2-octyl, -Dodecyl, 2-hexadecyl, t-pentadecyl), C number 3-18 (preferably 5
To 12) a cyclic aliphatic hydrocarbon group (for example, cyclopentyl or cyclohexyl), having 2 to 24 C atoms (preferably 5
To 17) aliphatic hydrocarbon oxycarbonyl groups (for example, n-butoxycarbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl), and a C number of 1
To 24 (preferably 1 to 18) aliphatic hydrocarbon sulfonyl groups (e.g., methylsulfonyl, n-butylsulfonyl, n-dodecylsulfonyl), and arylsulfonyl groups having 6 to 30 (preferably 6 to 24) C atoms ( For example, p-
Tolylsulfonyl, p-dodecylphenylsulfonyl,
p-hexadecyloxyphenylsulfonyl), C number 6
To 32 (preferably 6 to 24) aryl group (e.g. phenyl, p- tolyl) or contains a cyano group, R ₁₆ is a halogen atom (preferably Cl), C the number 1 to 24 (preferably 1 to 18) An aliphatic hydrocarbon group (for example, the aforementioned R ₁₅
Aliphatic hydrocarbon groups mentioned above), cyclic aliphatic hydrocarbon groups having 3 to 18 (preferably 5 to 17) C atoms (e.g., cyclopentyl, cyclohexyl), and aryl having 6 to 32 (preferably 6 to 24) C atoms Groups (eg phenyl, p
-Tolyl), an aliphatic hydrocarbonoxy group having 1 to 24 (preferably 1 to 18) C atoms (for example, methoxy, n-butoxy, 2-ethylhexyloxy, benzyloxy, n-
Dodecyloxy, n-hexadecyloxy) or an aryloxy group having a C number of 6 to 32 (preferably 6 to 24) (for example, phenoxy, pt-butylphenoxy, p-
t-octylphenoxy, m-pentadecylphenoxy, p-dodecyloxyphenoxy) and e is 0
To 3 (preferably 1 or 2).

In the formula [S-8], R₁₇And R₁₈Is before
Note R₁₃And R₁₄Is the same as ₁₉Is R₁₆Same as
It is. f is an integer of 0 to 4 (preferably 0 to 2)
You.

Among the high-boiling organic solvents represented by the general formulas [S-1] to [S-8], the general formula [S-1] (R ₁ ,
R ₂ and R ₃ are preferably alkyl groups), [S-2], [S
-3] (b is preferably 1), [S-4], [S-5]
And high-boiling organic solvents represented by [S-7] are particularly preferable, and high-boiling organic solvents represented by general formulas [S-1], [S-2], [S-4] and [S-5] are preferable. Most preferred. Hereinafter, specific examples of the high boiling point organic solvent used in the present invention will be shown.

[0486]

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[0487]

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[0488]

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[0489]

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[0490]

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[0490]

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[0492]

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[0493]

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[0494]

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[0495]

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[0496]

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[0497]

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[0498]

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[0499]

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[0500]

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[0501]

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[0502]

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[0503]

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[0504]

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[0505]

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[0506]

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[0507]

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[0508]

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[0509]

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[0510]

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[0511]

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[0512]

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[0513]

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[0514]

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[0515]

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[0516]

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[0517]

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[0518]

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[0519]

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[0520]

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[0521]

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[0522]

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These high-boiling organic solvents may be used alone or in combination of two or more [eg, di (2-ethylhexyl)].
Phthalate and trioctyl phosphate, di (2-ethylhexyl) sebacate and triisononyl phosphate, dibutyl phthalate and di (2-ethylhexyl) adipate]. When two or more high-boiling organic solvents are used as a mixture, the dielectric constant after mixing is preferably 7.0 or less.

Examples of other high-boiling organic solvents used in the present invention and / or methods for synthesizing these high-boiling organic solvents are described, for example, in US Pat. No. 2,322,027.
No. 2,533,514, No. 2,772,16
No. 3, No. 2,835,579, No. 3,594,1
No. 71, No. 3,676,137, No. 3,689,
No. 271, No. 3,700,454, No. 3,74
No. 8,141, No. 3,764,336, No. 3,7
No. 65,897, No. 3,912,515, No. 3,
936,303, 4,004,929, 4,080,209, 4,127,413, 4,193,802, 4,207,393,
Nos. 4,220,711 and 4,239,851
No. 4,278,757, No. 4,353,97
No. 9, No. 4,363,873, No. 4,430, 4
No. 21, No. 4,464,464, No. 4,483,
No. 918, No. 4,540,657, No. 4,68
No. 4,606, No. 4,728,599, No. 4,7
Nos. 45,049, EP 276,319A, 286,253A, 289,820A, and 3
09,158A, 309,159A, 30
9,160A, JP-A-48-47335, 50-
No. 26530, No. 51-25133, No. 51-260
No. 36, No. 51-277921, No. 51-27922
No. 51-49028, No. 52-46816,
Nos. 53-1520, 53-1521, 53-1
Nos. 5127, 53-146622, 54-106
No. 228, No. 56-64333, No. 56-81836
Nos. 59-204041, 61-84641,
Nos. 62-118345, 62-247364, 63-167357, 63-214744, and 6
Nos. 3-301941 and 64-68745;
-101543 and 1-1024454.

In the present invention, the high boiling point organic solvent is preferably contained as an emulsion (fine dispersion). The average particle size of the emulsion is preferably 50 μm or less, more preferably 10 μm or less, particularly preferably 2 μm or less, and most preferably 0.5 μm or less. In preparing the emulsion, it can be dispersed only by mechanical stirring,
It is also preferred to use surfactants. It is also preferable to prepare the emulsion by adding a polymer such as gelatin to the emulsion.

The content of the high-boiling point organic solvent in the emulsion was% by mass.
(Mass of organic solvent contained in 100 g of emulsion) is preferably 0.05% to 10%, more preferably 0.1% to 10%.
% To 10%, and more preferably 0.2% to 10%.

The general formulas (IV) and (V) will be described in detail. In the general formula (IV), Q represents an N or P atom. Ra1, Ra2, Ra3, and Ra4 each preferably have 1 carbon atom
Substituted or unsubstituted alkyl (e.g., methyl, butyl, hexyl, dodecyl, hydroxyethyl and trimethylammonioethyl, and C7-C20 such as benzyl, phenethyl and p-chlorobenzyl);
Aryl-substituted alkyl), preferably having 6 to 2 carbon atoms
0 represents a substituted or unsubstituted aryl (for example, phenyl, p-chlorophenyl) or a substituted or unsubstituted heterocyclic ring (for example, thienyl, furyl, pyrrolyl, imidazolyl, pyridyl), and Ra1, Ra2, Ra3, and Ra4 represent Two of these may combine to form a saturated ring (eg, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring), or three of Ra1, Ra2, Ra3, and Ra4 are jointly unsaturated. Ring (for example, pyridine ring, imidazole ring,
(Quinoline ring, isoquinoline ring). Ra
Examples of the substituted alkyl of 1, Ra2, Ra3 and Ra4 may have a quaternary ammonium salt, a quaternary pyridinium salt or a quaternary phosphonium salt as a substituent.

Although Y represents an anionic group, Y is not present in the case of an inner salt. Examples of Y include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonic acid ion, and oxalate.

In the general formula (V), Ra5, Ra6 and Ra7 are each
Preferably, a substituted or unsubstituted alkyl having 1 to 20 carbons (eg, an aryl-substituted alkyl having 7 to 20 carbons such as methyl, butyl, hexyl, dodecyl and hydroxyethyl, and benzyl, phenethyl and p-chlorobenzyl) ), Substituted or unsubstituted aryl (e.g., phenyl, p-chlorophenyl) having 6 to 20 carbon atoms, and substituted or unsubstituted heterocyclic (e.g., thienyl, furyl, pyrrolyl, imidazolyl, pyridyl). Ra6 and Ra7 may combine two of them to form a saturated ring (eg, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring);
Three of a6 and Ra7 may jointly form an unsaturated ring (for example, a pyridine ring, an imidazole ring, a quinoline ring, an isoquinoline ring).

Ra8 represents alkylene, arylene, —O—,
-S -, - CO ₂ - a representative of those constituted singly or in combination. However, —O—, —S—, and —CO ₂ — are respectively linked adjacent to alkylene or arylene. A substituent such as a hydroxy group may be substituted as a substituent of the alkylene. The alkylene group has 1 to 1 carbon atoms.
0 is preferable, for example, trimethylene, pentamethylene, heptamethylene, nonamethylene, —CH ₂ CH ₂ OC
_{H 2 CH 2 -, - (} CH 2 CH 2 O) 2 -CH 2 CH 2 -, -
_{(CH 2 CH 2 O) 3} -CH 2 CH 2 -, - (CH 2 CH
₂ S) ₃ —CH ₂ CH ₂ —, —CH ₂ CH ₂ COOCH ₂ CH ₂
OCOCH ₂ CH ₂ — can be mentioned. Ra9, Ra1
0 and Ra11 are synonymous with Ra5, Ra6 and Ra7.

The compound of the general formula (IV) of the present invention is preferably a compound of the general formula (V). The compounds represented by the general formulas (IV) and (V) of the present invention are preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof.

The compound of formulas (IV) and (V) of the present invention may be added at any time before or after the time of addition of the sensitizing dye. 50 mol%, more preferably 2 mol% to 25 mol%
In a silver halide emulsion. If the amount of the compound represented by the general formula (IV) or (V) used in the present invention is too large, the amount of the sensitizing dye that can be adsorbed on the emulsion grains may decrease, and the above-mentioned amount is preferable. .

The compounds represented by formulas (IV) and (V) of the present invention can be easily synthesized by a method similar to that described in Quart. Rev., 16,163 (1962). . Representative examples of the compounds represented by formulas (IV) and (V) used in the present invention are shown below, but the present invention is not limited thereto.

[0534]

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[0535]

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[0536]

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Next, the general formulas (VI) to (XI) will be described in detail. The compounds represented by the general formulas (VI) to (XI) of the present invention are all reducing compounds, and their oxidation potentials are measured by the method of Akira Fujishima, "Electrochemical Measurement Method" (pp. 150-208, Gihodo Publishing) and The Chemical Society of Japan “Experimental Chemistry Course” 4th edition (9 volumes
282-344, Maruzen). For example, by the technique of rotating disk voltammetry, specifically, a sample is prepared by mixing methanol: pH 6.5, Britton-Robinson buffer = 1.
0%: Dissolved in a 90% (volume%) solution, and after passing nitrogen gas for 10 minutes, using a rotating disk electrode (RDE) made of glassy carbon as a working electrode, a platinum wire as a counter electrode, and a saturated calomel electrode At 25 ° C., 1
It can be measured at a sweep speed of 2,000 revolutions / minute and 20 mV / sec. Half wave potential (E _1/2 ) from the obtained voltammogram
Can be requested. The reducing compound of the present invention preferably has an oxidation potential in the range of about -0.3 V to about 1.0 V when measured by the above-mentioned measuring method. It is more preferably in the range of about -0.1V to about 0.8V, and particularly preferably in the range of about 0 to about 0.6V.

In the general formula (VI), as the alkyl group, alkenyl group and alkynyl group represented by Rb1 and Rb2, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, Ethyl, isopropyl, n
-Propyl, n-butyl, t-butyl, 2-pentyl,
n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxypropyl, methoxymethyl), having 3 to 6 carbon atoms A substituted or unsubstituted cyclic alkyl group (eg, cyclopropyl, cyclopentyl, cyclohexyl), an alkenyl group having 2 to 10 carbon atoms (eg, allyl, 2-butenyl, 3-pentenyl, 2-cyclohexenyl), 10 alkynyl groups (e.g., propargyl, 3-pentynyl), having 7 to 12 carbon atoms
(E.g., benzyl), and the aryl group includes a substituted or unsubstituted phenyl group having 6 to 12 carbon atoms (e.g., unsubstituted phenyl, 4-methylphenyl).

In the general formula (VI), as the alkyl group, alkenyl group and alkynyl group represented by Rb3 and Rb4, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, Ethyl, isopropyl, n
-Propyl, n-butyl, t-butyl, 2-pentyl,
n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, methoxyethyl, ethoxyethoxyethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (E.g., cyclopropyl, cyclopentyl, cyclohexyl), an alkenyl group having 2 to 10 carbon atoms (e.g., allyl, 2-butenyl, 3-pentenyl, 2-cyclohexenyl), an alkynyl group having 2 to 10 carbon atoms (e.g., propargyl, 3-pentynyl), an aralkyl group having 7 to 12 carbon atoms (e.g., benzyl) and the like. As the aryl group, a substituted or unsubstituted phenyl group having 6 to 12 carbon atoms (e.g., unsubstituted phenyl,
4-methylphenyl), and substituted or unsubstituted naphthyl having 10 to 16 carbon atoms (for example, unsubstituted naphthyl). Also, Rb1 or Rb2 and Rb3 or Rb4 are
They may be linked to form a ring.

In the general formula (VI), the alkyl group, alkenyl group and alkynyl group represented by Rb5 have 1 to 1 carbon atoms.
8 substituted or unsubstituted linear or branched alkyl groups (eg, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, diethylaminoethyl),
A substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (eg, cyclopropyl, cyclopentyl, cyclohexyl), an alkenyl group having 2 to 10 carbon atoms (eg, allyl, 2-butenyl, 3-pentenyl, 2-cyclohexenyl) An alkynyl group having 2 to 10 carbon atoms (e.g., propargyl, 3-pentynyl), an aralkyl group having 7 to 12 carbon atoms (e.g., benzyl), and the like. An unsubstituted phenyl group (eg, unsubstituted phenyl, 4-methylphenyl,
4- (2-hydroxyethyl) -phenyl, 4-sulfophenyl, 4-chlorophenyl, 4-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-carboxyphenyl, 2,5-dimethylphenyl, 4-dimethyl Aminophenyl, 4- (3-carboxypropionylamino) -phenyl, 4-methoxyphenyl, 2-methoxyphenyl, 2,5-dimethoxyphenyl, 2,
4,6-trimethylphenyl) and 10 to 1 carbon atoms
And naphthyl (e.g., unsubstituted naphthyl group and 4-methylnaphthyl), and examples of the heterocyclic group include pyridyl, furyl, imidazolyl, piperidyl and morpholyl.

Further, Rb1 and Rb in the above general formula (VI)
2, Rb3, Rb4 and Rb5 further have a substituent Yy shown below.
May be provided. Examples of the substituent Yy include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, methyl, ethyl, isopropyl, n-propyl, t-butyl), an alkenyl group (eg, allyl, -Butenyl), alkynyl groups (eg, propargyl), aralkyl groups (eg, benzyl), aryl groups (eg, phenyl, naphthyl, 4-
Methylphenyl), heterocyclic groups (eg, pyridyl, furyl, imidazolyl, piperidinyl, morpholyl), alkoxy groups (eg, methoxy, ethoxy, butoxy,
-Ethylhexyloxy, ethoxyethoxy, methoxyethoxy), aryloxy groups (e.g., phenoxy,
2-naphthyloxy), amino group (eg, unsubstituted amino, dimethylamino, diethylamino, dipropylamino, dibutylamino, ethylamino, anilino), acylamino group (eg, acetylamino, benzoylamino), ureido group (eg, Unsubstituted ureido, N-methylureido), urethane group (for example, methoxycarbonylamino, phenoxycarbonylamino), sulfonylamino group (for example, methylsulfonylamino, phenylsulfonylamino), sulfamoyl group (for example, unsubstituted sulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (eg, unsubstituted carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl), sulfonyl group (eg, mesyl Tosyl), a sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), an alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), an acyl group (eg, acetyl, benzoyl, formyl) , Pivaloyl),
Acyloxy groups (eg, acetoxy, benzoyloxy), phosphoric amide groups (eg, N, N-diethylphosphoramide), cyano groups, sulfo groups, thiosulfonic acid groups,
Examples include a sulfinic acid group, a carboxy group, a hydroxy group, a phosphono group, a nitro group, an ammonium group, a phosphonio group, a hydrazino group, and a thiazolino group. When the substituent is 2
When there are two or more, they may be the same or different, and the substituent may further have a substituent. In general formula (VI), Rb
1 and Rb2 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms;
3 and Rb4 are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and Rb5 is a carbon atom. It is preferable that the compound is a substituted or unsubstituted phenyl group of the formulas 6 to 12, and the molecular weight of the compound represented by the general formula (VI) is 350 or less.

Further, in the general formula (VI), Rb1 and Rb2
Is a substituted or unsubstituted linear alkyl group having 1 to 3 carbon atoms, Rb3 and Rb4 are hydrogen atoms, and Rb5 is a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms,
And the molecular weight of the compound represented by the general formula (VI) is 300
It is more preferable that: Furthermore, the general formula (VI)
Among them, it is most preferable that the total number of carbon atoms of Rb1 to Rb5 is 11 or less. Specific examples of the compound represented by the general formula (VI) are shown below, but the present invention is not limited thereto.

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[0544]

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The compound represented by the general formula (VI) can be easily obtained as a commercially available drug or a compound synthesized from a commercially available drug by a known method. As a method for synthesizing the general formula (VI), Journal of Chemical Society (J. Chem. Soc.) 40
8 (1954), U.S. Patent 2,743,279 (1
953), U.S. Patent 2,772,282 (1953).
The compound can be easily synthesized by the method described in (Year) and the like or a method analogous thereto.

The compound represented by the general formula (VI) is preferably added to an adjacent layer or another layer of the emulsion layer before or at the time of coating the coating solution and diffused into the emulsion layer.
It can also be added before, during or after chemical sensitization during the preparation of the emulsion. The compound represented by the general formula (VI) can be added to a light-sensitive layer or a light-insensitive layer.

The preferred addition amount largely depends on the above-mentioned addition method and the kind of compound to be added, but is generally from 5 × 10 ^-6 mol to 0.05 mol, more preferably 1 × 10 ^-6 mol, per mol of light-sensitive silver halide. ^-5 mol to 0.005 mol is used. If the amount is larger than the above-mentioned amount, adverse effects such as an increase in fog are caused, which is not preferable.

The compound represented by the general formula (VI) is preferably added after being dissolved in a water-soluble solvent. The pH may be lowered or raised by an acid or a base, or a surfactant may be present. It may be added as an emulsified dispersion by dissolving it in a high-boiling organic solvent, or may be added as a microcrystalline dispersion by a known dispersion method.

The compound represented by formula (VII) will be described in more detail. First, the hydrazine structure represented by Rb6Rb7N-NRb8Rb9, which is preferably used as Hy, will be described in detail.

Rb6, Rb7, Rb8 and Rb9 represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Further, Rb6 and Rb7, Rb8 and Rb9, Rb6 and Rb8, and Rb7 and Rb9 may be bonded to each other to form a ring, but they do not form an aromatic heterocyclic ring (eg, pyridazine, pyrazole). However, at least one of Rb6, Rb7, Rb8 and Rb9 is-(M) k2- (He
t) k1 is an alkylene group, alkenylene group, alkynylene group, arylene group or divalent heterocyclic residue to be substituted.

As Rb6, Rb7, Rb8 and Rb9, for example, an unsubstituted alkyl, alkenyl or alkynyl group having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl) , Isobutyl, hexyl, octyl, dodecyl, octadecyl, cyclopentyl, cyclopropyl, cyclohexyl, allyl, 2-butenyl), substituted alkyl, alkenyl, and alkynyl groups having 1 to 18 carbon atoms, and more preferably 1 to 8 carbon atoms. Can be

Further, Rb6 and Rb7, Rb8 and Rb9, Rb6 and Rb8, and Rb7 and Rb9 may be bonded to each other to form a ring. However, it does not form an aromatic heterocycle. These rings may be substituted, for example, by the aforementioned substituent Yy.

More preferably, Rb6, Rb7, Rb8 and Rb9 are unsubstituted alkyl, alkenyl, alkynyl, substituted alkyl, alkenyl, alkynyl, and Rb6 and Rb7, Rb8, Rb9, Rb6 and Rb8, and Rb7 and Rb9 are bonded to each other to form an alkylene group containing no atoms other than carbon atoms (for example, an oxygen atom, a sulfur atom, or a nitrogen atom) in the ring.
y) is the case where｝ may be formed.

More preferably, Rb6, Rb7, Rb8 and Rb9 are those in which the carbon atom directly bonded to the hydrazine nitrogen atom is an unsubstituted methylene group. Rb6, Rb7, Rb
8, Rb9 is particularly preferably an unsubstituted alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, butyl), a substituted alkyl group having 1 to 8 carbon atoms {eg, a sulfoalkyl group (eg, 2-sulfoethyl) , 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl), carboxyalkyl groups (eg, carboxymethyl, 2-carboxyethyl), hydroxyalkyl groups (eg, 2-hydroxyethyl)} and Rb6 and Rb7, Rb8 and Rb9, Rb6 And R
This is the case where b8 and Rb7 and Rb9 are bonded to each other by an alkylene chain to form a 5-, 6- and 7-membered ring.

The hydrazine group represented by Rb6Rb7N-NRb8Rb9 has at least one-(M) k2- (Het) k1 substituted. The substitution positions are Rb6, Rb7, Rb8 and Rb9
May be any of

Further, Rb6Rb7NN used in the present invention
The compound represented by Rb8Rb9 has the following general formula (Hy-
Particularly preferred is a compound selected from 1), (Hy-2) and (Hy-3).

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In the formula, Rb39, Rb40, Rb41 and Rb42 each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Also, Rb39 and Rb40, Rb
41 and Rb42 may combine with each other to form a ring.

Z ₄ represents an alkylene group having 4, 5 or 6 carbon atoms. Z ₅ represents an alkylene group having 2 carbon atoms. Z ₆ represents an alkylene group having 1 or 2 carbon atoms. Z ₇ and Z ₈ represent an alkylene group having 3 carbon atoms. L ₃ and L ₄ represent a methine group.

Also, formulas (Hy-1) and (Hy-2)
And (Hy-3) each have at least one-
(M) k2- (Het) k1 is substituted. More preferred are compounds selected from the general formulas (Hy-1) and (Hy-2), and particularly preferred are the compounds represented by the general formula (Hy-
It is a compound selected from 1).

The general formula (Hy-1) will be described below in detail. Rb39 and Rb40 have the same meanings as Rb6, Rb7, Rb8 and Rb9, and the preferred ranges are also the same. Particularly preferred is the case where the alkyl group and Rb39 and Rb40 combine with each other to form an unsubstituted tetramethylene group or pentamethylene group.

Z ₄ represents an alkylene group having 4, 5 or 6 carbon atoms, preferably an alkylene group having 4 or 5 carbon atoms. However, the oxo group is not substituted on the carbon atom directly bonded to the nitrogen atom of hydrazine. This alkylene group may be unsubstituted or substituted. Examples of the substituent include the above-described substituent Yy, and the case where the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group is preferable. Z4 is particularly preferably an unsubstituted tetramethylene group or an unsubstituted pentamethylene group. The hydrazine group represented by the general formula (Hy-1) has at least one
Two-(M) k2- (Het) k1 are substituted. The substitution position may be any of Rb39, Rb40 and Z4. Preferably, Rb39 and Rb40.

Hereinafter, the general formula (Hy-2) will be described in detail. Rb41 and Rb42 have the same meanings as Rb6, Rb7, Rb8 and Rb9, and the preferred ranges are also the same. Particularly preferred is a case where an alkyl group and Rb41 and Rb42 are bonded to each other to form a trimethylene group. Z ₅ has 2 carbon atoms
Represents an alkylene group. Z ₆ has 1 or 2 carbon atoms
Represents an alkylene group. Further, these alkylene groups may be unsubstituted or substituted. As the substituent,
For example, the aforementioned substituent Yy can be mentioned. More preferably, Z5 is an unsubstituted ethylene group. More preferably, Z ₆ is an unsubstituted methylene group or an ethylene group. L ₃ and L ₄ represent a substituted and unsubstituted methine group. Examples of the substituent include the aforementioned substituent Yy, preferably an unsubstituted alkyl group (for example, a methyl group,
t-butyl group). More preferably, it is an unsubstituted methine group. The hydrazine group represented by the general formula (Hy-2) is substituted with at least one-(M) k2- (Het) k1. The substitution position is _{Rb41, Rb42, Z 5, Z} 6, L
It may be any of _3, and L _4. Preferably Rb41 and Rb
42.

The formula (Hy-3) will be described in detail. Z ₇ and Z ₈ each independently represent an alkylene group having 3 carbon atoms. However, the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group. Further, these alkylene groups may be unsubstituted or substituted. As the substituent, for example, the aforementioned substituent Yy
Wherein the carbon atom directly bonded to the nitrogen atom of hydrazine is preferably an unsubstituted methylene group. Particularly preferred as Z ₇ and Z ₈ are unsubstituted trimethylene and a trimethylene group substituted with an unsubstituted alkyl group (for example, 2,2-dimethyltrimethylene). The hydrazine group represented by the general formula (Hy-3) is substituted with at least one-(M) k2- (Het) k1. The substitution position may be either Z ₇ or Z ₈ .

In the general formula (VII), the group represented by Het preferably has any one of the following structures. 5, 6, or 7 represented by the following B having a 5, 6 or 7-membered nitrogen-containing heterocyclic thioxo group represented by A having a 5, 6 or 7-membered heterocyclic quaternary nitrogen atom having two or more hetero atoms Or 7
Membered nitrogen-containing heterocycle 5, 6, or 7-membered nitrogen-containing heterocycle represented by C below 5, 6, or 7-membered nitrogen-containing heterocycle represented by D and E below

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As Ra, Rb6, Rb7 and Rb described above are preferred.
Examples of the alkyl group, alkenyl group and alkynyl group of 8 and Rb9 include those described above.

The nitrogen-containing heterocyclic ring containing Zc as a ring-constituting atom contains at least one nitrogen atom and also contains a hetero atom other than a nitrogen atom (eg, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom). A 5-, 6- or 7-membered heterocyclic ring, which may be an azole ring (for example, imidazole, triazole, tetrazole, oxazole, thiazole, selenazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, thiadiazole, Oxadiazole, benzoselenazole, pyrazole, naphthothiazole, naphthoimidazole, naphthooxazole, azabenzimidazole, purine), pyrimidine ring, triazine ring, azaindene ring (for example, triazaindene, tetrazaindene, pentaaza) Nden), and the like. However, the group represented by Het has at least one-(M) k
2- (Hy) is substituted.

More preferred Het is represented by the following general formulas (Het-a), (Het-b) and (Het-b).
c) Compounds represented by (Het-d) and (Het-e).

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[0571]

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[0572]

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[0573]

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[0574]

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In the formula, Rb43, Rb44, Rb45, Rb46, Rb47 and Rb48 each independently represent a hydrogen atom or a monovalent substituent. Rb49 is an alkyl group, an alkenyl group, an alkynyl group,
Represents an aryl group or a heterocyclic group. X ₁ is a hydrogen atom,
Represents an alkali metal atom, an ammonium group or a blocking group. Y ₁ is an oxygen atom, a sulfur atom,>NH,> N-
(L4) is a _{p3-Rb53, L 3, L} 4 represents a divalent linking group, Rb50, Rb53 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. X ₂ has the same meaning as X ₁ . p2 and p3 are each independently an integer of 0 to 3. Preferably, p2 and p3 are 1.

Z ₉ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. Rb51 represents an alkyl group, an alkenyl group, or an alkynyl group. Rb52 represents a hydrogen atom or an alkyl, alkenyl, or alkynyl group. However, the general formulas (Het-a) to (Het-
e) includes at least one-(M) k2- (H
y) is substituted. However, the general formula (Het-c),
_{(Het-d) X 1,} X 2 are not be replaced by the. Of the general formulas (Het-a) to (Het-e), preferably, the general formulas (Het-a), (Het-c) and (Het-c)
-D), more preferably the general formula (Het-c)
It is.

Next, formulas (Het-a) to (Het-a)
e) will be described in more detail. Rb43, Rb44, R
b45, Rb46, Rb47 and Rb48 each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the aforementioned Rb6, Rb7, Rb8, Rb9 and the substituent Y
y and the like. More preferably, a lower alkyl group (preferably substituted or unsubstituted C 1 -C 1)
Four, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, methoxyethyl, hydroxyethyl, hydroxymethyl, vinyl, allyl), carboxy, alkoxy (preferably substituted or unsubstituted) Having 1 to 5 carbon atoms, for example, methoxy, ethoxy, methoxyethoxy, hydroxyethoxy), an aralkyl group (preferably substituted or unsubstituted having 7 to 12 carbon atoms, for example, benzyl, phenethyl, phenylpropyl), aryl Groups (preferably substituted or unsubstituted ones having 6 to 12 carbon atoms such as phenyl, 4
-Methylphenyl, 4-methoxyphenyl), a heterocyclic group (eg, 2-pyridyl), an alkylthio group (preferably substituted or unsubstituted one having 1 to 10 carbon atoms, eg, methylthio, ethylthio), an arylthio group (preferably substituted Or an unsubstituted group having 6 to 12 carbon atoms such as phenylthio), an aryloxy group (preferably substituted or unsubstituted group having 6 to 12 carbon atoms such as phenoxy), an alkylamino group having 3 or more carbon atoms (eg, , Propylamino, butylamino), arylamino groups (for example,
Anilino), a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom), or the following substituents.

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Here, L ₅ , L ₆ and L ₇ represent a linking group represented by an alkylene group (preferably having 1 to 5 carbon atoms, for example, methylene, propylene, 2-hydroxypropylene). Rb54 and Rb55 may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group (preferably substituted or unsubstituted one having 1 to 10 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl , N-butyl, t-butyl, n-octyl, methoxyethyl, hydroxyethyl, allyl, propargyl), aralkyl group (preferably substituted or unsubstituted one having 7 to 12 carbon atoms, for example, benzyl, phenethyl, vinylbenzyl) ), An aryl group (preferably substituted or unsubstituted one having 6 to 12 carbon atoms, such as phenyl or 4-methylphenyl), or a heterocyclic group (such as 2-pyridyl).

The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group of Rb49 may be unsubstituted or substituted. Preferably Rb6, Rb7, Rb8, Rb9
And the substituents exemplified as Yy.

More preferably, a halogen atom (for example, chlorine atom, bromine atom, fluorine atom), a nitro group, a cyano group, a hydroxy group, an alkoxy group (for example, methoxy),
An aryl group (eg, phenyl), an acylamino group (eg, propionylamino), an alkoxycarbonylamino group (eg, methoxycarbonylamino), a ureido group,
Amino group, heterocyclic group (eg, 2-pyridyl), acyl group (eg, acetyl), sulfamoyl group, sulfonamide group, thioureido group, carbamoyl group, alkylthio group (eg, methylthio), arylthio group (eg, phenylthio, heterocyclic thio group) (For example, 2-benzothiazolylthio), a carboxylic acid group, a sulfo group or a salt thereof, etc. The above ureido group, thioureido group, sulfamoyl group, carbamoyl group and amino group are each unsubstituted. N-alkyl-substituted, N-
Includes those with aryl substitution. Examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent include the aforementioned Rb6, Rb7, Rb8, Rb9 and the substituent Yy.

The alkali metal atoms represented by X ₁ and X ₂ are, for example, a sodium atom and a potassium atom,
The ammonium group is, for example, tetramethylammonium or trimethylbenzylammonium. A blocking group is a group that can be cleaved under alkaline conditions.
For example, it represents acetyl, cyanoethyl, methanesulfonylethyl.

Specific examples of the divalent linking group represented by L ₃ and L ₄ include the following linking groups. These linking groups are preferably used alone, but may be combined. When combined, the total carbon number is preferably from 0 to 20.

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Rb56, Rb57, Rb58, Rb59, Rb6
0, Rb61, Rb62, Rb63, Rb64 and Rb65 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group (preferably substituted or unsubstituted C 1-4
Such as methyl, ethyl, n-butyl, methoxyethyl, hydroxyethyl, allyl) or an aralkyl group (preferably substituted or unsubstituted having 7 to 12 carbon atoms).
Benzyl, phenethyl, phenylpropyl). Rb50 and Rb53 are preferably the same as those described above for Rb49.

As the heterocyclic group having Z ₉ as a ring constituent atom, thiazoliums such as thiazolium, 4-methylthiazolium, benzothiazolium,
-Methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,
1-d] thiazolium}, oxazolium {eg oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium {, imidazoliums} such as 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium,
1-ethyl-5,6-cyclolobenzimidazolium,
1-allyl-5-trifluoromethyl-6-chloro-benzimidazolium), selenazoliums {e.g., benzoselenazolium, 5-chlorobenzoselenazolium, 5
-Methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [1,2-d] selenazolium
And the like. Particularly preferably, thiazoliums (for example, benzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, naphtho [1,
2-d] thiazolium).

Rb51 and Rb52 are preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 18 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or a carbon atom having 2 to 18 carbon atoms. 18 substituted alkyl groups ｛As the substituent, for example, a vinyl group, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine, or bromine), a hydroxy group, an alkoxycarbonyl group having 1 to 8 carbon atoms ( For example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), having 1 to 8 carbon atoms
(E.g., methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group having 6 to 10 carbon atoms (e.g., phenoxy, p-tolyloxy), an acyloxy group having 1 to 3 carbon atoms (e.g., acetyloxy , Propionyloxy), an acyl group having 1 to 8 carbon atoms (eg, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (eg, carbamoyl, N, N
-Dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a sulfamoyl group (for example, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), and having 6 to 1 carbon atoms
And an alkyl group having 1 to 18 carbon atoms で substituted with a zero aryl group (for example, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl). However,
Rb51 is not a hydrogen atom. More preferably, Rb51 is an unsubstituted alkyl group (for example, methyl or ethyl) or an alkenyl group (for example, allyl group).
Is a hydrogen atom and an unsubstituted lower alkyl group (eg, methyl, ethyl).

When necessary to neutralize the ionic charge of the compound represented by the general formula (Het-e), M 1 and m 1 represent the presence or absence of a cation or an anion in the formula. Included in Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion can be specifically either an inorganic or organic anion, such as a halogen anion (eg, a fluoride ion, Chlorine ion, bromine ion, iodine ion, substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion), 1 2,5-naphthalenedisulfonic acid imide, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, Acetate ion, trifluoromethane Sulfonic acid ions. Preferably, they are an ammonium ion, an iodine ion, a bromine ion, and a p-toluenesulfonic acid ion.

The nitrogen-containing heterocycles represented by formulas (Het-a) to (Het-e) are each substituted by at least one-(M) k2- (Hy). The substitution positions are Rb43, Rb44, Rb45, Rb46, Rb47, Rb4
8, Rb49, Rb50, Rb51, and the like Y _1, L ₃ and Z _9.

In the general formula (VII), M represents a divalent linking group comprising an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom.
Preferably, an alkylene group having 1 to 8 carbon atoms (eg, methylene, ethylene, propylene, butylene, pentylene), an arylene group having 6 to 12 carbon atoms (eg, phenylene, naphthylene), an alkenylene group having 2 to 8 carbon atoms ( For example, ethynylene, propenylene), amide group, ester group, sulfamide group, sulfonic ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (R0)-(R0
Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ) Divalent heterocyclic residue (for example, 6-chloro-1,3,5-triazine-
2,4-diyl, pyrimidine-2,4-diyl, quinoxaline-2,3-diyl) and a divalent linking group having 4 to 20 carbon atoms.
More preferred are ureido, ester and amide groups.

In the general formula (VII), k1 and k3 are preferably 1 or 2. More preferably, k1, k2 and k3 are all 1. When k1 or k3 is 2 or more, Hy and Het may be the same or different. Among the compounds represented by the general formula (VII) of the present invention, more preferred compounds are the following general formulas (VII-A), (V
II-B), (VII-C), (VII-D) and (VII-
E).

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Further, a particularly preferred compound in the present invention is represented by the following formula (VII-F).

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In the formula, Ma has the same meaning as M in formula (VII). Zd has the same meaning as Z ₄ in the general formula (Hy-1). Rb
69 represents a monovalent substituent. Rb66 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rb67 and Rb68 each independently represent a hydrogen atom or a monovalent substituent. n1 represents an integer of 0 to 4;
n2 represents 0 or 1. n3 represents an integer of 1 to 6. X ₁ has the same meaning as X ₁ in the general formula (Het-c). Y
_1, L _3, p2 is Y ₁ in formula _{(Het-d), L 3} , p2 and respectively the same. Rb51 has the same meaning as Rb51 in formula (Het-e). When n1 and n3 are 2 or more, R
b69 and C (Rb67) (Rb68) are repeated but need not be identical.

More specifically, Ma is represented by the general formula (VII):
The same is preferable, and a ureide group, an ester group or an amide group is more preferable. Zd is of the general formula similar to Z ₄ of (Hy-1) is preferably used, more preferably an unsubstituted tetramethylene group, pentamethylene group. Rb69 is preferably the same as Rb43. Rb66
Is preferably the same as Rb6, Rb7, Rb8 and Rb9, particularly preferably an unsubstituted alkyl group having 1 to 4 carbon atoms (for example, methyl and ethyl). Rb67 and Rb68
Is preferably the same as Rb43, particularly preferably a hydrogen atom. n1 is preferably 0 or 1.
n2 is preferably 1. n3 is preferably 2
~ 4. Next, typical examples of the compound used in the present invention will be described, but the present invention is not limited thereto.

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[0597]

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[0598]

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[0599]

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The Het of general formula (VII) used in the present invention
U.S. Pat. No. 3,266,897, Belgian Patent No. 671,402, JP-A-60-138548, JP-A-59-68732, JP-A-59-123838,
JP-B-58-9939, JP-A-59-137951
JP-A-57-202531, JP-A-57-164
No. 734, JP-A-57-14836, JP-A-57-1
No. 16340, U.S. Pat. No. 4,418,140, JP-A-58-95728, JP-A-55-79436, O
LS 2,205,029, OLS 1,962,605
No., JP-A-55-59463, and JP-B-48-1825.
7, JP-B-53-28084, JP-A-53-487
No. 23, JP-B-59-52414, JP-A-58-21
No. 7928, JP-B-49-8334, U.S. Pat.
No. 598,602; U.S. Pat. No. 887,009; British Patent No. 965,047; Belgian Patent No. 737809.
No. 3,622,340, JP-A-60-8
No. 7322, JP-A-57-211142, JP-A-58
-158631, JP-A-59-15240, U.S. Pat. No. 3,671,255, JP-B-48-34166,
JP-B-48-322112, JP-A-58-22183
9, JP-B-48-32367, JP-A-60-130
No. 731, JP-A-60-122936, JP-A-60-122
No. 117240, U.S. Pat. No. 3,228,770, JP-B-43-13496, JP-B-43-10256, JP-B-47-8725, JP-B-47-30206, JP-B-47-4417, and JP-B-51 -25340, British Patent 1,165,075, U.S. Patent 3,512,9
No. 82, U.S. Pat. No. 1,472,845, JP-B-39-
No. 22067, JP-B-39-22068, U.S. Pat. No. 3,148,067, U.S. Pat. No. 3,759,901
No. 3,909,268, Japanese Patent Publication No. 50-40
No. 665, Japanese Patent Publication No. 39-2829, U.S. Pat.
8,066, JP-B-45-22190, U.S. Pat. No. 1,399,449, British Patent 1,287,284
No. 3,900,321, U.S. Pat.
5,391, U.S. Pat. No. 3,910,792, British Patent 1,064,805, U.S. Pat. No. 3,544,336
No. 4,003,746, British Patent 1,34
No. 4,525, British Patent No. 972, 211, Japanese Patent Publication No. 43
-4136, U.S. Patent 3,140,178, French Patent 2,015,456, U.S. Patent 3,114,637
, Belgian Patent 681,359, US Patent 3,22
0,839, British Patent 1,290,868, US Patent 3,137,578, US Patent 3,420,670
No. 2,759,908, US Pat. No. 3,62.
2,340, OLS2,501,261, DAS
No. 1,772,424, U.S. Pat. No. 3,157,509
No. 1, French Patent 1,351,234, US Patent 3,63
0,745, French Patent 2,005,204, German Patent 1,447,796, US Patent 3,915,710
No. JP-B-49-8334, British Patent 1,021,1
No. 99, UK Patent 919,061, Japanese Patent Publication No. 46-17
No. 513, U.S. Pat. No. 3,202,512, OLS2.
553,127, JP-A-50-104927, French Patent 1,467,510, U.S. Pat.
No. 6, U.S. Pat. No. 3,503,936, U.S. Pat.
No. 76,638, French Patent 2,093,209, British Patent 1,246,311, US Patent 3,844,78
No. 8, US Pat. No. 3,535,115, British Patent 1,1
No. 61,264, U.S. Pat. No. 3,841,878, U.S. Pat. No. 3,615,616, JP-A-48-39039.
No., UK Patent 1,249,077, JP-B-48-34
No. 166, US Pat. No. 3,671,255, British Patent 1
No. 459160, JP-A-50-6323, British Patent 1,402,819, OLS 2,031,314,
Research Disclosure 13651, US Patent 3,910,791, US Patent 3,954,478
No. 3,813,249, UK Patent 1,38
7,654, JP-A-57-135945, JP-A-5-135
7-96331, JP-A-57-22234, JP-A-59-26731, OLS2,217,153, British Patent 1,394,371, British Patent 1,308,7
77, British Patent 1,389,089, British Patent 1,
No. 347,544, German Patent 1,107,508, U.S. Pat. No. 3,386,831, British Patent 1,129,6
No. 23, JP-A-49-14120, JP-B-46-34
675, JP-A-50-43923, U.S. Pat.
No. 42,481, British Patent 1,269,268, U.S. Pat. No. 3,128,185, U.S. Pat.
No. 1, US Pat. No. 3,396,023, US Pat.
No. 95,827, JP-B-48-38418, JP-A-Showa 4
8-47335, JP-A-50-87028, U.S. Pat. No. 3,236,652, U.S. Pat. No. 3,443,951
No. 3,065,669, U.S. Pat.
2,552, U.S. Patent 3,310,405, U.S. Patent 3,300,312, British Patent 952,162,
UK Patent 952,162, UK Patent 948,442
No., JP-A-49-120628, JP-B-48-353
No. 72, JP-B-47-5315, JP-B-39-187
06, JP-B-43-4941, JP-A-59-345
No. 30, etc., and can be synthesized with reference to these.

Hy in the general formula (VII) of the present invention can be synthesized by various methods. For example, it can be synthesized by a method of alkylating hydrazine. Examples of the alkylation method include substitution alkylation using an alkyl halide and an alkyl sulfonate, reductive alkylation using a carbonyl compound and sodium cyanoborohydride, and hydrogenation after acylation. A reduction method using lithium aluminum and the like are known. For example, SRSandle
r), W. Karo, "Organic
Functional Group Preparations (Or
ganic Fanctional Group Preparation) ", Volume 1, 14
Chapter, pages 434-465 (1968), Academic Press (Ac
ademic Press), EL Crennan (EL Cl)
ennan), etc. Journal of the American Chemical Society
Society, Vol. 112, No. 13, p. 5080 (1990), etc., and can be synthesized by referring to them.

For the bond formation reaction including the amide bond formation reaction and the ester bond formation reaction of the-(M) k2- (Hy) portion, a method known in organic chemistry can be used. That is, a method of linking Het and Hy, a method of linking Het to a Het synthesis raw material and an intermediate, and then synthesizing Het, and conversely, a method of linking a Hy synthesis raw material and an intermediate to a Het portion, and then connecting Hy.
Any method, such as a method of synthesizing the compound, may be used. For the synthesis reactions for these linkages, for example, edited by The Chemical Society of Japan, New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds, Vol. IV, Maruzen, Tokyo (1977), Yoshiro Ogata, Organic Reaction Theory , Maruzen, Tokyo (1962) LFFieser
and M. Fieser, Advanced Organic Chemistry, Maruzen,
You can refer to books on many organic synthesis reactions, such as Tokyo (1962). More specifically, Japanese Patent Application Laid-Open
The compound can be synthesized by the method shown in Examples 1 and 2 of JP-A-135341.

When it is added during the preparation of an emulsion, it can be added at any time during the process. Examples thereof include a step of forming silver halide grains, a step before the start of a desalting step, a step of desalting, Before the start of chemical ripening, a step of chemical ripening, a step before preparation of a finished emulsion and the like can be mentioned. Further, it can be added in plural times during these steps. The compound represented by the general formula (VII) of the present invention is preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. In the case of dissolving in water, a compound whose solubility increases when the pH is increased or decreased may be dissolved by increasing or decreasing the pH, and then added.

The compound represented by the general formula (VII) is preferably used in an emulsion layer, but may be added to a protective layer or an intermediate layer together with the emulsion layer and diffused during coating. The addition time of the compound represented by formula (VII) of the present invention is preferably 1 × 10 ^{−9 to} 5 × 10 ⁻² mol, more preferably 1 mol / mol of silver halide, regardless of before or after the sensitizing dye. Is contained in the silver halide emulsion at a ratio of 1.times.10.sup.- ⁸ to 2.times.10.sup.- ³ mol.

The following formulas (VIII-1) and (VIII-
The compound represented by 2) will be described in detail. In the general formula (VIII-1), the substituent represented by Rb10, Rb11, Rb12 and Rb13 is an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms such as methyl, ethyl, iso- Propyl), an aralkyl group (preferably having 7 to 30, more preferably 7 to 20, for example, phenylmethyl), and an alkenyl group (preferably having 2 to 20, more preferably 2 to 10, for example, allyl). , An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10; for example, methoxy and ethoxy), an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20), and an acylamino group (preferably having A carbon number of 2 to 30, more preferably 2 to 20; for example, acetylamino; a sulfonylamino group (preferably 1 to 30 carbon atoms, more preferably 1 to 20. For example, methanesulfonylamino.), A ureido group (preferably having 1 to carbon atoms)
30, more preferably 1 to 20. For example, methyl ureide. ), An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms such as methoxycarbonylamino), an aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably 7 carbon atoms).
~ 20. For example, a phenyloxycarbonylamino group. ), An aryloxy group (preferably having 6 to 3 carbon atoms)
0, more preferably 6-20. For example, phenyloxy. ), A sulfamoyl group (preferably having 0 to 3 carbon atoms)
0, more preferably 0-20. For example, methylsulfamoyl. ), A carbamoyl group (preferably having 1 to 3 carbon atoms)
0, more preferably 1 to 20. For example, carbamoyl, methylcarbamoyl. ), Mercapto group, alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 2 carbon atoms)
0. For example, methylthio, carboxymethylthio. ), An arylthio group (preferably having 6 to 30, more preferably 6 to 20; for example, phenylthio), a sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 2 carbon atoms).
0. For example, methanesulfonyl. ), A sulfinyl group (preferably having 1 to 30, more preferably 1 to 20; for example, methanesulfinyl), a hydroxy group, a halogen atom (for example, a chlorine atom, a bromine atom, and a fluorine atom), a cyano group, a sulfo group, and a carboxyl group Group, phosphono group, amino group (preferably having 0 to 30 carbon atoms, more preferably 1 to 2 carbon atoms)
0. For example, methylamino. ), Aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 30 carbon atoms)
20. ), An acyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms such as acetyl and benzoyl), an alkoxycarbonyl group (preferably having 2 carbon atoms).
~ 30, more preferably 2-20. For example, methoxycarbonyl. ), An acyloxy group (preferably having 2 to 3 carbon atoms)
0, more preferably 2 to 20. For example, acetoxy. ),
Examples include a nitro group, a hydroxamic acid group, and a heterocyclic group (eg, pyridyl, furyl, thienyl). Further, these substituents may be further substituted.

Preferred substituents represented by Rb10, Rb11, Rb12 and Rb13 are alkyl, alkoxy, hydroxy, halogen, sulfo, carboxyl, acylamino, sulfonylamino,
A ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylthio group, an arylthio group, an amino group and an acyloxy group, more preferably an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxyl group, an acylamino group, and a sulfonyl. Amino group, ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, particularly preferably an alkyl group, a halogen atom, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group. is there.

Of the Rb10, Rb11, Rb12 and Rb13, preferably one or more and three or less are hydrogen atoms, more preferably two or more and three or less are hydrogen atoms. Particularly preferred is the case of three hydrogen atoms. R
When b10 and Rb13 are an alkyl group at the same time, they do not take a substituent having exactly the same carbon number. For example, Rb10 = t-
C ₈ H ₁₇ and Rb 13 = n−C ₁₅ H ₃₁ are possible, but at the same time, neither Rb 10 nor Rb 13 is tC ₈ H ₁₇ . When the substituents are of the same type, the difference between the carbon numbers of the substituents of Rb10 and Rb13 is preferably 5 or more, more preferably 10 or more. Rb11 and Rb12 are the same as Rb10 and Rb13.

Of the compounds represented by the general formula (VIII-1), the compound is preferably the general formula (VIII-1-a), more preferably the general formula (VIII-1-b), and particularly preferably (VIII
-1-c).

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In the formula, Rb31 and Rb34 are represented by the general formula (VI
It has the same meaning as Rb10 and Rb13 in II-1), and the preferred range is also the same.

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In the formula, Rb31 represents R of the general formula (VIII-1)
It has the same meaning as b10, and the preferred range is also the same.

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In the formula, Rb70 is an alkyl group which may have a substituent. As the substituent which the alkyl group may have, those mentioned as the substituent represented by Rb31 can be applied.

In the general formula (VIII-2), Rb14, Rb
Examples of the substituent represented by b15 and Rb16 include R
Substituents which the substituents represented by b10, Rb11, Rb12 and Rb13 may have may be mentioned. Preferred examples of the substituent represented by Rb14 include an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, a sulfo group, a carboxyl group, an acylamino group, a sulfonylamino group,
A ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylthio group, an arylthio group, an amino group, and an acyloxy group, more preferably an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxyl group, an acylamino group, and a sulfonyl group. Amino group, ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, particularly preferably an alkyl group, a halogen atom, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group. is there.

Preferred substituents represented by Rb15 include an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, and an alkylthio group. , Arylthio group, amino group, acyloxy group, more preferably an alkyl group, an alkoxy group, a hydroxy group, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, particularly preferably Alkyl group, acylamino group,
A sulfonylamino group, a ureido group, an alkoxycarbonylamino group, and an aryloxycarbonylamino group.

Preferred substituents represented by Rb16 include an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, a sulfo group, a carboxyl group, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, and an aryloxy group. Carbonylamino group,
Alkylthio group, arylthio group, amino group, acyloxy group, more preferably alkyl group, alkoxy group, halogen atom, sulfo group, carboxyl group, acylamino group, sulfonylamino group, ureido group, alkoxycarbonylamino group, aryloxycarbonyl It is an amino group, particularly preferably an alkyl group.

Z represents a group of nonmetal atoms necessary for forming a 4- to 6-membered ring. Non-metallic atoms are preferably carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, more preferably carbon atoms and oxygen atoms, and particularly preferably carbon atoms. The preferred number of ring members is 5 or 6, more preferably a 6-membered ring. The ring may have a substituent, and examples of the substituent include those described as the substituent represented by Rb14. The substituent is preferably an alkyl group, an alkenyl group or an alkoxy group, and more preferably an alkyl group or an alkenyl group. These substituents may further have a substituent.

Of the compounds represented by the general formula (VIII-2), the compound represented by the general formula (VIII-2-a) is preferable, and the compound represented by the general formula (VIII-2-b) is more preferable. is there.

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In the formula, Rb14, Rb15 and Rb16 have the same meanings as those in formula (VIII-2), and the preferred ranges are also the same. n represents 1 or 2. Rb71 and Rb72 represent an alkyl group, an alkenyl group, and an alkoxy group, respectively.

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In the formula, Rb14, Rb15 and Rb16 have the same meanings as those in formula (VIII-2), and the preferred ranges are also the same. Rb71 represents an alkyl group, an alkenyl group,
Represents an alkoxy group. n is preferably 2. Rb
The alkyl group and alkenyl group represented by 71 and Rb72 may be linear, branched, or cyclic, and are preferably linear or branched. The preferred number of carbon atoms is 1 to 3.
0, more preferably 1-20. Examples of the alkyl group include methyl, ethyl and iso-propyl, and examples of the alkenyl group include allyl. Rb
In the alkoxy group represented by 71 and Rb72, the alkyl portion may be any of linear, branched or cyclic, and Rb71 and Rb72 may form a ring like spirochromans.
It preferably has 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms.
It is 10. For example, methoxy and ethoxy can be mentioned.

In the following, formulas (VIII-1) and (VIII-
Specific examples of the compound represented by 2) are shown below, but it should not be construed that the invention is limited thereto.

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The compounds represented by formulas (VIII-1) and (VIII-2) are described, for example, in US Pat. No. 2,728,659.
No. 2,549,118, No. 2,732,300
Issue, Journal of America Chemical Society
Vol. 111, No. 20, 1989, p. 7932 (Journal
of American Chemical Society, 111, 20, 1989, 793
2), Synthesis, 12, 1995, p. 1549 (S
ynthesis, 12, 1995, 1549), QJ Pharm, Pharmaco
l., 17, 1944, 325; Chem. Pharm, Bull., 14, 1966, 1
052, Chem. Pharm, Bull., 16, 1968, 853 and the like.

Further, the compound represented by the general formula (VIII-1) or (VIII-
The compound represented by 2) is described, for example, in US Pat. No. 2,421,8.
11, 2,421,812, 2,411,967, 2,681,371, J. Amer. Chem. Soc., 65, 1943, 1
276, J. Amer. Chem. Soc., 65, 1943, 1281, J. Ame
r. Chem. Soc., 63, 1941, 1887, J. Amer. Chem. So
c., 107, 24, 1985, 7053; Helv. Chim. Acta., 21, 193
8, 939; Helv. Chim. Acta., 28, 1945, 438; Chem. Be
r., 71, 1938, 2637, J. Org. Chem., 4, 1939, 311,
J. Org. Chem., 6, 1941, 229; J. Chem. Soc., 1938,
1382, Helv. Chim. Acta., 21, 1931, 1234, Tetrahedr
on Lett., 33, 26, 1992, 3795, J. Chem. Soc. Perki
n. Trans. 1, 1981, 1437, Synthesis, 6, 1995, 693, and the like.

The formulas (VIII-1) and (VIII-
The compound represented by 2) is preferably added as an emulsified dispersion by a known dispersion method. In the case of emulsifying and dispersing, it can be made to coexist with an additive generally used in the photographic industry, such as a dye-forming coupler or a high-boiling organic solvent. It can also be added as a microcrystal dispersion. The amount of the compound represented by formulas (VIII-1) and (VIII-2) of the present invention is 5 × / mol of silver halide in the added emulsion layer.
It is 10 ^-4 to 1 mol, more preferably 1 × 10 ^{-3 to} 5 × 10 ^-1 mol.

In the combination of the compound of the general formula (VII) with the compound of the general formula (VIII-1) or (VIII-2),
-F) and the general formula (VIII-1-b) or (VIII-2)
Are preferred.

In the present invention, a compound selected from the group consisting of compounds represented by the general formula (VII), compounds represented by the general formulas (VIII-1) and (VIII-2), and a compound represented by the general formula (IX) Compounds selected from the group consisting of compounds represented by -1), (IX-2) and (X) can be added to the same layer or to different layers, respectively.

The compound represented by formula (IX-1) will be described in more detail. In the formula, the alkyl group is a linear, branched, or cyclic alkyl group, and may have a substituent. In the general formula (IX-1), Rc1 is an alkyl group (preferably an alkyl group having 1 to 13 carbon atoms such as methyl, ethyl, i-propyl, cyclopropyl, butyl,
Isobutyl, cyclohexyl, t-octyl, decyl,
Dodecyl, hexadecyl, benzyl), a substituted or unsubstituted alkenyl group (preferably an alkenyl group having 2 to 14 carbon atoms, for example, allyl, 2-butenyl, isopropenyl, oleyl, vinyl), a substituted or unsubstituted aryl group ( Preferably, it is an aryl group having 6 to 14 carbon atoms, for example, phenyl, naphthyl). Rc2 is a hydrogen atom or Rc1
Represents a group represented by Rc3 is a hydrogen atom or carbon number 1
Represents a substituted or unsubstituted alkyl group (e.g., methyl, i-butyl, cyclohexyl) or a substituted or unsubstituted alkenyl group (e.g., vinyl, i-propenyl). The total number of carbon atoms contained in Rc1, Rc2 and Rc3 is 20 or less, more preferably 12 or less. Rc1
When Rc1 has a substituent, examples of the substituent include a hydroxy group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, an alkylamino group, Arylamino group, carbamoyl group,
Examples include a sulfamoyl group, a sulfo group, a carboxyl group, a halogen atom, a cyano group, a nitro group, a sulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a hydroxyamino group, and a heterocyclic group. Rc1 and Rc3 or Rc2 and Rc3
May combine with each other to form a 5- to 7-membered ring.

Of the compounds represented by formula (IX-1), those having a total carbon number of 20 or less are preferred, and those of 12 or less are more preferred.

The following are specific examples of the compound represented by formula (IX-1) of the present invention, but the present invention is not limited thereto.

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These compounds used in the present invention are:
J. Org. Chem., 27, 4054 ('62), J. Amer. Chem. Soc.,
73, 2981 ('51), JP-B-49-10692, and the like, or a method analogous thereto can be easily synthesized.

In the present invention, the compound represented by the general formula (IX-1) may be added by dissolving in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof, or by emulsifying and dispersing. May be. In the case of dissolving in water, if the solubility is increased by raising or lowering the pH, it may be dissolved by increasing or lowering the pH, and this may be added, or a surfactant may be allowed to coexist.

In the present invention, the compound represented by formula (IX-1) is preferably added at the time of preparing an emulsion. When it is added during the preparation of the emulsion, it can be added at any time during the process, and examples thereof include a silver halide grain forming process, before the start of a desalting process, a desalting process, and a chemical ripening process. Before the start, a step of chemical ripening, a step before preparation of a finished emulsion and the like can be mentioned. Further, it can be added in plural times during these steps. It is preferably added before, during or after chemical sensitization. Further, it can be added before coating the coating solution, or can be added to an adjacent layer or another layer at the time of coating and diffused into the emulsion layer. Further, those dispersed and dissolved in an emulsion can be used by mixing with the emulsion.

In the present invention, the addition amount of the compound represented by the general formula (IX-1) depends on the above-mentioned addition method and the kind of the compound to be added. 1 × 10 ^-6 mol to 5 × 10 ^-2 per
Mole is preferred, and 1 × 10 ⁻⁵ mole to 5 × 10 −3 mole is more preferred.

Next, the compound represented by formula (IX-2) of the present invention will be described in detail. G1 and G2 represent a hydrogen atom or a monovalent substituent. Further, they may combine with each other to form a ring. The monovalent substituent may be any, but preferably includes the aforementioned Yy. Preferred are compounds selected from the following formulas (AI), (A-II), (A-III), (A-IV), and (AV).

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In the general formula (AI), Rd1 represents an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxy group. Rd2 represents a hydrogen atom or a group represented by Rd1. However, when Rd1 is an alkyl group, an alkenyl group or an aryl group, Rd2 is an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. Rd1 and Rd2 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-II), X represents a heterocyclic group, and Re1 represents an alkyl group, an alkenyl group or an aryl group. X and Re1 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-III), Y represents a nonmetallic atom group necessary for forming a 5-membered ring together with -N = C-. Y further represents a nonmetallic atom group necessary for forming a 6-membered ring together with the -N = C- group, and-
The terminal of Y bonded to the carbon atom of the N = C- group is -N (Rf1)-,
A group selected from -C (Rf2) (Rf3)-, -C (Rf4) =, -O- and -S- (bonded to the carbon atom of -N = C- on the left side of each group) Express. Rf1 to Rf4 represent a hydrogen atom or a substituent. In formula (A-IV), Rg1 and Rg2 may be the same or different and each represents an alkyl group or an aryl group. However, when Rg1 and Rg2 are unsubstituted alkyl groups at the same time and Rg1 and Rg2 are the same group, Rg1 and Rg2 are alkyl groups having 8 or more carbon atoms. In the general formula (A-V), Rh1 and Rh2 may be the same or different and each is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group, Represents an arylthio group, an alkyl group or an aryl group. However, Rh1 and Rh2 are not simultaneously -NHRh3 (Rh3 is an alkyl group or an aryl group). Rd1 and Rd2 and X and Re1 may be bonded to each other to form a 5- to 7-membered ring. The present inventors have found that oxygen is involved in one of the causes of the fluctuation of photographic properties due to the preservation of the photosensitive material and the fluctuation of photographic properties after photographing and until development processing. Some compounds in the light-sensitive material react with oxygen, which affects the photographic properties. However, the compounds represented by the above general formulas (AI) to (AV) may capture the compounds. It is estimated that there is not. Increasing the amount of gelatin applied may increase photographic properties. It is presumed that a trace amount of impurities in gelatin react with oxygen, which affects photographic properties. In addition, the general formulas (AI) to (A-
It was found that the compound represented by V) can improve pressure resistance. Hereinafter, the present invention will be described in more detail.

The compounds represented by formulas (AI) to (AV) will be described in more detail. In these formulas, the alkyl group is a linear, branched, or cyclic alkyl group, which may have a substituent. In the general formula (AI), Rd1 represents an alkyl group (preferably having 1 to 36 carbon atoms).
In the alkyl group of, for example, methyl, ethyl, i-propyl,
Cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl,
Benzyl), alkenyl group (preferably having 2 to 36 carbon atoms)
Alkenyl groups such as allyl, 2-butenyl, isopropenyl, oleyl and vinyl), aryl groups (preferably aryl groups having 6 to 40 carbon atoms such as phenyl and naphthyl), and acyl groups (preferably having 2 to 36 carbon atoms) Acetyl, benzoyl, pivaloyl, α-
(2,4-di-tert-amylphenoxy) butyryl, myristoyl, stearoyl, naphthoyl, m-pentadecylbenzoyl, isonicotinoyl), alkyl or arylsulfonyl group (preferably alkyl having 1 to 36 carbon atoms or 6 to 36 carbon atoms) Arylsulfonyl group such as methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyl or arylsulfinyl group (preferably alkyl having 1 to 40 carbon atoms or arylsulfinyl group having 6 to 40 carbon atoms such as methanesulfinyl, benzene Sulfinyl), carbamoyl group (including an N-substituted carbamoyl group, preferably a carbamoyl group having 0 to 40 carbon atoms such as N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-
Dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl), a sulfamoyl group (including an N-substituted sulfamoyl group, preferably a sulfamoyl group having 1 to 40 carbon atoms, for example, N-methylsulfamoyl, N, N-diethylsulfo) Famoyl, N-phenylsulfamoyl,
N-cyclohexyl-N-phenylsulfamoyl, N
-Ethyl-N-dodecylsulfamoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 36 carbon atoms such as methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl) or aryl Represents an oxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 40 carbon atoms, for example, phenoxycarbonyl, naphthoxycarbonyl). Rd2 represents a hydrogen atom or a group represented by Rd1.

In the general formula (A-II), X represents a heterocyclic group (a 5- to 7-membered heterocyclic ring having at least one of a nitrogen atom, a sulfur atom, an oxygen atom and a phosphorus atom as a ring-constituting atom) And the bonding position of the heterocyclic ring (position of the monovalent group) is preferably a carbon atom.
5-triazin-2-yl, 1,2,4-triazine-
3-yl, pyridin-2-yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, 1,2,4
-Triazol-3-yl, benzimidazole-2-
Yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, morpholinyl, phosphinolin-2-yl). Re1 represents an alkyl group, alkenyl group or aryl group having the same meaning as Rd1 in formula (AI).

In the general formula (A-III), Y is -N = C
-A non-metallic atom group necessary for forming a 5-membered ring together with (for example, the ring group formed is imidazolyl, benzimidazolyl, 1,3-thiazol-2-yl, 2-imidazolin-2-yl, purinyl, 3H -Indol-2-yl). Y is a group of nonmetallic atoms necessary for forming a 6-membered ring together with the -N = C- group, and -N
= The terminal of Y bonded to the carbon atom of the C- group is -N (Rf1)-, -C
Represents a group selected from (Rf2) (Rf3)-, -C (Rf4) =, -O- and -S- (bonded to the carbon atom -N = C- on the left side of each group). Rf1 to Rf4 may be the same or different,
Represents a hydrogen atom or a substituent (eg, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, and a halogen atom). Examples of the 6-membered ring group formed by Y include quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, 1,3,5-triazin-5-yl, and 6H-1,2,5-thiadiazin-6-yl.

In the general formula (A-IV), Rg1 and Rg
2 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms, for example, methyl, ethyl, i-propyl, cyclopropyl, n-butyl, isobutyl, hexyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl ) Or an aryl group (preferably having 6 carbon atoms)
-40 aryl groups, for example, phenyl, naphthyl). However, when Rg1 and Rg2 are simultaneously unsubstituted alkyl groups and Rg1 and Rg2 are the same group, Rg1 and Rg2 are alkyl groups having 8 or more carbon atoms.

In the general formula (AV), Rh1 and R1
h2 is a hydroxylamino group, a hydroxyl group, an amino group or an alkylamino group (preferably an alkylamino group having 1 to 50 carbon atoms, such as methylamino, ethylamino, diethylamino, methylethylamino, propylamino, dibutylamino, cyclohexyl Amino, t-octylamino, dodecylamino, hexadecylamino,
Benzylamino, benzylbutylamino), an arylamino group (preferably an arylamino group having 6 to 50 carbon atoms such as phenylamino, phenylmethylamino, diphenylamino, naphthylamino), and an alkoxy group (preferably having 1 to 36 carbon atoms) For example, methoxy, ethoxy, butoxy, t-butoxy, cyclohexyloxy, benzyloxy, octyloxy, tridecyloxy, hexadecyloxy), an aryloxy group (preferably an aryloxy group having 6 to 40 carbon atoms) For example, phenoxy, naphthoxy), an alkylthio group (preferably an alkylthio group having 1 to 36 carbon atoms, for example, methylthio, ethylthio, i-propylthio, butylthio,
Cyclohexylthio, benzylthio, t-octylthio, dodecylthio), an arylthio group (preferably an arylthio group having 6 to 40 carbon atoms, for example, phenylthio,
Naphthylthio), an alkyl group (preferably having 1 to 3 carbon atoms)
6 alkyl groups such as methyl, ethyl, propyl,
Butyl, cyclohexyl, i-amyl, sec-hexyl, t-octyl, dodecyl, hexadecyl), and an aryl group (preferably an aryl group having 6 to 40 carbon atoms, such as phenyl and naphthyl). However, Rh1 and Rh2
Are not simultaneously -NHR (R is an alkyl group or an aryl group).

Rd1 and Rd2, X and Re1 are bonded to each other to form 5
May form a 7-membered ring, for example, a succinimide ring,
Examples include a phthalimide ring, a triazole ring, a urazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring. Each group of the compounds represented by the general formulas (AI) to (AV) may be further substituted with a substituent.
Examples of these substituents include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, an alkylamino group, Arylamino group, carbamoyl group,
Examples include a sulfamoyl group, a sulfo group, a carboxyl group, a halogen atom, a cyano group, a nitro group, a sulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and a hydroxyamino group.

In the general formula (AI), Rd2 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and Rd1 represents an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, A compound in which Rd2 is an alkyl group or an alkenyl group, and Rd1 is an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, more preferably an aryloxycarbonyl group. It is.
Most preferably, Rd2 is an alkyl group and Rd1 is an acyl group.

In the general formula (A-II), Re1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. On the other hand, the general formula (A-II) is preferably represented by the following general formula (A-II-1), and more preferably X is 1,3,5-triazin-2-yl; The compound represented by A-II-2) is most preferred.

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In the general formula (A-II-1), Re1 represents Re1 in the general formula (A-II), and X1 represents a nonmetallic atom group necessary for forming a 5- to 6-membered ring. General formula (A-
Of the compounds represented by II-1), the case where X1 forms a 5- to 6-membered heteroaromatic ring is more preferred.

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In the general formula (A-II-2), Re1 has the same meaning as Re1 in the general formula (A-II). Re2 and Re3 may be the same or different and each represent a hydrogen atom or a substituent. Among the compounds represented by the general formula (A-II-2), Re2 and Re3 are each a hydroxyamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group. , An alkyl group or an aryl group.

Of the compounds represented by the general formula (A-III), it is preferable that Y is a group of non-metallic atoms necessary for forming a 5-membered ring, More preferably, the terminal atom of Y is a nitrogen atom. Y
Most preferably forms an imidazoline ring. This imidazoline ring may be condensed with a benzene ring.

Of the compounds represented by formula (A-IV), those in which Rg1 and Rg2 are alkyl groups are preferred. On the other hand, in the general formula (AV), a group in which Rh1 and Rh2 are selected from a hydroxyamino group, an alkylamino group, and an alkoxy group is preferable. Particularly preferably, Rh1 is a hydroxylamino group and Rh2 is an alkylamino group.

Of the compounds represented by the general formulas (AI) to (AV), those having a total carbon number of 15 or less are preferable in that they act on layers other than the addition layer. Compounds having a total carbon number of 16 or more are preferred for the purpose of acting only on the additive layer. General formulas (AI) to (A-
V) Among the compounds represented by the general formula (AI),
Those represented by (A-II), (A-IV) and (A-V) are preferred, and more preferably those represented by the general formulas (AI) and (A-
IV) and (AV), and more preferably those represented by formulas (AI) and (AV). The general formulas (AI) to (AV) of the present invention are described below.
Specific examples of the compound represented by are shown below, but the invention is not limited thereto.

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[0663]

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These compounds are represented by the general formula (AI)
Correspondence with (A-V) is as follows. General formula (AI): A-33 to A-55 General formula (A-II): A-5 to A-7, A-10, A-2
0, A-30 General formula (A-III): A-21 to A-29, A-31, A
-32 General formula (A-IV): A-8, A-11, A-19 General formula (AV): A-1 to A-4, A-9, A-12
~ A-18

These compounds of the present invention are described in J. Org.
m., 27, 4054 ('62), J. Amer. Chem. Soc., 73, 2981 ('5
1) It can be easily synthesized by the method described in JP-B-49-10692 or a method analogous thereto.
In the present invention, the compounds represented by the general formulas (AI) to (AV) may be dissolved in a water-soluble solvent such as water, methanol, or ethanol, or a mixed solvent thereof, and may be added to the emulsion. You may add by dispersion. Further, it may be added in advance during the preparation of the emulsion. PH when dissolved in water
If the solubility is increased by increasing or decreasing the pH, it may be dissolved by increasing or decreasing the pH, and then added. In the present invention, general formulas (AI) to (A-)
Two or more of the compounds represented by V) may be used in combination. For example, a combination of a water-soluble substance and an oil-soluble substance is advantageous in photographic performance. Compound (AI) ~
The coating amount of (AV) is 10 ⁻⁴ mmol / m ^{2 to} 10 mmol / m ^2.
And more preferably ^{10 -3 mmol / m 2 ~1mmol /} m 2.

Next, the compound represented by formula (X) will be described. In the general formula (X), Rb17, Rb18,
And R b19 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Rb20 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; NR
represents b21Rb22, J represents -CO- or -SO ₂ - represents, n represents 0 or 1. Rb21 represents a hydrogen atom, a hydroxyl group, an amino group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group;
Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

In Rb17, Rb18 and Rb19, the alkyl group, alkenyl group and alkynyl group preferably have 1 to 30 carbon atoms, and particularly have a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms. An alkenyl group having 2 to 10 carbon atoms and an alkynyl group having 2 to 10 carbon atoms. Examples of the alkyl group, alkenyl group, alkynyl group, and aralkyl group include methyl, ethyl, propyl, cyclopropyl, allyl, propargyl, and benzyl. Rb1
In Rb18 and Rb19, the aryl group preferably has 6 to 30 carbon atoms, and particularly preferably has 6 to 12 carbon atoms.
And a monocyclic or condensed aryl group such as phenyl and naphthyl. In Rb17, Rb18 and Rb19, the heterocyclic group is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. These may be a single ring or may form a condensed ring with another aromatic ring. The heterocycle is preferably a 5- to 6-membered aromatic heterocycle, for example, pyridyl, imidazolyl, quinolyl, benzimidazolyl, pyrimidyl, pyrazolyl, isoquinolyl, thiazolyl, thienyl, furyl, benzothiazolyl and the like.

In Rb20, alkyl, alkenyl, alkynyl, aryl, and heterocyclic groups are Rb17, Rb
Synonymous with 18 and Rb19. In NRb21Rb22 of Rb20, an alkyl group, alkenyl group of Rb21 and Rb22,
An alkynyl group, an aryl group and a heterocyclic group have the same meanings as Rb17, Rb18 and Rb19. Rb17 and Rb1 of the general formula (X)
Each of the groups represented by 8, Rb19, Rb20, Rb21 and Rb22 may be substituted by the aforementioned substituent Yy.

In the general formula (X), Rb17 and Rb18;
Rb17 and Rb19, Rb19 and Rb20, or Rb20 and Rb18 may be linked to form a ring.

In the general formula (X), when n is 0, Rb17, Rb18 and Rb19 preferably have 1 to 10 carbon atoms.
An alkyl group, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a nitrogen-containing heterocyclic group, wherein Rb20 is a hydrogen atom, 1 to 10 carbon atoms. Alkyl group, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, 6 carbon atoms
To 10 aryl groups and nitrogen-containing heterocyclic groups, more preferably Rb17, Rb18 and Rb19 each have 1 to 10 carbon atoms.
An alkyl group, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a nitrogen-containing heterocyclic group, and Rb20 is a hydrogen atom. When n is 1, preferably Rb17, Rb18 and Rb1
9 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a nitrogen-containing heterocyclic group. Is -CO-, and Rb20 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and 6 carbon atoms.
To 10 aryl groups, nitrogen-containing heterocyclic groups, NRb21Rb22
Rb21 represents a hydrogen atom, a hydroxyl group, an amino group, an alkyl group having 1 to 10 carbon atoms,
An alkenyl group, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a nitrogen-containing heterocyclic group,
Rb22 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group, an aryl group having 6 to 10 carbon atoms, and a nitrogen-containing heterocyclic group. 6 to 10 aryl groups, Rb18 and Rb19 are hydrogen atoms, J is -CO-, Rb20 is NRb21 Rb22, Rb21 is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl A alkynyl group. Specific compounds represented by the general formula (X) are shown below, but the present invention is not limited thereto.

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[0675]

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The compound represented by formula (X) can be easily obtained as a commercially available drug or a compound synthesized from a commercially available drug by a known method. The compound represented by the general formula (X) is preferably added to a layer adjacent to an emulsion layer or another layer before or during application of a coating solution and diffused into the emulsion layer. It can also be added before, during or after chemical sensitization during the preparation of the emulsion. The preferred addition amount largely depends on the above-mentioned addition method and the kind of the compound to be added, but is generally from 5 × 10 ^-6 mol to 0.05 mol, more preferably 1 × 10 ^-5 mol, per mol of the photosensitive silver halide. To 0.005 mol is used. If the amount is larger than the above-mentioned amount, adverse effects such as an increase in fog are caused, which is not preferable. The compound represented by the general formula (X) is preferably dissolved in a water-soluble solvent and added. The pH may be lowered or raised by an acid or a base, or a surfactant may be present. It may be added as an emulsified dispersion by dissolving it in a high-boiling organic solvent, or may be added as a microcrystalline dispersion by a known dispersion method. Two or more compounds of the general formula (X) may be used in combination. When two or more kinds are used in combination, they may be added to the same layer or may be added to separate layers.

Now, the general formula (XI) will be described in more detail. In the general formula (XI), X ² and Y ² each independently represent a hydroxyl group, —NR i 23 Ri 24, or —NHSO ₂ Ri
Represents 25. Ri21 and Ri22 each independently represent a hydrogen atom or an optional substituent. As the optional substituent,
For example, an alkyl group (having preferably 1 to 20 carbon atoms, such as methyl, ethyl, octyl, hexadecyl,
t-butyl) and an aryl group (having 6 to 20 carbon atoms).
More preferably, for example, phenyl, p-tolyl), an amino group (having a carbon number of 0 to 20, preferably unsubstituted amino, diethylamino, diphenylamino, hexadecylamino), an amide group (having a carbon number of 1 to 20) Are preferred, for example, acetylamino, benzoylamino, octadecanoylamino, benzenesulfonamide), an alkoxy group (having a carbon number of 1 to 20 is preferable, for example, methoxy, ethoxy, hexadecyloxy), an alkylthio group (having a carbon number of 1 to 1) 20 are preferable, for example, methylthio, butylthio, octadecylthio), an acyl group (preferably having 1 to 20 carbon atoms, for example, acetyl, hexadecanoyl, benzoyl, benzenesulfonyl), and a carbamoyl group (having 1 to 20 carbon atoms) Those such as unsubstituted carbamoyl and N- Hexylcarbamoyl, N,
N-diphenylcarbamoyl), an alkoxycarbonyl group (having preferably 2 to 20 carbon atoms, for example, methoxycarbonyl, octyloxycarbonyl), a hydroxyl group, a halogen atom (F, Cl, Br, etc.), a cyano group, a nitro group, a sulfo group , A carboxyl group and the like. These substituents may be further substituted by another substituent (for example, those described as Yy).

Also, Ri21 and Ri22 may be bonded to each other to form a carbon ring or a heterocyclic ring (each preferably a 5- to 7-membered ring). Ri23 and Ri24 each independently represent a hydrogen atom, an alkyl group (preferably one having 1 to 10 carbon atoms, for example, ethyl, hydroxyethyl, octyl) and an aryl group (preferably one having 6 to 10 carbon atoms,
For example, phenyl, naphthyl) or a heterocyclic group (2 to 2 carbon atoms)
10 is preferable, for example, 2-furanyl, 4-pyridyl), which may be further substituted with a substituent.

Ri23 and Ri24 may combine with each other to form a nitrogen-containing heterocyclic ring (preferably a 5- to 7-membered ring). Ri25 is preferably an alkyl group (having 1 to 20 carbon atoms, for example, ethyl, octyl, hexadecyl) and an aryl group (having 6 to 20 carbon atoms, for example, phenyl, p-tolyl, and 4-dodecyloxyphenyl). ), An amino group (having preferably from 0 to 20 carbon atoms, for example, N,
N-diethylamino, N, N-diphenylamino, morpholino) or a heterocyclic group (preferably one having 2 to 20 carbon atoms, for example, 3-pyridyl), which may be further substituted.

In the formula (XI), X ² represents —N
Ri23Ri24 or -NHSO ₂ Ri25 is preferable. Ri21 and Ri22 are preferably a hydrogen atom, an alkyl group or an aryl group, and may be bonded to each other to form a carbon ring or a heterocyclic ring. For details of these groups, see Ri2
Same as 3 and Ri24. Specific compounds represented by the general formula (XI) are shown below, but the invention is not limited thereto.

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Among the compounds represented by formulas (VI) to (XI), compounds represented by formulas (IX-1), (IX-2), (VIII-1)
Compounds represented by (VIII-2), (VII), (VI) and (X) are preferred, and compounds represented by formulas (IX-1), (IX-2) and (VI
Compounds represented by II-1), (VIII-2) and (VII) are more preferable, and compounds represented by formulas (IX-1), (IX-2) and (VIII)
Compounds represented by -1) and (VIII-2) are more preferred. Particularly preferred are compounds represented by formulas (IX-1) and (IX-2).

The photosensitive layer of the present invention can be provided on a support in one or more layers. Further, the support may be provided not only on one side but also on both sides. The photosensitive layer of the present invention includes a black-and-white silver halide photographic light-sensitive material (for example, an X-ray light-sensitive material, a squirrel-type light-sensitive material, a negative film for black-and-white photography) and a color photographic light-sensitive material (for example, a color negative film, a color reversal film, Color paper). Further, it can be used as a photosensitive material for diffusion transfer (for example, a color diffusion transfer element, a silver salt diffusion transfer element), a heat development photosensitive material (black and white, color) and the like.

Hereinafter, the color photographic light-sensitive material will be described in detail, but the invention is not limited thereto. The light-sensitive material only needs to have at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There is no particular limitation on the number and order of the photosensitive layers. 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. Are arranged in order from the support side in the order of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. 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 layers are described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440,
1-20037, couplers such as those described in 61-20038 and DIR compounds may be contained,
It may contain a color mixing inhibitor 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 structure 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. In addition, Tokiko Sho 55-
As described in JP-A-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. Japanese Patent Application Laid-Open No. 56-2573
Nos. 8 and 62-63936, the blue-sensitive layer / GL / R from the side farthest from the support.
They can be installed in the order of L / GH / RH.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is 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 the support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer / a layer having the same color sensitivity is arranged from a side away from the support. They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. In addition, high-speed emulsion layer / low-speed emulsion layer /
Medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer /
They may be arranged in the order of a high-sensitivity emulsion layer and the like. 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. In addition, various additives can be used according to the purpose. These additives are
For more information, Research Disclosure Item
17643 (December 1978), Item 18
716 (November 1979) and Item 30
8119 (December 1989), and the relevant locations are summarized in the table below.

[0691]     Additive type RD17643 RD18716 RD308119    1 Chemical sensitizer page 23 648 page right column page 996    2 Sensitivity enhancer Same as above    3 Spectral sensitizer, page 23-24 page 648, right column-996 right-998 right       Supersensitizer page 649, right column    4 Brightener 24 pages 647 right column 998 right    5 Antifoggant, page 24-25 page 649, right column 998 right-1000 right       And stabilizers    6 Light absorber, page 25-26 page 649 right column ~ 1003 left ~ 1003 right       Filter dye, page 650, left column       UV absorber    7 Stain inhibitor 25 pages right column 650 left to right column 1002 right    8 Dye image stabilizer page 25 1002 right    9 Hardening agent Page 26 651 Left column 1004 right to 1005 left   10 Binder page 26 Same as above 1003 right to 1004 right   11 Plasticizers and lubricants 27 pages 650 pages right column 1006 left to 1006 right   12 Coating aids, pp. 26-27 Same as above 1005 left-1006 left       Surfactant   13 Static 27 pages Same as above 1006 right to 1007 left       Inhibitor   14 Matting agent 1008 left to 1009 left

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound capable of reacting with formaldehyde described in JP-A No. 7 and 4,435,503 to the light-sensitive material. Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. supra. 17643, VII-C ~
G, and the same No. 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
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 U.S. Pat. Nos. 4,310,619 and 4,351,897, EP 73,636, and U.S. Pat. 061, 43
No. 2, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure N
o. 24230 (June 1984), JP-A-60-43
No. 659, No. 61-72238, No. 60-35730
No. 55-118034, No. 60-185951
Nos. 4,500,630 and 4,54.
0,654, 4,556,630, International Publication W
Those described in O88 / 04795 are particularly preferred.

Examples of the cyan coupler include phenol-based and naphthol-based 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 U.S. Pat.
Nos. 0,211, 4,367,282, 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. Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure No.
No. 17643, section VII-G; VII-G of 307105
Item, U.S. Pat. No. 4,163,670, JP-B-57-3
No. 9413; 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 US 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 No. 307105, VII-F
And JP-A-57-151944, JP-A-57-154234, JP-A-60-184248 and JP-A-60-184248.
What is described in 3-37346, 63-37350, U.S. Pat. Nos. 4,248,962 and 4,782,012 is preferred.

As a coupler which releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,099
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 that can be used 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, JP 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 which release dyes which discolor after release as described in EP 173,302A and 313,308A , RD. No. 1
1449, 24241, and bleaching accelerator releasing couplers described in JP-A-61-201247, U.S. Pat.
55,477 and the like, a coupler releasing a leuco dye described in JP-A-63-75747, and a coupler releasing a fluorescent dye described in U.S. Pat. No. 4,774,181. .

The coupler used in the present invention can be introduced into a photographic 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 high-boiling organic solvents 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-ter
t-amylphenyl) phthalate, bis (2,4-di-
tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); esters of phosphoric acid or phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, Tri-2-ethylhexyl phosphate,
Tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate); benzoic esters (eg, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate); amides ( For example, N, N-diethyldodecaneamide, N, N-diethyllauramide,
N-tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,
4-di-tert-amylphenol); aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl)
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octyl aniline); hydrocarbons (eg, Paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, the boiling point is about 30 ° C.
As described above, an organic solvent having a temperature of preferably 50 ° C. or more and about 160 ° C. or less can be used, and typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide. Can be

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described, for example, in US Pat.
No. 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 or JP-A-63-257747, JP-A-62-257747 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, a color negative film for general use or a movie, a color reversal film for slides or a television, a color paper, a color positive film and a color reversal paper 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
For example, the RD. No. Page 17643, N
o. 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. The film thickness here means the film thickness measured under humidity control at 25 ° C. and 55% relative humidity (2 days). In addition, 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 by changing the aging conditions after coating.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains, for example, the above-mentioned 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 the usual method described on pages 880 to 881 of No. 7105. The color developing solution used for the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 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, a sulfate of 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution is, for example, a pH buffer such as an alkali metal carbonate, borate or phosphate,
It generally contains a development inhibitor or 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, 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.

In the case where 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. 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 L 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 oxidizing the air by reducing the contact area of the processing liquid with air.

The area of contact between the photographic processing solution and air in the processing tank can be represented by the following aperture ratio. That is, aperture ratio = [contact area between processing solution and air (cm ² )] ÷
[Capacity of treatment liquid (cm ³ )] The above opening ratio is preferably 0.1 or less, more preferably 0.001 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. Method, JP-A-63-2160
No. 50 can be mentioned. 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 following various 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 color development time is usually 2 to
The time is set within 5 minutes, but the processing time can be further reduced 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 bleached. 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 a bleach-fixing process after the bleaching process may be used. Furthermore, processing in two continuous bleach-fixing baths, fixing before bleach-fixing,
Alternatively, bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids (particularly, sodium persulfate is suitable for color negative films 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, glycol etherdiaminetetraacetic acid, or, for example, citric acid, tartaric acid, malic acid Can be used. Of these, iron (III) aminopolycarboxylate complexes, including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate,
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 bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH to speed up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and a prebath thereof, 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.
Nos. 53-37418, 53-72623, 53-95630, 53-95763, 53-53
No. 104232, No. 53-124424, No. 53-1
41623, 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, thiourea derivatives, West German Patent No. 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
-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. 3,893,8
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. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. 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 iodide salts. Of these, use of thiosulfates is common, and in particular, ammonium thiosulfate can be used most widely. Also, thiosulfate, 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, a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, or 2-methyl is used in the fixing solution or the bleach-fixing solution for adjusting pH. It is preferable to add imidazoles such as imidazole in an amount of 0.1 to 10 mol / L.

[0715] The total time of the desilvering step is preferably as short as possible without causing desilvering failure. Preferred time is 1 minute to 3
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 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 for enhancing the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method described in JP-A-62-183461, using a rotating means. There is a method to increase the effect. Furthermore, 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 the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, thereby increasing the desilvering speed. Further, the above-mentioned means for improving 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.

An automatic developing machine used for developing the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-1919.
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 conveying 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 process 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 represented by Journal of
the Society of Motion Pi
cure and Television Engi
neers, vol. 64, p. 248-253 (1955)
May issue).

According to the multi-stage 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 water in the tank, and a generated floating substance adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, a method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Also described in JP-A-57-8542, for example, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and others, such as benzotriazole, by Horiguchi Hiroshi "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 "Encyclopedia of fungicides" (1986) can also be used.

[0720] 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 temperature and the washing time can be variously set depending on, for example, the characteristics of the photographic material and the application.
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
And all known methods described in JP-A-58-14834 and JP-A-60-220345 can be used.

[0721] In some cases, a stabilization treatment may be further performed after the water washing treatment. 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.

[0722] 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 the case of processing using an automatic developing machine, when the above processing solutions are 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.
Nos. 15, 15 and 159; 1
Aldol compounds described in U.S. Pat.
719,492, a metal salt complex described in JP-A-53-1
And the urethane compounds described in JP-A-35628.

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.

[0725] The various processing solutions in the present invention may be used at a temperature of 10 ° C to 5 ° C.
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 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 is disclosed in U.S. Pat.
626, JP-A-60-133449, and JP-A-59-21.
8443, 61-238056, European Patent No. 21
Also, the present invention can be applied to a photothermographic material described in U.S. Pat. The silver halide color photographic light-sensitive material of the present invention is disclosed in JP-B-2-32615 and JP-B-3-3.
When applied to a film unit with a lens described in No. 9784 or the like, the effect is more easily exhibited and is effective.

[0726]

Embodiments of the present invention will be described below. However, the present invention is not limited to this embodiment. (Example 1) A silver halide emulsion Em-
A1 was prepared from A1. (Em-A1) Phthalated 97% phthalated low molecular weight gelatin having a molecular weight of 15,000 31.7 g, KBr3
42.2 L of an aqueous solution containing 1.7 g was maintained at 35 ° C. and stirred vigorously. Aqueous solution 15 containing 316.7 g of AgNO ₃
1583 mL of aqueous solution containing 83 mL and 52.7 g of low molecular weight gelatin having a molecular weight of 15000 and KBr of 221.5 g
Was added by the double jet method over 1 minute. Immediately after the addition was completed, 52.8 g of KBr was added, and AgNO ₃ , 3 was added.
2485 mL of an aqueous solution containing 98.2 g and KBr, 29
2581 mL of an aqueous solution containing 1.1 g was added by a double jet method over 2 minutes. Immediately after the addition, KBr,
47.8 g were added. Thereafter, the temperature was raised to 40 ° C., and the mixture was aged sufficiently. After ripening, 923 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000 and KBr, 7
9.2 g was added, and 15947 mL of an aqueous solution containing 5103 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 12 minutes while accelerating the flow rate so that the final flow rate was 1.4 times the initial flow rate. At this time, the silver potential was kept at -60 mV with respect to the saturated calomel electrode. After washing with water, gelatin was added, pH, 5.7, pAg, 8.8, emulsion 1k
131.8 g of silver equivalent per gram, 6 mass of gelatin
It was adjusted to 4.1 g to obtain a seed emulsion.

A phthalated gelatin 46 having a phthalation rate of 97%
g, 1.71 g of KBr in an aqueous solution at 75 ° C.
And stirred vigorously. After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , 7.0 g of AgNO ₃ was added.
And a KBr aqueous solution were added over 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Sodium benzenethiosulfonate, 2mg and thiourea dioxide 2
After addition of mg, an aqueous solution containing 144.5 g of AgNO ₃ , 410 mL and KBr and KI containing 7 mol% of KI
Was added by a double jet method over a period of 56 minutes while accelerating the flow rate so that the final flow rate was 3.7 times the initial flow rate. At this time, the silver potential is-with respect to the saturated calomel electrode.
It was kept at 30 mV. 121.3 mL of an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 22 minutes by a double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. Temperature to 82 ° C,
After adding KBr to adjust the silver potential to -80 mV,
AgI fine grain emulsion having a grain size of 0.037 μm
6.33 g in terms of mass was added. Immediately after the addition,
206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. During the initial 5 minutes of the addition, the silver potential was maintained at -80 mV with an aqueous KBr solution. After washing with water, PAGI
The components having a molecular weight of 280,000 or more
% At 40 ° C., pH 5.8, pA
g, adjusted to 8.7. After adding compounds 11 and 12, the temperature was raised to 60 ° C. After the addition of sensitizing dyes 11 and 12, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. At the end of the chemical sensitization, Compound 13 and Compound 14 were added. Here, the optimal chemical sensitization means that the sensitizing dye and each compound are mixed with 1 mol of silver halide
It means that it was selected from the added amount range of 10 ^-1 to 10 ^-8 mol per ¹ .

[0728]

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[0729]

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[0730]

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[0731]

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[0732]

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[0733]

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[0734] The obtained particles were observed with a transmission electron microscope while cooling with liquid nitrogen. As a result, 10 or more dislocation lines per particle were observed in the vicinity of the side surfaces of the particles.

(Em-A2) Emulsion Em-A2 was obtained in the same manner as (Em-A1) except that compound (I-13) of the present invention was added at 1 × 10 ⁻⁴ mol / mol Ag during chemical sensitization. Was. (Em-A3) The compound of the present invention (IX-2-
(Em-A) except that 3) was added at 1 × 10 ⁻⁴ mol / mol Ag.
Emulsion Em-A3 was obtained in the same manner as in 2).

(Em-A4) 9.9 g of the aforementioned seed emulsion
After the addition, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , AgNO ₃ , 7.0
67.6 mL of an aqueous solution containing g and a KBr aqueous solution were added over 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 134.4 g of AgNO ₃ and 381 mL of an aqueous solution of KBr were subjected to a double jet method so that the final flow rate was 3.7 times the initial flow rate. Was added over a period of 56 minutes. At this time, 0.037μ
An AgI fine grain emulsion having a grain size of m was simultaneously added at an accelerated flow rate such that the silver iodide content became 7 mol%, and the silver potential was kept at -30 mV with respect to the saturated calomel electrode. 121.3 m of aqueous solution containing 45.6 g of AgNO ₃
L and KBr aqueous solution were added by a double jet method over 22 minutes. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. After the temperature was raised to 82 ° C and KBr was added to adjust the silver potential to -80 mV, an AgI fine grain emulsion having a grain size of 0.037 µm was converted to 6.3 in terms of KI mass.
3 g were added. Immediately after the addition, AgNO ₃ , 6
206.2 mL of an aqueous solution containing 6.4 g was added over 16 minutes. During the initial 5 minutes of the addition, the silver potential was maintained at -80 mV with an aqueous KBr solution. After washing with water, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added at the time of measurement according to the PAGI method, and adjusted to pH 5.8, pAg, 8.7 at 40 ° C. In the subsequent steps, the same treatment as in Em-A1 was performed. As a result of observing the obtained particles with a transmission electron microscope while cooling with liquid nitrogen, 10 or more dislocation lines per particle were observed in the vicinity of the particle side surface.

(Em-A5) The compound (I-13) of the present invention was added to 1 × 10 ⁻⁴ at the time of chemical sensitization.
Except that mol / molAg was added, the emulsion Em-
A5 was obtained. (Em-A6) Compound (IX-2-3) of the present invention was added to 1 × 10
^-4 mol / mol Ag was added which had had in the same manner as Em-A 5 to give the emulsion Em-A6.

(Em-A7) 9.9 g of the seed emulsion described above
After the addition, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , AgNO ₃ , 7.0
67.6 mL of an aqueous solution containing g and a KBr aqueous solution were added over 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 134.4 g of AgNO ₃ and 381 mL of an aqueous solution of KBr were subjected to a double jet method so that the final flow rate was 3.7 times the initial flow rate. Was added over a period of 56 minutes. At this time, 0.037μ
An AgI fine grain emulsion having a grain size of m was simultaneously added at an accelerated flow rate such that the silver iodide content became 7 mol%, and the silver potential was kept at -30 mV with respect to the saturated calomel electrode. 121.3 m of aqueous solution containing 45.6 g of AgNO ₃
L and KBr aqueous solution were added by a double jet method over 22 minutes. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. After the temperature was lowered to 40 ° C., KBr was added to adjust the silver potential to −40 mV, an aqueous solution containing 14.5 g of sodium p-iodoacetamidobenzenesulfonate (monohydrate) was added, and then 0.8M of 0.8M was added. 57 mL of an aqueous solution of sodium sulfite was added at a fixed rate for 1 minute, and the pH was adjusted.
Is controlled to 9.0 to generate iodide ions, and 2
After 5 minutes, the temperature was raised to 55 ° C. over 15 minutes, and then the pH was adjusted to 5.
Returned to 5. Thereafter, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. During the addition, the silver potential was kept at -50 mV with an aqueous KBr solution. After washing with water, when measured according to the PAGI method, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added.
Adjusted to 5.8, pAg, 8.7. The subsequent process is Em
The same processing as -A1 was performed. As a result of observing the obtained particles with a transmission electron microscope while cooling with liquid nitrogen, 10 or more dislocation lines per particle were observed in the vicinity of the particle side surface. At this time, the dislocation existing near the side face was localized near the vertex of the tabular grains.

(Em-A8) The compound (I-13) of the present invention was added to 1 × 10 ⁻⁴ at the time of chemical sensitization.
Emulsion E was prepared in the same manner as Em-A7 except that mol / molAg was added.
m-A8 was obtained. (Em-A9) Compound (IX-2-3) of the present invention was added to 1 × 10
^-4 mol / mol Ag was added which had had in the same manner as Em-A 8 obtained emulsion Em-A9.

(Em-A10) 9.9 of the above-mentioned seed emulsion was prepared.
g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , AgNO ₃ , 7.
67.6 mL of an aqueous solution containing 0 g and an aqueous KBr solution were added over 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 134.4 g of AgNO ₃ and 381 mL of an aqueous solution of KBr were subjected to a double jet method so that the final flow rate was 3.7 times the initial flow rate. Was added over a period of 56 minutes. At this time, 0.037
An AgI fine grain emulsion having a grain size of μm is simultaneously added at an accelerated flow rate such that the silver iodide content becomes 7 mol%,
The silver potential was kept at -30 mV with respect to the saturated calomel electrode. Aqueous solution containing 102.4 g of AgNO ₃ 330.
8 mL and an aqueous KBr solution were added by the double jet method over 60 minutes. At this time, the silver potential was maintained at +20 mV with respect to the saturated calomel electrode for the first 50 minutes, and at 120 mV for the remaining 10 minutes. After cooling down to 50 ° C, 0.3% K
55 mL of I aqueous solution was added over 10 minutes. Immediately thereafter, 100 mL of an aqueous solution containing 14.2 g of AgNO ₃ and N
aqueous solution containing 2.1 g of aCl and 4.17 g of KBr 120 m
A solution containing L and 0.0133 mol of AgI fine particles was added simultaneously. At this time, 9.4 × 10 ⁻⁴ mol of K ₄ [RuCN ₆ ] was present per 1 mol of AgNO ₃ added. Thereafter, a sensitizing dye was added (for epitaxial stabilization). After washing with water, when the molecular weight distribution was measured in accordance with the PAGI method, components having a molecular weight of
% At 40 ° C., pH 5.8, pA
g, adjusted to 8.7. In the subsequent steps, the same treatment as in Em-A1 was performed. Observation of the obtained particles with a scanning electron microscope revealed that an epitaxial layer had adhered to the apexes of the tabular particles.

(Em-A11) The compound (I-13) of the present invention was added to 1 × 10 ⁻⁴ at the time of chemical sensitization.
Emulsion E was prepared in the same manner as Em-A10 except that mol / molAg was added.
m-A11 was obtained. (Em-A12) Compound (IX-2-3) of the present invention was added to 1 × 10
^-4 mol / mol Ag was added which had had in the same manner as Em-A1 1 to give an emulsion Em-A12.

(Em-A13) 9.9 of the above-described seed emulsion
g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , AgNO ₃ , 7.
67.6 mL of an aqueous solution containing 0 g and an aqueous KBr solution were added over 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 134.4 g of AgNO ₃ , 762 m 2 was added to a stirring device installed outside the reaction vessel.
L, KBr 90.1 g, KI 9.46 g and molecular weight 2
762 m of aqueous solution containing 38.1 g of 0000 gelatin
L at the same time to add AgBr having a silver iodide content of 7 mol%.
This AgBrI emulsion was added to the reaction vessel over 90 minutes while preparing an I fine grain emulsion (average size: 0.015 μm). At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode. 121.3 mL of an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 22 minutes by a double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. After the temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and then 6.33 g of an AgI fine grain emulsion having a grain size of 0.037 μm in terms of KI mass was added. Immediately after the addition, 206.2 m of an aqueous solution containing 66.4 g of AgNO ₃ .
L was added over 16 minutes. KB for 5 minutes at the beginning of addition
The silver potential was maintained at -80 mV with the r aqueous solution. After washing with water,
When measured according to the PAGI method, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added, and at 40 ° C., pH, 5.8, p.
Ag, adjusted to 8.7. In the subsequent steps, the same processing as in Em-A1 was performed. As a result of observing the obtained particles with a transmission electron microscope while cooling with liquid nitrogen, 10 or more dislocation lines per particle were observed in the vicinity of the particle side surface.

(Em-A14) The compound (I-13) of the present invention was added to 1 × 10 ⁻⁴ at the time of chemical sensitization.
Emulsion Em-A14 was obtained in the same manner as Em-A13 except that mol / molAg was added. (Em-A15) Compound (IX-2-3) of the present invention was added to 1 × 10
^-4 mol / mol Ag was added which had got an emulsion Em-A15 in the same manner as Em-A1 4.

(Em-B) (Emulsion for Low-Sensitivity Blue-Sensitive Layer) 1192 mL of an aqueous solution containing 0.96 g of low-molecular-weight gelatin, 0.9 g of KBr was maintained at 40 ° C., and vigorously stirred.
37.5 mL of an aqueous solution containing 1.49 g of AgNO ₃ and K
37.5 mL of an aqueous solution containing 1.5 g of Br was added over 30 seconds by the double jet method. After adding 1.2 g of KBr, the temperature was raised to 75 ° C. to ripen. After sufficient aging, the amino group is chemically modified with trimellitic acid and has a molecular weight of 1,000.
30 g of trimellitized gelatin of 00, pH
Was adjusted to 7. 6 mg of thiourea dioxide were added. A
116 mL of an aqueous solution containing 29 g of gNO ₃ and an aqueous KBr solution were added by a double jet method at an accelerated flow rate such that the final flow rate was three times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. AgN
440.6 mL of an aqueous solution containing 110.2 g of O ₃ and KB
The r aqueous solution was added by a double jet method over a period of 30 minutes while accelerating the flow so that the final flow was 5.1 times the initial flow. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at an accelerated flow rate so that the silver iodide content became 15.8 mol%, and the silver potential was kept at 0 mV with respect to the saturated calomel electrode. Was. AgNO ₃ , 24.1
g and an aqueous solution of KBr were added over 3 minutes by the double jet method. At this time, the silver potential is set to 0
mV. Sodium ethylthiosulfonate, 26
After adding mg, the temperature was lowered to 55 ° C., and an aqueous KBr solution was added to adjust the silver potential to −90 mV. 8.5 g of the above-mentioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition is completed, 228 mL of an aqueous solution containing 57 g of AgNO ₃
Was added over 5 minutes. At this time, it was adjusted with an aqueous KBr solution so that the potential at the end of the addition was +20 mV. Em
It was washed with water and chemically sensitized almost as in -A1.

(Em-C) (Emulsion for low-sensitivity blue-sensitive layer) An aqueous solution containing 1.02 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000 containing 35 μmol of methionine per gram, and 0.97 g of KBr is 1192 m.
L was kept at 35 ° C. and stirred vigorously. AgNO ₃ , 4.
An aqueous solution containing 47 g, 42 mL, and an aqueous solution containing 3.16 g of KBr and 42 mL were added over 9 seconds by a double jet method. After adding 2.6 g of KBr, the temperature was raised to 66 ° C., and the mixture was sufficiently aged. After ripening, trimellited gelatin 4 having a molecular weight of 100,000 used in the preparation of Em-B 4
1.2 g and 18.5 g of NaCl were added. After adjusting the pH to 7.2, dimethylamine borane, 8 mg, was added. 203 mL of aqueous solution containing 26 g of AgNO ₃
And KBr aqueous solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode. AgN
440.6 mL of an aqueous solution containing 110.2 g of O ₃ and KB
The r aqueous solution was added over a period of 24 minutes by a double jet method with the flow rate accelerated so that the final flow rate was 5.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at an accelerated flow rate such that the silver iodide content became 2.3 mol%, and the silver potential was set to -20 mV with respect to the saturated calomel electrode. Kept. After adding 10.7 mL of a 1N aqueous potassium thiocyanate solution, AgN
153.5 mL of an aqueous solution containing 24.1 g of O ₃ and KBr
The aqueous solution was added by a double jet method over 2 minutes and 30 seconds. At this time, the silver potential was kept at 10 mV. An aqueous KBr solution was added to adjust the silver potential to -70 mV. A mentioned above
6.4 g of the gI fine grain emulsion was added in terms of KI mass. Immediately after the addition, an aqueous solution 40 containing 57 g of AgNO ₃
4 mL was added over 45 minutes. At this time, it was adjusted with an aqueous KBr solution so that the potential at the end of the addition was -30 mV. It was washed with water and chemically sensitized almost in the same manner as Em-A1.

(Em-D) (Emulsion of low-sensitivity blue-sensitive layer) In the preparation of Em-C, the amount of AgNO ₃ added at the time of nucleation was changed to 2.0 times. And the final AgNO ₃ , 57
g at the end of the addition of 404 mL of an aqueous solution containing
It changed so that it might adjust with KBr aqueous solution so that it might become mV. Except for this, it was prepared almost in the same manner as Em-C.

(Em-E) (Magenta color-forming layer having a spectral sensitivity peak at 480 to 550 nm) (Layer giving a layer effect to the red-sensitive layer) Low molecular weight gelatin having a molecular weight of 15000, 0.71 g, KBr, 0.92 g,
Modified silicone oil 0.2 used in the preparation of Em-A1
The aqueous solution containing 1200 g was maintained at 39 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred. AgNO ₃ , 0.45
g and an aqueous KBr solution containing 1.5 mol% of KI were added over 17 seconds by a double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 56 ° C. and ripened. After aging, 35μmol / g
Of phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97%. After adjusting the pH to 5.9, 2.9 g of KBr was added. A
Gno _3, an aqueous solution containing 28.8 g 288 mL of KBr
The aqueous solution was added by the double jet method over 53 minutes.
At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added so that the silver iodide content became 4.1 mol%, and the silver potential was lowered by -60 with respect to the saturated calomel electrode.
mV. After adding 2.5 g of KBr, AgN
An aqueous solution containing 87.7 g of O ₃ and an aqueous KBr solution were added by a double jet method over a period of 63 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the AgI fine grain emulsion was mixed with a silver iodide content of 10.5 mol.
% While simultaneously accelerating the flow and adding the silver potential at -70 mV. After adding 1 mg of thiourea dioxide, 132 m of an aqueous solution containing 41.8 g of AgNO ₃
L and KBr aqueous solution were added over 25 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After adding 2 mg of sodium benzenethiosulfonate, the pH was adjusted to 7.3. After adding KBr to adjust the silver potential to -70 mV, the above AgI fine grain emulsion was converted to 5.7 in terms of KI mass.
3 g were added. Immediately after the addition is completed, AgNO ₃ , 66.
609 mL of an aqueous solution containing 4 g was added over 10 minutes. During the initial 6 minutes of the addition, the silver potential was lowered to -70 with an aqueous KBr solution.
mV. After washing with water, gelatin was added and the pH and pAg were adjusted at 40 ° C. to 6.5 and 8.2, respectively. After adding compounds 1 and 2, the temperature was raised to 56 ° C. AgI mentioned above
After adding 0.0004 mol of the fine grain emulsion to 1 mol of silver, sensitizing dyes 13 and 14 were added. Potassium thiocyanate, chloroauric acid, sodium thiosulfate, N,
N-dimethylselenourea was added for optimal chemical sensitization. At the end of chemical sensitization, compounds 13 and 14 were added.

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[0749]

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(Em-F) (Emulsion for Medium-Sensitive Green-Sensitive Layer) Prepared in almost the same manner as Em-E except that the amount of AgNO ₃ added during nucleation was changed to 3.1 times in the preparation of Em-E. did. However, the sensitizing dye of Em-E was replaced with sensitizing dyes 15, 16
And changed to 17.

[0751]

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[0752]

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[0753]

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(Em-G) (Emulsion for low-sensitive green-sensitive layer) 0.70 g of low-molecular-weight gelatin having a molecular weight of 15,000, KB
r, 0.9 g, KI, 0.175 g, aqueous solution 1 containing modified silicone oil 0.2 g used in the preparation of Em-A1
200 mL was maintained at 33 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred. 2. an aqueous solution containing 1.8 g of AgNO ₃ and
An aqueous KBr solution containing 2 mol% of KI was added by a double jet method over 9 seconds. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 69 ° C. to ripen. After completion of the ripening, 27.8 g of trimellitated gelatin containing 35 μmol of methionine per gram and amino groups having a molecular weight of 100,000 and chemically modified with trimellitic acid was added.
After adjusting the pH to 6.3, 2.9 g of KBr was added. 270 mL of an aqueous solution containing 27.58 g of AgNO ₃
And an aqueous KBr solution were added by the double jet method over 37 minutes. At this time, an aqueous solution of low molecular weight gelatin having a molecular weight of 15,000, an aqueous solution of AgNO _{3, and an} aqueous solution of KI were prepared as disclosed in
An AgI fine grain emulsion having a grain size of 0.008 μm prepared by mixing immediately before addition in a separate chamber having a magnetic coupling induction type stirrer described in No. 43570 so that the silver iodide content becomes 4.1 mol%. At the same time,
The silver potential was kept at -60 mV with respect to the saturated calomel electrode. After adding 2.6 g of KBr, AgNO ₃ , 8 was added.
An aqueous solution containing 7.7 g and an aqueous KBr solution were added over a period of 49 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 3.1 times the initial flow rate. At this time, the AgI fine grain emulsion prepared by mixing immediately before the addition was accelerated simultaneously so that the silver iodide content became 7.9 mol%, and the silver potential was kept at -70 mV. Thiourea dioxide, 1m
After adding g, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After raising the temperature to 78 ° C. and adjusting the pH to 9.1, KBr was added to adjust the potential to −60 mV. Ag used in the preparation of Em-A1
5.73 g of I fine grain emulsion was added in terms of KI mass. Immediately after the addition was completed, 321 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 4 minutes. The silver potential was maintained at −60 mV with an aqueous KBr solution for 2 minutes at the beginning of the addition. Em-
Washed with water in almost the same manner as in F and chemically sensitized.

(Em-H) (Emulsion for low-sensitive green-sensitive layer) Ion-exchanged gelatin having a molecular weight of 100,000 and 17.8.
g, KBr, 6.2 g, KI, and 0.46 g of the aqueous solution were maintained at 45 ° C. and stirred vigorously. AgNO ₃ , 11.8
An aqueous solution containing 5 g and an aqueous solution containing 3.8 g of KBr were added over 47 seconds by the double jet method. After heating to 63 ° C., ion-exchanged gelatin having a molecular weight of 100,000
4.1 g was added and the mixture was aged. After aging sufficiently, AgN
An aqueous solution containing 133.4 g of O ₃ and an aqueous KBr solution were added by a double jet method over a period of 20 minutes so that the final flow rate was 2.6 times the initial flow rate. At this time, the silver potential was kept at +40 mV with respect to the saturated calomel electrode. Ten minutes after the start of the addition, 0.1 mg of K ₂ IrCl ₆ was added. Na
After adding 7 g of Cl, an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 12 minutes by a double jet method. At this time, the silver potential was kept at +90 mV.
Further, 100 mL of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of the addition. After adding 14.4 g of KBr, 6.3 g of the AgI fine grain emulsion used in the preparation of Em-A1 was added in terms of KI mass. Immediately after the addition was completed, an aqueous solution containing 42.7 g of AgNO ₃ and an aqueous KBr solution were added over 11 minutes by the double jet method. At this time, the silver potential was kept at +90 mV. It was washed with water and chemically sensitized almost in the same manner as Em-F. (Em-I) (Emulsion for low-sensitivity green-sensitive layer) The emulsion was prepared in substantially the same manner as in Em-H except that the temperature at the time of nucleation was changed to 38 ° C.

(Em-J1) (Emulsion for Highly Sensitive Red-Sensitive Layer) An aqueous solution 1 containing 0.38 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000, 0.38 g of KBr and 0.99 g of KBr
200 mL was kept at 60 ° C., the pH was adjusted to 2, and the mixture was vigorously stirred. Aqueous solution containing 1.96 g of AgNO ₃ and KB
An aqueous solution containing 1.97 g of r and 0.172 g of KI was added over 30 seconds by the double jet method. After completion of the ripening, 12.8 g of trimellitated gelatin containing 35 μmol of methionine per gram and amino groups having a molecular weight of 100,000 and chemically modified with trimellitic acid was added.
After adjusting the pH to 5.9, 2.99 g of KBr, Na
6.2 g of Cl were added. 60.7 mL of an aqueous solution containing 27.3 g of AgNO ₃ and an aqueous KBr solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at -50 mV with respect to the saturated calomel electrode. AgNO ₃ ,
An aqueous solution containing 65.6 g and a KBr aqueous solution were added over a period of 37 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate. At this time, Em-A1
The AgI fine grain emulsion used in the preparation of the above was added at the same time by accelerating the flow rate so that the silver iodide content became 6.5 mol%, and the silver potential was kept at -50 mV. After adding 1.5 mg of thiourea dioxide, 41.8 g of AgNO ₃ was added.
And an aqueous KBr solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to -100 mV. The above AgI fine grain emulsion was 6.2 in terms of KI mass.
g was added. Immediately after the addition, AgNO ₃ , 88.5
g of an aqueous solution containing 300 g was added over 8 minutes. Adjustment was made by adding an aqueous KBr solution so that the potential at the end of the addition was +60 mV. After washing with water, add gelatin and add
The pH was adjusted to 6.5 and pAg at 8.2 ° C. Compound 1
After adding 1 and 12, the temperature was raised to 61 ° C. After the addition of sensitizing dyes 18, 19, 20 and 21, K ₂ Ir
Optimum chemical sensitization was performed by adding Cl ₆ , potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea. Compounds 13 and 1 at the end of chemical sensitization
4 was added.

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[0759]

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[0760]

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(Em-J2) The compound (I-13) of the present invention was added to 1 × 10 ⁻⁴ at the time of chemical sensitization.
Emulsion Em-J2 was obtained in the same manner as Em-J1, except that mol / molAg was added. (Em-J3) Compound (IX-2-50) of the present invention was added to 1 × 1 at the time of chemical sensitization.
0 ^-4 mol / mol Ag was added which had got an emulsion Em-J3 in the same manner as Em-J 2.

(Em-J4 to J8) The compound (IV-2) of the present invention was added at the time of chemical sensitization to the sensitizing dye added at the time of chemical sensitization so as to have the content shown in (Table 1). Em except for
In the same manner as in -J1, emulsions Em-J4 to Em-J8 were obtained. (Em-J9 to J13) The compound of the present invention was converted to (IV-
Em-J9 to J13 were obtained in the same manner as Em-J2, except that the sensitizing dye added during chemical sensitization with addition of 2) was added as shown in (Table 1).

(Em-J14) Phthalated gelatin having a phthalation ratio of 97% and a molecular weight of 100,000, 0.38 g, KB
1,200 mL of an aqueous solution containing 0.99 g of r was maintained at 60 ° C., the pH was adjusted to 2, and the mixture was vigorously stirred. AgNO ₃ ,
An aqueous solution containing 1.96 g, KBr, 1.97 g, KI,
An aqueous solution containing 0.172 g was added over 30 seconds by the double jet method. After ripening, 35 μmo per g
12.8 g of trimellitated gelatin containing 1 methionine and chemically modifying amino groups having a molecular weight of 100,000 with trimellitic acid was added. After adjusting the pH to 5.9, 2.99 g of KBr and 6.2 g of NaCl were added. 60.7 mL of an aqueous solution containing 27.3 g of AgNO ₃
And an aqueous KBr solution were added by the double jet method over 35 minutes. At this time, the silver potential is-with respect to the saturated calomel electrode.
It was kept at 50 mV. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were added over a period of 37 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at an accelerated flow rate such that the silver iodide content became 6.5 mol%, and the silver potential was adjusted to -50 mV.
Kept. After adding 1.5 mg of thiourea dioxide,
132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and KB
The r aqueous solution was added by the double jet method over 13 minutes. KB so that the silver potential at the end of the addition becomes +40 mV.
The addition of the aqueous solution was adjusted. After adding 2 mg of sodium benzenethiosulfonate, the temperature was lowered to 40 ° C., and KB
r was added to adjust the silver potential to -40 mV. While maintaining the temperature at 40 ° C., an aqueous solution containing 14.2 g of sodium p-iodoacetamidobenzenesulfonate (monohydrate) was added.
mL was added at a fixed rate for 1 minute to generate iodide ions while controlling the pH at 9.0.
After raising the temperature over a period of minutes, the pH was returned to 5.5. Then, immediately, an aqueous solution 300 containing 88.5 g of AgNO ₃
mL was added over 20 minutes. During the addition, use KBr aqueous solution-
It was kept at 50mV. After washing with water, gelatin was added and the pH was adjusted to 6.5 and pAg at 8.2 at 40 ° C. Subsequent steps were the same as those for Em-J1.

(Em-J15) Em-J15 was obtained in the same manner as Em-J14, except that 1 × 10 ⁻⁴ mol / mol Ag of compound (I-13) of the present invention was added during chemical sensitization. (Em-J16) Em-J16 was obtained in the same manner as Em-J15, except that the compound (IV-2) of the present invention was added at 25 mol% to the sensitizing dye added during chemical sensitization. . (Em-J17) Compound of the present invention (IX-2-5) upon chemical sensitization
Emulsion Em-J17 was obtained in the same manner as Em-J16 except that 0) was added at 1 × 10 ⁻⁴ mol / molAg.

(Em-J18) Molecular weight 10 at 97% phthalation
0000 phthalated gelatin, 0.38 g, KBr,
1200 mL of an aqueous solution containing 0.99 g was kept at 60 ° C.
The pH was adjusted to 2 and stirred vigorously. AgNO ₃ , 1.9
Aqueous solution containing 6 g, KBr, 1.97 g, KI, 0.1
An aqueous solution containing 72 g was added by the double jet method over 30 seconds. After ripening, trimellited gelatin containing 35 μmol of methionine per gram and having 100,000 molecular weight amino groups chemically modified with trimellitic acid 1
2.8 g were added. After adjusting the pH to 5.9, KB
2.99 g of r and 6.2 g of NaCl were added. AgN
60.7 mL of an aqueous solution containing 27.3 g of O ₃ and an aqueous KBr solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at -50 mV with respect to the saturated calomel electrode. Aqueous solution containing 65.6 g of AgNO ₃ and KBr
The final flow rate of the aqueous solution is double jet method and the final flow rate is 2.
The flow rate was accelerated so as to be one-fold, and added over 37 minutes. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at an accelerated flow rate such that the silver iodide content became 6.5 mol%, and the silver potential was kept at -50 mV. After adding 1.5 mg of thiourea dioxide, AgN
132 mL of an aqueous solution containing 41.8 g of O ₃ and an aqueous KBr solution were added over 13 minutes by a double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV. After adding 2 mg of sodium benzenethiosulfonate, the temperature was lowered to 50 ° C. While keeping the temperature at 50 ° C., 55 mL of a 0.3% KI aqueous solution was added over 10 minutes. Immediately thereafter, 100 mL of an aqueous solution containing 14.2 g of AgNO ₃ , 2.1 g of NaCl, and KBr 4.1.
120 mL of aqueous solution containing 7 g and 0.0133 AgI fine particles
The solution containing mol was added at the same time. At this time, 9.4 × 10 ⁻⁴ mol of K ₄ [RuCN ₆ ] was present per 1 mol of AgNO ₃ added. Thereafter, a sensitizing dye was added (for epitaxial stabilization). After washing with water, gelatin was added and pH 6.5 at 40 ° C., pAg,
Adjusted to 8.2. Subsequent steps were the same as those for Em-J1.

(Em-J19) Em-J19 was obtained in the same manner as Em-J18, except that compound (I-13) of the present invention was added at 1 × 10 ⁻⁴ mol / mol Ag during chemical sensitization. (Em-J20) Em-J20 was obtained in the same manner as Em-J19, except that the compound (IV-2) of the present invention was added during chemical sensitization so as to be 25 mol% with respect to the sensitizing dye. . (Em-J21) Compound of the present invention (IX-2-5) upon chemical sensitization
Emulsion Em-J21 was obtained in the same manner as Em-J20 except that 1) was added at 1 × 10 ⁻⁴ mol / mol Ag.

(Em-J22) Molecular weight 10 at 97% phthalation
0000 phthalated gelatin, 0.38 g, KBr,
1200 mL of an aqueous solution containing 0.99 g is kept at 60 ° C.
The pH was adjusted to 2 and stirred vigorously. AgNO ₃ , 1.9
Aqueous solution containing 6 g, KBr, 1.97 g, KI, 0.1
An aqueous solution containing 72 g was added by the double jet method over 30 seconds. After ripening, trimellited gelatin containing 35 μmol of methionine per gram and having 100,000 molecular weight amino groups chemically modified with trimellitic acid 1
2.8 g were added. After adjusting the pH to 5.9, KB
2.99 g of r and 6.2 g of NaCl were added. An aqueous solution containing 92.9 g of AgNO _3, 762 mL of an aqueous solution containing 60.8 g of KBr, 5.9 g of KI, and 762 mL of an aqueous solution containing 38.1 g of gelatin having a molecular weight of 20,000 were simultaneously added to a stirring device installed outside the reaction vessel, and the silver iodide content was changed. 6.5mol%
AgBrI fine grain emulsion (average size: 0.015 μm)
While preparing m), this AgBrI emulsion was added into the reaction vessel over 90 minutes. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode. Thiourea dioxide,
After adding 1.5 mg, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 13 minutes by a double jet method. The silver potential at the end of the addition is +4
The addition of the aqueous KBr solution was adjusted to be 0 mV. After adding 2 mg of sodium benzenethiosulfonate, the temperature was lowered to 50 ° C. The temperature was lowered to 40 ° C., and KBr was added to adjust the silver potential to −40 mV. While maintaining the temperature at 40 ° C., an aqueous solution containing 14.2 g of sodium p-iodoacetamidobenzenesulfonate (monohydrate) was added, and then 57 mL of a 0.8 M aqueous sodium sulfite solution was quantitatively added for 1 minute to adjust the pH. Iodide ions were generated while controlling the pH at 9.0, and after 2 minutes, the temperature was raised to 55 ° C. over 15 minutes, and then the pH was returned to 5.5. Then immediately A
300 mL of an aqueous solution containing 88.5 g of gNO ₃ was added over 20 minutes. During the addition, the solution was kept at -50 mV with an aqueous KBr solution. After washing with water, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added when measured according to the PAGI method.
Adjusted to 6.5, pAg, 8.2. The subsequent process is Em
The same processing as -J1 was performed.

(Em-J23) Em-J23 was obtained in the same manner as Em-J22, except that compound (I-13) of the present invention was added at 1 × 10 ⁻⁴ mol / mol Ag during chemical sensitization. (Em-J24) Em-J24 was obtained in the same manner as Em-J23 except that the compound (IV-2) of the present invention was added so as to be 25 mol% with respect to the sensitizing dye added during chemical sensitization. . (Em-J25) 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention and the compound (IX-2-50) during chemical sensitization
Was obtained in the same manner as Em-J24 except that 1 × 10 ⁻⁴ mol / molAg was added.

[0769]

[Table 1]

(Em-K) (Emulsion for middle-sensitivity red-sensitive layer) 4.9 g of low molecular weight gelatin having a molecular weight of 15,000, KB
1200 mL of an aqueous solution containing 5.3 g of r was maintained at 60 ° C. and stirred vigorously. 27 mL of an aqueous solution containing 8.75 g of AgNO ₃ and 36 mL of an aqueous solution containing 6.45 g of KBr were added by a double jet method over 1 minute. After heating to 77 ° C., 21 mL of an aqueous solution containing 6.9 g of AgNO ₃
Was added over 2.5 minutes. NH ₄ NO ₃ , 26 g, 1
After successive addition of N, NaOH and 56 mL, the mixture was aged. After aging, the pH was adjusted to 4.8. AgNO ₃ ,
438 mL of an aqueous solution containing 141 g and 102.6 of KBr.
g of an aqueous solution was added by a double jet method so that the final flow rate was four times the initial flow rate. After cooling to 55 ° C., 240 mL of an aqueous solution containing 7.1 g of AgNO ₃
And an aqueous solution containing 6.46 g of KI by the double jet method.
Added over minutes. After adding 7.1 g of KBr, 4 mg of sodium benzenethiosulfonate and K ₂ IrC
l _6, was 0.05mg added. 177 mL of an aqueous solution containing 57.2 g of AgNO ₃ and 223 mL of an aqueous solution containing 40.2 g of KBr were added by a double jet method over 8 minutes. It was washed with water and chemically sensitized almost in the same manner as Em-J.

(Em-L) (Emulsion for Medium-Sensitive Red-Sensitive Layer) The emulsion was prepared in substantially the same manner as in the preparation of Em-K except that the temperature during nucleation was changed to 42 ° C. (Em-M, N, O) (Emulsion for low-sensitivity red-sensitive layer) It was prepared almost in the same manner as Em-H or Em-I. However, the chemical sensitization was carried out in substantially the same manner as in Em-J1.

(Em-P1) (Emulsion for high-sensitivity green-sensitive layer) Em-J1 was obtained by changing the sensitizing dyes to 15, 16 and 17 and optimally performing chemical sensitization. Was. (Em-P2) 1 × 10 ⁻⁴ mol / mol of the compound (I-13) of the present invention during chemical sensitization
Except for adding Ag, Em-P2 was obtained in the same manner as Em-P1. (Em-P3) 1 × 1 of the compound (IX-2-50) of the present invention during chemical sensitization
0 ^-4 mol / mol Ag was added which had had in the same manner as Em-P 2 obtained emulsion Em-P3.

(Em-P4) A sensitizing dye was added to Em-J14.
Change to 5, 16 and 17 for optimal chemical sensitization
Em-P4 was obtained. (Em-P5) Compound (I-13) of the present invention was added to 1 × 10
Em-P5 in the same manner as Em-P4 except that ^-4 mol / molAg was added.
Got. (Em-P6) Compound of the present invention (IX-2-5) upon chemical sensitization
Emulsion Em-P6 was obtained in the same manner as Em-P5 except that 1) was added at 1 × 10 ⁻⁴ mol / mol Ag.

(Em-P7) 1 sensitizing dye was added to Em-J18.
Change to 5, 16 and 17 for optimal chemical sensitization
Em-P7 was obtained. (Em-P8) Compound (I-13) of the present invention was added to 1 × 10
Em-P8 in the same manner as Em-P7 except that ^-4 mol / molAg was added.
Got. (Em-P9) The compound of the present invention (IX-2-5) upon chemical sensitization
Emulsion Em-P9 was obtained in the same manner as Em-P8 except that 1) was added at 1 × 10 ⁻⁴ mol / mol Ag.

(Em-P10) A sensitizing dye was added to Em-J22.
Change to 5, 16 and 17 for optimal chemical sensitization
Em-P10 was obtained. (Em-P11) Compound (I-13) of the present invention was added 1 × 1 during chemical sensitization.
Except that 0 ^-4 mol / molAg was added, Em-P
I got 11. (Em-P12) Compound of the present invention (IX-2-5) upon chemical sensitization
Emulsion Em-P12 was obtained in the same manner as Em-P11, except that 0) was added at 1 × 10 ⁻⁴ mol / molAg. The properties of the silver halide emulsions Em-A to P thus obtained are shown in Table 2.

[0776]

[Table 2]

[0777] The outline of the preparation of the emulsion of the present invention is shown below. A solution in which the coupler is dissolved in ethyl acetate, a high-boiling organic solvent, and a surfactant are added to a 10% gelatin solution, and the mixture is emulsified using a mixed homogenizer (Nippon Seiki) to obtain an emulsion.

1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
0 parts by mass and Tinuvin P. as an ultraviolet absorber. 3
26 (manufactured by Ciba-Geigy), 2 parts by weight, and after melting at 300 ° C., extruding from a T-die, performing longitudinal stretching 3.3 times at 140 ° C., and then 130 ° C. And then stretched 3.3 times in the horizontal direction.
For 6 seconds to obtain a PEN (polyethylene naphthalate) film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye and a yellow dye (public technique: I-1, described in Japanese Patent Publication No. 94-6023).
I-4, I-6, I-24, I-26, I-27, II-
5) was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of Undercoat Layer The above support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both surfaces, and then gelatin 0.1 g / m ² and sodium α- Sulfodi-2-
Ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g
/ M ² , (CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH
₂ 0.012 g / m ² , a polyamide-epichlorohydrin polycondensate 0.02 g / m ² primer solution (10 m
L / m ² , using a bar coater), and an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer On one side of the support after the undercoating, an antistatic layer, a magnetic recording layer and a slip layer having the following composition were coated as a back layer. 3-1) Coating of antistatic layer The specific resistance of the tin oxide-antimony oxide composite having an average particle size of 0.005 μm is 0 μm in a dispersion of fine particle powder (secondary aggregated particle size of about 0.08 μm) of 5 Ω · cm. .2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 N
HCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g /
It was coated with m ² and resorcin.

3-2) Coating of Magnetic Recording Layer 3-Cobalt-γ-iron oxide coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) (specific surface area 43 m ²⁾ / G, major axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 Am ²
/ Kg, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface of which is treated with aluminum oxide silicon oxide at 2% by mass of iron oxide) 0.0
6 g / m ² was added to diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out by an open kneader and a sand mill), and C ₂ H ₅ C (CH ₂ OCONH-C ₆ H) was used as a curing agent.
₃ (CH ₃ ) NCO) ₃ was applied with a bar coater using 0.3 g / m ² of acetone, methyl ethyl ketone and cyclohexanone as a solvent to obtain a 1.2 μm-thick magnetic recording layer. Silica particles (0.3 μm) and 3-
Abrasive aluminum oxide (0.15 μm) coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) was coated at 10 mg /
m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.).
° C). X- light increase of the color density of about 0.1 D ^B of the magnetic recording layer in the (blue filter), and saturation magnetization moment of the magnetic recording layer is 4.2Am ² / kg, a coercive force 7.3
× 10 ⁴ A / m, and the squareness ratio was 65%.

3-3) Preparation of Sliding Layer Diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH
(OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg /
m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b,
9 mg / m ² ) mixture was applied. In addition, this mixture is xylene / propylene monomethyl ether (1/1 /
In 1), the mixture was melted at 105 ° C. and poured into and dispersed in propylene monomethyl ether (10-fold amount) at room temperature to prepare a dispersion, which was then dispersed in acetone (average particle size: 0.01 μm) and then added. As a matting agent, silica particles (0.3 μm) and aluminum oxide (0.15 μm) coated with 3-poly (degree of polymerization 15) oxyethylenepropyloxytrimethoxysilane (15% by mass) as an abrasive are each 15 mg / m 2.
² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.).
° C). The sliding layer has a dynamic friction coefficient of 0.06 (stainless steel hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (clip method), and a dynamic friction coefficient of an emulsion surface and a sliding layer described later of 0.12. Excellent characteristics.

4) Coating of Photosensitive Layer Next, on the side opposite to the support of the back layer obtained above, each layer having the following composition was applied in multiple layers to prepare a sample as a color negative photosensitive material. The samples are (Table 3), (Table 4),
And using emulsions, emulsions and couplers as shown in Table 5 below. Emulsions, couplers, high boiling organic solvents and surfactants were replaced in equal amounts. When a plurality is used, replacement is performed so that the total is replaced by an equal amount. Specifically, in the case of two, it is 1/3 each, and in the case of three, it is 1
Replaced by / 3.

(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 hardener (specific compounds are described below, numbers are added after symbols, and chemical formulas are listed after the numbers.) The numbers corresponding to each component are expressed in g / m ^2. In the case of silver halide, the coating amount is expressed in terms of silver.

[0785]   First layer (first antihalation layer)   Black colloidal silver silver 0.155   0.07 μm surface fogging AgBrI (2) silver 0.01   Gelatin 0.87   ExC-1 0.002   ExC-3 0.002   Cpd-2 0.001   HBS-1 0.004   HBS-2 0.002

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.066 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid Disperse Dye ExF -2 0.015 solid disperse dye ExF-3 0.020

[0787]   Third layer (middle layer)   0.07μ AgBrI (2) 0.020   ExC-2 0.022   Polyethyl acrylate latex 0.085   Gelatin 0.294

[0788]   4th layer (low-sensitivity red-sensitive emulsion layer)   Silver iodobromide emulsion M silver 0.065   Silver iodobromide emulsion N silver 0.100   Silver iodobromide emulsion O silver 0.158   ExC-1 0.109   ExC-3 0.044   ExC-4 0.072   ExC-5 0.011   ExC-6 0.003   Cpd-2 0.025   Cpd-4 0.025   HBS-1 0.17   Gelatin 0.80

[0789]   Fifth layer (medium-speed red-sensitive emulsion layer)   Silver iodobromide emulsion K silver 0.21   Silver iodobromide emulsion L silver 0.62   ExC-1 0.14   ExC-2 0.026   ExC-3 0.020   ExC-4 0.12   ExC-5 0.016   ExC-6 0.007   Cpd-2 0.036   Cpd-4 0.028   HBS-1 0.16   Gelatin 1.18

[0790]   6th layer (high sensitivity red-sensitive emulsion layer)   Silver iodobromide emulsion J silver 1.67   ExC-1 0.18   ExC-3 0.07   ExC-6 0.047   Cpd-2 0.046   Cpd-4 0.077   HBS-1 0.25   HBS-2 0.12   Gelatin 2.12

[0791]   7th layer (middle layer)   Cpd-1 0.089   Solid disperse dye ExF-4 0.030   HBS-1 0.050   Polyethyl acrylate latex 0.83   Gelatin 0.84

[0792]   Eighth layer (multilayer effect donor layer (layer giving multilayer effect to red sensitive layer))   Silver iodobromide emulsion E silver 0.560   Cpd-4 0.030   ExM-2 0.096   ExM-3 0.028   ExY-1 0.031   ExG-1 0.006   HBS-1 0.085   HBS-3 0.003   Gelatin 0.58

[0793]   9th layer (low sensitivity green-sensitive emulsion layer)   Silver iodobromide emulsion G silver 0.39   Silver iodobromide emulsion H silver 0.28   Silver iodobromide emulsion I silver 0.35   ExM-2 0.36   ExM-3 0.045   ExG-1 0.005   HBS-1 0.28   HBS-3 0.01   HSB-4 0.27   Gelatin 1.39

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion F 0.20 Silver Iodobromide Emulsion G Silver 0.25 ExC-6 0.009 ExM-2 0.031 ExM-30 0.029 ExY-1 0.006 ExM-4 0.028 ExG-1 0.005 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 Gelatin 0.44

[0795]   11th layer (high-sensitivity green-sensitive emulsion layer)   Emulsion Em-P1 of Example 1 silver 1.200   ExC-6 0.004   ExM-1 0.016   ExM-3 0.036   ExM-4 0.020   ExM-5 0.004   ExY-5 0.008   ExM-2 0.013   Cpd-4 0.007   HBS-1 0.18   Polyethyl acrylate latex 0.099   Gelatin 1.11

[0796]   12th layer (yellow filter layer)   Yellow colloidal silver silver 0.047   Cpd-1 0.16   ExF-5 0.010   Solid disperse dye ExF-6 0.010   HBS-1 0.082   Gelatin 1.057

13th Layer (Low Sensitive Blue Sensitive Emulsion Layer) Silver iodobromide emulsion B silver 0.18 silver iodobromide emulsion C silver 0.20 silver iodobromide emulsion D silver 0.07 ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-10 .24 Gelatin 1.41

Fourteenth Layer (High Sensitive Blue Sensitive Emulsion Layer) Silver Iodobromide Emulsion A Silver 0.75 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd- 2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91

15th layer (first protective layer) AgBrI (2) 0.07 μm silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F- 11 0.009 F-18 0.005 F-19 0.005 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3

Sixteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.15 B-30 .05 S-1 0.20 Gelatin 0.75

Further, in each layer, storability, processability, pressure resistance, fungicidal / bactericidal properties, B-4 to B-6, F-1 to F-17 and iron salts, lead salts, gold salts , Platinum salts, palladium salts, iridium salts, ruthenium salts and rhodium salts. The coating liquid for the eighth layer was 8.5 × 10 ⁻³ g per mol of silver halide, and the coating solution for the eleventh layer was 7.9 × 1-3.
0 ^-3 grams of calcium was added at calcium nitrate solution, to prepare a sample. Further, at least one kind of W-1, W-6, W-7 and W-8 is contained for improving the antistatic property, and at least one kind of W-2 and W-5 is contained for improving the coating property. Contains.

Preparation of Organic Solid Disperse Dye ExF-3 shown below was dispersed by the following method. That is, water 2
1.7 mL and 5 mL of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonic acid 3 mL and 5 mL
A 0.5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was placed in a 700 mL pot mill, and 5.0 g of the dye ExF-3 and 500 mL of zirconium oxide beads (1 mm in diameter) were added. Was dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, take out the contents,
The solution was added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

[0813] In the same manner, a solid dispersion of ExF-4 was obtained. The average particle diameter of the fine dye particles was 0.24 μm. ExF-2 is disclosed in European Patent Application Publication (EP) 54
No. 9,489A, the microprecipitation (M
(microprecipitation). The average particle size was 0.06 μm. ExF-
The solid dispersion of No. 6 was dispersed by the following method. 4000g per 2800g of ExF-6 wet cake containing 18% water
Of water and 376 g of a 3% solution of W-2 were added and stirred.
A slurry having a concentration of 32% of xF-6 was obtained. Next, 1700 mL of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and the mixture was crushed for 8 hours at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min through the slurry. did. Average particle size is 0.4
It was 5 μm. The compounds used for forming each of the above layers are as shown below.

[0804]

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[0805]

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[0806]

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[0807]

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[0808]

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[0809]

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[0810]

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[0811]

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[0812]

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[0813]

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[0814]

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[0815]

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[0816]

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[0817]

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[0818]

[Table 3]

[0819]

[Table 4]

[0820]

[Table 5]

[0821] The evaluation method of the sample is as follows. Exposure was performed for 1/100 second through a gelatin filter SC-39 (a long-wavelength light transmission filter having a cut-off wavelength of 390 nm) manufactured by FUJIFILM Corporation and a continuous wedge. The development was performed as follows using an automatic developing machine FP-360B manufactured by Fuji Photo Film Co., Ltd. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged into the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in Hatsumei Kyokai Disclosure Technique No. 94-4992.

The processing steps and the composition of the processing solution are shown below. (Processing process) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C-5L fixing (2) 50 38.0 ℃ 8mL 5L Washing with water 30sec 38.0 ℃ 17mL 3L stable (1) 20sec 38.0 ℃-3L stable (2) 20sec 38.0 ℃ 15mL 3L Drying 1min 30sec 60.0 ℃ * Replenishment amount is photosensitive material The stabilizing solution and the fixing solution were counter-current systems from (2) to (1) per 1.1 m of 35 mm width and the overflow solution of washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 2.5 mL and 2.0 mL per 1.1 mm width of the photosensitive material, respectively. It was 2.0 mL. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous process. The opening area of the above processor is 100 cm ^{2 for the} color developing solution and 120 c for the bleaching solution.
m ² and other treatment liquids were about 100 cm ² .

[0823] The composition of the treatment liquid is shown below.   (Color developing solution) Tank solution (g) Replenisher (g)   Diethylenetriaminepentaacetic acid 3.0 3.0   Catechol-3,5-disulfonic acid     Disodium 0.3 0.3   Sodium sulfite 3.9 5.3   Potassium carbonate 39.0 39.0   Disodium-N, N-bis (2-sul     Honatoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   1.3 mg of potassium iodide   4-hydroxy-6-methyl-1,3,3     3a, 7-tetrazaindene 0.05-   Hydroxylamine sulfate 2.4 3.3   2-methyl-4- [N-ethyl-N-     (Β-hydroxyethyl) amino]     Aniline sulfate 4.5 6.5   Add water 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching solution) Tank solution (g) Replenisher (g) 1,3-diaminopropanetetraacetic acid ferric ammonium ammonium monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Add water 1.0L 1.0L pH [adjusted with ammonia water] 4.6 4.0 (Fixing (1) tank liquid) 5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid (PH 6.8)

[0825]   (Fixing (2)) Tank liquid (g) Replenisher (g)   Ammonium thiosulfate aqueous solution 240 mL 720 mL   (750 g / L)   Imidazole 7 21   Ammonium methanethiosulfonate 515   Ammonium methanesulfinate 10 30   Ethylenediaminetetraacetic acid 13 39   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Co.)
120B) and a mixed bed column filled with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / L or less, followed by sodium diisocyanurate 20 mg / L and sodium sulfate 150 mg / L.
Was added. The pH of this solution was in the range of 6.5 to 7.5.

[0827]   (Stabilizer) Common to tank and replenisher (g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether 0.2     (Average degree of polymerization 10)   1,2-benzisothiazolin-3-one sodium 0.10   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) piperazine 0.75   Add water and 1.0L   pH 8.5

[0827] The above-mentioned treatment was applied to Samples 101 to 125. The same treatment was applied to a sample aged for 3 days at 50 ° C. and 80% RH. The photographic performance was evaluated by measuring the density of the processed sample with a blue filter. The results obtained are shown in (Table 6).

In the emulsion of the present invention, a combination of the compound of the general formula (I) of the present invention with the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention and By the combination with the high boiling organic solvent of the invention and the combination of the general formula (I) of the present invention and the general formula (IV) or (V) of the present invention, a photosensitive material having low fog and high sensitivity can be achieved. Further, as described above, the general formula (VI) of the present invention
By combining the compounds of (X) to (X), a photosensitive material having strong storage fog resistance was achieved.

[0830]

[Table 6]

[0831] Samples 201 to 216 were subjected to the above treatment. The same treatment was applied to a sample aged for 3 days at 50 ° C. and 80% RH. The photographic performance was evaluated by measuring the density of the processed sample with a green filter. The results obtained are shown in (Table 7).

In the emulsion of the present invention, the combination of the compound of the general formula (I) of the present invention with the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention and By the combination with the high boiling organic solvent of the invention and the combination of the general formula (I) of the present invention and the general formula (IV) or (V) of the present invention, a photosensitive material having low fog and high sensitivity can be achieved. Further, as described above, the general formula (VI) of the present invention
By combining the compounds of (X) to (X), a photosensitive material having strong storage fog resistance was achieved.

[0832]

[Table 7]

[0834] Samples 301 to 330 were subjected to the above treatment. The same treatment was applied to a sample aged for 3 days at 50 ° C. and 80% RH. The photographic performance was evaluated by measuring the density of the processed sample with a red filter. The results obtained are shown in (Table 8).

In the emulsion of the present invention, the combination of the compound of the general formula (I) of the present invention with the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention and By the combination with the high boiling organic solvent of the invention and the combination of the general formula (I) of the present invention and the general formula (IV) or (V) of the present invention, a photosensitive material having low fog and high sensitivity can be achieved. Further, as described above, the general formula (VI) of the present invention
By combining the compounds of (X) to (X), a photosensitive material having strong storage fog resistance was achieved.

[0836]

[Table 8]

From the above results, it can be seen that the combination of the compounds of the present invention can provide a silver halide photographic light-sensitive material having high sensitivity and low fogging, little desensitization after thermostat and little increase in fogging.

(Example 2) Emulsion Em-X1: (100) Silver iodobromide tabular emulsion In a reaction vessel, polyvinyl alcohol (polyvinyl alcohol having a polymerization degree of vinyl acetate of 1700 and an average saponification rate to the alcohol of 98%; Polymer (PV)) and an aqueous gelatin solution (containing 5 g of the polymer (PV) and 8 g of deionized alkali-treated gelatin in 1200 mL of water) were prepared.
Adjust to 1 and maintain temperature at 55 ° C. Ag-1 with stirring
Solution (containing 0.58mol / L of AgNO ₃ ) 200mL and X-1 solution (KBr 0.58m
ol / L) (200 mL) was added over 40 minutes. The addition was performed by a double jet method using a precision liquid sending pump.

After 5 minutes, the pH was adjusted to 6, and the Ag-2 solution (A
gNO ₃ 1.177mol / L) and X-2 solution (KBr 1.177mol / L).
A 600 mL quantitative double jet was added at a rate of / jet / min. Next, an aqueous gelatin solution (200 mL of water containing 30 g of gelatin) and spectral sensitizing dye 2
2, 23, and 24 were added, and the Ag-3 solution (AgNO ₃ 2.94m
ol / L) and X-3 solution (KBr 2.7mol / L, KI 0.24mol / L)
Was added at 5 mL / min to complete the particle formation. Thereafter, the temperature was lowered to 35 ° C., and water was washed by a precipitation washing method.
An aqueous gelatin solution was added to redisperse the emulsion, and the pH was adjusted to 6, p.
Ag was adjusted to 8.3.

Embedded image

[0838] The grains prepared by the above method were found to have a total projected area of 9 as a result of being determined from a replica TEM image of the emulsion grains.
3% were the following particles. The main plane was a (100) plane, the equivalent sphere diameter was 0.4 μm or more, the particle thickness was 0.08 μm, and the aspect ratio was 9.5 or more. The above emulsion was optimally subjected to chemical sensitization with reference to Em-J1 shown in Example 1 except for the sensitizing dye to obtain Em-X1.

(Em-X2) The compound (I-13) of the present invention was added at 1 × 10 ⁻⁴ mol / mol during chemical sensitization.
Em-X2 was obtained in the same manner as Em-X1, except that Ag was added. It was obtained (Em-X3) Em-X3 except for adding 10 mol% relative to the compound (IV-2) sensitizing dye was added in the same manner as Em-X 2 of the present invention at the time of chemical sensitization. (Em-X4) Compound (IX-2-50) of the present invention was added to 1 × 1 at the time of chemical sensitization.
0 ^-4 mol / mol Ag was added which had had in the same manner as Em-X3 to give the emulsion Em-X4.

Each of the emulsions was dissolved and allowed to stand at 40 ° C. for 30 minutes on a cellulose triacetate film support provided with an undercoat layer.
-X1 to X4 were applied.

[0843]

[Table 9]

Samples 401 to 405 were prepared by changing the emulsion to be coated as shown in Table 10.

[0845]

[Table 10]

[0846] These samples were subjected to a hardening treatment at 40 ° C and a relative humidity of 70% for 14 hours. Thereafter, the sample was exposed to light for 1/100 second through a continuous wedge, and the density of the processed sample was measured with a green filter to determine the photographic sensitivity and the fog density before long-term storage. The sensitivity was indicated by a relative value of the reciprocal of the exposure required to reach a density of fog density plus 0.2. To evaluate the storage fog of the photographic material, the sample was stored for 14 days under conditions of 40 ° C. and 60% relative humidity, exposed for 1/100 second, and the sample subjected to the following development processing was measured for density using a green filter for a long time. The fog density after storage was determined, and the difference in fog density before and after storage was determined. Developed by Fuji Photo Film Co., Ltd. automatic developing machine FP-36
Performed as follows using 2B.

The processing steps and the composition of the processing solution are shown below. (Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 15 mL 10.3 L Bleaching 50 seconds 38 ° C 5 mL 3.6 L Fixing (1) 50 seconds 38 ° C-3.6 L Fixing (2) 50 seconds 38 ° C 7.5mL 3.6L stable (1) 30 seconds 38 ° C-1.9L stable (2) 20 seconds 38 ° C-1.9L stable (3) 20 seconds 38 ° C 30mL 1.9L dry 1 minute 30 seconds 60 ° C * Replenishment amount is 35 mm of photosensitive material and 1.1 m width (equivalent to 24 Ex. 1 bottle).
The fixing solution is also connected from (2) to (1) by a countercurrent pipe. Further, 15 mL corresponding to the replenishing amount of the tank solution of the stabilizing solution (2) is supplied to the fixing solution (2). Further, the color developer is a replenisher and a color developer (B) having the following formulation.
The replenisher was divided into 12 mL and 3 mL, each corresponding to the replenishment amount, and replenished to a total of 15 mL. Note that the amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step are all the same.
It was 2.0 mL per 1.1 m in mm width. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous process.

[0848] The composition of the treatment liquid is shown below.   (Color developing solution (A)) <Tank solution> <Replenisher> Diethylenetriaminepentaacetic acid 2.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate                                                 0.4g 0.5g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine                                               10.0g 15.0g Sodium sulfite 4.0 g 9.0 g Hydroxylamine sulfate 2.0 g − 1.4 g of potassium bromide- Diethylene glycol 10.0 g 17.0 g Ethylene urea 3.0 g 5.5 g 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino]         Aniline sulfate 4.7 g 11.4 g Potassium carbonate 39g 59g Add water 1.0L 1.0L pH (prepared with sulfuric acid and KOH) 10.05 10.50

The above-mentioned tank liquid is as follows (color developing solution (B))
The composition after mixing is shown. (Color developing solution (B)) <Tank solution><Replenisher> Hydroxylamine sulfate 2.0 g 4.0 g Water was added to 1.0 L 1.0 L pH (prepared with sulfuric acid and KOH) 10.05 4.0 The above-mentioned tank liquid shows the composition after mixing the (color developing solution (A)).

[0850]   (Bleaching solution) <Tank solution> <Replenisher> Ferric ammonium salt of 1,3-diaminopropanetetraacetic acid-water salt                                         120g 180g Ammonium bromide 50g 70g Succinic acid 30g 50g Maleic acid 40g 60g Imidazole 20g 30g Add water 1.0L 1.0L pH (adjusted with aqueous ammonia and nitric acid) 4.6 4.0

[0851]   (Fixing solution) <Tank solution> <Replenisher> Ammonium thiosulfate (750 g / L) 280 mL 1000 mL Ammonium bisulfite aqueous solution (72%) 20g 80g Imidazole 5g 45g 1-mercapto-2- (N, N-dimethylaminoethyl) -tetrazole                                             1g 3g Ethylenediaminetetraacetic acid 8g 12g Add water 1L 1L pH (adjusted with aqueous ammonia and nitric acid) 7.0 7.0

[0852]   (Stabilizer) <Common to tank and replenisher> Sodium p-toluenesulfinate 0.03 g p-Nonylphenoxy polyglycidol (glycidol average polymerization degree 10)                                               0.4g Ethylenediaminetetraacetic acid disodium salt 0.05g 1.3 g of 1,2,4-triazole 1,4-bis (1,2,4-triazol-1-ylmethyl)     0.75 g of piperazine 1,2-benzisothiazolin-3-one 0.10 g Add water and 1.0L pH 8.5

The results of evaluation by the above method are shown in Table 11
Shown in The sensitivity was indicated by a relative value of the reciprocal of the exposure required to reach a density of fog density plus 0.2. In the emulsion of the present invention, the combination of the compound of the general formula (I) of the present invention with the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention and By the combination with the boiling point organic solvent and the combination of the general formula (I) of the present invention and the general formula (IV) of the present invention, a photosensitive material having low fogging and high sensitivity was able to be achieved. Furthermore, by combining the compounds of the general formulas (VI) to (X) of the present invention as described above, a photosensitive material having high storage fog resistance was able to be achieved.

[0854]

[Table 11]

(Example 3) Emulsion Em-Y1: 2.0 g of sodium chloride and 2.8 g of inert gelatin were added to 1.2 L of (111) silver chloride tabular grain water, and the mixture was stirred in a container maintained at 35 ° C. Ag while
Solution-1 (60 mL, containing silver nitrate 9 g) and Solution X-1 (60 mL, containing sodium chloride 3.2 g) were added in one minute by the double jet method. One minute after the completion of the addition, 0.8 mmol of N-benzyl-4-phenylpyridinium chloride was added. One minute later, 3.0 g of sodium chloride was added. During the next 25 minutes, the temperature of the reaction vessel was raised to 60 ° C. After aging at 60 ° C. for 16 minutes, 560 g of a 10% aqueous solution of phthalated gelatin and 1 × 10 ⁻⁵ mol of sodium thiosulfonate were added. After this Ag
-2 solution 317.5mL (including silver nitrate 127g), X-2 solution (including sodium chloride 54.1g), and crystal phase controlling agent 1 aqueous solution (M / 50) 160
mL was added at an accelerated rate over 20 minutes. Furthermore, 2
After 5 minutes, the Ag-3 solution (containing 34 g of silver nitrate) and the X-3 solution (containing 11.6 g of sodium chloride and 1.27 mg of yellow blood salt) were added over 5 minutes. Next, 33.5 mL of a 0.1 N thiocyanic acid solution, 0.32 mmol of sensitizing dye 25, 0.48 mmol of sensitizing dye 26, and 0.05 mmol of sensitizing dye 27 were added.

Embedded image

[0856] The temperature was lowered to 40 ° C, and the precipitate was washed with a precipitation washing method. An aqueous gelatin solution was added to redisperse the emulsion, and the pH was adjusted to 6.2 and the pAg to 7.5. Particles prepared by the above method, the results obtained from replica TEM images of emulsion particles,
The following particles accounted for 50% or more of the total projected area. Principal plane is (111) plane, sphere equivalent diameter 0.56 ~ 0.66μm, projected area diameter 0.5.
The particle diameter was 95 to 1.15 µm and the particle thickness was 0.12 to 0.16 µm. The above emulsion was optimally subjected to chemical sensitization with reference to Em-J1 shown in Example 1 except for the sensitizing dye to obtain Em-Y1.

(Em-Y2) The compound (I-13) of the present invention was added at 1 × 10 ⁻⁴ mol / mol during chemical sensitization.
Em-Y2 was obtained in the same manner as Em-Y1, except that Ag was added. It was obtained (Em-Y3) Em-Y3 except for adding 10 mol% relative to the compound of the present invention at the time of chemical sensitization (IV-2) sensitizing dye was added in the same manner as Em-Y 2. (Em-Y4) Compound (IX-2-50) of the present invention was added to 1 × 1 at the time of chemical sensitization.
0 ^-4 mol / mol Ag was added which had had in the same manner as Em-Y3 obtain an emulsion Em-Y4. After dissolving each emulsion at 40 ° C. for 30 minutes on a cellulose triacetate film support provided with an undercoat layer, coating the emulsions Em-Y1 to Y4 under the coating conditions shown in Table 9 above. went. Table 1 shows the emulsions to be coated.
Samples 501 to 505 were prepared by substituting as in Example 2.

[0858]

[Table 12]

Table 13 shows the results of the evaluation performed in the same manner as in Example 3. The sensitivity was indicated by a relative value of the reciprocal of the exposure required to reach a density of fog density plus 0.2. In the emulsion of the present invention, the combination of the compound of the general formula (I) of the present invention with the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention and By the combination with the boiling point organic solvent and the combination of the general formula (I) of the present invention and the general formula (IV) of the present invention, a photosensitive material having low fogging and high sensitivity was able to be achieved. further,
By combining the compounds of the general formulas (VI) to (X) of the present invention as described above, a photographic material having high storage fog resistance was able to be achieved.

[0860]

[Table 13]

(Example 4) Emulsion Em-Z1: A shell part containing 0.4 mol% of iodine based on the total silver amount (100) Silver chloride tabular grains In a reaction vessel, 1200 mL of water, 25 g of gelatin, 0.4 g of sodium chloride were placed.
g, 4.5 mL of a 1N aqueous nitric acid solution was added (pH 4.5), and the mixture was maintained at 40 ° C. Next, the Ag-1 solution (silver nitrate 0.2 g / mL) and the X-1 solution (sodium chloride 0.069 g / mL) were added and mixed at 48 mL / min for 4 minutes with vigorous stirring. Fifteen seconds later, 150 mL of a polyvinyl alcohol aqueous solution (average degree of polymerization of vinyl acetate is 1700, 6.7 g of polyvinyl alcohol having an average saponification rate to alcohol of 98% or more (hereinafter referred to as PVA-1), and contained in 1 L of water) was added thereto. .
Adjusted to 5. The temperature was raised to 75 ° C. in 15 minutes, 23 mL of a 1N aqueous sodium hydroxide solution was added to adjust the pH to 6.5, and 1- (5-methylureidophenyl) -5-mercaptotetrazole (0.1%) was added.
05%) in 4.0 mL of N, N'-dimethylimidazolidin-2-
4.0 mL of thione (1% aqueous solution) was added.

[0861] After adding 4 g of sodium chloride and adjusting the silver potential (to a room temperature saturated calomel electrode) to 100 mV, the Ag-1 solution and the X-1 solution were linearly increased from a flow rate of 40 mL / min to 42 mL / min as a growth process. For 15 minutes while keeping the silver potential at 100 mV. Further, add 12.5 mL of 1N nitric acid aqueous solution
pH 4.0. 28.8 g of sodium chloride was added, and the silver potential was increased to 60
mV, 0.38 mmol of sensitizing dye 25, sensitizing dye 2
6 and 0.56 mmol of sensitizing dye 27 were added, and Ag-2 solution (silver nitrate 0.1 / mL) and X-2 solution (chloride in 1 L so that the total amount of iodine was 0.4 mol% of the total silver amount). Aqueous solution containing 33.8 g of sodium and 1.95 g of potassium iodide)
After addition at 40 mL / min for 10 minutes, the mixture was allowed to stand at 75 ° C. for 10 minutes.

[0863] The temperature was lowered to 40 ° C, and the precipitate was washed with a precipitation washing method. An aqueous gelatin solution was added to redisperse the emulsion, and the pH was adjusted to 6.0 and the pAg to 7.3. The particles prepared by the above method, the results obtained from replica TEM images of emulsion particles,
The following particles accounted for 50% or more of the total projected area. Principal plane is (100) plane, sphere equivalent diameter 0.4 to 0.5 μm, particle thickness 0.10
0.10.12 μm, aspect ratio 6.5 or more, adjacent side ratio 1.1-1.3. The above emulsion is shown in Example 1 except for the sensitizing dye.
Optimum chemical sensitization was performed with reference to Em-J1, to obtain Em-Z1.

(Em-Z2) The compound (I-13) of the present invention was subjected to 1 × 10 ⁻⁴ mol / mol during chemical sensitization.
Except for adding Ag, Em-Z2 was obtained in the same manner as Em-Z1. It was obtained (Em-Z3) Em-Z3 except for adding 10 mol% relative to the compound (IV-2) sensitizing dye was added in the same manner as Em-Z 2 of the present invention at the time of chemical sensitization. (Em-Z4) 1 × 1 of the compound (IX-2-50) of the present invention during chemical sensitization
0 ^-4 mol / mol Ag was added which had had in the same manner as Em-Z3 obtain an emulsion Em-Z4.

Each emulsion was dissolved in a cellulose triacetate film support provided with an undercoat layer at 40 ° C. for 30 minutes, and then dissolved under a coating condition shown in Table 9 above.
Em-Z1 to Z4 were applied. Samples 601 to 605 were prepared by changing the emulsion to be coated as shown in Table 14.

[0866]

[Table 14]

Table 15 shows the results of the evaluation performed in the same manner as in Example 3.

[0868]

[Table 15]

The sensitivity was represented by the relative value of the reciprocal of the amount of exposure necessary to reach the density of fog density plus 0.2. In the emulsion of the present invention, the combination of the compound of the general formula (I) of the present invention with the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention and By the combination with the boiling point organic solvent and the combination of the general formula (I) of the present invention with the general formula (IV) or (V) of the present invention, a photosensitive material having low fog and high sensitivity could be achieved. Furthermore, by combining the compounds of the general formulas (VI) to (X) of the present invention as described above, a photosensitive material having high storage fog resistance was able to be achieved.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI G03C 7/305 G03C 7/305 7/388 7/388 (56) References JP-A-11-72862 (JP, A) JP-A-11-72862 58-162949 (JP, A) JP-A-2000-314945 (JP, A) JP-A-5-232610 (JP, A) JP-A-6-19028 (JP, A) (58) Fields investigated (Int. Cl ^7, DB name) G03C 1/00 -. 7/392

Claims (8)

(57) [Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, comprising a compound of the following formula (I) and coupling with an oxidized developing agent: A silver halide photographic light-sensitive material comprising at least one photographically useful group-releasing compound represented by the following general formula (II) or (III), which subsequently produces a compound that does not substantially contribute to a dye. Formula (I) (X) k- (L) m- (AB) n wherein X is a halogenated atom having at least one atom selected from the group consisting of N, S, P, Se and Te. Represents a silver adsorption group or a light absorption group. L is C, N, S and O
Represents a divalent linking group having at least one atom selected from the group consisting of A represents an electron donating group, B represents a leaving group or a hydrogen atom, and after oxidization, is eliminated or deprotonated to form a radical A. k and m each independently represent an integer of 0 to 3, and n represents 1 or 2. Formula (II) COUP1-D1 In the formula, COUP1 represents a coupler residue that releases D1 by a coupling reaction with an oxidized developing agent and generates a water-soluble or alkali-soluble compound. D1
Represents a photographically useful group linked at the coupling position of COUP1 or a precursor thereof. Formula (III) COUP2-CED2 wherein COUP2 represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and C represents
In the coupling product of COUP2 and oxidized developing agent, an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and an electrophilic site E results in 4
Represents a divalent linking group or a single bond capable of releasing D2 with ring formation of up to 8 members, and may be bonded to COUP2 at the coupling position of COUP2,
It may bind to COUP2 at a position other than the coupling position of 2. D2 represents a photographically useful group or a precursor thereof. 2. D1 in the general formula ( II ) is- (TIME ) _m -PUG or- (TIME ) _i- RED-PUG (wherein TIME is COUP1 by a coupling reaction).
Cleavage PUG or RED-PUG after more detachment
RED represents COUP1 or TIM
Reacts with oxidized developing agent after leaving from E to form PUG
Represents a cleaving group, and PUG is a development inhibitor and a bleaching accelerator
Represents a photographically useful group selected from: m is an integer of 0 to 2
Represents a number, and i represents 0 or 1. 2 when m is 2
TIMEs represent the same or different. )
Represents the D2 of the general formula (III) _{is, - (T) k - PUG} (T is capable of releasing a PUG after being released from E
K represents an integer of 0 to 2;
UG is a photographic property selected from development inhibitors and bleach accelerators
Represents a useful group. ).
Silver halide photographic light-sensitive material. 3. The method according to claim 1, wherein the amount of said silver halide photographic material is small.
In both cases, the emulsion dispersion is contained in one photosensitive silver halide emulsion layer.
And the critical micelle concentration of the emulsified dispersion is 4.0 × 10
^-3 mol / L or less of a surfactant is added to the photosensitive layer.
3. The composition of claim 1, wherein the content is 1% by mass or more.
3. The silver halide photographic light-sensitive material described in 1. above. 4. The above-mentioned emulsified dispersion has a dielectric constant of 7.0 or less.
Claims characterized by containing a high boiling organic solvent below
3. The silver halide light-sensitive material according to item 3. 5. A silver halide contained in said photosensitive layer.
50% or more of the total projected area of the particles is the following (a) or
5. The method according to claim 1, wherein (d) is satisfied.
A silver halide photographic light-sensitive material according to any one of the preceding claims . (A) a parallel main plane having a (111) plane; (b) an aspect ratio of 2 or more; (c) containing at least 10 or more dislocation lines per grain; and (d) iodobromide having a silver chloride content of less than 10 mol%. Silver or
Tabular silver halide grains composed of silver chloroiodobromide 6. Silver halide contained in said photosensitive layer
More than 50% of the total projected area of the grains is as follows (a), (d)
And (e) are satisfied.
5. The silver halide photographic light-sensitive material according to any one of the above items 4. (A) a parallel main plane having a (111) plane; (d) silver iodobromide having a silver chloride content of less than 10 mol% or
Tabular silver halide grains composed of silver chloroiodobromide (e) Apex portions of hexagonal silver halide grains and / or
At least one particle per side and / or main plane
Has one epitaxial junction 7. A silver halide contained in said photosensitive layer
50% or more of the total projected area of the grains is as follows (d), (f) and
And (g) are satisfied.
A silver halide photographic light-sensitive material according to any one of the above. (D) silver iodobromide having a silver chloride content of less than 10 mol% or
Tabular silver halide grains composed of silver chloroiodobromide (f) Parallel main planes are (100) planes (g) Aspect ratio is 2 or more 8. A silver halide contained in said photosensitive layer
(G), (h) and 50% or more of the total projected area of the grains
5. The method according to claim 1, wherein (i) is satisfied.
2. The silver halide photographic light-sensitive material according to claim 1. (G) Aspect ratio of 2 or more (h) Parallel main plane is (111) plane or (100)
Surface (i) A flat surface containing at least 80 mol% or more of silver chloride
Plate-like particles