JPH04355748A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material superior in pressure resistance and high in image quality and sensitivity by incorporating a specified spectral sensitizer in at least one emulsion layer. CONSTITUTION:The silver halide photographic sensitive material having at least one photosensitive silver halide emulsion layer on a support contains in at least one emulsion layer the spectral sensitizer represented by formula I in which each of R<1> and R<2> is alkyl and at least one carbon atom of it combines 3 atoms other than H; each of Z<1> and Z<2> is an atomic group necessary to form a 5- or 6-membered N-containing hetero ring; X is an anion; p is 0 or 1 necessary for balancing electric charge; each of L1 and L2 is optionally substituted methine: and l is 0, 1, or 2. Thus permitting the obtained photosensitive material to be superior in pressure resistance and high in image quality and sensitivity and stable in performances also with the lapse of time.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to silver halide photographic materials. In particular, the present invention relates to a silver halide photographic material containing particles subjected to reduction sensitization and having excellent pressure resistance.

0002

2. Description of the Related Art Various pressures are generally applied to photographic materials coated with silver halide emulsions. For example, general photographic negative film may be folded or folded when rolled into a cartridge or loaded into a camera.
Sometimes it's pulled to advance frame by frame.

On the other hand, sheet films such as printing sensitive materials and direct medical X-ray sensitive materials are often bent or bent because they are handled directly by humans.

[0004] Furthermore, all photosensitive materials are subjected to great pressure during cutting and processing.

As described above, when various pressures are applied to a photographic material, pressure is applied to the silver halide grains using gelatin, which is a holder (binder) for the silver halide grains, and a plastic film, which is a support, as a medium. It is known that when pressure is applied to silver halide grains, the photographic properties of the photographic material change. B. Mother,
J. Opt. Soc. Am. , 38.1054 (194
8). P. Faelens and P. de
Smet. Sci. et Ind Photo. ,2
5. No. 5.178 (1954). P. Faelen
s. J. Photo. Sci. 2.105 (1954), etc., in detail.

[0006] In recent years, demands on silver halide emulsions for photography have become increasingly strict, and photographic properties such as sensitivity, graininess,
In addition to image quality such as sharpness, even higher standards are being required for so-called toughness such as storage stability and pressure resistance. However, it is obvious that pressure fog increases as sensitivity increases, and an emulsion with high sensitivity and low pressure fog is desired.

[0007] In order to increase sensitivity, reduction sensitization has been studied for a long time. Carroll, in U.S. Pat. No. 2,487,850, said that a tin compound is
Owe et al. in British Patent No. 2,512,925 disclose that polyamine compounds are useful as reduction sensitizers, and Fallens et al. in British Patent No. 789,823 disclose that thiourea dioxide-based compounds are useful as reduction sensitizers. disclosed. Furthermore, Collier (Collier) is Phot
graphic Science and Engineering
eering, Vol. 23, p. 113 (1979), compares the properties of silver nuclei produced by various reduction sensitization methods. She employed dimethylamine borane, stannous chloride, hydrazine, high pH ripening, and low pAg ripening methods. The method of reduction sensitization is further described in U.S. Patent Nos. 2 and 5.
No. 18,698, No. 3,201,254, No. 3,
No. 411,917, No. 3,779,777, No. 3
, 930,867. In addition to the selection of reduction sensitizers, the publication of the Special Publication in 1984
-33572 and 58-1410.

However, the inventors' research has revealed that by adsorbing a sensitizing dye onto reduction-sensitized silver halide grains, the fog that occurs when pressure is applied to a photosensitive material increases. It has become.

In addition, in order to prevent the sensitizing dye from being desorbed from the silver halide grains in the light-sensitive material (especially at high humidity),
Sensitizing dyes may be adsorbed at high temperatures (50° C. or higher), but this operation also worsens pressure fog. Furthermore, as a method for increasing sensitivity, there is a method of adsorbing a sensitizing dye before chemical sensitization, but this method also worsens pressure fog.

0010

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having excellent pressure resistance, high image quality, and high sensitivity.

[0011]

[Means for Solving the Problems] As a result of intensive research, the problems of the present invention were achieved by the following means. That is, (1) a photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers containing a spectral sensitizer represented by the following general formula (I), A silver halide photographic light-sensitive material, characterized in that silver halide grains in the emulsion layer have been subjected to reduction sensitization.

0012

embedded image In the formula, R1 and R2 represent an alkyl group, and at least one of the alkyl groups has at least 1
carbon atoms bond with at least three atoms that are not hydrogen atoms, Z1 and Z2 represent the atomic group necessary to form a 5- to 6-membered nitrogen-containing heterocycle, X represents an anion, and p represents the charge L1 and L2 represent a methine group or a substituted methine group, and L represents 0, 1 or 2.

(2) In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers contains a spectral sensitizer represented by the general formula (I), The silver halide grains in the emulsion layer have been subjected to reduction sensitization and have the following general formulas (II) and (III).
) or (IV).

General formula (II) R-SO2 SM General formula (III) R-SO2 S-R3 General formula (IV) R-SO2 S-Lm -SSO
2 -R4 In the formula, R, R3, and R4 may be the same or different,
represents an aliphatic group, an aromatic group, or a heterocyclic group, M represents a cation, L represents a divalent linking group, m is 0
or 1.

The compounds of general formulas (II) to (IV) may be polymers containing divalent groups derived from the structures shown in (II) to (IV) as repeating units.

(3) In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers contains a spectral sensitizer represented by the general formula (I), The silver halide grains in the emulsion layer have been subjected to reduction sensitization and have the following general formulas (II) and (III).
) or (IV), and has an aspect ratio of 3 or more, in which at least 60% of the total projected area of the silver halide grains has 10 or more dislocation lines in one grain. A silver halide photographic material comprising tabular silver halide grains.

The compound of general formula (I) used in the present invention will be explained below.

[0018]

embedded image R1 and R2 are alkyl groups. The alkyl group represented by R1 and R2 includes, for example, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms {unsubstituted alkyl group (e.g., methyl, ethyl, propyl, isopropyl, still, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups such as aralkyl groups (e.g. benzyl, 2-
phenylethyl), hydroxyalkyl group (e.g. 2
-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl groups (e.g. 2-carboxyethyl, 3-hydroxypropyl), carboxyalkyl groups (e.g. 2-carboxyethyl, 3-hydroxypropyl),
-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl groups (e.g. 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl)
, sulfoalkyl groups (e.g. 2-sulfoethyl, 3-
sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-[3-sulfopropoxy]ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl groups (e.g. 3-sulfatopropyl) , 4-sulfatobutyl), heterocyclic-substituted alkyl groups (e.g. 2-(pyrrolidin-2-one-1-
ethyl), tetrahydrofurfuryl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl, allyl group, etc.

At least one, preferably both, alkyl groups of R1 and R2 have at least one carbon atom bonded to at least three non-hydrogen atoms. At least one of R1 and R2 is an alkyl group having an organic acid and is represented by general formula (V).

[0020]

embedded image In the formula, A represents an organic acid group, and m and n each represent an integer from 0 to 5.

At least one carbon atom is at least 3
Particularly detailed examples are given of alkyl groups bonded to atoms other than hydrogen atoms.

2-Methylpropyl, t-butyl, 2-methylbutyl, 1,1-dimethylpropyl, 3-methylbutyl, 1,2-dimethylpropyl, 2-methylpentyl, 1,1-dimethylbutyl, 1-isopropylpropyl , 3-methylpentyl, 1,2-dimethylbutyl, 1-
Ethyl-1-methylpropyl, 4-methylpentyl, 1
, 3-dimethylbutyl, 1,1-dimethylpentyl, 1
-isopropylbutyl, 1,4-dimethylpentyl, 1
-Methylpropyl, 1-methylbutyl, 1-methylpentyl, 2-methylhexyl, 1-methyl-4,4dimethylpentyl, 3,4,4-trimethylpentyl, 3,5
, 5-trimethylhexyl, 3-carboxy-1-methylpropyl, 3-carboxybutyl, 3-carboxy-
1-Methylbutyl, 3-carboxy-1,1-dimethylpropyl, 4-carboxy-3-methylbutyl, 2-carboxy-2-methylpropyl, 3-carboxy-2-
Methylpropyl, 3-sulfo-1-methylpropyl, 3
-sulfobutyl, 3-sulfo-1-methylbutyl, 3-
Sulfo-1,1-dimethylpropyl, 4-sulfo-3-
Methylbutyl, 2-sulfo-2-methylpropyl, 3-
Sulfo-2-methylpropyl.

Among the general formula (V), m=2,3,
Preferably, n=0, 1, A=sulfo group, more preferably m=2, n=0.

[0024] Examples of the organic acid group include a carboxy group, a sulfo group, and a phosphoryl group.

[0025] Examples of the anion represented by X include:
Halogen anions (Cl-, Br-, I-), alkyl sulfates (methyl sulfate, ethyl sulfate), arylsulfonates (benzenesulfonate, toluenesulfonate, 4-chlorobenzenesulfonate, naphthalene-1,5- disulfonates), perchlorates, and alkyl carboxylates (acetates, propionates). p represents a value between 0 and 1 necessary to balance the charges, and is 0 when a salt is formed within the molecule.

Examples of the 5- or 6-membered heterocycle formed by Z1 and Z2 include the following.

[0027] Thiazole nucleus (eg, thiazole, 4-
Methylthiazole, 4-phenylthiazole, 4,5-
dimethylthiazole, 4,5-diphenylthiazole)
, benzothiazole nucleus (e.g. benzothiazole, 4
-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6- Bromobenzothiazole, 5
-Iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-
Ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole,
5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, 5-styrylbenzothiazole) , naphthothiazole core (e.g. naphtho[2,1-d]thiazole,
naphtho[1,2-d]thiazole, naphtho[2,3-d
] Thiazole, 5-methoxynaphtho[1,2-d]thiazole, 7-ethoxynaphtho[2,1-d]thiazole, 8-methoxynaphtho[2,1-d]thiazole, 5-
methoxynaphtho[2,3-d]thiazole), thiazoline cores (e.g. thiazoline, 4-methylthiazoline, 4-
Nitrothiazoline), oxazole nucleus (e.g. oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (e.g. benzoxazole), Oxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5
-Nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6
-Nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6
-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole),
naphthoxazole core (e.g. naphtho[2,1-d]
Oxazole, naphtho[1,2-d]oxazole, naphtho[2,3-d]oxazole, 5-nitronaphtho[
2,1-d]oxazole, oxazoline core (e.g.
4,4-dimethyloxazoline), selenazole core (e.g. 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole core (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-
6-nitrobenzoselenazole), naphthoselenazole core (e.g. naphtho[2,1-d]selenazole, naphtho[1,2-d]selenazole), tellazole core (e.g. benzotellazole, 5-methylbenzotellazole) sol, 5-methoxybenzotellurazole, naphtho[1,
2-d] Tellurazole), 3,3-dialkylindolenine core (e.g. 3,3-dimethylindolenine, 3,3
-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dimethyl-5-nitroindolenine,
3,3-dimethyl-5-methoxyindolenine, 3,3
, 5-trimethylindolenine, 3,3-dimethyl-5
-chloroindolenine), imidazole nucleus {e.g. 1
-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-alkylbenzimidazole, 1-
Alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5
-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-
6-chloro-5-trifluoromethylbenzimidazole, 1-alkylnaphtho[1,2-d]imidazole,
1-allyl-5,6-dichlorobenzimidazole, 1
-Allyl-5-chlorobenzimidazole, 1-arylimidazole, 1-arylbenzimidazole, 1
-Aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole, 1-arylnaphtho[1,2- d] Imidazole, the alkyl group mentioned above has 1 to 8 carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, or a hydroxyalkyl group (for example, 2-hydroxyethyl,
3-hydroxypropyl, etc.) are preferred. Particularly preferred are methyl group and ethyl group. The aforementioned aryl represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl, and the like. }, pyridine nucleus (e.g. 2-pyridine, 5-methyl-2-pyridine), quinoline nucleus (e.g. 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2 -quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline,
6-hydroxy-2-quinoline, 8-chloro-2-quinoline, isoquinoline, 6-nitro-1-isoquinoline,
3,4-dihydro-1-isoquinoline, 6-nitro-3
-isoquinoline), imidazo[4,5-b]quinoxaline core (e.g. 1,3-diethylimidazo[4,5-d
] quinoxaline, 6-chloro-1,3-diallylimidazo[4,5-b]quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, and the like.

L1 or L2 represents a methine group or a substituted methine group. Examples of substituted methine groups include methine groups substituted with lower alkyl groups such as methyl and ethyl, phenyl, substituted phenyl, methoxy, and ethoxy. l represents 0, 1 or 2.

Specific examples of the compound of general formula (I) of the present invention are shown below.

Specific examples of compounds of general formula (I)

0031
]

[C5]

[0032]

[C6]

[0033]

[C7]

[0034]

[Chemical formula 8]

[0035]

embedded image The saturated adsorption amount of the sensitizing dye can be determined from the adsorption isotherm by centrifuging the dye-adsorbed emulsion.

The amount of the spectral sensitizer (sensitizing dye) represented by the general formula (I) is preferably 40% or more of the saturated adsorption amount, more preferably 40 to 120%, still more preferably 70% to 100%. %.

The sensitizing dye is used in the formation process of silver halide grains,
Alternatively, it may be added during the chemical sensitization process or during coating.

In particular, a method for adding a sensitizing dye during the formation of silver halide emulsion grains is described in US Pat. No. 4,225,666.
No. 4,828,972, JP-A-61-103,1
You can refer to No. 49. Furthermore, methods for adding sensitizing dyes in the desalting process of silver halide emulsions include European Patent No. 291,339-A, Japanese Patent Application Laid-Open No. 64-52,
No. 137 can be referred to. In addition, a method of adding a sensitizing dye in the chemical sensitization process was disclosed in Japanese Patent Application Laid-Open No. 59-48.
, No. 756 may be referred to.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. Nos. 2,933,390, 3,
635,721), aromatic organic acid formaldehyde condensates (e.g., U.S. Pat. No. 3,743,51),
0), cadmium salts, azaindene compounds, etc. U.S. Patent No. 3,615,613, U.S. Patent No. 3,615,641, U.S. Patent No. 3,617,295,
The combination described in No. 3,635,721 is particularly useful.

The manufacturing process of silver halide emulsions is roughly divided into steps such as grain formation, desalting, and chemical sensitization. Particle formation is divided into nucleation, ripening, and growth. These steps are not performed uniformly; the order of the steps may be reversed, or the steps may be repeated. The term "reduction sensitization" being carried out during the production process of the silver halide emulsion basically means that it can be carried out at any step. Reduction sensitization may be performed during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth, and may be performed prior to or after chemical sensitization other than reduction sensitization. . When chemical sensitization is carried out in combination with gold sensitization, reduction sensitization is preferably carried out prior to chemical sensitization to avoid undesirable fogging. The most preferred method is reduction sensitization during the growth of silver halide grains. Growing is a method in which reduction sensitization is performed while silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. This means that it also includes a method in which reduction sensitization is performed in the same state and then further growth is performed.

The reduction sensitization of the present invention refers to a method of adding a known reducing agent to a silver halide emulsion, and a pA method called silver ripening.
Either a method of growing or aging in an atmosphere with a low pAg of g 1 to 7 or a method of growing or aging in an atmosphere with a high pH of 8 to 11, which is called high pH aging, can be selected. Moreover, two or more methods can also be used together.

The method of adding a reduction sensitizer is a preferred method since the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, stannous salts, amines and polyamic acids, hydrazine derivatives, formamidine sulfinic acids, silane compounds, borane compounds and the like are known. In the present invention, a compound selected from these known compounds can be used, or two or more kinds of compounds can be used in combination. Preferred compounds as reduction sensitizers are stannous chloride, thiourea dioxide, and dimethylamine borane. The amount of reduction sensitizer added depends on the emulsion manufacturing conditions, so it is necessary to select the amount added, but it is 10-7 to 10 per mole of silver halide.
A range of -3 moles is suitable.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention.

Ascorbic acid and its derivatives (hereinafter referred to as
It's called an "ascorbic acid compound." ) Specific examples include the following. (A-1) L-ascorbic acid (A-2)
Sodium L-ascorbate (A-3)
Potassium L-ascorbate (A-4) DL-
Ascorbic acid (A-5) D-Sodium ascorbate (A-6) L-Ascorbic acid-6
-Acetate (A-7) L-ascorbic acid-
6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-5,6-diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene The ascorbic acid compound used in the present invention is desirably used in a larger amount than the amount in which conventional reduction sensitizers are preferably used. For example, Tokuko Sho 57-33572
The issue states, ``The amount of reducing agent is usually 0.75x per gram of silver ion.
10-2 milliequivalent (8 x 10-4 mol/AgX mol)
not exceed. An amount of 0.1 to 10 mg per kg of silver nitrate (
As ascorbic acid, 10-7 to 10-5 mol/Ag
X moles) are often effective. ” (converted value is by the inventors). US-2,487,
No. 850 states that "the amount of tin compound that can be added as a reduction sensitizer is 1.times.10@-7 to 44.times.10@-6 mol". Furthermore, in JP-A-57-179835, the amount of thiourea dioxide added is about 0.01 mg to about 2 mg per mole of silver halide, and about 0.0 mg of stannous chloride.
It is stated that it is appropriate to use 1 mg to about 3 mg. The ascorbic acid compound used in the present invention depends on the emulsion grain size, halogen composition, emulsion preparation temperature, pH, p
Although the preferable addition amount depends on factors such as Ag, it is 5 x 10-5 to 1 x 10-1 per mole of silver halide.
It is desirable to select from the molar range. More preferably, it is selected from the range of 5 x 10-4 mol to 1 x 10-2 mol. Particularly preferred is 1 x 10-3 mol to 1
The amount should be selected from the range of x10-2 moles.

The reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters, amides, etc., and added during particle formation, before or after chemical sensitization. Although it may be added at any stage of the emulsion manufacturing process, it is particularly preferable to add it during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and these aqueous solutions may be used to form particles. It is also a preferable method to add the solution of the reduction sensitizer in several portions or continuously over a long period of time as the particles are formed.

The silver halide photographic light-sensitive material of the present invention preferably has general formula (II), (III) or (IV
) contains at least one compound selected from the compounds represented by.

General formulas (II), (III) and (IV
) to explain the compound in more detail, R, R1 and R
When 2 is an aliphatic group, it preferably has 1 to 22 carbon atoms.
an alkyl group, an alkenyl group having 2 to 22 carbon atoms, and an alkynyl group, which may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic group for R, R1 and R2 preferably has 6 to 20 carbon atoms, such as phenyl group and naphthyl group. These may be substituted.

The heterocyclic group for R, R1 and R2 is a 3- to 15-membered ring containing at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium,
For example, pyrrolidine ring, piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, selenazole ring, benzoselenazole ring, tellazole ring, triazole ring , benzotriazole ring, tetrazole ring,
Examples include oxadiazole ring and thiadiazole ring.

[0053] As substituents for R, R1 and R2,
For example, alkyl groups (e.g. methyl, ethyl, hexyl)
, alkoxy groups (e.g. methoxy, ethoxy, octyloxy), aryl groups (phenyl, naphthyl, tolyl), hydroxy groups, halogen atoms (e.g. fluorine, chlorine, bromine, iodine), aryloxy groups (e.g. phenoxy)
, alkylthio groups (e.g. methylthio, butylthio),
Arylthio groups (e.g. phenylthio), acyl groups (e.g. acetyl, propionyl, butyryl, valeryl),
Sulfonyl groups (e.g. methylsulfonyl, phenylsulfonyl), acylamino groups (e.g. acetylamino, benzamino), sulfonylamino acids (e.g. methanesulfonylamino, benzenesulfonylamino), acyloxy groups (e.g. acetoxy, benzoxy), carboxyl groups, cyano groups, sulfonyl groups. group, amino group, etc.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include -(CH2)n- (n=1-12), -CH
2 -CH=CH-CH2 -, -CH2 C3CCH
2-,

[0055]

[Image Omitted] Examples include xylylene group. Examples of the divalent aromatic group for L include phenylene and naphthylene.

These substituents may be further substituted with the substituents described above.

[0057] M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Examples of organic cations include ammonium ions (eg ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ions (tetraphenylphosphonium), guanidine groups, and the like.

General formula (II), (III) or (IV)
Specific examples of compounds represented by are listed below, but the invention is not limited thereto.

[0059]

[Chemical formula 11]

[0060]

[Chemical formula 12]

[0061]

[Chemical formula 13]

[0062]

[Chemical formula 14]

[0063]

[Chemical formula 15]

[0064]

[Chemical formula 16]

[0065]

[Chemical formula 17]

[0066]

[Chemical formula 18]

[0067]

[Chemical formula 19]

[0068]

embedded image The compound of general formula (II) can be easily synthesized by the method described in JP-A-54-1019 and British Patent No. 972,211.

General formula (II), (III) or (IV)
The compound represented by 10-1 mole of silver halide
Preferably, it is added in an amount of 7 to 10-1 mol. 10 more
-6 to 10-2, especially 10-5 to 10-3 mol/
The addition amount of molar Ag is preferred.

The compounds represented by the general formulas (II) to (IV) can be added during the manufacturing process by a method commonly used for adding additives to photographic emulsions. For example, water-soluble compounds should be prepared in an aqueous solution with an appropriate concentration, and compounds that are insoluble or poorly soluble in water should be prepared in an appropriate organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, and amides. It can be dissolved in a solvent that does not adversely affect photographic properties and added as a solution.

General formula (II), (III) or (IV
) may be added at any stage during the grain formation of the silver halide emulsion, before or after chemical sensitization. Preferred is a method in which the compound is added before or during reduction sensitization. Particularly preferred is a method in which it is added during grain growth.

[0072] Although it is possible to add it to the reaction vessel in advance, it is preferable to add it at an appropriate time during particle formation. Alternatively, the compounds of general formulas (II) to (IV) may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and these aqueous solutions may be used to form particles. It is also a preferable method to add the solution of the compound of general formulas (II) to (IV) in several portions or continuously for a long period of time as particles are formed.

Among the compounds represented by formulas (II) to (IV), the most preferred compound for the present invention is the compound represented by formula (II).

The emulsion of the present invention preferably has an aspect ratio of 3 or more, more preferably an average aspect ratio of 3 or more and 8
The tabular silver halide grains are less than or equal to . The tabular grain herein is a general term for grains having one twin plane or two or more parallel twin planes. In this case, the twin plane is (111)
This (111) plane is referred to when the ions at all lattice points on both sides of the plane are mirror images. These tabular grains have a triangular, hexagonal, or rounded circular shape when viewed from above; triangular grains have a triangular shape, hexagonal grains have a hexagonal shape, or a circular shape. have circular, mutually parallel outer surfaces.

In the present invention, the aspect ratio of tabular grains refers to the value obtained by dividing the grain diameter by the thickness of each tabular grain having a grain diameter of 0.1 μm or more. The thickness of the particles is measured by depositing metal along with latex as a reference from an oblique direction on the particles, measuring the length of the shadow on an electron micrograph, and calculating using the length of the latex shadow as a reference. It's easy to do.

The particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle.

The projected area of the particles is obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

The diameter of the tabular grains is 0.15 to 5.
Preferably, it is 0 μm. The thickness of the tabular grains is preferably 0.05 to 1.0 μm.

The average aspect ratio is determined as the arithmetic mean of the aspect ratios of at least 100 silver halide grains. It can also be determined as the ratio of the average diameter to the average thickness of the particles.

The emulsion of the present invention contains tabular silver halide grains having an aspect ratio of 3 or more, preferably tabular silver halide grains having an average aspect ratio of 3 or more and less than 8, preferably 60% of the total projected area. % or more is occupied by such tabular silver halide grains.

The proportion of the tabular grains is preferably 60% or more, particularly preferably 80% or more of the total projected area.

Further, even more preferable results may be obtained by using monodisperse tabular grains. The structure and manufacturing method of monodispersed tabular grains are described in, for example, Japanese Patent Application Laid-Open No. 1516-1983.
18, etc., but to briefly describe its shape, 70% or more of the total projected area of silver halide grains is the length of the side with the maximum length relative to the length of the side with the minimum length. The hexagonal tabular silver halide grains are hexagonal and have two parallel surfaces as outer surfaces, and the grain size distribution of the hexagonal tabular silver halide grains is Coefficient of variation (dispersion (standard deviation) of the particle size expressed as the circular diameter of its projected area)
divided by the average particle size) has a monodispersity of 20% or less.

Furthermore, the emulsion of the present invention preferably has dislocation lines. Dislocations in tabular grains are described, for example, in J. F. Ha
Milton, Phot. Sci. Eng. ,11,5
7, (1967) and T. Shiozawa, J. Soc.
．． Photo. Sci. Japan, 35, 213, (1
It can be observed by a direct method using a transmission electron microscope at low temperature, as described in 972). In other words, the silver halide grains were taken out from the emulsion with care so as not to apply pressure that would cause dislocations to the grains, and placed on a mesh for electron microscopy, and the sample was carefully placed to prevent damage (printout, etc.) from the electron beam. Observation is performed using the transmission method in a cooled state. At this time, the thicker the particles, the more difficult it is for the electron beam to pass through them, so it is better to use a high-voltage electron microscope (200 kV or more for particles with a thickness of 0.25 μm) for clearer observation. . From photographs of particles obtained by such a method, it is possible to determine the position and number of dislocations in each particle when viewed from the direction perpendicular to the main plane.

[0084] The average number of dislocation lines per particle is 10 or more. More preferably, the average number of fibers per particle is 20 or more. When dislocation lines exist densely or when dislocation lines are observed to intersect with each other, the number of dislocation lines per particle may not be clearly counted. However, even in these cases, approximately 10 pieces,
It is possible to count as many as 20 or 30 pieces, which is clearly distinguishable from the case where there are only a few pieces. The average number of dislocation lines per grain is determined by counting the number of dislocation lines for 100 or more grains and determining the number average.

[0085] Dislocation lines can be introduced, for example, near the outer periphery of tabular grains. In this case, the dislocations are almost perpendicular to the outer periphery, and the dislocation lines are generated starting from a position x% of the distance from the center of the tabular grain to the side (outer periphery) and extending to the outer periphery. The value of this x is preferably 10 or more and 100
more preferably 30 or more and less than 99,
Most preferably it is 50 or more and less than 98. At this time, the shape created by connecting the starting positions of these dislocations is close to similar to the particle shape, but it is not completely similar and may be distorted. This type of dislocation is not found in the central region of the grain. Although the direction of the dislocation lines is approximately the (211) direction in crystallography, they often meander and sometimes intersect with each other.

Further, the tabular grains may have dislocation lines almost uniformly over the entire area on the outer periphery, or may have dislocation lines at local positions on the outer periphery. That is, taking a hexagonal tabular silver halide grain as an example, the dislocation lines may be limited only to the vicinity of six vertices, or the dislocation lines may be limited to only the vicinity of one of the vertices. . Conversely, it is also possible that the dislocation lines are limited to only the edges excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the centers of two parallel main planes of the tabular grain. When dislocation lines are formed over the entire principal plane, the direction of the dislocation line may be approximately the (211) crystallographic direction when viewed from the direction perpendicular to the principal plane; however, the direction of the dislocation line may be the (110) direction or Sometimes they are formed randomly, and the length of each dislocation line is also random, and sometimes they are observed as short lines on the main plane, and sometimes as long lines reaching the edges (outer periphery). be. Dislocation lines may be straight or meandering. They also intersect with each other in many cases.

[0088] As described above, the position of the dislocation may be limited to the outer periphery, the main plane, or a local position, or
These may be formed by combining them. That is, it may exist on the outer periphery and on the main plane at the same time.

Introducing dislocation lines on the outer periphery of tabular grains can be achieved by providing a specific high silver iodide layer inside the grains. Here, the high silver iodide layer includes cases where high silver iodide regions are provided discontinuously. Specifically, it is obtained by preparing a base grain, providing a high silver iodide layer, and covering the outside thereof with a layer having a lower silver iodide content than the high silver iodide layer. The silver iodide content of the base tabular grains is lower than that of the high silver iodide layer, preferably from 0 to 20 mol%, more preferably from 0 to 15 mol%.

The high silver iodide layer inside the grains refers to a silver halide solid solution containing silver iodide. The silver halide in this case is preferably silver iodide, silver iodobromide, or silver chloroiodobromide, but silver iodide or silver iodobromide (silver iodide content 10 to 40 mol%) is preferable. More preferred. A high silver iodide layer inside this grain (
In order to selectively make the internal high silver iodide layer (hereinafter referred to as an internal high silver iodide layer) exist either on the sides or corners of the base grain, it is controlled by the formation conditions of the base grain and the formation conditions of the internal high silver iodide layer. can do. Important factors for the formation conditions of base silver particles are pAg (logarithm of the reciprocal of silver ion concentration), the presence or absence, type and amount of a silver halide solvent, and temperature. By growing the base grain at pAg of 8.5 or less, preferably 8 or less, the internal high silver iodide layer can be selectively present near the apex of the base grain. On the other hand, by growing the base grains at pAg of 8.5 or more, preferably 9 or more, an internal high silver iodide layer can be made to exist on the sides of the base grains. These pAg threshold values vary up and down depending on the temperature and the presence/absence, type, and amount of silver halide solvent. When, for example, thiocyanate is used as the silver halide solvent, this pAg threshold value shifts toward a higher value. What is particularly important as the pAg during growth is the pAg at the final stage of growth of the base grain. On the other hand, pA during growth
Even if g does not satisfy the above value, by adjusting to the pAg after growing the base particles and aging,
It is also possible to control the selected location of the internal high silver iodide layer. At this time, ammonia, amine compounds, and thiocyanate salts are effective as silver halide solvents. A so-called conversion method can be used to generate the internal high silver iodide layer. This method includes adding halogen ions, which have a lower solubility in the salt that creates silver ions than the halogen ions forming the particles or near the surface of the particles, during grain formation. In the invention, it is preferable that the amount of halogen ions with low solubility to be added is at least a certain value (related to the halogen composition) relative to the surface area of the particles at that time. For example, during particle formation, it is preferable to add a certain amount or more of KI to the surface area of the AgBr particles at that point. Specifically, it is preferable to add 8.2×10 −5 mol/m 2 or more of iodide salt.

A more preferred method for forming the internal high silver iodide layer is to add an aqueous silver salt solution simultaneously with the addition of an aqueous halide salt solution containing an iodide salt.

For example, at the same time as adding KI aqueous solution, AgNO
3 Add the aqueous solution with a double jet. At this time, the addition start time and addition end time of the KI aqueous solution and the AgNO3 aqueous solution may be shifted from each other. The molar ratio of the AgNO3 aqueous solution to the KI aqueous solution is preferably 0.1 or more, more preferably 0.5 or more. More preferably, it is 1 or more. The total molar amount of the AgNO3 aqueous solution added to the halogen ions and added iodide ions in the system may be in the silver excess region. It is preferable that pAg at the time of double jet addition of an aqueous halide solution containing these iodide ions and an aqueous silver salt solution decreases with the addition time of the double jet. The pAg before the start of addition is preferably 6.5 or more and 13 or less. More preferably, it is 7.0 or more and 11 or less. The pAg at the end of addition is most preferably 6.5 or more and 10.0 or less.

When carrying out the above method, it is preferable that the solubility of the silver halide in the mixed system is as low as possible. Therefore, the temperature of the mixed system when forming the high silver iodide layer is preferably 30°C or more and 70°C or less, more preferably 30°C or more and 50°C or less.
The temperature is below 0°C.

Most preferably, the internal high silver iodide layer is formed using fine grain silver iodide (meaning fine silver iodide, hereinafter the same).
Alternatively, fine grain silver iodobromide, fine grain silver chloroiodide, or fine grain silver chloroiodobromide may be added. In particular, it is preferable to add fine grain silver iodide. These fine particles usually have a particle size of 0.01 μm or more and 0.1 μm, but fine particles with a particle size of 0.01 μm or less or 0.1 μm or more can also be used. Regarding the preparation method of these fine silver halide grains, Japanese Patent Application No. 63-7
No. 851, No. 63-195778, No. 63-7852
No. 63-7853, No. 63-194861, and No. 63-194862 can be referred to. It is possible to provide an internal high silver iodide layer by adding these fine grain silver halides and ripening. When ripening and dissolving fine grains, it is also possible to use the above-mentioned silver halide solvent. It is not necessary for all of these added fine particles to immediately dissolve and disappear, but it is sufficient that they dissolve and disappear when the final particles are completed.

The outer layer covering the inner high silver iodide layer has a silver iodide content lower than that of the high silver iodide layer, preferably the silver iodide content is 0 to 30 mol %, more preferably 0 to 20 mol %. mole%
Most preferably it is 0 to 10 mol%. The position of this internal high silver iodide layer is measured from the center of the projected hexagon of the grain, and is preferably present in a range of 5 mol % or more and less than 100 mol % based on the total silver amount of the grain. 2
0 mol% or more and less than 95 mol%, especially 50 mol% or more and 90
Preferably, it is within a range of less than mol %. The amount of silver halide forming these internal high silver iodide layers is 50 mol % or less, more preferably 20 mol % or less of the total silver amount of the grains. These high silver iodide layers are based on prescription values for producing silver halide emulsions, and are not values measured by various analytical methods for the halogen composition of the final grains. The internal high silver iodide layer often disappears in the final grain due to the recrystallization process, etc., and the above is all related to its manufacturing method.

Therefore, although dislocation lines can be easily observed in the final grain by the method described above, the internal silver iodide layer introduced to introduce dislocation lines cannot be confirmed as a clear layer in many cases. For example, in some cases, the entire outer peripheral region of a tabular grain is observed as a high silver iodide layer. Regarding these halogen compositions, X-ray diffraction, EP
MA (sometimes called XMA) method (a method for detecting silver halide composition by scanning silver halide grains with an electron beam)
, ESCA (also known as XPS) method (a method of irradiating X-rays and spectroscopy of photoelectrons emerging from the particle surface), etc. can be used in combination.

The temperature pAg during formation of the outer layer covering the internal high silver iodide layer is arbitrary, but the preferred temperature is 30°C or higher and 80°C or lower. most preferably 35°C
The temperature is above 70°C. A preferable pAg is 6.5 or more and 11.5 or less. It may be preferable to use the silver halide solvents described above, with the most preferred silver halide solvent being a thiocyanate salt.

In order to introduce dislocation lines on the main surfaces of tabular grains, after preparing the base grains, silver halochloride is deposited on the main surfaces, and the silver halochloride is converted into high silver bromide or high silver iodide. It is sufficient to form a layer and further provide a shell on the outside of the layer. Examples of the silver halochloride include silver chloride or silver chlorobromide or silver chloroiodobromide having a silver chloride content of 10 mol % or more, preferably 60 mol % or more. Deposition of these silver halochlorides onto the main planes of the base grains can be achieved by adding an aqueous solution of silver nitrate and an aqueous solution of a suitable alkali metal salt (for example, potassium chloride) separately or simultaneously, or by adding emulsions made of these silver salts. It can also be deposited by adding and aging. Deposition of these silver halochlorides is possible in any pAg range, but is most preferably 5.0 or more and 9.5 or less. In this method, tabular grains are grown primarily in the thickness direction. The amount of this silver halochloride layer is 1 mol % or more and 80 mol % or less in terms of silver mol % based on the base grain. More preferably 2 mol%
The content is 60 mol% or less. By converting this silver halochloride layer with an aqueous halide solution capable of producing a silver salt having lower solubility than silver halochloride, it is possible to introduce dislocation lines onto the main planes of the tabular grains. After conversion of this silver halochloride layer, for example by an aqueous KI solution, it is possible to grow the shell to obtain the final grain. The halogen conversion of these silver halochloride layers does not mean that silver salts having lower solubility than silver halochloride are completely replaced, but preferably 5% or more, more preferably 10% or more, most preferably 20% or more, Replaces silver salts with low solubility. By controlling the halogen structure of the base grain on which the silver halochloride layer is provided, it is possible to introduce dislocation lines at local sites on the main plane. For example, if a base grain having an internal high silver iodide structure is used by displacing the base tabular grain in the lateral direction, it is possible to introduce dislocation lines only in the main planes in the peripheral area excluding the central part of the main planes. Further, by displacing the base tabular grain in the lateral direction and using a base grain having an outer high silver iodide structure, it is possible to introduce dislocation lines only in the central part of the main plane excluding the peripheral part. Furthermore, it is also possible to deposit silver halochloride only in area-limited areas using a substance that locally controls the epitaxial growth of silver halochloride, such as iodide, and to introduce dislocation lines only in those areas. The temperature during deposition of silver halochloride is 30°C or higher,
The temperature is preferably 70°C or lower, more preferably 30°C or higher.
The temperature is below 0°C. Although it is possible to perform conversion after depositing these silver halochlorides and then grow a shell, it is also possible to perform halogen conversion while growing a shell after depositing silver halochlorides.

The position of the internal silver halochloride layer formed almost parallel to the main plane may be present on both sides from the center of the grain thickness in a range of 5 mol % or more and less than 100 mol % based on the total silver content of the grain. Preferably, it is more preferably 20 mol% or more and less than 95 mol%, particularly preferably 50 mol% or more and less than 90 mol%.

[0100] The silver iodide content of the shell is preferably 0 to 3.
It is 0 mol%, more preferably 0 to 20 mol%. The temperature during shell formation, pAg, is arbitrary, but the preferred temperature is 30°C or higher and 80°C or lower. most preferably 3
The temperature is 5°C or higher and 70°C or lower. Preferred pAg is 6.5
11.5 or less. It may be preferable to use the silver halide solvents described above, with the most preferred silver halide solvent being a thiocyanate salt. In the final grain, the internal silver halochloride layer that has undergone halogen conversion may not be confirmed by the above-mentioned halogen composition analysis method depending on conditions such as the degree of halogen conversion. However, dislocation lines can be clearly observed.

[0101] The method of introducing dislocation lines at arbitrary positions on the main plane of the tabular grains and the method of introducing dislocation lines at arbitrary positions on the outer periphery of the tabular grains described above are used in combination as appropriate. It is also possible to introduce dislocation lines.

The silver halide emulsion that can be used in combination with the present invention may include any of silver bromide, silver iodobromide, silver iodochlorobromide, and silver chlorobromide. Preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol % or less of silver iodide.

The tabular grains of the present invention are described in "Theory and Practice of Photography" by Cleve.
Theory and Practice (19
30)), p. 131; Gutoff, Photographic Science and Engineering (Gutoff, P.
photographic science and
Engineering), Volume 14, 248-2
57 pages (1970); U.S. Patent No. 4,434,226
No. 4,414,310, No. 4,433,048, No. 4,439,520 and British Patent No. 2,112
, No. 157 and the like.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Frisel (H
．． Frieser, ed.
der Photographischen Pr
ozesse mit Silverhaloge
(Academische Verlags Gesellschacht 1968) pages 675-734 can be used.

That is, sulfur-containing compounds that can react with active gelatin and silver (for example, thiosulfates, thioureas,
mercapto compounds, rhodanines); reduction sensitization using reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g. In addition to gold complex salts, periodic table VIII of Pt, Ir, Pd, etc.
A noble metal sensitization method using a complex salt of a group metal), a selenium sensitization method using a selenium compound (selenoureas, selenoketones, selenides, etc.) can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; The above-mentioned heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene (particularly 4-hydroxy substituted (1,3,3a
, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and many other compounds known as antifoggants or stabilizers can be added.

[0107] The antifoggant or stabilizer is usually added after chemical sensitization, but more preferably it can be selected during chemical ripening or before the start of chemical ripening. That is, in the process of forming silver halide emulsion grains, during the addition of the silver salt solution, and after the addition until the start of chemical ripening, during the chemical ripening (during the chemical ripening time, preferably within 50% of the start), more preferably up to 20% of the time).

The amount of the above-mentioned compound used in the present invention cannot be determined uniquely depending on the method of addition or the amount of silver halide, but it is preferably 10-7 mol to 10-2 mol per mol of silver halide. , more preferably 10-5 to 10-2 mol.

As the preservative (binding agent or protective colloid) for the photographic emulsion of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives. ; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin and Bull. Soc. Sci. Photo
．． Japan. No. 16, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used.

[0112] Specifically, as the dispersion medium used in the present invention, research disclosure (RESEARCH
DISCLOSURE) Volume 176, No. 1764
3 (December 1978), Section IX.

The present invention can be used in color photographic materials. It is sufficient that at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer is provided on the support; There are no particular restrictions on the number of layers or the order of the layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. and
The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally as follows: A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

[0114] Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

[0115] The intermediate layer includes JP-A-61-43748, JP-A-59-113438, JP-A-59-113440,
It may contain a coupler, a DIR compound, etc. as described in JP 61-20037 and JP 61-20038, and may also contain a commonly used color mixing inhibitor.

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

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL
)/High-sensitivity red-sensitive layer (RH)/Low-sensitivity red-sensitive layer (R
L) or BH/BL/GL/GH/RH/RL
or in the order of BH/BL/GH/GL/RL/RH.

Alternatively, as described in Japanese Patent Publication No. 55-34932, the layers may be arranged in the order of blue-sensitive layer/GH/RH/GL/RL from the side farthest from the support. Also, JP-A-56-25738, JP-A No. 62-6393
As described in No. 6, the layers may be arranged in the order of blue-sensitive layer/GL/RL/GH/RH from the side farthest from the support.

Furthermore, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is a silver halide emulsion layer with the highest sensitivity. Another example is an arrangement in which a silver halide emulsion layer with lower photosensitivity is further arranged, and the photosensitivity is successively lowered toward the support, and is composed of three layers having different photosensitivity. Even in the case where the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, medium-sensitivity emulsion is added from the side remote from the support in the same color-sensitive layer. They may be arranged in the following order: layer/high-speed emulsion layer/low-speed emulsion layer.

In addition, they may be arranged in the following order: high-speed emulsion layer/low-speed emulsion layer/medium-speed emulsion layer, or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer.

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

As described above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred amount of silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides: Particularly preferred is about 2 mol%.
silver iodobromide or silver iodochlorobromide containing up to about 10 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with irregular crystal shapes such as spherical and plate shapes. It may be one having crystal defects such as crystal planes, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No.
．． 17643 (December 1978), pp. 22-23, “
I. Emulsion preparation
ion and types)”, and No. 18 of the same
716 (November 1979), p. 648, No. 30
7105 (November 1989), pp. 863-865, and "Physics and Chemistry of Photography" by P. Glafkides, published by Paul Montell.
tPhisique Photographique
, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.F.D.
uffin, Photographic Emuls
ion Chemistry (Focal Pre
ss, 1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V.L. Zelik
man et al. ,Making and
Coating Photographic E
mulsion, Focal Press, 1964
), etc.).

[0127] US Patent No. 3,574,628, US Patent No. 3,
655,394 and British Patent No. 1,413,748
The monodispersed emulsions described in No. 1, etc. are also preferred.

[0128] Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
ic Science and Engineering
ring), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,226, No. 4,414,
No. 310, No. 4,433,048, No. 4,499,5
20 and British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Also, mixtures of particles of various crystal forms may be used.

The above-mentioned emulsion may be of a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside the grain, or a type in which a latent image is formed both on the surface and inside the grains. type emulsion. Among the internal latent image types, the core/
It may also be a shell-type internal latent image type emulsion. The method for preparing this core/shell type internal latent image type emulsion was disclosed in Japanese Patent Application Laid-Open No. 59-13
It is described in No. 3542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17643, same No. 18716 and the same No. 307105, and the relevant parts are summarized in Table 1 below.

The photosensitive material of the present invention includes grain size, grain size distribution, halogen composition, and
Two or more types of emulsions differing in at least one characteristic such as grain shape and sensitivity can be mixed and used in the same layer.

Silver halide grains covered with grain surfaces as described in US Pat. No. 4,082,553, US Pat. No. 4
, 626,498, and JP-A-59-214852, silver halide grains and colloidal silver with fogged insides of the grains are coated with a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic layer. It can be preferably used in colloid layers. Silver halide grains that are coated inside or on the surface are uniformly coated with (
refers to silver halide grains that can be developed (non-imagewise). A method for preparing silver halide grains with a fogging inside or on the grain surface is described in U.S. Pat.

The silver halides forming the inner core of the core/shell type silver halide grains whose interiors are fogged may have the same halogen composition or may have different halogen compositions. As the silver halide coated inside or on the surface of the grain, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.7.
5 μm, particularly 0.05 to 0.6 μm is preferred. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or number of silver halide grains is within ±40% of the average grain size). % or less).

[0135] In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is a silver halide fine grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process, and is preferably not fogged in advance. .

[0136] The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and silver chloride and/or silver bromide are optionally added.
Alternatively, it may contain silver iodide. Preferably silver iodide is 0
．． It contains 5 to 10 mol%.

[0137] The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 2 μm.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized;
Also, spectral sensitization is not required. However, prior to adding this to the coating solution, it is preferable to add in advance a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound, or a zinc compound. This layer containing fine silver halide grains can preferably contain colloidal silver.

[0139] The amount of coated silver in the photosensitive material of the present invention is 6.0 g.
/m2 or less is preferable, and 4.5g/m2 or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures mentioned above, and relevant descriptions are shown in Table 1 below.

[0141]

[Table 1] In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, it can be fixed by reacting with formaldehyde as described in U.S. Patent Nos. 4,411,987 and 4,435,503. It is preferable to add the compound to the photosensitive material.

[0142] The photosensitive material of the present invention is disclosed in US Pat. No. 4,74
No. 0,454, No. 4,788,132, JP-A-62
It is preferable to include a mercapto compound described in No. 18539 and JP-A No. 1-283551.

[0143] The photosensitive material of the present invention is disclosed in JP-A-1-1060.
It is preferable to contain a compound described in No. 52 that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof regardless of the amount of developed silver produced by the development process.

[0144] The photosensitive material of the present invention is disclosed in International Publication WO88/
No. 04794, dyes dispersed by the method described in Japanese Patent Publication No. 1-502912 or EP No. 317,308A,
U.S. Patent No. 4,420,555, Japanese Patent Publication No. 1-25935
It is preferable to contain the dye described in No. 8.

[0145] Various color couplers can be used in the present invention, specific examples of which can be found in the aforementioned Research Disclosure No. 17643, VII-C to G, and the same No. No. 307105, VII-CG.

Examples of yellow couplers include US Pat. Nos. 3,933,501, 4,022,620, 4,326,024 and 4,401,752
No. 4,248,961, Special Publication No. 58-1073
9, British Patent No. 1,425,020, British Patent No. 1,47
Preferred are those described in US Pat. No. 6,760, US Pat. No. 3,973,968, US Pat. No. 4,314,023, US Pat.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and are described in US Pat. No. 4,310,619, US Pat. No. 3,061,
No. 432, No. 3,725,067, Research Disclosure No. 24220 (June 1984),
Japanese Patent Publication No. 60-33552, Research Disclosure No. 24230 (June 1984), Japanese Patent Application Publication No. 1986
-43659, 61-72238, 60-35
No. 730, No. 55-118034, No. 60-1859
No. 51, U.S. Patent No. 4,500,630, U.S. Patent No. 4,5
Particularly preferred are those described in No. 40,654, No. 4,556,630, International Publication No. WO88/04795, and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2
, No. 369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308 ,
4,334,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 1
No. 21,365A, No. 249,453A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,333,999,
Same No. 4,775,616, Same No. 4,451,559, Same No. 4,427,767, Same No. 4,690,889
No. 4,254,212, No. 4,296,19
No. 9, JP-A No. 61-42658, etc. are preferred.

Typical examples of polymerized dye-forming couplers are US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
No. 09,320, British Patent No. 4,576,910, British Patent No. 2,102,137, European Patent No. 341,188A, etc.

[0150] Couplers whose coloring dyes have appropriate diffusivity include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570,
Preference is given to those described in German Patent No. 3,234,533.

[0151] Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No.
．． Section VII-G of 17643, No. 307105
Section VII-G of U.S. Pat. No. 4,163,670;
Special Publication No. 57-39413, U.S. Patent No. 4,004,9
No. 29, No. 4,138,258, British Patent No. 1,1
46,368 is preferred. In addition, couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in U.S. Pat. No. 4,774,181 and reacting with developing agents as described in U.S. Pat. No. 4,777,120 are also available. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds which release photographically useful residues upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the RD1 described above.
7643, Section VII-F and the same No. 307105,
Patent listed in Section VII-F, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, No. 63-37350,
U.S. Patent No. 4,248,962, U.S. Patent No. 4,782,012
Preferably, those listed in No.

[0153] As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,097
, No. 140, No. 2,131,188, JP-A-59-
Those described in No. 157638 and No. 59-170840 are preferred. Also, JP-A-60-107029, JP-A No. 60-107029,
No. 0-252340, JP-A No. 1-44940, JP-A No. 1-
Compounds that release fogging agents, development accelerators, silver halide solvents, etc. through redox reactions with oxidized forms of developing agents described in No. 45687 are also preferred.

Other compounds that can be used in the photosensitive material of the present invention include US Pat. No. 4,130,427.
Competitive coupler described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
Multi-equivalent coupler described in No. 618 etc., JP-A-60-18
DI described in No. 5950, JP-A No. 62-24252, etc.
R redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers that release dyes that recolor after separation as described in EP 173,302A and EP 313,308A. , R. D. No
．． 11449, 24241, JP-A-61-20124
Bleach accelerator releasing coupler described in US Pat. No. 7, etc., U.S. Pat.
, 555, 477, etc.;
Couplers that emit leuco dyes as described in JP-A-63-75747, couplers that emit fluorescent dyes as described in U.S. Pat. No. 4,774,181, and the like.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

[0157] Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, Decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-di-ethylpropyl) phthalate), phosphoric acid or esters of phosphonic acids (e.g. triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-
2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate), benzoic acid esters (e.g. 2-ethylhexyl benzoate, dodecyl benzoate,
-ethylhexyl-p-hydroxybenzoate), amides (e.g. N,N-diethyldodecanamide, N,
N-diethyl laurylamide, N-tetradecylpyrrolidone), alcohols or phenols (e.g. isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (e.g. bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (e.g. N,N-dibutyl-2-butoxy-5-
tert-octylaniline, etc.), hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

[0158] The steps, effects, and specific examples of latex for impregnation of latex dispersion methods are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230, etc.

The color light-sensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747 and JP-A-62-62.
272248 and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, described in JP-A-1-80941. It is preferable to add various preservatives or fungicides such as 2-(4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned RD. No. 17643, page 28, No.
18716, page 647 right column to page 648 left column, and the same No. 307105, page 879.

In the photosensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 1
The thickness is more preferably 8 μm or less, and particularly preferably 16 μm or less. Further, the membrane swelling rate T1/2 is preferably 30 seconds or less, and 2
More preferably, the time is 0 seconds or less. The film thickness is 25℃ relative humidity 55
%, which means the film thickness measured under humidity control (2 days), and the film swelling rate T1/2 can be measured according to a method known in the art. For example, A. Green (A.
Photographic Science and Engineering (Photogr.Sci) by Green) et al.
．． Eng. ), Vol. 19, No. 2, pp. 124-129.
90% of the maximum swollen film thickness reached when treated for 5 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The membrane swelling rate T1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned above, using the formula: (
It can be calculated according to the maximum swelling film thickness - film thickness)/film thickness.

In the photographic material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorbers, filter dyes, ultraviolet absorbers, static inhibitors, hardeners, binders, plasticizers, lubricants, coating aids, surfactants, and the like. The swelling rate of this back layer is 150
~500% is preferred.

[0165] The color photographic light-sensitive material according to the present invention has the above-mentioned RD. No. 17643, pages 28-29, same No.
．． 651 left column to right column of 18716, and the same No. 30
7105, pages 880-881.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a representative example thereof is 3-methyl-4-amino-N
, N-diethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It generally contains a development inhibitor or an antifoggant such as. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Various chelating agents such as acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene- 1,
1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine-di(o-
Typical examples include hydroxyphenylacetic acid) and salts thereof.

[0168] When reversal processing is performed, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

[0169] pH of these color developing solutions and black and white developing solutions
is generally from 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but is generally less than 3 liters per square meter of light-sensitive material, and can be reduced to less than 500 ml by reducing the bromide ion concentration in the replenisher. You can also. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

[0170] The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, aperture ratio={contact area between processing liquid and air (cm2)
}÷Capacity of processing liquid (cm3) The above aperture ratio is 0.1
It is preferably less than or equal to 0.001, more preferably 0.001
~0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, methods using a movable lid described in JP-A No. 1-82033, The slit development processing method described in No. 63-216050 can be mentioned. It is preferable to reduce the aperture ratio not only in both color development and black-and-white development steps, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

[0172] The time for color development processing is usually set between 2 to 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent. can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment in two continuous bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (III), such as amino acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts, including ethylenediaminetetraacetic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) complex salt, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the pH can be lowered to speed up the processing.

[0174] A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Compounds having a mercapto group or disulfide group as described in JP-A No. 17129 (July 1978); thiazolidine derivatives as described in JP-A-51-140129; JP-A No. 45-8506, JP-A-52-20832; 53-32735, U.S. Patent No. 3,706,56
Thiourea derivative described in No. 1; West German Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-40,943, 49-59,644, 53-
No. 94,927, No. 54-35,727, No. 55-2
Compounds described in No. 6,506 and No. 58-163,940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,858.
No., West German Patent No. 1,290,812, Japanese Unexamined Patent Publication No. 1983-9
The compounds described in No. 5,630 are preferred. Also preferred are the compounds described in US Pat. No. 4,552,884. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

[0175] In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleaching stains. Particularly preferred organic acids have an acid dissociation constant (
A compound having a pKa) of 2 to 5, specifically acetic acid, propionic acid, etc. are preferred.

[0176] Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. The most common, especially ammonium thiosulfate, is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

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

[0178] The total time of the desilvering process is preferably as short as possible without causing defective desilvering. The preferred time is 1 minute to 3 minutes.
minutes, more preferably 1 to 2 minutes. Further, the treatment temperature is 25°C to 50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and stain generation after treatment is effectively prevented.

[0179] In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening the stirring include a method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material as described in JP-A-62-183460, and a method of stirring using a rotating means as described in JP-A-62-183461. A method to improve the stirring effect, and a method to improve the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade installed in the solution to create turbulence on the emulsion surface, and circulation of the entire processing solution. One method is to increase the flow rate. Such stirring improvement means can be used for bleaching solution, bleach-fixing solution,
It is effective for any fixer. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improvement means described above are more effective when a bleach accelerator is used, and the amount of the accelerator can be significantly increased or the fixing inhibiting effect can be eliminated by the bleach accelerator.

[0180] The automatic developing machine used for the photosensitive material of the present invention is disclosed in JP-A-60-191257 and JP-A-60-19125.
It is preferable to have a photosensitive material conveying means described in No. 8 and No. 60-191259. The above-mentioned JP-A-60-1
As described in No. 91257, such a conveyance means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing performance deterioration of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society.
Ty of Motion Picture
andTelevision Engineers Vol. 64, P. 248-253 (May 1955 issue).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of water used for washing can be significantly reduced, the increased residence time of water in the tank causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. In processing the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. In addition, JP-A-57
-8,542, chlorine-based disinfectants such as isothiazolone compounds and cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal agents" (1986) "Sterilization, sterilization, and anti-mildew technology of microorganisms" edited by Sankyo Publishing, Hygiene Technology Society (1982)
It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by the Society of Industrial Science and Technology and the Japan Society of Antibacterial and Antifungal Agents.

[0183] The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally, it is carried out at 15 to 45°C for 20 seconds to 10 minutes.
Preferably, the temperature range is 30 seconds to 5 minutes at 25 to 40°C. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Laid-Open Nos. 57-8543 and 58
All known methods described in Japanese Patent No. 14834 and No. 60-220345 can be used.

[0184]Furthermore, following the water washing treatment, a further stabilization treatment may be carried out, for example, a stabilization treatment containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. You can mention bathing. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

[0186] The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the desilvering process.

[0187] When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No.
Indoaniline compounds described in No. 342,597, Research Disclosure No. 3,342,599; 14,850 and the same No. Examples include Schiff base type compounds described in No. 15,159, aldol compounds described in No. 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. be able to.

The silver halide color photosensitive material of the present invention is
If necessary, various types of 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
No. 4547 and No. 58-115438.

[0190] Various processing solutions in the present invention can be used at temperatures ranging from 10°C to 50°C.
Used at ℃. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to.

[0191] The silver halide photosensitive material of the present invention is also disclosed in US Pat.
No. 49, No. 59-218443, No. 61-23805
The present invention can also be applied to heat-developable photosensitive materials such as those described in European Patent No. 6 and European Patent No. 210,660A2.

[0192]

[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is of course not limited to these Examples. Example 1 (1) Preparation of emulsion An aqueous solution prepared by dissolving 6 g of potassium bromide and 30 g of inert gelatin with an average molecular weight of 15,000 in 3.7 liters of distilled water was mixed with good stirring and mixed with a 14% emulsion by the double jet method.
of potassium bromide and a 20% silver nitrate aqueous solution were added at a constant flow rate over 1 minute at 55° C. and pBr 1.0 (this addition consumed 2.4% of the total silver amount).

After adding an aqueous gelatin solution (17%, 300 cc) and stirring at 55°C, a 20% aqueous silver nitrate solution was added at a constant flow rate until the pBr reached 1.4 (this addition increased the total silver amount by 5.5 cc). (consumed 0%). In addition, 20
% potassium iodobromide solution (KBr1-x Ix :x
=0.04) and a 33% aqueous silver nitrate solution were added by double jet method over a period of 43 minutes (this addition consumed 50% of the total silver amount). Here, after adding an aqueous solution containing 8.3 g of potassium iodide, 0.001/wt%
Add 14.5 ml of K3 IrCl6 aqueous solution to 20
% potassium bromide solution and a 33% aqueous silver nitrate solution were added by double wet method over 39 minutes (this addition consumed 42.6% of the total silver amount). The amount of silver nitrate used in this emulsion was 425 g. Then, after desalting by the usual flocculation method, the pAg was 8.2 at 40°C.
The pH was adjusted to 5.8. A tabular silver iodobromide emulsion (Em-1) having an average aspect ratio of 6.5, a coefficient of variation of 18%, and an equivalent sphere diameter of 0.8 μm was prepared. Observation using a 200 kV transmission electron microscope at a liquid N2 temperature revealed that an average of 50 or more dislocation lines per grain were present near the outer periphery of the tabular grains. In contrast, emulsion Em-1 was used except that grain formation was carried out by adding 1.2 x 10-5 mol of thiourea dioxide per mol of silver into the reaction pot after pBr reached 1.4.
Emulsion Em-2 was prepared in exactly the same manner as above. Further, emulsion Em-3 was prepared in exactly the same manner as emulsion Em-2 except that thiourea dioxide was replaced with L-ascorbic acid 2.5 x 10 -3 mol/mol Ag.

When forming grains in the same manner as emulsion Em-2, compound II-2 was added to silver 10 minutes after starting the final shell formation.
Emulsion Em-4 was prepared in exactly the same manner as emulsion Em-2 except that 1.2 x 10 -4 mol was added per mol.

Emulsions Em-1 to Em-4 thus prepared
The sensitizing dye A shown in Table 2 was added to 4 x 10-4 mol/mol Ag.
, after adding 2 x 10-5 mol/mol Ag of sensitizing dye B and 6 x 10-4 mol/mol Ag of sensitizing dye C, sodium thiosulfate, chloroauric acid, and N,N-dimethylselenourea were added. Emulsions 101 to 104 were prepared by optimal gold-selenium-sulfur sensitization using potassium thiocyanate.

[0196]

[Table 2] In addition, sensitizing dye A was added to emulsions Em-1 to Em-4 as I-8.
Emulsion 101 except that sensitizing dye C was changed to I-14.
Emulsions 105 to 108 were prepared in the same manner as Emulsions 105 to 104.

An emulsion layer and a protective layer were coated on a triacetyl cellulose support provided with an undercoat layer in the coating amounts shown in Table 3, and Sample 10 was prepared using emulsions 101 to 108.
01 to 1008 were produced.

[0198]

[Table 3] Pressure characteristics were evaluated as follows. relative humidity 4
Under conditions of 0% humidity control, the coated sample was fixed at one end with the emulsion side facing inside, and bent along a stainless steel pipe with a diameter of 10 mm while rotating 180 degrees at a bending speed of 360 degrees/second. These folds were made 10 seconds before exposure.

These samples were subjected to 1/100 second sensitometric exposure through a continuous wedge at a color temperature of 4800°K, and then subjected to the following color development process.

[0200] The development process used here was 38% under the following conditions.
It was carried out at ℃.

[0201]
Processing method Process
Processing time Processing temperature Refill amount
Tank capacity Color development 2 minutes 45
seconds 38℃ 33ml
20L bleach 6 minutes 30
seconds 38℃ 25ml
40L water wash 2 minutes 10
seconds 24℃ 1200ml 2
0L fixation 4 minutes 20 seconds
38℃ 25ml 3
0L water washing (1) 1 minute 05 seconds
24 ℃ (2) to (1) 10L

Countercurrent piping system
Washing with water (2) 1 minute 00 seconds 24 ℃
1200ml 10L Stable (
3) 1 minute 05 seconds 38 ℃ 2
5ml 10L dry
4 minutes 20 seconds 55℃ Replenishment amount is 35m
Next, the composition of the treatment liquid per m width and 1 m length is described. (color developer)
Mother liquor (g)
Replenisher (g) Diethylenetriaminepentaacetic acid 1.0
1.1 1-Hydroxyethylidene-
3.0
3.2 1,1-Diphosphonic acid Sodium sulfite
4.0 4
．． 4 Potassium carbonate
30.0
37.0 Potassium Bromide
1.4
0.7 Potassium iodide
1.5mg
- Hydroxylamine sulfate 2.4
2.8 4-[N-ethyl-N
-β- 4.5
5.5 Hydroxyethylamino]-2-methylaniline sulfate
add salt and water
1.0L
1.0L pH
1
0.05 10.10 (bleaching solution)
Mother liquor (g)
Replenisher (g) Ethylenediaminetetraacetic acid 2 100.0 1
20.0 Sodium iron trihydrate Ethylenediaminetetraacetic acid dibasic acid
10.0 11.0
Thorium salt Ammonium bromide
140.0 160.0
ammonium nitrate
30.0 35
．． 0 Ammonia water (27%)
6.5ml
Add 4.0ml water
1.0L
1.0L pH

6.0 5.7 (Fixer)
Mother liquor (g)
Replenisher (g) Ethylenediaminetetraacetic acid
0.5
0.7 Sodium salt Sodium sulfite
7.0 8
．． 0 Sodium bisulfite
5.0
5.5 Ammonium thiosulfate aqueous solution
170.0ml 200.0ml
(70%) Add water
1.0L
1.0L pH

6.7 6.6 (stabilizer)
Mother liquor (g)
Replenisher (g) Formalin (37%)
2.0ml
3.0ml polyoxyethylene
p-mo 0.3
0.45 Nononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid dina
0.05 0.08
Add thorium salt and water
1.0L
1.0L pH
5.8
-8.0 5.8-8.0 The concentration of the treatment agent sample was measured using a green filter.

The resulting sensitivity and fog were evaluated for the portions with and without bending. The sensitivity was expressed as the relative value of the reciprocal of the exposure amount required for the optical density to become higher than the fog by 0.2.

Table 4 shows the results thus obtained.

[0204]

[Table 4] As is clear from Table 4, samples 1006 to 100 of the present invention
Sample No. 8 has a higher sensitivity than the comparative samples, and compared with the comparative samples Nos. 1002 to 1004 which were subjected to reduction sensitization, the fogging and change in sensitivity with respect to pressure are small, and the effect of the present invention is remarkable.

[0205] Sample 100 using thiosulfonic acid
8, the effect is particularly remarkable.

Example 2 Sensitizing dyes in emulsions 101 to 104 of Example 1 are shown in Table 5.
Sensitizing dye D5×10−4 mol/mol Ag, E2× shown in
10-4 mol/mol Ag, F2 x 10-4 mol/mol A
Emulsions 201 to 204 were prepared in the same manner except that the emulsions were changed to g.

In emulsions 105 to 106 of Example 1, the sensitizing dyes were I-5, 5 x 10-4 mol/mol Ag, and I-7.
, 2 x 10-4 mol/mol Ag, I-9, 2 x 10-4
Emulsion 205 was prepared in the same manner except that the ratio was changed to mol/mol Ag.
~208 was created.

[0208]

[Table 5] Samples 2001 to 2008 were prepared by coating emulsions 201 to 208 in the same manner as in Example 1, and the results of the same evaluation as in Example 1 are shown in Table 6.

[0209]

[Table 6] As is clear from Table 6, samples 2006 to 200 of the present invention
Sample No. 8 has a higher sensitivity than the comparative sample, and compared to the comparative samples 2002 to 2004 which were subjected to reduction sensitization, the fogging and change in sensitivity with respect to pressure are small, and the effect of the present invention is remarkable. Moreover, the effect is particularly remarkable in sample 2008 using thiosulfonic acid. Example 3 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below. (Photosensitive layer composition)
The numbers corresponding to each component indicate the coating weight in g/m2, and for silver halide, the coating weight in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer. (Sample 10
1) 1st layer (antihalation layer) black colloidal silver
silver 0.09
0 Dispersion A of organic solid disperse dye
10.0 Dispersion B of organic solid disperse dye
5.0 Gelatin

1.4 Second layer (middle layer) 2,5-di-t-pentadecyl hydroquinone
0.18Ex
M-1
0.070
ExC-1
0.0
20 ExS-1
0
．． 0020 ExU-1

0.060 ExU-2

0.080 ExU-3

0.10 HBS-1

0.10HB
S-2
0.020
gelatin
1.
03rd layer (donor layer for multilayer effect on red-sensitive layer)
Emulsion J
silver 1.2
Emulsion K
Silver
2.0 ExS-2

4.0×10-4 ExC-2

0.10 ExM-2

0.10 HBS-1

0.10 HBS-
2
0.10 Gelatin
0.80 4th layer (middle layer) ExO-1
0
．． 040 HBS-1

0.020 Gelatin

0.80 5th layer (first red-sensitive emulsion layer) Emulsion A
Silver
0.25 Emulsion B
Silver 0.25 ExS-3

1.5×10-4 ExS-4

1.8×10-5 ExS
-5
2.5×10-4
ExC-2
0.0
20 ExC-3

0.17 ExC-4

0.17 ExC-5

0.020 ExM-3

0.020 ExU-1

0.070E
xU-2
0.050
ExU-3
0.
070 HBS-1

0.060 Gelatin

0.87 6th layer (second red-sensitive emulsion layer) Emulsion D
Silver
1.60 ExS-3

1.0×10-4 ExS-4

1.4×10-5 ExS-5

2.0×10-4 Ex
C-1
0.010
ExC-2
0.0
10 ExC-3

0.050 ExC-4

0.050 ExC-6

0.080 Gelatin

0.70 7th layer (3rd red-sensitive emulsion layer) Emulsions 101 to 108
silver 1.0
ExC-1
0.05
0 ExC-2

0.015 ExC-3

0.20 ExC-4

0.20 ExC-7

0.20 ExC-8

0.020 ExU
-1
0.070
ExU-2
0.05
0 ExU-3

0.070 HBS-1

0.22 HBS-2

0.10 Gelatin

1.6 8th layer (middle layer) ExO-1
0
．． 040 ExM-4

0.050 HBS-1

0.020 Gelatin

0.8 9th layer (first green-sensitive emulsion layer) Emulsion A
Silver
0.15 Emulsion B
Silver 0.15 Emulsion C

Silver 0.10 ExS-2

5.0×10-5 ExS-
6
3.0×10-5
ExS-7
1.0×10
-4 ExS-8
3
．． 8×10-4 ExM-1

0.021 ExM-3

0.030 ExM-5

0.20 ExM
-6
0.0050
ExM-7
0.10
HBS-1
0.
10 HBS-3

0.010 Gelatin

0.63 10th layer (middle layer) ExM-4
0
．． 018 ExC-8

0.040 HBS-1

0.16 HBS-3

0.0080 Gelatin

0.50 11th layer (2nd
green emulsion layer)
Emulsions 201-208
silver 1.2
ExS-8
3.0
×10-4 ExM-3

0.025 ExM-8

0.015 ExM-9

0.50 ExY-1

0.020H
BS-1
0.25
HBS-2
0.1
0 gelatin

1.5 12th layer (yellow filter layer) Yellow colloidal silver
silver 0.05
0 Dispersion B of organic solid disperse dye
15.0Ex
O-1
0.080
HBS-1
0.0
30 Gelatin

0.95 13th layer (first blue-sensitive emulsion layer) Emulsion A
Silver
0.080 Emulsion B

Silver 0.070 Emulsion F

Silver 0.070 ExS-9

3.5×10-4 E
xC-3
0.042
ExY-2
0.
72 ExY-3

0.020 HBS-1

0.28 Gelatin

1.1 14th layer (second blue-sensitive emulsion layer) Emulsion G
Silver
0.45 ExS-9

2.1×10-4 ExY-2

0.15 ExC-2

0.0070 HBS-1

0.050 Gelatin
0.78 1st
5 layers (3rd blue-sensitive emulsion layer) Emulsion H
Silver
0.77 ExS-9

2.2×10-4 ExY-1

0.010 ExY-2

0.60 ExY-3

0.010H
BS-1
0.070
gelatin
0
．． 69 16th layer (protective layer) Emulsion I
Silver
0.20 ExU-4

0.11 ExU-5

0.17 HBS-1

0.050 Dispersion A of organic solid disperse dye
0.50 Dispersion B of organic solid disperse dye
0.50 W-1

0.020 H-1

0.40 B-1 (diameter approx. 1.5 μm)
0.10 B-2 (diameter approx. 1
．． 5μm)
0.10 B-3

0.020 S-1

0.20 Gelatin
1.8 The samples thus prepared contained, in addition to the above, 1,2-benzisothiazolin-3-one (an average of 200 ppp based on gelatin).
m), n-butyl-p-hydroxybenzoate (approximately 1,000 ppm), and 2-phenoxyethanol (approximately 10,000 ppm) were added. Furthermore, W
-2, W-3, B-4, B-5, F-1, F-2, F-
3, F-4, F-5, F-6, F-7, F-8, F-9
, F-10, F-11, F-12, F-13 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts. Preparation of dispersion A of organic solid disperse dye ExF-1 was dispersed by the following method. That is, 21.7 meters of water
1 and 3 ml of a 5% aqueous solution of sodium P-octylphenoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of P-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 ml pot mill, and dye ExF-1 was added. and 500ml of zirconium oxide beads (diameter 1mm) to dilute the contents.
Spread out time. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion.

After dispersion, the contents were taken out and added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain gelatin dispersion A of dye. Preparation of Dispersion B of Organic Fixed Disperse Dye ExF-2 was replaced with ExF-1 in Dispersion A above. The following was produced in the same manner as dispersion A.

The contents of the emulsions used are shown in Table 7, and the structural formulas of the compounds are shown in Chemical Formulas 21 to 36.

[0212]

[Table 7]

[0213]

[C21]

[0214]

[C22]

[0215]

[C23]

[0216]

[C24]

[0217]

[C25]

[0218]

[C26]

[0219]

[C27]

[0220]

[C28]

[0221]

[C29]

[0222]

[C30]

[0223]

[Chemical formula 31]

[0224]

[Chem.32]

[0225]

[Chemical formula 33]

[0226]

[C34]

[0227]

[C35]

[0228]

Samples 3001 to 3008 were prepared using emulsions 101 to 108 prepared in Example 1 in the 7th layer and emulsions 201 to 208 prepared in Example 2 in the 11th layer. It was bent, exposed and processed. However, the color development time of the treatment was changed to 3 minutes and 15 seconds.

Emulsions 106 to 108 and 206 of the present invention
As shown in Examples 1 and 2, the samples using 1 to 208 had high sensitivity, and the fog and sensitivity change with respect to pressure were small.

[0230] The same sample was heated at 50°C and relative humidity 30% and 60%.
The film was stored at 80% and 80% for one month, exposed and processed in the same manner, and changes in fog density were measured. The results obtained are shown in Table 8.

[0231]

[Table 8] It is clear that samples 3006 to 3008 using emulsions 106 to 108 and 206 to 208 of the present invention not only have high sensitivity and excellent pressure resistance, but also have very little change in fog density at high temperatures. became.

[0232]

According to the present invention, a silver halide photographic material having excellent pressure resistance, high image quality, and high sensitivity can be obtained. Furthermore, it is stable against changes in performance over time.

Claims (3)

[Claims] [Claim 1] A photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the emulsion layers has a spectral sensitization represented by the general formula (I) shown in Chemical formula 1 below. 1. A silver halide photographic light-sensitive material, characterized in that the silver halide grains in the emulsion layer have been subjected to reduction sensitization. embedded image In the formula, R1 and R2 represent an alkyl group, and at least one of the alkyl groups has at least 1
carbon atoms are bonded to at least three atoms that are not hydrogen atoms, Z1 and Z2 represent the atomic group necessary to form a 5- to 6-membered nitrogen-containing heterocycle, X represents an anion, and p represents a value from 0 to 1 necessary to balance the charge, L1 and L2 represent a methine group or a substituted methine group, and L represents 0, 1 or 2. 2. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the emulsion layers contains a spectral sensitizer represented by general formula (I); The silver halide grains in the emulsion layer have been subjected to reduction sensitization, and have the following general formulas (II) and (III).
A silver halide photographic material containing at least one compound selected from the compounds represented by (IV) and (IV). General formula (II) R-SO2 SM General formula (III) R-SO2 S-R3 General formula (IV) R-SO2 S-Lm -SSO
2 -R4 In the formula, R, R3, and R4 may be the same or different,
represents an aliphatic group, an aromatic group, or a heterocyclic group, M represents a cation, L represents a divalent linking group, m is 0
or 1. The compounds of general formulas (II) to (IV) may be polymers containing divalent groups derived from the structures represented by (II) to (IV) as repeating units. 3. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers containing a spectral sensitizer represented by general formula (I); The silver halide grains in the emulsion layer have been subjected to reduction sensitization, and have the following general formulas (II) and (III).
or (IV), and at least 60% of the total projected area of the silver halide grains contains one dislocation line within one grain.
A silver halide photographic light-sensitive material comprising tabular silver halide grains having an aspect ratio of 3 or more and having 0 or more grains. General formula (II) R-SO2 SM General formula (III) R-SO2 S-R3 General formula (IV) R-SO2 S-Lm -SSO
2 -R4 In the formula, R, R3, and R4 may be the same or different,
represents an aliphatic group, an aromatic group, or a heterocyclic group, M represents a cation, L represents a divalent linking group, m is 0
or 1. The compounds of general formulas (II) to (IV) may be polymers containing divalent groups derived from the structures represented by (II) to (IV) as repeating units.