JPH0862768A - Silver halide emulsion, its manufacture, and photosensitive material using this emulsion - Google Patents

Abstract

PURPOSE: To obtain a silver halide photographic sensitive material low in fog and high in sensitivity by executing reduction sensitization and gold.chalcogen sensitization and incorporating a specified radical scavenger. CONSTITUTION: This silver halide color photographic sensitive material is formed by executing the reduction sensitization and the gold.chalcogen sensitization of a silver halide emulsion layer and before the end of the gold.chalcogen sensitization adding the radical scavenger represented by the formula in which Ra2 is a heterocyclic group, an acyl, sulfonyl, sulfinyl, carbamoyl, sulfamoyl, alkoxycarbonyl, or aryloxycarbonyl group, when Ra1 is an alkyl, alkenyl, or aryl group. It is preferred that silver halide grains are flat grains occupying >=60% of the projection areas of the total silver halide grains and having dislocation lines and an aspect ratio of >=3.

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 containing reduction-sensitized grains and having high sensitivity and excellent graininess.

[0002]

2. Description of the Related Art Attempts for reduction sensitization have been studied for a long time in order to improve sensitivity. Carroll in US Pat. No. 2,487,850 describes tin compounds as
Lowe et al., Usefulness of Polyamine Compounds in No. 2,512,925 and Fallens et al., Use of Thiourea Dioxide Compounds as Reduction Sensitizer in British Patent No. 789,823. Was disclosed. Collier is Pho
toographic Science and Engi
Neering, Vol. 23, page 113 (1979), compares the properties of silver nuclei made by various reduction sensitization methods. She adopted the methods of dimethylamine borane, stannous chloride, hydrazine, high pH aging, low pAg aging. The method of reduction sensitization is further described in US Pat. No. 2,518,
No. 698, No. 3,201,254, No. 3,41
No. 1,917, No. 3,779,777, No. 3,9
No. 30,867. Regarding the improvement of reduction sensitization method as well as the selection of reduction sensitizer,
3572 and 58-1410. Further, techniques for improving the storage stability of reduction-sensitized emulsions are also disclosed in JP-A-57-82831 and 60-178445. Furthermore, Takada et al.
No. 38 discloses a method for preparing a reduction sensitized emulsion using thiosulfonic acid. In spite of such many studies, the width of increase in sensitivity was insufficient as compared with the hydrogen sensitization in which the photosensitive material was treated with hydrogen gas. This is the Journal of Imaging Scie
No. 29, page 233 (1985), Moisa
r (Moiser) et al. On the other hand, JP-A-59-162546 describes a method for improving latent image intensification by using a hydroxylamine compound, but it does not make a silver halide emulsion highly sensitive.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity without raising fog.

[0004]

As a result of earnest studies, the inventors of the present invention were able to achieve the solution to the above-mentioned problems by the following means. That is,

(1) It is characterized in that it is subjected to reduction sensitization and gold / chalcogen sensitization (normal gold sensitization and chalcogen sensitization are all right) and contains at least one radical scavenger. Silver halide emulsion, (2)
A method for producing a silver halide emulsion, which comprises adding at least one radical scavenger after the reduction sensitization and before the end of the gold / chalcogen sensitization,

(3) It contains a silver halide emulsion prepared after reduction sensitization and before the end of gold / chalcogen sensitization by adding at least one radical scavenger. A silver halide photographic light-sensitive material characterized by having at least one silver halide emulsion layer on a support, (4) a photographic light-sensitive material having at least one silver halide emulsion layer on a support, A silver halide photographic light-sensitive material characterized in that the silver halide grains in the emulsion layer are subjected to reduction sensitization and contain a radical scavenger represented by the following general formula (A) before the completion of chemical sensitization. ,

[0007]

Embedded image

In the general formula [A], R _a1 is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group,
It represents a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and R _a2 represents a hydrogen atom 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 a heterocyclic group,
It is an acyl group, a sulfonyl group, a 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.

(5) The silver halide grains which have been subjected to reduction sensitization in the emulsion layer and which contain a radical scavenger represented by the general formula (A), account for at least 60% of the total projected area thereof. Aspect ratio 3 with dislocation lines
(4) The silver halide photographic light-sensitive material described in (4) above, which is a tabular silver halide grain described above.
The color silver halide photographic light-sensitive material according to item (3), (4) or (5), which contains at least one color coupler.

The reduction sensitization used in the present invention will be described below.

The steps for producing a silver halide emulsion are roughly classified into steps such as grain formation, desalting and chemical sensitization. Particle formation is divided into nucleation, ripening and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. The fact that reduction sensitization is performed 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 during nucleation which is an initial stage of grain formation, during physical ripening, during growth, or before chemical sensitization other than reduction sensitization or after this chemical sensitization. . Here, the chemical sensitization refers to chemical sensitization other than reduction 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 growth of silver halide grains. The term "during growth" here also refers to a method in which the silver halide grains are physically ripened or subjected to reduction sensitization while they are growing by the addition of a water-soluble silver salt and a water-soluble alkali halide, and the growth is temporarily stopped during the growth. 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 means 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 include stannous salts, amines and polyamines, 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. (AA-1) L-ascorbic acid (AA-2) L-ascorbic acid sodium (AA-3) L-ascorbic acid potassium (AA-4) DL-ascorbic acid (AA-5) D-ascorbic acid sodium (AA) -6) L-ascorbic acid-6-acetate (AA-7) L-ascorbic acid-6-palmitate (AA-8) L-ascorbic acid-6-benzoate (AA-9) L-ascorbic acid-5,6 -Diacetate (AA-10) L-ascorbic acid-5,6-O-isopropylidene (AA-11) D-ascorbic acid As the ascorbic acid compound used in the present invention, a conventional reduction sensitizer is preferably used. It is desirable to use a large amount compared to the amount added. 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. The amount of the ascorbic acid compound used in the present invention depends on factors such as the grain size of the emulsion, the halogen composition, the temperature for emulsion preparation, pH and pAg, but the preferred addition amount depends on 5 × 10 ^-5 to 1 per mol of silver halide.
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 may be dissolved in water or a solvent such as alcohols, 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, but it is preferable to add it at an appropriate time for particle 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. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

[0018] 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
It refers to a compound that substantially eliminates the color of galvinoxyl (decreases the absorbance at 430 nm) by measuring the time change of the absorbance at nm. (If the above-mentioned concentration does not dissolve, the concentration may be lowered for measurement.)

Preferably, the decoloration rate constant of galvinoxyl determined by the above method is 0.01 mmol ^-1 s ^-1
dm ³ or more, more preferably 0.1 mmol ⁻¹ s ⁻¹ dm ³ or more.

The method for determining the radical scavenging rate using galvinoxyl is described in Microchemical Journal 31, 18
-21 (1985), the stopped flow method is described in, for example, Spectroscopic Research Vol. 19, No. 6, (1970), p. 321.

In the present invention, it is more preferable to use the compound represented by the general formula [A] as the radical scavenger. The compound represented by formula (A) is described in detail below.

[0022]

[Chemical 3]

In the general formula [A], R _a1 is an alkyl group (which preferably has 1 to 36 carbon atoms, more preferably 1 to 2 carbon atoms).
6 things, for example, methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t
-Octyl, decyl, dodecyl, hexadecyl, benzyl), alkenyl groups (having preferably 2 to 36 carbon atoms, more preferably 2 to 26 carbon atoms such as allyl, 2-butenyl, isopropenyl, oleyl, vinyl), aryl groups (The carbon number is preferably 6 to 40, more preferably 6 to
30 groups such as phenyl, naphthyl, and heterocyclic groups (groups forming a 5- to 7-membered heterocycle having at least one of nitrogen atom, sulfur atom, oxygen atom or phosphorus atom as a ring-constituting atom, preferably A nitrogen-containing heterocycle having 1 to 4 nitrogen atoms is preferable, and a 5- to 6-membered heterocyclic group having 1 to 3 nitrogen atoms is most preferable. 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, tetrahydrofuranyl, morpholinyl), acyl group (for example, acetyl, benzoyl, pivaloyl, α- (2,4 -Di-tert-amylphenoxy) butyryl, myristoyl, stearoyl, naphthoyl, m-pentadecylbenzoyl, isonicotinoyl), sulfonyl groups (preferably alkane or aryl sulfonyls such as methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluene) Sulfonyl), sulfinyl group (preferably alkane or aryl sulfinyl such as methanesulfinyl, benzenesulfinyl), carbamoyl group (eg, N-ethylcarbamoyl) N- phenylcarbamoyl, N, N- dimethylcarbamoyl, N- butyl -N-
Phenylcarbamoyl), sulfamoyl group (for example,
N-methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-
Dodecylsulfamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl) or an aryloxycarbonyl group (eg, phenoxycarbonyl, naphthoxycarbonyl). Represent R _a2 represents a hydrogen atom or the group represented by R _a1 . R _a1 and R _a2 may combine with each other to form a 5- to 7-membered ring, and examples thereof include a succinimide ring, a phthalimide ring, a triazole ring, a urazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring. .

R _a1 and R _a2 represented by the general formula [A]
The group may be further substituted with a substituent. Examples of these substituents include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, an 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, hydridoxyamino group, etc. To be

Of the compounds represented by the general formula [A], R
_It is preferable that _a1 is a heterocyclic group. More preferably, R _a1 is a heteroaromatic ring group (including a heterocyclic group that can formally form a heteroaromatic ring in the equilibrium structure; hereinafter used in this sense). More preferable ones are represented by the following general formula [AI].

[0026]

[Chemical 4]

[0027] In general formula [A-I], R _^'a2 represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. Z represents a heteroaromatic ring group.

[0028] Among the general formula [A-I] a compound represented by those R _^'a2 are a hydrogen atom or an alkyl group. Further, Z is preferably one in which the ring-constituting atom is composed of a carbon atom or a nitrogen atom, and Z is a non-metal atom group necessary for forming a 5- to 7-membered heterocycle having 1 to 4 nitrogen atoms. Is preferred.

Most preferably, there is a compound represented by the following general formula [A-II].

[0030]

[Chemical 5]

[0031] In general formula [A-II], R _^'a2 are R in the general formula ^[A-I]' represents the same group as _a2. R _a3 and R _{a4, which} may be the same or different, each represents a hydrogen atom or a substituent.

Of the compounds represented by the general formula [A-II], R _a3 and R _a4 are hydroxyamino group, hydroxyl group, amino group, alkylamino group, arylamino group, alkoxy group, aryloxy group, alkylthio group. Particularly preferred is a group, an arylthio group, an alkyl group or an aryl group.

Specific examples of the compound represented by the general formula [A] of the present invention will be given below, but the present invention is not limited thereto.

[0034]

[Chemical 6]

[0035]

[Chemical 7]

[0036]

Embedded image

[0037]

[Chemical 9]

[0038]

[Chemical 10]

These compounds of the present invention are described in J. Org. Chem.,
27, 4054 ('62), J. Amer. Chem. Soc., 73, 2981 ('51),
It can be easily synthesized by the method described in JP-B-49-10692 or the like.

Table 1 shows the decolorization rate constants of galvinoxyl, which is a radical scavenger.

[0041]

[Table 1]

In the present invention, the radical scavenger may be dissolved in water or a water-soluble liquid such as methanol or ethanol and added, or may be added by emulsion dispersion. When it is dissolved in water, if the solubility is increased by increasing or decreasing the pH, it may be dissolved by increasing or decreasing the pH and then added.

In the present invention, two or more kinds of radical scavengers may be used in combination.

In the present invention, the radical scavenger can be added at any time during the grain formation and before the end of chemical sensitization, but it is preferable to add it after the completion of reduction sensitization. It is preferable to add it before the start of feeling. Further, the pH when adding the radical scavenger is preferably 7 or less, more preferably 6 or less. In the present invention, before the chemical sensitization is started, before the chalcogen sensitizer or the gold sensitizer is added, and when the chemical sensitization is finished, the temperature after the chemical sensitization is lowered.

In the present invention, the amount of radical scavenger added is 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol / mol.
Ag is preferable, and further 1 × 10 ⁻⁴ to 5 × 10 ⁻³ m
ol / molAg is preferred.

In a multilayer silver halide photographic light-sensitive material, it is customary to use a plurality of silver halide emulsions, and when some of the emulsions are emulsions of the present invention, a radical scavenger diffuses into the light-sensitive material. Therefore, the amount added to the emulsion of the present invention is substantially reduced.
Radical scavengers can be further added at the time of application.

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

General formula (B) R ³ -SO ₂ S-M General formula (C) R ³ -SO ₂ S-R ⁴ General formula (D) R ³ -SO ₂ S-L _m -SSO ₂ -R
^{5 In} general formula (B), general formula (C), and general formula (D),
R ³ , R ⁴ and R ^{5, which} may be the same or different, each represents an aliphatic group, an aromatic group or an aromatic ring group, L represents a divalent group, M represents a cation and m represents 0. Or represents an integer of 1.

The compounds of the general formulas (B), (C) and (D) will be described in more detail. When R ³ , R ⁴ and R ⁵ are aliphatic groups, an alkyl group having 1 to 22 carbon atoms is preferable. , 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.

The aromatic groups for R ³ , R ⁴ and R ⁵ include
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 of R ³ , R ⁴ and R ⁵ is a 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 ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, selenazole ring, benzoselenazole ring, tetrazole ring, triazole ring. , Benzotriazole ring, tetrazole ring,
Examples thereof include an oxadiazole ring and a thiadiazole ring.

Substituents for R ³ , R ⁴ and R ⁵ include, for example, alkyl groups (eg methyl, ethyl, hexyl),
Alkoxy groups (eg methoxy, ethoxy, octyloxy), aryl groups (phenyl, naphthyl, tolyl), hydroxy groups, halogen atoms (eg fluorine, chlorine, bromine, iodine), aryloxy groups (eg phenoxy), alkylthio groups (eg Methylthio, butylthio), arylthio groups (eg phenylthio), acyl groups (eg acetyl, propionyl, butyryl, valeryl), sulfonyl groups (eg methylsulfonyl, phenylsulfonyl), acylamino groups (eg acetylamino, benzamino), sulfonyl amino acids (eg Examples thereof include methanesulfonylamino, benzenesulfonylamino), acyloxy groups (eg acetoxy, benzoxy), carboxyl groups, cyano groups, sulfo groups, amino groups and the like. L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include-(C
_{H 2) n - (n =} 1~12), - CH 2 -CH = CH
_{-CH 2 -, - CH 2 C≡CCH} 2 -,

[0055]

[Chemical 11]

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), guanidine group and the like.

Specific examples of the compound represented by formula (B), (C) or (D) are shown below, but the invention is not limited thereto.

[0060]

[Chemical 12]

[0061]

[Chemical 13]

[0062]

Embedded image

[0063]

[Chemical 15]

[0064]

Embedded image

[0065]

[Chemical 17]

[0066]

[Chemical 18]

[0067]

[Chemical 19]

[0068]

Embedded image

[0069]

[Chemical 21]

Compounds of general formula (B), JP-A-54-10
19 and British Patent 972,211 for easy synthesis. General formula (B), (C) or (D)
The compound represented is 10 ^-7 per mol of silver halide.
It is preferable to add from 10 to ¹ mol. Further, the addition amount of 10 ⁻⁶ to 10 ⁻² , particularly 10 ⁻⁵ to 10 ⁻³ mol / mol Ag is preferable.

To add the compounds represented by the general formulas (B) to (D) 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 characteristics and added as a solution.

The compound represented by formula (B), (C) or (D) 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 to the reaction vessel in advance, but it is preferable to add it at an appropriate time for grain formation. Further, the compounds of the general formulas (B) to (D) may be previously added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions.
It is also a preferable method to add the solutions of the compounds of the general formulas (B) to (D) in several times with the formation of particles or to continuously add them for a long time.

Of the compounds represented by the general formulas (B) to (D), the most preferred compound for the present invention is the compound represented by the general formula (B).

The emulsion of the present invention preferably has an aspect ratio of 3 or more, more preferably an average aspect ratio of 3 or more 8
Less than tabular silver halide grains. Here, the 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 is (111)
This refers to the (111) plane when ions at all lattice points on both sides of the 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 the 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 oblique 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 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 average aspect ratio is calculated as the arithmetic mean of the aspect ratios of at least 100 silver halide grains. It can also be obtained as the ratio of the average diameter to the average thickness of the particles.

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

The proportion of tabular grains is preferably 60% or more and particularly 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 dislocation to the grains from the emulsion are placed on a mesh for electron microscope observation, and the sample is placed so as 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 type (200 kV or more for a particle having a thickness of 0.25 μm) electron microscope. . 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 or more, and the number is determined as a number average.

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 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 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.

Further, dislocation lines may be formed over a region including the centers of two parallel main planes of the tabular grain.
When dislocation lines are formed over the entire main plane, the direction of the dislocation lines may be crystallographically approximately (211) when viewed from a direction perpendicular to the main plane, but (110) or In some cases, they 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, type and amount, and temperature are important factors. By setting the pAg during the growth of the base grains to be 8.5 or less, more preferably 8 or less, the internal high silver iodide layer can be made to selectively exist near the apexes of the base grains. 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 selected 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 smaller solubility of a salt forming silver ion than a halogen ion forming the particle or the surface vicinity 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 an aqueous silver salt solution at the same time as adding an aqueous halide salt 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 mixed silver halide 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. Regarding the preparation method of these fine silver halide grains, Japanese Patent Application No. 63-785
1, No. 63-195778, No. 63-7852,
Reference can be made to the descriptions relating to 63-7853, 63-194861 and 63-194862. 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 that all of the added fine particles dissolve and disappear immediately, and it is sufficient that the fine particles dissolve and disappear 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 with X-rays and emitted from the grain surface 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 internal 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 silver halochloride 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 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 principal planes of the 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 into the peripheral main planes excluding the central portion of the main plane. When the base grains having an outer silver iodide-rich structure are displaced in the lateral direction of the base tabular grains, dislocation lines can be introduced only into the central portion excluding the peripheral portion of the main plane. Further, it is also possible to deposit a halosilver chloride only on 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 to the 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 principal plane may be in the range of 5 mol% or more and less than 100 mol% with respect to the total amount of silver in the grain 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 0-3.
It is 0 mol%, more preferably 0 to 20 mol%. The temperature at the time of shell formation 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 any position on the principal plane of the tabular grain and the method of introducing dislocation lines at any position on the outer periphery of the tabular grain described above are appropriately combined and used. It is also possible to introduce dislocation lines.

Any of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide may be used in the silver halide emulsion usable in the present invention. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide.

The tabular grains of the present invention are described in "Theory and Practice of Photography" by Cleeve (Cleve, Photography).
Theory and Practice (193
0)), page 131; Gaft, Photographic Science and Engineering (Gutoff, Ph.
otographic Science and En
Gineering), Vol. 14, pp. 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,1
It can be easily prepared by the method described in No. 57, etc.

The silver halide emulsion is usually chemically sensitized. For chemical sensitization, for example, H. H. Frieser, Di Grundragel
Dell Photography Shen Plotse Mitt Gilberhalogeniden (Die Grundlagen)
der Photographischen Proz
ess mit Silberhalogenide
n) (Academia Michel Ferragus Gezel Shaft 1
968) The method described on pages 675 to 734 can be used.

That is, compounds containing sulfur capable of reacting with active gelatin or silver (eg, thiosulfates, thioureas,
Sulfur sensitization method using mercapto compounds, rhodanins); Reduction sensitization method using reducing substances (eg, primary tin salt, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); noble metal compounds (eg, , Gold complex salts, complex salts of metals of Group VIII such as Pt, Ir, Pd), and selenium sensitization methods using selenium compounds (selenoureas, selenoketones, selenides, etc.) Etc. can be used alone or in combination.

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

The timing of addition of these antifoggants or stabilizers is usually carried out after chemical sensitization, but more preferably during chemical ripening or before the start of chemical ripening. That is, in the process of forming silver halide emulsion grains, during the addition of the silver salt solution, after the addition until the start of chemical ripening, during the chemical ripening (during the chemical ripening time, preferably within 50% from the start, More preferably within 20% of the time).

The addition amount of the above-mentioned compound used in the present invention cannot be uniquely determined by the addition method and the amount of silver halide, but is preferably 10 ^-7 mol to 10 ^-2 mol per mol of silver halide. , And more preferably 10
^{It is -5} to 10 ^-2 mol.

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

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate and starch derivatives. Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinyl imidazole and polyvinyl pyrazole can be used.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin and Bull. Soc. Sci. Pho
t. Japan. No. The enzyme-treated gelatin as described in pages 16 and 30 (1966) may be used, or a hydrolyzate or an enzymatic hydrolyzate of gelatin may be used.
As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used.

Specific examples of the dispersion medium used in the present invention include Research Disclosure (RESEARCH).
DISCROSURE) Volume 176, No. 17643
(December 1978) Section IX.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. A particularly useful dye is a cyanine dye.
Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon ring fused to nuclei of, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus,
Benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

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

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, 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 (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and Id. No. 187.
16 (November 1979), p.648, ibid. 3071
05 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by P. Glafkides, Chemie et Ph.
isique Photographie, Pau
L Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating P
photographic Emulsion, Foca
l Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable.

The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed, or a type having a latent image on both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498,
It is described in JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. 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 grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). (Having a particle size of 1).

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

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

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 2 μm.

The amount of silver coated on the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable. The silver halide emulsion used in the present invention is usually
Those that have been physically aged, chemically aged and spectrally sensitized are used. Additives used in such processes are research
Disclosure No. 17643, the same No. 187
16 and No. 16 No. 307105, and the relevant parts are summarized in the table below.

Types of Additives RD17643 RD18716 RD307105 [December 1978] [November 1979] [November 1989] 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggants, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7. Anti-staining agent Page 25 Right column Page 650 Left-Right column Page 872 8. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 left column 873 to page 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Antistatic agent Page 27 Page 650 Right column 876-877 Page 14. Matting agents 878 to 879 Other techniques and inorganic / organic materials that can be used in the color photographic light-sensitive material of the present invention are described in the following parts of EP 436,938A2 and the patents cited below. There is. 1. Layer structure: Page 146, line 34-147.
Page 25 line 2. Yellow coupler: Page 137, line 35 to line 146
Page 33, line 149, lines 21-23. Magenta coupler: page 149, line 24 to line 28; EP 421,453A1, page 3, line 5 to
Page 25, line 55 4. 4. Cyan coupler: Page 149, lines 29 to 33; European Patent No. 432,804A2, page 3, line 28 to page 40, line 2. Polymer coupler: page 149, lines 34-38; EP 435,334A2, page 113, 39.
Line 1 to page 123, line 37 6. Colored coupler: Page 53, line 42 to Page 137, line 34, Page 149, line 39 to line 45 7. Other functional couplers: page 7, line 1 to page 53, line 41, page 149, line 46 to page 150, line 3; EP 435,334A2, page 3, line 1 to line 29
Page 50 line 8. Antiseptic / antifungal agent: Page 150, lines 25 to 28 9. Formalin Scavenger: Page 149, Line 15-
17th line 10. Other additives: p. 153, line 38 to line 47; p. 75, line 21 to page 84, line 56, page 27, line 40 to page 37 of EP 421,453A1.
Line 0 11. Dispersion method: Page 150, lines 4 to 24 12. Support: Page 150, lines 32 to 34 13. Film thickness and film properties: Page 150, lines 35 to 49 14. Color development step: page 150, line 50 to page 151, line 47 15. Desilvering process: Page 151, Line 48-152
Page 53 Line 16 Automatic processor: Page 152, Line 54-153
Page 2nd line 17. Washing / stabilization process: Page 153, lines 3 to 37

[0128]

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 (1) Preparation of emulsion

(Em-1) Double twinned grains of silver iodobromide having an average iodine content of 20 mol% and an average sphere-equivalent diameter of 0.8 μm were used as seed crystals to form core crystals by a control double jet method in a gelatin aqueous solution. Average sphere-equivalent diameter 1.2 μm such that the shell ratio is 1: 2 and the shell iodine content is 2 mol%.
To form a silver iodobromide emulsion composed of twinned grains.

After the grain formation, the emulsion was redispersed at 40 ° C. under the conditions of pAg 8.9 and pH 6.3 by subjecting it to an ordinary desalting water washing step. Further, a gold / sulfur sensitized emulsion was prepared using sodium thiosulfate and chloroauric acid. The emulsion thus obtained is designated as Em-1.

(Em-2) One minute before the start of shell formation in Em-1, the following thiosulfonic acid compound 3 × 10 ^{−5 was used.}
Mol / mol Ag was added, and 1 minute after the start of shell formation, dimethylamine borane was added as a reduction sensitizer in the same manner as Em-1 except that 1 × 10 ⁻⁵ mol / mol Ag was added.
2 was prepared.

Thiosulphonic acid compound C ₂ H ₅ SO ₂
SNa

(Em-3) Demineralized water washing with EM-2,
After re-dispersion, E was added except that the compound (A-4) of the present invention was added at 5 × 10 ⁻⁵ mol / mol Ag and then gold / sulfur sensitization was performed.
Em-3 was prepared in exactly the same manner as m-2.

A triacetyl cellulose support provided with an undercoat layer was coated with the emulsion layer and the protective layer in the coating amounts shown in Table 2, and samples 1001 to 1001 were prepared by using Em-1 to 3.
1003 was produced.

[0135]

[Table 2]

These samples were exposed to sensitometry for 1/100 seconds through a continuous wedge at a color temperature of 4800 ° K and subjected to the following color development processing. The developing treatment used here was carried out at 38 ° C. under the following conditions.

Treatment Method Process Treatment Time Treatment Temperature Replenishment Amount Tank Capacity Color Development 2 minutes 45 seconds 38 ° C. 33 ml 20 L Bleach 6 minutes 30 seconds 38 ° C. 25 ml 40 L water wash 2 minutes 10 seconds 24 ° C. 1200 ml 20 L fixed 4 minutes 20 seconds 38 ℃ 25ml 30L Washing with water (1) 1 minute 05 seconds 24 ℃ From (2) to (1) 10L countercurrent piping system Washing with water (2) 1 minute 00 seconds 24 ℃ 1200ml 10L Stable (3) 1 minute 05 seconds 38 ℃ 25ml 10L Dry 4 minutes 20 seconds 55 ℃ Replenishment amount is 35mm width 1m per length

Next, the composition of the processing liquid will be described. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-3.0 3.2 1,1-Diphosphonic acid Sodium sulfite 4.0 4.0 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-4.5 5.5 5.5 Hydroxy Ethylamino] -2-methylaniline sulfate Water was added to 1.0 L 1.0 L pH 10.05 10.10

(Bleaching solution) Mother liquor (g) Replenishing solution (g) Ethylenediaminetetraacetic acid second 100.0 120.0 Sodium iron trihydrate Ethylenediaminetetraacetic acid di-na 10.0 11.0 Thorium salt 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 L 1.0 L pH 6.0 5.7

(Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid 0.5 0.7 Sodium salt sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution 170.0 ml 200.0 ml (70%) Add water 1.0 L 1.0 L pH 6.7 6.6

(Stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-mo 0.3 0.45 Nononyl phenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid dina 0.05 0.08 Thorium salt water was added and 1.0 L 1.0 L pH 5.8-8.0 5.8-8.0 The concentration of the treated sample was measured with a green filter.

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.

Table 3 shows the results thus obtained.

[0144]

[Table 3]

Sensitization is enhanced by adding thiosulfonic acid and dimethylamine as a reduction sensitizer (JP-A-2-191938), but it is further enhanced by using the compound of the present invention. Further, at this time, the fog was at a level before reduction sensitization, and it is understood that the present invention provided an emulsion having a low fog and a high sensitivity.

Example 2 (1) Preparation of emulsion (Em-11) 6 g of potassium bromide, average molecular weight 1500
An aqueous solution prepared by dissolving 30 g of 0 inactive gelatin in 3.7 l of distilled water was well stirred, and a 14% potassium bromide aqueous solution and a 20% silver nitrate aqueous solution were added thereto by a double jet method at a constant flow rate for 1 minute. 55 ° C, pBr
Added at 1.0 (this addition consumed 2.4% of total silver).

An aqueous gelatin solution (17%, 300 cc) was added, and after stirring at 55 ° C., a 20% aqueous silver nitrate solution was added at a constant flow rate until pBr reached 1.4 (this addition of 5. 0% consumed). Here, thiourea dioxide was added to the reaction vessel in an amount of 1.2 × 10 ⁻⁵ mol per mol of silver. Furthermore, a 20% potassium iodobromide solution (KBr _1-x I _x : x = 0.04) and a 33% aqueous silver nitrate solution were added by the double jet method over 43 minutes (50% of the total silver amount was added by this addition). Consumed). Here, after adding an aqueous solution containing 8.3 g of potassium iodide, a 0.001 / wt% K ₃ IrCl ₆ aqueous solution 14.
5 ml was added and 20% potassium bromide solution and 33% aqueous silver nitrate solution were added by the double-bet method over 39 minutes (this addition consumed 42.6% of the total silver. 10 minutes after the start of this final shell formation. A thiosulfonic acid compound (described in Example 1) was added at 1.2 × 10 ⁻⁴ mol / mol Ag). 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 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 the emulsion thus produced, sensitizing dye A shown in Table 4 was added at 4 × 10 ^-4 mol / mol Ag, sensitizing dye B was 2 × 10 ^-5 mol / mol Ag, and sensitizing dye C was added. After addition of 6 × 10 ⁻⁴ mol / mol Ag, gold-selenium-sulfur sensitization was optimally carried out using sodium thiosulfate, chloroauric acid, N, N-dimethylselenourea and potassium thiocyanate to prepare emulsion Em.
-11 was produced.

[0149]

[Table 4]

(Em-12) In Em-11, 11 minutes after the start of the final shell formation, compound A-4 of the present invention was added 3.3.
× 10 ⁻⁴ mol / mol Ag was added.

(Em-13) In Em-11, 3.3 × 10 ⁻⁴ mol / mol Ag of the compound A-4 of the present invention was added immediately before washing with water.

(Em-14) In Em-11, 3.3 × 10 ⁻⁴ mol / mol Ag of the compound A-4 of the present invention was added before addition of the sensitizing dye.

(Em-15) After chemical sensitization in Em-11, the compound A-4 of the present invention was added in an amount of 3.3 × 10 ^-4 mol / mol Ag.

(Em-16) In Em-11, 3.3 × 10 ⁻⁴ mol / mol-Ag of compound A-3 of the present invention was added before addition of the sensitizing dye.

(Em-17) In Em-11, 3.3 × 10 ⁻⁴ mol / mol Ag of the compound A-1 of the present invention was added before addition of the sensitizing dye.

(Em-18) In Em-11, 3.3 × 10 ⁻⁵ mol / mol Ag of the compound A-1 of the present invention was added before addition of the sensitizing dye.

(Em-19) In Em-11, 3.3 × 10 ⁻³ mol / mol-Ag of the compound A-1 of the present invention was added before addition of the sensitizing dye.

An emulsion layer and a protective layer were coated on a triacetyl cellulose support provided with an undercoat layer in the same manner as in Example 1, and samples 1011 to 1019 were prepared using Em-11 to 19.
Was produced. The samples 1011 to 1019 were exposed and developed in the same manner as in Example 1.

Table 5 shows the results thus obtained.

[0160]

[Table 5]

As is clear from Table 5, sample 1012 of the present invention was compared with sample 1011 containing no compound of the present invention.
-1014, 1016 to 1019 showed a remarkable increase in sensitivity without increasing fog, but Sample 1015 containing the compound of the present invention after the chemical sensitization did not show an increase in sensitivity.

Example 3 (Sample 101) Sample 101, which is a multi-layer color light-sensitive material consisting of each layer having the following composition, was prepared on an undercoated cellulose triacetate film support. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, Ex
F: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive

First Layer (Antihalation Layer) Black Colloidal Silver 0.15 Gelatin 2.33 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 1.0 × 10 ^-2 ExF -2 4.0 x 10 ^-2 ExF-3 5.0 x 10 ^-3 ExM-3 0.11 Cpd-5 1.0 x 10 ^-3 Solv-1 0.16 Solv-2 0.10

Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Coating amount 0.35 Silver iodobromide emulsion B Coating silver amount 0.18 Gelatin 0.77 ExS-1 6.5 × 10 ^-4 ExS-2 3.6 × 10 ^-4 ExS-5 6.2 x 10 ^-4 ExS-7 4.1 x 10 ^-6 ExC-1 9.0 x 10 ^-2 ExC-2 5.0 x 10 ^-3 ExC-3 4.0 x 10 ^-2 ExC-5 8.0 x 10 ^-2 ExC-6 2.0 x 10 ^-2 ExC-9 2.5 x 10 ^-2 Cpd-1 2.2 x 10 ^-2

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Coating amount 0.55 Gelatin 1.46 ExS-1 4.3 × 10 ^-4 ExS-2 2.4 × 10 ^-4 ExS-5 4.1 × 10 ^-4 ExS-7 4.3 × 10 ^-6 ExC-1 0.19 ExC-2 1.0 × 10 ^-2 ExC-3 1.0 × 10 ^-2 ExC-4 1.6 × 10 ^-2 ExC-5 0.19 ExC-6 2.0 × 10 ^-2 ExC- 7 2.5 x 10 ^-2 ExC-9 3.0 x 10 ^-2 Cpd-4 1.5 x 10 ^-2

4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Coating amount 1.05 Gelatin 1.38 ExS-1 3.6 × 10 ^-4 ExS-2 2.0 × 10 ^-4 ExS-5 3.4 × 10 ^-4 ExS-7 1.4 x 10 ^-5 ExC-1 2.0 x 10 ^-2 ExC-3 2.0 x 10 ^-2 ExC-4 9.0 x 10 ^-2 ExC-5 5.0 x 10 ^-2 ExC-8 1.0 x10 ^-2 ExC- 9 1.0 x 10 ^-2 Cpd-4 1.0 x 10 ^-3 Solv-1 0.70 Solv-2 0.15

Fifth layer (intermediate layer) Gelatin 0.62 Cpd-1 0.13 Polyethyl acrylate latex 8.0 × 10 ^-2 Solv-1 8.0 × 10 ^-2

Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion B Coating amount of silver 0.10 Silver iodobromide emulsion A Coating amount of 0.28 Gelatin 0.31 ExS-4 12.8 × 10 ^-4 ExS-5 2.1 × 10 ^-4 ExS-8 1.2x10 ^-4 ExM-1 0.12 ExM-7 2.1x10 ^-2 Solv-1 0.09 Solv-3 7.0x10 ^-3

Seventh Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Coating amount 0.37 Gelatin 0.54 ExS-4 8.5 × 10 ^-4 ExS-5 1.4 × 10 ^-4 ExS-8 8.3 × 10 ^-5 ExM-1 0.27 ExM-7 7.2 x 10 ^-2 ExY-1 5.4 x 10 ^-2 Solv-1 0.23 Solv-3 1.8 x 10 ^-2

Eighth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion D Coating amount 0.53 Gelatin 0.61 ExS-4 7.1 × 10 ^-4 ExS-5 1.4 × 10 ^-4 ExS-8 4.6 × 10 ^-5 ExM-2 5.5 x 10 ^-3 ExM-3 1.0 x 10 ^-2 ExM-5 1.0 x 10 ^-2 ExM-6 3.0 x 10 ^-2 ExY-1 1.0 x 10 ^-2 ExC-1 4.0 x10 ^-3 ExC- 4 2.5 × 10 ^-3 Cpd-6 1.0 × 10 ^-2 Solv-1 0.12

Ninth layer (intermediate layer) Gelatin 0.56 UV-4 4.0 × 10 ^-2 UV-5 3.0 × 10 ^-2 Cpd-1 4.0 × 10 ^-2 Polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2

The tenth layer (donor layer having a multi-layer effect on the red-sensitive layer) Silver iodobromide emulsion E Coating amount 0.40 Silver iodobromide emulsion F Coating amount 0.20 Silver iodobromide emulsion G Coating amount 0.39 Gelatin 0.87 ExS -3 9.8 x 10 ^-4 ExM-2 0.16 ExM-4 3.0 x 10 ^-2 ExM-5 5.0 x 10 ^-2 ExY-2 2.5 x 10 ^-3 ExY-5 2.0 x 10 ^-2 Solv-1 0.30 Solv-5 3.0 x 10 ^-2

Eleventh layer (yellow filter layer) Yellow colloidal silver 4.2 × 10 ^-2 DYE-1 1.02 × 10 ^-1 gelatin 0.84 Cpd-1 5.0 × 10 ^-2 Cpd-2 5.0 × 10 ^-2 Cpd-5 2.0 × 10 ^-3 Solv-1 0.13 H-1 0.25

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion A Coating amount 0.50 Silver iodobromide emulsion H Coating amount 0.40 Gelatin 1.75 ExS-6 9.0 × 10 ^-4 ExY-1 8.5 × 10 ^-2 ExY-2 5.5 x 10 ^-3 ExY-3 6.0 x 10 ^-2 ExY-5 1.00 ExC-1 5.0 x 10 ^-2 ExC-2 8.0 x 10 ^-2 Solv-1 0.54

Thirteenth layer (intermediate layer) Gelatin 0.30 ExY-1 0.14 Solv-1 0.14

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion I Coating amount of 0.40 Gelatin 0.95 ExS-6 6.3 × 10 ^-4 ExY-2 1.0 × 10 ^-2 ExY-3 2.0 × 10 ^-2 ExY-5 0.18 ExC-1 1.0 × 10 ^-2 Solv-1 9.0 × 10 ^-2

Fifteenth Layer (First Protective Layer) Fine grain silver iodobromide emulsion J Coating amount 0.12 Gelatin 0.63 UV-4 0.11 UV-5 0.18 Cpd-3 0.10 Solv-1 2.0 × 10 ^-2 Polyethyl acrylate latex 9.0 × 10 ^-2

16th layer (second protective layer) Fine grain silver iodobromide emulsion J Coating amount of silver 0.36 Gelatin 0.85 B-1 (diameter 2.0 μm) 8.0 × 10 ⁻² B-2 (diameter 2.0 μm) 8.0 × 10 ^{− 2} B-3 2.0 x 10 ^-2 W-5 2.0 x 10 ^-2 H-1 0.18

In addition to the above, the sample thus prepared
1,2-Benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. In addition, each layer has appropriate storage properties, processability, pressure resistance, mildew / bacterial resistance,
In order to improve the antistatic property and coating property, W-1 to W-
6, B-1 to B-6, F-1 to F-10, F-13 to F
-16 and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.

[0180]

[Table 6]

In Table 6, (1) Emulsions A to I were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (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) Emulsions A to N are BH Carroll, Photographic Scien
Ce and Engineering, 24, 265 (1980) and the like contain iridium inside the particles.

[0182]

[Chemical formula 22]

[0183]

[Chemical formula 23]

[0184]

[Chemical formula 24]

[0185]

[Chemical 25]

[0186]

[Chemical formula 26]

[0187]

[Chemical 27]

[0188]

[Chemical 28]

[0189]

[Chemical 29]

[0190]

[Chemical 30]

[0191]

[Chemical 31]

[0192]

[Chemical 32]

[0193]

[Chemical 33]

[0194]

Embedded image

[0195]

Embedded image

[0196]

Embedded image

[0197]

Embedded image

[0198]

[Chemical 38]

(Sample 102) In Sample 101, the compound (A-3) of the present invention was added to each emulsion layer in an amount of 3 × 10 ^-4 mol / mol Ag.

(Sample 103) In Sample 101, the compound (A-3) of the present invention was added to each emulsion layer at 6 × 10 ⁻⁴ mol / mol Ag.

(Sample 104) Emulsion A in Sample 101
To the compound (A-3) of the present invention before chemical sensitization of
0 ⁻⁴ mol / mol Ag was added.

(Sample 105) In Sample 104, the compound (A-3) of the present invention was added to each emulsion layer in an amount of 3 × 10 ^-4 mol / mol Ag.

Samples 101 to 10 thus prepared
No. 5 was exposed to an ordinary wedge for 1/100 second, and the developing treatment of Example 1 was performed. However, the color development time is 3'1
After that, the magenta density was measured, and the sensitivity was expressed by the logarithm of the reciprocal of the exposure amount that gives a density of fog +0.2 in magenta density. .) The results are shown in Table 7.

[0204]

[Table 7]

There was almost no change when the compound of the present invention was added to Sample 101 during coating (Sample 102,
103), the sample 104 in which the compound of the present invention was added to the emulsion before the chemical sensitization of the emulsion was highly sensitive. Further, the sensitization was further enhanced by adding the compound of the present invention to this sample. (Sample 105) Similar results were obtained for cyan density and yellow density.

[0206]

According to the present invention, a silver halide photographic light-sensitive material having low fog and high sensitivity can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 1/09 7/00 510 7/32 7/392 A

Claims (6)

[Claims] 1. A silver halide emulsion characterized by being subjected to reduction sensitization and gold / chalcogen sensitization, and containing at least one radical scavenger. 2. A method for producing a silver halide emulsion, which comprises adding at least one radical scavenger after reduction sensitization and before completion of gold / chalcogen sensitization. 3. At least a silver halide emulsion produced after reduction sensitization and before the end of gold / chalcogen sensitization by adding at least one radical scavenger. A silver halide photographic light-sensitive material comprising one support having one silver halide emulsion layer. 4. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide grains in the emulsion layer are subjected to reduction sensitization and before chemical sensitization is completed. A silver halide photographic light-sensitive material comprising a radical scavenger represented by the following general formula (A). Embedded image In the general formula [A], R _a1 represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and R _a2 represents a hydrogen atom or a group represented by R _a1 . However, when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1 and R _a2 are bound to each other,
A 5- to 7-membered ring may be formed. 5. The silver halide grain which has been subjected to reduction sensitization in the emulsion layer and which contains a radical scavenger represented by the general formula (A), has at least 60% of its total projected area. The silver halide photographic light-sensitive material according to claim 4, which is a tabular silver halide grain having a dislocation line and an aspect ratio of 3 or more. 6. The color silver halide photographic light-sensitive material according to claim 3, 4 or 5, which contains at least one color coupler.