JPH06250311A - Formation of silver halide particles and production of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To attain uniform distribution of silver iodide among silver halide particles having distribution of silver iodide in the particles and to provide a silver halide emulsion and a silver halide photographic sensitive material ensuring low fog, improved sensitivity and pressure resistance. CONSTITUTION:Silver halide particles are formed using at least one kind of iodide ion releasing compd. represented by a formula I-L-COOH (where L is a divalent org. group contg. an arom. ring). A base is coated with an emulsion contg. the silver halide particles in the form of a silver halide emulsion layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming silver halide grains, and more specifically, a method for forming silver halide grains for a photographic emulsion having a low fog, a high sensitivity and an improved pressure property, and a method for using the same. The present invention relates to a method for producing a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, the demands on the performance of silver halide emulsions for photography have become more and more stringent, and in addition to photographic properties such as high sensitivity and excellent graininess, higher level requirements have been made regarding toughness such as pressure. Is coming. In order to increase the sensitivity of the silver halide grains and to improve the pressure resistance, it is considered preferable that the silver iodide (iodide ion) content is uniform among the individual grains from the viewpoint of uniform chemical sensitization. .

Conventionally, when forming a silver halide phase containing silver iodide in the step of forming silver halide grains, there has been the following iodide ion supply method. That is, a method using an iodide salt aqueous solution such as a KI aqueous solution, JP-A-2-68.
This is a method of using silver halide fine grains containing silver iodide or an iodide ion-releasing compound disclosed in Japanese Patent Application No. 538 (1987) -220187. However,
In the method using an aqueous iodide salt solution, by adding iodide ions to the reaction solution in a free state, a region having a large non-uniformity in the iodide ion concentration distribution occurs. Therefore, it was not possible to uniformly grow the particles. On the other hand, the technique disclosed in the above-mentioned patent application eliminates variation in the halogen composition (microscopic distribution of silver iodide) within and between grains by slowly releasing iodide ions to achieve uniform grain growth. Is the technology of doing. However, even if silver halide grains are formed using the exemplified compounds of the iodide ion-releasing compounds described in the above-mentioned patent application, it is not sufficient to meet the demands for sufficient reduction of fog, high sensitivity, and improvement of pressure resistance. It is enough.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to make the distribution of silver iodide grains having a grain distribution of silver iodide uniform among grains. Another object of the present invention is to provide a silver halide emulsion having low fog and improved sensitivity and pressure resistance. A further object of the present invention is to provide a method for producing a silver halide photographic light-sensitive material having low fog and improved sensitivity and pressure resistance.

[0005]

The above objects have been achieved by the following. (1) A method for forming silver halide grains, which comprises using at least one iodide ion-releasing compound represented by the following formula (I). IL-COOH (I) (In the formula, L represents a divalent organic group containing an aromatic ring.) (2) A silver halide grain containing silver iodide, wherein the inside of the silver halide grain is Has a high silver iodide region having a silver iodide content higher than the average silver iodide content of the entire silver halide grain, and the high silver iodide region is the iodide ion of the above formula (I). The method for forming silver halide grains according to item (1), wherein the silver halide grains are formed using a releasing compound. (3) The method for forming silver halide grains according to (1) or (2), wherein the iodide ion-releasing compound is used in the presence of an iodide ion-releasing agent. (4) The method of forming a silver halide grain according to the item (1), wherein a silver halide grain group having a variation coefficient of a silver iodide content distribution between silver halide grains of 3 to 20% is formed. (5) Silver halide grains are formed in the presence of at least one iodide ion-releasing compound represented by the following formula (I), and an emulsion containing the silver halide grains is formed on a support in an amount of at least 1. A method for producing a silver halide photographic light-sensitive material, which comprises coating as a silver halide emulsion layer of the layer. IL-COOH (I) (In the formula, L represents a divalent organic group containing an aromatic ring.)

The present invention will be described in more detail below. The iodide ion-releasing compound represented by the formula (I) of the present invention is a compound that releases iodide ion by a reaction with a base and / or a nucleophile, a substitution reaction, a elimination reaction or a hydrolysis reaction. In the formula (I), the divalent organic group containing an aromatic ring represented by L is a simple aromatic ring group or those groups and an aliphatic group, -O- group, -N (R)-group, -C.
O- group, -CS- group, -S- group, -SO- group, -SO ₂
A group formed by combining a -group, a -P (R)-group, and a -PO (R)-group (wherein, R represents a hydrogen atom or a monovalent group). The aromatic ring contained in L is preferably a monocyclic or bicyclic aryl group, which may be condensed with another heterocycle, and is preferably a phenylene group. The aliphatic group which is combined with the aromatic ring contained in L is preferably an aliphatic group having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, and particularly preferably the carbon number. It is a linear, branched or cyclic alkylene group of 1-8.

The divalent organic group containing an aromatic ring represented by L in the formula (I) may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group and an alkoxy group. Group, aryl group, substituted amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group , A sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, and an imide group. As a preferable substituent, an alkyl group (preferably having a carbon number of 1 to 20),
Aralkyl group (preferably having 7 to 30 carbon atoms), alkoxy group (preferably having 1 to 20 carbon atoms), substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms), Acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (Preferably having 1 to 30 carbon atoms) and the like, and particularly preferably a carboxyl group. These groups may be substituted.

The iodine ion represented by I in the formula (I) is preferably bonded to a carbon atom of a divalent organic group represented by L and containing an aromatic ring. Particularly preferably I
Is bonded to the portion of the aliphatic group bonded to the aromatic ring contained in L. When I is directly bonded to the aromatic ring contained in L, the aromatic ring is a benzene ring (including a condensed ring), and a cyano group, a nitro group, a sulfonyl group at the ortho or para position of I. It is preferable to have an electron-withdrawing group such as

Specific examples of the compound of formula (I) are shown below, but the invention is not limited thereto.

[0010]

[Chemical 1]

[0011]

[Chemical 2]

Regarding the method for synthesizing the iodide ion-releasing compound of the formula (I) used in the present invention, the following documents can be referred to. J. Am. Chem. Soc., 76 , 3277-8 (195
4), J. Org. Chem., 16 , 798 (1951), Chem. Ber., 97 ,
390 (1964), Org. Synth., V, 478 (1973), J. Chem. So
c., 1951 , 1851, J. Org. Chem., 19 , 1571 (1954), J. C
hem.Soc., 1952 , 142, J. Chem.Soc., 1955, 1383, An
gew, Chem., Int. Ed., 11 , 229 (1972), Chem, Commu.,
1971 , 1112. A typical synthesis example is shown below. Other compounds can be synthesized by similar methods.

Synthesis Example 1 [Synthesis of Compound 1] 4-chloromethylbenzoic acid (10
g) and sodium iodide (13.1 g) in acetone (10
(0 ml) and then heated under reflux for 8 hours.
After completion of the reaction, the reaction solution was cooled to room temperature, and then ice water (5
00 ml). The precipitated crystals were collected by filtration and dried to obtain the desired product. Yield: 13 g The chemical structure was confirmed by NMR spectrum, MS spectrum, IR spectrum and elemental analysis.

Synthesis Example 2 [Synthesis of Compound 8] 5-Aminoisophthalic Acid (27.5)
g) and sodium hydrogen carbonate (40.5 g) in water (330
ml), and then iodoacetyl chloride (36.8 g) was slowly added dropwise under ice cooling. After 30 minutes as it was after the dropping was completed, concentrated hydrochloric acid (31 cc) was then slowly added dropwise. The precipitated crystals were collected by filtration and dried to obtain the desired product. Yield 50 g The chemical structure was confirmed by NMR spectrum, MS spectrum, IR spectrum and elemental analysis.

In the present invention, the iodide ion-releasing compound of the formula (I) releases iodide ion upon reaction with an iodide ion-releasing agent (base and / or nucleophile). The reagents preferably include the following chemical species. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates, ammonia, amines, alcohols , Ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines, sulfides and the like. In the present invention, the release rate or timing of the iodide ion of the iodide ion-releasing compound can be controlled by controlling the pH, the concentration of the nucleophilic reagent, the addition method, and the temperature of the reaction solution. Alkali hydroxide is preferably used as the base for pH control. The preferred concentration range of each of the iodide ion-releasing compound and the iodide ion-releasing agent used for rapidly generating iodide ions is 1 × 1.
0 ^{-7 to} 20 M, more preferably 1 x 10 ^-5 to 10 M
M, more preferably 1 × 10 ^{−4 to} 5M, and particularly preferably 1 × 10 ^{−3 to} 2M. The preferred temperature range is 3
It is 0 to 80 ° C, more preferably 35 to 75 ° C, and particularly preferably 35 to 60 ° C.

In the present invention, when a base is used for releasing iodide ions, the pH of the reaction solution for forming silver halide grains may be changed. At this time, the preferable pH range (pH after pH adjustment) for controlling the iodide ion release rate and timing is 2 to 12,
It is more preferably 3 to 11, particularly preferably 4 to 10, and most preferably 7 to 10. Even under neutral conditions of pH 7, the hydroxide ion determined by the ionic product of water acts as a regulator. Also, a nucleophile and a base may be used in combination,
At this time, the pH may be controlled within the above range to control the iodide ion release rate and timing.

The preferred range of the amount of iodide ions released from the iodide ion-releasing compound is not particularly limited and varies depending on the intended characteristics of the silver halide grains formed,
Generally speaking, it is 0.1-2 with respect to the total amount of silver halide.
0 mol%, more preferably 0.3 to 15 mol%,
It is particularly preferably 1 to 10 mol%. When iodine atoms are released from the iodide ion-releasing compound in the form of iodide ions, all iodine atoms may be released or some of them may remain without being decomposed. A method for controlling the iodide ion release from the iodide ion releasing compound will be described below.

If the supply rate of iodide ions from the iodide ion-releasing compound is too slow, that is, if the time for forming the silver halide phase containing silver iodide is too long, the silver halide phase containing silver iodide in the meantime. Are redissolved, and the dislocation density for dislocations, which will be described later, decreases. On the other hand, it is preferable to slowly supply the iodide ions in order to form grains so that the dislocation amount distribution does not become uneven among grains. Therefore, in this case, it is important to generate iodide ions rapidly without causing locality (non-uniform distribution). The region where iodide ion has a high locality is formed because when an iodide ion-releasing compound or an iodide ion-releasing agent used in combination with the iodide ion-releasing compound is added to the reaction solution in the grain forming container, it is near the addition port. This is because the iodide ion-releasing reaction is too fast, corresponding to the non-uniform distribution of the local concentration of the additive.

The time for the released iodide ions to deposit on the host grains is extremely fast, and since grain growth occurs in the region near the addition port where the iodide ion has a high locality, uneven grain growth between grains occurs. Occur. Therefore, it is necessary to select an iodide ion release rate that does not cause iodide ion locality. In the conventional method (for example, adding an aqueous solution of potassium iodide), the iodide ion is added in a free state even if the aqueous solution of potassium iodide is diluted and added. There is a limit even if we try to reduce it. That is, it has been difficult to form particles by eliminating nonuniformity between particles by the conventional method.

However, according to the present invention in which the iodide ion release rate or timing can be controlled, the locality of iodide ions can be reduced as compared with the conventional method. In the above example, iodide ions are rapidly
Moreover, according to the present invention in which particles are formed while being produced without causing locality, it is possible to introduce dislocations between particles more uniformly and at a higher density than in the conventional method. Not limited to this, it is possible to control the iodide ion release rate or timing according to the purpose, and it is possible to form grains with less unevenness between grains. For controlling the release of iodide ions in the present invention, for example, the following method is preferable. That is, by changing the pH, the concentration of the nucleophile, the temperature, etc. from the already uniformly distributed iodide ion-releasing compound added to the reaction solution in the grain forming container, it is usually possible to adjust the pH from a low pH to a high pH. It is a method of uniformly releasing the iodide ion in the entire reaction liquid by controlling the change to In these cases, the pH when releasing iodide ions
It is preferable to add an iodide ion release controlling agent such as an alkali or a nucleophilic substance for increasing the amount of the iodide ion releasing compound in a state where the iodide ion releasing compound is evenly distributed throughout.

The silver halide emulsion grains formed by the method of the present invention (hereinafter referred to as the emulsion grains of the present invention) will be described below. The emulsion grains of the present invention are silver halide containing silver iodide. The emulsion grains of the present invention contain at least one of a silver iodide phase, a silver iodobromide phase, a silver chloroiodobromide phase and a silver chloroiodide phase. These are other silver salts, such as Rhodan silver,
Silver sulfide, silver selenium, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. The emulsion grains of the present invention preferably have the following structure depending on the halogen composition. In the case of a particle having one or more coating shells (shells) for a base particle (core), a double structure, a triple structure, a quadruple structure, a quintuple structure, ... Those formed using the iodide ion releasing method of the present invention. In the case of particles in which one or more layers (shell regions) that do not completely cover the base particles (core) are deposited: two-layer structure, three-layer structure, four-layer structure, five-layer structure ... A layer or outermost layer formed by using the iodide ion releasing method of the present invention. In the case of a junction grain in which epitaxy is grown on a selective portion of a base grain, the apex of the grain, the peripheral portion of the grain, and the epitaxial portion of the main plane portion of the grain are formed by using the iodide ion releasing method of the present invention.

The composition of the coating shell of silver halide containing silver iodide, the deposition layer and the epitaxial portion formed by the method of releasing iodide ions of the present invention preferably has a high silver iodide content. The silver halide phase may be any of silver iodide, silver iodobromide, silver chloroiodobromide and silver chloroiodide, but is preferably silver iodide or silver iodobromide, and is preferably silver iodide. It is more preferable that there is. In the case of silver iodobromide, the silver iodide (iodide ion) content is preferably 1 to 45 mol%, more preferably 5 to 45 mol%, and particularly preferably 10 to 4 mol%.
It is 5 mol%. As an embodiment of the method for releasing iodide ions of the present invention, it is preferable to prepare silver halide grains containing dislocations, and it is particularly preferable to introduce dislocations into the silver halide grains at a high density. For example, in the process of introducing dislocations into tabular grains, a silver halide phase containing silver iodide may be formed at the edges of grains (for example, tabular grains) while rapidly generating iodide ions. It is preferable for introducing density. Dislocations are linear lattice defects on the slip plane of a crystal at the boundary between a region that has already slipped and a region that has not slipped yet.

Regarding dislocations of silver halide crystals, 1)
CR Berry. J. Appl. Phys., 27,636 (1956), 2) C.
R. Berry. DC Skilman, J. Appl. Phys., 35, 2165
(1964), 3) JF Hamilton, Phot. Sci. Eng., 11, 5
7 (1967), 4) T. Shiozawa, J. Soc. Phot. Sci. Jap.,
34, 16 (1971), 5) T. Shiozawa, J. Soc. Phot. Sci.
Jap., 35, 213 (1972) and the like are available, and can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope. When observing dislocations directly with a transmission electron microscope, be careful not to apply pressure enough to cause dislocations on the grains, place the silver halide grains taken out from the emulsion on a mesh for electron microscope observation, and use an electron beam. Observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (for example, printout) due to damage. In this case, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for a thickness of 0.25 μm). On the other hand, G.
C. Farnell, RB Flint, JB Chanter, J. Phot. Sc
i., 13, 25 (1965), there is a close relation between the place where latent image nuclei are formed and the defect in the grain in a large size high aspect ratio tabular silver halide grain. It is shown. JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains in which dislocations are intentionally introduced. In these patent applications, it is shown that tabular grains having dislocation lines introduced therein are superior in photographic characteristics such as sensitivity and reciprocity law to tabular grains having no dislocation lines.

Based on the method of the present invention, it is preferable to introduce dislocations into the silver halide grains as follows. That is, a base silver halide grain is prepared, and a silver halide phase containing silver iodide (the above-described silver halide coating shell, a deposition layer, and an epitaxial growth) is formed on the base grain. As described above, the higher the silver iodide content of these silver halide phases, the more preferable. The average silver iodide content of the base grains is preferably 0 to 15 mol%, more preferably 0 to 12 mol%, and particularly preferably 0 to 10 mol%. The amount of halogen added to form a high silver iodide content phase (synonymous with a high silver iodide content region; hereinafter referred to as a high silver iodide phase) on this base grain is 2 to the silver amount of the base grain. 15 mol% is preferable, 2 to 10 mol% is more preferable, and 2 to 5 mol% is particularly preferable. At this time, the high silver iodide phase accounts for 5 to 80 mol% of the total amount of silver from the center of the grain.
Is preferably present within the range of, more preferably 1
It is present in the range of 0 to 70 mol%, particularly preferably 20 to 60 mol%.

Further, the place (site) where the high silver iodide phase is formed on the base grain can be arbitrarily selected. As will be described later in detail, for tabular grains, only the vicinity of hexagonal vertices and the entire fringe can be selected. The base grains may be covered or may be formed only on a specific site, but it is preferable to control the position of dislocations within the grain by selecting a specific site and performing epitaxial growth. Further, in the formation of the high silver iodide phase, the composition of the added halogen, the addition method,
The temperature, pAg, solvent concentration, gelatin concentration, ionic strength, etc. of the reaction liquid may be freely selected and used. Thereafter, dislocations can be introduced by forming a silver halide shell (region) which is not the high silver iodide phase outside the high silver iodide phase. The composition of the silver halide shell may be any of silver bromide, silver iodobromide and silver chloroiodobromide, but silver bromide or silver iodobromide is preferred. In the case of silver iodobromide, the silver iodide content is preferably 0.1 to 12 mol%, more preferably 0.1 to 10 mol%, and most preferably 0.1 to 3 mol%. A preferable temperature in the above-mentioned dislocation introduction process is 30 to 80 ° C, more preferably 35 to 75 ° C, and particularly preferably 35 to 60 ° C.
Moreover, preferable pAg is 6.4 to 10.5.

In the case of tabular silver halide grains, the position and number of dislocations of each grain when viewed from the direction perpendicular to the main plane are determined from the photograph of the grain taken by using an electron microscope as described above. You can Since dislocation lines may or may not be seen depending on the tilt angle of the sample with respect to the electron beam, in order to observe the dislocation lines without omission, the particle images of the same grain at as many sample tilt angles as possible should be observed. It is necessary to find the location. In the present invention, a high-voltage electron microscope is used to obtain 5 ° for the same particle.
It is preferable to change the tilt angle in steps and take five types of grain photographs to obtain the positions and number of dislocation lines.
When dislocations are introduced into the tabular silver halide grains in the present invention, the positions thereof can be selected, for example, from the apex portion and the fringe portion of the grain, or the introduction over the entire main plane portion. It is particularly preferable to limit to the fringe portion. The fringe portion referred to in the present invention refers to the outer periphery of the tabular grain. Specifically, in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide content at a certain point when viewed from the side is the whole grain. The point outside the point where the average silver iodide content is exceeded or below the average silver iodide content.

When dislocations are introduced into the tabular grains, when the number of dislocation lines is counted by the above-mentioned method using an electron microscope, tabular grains having about 1000 or less and 10 or more dislocation lines per grain in the grain fringe portion. Is preferable, and more preferably 3
The number is 0 or more, particularly preferably 50 or more. When the dislocation lines are densely present or when the 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, the number can be counted to be about 10, 20 or 30. It is desirable that the distribution of dislocation amounts among silver halide grains be uniform. When dislocations are introduced into the tabular grains in the present invention, tabular grains having 10 or more dislocation lines per grain in the grain fringe portion account for 100 to 50% (number) of all grains.
It is preferable to occupy 100% to 70%, more preferably 100 to 70%, and particularly preferably 100 to 90%.

In the present invention, when determining the proportion of grains containing dislocations and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 grains, more preferably 200 grains or more, particularly preferably 300 grains. Observe and obtain the above. The tabular silver halide grains mentioned above are silver halide grains having two parallel main planes facing each other. The silver halide tabular grains have one twin plane or two or more parallel twin planes. 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.
This tabular grain has a triangular shape, a hexagonal shape, or a rounded circular shape when these particles are viewed from above,
The outer surfaces are parallel to each other. The equivalent-circle diameter of the tabular grains is preferably 0.3 to 10 μm, more preferably 0.4 to 5 μm, and particularly preferably 0.5 to 4 μm. The grain thickness of the tabular grains is preferably 0.05 to 1.0 μm, more preferably 0.08 to 0.5 μm, and particularly preferably 0.08.
Is about 0.3 μm. The aspect ratio of tabular grains is preferably 2 to 30, and more preferably 3 to 2.
It is 5.

The aspect ratio is a value obtained by dividing the circle-equivalent diameter of the projected area of a silver halide grain by the grain thickness. As an example of the method of measuring the aspect ratio, there is a method of taking a transmission electron microscope photograph by the replica method and obtaining the equivalent circle diameter and thickness of the projected area of each particle. In this case, the thickness is calculated from the length of the shadow of the replica. In addition, it is preferable as an embodiment to prepare the outermost shell near the surface of the silver halide grain by using the iodide ion releasing method of the present invention. Forming a silver halide phase containing silver iodide near the grain surface is important from the viewpoint of enhancing the dye adsorbing power and controlling the developing rate. In the present invention, these can be controlled by selecting the silver iodide content of the silver halide phase of the outermost shell near the grain surface according to the purpose. It is desirable that the halogen composition on the surface of silver halide grains be uniform among grains, and according to the method of the present invention, it is possible to achieve the grain-to-grain homogeneity which cannot be attained by the conventional techniques. In this case, the particle surface means a region up to a depth of about 50Å from the surface. The halogen composition in such a region is determined by XPS (X-ray photoelectron spectroscopy) method or ISS.
It can be measured by a surface analysis method such as (ion scattering spectroscopy).

In this embodiment, silver halide grains in which the silver iodide content of the silver halide phase on the grain surface of the emulsion grains measured by these surface analysis methods is 0.1 to 15 mol% are preferable, and more preferable. Is 0.3 to 12 mol%, particularly preferably 1 to 10 mol%, most preferably 3 to 8 mol%.
Is. According to the present invention, the halogen composition in the entire particles can be made uniform among the particles, and also in this respect, the present invention achieves the uniformity between the particles which cannot be reached by the conventional techniques. . The coefficient of variation of the silver iodide content distribution among individual emulsion grains obtained by the method of the present invention is 20%.
Is preferably 3%, more preferably 15%
3%, particularly preferably 10% to 3%. The silver iodide content of each individual emulsion grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer. The variation coefficient of the silver iodide content distribution is a value obtained by dividing the variation (standard deviation) of the silver iodide content of each grain by the average silver iodide content.

The following is a description of the emulsion of the present invention and the emulsions other than the present invention which are used in combination therewith. The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. Other silver salts such as silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate and silver organic acid may be contained as separate grains or as a part of silver halide grains. The silver halide emulsion of the present invention preferably has a distribution or structure in terms of halogen composition in its grains. Typical examples thereof are JP-B-43-13162 and JP-A-6-6.
No. 1-215540, JP-A-60-222845, JP-A-60-143331, JP-A-61-75337, etc. The core-shell having a halogen composition in which the inside and the surface of the grain are different from each other. Type or double structure type particles. Also, it is not a simple double structure,
A triple structure as disclosed in 0-222844, or a multilayer structure of more than that;
A silver halide having a different composition can be thinly applied to the surface of the double-structured grain of the shell. In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called junction structure can be formed. Examples of these are JP-A-59-133540, JP-A-58-108526, and European Patent 199,290.
A2, JP-B-58-24772, JP-A-59-16
No. 254 and the like. The crystal to be bonded can have a composition different from that of the crystal serving as the host and can be generated by bonding to the edge, corner, or surface of the host crystal. Such a junction crystal can be formed even if the host crystal has a uniform halogen composition or has a core-shell type structure.

In the case of a junction structure, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure such as silver rhodanide and silver carbonate may be combined with silver halide to form a junction structure. In addition, a non-silver salt compound such as lead oxide may be used as long as a joint structure is possible. In the case of silver iodobromide grains having these structures, it is a preferred embodiment that the core portion has a higher silver iodobromide content than the shell portion. On the contrary, in some cases, grains having a low silver iodide content in the core part and a high shell part are preferable. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and having a relatively low silver iodide content in the junction crystal may be used, or vice versa. Further, the boundary portion having different halogen compositions of the particles having these structures may be a clear boundary or an unclear boundary. In addition, a positive embodiment in which the composition is positively and continuously changed is also a preferred embodiment. In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or have a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% to 3% is preferable. Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. For example, there is a correlation in which larger size particles have a higher iodine content, while smaller particles have a lower iodine content. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the surface of the grain. Increasing the silver iodide content in the vicinity of the surface or increasing the silver chloride content changes the adsorbability of the dye and the developing rate and can be selected according to the purpose. When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that attaches only to a part of the grain. For example, the halogen composition may be changed only on one surface of the tetrahedral grain composed of the (100) plane and the (111) plane, or on one of the main plane and the side surface of the tabular grain. Even if the silver halide grains used in the present invention are normal crystals that do not contain twin planes, examples such as those described on page 163, edited by The Photographic Society of Japan, Fundamentals of Photography Industry, Silver Salt Photography (Corona Publishing Co., Ltd.), for example, Select from twin twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, and non-parallel multiple twins containing two or more non-parallel twin planes. Can be used.
An example of mixing particles having different shapes is described in US Pat.
Although disclosed in Japanese Patent No. 865,964, this method can be selected if necessary. In case of normal crystal (100)
A cubic having a plane, an octahedron having a (111) plane, and a dodecahedron grain having a (110) plane disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. In addition, the Journal of Imaging Scienc
e30, p. 247, (hl1) plane particles represented by (211) as reported in 1986, (3
31) is a typical (hh1) plane particle, (210) plane is a representative (hk0) plane particle and (321) is a representative (hk1) plane particle. It can be selected and used. (100) plane and (11
(1) 14-sided grains whose faces coexist in one grain, (10
Particles in which (0) plane and (110) plane coexist, or (11
Particles in which two planes or a large number of planes coexist, such as particles in which 1) planes and (110) planes coexist can be selected and used according to the purpose.

Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Prac.
tice (1930), p. 131; Gatov, Photographic Science and Engineering (Guto
ff, Photographic Science and Engineering), 14th
Volume 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
It can be prepared by the method described in 33,048, 4,439,520 and British Patent 2,112,157. When the tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by the sensitizing dye, and the above-cited US Pat.
No. 26 for details. 8 of total projected area of particles
The average aspect ratio of 0% or more is preferably 1 or more and less than 100. It is more preferably 2 or more and less than 30, and particularly preferably 3 or more and less than 25. The shape of tabular grains can be selected from triangles, hexagons, circles, and the like. A regular hexagon with approximately six sides of equal length, as described in U.S. Pat. No. 4,797,354, is a preferred form.

The equivalent circle diameter of the tabular grains is 0.15 to 5.0 μm.
It is preferably m. The thickness of the tabular grain is 0.
It is preferably from 05 to 1.0 μm. As a ratio of tabular grains, tabular grains having an aspect ratio of 2 or more are preferably 50% or more, more preferably 80% of the total projected area.
% Or more, particularly preferably 90% or more. Further, more preferable results may be obtained by using monodisperse tabular grains. The structure and manufacturing method of the monodisperse tabular grains are described in, for example, JP-A-63-151618. Briefly describing the shape, 70% or more of the total projected area of silver halide grains is the minimum. It is occupied by a tabular silver halide having a hexagonal shape in which the ratio of the length of the side having the maximum length to the length of the side having the length is 2 or less and having two parallel parallel outer surfaces. Furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains (the variation of the grain size (standard deviation) represented by the circle equivalent diameter of the projected area divided by the average grain size) Has a monodispersity of 20% to 3%.

It is also preferable to use grains having dislocations. In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. Particles containing no dislocation lines,
It is preferable to select particles containing several dislocations or particles containing many dislocations according to the purpose. It is also possible to select dislocations or curved dislocations introduced linearly with respect to a specific direction of the crystal orientation of the particles, or to introduce the dislocations throughout the particles or only in specific parts of the particles.
For example, dislocations can be introduced only in the fringe portion of the grain. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. In this case as well, it is a preferable form to limit the particles to specific portions such as vertices and edges. The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1, or West German Patent No. 2,306,447C2. The surface may be modified as disclosed in JP-A-60-22130. A structure having a flat particle surface is generally used, but intentionally forming irregularities is sometimes preferable. JP-A-58-106532, JP-A-60-2
Examples are the part of the crystals described in 21320, for example the method of drilling holes in the centers of vertices or planes, or the ruffled particles described in US Pat. No. 4,643,966. The grain size of the emulsion used in the present invention can be evaluated by the equivalent circle diameter of the projected area using an electron microscope, the equivalent spherical diameter of the particle volume calculated from the projected area and the grain thickness, or the equivalent spherical diameter of the volume determined by the Coulter counter method. It can be used by selecting from ultrafine particles having a sphere-equivalent diameter of 0.05 micron or less, and coarse particles having a sphere-equivalent diameter of more than 10 microns. Preferably, grains having a size of 0.1 micron or more and 3 microns or less are used as the photosensitive silver halide grains. The normal crystal emulsion used in the present invention has a wide grain size distribution, so-called polydisperse emulsion,
A monodisperse emulsion having a narrow size distribution can be selected and used according to the purpose. As a scale representing the size distribution, the variation coefficient of the projected area circle diameter of particles or the sphere equivalent diameter of volume may be used. When a monodisperse emulsion is used, the coefficient of variation is 25% to 3%, more preferably 20% to 3%,
It is more preferable to use an emulsion having a size distribution of 15% to 3%.

In some cases, the monodisperse emulsion is defined as a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size in terms of number of grains or weight. In order to satisfy the target gradation of the light-sensitive material, the emulsion layers having substantially the same color sensitivity have different grain sizes.
One or more kinds of monodisperse silver halide emulsions can be mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used. The emulsion of the present invention and the photographic emulsion used in combination therewith are
Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P.Glafkides, Chimie et Physique Photographiqu
e, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photogra
phic Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VL Zelikman et al., Making and Coating).
It can be prepared using the method described in Photographic Emulsion, Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

A method of adding silver halide grains that have been preliminarily formed into a reaction vessel for emulsion preparation is described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. The above method is preferable in some cases. These can be used as seed crystals, and are effectively supplied as silver halide for growth.
In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method may be selected from total addition at once, addition in plural times or continuous addition. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface. A method of converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in US Pat. Nos. 3,477,852 and 4,142,
900, European Patent Nos. 273,429, 273,4
No. 30, West German Laid-Open Patent No. 3,819,241 and the like are effective particle forming methods. A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. Further, it is possible to select from a method such as conversion at once, conversion by dividing into plural times, or continuous conversion.

In addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate as a method for growing grains, British Patent No. 1,469,480 and US Pat.
A particle forming method in which the concentration is changed or the flow rate is changed as described in Nos. 0,757 and 4,242,445 is a preferable method. Increase the concentration,
Alternatively, by increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is. A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is disclosed in US Pat. Nos. 2,996,287 and 3,342,6.
No. 05, No. 3,415, 650, No. 3, 785, 77
7, West German published patents 2,556,885, 2,55
It can be used by selecting from the methods described in 5,364. Silver halide solvents are useful for the purpose of promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Other ripening agents can also be used.
The total amount of these ripening agents can be compounded in the dispersion medium in the reactor before adding silver and halide salts, and the halide salts, silver salts or peptizers can be added in the reactor as well. Can also be introduced. As another variation, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

Ammonia, thiocyanates (for example, rhodan potassium, rhodan ammonium), organic thioether compounds (for example, US Pat. Nos. 3,574,628 and 3,
021,215, 3,057,724, 3,0
38,805, 4,276,374, 4,29
7,439, 3,704,130, 4,78
2,013, compounds described in JP-A-57-104926 and the like. ), A thione compound (for example, JP-A-53-82).
408, 55-77737, U.S. Pat. No. 4,22.
Growth of tetra-substituted thioureas described in 1,863, etc., compounds described in JP-A-53-144319), and silver halide grains described in JP-A-57-202531. Examples thereof include mercapto compounds, amine compounds (for example, JP-A No. 54-100717, etc.), etc. that can accelerate the reaction.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can In addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan. No. 16.
The enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of washing with water can be selected according to the purpose, but it is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semitransparent membrane,
It can be selected and used from a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Mg, Ca, Sr, Ba, Al, S
c, Y, La, Cr, Mn, Fe, Co, Ni, Cu,
Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates, hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example CdB
_{r 2, CdCl 2, Cd (} NO 3) 2, Pb (NO 3)
₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN)
₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl
₆ , (NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) _{6 and the} like. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, or may use two or more types in combination.

The metal compound is preferably added after being dissolved in water or a suitable solvent such as methanol or acetone.
Aqueous hydrogen halide solution (eg HC to stabilize the solution)
l, HBr, etc. or alkali halide (eg KC)
1, NaCl, KBr, NaBr, etc.) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. It is also possible to add it to a water-soluble silver salt (eg AgNO ₃ ) or an aqueous alkali halide solution (eg NaCl, KBr, KI) and continuously add it during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods. The method of adding a chalcogen compound as described in U.S. Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present. The silver halide grain of the present invention is subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization, noble metal sensitization and reduction sensitization at any step of the silver halide emulsion production process. You can
It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations that can be preferably carried out in the present invention is chalcogenide sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th Edition. Published by Macmillan, 1
977 (TH James, The Theory of the Photogr
aphic Process, 4 th ed, Macmillan, 1977) 67-7
It can be carried out using activated gelatin as described on page 6, and also Research Disclosure 120.
Vol., Apr. 1974, 12008; Research Disclosure, Vol. 34, Jun. 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446.
No. 3,772,031, No. 3,857,711
Nos. 3,901,714, 4,266,018 and 3,904,415, and British Patent Nos. 1,3.
PAg5-10, p as described in No. 15,755.
Sulfur, selenium, at H5-8 and temperature 30-80 ° C
It can be tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a divalent or tetravalent palladium salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate. As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,853.
7,711, 4,266,018 and 4,05
The sulfur-containing compounds described in 4,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity in the process of chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Chemical sensitization aid,
Examples of modifiers include U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and Daffin's "Photoemulsion Chemistry", 138-143. The emulsion of the present invention is preferably combined with gold sensitization. The preferred amount of gold sensitizer is 1 × 10 ^-4 to 1 per mol of silver halide.
^{X10 -7} mol, more preferably 1 x 10 ^-5 ~
It is 5 × 10 ⁻⁷ mol. The preferred range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ per mol of silver halide.
It is a mole. The preferred range of the thiocyan compound or selenocyan compound is 5 × 10 ⁻² to 1 × 10 ⁻⁶ mol. The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × 10 ⁻⁴ per mol of silver halide.
To 1 × 10 ⁻⁷ mol, more preferably 1 × 10 ^7
-5 to 5 x 10 ^-7 mol.

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both. The silver halide emulsion of the present invention is preferably subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere of pAg 1 to 7 called silver ripening, and a pH of 8 to 8 called high pH ripening. It is also possible to select either the method of growing or aging in 11 high pH atmosphere. 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, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. It may be added to the reaction vessel in advance, but a method of adding it at an appropriate time during grain growth is preferred. Further, the reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. Especially, the extremely fine silver particles produced as a by-product in the process of forming the silver halide grains and the chemical sensitization process,
Compounds that can be converted to silver ions are effective. The silver ions generated here may form a poorly soluble silver salt such as silver halide, silver sulfide and silver selenide, or may form a readily soluble silver salt such as silver nitrate. Good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Inorganic oxidants include ozone, hydrogen peroxide and its adducts (eg NaBO ₂ · H ₂ O ₂ · 3H ₂ O, 2NaC).
_{O 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2N
a ₂ SO ₄ .H ₂ O ₂ .2H ₂ O), peroxy acid salts (eg K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O)
₈ ), a peroxy complex compound (for example, K ₂ [Ti (O
₂ ) C ₂ O ₄ ] ・ 3H ₂ O, 4K ₂ SO ₄・ Ti (O
₂ ) OH ・ SO ₄・ 2H ₂ O, Na ₃ [VO (O ₂ )
_{(C 2 H 4) 2 ·} 6H 2 O ], permanganate (e.g., KMnO _4), chromates (e.g., K ₂ Cr ₂ O
₇ ) and other oxyacid salts, iodine and bromine and other halogen elements,
Perhalogenates (eg potassium periodate), salts of high valent metals (eg potassium hexacyanoferrate)
And thiosulfonate.

As the organic oxidizing agent, quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T). , Chloramine B). Preferred oxidizing agents used in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents and quinone type organic oxidizing agents. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. The method can be selected from a method of using an oxidant and then reduction sensitization, the reverse method thereof, or a method of coexisting both of them. These methods can be selectively used in the grain forming step and the chemical sensitization step. The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes What is known as antifoggants or stabilizers, can be added a number of compounds.
For example, US Pat. Nos. 3,954,474 and 3,98.
Nos. 2,947 and 52-28660 can be used. One of the preferred compounds is the compound described in JP-A-63-212932.
Antifoggants and stabilizers can be used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to expressing the original antifoggant and stabilizing effects by adding during emulsion preparation, it controls the crystal habit of grains, reduces the grain size, reduces the solubility of grains, controls chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

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. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. 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 thiazoline 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 A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, indolenine nucleus, benzoindolenine 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 have a substituent on a carbon atom. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641 and 3,617. , 293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301. No. 3,814,609, No. 3,837,862, No. 4,026,707, and British Patent No. 1,344,281.
No. 1,507,803, Japanese Patent Publication No. 43-4936
No. 53-12375, JP-A No. 52-110618.
No. 52-109925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and may be contained in an emulsion exhibiting supersensitization. The sensitizing dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but as described in US Pat. Nos. 3,628,969 and 4,225,666, a chemical sensitizer is used. Spectral sensitization can be carried out simultaneously with chemical sensitization by adding at the same time, or prior to chemical sensitization as described in JP-A-58-113928, and silver halide grain precipitate formation. It is also possible to start the spectral sensitization by adding before completion of the above. Furthermore, US Pat. No. 4,225
It is also possible to add these said compounds separately, as taught in US Pat. No. 666, ie to add some of these compounds prior to chemical sensitization and the rest after chemical sensitization. And U.S. Pat. No. 4,183,756.
It can be at any time during the formation of silver halide grains including the method disclosed in No. The addition amount can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide, but about 5 × in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm. 10 ^{-5 to} 2 x 10 ^-3
Moles are effective.

The light-sensitive material produced by using the silver halide emulsion obtained in the present invention comprises a silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer on a support. It suffices that at least one layer is provided, and there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one color-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The material is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is generally used. Are sequentially arranged from the support side in the order of a red color-sensitive layer, a green color-sensitive layer and a blue color-sensitive layer. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-11.
No. 3438, No. 59-113440, No. 61-200.
Nos. 37 and 61-20038 may contain a coupler, a DIR compound and the like, and may contain a color mixing inhibitor as is commonly used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, JP-A-57-112751, JP-A-62-20035.
No. 0, No. 62-206541, No. 62-206543
As described in the publications, etc., a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close 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 (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of. In addition, Japanese Examined Japanese Patent Publication Sho 55-34
As described in Japanese Patent No. 932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738
No. 62-63936, the blue-sensitive layer / GL / RL from the side farthest from the support.
It can also be installed in the order of / GH / RH.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a low photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above.

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

Although the above-mentioned various additives are used in the light-sensitive material of the present technology, various additives other than the above can be used according to the purpose. These additives are
For more details, Research Disclosure Item 17
643 (December 1978), Item 18716.
(November 1979), and Item 308119 (1)
(November 989), the relevant parts are summarized in the table below.

───────────────────────────────── Additive type RD17643 RD18716 RD308119 ──────── ───────────────────────── 1 Chemical sensitizer Page 23 Page 648 Right column Page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, 23 ~ Page 24 page 648 right column ~ 996 right ~ 998 right supersensitizer page 649 right column 4 whitening agent page 24 647 page right column 998 right 5 antifoggant, pages 24 ~ 25 page 649 right column 998 right ~ 1000 right and stabilizer 6 light absorber, page 25-26 page 649 right column-1003 left-1003 right filter dye page 650 left column UV absorber 7 stain inhibitor page 25 right column page 650 left-right column 8 dye image Stabilizer page 25 9 Hardener page 26 page 651 Left column 1004 right to 1005 left 10 Binder page 26 same as above 1003 right to 1004 right 11 Plasticizer, lubricant page 27 page 650 right column 1006 left to 1006 right 12 Coating aid , Pages 26 to 27 Same as above 1005 Left to 1006 Left Surfactant 13 Stat Page 27 Same as above 1006 Right to 1007 Left Preventive agent 14 Matting agent 1008 Left to 1009 Left

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add to the photographic material a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-C to G, and No.
307105, VII-C to G. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501 and 4,022,620.
No. 4,326,024, No. 4,401,752
No. 4,248,961, Japanese Patent Publication No. 58-1073.
No. 9, British Patent Nos. 1,425,020 and 1,47
Preferred are those described in US Pat. No. 6,760, US Pat. Nos. 3,973,968, 4,314,023, 4,511,649, and European Patent 249,473A. As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat.
310,619, 4,351,897, EP 73,636, and US 3,061,432.
No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-6
0-33552, Research Disclosure No.
24230 (June 1984), JP-A-60-4365.
No. 9, No. 61-72238, No. 60-35730,
No. 55-118034, No. 60-185951, U.S. Pat. Nos. 4,500,630, and 4,540,65.
No. 4, No. 4,556,630, International Publication WO88 /
Those described in No. 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,080,
No. 211, No. 4,367,282, No. 4,40
No. 9,320, No. 4,576,910, British Patent No. 2,102,137, European Patent No. 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent (Published) No. 3 , 234,533 are preferred. Researched Disclosure No. 1 is a colored coupler for correcting unwanted absorption of color forming dyes.
7643, Item VII-G, No. 307105, Item VII-G
, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-3
9413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers releasing a development inhibitor are disclosed in the above-mentioned RD17643, VII-F and No. 307105, VII-F patents, JP-A-57-151944 and 57-15423.
No. 4, No. 60-184248, No. 63-37346.
No. 63-37350, U.S. Pat. No. 4,248,9.
Those described in No. 62 and No. 4,782, 012 are preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable. Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. Nos. 4,283,472, and 4,338,393.
No. 4,310,618 and the like, multiequivalent couplers, JP-A-60-185950 and JP-A-62-242.
52, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 31
No. 3,308A, a coupler that releases a dye that recovers color after separation, R.I. D. No. 11449, No. 24241, bleach accelerator releasing couplers described in JP-A No. 61-201247, ligand releasing couplers described in US Pat. No. 4,555,477, etc., and JP-A No. 63-75747. Leuco Dye-releasing Coupler, US Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 4,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate,
Bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl Phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example, N, N-diethyldodecane amide, N, N-diethyllaurylamide,
N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4
-Di-t-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-
Butoxy-5-tert-octylaniline), hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248 are used.
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-described in JP-A No. 1-80941.
Dimethylphenol, 2-phenoxyethanol, 2-
It is preferable to add various antiseptics or antifungal agents such as (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No. 17643, page 28, No. 18716, 64.
From page 7, right column to page 648, left column, and No. 307105, page 879.

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, and 18 μm or less.
m 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,
20 seconds or less is more preferable. The film thickness is 25 ° C and relative humidity is 5
Mean film thickness measured under 5% humidity control (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A Green (A. G
Reen) et al., Photographic Science and Engineering (Photogr. Sci. Eng.), 19
It can be measured by using a swellometer (swelling meter) of the type described in Vol. 2, No. 2, pp. 124-129, T _1/2
Is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as 1% of the saturated film thickness.
It is defined as the time to reach / 2. Membrane swelling speed 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 150 to 400.
% Is preferred. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula: (maximum swollen film thickness-film thickness) / film thickness
Can be calculated according to. The photographic material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide the hydrophilic colloid layer (referred to as a back layer). In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener,
It is preferable to contain a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, No. 18
Development can be carried out by a usual method described in 651, left column to right column, and No. 307105, pages 880 to 881. 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.
Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Examples thereof include amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, 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. Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

When reversal processing is carried out, black and white development is usually carried out before color development. 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 contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio (cm ⁻¹ ) is preferably 0.1 or less, More preferably, it is 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, Japanese Patent Laid-Open No. Hei 1
The method using a movable lid described in JP-A-82033 and the slit development processing method described in JP-A-63-216050 can be mentioned. Reducing the aperture ratio is preferably applied not only in both the color development and black-and-white development steps but also in the subsequent steps, for example, all steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent. it can. The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. In addition, processing with two continuous bleach-fixing baths, fixing before bleach-fixing,
Alternatively, the bleaching process may be performed after the bleach-fixing process 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. Typical bleaching agents are organic complex salts of iron (III), such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetate iron (III) complex salt are used from the viewpoint of rapid treatment and prevention of environmental pollution. preferable. 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 containing these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8.0, but it should be processed at a lower pH in order to speed up the processing. You can also

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 Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A No. 50-140129; -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40943, JP-A-49-59644 and JP-A-53-
94927, 54-35727, 55-265.
Compounds described in No. 06 and No. 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, US Pat.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 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. A particularly preferred organic acid is a compound having an acid dissociation constant (pka) of 2 to 5, specifically, acetic acid,
Propionic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate with thiocyanate, thioether compound, thiourea and the like 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, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution 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 imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole. The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 1 to 3 minutes, more preferably 1 to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 4 ° C.
It is 5 ° 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. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-183460.
A method of increasing the stirring effect using the rotating means of No. 183461, and further moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. How to improve,
There is a method of increasing the circulation flow rate of the entire processing liquid.
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 agitation 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 developing machine used for the light-sensitive material of the present invention preferably has the light-sensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the deterioration of the performance of the treatment liquid.
Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, and the temperature of rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Pictur.
e and Television Engineers Volume 64, p. 248 ~
253 (May 1955 issue). According to the multistage countercurrent method described in the above document,
Although the amount of water to be washed can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and the resulting suspended matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
No. 8542, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology "Sterilization, sterilization, and antifungal technology of microorganisms" edited by the Society (1982) Industrial Technology Association, "Antibacterial and antifungal agent encyclopedia" edited by Japan Society for Antibacterial and Antifungal (1
It is also possible to use the fungicide described in 986).

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and the washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C is preferably selected. Further, 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, Japanese Patent Laid-Open No. 57-8543,
All known methods described in JP-A-58-14834 and JP-A-60-220345 can be used. In addition, following the water washing treatment, there is a case where further stabilization treatment is performed,
An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. 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 silver halide color light-sensitive 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 various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597, No. 3,342,599, Research Disclosure No. 14850 and N.
Schiff base type compound described in No. 15159, No. 1
Aldol compounds described in 3924, US Pat. No. 3,7
Metal salt complexes described in JP-A-53-135.
The urethane compound described in No. 628 can be mentioned. The silver halide color light-sensitive 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 and JP-A-57-144547.
No. 58-115438 and the like.
Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to. The silver halide photographic light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,626,
JP-A-60-133449 and 59-218443.
No. 61-238056, European Patent 210,660.
It can also be applied to the photothermographic materials described in A2 and the like. The silver halide light-sensitive material of the present invention is described in JP-A 2-3
When applied to the film unit with a lens described in No. 2615, Jpn.

[0079]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of emulsion Tabular silver bromide core emulsion 1-A 1200 cc of aqueous solution containing 8 g of gelatin and 5 g of KBr
Was stirred at 60 ° C., and AgNO ₃ (9.7 g) aqueous solution and K were added.
An aqueous solution of Br (7 g) was added with a double jet in 45 seconds. (In each of the Examples and Comparative Examples, the emulsion preparation operation was performed by the controlled double jet method.) After adding 40 g of gelatin, the temperature was raised to 75 ° C. and N
Aged for 20 minutes in the presence of H ₃ . After neutralizing with HNO ₃ ,
An AgNO ₃ (130 g) aqueous solution and a KBr aqueous solution were added over 80 minutes while accelerating the flow rate (the flow rate at the end is twice the start rate). At this time, pAg was kept at 8.2. After this,
The emulsion was cooled to 35 ° C. and desalted by a conventional flocculation method. The obtained emulsion was tabular grains having an average equivalent circle diameter of 1.3 μm and an average thickness of 0.2 μm.

Tabular Silver Iodobromide Emulsion 1-B (Comparative Emulsion) Emulsion 1 containing silver bromide equivalent to 164 g of AgNO ₃ 1-
A was added to 1950 cc of water, keeping the temperature at 55 ° C, pAg at 8.9 and pH at 5.6. After that, 126 cc of 0.32 M KI aqueous solution was added quantitatively for 1 minute. Successively, AgNO ₃ (66 g) aqueous solution and KBr aqueous solution were pAg
Was added over 36 minutes to maintain 8.9. After that, desalting was performed by a conventional flocculation method. The obtained silver iodobromide grains were tabular grains having an average equivalent circle diameter of 1.4 μm and an average grain thickness of 0.25 μm. Further, grains having an aspect ratio of 3 or more account for 95% of the total projected area, and the same applies to the tabular grain emulsions below.

Tabular Silver Iodobromide Emulsion 1-C (Comparative Emulsion) It was prepared in the same manner as Emulsion 1-B except for the following. Instead of adding KI aqueous solution, AgNO ₃ prepared separately beforehand
A silver iodide fine grain emulsion having a tabular grain size of 0.02 μm corresponding to (6.8 g) was added. Tabular Silver Iodobromide Emulsion 1-D (Comparative Emulsion) It was prepared in the same manner as Emulsion 1-B except for the following. After adding 2-iodopropionic acid in an equimolar amount to KI instead of adding the KI aqueous solution, 0.8M sodium sulfite aqueous solution (60 cc) was added, and the pH was raised to 9.0 and kept for 8 minutes. Returned to 5.6.

Tabular Silver Iodobromide Emulsion 1-E (Comparative Emulsion) It was prepared in the same manner as Emulsion 1-D except for the following. Instead of adding 2-iodopropionic acid, iodoacetic acid was added equimolar to KI. Tabular Silver Iodobromide Emulsion 1-F (Comparative Emulsion) It was prepared in the same manner as Emulsion 1-D except for the following. Instead of adding 2-iodopropionic acid, cyanomethane iodide
Only equimolar to I was added. Tabular silver iodobromide emulsion 1-G (invention emulsion) was prepared in the same manner as emulsion 1-D except for the following. Instead of adding 2-iodopropionic acid, compound 1 below was added. Tabular Silver Iodobromide Emulsion 1-H (Emulsion of the Invention) It was prepared in the same manner as Emulsion 1-D except for the following. Instead of adding 2-iodopropionic acid, compound 7 described below was added. Tabular silver iodobromide emulsion 1-I (emulsion of the present invention) was prepared in the same manner as emulsion 1-D except for the following. Instead of adding 2-iodopropionic acid, compound 8 described below was added.

(2) Chemical Sensitization Emulsions 1-B to 1-I were subjected to gold sulfur sensitization as follows. The emulsion was heated to 64 ° C., and the sensitizing dye ExS-1 described later was added to 2.6 × 10 ⁻⁴ mol / mol Ag, ExS-.
1.1 × 10 ⁻⁵ mol / mol Ag, and ExS-3 3.
Only 6 × 10 ⁻⁴ mol / mol Ag was added, and then potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to perform optimum chemical sensitization. Here, "optimally perform chemical sensitization" means chemical sensitization that maximizes the sensitivity when exposed for 1/100 second.

(3) Preparation of coated sample and its evaluation On a cellulose triacetate film support provided with an undercoat layer, the emulsions and protections shown in Table 1 were coated at the coating amounts shown in Table A below. The layers were applied to make Application Samples 1-8. Table A Emulsion coating conditions (1) Emulsion layer ・ Emulsion ... Various emulsions (silver 3.6 × 10 ^-2 mol / m ² ) ・ Coupler (1.5 × 10 ^-3 mol / m ² ).

[0086]

[Chemical 3]

Tricresyl phosphate (1.10 g / m ² ), gelatin (2.30 g / m ² ) (2) protective layer, 2,4-dichloro-6-hydroxy-s-triazine sodium salt (0 .08g / m ²⁾ · gelatin (1.80g / m ²⁾

These samples were left at 40 ° C. and 70% relative humidity for 14 hours and then passed through a continuous wedge to
After exposure for 100 seconds, color development shown in Table B below was performed. The treated sample was measured for density with a green filter. Table B Steps Processing time Processing temperature Color development 2 minutes 30 seconds 40 ° C Bleach-fixing 3 minutes 00 seconds 40 ° C Washing with water (1) 20 seconds 35 ° C Washing with water (2) 20 seconds 35 ° C Stability 20 seconds 35 ° C Drying 50 seconds 65 ° C

Next, the composition of the treatment liquid will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg Hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH 10.05

(Bleaching Fixing Solution) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 90.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleaching accelerator 0.01 mol

[0091]

[Chemical 4] 1.0 liter pH 6.0 by adding water

(Washing Solution) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH type anion exchange resin (Amberlite IR-400) were passed through the column to treat calcium and magnesium ions at a concentration of 3 mg / L or less, followed by isocyanuric dichloride. Sodium 20 mg / L and sodium sulfate 1.5 g / L were added. The pH of this solution is in the range 6.5-7.5.

(Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added. 1.0 liter pH 5.0-8.0

The sensitivity was represented by the relative value of the logarithm of the reciprocal of the exposure amount displayed in lux · sec which gives a density of 0.2 on fog. Regarding the pressure characteristics, the pressure characteristics were tested by the following test method A. Then, exposure for sensitometry was performed and color development shown in Table B was performed. Test method A After placing in an atmosphere with a relative humidity of 55% for 3 hours or more, a load of 4 g was applied with a needle having a thickness of 0.1 mm in the same atmosphere, and the emulsion surface was scratched at a speed of 1 cm / sec. .

The developed sample was measured with a measuring slit of 5 μm × 1 mm to measure the densities of a portion under pressure and a portion without pressure. Increase in fogging due to pressure Δ
Fog. Further, in an exposure area equal to or less than 100 times the exposure amount E ₀ which gives a density of fog +0.2, the density is 0.0 due to the pressure between certain exposure amounts E ₁ and E _2.
When it decreases by 1 or more Pressure desensitization area = ((logE ₂ −logE ₁ ) / 2) × 100
(%). The results obtained are shown in Table 1.

[0096]

[Table 1]

In Table 1, the sensitivities of Samples 2 to 8 are as follows.
The sensitivity was expressed as a relative value with the sensitivity of 100 as 100. As is clear from Table 1, according to the present invention, an emulsion having low fog, high sensitivity, small increase in pressure fog and small pressure desensitization could be obtained.

Example 2 On a subbed cellulose triacetate film support,
Samples 101 to 108 containing the emulsions 1-B to 1-I described in Example 1 in the fifth layer (red-sensitive emulsion layer) of the multilayer color light-sensitive material were prepared by coating each layer having the composition as shown below. . (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 Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate 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.

(Samples 101 to 108) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ⁻³ HBS-1 0.20 Second layer (intermediate layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0. 10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 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-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS- 1 0.010 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D 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 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS- 1 0.010 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion (any of 1-B to 1-I) Silver 1.40 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC -8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 gelatin 1.20 Sixth layer (intermediate layer) Cpd-1 0.010 HBS-1 0.50 gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ⁻⁵ ExS-5 2.1 × 10 ⁻⁴ ExS-6 8.0 × 10 ⁻⁴ ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 Eighth layer (medium sensitive green emulsion layer) ) Emulsion D Silver 0.80 ExS- ⁴ 3.2x10 ^-5 ExS-5 2.2x10 ^-4 ExS-6 8.4x10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY -1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.90

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ⁻⁵ ExS-5 8.1 × 10 ⁻⁵ ExS-6 3.2 × 10 ⁻⁴ ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44 10th layer ( Yellow filter layer) Yellow colloidal silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY− 4 0.020 HBS-1 0.28 Gelatin 1.10 12th layer (medium sensitivity blue emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ⁻⁴ ExC-7 7.0 × 10 ^{− 3} ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

Thirteenth Layer (High Sensitivity Blue Sensitive Emulsion Layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0 .86 14th layer (1st protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00 15th layer (2nd protective layer) Layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1 .20

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 are appropriately added. -6,
F-1 to F-17 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained.

[0108]

[Table 2]

In Table 2, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-23740 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope. (5) Emulsions A to G are silver iodobromide.

[0110]

[Chemical 5]

[0111]

[Chemical 6]

[0112]

[Chemical 7]

[0113]

[Chemical 8]

[0114]

[Chemical 9]

[0115]

[Chemical 10]

[0116]

[Chemical 11]

[0117]

[Chemical 12]

[0118]

[Chemical 13]

[0119]

[Chemical 14]

[0120]

[Chemical 15]

[0121]

[Chemical 16]

[0122]

[Chemical 17]

[0123]

[Chemical 18]

[0124]

[Chemical 19]

Samples 101 to 10 thus obtained
8 was exposed and then processed by the method described below. Table C Treatment Method Process Treatment time Treatment temperature Color development 3 minutes 15 seconds 38 ° C Bleach 1 minute 00 seconds 38 ° C Bleach fixing 3 minutes 15 seconds 38 ° C water wash (1) 40 seconds 35 ° C water wash (2) 1 minute 00 seconds 35 ℃ Stability 40 seconds 38 ℃ Dry 1 minute 15 seconds 55 ℃

Next, the composition of the processing liquid will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg Hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH 10.05 (bleaching solution) ( Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol ((CH ₃ ) ₂ N- _{CH 2 -CH 2 -S-) 2 ·} 2HCl aqueous ammonia (27%) 15.0 ml water to make 1.0 l pH 6.3

(Bleaching Fixing Solution) (Unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia Water (27%) 6.0 ml Water was added to 1.0 liter pH 7.2 (Washing liquid) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas).
And OH type anion exchange resin (the same Amberlite IR-
400) and passed through a mixed bed type column to treat calcium and magnesium ions at a concentration of 3 mg / L or less, and then 20 mg of sodium diisocyanurate dichloride.
/ L and 0.15 g / L sodium sulfate were added. The pH of this liquid was in the range of 6.5-7.5.

(Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added. With respect to the characteristic curve of 1.0 liter pH 5.0-8.0 cyan dye, the sensitivity was indicated by the relative value of the reciprocal of the fog density and the reciprocal of the exposure amount that gives a density 0.2 higher than the fog density. Regarding the pressure characteristics, a test was conducted using the test method A as in Example 1, and after exposure and development, the densities of the pressured portion and the non-pressured portion of the characteristic curve of the cyan dye were measured. The increase in fog due to ΔFog and the pressure desensitization region are shown. Table 3 shows the obtained results.
Shown in.

[0129]

[Table 3]

As in Example 2, the emulsion of the present invention had a low fog, high sensitivity, improved pressure property, and the effect of the present invention was remarkable.

[0131]

According to the present invention, it is possible to obtain a silver halide emulsion and a photographic light-sensitive material having high sensitivity, low fog and improved pressure.

Claims (5)

[Claims] 1. A method for forming silver halide grains, which comprises using at least one iodide ion-releasing compound represented by the following formula (I). IL-COOH (I) (In the formula, L represents a divalent organic group containing an aromatic ring.) 2. A silver halide grain containing silver iodide, wherein the silver iodide content inside the silver halide grain is higher than the average silver iodide content of the entire silver halide grain. 2. The method for forming silver halide grains according to claim 1, which has a silver iodide region, and the high silver iodide region is formed by using the iodide ion-releasing compound of the formula (I). 3. The method for forming silver halide grains according to claim 1, wherein the iodide ion-releasing compound is used in the presence of an iodide ion-releasing agent. 4. The method for forming silver halide grains according to claim 1, wherein a group of silver halide grains having a variation coefficient of a silver iodide content distribution between silver halide grains of 3 to 20% is formed. 5. Silver halide grains are formed in the presence of at least one iodide ion-releasing compound represented by the following formula (I), and an emulsion containing the silver halide grains is formed on a support. A method for producing a silver halide photographic light-sensitive material, which comprises coating as at least one silver halide emulsion layer. IL-COOH (I) (In the formula, L represents a divalent organic group containing an aromatic ring.)