JPH1165015A - Silver halide photographic sensitive material and silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase sensitivity, provide lament image stability with fogging reduced, provide raw preservability, latent image stability reciprocity failure characteristics in high illuminance, and further provide excellent pressure fogging resistance by setting a silver potential in a coating of a layer containing silver halide grains to a specific value. SOLUTION: This silver halide photographic sensitive material has silver halide emulsion containing a compound inside silver halide grains where is the electron capturing center, and a silver potential in a coating of a layer containing the silver halide grains is 50 to 120 mV. The electron capturing center is a fine area that has characteristics to capture electrons specifically in the silver halide grains. The size corresponds to a numerical unit cell or less. The silver halide emulsion of the silver halide photographic sensitive material comprises an optionally halide composed silver halide, and it is desirably a silver iodide bromide or a silver bromide. Core/shell type silver iodide bromide grains having a high iodide content phase inside grains are more desirable, especially 3 mol.% total silver iodide content or more and 6 mol.% inner high silver iodide content or more are desirable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material and a silver halide color photographic material.
Specifically, high sensitivity and low fog, and latent image stability,
The present invention relates to a silver halide photographic light-sensitive material and a silver halide color photographic light-sensitive material excellent in raw storage stability, high illuminance failure characteristics, and pressure fog resistance.

[0002]

2. Description of the Related Art In recent years, demands for photographic silver halide emulsions have become increasingly severe. For example, there has been a high demand for photographic performance such as high sensitivity and excellent graininess, high sharpness and high optical density and low fog. Is being done. These problems are often solved by high-sensitivity, low-fogging silver halide emulsion manufacturing techniques.

Heretofore, silver halide photographic materials have tended to produce fog due to the presence of nuclei that can be developed without exposure, and in particular, during storage over time, the sensitivity is reduced due to the occurrence of fog, or In many cases, the gradation is deteriorated.

Since it is desirable to reduce such undesirable phenomena as much as possible, conventionally, antifoggants,
It is known to add a stabilizer or the like to a silver halide emulsion. For example, 1-phenyl-5-mercaptotetrazole described in U.S. Pat. Nos. 2,403,927 and 3,804,633, JP-B-39-2825, etc., or 4-hydroxy-6-methyl-1,4 3,3a, 7-
Tetrazaindene and the like have been used as fog inhibitors.

[0005] However, these compounds are not always satisfactory because of their insufficient fogging suppressing effect during storage over time, and have disadvantages such as reduction in sensitivity and deterioration of gradation.

Another important characteristic is the stability during the period from exposure to development until development, that is, the stability of the latent image.

When a silver halide is exposed to light, a latent image is formed, but the latent image is unstable, and retreats or is intensified with the passage of time or by heat or the like. This appears as a decrease or increase in sensitivity in terms of photographic performance.

The latent image storability depends on the production method and structure of silver halide, surface treatment, methods of chemical sensitization and spectral sensitization, binder properties such as gelatin, hardener type, pH of coating solution, silver ion It is greatly affected by the concentration.

Various methods have been proposed for improving the stability of the latent image. For example, Japanese Patent Application Laid-Open No. 50-9491
8, a method using benzthiazolium as disclosed in EP490297, and a method using a Schiff base as disclosed in Japanese Patent Application Laid-Open No. 57-100425.

However, it has been found that even when these techniques are used, the degree of improvement in the stability of the latent image is insufficient, or the sensitivity is reduced and the fog is increased. In contrast, Japanese Unexamined Patent Publication No.
140582 discloses a technique for using a styryl-based dye and a nitrogen-containing heterocyclic compound in combination. Although the above-described performance is remarkably improved by this technique, a further improved technique has been desired in order to achieve the object of the present invention.

On the other hand, as a technique for controlling charge carriers (carriers) in silver halide grains, such as free electrons and holes, a metal doping technique is known. For example, it is reported by Leubner that doping a silver halide with an iridium complex exhibits an electron trapping property. (The Journal Of Photo
ogrgic Science Vol. 31,
93 (1983)). That is, it can be said that the iridium complex imparts an electron capture center to silver halide grains. This technique is extremely effective for improving the high illuminance failure (exposure for about 1 / 10,000 second) characteristic and for preventing pressure fog, which causes blackening of an unexposed area due to pressurization.
No. 438 discloses a technique for improving photographic properties by doping an iridium complex into silver halide.

However, it has been found that in this technique, an undesired phenomenon such as a decrease in photographic sensitivity and softening occurs due to the iridium complex exposed on the grain surface because it cannot be completely doped into the silver halide grains. On the other hand,
US Pat. No. 5,132,203 discloses an emulsion containing iridium ions inside silver halide grains and having no iridium ions on the surface of the grains, and US Pat. A tabular emulsion containing no metal dopant in the outermost phase of a grain and containing a metal dopant in an adjacent subsurface phase is disclosed. However, in these patents, although the addition position of the dopant is controlled, the actual control of the dopant distribution in the grains, that is, the control of the carrier control center existing phase is not effectively performed. Specifically, only by controlling the timing of addition of the dopant, since there is a dopant remaining and remaining in the reaction solution without being doped until then, it is necessary to form a surface phase containing no dopant. It is considered impossible.

Therefore, the prior art was not sufficient to achieve the object of the present invention.

[0014]

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a high sensitivity and low fog, a latent image stability, a raw storage property, a high illuminance failure property, and a pressure fog resistance. Another object of the present invention is to provide a silver halide photographic light-sensitive material and a silver halide color photographic light-sensitive material which are excellent in quality.

[0015]

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

(1) In a silver halide photographic light-sensitive material having a silver halide emulsion containing at least one compound serving as an electron capture center inside the silver halide grains, a layer containing the silver halide grains Silver potential of coating film is 5
A silver halide photographic light-sensitive material, which has a voltage of 0 to 120 mV.

(2) A layer containing the silver halide grains in a silver halide photographic material having a silver halide emulsion containing at least one compound serving as a hole trapping center on the surface of the silver halide grains. Silver potential of 5
A silver halide photographic light-sensitive material, which has a voltage of 0 to 120 mV.

(3) At least one compound serving as an electron trapping center is contained in the silver halide grains, and at least one compound serving as a hole trapping center is adsorbed on the surface of the silver halide grains. In a silver halide photographic light-sensitive material having a silver halide emulsion, the spectral absorption maximum wavelength in a state where a compound serving as a hole trapping center of the silver halide emulsion is adsorbed on the surface of silver halide grains is 450 nm or less. A silver halide photographic light-sensitive material comprising:

(4) The silver halide photographic material as described in (3), wherein the layer containing the silver halide grains has a silver potential of 50 to 120 mV.

(5) The compound serving as the electron capture center is at least one kind of polyvalent metal ion selected from Ir, Os, Ru, Rh, Pd, Pt, Re, Co and Fe ( The silver halide photographic light-sensitive material according to 1), (3) or (4).

(6) The halogenated compound according to (2), (3) or (4), wherein the compound serving as a hole trapping center is a compound represented by the following general formula (I). Silver photographic photosensitive material.

[0022]

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[Wherein R ₁ , R ₂ , 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, and R ₅ , R ₆ , R ₇ And R ₈ each represent a substituent. L ₁ and L ₂ each represent a methine group, and Z ₁ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, —C (R ₉ ) (R ₁₀ ) — or —N (R ₉ ) —.
R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , and R ₉ and R ₁₀ may be bonded to each other to form a ring. (7) A silver halide color photographic light-sensitive material having a photographic constituent layer comprising at least one red light-sensitive layer, green light-sensitive layer, blue light-sensitive layer and non-light-sensitive layer on one side on a support. Wherein at least one of the blue-sensitive layers contains at least one compound serving as an electron-capturing center inside the silver halide grains, and a compound serving as a hole-capturing center on the surface of the silver halide grains. A silver halide emulsion having at least one type of adsorbed thereon, and having a maximum spectral absorption wavelength of 450 nm or less when a compound serving as a hole trapping center of the silver halide emulsion is adsorbed on the surface of the silver halide grains. A silver halide color photographic light-sensitive material comprising:

(8) A silver halide color photograph having, on one side on a support, at least one photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In a light-sensitive material, at least one of the blue light-sensitive layers comprises: A silver halide emulsion containing at least one compound serving as an electron trapping center inside the silver halide grain and adsorbing at least one compound serving as a hole trapping center on the surface of the silver halide grain; The compound having a hole trapping center of a silver halide emulsion adsorbed on the surface of silver halide grains has a spectral absorption maximum wavelength of 450 nm or less; A silver halide color photographic light-sensitive material having a coating silver potential of 50 to 120 mV.

Hereinafter, the present invention will be described in detail.

The silver halide emulsion of the silver halide photographic light-sensitive material of the present invention comprises silver halide having an arbitrary halide composition, and is preferably silver iodobromide or silver bromide. Core / shell type silver iodobromide grains having a high silver iodide content phase inside the grains are more preferable, and the iodide having a total silver iodide content of 3 mol% or more and an internal high silver iodide content phase is preferred. Core / shell grains having a silver halide content of at least 6 mol% are particularly preferred.

In the present invention, the grain size of a silver halide grain is represented by a circle equivalent diameter of a projected area of the silver halide grain (diameter of a circle having the same projected area as the silver halide grain). To 5.0 μm, more preferably 0.2 to 2.0 μm. The particle diameter can be obtained by, for example, photographing the particle with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is 1000). Or more).

[0028] Here, the average particle diameter r is the product n _i × r _i ³ of the frequency n _i and r _i ³ of particles having a particle size r _i is defined as a particle diameter r _i at which the maximum (effective 3 digits, minimum 4 digits
Round off 5).

In the present invention, the term "doping" or "doping" means that a substance other than silver ions or halide ions is contained in silver halide grains. The term "dopant" refers to a compound doped into silver halide grains, and the term "metal dopant" refers to a polyvalent metal compound doped into silver halide grains.

Incidentally, a polyvalent metal ion or a polyvalent metal atom which is a main element of the metal dopant is hereinafter referred to as a metal.

Next, in the present invention, the electron trapping center means a minute portion having a property of specifically trapping electrons in silver halide grains. Its size corresponds to several unit cells or less. The electron capture center of the present invention does not itself contribute to latent image formation.

In that it does not form a developable latent image nucleus, it is distinguished from, for example, a chemically sensitized nucleus formed by a chalcogen compound or a noble metal compound. The photosensitive nuclei formed inside the grains of the internal latent image type emulsion are also distinguished in the same manner.

In the present invention, specific electron trapping centers are MX _x (CN) _y ^n- (M is a polyvalent metal having m valence, m and y
Represents an integer of 2 or more, and X _x represents an arbitrary x combinations selected from Cl ⁻ , Br ⁻ , and I ⁻ . n represents an integer of (x + y) -m. ) Or MX ₆ ^n- (M is an m-valent polyvalent metal, X ₆
Represents an arbitrary combination of six selected from Cl ⁻ , Br ⁻ , and I ⁻ . n is an integer of 6-m. ).

As a specific means for imparting an electron trapping center, _An MX _x (CN) _y during silver halide grain growth
(A represents an alkali metal ion or an ammonium ion or a derivative thereof, M is an m-valent polyvalent metal, and m and y are 2
The above integer, X _x , represents any x combinations selected from Cl ⁻ , Br ⁻ , and I ⁻ . n represents an integer of (x + y) -m. Includes any adducts such as water of crystallization. ) Or MX
₆ ^n- alkali metal salts or salts of ammonium or its derivatives (M is an m-valent polyvalent metal, Ir ³⁺ , I
It is selected from r ⁴⁺ , Rh ³⁺ , Re ³⁺ , Re ⁴⁺ , Pd ²⁺ and Pt ²⁺ . X ₆ is any 6 selected from Cl ⁻ , Br ⁻ , and I ⁻
Represents a combination of n is an integer of 6-m. ),
Alternatively, Ir ³⁺ , Ir ⁴⁺ , Rh ³⁺ , Re ³⁺ , Re ⁴⁺ , Pd
²⁺ , Pt ²⁺ salt compounds such as halides, nitrates,
Addition of sulfate and perchlorate may be mentioned.

A preferred electron capture center is Os (C
^{_{N) 6 4-, Ru (CN}} ) 6 4-, Fe (CN) 6 4-, Co
_{^{(CN) 6 3-, MX 6}} n- (M is a polyvalent metal m-valent, I
It is selected from r ³⁺ , Ir ⁴⁺ and Rh ³⁺ . X ₆ is Cl ⁻ , B
r ^-, I ^- represents any of the six combinations chose from. n
= 6-m is an integer. ).

[0036] Further, the alkali metal salt Fe (CN) ₆ ^4- of as a means for imparting a preferred electron trapping centers, ammonium or salts of derivatives thereof, Ru (CN) ₆ ^4- alkali metal salts of, ammonium or a derivative thereof Salt of Os
(CN) ₆ ^4- alkali metal salts, salts of ammonium or derivatives thereof, Ir ³⁺ , Ir ⁴⁺ , Rh ³⁺ halide complexes or Ir ³⁺ , Ir ⁴⁺ , Rh ³⁺ salt compounds such as halogens Chloride, nitrate, sulfate and perchlorate during the growth of silver halide grains.

As means for providing more preferable electron trapping centers, IrCl ₃ , IrBr ₃ , IrI ₃ , RhCl ₃ ,
RhBr ₃ , RhI ₃ , K ₂ [IrCl ₆ ], Na ₂ [Ir
Cl ₆ ], K ₂ [IrBr ₆ ], Na ₂ [IrBr ₆ ], K ₂
[IrI ₆ ], Na ₂ [IrI ₆ ], K ₃ [IrCl ₆ ],
Na ₃ [IrCl ₆ ], K ₃ [IrBr ₆ ], Na ₃ [Ir
Br ₆ ], K ₃ [IrI ₆ ], Na ₃ [IrI ₆ ], K ₃ [R
hCl ₆ ], Na ₃ [RhCl ₆ ], K ₃ [RhBr ₆ ],
Na ₃ [RhBr ₆ ], K ₃ [RhI ₆ ] or Na ₃ [R
hI ₆ ] during the growth of silver halide grains.

The means for providing the most preferable electron trapping centers are K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₃ [Ir
Cl ₆ ] or K ₃ [IrBr ₆ ] during the growth of silver halide grains.

In the present invention, the particle surface or its vicinity is defined as
It refers to a place where electrons or holes can be transferred to and from silver halide or an adsorbed substance to silver halide except inside the silver halide grains.

In the present invention, the term "hole trapping center" refers to a minute portion having the property of specifically trapping holes at or near the surface of a silver halide grain.

The maximum absorption wavelength of the hole trapping center compound at the time of adsorption on the surface of the silver halide grains is 450 nm.
The following means that the hole-capturing center compound has a particle diameter of 1.0 μm.
When the compound is adsorbed on m AgBr cubic particles, the compound has a spectral absorption maximum wavelength of 450 nm or less. If the spectral absorption maximum wavelength is longer than 450 nm, not only the effect of the present invention cannot be exerted, but also color turbidity is caused, which is not preferable.

Specific examples of the compound serving as a hole trapping center include styryl dyes, metallocene compounds, tetra-substituted hydrazine compounds, alkynylamine compounds, tetrazaindenols, and aminostilbene compounds. Particularly preferred.

Next, the compound represented by formula (I) will be described.

In the general formula (I), R ₁ , R ₂ ,
Examples of the alkyl group represented by R ₃ and R ₄ include groups such as methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and dodecyl. These alkyl groups further include a halogen atom (eg, chlorine,
Bromine, fluorine, etc.), an alkoxy group (for example, methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), an aryloxy group (for example, phenoxy, naphthyloxy, etc.), an aryl group ( For example, each group such as phenyl and naphthyl), an alkoxycarbonyl group (for example, each group such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, and 2-ethylhexylcarbonyl), and an aryloxycarbonyl group (for example, each group such as phenoxycarbonyl and naphthyloxycarbonyl) ), Alkenyl groups (for example, vinyl, allyl and the like), heterocyclic groups (for example, 2-pyridyl, 3-pyridyl,
4-pyridyl, morpholyl, piperidyl, piperazil,
Groups such as pyrimidyl, pyrazolyl and furyl), alkynyl groups (such as propargyl group), amino groups (such as amino, N, N-dimethylamino and anilino),
It may be substituted by a cyano group, a sulfonamide group (for example, each group of methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.) and the like.

The alkenyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ include, for example, vinyl groups and allyl groups.

The alkynyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ include, for example, a propargyl group.

The aryl group represented by R ₁ , R ₂ , R ₃ and R ₄ includes, for example, a phenyl group and a naphthyl group.

The heterocyclic group represented by R ₁ , R ₂ , R ₃ and R ₄ is, for example, a pyridyl group (for example, 2-pyridyl, 3-pyridyl)
Pyridyl, 4-pyridyl, etc.), thiazolyl group, oxazolyl group, imidazolyl group, furyl group, thiecol group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, And a tetrazolyl group.

The alkenyl group, alkynyl group, aryl group and heterocyclic group are all the same as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the groups shown as substituents of the alkyl groups. Can be substituted by a group.

Examples of the substituent represented by R ₅ , R ₆ , R ₇ , and R ₈ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, and an alkoxy group. Carbonyl group, aryloxycarbonyl group, sulfonamide group, sulfamoyl group, ureido group, acyl group, carbamoyl group, amide group, sulfonyl group, amino group, cyano group, nitro group, hydrogen atom, mercapto group, alkylthio group, arylthio group , An alkenylthio group, a heterocyclic thio group and the like. These groups can be substituted by the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the groups shown as the substituents of the alkyl groups.

The ring formed by R ₁ and R ₂ includes, for example, benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole,
And rings such as pyrazine and indole.

It is more preferable that R ₃ and R ₄ form a ring. Examples of the ring that can be formed by R ₃ and R ₄ include rings such as piperidine, pyrrolidine, morpholine, pyrrole, pyrazole and piperazine.

The ring formed by R ₅ and R ₆ , and R ₇ and R ₈ includes, for example, rings such as benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole, pyrazine, indole and the like.

The above-mentioned rings can be substituted by the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the rings exemplified as the substituents of the alkyl groups.

The methine groups represented by L ₁ and L ₂ may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group,
Examples include an alkoxycarbonyl group and an aryloxycarbonyl group. These groups further include R ₁ , R ₂ ,
It can be substituted by the same substituents as the alkyl groups represented by R ₃ and R ₄ and the groups exemplified as the substituents of the alkyl group.

Specific examples of the compound represented by formula (I) (hereinafter, also referred to as the compound of the present invention) used in the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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Specific examples of the synthesis of the compound represented by formula (I) of the present invention are shown below. Other compounds represented by formula (I) can be easily synthesized by the same method. it can.

Synthesis Example 1 (Synthesis of Exemplified Compound I-4) To 14.9 g of 2-methylbenzothiazole, 17.7 g of p-diethylaminobenzaldehyde, 6 g of sodium hydride (hard oil 60%) and 60 cc of dimethylformamide were added. For 30 minutes. The reaction solution was poured into water, and the precipitated solid was separated by filtration. After drying the solid, the desired product was obtained by recrystallization from methanol. Yield 19.4
g (63%) The addition amount of the compound represented by formula (I) of the present invention is preferably 2 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver halide, and more preferably 2 × 10 ⁻⁷ mol. It is preferably from 10 ^{-7 to} 5 × 10 ^-3 mol.

As a method for adding the compound represented by the general formula (I) of the present invention to a silver halide emulsion, a method well known in the art can be used. For example, the compound can be dispersed directly in the emulsion, or pyridine,
Dissolved in a water-soluble solvent such as methanol, ethanol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide or a mixture thereof, or diluted with water,
Alternatively, it can be dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibration can be used during the dissolution process.

Further, the compound represented by the general formula (I) of the present invention is dissolved in a volatile organic solvent as described in US Pat. No. 3,469,987 and the like, and this solution is added to a hydrophilic colloid. A method of adding a dispersed dispersion to an emulsion, JP-B-46
A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving and adding this dispersion to an emulsion as described in JP-A-24185 or the like is also used.

The compound represented by formula (I) of the present invention can be added to an emulsion in the form of a dispersion by an acid dispersing method.

The compound represented by the general formula (I) of the present invention may be added at any time during the period from the formation of silver halide grains to the time of coating. It is preferable to add during.

In the present invention, the coating silver potential (hereinafter referred to as coating E)
"Ag" is also referred to as) cutting a 500 cm ² silver halide color light-sensitive material coated on a support into strips, immersing it in 100 cc of pure water for 6 hours in a dark room, and comparing a commercially available saturated silver-silver chloride electrode. It is measured using a silver ion electrode as an electrode.

At this time, if a non-photosensitive layer such as a backing layer is provided on the side opposite to the emulsion surface, it must be removed beforehand.

The method of adjusting the coating film EAg is as follows.
An aqueous solution of O ₃ , KBr, NaBr, KCl or the like may be added so as to obtain the target coating film EAg.

In order to adjust the coating EAg, the coating liquid for controlling the EAg may be a coating liquid forming a layer containing the compound of the general formula (1) or a coating liquid forming another layer. It may be adjusted by diffusion during coating and drying, or by controlling the pH of all coating solutions.

In order to obtain the effect of the present invention, the coating EAg is 1
It is preferably 20 mV or less, and in order to obtain a more preferable effect, it is adjusted to 100 mV or less.

The silver halide emulsion of the present invention can be used for research
Disclosure (Research Disclo
sure) No. 308119 (hereinafter RD30811)
9) can be used. The description places are shown below.

[0078]

[Table 1]

The silver halide emulsion of the present invention may be subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are Research Disclosure N
o. No. 17643, ibid. No. 18716 and the same No. 30
8119 (hereinafter RD17643, RD187, respectively)
16 and RD308119).
The description places are shown below.

[0080]

[Table 2]

The photographic additives which can be used in the silver halide emulsion of the present invention are also described in the above RD. The description places are shown below.

[0082]

[Table 3]

Various couplers can be used in the silver halide emulsion of the present invention, and specific examples are also described in the above RD. The relevant descriptions are shown below.

[0084]

[Table 4]

The additives used in the light-sensitive material using the silver halide emulsion of the present invention can be added by a dispersion method described in RD308119XIV.

In the light-sensitive material using the silver halide of the present invention, see RD17643, page 28, RD187.
Supports described in X.16, pages 647-8 and RD308119, can be used.

The light-sensitive material using the silver halide 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 light-sensitive material using the silver halide of the present invention can have various layer constitutions such as a forward layer, a reverse layer, and a unit constitution described in RD308119VII-K.

The silver halide emulsion of the present invention can be applied to various color light-sensitive materials typified by color negative films for general use or movies, color reversal films for slides or televisions, and color positive films.

The light-sensitive material using the silver halide emulsion of the present invention is described in RD17643, pp. 28-19, RD187.
Development can be carried out by a usual method described on page 16 615 and XIX of RD308119.

[0091]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Twin Seed Emulsion T-1>
A seed emulsion T-1 having two parallel twin planes was prepared.

Solution A Ossein gelatin 80.0 g Potassium bromide 47.4 g HO (CH ₂ CH ₂ O) _m (CH [CH ₃ ] CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9) .77) 10% by weight methanol solution 0.48 ml Make up to 8000 ml with distilled water Solution B Silver nitrate 1200.0 g Make up to 1600 ml with distilled water Solution C Ossein gelatin 32.2 g Potassium bromide 823.8 g Potassium iodide 23.45 g Solution D Finished to 1600 ml with distilled water Solution D Ammonia water 470.0 ml Solution B and solution C were added to solution A vigorously stirred at 40 ° C. by a double jet method for 7.7 minutes to generate nuclei. During this time, pBr was kept at 1.60. Then 30
The temperature was reduced to 20 ° C over a minute. Further, the solution D was added for 1 minute, followed by aging for 5 minutes. During ripening, the KBr concentration was 0.03 mol / l, and the ammonia concentration was 0.1.
It was 66 mol / l.

After completion of the ripening, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. A 10% by weight aqueous gelatin solution was added to the desalted emulsion, and the mixture was stirred and dispersed at 60 ° C. for 30 minutes, and then distilled water was added to complete the emulsion as 5360 g.

When the seed emulsion grains were observed by an electron microscope, they were tabular grains having two twin planes parallel to each other.

The average grain size of the seed emulsion grains was 0.295 μm.
The number of particles having two parallel twin planes at m and an average aspect ratio of 5.0 was 80% (number ratio) of all the particles.

<Preparation of Comparative Emulsion Em-1> A comparative tabular emulsion Em-1 was prepared by the following method.

Solution A 68.1 g of ossein gelatin 10 weights of HO (CH ₂ CH ₂ O) _m (CH [CH ₃ ] CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) % Methanol solution 2.50 ml Seed emulsion (T-1) 74.13 g Finished to 3500 ml with distilled water Solution B 3.5 N aqueous silver nitrate solution 5000 ml Solution C Potassium bromide 2082.6 g ossein gelatin 200 g Finished to 5000 ml with distilled water Solution D Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) (preparation method is shown in the following * ¹ ) 492.8 g * ¹ ); 0.06 mol of potassium iodide In 5000 ml of a 6.0% by weight gelatin solution containing 20% aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide.
00 ml was added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

Solution E 1.75N Aqueous potassium bromide solution Solution F 2631.3 g Fine grain emulsion consisting of 3% by weight of gelatin and silver bromide particles (average particle size 0.04 μm) (preparation method is shown in the following * ² ) * ² ): An aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium bromide in 5000 ml of a 6.0% by weight gelatin solution containing 0.06 mol of potassium bromide was used.
00 ml was added over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 30 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

The solution A was added to the reaction vessel, and the solutions B to D were added by the simultaneous mixing method according to the combination shown in Table 5 with vigorous stirring to grow a seed crystal to form a core / shell type silver halide emulsion. Was prepared.

Here, (1) the rate of addition of the solution B, the solution C and the solution D, and (2) the rate of addition of the solution B and the solution C are adjusted in time so as to correspond to the critical growth rate of the silver halide grains. On the other hand, the addition rate was changed in a function-like manner, and the rate of addition was controlled to an appropriate addition rate so as to prevent generation of small particles other than growing seed crystals and polydispersion by Ostwald ripening. Further, the addition rate ratio between the solution B and the solution C was controlled to be 1: 0.95.

Further, the solution temperature in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. Solution E was added as needed for pAg control.

Table 5 shows the grain size at that time with respect to the addition time of the reaction solution, and the silver iodide content of the silver halide phase forming the surface.

When the growth particle size was 1.620 μm, the addition of the solutions B and C was terminated, and the solution F was added at a constant rate over 20 minutes, and subjected to a desalting treatment according to the method described in JP-A-5-72658. Then, gelatin was added and redispersed at 50 ° C. for 30 minutes. Thereafter, the temperature was lowered to 40 ° C. to adjust the pH to 5.8.
0 and pAg were adjusted to 8.06 to obtain Emulsion Em-1.

From the electron micrograph of the obtained emulsion particles, tabular grains having an average particle size of 1.668 μm, an average aspect ratio of 5.0 and a particle size distribution of 18.0% were confirmed.

[0106]

[Table 5]

<Preparation of Comparative Emulsion Em-2> Comparative Emulsion Em
The growth of the seed emulsion was carried out in the same manner as in Example 1, and the addition of the solutions B and C was terminated when the growth grain size was 1.620 μm.
Desalting was performed according to the method described in JP-A-5-72658. Then, gelatin was added, the mixture was redispersed at 50 ° C. for 20 minutes, and Solution F was added at a constant speed over 20 minutes.
Redispersion was performed at 50 ° C. for 30 minutes.

Thereafter, the temperature was lowered to 40 ° C. to adjust the pH to 5.8.
0 and pAg were adjusted to 8.06 to obtain Emulsion Em-2.

From the electron micrograph of the obtained emulsion particles, E
It was confirmed that the particles had the same size and crystal habit as m-1.

(The same operation is performed as in the case where the outermost phase containing substantially no metal dopant is imparted to the metal-doped emulsion.) <Preparation of Comparative Emulsion Em-3> Em-3 was obtained in the same manner as Em-2, except that the MA solution described later was added at a constant speed from another nozzle introduced into the reaction solution during 610 μm. From the electron micrograph of the obtained emulsion particles, it was confirmed that the particles had the same size and crystal habit as Em-1.

<Preparation of Comparative Emulsion Em-4> Particle size 1.55
Between 2 μm and 1.610 μm, except that the following MB solution was added at a constant speed from another nozzle introduced into the reaction solution.
Em-4 was obtained in the same manner as m-2. From the electron micrograph of the obtained emulsion particles, it was confirmed that the particles had the same size and crystal habit as Em-1.

(Breakdown of MA solution and MB solution) MA solution Ferrocyanide potassium trihydrate 1.8 × 10 ^-4 mol Finished to 100.0 ml with distilled water MB solution K ₂ IrCl ₆ 3.5 × 10 ⁻⁶ mol Nitric acid (specific gravity: 1.38) 0.005 ml Finish to 100.0 ml with distilled water The ratio of the metal dopant used in Em-3 and Em-4 to the particle volume is 80. It ranged from 4% to 90%.

Em-1 to Em-4 obtained by the above operation were respectively divided, and the following sensitizing dye (SD-
9), (SD-10) and optimally spectral sensitization and chemical sensitization with triphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate, and then the present invention as described in Table 6 below. And the like, and 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene and 1-phenyl-5-mercaptotetrazole were added, and the temperature was lowered.
R was prepared.

Further, the following yellow coupler (Y-1) was dissolved in ethyl acetate and tricresyl phosphate and dispersed in an aqueous solution containing gelatin, and a general dispersion such as a spreading agent and a hardening agent was used. A photographic additive was added to prepare a coating solution, which was coated on a subbed cellulose triacetate support by a conventional method and dried to prepare photosensitive materials / samples 101 to 118 as shown in Table 7 below. The coating silver potential of each sample was all adjusted to 140 mV.

[0115]

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Samples 101 to 118 were each divided into five parts to obtain A, B, C, D, and E. Reference processing A was performed by subjecting A to wedge exposure using white light in accordance with a conventional method, and immediately developing according to the following processing steps. Was done.

In the forced deterioration treatment B, B was heated at 55 ° C. and 60%
After standing for 4 days under the condition of RH, wedge exposure was performed with white light, and then development processing similar to that of the forced degradation treatment material A was performed.

Further, in the forced deterioration treatment C, C was exposed to wedges with white light, and then left at 40 ° C. and 80% RH for 7 days. went.

<< Development processing >> (Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 cc Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishment amount is a value per m ² of the photosensitive material.

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

<Color developing solution and color developing replenishing solution> Developer replenishing solution Water 800 cc 800 cc Potassium carbonate 30 g 35 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Iodine 5. Potassium chloride 1.2 mg-Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-4-Amino-3-methyl-N-ethyl-N-([beta] -hydroxylethyl) aniline sulfate 4.5 g 6. 3 g diethylenetriaminepentaacetic acid 3.0 g 3.0 g potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, and add potassium hydroxide or 20%
The color developing solution is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18 using sulfuric acid.

<Bleaching Solution and Bleaching Replenisher> Bleaching Solution Replenishing Solution Water 700 cc 700 cc 1,3-diaminopropanetetraacetate ammonium (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g Add 56 g of water to make up to 1 liter, and adjust the pH of the bleaching solution to 4.4 and the pH of the replenishing solution to 4.0 using ammonia water or glacial acetic acid.

<Fixing Solution and Fixing Replenisher> Fixing Solution Replenisher Water 800 cc 800 cc Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid is used to adjust the pH of the fixing solution to 6.2.
Then, the pH of the replenisher is adjusted to 6.5, and then water is added to make 1 liter.

<Stabilizing Solution and Stabilizing Replenishing Solution> Water 900 cc p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylol urea 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 cc Add water to make 1 liter, then add ammonia water or 50
Adjust to pH 8.5 with% sulfuric acid.

The sensitivity of each sample was such that the blue density was the fog density +
It is represented by the reciprocal of the exposure amount that gives an optical density of 0.15, and is represented by a relative value with the value of Sample A of Sample 101 being 100.

Table 7 shows the results.

[0127]

[Table 6]

[0128]

[Table 7]

[0129]

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As is clear from Tables 6 and 7, Claim 3,
It can be seen that the photosensitive materials of the invention described in 5, 6, and 7 have high sensitivity, low fog, and excellent storage stability and latent image stability.

Example 2 Using D and E divided in Example 1, evaluation of pressure resistance (pressure fog) and evaluation of reciprocity failure property were performed.

Regarding evaluation D (evaluation D of pressure fog), the film was allowed to stand in an atmosphere of 23 ° C. and 55% RH for 24 hours.
After equalizing the water content of each sample, a radius of curvature of 0.3 was obtained under the same atmosphere.
5 g of weight was applied to a needle having sapphire of 025 mmφ at the tip, and each sample was scratched at a speed of 1.0 cm / sec. Subsequently, each sample was exposed and developed in the same manner as in Example 1. Minimum density (Dmi
The change in density due to pressurization in part n) was measured using a 2 μm aperture. The pressure fog characteristic of each sample was evaluated as the following equation.

ΔDmin = [(non-pressing portion Dmax−pressing portion Dmin) / (non-pressing portion Dmax−non-pressing portion Dmi
n)] In the above equation, the closer the ΔDmin value is to 1, the better the pressure fog resistance is. Table 8 shows the relative values with the value of Sample D of Sample 101 taken as 100. Table 8 shows the obtained results.

Regarding the evaluation E (Evaluation E of reciprocity failure property), exposure and development were performed in the same manner as in Example 1 except that the exposure time was changed, and the reciprocity failure property was evaluated.
In this case, the exposure amount was set to be constant regardless of the exposure time. In addition, the sensitivity of each sample is as follows: blue density is fog density +
It is represented by the reciprocal of the exposure amount giving an optical density of 0.15, and is represented by a relative value with the value of A of the sample 101 in Example 1 being 100. Table 8 shows the results.

[0135]

[Table 8]

As is clear from Table 8, the emulsions of the present invention have excellent pressure fog resistance and high illuminance failure characteristics.

Example 3 In the process of preparing the samples 106, 108 and 110 used in Example 1, the silver potential of the coating film was 110 m for each sample.
Samples 119 to 124 were prepared in exactly the same manner as in Example 1 except that a coating solution for each layer was prepared using an aqueous solution of silver nitrate and an aqueous solution of potassium bromide so that V and 90 mV were obtained. The silver potential of the coated films of Samples 106, 108 and 110 was 140 mV. Example 1 was used for these samples.
And 2 were evaluated in exactly the same manner.

Table 9 shows the results.

[0139]

[Table 9]

As is clear from Table 9, the light-sensitive material of the present invention is excellent in all the characteristics such as sensitivity, fog, storage stability, latent image stability, pressure fog resistance and high illuminance failure.

Example 4 A multilayer color photographic light-sensitive material sample 401 was prepared by sequentially forming each layer having the following composition on a triacetyl cellulose film support provided with an undercoat layer from the support side.

The amount of addition is expressed in grams per m ² .
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-2 0.123 CC-1 0.044 OIL-1 0.176 Gelatin 1.34 Second Layer (Auxiliary) Layer) AS-1 0.13 OIL-1 0.008 Gelatin 0.69 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 SD-12 37 × 10 ^-5 SD-2 1.2 × 10 ^-4 SD-3 2.4 × 10 ^-4 SD-4 2.4 × 10 ^-6 C-1 0.32 CC-1 0.038 OIL- 2 0.30 AS-2 0.002 Gelatin 0.73 4th layer (medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide b 0.86 SD-1 4.5 × 10 ^-5 SD-2 2.3 × 10 ^-4 SD-3 4.5 × 10 ^-4 C-2 0.52 CC-1 0.06 DI-1 0.04 7 OIL-2 0.500 AS-2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 SD-1 0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.047 C-3 0.09 CC-1 0.036 DI-1 0.024 OIL -2 0.053 AS-2 0.006 gelatin 1.28 6th layer (first intermediate layer) OIL-1 0.02 AS-1 0.18 gelatin 1.00 7th layer (low sensitivity green color sensitivity) Layer) Silver iodobromide a 0.19 Silver iodobromide b 0.062 SD-4 3.6 × 10 ^-4 SD-5 3.6 × 10 ^-4 M-1 0.18 CM-2 0.033 OIL-1 0.210 AS-2 0.002 AS-3 0.05 Gelatin 0.61 Eighth layer (second intermediate layer) OIL-1 0.110 AS -1 0.054 Gelatin 0.80 Ninth layer (medium speed green-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 SD-6 3.7 × 10 ^-4 SD-7 7.4 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-1 0.17 M-2 0.33 CM-2 0.024 CM-3 0.029 DI-2 0.024 DI-3 0.005 OIL-1 0.73 AS-3 0.35 AS-2 0.003 Gelatin 1.80 10th layer (high-sensitivity green color-sensitive layer) Silver iodobromide f 1.19 SD-6 4. 0 × 10 ^-4 SD-7 8.0 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-1 0.065 CM-3 0.026 CM-2 0.022 DI-3 0.003 DI -2 0.003 OIL-1 0.145 AS-3 0.017 AS-2 0.014 Gelatin 1.23 11th layer (yellow filter layer Third intermediate layer) Yellow colloidal silver 0.05 OIL-1 0.04 AS-1 0.16 Gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide b 0.22 Iodobromide Silver a 0.08 Silver iodobromide h 0.09 SD-9 6.5 × 10 ^-4 SD-10 2.5 × 10 ^-4 Y-1 0.77 DI-4 0.017 OIL-1 407 AS-2 0.002 Gelatin 1.30 13th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.41 Em-A (prepared in Example 1) 0.61 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^-4 Y-1 0.23 OIL-1 0.10 AS-2 0.004 Gelatin 1.20 14th layer (first protective layer) Silver iodobromide i 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.271 Gelatin 1.32 15th layer (second protective layer) PM 1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Gelatin 0.55 The characteristics of the above silver iodobromide are shown below (one side of a cube having the same volume as the average particle size). Long).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 c 0.60 7.0 3.0. 1 d 0.74 7.0 5.0 e 0.60 7.0 4.1 f 0.65 8.7 6.5 g 0.40 2.0 4.0 h 0.65 8.0 1. 4 i 0.05 2.0 1.0 As a typical example of forming silver halide grains, a production example of silver iodobromide d and f is shown below.

For the silver halide emulsion according to the present invention, a seed crystal emulsion-1 was first prepared as follows.

Preparation of Seed Emulsion-1 A seed emulsion was prepared as follows.

JP-B-58-58288, 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. For 2 minutes to form nuclei. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side length ratio of 90% or more of the total projected area of the silver halide grains (maximum ratio of each grain). The emulsion was composed of hexagonal tabular grains having a ratio of a side length to a minimum side length of 1.0 to 2.0. This emulsion is referred to as seed emulsion-1.

[Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide While stirring 5 liters vigorously, 7.06
2 liters of an aqueous silver nitrate solution and 2 liters of a 7.06 mol aqueous potassium iodide solution were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are prepared, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 5.0. The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is designated as SMC-1.

Preparation of silver iodobromide d 0.178 moles of seed crystal emulsion-1 and HO (CH ₂ CH ₂
O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n
H (m + n = 9.77) in 10% ethanol solution 0.5
4.5% by weight of an aqueous inert gelatin solution 70
0 ml at 75 ° C., pAg 8.4, pH 5.0.
Then, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.

1) An aqueous solution of 3.093 mol of silver nitrate, 0.287 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining pAg at 8.4 and pH at 5.0.

2) Subsequently, the solution was cooled to 60 ° C.
g was adjusted to 9.8. Thereafter, 0.071 mol of SM
C-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) An aqueous solution of 0.959 mol of silver nitrate, 0.03 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 9.8 and the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so that the formation of new nuclei and the Ostwald ripening between particles did not proceed. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.74 μm, an average aspect ratio of 5.0, and a silver iodide content of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.7 mol%.

Preparation of silver iodobromide f In the preparation of silver iodobromide d, pAg was adjusted to 8.8 in step 1).
8 and the amount of silver nitrate to be added was 2.077 mol SMC-1.
And the amount of silver nitrate added in step 3) was 0.91 mol and the amount of SMC-1 was 0.079 mol in the same manner as for silver iodobromide d. Silver fide f was prepared.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Edge length) 0.65 μm, average aspect ratio 6.5, silver iodide content 2 / 9.5 / X / 8.0 mol% from the inside of the grain
The emulsion was composed of tabular grains having a halogen composition of (X is a dislocation line introduction position). When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-mentioned sensitizing dyes were added to each of the above emulsions and ripened, triphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added, and the fogging and sensitivity were optimized according to a conventional method. Spectral sensitization and chemical sensitization were performed to achieve the desired results.

Silver iodobromide a, b, c, e, g, and h were also prepared according to the above silver iodobromide d and f and subjected to spectral sensitization and chemical sensitization.

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, antifoggant A
F-1, two types of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000, inhibitors AF-3, AF-4 and AF-
5. Hardeners H-1, H-2 and preservative Ase-1 were added.

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

[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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Next, with respect to the sample 401, the Em-
Samples 402 to 418 described in Table 10 below were prepared in the same manner as Sample 401 except that A was changed as shown in Table 10 below. The coating silver potential of each sample was all adjusted to 140 mV.

[0172]

[Table 10]

Each of the samples 401 to 418 was divided into five parts to obtain A, B, C, D, and E. In the standard processing A, A was subjected to wedge exposure with white light according to a conventional method, and immediately developed according to the following processing steps. Was done.

In the forced deterioration treatment B, B was heated at 40 ° C. and 55%
After standing for 4 weeks under the condition of RH, wedge exposure was performed with white light, and then the same processing as in A was performed.

Further, in the forced deterioration treatment C, C was subjected to wedge exposure with white light, then allowed to stand at 40 ° C. and 80% RH for 7 days, and then subjected to the same development treatment as A.

Further, as the evaluation D, the pressure resistance was evaluated in exactly the same manner as in Example 2. Note that ΔDmin was evaluated based on a change in yellow density due to scratching of a sapphire needle in the processed sample.

Finally, as an evaluation E, exposure and development were performed in the same manner as in A except that the exposure time was changed, and the reciprocity failure property was evaluated. In this case, the exposure amount was kept constant regardless of the exposure time.

The sensitivities of A, B, C, and E are represented by the reciprocal of the exposure amount that gives an optical density of blue density: fog density + 0.15, and are represented by relative values with the value of A of sample 401 being 100. . Table 11 shows the results.

[0179]

[Table 11]

As is clear from Table 11, the silver halide color photographic light-sensitive material using the emulsion of the present invention has high sensitivity, low fog, excellent storage stability, latent image stability, and pressure. It turns out that it is excellent in fog resistance and high illuminance failure characteristics.

Example 5 In the process of preparing the samples 406, 415 and 416 used in Example 4, the silver potential of the coating film was 110 m for each sample.
V, except for using a silver nitrate aqueous solution and a potassium bromide aqueous solution at the time of preparing the coating solution for each layer so as to be 90 mV,
Samples 419 to 424 were prepared in exactly the same manner as in Example 4. Samples 406, 415, and 416 had a coating silver potential of 140 mV. These samples were evaluated exactly as in Example 4.

Table 12 shows the results.

[0183]

[Table 12]

As is clear from Table 12, the silver halide color photographic light-sensitive material of the present invention has sensitivity, fog, storage stability,
It can be seen that the latent image stability, pressure fog resistance, and high illuminance failure are all excellent.

As described above, according to the present invention, a halogenated photographic light-sensitive material and a halogenated photographic material having high sensitivity and low fog, and excellent in latent image stability, raw storage stability, high illuminance failure property, and pressure fog resistance are provided. It can be seen that a silver color photographic light-sensitive material can be provided.

[0186]

According to the present invention, there is provided a silver halide photographic light-sensitive material having high sensitivity and low fog, and excellent in latent image stability, raw storage stability, high illuminance failure characteristics, and pressure fog resistance. A silver color photographic light-sensitive material could be provided.

Claims (8)

[Claims] Claims: 1. A silver halide photographic material having a silver halide emulsion containing at least one compound serving as an electron capture center inside silver halide grains, wherein a layer containing the silver halide grains is coated. Membrane silver potential is 50-12
A silver halide photographic light-sensitive material, which is 0 mV. 2. In a silver halide photographic material having a silver halide emulsion containing at least one compound serving as a hole trapping center on the surface of the silver halide grains, a layer containing the silver halide grains may be used. Coating silver potential is 50-12
A silver halide photographic light-sensitive material, which is 0 mV. 3. A halogen containing at least one compound serving as an electron capture center inside a silver halide grain, and adsorbing at least one compound serving as a hole capture center on the surface of the silver halide grain. In a silver halide photographic light-sensitive material having a silver halide emulsion, the spectral absorption maximum wavelength in a state where a compound serving as a hole trapping center of the silver halide emulsion is adsorbed on the surface of silver halide grains is 450 nm or less. Characteristic silver halide photographic material. 4. A silver halide photographic light-sensitive material according to claim 3, wherein the silver halide grain-containing layer has a coating silver potential of 50 to 120 mV. 5. The compound serving as an electron capture center is Ir,
Os, Ru, Rh, Pd, Pt, Re, Co and Fe
5. The silver halide photographic material according to claim 1, wherein the material is at least one kind of polyvalent metal ion selected from the group consisting of: 6. The silver halide photographic material according to claim 2, wherein the compound serving as a hole trapping center is a compound represented by the following general formula (I). Embedded image [Wherein, R ₁ , R ₂ , 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, and R ₅ , R ₆ , R ₇ and R ₈ Each represents a substituent. L ₁ and L ₂ each represent a methine group, and Z ₁ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, —C
(R ₉ ) represents (R ₁₀ ) — or —N (R ₉ ) —. R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Also, 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 ,
You may combine with each other to form a ring. ] 7. A silver halide color photographic light-sensitive material having, on one side on a support, at least one photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In the material, at least one of the blue-sensitive layers contains at least one kind of compound serving as an electron trapping center inside silver halide grains, and a compound serving as a hole trapping center on the surface of the silver halide grains. At least one of
A silver halide emulsion having seeds adsorbed thereon, wherein the compound serving as a hole trapping center of the silver halide emulsion has a spectral absorption maximum wavelength of 450 nm in a state where the compound is adsorbed on the surface of silver halide grains.
A silver halide color photographic material characterized by the following. 8. A silver halide color photographic light-sensitive material having, on one side on a support, at least one photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In a material, at least one of the blue-sensitive layers comprises: A silver halide emulsion containing at least one compound serving as an electron trapping center inside the silver halide grain and adsorbing at least one compound serving as a hole trapping center on the surface of the silver halide grain; The compound having a hole trapping center of a silver halide emulsion adsorbed on the surface of silver halide grains has a spectral absorption maximum wavelength of 450 nm or less; A silver halide color photographic light-sensitive material having a coating silver potential of 50 to 120 mV.