JPH1097020A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic emulsion high in sensitivity and superior in latent image stability and improved in fog stability by incorporating a specified compound and subjecting the insides of silver halide grains to reduction sensitization. SOLUTION: The photographic emulsion contains the compound represented by R11 -(S)n -R12 , the compound represented by R21 -(S)n -R22 , the compound of the formulae and the like, or a compound to be allowed to release a development inhibitor, and the insides of the silver halide grains are subjected to the reduction sensitization. In the formula, each of R11 and R12 is an aliphatic or aromatic or a heterocyclic group; each of R31 -R34 is an H or halogen atom or the like; Y1 is an atomic group necessary to form an aromatic hydrocarbon or aromatic heterocyclic group; Z1 is an O or S atom; and B1 is a group capable of adsorbing silver halide alone or in the form of Z1 -B1 .

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 emulsion and a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic emulsion excellent in sensitivity, latent image storability and fog stability. Silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art With the advent of digital photography, silver halide photographic light-sensitive materials (hereinafter also referred to as "photosensitive materials") have been required to have higher quality. Further, the silver halide photograph itself has a small format, and high performance has been required for the silver halide constituting the small format.

For example, in a digital photograph, since information is recorded digitally, deterioration of the information with time is small. On the other hand, an undeveloped silver halide photograph is less advantageous than a digital photograph because it has an increase in fog due to heat and temperature before photographing, and a deteriorated latent image after photographing. or,
Small format means an increase in the magnification at the time of printing, and if provided to the customer as it is, deterioration of graininess and the like is inevitable, and the size of silver halide grains must be reduced, but sensitivity decreases. Need to be supplemented with other technologies.

Therefore, in recent years, there has been a particularly high demand for a technique for improving sensitivity, fog preservation, and latent image preservation.

As one method for solving this problem, reduction sensitization is known.

[0006] Journal of Photographic
Science (J. Photo. Sci.) Vol. 25, 19-
27 (1977) and Photographic Science and Engineering (Photo. Sci. E).
ng. As described in Vol. 23, pp. 113-117 (1979), appropriately-applied reduction sensitizing nuclei are available from Photographic Correspondents (Photo. Korr.).
1, page 20- (1957) and Photo. Sci. E
ng. As described by Michel and Lowe in the report of Vol. 19, pp. 49-55 (1975), it is thought to contribute to sensitization through the reaction represented by the following formula at the time of exposure. .

AgX + hν → e ⁻ + h ⁺ (1) Ag ₂ + h ⁺ → Ag ⁺ + Ag (2) Ag → Ag ⁺ + e ⁻ (3) where h ⁺ and e ⁻ are free holes and free holes generated by exposure. Electrons, hν indicate photons, and Ag ₂ indicates a reduction sensitization nucleus.

Assuming that this theory is correct, it is considered that the reduction sensitization nucleus prevents a decrease in efficiency caused by recombination of electrons with holes and contributes to an increase in sensitivity.

However, Photo. Sci. Eng. (Supra) Volume 16, pages 35-42 (1971) and Volume 23, ibid.
According to pages 113 to 117 (1979), the reduction sensitization nucleus has a property of trapping not only holes but also electrons, and cannot be sufficiently explained by the above theory alone.

Unlike the above-described photosensitive nuclei peculiar to silver halide grains, the function of reduction sensitization in the color sensitized region of spectrally sensitized silver halide cannot be predicted due to the complexity of the photosensitive process. Truly difficult.

In the spectrally sensitized silver halide emulsion, it is the sensitizing dye that absorbs light differently from the intrinsic photosensitive region, and the initial stage of exposure is represented by the formula (4) instead of the formula (1). It is.

[0012] ^{Dye + hν → Dye + + e} - (4) dye holes shown on the right side (Dye ⁺⁾ and electrons (e ^-) is largely Whether transmitted to the silver halide grains due to the nature of the dye. When attention is paid to dye holes, it is generally considered that the sensitization efficiency is better when the dye holes are not transmitted to the inside of the grains.

This is described, for example, in Photo. Sci. E
ng. (Supra) 24, 138-143 (1980)
Are discussed in connection with the oxidation potential (Eox) of the dye.

However, the International Congress of Photographic Science (Inter)
nati. Congr. Photo. Sci. ) Abstract collection,
159-162 (1978) and Photo. Sci.
Eng. (Supra), Vol. 17, pp. 235-244 (197
3) suggests that a sensitizing dye in which dye holes (Dye ⁺ ) generated during exposure remain on the surface of silver halide grains bleaches fog nuclei and reduction sensitizing nuclei on the surface,
In the most common surface latent image type emulsion, it is expected that the latent image on the surface is bleached and rather causes desensitization.

However, as described above, in the spectrally sensitized system, whether reduction sensitization should be performed on the surface or inside of the silver halide grains, and when combined with any dye, It is not known yet whether this effect is exhibited.

As a method of reduction sensitization, a method applied to the surface of a silver halide grain, a method applied during the growth of silver halide grains, or, when a seed crystal is used for grain growth, the seed crystal is previously subjected to reduction sensitization. There is a known method for performing the above.

The method of applying to the grain surface, when used in combination with other sensitization methods (for example, gold sensitization or sulfur sensitization), causes an undesirable increase in fog, which is not suitable for practical use. In contrast, the method of performing reduction sensitization during the growth of silver halide grains, in other words, the method of performing reduction sensitization inside the grains, does not have the above-mentioned disadvantages even when used in combination with other sensitization methods.

However, even if reduction sensitization is performed inside the grains, fog and storage fog increase on the same day. This is because silver nuclei exist on the grain surface even when reduction sensitization is performed during grain formation.

On the other hand, JP-A-8-69064 discloses a method in which a halogen such as iodine is added after grain formation and before addition of a chemical sensitizer and a spectral sensitizer. This method is intended to add iodine to the grain surface and bleach silver nuclei on the surface generated by reduction sensitization,
Not only silver nuclei that cause fogging but also other silver ions that contribute to sensitivity are bleached, so that a decrease in sensitivity, particularly a decrease in storage stability of a latent image, cannot be avoided. Means for coping with this fog by increasing the amount of a specific fog inhibitor added is disclosed in
No. 6,690,795, etc., but this also does not satisfy all of the sensitivity, latent image storability and fog storability at a high level, and further development of a solution has been desired.

[0020]

Accordingly, an object of the present invention is to provide a silver halide photographic emulsion having high sensitivity, excellent latent image stability and improved fog stability, and a silver halide photographic emulsion using the emulsion. Provided is a photosensitive material.

[0021]

The above object of the present invention has been attained by the following constitutions.

(1) The following general formulas (1), (2) and (3-
(a), (3-b), (4) or a halogen containing at least one of compounds capable of releasing a development inhibitor by being oxidized, and the inside of a silver halide grain is reduction-sensitized. Silver halide photographic emulsion.

[0023] Formula _{(1) R 11 - (S} ) in _n -R ₁₂ Formula, R ₁₁ and R ₁₂ each represent an aliphatic group, an aromatic group or a heterocyclic group. R ₁₁ and R ₁₂ may be the same or different, and when R ₁₁ and R ₁₂ are an aliphatic group, they may combine with each other to form a ring. n represents an integer of 2 or more.

Formula (2) R ₂₁ -IR _{22 In the} formula, R ₂₁ and R ₂₂ each represent an aromatic group or an aromatic heterocyclic group. R ₂₁ and R ₂₂ may be the same or different.

[0025]

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Wherein R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each
Hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, cyano group, acylamino group, alkylthio group, arylthio group, sulfonylamino group, ureido group, sulfamoylamino group, carbamoyl group , A sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an amino group, a hydroxyl group, a nitro group, an imide group or a heterocyclic group. Y ₁ represents a group of atoms capable of forming an aromatic carbocycle or an aromatic heterocycle. Z ₁ represents an oxygen atom or a sulfur atom, and B ₁ represents a single group or a group having an adsorbing ability to silver halide as Z ₁ -B ₁ .

[0027]

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In the formula, R ₄₁ is the same as R _{31 in the} above formula (3-a).
And Z ₂ has the same meaning as R _{31 in} formula (3-a), and B ₂
Has the same meaning as B _{1 in the} general formula (3-a).

[0029]

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In the formula, R ₅₁ , R ₅₂ and R ₅₃ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. X ₅ represents an ion for neutralizing the charge, and n ₅ represents the number of ions required for neutralizing the charge.

(2) The general formulas (1), (2) and (3-
(a), (3-b), (4) or at least one of compounds capable of releasing a development inhibitor by being oxidized, and at least 50% of the projected area of the silver halide grains is 10 or more. A silver halide photographic emulsion having at least two dislocation lines.

(3) The projected area of the silver halide grains is 50
% Or more of the silver halide photographic emulsion according to (1), having 10 or more dislocation lines.

(4) The silver halide photographic emulsion according to (1), (2) or (3), wherein the average silver iodide content is 1 mol% or more.

(5) The silver halide photographic emulsion according to any one of (1) to (4), wherein 50% or more of the silver halide grains are tabular grains having an aspect ratio of 2 or more.

(6) The silver halide photographic emulsion according to any one of (1) to (5), which is subjected to at least one of selenium sensitization and tellurium sensitization.

(7) The average silver iodide content is at least 1 mol%, and at least 50% of the silver halide grains have an aspect ratio of 2
(3) The silver halide photographic emulsion as described in (3) above, wherein the tabular grains are subjected to at least one of selenium sensitization and tellurium sensitization.

(8) Halogen halide wherein at least one of the photosensitive silver halide emulsion layers provided on the support contains the silver halide photographic emulsion described in any one of (1) to (7). Silver photographic photosensitive material.

Hereinafter, the present invention will be described in detail for each item.
First, the general formulas (1), (2), (3-a), (3-
b), (4) or a compound capable of releasing a development inhibitor by being oxidized will be described.

In the general formula (1), R ₁₁ and R ₁₂
Examples of the aliphatic group represented by 1 include a linear or branched alkyl, alkenyl, alkynyl or cycloalkyl group having 1 to 30, preferably 1 to 20 carbon atoms. Specifically, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, i-propyl, t-butyl,
-Ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2-butynyl, cyclopropyl,
Cyclopentyl, cyclohexyl, cyclododecyl are mentioned.

The aromatic groups represented by R ₁₁ and R ₁₂ include those having 6 to 20 carbon atoms, and specific examples include phenyl, naphthyl and anthranyl groups. The heterocyclic group represented by R ₁₁ and R ₁₂ may be a single ring or a condensed ring, and includes a 5- to 6-membered heterocyclic ring having at least one of O, S, and N atoms in the ring. Specifically, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan, thiophene, imidazole, pyrazole,
Oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole and their benzerogues. R ₁₁ and R ₁₂ form a ring;
Although a 7-membered ring can be mentioned, a 5-membered ring is preferable. Preferred groups for R ₁₁ and R ₁₂ are heterocyclic groups, and more preferred are aromatic heterocyclic groups.

The aliphatic group, aromatic group or heterocyclic group represented by R ₁₁ and R ₁₂ may be further substituted. Examples of the substituent include a halogen atom (chlorine, bromine, etc.) and an alkyl group (methyl , Ethyl, i-propyl, hydroxyethyl,
Methoxymethyl, trifluoromethyl, t-butyl, etc.),
Cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), aralkyl groups (benzyl, 2-phenethyl, etc.),
Aryl group (phenyl, naphthyl, p-tolyl, p-chlorophenyl, etc.), alkoxy group (methoxy, ethoxy, i-propoxy, butoxy, etc.), aryloxy group (phenoxy, etc.), cyano group, acylamino group (acetylamino, propionyl) Amino), alkylthio groups (methylthio, ethylthio, butylthio), arylthio (phenylthio, etc.), sulfonylamino groups (methanesulfonylamino, benzenesulfonylamino, etc.), ureido groups (3-methylureido, 3,3-dimethylureido, 1 , 3-dimethylureido, etc.), sulfamoylamino group (dimethylsulfamoylamino, etc.), carbamoyl group (methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, etc.), sulfamoyl group (ethylsulfamoyl, dimethyl Sulfamoyl, etc.), alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, etc.), sulfonyl group (methanesulfonyl, butanesulfonyl, phenylsulfonyl, etc.), acyl group (acetyl, propanoyl, butyroyl, etc.) , Amino group (methylamino, ethylamino, dimethylamino, etc.), hydroxyl group, nitro group, nitroso group, amine oxide group (pyridine oxide, etc.), imide group (phthalimide, etc.), disulfide group (benzenedisulfide, benzothiazolyl 2-disulfide) Group) and a heterocyclic group (pyridyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, etc.).

R ₁₁ and R ₁₂ may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent. n is an integer of 2 or more, preferably 2 to 6, more preferably n
= 2.

Specific examples of the compound represented by the general formula (1) are listed below, but the present invention is not limited thereto.

[0044]

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[0045]

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[0046]

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Next, in the general formula (2) of the present invention, R ₂₁
And the aromatic group represented by R ₂₂ include those having 6 to 20 carbon atoms, specifically phenyl, naphthyl, anthranyl group. The aromatic heterocyclic group represented by R ₂₁ and R ₂₂ may be a monocyclic ring or a condensed ring, and includes a 5- to 6-membered aromatic heterocyclic ring having at least one of O, S and N atoms in the ring. Can be Specifically, pyrrole, pyridine, pyrimidine, triazine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole,
Examples include isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole and their benzerogues.

Most preferred as R ₂₁ and R ₂₂ is a benzene ring. The aromatic group or aromatic heterocyclic group represented by R ₂₁ and R ₂₂ may be further substituted, and the substituent may be a halogen atom (chlorine, bromine, etc.), an alkyl group (methyl, ethyl, i- Propyl, hydroxyethyl, methoxymethyl, trifluoromethyl, t-butyl, etc.), cycloalkyl group (cyclopentyl, cyclohexyl, etc.), aralkyl group (benzyl, 2-phenethyl, etc.),
Aryl group (phenyl, naphthyl, p-tolyl, p-
Chlorophenyl, etc.), alkoxy group (methoxy, ethoxy, i-propoxy, butoxy, etc.), aryloxy group (phenoxy, etc.), cyano group, acylamino group (acetylamino, propionylamino, etc.), alkylthio group (methylthio, ethylthio, butylthio, etc.) ), An arylthio group (such as phenylthio), a sulfonylamino group (such as methanesulfonylamino and benzenesulfonylamino),
Ureido group (3-methylureido, 3,3-dimethylureide, 1,3-dimethylureide, etc.), sulfamoylamino group (dimethylsulfamoylamino, etc.), carbamoyl group (methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, etc.) ), Sulfamoyl group (ethylsulfamoyl, dimethylsulfamoyl, etc.), alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, etc.), sulfonyl group (methanesulfonyl, butanesulfonyl, phenylsulfonyl) ), Acyl group (acetyl, propanoyl, butyroyl, etc.), amino group (methylamino, ethylamino, dimethylamino, etc.), hydroxyl group, nitro group, nitroso group, amine oxide group (pyridine Sid, etc.), an imido group (phthalimide), a disulfide group (benzene disulfide,
Benzothiazolyl-2-disulfide, etc.), heterocyclic groups (pyridyl, benzimidazolyl, benzthiazolyl,
Benzoxazolyl), carboxyl group, sulfo group and the like. Preferably as the substituent, a carboxyl group, a sulfo group, an amino group, a hydroxyl group,
Particularly preferred are a carboxyl group and a sulfo group.

R ₂₁ and R ₂₂ may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent.

Specific examples of the compound represented by the general formula (2) are listed below, but the present invention is not limited thereto.

[0051]

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[0052]

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Next, in the general formula (3-a) of the present invention,
The ring moiety formed by Y ₁ is preferably an aromatic carbocyclic ring, for example, a benzene, naphthalene, furan, or thiophene ring, and particularly preferably a benzene ring.

The group represented by R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ is, for example, a hydrogen atom or R ₁₁ and R of the general formula (1).
Examples of the substituent of the group represented by ₁₂ include a hydrogen atom, a substituted or unsubstituted alkyl group, and a halogen atom, and particularly preferably a hydrogen atom or an unsubstituted alkyl group.

Z ₁ represents an oxygen atom or a sulfur atom, preferably a sulfur atom.

Examples of the group represented by B ₁ alone or Z ₁ -B ₁ having the ability to adsorb silver halide include, for example, 5-
Examples include a 6-membered nitrogen-containing heterocyclic group, preferably benzotriazolyl, triazolyl, tetrazolyl, indazolyl, benzimidazolyl, imidazolyl, benzothiazolyl, thiazolyl, benzoxazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, pyrimidinyl, pyridyl or triazinyl. And particularly preferably tetrazolyl, benzimidazolyl or pyrimidinyl. These may further have a substituent, and examples of the substituent include those described above as examples of the substituent of R ₃₁ and R ₃₂ .

Among the compounds represented by the general formula (3-a), the compound represented by the general formula (3-b) is particularly preferable.

In the general formula (3-b), R ₄₁ is R ₃₃ in the general formula (3-a), Z ₂ is Z ₁ in the general formula (3-a), and B ₂ is a general formula (3-a). B ₁ in 3-a)
And are synonymous with each other.

Specific examples of the compounds represented by formulas (3-a) and (3-b) are listed below, but the present invention is not limited thereto.

[0060]

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[0061]

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[0062]

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[0063]

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Next, in the tetrazolium compound of the general formula (4) of the present invention, the group represented by R ₅₁ , R ₅₂ and R ₅₃ is, for example, a hydrogen atom or R ₁₁ and R of the general formula (1).
_The groups exemplified as the substituent of the group represented by ₁₂ are exemplified.
X ₅ represents an ion for neutralizing the charge (a halogen ion such as chloride ion or bromide ion, an acid radical of an inorganic acid, an acid radical of an organic acid, an alkali metal ion, etc.), and n ₅ represents a neutralizing charge. Represents the number required for.

Specific examples of the compound represented by formula (4) are listed below, but the present invention is not limited to these.

[0066]

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Next, a compound (redox compound) which releases a development inhibitor by being oxidized will be described.

The redox compounds include hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones and the like as redox groups. Preferred redox compounds are compounds having an —NHNH— group as a redox group and the following general formulas (RE-I) to (RE-VI)
It is a compound represented by these.

[0069]

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[0070]

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As the compound having a —NHNH— group as a redox group, the following general formula (RE-a) or (RE
-B).

Formula (RE-a) T ₁ -NHNHCOV _1- (Time) -PUG Formula (RE-b) T ₂ -NHNHCOCO _2- (Time) -PUG Formulas (RE-a) and (RE-a) b) Medium, T ₁ , T ₂ , V
₁ and V ₂ each represent an optionally substituted aryl group or an optionally substituted alkyl group.

The aryl group represented by T ₁ , T ₂ , V ₁ and V ₂ includes, for example, a benzene ring and a naphthalene ring, and these rings may be substituted with various substituents. Examples of the group include a linear or branched alkyl group (preferably having 2 to 20 carbon atoms, such as methyl, ethyl, i-propyl, dodecyl) and an alkoxy group (preferably having 2 carbon atoms).
To 21, methoxy, ethoxy, etc.), an aliphatic acylamino group (preferably having an alkyl group having 2 to 21 carbon atoms, acetylamino, heptylamino, etc.), an aromatic acylamino group, and the like. Has, for example, the above-mentioned substituted or unsubstituted aromatic ring is -CONH-,
_{-O -, - SO 2 NH -} , - NHCONH -, - CH 2 C
Also included are those linked by a linking group such as H = N-.

As PUG, 5-nitroindazole,
4-nitroindazole, 1-phenyltetrazole,
1- (3-sulfophenyl) tetrazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole,
5-nitroimidazole, 4-nitroimidazole and the like. These development inhibiting compounds are T ₁ -NHNH
-CO- the CO site or T ₂ -NHNH-COCO- of the COCO site directly through a hetero atom such as N or S, or an alkylene, through phenylene, aralkylene, heteroatoms further N or S via an aryl group Can be connected. In addition, those in which a development inhibiting group such as triazole, indazole, imidazole, thiazole, and thiadiazole are introduced into a hydroquinone compound having a ballast group can also be used. For example, 2- (dodecylethylene oxide thiopropionamide) -5- (5-nitroindazol-2-yl) hydroquinone,
(Stearylamide) -5- (1-phenyltetrazol-5-thio) hydroquinone, 2- (2,4-di-t)
-Aminophenoxypropionamide) -5- (5-
Nitrotriazol-2-yl) hydroquinone, 2-
Dodecylthio-5- (2-mercaptothiothiadiazole-5-thio) hydroquinone;

Redox compounds are disclosed in US Pat. No. 4,269,
929 can be synthesized. The redox compound can be contained in the emulsion layer, in the hydrophilic colloid layer adjacent to the emulsion layer, or in the hydrophilic colloid layer via the intermediate layer.

Redox compounds can be added by adding alcohols such as methanol and ethanol; glycols such as ethylene glycol, triethylene glycol and propylene glycol; esters such as ether, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and ethyl acetate; And can be added after dissolving in ketones such as methyl ethyl ketone. or,
For those that are hardly soluble in water or organic solvents, high-speed impeller dispersion,
The average particle size can be arbitrarily dispersed from 0.01 to 6 μm by sand mill dispersion, ultrasonic dispersion, ball mill dispersion, or the like. For dispersion, a surfactant such as an anion or nonion, a thickener, a latex, or the like can be added and dispersed.

The amount of the redox compound is from 10 ^-6 to 10 ^-1 mol, preferably from 10 ^-4 mol to 10 ^-2 mol, per mol of silver halide.

Among the compounds represented by formula (RE-a) or (RE-b), particularly preferred compounds are shown below.

[0079]

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[0080]

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Specific examples of other preferred redox compounds include R-1 to R-50 described in JP-A-4-245243.

Next, the general formulas (RE-I) to (RE-
The redox compound represented by VI) will be described.

In the general formulas (RE-I) to (RE-VI), R ₆₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₆₂ and R ₆₃ each represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₆₄ represents a hydrogen atom. R _{65 to} R ₇₀ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r ₁ , r ₂ and r ₃ each represent a substituent that can be substituted on a benzene ring. X ₂ and X ₃ each represent O or NH. Z ₃ represents an atom group necessary for constituting a 5- to 6-membered heterocyclic ring. W ₁ represents N (R ₇₁ ) R ₇₂ or O; W ₂ represents N (R ₇₃ ) R ₇₄ or OH;
R ₇₁ , R ₇₂ , R ₇₃ or R ₇₄ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. COUP represents a coupler residue capable of causing a coupling reaction with an oxidized form of an aromatic primary amine developing agent, and * represents a coupling site of the coupler. Tm represents a timing group. m ₁ and p ₁ each represent an integer of 0 to 3. q ₁ represents an integer of 0-4. n
Represents 0 or 1. PUG represents a development inhibitor residue.

The above general formulas (RE-I) to (RE-VI)
In the following, the alkyl group, the aryl group, and the heterocyclic group represented by R ₆₁ and R _{65 to} R ₇₀ preferably include a methyl group, a p-methoxyphenyl group, and a pyridyl group. . Acyl groups represented by R ₆₂ and R ₆₃ ,
Carbamoyl group, cyano group, nitro group, sulfonyl group,
Among the aryl group, oxalyl group, heterocyclic group, alkoxycarbonyl group and aryloxycarbonyl group, preferred are an acyl group, a carbamoyl group and a cyano group. The total number of carbon atoms in these groups is preferably 1 to 20.

R _{61 to} R ₇₄ may further have a substituent. Examples of the substituent include the groups mentioned as the substituents of the groups represented by R ₁₁ and R ₁₂ in the above formula (1). No.

The following can be mentioned as the coupler residue represented by COUP. Examples of the cyan coupler residue include a phenol coupler and a naphthol coupler;
5-pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, indazolone couplers, etc. as magenta coupler residues; benzoylacetanilide couplers, pivaloylacetoanilide couplers, malondianilide couplers as yellow coupler residues And the like, and non-colored coupler residues include open-chain or cyclic active methylene compounds (indanone, cyclopentanone, malonic diester, imidazolinone, oxazolinone, thiazolinone, etc.).

Among the coupler residues represented by COUP,
What is preferably used in the present invention has the general formula (C
(up-1) to (Coup-8).

[0088]

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In the formula, R ¹¹ represents an acylamide group, anilino group or ureido group, and R ¹² represents a phenyl group which may be substituted by one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups. .

[0090]

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In the formula, R ¹³ and R ¹⁴ represent a halogen atom, an acylamide group, an alkoxycarbonylamide group, a sulfoureido group, an alkoxy group, an alkylthio group, a hydroxyl group or an aliphatic group, and R ¹⁵ and R ¹⁶ each represent It represents an aliphatic group, an aromatic group or a heterocyclic group, and one of R ¹⁵ and R ¹⁶ may be a hydrogen atom. a represents an integer of 1 to 4; b represents an integer of 0 to 5; When a and b are 2 or more, a plurality of R ¹³ and R ¹⁴ may be the same or different.

[0092]

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In the formula, R ¹⁷ represents a tertiary alkyl group or an aromatic group, and R ¹⁸ represents a hydrogen atom, a halogen atom or an alkoxy group. R ¹⁹ represents an acylamide group, an aliphatic group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group,
Represents an alkoxy group, a halogen atom or a sulfonamide group.

[0094]

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In the formula, R ²⁰ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group or a diacylamino group, and R ²¹ represents a hydrogen atom, a halogen atom or a nitro group.

[0096]

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In the formula, R ²² and R ²³ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

In the general formula (RE-II), Z ₃
The 5- or 6-membered heterocyclic ring represented by may be a single ring or a condensed ring, and includes a 5- to 6-membered heterocyclic ring having at least one kind of O, S and N atoms in the ring. These rings may have a substituent, and specific examples include the aforementioned substituents.

The timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,40.
Nos. 9,323 and 3,674,478, Research Disclosure (Research Disclosure)
re, RD) 21228 (December 1981),
JP-A-57-56837 and JP-A-4-438 are examples.

Preferred development inhibitors as PUG are described in, for example, US Pat. No. 4,477,563 and JP-A-60-218.
No. 644, No. 60-221750, No. 60-2336
Nos. 50 and 61-11743.

The following formulas (RE-I) to (RE-V)
Specific examples of compounds having one timing group among the compounds represented by I) are listed, but the present invention is not limited thereto.

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The formulas (1) to (1) used in the present invention
(4) The compounds represented by the general formulas (RE-a) to (RE-b) and the general formulas (RE-I) to (RE-VI) each have an amount of 1 × 10 ^-8 to 1 mol per mol of silver halide. It is preferably contained in an amount of 5 × 10 ⁻² mol, particularly preferably 1 × 10 ⁻⁷ to 2 × 10 ⁻² mol.

The general formulas (1) to (4) and the general formula (R
Ea) to (RE-b) and general formulas (RE-I) to (R
The compound represented by E-VI) is a suitable water-miscible organic solvent,
For example, it can be used by dissolving it in alcohols, ketones, dimethyl sulfoxide, dimethylformamide, methyl cellosolve and the like. It can also be added as an emulsified dispersion using a known oil. Further, the compound powder can be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves by a method known as a solid dispersion method.

In the present invention, these compounds represented by the general formulas (1) to (5)
(4) The compounds represented by the general formulas (RE-a) and (RE-b) and the general formulas (RE-I) to (RE-VI) are used in a silver halide emulsion layer adjacent to the emulsion layer. Can be present in another layer via an adjacent layer. Particularly preferred is an emulsion layer and / or a hydrophilic colloid layer adjacent to the emulsion layer, which may be contained in a plurality of different layers. These compounds may be added at any step during the preparation of the light-sensitive material, but preferably from 2 hours before the start of chemical sensitization of the silver halide emulsion to immediately before coating the silver halide emulsion on the support of the light-sensitive material. It is preferable to add them up to this time.

The silver halide grains used in the present invention are:
It is preferable that the particles have been subjected to reduction sensitization in advance, and in particular, those having undergone reduction sensitization inside the grains are preferable. The term "particle interior" as used herein means a portion closer to the center than 90% of the inner volume of the whole particle, and is preferably a portion closer to the center than 70% of the inner volume.

Reduction sensitization is carried out by adding a reducing agent to a silver halide emulsion or a mixed solution for grain growth, or adding this solution to a low pAg condition of pAg = 7 or less or a high pAg condition of pH = 7 or more.
The ripening of the emulsion and the grain growth are performed under the H condition.

A silver salt can be added to achieve low pAg conditions, and a water-soluble silver salt is preferred. Silver nitrate is preferred as the water-soluble silver salt. The pAg at the time of aging is suitably 7 or less, preferably 6 or less, and more preferably 1 to 3. Note that pAg = -log [Ag ⁺ ]. High pH
The reduction sensitization under the conditions is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. When ammoniacal silver nitrate is used for silver halide formation, an alkaline compound other than ammonia is preferably used.

As a method for adding a silver salt or an alkaline compound for reduction sensitization, rush addition or addition over a certain period of time may be used. If you want to spend a certain amount of time,
The addition may be performed at a constant flow rate, or may be performed by changing the flow rate like a function. Also, the required amount may be added in several portions. Prior to adding the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed in the solution of the soluble halide,
It may be added together with the halide. Further, it may be added separately from the soluble silver salt and the soluble halide.

In the preparation of a silver halide emulsion, a method of growing from seed grains is preferably used. Specifically, an aqueous solution and a seed particle containing a protective colloid are present in a reaction vessel in advance, and silver ions, halide ions or silver halide particles are supplied as necessary to grow the seed particles. Seed particles can be prepared by a single jet method, a controlled double jet method, or the like well known in the art. The halogen composition of the seed grains is optional, and may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chloroiodide, silver chlorobromide, and silver chloroiodobromide. Silver bromide and silver iodobromide are preferred. In the case of silver iodobromide, the average silver iodide content is preferably 1 to 20 mol%.

In the case of growing from seed grains, in the case of low pAg ripening, it is preferable to ripen by adding silver nitrate after the formation of the seed emulsion, that is, during the steps from immediately before desalting to after desalting of the seed grains. In particular, it is preferable to ripen by adding silver nitrate after desalting of the seed particles, and the ripening temperature is 40 ° C. or more and 50 ° C. to 8 ° C.
0 ° C. is preferred. Aging time is 30 minutes or more, preferably 5 minutes
0 to 150 minutes.

When growing from seed particles, in high pH ripening, particles may be grown at least once through an environment having a pH of 7 or more until a portion corresponding to 70% of the volume of the grown particles grows. Preferably, a pH of 7 is reached until a portion corresponding to 50% of the volume of the grown particles grows.
More preferably, the particles grow through the above environment,
Most preferably, the particles grow at least once through an environment of pH 8 or more until a portion corresponding to 40% of the volume of the grown particles grows.

An oxidizing agent is preferably used in the emulsion of the present invention comprising silver halide grains whose inside is reduction-sensitized, and specifically, H ₂ O ₂ , NaBO ₂ , H ₂ O _{2.
3H 2 O 2, Na 4 P} 2 O 7 · 2H 2 O 2, 2Na 2 SO 4 · H 2
O ₂ · 2H ₂ O or the like of hydrogen peroxide (water) and its adduct, K
₂ S ₂ O ₃ , K ₂ C ₂ O ₃ , K ₄ P ₂ O ₃ , K ₂ [Ti (O ₂ ) C ₂
O ₄ ] .3H ₂ O and the like, peroxyacetic acid, ozone, iodine, bromine, thiosulfonic acid compounds and the like. The addition may be made at any time during the production process of the silver halide emulsion. It can be added prior to the addition of the reducing agent.
Further, after the oxidizing agent is added, a reducing substance may be newly added to neutralize the excess oxidizing agent.

These reducing substances are substances capable of reducing the above-mentioned oxidizing agents, such as sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazines and hydrazides, p-phenylenediamines, aldehydes, amino acids and the like. Examples include phenols, enediols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives.

The silver halide grains contained in the silver halide emulsion are preferably those having a regular crystal form such as cubic, octahedral or tetradecahedral, or tabular grains. Twinned silver halide grains having faces are preferred. Twins are silver halide crystals having one or more twin planes in one grain, and the classification of twin morphology is based on the report by Klein and Moiser, Photographiche Korspondents (Photographiche Kor).
respondenz) 99, 99, 100,
This is described in detail on page 57.

When tabular silver halide grains are used, it is preferred that grains having a ratio of the grain size to the thickness of the tabular grains (aspect ratio) of 2 or more exist in an amount of 50% or more of the projected area of all grains. More preferably, 70% or more of particles having an aspect ratio of 3 to less than 20 are present.

The average grain size r of the silver halide grains is as follows:
0.1 to 5.0 μm is preferred, and particularly 0.2 to 4.0 μm.
m is preferable, and 0.3 to 3.0 μm is most preferable. The average particle diameter r is defined as an average volume diameter based on the product of the frequency ni of particles having the particle diameter ri and ri ³ (ni × ri ³ ).

The particle size as referred to herein is a diameter when a projected image of a silver halide grain is converted into a circular image having the same area. For example, the grain is magnified 10,000 to 70,000 times with an electron microscope. It can be obtained by photographing and actually measuring the particle diameter or projected area on the print (the number of measured particles is indiscriminately 1,000 or more).

The silver halide emulsion is preferably a monodisperse emulsion. Here, the monodispersed emulsion is defined as a range of particle size distribution (%) = (standard deviation / average particle size) × 1.
When the width of the particle size distribution is defined by 00, the width of the distribution is 20% or less. Here, the average particle diameter and the standard deviation are determined from the particle diameter ri defined above and the frequency ni of the particles having the particle diameter ri.

In the present invention, the width of this distribution is 15
% Or less is preferable.

The average silver iodide content of the whole silver halide grains is 1 mol% or more (especially 2 mol% or more, more preferably 3 mol% or more).
Or less), preferably 15 mol% or less (especially 12 mol% or less, more preferably 10 mol% or less).

The silver halide composition structure of the silver halide grains is preferably one in which the silver halide composition changes continuously or adopts a core / shell structure in order to achieve efficient sensitization.

In this case, it is preferable that a high silver iodide-containing phase having a silver iodide content of 8 mol% or more (especially 10 mol% or more, more preferably 20 mol% or more) is provided inside the grains. However, the content is good enough not to precipitate the silver iodide phase, and is preferably 45 mol% or less (particularly 40 mol% or less). Further, the outermost phase of the silver halide grains having a high silver iodide-containing phase inside the grains,
It is preferable to be formed in a low silver iodide content phase having a lower silver iodide content than a high silver iodide content phase. The silver iodide content of the low silver iodide-containing phase forming the outermost phase is preferably 10 mol% or less (particularly 6 mol% or less, more preferably 4 mol% or less).

An intermediate phase having a different silver iodide content may exist between the outermost phase and the high silver iodide content phase. The silver iodide content of the intermediate phase is preferably at least 10 mol% (particularly at least 12 mol%), and is at most 22 mol% (particularly at most 20 mol%). The silver iodide content of the outermost phase and the intermediate phase, and the silver iodide content of the intermediate phase and the high silver iodide-containing phase each preferably have a difference of 6 mol% or more, and particularly preferably each has a difference of 10 mol% or more. Good.

In the above embodiment, the center of the internal high silver iodide-containing phase, the internal high silver iodide-containing phase and the intermediate phase, or
A further silver halide phase may be present between the intermediate phase and the outermost phase.

The volume of the outermost phase is preferably 4% or more (particularly 10% or more) of the whole particles, and more preferably 70% or less (particularly 50% or less). The volume of the high silver iodide-containing phase is preferably at least 10% (particularly at least 20%) of the whole grains.
It is preferably 80% or less (particularly 50% or less). The volume of the intermediate phase is preferably 5% or more (particularly 20% or more) of the whole particles, and more preferably 60% or less (particularly 55% or less).

These phases are a single phase having a substantially uniform composition, a group of phases whose composition changes stepwise composed of a plurality of phases having a uniform composition, and a continuous phase whose composition continuously changes in an arbitrary phase. Phase or any combination thereof.

As for the silver halide particles contained in the silver halide emulsion, an aqueous solution containing a protective colloid and seed particles are previously present in a reaction vessel, and silver ions, halide ions or silver halide fine particles are supplied as necessary. It is obtained by growing seed particles in crystals. Here, the seed particles can be prepared by a single jet method or a controlled double jet method well known in the art. The halogen composition of the seed grains is arbitrary, and may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. Silver bromide and silver iodobromide are preferred.

When seed particles are used, the seed particles may have a regular crystal form such as a cube, an octahedron, or a tetrahedron, or may have an irregular crystal form such as a sphere or a plate. You may have one. In these particles, any ratio can be used for the (100) plane and the (111) plane. or,
These may have a composite form of the crystal forms, and particles of various crystal forms may be mixed, but it is preferable to use spherical seed particles having two opposed parallel twin planes.

As a means for forming a silver halide emulsion, various methods well known in the art can be used. That is, the single jet method, the double jet method, the triple jet method, and the like can be used in any combination. Further, the pH and pAg in the liquid phase in which the silver halide grains are formed are determined by determining the growth rate of the silver halide grains.
A method of controlling according to stages can also be used together. The silver halide emulsion can be produced by any of an acidic method, a neutral method, and an ammonia method.

In the production of a silver halide emulsion, halide ions and silver ions may be mixed at the same time, or one of them may be mixed in the presence of the other. Further, the growth may be carried out by sequentially or simultaneously adding halide ions and silver ions to the mixing vessel while controlling the pAg and pH while taking into consideration the critical growth rate of the silver halide crystals. In any step of silver halide formation, the silver halide composition of the grains may be changed by using a conversion method. Further, halide ions and silver ions may be supplied as fine silver halide particles into the mixing vessel. In the production of a silver halide emulsion, a known silver halide solvent such as ammonia, thioether, and thiourea can be present.

In the silver halide emulsion, unnecessary soluble salts may be removed at the end of the growth of the silver halide grains.
Alternatively, it may be kept contained. The removal of the salts can be carried out according to the method described in RD17643, section II.

In the present invention, in particular, 50% of the total number of particles is used.
% Or more preferably uses a silver halide photographic emulsion having 10 or more dislocation lines per grain.

The dislocation lines of the silver halide emulsion can be incorporated into the silver halide grains by intentionally introducing a controlled recrystallization process of the silver halide grains during the preparation of the silver halide emulsion grains. There are various methods for specific observation of dislocation lines.
New edition "Dislocation theory-its application to metallurgy-", Maruzen, 197
One year, direct observation with an electron microscope as described on pages 627 to 645 is possible. Regarding the number of dislocation lines, see James, TH, edited by The Theory
Of the Photographic Process, 3rd Edition, New York, Macramin, 1967, p. 17, "The number of dislocation lines found in an emulsion crystal is usually as small as 5 to 5
There are ten. However, in some silver halide precipitations, the number is zero. There is a description.

As for the number of dislocation lines, it is sufficient that an average of 10 or more dislocation lines per one grain of 50% or more of the total number of silver halide grains in the emulsion.
It is preferable to have at least 30 dislocation lines, and it is particularly preferable to have at least 30 dislocation lines on average per particle.

In the present invention, the number of dislocation lines is 30 or more, preferably 30 to 10,000. In an area of more than 10,000 lines, it is difficult to confirm the number of lines and the photographic characteristics are not improved.

In order to introduce dislocation lines into a silver halide crystal, it is necessary to aperiodicly disturb the periodic structure of the crystal. That is, different ions or organic compounds different from silver ions and silver ions used for silver halide growth are introduced during the crystal growth process in some way so that the lattice constant changes discontinuously at a certain position of the crystal lattice. Alternatively, if a halogen ion and a silver ion are supplied so that the halogen composition changes rapidly, dislocation lines can be introduced.
If an organic compound is added for this purpose, it is preferred that it interacts in some way with the silver halide. Specifically, sensitizing dyes and stabilizers commonly used in the art can be used for this purpose. Examples of a method of rapidly changing the composition of silver halide include a method of adding a potassium iodide solution during silver bromide grain formation, and a method of growing silver iodide or silver chloride during silver bromide grain formation. And then ripening or subsequently adding more silver bromide grain formation. Or on the contrary, Ag ⁺ in the system of the nuclear particle of small size very high iodide composition, Br ^-
Is added to cause significant recrystallization. In short, crystallization may be performed such that when the silver halide minimizes the energy of forming the crystal lattice during the growth process, the lattice constant is stabilized in a state where the lattice constant is suddenly changed in a certain region of the crystal lattice.

In the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used as a chemical sensitizer.

Examples of applicable sulfur sensitizers include 1,3-
Examples thereof include thiourea derivatives such as diphenylthiourea, triethylthiourea, and 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithicarbamic acids, polysulfide organic compounds, sodium thiosulfate, and sulfur alone. In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable. In addition, as a sulfur sensitizer,
U.S. Pat. Nos. 1,574,944 and 2,410,689
No. 2,278,947 and No. 2,728,668
Nos. 3,501,313, 3,656,955
And sulfur sensitizers described in West German Application (OLS) 1,422,869, JP-A-56-24937, and JP-A-55-45016.

The selenium sensitizers that can be used include a wide variety of selenium compounds. For example, US Pat. No. 1,574,944
No. 1,602,592, 1,623,499
JP-A-60-150046, JP-A-4-2583
2, No. 4-109240, and No. 4-147250. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (allyl isoselenocyanate), selenoureas (N, N-dimethylselenourea, N, N, N'-triethylselenourea)
N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4- Nitrophenylcarbonylselenourea, etc.), selenoketones (selenoacetone, selenoacetophenone, etc.), selenoamides (selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (2-selenopropionic acid, methyl- 3-selenobutyrate), selenophosphates (tri-p-triselenophosphate),
Selenides (dimethyl selenide, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides and selenides.

Specific examples of techniques for using these selenium sensitizers are described in US Pat. Nos. 3,420,670 and 3,591,3.
No. 85, JP-A-4-190225, JP-A-4-19172
No. 9, No. 4-195035 and the like.

It should be noted that H. E. FIG. By Spencer et al.
Photo. Sci. 31, pp. 158-169 (198
It is also disclosed in research papers such as 3).

Regarding tellurium sensitizers and sensitization methods that can be used, see US Pat. Nos. 1,623,499 and 3,320,
Nos. 069, 3,772,031, 3,531,
Nos. 89 and 3,655,394; British Patent 235,2
No. 11, No. 1, 121, 469, No. 1, 295, 46
No. 2, No. 1,396,696, Canadian Patent 800,9
No. 58, JP-A-4-20464 and the like.
Specific examples of useful tellurium sensitizers include telluroureas, telluroamides, and the like.

The addition amounts of the sulfur sensitizer, the selenium sensitizer and the tellurium sensitizer are not uniform depending on the type of the silver halide emulsion, the type of the compound to be used and the ripening conditions. It is preferably from 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol per mol. More preferably, 1 × 10 ^-5 to 1
× 10 ^-8 mol.

In chemical sensitization, sensitivity can be further increased by using gold sensitization in combination. Useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and the like.
U.S. Pat. Nos. 2,597,856 and 5,049,484
No. 5,049,485, JP-B-44-15748
And gold complexes of organic compounds disclosed in JP-A Nos. 1-147537 and 4-70650.

The above-mentioned various sensitizers can be added by dissolving them in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, depending on the properties of the compound to be used. The method of mixing and adding in advance, or the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer may be used.

When the chemical sensitization is performed in the presence of a sensitizing dye or a nitrogen-containing heterocyclic compound, the effects of the present invention are further exhibited.
The heterocyclic compound is disclosed in JP-A-58-126526.
Sensitizing dyes disclosed in JP-A-59-193448 and the like;
Nitrogen-containing heterocyclic compounds can be used.

The silver halide emulsion can be optically sensitized to a desired wavelength region using a dye known in the art as a sensitizing dye. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light, and which contains a supersensitizer which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. You may.

Examples of the sensitizing dye include polymethine dyes containing cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl, and hemioxonol dyes, oxonol, merostyryl, and streptocyanin.

Examples of antifoggants and stabilizers include tetrazaindenes and azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, Mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; and mercaptopyrimidines, mercaptotriazines, for example, thioketo such as oxazolythion Compounds, furthermore, benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonamide, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid It can be mentioned conductor like.

In the present invention, good results are often obtained when sensitization is performed in the presence of a silver halide solvent. As the silver halide solvent used, US Pat.
Nos. 1,157, 3,531,2891, 3,57
4,628, JP-A-54-1019, JP-A-54-15
(A) Organic thioethyls described in 8917 and the like;
(B) thiourea derivatives described in JP-A-53-82408, JP-A-55-77737, and JP-A-55-2982; and (c) oxygen or sulfur atoms described in JP-A-53-144319. A silver halide solvent having a thiocarbonyl group sandwiched between nitrogen atoms;
(D) imidazoles described in No. 7; (e) sulfite; (f) thiocyanate and the like.

Known photographic additives that can be used in the color light-sensitive material of the present invention include RD17643, page 25, VIII-A to page 27, XIII, RD18716, 650 to 651,
RD308119, page 1003, paragraphs VIII-A to 1012
In Section XXI-E, and specific examples of various couplers, RD17
Pp. 643, 25, VII-C to G, RD308119, 1
Page 001, paragraphs VII-CG.

In the present invention, the aforementioned RD17643,
Page 28, section XVII, RD 18716, pages 647-8, and RD
The support described in section 308119, page 1009, XVII can be used.

The RD308119, 1
An auxiliary layer such as a filter layer or an intermediate layer described in section VII-K on page 002 can be provided.

The light-sensitive material is RD308119, VII
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section -K can be adopted.

[0164]

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 Emulsion Em-1 >> Referring to the description of JP-A-5-34851, a seed emulsion (T-1) having two parallel twin planes was obtained by the following method. 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 g Water 8000 cc solution B Silver nitrate 1200 g Water 1600 cc solution C ossein gelatin 32.2 g Potassium bromide 790 g Potassium iodide 70.34 g Water 1600 cc solution D ammonia water 470 cc Using a stirrer described in JP-A-62-160128, 4
The solution B and the solution C were added to the solution A vigorously stirred at 0 ° C. for 7.7 minutes by a double jet method to generate nuclei. During this time, pBr was kept at 1.60.

Then, the temperature was lowered to 20 ° C. over 35 minutes. Further, the solution D was added for 1 minute, followed by aging for 5 minutes. Potassium bromide concentration during aging is 0.0
3 mol / l and the ammonia concentration was 0.66 mol / l.

After the completion of ripening, the pH was adjusted to 6.0, and desalting was carried out according to a conventional method. When the seed emulsion particles were observed with an electron microscope, the average grain size was 0.225 μm, and the ratio of two twin planes was 75% by number of all the grains.

Next, two solutions were prepared using the following seven types of solutions.
Monodispersed comparative emulsion Em having a plate shape having two parallel twin planes
-1 was prepared.

[0170] The solution A ₁ ossein gelatin 69.0g Distilled water _{3268cc 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 2.50 cc Seed emulsion (T-1) 71.8 g Finished to 3500 cc with distilled water.

Solution B ₁ 959.0 cc of 0.5N aqueous silver nitrate solution C ₁ 52.88 g of potassium bromide 35.55 g of ossein gelatin Finished to 959 cc with distilled water.

[0172] The solution D ₁ 3.5 N aqueous silver nitrate solution 4475.0cc solution E ₁ and Solution F ₁ 3% by weight of gelatin finish 4475cc potassium bromide 1863.8g ossein gelatin 179.0g distilled water, silver iodide grains ( Fine particle emulsion having an average particle size of 0.05 μm (preparation method is shown below *) 2492.0 g * 6.06% by weight of a 6.0 wt% gelatin solution containing 0.06 mol of potassium iodide Of silver nitrate and 2000 cc of an aqueous solution containing 7.06 mol of potassium iodide were added over 10 minutes. The temperature during the formation of the fine particles was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate. The finished weight was 12.53 kg.

Solution G ₁ 1.75N Aqueous potassium bromide solution Required amount Solution A ₁ is added to the reaction vessel, and while vigorously stirring, solutions B ₁ to F ₁ are added by the double-mixing method according to the combination shown in Table 1. And a seed crystal was grown to prepare a core / shell type silver halide emulsion. However, the solution B ₁ ,
At 114.95 minutes after the start of the addition of C ₁ and F ₁ , the pH was adjusted to 7.2 using 10% potassium hydroxide. As a result, reduction sensitization was performed inside the grains.

Here, (1) solution B ₁ , solution C ₁ and solution F ₁ addition rates, (2) solution D ₁ , solution E ₁ and solution F ₁ addition rates, and (3) solution D ₁ and solution F ₁ The addition rate of E ₁ is varied in a function with respect to time so as to correspond to the critical growth rate of silver halide grains. In addition to the growing seed crystal, generation of small grains and polydispersion by Ostwald ripening are performed. Was controlled to an appropriate addition rate so as not to cause the addition.

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 p for control of pAg
₁ was added.

Table 1 also shows the amount of silver added 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.

After the grain growth, a desalting treatment was performed according to the method described in Japanese Patent Application No. 4-59351, followed by redispersion by adding an aqueous gelatin solution, and at 40 ° C., a pH of 5.80 and pAg.
Was adjusted to 8.06.

The silver halide grains contained in the obtained silver halide emulsion had an average particle size of 1.42 μm (diameter in terms of projected area circle) and 85% of particles having an average aspect ratio of 3.0 or more.
Tabular silver halide grains having a particle size distribution of 14.0% were obtained.

[0179]

[Table 1]

<< Preparation of Emulsion Em-2 >> A monodisperse spherical seed emulsion (T-2) was prepared by the following method.

Solution A ₂ Ossein gelatin 80 g Potassium bromide 47.4 g 10% methanol solution of polyisopropylene-polyethyleneoxy-disuccinate sodium salt 20 cc Make up to 8000 cc with water.

[0182] and 1600cc with a solution B ₂ silver nitrate 1200g water.

Solution C ₂ Ossein gelatin 32.2 g Potassium bromide 840 g Make up to 1600 cc with water.

Solution D ₂ 470 cc of aqueous ammonia The solution B ₂ and the solution C ₂ were added to the solution A ₂ vigorously stirred at 40 ° C.
Was added by a double jet method for 11 minutes to generate nuclei. During this time, pBr was kept at 1.60. Thereafter, the temperature was lowered to 30 ° C. over 12 minutes, and ripening was further performed for 18 minutes. Moreover, a solution D ₂ at 1 minute and subsequently ripened for 5 minutes. The potassium bromide concentration during aging is 0.07 mol / l, and the ammonia concentration is 0.63
Mol / l.

After the completion of the ripening, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method to obtain a spherical seed emulsion (T-2). When this seed emulsion was observed with an electron microscope, it was a spherical emulsion having two twin planes parallel to each other and an average grain size of 0.318 μm.

Next, Emulsion Em-2 was prepared using the following seven kinds of solutions.

[0187] The solution A ₃ ossein gelatin 268.2g distilled water 4000cc polyisopropylene - polyethyleneoxy - 10% methanol solution 1.5cc Seed emulsion of disuccinic acid sodium salt (T-2) 0.286 mol of 28% by weight Aqueous ammonia solution 528.0 cc 56 wt% aqueous acetic acid solution 795.0 cc Methanol solution containing 0.001 mol of iodine 50.0 cc Make up to 5930.0 cc with distilled water.

Solution B ₃ 3.5N aqueous ammoniacal silver nitrate aqueous solution (pH adjusted to 9.0 with ammonium nitrate) Solution C ₃ 3.5N aqueous potassium bromide solution containing 4.0% by weight of gelatin D ₃ % by weight % Of gelatin and silver iodide grains (average grain size: 0.05 μm) Emulsion (Preparation method is shown below *) 0.844 mol * 6.0% by weight containing 0.06 mol of potassium iodide 2000 cc of a solution containing 7.06 mol of silver nitrate and 2000 cc of a water solution containing 7.06 mol of potassium iodide were added to 5000 cc of the gelatin solution 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 40 ° C. After particle size formation, the pH was adjusted to 6.0 using aqueous sodium carbonate solution.

Solution E ₃ Fine grain emulsion composed of silver iodobromide grains (average grain size 0.04 μm) containing 1 mol% of silver iodide, prepared in the same manner as the above silver iodide fine grain emulsion 2.20 Mol (however, the temperature during the formation of fine particles was controlled at 3.0 ° C.) Solution F ₃ 1.75 N aqueous potassium bromide solution G ₃ 56% by weight acetic acid aqueous solution To solution A ₃ kept at 70 ° C. in a reaction vessel, After the solution B ₃ , the solution C ₃ and the solution D ₃ were added by the simultaneous mixing method over a period of 163 minutes, the solution E ₃ was added independently at a constant speed for 12 minutes, and the seed crystal was added at a rate of 1.0 μm. Grown up.

Here, the addition rates of the solution B ₃ and the solution C ₃ were changed as a function of time in accordance with the critical growth rate to generate small particles other than the growing seed crystal and Ostwald ripening. At an appropriate rate so as not to cause polydispersion. The solution D _{3, that} is, the silver iodide fine grain emulsion was supplied by changing the rate ratio (molar ratio) with the aqueous solution of ammoniacal silver nitrate with respect to the particle size as shown in Table 2.
A core / shell type silver halide emulsion having a multiple structure was prepared.

By using the solution F ₃ and the solution G ₃ , pAg and pH during crystal growth were controlled as shown in Table 2. However, at 82.6 minutes after the addition, the pH was adjusted to 8.4 using a 10% aqueous sodium hydroxide solution, whereby reduction sensitization was performed inside the grains. Note that pAg,
The pH was measured using a silver sulfide electrode and a glass electrode according to a conventional method. After the formation of the particles, a desalting treatment was performed according to the method described in JP-A-5-34851, and then gelatin was added and redispersed, and the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained emulsion particles were observed by an electron microscope, the twin ratio was 1.2% to 1.6, which consisted of 100% twin particles and had two or more parallel twin planes.
It consisted of slightly distorted octahedral twin monodisperse particles having a distribution of 5%, a distribution width of 10% and an average particle size of 1.0 μm.

[0193]

[Table 2]

<< Preparation of Emulsion Em-3 >> In the preparation of Emulsion Em-1, reduction was carried out in the same manner except that potassium hydroxide added 114.95 minutes after the addition of solutions B ₁ , C ₁ and F ₁ was not added. Emulsion Em-3 without sensitization was prepared.

<< Preparation of Emulsion A >>
After dissolving by heating at 5 ° C. and adjusting the pH to 5.80, 8 mol of sensitizing dye (sd-1) per mol of silver halide was used.
g, (sd-2) 55.5 mg, (sd-3) 60.0
mg was added. Twenty minutes after the addition of the sensitizing dye, sodium thiosulfate pentahydrate 5 × 10 ⁻⁶ per mole of silver halide
Mol, then 1.42 × 10 ^-6 mol of chloroauric acid,
3.15 × 10 ⁻⁴ mol of ammonium thiocyanate was added and the mixture was aged for an appropriate time.

At the end of aging, a stabilizer (ST-1) was added.
Emulsion A was obtained by cooling and solidifying.

ST-1: 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene

[0198]

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<< Preparation of Emulsions B to P >> The amount of various additives (sodium thiosulfate, sensitizing dye, chloroauric acid) added to Emulsion A was 0.75 to 1.15 of the amount used when Emulsion A was prepared. An optimum amount is applied to each emulsion in a range of 5 times, and the ripening time is also set to the optimum time (the best result is obtained in the evaluation of fog sensitivity), and the emulsions Em-2 and Em-3 are used. Emulsions B and C were prepared. Emulsions A, B and C were prepared in the same manner as in Emulsions A and B except that the compound of the present invention and Comparative Compound (R) were added 4 × 10 ⁻⁶ mol per mol of silver halide 10 minutes before the addition of the sensitizing dye. D to P were prepared.

Compound R: 1-phenyl-5-mercaptotetrazole

[0201]

[Table 3]

(Preparation of Single Emulsion Layer Coated Samples 101 to 116) Emulsions A to P obtained as described above were sequentially coated on a triacetyl cellulose film support which had been subjected to a subbing process according to the following coating formulation. It dried and the application samples 101-116 were produced.

Coating formulation First layer: Green-sensitive silver halide emulsion layer Emulsion (described in Table 2) 2.5 g / m ² magenta coupler (m-1) 0.01 mol / mol Ag Colored magenta coupler (cm-1) 0.005 mol / mol Ag DIR compound (d-1) 0.0002 mol / mol Ag High boiling solvent (TCP) 0.02 g / m ² Second layer: yellow filter layer Yellow colloidal silver 0.08 g / m ² hard Membrane agent (HI) 10 mg / g gelatin TCP: tricresyl phosphate H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium

[0204]

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<Sensitometry Evaluation> The coated samples 101 to 116 obtained as described above were evaluated for 1 /
After a step wedge exposure of 3.2 seconds for 3.2 seconds, processing is performed in the following processing steps to obtain a characteristic curve, and the relative sensitivity (the reciprocal of the exposure amount that gives a density of fog density + 0.10,
(Represented by a relative value with the sample 101 being 100).

Processing step (38 ° C.) Color development (2 minutes 50 seconds) → Bleaching (6 minutes 30 seconds) → Washing (3 minutes 15 seconds) → Fixing (6 minutes 30 seconds) → Washing (3 minutes 15 seconds)
Sec) → stabilization (1 minute 30 seconds) → drying The composition of the processing solution used in each processing step is as follows.

Color developing solution 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxyamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.0.

Bleaching solution Iron ammonium salt of ethylenediaminetetraacetic acid 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and the pH was adjusted to 6 using aqueous ammonia. Adjust to .0.

Fixing solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to 1 liter, and the pH was adjusted to 6.0 using acetic acid.

Stabilizing solution Formalin (37% aqueous solution) 1.5 cc. KONIDAX (manufactured by Konica Corporation) 7.5 cc. Add water to make 1 liter.

<Evaluation of Stability of Latent Image> Samples 101 to 116
After preparing two sets and performing wedge exposure using green light,
One set was stored under temperature and humidity conditions of 40 ° C. and 55% RH for 4 days, and the other set was stored at −20 ° C. as a control, and the same development processing as in sensitometry was performed to obtain a characteristic curve. . The latent image stability was determined from the characteristic curve of each sample as the reciprocal of the exposure amount giving a density of fog density + 0.10 as the sensitivity, and evaluated as a relative value with the sensitivity of each control sample being 100. The larger the value, the better the latent image stability.

<Evaluation of fog stability>
After one week of forced deterioration at 20% RH, exposure and development were performed in the same manner as in the sensitometric evaluation, and the difference in fog between the sample and the sample not subjected to the forced deterioration was determined. Indicated by value. The smaller the value, the better the fog stability.

Table 4 shows the obtained results.

[0214]

[Table 4]

As is clear from the table, the sample of the present invention shows high fog stability and is excellent in sensitivity and latent image stability.

The mechanism showing such an effect has not been sufficiently elucidated yet, but it is expected that the compound of the present invention will be cleaved when it enters a developer. It is thought that this cleavage oxidizes silver nuclei formed by reduction sensitization and introduction of dislocation lines, and further significantly reduces fog due to generated inhibitors. Therefore, the number of silver nuclei during storage of the latent image can be increased as compared with a method in which silver nuclei are bleached by adding iodine or the like during grain formation, and the latent image stability is good.
Fogging after development can be reduced by the dual effects of oxidation of the inhibitor and the inhibitor, and it is presumed that the effects of the present invention are obtained, but the present invention is not limited to this.

Example 2 A study was conducted to introduce dislocation lines into silver halide grains.

<< Preparation of Seed Crystal Emulsion α >>
618, U.S. Pat. No. 4,797,354, and West German Patent 3,707,135-A1, the following silver iodobromide tabular silver halide seed emulsion α having a double structure was prepared. .

Core: 13% of the total seed silver, shell: 87% of the total seed silver, thiourea dioxide in the presence of 5 × 10 ^-6 mol / mol Ag of silver in the entire seed crystal to form a shell. After that, the compound A was added in an amount of 2 × 10 ⁻⁴ mol / mol Ag with respect to the silver of the entire seed crystal, followed by aging for 5 minutes.

Compound A: sodium ethanethiosulfonate << Preparation of emulsion EM-1 >> Seed emulsion α maintained at 60 ° C. (containing 170 g of silver in terms of AgNO _{3 and} 40 g of gelatin)
While stirring, the solution 1-1a and the solution 1-1b were added simultaneously over 5 minutes.

Liquid 1-1a silver nitrate 8 g water 200 cc water 1-1b liquid potassium iodide 6 g water 200 cc Next, while keeping the pAg at 9.0, the 1-2a liquid and 1-2b
The liquid was added simultaneously over 30 minutes.

1-2a liquid silver nitrate 70 g water 300 cc 1-2b liquid potassium bromide 49 g water 300 cc Thereafter, desalting was carried out according to a conventional method, gelatin was added, and gold / gold was optimally added using chloroauric acid and sodium thiosulfate. Sulfur sensitized. This silver halide emulsion is designated as emulsion EM-1.

<< Preparation of EM-2 >> In the formation of particles of EM-1, 1-1b solution was converted to 2-1b solution, and 1-2b solution was converted to 2-b solution.
Particle formation was performed in the same manner as in EM-1 except that the solution was changed to the 2b solution.

[0224] 2-1b liquid Likewise after grain formation and potassium bromide 5g Potassium iodide 0.6g Water 200 cc 2-2b solution Potassium 4.4g Potassium iodide bromide 5.4g Water 300 cc EM-1, desalting and Chemical sensitization was performed. This silver halide emulsion is designated as EM-2. EM-1
Table 5 shows an overview of EM-2.

[0225]

[Table 5]

(Preparation of Emulsion EM-3) Further, Emulsion EM-1
, A 10% aqueous sodium hydroxide solution was added to adjust the pH to 8.4 during the addition of the 1-2a solution and the 1-2b solution. Thereby, except that reduction sensitization was performed inside the grains, E
Emulsion EM-3 was prepared in the same manner as M-1. In addition, chemical sensitization was performed in the same manner as in EM-1.

Further, with respect to emulsions EM-1 to EM-3,
An emulsion was prepared in which the compound of the present invention was added 4 × 10 ⁻⁶ mol / mol Ag 10 minutes before the addition of the sensitizing dye, and an emulsion in which selenium sensitization was combined with this emulsion was prepared.

Using these emulsions, single emulsion coated samples 201 to 212 were prepared in the same manner as in Example 1.
The same evaluation was performed. Table 6 shows the results.

[0229]

[Table 6]

As is clear from the table, when the compound of the present invention is added, an emulsion having good fog stability and latent image stability and high sensitivity can be obtained. Further, it can be seen that the combination with selenium sensitization and reduction sensitization is preferable.

Example 3 A tabular emulsion having an aspect ratio of 4 and having been subjected to reduction sensitization was prepared without using silver iodide or potassium iodide during grain preparation. Samples 301 to 303 were prepared by subjecting this emulsion to chemical ripening by combining the compounds of the present invention in the same manner as in Example 1.

Samples 301 to 303 and Sample 10 of Example 1
The same evaluation as in Example 1 was performed together with 2, 105 and 108. Table 7 shows the results. Note that the sample 102 was used as a reference.

[0233]

[Table 7]

Looking at the changes from Samples 301 and 302 to 303, it was found that the fog stability and the
It can be seen that the latent image stability was improved and the sensitivity was maintained.
Also, it can be seen that a sample with a higher iodine content has a greater effect.

Example 4 On an undercoated cellulose triacetate film support,
A multilayer color light-sensitive material sample including the following layers was prepared, and was referred to as Sample 401. The amount of the additive used is the amount expressed in g / m ² in terms of silver per m ² of the light-sensitive material for silver halide and colloidal silver, and the amount of the halide in the same layer for sensitizing dye. It indicates the number of moles per mole of silver, and the amount of other additives such as couplers is expressed in g / m ² per m ² of the light-sensitive material.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound ( SC-1) 0.14 High-boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion IA 0.15 Silver iodobromide emulsion IB 0.35 increase Sensitizing dye (SD-1) 2.0 × 10 ^-4 sensitizing dye (SD-2) 1.4 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 ^-5 sensitizing dye (SD- 4) 0.7 × 10 ^-4 cyan coupler (C-1) 0.53 colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.025 high boiling point solvent (OIL-3) 48 Gelatin 1.09 Fourth layer: Medium-speed red-sensitive layer Silver iodobromide emulsion IB 0.30 Silver iodobromide Agents IC 0.34 Sensitizing dye (SD-1) 1.7 × 10 -4 Sensitizing dye (SD-2) 0.86 × 10 -4 Sensitizing dye (SD-3) 1.15 × 10 -5 Sensitizing dye (SD-4) 0.86 × 10 ⁻⁴ Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling solvent ( OIL-1) 0.16 gelatin 0.79 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion ID 0.95 sensitizing dye (SD-1) 1.0 × 10 ^-4 sensitizing dye (SD- 2) 1.0 × 10 ^-4 sensitizing dye (SD-3) 1.2 × 10 ^-5 cyan coupler (C-2) 0.14 colored cyan coupler (CC-1) 0.016 high boiling point solvent (OIL -1) 0.16 gelatin 0.79 6th layer: intermediate layer Compound (SC-1) 0.09 high boiling point solvent (OIL- ) 0.11 Gelatin 0.80 Seventh layer: low sensitivity green-sensitive layer Silver iodobromide emulsion IA 0.12 iodobromide emulsion IB 0.38 Sensitizing dye (SD-4) 4.6 × 10 -5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling solvent ( OIL-4) 0.34 gelatin 0.70 8th layer: intermediate layer gelatin 0.41 ninth layer: medium-speed green-sensitive layer silver iodobromide emulsion IB 0.30 silver iodobromide emulsion IC 0.34 sensitization Dye (SD-6) 1.2 × 10 ^-4 sensitizing dye (SD-7) 1.2 × 10 ^-4 sensitizing dye (SD-8) 1.2 × 10 ^-4 magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DI R compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: Highly sensitive green-sensitive layer Emulsion ID 0.95 Magenta Coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 Compound of the present invention (Exemplary I-4) 0.002 High boiling solvent (OIL-4) 0.11 Gelatin 0.79 Compound I-4 is in the same dispersion as M-1 and CM-1 and is in the same oil droplet.

Eleventh layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling solvent (OIL-2) 0.19 Gelatin 1.10 12th layer: Low-sensitivity blue-sensitive layer Silver bromide emulsion IA 0.12 Silver iodobromide emulsion IB 0.24 Silver iodobromide emulsion IC 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1 .0 × 10 ^-5 yellow coupler (Y-1) 0.50 yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 high boiling solvent ( OIL-2) 0.42 gelatin 1.40 13th layer: high-sensitivity blue-sensitive layer silver iodobromide emulsion IC 0.15 silver iodobromide emulsion IE 0.80 sensitizing dye (SD-9) 8.0 × ^10-5 sensitizing dye (SD-11) 3.1 x ^10-5 yellow coupler (Y- 1) 0.12 High boiling solvent (OIL-2) 0.05 Gelatin 0.79 Fourteenth layer: First protective layer Silver iodobromide emulsion IF 0.40 Ultraviolet absorber (UV-1) 0.065 High boiling point Solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl methacrylate (average) Particle size 3 μm) 0.04 Slip agent (WAX-1) 0.04 Surfactant (Su-3) Surfactant (Su-4) Gelatin 0.55 In addition to the above composition, a coating aid Su is added. -1, dispersion aid Su-2, viscosity modifier, hardener H-1, H-2, stabilizer ST-1, antifoggant AF-1, average molecular weight = 10,
000 and two kinds of A having an average molecular weight of 1,100,000
F-2 and preservative DI-1 were added.

In the emulsions used in the above samples, IA to IE had internal reduction sensitization, a high iodine type core / shell structure, and IF had a uniform structure. In addition, the average particle diameter was shown by the particle diameter converted into a cube. Each emulsion was optimally subjected to selenium and gold / sulfur sensitization in the same manner as in Emulsion H of Example 1.

[0239]

[Table 8]

Su-1: dioctyl sulfosuccinate sodium salt Su-2: sodium tri-i-propylnaphthalene sulfonate H-2: bis (vinylsulfonylmethyl) ether AF-1: 1-phenyl-5-mercaptotetrazole (Same as the comparative compound R) AF-2: poly-N-vinylpyrrolidone OIL-1: dioctyl phthalate OIL-2: tricresyl phosphate OIL-3: dibutyl phthalate SC-1: 2-methyl-5-sec-octadecyl Hydroquinone

[0241]

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[0242]

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[0243]

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[0244]

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[0245]

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[0246]

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[0247]

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[0248]

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With respect to the sample 401, emulsions IB, IC,
Emulsions IIB and II chemically sensitized with Compound I-16 of the present invention with reference to the emulsion of Example 1 for ID and IE
Sample 402 was prepared in the same manner except that C, IID, and IIE were used.

Similarly, sample 403 using emulsions IIIB, IIIC, IIID and IIIE chemically sensitized using comparative compound R
Was also prepared. This multilayer photosensitive material sample was subjected to step wedge exposure using white light, and sensitometry was evaluated through the same development processing steps as in Example 1. Latent image stability and fog stability were evaluated in the same manner as in Example 1. Table 9 shows the results.

[0251]

[Table 9]

As is clear from the table, the effect of the present invention is remarkable also in a multilayer color photosensitive material.

[0253]

According to the present invention, a silver halide color photographic material having high sensitivity, excellent latent image stability and improved fog stability can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/43 G03C 1/43 7/00 510 7/00 510 7/305 7/305 7/392 7/392 A

Claims (8)

[Claims] 1. The method according to claim 1, wherein the following general formulas (1), (2), (3-
(a), (3-b), (4) or containing at least one of compounds capable of releasing a development inhibitor by being oxidized, and the inside of silver halide grains being reduction sensitized. A silver halide photographic emulsion comprising: Formula _{(1) R 11 - (S} ) n -R 12 wherein, R ₁₁ and R ₁₂ each represent an aliphatic group, an aromatic group or a heterocyclic group. R ₁₁ and R ₁₂ may be the same or different, and when R ₁₁ and R ₁₂ are an aliphatic group, they may combine with each other to form a ring. n represents an integer of 2 or more. General formula (2): R ₂₁ -IR ₂₂ [wherein, R ₂₁ and R ₂₂ each represent an aromatic group or an aromatic heterocyclic group. R ₂₁ and R ₂₂ may be the same or different. [Formula 1] [Wherein, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each represent a hydrogen atom,
Halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, cyano group, acylamino group, alkylthio group, arylthio group, sulfonylamino group, ureido group, sulfamoylamino group, carbamoyl group, sulfamoyl group , An alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group,
Represents an amino group, a hydroxyl group, a nitro group, an imide group or a heterocyclic group. Y ₁ represents a group of atoms capable of forming an aromatic carbocycle or an aromatic heterocycle. Z ₁ represents an oxygen atom or a sulfur atom, B ₁ is used alone or Z ₁ -B ₁
Represents a group capable of adsorbing silver halide. [Chemical formula 2] [Wherein, R ₄₁ has the same meaning as R _{31 in} formula (3-a);
₂ same meaning as R ₃₁ in the general formula (3-a), B ₂ has the same meaning as B ₁ in the general formula (3-a). [Chemical formula 3] [Wherein, R ₅₁ , R ₅₂ and R ₅₃ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. X ₅ represents an ion for neutralizing the charge, and n ₅ represents the number of ions required for neutralizing the charge. ] 2. The general formulas (1), (2) and (3-
(a), (3-b), (4) or at least one of compounds capable of releasing a development inhibitor by being oxidized, and at least 50% of the projected area of the silver halide grains is 10 or more. A silver halide photographic emulsion having at least two dislocation lines. 3. The silver halide photographic emulsion according to claim 1, wherein 50% or more of the projected area of the silver halide grains has 10 or more dislocation lines. 4. The silver halide photographic emulsion according to claim 1, wherein the average silver iodide content is 1 mol% or more. 5. The silver halide photographic emulsion according to claim 1, wherein 50% or more of the silver halide grains are tabular grains having an aspect ratio of 2 or more. 6. The silver halide photographic emulsion according to claim 1, wherein at least one of selenium sensitization and tellurium sensitization is performed. 7. An average silver iodide content of 1 mol% or more, 50% or more of silver halide grains are tabular grains having an aspect ratio of 2 or more, and at least one of selenium sensitization and tellurium sensitization. 4. The method according to claim 3, wherein
A silver halide photographic emulsion as described above. 8. The method according to claim 1, wherein at least one of the photosensitive silver halide emulsion layers provided on the support comprises
13. A silver halide photographic light-sensitive material, comprising the silver halide photographic emulsion described in item 8.