JP2002072396A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having high sensitivity, low fog and improved shelf stability. SOLUTION: In the silver halide color photographic sensitive material with photographic constitutive layers comprising at least two red-sensitive layers, at least two green-sensitive layers, at least two blue-sensitive layers and a non-photosensitive layer on one side of the base, a silver halide emulsion contained in at least one of the sensitive layers is a silver halide emulsion in which >=50% of the projected area is occupied by flat platy silver halide grains each having an aspect ratio of >=8 and a compound of the formula R1-(S)m-R2 is contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having high sensitivity, low fog, and excellent storage stability.

[0002]

2. Description of the Related Art While silver halide color photographic materials (hereinafter, also referred to as "color photographic materials" or simply "photosensitive materials") are said to be mature products with extremely high perfection, the required performance is as follows. , High sensitivity, high image quality, little fluctuation in performance due to storage conditions, etc., and in the future, it is necessary to take into account rapid processing suitability such as rapid development progress.
The required level has been increasing in recent years.

[0003] In particular, in terms of high sensitivity, due to recent technological advances in digital cameras, in order to maintain the superiority of the photosensitive material, a further high sensitivity compatible with preservation while keeping fog low. Is necessary.

A technique for increasing the sensitivity of a silver halide emulsion, that is, a sensitization technique, relates to a method for producing a silver halide emulsion,
Regarding the chemical sensitization of silver halide emulsions, those related to spectral sensitization of silver halide emulsions, those based on photosensitive material design methods, those related to the development process of photosensitive materials, etc.
Various methods are known. Among them, the most preferable and essential method is to reduce the inefficiency of the silver halide crystal during the photosensitive process and improve the quantum efficiency.

One of the means is chemical sensitization, which is chalcogen sensitization such as sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization using a noble metal such as gold, and reduction sensitization using a reducing agent. Yes, these are used alone or in combination. Above all, when gold sensitization is used in combination with sulfur sensitization, selenium sensitization, and tellurium sensitization, a remarkable increase in sensitivity can be obtained, but fog also increases. In particular, gold / selenium sensitization and tellurium sensitization have a large rise in fog compared to gold / sulfur sensitization, and there has been a demand for a technique for suppressing fog generation, and a sensitization technique with less fogging during storage and less sensitivity fluctuation.

[0006] It is known to use an inhibitor as a method for improving fog, storage stability, and the like of a photosensitive material. For example,
JP-A Nos. 5-53234, 5-27360, 5-
Nos. 19395 and 5-17540 disclose various combinations of inhibitors, but they have not yet solved all the problems such as desensitization when fog and storage stability are improved. As an inhibitor having a mercapto group and a water-soluble group,
JP-A-2-837 discloses a fog-preventing agent for tabular grains and an agent for improving low-light-intensity failure, and JP-A-4-16838 discloses an antifoggant for selenium sensitization.
JP-A-6-19024, JP-A-6-19026, and JP-A-6-19037 disclose that a reaction-inactive chalcogen compound is effective in preventing fog.

[0007] There are two fogging problems: fog (absolute fog value) of the final silver halide emulsion itself introduced into the light-sensitive material and fog progression during the process of optimal chemical ripening. In terms of production stability, it is preferable that fog progress slowly, and in terms of photographic performance,
A silver halide emulsion having a low absolute fog value is considered to be ideal, but the level does not satisfy both.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic material having high sensitivity, low fog, and excellent storage stability.

[0009]

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

[0010] 1. A silver halide color photographic light-sensitive material having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. The silver halide emulsion contained in at least one of the photosensitive layers accounts for 50% of the projected area.
A silver halide color photographic light-sensitive material characterized in that the above are tabular silver halide grains having an aspect ratio of 8 or more, and are silver halide emulsions containing the compound represented by the general formula (1).

2. A silver halide color photographic light-sensitive material having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. The silver halide emulsion contained in at least one of the photosensitive layers accounts for 50% of the projected area.
The above are tabular silver halide grains having an aspect ratio of 8 or more, and the silver potential of the silver halide emulsion is from 40 mV to 7
A silver halide color photographic light-sensitive material, which is 0 mV and is a selenium-sensitized silver halide emulsion.

3. A silver halide color photographic light-sensitive material having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. The silver halide emulsion contained in at least one of the photosensitive layers accounts for 50% of the projected area.
The above is a tabular silver halide grain having an aspect ratio of 8 or more, and a silver halide emulsion obtained by adding a chalcogen sensitizer and then adding silver halide fine grains. material.

4. A silver halide color photographic light-sensitive material having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. The silver halide emulsion contained in at least one of the photosensitive layers accounts for 50% of the projected area.
The above are the tabular silver halide grains having an aspect ratio of 8 or more, and the compound represented by the general formula (2) is added during the respective addition periods of the spectral sensitizing dye and the chalcogen sensitizer. A silver halide color photographic light-sensitive material, which is a silver halide emulsion.

5. A silver halide color photographic light-sensitive material having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. The silver halide emulsion contained in at least one of the photosensitive layers accounts for 50% of the projected area.
A silver halide color photographic light-sensitive material characterized in that the above are silver halide emulsions containing tabular silver halide grains having an aspect ratio of 8 or more and containing a compound capable of forming a divalent cation by oxidation.

6. 6. At least one of the photosensitive layers of the silver halide color photographic light-sensitive material according to any one of 1 to 5 above.
The silver halide emulsion contained in the layer is tabular silver halide grains having an aspect ratio of 8 or more in 50% or more of the projected area, and has a pH of 5.0 to 7.0 and a silver potential of 40 mV to 7
A silver halide color photographic light-sensitive material, which is a silver halide emulsion chemically sensitized at 0 mV.

[7] 7. At least one of the photosensitive layers of the silver halide color photographic light-sensitive material according to any one of the above items 1 to 6
A silver halide emulsion wherein the silver halide emulsion contained in the layer is tabular silver halide grains having an aspect ratio of 8 or more in an area of 50% or more of a projected area, and a sensitizing dye is added in a fine solid dispersion state. Silver halide color photographic material.

Hereinafter, the present invention will be described in more detail. Tabular silver halide grains (hereinafter sometimes referred to as “tabular grains”) related to the present invention have an aspect ratio of more than 8, and a preferred aspect ratio is 8 to 100;
It is more preferably from 10 to 80, more preferably from 12 to 50. 15 to 30 is most preferred. In the present invention, the aspect ratio is represented by a ratio of a diameter to a thickness of a tabular grain. Grain diameter refers to the diameter of a circle having an area equal to the projected area of the silver halide grain. The thickness refers to the distance between two parallel surfaces constituting the tabular silver halide.

The diameter (corresponding to a circle) of the tabular grains related to the present invention is 0.3 to 20 μm, preferably 0.5 to 15 μm.
m, more preferably 0.5 to 10 μm. The particle thickness is 0.3 μm or less, preferably 0.25 μm or less,
More preferably, it is 0.05 to 0.20 μm. Measurement of particle diameter and particle thickness in the present invention is described in U.S. Pat.
It can be determined from an electron micrograph of particles as in the method described in JP-A-434,226. That is, the measurement of the thickness of the particles is as follows.
A metal is vapor-deposited from the oblique direction of the particles together with a reference latex, the length of the shadow is measured on an electron micrograph, and calculated by referring to the length of the latex shadow.

The main surface of the tabular grain relating to the present invention is a {111} plane. A tabular grain having a {111} plane as a main surface is a general term for silver halide grains having one twin plane or two or more parallel twin planes. What is a twin plane?
This means the {111} plane when ions at all lattice points on both sides of the 1} plane are in a mirror image relationship. These tabular grains have a triangular shape, a hexagonal shape or a rounded shape when viewed from above, and the triangular shape is triangular, and the hexagonal shape is hexagonal, rounded. Tabular grains have mutually parallel outer surfaces with rounded corners.

US Pat. No. 4,434,226 discloses a method for producing {111} major surface type tabular grains related to the present invention.
Nos. 4,439,520 and 4,414,310
Nos. 4,433,048 and 4,414,306
No. 4,459,353, Tokuhei 4-36374
No., JP-B-5-16015, JP-B-6-44132, and the like disclose the manufacturing method and the use technology. Also, as disclosed in JP-A-6-214331, once a seed crystal emulsion is obtained by nucleation, conditions such as pH and pAg are set so as to be convenient for growth. , Silver and a halogen solution can be added for growth to form tabular grains. Also, JP-A-6-43605 and JP-A-6-4
No. 3606, No. 6-222488, No. 6-23049
No. 1, 6-230493, 6-235988,
The technology described in JP-A-6-258745 and the like can also be applied.

The tabular grains related to the present invention are preferably monodisperse tabular grains. In this regard, JP-A-63-11928 and JP-B-5-61205 disclose monodisperse hexagonal tabular grains, and JP-A-1-131541 discloses circular monodisperse tabular grains. JP-A-2-838 discloses that 95% or more of the total projected area is occupied by tabular grains having two twin planes parallel to the main surface, and the size distribution of the tabular grains is monodispersed. Are disclosed. EP 514,742A discloses tabular grain emulsions prepared using a polyalkylene oxide block copolymer and having a coefficient of variation in grain size of 10% or less.

It is also preferred that the tabular grains related to the present invention increase the specific surface area of the tabular grains to greatly utilize the advantages of the tabular grains. In this regard, JP-A-8-69069 discloses that a grain having a {111} main surface, having an average equivalent circle diameter of 0.7 μm or more and an average thickness of less than 0.07 μm accounts for 90% of the total projected area. A silver halide emulsion occupying a proportion exceeding the above ratio is disclosed in JP-A-63-264739 and JP-A-2000-2959.
A silver halide grain emulsion present at μm ² is disclosed. Further, Japanese Patent Publication No. Hei 8-12390 discloses a silver halide grain having a raffle surface composed of minute projections by extending a silver halide lattice on a main surface on a host grain surface.

In the production of tabular grains related to the present invention, a method of forming tabular grains by adding silver halide fine particles instead of adding an aqueous solution of silver salt and an aqueous solution of halide to a reaction vessel holding an aqueous solution of protective colloid. Can be used. Regarding this method, US Pat. No. 4,879,
No. 208, No. 5,035,991, No. 5,270,1
No. 59, 5,250, 403, EP 507,
No. 701, JP-A-1-183644 and JP-A-2-4435.
Nos. 2,435,535 and 2-68538 disclose the technology. As a method for supplying iodine ions in forming tabular grains, fine-grain silver iodide (having a particle diameter of 0.1 mm) is used.
(1 μm or less, preferably 0.06 μm or less). An emulsion may be added. In this case, a production method disclosed in US Pat. No. 4,879,208 can be used as a method for supplying silver iodide fine particles. .

Techniques relating to high silver bromide {111} major surface tabular grains related to the present invention are also described in the following patents. U.S. Pat. Nos. 4,425,425 and 4,42
5,426, 443,426, 4,439,5
No. 20, 4,414, 310, 4,433, 04
No. 8, 4,647,528, 4,665,012
Nos. 4,672,027 and 4,678,745
Nos. 4,684,607 and 4,593,964
No. 4,722,886, No. 4,722,886
Nos. 4,755,617 and 4,755,456
Nos. 4,806,461 and 4,801,522
Nos. 4,835,322 and 4,839,268
Nos. 4,914,014 and 4,962,015
Nos. 4,977,074 and 4,985,350
No. 5,061,609 and 5,061,616
No. 5,068,173 and 5,132,203
No. 5,272,048, 5,334,469
No. 5,334,495 and 5,358,840
No. 5,372,927.

The halogen composition of the tabular grains relating to the present invention is silver iodobromide, silver chloroiodobromide, and silver bromide. The structure relating to the halogen composition is described by X-ray diffraction and electron beam. (2) An analysis method such as EPMA (also referred to as XMA) for detecting a silver halide composition by scanning with X-rays, ESCA for irradiating X-rays and spectroscopy of photoelectrons emitted from the particle surface, or the like is selected. It can be confirmed by using them in combination. In the present invention, the grain surface refers to a region up to a depth of about 50 ° from the surface, and its halogen composition can be usually measured by the ESCA method. The inside of the particle refers to a region other than the above-described surface region.

In producing the silver halide emulsion relating to the present invention, there are no particular restrictions on the additives that can be added from the time of grain formation to the time of coating. Also, combinations with all known techniques can be used. Regarding these, the description in the following literature can be referred to.
A silver halide solvent can be used to promote growth during the crystal formation process and to effectively make chemical sensitization effective during grain formation and / or chemical sensitization. Examples of frequently used silver halide solvents include water-soluble thiocyanates, ammonia, thioethers and thioureas. For example, thiocyanates (U.S. Pat. Nos. 2,222,264 and 2,448,534)
No. 3,320,069), ammonia, thioether compounds (for example, US Pat. No. 3,27
1,157, 3,574,628, 3,70
No. 4,130, No. 4,297,439, No. 4,27
No. 6,347, each specification), thione compounds (for example, JP-A-53-144319, JP-A-53-82408, and JP-A-55-77737), amine compounds (for example, JP-A-54-100717). And the like, thiourea derivatives (for example, JP-A-55-2982), imidazoles (JP-A-54-100717), substituted mercaptotetrazole (JP-A-57-202531) and the like. it can.

For the production of the silver halide emulsion relating to the present invention, any method known so far can be used. That is, a silver salt aqueous solution and a halogen salt aqueous solution are added to a reaction vessel having an aqueous gelatin solution with efficient stirring. As a specific method, see Glafk
by ides Chemie et PhysiqueP
photographique (Paul Montel)
G., 1967); F. Duffin's Pho
graphical Emulsion Chemis
try (published by The Focal Press, 1966)
Year), V. L. Ma by Zelikman et al
king and CoatingPhotograph
hic Emulsion (The Focal Pr
ess, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide is a one-sided mixing method,
Any of the simultaneous mixing method and a combination thereof may be used. One type of the double jet method is to maintain a constant pAg in the liquid phase in which silver halide is produced,
The so-called controlled double jet method can also be used. Also, British Patent No. 1,535,016, JP-B-48-36890, and JP-B-52-16364.
No. 4,242,445, US Pat. No. 4,242,445, and US Pat. It is preferable to use a method for changing the concentration of the aqueous solution as described in JP-A-158124 or the like to quickly grow the solution within a range not exceeding the critical supersaturation degree. These methods are preferably used because they do not cause renucleation and the silver halide grains grow uniformly.
Instead of adding a silver salt solution and a halogen salt solution to a reaction vessel, a method of adding previously prepared fine particles to the reaction vessel to cause nucleation and / or grain growth to obtain silver halide grains. Can also. This technique is disclosed in JP-A-1-183644, JP-A-1-18
No. 3645, U.S. Pat. No. 4,879,208, JP-A-2-44335, JP-A-2-43534.
And JP-A-2-43535.
According to this method, the distribution of halogen ions in the emulsion grain crystals can be made completely uniform, and favorable photographic characteristics can be obtained.

Further, as the tabular grains related to the present invention, emulsion grains having various structures can be used. So-called core / shell double-structured particles composed of the inside (core portion) and the outside (shell portion) of the particles, triple-structured particles as disclosed in JP-A-60-222844, and multilayers of more than that. Structural particles are used. When a structure is provided inside the emulsion grains, not only the above-described wrapping structure but also a grain having a so-called junction structure can be produced. These examples are disclosed in JP-A-59-133.
540, JP-A-58-108526, European Patent 199290A2, JP-B-58-24772.
And JP-A-59-16254. The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in halogen composition or has a core-shell structure. In the case of a joint structure,
Combinations of silver halides are of course possible, but any silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, may be used in combination with silver halide to form a combined structure.

In the case of silver iodobromide particles having these structures, for example, in core-shell type particles, even if the silver iodide content in the core portion is high and the silver iodide content in the shell portion is low, Conversely, grains having a low silver iodide content in the core portion and a high silver iodide content in the shell portion may be used. Similarly, particles having a bonding structure may be particles having a high silver iodide content in the host crystal and a relatively low silver iodide content in the bonding crystal, or vice versa. Also,
The boundary portions having different halogen compositions in the grains having these structures may be clear boundaries, or may be unclear boundaries due to the formation of a mixed crystal due to a composition difference. It may have a structural change. The silver halide emulsion used in the present invention is described in EP-0097727B1, EP
-006412B1 A treatment for imparting roundness to particles as disclosed in each specification, or DE-23.
The surface may be modified as disclosed in the specification of JP 0664747 C2 and JP-A-60-221320.

The silver halide grains in the silver halide emulsion of the present invention preferably have dislocation lines therein.
There is no particular limitation on the position where the dislocation line exists, but it is preferable that it exists near the outer peripheral portion, near the ridge line, or near the vertex of the silver halide grain. The dislocation lines are introduced in the silver halide grains preferably in a region where the added position is 50% or more when the distance from the center of the silver halide grains to the surface is 100%.
% Is more preferably introduced into a region of not less than 85%. The number of dislocation lines is preferably 30% or more (number) of silver halide grains having 5 or more dislocation lines, more preferably 50% or more, and further preferably 80% or more. preferable. In each case, the number of dislocation lines in one grain is preferably 10 or more, more preferably 20 or more, and further preferably 30 or more.

The dislocation lines of the silver halide grains are described, for example, in J. Am. F. Hamilton; Photo. Sci.
Eng. , 11 (1967) 57; Shioza
wa; Soc. Photo. Sci. , Japan
35 (1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature.
That is, the silver halide grains taken out carefully are placed on a mesh of an electron microscope so as not to apply a pressure enough to newly generate dislocation lines from the emulsion, and damage (printout etc.) by the electron beam is caused. In order to prevent this, the sample is observed by a transmission method in a cooled state. At this time, the thicker the silver halide grains, the more difficult it is for an electron beam to pass therethrough. Therefore, the use of a high-pressure electron microscope enables clearer observation. From the particle photograph obtained by such a method,
The position and number of dislocation lines in each silver halide grain can be determined.

The method for introducing dislocation lines into silver halide grains is not particularly limited. For example, a method of adding an aqueous solution of iodide ion such as potassium iodide and a solution of a water-soluble silver salt by double jet, a method of adding silver iodide fine grains A dislocation line of a desired position and amount is introduced by a known method such as a method of adding iodine ion solution, a method of adding only an iodide ion solution, and a method of using an iodide ion releasing compound described in JP-A-6-11781. Can be.

As an embodiment of the production of the silver halide emulsion of the present invention, tabular silver halide grains serving as a base are first prepared, and the tabular silver halide grains are firstly oriented in the lateral direction. A method in which a low iodide silver halide phase is preferentially grown and then a high iodide silver halide phase is grown in the main plane direction, or conversely, first, a high iodine halide is formed in the main plane direction. The silver halide phase is preferentially grown,
Then, utilizing the method of growing a low iodide silver halide phase in the lateral direction, etc., and combining the following various methods and conditions, the composition of the extremely thin silver halide layer is precisely controlled. It is possible to use a method of forming while forming.

In order to grow the tabular silver halide grains preferentially in the lateral direction or in the main plane direction, silver ions or halide ions during the growth of the silver halide grains, or halogens during the growth due to dissolution thereof. It is important to select the concentration, growth temperature, pBr, pH, gelatin concentration, etc. of the additive solution containing silver halide fine particles for supplying silver ions and halide ions to the silver halide particles. It can be controlled to some extent by the combination of the shape of the tabular substrate grains, the halogen composition, the ratio of the {100} face / {111} face of the side face, and the like.

For example, the preferred pBr for growing preferentially in the lateral direction is 1.0 to 2.5, and the gelatin concentration is 0.5 to 2.0%. In order to form high aspect ratio tabular silver halide grains not to be formed, the pH is preferably set to 2.0 to 5.0. On the other hand, the preferred pBr for growing preferentially in the main plane direction is 2.5 to 4.5.

In order to precisely and uniformly control and form the thickness of the outermost layer of silver halide crystal and the composition of silver halide,
A supply method using silver halide fine particles for supplying silver ions and halide ions to growing silver halide particles by dissolution is more suitable than a supply method using ions.

In the general formula (1), the aliphatic group represented by R ¹ and R ² is a straight-chain or branched alkyl or alkenyl having 1 to 30, preferably 1 to 20 carbon atoms.
Each group such as alkynyl or cycloalkyl is exemplified.
Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-
Butyl, 2-ethylhexyl, allyl, 2-butenyl,
Each group includes 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclododecyl and the like. Examples of the aromatic group represented by R ¹ and R ² include those having 6 to 20 carbon atoms, and specific examples include phenyl, naphthyl, and anthranyl. The heterocyclic group represented by R ¹ and R ² may be a single ring or a condensed ring, and is a 5- to 6-membered heterocyclic group having at least one of O, S and N atoms and an amine oxide group in the ring. Is mentioned.

Specifically, for example, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan,
Examples include thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole, and groups derived from these benzerogues. R ¹ and R ² form a ring,
A 4- to 7-membered ring can be mentioned. It is preferably a 5- to 7-membered ring.

Preferred groups for R ¹ and R ² are a heterocyclic group and an aromatic group, more preferably a heteroaromatic group. The aliphatic group, aromatic group or heterocyclic group represented by R ¹ and R ² may be further substituted with a substituent, and the substituent may be a halogen atom (eg, a chlorine atom, a bromine atom, etc.). An alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a t-butyl group, etc.), a cycloalkyl group (eg, a cyclopentyl group,
Cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (eg, methoxy group) Ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, 4-methoxyphenoxy group, etc.), cyano group, acylamino group (eg, acetylamino group, propionylamino group, etc.), alkylthio group (E.g., methylthio, ethylthio, butylthio, etc.), arylthio (e.g., phenylthio,
p-methylphenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido group, 3,3-dimethylureido group, 1,3- Dimethylureido group, etc.), sulfamoylamino group (eg, dimethylsulfamoylamino group, diethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl Group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, p-chlorophenoxycarbonyl Base ), A sulfonyl group (for example,
Methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (eg, methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy Group, nitro group, nitroso group, amine oxide group (eg, pyridine oxide group), imide group (eg, phthalimide group), disulfide group (eg, benzene disulfide group, benzothiazolyl-2)
-Disulfide group, etc.) and heterocyclic groups (eg, pyridyl group, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group, etc.). Substituents containing an electron withdrawing group are particularly preferred. R ¹ and R ² may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent. m is an integer of 2 to 6, preferably 2 to 3.

The following is a general formula (1) used in the present invention.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0041]

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[0042]

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[0043]

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[0044]

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The compound represented by the general formula (1) can be synthesized by an ordinary method well known to those skilled in the art.

The compound represented by the general formula (1) can be added and used at any stage in the production process of a silver halide emulsion, or can be added and used at any stage immediately before coating after emulsion production. Can be. The preferred addition step in the present invention is effective immediately after the completion of chemical ripening and immediately before coating. The preferable addition amount of the compound represented by the general formula (1) is 1 × 10 ⁻⁸ to 1 mol / Ag mol, more preferably 1 × 10 ⁻⁶ to 1 × 0.3 mol / Ag mol.

The silver potential of the silver halide emulsion in the present invention refers to the silver potential of the silver halide emulsion before it is subjected to spectral sensitization and chemical sensitization. It can be determined by measuring with a silver ion selective electrode using a silver chloride electrode as a reference electrode. The silver potential of the silver halide emulsion in the invention is from 40 to 70 mV, preferably from 40 to 60 mV, and more preferably from 45 to 70 mV.
55 mV.

As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. That is, it is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. As the unstable selenium compound, for example, compounds described in JP-B-44-15748, JP-B-43-13489, JP-A-4-25832 and JP-A-4-109240 are preferably used. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, and colloidal metal selenium. Can be

While the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. One skilled in the art would speak of an unstable selenium compound as a sensitizer for photographic emulsions, as long as selenium is unstable, the structure of the compound is not critical and the organic moiety of the selenium sensitizer molecule Is generally understood to have no role other than to carry selenium and make it present in the emulsion in an unstable form, and unstable selenium compounds having such a broad concept are advantageously used.

Non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-3449.
Compounds described in Nos. 2 and 52-34491 are used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, 2-selenooxazolidinethione and derivatives thereof.

Preferred examples of the selenium sensitizer that can be used in the present invention are shown below, but it should not be construed that the invention is limited thereto.

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These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or as a mixture, or disclosed in JP-A-4-140738 and JP-A-4-1407.
No. 42, 5-11381, 51-1385 or 51-1388. They can be added at the time of chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one, and two or more of the above-described selenium sensitizers can be used in combination.
An unstable selenium compound and a non-unstable selenium compound may be used in combination. The addition amount of the selenium sensitizer used in the present invention,
It varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the ripening temperature and the time, but is preferably 1 × 10 ⁻⁸ mol or more per mol of silver halide. More preferably, it is 1 × 10 ⁻⁷ mol or more and 3 × 10 ⁻⁵ mol or less. The temperature for chemical ripening when using a selenium sensitizer is preferably 45 ° C. or higher. More preferably 50
The temperature is not less than 80 ° C and not less than 80 ° C. pAg and pH are arbitrary. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9. Preferably, the pH is between 5.0 and 7.0. The silver potential is preferably from 40 mV to 120 mV, particularly preferably from 40 mV to 70 mV. It is more effective to perform selenium sensitization in the presence of a silver halide solvent.

In the general formula (2), examples of the alkyl group represented by R ³ and R ⁴ include methyl, ethyl,
Examples include propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl, and the like. These alkyl groups further include a halogen atom (eg, chlorine, bromine, fluorine, etc.) and an alkoxy group (eg, methoxy, ethoxy,
1,1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), aryloxy groups (eg, phenoxy, naphthyloxy, etc.), aryl groups (eg, phenyl, naphthyl, etc.), alkoxycarbonyl Groups (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl, naphthyloxycarbonyl, etc.), alkenyl groups (eg, vinyl, allyl) Etc.), a heterocyclic group (for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, morpholyl, piperidyl, piperazyl, selenazolyl, sulfolanyl, piperidinyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, pyrrolyl) Pyrazinyl, pyrimidinyl,
Groups such as pyridazinyl, pyrimidyl, pyrazolyl, and furyl), alkynyl groups (eg, groups of propargyl),
An amino group (e.g., amino, N, N-dimethylamino,
Each group such as anilino), a hydroxy group, a cyano group, a sulfo group, a carboxy group, a sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.) You may.

The alkenyl groups represented by R ³ and R ⁴ include, for example, vinyl and allyl, the alkynyl group includes, for example, propargyl, and the aryl group includes, for example, phenyl, naphthyl and the like. Examples of the heterocyclic group include, for example, a pyridyl group (for example, each group such as 2-pyridyl, 3-pyridyl, and 4-pyridyl), a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a phenyl group, and a pyrrolyl group. Group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group,
And a tetrazolyl group.

The above-mentioned alkenyl group, alkynyl group, aryl group and heterocyclic group can be substituted by the same groups as the alkyl groups represented by R ³ and R ⁴ and the substituents of the alkyl groups. it can.

Hereinafter, specific examples of the compound represented by formula (2) are shown, but the present invention is not limited to these.

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The compound represented by the general formula (2) can be synthesized by a usual method well known to those skilled in the art.

The present invention is characterized in that the compound of the general formula (2) is added between the addition of the spectral sensitizing dye and the chalcogen sensitizer. In the present invention, the timing of addition refers to the time when spectral sensitization and chemical sensitization additives are added. In the present invention, the compound of the general formula (2) is added during the respective addition periods of the spectral sensitizing dye and the chalcogen sensitizer, thereby limiting the chemical sensitizing site of the silver halide grains and efficiently increasing the chemical sensitizing sites. Sensitivity can be increased.

Next, the compounds contained in the silver halide emulsion of the present invention and capable of forming a divalent cation by oxidation will be described.

The compound capable of forming a divalent cation by oxidation contained in the silver halide emulsion of the present invention refers to a compound capable of forming a divalent cation by oxidation, for example, by the following reaction mechanism.

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The enthalpy of formation (ΔΔH) between the divalent cation generated by oxidation and its neutral state is 1700 k
A compound having a molar ratio of more than J / mol and less than 2000 kJ / mol is preferable, and a compound having a molecular weight of more than 1900 kJ / mol and less than 2000 kJ / mol is preferable.

ΔΔH is a value calculated by a semi-empirical molecular orbital method using AM1 Hamiltonian.

The AM1 Hamiltonian is one of the NDDO approximations used in the semi-empirical molecular orbital method.
P. Stewart joined the Journal of the American Chemical Society in 1985
Vol., P. 3902, which is a widely used approximation method.

Representative software for calculating ΔΔH includes WinMOPAC ver. 2 (manufactured by Fujitsu Limited, JCPE-P116).

In the case of using such software, as a keyword to be used, a keyword for structure optimization may be appropriately selected and used in addition to AM1.
It is preferable to use

The hardware used for the calculation of the present invention only needs to be capable of performing semi-empirical molecular orbital calculation using the AM1 Hamiltonian, and the calculation can be performed at a sufficiently high speed by a personal computer.

In the present invention, the compound having a group capable of adsorbing on the surface of silver halide and capable of forming a divalent cation by oxidation is preferably a compound having a group capable of adsorbing on the surface of silver halide.

Specific examples of the group capable of adsorbing to silver halide in the above compound include an atom group constituting a styryl dye, a cyanine dye and a merocyanine dye, and an atom group having a mercapto group (for example, mercaptooxadiazole, mercaptotetrazole). , Mercaptotriazole, mercaptodiazole, mercaptothiazole, mercaptothiadiazole, mercaptooxazole, mercaptoimidazole, mercaptobenzothiazole,
Mercaptobenzoxazole, mercaptobenzimidazole, mercaptotetrazaindene, mercaptopyridyl, mercaptoquinolyl, 2-mercaptopyridyl, mercaptophenyl, mercaptonaphthyl, etc.), an atom group having a thione group (for example, thiazoline-
Atomic groups forming imino silver (for example, 2-thione, oxazoline-2-thione, imidazoline-2-thione, benzothiazoline-2-thione, benzimidazoline-2-thione, thiazolidine-2-thione). , Triazole, tetrazole, benzotriazole, hydroxyazaindene, benzimidazole, indazole, etc.), an atom group having an ethynyl group (for example, 2-
[N- (2-propynyl) amino] benzothiazole,
Atomic groups including N- (2-propynyl) carbazole, etc.) and mesoionic compounds; Baker and W.C. D. Ollis Quarterly Review (Qua)
rt. Rev .. ) 11, 15 (1957), Advances in heterocyclic chemistry (Ad
vancesin Heterocyclic Che
mistry) 19, 1 (1976), which is a 5- or 6-membered heterocyclic compound, cannot be satisfactorily represented by one covalent structural formula or polar structural formula, and Compounds that have π electrons associated with all the atoms that make up the ring, and that the ring is partially positively charged and balanced with an equal negative charge on the exocyclic atom or group. Examples of the mesoionic ring of the mesoionic compound include an imidazolium ring, a pyrazolium ring, an oxazolium ring, a thiazolium ring, a triazolium ring, a tetrazolium ring, a thiadiazolium ring, an oxadiazolium ring, a thiatriazolium ring, and an oxatriazolium ring. And the like.

In the present invention, the compound capable of forming a divalent cation by oxidation is preferably a compound represented by the following formula (3).

Formula (3) (E) _k -L _0- (Z ₀ ) _{1 In the} formula, E represents a group which can be adsorbed on the surface of silver halide grains, and L ₀ represents a direct bond between E and Z _0. It represents an indirect bond through a bond or a linking group, and Z ₀ represents a group that forms a two-electron oxidized structure by oxidation. k is an integer of 1 to 3, and 1 is 1
Represents an integer of ２2.

In the general formula (3), the group adsorbable on the surface of the silver halide grains represented by E is the same as the group adsorbable on the silver halide described above. The groups exemplified in the description of the groups that can be adsorbed to silver halide are exemplified.

In the general formula (3), E represented by L ₀
And a linking group for bonding Z ₀ , specifically, a substituted or unsubstituted saturated alkylene group having 1 to 10 carbon atoms;
Examples include groups derived from an aromatic ring, a hetero ring, and the like. The substituted or unsubstituted saturated alkylene group having 1 to 10 carbon atoms may contain a hetero atom and may partially form a ring.

In the general formula (3), the group forming a two-electron oxidized structure by oxidation represented by Z ₀ is a sulfur atom,
It is preferable that at least two atoms selected from a selenium atom and a tellurium atom are contained in the molecule, and it is most preferable that a sulfur atom is contained in the molecule.

In the present invention, the compound capable of forming a divalent cation by oxidation is preferably a compound represented by the following formula (4).

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In the formula, X ₁ and X ₂ each represent a sulfur atom, a selenium atom or a tellurium atom. R ₁ , R ₂ , R ₃ , R ₄ , R
₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ each represent a hydrogen atom, an aliphatic group, an aromatic group, or R ₁ and R ₂ , R ₃
And R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , R ₉ and R ₁₀ , non-metallic atoms forming a ring between R ₁₁ and R ₁₂ , or R ₁ and R ₃ or R
_4, R ₂ and R ₃ or R _4, R ₃ and R ₅ or R _6, R ₄ and R ₅ or R _6, R ₅ and R ₇ or R _8, R ₆ and R ₇ or R _8, R ₇ R ₉ or R ₁₀ , R ₈ and R ₉ or R ₁₀ , R ₉ and R ₁₁ or R ₁₂ , R ₁₀
And R ₁₁ or R ₁₂ , R ₁ and R ₁₁ or R ₁₂ , R ₂ and R ₁₁ or R
Represents a group of non-metallic atoms forming a condensed ring between ₁₂ ; Also, R
_{1, R 2, R 3,} R 4, R 5, R 6, R 7, R 8, R 9, R 10,
When the condensed ring formed between R ₁₁ and R ₁₂ is an unsaturated ring, the bonding carbon atom at the site forming the condensed ring may form a double bond.

In the general formula (4), R ₁ , R ₂ , R ₃ ,
R _4, R _5, as the _{R 6, R 7, R 8} , R 9, R 1 0, R 11, an aliphatic group, each represented by R _12, for example, 1 carbon atoms
10 branched or straight-chain alkyl groups (for example, methyl group,
Ethyl group, propyl group, butyl group, pentyl group, iso
-Pentyl group, 2-ethyl-hexyl group, octyl group,
Decyl group), an alkenyl group having 3 to 10 carbon atoms (for example, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-
3-butenyl group, 4-hexenyl group, etc.), having 7 carbon atoms
To 10 aralkyl groups (for example, benzyl group, phenethyl group, etc.).

The above-mentioned groups further include a lower alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.),
Vinyl group, aryl group (for example, phenyl group, p-tolyl group, p-bromophenyl group, etc.), trifluoromethyl group, alkoxy group (for example, methoxy group, ethoxy group,
Methoxyethoxy group etc.), aryloxy group (for example,
Phenoxy group, p-tolyloxy group, etc.), cyano group, sulfonyl group (eg, methanesulfonyl group, trifluoromethanesulfonyl group, p-toluenesulfonyl group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.) An amino group (eg, amino group, biscarboxymethylamino group, etc.), an aryl group (eg, phenyl group, carboxyphenyl group, etc.), a heterocyclic group (eg, tetrahydrofurfuryl group,
2-pyrrolidinone-1-yl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), ureido group (eg, ureido group, 3-methylureido group, 3-phenylureido group, etc.), thioureido group (eg, Thioureido group, 3-methylthioureido group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), arylthio group (eg, phenylthio group, etc.), heterocyclic thio group (eg, 2-thienylthio group, 3-thienylthio group) Group), carbonyloxy group (eg, acetyloxy group, propanoyloxy group, benzoyloxy group, etc.),
A group such as an acylamino group (eg, an acetylamino group, a benzoylamino group), a thioamide group (eg, a thioacetamide group, a thiobenzoylamino group), or a sulfo group, a carboxy group, a phosphono group,
Sulfate group, hydroxy group, mercapto group, sulfino group, carbamoyl group (for example, carbamoyl group, N
-Methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), sulfonamide group (eg, methanesulfonamide group, Butanesulfonamide group, etc.), sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.), acylaminosulfonyl group (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), acylaminocarbonyl group (Eg, acetamidocarbonyl group, methoxyacetamidocarbonyl group, etc.), sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl group, ethanesulfinylaminocarbonyl group) Etc.), it may be substituted with a hydrophilic group such as a sulfoamino group.

Specific examples of the aliphatic group substituted with a hydrophilic group include a carboxymethyl group, a carboxyethyl group, a carboxybutyl group, a carboxypentyl group and a carboxypentyl group.
-Sulfobutyl group, 3-sulfopropyl group, 2-hydroxy-3-sulfopropyl group, 4-sulfobutyl group, 5
-Sulfopentyl group, 3-sulfopentyl group, 3-sulfinobutyl group, 3-phosphonopropyl group, hydroxyethyl group, N-methanesulfonylcarbamoylmethyl group, N-acetylaminosulfonylmethyl group, sulfoaminopropyl group, 2-carboxy-2-propenyl group,
o-sulfobenzyl group, p-sulfophenethyl group, p-
And a carboxybenzyl group.

Further, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
_7, the _{R 8, R 9, R 10} , R 11, an aromatic group represented by each of R _12, for example, a phenyl group, a naphthyl group, which may have a substituent.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are R ₁ and R ₂ , R ₃ and R ₄ ,
R ₅ and R ₆ , R ₇ and R ₈ , R ₉ and R ₁₀ , and R ₁₁ and R ₁₂ , a non-metallic atom group forming a ring, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R _6, examples of the ring formed between R ₇ and R _8, R ₉ and R _{1 0,} R ₁₁ and R ₁₂ are, for example, cyclohexane ring, and these rings have a substituent You may.

R ₁ and R ₃ or R ₄ , R ₂ and R ₃ or R ₄ , R ₃ and R ₅ or R ₆ , R ₄ and R ₅ or R ₆ , R ₅ and R ₇ or R ₈ , R ₆ and R ₇ or R _8, R ₇ and R ₉ or R _10, R ₈ and R ₉
Or R _{1 0,} R ₉ and R ₁₁ or R _12, R ₁₀ and R ₁₁ or R _12,
A group of non-metallic atoms forming a condensed ring between R ₁ and R ₁₁ or R ₁₂ , R ₂ and R ₁₁ or R ₁₂ , R ₅ and R ₇ or R ₈ , R ₆ and R ₇ or R ₈ ; R ₁ and R ₃ or R ₄ , R ₂ and R ₃ or R ₄ , R
₃ and R ₅ or R ₆ , R ₄ and R ₅ or R ₆ , R ₅ and R ₇ or R ₈ ,
R ₆ and R ₇ or R ₈ , R ₇ and R ₉ or R ₁₀ , R ₈ and R ₉ or R
_10, R ₉ and R ₁₁ or R _12, R ₁₀ and R ₁₁ or R _12, R ₁ and R
₁₁ or R ₁₂ , R ₂ and R ₁₁ or R ₁₂ , R ₅ and R ₇ or R ₈ , R
Examples of the condensed ring formed between ₆ and R ₇ or R ₈ include a benzene ring and a naphthalene ring, and these condensed rings may have a substituent.

The following are specific examples of the compound of the present invention capable of forming a divalent cation by oxidation and the compound of the present invention having an adsorptive group to silver halide and capable of forming a divalent cation by oxidation. By way of example, the invention is not limited to these compounds.

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These compounds can be added to the photosensitive layer or the non-photosensitive layer. The addition layer is preferably a photosensitive layer. The amount added depends on the desired purpose.
In terms of the amount added per mol, 10 ^-8 to 1 mol / Ag,
Preferably, 10 ^{-7 to} 0.01 mol / Ag, more preferably, 10 ^{-6 to} 5 × 10 ^-4 mol / Ag is added. Also, two or more kinds may be used in combination.

These compounds can be directly dispersed in an emulsion. These are first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, n-propanol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. You can also. Ultrasound can also be used for lysis.

Next, the silver halide fine particles to be added to the silver halide emulsion in the present invention will be described. In the present invention, silver halide fine grains are silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodochlorobromide, silver iodobromide, and silver iodobromide and silver iodide. Preferably, there is. Particularly preferred is silver iodide.

The grain size of the silver halide fine grains is preferably between 0.1 and 0.1.
It is preferably 2 μm or less, more preferably 0.02 to 0.2 μm.
1 μm.

The addition amount of silver halide fine particles is preferably 1/100 dmol or less per mol of silver halide, where the average particle size of silver halide is d (μm). Further, the range is preferably from 1 / 20000d to 1 / 300dmol of silver halide. Most preferably, it is 1/5000 d to 1/500 d mol per mol of silver halide.

The temperature of the silver halide emulsion when adding silver halide fine grains is preferably in the range of 30 to 80 ° C.
Particularly, a range of 40 to 65 ° C. is preferable.

The present invention is preferably carried out under the condition that a part or all of the silver halide fine grains disappear after the addition of the silver halide fine grains until immediately before coating, and more preferably the added silver halide fine grains. 20% or more has disappeared immediately before coating.

In the present invention, the silver halide fine grains are added to the silver halide emulsion after the chalcogen sensitizer is added.

The term "dispersed state of fine particles of the sensitizing dye in the present invention" in the present invention means a solution containing a solute present as a solid phase, and refers to a solution containing mechanically dispersed solid fine particles of 1 μm or less. In order to prepare a solution containing solid fine particles of a sensitizing dye, for example, the solubility at 27 ° C. in an aqueous system in the absence of an organic solvent and / or a surfactant is 1 × 1.
A spectral sensitizing dye having a solubility of 0 ^-4 to 4 × 10 ^-2 mol / l may be added to a dispersion medium in an amount exceeding the solubility and mechanically dispersed, as disclosed in JP-A-3-288842 and JP-A-5-288842. 29
It can be prepared with reference to the methods described in, for example, Nos. 7496 and 6-186657.

The solid dispersion of the sensitizing dye in fine particles will be further described. In the present invention, the mechanically dispersed solid fine particles of 1 μm or less are those dispersed in solid fine particles having an average particle size of 1 μm or less based on a volume particle size equivalent to a sphere, and can be measured by a general method.

In the present invention, the dispersion medium preferably does not substantially contain an organic solvent and a surfactant. As used herein, the organic solvent refers to a solvent containing carbon atoms and being liquid at room temperature, and examples thereof include alcohols, ketones, nitriles, and alkoxy alcohols. Specifically, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol,
Examples include 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol, dimethylformamide and the like.

The surfactant includes an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant.

"Contains substantially no organic solvent or surfactant" means that it does not contain an organic solvent or surfactant in an amount that adversely affects the silver halide emulsion.

In the present invention, various dispersers are effectively used for mechanically pulverizing and dispersing the sensitizing dye in an aqueous solvent. Specifically, a high-speed stirrer, a ball mill, a sand mill, a colloid mill, an attritor, an ultrasonic disperser, or the like is used. In the present invention, a high-speed stirrer is preferable.

The high-speed stirring type disperser may have a dissolver having a plurality of impellers mounted on a vertical axis or a multi-axis dissolver having a plurality of vertical axes. In addition to the dissolver alone, a high-speed stirring type disperser having an anchor blade is more preferable.

As a specific working example, water is put into a temperature-adjustable tank, then a certain amount of spectral sensitizing dye powder is put into the tank, and a high-speed stirrer is used for a certain time under temperature control. Stir, grind and disperse. The pH and temperature at the time of mechanically dispersing the spectral sensitizing dye are not particularly limited. However, at low temperatures, the dispersion does not reach a desired particle size even after long-time dispersion, and at high temperatures, reaggregation or decomposition occurs. And the problem that desired photographic performance cannot be obtained, and that when the temperature is increased, the viscosity of the solution system decreases, so that the efficiency of pulverization and dispersion of solids is greatly reduced. Therefore, dispersion temperature 15 ~
The temperature is more preferably 50 ° C. Further, the stirring rotation speed at the time of dispersion requires a long time to obtain a desired particle size at a low rotation speed, and at a high rotation speed, bubbles are entrained and the dispersion efficiency is reduced. Is more preferable.

The sensitizing dyes preferably used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonol, merostyril, and strepto dyes. Examples thereof include polymethine dyes containing cyanine.
Particularly effective sensitizing dyes include sensitizing dyes belonging to cyanine dyes, merocyanine dyes, complex cyanine dyes and complex merocyanine dyes. The above sensitizing dyes may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. You may.

The amount of such a sensitizing dye greatly depends on the type of silver halide emulsion, and in the case of an ordinary preferred silver halide size of 0.2 to 1.5 μm, 1 per mole of silver halide. It is preferably from × 10 ^-6 to 1 × 10 ^-4 mol.

In the present invention, it is also possible to use a reduction sensitizer in combination.
Sure Magazine, Vol. 307, No. 307105, and JP-A-7-786
No. 85 or the like can be used.

Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compounds (eg, dimethylamine borane), hydrazine compounds (eg, hydrazine, p-tolylhydrazine, etc.), polyamine compounds (eg, , Diethylenetriamine, triethylenetetramine, etc.), stannous chloride, silane compounds, reductones (eg, ascorbic acid etc.), sodium sulfite, aldehyde compounds, hydrogen gas and the like. JP-A-10-123656 and JP-A-10-970
No. 20, No. 10-26810, etc.
Reduction sensitization may be performed in an atmosphere containing excess H or silver ions.

In the present invention, regarding the silver halide emulsion, in addition to the above, Research Disclosure
ure No. 308119 (hereinafter abbreviated as RD308119) can be used.

The following shows the places to be described. [Item] [Page RD308119] Iodine composition 993 IA Section Production method 993 IA and 994 E Crystal wall Normal crystal 993 IA Crystal wall twin crystal 993 IA Section Epitaxial 993 IA Item Halogen composition uniform 993 IB Item Halogen composition non-uniform 993 IB Item Halogen conversion 994 IC Halogen substitution 994 IC Item Metal-containing 994 ID Monodispersion 975 IF Item Solvent addition 995 I-F Latent image forming position Surface 995 I-G Latent image forming position Inside 995 I-G Applicable photosensitive material negative 995 I-H Positive (including internal fog particles) 995 I-H Emulsion mixed Item 995 IJ Item Desalting 995 II-A In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. I do. The additives used in such a process are Research
DisclosureNo. 17643, no. 187
16 and No. 308119 (hereinafter referred to as RD17
643, RD18716 and RD308119)
It is described in. The places to be described are shown below.

[Item] [RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-AA, B, C, D, 23 to 24 648 to 649 H, I, J section Supersensitizer 996 IV-AE, J section 23-24 648-649 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known examples usable in the present invention. The photographic additives described in the above Res.
ear Disclosure.
The relevant sections are described below.

[Item] [Page RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J Item 25 Brightener 998 V 24 UV absorber 1003 VIII-I, XIII -C section 25-26 Light absorber 1003VIII 25-26 Light scattering agent 1003VIII Filter dye 1003VIII 25-26 Binder 1003IX 26 651 Static inhibitor 1006XIII 27 650 Hardener 1004X 26 651 Plasticizer 1006XII 27 650 Lubricant 1006XII 27650 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) Section 1001 XXB Various couplers can be used in the present invention, and specific examples thereof are described above in Research Di. cl
osure. The relevant sections are described below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D Section VIIC-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC-G Colored coupler 1002 VII-G Section VIIG DIR coupler 1001 VII-F Section VIIF BAR coupler 1002 VII-F Other useful residue release 1001 VII-F Coupler Alkali-soluble coupler 1001 VII-E The additives used in the present invention are described in RD308119XIV It can be added by a dispersion method or the like.

In the present invention, the aforementioned RD17643
Page 28, RD18716 pages 647 to 648, and RD3
The support described in XIX of 08119 can be used.

The silver halide light-sensitive material of the present invention can be provided with an auxiliary layer such as a filter layer or an intermediate layer described in RD308119VII-K.

The silver halide light-sensitive material of the present invention has the above-mentioned R
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in D308119VII-K can be employed.

To develop the silver halide light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (The
Theory of The Photographi
c Process 4th Ed. ) Pp. 291-3
34 pages and Journal of the American Chemical Society (Journal of the Am
and RD17643, RD18743, RD18743, RD17643, RD17643, RD17643, RD17643.
Development can be carried out by a usual method described on page 16615 and RD308119XIX.

[0123]

Example 1 Preparation of Tabular Seed Emulsion I A tabular seed emulsion I was prepared in the following procedure.

[Nucleation Step] In a reaction vessel, a 28.3 liter aqueous solution containing 162.8 g of low molecular weight gelatin (average molecular weight: 15,000) and 23.6 g of potassium bromide was kept at 15 ° C. The pH was adjusted to 1.90 with 0.5 mol / l sulfuric acid while stirring at high speed using a mixing and stirring device described in JP-A-62-160128. Thereafter, the S-01 solution and the X-01 solution were added at a constant flow rate for one minute using a double jet method to form nuclei, and then the G-01 solution was added. (S-01) 1.25 mol / l silver nitrate aqueous solution 20
5.7 ml (X-01) 1.25 mol / l aqueous solution of potassium bromide 205.7 ml (G-01) 120.5 g of alkali-treated inert gelatin (average molecular weight 100,000) and 10 mass of the following surfactant A 7.% methanol solution
2921 ml of an aqueous solution containing 8 ml.

Surfactant A: HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O]
₂₀ (CH ₂ CH ₂ O) _n H (m + n = 10) [Maturation Step] It takes 45 minutes after the nucleation step to complete.
The temperature was raised to 0 ° C. and the pAg was adjusted to 9.2. Then 0.1
An aqueous solution containing 36 mol of ammonia and an aqueous solution of potassium hydroxide were added to adjust the pH to 9.3, and the mixture was maintained for 6 minutes. Then, the pH was adjusted to 6.1 using 1 mol / l nitric acid.

[Growth Step] After completion of the ripening step, the flow rates of the S-02 solution and the X-02 solution were accelerated by the double jet method while maintaining the pAg at 9.2 (addition flow rates at the end and at the start). (The ratio is about 5 times). (S-02) 1.25 mol / l silver nitrate aqueous solution 26
20 ml (X-02) 1.25 mol / l potassium bromide 26
20 ml after the completion of the addition, subject to desalting and washing according to a conventional method,
Additional gelatin was added and dispersed well. The emulsion thus obtained was a tabular emulsion having a cubic equivalent particle size of 0.27 μm, an average aspect ratio of 12.0 and a variation coefficient of the particle size of 14.2%. This is designated as tabular seed emulsion I.

[Preparation of Emulsion A] Emulsion A was prepared by continuously growing tabular seed emulsion I according to the following procedure.

[Formation of Core A Phase] 0.21 mol of tabular seed emulsion I and 15 l of a 1% aqueous gelatin solution containing 1.0 ml of a 10% by mass methanol solution of the above-mentioned surfactant A were added to
While maintaining the temperature at 60 ° C. and the pAg at 8.4, the S-11 solution and the X-11 solution were added using the double jet method while accelerating the flow rates (the ratio of the end and start addition flow rates was about 10 times). To form a core A phase. (S-11) 3.5 mol / l silver nitrate aqueous solution 205
9 ml (X-11) aqueous solution 205 containing 3.45 mol / l potassium bromide and 0.05 mol / l potassium iodide
9 ml [Formation of core B phase] After the formation of the phase A, an aqueous solution containing 57.7 g of sodium p-iodoacetamidobenzenesulfonate and an aqueous solution containing 20.0 g of sodium sulfite were added, and the pH was adjusted to 9.9 with an aqueous potassium hydroxide solution. Adjust to 3 and 6
After holding for 1 minute, the pH was adjusted to 5.0 with an aqueous solution of acetic acid, and the pAg was adjusted to 9.7 with an aqueous solution of potassium bromide. Subsequently, the S-12 liquid and the X-12 liquid were added while accelerating the flow rates (the ratio of the addition flow rates at the end and at the start was about 2.2 times) to form a core B phase. (S-12) 3.5 mol / l silver nitrate aqueous solution 726
ml (X-12) Aqueous solution 726 containing 3.25 mol / l potassium bromide and 0.25 mol / l potassium iodide
ml [Formation of outermost phase] Following formation of phase B, liquid S-13 and X-
Thirteen solutions were added while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was about 1.4 times) to form the outermost phase. (S-13) 1.25 mol / l silver nitrate aqueous solution 50
9 ml (X-13) 509 ml of a 1.25 mol / l aqueous solution of potassium bromide After completion of the formation of the outermost phase, a desalting and washing treatment was carried out according to the method described in JP-A-5-72658, and gelatin was added and dispersed well. PH 5.8 and EAg 100 mV at ℃
Was adjusted. Thus, a tabular silver halide emulsion A was obtained. As a result of the analysis, Emulsion A was tabular grains having a cubic equivalent average particle size of 1.0 μm and an average aspect ratio of 6.5. In the emulsion A, tabular grains having 5 or more dislocation lines on each side occupy 85% or more of the projected area, and the ratio of the length of adjacent sides is 0.5 to 2.0. It was found that 95% or more of the particles were present.

[Preparation of Emulsion B] After desalting and washing, EA
Emulsion B was prepared in the same manner as Emulsion A, except that g was adjusted to 70 mV.

[Preparation of Emulsion C] pAg in preparation of core A phase
Emulsion C was prepared in the same manner as Emulsion A, except that was changed to 8.7. Emulsion C has a cubic equivalent average particle size of 1.0 μm.
m and tabular grains having an average aspect ratio of 9.2.
In the emulsion C, tabular grains having five or more dislocation lines on each side occupy 85% or more of the projected area.
It was found that 95% or more tabular grains having a ratio of lengths of adjacent sides of 0.5 to 2.0 were present.

[Preparation of Emulsion D] EA after desalting and washing
Emulsion D was prepared in the same manner as Emulsion C except that g was adjusted to 70 mV.

[Preparation of Emulsion E] pAg during preparation of core A phase
Emulsion E was prepared in the same manner as Emulsion A, except that was changed to 9.0. Emulsion E had a cubic equivalent average particle size of 1.0 μm.
m and tabular grains having an average aspect ratio of 13.3. In the emulsion E, tabular grains each having at least 5 dislocation lines on each side occupy 85% or more of the projected area, and the ratio of the length of adjacent sides is 0.5 to 2.0. It was found that 95% or more of the particles were present.

[Preparation of Emulsion F] EA after desalting and washing
Emulsion F was prepared in the same manner as Emulsion E except that g was adjusted to 70 mV.

[Preparation of Emulsion G] pAg during preparation of core A phase
Emulsion G was prepared in the same manner as Emulsion A, except that was changed to 9.5. Emulsion G has a cubic equivalent average particle size of 1.0 μm.
m and tabular grains having an average aspect ratio of 18.0. In the emulsion G, tabular grains having 5 or more dislocation lines on each side occupy 85% or more of the projected area, and the ratio of the length of adjacent sides is 0.5 to 2.0. It was found that 95% or more of the particles were present.

[Preparation of Emulsion H] EA after desalting and washing
Emulsion H was prepared in the same manner as Emulsion G except that g was adjusted to 70 mV.

[Preparation of Emulsions 101-117] A portion of Emulsion A was heated and dissolved at 55 ° C., and 6.0 × 10 ⁻⁵ mol of sensitizing dye (SD-6) per mol of silver halide, 8)
5.0 × 10 ⁻⁴ mol and 6.0 × 10 ⁻⁵ mol of (SD-10) were added as 0.5% methanol solutions, respectively.
After 0 minutes, a mixture of sodium thiosulfate pentahydrate (7.0 × 10 ⁻⁶ mol, 2.0 × 10 ⁻⁶ mol of chloroauric acid and 2.5 × 10 ⁻⁴ mol of potassium thiocyanate) was added at intervals of 10 minutes. And aged to optimize sensitivity. After aging, 3.0 × 10 ⁻³ mol of stabilizer (ST-1), (AF-3) 5.
Emulsion 101 was obtained by adding 0 × 10 ⁻⁵ mol, lowering the temperature to 35 ° C., and further cooling and solidifying.

Emulsion 102 was prepared in the same manner as Emulsion 101 except that Emulsion B was used. Emulsion 103 was prepared in the same manner as Emulsion 101, except that Emulsion C was used and the amount of sensitizing dye added was changed to 1.2 times that of Emulsion 101.

Emulsion 104 was prepared in the same manner as Emulsion 103 except that Emulsion D was used. Emulsion 1 was prepared in the same manner as Emulsion 101 except that Emulsion E was used and the amount of the sensitizing dye added was changed to 1.3 times.
05 was produced.

Emulsion 106 was prepared in the same manner as Emulsion 105 except that Emulsion F was used. Emulsion 1 was prepared in the same manner as Emulsion 101, except that Emulsion G was used and the addition amount of the sensitizing dye was changed to 1.5 times.
07 was produced.

Emulsion 108 was prepared in the same manner as Emulsion 107 except that Emulsion H was used. Further, emulsions 109 to 108 were added to emulsions A to H in the same manner as emulsions 101 to 108 except that 5.0 × 10 ^-5 mol of compound 1-6 of the present invention was added after completion of ripening.
~ 116 was obtained.

Emulsion 117 was obtained in the same manner as Emulsion 116, except that the sensitizing dye was added in a fine solid state.

[0142]

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[Preparation of Emulsions 201 to 209] Emulsions A to H
10 minutes after the addition of the sensitizing dye, 1.0 × 10 ⁻⁶ mol of the selenium sensitizer (Se-6) of the present invention was added, and the added amount of sodium thiosulfate pentahydrate was 5.0 ×. Emulsions 201 to 20 were prepared in the same manner as emulsions 101 to 108 except that the amount was 10 ^-6 mol.
8 was obtained.

An emulsion 209 was obtained in the same manner as the emulsion 208 except that the sensitizing dye was added in a fine solid state.

[Preparation of Emulsions 301 to 317] Emulsions A to H
Emulsions 301 to 308 in the same manner as emulsions 101 to 108 except that 2 × 10 ^-3 mol of silver iodide fine grains having an average particle size of 0.05 μm was added 10 minutes before the sensitizing dye was added.
I got

After the chalcogen sensitizer was added to the emulsions A to H, 10 minutes before the addition of the stabilizer (ST-1), silver iodide fine grains having an average grain size of 0.05 μm were added to 2 × 10 ^-3
Emulsion 3 was prepared in the same manner as emulsions 101 to 108 except that mol 3 was added.
09-316 were obtained. Further, an emulsion 317 was obtained in the same manner as the emulsion 316, except that the sensitizing dye was added in a fine solid state.

[Preparation of Emulsions 401 to 417] Emulsions A to H
Emulsion 10-2 except that 2.0 × 10 ⁻⁵ mol of compound 2-23 of the present invention was added simultaneously with stabilizer (ST-1).
Emulsions 401 to 408 were obtained in the same manner as in Nos. 1 to 108.

Also, 10 minutes after the addition of the sensitizing dye to the emulsions A to H, the compound 2-23 of the present invention was 2.0 × 10
Emulsions 409-416 were obtained in the same manner as Emulsions 101-108 except that ^-5 mol was added.

Further, an emulsion 417 was obtained in the same manner as the emulsion 416, except that the sensitizing dye was added in a fine solid state.

[Preparation of emulsions 501 to 509] Emulsions A to H
Emulsion 101 except that 7 × 10 ⁻⁵ mol of compound (T-1) of the present invention was added simultaneously with stabilizer (ST-1).
To 108, emulsions 501 to 508 were obtained.

An emulsion 509 was obtained in the same manner as the emulsion 508, except that the sensitizing dye was added in a fine solid state.

[Preparation of Emulsions 601 to 602] A part of Emulsion H was dissolved by heating at 55 ° C., and 9.0 × 10 ^-5 mol of sensitizing dye (SD-6) per mol of silver halide, 8)
7.5 × 10 ^-4 mol and (SD-10) 9.0 × 10 ^-5 mol were added in the form of fine solid particles, and the compound 2-23 of the present invention was 2.0 × 10 ^-5 at 10 minute intervals. Mol, selenium sensitizer 1.0 × 10 ^-6 mol, sodium thiosulfate pentahydrate 5.0 × 10 ^-6 mol, chloroauric acid 2.0 × 10 ^-6 mol and potassium thiocyanate 2.5 × 10 ⁶ mol ^-4 mol of the mixture was added. Thereafter, when the sensitivity becomes optimal, the average particle size is 0.0
2.0 × 10 ⁻³ mol of silver iodide fine grains of 5 μm was added, and 10 minutes later, 3.0 × 10 ⁻³ mol of the stabilizer (ST-1) was added.
Compound 1-6 of the present invention at 5.0 × 10 ⁻⁵ mol, (AF-
3) 5.0 × 10 ^-5 mol was added, the temperature was lowered to 35 ° C., and the mixture was cooled and solidified to obtain an emulsion 601.

The stabilizer (ST-1) and the present invention
Compound (T-1) of 7.0 × 10 ^-FiveOther than adding mol
Prepared emulsion 602 in the same manner as emulsion 601.

Example 2 [Preparation of color light-sensitive material sample] On a cellulose triacetate film support provided with an undercoat layer, layers having the following compositions were successively applied from the support side to form a silver halide multilayer color photograph. A photosensitive material sample 1001 was prepared.

[0155] The addition amount is the number of grams per 1 m ^2, unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes (shown by SD) are shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.30 CM-1 0.12 CC-1 0.03 OIL-1 0.24 Gelatin 1.33 Second Layer (Intermediate) Layer) Silver iodobromide emulsion j 0.10 AS-1 0.12 OIL-1 0.15 Gelatin 0.67 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide emulsion c 0.053 Silver iodide emulsion d 0.11 Silver iodobromide emulsion e 0.11 SD-1 2.2 × 10 ^-5 SD-2 5.9 × 10 ^-5 SD-3 1.2 × 10 ^-4 SD-4 1 0.6 × 10 ^-4 SD-5 1.6 × 10 ^-4 C-1 0.19 CC-1 0.003 OIL-2 0.096 AS-2 0.001 Gelatin 0.44 4th layer (medium sensitivity) Red-sensitive layer) Silver iodobromide emulsion b 0.28 Silver iodobromide emulsion c 0.34 Silver iodobromide emulsion d 0.50 SD-1 1.8 × 1 ^{0 -5 SD-4 2.6 × 10} -4 SD-5 2.8 × 10 -4 C-1 0.74 CC-1 0.081 DI-1 0.020 DI-4 0.008 OIL-2 0.42 AS-2 0.003 Gelatin 1.95 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide emulsion a 1.45 Silver iodobromide emulsion e 0.076 SD-1 2.3 × 10 ^-5 SD-2 1.1 × 10 ^-4 SD-3 1.5 × 10 ^-5 SD-4 2.1 × 10 ^-4 C-2 0.087 C-3 0.12 CC-10 036 DI-1 0.021 DI-3 0.005 BAR-1 0.022 OIL-2 0.15 AS-2 0.004 Gelatin 1.40 6th layer (intermediate layer) F-1 0.03 AS- 1 0.18 OIL-1 0.22 Gelatin 1.00 Seventh layer (low-sensitivity green-sensitive layer) Silver iodobromide emulsion c 0.22 Silver iodobromide emulsion e 0 ^{22 SD-6 4.7 × 10 -5} SD-7 2.6 × 10 -4 SD-8 1.9 × 10 -4 SD-9 1.1 × 10 -4 SD-10 2.4 × 10 - ⁵ M-1 0.35 CM-1 0.044 DI-2 0.010 OIL-1 0.41 AS-2 0.001 AS-3 0.11 Gelatin 1.29 Eighth layer (medium green color sensitivity) Silver iodobromide emulsion b 0.90 Silver iodobromide emulsion e 0.048 SD-6 3.8 × 10 ^-5 SD-7 2.6 × 10 ^-4 SD-8 3.4 × 10 ^{− 4} SD-9 1.6 × 10 ^-4 SD-10 4.4 × 10 ^-5 M-1 0.15 CM-1 0.062 CM-2 0.030 DI-2 0.032 OIL-1 28 AS-2 0.005 AS-3 0.045 Gelatin 1.00 Ninth layer (highly sensitive green color-sensitive layer) Emulsion 101 1.39 Silver iodobromide emulsion e 0.073 SD- ^{4.1 × 10 -5 SD-7 2.6} × 10 -5 SD-8 3.7 × 10 -4 SD-10 4.9 × 10 -5 M-1 0.071 M-2 0.073 CM -2 0.013 DI-2 0.004 DI-3 0.003 OIL-1 0.27 AS-2 0.008 AS-3 0.043 Gelatin 1.35 10th layer (yellow filter layer) Yellow colloidal silver 0.053 AS-1 0.15 OIL-1 0.18 X-1 0.06 Gelatin 0.83 Eleventh layer (low-sensitivity blue-sensitive layer) Silver iodobromide emulsion g 0.22 Silver iodobromide Emulsion h 0.099 Silver iodobromide emulsion i 0.17 SD-11 2.4 × 10 ^-4 SD-12 5.7 × 10 ^-4 SD-13 1.3 × 10 ^-4 Y-1 1.02 BAR-1 0.022 OIL-1 0.42 AS-2 0.003 X-1 0.11 X-2 0.18 Zera Down 1.95 12th layer (high sensitivity blue-sensitive layer) Silver iodobromide emulsion f 1.52 SD-11 8.3 × 10 -5 SD-12 2.3 × 10 -4 Y-1 0. 22 DI-5 0.11 OIL-1 0.13 AS-2 0.003 X-1 0.15 X-2 0.20 Gelatin 1.20 13th layer (first protective layer) Silver iodobromide emulsion j 0.30 UV-1 0.11 UV-2 0.055 Liquid paraffin 0.28 X-1 0.079 Gelatin 1.00 Fourteenth layer (second protective layer) PM-1 0.13 PM-2 018 WAX-1 0.021 Gelatin 0.55 The characteristics of the silver iodobromide emulsion used above are shown below (the average particle size is one side length of a cube of the same volume).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide emulsion a 0.85 4.2 7.0 Silver iodobromide emulsion b 0.70 4.2 6.0 iodobromide Silver emulsion c 0.50 4.2 5.0 silver iodobromide emulsion d 0.38 8.0 octahedral twin silver iodobromide emulsion e 0.27 2.0 tetradecahedral normal crystal silver iodobromide emulsion f 1.00 8.0 4.5 Silver iodobromide emulsion g 0.74 3.5 6.2 Silver iodobromide emulsion h 0.44 4.2 6.1 Silver iodobromide emulsion i 0.30 9 5.5 Silver iodobromide emulsion j 0.03 2.0 1.0 The above sensitizing dyes were added to each of the above emulsions, and after ripening, triphenylphosphine selenide, sodium thiosulfate, chloroauric acid Then, potassium thiocyanate was added thereto, and subjected to chemical sensitization according to a conventional method so as to optimize fog and sensitivity.

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, weight average molecular weight: 10,000 and weight average molecular weight: 100,000
Of two types of polyvinylpyrrolidone (AF-1, AF-
2), inhibitors AF-3, AF-4, AF-5, hardener H
-1, H-2 and the preservative Ase-1 were added.

The structures of the compounds used in the above samples are shown below.

[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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Samples 1002 to 6002 were prepared by replacing the emulsion 101 of the ninth layer with the emulsions 102 to 602 prepared in Example 1 shown in Tables 1 to 5.

Each sample was subjected to wedge exposure with white light and subjected to the following developing treatment to determine the sensitivity of the green-sensitive layer. The sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog +0.1, and is a relative value with respect to the value of sample 1001 as 100.
It was shown to.

Each sample was left standing at 55 ° C. for 7 days, subjected to wedge exposure with white light, and subjected to the following development to determine the sensitivity of the green-sensitive layer. The sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog +0.1, and is shown in Tables 1 to 5 as relative values with the value of Sample 1001 not subjected to heat treatment being 100.

<< Reference Color Development Processing >> Processing Step Processing Time Processing Temperature Replenishment Amount * Color Development 3 min 15 sec 38 ± 0.3 ° C. 780 ml Bleaching 45 sec 38 ± 2.0 ° C. 150 ml Fixing 1 min 30 sec 38 ± 2.0 ° C. 830 ml Stabilizing 60 seconds 38 ± 5.0 ° C. 830 ml drying 1 min 55 ± 5.0 ℃ - * the replenishing amount is a value per photosensitive material 1 m ^2.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developing solution Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and add potassium hydroxide or 20
The pH is adjusted to 10.06 with% sulfuric acid.

Color developing replenisher Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 liter, and add potassium hydroxide or 20
Adjust to pH 10.18 with%.

Bleaching solution Water 700 ml 1,3-Diaminopropanetetraacetic acid ammonium (III) ammonium salt 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Add water to make 1 liter, and use ammonia water or glacial acetic acid. And adjust to pH 4.4.

Bleach replenisher Water 700 ml 1,3-Diaminopropanetetraacetate iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting to pH 4.4 using aqueous ammonia or glacial acetic acid Add water to make 1 liter.

Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 ml Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzoisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Add water to make 1 liter, then add ammonia water or 5
Adjust to pH 8.5 with 0% sulfuric acid.

[0183]

[Table 1]

[0184]

[Table 2]

[0185]

[Table 3]

[0186]

[Table 4]

[0187]

[Table 5]

Tables 1 to 5 show that the sample of the present invention has high sensitivity, low fog, and excellent storage stability at high temperatures.

[0189]

According to the present invention, high sensitivity, low fog,
A silver halide color photographic material having excellent storage stability can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/09 G03C 1/09 1/34 1/34 7/392 7/392 AB

Claims (7)

[Claims] 1. A silver halide color photographic apparatus having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In a photosensitive material, at least one of the photosensitive layers
The silver halide emulsion contained in the layer is tabular silver halide grains having an aspect ratio of 8 or more in a projected area of 50% or more of a projected area, and a silver halide emulsion containing a compound represented by the following general formula (1). A silver halide color photographic light-sensitive material, characterized in that: General formula (1) R ^1- (S) m-R ^{2 wherein} R ¹ and R ² are each an aliphatic group, an aromatic group, a heterocyclic group or an atom capable of forming a ring by bonding to each other Represents a group. When R ¹ and R ² are an aliphatic group, they may combine with each other to form a ring. m represents an integer of 2 to 6. ] 2. A silver halide color photographic device having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In a photosensitive material, at least one of the photosensitive layers
The silver halide emulsion contained in the layer is tabular silver halide grains having an aspect ratio of 8 or more in 50% or more of the projected area, and the silver potential of the silver halide emulsion is from 40 mV to 70%.
A silver halide color photographic light-sensitive material, which is a silver halide emulsion which has a mV of selenium sensitization. 3. A silver halide color photographic device having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In a photosensitive material, at least one of the photosensitive layers
The silver halide emulsion contained in the layer is tabular silver halide grains having an aspect ratio of 8 or more in a projected area of 50% or more of the silver halide emulsion, and after addition of a chalcogen sensitizer, silver halide fine grains are added. A silver halide color photographic light-sensitive material, which is a silver emulsion. 4. A silver halide color photograph having on one side on a support at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In a photosensitive material, at least one of the photosensitive layers
The silver halide emulsion contained in the layer is tabular silver halide grains having an aspect ratio of 8 or more in 50% or more of the projected area, and the compound represented by the following general formula (2) contains a spectral sensitizing dye and a chalcogen. A silver halide color photographic light-sensitive material, which is a silver halide emulsion added during each time of addition of a sensitizer. Embedded image Wherein X represents N or CR ′, R ′ is a hydrogen atom,
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ³ and R ⁴ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. n represents 0 or 1. R
³ and R ⁴ are —SO ₃ H, —COOH, —OH and —N
At least one group selected from HR ⁵ and salts thereof.
Have one directly or indirectly. R ⁵ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group. ] 5. A silver halide color photographic having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In a photosensitive material, at least one of the photosensitive layers
The silver halide emulsion contained in the layer is tabular silver halide grains having an aspect ratio of 8 or more in a projected area of 50% or more of a projected area and containing a compound capable of forming a divalent cation by oxidation. A silver halide color photographic light-sensitive material, characterized in that: 6. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one of the light-sensitive layers is a light-sensitive layer.
The silver halide emulsion contained in the layer is tabular silver halide grains having an aspect ratio of 8 or more in 50% or more of the projected area, and has a pH of 5.0 to 7.0 and a silver potential of 40 mV to 7
A silver halide color photographic light-sensitive material, which is a silver halide emulsion chemically sensitized at 0 mV. 7. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one of the light-sensitive layers in the light-sensitive layer is a light-sensitive material.
A silver halide emulsion wherein the silver halide emulsion contained in the layer is tabular silver halide grains having an aspect ratio of 8 or more in an area of 50% or more of a projected area, and a sensitizing dye is added in a fine solid dispersion state. Silver halide color photographic material.