JP3484238B2 - Silver halide photographic material - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material. In particular, the present invention relates to a silver halide photographic light-sensitive material which contains grains subjected to reduction sensitization and has high sensitivity and excellent pressure resistance and storage performance.

[0002]

2. Description of the Related Art Generally, various pressures are applied to a photographic light-sensitive material coated with a silver halide emulsion. For example,
The negative film for general photography is bent or pulled for frame advance when it is rolled up in a cartridge or mounted on a camera.

On the other hand, a sheet-shaped film such as a printing photosensitive material or a direct medical X-ray sensitive material is often bent or bent because a person directly handles it.

Further, all sensitive materials are subjected to great pressure during cutting and processing.

As described above, when various pressures are applied to the photographic light-sensitive material, the pressure is applied to the silver halide grains by using gelatin as a holder (binder) of silver halide grains or a plastic film as a medium. It is known that the photographic properties of photographic light-sensitive materials change when pressure is applied to silver halide grains. For example, KB Mather, J. Op.
t. Soc. Am., 38, 1054 (1948), P. Faelen
s and P. de Smet. Sci. et Ind Phot., 25, No.
5, 178 (1954), P. Faelens. J. Phot. Sci.
2, 105 (1954) and the like.

On the other hand, in recent years, the image quality of color light-sensitive materials, that is, the color reproducibility, sharpness, and graininess has made remarkable progress. However, the demand for the image quality of the light-sensitive material is not limited, and further progress is required.
For this reason, various emulsion techniques and coupler techniques have been studied and each has achieved great results. However, among these technologies, the storage performance of sensitive materials, especially the increase of fog,
There are many cases in which latent image assisting power is deteriorated, and a countermeasure technology therefor has been long awaited. The photosensitive material for photographing may be developed from immediately after photographing to several months or one year after photographing, and it is desirable that its performance does not change during such aging period. The stability of the latent image after exposure has been known for a long time as regression that moves as if sensitivity decreased at first glance and assist force that moves as if it rose, and recently, for example, The Jounal of EF Thurston. Photo
graphic Science Volume 38 (34-40 pages, 199)
There is a research example such as 0 years.

It is well known in the art that a sensitizing technique for making fine silver halide grains is important for improving the graininess of a light-sensitive material. In recent years, in order to increase the sensitivity of fine particles of silver halide grains, for example, devising a reduction sensitization method described later has been studied, and great results have been achieved. However, it was found that the sensitivity increase due to reduction sensitization is accompanied by storage fog and deterioration of latent image assisting force.

In recent years, demands for silver halide emulsions for photography have become more and more strict, and photographic characteristics such as sensitivity and graininess,
In addition to image quality such as sharpness, so-called toughness such as storability and pressure resistance is required at a higher level. However, as described above, it is obvious that the pressure fog and the fog during storage increase with the increase in sensitivity, and an emulsion having high sensitivity and pressure fog and less fog during storage is desired.

[0009] Attempts for reduction sensitization have been studied for a long time in order to increase the sensitivity. Carroll disclosed in US Pat. No. 2,487,850 that a tin compound is
owe et al., Usefulness of Polyamine Compound as No. 2,512,925 and Fallens et al. Was disclosed. Furthermore, Collier is Photo
Graphic Science and Engineering, Volume 23, page 113 (1979), compares the properties of silver nuclei produced by various reduction sensitization methods. She has dimethylamine borane, stannous chloride, hydrazine, high pH aging, low p
The Ag aging method was adopted. The method of reduction sensitization is further described in US Pat. Nos. 2,518,698 and 3,201,25.
No. 4, No. 3,411, 917, No. 3,779, 7
77 and 3,930,867. Not only selection of reduction sensitizer but also devising of reduction sensitization method is described in JP-B Nos. 57-33572 and 58-1410.

[0010]

An object of the present invention is to provide a silver halide photographic light-sensitive material having high image quality and high sensitivity which is excellent in pressure resistance and storage performance.

[0011]

As a result of intensive studies, the object of the present invention could be achieved by the following means. That is, (1) in a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one radical scavenger (provided that the following compound (VII-2)
Except for the above), and the photosensitive silver halide grains in the emulsion layer are subjected to reduction sensitization.

[Chemical 2-1] The radical scavenger is a galbino at 25 ° C.
Test compound with 0.05 mmoldm ^-3 ethanol solution of xyl
2.5 mmoldm ^-3 ethanol solution of
Mixing by the Rho method, absorbance time at 430 nm
The change was measured, and the galvinoxyl was substantially erased (430
a compound that reduces the absorbance at nm)
U (If the above concentration does not dissolve, lower the concentration and measure.
You may set it. ) (2) In the radical scavenger, a silver halide photographic material according to, characterized in that except for the compound represented by the following general formula (VII) (1).

[Chemical 2-2] In the formula, R ⁷¹ is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an alkenyl group, an alkynyl group or a hydrazino group, and G ⁷¹ is —SO ₂ -, -SO-, -PO
(R ³⁵⁾ -, iminomethylene, -COCO- or -CO
And R ³⁵ is an alkyl group or an aryl group,
⁷⁴ is a hydrogen atom or a group removed under alkaline conditions, R ⁷³ may be an alkyl group, and q is 0, 1 or 2. The groups described above may have a substituent. (3) The silver halide photographic light-sensitive material according to (1), wherein the radical scavenger does not include a compound represented by the following general formula (AI) ′.

[Chemical 2-3] In formula (AI) ′, R _a1 represents an arylsulfonyl group and R _a2 represents a hydrogen atom. (4) The silver halide photographic light-sensitive material according to (1), wherein the radical scavenger does not include a compound represented by the following general formula (AI) ″.

[Chemical 2-4] In the general formula (AI) ", R _a1 represents an arylsulfonyl group, R _a2 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, It represents a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. (5) The silver halide grains in the emulsion layer are subjected to reduction sensitization, and the following general formulas (I), (II) or At least 1 selected from the compounds represented by (III)
The silver halide photographic light-sensitive material as described in any one of (1) to (4), which contains two compounds. General formula _{(I) R-SO 2 S} -M Formula _{(II) R-SO 2 S} -R 3 formula (III) in _{R-SO 2 S-L m} -SSO 2 -R 4 Formula, R, R ³ , R ⁴ may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a cation, L represents a divalent linking group, m is 0 or 1. is there. The compounds of the general formulas (I) to (III) may be polymers containing a divalent group derived from the structures represented by (I) to (III) as a repeating unit. (6) It is characterized in that at least 60% of the total projected area of the photosensitive silver halide grains is tabular silver halide grains having an aspect ratio of 3 or more and having 10 or more dislocation lines in one grain ( The silver halide photographic light-sensitive material according to any one of 1) to (5). (7) The radical scavenger is a compound represented by any one of the following general formulas (AI) to (AV), wherein the radical scavenger is (1) to (6). Silver halide photographic light-sensitive material.

[Chemical 2-5] In formula (AI), R _a1 represents an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. , R _a2 represents a hydrogen atom, an arylsulfonyl group or the group represented by R _a1 . Provided that when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group,
It is a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1
And R _a2 may combine with each other to form a 5- to 7-membered ring. In formula (A-II), X represents a heterocyclic group, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. X and R _b1 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-III), Y is -N =
It represents a group of non-metal atoms necessary for forming a 5-membered ring with C-. Y represents a group of non-metal atoms necessary for forming a 6-membered ring together with a -N = C- group, and -N = C
The end of Y bonded to the carbon atom of the -group is -N (R _c1 )-, -C
(R _c2 ) (R _c3 )-, —C (R _C4 ) =, —O—, a group selected from —S— (bonded to the carbon atom of —N═C— on the left side of each group) Represents R _{c1 to} R _c4 represent a hydrogen atom or a substituent. In formula (A-IV), R _d1 and R _{d2, which} may be the same or different, each represents an alkyl group or an aryl group. However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2 are alkyl groups having 8 or more carbon atoms. In formula (A-V), R _e1 and R _e2 may be the same or different and each is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group. Represents a group, an arylthio group, an alkyl group or an aryl group. However, R _e1 and R _e2 are not —NHR _e3 (R _e3 is an alkyl group or an aryl group) at the same time. R _a1 and R _a2 , and X and R _b1 may combine with each other to form a 5- to 7-membered ring.

[0012]

[0013]

(8) The silver halide photographic light-sensitive material as described in (7), wherein the radical scavenger is a compound represented by the general formula (AI) or (A-II). (9) The silver halide according to any one of (1) to (8), wherein the radical scavenger galvinoxyl has a decolorization rate constant of 0.01 mmol ^-1 s ^-1 dm ³ or more. Photographic material. (10) The silver halide according to any one of (1) to (9), wherein the radical scavenger galvinoxyl has a decolorization rate constant of 0.1 mmol ^-1 s ^-1 dm ³ or more. Photographic material.

The present invention will be described in more detail below.
First, reduction sensitization in the present invention will be described. The process for producing a silver halide emulsion is roughly divided into processes such as grain formation, desalting, and chemical sensitization. Grain formation is divided into nucleation, ripening, and growth. These steps are not performed uniformly, but the order of the steps is reversed, or the steps are repeated. The fact that reduction sensitization is carried out during the production process of a silver halide emulsion basically means that it may be performed at any process. The reduction sensitization may be carried out at the initial stage of grain formation during nucleation, physical ripening, or during growth, and may be performed prior to chemical sensitization other than reduction sensitization or after this chemical sensitization. . When chemical sensitization is performed in combination with gold sensitization, it is preferable to carry out reduction sensitization prior to chemical sensitization so that unfavorable fog does not occur. Most preferred is a method of reduction sensitization during the growth of silver halide grains. The term "during growth" here refers to a method in which reduction sensitization is performed while the silver halide grains are physically ripening or are being grown by the addition of a water-soluble silver salt and a water-soluble alkali halide. It means that the method also includes a method of performing reduction sensitization in the above state and then further growing.

The reduction sensitization of the present invention is a method of adding a known reducing agent to a silver halide emulsion, pAg called silver ripening.
Either a method of growing or aging in a low pAg atmosphere of 1 to 7 or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

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

Known reduction sensitizers are stannous salts, amines and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. In the present invention, these known compounds can be selected and used, and two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide and dimethylamine borane are preferred compounds. The addition amount of the reduction sensitizer depends on the emulsion production conditions, so it is necessary to select the addition amount, but 10 ^-7 to 10 ^-3 per mol of silver halide.
A molar range is suitable.

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

Ascorbic acid and its derivatives (hereinafter
It is called "ascorbic acid compound". Specific examples of () include the following. (A-1) L-ascorbic acid (A-2) L-sodium ascorbate (A-3) L-potassium ascorbate (A-4) DL-ascorbic acid (A-5) D-ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-5,6 -Diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene The ascorbic acid compound used in the present invention is used in a large amount as compared with the addition amount in which a reduction sensitizer is conventionally used preferably. Is desirable. For example, Japanese Patent Publication No. 57-33572
"The amount of reducing agent is usually 0.75 x per g of silver ion"
Do not exceed 10 ^-2 milliequivalents (8 x 10 ^-4 mol / AgX mol). An amount of 0.1 to 10 mg per kg of silver nitrate (10 ^-7 to 10 ^-5 mol / AgX mol as ascorbic acid) is often effective. (The converted value is by the inventors). US Pat. No. 2,487,850 states that "a tin compound can be used as a reduction sensitizer in an amount of 1
× 10 ^{−7 to} 44 × 10 ⁻⁶ mol ”. Further, in JP-A-57-179835, it is appropriate that the addition amount of thiourea dioxide is about 0.01 mg to about 2 mg per mol of silver halide and the addition amount of stannous chloride is about 0.01 mg to about 3 mg. It has been described. Ascorbic acid compound used in the present invention the particle size of the emulsion, the halogen composition, the temperature of emulsion preparation, pH, depends preferably amount by factors such as pAg, per mole of silver halide 5 × 10 ^-5 to 1
It is desirable to select from the range of × 10 ^-1 mol. More preferably, it is selected from the range of 5 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol. Particularly preferred is 1 × 10 ^-3 mol-
It is to select from the range of 1 × 10 ^-2 mol.

The reduction sensitizer is water or alcohols,
It can be dissolved in a solvent such as glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. It may be added at any stage of the emulsion production process, but the method of addition during grain growth is particularly preferred. It may be added to the reaction vessel in advance,
It is preferable to add it at an appropriate time for grain formation. It is also possible to add a reduction sensitizer to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance and use these aqueous solutions to form grains. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times with the grain formation or to continuously add it for a long time.

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

The compounds of the general formulas (II), (III) and (IV) will be described in more detail. When R, R ¹ and R ² are aliphatic groups, preferably an alkyl group having 1 to 22 carbon atoms, An alkenyl group and an alkynyl group each having 2 to 22 carbon atoms, which may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl,
Examples thereof include cyclohexyl, isopropyl and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

As the aromatic group of R, R ¹ and R ² ,
It preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. These may be substituted.

The heterocyclic group for R, R ¹ and R ² includes
3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium, for example, pyrrolidine ring, piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole Examples thereof include a ring, a benzothiazole ring, a benzoxazole ring, a benzimidazole ring, a selenazole ring, a benzoselenazole ring, a tellurazole ring, a triazole ring, a benzotriazole ring, a tetrazole ring, an oxadiazole ring and a thiadiazole ring.

Examples of the substituents of R, R ¹ and R ² include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyloxy), an aryl group (phenyl, naphthyl, tolyl). ,
Hydroxy group, halogen atom (eg fluorine, chlorine, bromine, iodine), aryloxy group (eg phenoxy), alkylthio group (eg methylthio, butylthio), arylthio group (eg phenylthio), acyl group (eg acetyl, propionyl, butyryl, valeryl) ), A sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), an acylamino group (eg, acetylamino, benzamino), a sulfonylamino acid (eg, methanesulfonylamino, benzenesulfonylamino), an acyloxy group (eg, acetoxy, benzoxy), a carboxyl group,
Examples thereof include a cyano group, a sulfo group and an amino group.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include — (CH ₂ ) _n — (n = 1 to 12) and —CH ₂ —C.
_{H = CH-CH 2 -,} - CH 2 C three CCH ₂ -,

[0030]

[Chemical 3]

Examples thereof include a xylylene group. Examples of the divalent aromatic group of L include phenylene and naphthylene.

These substituents may be further substituted with the above-mentioned substituents.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions.
Examples of the organic cation include ammonium ion (for example, ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ion (tetraphenylphosphonium), guanidinium ion and the like.

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

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

[0040]

[Chemical 9]

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

Compounds of general formula (I), JP-A-54-10
19 and British Patent 972,211 for easy synthesis.

The compound represented by formula (I), (II) or (III) is 10 ^-7 to 10 per mol of silver halide.
^-1 mol is preferably added. From 10 ^-6 to 1
An addition amount of 0 ^-2 , particularly 10 ^-5 to 10 ^-3 mol / mol Ag is preferable.

To add the compounds represented by the general formulas (I) to (III) during the production process, a method usually used when adding an additive to a photographic emulsion can be applied. For example, the water-soluble compound is an aqueous solution having an appropriate concentration, and the water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones,
Of the esters and amides, it can be dissolved in a solvent that does not adversely affect the photographic properties and added as a solution.

The compound represented by formula (I), (II) or (III) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization.
Preferred is a method of adding the compound before or during the reduction sensitization. Particularly preferred is the method of addition during grain growth.

It may be added in advance to the reaction vessel, but it is preferable to add it at an appropriate time for grain formation. It is also possible to add the compounds of the general formulas (I) to (III) to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance and use these aqueous solutions to form particles.
It is also a preferable method to add the solutions of the compounds of the general formulas (I) to (III) in several times with the formation of particles or to continuously add them for a long time.

Among the compounds represented by the general formulas (I) to (III), the most preferable compound for the present invention is the compound represented by the general formula (I).

The emulsion of the present invention is preferably tabular silver halide grains having an aspect ratio of 3 or more, more preferably 3 or more and less than 8. Here, 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 means the (111) plane when ions at all lattice points on both sides of the (111) plane have a mirror image relationship. When viewed from above, the tabular grains have a triangular shape, a hexagonal shape, or a rounded circular shape.The triangular shape is a triangular shape, the hexagonal shape is a hexagonal shape, and a circular shape. Have circular outer surfaces parallel to each other.

The aspect ratio of the tabular grains in the present invention means a value obtained by dividing the grain diameter of each tabular grain having a grain diameter of 0.1 μm or more by the thickness. The thickness of the particles is measured by evaporating the metal from the diagonal direction of the particles together with the latex for reference, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. You can easily.

The grain 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 grain.

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

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

The emulsion of the present invention contains tabular silver halide grains having an aspect ratio of 3 or more, preferably an aspect ratio of 3.
It contains tabular silver halide grains of not less than 8 and preferably 60% or more of the total projected area is occupied by such tabular silver halide grains.

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

Further, more preferable results may be obtained by using monodisperse tabular grains. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-1516.
According to the description of No. 18, etc., but its shape is simply stated, 70% or more of the total projected area of the silver halide grains is such that The hexagonal tabular silver halide grains have a hexagonal ratio of 2 or less, and are occupied by tabular silver halide having two parallel outer surfaces, and the hexagonal tabular silver halide grains have a grain size distribution. Has a monodispersity of 20% or less (a value obtained by dividing the variation (standard deviation) in particle size represented by the circle-converted diameter of the projected area by the average particle size).

Further, the emulsion of the present invention preferably has dislocation lines. Dislocations of tabular grains are described, for example, in J. F. Ha
milton, Photo. Sci. Eng. , 11, 5
7, (1967) and T.S. Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
It can be observed by a direct method using a transmission electron microscope at low temperature described in (1972). In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscope observation, and the sample is placed to prevent damage (printout, etc.) due to electron beams. Observation is carried out by the transmission method in the cooled state. At this time, the thicker the particles, the more difficult it is for the electron beam to pass through. Therefore, it is possible to observe more clearly by using a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). . From the photograph of the grain obtained by such a method, the position and number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

The average number of dislocation lines is 10 or more per grain. More preferably, the average number of particles is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, about 10
It is possible to count as many as 20 or 30, which is clearly distinguishable from the case where there are only a few. The average number of dislocation lines per grain is 100.
The number of dislocation lines is counted for particles and above, and the number average is obtained.

Dislocation lines can be introduced, for example, in the vicinity of the outer periphery of tabular grains. In this case, the dislocations are almost perpendicular to the outer circumference, and the dislocation lines are generated starting from the position of x% of the length of the distance from the center of the tabular grain to the side (outer circumference) and reaching the outer circumference. The value of x is preferably 10 or more and 100
Less than, more preferably 30 or more and less than 99,
Most preferably, it is 50 or more and less than 98. At this time, the shape formed by connecting the positions where the dislocations start is similar to the particle shape, but it is not a perfect similar shape and may be distorted. This type of dislocation is not found in the central region of the grain. The dislocation lines are crystallographically in the (211) direction, but they are often meandering and may intersect with each other.

Further, the dislocation lines may be almost uniformly distributed over the entire outer circumference of the tabular grain, or may be locally located on the outer circumference. That is, taking a hexagonal tabular silver halide grain as an example, dislocation lines may be limited only in the vicinity of the six vertices, or dislocation lines may be limited in the vicinity of one of the vertices. . On the contrary, it is possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices.

Dislocation lines may be formed over a region including the centers of two main planes of the tabular grain which are parallel to each other.
When dislocation lines are formed over the entire main plane, the dislocation lines may be crystallographically approximately (211) when viewed from a direction perpendicular to the main plane, but (110) or In some cases, the dislocation lines are randomly formed, and the length of each dislocation line is also random. In some cases, they are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer periphery). is there. Dislocation lines are often straight or meandering. Also, they often intersect with each other.

The position of dislocation may be limited to the outer periphery, the main plane, or the local position as described above.
These may be formed in combination. That is, they may exist on the outer circumference and the main plane at the same time.

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

The high silver iodide layer inside the grain means a silver halide solid solution containing silver iodide. The silver halide in this case is preferably silver iodide, silver iodobromide or silver chloroiodobromide, but is silver iodide or silver iodobromide (silver iodide content of 10 to 40 mol%). More preferable. In order to selectively cause the high silver iodide layer inside the grain (hereinafter referred to as the internal high silver iodide layer) to be present on any side or corner of the base grain, the generation condition of the base grain and the internal It can be controlled by the production conditions of the high silver iodide layer. As the conditions for forming the base silver grains, pAg (logarithm of reciprocal of silver ion concentration), presence / absence of silver halide solvent, kind and amount, and temperature are important factors. By setting the pAg at the time of growth of the base grain to 8.5 or less, more preferably 8 or less, the internal high silver iodide layer can be made to selectively exist near the apex of the base grain. On the other hand, the internal high silver iodide layer can be made to exist on the sides of the base grains by setting the pAg during the growth of the base grains to be 8.5 or more, more preferably 9 or more. These pAg
The threshold of changes up and down depending on the temperature and the presence, type, and amount of silver halide solvent. When thiocyanate is used as the silver halide solvent, the pAg
The threshold of shifts toward higher values. The most important pAg during growth is the pAg at the end of the growth of the base grain.
Is. On the other hand, even when the pAg during growth does not satisfy the above value, it is possible to control the selective position of the internal high silver iodide layer by adjusting the pAg to the pAg after the growth of the base grain and ripening. is there. At this time, ammonia, amine compounds and thiocyanate salts are effective as silver halide solvents. The so-called conversion method can be used to form the internal high silver iodide layer. This method includes a method of adding a halogen ion having a lower solubility of a salt forming a silver ion than a halogen ion forming the particle or the vicinity of the surface of the particle at the time of grain formation. In the present invention, it is preferable that the amount of halogen ion having a small solubility to be added with respect to the surface area of the particle at that time is a certain value (related to the halogen composition) or more. For example, during particle formation, AgB at that time
It is preferable to add a certain amount or more of KI with respect to the surface area of the r particles. Specifically, it is 8.2 × 10 ^-5 mol / m ^2.
It is preferable to add the above iodide salts.

A more preferable method of forming an internal high silver iodide layer is a method of adding a silver salt aqueous solution at the same time as adding a halide salt aqueous solution containing an iodide salt.

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

In carrying out the above method, it is preferable that the solubility of the silver halide in the mixed system is as low as possible. Therefore, the temperature of the mixed system for forming the high silver iodide layer is preferably 30 ° C. or higher and 70 ° C. or lower, more preferably 30 ° C. or higher and 5 ° C. or higher.
It is 0 ° C or lower.

Most preferably, the formation of the internal high silver iodide layer is fine grain silver iodide (fine silver iodide, hereinafter the same).
Alternatively, fine grain silver iodobromide, fine grain silver chloroiodobromide or fine grain silver chloroiodobromide can be added. It is particularly preferable to add fine grain silver iodide. These fine particles usually have a particle size of 0.01 μm or more and 0.1 μm, but particles having a particle size of 0.01 μm or less or 0.1 μm or more can also be used. For the preparation method of these fine silver halide grains, see WO 89/683.
0, WO 89/6831 and WO 90/1462 can be referred to. An internal high silver iodide layer can be provided by adding and ripening these fine grain silver halides. When dissolving the fine particles by ripening, it is also possible to use the above-mentioned silver halide solvent. It is not necessary for all of the added fine particles to be dissolved and disappeared immediately, as long as they are dissolved and disappeared when the final particles are completed.

The outer layer covering the internal high silver iodide layer is lower than the silver iodide content of the high silver iodide layer, preferably the silver iodide content is 0 to 30 mol%, more preferably 0 to 20 mol%. Mol%
Most preferably, it is 0 to 10 mol%. The position of this internal high silver iodide layer is measured from the center of the projected hexagon or the like of the grain, and is 5 mol% to 100 mol% with respect to the total silver amount of the grain.
It is preferably present in the range of less than 20% by mole, more preferably 20% by mole or more and less than 95% by mole, particularly 50% by mole or more and 9% by mole or more.
It is preferably within the range of less than 0 mol%. The amount of silver halide forming these internal high silver iodide layers is 50 mol% or less, and more preferably 20 mol% or less, based on the total silver amount of the grains in terms of silver amount. These high silver iodide layers are prescribed values for producing a silver halide emulsion, and are not values obtained by measuring the halogen composition of final grains by various analytical methods. The internal high silver iodide layer often disappears in the final grain due to the recrystallization process or the like, and the above is all about the manufacturing method thereof.

Therefore, in the final grain, the dislocation line can be easily observed by the above-mentioned method, but the internal silver iodide layer introduced for introducing the dislocation line cannot be confirmed as a clear layer in many cases. In some cases, for example, the entire peripheral area of the tabular grains may be observed as a high silver iodide layer. X-ray diffraction and EP
MA (also called XMA) method (a method of scanning silver halide grains with an electron beam to detect the silver halide composition), ESCA (also called XPS) method (irradiated from the grain surface by irradiating X-rays) It can be confirmed by combining the method of separating the coming photoelectrons).

The temperature at the time of forming the outer layer covering the inner high silver iodide layer, pAg, is arbitrary, but the preferred temperature is 30.
The temperature is not less than 0 ° C and not more than 80 ° C. Most preferably, it is 35 ° C. or higher and 70 ° C. or lower. Preferred pAg is 6.5 or more 11.5
It is the following. It may be preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt.

In order to introduce dislocation lines on the main surface of tabular grains, after preparing the base grains, silver halochloride is deposited on the main surface, and the halosilver chloride is subjected to conversion to obtain high silver bromide or high silver iodide. A layer may be formed and a shell may be further provided on the outside thereof. Examples of the halosilver chloride include silver chloride or silver chlorobromide having a silver chloride content of 10 mol% or more, preferably 60 mol% or more, or silver chloroiodobromide. Deposition of these halosilver chloride base grains on the principal plane can be carried out by adding an aqueous solution of silver nitrate and an appropriate aqueous solution of an alkali metal salt (eg potassium chloride) separately or simultaneously, or an emulsion comprising these silver salts. It is also possible to deposit by adding and aging. Deposition of these silver halochlorides is possible in all pAg regions, but most preferably between 5.0 and 9.5. In this method, tabular grains are mainly grown in the thickness direction. The amount of this halosilver chloride layer is 1 mol% or more and 80 mol% or less in terms of silver mol based on the base grains. It is more preferably 2 mol% or more and 60 mol% or less. By converting this halosilver chloride layer with an aqueous solution of a halide capable of forming a silver salt having a solubility lower than that of halosilver chloride, dislocation lines can be introduced on the main planes of tabular grains. After conversion of this silver halochloride layer, for example with an aqueous solution of KI, it is possible to grow the shell and obtain the final grains. The halogen conversion of these halosilver chloride layers does not mean that all of them are replaced with silver salts having a lower solubility than halosilver chloride, but preferably 5% or more, more preferably 10% or more, most preferably 20% or more, It replaces the low-solubility silver salt. By controlling the halogen structure of the base grain on which the halosilver chloride layer is provided, it is possible to introduce dislocation lines into local sites on the principal plane. For example, when a base grain having an internal high silver iodide structure is used by laterally displacing the base tabular grain, dislocation lines can be introduced only in the peripheral main planes excluding the central portion of the main plane. When the base tabular grains are laterally displaced and the base grains having the outer high silver iodide structure are used, dislocation lines can be introduced only in the central portion of the main plane except the peripheral portion. Further, it is also possible to deposit a halosilver chloride only in a site limited in area by using a locally dominant substance for epitaxial growth of halosilver chloride, for example, iodide, and introduce a dislocation line only in that site. The temperature during the deposition of silver halochloride is 30 ° C or higher, 70
℃ or less is preferable, more preferably 30 ℃ or more 50 ℃
It is the following. It is possible to carry out conversion after the deposition of these silver halochlorides and then grow the shell, but it is also possible to carry out halogen conversion while the growth of the shells is carried out after the deposition of the silver halochloride.

The position of the internal halosilver chloride layer formed substantially parallel to the main plane may be present in the range of 5 mol% or more and less than 100 mol% with respect to the total amount of silver in the grains on both sides from the center of the grain thickness. It is more preferably 20 mol% or more and less than 95 mol%, and particularly preferably 50 mol% or more and less than 90 mol%.

The silver iodide content of the shell is preferably 0 to 3
It is 0 mol%, more preferably 0 to 20 mol%. The temperature at which the shell is formed and pAg are arbitrary, but the preferred temperature is 30 ° C. or higher and 80 ° C. or lower. Most preferably 35 ° C
It is above 70 ° C. Preferred pAg is 6.5 or more 1
It is 1.5 or less. It may be preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt. In the final grain, the internal halosilver chloride layer that has undergone halogen conversion may not be confirmed by the above-described method for analyzing halogen composition, depending on conditions such as the degree of halogen conversion. However, dislocation lines can be clearly observed.

The method of introducing dislocation lines at arbitrary positions on the principal plane of the tabular grain and the method of introducing dislocation lines at arbitrary positions on the outer periphery of the tabular grains described above are appropriately combined and used. It is also possible to introduce dislocation lines.

[0078] a radical scavenger in the present invention, under 25 ° C., and a 2.5Mmoldm ^-3 ethanol solution of 0.05Mmoldm ^-3 ethanol solution and the test compound of galvinoxyl, mixed by stopped-flow method, 430
Substantially decolorized galvinoxyl by measuring the time change of absorbance at nm (decrease absorbance at 430 nm)
It refers to the compound that causes it. (If the above-mentioned concentration does not dissolve, the concentration may be lowered to be measured.) Preferably,
The decoloration rate constant of galvinoxyl determined by the above method is 0.01 mmol ^-1 s ^-1 dm ³ or more, and more preferably 0.1 mmol ^-1 s ^-1 dm ³ or more. To determine the radical scavenging rate using galvinoxyl, see Micr
The stopped flow method is described in Ochemical Journal 31, 18-21 (1985), for example, on page 321 of Spectroscopic Research Vol. 19, No. 6 (1970). In the present invention, the radical scavenger is represented by the general formula (A-
It is further preferable to use the compounds represented by I) to (A-V). In addition, the general formula (AI) or (A-II)
Are more preferable among them.

In the general formula (AI), R _a1 is an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkylsulfonyl group, an alkyl or arylsulfinyl group,
Represents a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, R
_a2 represents a hydrogen atom, an arylsulfonyl group or a group represented by R _a1 . Provided that when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. . R _a1 and R _a2 may combine with each other to form a 5- to 7-membered ring. In formula (A-II), X represents a heterocyclic group, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. X and R _b1 are bonded to each other to form 5 to 7
A member ring may be formed. In the general formula (A-III), Y
Represents a group of non-metal atoms necessary for forming a 5-membered ring with -N = C-. Y is further 6 together with a -N = C- group.
Represents a group of non-metal atoms necessary for forming a member ring, and the terminus of Y bonded to the carbon atom of the -N = C- group is -N (R _c1 ).
-, -C (R _c2 ) (R _c3 )-, -C (R _C4 ) =, -O-, a group selected from -S- (a carbon atom of -N = C- on the left side of each group). Is combined with). R _{c1 to} R _c4 represent a hydrogen atom or a substituent. In the general formula (A-IV), R _d1 and R
_d2 may be the same or different and each represents an alkyl group or an aryl group. However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2 are alkyl groups having 8 or more carbon atoms. In formula (A-V), R _e1 and R _e2 may be the same or different and each is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group. Represents a group, an arylthio group, an alkyl group or an aryl group. However, R _e1 and R _e2 are simultaneously -NHR
It is not _e3 (R _e3 is an alkyl group or an aryl group). R _a1 and R _a2 , X and R _b1 are bonded to each other to form 5 to 7
A member ring may be formed. The present inventors have found that oxygen is involved in one of the causes of fluctuations in photographic properties due to storage of light-sensitive materials and fluctuations in photographic properties after photography and before development processing.
Some compound in the light-sensitive material reacts with oxygen, which affects the photographic properties, but the above general formulas (A-I) to (A-V)
It is presumed that the compound represented by is trapping this. The variation of photographic properties may increase by increasing the gelatin coating amount. It is estimated that trace amounts of impurities in gelatin react with oxygen, which affects photographic properties. In addition, the general formula (A-
It was found that the compounds represented by I) to (A-V) can improve the pressure resistance. Hereinafter, the present invention will be described in more detail.

The compounds represented by formulas (AI) to (AV) will be described in more detail. In formula (AI), R _a1 is an alkyl group (preferably having 1 to 36 carbon atoms).
Alkyl groups such as methyl, ethyl, i-propyl,
Cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl,
Benzyl), alkenyl group (preferably having 2 to 36 carbon atoms)
Is an alkenyl group such as allyl, 2-butenyl, isopropenyl, oleyl, vinyl), an aryl group (preferably an aryl group having 6 to 40 carbon atoms such as phenyl and naphthyl), an acyl group (preferably having 2 to 36 carbon atoms). An acyl group of, for example, acetyl, benzoyl, pivaloyl, α-
(2,4-di-tert-amylphenoxy) butyryl, myristoyl, stearoyl, naphthoyl, m-pentadecylbenzoyl, isonicotinoyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 36 carbon atoms such as methanesulfonyl and octane). Sulfonyl), an alkyl or arylsulfinyl group (this is preferably an alkyl or arylsulfinyl group having 1 to 40 carbon atoms, for example, methanesulfinyl, benzenesulfinyl), a carbamoyl group (including an N-substituted carbamoyl group, and preferably 1 to 1 carbon atoms. 40 carbamoyl groups such as N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-
(Phenylcarbamoyl), sulfamoyl group (including N-substituted sulfamoyl group, preferably having 1 to 40 carbon atoms)
A sulfamoyl group of N-methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl) , An alkoxycarbonyl group (preferably having 2 to 2 carbon atoms)
36 alkoxycarbonyl groups such as methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl) or aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 7 to 40 carbon atoms, such as phenoxycarbonyl). , Naphthoxycarbonyl). R _a2 is a hydrogen atom, arylsulfur
A sulfonyl group or a group represented by R _a1 .

In the general formula (A-II), a heterocyclic group (a group forming a 5- to 7-membered hetero ring having at least one of a nitrogen atom, a sulfur atom, an oxygen atom or a phosphorus atom as a ring-constituting atom) The bonding position of the heterocycle (position of the monovalent group) is preferably a carbon atom, for example, 1,
3,5-triazin-2-yl, 1,2,4-triazin-3-yl, pyridin-2-yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, 1,
2,4-triazol-3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, morpholinyl, phosphinolin-2-yl). R _b1 is represented by the general formula (A−
It represents an alkyl group, an alkenyl group or an aryl group having the same meaning as R _{a1 in} I).

In the general formula (A-III), Y is -N = C.
A group of non-metal atoms necessary for forming a 5-membered ring together with-(for example, the ring group formed is imidazolyl, benzimidazolyl, 1,3-thiazol-2-yl, 2-imidazolin-2-yl, purinyl, 3H -Indol-2-yl). Y is a group of non-metal atoms necessary for forming a 6-membered ring together with -N = C- group, and -N
The terminal of Y bonded to the carbon atom of the ═C-group is -N (R _c1 )-, -C
(R _c2 ) (R _c3 )-, —C (R _c4 ) =, —O—, a group selected from —S— (bonded to the carbon atom of —N═C— on the left side of each group) Represents R _{c1 to} R _c4 may be the same or different,
It represents a hydrogen atom or a substituent (for example, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, a halogen atom). Examples of the 6-membered ring group formed by Y include quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, 1,3,5-triazin-5-yl, 6H-1,2,5-thiadiazin-6-yl.

In the general formula (A-IV), R _d1 and R
_d2 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms, such as methyl, ethyl, i-propyl, cyclopropyl, n-butyl, isobutyl, hexyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl. ) Or an aryl group (preferably having 6 carbon atoms)
An aryl group of ˜40, for example phenyl, naphthyl). However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2 are alkyl groups having 8 or more carbon atoms.

In the general formula (A-V), R _e1 and R _e
e2 is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group (preferably an alkylamino group having 1 to 50 carbon atoms, such as methylamino, ethylamino, diethylamino, methylethylamino, propylamino, dibutylamino, cyclohexyl. Amino, t-octylamino, dodecylamino, hexadecylamino,
Benzylamino, benzylbutylamino), an arylamino group (preferably an arylamino group having 6 to 50 carbon atoms, for example, phenylamino, phenylmethylamino, diphenylamino, naphthylamino), an alkoxy group (preferably having 1 to 36 carbon atoms). An alkoxy group of, for example, methoxy, ethoxy, butoxy, t-butoxy, cyclohexyloxy, benzyloxy, octyloxy, tridecyloxy, hexadecyloxy), an aryloxy group (preferably an aryloxy group having 6 to 40 carbon atoms). , For example, phenoxy, naphthoxy), an alkylthio group (preferably an alkylthio group having 1 to 36 carbon atoms, such as methylthio, ethylthio, i-propylthio, butylthio,
Cyclohexylthio, benzylthio, t-octylthio, dodecylthio), an arylthio group (preferably an arylthio group having 6 to 40 carbon atoms, for example, phenylthio,
Naphthylthio), alkyl group (preferably having 1 to 3 carbon atoms)
6 alkyl groups such as methyl, ethyl, propyl,
Butyl, cyclohexyl, i-amyl, sec-hexyl, t-octyl, dodecyl, hexadecyl) and an aryl group (preferably an aryl group having 6 to 40 carbon atoms, for example, phenyl or naphthyl). However, R _e1 and R _e2
Are not simultaneously -NHR (R is an alkyl group or an aryl group).

R _a1 and R _a2 , X and R _b1 are bonded to each other to form 5
~ 7-membered ring may be formed, for example, a succinimide ring,
Examples thereof include a phthalimide ring, a triazole ring, a urazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring. Each group of the compounds represented by formulas (AI) to (AV) may be further substituted with a substituent.
Examples of these substituents include alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, hydroxy groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, acylamino groups, sulfonamide groups,
Alkylamino group, arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, hydroxyamino group And so on.

In formula (AI), R _a2 is a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and R _a1 is an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group or an alkoxycarbonyl group. Group, an aryloxycarbonyl group, and more preferably, R _a2 is an alkyl group or an alkenyl group, and R _a1 is an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. A compound that is a group.
Most preferably, R _a2 is an alkyl group and R _a1 is an acyl group.

In the general formula (A-II), R _b1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. On the other hand, X is the following general formula (A-II-
The compound represented by 1) is preferable, 1,3,5-triazin-2-yl is more preferable, and the compound represented by the following general formula (A-II-2) is most preferable.

[0088]

[Chemical 14]

[0089] In formula (A-II-1), R b1 represents R _b1 of the general formula (A-II), a non-metallic atomic group necessary for X ₁ to form a 5- or 6-membered ring Represent. General formula (A-
Of the compounds represented by II-1), it is more preferable that X ₁ forms a 5- or 6-membered heteroaromatic ring.

[0090]

[Chemical 15]

[0091] In formula (A-II-2), R b1 represents a R _b1 in formula (A-II). R _b2 and R _{b3, which} may be the same or different, each represents a hydrogen atom or a substituent. In the compound represented by formula (A-II-2), R _b2 and R _b3 are hydroxyamino group, hydroxyl group, amino group, alkylamino group, arylamino group, alkoxy group, aryloxy group, alkylthio group, Particularly preferred is an arylthio group, an alkyl group or an aryl group.

Of the compounds represented by the general formula (A-III), it is preferable that Y is a group of non-metal atoms necessary for forming a 5-membered ring, and it is bonded to the carbon atom of the -N = C- group. It is more preferable that the terminal atom of Y is a nitrogen atom. Y
Most preferably forms an imidazoline ring. This imidazoline ring may be condensed with a benzene ring.

Of the compounds represented by formula (A-IV), those in which R _d1 and R _d2 are alkyl groups are preferable. On the other hand, in the general formula (A-V), R _c1 and R _c2 are preferably a group selected from a hydroxyamino group, an alkylamino group and an alkoxy group. Particularly preferably, R _c1 is a hydroxylamino group and R _c2 is an alkylamino group.

Among the compounds represented by the general formulas (AI) to (AV), compounds having a total carbon number of 15 or less are preferable in that they act on layers other than the additive layer, and vice versa. It is preferable that the total number of carbon atoms is 16 or more for the purpose of acting only on the additive layer. General formula (AI)-(A-
V) among the compounds represented by the general formula (AI),
Those represented by (A-II), (A-IV) and (AV) are preferable, and more preferably those represented by the general formulas (AI) and (A-
IV) and (A-V), more preferably those represented by the general formulas (AI) and (A-V). The general formulas (A-I) to (A-V) of the present invention are shown below.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0095]

[Chemical 16]

[0096]

[Chemical 17]

[0097]

[Chemical 18]

[0098]

[Chemical 19]

[0099]

[Chemical 20]

These compounds and the above-mentioned general formula (AI)
Correspondence with ~ (A-V) is as follows. General formula (AI): A-33 to A- 45, A-47 to A- 55. General formula (A-II): A-5 to A-7, A-10, A-20. General formula (A-III): A-21 to A-32. General formula (A-IV): A-8, A-11, A-19. General formula (AV): A-1 to A-4, A-9, A-12 to A-18. These compounds of the present invention are described in J. Org. Chem., 27, 4054 ('
62), J. Amer. Chem. Soc., 73, 2981 ('51), Japanese Patent Publication No.49-
It can be easily synthesized by the method described in 10692 or the like or a method similar thereto. In the present invention,
The compounds represented by the general formulas (A-I) to (A-V) are
It may be added by dissolving it in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof, or by emulsifying and dispersing. When it dissolves in water, the higher or lower the pH, the higher the solubility,
It may be dissolved by increasing or decreasing the pH and then added. In the present invention, two or more kinds of the compounds represented by the general formulas (AI) to (AV) may be used in combination. For example, the combined use of a water-soluble one and an oil-soluble one may be advantageous in photographic performance.

The silver halide photographic light-sensitive material of the present invention is a color negative film, a reversal film, a color negative film for motion picture, a color positive film, a positive film for motion picture, a color light-sensitive material for motion picture, a black and white negative film, a micro film , X-ray film and the like. Preferred are general-purpose color and black-and-white photographic light-sensitive materials.

When the present invention is applied to a color photographic material, at least one photosensitive layer may be provided on the support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is blue light,
In a multilayer silver halide color photographic light-sensitive material, which is a unit photosensitive layer having color sensitivity to either green light or red light, the unit photosensitive layer is generally arranged in order from the support side to red color sensitivity. Layer, green color sensitive layer and blue color sensitive layer are installed in this order. However, even if the above installation order is reversed depending on the purpose,
Further, the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.
These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. The number of silver halide emulsion layers constituting each unit photosensitive layer is DE 1,121,470 or GB.
It is preferable to arrange two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in 923,045 so that the sensitivities of the layers are gradually decreased toward the support. In addition, JP-A-57-112751
No. 62-200350, No. 62-206541 and No. 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL /
It can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer / GL / RL from the side farthest from the support is used.
It can also be arranged in the order of / GH / RH. In addition, Japanese Examined Sho 49-1
As described in 5495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is a lower sensitivity silver halide emulsion layer, and the lower layer is a lower sensitivity silver halide emulsion. An example is an arrangement in which layers are arranged and three layers having different sensitivities are sequentially lowered toward the support, and the sensitivities are different from each other. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. Other, high sensitivity emulsion layer / low sensitivity emulsion layer /
Medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer /
The high-sensitivity emulsion layers may be arranged in this order. Also, in the case of four or more layers, the arrangement may be changed as described above. US 4,663,271, US 4,705,744, US
4,707,436, JP-A-62-160448 and 63-89850, a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL and RL is adjacent to the main photosensitive layer. Alternatively, it is preferable to arrange them in close proximity.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-.
Page 23, "I. Emulsion preparation and typ
es) ”, and No. 18716 (November 1979), p.648,
No. 307105 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Glafkides, Chemie et PhisiquePhotographique, P.
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emul
sion Chemistry, Focal Press, 1966), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (V.
L. Zelikman, et al., Making and Coating Photograph
ic Emulsion, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
The monodisperse emulsions described in 13,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the method described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image on both the surface and the inside may be used, but a negative type emulsion is required. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method 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 is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are RD No. 17643 and RD No. 17643.
18716 and No. 307105, and the relevant parts are summarized in the table below. The light-sensitive material of the present invention includes a light-sensitive silver halide emulsion having a grain size, a grain size distribution,
Two or more kinds of emulsions having different characteristics of at least one of halogen composition, grain shape, and sensitivity can be mixed and used in the same layer. US Pat. No. 4,082,553, the surface of which is covered with a silver halide grain, US Pat.
It is preferable to apply the internally fogged silver halide grains and colloidal silver described in 9-214852 to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm.
, Particularly preferably 0.05 to 0.6 μm. The grain shape may be a regular grain or a polydisperse emulsion, but monodispersity (at least the weight or the number of grains of silver halide grains)
95% has a particle size within ± 40% of the average particle size)
Is preferred.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 page right column page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868, 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right columns 875-876 Pages Surfactants 9. Static 27 Pages 650 650 Right columns 876-877 Inhibitors 10. Matting agents 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, but the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); Japanese Patent Application No. 4 -134523 represented by the general formula (I) of claim 1; US 5,066,576, column 1, lines 45 to 55; the coupler represented by the general formula (I); JP-A-4-274425, paragraph 0008; Couplers of the formula I); couplers according to claim 1 of EP 498,381A1 on page 40 (in particular D-35 on page 18); formulas of page 4 of EP 447,969A1
A coupler represented by (Y) (especially Y-1 (page 17), Y-54 (41
)); US 4,476,219, column 7, lines 36-58, formulas (II)-(I
V) couplers (especially II-17, 19 (column 17), II
-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (bottom right of page 12), L-77 (bottom right of page 13); EP 456,257, A-4 -6
3 (134 pages), A-4 -73, -75 (139 pages); EP 486,965 M-4, -6
(Page 26), M-7 (Page 27); M-4 of Paragraph 0024 of Japanese Patent Application No. 4-234120
5; M-1 in paragraph 0036 of Japanese Patent Application No. 4-36917; M-22 in paragraph 0237 of Japanese Patent Application Laid-Open No. 4-362631. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42-43); Japanese Patent Application No. 4-23633
A coupler represented by the general formula (Ia) or (Ib) of claim 1. Polymer coupler: JP-A-2-44345, P-1, P-5 (page 11).

Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. The coupler for correcting the unwanted absorption of the color forming dye is a yellow-colored cyan coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
Page), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), US 4,837,136 (2) (column 8),
The colorless masking couplers represented by formula (A) in claim 1 of WO92 / 11575 (in particular, the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized product of a developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
Page), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP436, 93
Compounds represented by formula (I) on page 7 of 8A2 (especially D-4
9 (page 51)), a compound represented by the formula (1) of Japanese Patent Application No. 4-134523 (particularly (23) in paragraph 0027), and formulas (I) and (II in EP 440,195A2 on pages 5 to 6). ), (III) (particularly I- (1) on page 29); Bleach accelerator releasing compounds: EP 310,125A2-5
Compounds represented by formulas (I) and (I ') on page (especially (60) on page 61,
(61)) and a compound represented by the formula (I) in claim 1 of Japanese Patent Application No. 4-325564 (particularly (7) in paragraph 0022); a ligand-releasing compound: LIG-X described in claim 1 of US 4,555,478. Compounds represented (especially compounds on lines 21 to 41 of column 12); Leuco dye releasing compounds: compounds 1 to 6 of columns 3 to 8 of US 4,749,641; fluorescent dye releasing compounds: COUP-DYE of claim 1 of US 4,774,181 Compounds represented (especially columns 7-10)
Compounds 1 to 11); development accelerator or fogging agent releasing compounds: compounds represented by formulas (1), (2) and (3) of column 3, US Pat. No. 4,656,123 (particularly (I-22) of column 25) and EP 450,6
ExZK-2 on page 75, lines 36-38 of 37A2; Compounds that release a dye group only upon leaving: a compound of formula (I) of claim 1 of US 4,857,447 (especially Y- of columns 25-36). 1 ~
Y-19).

The following additives are preferable as additives other than the coupler. Dispersion medium of oil-soluble organic compound: P-3,5 of JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140〜144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US 4,978,606 (particularly I-, (1), (2), (6), (12 ) (Column 4-
5), US Pat. No. 4,923,787, column 2, lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP 298321A, 4).
Formulas (I)-(III) on pages 30-33, especially I-47, 72, III-1, 27 (24
~ Page 48); Anti-fading agent: A-6,7,20,21,23,2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69〜118
Pp.), US 5,122,444, columns 25-38, II-1 to III-23, especially
III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Materials that reduce the use of color enhancers or color mixing inhibitors: EP 411324A, pages 1 to 24, I-1 to II-15, especially I-46;
Formalin Scavenger: EP 477932A SC on pages 24-29
V-1 to 28, especially SCV-8; Hardener: H-1,4,6,8,14, US Pat.
Compounds (H-1 to 54) represented by I) to (XII), JP-A-2-214
852 compound (H-1 to 76) represented by the formula (6) at the lower right of page 8,
In particular H-14, a compound according to claim 1 of US 3,325,287;
Development inhibitor precursor: P-24,37 of JP-A-62-168139,
39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US 4,92.
Columns 3 to 15 of 3,790 I-1 to III-43, especially II-1,9,10,1
8, III-25; Stabilizer, antifoggant: US Pat. No. 4,923,793, columns 6 to 16 I-1 to (14), especially I-1,60, (2), (13), US 4,
952, 483 columns 25-32 compounds 1-65, especially 36: chemical sensitizer: triphenylphosphine selenide, JP
40324 Compound 50; Dye: JP-A-3-156450, pages 15-18
a-1 to b-20, especially a-1, 12, 18, 27, 35, 36, b-5, V on pages 27-29
-1 to 23, especially V-1, EP 445627A, FI-1 to F on pages 33 to 55
-II-43, especially FI-11, F-II-8, EP 457153A, pages 17-28, I
II-1 to 36, especially III-1,3, WO 88/04794 8-26 Dye-1
~ 124 microcrystalline dispersion, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, formula (1) to EP 519306A
Compound D-1 represented by (3) -87 (pages 3-28), US 4,268,6
22 compounds 1 to 22 (columns 3 to 10) represented by formula (I),
Compounds (1) to (31) represented by the formula (I) of US 4,923,788
(Columns 2 to 9); UV absorber: Compounds (18b) to (18r), 101 to 427 (pages 6 to 9), represented by formula (1) of JP-A-46-3335, EP
Compounds (3) to (66) (10 to 520938A represented by the formula (I)
Page 44) and compounds of formula (III) HBT-1 to 10 (14
Page), compounds (1) to (3) represented by the formula (1) of EP 521823A.
1) (columns 2-9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention include
For example, the RD. No. 17643, page 28, No. 18716
Page 647, right column to page 648, left column, and No. 307105, 8
It is described on page 79. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less,
18 μm or less is more preferable, and 16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is a color developer at 30 ° C, 3
When 90% of the maximum swollen film thickness reached after processing for 15 minutes is the saturated film thickness, it is defined as the time until the film thickness reaches 1/2. The film thickness is 25 ° C and 55% relative humidity (2
Meaning the film thickness measured in days), T _1/2 is A. Green et al.'S Photographic Science and Engineering (Photogr.Sci.Eng.), 19 squares,
It can be measured by using a swellometer of the type described on pages 2,124 to 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. Swelling rate, from the maximum swollen film thickness under the conditions described above,
It can be calculated by the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. The swelling ratio of this back layer is preferably 150 to 500%.

The light-sensitive material of the present invention is the same as RD. No. 17
Development can be carried out by a usual method described on pages 28 to 29 of 643, 651 left column to right column of No. 18716, and pages 880 to 881 of No. 307105. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples and preferred examples thereof are compounds described in EP 556700A, page 28, lines 43 to 52. Is mentioned. Two or more of these compounds can be used in combination depending on the purpose. Color developing solutions include alkali metal carbonates, pH buffers such as borate or phosphate, chloride salts, bromide salts, iodide salts, benzimidazoles,
A development inhibitor such as benzothiazoles or mercapto compounds or an antifoggant is generally contained. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanedia Mine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, Add ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, 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 are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The processing effect of the contact between the photographic processing liquid and air in the processing tank is the aperture ratio (= [contact area between processing liquid and air c
m ² ] ÷ [volume of treatment liquid cm ³ ]). The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 and JP-A-63-216050 are disclosed. The slit development processing method described can be mentioned. The aperture ratio is preferably reduced not only in both the color development step and the black-and-white development step but also in the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing, stabilizing and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The time of color development processing is usually set between 2 and 5 minutes, but by using a high temperature, high pH and using a color developing agent at a high concentration,
Further, the processing time can be shortened.

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 individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Of these, iron (III) aminopolycarboxylates including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts
Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US 3,893,858, DE 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53-37418, 53-72623. ,
53-95630, 53-95631, 53-104232, 53-12442
4, compounds 53-141623, 53-28426 and RD No. 17129 (July 1978), compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506. , JP-A-52-20832, JP-A-53-32735,
Thiourea derivatives described in US 3,706,561; DE 1,127,715,
Iodide salts described in JP-A-58-16,235; DE 966,410,
2,748,430, polyoxyethylene compounds; JP-B-45-8836, polyamine compounds; and others, JP-A-49-4
0,943, 49-59,644, 53-94,927, 54-35,727,
55-26,506 and 58-163,940; bromide ions can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, US 3,893,858, DE 1,290,812, JP-A-53-95,63.
The compounds described in 0 are preferred. Further, the compounds described in US 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. Yes, especially ammonium thiosulfate can be used most widely. Also,
Thiosulfates and thiocyanates, thioether compounds,
A combined use of thiourea is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, addition of aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution is preferable for the purpose of stabilizing the solution. In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole or 2-methylimidazole. It is preferable to add 0.1 to 10 mol per liter.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or a stirring effect by using a rotating means of JP-A-62-183461 is used. Method of raising, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, the circulation flow rate of the entire processing solution There is a method of increasing it. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
It is preferable to have the photosensitive material transporting means described in 60-191258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid. It is particularly effective in shortening the processing time and reducing the replenishment amount of the processing liquid.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent and forward flow, and various other conditions. Can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of t
he Society of MotionPicture and Television Enginee
It can be determined by the method described in rs Volume 64, P. 248 to 253 (May 1955). According to the multi-stage countercurrent method described in this document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced adheres to the photosensitive material. Problem arises. As a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 is extremely effective. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicide"
(1986) Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used. The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8.
The washing water temperature and washing time can be set depending on the characteristics and use of the light-sensitive material, but in general, a range of 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C is selected. . Furthermore,
The light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-58-220345 can be applied. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and as an example thereof, a stabilizing bath containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is mentioned. You can Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The photographic material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use a precursor of a color developing agent. For example US 3,34
2,597 described indoaniline compound, 3,342,599,
Research Disclosure No.14,850 and No.1
Examples thereof include Schiff base type compounds described in 5,159, aldol compounds described in 13,924, metal salt complexes described in US 3,719,492, and urethane compounds described in JP-A-53-135628. The photographic material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339,
57-144547 and 58-115438.
The processing liquid used for processing the light-sensitive material of the present invention is 10 ° C to 50 ° C.
Used at ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the processing to shorten the processing time, and to lower the temperature to improve the image quality and the stability of the processing liquid. it can.

There are no particular restrictions on various additives and development processing methods used when the present invention is applied to a black-and-white light-sensitive material. For example, JP-A-2-68539 and JP-A-5-1138.
Nos. 9 and 2-58041 described below can be preferably used.

1. Silver halide emulsion and its manufacturing method
2-68539, page 8, lower right column, line 6 from bottom to page 10 upper right column, line 12 2. Chemical sensitization method: page 10, upper right column, line 13 to left lower column 16,
Line, selenium sensitization method described in JP-A-5-11389. 3. Anti-fogging agent / stabilizer: JP-A-2-68539, No. 10
Page 17, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column. 4. Spectral sensitizing dyes: page 4, lower right column, line 4 to page 8, lower right column, and JP-A-2-58041, page 12, lower left column, line 8 to lower right column, line 19. 5. Surfactants / antistatic agents: JP-A-2-68539
Page 11, upper left column, line 14 to page 12, upper left column, line 9 and JP-A-2-
No. 58041, page 2, lower left column, line 14 to page 5, line 12 6. Matting agents, plasticizers, and slip agents: page 12, upper left column, line 10 to upper right column, line 10 and JP-A-2-58041, page 5, lower left column, line 13 to page 10, lower left column, line 3 Eye. 7. Hydrophilic colloid: JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16 8. Hardener: Page 12, lower left column, line 17 to page 13, upper right column 6
Line. 9. Development method: page 15, upper left column, line 14 to same lower left column 13
Line.

[0121]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 This example illustrates the effect of combining a radical scavenger and a reduction sensitized emulsion. (1) Preparation of Emulsion An aqueous solution prepared by dissolving 6 g of potassium bromide and 30 g of an inactive gelatin having an average molecular weight of 15,000 in 3.71 of distilled water was stirred well, and a 14% aqueous solution of potassium bromide was added thereto by the double jet method. A 20% aqueous solution of silver nitrate was added at a constant flow rate over 1 minute at 55 ° C. and pBr of 1.0 (this addition consumed 2.4% of the total silver).

A gelatin aqueous solution (17%, 300 cc) was added, and the mixture was stirred at 55 ° C., and then a 20% silver nitrate aqueous solution was added at a constant flow rate until pBr reached 1.4 (this addition of 5. 0% consumed). Furthermore, 20%
Solution of potassium iodobromide (KBr _1-x I _x : x = 0.0
4) and 33% aqueous silver nitrate solution were added over 43 minutes by the double jet method (with this addition, 5% of the total silver amount was added).
0% consumed). Here, after adding an aqueous solution containing 8.3 g of potassium iodide, 0.001 / wt% of K ₃ I was added.
14.5 ml of an aqueous rCl ₆ solution was added, and a 20% potassium bromide solution and a 33% silver nitrate aqueous solution were added by the double jet method over 39 minutes (this addition consumed 42.6% of the total silver amount). The amount of silver nitrate used in this emulsion was 425 g. Then, after desalting by a usual flocculation method, pAg was adjusted to 8.2 and pH was adjusted to 5.8 at 40 ° C. A tabular silver iodobromide emulsion having an average aspect ratio of 6.5, a coefficient of variation of 18% and a sphere equivalent diameter of 0.8 μm (Em-
1) was prepared. Observation with a 200 kV transmission electron microscope at a liquid N ₂ temperature revealed that, on average, 50 or more dislocation lines per grain exist near the outer periphery of the tabular grain. In contrast,
After pBr reached 1.4, Emulsion E was prepared in the same manner as Emulsion Em-1 except that thiourea dioxide was added to the reaction pot in an amount of 1.2 × 10 ^-5 mol per mol of silver to form grains.
m-2 was produced. Emulsion Em-3 was prepared in exactly the same manner as emulsion Em-2, except that thiourea dioxide was changed to 2.5 × 10 ⁻³ mol / mol Ag of L-ascorbic acid.

When grains are formed in the same manner as Emulsion Em-2, Emulsion Em- except that Compound (1-2) is added in an amount of 1.2 × 10 ^-4 mol per mol of silver 10 minutes after the start of the final shell formation. Emulsion Em-4 was prepared in exactly the same manner as in 2.

Emulsions Em-1 to 4 thus prepared
Sensitizing dye EXS-1 described below in 3 × 10 ⁻⁴ mol / mol Ag, sensitizing dye EXS-2 at 1.5 × 10 ⁻⁵ mol / mol Ag, and sensitizing dye EXS-3 at 4.5 ×. After adding 10 ⁻⁴ mol / mol Ag, sodium thiosulfate and chloroauric acid were added,
Optimum gold-selenium-sulfur sensitization using N, N-dimethylselenourea and potassium thiocyanate, emulsions 101-1
04 was produced. Further, in the emulsions Em-1 to 4, the sensitizing dye EXS-4 was added at 5 × 10 ⁻⁵ mol / mol Ag and the sensitizing dye EX was added.
1.1 × 10 ⁻⁴ mol / mol Ag of S-5, sensitizing dye EX
Emulsions 105-108 were prepared in the same manner as emulsions 101-104 except that S-6 was changed to 4.5 × 10 ^-4 mol / mol Ag.
Was produced.

(2) Preparation of multi-layer color light-sensitive material On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 1001 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Hardening agent ExS: Number corresponding to each component of the sensitizing dye indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.09 Silver iodobromide emulsion with surface and internal fog N Silver 0.05 ExC-1 0.02 ExC-3 0.03 HSB-1 0.05 HSB-2 0.02 Gelatin 0.70 Second layer (second antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.00 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

[0127] Third layer (middle layer) Silver iodobromide emulsion M Silver 0.04 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Fourth Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion A Silver 0.25 Silver Iodobromide Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-2 0.02 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 HBS-1 0.10 Gelatin 0.87

Fifth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.6 × 10 ⁻⁵ ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.13 ExC-2 0.04 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 HBS-1 0.10 Gelatin 0.75

Sixth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion 101 Silver 1.40 ExS-1 3 × 10 ^-4 ExS-2 1.5 × 10 ^-4 ExS-3 4.5 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

[0131] 7th layer (middle layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Eighth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-3 0.33 ExM-4 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Ninth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-3 0.10 ExM-4 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

10th Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion 105 Silver 1.25 ExS-4 5 × 10 ^-5 ExS-5 1.1 × 10 ^-4 ExS-6 4.5 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-2 0.020 ExM-5 0.025 ExM-6 0.020 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

[0135] 11th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Twelfth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ⁻⁴ ExC-1 0.03 ExC-8 7.0 × 10 ⁻³ ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-3 1.0 × 10 ⁻³ HBS-1 0.070 Gelatin 0.70

14th layer (first protective layer) UV-1 0.15 UV-2 0.075 UV-3 0.065 UV-4 0.025 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8

Fifteenth layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0141]

[Table 1]

In Table 1, (1) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (2) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (3) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (4) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% aqueous solution of p-octylphenoxyethoxyethoxyethaneethanesulfonate and 5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree: 10) (0.5 g) were put in a 700 ml pot mill, and the dye was added. 5.0 g of ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added to disperse the contents for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0145]

[Chemical 21]

[0146]

[Chemical formula 22]

[0147]

[Chemical formula 23]

[0148]

[Chemical formula 24]

[0149]

[Chemical 25]

[0150]

[Chemical formula 26]

[0151]

[Chemical 27]

[0152]

[Chemical 28]

[0153]

[Chemical 29]

[0154]

[Chemical 30]

[0155]

[Chemical 31]

[0156]

[Chemical 32]

[0157]

[Chemical 33]

[0158]

[Chemical 34]

[0159]

[Chemical 35]

[0160]

[Chemical 36]

Samples 1002 to 1013 were prepared by changing the emulsions of the sixth and tenth layers as shown in Table 2 to the sample 1001 and further adding the radical scavenger of the present invention.

[0162]

[Table 2]

These samples were exposed for sensitometry at a color temperature of 4800 ° K through a continuous wedge for 1/100 seconds and subjected to the following color development processing.

The developing process used here is 38 under the following conditions.
Performed at ° C.

[0165]                           Processing method       Process processing time Processing temperature Replenishment amount Tank capacity     Color development 3 minutes 15 seconds 38 ℃ 33ml 20 liters     Bleach 6 minutes 30 seconds 38 ℃ 25ml 40 liters     Washing with water 2 minutes 10 seconds 24 ° C 1200 ml 20 liters     Stationary 4 minutes 20 seconds 38 ℃ 25ml 30 liters     Washing with water (1) 1 minute 05 seconds 24 ℃ From (2) to (1) 10 liters                                           Countercurrent piping system     Washing with water (2) 1 minute 00 seconds 24 ° C 1200 ml 10 liters     Stable (3) 1 minute 05 seconds 38 ℃ 25 ml 10 liters     Dry 4 minutes 20 seconds 55 ℃       Replenishment amount is 35mm width 1m per length Next, the composition of the treatment liquid will be described. (Color developer)                                             Mother liquor (g) Replenisher (g)     Diethylenetriamine pentaacetic acid 1.0 1.1     1-Hydroxyethylidene-1,1-3.0 3.2       Diphosphonic acid     Sodium sulfite 4.0 4.4     Potassium carbonate 30.0 37.0     Potassium bromide 1.4 0.7     Potassium iodide 1.5 mg-     Hydroxylamine sulfate 2.4 2.8     4- [N-ethyl-N-β-hydroxy 4.5 5.5       Ethylaniline sulfate     Add water 1.0 liter 1.0 liter     pH 10.05 10.10 (Bleaching solution)                                             Mother liquor (g) Replenisher (g)     Ethylenediaminetetraacetic acid second 100.0 120.0       Sodium iron trihydrate     Ethylenediaminetetraacetic acid disodium salt 10.0 11.0     Ammonium bromide 140.0 160.0     Ammonium nitrate 30.0 35.0     Ammonia water (27%) 6.5 ml 4.0 ml     Add water 1.0 liter 1.0 liter     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%) 170.0 ml 200.0 ml     Add water 1.0 liter 1.0 liter     pH 6.7 6.6 (Stabilizer)                                             Mother liquor (g) Replenisher (g)     Formalin (37%) 2.0 ml 3.0 ml     Polyoxyethylene-p-monononyl 0.3 0.45       Phenyl ether (average degree of polymerization 10)     Ethylenediaminetetraacetic acid disodium salt 0.05 0.08     Add water 1.0 liter 1.0 liter     pH 5.8-8.0 5.8-8.0 The concentration of the treatment agent sample was measured according to a conventional method.

The obtained sensitivity and fog were evaluated.
Regarding the sensitivity, the relative value of the reciprocal of the exposure amount required for the optical density to be higher than the fog by 0.2 is shown as the sensitivity.

Next, the following processing was carried out in order to evaluate the latent image storability and the fog with time. After each sample was wedge-exposed in the same manner as before, after aged for 14 days in an atmosphere of a temperature of 50 ° C. and a relative humidity of 30%, the same color development processing as before was performed, and compared with the data developed immediately after exposure, The difference in fog was taken as a representative value of fog over time, and the difference in sensitivity was taken as a representative value of latent image assisting force and latent image regression. The results thus obtained are shown in Table 3.

[0168]

[Table 3]

As is clear from Table 3, Sample 10 of the present invention
Nos. 06 to 1012 have higher sensitivity to the comparative samples 1001 and 1005, and the comparative sample 1002 subjected to reduction sensitization.
The fog is low with respect to 1004, the increase in fog after aging is small, and the change in sensitivity after aging of the latent image is small, and the effect of the present invention is clear.

Further, the effect of the compound of the general formula (I) is shown in the comparison between the samples 1008 and 1006, and the effects of the general formulas (A-I) to (A).
-V) radical scavenger effect is 1008-1
From the comparison between 011 and 1012, it is clear that it is more preferable.

Example 2 This example is for explaining the effect of the present invention on pressure fog and the effect of dislocation lines. Emulsion E of Example 1
0.001 / wt% of K ₃ IrC based on M-1,4
The amount of dislocation lines was adjusted as shown in Table 4 by changing the amount and method of addition of potassium iodide before the addition of the ₁₆ aqueous solution.
-5, 6, and 7 were created. Emulsion 10 of Example 1, respectively
Emulsion 10 after spectral sensitization and chemical sensitization similar to 1 and 104
9,110,111 were created. Sample 100 of Example 1
The emulsion of the 10th layer was changed as shown in Table 4 for 1 and
Further, the radical scavenger of the present invention was added to prepare samples 2001 to 20.

The pressure characteristics were evaluated as follows. One end of the coated sample was fixed with the emulsion surface facing inward under a humidity condition of 40% relative humidity, and was bent along a stainless pipe having a diameter of 10 mm while being rotated 180 ° at a bending speed of 360 ° / sec. These folds were made 10 seconds before exposure. With respect to the obtained fog, the portions that were bent and the portions that were not bent were evaluated. These results are also shown in Table 4.

[0173]

[Table 4]

As is clear from Table 4, the sample of the present invention showed that both the high sensitivity, the fog with time, and the small change in sensitivity after the latent image were compatible with each other in Example 1. It is clear from the invention that high sensitivity and small pressure fog are compatible. In addition, 2007-201
By comparing 0, the usefulness of having 10 or more dislocation lines is also clear.

[0175]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having high image quality and high sensitivity which is excellent in storage performance and pressure resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 1/34 G03C 1/08 G03C 7/392

Claims (10)

(57) [Claims] 1. A photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one radical scavenger (provided that the following compound
(Except for VII-2)), and the light-sensitive silver halide grains in the emulsion layer are subjected to reduction sensitization. [Chemical 1-1] The radical scavenger is a galbino at 25 ° C.
Test compound with 0.05 mmoldm ^-3 ethanol solution of xyl
2.5 mmoldm ^-3 ethanol solution of
Mixing by the Rho method, absorbance time at 430 nm
The change was measured, and the galvinoxyl was substantially erased (430
a compound that reduces the absorbance at nm)
U (If the above concentration does not dissolve, lower the concentration and measure.
You may set it. ) 2. The silver halide photographic light-sensitive material according to claim 1, wherein the radical scavenger does not include a compound represented by the following general formula (VII). [Chemical 1-2] In the formula, R ⁷¹ is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an alkenyl group, an alkynyl group or a hydrazino group, and G ⁷¹ is —SO ₂ -, -SO-, -PO
(R ³⁵⁾ -, iminomethylene, -COCO- or -CO
And R ³⁵ is an alkyl group or an aryl group,
⁷⁴ is a hydrogen atom or a group removed under alkaline conditions, R ⁷³ may be an alkyl group, and q is 0, 1 or 2. The groups described above may have a substituent. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the radical scavenger does not include a compound represented by the following general formula (AI) ′. [Chemical 1-3] In formula (AI) ′, R _a1 represents an arylsulfonyl group and R _a2 represents a hydrogen atom. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the radical scavenger does not include a compound represented by the following general formula (AI) ″. In the general formula (AI) ”, R _a1 represents an arylsulfonyl group, R _a2 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, It represents a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. 5. The silver halide grains in the emulsion layer have been subjected to reduction sensitization, and have the following general formulas (I) and (I
2. At least one compound selected from the compounds represented by I) or (III) is contained.
5. The silver halide photographic light-sensitive material according to any one of items 1 to 4. General formula _{(I) R-SO 2 S} -M Formula _{(II) R-SO 2 S} -R 3 formula (III) in _{R-SO 2 S-L m} -SSO 2 -R 4 Formula, R, R ³ , R ⁴ may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a cation, L represents a divalent linking group, m is 0 or 1. is there. The compounds of the general formulas (I) to (III) may be polymers containing a divalent group derived from the structures represented by (I) to (III) as a repeating unit. 6. A tabular silver halide grain having an aspect ratio of 3 or more having at least 10 dislocation lines in one grain, at least 60% of the total projected area of said photosensitive silver halide grain. 6. The silver halide photographic light-sensitive material according to claim 1. 7. The radical scavenger according to claim 1, wherein the radical scavenger is a compound represented by the following general formulas (AI) to (AV). Silver halide photographic light-sensitive material. [Chemical 1-5] In formula (AI), R _a1 represents an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. , R _a2 represents a hydrogen atom, an arylsulfonyl group or the group represented by R _a1 . Provided that when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group,
It is a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1
And R _a2 may combine with each other to form a 5- to 7-membered ring. In formula (A-II), X represents a heterocyclic group, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. X and R _b1 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-III), Y is -N =
It represents a group of non-metal atoms necessary for forming a 5-membered ring with C-. Y represents a group of non-metal atoms necessary for forming a 6-membered ring together with a -N = C- group, and -N = C
The end of Y bonded to the carbon atom of the -group is -N (R _c1 )-, -C
(R _c2 ) (R _c3 )-, —C (R _C4 ) =, —O—, a group selected from —S— (bonded to the carbon atom of —N═C— on the left side of each group) Represents R _{c1 to} R _c4 represent a hydrogen atom or a substituent. In formula (A-IV), R _d1 and R _{d2, which} may be the same or different, each represents an alkyl group or an aryl group. However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2 are alkyl groups having 8 or more carbon atoms. In formula (A-V), R _e1 and R _e2 may be the same or different and each is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group. Represents a group, an arylthio group, an alkyl group or an aryl group. However, R _e1 and R _e2 are not —NHR _e3 (R _e3 is an alkyl group or an aryl group) at the same time. R _a1 and R _a2 , and X and R _b1 may combine with each other to form a 5- to 7-membered ring. 8. The silver halide photographic light-sensitive material according to claim 7, wherein the radical scavenger is a compound represented by the general formula (AI) or (A-II). 9. The silver halide according to claim 1, wherein the radical scavenger galvinoxyl has a decolorization rate constant of 0.01 mmol ⁻¹ s ⁻¹ dm ³ or more. Photographic material. 10. The silver halide according to claim 1, wherein the radical scavenger galvinoxyl has a decolorization rate constant of 0.1 mmol ⁻¹ s ⁻¹ dm ³ or more. Photographic material.