JPH04362930A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase picture qualities and sensitivity and to improve pressure resistance by incorporating a specified compd. and plate type silver halide particles having <8 average aspect ratio into at least one emulsion layer. CONSTITUTION:At least one layer of emulsion layers contains a compd. expressed by formula 1 and plate type silver halide particles having <8 average aspect ratio. In formula, R<1> and R<2> are alkyl groups, and in at least one alkyl group of the two, one carbon couples with three atoms except for hydrogen. Z<1> and Z<2> are groups of atoms necessary to form 5- or 6-member nitrogen-contg. heterocycles, L<1> and L<2> are substd. or unsubstd. methine groups, and X is an anion, I is 0, 1 or 2, and P is an integer necessary to equilibrate the charge. Moreover, plate type silver halide particles have dislocation lines.

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 tabular grains and having excellent sensitivity, graininess, sharpness, and 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 is folded or pulled for frame advance when it is rolled into a cartridge or loaded into a camera.

On the other hand, sheet-like films such as photosensitive materials for printing and x-ray photosensitive materials for direct medical use are frequently folded or bent because they are handled directly by humans.

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

As described above, when various pressures are applied to a photographic light-sensitive material, pressure is applied to the silver halide grains using gelatin, which is a holder (binder) for the silver halide grains, or a plastic film, which is a support, as a medium. It is known that the photographic properties of photographic materials change when pressure is applied to silver halide grains. B. Mat
her, J. Opt. Soc. Am. ,38.1054
(1948), P. Faelens and P.
de Smet. Sci. et IndPhoto.
, 25. No. 5.178 (1954). P. Fael
ens. J. Photo. Sci. 2.105 (1954
) is reported in detail.

[0006] In recent years, demands on silver halide granules for photography have become increasingly strict. Therefore, even higher standards are being demanded. However, it is obvious that pressure fog increases as sensitivity increases, and an emulsion with high sensitivity and low pressure fog is desired. JP-A-63-220
No. 228 discloses tabular grains with improved exposure illuminance dependence, storage stability, and pressure resistance, but the improvement in pressure fog caused by scratching in a camera or scratching with a fingernail was not sufficient.

The inventors' research has revealed that by adsorbing a sensitizing dye onto silver halide grains, fog that occurs when pressure is applied to a light-sensitive material increases. This phenomenon was particularly noticeable in tabular grains with a large specific surface area (ratio of surface area to volume). 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), the sensitizing dye is sometimes adsorbed at high temperatures (50°C or higher).
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.

On the other hand, a method of using tabular grains is known as a means of improving sharpness, but tabular grains with a high aspect ratio cause a lot of reflection within their own layers, impairing the sharpness of their own layers. This has become clear in recent research.

Furthermore, by increasing the amount of iodine in silver halide grains, it is possible to suppress the spread of dye clouds during development and improve graininess, but in the presence of sensitizing dyes, pressure resistance is impaired. There is.

0010

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material with improved sharpness and graininess, high image quality, and high sensitivity.

Another object of the present invention is to provide a silver halide photographic material having excellent pressure resistance.

0012

[Means for Solving the Problems] The object of the present invention is to provide 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 the following formula 2. This is achieved by a silver halide photographic material containing a compound of general formula (I) shown below and tabular silver halide grains having an average aspect ratio of less than 8.

[0013]

[Formula 2] The abbreviations in the formula represent the following, respectively: R1, R2: Alkyl group, provided that at least one carbon in at least one of the alkyl groups is bonded to at least three atoms other than hydrogen. are doing. Z1, Z2: Atom group necessary to form a 5- to 6-membered nitrogen-containing heterocycle L1, L2: Substituted or unsubstituted methine group X: Anion l: 0, 1, or 2 p: For balancing charges The details of the present invention will be explained below the necessary integers.

The silver halide photographic light-sensitive material of the present invention contains, in the emulsion layer, a compound represented by formula (I) shown below as a spectral sensitizer.

[0015]

embedded image In the general formula (I), R1 and R2 are alkyl groups. Examples of the alkyl group represented by R1 and R2 include alkyl groups having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Specifically, unsubstituted alkyl groups (e.g. methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups such as aralkyl groups (e.g. benzyl, 2-phenylethyl), hydroxyalkyl groups (e.g. 2-hydroxyethyl, 3 -hydroxypropyl), carboxyalkyl groups (e.g. 2-carboxyethyl, 3-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-yl)ethyl, tetrahydrofurfuryl), 2
-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl, and allyl group.

In at least one, preferably both, of the alkyl groups of R1 and R2, at least one carbon atom is bonded to at least three atoms that are not hydrogen atoms. Further, at least one of R1 and R2 is an alkyl group having an organic acid, and is represented by the general formula (II) shown in Chemical Formula 4 below.

[0017]

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

The alkyl group R1 and/or R2 in which at least one carbon atom is bonded to at least three atoms other than hydrogen atoms include 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-4,4-dimethylpentyl, 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, 1-methyl-3-sulfopropyl, 3-sulfobutyl, 3- Examples include methyl-4-sulfobutyl, 1-methyl-3-sulfobutyl, 1,1-dimethyl-3-sulfopropyl, 2-methyl-2-sulfopropyl, and 2-methyl-3-sulfopropyl. In particular, general formula (II), m
=2,3, n=0,1, A=sulfo group is preferable, and m=2, n=0 is more preferable.

Examples of the organic acid group A in the general formula (II) include a carboxy group, a sulfo group, and a phosphoryl group.

[0020] 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-disulfonate)
, perchlorate, and alkyl carboxylates (acetates, propionates).

[0021] The above p represents a value between 0 and 1 necessary to balance the charges, and is 0 when a salt is formed within the molecule.

5 formed by Z1 and Z2
Examples of the to 6-membered heterocycle include thiazole nuclei (e.g., thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nuclei (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[2,1-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 core (e.g. thiazoline, 4-
methylthiazoline, 4-nitrothiazoline), oxazole nuclei (e.g., oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzo Oxazole nucleus (benzoxazole, 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]
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-aryl-imidazole, 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, provided that the alkyl group in the imidazole nucleus is preferably one having 1 to 8 carbon atoms, such as unsubstituted methyl, ethyl, propyl, isopropyl, butyl. Alkyl groups and hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl) are preferred. Particularly preferred are methyl and ethyl. Further, the aryl group in the imidazole nucleus is, for example, phenyl, halogen (e.g., chloro) substituted phenyl, alkyl (e.g., methyl) substituted phenyl, alkoxy (e.g., methoxy)
It is substituted phenyl. }, 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-quinoli, 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-d]quinoxaline core (e.g. 1,3-diethylimidazo[4,5-b ] quinoxaline, 6-chloro-1,3-diallylimidazo[4,5-b]quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus.

Among the substituted or unsubstituted methine groups represented by L1 or L2, the substituted methine groups include:
Examples include methine groups substituted with lower alkyl groups such as methyl and ethyl, phenyl, substituted phenyl, methoxy, and ethoxy. l is 0, 1 or 2.

Specific examples I-1 to I-19 of the compound of general formula (I) used in the present invention are shown in Chemical formulas 7 to 11 below.

Tabular silver halide grains in the present invention (
Tabular grains (hereinafter referred to as tabular grains) are a general term for grains having one twin plane or two or more parallel twin planes. In this case, the twin plane refers to the (111) plane when ions at all lattice points are in a mirror image relationship on the (111) plane side. These tabular grains have a triangular shape, a hexagonal shape, or a rounded circular shape when viewed from above. Triangular grains have a triangular shape, and hexagonal grains have a hexagonal shape. The shape has circular, mutually parallel outer surfaces.

In the present invention, the average aspect ratio of the tabular grains is preferably 2 or more. More preferably, the number is 3 or more, and more preferably 4 or more, which is more effective for the present invention. The upper limit is preferably less than 8. The average aspect ratio of tabular grains in the present invention is the average value obtained by dividing the grain diameter by the thickness of each tabular grain having a grain diameter with a circular equivalent diameter of 0.1 μm or more. be. 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. Incidentally, the projected area of the particles is obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

In the present invention, the diameter of the tabular grains is 0.
．． It is preferable that it is 15-5.0 micrometers. The thickness of the tabular grains is preferably 0.05 to 1.0 μm.

In the present invention, the size distribution of the tabular grains may be polydisperse, but is preferably monodisperse (with a coefficient of variation defined by the following formula of 25% or less).

Coefficient of variation=standard deviation of grain size/average grain size×100 In the present invention, the proportion of tabular grains in the emulsion is preferably 30% of the total projected area of all silver halide grains in the emulsion. or more, preferably 50
%, particularly preferably 80% or more.

The tabular grains used in the present invention are silver iodobromide and silver iodochlorobromide containing 3 mol % or more, preferably 5 mol % or more and 30 mol % or less of iodine.

The tabular grains may have a layered structure of at least two layers having substantially different iodide compositions or chlorine compositions within the silver halide grains, or may have a uniform composition. For example, in an emulsion with a layered structure with different iodine compositions, an emulsion containing a high iodine layer in the core and a low iodine layer in the outermost layer may be different from an emulsion containing a low iodine layer in the core and a high iodine layer in the outermost layer. You can. Furthermore, the layered structure may consist of three or more layers.

The tabular grains in the present invention can be prepared by the following precipitation method. That is, the dispersion medium is placed in a commonly used reactor for producing silver halide precipitation, which is equipped with a stirring mechanism. Typically, the amount of dispersion medium introduced into the reactor in the first stage is at least about 10%, preferably 20%, of the amount of dispersion medium present in the emulsion during the final grain precipitation stage.
~80%. The dispersion medium initially introduced into the reactor is water or a dispersion medium of a peptizer in water, and this dispersion medium may optionally contain other components such as one or more halogens. A silver oxide ripening agent and/or a metal dopant, which will be described later, are blended. A peptizer may also be initially present in the reaction solution, in which case the concentration may be at least 10%, in particular at least 20%, of the total amount of peptizer present in the final stage of silver halide precipitate formation. preferable. Additional dispersion medium is added into the reactor along with the silver and halide salt, which can be introduced from a separate jet. Generally, the proportion of dispersion medium is adjusted after the halide salt introduction is completed, especially to increase the proportion of peptizer.

Additionally, usually less than 10% by weight of the bromide salt used to form silver halide grains is initially present in the reactor to control the bromide ion concentration in the dispersion medium at the beginning of silver halide precipitation formation. do. Here, the dispersion medium in the reactor initially does not substantially contain iodide ions. This is because thick non-tabular grains are likely to be formed if iodide ions are present before silver, bromide salt, and chloride salt are added simultaneously. Here, "substantially free of iodide ions" means that iodide ions are contained in a separate silver iodide phase (β-
AgI or γ-AgI), meaning that it is present in insufficient amounts to precipitate. The iodine concentration in the reactor prior to introducing the silver salt is desirably maintained at less than 0.5 mole percent of the total halide ion concentration in the reactor. If the pBr of the dispersion medium is initially too high, the tabular grains produced will be relatively thick and the thickness distribution of the grains will be wide. Also, non-tabular grains increase. On the other hand, p
If Br is too low, non-tabular grains are likely to be produced. Here, pBr is defined as the negative value of the logarithm of the bromide ion concentration.

During precipitation, silver, bromide, chloride and iodide salts are added to the reactor according to techniques well known for precipitation of silver halide grains. Typically, an aqueous solution of a soluble silver salt, such as silver nitrate, is introduced into the reactor at the same time as the bromide, chloride, and iodo salts are introduced. Bromide, chloride and iodo salts are also introduced as aqueous salt solutions, such as aqueous solutions of soluble ammonium, alkali metal (eg, sodium or potassium) or alkaline earth metal (eg, magnesium, or calcium) halide salts. The silver salt, at least initially, is introduced into the reactor separately from the bromide, chloride, and iodo salts. The bromide salt, chloride salt and iodo salt may be added separately or introduced as a mixture.

The introduction of the silver salt into the reactor initiates the particle nucleation step. Continued introduction of silver, bromide, chloride, and iodo salts forms a population of grain nuclei that serve as precipitation sites for bromide, silver chloride, and silver iodide. The grains enter the growth stage by precipitation of silver bromide, silver chloride, and silver iodide onto the existing grain cores. Nucleation conditions can refer to the method described in JP-A-63-11928, but are not limited to this method; for example, the nucleation temperature may be in the range of 5 to 55°C. Can be done.

The size distribution of the tabular grains formed in the present invention is greatly influenced by the bromide salt, chloride salt and iodo salt concentrations during the growth stage. That is, if pBr is too low, tabular grains with high aspect ratios are formed;
The coefficient of variation of the projected area becomes significantly large. By maintaining pBr between about 2.2 and 5, tabular grains with a small coefficient of variation in projected area can be formed.

Provided that the above pBr conditions are met, the concentrations and rates of introduction of silver, bromide, chloride and iodo salts may be similar to those conventionally used. 0 silver and halide salts per liter
．． It is desirable to introduce it in a concentration of 1 to 5 molar. However, a wider concentration range than conventionally used may be employed, for example from 0.01 mole per liter to saturation. A particularly preferred method of precipitation is to increase the rate of silver and halide salt introduction to shorten the precipitation time. The rate of introduction of silver and halide salts is
It can be increased by increasing the rate of introduction of the dispersion medium and silver and halide salts, or by increasing the concentration of silver and halide salts in the dispersion medium introduced. By maintaining the addition rate of silver and halide salts near the limit value at which new particle nuclei are generated, as described in JP-A-55-142329, the coefficient of variation in the projected area of the particles can be further reduced. .

The amount of gelatin in the reactor at the time of nucleation significantly influences the particle size distribution. The gelatin concentration is preferably 0.5 to 10 wt%, more preferably 0.5 to 6 wt%.

[0040] In addition, the stirring rotation speed and the shape of the reactor also affect the particle size distribution formed.

In the present invention, the stirring and mixing device used for forming tabular grains is disclosed in US Pat. No. 378,577.
An apparatus that adds and mixes the reaction liquid into the liquid as described in No. 7 is preferable, and the set stirring rotation speed should not be too low or too high. If the stirring rotation speed is low, the generation rate of non-parallel twin grains will increase, and if it is too high, the frequency of generation of tabular grains will decrease and the size distribution will widen.

[0042] Furthermore, the shape of the reactor used to form the tabular grains is most preferably one in which the bottom is a semicircle.

The tabular silver halide grains in the present invention preferably have dislocation lines. Dislocations in tabular grains are described, for example, in J.F. Hamilton, Phot. Sc
i. Eng. , 11, 57, (1967) and T. Sh
iozawa, J. Soc. Photo. Sci. Jap
An, 35, 213, (1972), it can be directly observed using a low-temperature transmission electron microscope. That is, first, silver halide grains are taken out of the emulsion without applying any pressure that could cause dislocation. Next, the particles are placed on a mesh for electron microscopic observation, and observation is performed by a transmission method while the sample is cooled to prevent damage by electron beams (for example, printout). In this case, the thicker the particle, the more difficult it is for the electron beam to pass through it, so it is better to use a high-pressure electron microscope (200 kV or more for particles with a thickness of 0.25 μm) for clearer observation. It is.

In the present invention, the number of tabular grains having dislocation lines is preferably 50% or more, more preferably 70% or more of the total number of tabular grains.

[0045] Dislocation lines are, for example, in tabular grains,
It can be introduced near the outer periphery. In this case, the dislocations are approximately perpendicular to the outer periphery of the grain, and the dislocation lines are generated in a region 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 x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. Further, at this time, the shape of the region formed by connecting the positions where dislocations start is close to a figure similar to the particle shape, but it may not be a completely similar figure but a distorted figure. The dislocations that form this distorted shape are not found in the central region of the grain. Although the direction of the dislocation lines is about the (211) direction in crystallography, they often meander and sometimes intersect with each other.

Further, in the present invention, the tabular grains may have dislocation lines substantially uniformly over the entire outer periphery, or may have dislocation lines localized on the outer periphery. That is, taking a hexagonal tabular silver halide grain as an example, dislocation lines may exist only in the vicinity of six vertices, or dislocation lines may be localized only in the vicinity of one of the six vertices. Conversely, it is also possible for dislocation lines to exist only on each side of the hexagon except for the vicinity of the six vertices.

Further, the dislocation line may be formed over a region including the centers of two parallel main surfaces of the tabular grain. When dislocation lines are formed over the entire main surface, the direction of the dislocation lines is approximately (211) direction, (110) direction, or random direction when viewed from the direction perpendicular to the main surface. There are cases. Furthermore, the length of each dislocation line is also random, and may be observed as a short line on the main surface, or as a long line reaching the outer periphery of the main surface. Dislocation lines may be straight or meandering, and often intersect with each other.

[0048] In the tabular grains, the positions at which dislocations are introduced may be on the outer periphery of the grain, on the main surface, local positions, or a combination thereof, as described above. That is, dislocations may exist simultaneously on the outer periphery and on the main surface. - Dislocations in the tabular grains of the present invention can be controlled by providing a specific phase with a high silver iodide content inside the grains. Specifically, a substrate grain is prepared, an internal high iodine phase is provided on the grain by the method 1), 2) or 3) below, and the outside of this phase has a higher iodide content than the internal high iodine phase. By coating with a phase with a low index, it is possible to control dislocations within the grain.

The silver iodide content of the tabular grains serving as the substrate grains is lower than that of the internal high iodine phase, preferably from 0 to 0.
It is 12 mol%, more preferably 0 to 10 mol%.

The internal high iodine phase refers to a silver halide solid solution containing a relatively high content of silver iodide. In this case, the silver halide is preferably silver iodide, silver iodobromide, or silver chloroiodobromide emulsion, and silver iodide or silver iodobromide (silver iodide content 10 to 40 mol%) is more preferable. Silver iodide is particularly preferred.

It is important that this internal high iodine phase is not uniformly deposited on the plane of the tabular grain of the substrate, but rather exists locally. Such a localized location of the high iodine phase may be any location on the main surface, side surface, side, or corner of the tabular grain. Further, the internal high iodine phase may selectively epitaxially coordinate to the sites as described above.

[0052] Below, methods 1) to 3) of forming a high iodine phase will be described.
Explain.

1) For example, E. Klein, E. Moi
sar, G. Murch, Photo. Xorr. ,10
2(4), 59-63 (1966). This method includes, for example:
There is a method of adding halogen ions during grain formation so that the solubility of the salt providing silver ions is lower than that of the halogen ions forming the grains (or near the surface of the grains) at that point. In the present invention, the amount of halogen ions with low solubility to be added is a certain value (related to the halogen composition) with respect to the unit surface area of the particles at that time.
It is preferable that the amount is above. For example, during particle formation, with respect to the surface area of AgBr particles at that point,
It is preferable to add more than a certain amount of KI. Specifically, it is preferable to add 8.2×10 −5 mol/m 2 or more of KI.

2) For example, the epitaxial bonding method described in JP-A-59-133540, JP-A-58-108526, and JP-A-59-162540. In this method, a substance that locally controls epitaxial growth, such as a spectral sensitizing dye having adsorptive properties, can be used. An internal high iodine phase can be formed by adding these substances or by selecting grain growth conditions (e.g., pAg, pH, temperature) and adding a halide solution containing silver salts and iodine. .

3) Alternatively, an internal high iodine phase can be formed by adding fine silver iodide grains during tabular grain formation. The equivalent sphere diameter of the fine silver iodide grains used in this method is 0.3 μm or less, more preferably 0.1 μm or less.

In the present invention, the outer phase covering the high iodine phase has a silver iodide content lower than that of the high iodine phase, preferably 0 to 12 mol %, more preferably 0 to 1 mol %.
0 mol%, most preferably 0-3 mol%.

In the silver halide emulsion constituting the light-sensitive material of the present invention, for example, cadmium salt, zinc salt, thallium salt, iridium salt or a complex salt thereof, A rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be coexisting as a metal dopant.

The amount of the sensitizing dye used in the photographic material of the present invention is preferably 40% or more of the saturated adsorption amount, more preferably 40 to 120%, still more preferably 70% to 100%. be. The saturated adsorption amount of the sensitizing dye can be determined from the adsorption isotherm by centrifuging the dye-adsorbed emulsion.

The sensitizing dye may be added during the process of forming silver halide grains or during the chemical sensitization process, or may be added during coating.

In particular, as a method for adding a sensitizing dye during the formation of silver halide emulsion grains, US Pat.
No. 66, No. 4,828,972, JP-A-61-103
, No. 149 may be referred to. Furthermore, methods for adding sensitizing dyes in the desalting step of silver halide emulsions include European Patent No. 291,339-A,
No. 52,137 may be referred to. In addition, the method of adding a sensitizing dye in the chemical sensitization process was disclosed in Japanese Patent Application Laid-open No. 5
No. 9-48,756 may be referred to.

[0061] 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. No. 2,933,390,
No. 3,636,721), aromatic organic acid formaldehyde condensates (for example, US Pat. No. 3,743)
, 510), cadmium salts, azaindene compounds, and the like. U.S. Patent 3,615,6
No. 13, No. 3,615,641, No. 3,617,29
The combinations described in No. 5, No. 3,635,721 are particularly useful.

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, in the present invention, for example, activated gelatin or a sulfur-containing compound that can react with silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanine) is used in the silver halide emulsion. Sulfur sensitization method; reduction sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g. gold complex salts, Pt, Ir Chemical sensitization is carried out by a noble metal sensitization method using selenium compounds (e.g., selenium ureas, selenoketones, selenides), obtain.

In particular, in the present invention, the tabular silver halide grains are chemically sensitized with at least one of a selenium sensitizer, a gold sensitizer, and a sulfur sensitizer.

As the selenium sensitizer, selenium compounds disclosed in known publications can be used. That is,
An unstable selenium compound and/or a non-unstable selenium compound are added to the silver halide emulsion containing the tabular silver halide grains, and the mixture is stirred at a high temperature, preferably 40° C. or higher, for a certain period of time.

Examples of the unstable selenium compounds include those disclosed in Japanese Patent Publication No. 44-15748 and Japanese Patent Publication No. 43-1348.
No. 9, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-2293
Compounds described in No. 00 may be used. Specific examples of the unstable selenium compounds include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2 −
selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (e.g. bis(3-chloro-
(2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, and colloidal metal selenium.

However, in the present invention, the unstable selenium compound is not particularly limited to the above-mentioned compounds. Those skilled in the art understand that the structure of unstable selenium compounds as sensitizers for photographic emulsions is not important as long as the selenium is unstable; It is generally understood that it has no function other than allowing it to exist in the emulsion in an unstable form. In the present invention, various unstable selenium compounds can be used based on such a wide range of concepts.

[0068] Examples of the non-unstable selenium compounds include those disclosed in Japanese Patent Publication No. 46-4553 and Japanese Patent Publication No. 52-3.
Compounds described in Japanese Patent Publication No. 4492 and Japanese Patent Publication No. 52-34491 may be used. Specific examples of the non-labile selenium compounds include selenite, potassium selenocyanide, selenazole, quaternary salts of selenazole, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazole. Examples include lysinedione, 2-selenooxazolidinethione, and derivatives thereof.

Among the above selenium compounds, the compound represented by the general formula (III) shown in the following chemical formula (5) and the compound represented by the general formula (IV) shown in the chemical formula 6 are preferred.

[0070]

embedded image In the formula, Z3 and Z4 may be the same or different, and each represents an alkyl group (for example, methyl, ethyl,
t-butyl, adamantyl, t-octyl), alkenyl groups (e.g. vinyl, propenyl), aralkyl groups (
(e.g., benzyl, phenethyl), aryl groups (e.g., phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic groups (e.g., pyridyl, thienyl, furyl, imidazolyl), -NR3
(R4), -OR5 or -SR6.

[0071] The above R3, R4, R5, and R6
may be the same or different, and represent an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. Specific examples of these alkyl groups, aralkyl groups, aryl groups, and heterocyclic groups include the same groups as in the case of Z3 described above. In addition, the above R3, R4
is a hydrogen atom or an acyl group (e.g., acetyl, propanoyl, benzoyl, heptafluorobutanoyl,
difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl).

In the general formula (III), preferably,
Z3 is an alkyl group, an aryl group, or -NR3 (
R4 ), and Z4 represents -NR7 (R8 ). However, R3, R4, R7, and R8 may be the same or different, and each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.

The general formula (III) is more preferably N,N-dialkylselenourea, N,N,N'-trialkyl-N'-acylselenourea, tetraalkylselenourea N,N-dialkyl-aryl Selenoamide, N-alkyl-N-aryl-arylselenoamide.

[0074]

embedded image In the formula, Z5, Z6, and Z7 may be the same or different, and each represents an aliphatic group, an aromatic group, a heterocyclic group, -OR9, -OR10 (R11), -SR12
, -SeR13,X represents a hydrogen atom.

The above R9, R12, and R13 represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom, or a cation, and the above R10 and R11 represent an aliphatic group, an aromatic group, a heterocyclic group, Alternatively, it represents a hydrogen atom, and the X represents a halogen atom.

In the general formula (IV), Z5, Z
The aliphatic groups represented by 6, Z7, R9, R10, R11, R12, and R13 include linear, branched, or cyclic alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups (for example, methyl, ethyl, n -propyl,
isopropyl, t-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the general formula (IV), Z5, Z
The aromatic groups represented by 6, Z7, R9, R10, R11, R12, and R13 include monocyclic or condensed aryl groups (e.g., phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α -naphthyl, 4-methylphenyl).

In the general formula (IV), Z5, Z
The heterocyclic group represented by 6, Z7, R9, R10, R11, R12, and R13 is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom or an oxygen atom. (For example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, benzimidazolyl).

In the general formula (IV), R9, R
Examples of the cation represented by 12 and R13 include alkali metal atoms and ammonium, and examples of the halogen atom represented by X include fluorine, chlorine, bromine, and iodine.

In the general formula (IV), preferably Z5
, Z6, and Z7 represent an aliphatic group, an aromatic group, or -OR9, and R9 represents an aliphatic group or an aromatic group.

The general formula (IV) is more preferably:
Represents trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate, or triarylselenophosphate.

[0082] Chemical formulas 12 to 19 shown below have the general formula (III
) and (IV) Specific example 1 of selenium compounds
Although selenium sensitizers used in the present invention are listed below, the selenium sensitizers used in the present invention are not limited to these.

The selenium sensitizer as described above is dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, and added to the silver halide emulsion during chemical sensitization. Preferably, it is added before starting chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more of the above selenium compounds may be used in combination. The combination of the unstable selenium compound and the non-labile selenium compound is preferred.

The amount of the selenium sensitizer used in the present invention varies depending on, for example, the activity of the selenium sensitizer used, the type and grain size of the silver halide, and the temperature and time of ripening. is 1×1 per mole of silver halide
The amount is 0-7 mol or more and 5 x 10-5 mol or less. In the present invention, the temperature of chemical sensitization when using a selenium sensitizer is preferably 45° C. or higher. More preferably 50
℃ or higher and 80℃ or lower. The pAg and pH are arbitrary; for example, the effect of selenium sensitization can be obtained over a wide range of pH 4 to 9.

In the present invention, it is more effective to carry out the selenium sensitization in the presence of a silver halide solvent.

Silver halide solvents that can be used in the present invention include, for example, US Pat. No. 3,271,157, US Pat. No. 3,531,289, US Pat.
(a) organic thioethers described in JP-A-54-1019 and JP-A-54-158917, for example, JP-A-54-158917;
No. 82408, No. 55-77737, No. 55-298
(b) Thiourea derivative described in No. 2, JP-A-53-14
(c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, as described in No. 4319, (d) imidazoles, and (e) sulfurous acid as described in JP-A-54-100717. (f) thiocyanate.

Particularly preferred silver halide solvents include:
Includes thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the type, but for example, in the case of thiocyanate, the preferred amount is 1 x 10-4 mol or more per 1 mol of silver halide.
It is as follows.

The silver halide emulsion containing tabular grains in the light-sensitive material of the present invention may be chemically sensitized by a combination of sulfur sensitization and gold sensitization.

Sulfur sensitization is usually carried out by adding a sulfur sensitizer to the emulsion and stirring at a high temperature, preferably 40° C. or higher, for a certain period of time.

Gold sensitization is usually carried out by adding a gold sensitizer to the emulsion and stirring at a high temperature, preferably 40° C. or higher, for a certain period of time.

For the above sulfur sensitization, compounds known as sulfur sensitizers can be used. Specifically, for example, allylthiocarbamide thiourea, allyl isothiacyanate,
Examples include cystine, p-toluenethiosulfonate, and rhodanine. Others, U.S. Patent No. 1,574,944
No. 2,410,689, No. 2,278,94
No. 7, No. 2,728,668, No. 3,501,3
No. 13, No. 3,656,955, German Patent No. 1, 4
No. 22,869, Japanese Patent Publication No. 56-24937, Japanese Patent Publication No. 1983
The sulfur sensitizers described in Japanese Patent No. 5-45016 may be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the silver halide emulsion. This amount varies over a wide range under various conditions such as pH, temperature, and silver halide grain size, but may range from 1 x 10-7 to 5 x 10-7 moles per mole of silver halide.
It is preferably 5 mol or less.

The gold sensitizer used in the gold sensitization may have an oxidation number of +1 or +3, and gold compounds commonly used as gold sensitizers may be used. Typical examples thereof include chlorauric acid, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, and pyridyl trichlorogold.

The amount of the gold sensitizer added varies depending on various conditions, but is generally 1× per mole of silver halide.
It is preferably 10-7 mol or more and 5x10-5 mol or less.

In the present invention, during chemical ripening, the timing and order of addition of the silver halide solvent, selenium sensitizer, sulfur sensitizer, and gold sensitizer are not particularly limited. For example, the above compounds may be added, preferably at the beginning of the chemical ripening, or simultaneously or at different times during the course of the chemical ripening. Regarding addition, the above-mentioned compound may be dissolved in water or an organic solvent miscible with water, such as methanol, ethanol, or acetone, either alone or in a mixed solution.

The photographic emulsion used in the present invention may 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,
For example, benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; carboxyl groups, sulfone groups, etc. The above-mentioned heterocyclic mercapto compounds having a water-soluble group of
Many compounds known as antifoggants or stabilizers can be added, such as (3,3a,7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid;

The time for adding these antifoggants or stabilizers is usually 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, after the addition until the start of chemical ripening, and during the chemical ripening (during the chemical ripening time, preferably within 50% of the start). , more preferably within 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 (binder or protective colloid) used in the photographic emulsion of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

[0099] Examples of the hydrophilic colloid include 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 sulfates; Sugar derivatives such as sodium alginate and starch derivatives; For example, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole.

Examples of the gelatin include lime-treated gelatin, acid-treated gelatin, and Bull. Soc. Sci. Ph
ot. Japan. No. 16, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. The gelatin derivatives include gelatin, for example, acid halides, acid anhydrides, isocyanates, bromoacetic acid,
Those obtained by reacting various compounds such as alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are used.

[0101] Specifically, the dispersion medium used in the present invention is specified by Research Disclosure (RESEARCH).
DISCLOSURE, hereinafter referred to as R. D. ) 1st
Volume 76, No. 17643 (December 1978) IX
It is described in the section.

The light-sensitive material of the present invention can be used as a color photographic light-sensitive material. The light-sensitive material may include at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of the non-photosensitive layers. As a typical example, on a support,
A silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities, and the light-sensitive layer has blue light, green light, It is a unit photosensitive layer that is sensitive to either light or red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in the following order from the support: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

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

[0104] In the intermediate layer, for example, Japanese Patent Laid-Open No. 61-43
No. 748, No. 59-113438, No. 59-1134
40, No. 61-20037, and No. 61-20038, and may contain a DIR compound, 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 far from the support, and a high-speed emulsion layer on the side close to the support. A sensitive emulsion layer may also be provided.

As a specific example, from the side farthest from the support, the low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BL)
H)/high sensitivity green photosensitive layer (GH)/low sensitivity green photosensitive layer (
GL)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL), or BH/BL/GL/GH/RH/
RL order or BH/BL/GH/GL/RL/RH
An example is an array of

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. 62-63
As described in No. 936, they can also be arranged in the order of blue-sensitive layer/GL/RL/GH/RH from the side farthest from the support.

In addition, 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. One example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity than the middle layer is arranged, and three layers having different photosensitivity are sequentially determined toward the support. 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, the layers 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.

[0110] Also, 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.

In the photographic light-sensitive material of the present invention, the preferred silver halide contained in the photographic emulsion layer is silver iodide of about 3
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 0 mol% or less. Particularly preferred is about 2 mol%
Silver iodobromide or iodochlorobromide salt containing up to about 10 mole percent silver iodide.

Silver halide grains in the photographic emulsion of the present invention include, in addition to the above-mentioned tabular grains, those having regular crystals such as cubic, octahedral, and tetradecahedral, and those having regular crystals such as spherical and tabular. It may have an irregular crystal shape, a crystal defect such as a twin plane, or a composite thereof.

The grain size of the silver halide grains 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 they may be polyacid emulsions or monodisperse emulsions.

Silver halide photographic emulsions that can be used in the present invention include, for example, R. D. No. 17643 (1978
February), pp. 22-23, “I. Emulsion Production (Emulsi
on preparation and types
)”, and No. 18716 (November 1979)
, 648 pages, same No. 307105 (November 1989), pp. 863-865, and "Physics and Chemistry of Photography" by P. Glafkid, published by Paul Montell.
es, Chemie et PhysiquePh
otographique, Paul Mont
el, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffin, Pho
tographic Emulsion Chem
istry (FocalPress, 1966)), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (V.L. Zelikmanet al.,
Making and Coating Photo
graphic emulsion, focus
Press, 1964).

[0116] In addition, as emulsions used in the present invention, US Pat.
Also preferred are the monodisperse emulsions described in No. 94 and British Patent No. 1,413,748.

[0117] Furthermore, as mentioned above, the aspect ratio is about 3.
The tabular grains as described above can be preferably used in the present invention. Tabular grains are described, for example, in Gutoff, Photographic Science and Engineering (Gu
toff, Photographic Science
e and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,
No. 434,226, No. 4,414,310, No. 4,4
33,048, 4,499,520 and British Patent No. 2,112,157.

The crystal structure of the silver halide grains in the present invention may be uniform, the inside and outside may have different halogen compositions, or they may have a layered structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. Also, mixtures of particles of various crystal forms may be used.

The above-mentioned emulsion according to the present invention 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 grains, or a type in which latent images are formed both on the surface and inside the grains. However, it is necessary that the emulsion is a negative type. Among the internal latent image type emulsions, JP-A-63-2647
It may also be a core/shell type internal latent image type emulsion as described in No. 40. A method for preparing this core/shell type internal latent image type emulsion is described in JP-A-59-133542. 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 in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are R. D.
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.

Further, the photosensitive silver halide emulsion layer and/or the substantially non-photosensitive hydrophilic colloid layer may be coated with a grain surface as described in US Pat. No. 4,082,553. Particles, U.S. Pat. No. 4,626,49
Silver halide grains and colloidal silver in which the inside of the grain is covered are preferably used as described in No. 8 and JP-A-59-214852. The term "silver halide grains with the inside or surface covered" refers to silver halide grains that can be developed uniformly (in a non-imagewise manner) regardless of the unexposed or exposed areas of the photosensitive material. say. A method for preparing silver halide grains with fogging inside or on the grain surface is described in U.S. Pat. No. 4,626,4.
No. 98 and JP-A No. 59-214852.

Here, the silver halide 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 grains, 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 0.0
1 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. 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).

In addition, it is preferable to use non-light-sensitive fine grain silver halide in the light-sensitive material of the present invention. 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 must not be fogged in advance. preferable.

The fine grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide if necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide.

[0126] The fine grain silver halide has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm.
is preferable, and 0.02 to 0.2 μm is more preferable.

[0127] The 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, nor is spectral sensitization necessary. 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 zinc compound. Furthermore, colloidal silver can preferably be contained in this layer containing fine silver halide grains.

[0128] 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 also include the above three R. D. Table 1 below shows the relevant descriptions.

[0130] In addition, the photosensitive material of the present invention is formulated with US Pat. No. 4,411,987 and US Pat.
It is preferable to add a compound that can be immobilized by reacting with formaldehyde as described in the above.

[0131] 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
-18539, a mercapto compound described in JP-A-1-283551, a fogging agent, a development accelerator, a silver halide solvent or Compounds that release those precursors, dyes dispersed by the method described in International Publication No. W088/04794, Japanese Patent Application Publication No. 1-502912, or EP 317,308A, U.S. Patent No. 4,
420,555 and JP-A-1-259358.

[0132] In the present invention, the following various color couplers can be used, and specific examples thereof include the above-mentioned R. D
．． No. 17643, VII-C to G, and the same No.
．． No. 307105, VII-CG.

Examples of yellow couplers include US Pat. No. 3,933,501 and US Pat. No. 4,022,620.
No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Special Publication No. 58-107
39, British Patent No. 1,425,020, British Patent No. 1,4
76,760, U.S. Patent No. 3,973,968, U.S. Patent No. 4,314,023, U.S. Patent No. 4,511,649,
Preference is given to those described in European Patent No. 249,473A.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, such as those described in US Pat. Nos. 4,310,619 and 4,351.
, 897, European Patent No. 73,636, U.S. Patent No. 3
, No. 061,432, No. 3,725,067, R.
D. No. 24220 (June 1984), Japanese Patent Application Publication No. 1983
-33552, R. D. No. 24230 (1984
(June), JP-A-60-43659, JP-A No. 61-722
No. 38, No. 60-35730, No. 55-118034
No. 60-185951, U.S. Patent No. 4,500,
No. 630, No. 4,540,654, No. 4,556
, No. 630, and those described in International Publication No. W088/04795 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, such as those disclosed in US Pat. No. 4,052,212, US Pat. No. 4,146,396,
No. 4,228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171
No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
No. 08, No. 4,334,001, No. 4,327,
173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, European Patent No. 249,453A,
U.S. Patent No. 3,446,622, U.S. Patent No. 4,333,9
No. 99, No. 4,775,616, No. 4,451,
No. 559, No. 4,427,767, No. 4,690,
No. 889, No. 4,254,212, No. 4,296
, No. 199 and JP-A-61-42658 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, and European Patent No. 341,188A.

[0137] 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.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from R. D. No. VII of 17643
-G term, same No. Section VII-G of 307105, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413
No. 4,004,929, U.S. Patent No. 4,138
, 258 and British Patent No. 1,146,368 are preferred. Also, U.S. Patent No. 4,774,181
Couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling, as described in No. 4,777,120, and dye precursor groups that can react with developing agents to form dyes as described in U.S. Pat. No. 4,777,120. It is also preferred to use couplers having as a leaving group.

Compounds which release photographically useful residues upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are those of the R. D.
17643, Section VII-F and the same No. 307105
, the patent described in Section VII-F, JP-A-57-15
No. 1944, No. 57-154234, No. 60-184
No. 248, No. 63-37346, No. 63-37350
No. 4,248,962, U.S. Patent No. 4,782,0
Those described in No. 12 are preferred.

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, for example, fogging agents, development accelerators, and silver halide solvents by 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, for example, US Pat. No. 4,130
, 427, U.S. Pat. No. 4,28
No. 3,472, No. 4,338,393, No. 4,3
Multi-equivalent coupler described in No. 10,618, JP-A-60-
D described in No. 185950 and JP-A No. 62-24252
IR 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. N
o. 11449, 24241, JP-A-61-2012
No. 47, bleach accelerator releasing couplers described in U.S. Pat.
, 555,477, a leuco dye-releasing coupler described in JP-A-63-75747, and a fluorescent dye-releasing coupler described in U.S. Pat. No. 4,774,181. .

The couplers used in the present invention as described above can be introduced into photosensitive materials by various known dispersion methods, such as oil-in-water dispersion methods and latex dispersion methods. Among these, examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

[0143] Specific examples of the high-boiling organic solvent having a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate,
Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t
-amylphenyl)phthalate, bis(2,4-di-t)
-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate), esters of phosphoric or 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-ethylhexylphenyl phosphonate), benzoic acid esters (e.g.
-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate)
, amides (e.g. N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (e.g. isostearyl alcohol, 2,4-di-tert
-amylphenol), aliphatic carboxylic acid esters (
For example, bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Aniline derivatives (e.g. N,N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (
Examples include paraffin, dodecylbenzene, diisopropylnaphthalene). In addition, as an auxiliary solvent,
For example, organic solvents with 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-ethoxyethyl acetate, dimethyl Formamide is mentioned.

[0144] The steps, effects, and specific examples of the latex for impregnation of the latex dispersion method are described in US Pat. No. 4,199.
, No. 363, West German Patent Application (OLS) No. 2,541,2
No. 74 and No. 2,541,230.

[0145] The color photosensitive material of the present invention contains, for example,
Phenethyl alcohol and JP-A No. 63-257747,
No. 62-272248, and JP-A-1-80941
1,2-benzisothiazolin-3-one described in No.
Adding various preservatives or antifungal agents such as n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)benzimidazole. is preferred.

The photosensitive material of the present invention can be applied to various color photosensitive materials. Typical examples include color negative films for general use or motion pictures, color reversal films for slides or television, color papers, color positive films, and color reversal papers.

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

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 1 μm or less.
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;
More preferably, the time is 0 seconds or less. The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate T1/2 can be measured according to a method known in the art. . For example, A.
Photographic Science and Engineering (Photo) by A. Green et al.
ogr. Sci. Eng. ) Volume 19, No. 2, 124-1
It can be measured using a swell meter (swell meter) of the type described on page 29, and T1/2 is 30% with a color developer.
9 of the maximum swelling film thickness reached when treated at ℃ for 3 minutes and 15 seconds.
0% 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 described above, using the formula:
It can be calculated according to (maximum swelling film thickness - film thickness)/film thickness.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry 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, for example, the aforementioned light absorber, filter dye, ultraviolet absorber, static inhibitor, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. . The swelling ratio of this back layer is preferably 150 to 500%.

[0151] The color photographic light-sensitive material of the present invention comprises the above-mentioned R.
D. No. 17643, pages 28-29, same No. 18
716, 651 left column to right column, and the same No. 30710
5, 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. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used. Typical examples include 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-
Examples include N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides, or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. Two or more of the above compounds can be used in combination depending on the purpose.

The color developing solution may contain a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. 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, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxy Ethyliminodiacetic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N
-tetramethylenephosphonic acid, ethylenediamine-di(
o-hydroxyphenylacetic acid) and salts thereof can be cited as representative examples.

[0154] When reversal processing is performed on the light-sensitive material of the present invention, black-and-white development is usually performed and then color development is performed. This black and white developer may contain 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. It can be used alone or in combination.

[0155] 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 this replenishment amount, 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.

[0156] The time for the color development process in the development process is usually set between 2 to 5 minutes, but the process time can be further shortened by using a high temperature, high pH, and a high concentration of color developing agent. It is also possible to aim for

In the development process, 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. Depending on the purpose, it is also possible to carry out treatment in two consecutive bleach-fixing baths, to carry out fixing treatment before bleach-fixing treatment, or to carry out bleaching treatment after bleach-fixing treatment. As a bleach,
For example, compounds of polyvalent metals such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents include organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
Aminopolycarboxylic acids such as -diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid can be used. Of these, iron(II) ethylenediaminetetraacetate
I) complex salt, and iron 1,3-diaminopropanetetraacetate (I
II) Aminopolycarboxylic acid iron (II) including complex salts
I) Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Additionally, aminocarboxylic 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.
It is also possible to process at lower pH for faster processing.

[0158] A bleach accelerator may be used in the bleach solution, bleach-fix solution, and their pre-bath in the development process, if necessary. Specific examples of useful bleach accelerators include U.S. Pat. No. 3,893,858, West German Pat.
No. 90,812, No. 2,059,988, JP-A-53
-32736, 53-57831, 53-37
No. 418, No. 53-72623, No. 53-95630
No. 53-95631, No. 53-104232,
No. 53-124424, No. 53-141623, No. 53-28426, R. D. No. No. 17129 (1
Compounds having a mercapto group or disulfide group described in JP-A No. 1978-140129; thiazolidine derivatives described in JP-A No. 45-8506, JP-A No. 52-20832, JP-A No. 53-32735 , thiourea derivatives as described in U.S. Pat. No. 3,706,561;
West German Patent No. 1,127,715, JP-A-58-16-2
Iodide salts described in West German Patent No. 35; polyoxyethylene compounds described in West German Patent No. 966,410 and West German Patent No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 8836/1983; Others No. 40,943, 49-5
No. 9,644, No. 53-94,927, No. 54-35
, No. 727, No. 55-26, 506, No. 58-163
, No. 940; a bromide ion 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 US Pat. No. 3,893,858 and West German Patent No. 1,290,81.
No. 2, JP-A No. 53-95,630 is preferred. Also preferred are the compounds described in US Pat. No. 4,552,884. These bleach accelerators may be added to the light-sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

[0159] In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stains. Particularly preferred organic acids have an acid dissociation constant (
A compound having a pKa) of 2 to 5, specifically, for example, acetic acid and propionic acid are preferred.

[0160] Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. ammonium thiosulfate is the most widely used. Further, for example, a combination of thiosulfate, thiocyanate, thioether compound, and thiourea is also preferred. Preservatives for fixing solutions and bleach-fixing solutions include sulfites, bisulfites, carbonyl bisulfite adducts, and European Patent No. 294769A.
The sulfinic acid compounds described in the above are preferred. Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the 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.

[0162] The total time of the desilvering step in the development process is preferably as short as possible so long as desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. Furthermore, the treatment temperature is 25°C to 50°C, preferably 3°C.
The temperature is 5°C to 45°C. In a preferred temperature range, the desilvering rate is improved and stain generation after treatment is effectively prevented.

[0163] In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening 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 means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions.

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

According to the multistage countercurrent system described in the above-mentioned document,
Although the amount of flushing water can be significantly reduced, the increased residence time of water in the tank can lead to the growth of bacteria, for example.
A problem arises in that the generated floating substances adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems have been solved by the method disclosed in Japanese Patent Application Laid-Open No. 62-288,838.
The method for reducing calcium ions and magnesium ions described in this issue can be used very effectively. In addition, isothiazolone compounds and cyabentazole compounds described in JP-A No. 57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and others such as benzotriazole, written by Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Institute of Technology "Sterilization of Microorganisms, Disinfection, and Antifungal Technology" (1982) Edited by Society of Industrial Engineers, Japan Antibacterial and Antifungal Society "Antibiotics and Antifungals" It is also possible to use the fungicides described in "Encyclopedia of Antibiotics" (1986).

[0166] The pH of the washing water in processing the photosensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics and application of the photosensitive material, but generally, the water temperature and washing time are 20 seconds to 1 hour at 15 to 45°C.
0 minutes, preferably in the range of 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 Application Laid-open No. 57-8543,
All known methods described in Japanese Patent Nos. 58-14834 and 60-220345 can be used.

[0167]Furthermore, subsequent to 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.

[0168] Various chelating agents and antifungal agents can also be added to this stabilizing bath.

[0169] 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.

[0170] In the processing using the automatic processor, when each of the processing liquids described above is concentrated by evaporation, it is preferable to correct the concentration by adding water.

[0171] Various processing solutions in the present invention can be used at temperatures ranging from 10°C to 5°C.
Used at 0°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, and conversely, lower temperatures can improve image quality and improve the stability of the processing solution. be able to.

[0172] The silver halide photographic light-sensitive material of the present invention is also disclosed in, for example, US Pat.
It is also applicable to the heat-developable photosensitive materials described in No. 1-238056 and European Patent No. 210,660A2.

[0173]

EXAMPLES Examples of the present invention will be described in detail below, but the embodiments of the present invention are not limited thereto. Example 1 (1) Preparation of emulsion 6 g of potassium bromide and 30 g of inert gelatin were mixed with distilled water 3.
While thoroughly stirring the aqueous solution dissolved in 7 liters, a 14% potassium bromide aqueous solution and a 20% silver nitrate aqueous solution were added thereto at a constant flow rate for 1 minute at 55°C and pBr 1.0 using the double jet method ( This addition consumed 2.4% of the total silver).

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 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). After adding an aqueous solution containing 8.3 g of potassium iodide, a 20% potassium bromide solution and a 33% silver nitrate aqueous solution were added over a period of 39 minutes using the double jet method (this addition resulted in 42.0 g of the total silver amount). (consumed 6%). The amount of silver nitrate used in this emulsion was 425 g. Next, after desalting by the usual flocculation method, sodium thiosulfate 0.8 x 1
0-5 mol/mol Ag, chloroauric acid 1.5 x 10-5 mol/mol Ag, potassium thiocyanide 1.6 x 10-3 mol/mol Ag, N,N-dimethylselenourea 0.4 x 1
Optimal chemical sensitization was performed by sequentially adding 0-5 mol/mol Ag. In this way, a silver iodobromide emulsion (emulsion A) having tabular grains with an average aspect ratio of 6.5, a coefficient of variation of 18%, and an equivalent sphere diameter of 0.8 μm was prepared. When these particles were observed using a transmission electron microscope, 70% of all particles
Dislocations were observed. (2) Preparation of coated samples An emulsion layer (added with various sensitizing dyes) and a protective layer as shown in Table 2 below were coated on a triacetyl cellulose film support provided with an undercoat layer, and sample A- 1~A-7
It was created.

[0175] These samples were left at 40°C and 70% relative humidity for 14 hours, then placed in an atmosphere at 55% relative humidity for more than 3 hours, and then cut into 0.1 m thick specimens in the same atmosphere.
A load of 4 g was applied with a needle of mφ, and the emulsion surface was scratched at a speed of 1 cm/sec. After developing this sample under the following conditions, the density was measured using an aperture of 25 μm φ. The results of this measurement and the types of sensitizing dyes used in each sample are shown in Table 3 below. The sensitizing dyes indicated by abbreviations in Table 3 are as follows:
These are the compounds shown in Chemical formulas 7 to 11.

[0176]
Processing method Process
Processing time Processing temperature Refill amount Tank capacity Color development 2 minutes 45 seconds 38℃ 3
3ml 20L floating
White 6 minutes 30 seconds 38℃
25ml
40L water washing 2 minutes 10 seconds
24℃ 1200ml
20L fixation
4 minutes 20 seconds 38℃
25ml 30L
Washing with water (1) 1 minute 05 seconds 2
From 4℃ (2) to (1)
10L
Countercurrent piping method Water washing (2) 1 minute 00 seconds
24℃ 1200ml
10L stable
1 minute 05 seconds 38℃
25ml 10L
Drying 4 minutes 20 seconds 55
℃ Refill amount is 35mm width 1
m length Next, the composition of the treatment liquid is described. (color developer)

Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid
1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid
3.0 3.2 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-hydroxyethylamino]-2-methylaniline sulfate
4.5 5.5 Add water

1.0L 1.0L
pH
1
0.05 10.05 (bleaching solution)

Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0
120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0
ammonium bromide
140.0 160.
0 ammonium nitrate
30.0
35.0 Ammonia water (27%)
6.5m
l Add 4.0ml water

1.0L 1.0L pH

6.
0 5.7 (Fixer)

Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid sodium salt
0.5 0.7 Sodium sulfite

7.0 8.0 Sodium bisulfite
5.0 5.5
Ammonium thiosulfate aqueous solution (70%)
170.0ml200.0ml 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-mononylphenyl ether (average degree of polymerization 10)
0.3 0.4
5 Ethylenediaminetetraacetic acid disodium salt
0.05 0.08 Add water
1.0L
1.0L pH

5.8-8.0 5.8-
8.0 From the results shown in Table 3, it can be seen that the degree of increase in fog caused by scratching was reduced in the samples corresponding to the present invention. Also, from the comparison between samples A-4 and A-5, it was found that the N
It can be seen that the effect is great when the substituent is R1 or R2 of the present invention. Example 2 Samples B-1 to B-7 were prepared by adding a sensitizing dye to samples A-1 to A-7 of Example 1 before chemical sensitization.

As in Example 1, it can be seen that the degree of increase in fog caused by scratching is reduced by the compound unique to the present invention. Example 3 (1) Preparation of Emulsions B and C In the same amounts as in Emulsion A of Example 1, JP-A-63-1
Emulsion B containing monodisperse silver iodobromide tabular grains (coefficient of variation 12%) and Emulsion C containing silver iodobromide tabular grains (coefficient of variation 30%) were prepared by the method described in 1928. (2) Preparation of Emulsions D and E In the method for preparing Emulsion A in Example 1, potassium iodobromide was added to KBr1 in the part where 50% of the total silver amount of silver nitrate and potassium iodobromide were added by double jet. -xIx, emulsions D and E (emulsion D: x=0.01, emulsion E:
x=0.08) was prepared. (3) Preparation of Emulsion F 8.3 g of potassium iodide in the preparation of Emulsion A was added to the potassium bromide aqueous solution in the subsequent addition of silver nitrate aqueous solution and potassium bromide aqueous solution by the double jet method. This was done by adding 8.3g. Emulsion F was prepared in the same manner as Emulsion A except for this. When grains in Emulsion F were observed using a transmission electron microscope, no dislocation lines were observed. (4) Preparation of emulsion G In the preparation of emulsion A, instead of gold/sulfur sensitization, sodium thiosulfate 1.0 x 10-5 mol/mol A
Optimal chemical sensitization was carried out by sequentially adding g, chloroauric acid 1.1 x 10-5 mol/mol Ag, and potassium thiocyanide 1.1 x 10-3 mol/mol Ag. Emulsion G was prepared in the same manner as Emulsion A except for this. (5) Preparation of Emulsion H In the preparation of Emulsion F, chemical sensitization was optimally carried out using sodium thiosulfate, chloroauric acid, and potassium thiocyanide. Emulsion H was prepared in the same manner as Emulsion F except for this.

Various sensitizing dyes were added to emulsions A to H in an amount of 80% of their saturated coverage, and the emulsions were coated on a support in the same manner as in Example 1.

Each of the above samples was examined for fog due to scratching in the same manner as in Example 1. Also, 10CM
S, 1/100" wedge exposure was applied, development was performed with the processing solution, and the density was measured. From this value, the sensitivity was
The relative value of the logarithm of the reciprocal of the exposure amount required to provide a density of fog+0.2 was determined.

Furthermore, graininess (RMS)...as a dye image density, it is the standard of variation in density value that occurs when a dye image with minimum density + 0.2 is scanned with a microdensitometer with a circular scanning aperture of 48 μm. The deviation (relative value when sample C-1 is taken as 100; the larger the value, the coarser the grains, which is unfavorable) was determined. The contents of the emulsion used in each sample, the type of sensitizing dye, and the test results are shown in Table 4 below.

From the results shown in Table 4, samples C-1 to C-3
From the comparison, it was found that tabular grains with smaller coefficients of variation had higher sensitivity and less increase in fog due to scratching. this is,
This seems to be because chemical sensitization can be performed more uniformly when the monodispersity is higher. In this case, graininess was also favorable.

[0182] Also, from the results of samples C-4 to C-7, the higher the iodine content, the higher the sensitivity and the better the graininess. on the other hand,
The increase in fog due to scratching is caused by Compound D as a sensitizing dye.
When using the sensitizing dye of the present invention, the iodine content was poor, but it could be improved by using the sensitizing dye of the present invention.

On the other hand, from the results of samples C-1, 8 to 10, it can be seen that emulsions having tabular grains having dislocations and selenium sensitization are most preferable because they have high sensitivity and little pressure fog. . Example 4 Preparation of Sample 101 Each layer having the composition shown below was coated on an undercoated cellulose triacetate film support to prepare a multilayer color light-sensitive material. (Photosensitive layer composition) The numbers for each component indicate the coating amount in units of g/m2, and for silver halide, the coating amount in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer. 1st layer (antihalation layer) Black colloidal silver
Silver 0.
18 Gelatin

1.40 Second layer (middle layer) 2,5-di-t-pentadecylhydroquinone
0.18 EX-1

0.07
EX-3

0.02 EX-12

0.002 U-1

0.06 U-2

0.08
U-3

0.10 HBS-1

0.10 HBS-2

0.02 gelatin

1.04 Third layer (donor layer for interlayer effect on red-sensitive layer) Emulsion (8)

Silver 1.2 Emulsion (3)
silver 2.0
Sensitizing dye IV

4×10-4 EX-12

0.10 HBS-1

0.10 HBS-2

0.10 Gelatin
2
．． 0 4th layer (middle layer) EX-5

0.040 HBS-1

0.020 Gelatin

0.80 5th layer (1st
Red-sensitive emulsion layer) Emulsion (1)
Silver
0.25 Emulsion (2)

Silver 0.25 Sensitizing dye I

1.5×10-4 Sensitizing dye II

1.8×10
-5 Sensitizing dye III

2.5×10-4 EX-2

0.335 EX-1
0
0.020
U-1

0.07 U-2

0.05 U-3

0.07 HB
S-1
0.0
60 Gelatin

0.87 6th layer (second red-sensitive emulsion layer) Emulsion (7)
Silver
1.0 Sensitizing dye I

1.0×10-4 Sensitizing dye II

1.4×10-5 Sensitizing dye III
2
．． 0x10-4 EX-2

0.400 EX-3

0.050EX
-10
0.0
15 U-1

0.07 U-2

0.05 U-3

0.07
gelatin

1.30 7th layer (3rd red-sensitive emulsion layer) Emulsion (4)
Silver
1.60 Sensitizing dye I

1.0×10-4 Sensitizing dye II

1.4×10-5
Sensitizing dye III

2.0×10-4 EX-3

0.010 EX-4

0.080E
X-2
0
．． 097 HBS-1

0.22 HBS-2

0.10 Gelatin

1.63 Sensitizing dye III
2.0
×10-4 EX-3

0.010 EX-4

0.080 EX-2

0.09
7 HBS-1

0.22 HBS-2

0.10 Gelatin

1.63 8th layer (middle layer) EX-5

0.040 HBS-1

0.020 Gelatin

0.80 9th layer (1st
Green-sensitive emulsion layer) Emulsion (1)
Silver
0.15 Emulsion (2)

Silver 0.15 Sensitizing dye V

3.0×10-5 Sensitizing dye VI

1.0×10
-4 Sensitizing dye VII

3.8×10-4 Sensitizing dye IV

5.0×10-5 E
X-6
0
．． 260 EX-1

0.021 EX-7

0.030 EX-8

0.005
HBS-1

0.100 HBS-3

0.010 gelatin

0.63 10th layer (2nd
Green-sensitive emulsion layer) Emulsion E
Silver 0.45 Sensitizing dye V

4.2×10-5 Sensitizing dye VI

1.4×10-4
Sensitizing dye VII

5.2×10-4 Sensitizing dye IV

1.0×10-4 EX-
6
0.0
94 EX-22

0.018 EX-7

0.026 HBS-1

0.160HB
S-3
0.0
08 Gelatin

0.50 11th layer (3rd green-sensitive emulsion layer) Emulsion (5)
Silver
1.2 Sensitizing dye V

3.5×10-5 Sensitizing dye VI

8.0×10-5 Sensitizing dye VII
3
．． 0x10-4 Sensitizing dye IV

0.5×10-5 EX-13

0.015
EX-11
0
．． 100 EX-1

0.025 HBS-1

0.25 HBS-2

0.10 Gelatin
1.
54 12th layer (yellow filter layer) Yellow colloidal silver
Silver 0.
05 EX-5

0.08 HBS-1

0.03 Gelatin

0.95 13th layer (first blue-sensitive emulsion layer) Emulsion (1)
Silver
0.08 Emulsion (2)

Silver 0.07 Emulsion (6)

Silver 0.07 Sensitizing dye VIII

3.5×10-4 E
X-9
0
．． 721 EX-8

0.042 HBS-1

0.28 Gelatin

1.10 No. 14
Layer (second blue-sensitive emulsion layer) Emulsion (7)
Silver
0.45 Sensitizing dye VIII

4.5×10-4 EX-9

0.154EX
-10
0.0
07 HBS-1

0.05 gelatin

0.78 15th layer (3rd blue-sensitive emulsion layer) Emulsion (8)
Silver
0.77 Sensitizing dye VIII

2.2×10-4 EX-9

0.20HBS
-1
0.07
gelatin

0.69 16th layer (first protective layer) Emulsion (9)
Silver
0.20 U-4

0.11 U-5

0.17 HBS-1

0.05
gelatin

1.00 17th layer (second protective layer) Polymethyl acrylate particles (approximately 1.5 μm in diameter
) 0.54 S-1

0.20 Gelatin
1.2
0 In addition to the above ingredients, each layer contains gelatin hardening agent H-1,
EX-14 to EX-21 and a surfactant were added. The contents of the emulsions (1) to (9) used are shown in Table 5 below, and the structural formulas of the compounds indicated by abbreviations are shown in Chemical Formulas 20 to 30 below. Preparation of Emulsion I Emulsion I containing monodisperse octahedral silver iodobromide grains with an iodine content of 6 mol % was prepared according to a conventional method. This emulsion was heated to 40°C.
H6.5 and pAg 8.5 were adjusted, and further gold and sulfur sensitization was optimally performed. The grains contained in the emulsion had an equivalent sphere diameter of 0.73 μm and a coefficient of variation of 14%. Preparation of Emulsion J In the preparation of Emulsion E in Example 1, the pBr of the portion where 50% of the total silver amount of silver nitrate and potassium iodobromide were added by double jet was adjusted to 0.9. Emulsion J containing silver iodobromide tabular grains having an aspect ratio of 9.0 was prepared in the same manner as in Emulsion A except for this. Preparation of sample 102 The sensitizing dye VII in the 10th layer of sample 101 was replaced with I-1,
Sample 102 was prepared by changing the sensitizing dye VI to I-9. Preparation of sample 103 Replace emulsion E in the 10th layer of sample 102 with emulsion I.
-1 at 2.6 x 10-4 mol/mol Ag, I-9 at 7.
Sample 103 was prepared by changing the content to 0x10-5 mol/mol Ag. Preparation of sample 104 Sample 104 was prepared by replacing emulsion E in the 10th layer of sample 102 with emulsion J.

Regarding Samples 101 to 104, the increase in fog due to scratching of the green sensitive layer was measured in the same manner as in Example 3. (The color development time was 3 minutes and 15 seconds.) In addition, the sharpness of the green-sensitive layer and the red-sensitive layer of Samples 101 to 104 was evaluated by measuring the MTF. MTF
The measurement method is described in “Journal of Light Photographic Engineering” Vol. 6 (1) 1-8.
(1980). The value of MTF was expressed as a relative value when the value of 30 lines/mm of sample 101 was taken as 100.

Further, for Examples 101 to 104, the increase in fog due to scratching of the blue-sensitive layer and the sharpness of the red-sensitive layer were examined in the same manner as in Example 3 (the color development time was 3 minutes and 15 seconds). ). The results are shown in Table 6 below.

The results shown in Table 6 show that the samples of the present invention have high sharpness of the red-sensitive layer and less fog due to scratches. Further, the sharpness of the green sensitive layer with an aspect ratio of 9 was not good.

[0187]

[Effects of the Invention] As detailed above, the present invention has remarkable effects in providing a silver halide photographic material that has high sharpness, graininess, image quality, and sensitivity, and is excellent in pressure resistance. It is something.

[0188]

[C7]

[0189]

[Chemical formula 8]

[0190]

[Chemical formula 9]

[0191]

[Chemical formula 10]

[0192]

[Chemical formula 11]

[0193]

[Chemical formula 12]

[0194]

[Chemical formula 13]

[0195]

[Chemical formula 14]

[0196]

[Chemical formula 15]

[0197]

[Chemical formula 16]

[0198]

[Chemical formula 17]

[0199]

[Chemical formula 18]

[0200]

[Chemical formula 19]

[0201]

[C20]

[0202]

[C21]

[0203]

[C22]

[0204]

[C23]

[0205]

[C24]

[0206]

[C25]

[0207]

[C26]

[0208]

[C27]

[0209]

[C28]

[0210]

[C29]

[0211]

[C30]

[0212]

[Table 1]

[0213]

[Table 2]

[0214]

[Table 3]

[0215]

[Table 4]

[0216]

[Table 5]

[0217]

[Table 6]

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers having the following formula 1.
1. A silver halide photographic material comprising a compound represented by formula (I) and tabular silver halide grains having an average aspect ratio of less than 8. [Chemical 1] The abbreviations in the formula represent the following, respectively: R1, R2: Alkyl group, provided that in at least one of the alkyl groups, at least one carbon is bonded to at least three atoms other than hydrogen. are doing. Z1, Z2: Atom group necessary to form a 5- to 6-membered nitrogen-containing heterocycle L1, L2: Substituted or unsubstituted methine group X: Anion l: 0, 1, or 2 p: For balancing charges required integer 2. The silver halide photographic material according to claim 1, wherein the tabular silver halide grains have dislocation lines. 3. The tabular silver halide grains are chemically sensitized with at least one selected from the group consisting of selenium sensitizers, gold sensitizers, and sulfur sensitizers. Silver halide photographic material. 4. The silver halide photographic material according to claim 3, wherein the tabular silver halide grains have an average iodine content of 3 mol % or more. 5. The silver halide photographic material according to claim 3, wherein the tabular silver halide grains have a coefficient of variation of a circle equivalent diameter of a projected area of 25% or less.