JP3091041B2 - Method for forming silver halide grains and method for producing silver halide photographic material - Google Patents

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 particularly, to a method for forming silver halide grains for photographic emulsions having low fog, high sensitivity and improved pressure characteristics, and 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 for the performance of silver halide emulsions for photography have become more and more severe. Is coming. In order to increase the sensitivity of silver halide grains and improve the pressure resistance, it is considered preferable that the silver iodide (iodide ion) content be uniform among individual grains from the viewpoint of uniform chemical sensitization. .

Conventionally, when a silver halide phase containing silver iodide is formed in a silver halide grain formation step, the following iodide ion supply method has been used. That is, a method using an iodide salt aqueous solution such as a KI aqueous solution, see JP-A-2-68.
No. 538 (Japanese Patent Application No. 63-220187) which uses silver iodide-containing fine silver halide grains or an iodide ion releasing compound. However,
In the method using an iodide salt aqueous solution, a region where the concentration distribution of iodide ions is highly non-uniform occurs by adding iodide ions to the reaction solution in a free state. Therefore, uniform particle growth between particles could not be performed. On the other hand, the technology disclosed in the above patent application eliminates fluctuations in the halogen composition within the grains and between grains (microscopic distribution of silver iodide) by slowly releasing iodide ions to achieve uniform grain growth. It is a technique that performs. However, even if silver halide grains are formed using the exemplary 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 in fog, high sensitivity, and improved 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 an intragranular distribution of silver iodide uniform among the grains. Another object of the present invention is to provide a silver halide emulsion having low fog and improved sensitivity and pressure. It is a further object of the present invention to provide a method for producing a silver halide photographic material having low fog and improved sensitivity and pressure characteristics.

[0005]

The above object has been attained by the following. (1) A method for forming silver halide grains, comprising using at least one iodide ion releasing compound represented by the following formula (I). ^{_{I-L-S0 3 - M}} + (I) (. Wherein, L represents a divalent organic group, M ⁺ is represents hydrogen ions or a monovalent cation,) (2) containing silver iodide A silver halide grain having a high silver iodide region in which the silver iodide content is higher than the average silver iodide content of the whole silver halide grain; The method for forming silver halide grains according to (1), wherein the silver halide region is formed using the iodide ion releasing compound of the formula (I). (3) The method according to (1) or (2), wherein an iodide ion releasing compound is used in the presence of an iodide ion release regulator. (4) The method for forming silver halide grains according to (1), wherein a group of silver halide grains having a variation coefficient of 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 the emulsion containing the silver halide grains is formed on at least one of the support. A method for producing a silver halide photographic light-sensitive material, which is coated as a silver halide emulsion layer. ^{_{I-L-S0 3 - M}} + (I) ( wherein, L represents a divalent organic group, M ⁺ represents a hydrogen ion or a monovalent cation.)

Hereinafter, the present invention will be described in more detail. The iodide ion releasing compound represented by the formula (I) of the present invention is a compound which releases iodide ions by a reaction with a base and / or a nucleophile, for example, a substitution reaction, a elimination reaction or a hydrolysis reaction. In the formula (I), the divalent organic group represented by L is an aliphatic group, an aromatic group, a heterocyclic group or a group formed by combining them, and furthermore, these groups and an —O— group, -N (R)-
Group, -CO- group, -CS- group, -S- group, -SO- group,
A —SO ₂ — group, a —P (R) group, a —PO (R) — group (where R represents a hydrogen atom or a monovalent group)
Is a group formed by combining The aliphatic group contained in L may be either saturated or unsaturated, preferably has 1 to 30 carbon atoms, and particularly has 1 to 30 carbon atoms.
20 linear, branched or cyclic alkylene groups. L
Is preferably a monocyclic or bicyclic aryl group, and may be condensed with another heterocyclic ring. The heterocyclic group contained in L may be either saturated or unsaturated;
A 5- or 6-membered ring containing at least one of O, P, S and Se is preferred. Particularly preferred is a 5- or 6-membered nitrogen-containing heteroaromatic ring, and typical examples include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a benzol ring thereof. And fused rings.

The divalent group represented by L in the formula (I) may be substituted. Representative examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, Amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group,
Alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, Examples include a phosphoric amide group, a diacylamino group, and an imide group. Preferred substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), and a substituted amino group (Preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 3 carbon atoms)
0), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) Things). These groups may be substituted.

In formula (I), the iodine atom represented by I is preferably bonded to the carbon atom of the divalent organic group represented by L. Particularly preferably, I is bonded to an aliphatic group moiety contained in L. When I is bonded to the aromatic group portion of L, the aromatic group is a benzene ring (including a condensed ring), and a cyano group, a nitro group or a sulfonyl group is located at the ortho or para position of I. It is preferable to have an electron-withdrawing substituent such as When I is bonded to the heterocyclic group moiety of L, the heterocyclic ring is a 5- or 6-membered nitrogen-containing heteroaromatic ring (including a condensed one), and I is a nitrogen atom on the heteroaromatic ring. It is preferred to bond to a carbon atom adjacent to the atom or to be located on a carbon atom which is two atoms in between the nitrogen atom.

In the formula (I), the cation represented by M ⁺ is a hydrogen ion or a monovalent cation. Preferably a substituted or unsubstituted ammonium ion, alkali metal ions (eg ^{Na +, K +, Li +} ) and other metal ions (e.g., ^{1 / 2Mg 2+, 1 / 2Ca} 2+ , etc.). Specific examples of the compound of the formula (I) are shown below, but the invention is not limited thereto.

[0010]

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[0011]

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The iodide ion of the formula (I) used in the present invention
For the method of synthesizing release compounds, refer to the following documents.
Can be J. Am. Chem. Soc.,76, 3277-8 (1954), J. Org. Che
m.,16, 798 (1951), Chem. Ber.,97, 390 (1964), Org.
 Synth., V, 478 (1973), J. Chem. Soc.,1951, 1851,
J. Org. Chem.,19, 1571 (1954), J. Chem. Soc.,195
Two, 142, J. Chem. Soc., 1955, 1383, Angew, Chem., In
t. Ed.,11, 229 (1972), Chem, Commu.,1971, 1112. A typical synthesis example is shown below. Class for other compounds
Can be synthesized in a similar way.

Next, a synthesis example of the compound of the formula (I) will be shown. Synthesis Example 1 Synthesis of Compound 3 After dissolving 2-aminoethane-1-sulfonic acid (33 g) and sodium bicarbonate (44.3 g) in water (390 ml), p-chloromethylbenzoyl chloride (50 g) was added at room temperature. ) Was slowly added dropwise. After the dropwise addition, the reaction was allowed to proceed for 5 hours, followed by filtration, and NaCl (40 g) was added to the filtrate. The precipitated crystals were collected by filtration, dissolved in water (850 ml), added with sodium iodide (48.8 g), and stirred at room temperature for 2 hours. The precipitated product was collected by filtration and dried to obtain the desired product.
(Yield 60 g) The chemical structure was confirmed by NMR spectrum, MS spectrum, IR spectrum and elemental analysis.

Synthesis Example 2 [Synthesis of Compound 6] Sodium hydrogen carbonate (57.5 g)
And sulfanilic acid (52 g) were dissolved in water (450 ml), and then chloracetyl chloride (38.6) was added under ice cooling.
g) was slowly added dropwise. After the dropwise addition, the reaction was allowed to proceed for 30 minutes, and then sodium iodide (68.5 g) was added, followed by a reaction at 70 ° C. for 2 hours. After completion of the reaction, hot filtration was performed, and the filtrate was cooled. The precipitated product was collected by filtration and dried to obtain the desired product. (Yield 79 g) Chemical structure is NM
Confirmed by R spectrum, MS spectrum, IR spectrum, and elemental analysis.

The iodide ion-releasing compound of the formula (I) releases iodide ions by reacting with an iodide ion release regulator (base and / or nucleophile). Preferably, the following chemical species are mentioned. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates,
Examples include 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 method of addition, and the temperature of the reaction solution. p
An alkali hydroxide is preferably used as the base for H control. The preferred concentration range of each of the iodide ion releasing compound and the iodide ion release controlling agent used to rapidly generate iodide ions is 1 × 10 ^{−7 to} 20 M.
And more preferably 1 × 10 ^{−5 to} 10 M, further preferably 1 × 10 ^{−4 to 5} M, and particularly preferably 1 × 10 ^−3.
２2M. The preferred temperature range is 30 to 80 ° C, more preferably 35 to 75 ° C, and particularly preferably 3 to 75 ° C.
5-60 ° 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 release rate and timing of iodide ions is 2 to 12,
More preferably, it is 3 to 11, particularly preferably 4 to 10, and most preferably 7 to 10. Even under neutral conditions at pH 7, hydroxide ions determined by the ionic product of water act as regulators. Also, a nucleophile and a base may be used in combination,
Also at this time, the release rate and timing of iodide ions may be controlled by controlling the pH within the above range.

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 desired characteristics of the formed silver halide grains.
Generally speaking, 0.1 to 2 with respect to the total amount of silver halide.
0 mol%, more preferably 0.3 to 15 mol%,
Particularly preferably, it is 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 iodide ion release from an 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 during that time Is redissolved, and, for example, the dislocation density relating to dislocations described below decreases. On the other hand, it is preferable to supply iodide ions slowly in order to form grains so as not to cause nonuniform dislocation distribution between grains. Therefore, in this case, it is important to generate iodide ions rapidly and without causing locality (non-uniform distribution). The region where the locality of iodide ions is large is formed when an iodide ion-releasing compound or an iodide ion-releasing modifier used in combination with the compound is added to the reaction solution in the particle forming container, in the vicinity of the addition port. This is because the iodide ion release reaction is too fast in response to the resulting uneven distribution of the local concentration of the additive.

The time required for the released iodide ions to deposit on the host grains is extremely fast, and the grain growth occurs in the region near the addition port where the iodide ions have a high locality. Occur. Therefore, the iodide ion release rate must be selected so as not to cause iodide ion locality. In the conventional method (for example, by adding an aqueous solution of potassium iodide), even if the aqueous solution of potassium iodide is diluted and added, the iodide ions are added in a free state. There is a limit to trying to reduce it. That is, it is difficult to form particles without eliminating non-uniformity among particles by the conventional method.

However, according to the present invention, which can control the iodide ion release rate or timing, the locality of iodide ions can be reduced as compared with the conventional method. In the above example, the iodide ion rapidly
Moreover, according to the present invention in which grains are formed while generating without causing locality, it is possible to introduce dislocations more uniformly and densely between grains than in the conventional method. However, the invention is characterized in that the iodide ion release rate or timing can be controlled according to the purpose, and particles can be formed with less unevenness between particles. For controlling iodide ion release in the present invention, for example, the following method is preferable. That is, by changing the pH, the concentration of the nucleophilic substance, the temperature, and the like from the already uniformly distributed iodide ion releasing compound added to the reaction solution of the particle forming vessel, the pH is usually changed from a low pH to a high pH. In this method, iodide ions are uniformly released while controlling the entire reaction solution by the change to. In these cases, the pH at the time of iodide ion release
It is preferable to add an iodide ion release regulator such as an alkali or a nucleophile in a state where the iodide ion releasing compound is uniformly distributed throughout.

Hereinafter, the silver halide emulsion grains formed by the method of the present invention (hereinafter referred to as emulsion grains of the present invention) will be described. The emulsion grains of the present invention are silver halides 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 rodin silver,
Silver sulfide, silver selenium, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as 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 particles having one or more layers of shells on the base particle (core), the inner shell or outermost shell of a double structure, triple structure, quadruple structure, quintuple structure,. What was formed using the iodide ion releasing method of the present invention. In the case of particles obtained by depositing one or more layers (shell regions) that do not completely cover the base particles (core), the inside of a 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 bonded particle in which epitaxy is grown at a selective site of a base particle: A particle formed by using the iodide ion emitting method of the present invention, wherein the apex of the particle, the peripheral portion of the particle, and the epitaxial portion of the main plane portion of the particle are formed.

The silver iodide-containing silver halide coating shell, deposited layer and epitaxial portion formed by the iodide ion releasing method of the present invention preferably have a higher silver iodide content. These silver halide phases may be any of silver iodide, silver iodobromide, silver chloroiodobromide and silver chloroiodide, but are preferably silver iodide or silver iodobromide. It is more preferred that there be. The preferred silver iodide (iodide ion) content in the case of silver iodobromide is 1 to 45 mol%, more preferably 5 to 45 mol%, and particularly preferably 10 to 4 mol%.
5 mol%. As an embodiment of the iodide ion releasing method of the present invention, it is preferable to prepare silver halide grains containing dislocations, and it is particularly preferable to introduce dislocations into silver halide grains at 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 the grains (eg, tabular grains) while rapidly generating iodide ions. It is preferable to introduce the density. A dislocation is a linear lattice defect 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 the dislocation 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), etc., which 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 using a transmission electron microscope, place the silver halide grains taken out of the emulsion on a mesh for electron microscopy, taking care not to apply enough pressure to the grains to generate dislocations, and place them on 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 the above. In this case, the thicker the particle, the more difficult it is for an electron beam to penetrate. Therefore, a clearer image can be observed with a high-pressure electron microscope (200 kV or more for a thickness of 0.25 μm). On the other hand, the effect of dislocation on photographic performance
C. Farnell, RB Flint, JB Chanter, J. Phot. Sc
i., 13, 25 (1965) shows that in large tabular silver halide grains with a high aspect ratio, the location where latent image nuclei are formed is closely related to defects in the grains. It is shown. JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains into which dislocations are intentionally introduced. In these patent applications, it is shown that tabular grains into which dislocation lines have been introduced are superior to tabular grains without dislocation lines in photographic properties such as sensitivity and reciprocity.

According to the method of the present invention, it is preferable to introduce dislocations into silver halide grains as follows. That is, a silver halide grain serving as a base is prepared, and a silver halide phase containing silver iodide (the above-described silver halide coating shell, deposition layer, and epitaxial growth) is formed on the base grain. As described above, the higher the silver iodide content of these silver halide phases, the better. 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 the base grain is 2 to 2 times the silver amount of the base grain. It is preferably 15 mol%, more preferably 2 to 10 mol%, particularly preferably 2 to 5 mol%. At this time, the high silver iodide phase is 5 to 80 mol% from the center of the grain in terms of silver content of the whole grain.
Preferably within the range of, more preferably 1
It is present in the range of 0 to 70 mol%, particularly preferably 20 to 60 mol%.

The site (site) where the high silver iodide phase is formed on the base grain can be arbitrarily selected. As described later in detail, for the tabular grains, the whole fringe can be selected only in the vicinity of the apex of the hexagon. Although the base particles may be covered or formed only at a specific site, it is preferable to control the dislocation position in the particle by selecting a specific site and epitaxially growing the same. Further, in forming the high silver iodide phase, the composition of the halogen to be added, the method of addition,
The temperature, pAg, solvent concentration, gelatin concentration, ionic strength and the like of the reaction solution may be freely selected and used. Thereafter, dislocations can be introduced by forming a silver halide shell (region) which is not a 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 is preferably silver bromide or silver iodobromide. In the case of silver iodobromide, the preferred silver iodide content is 0.1 to 12 mol%, more preferably 0.1 to 10 mol%, and most preferably 0.1 to 3 mol%. The preferred temperature in the above-described dislocation introduction step is 30 to 80 ° C, more preferably 35 to 75 ° C, and particularly preferably 35 to 60 ° C.
Further, the preferred pAg is 6.4 to 10.5.

In the case of tabular silver halide grains, the position and number of dislocations in each grain as viewed from the direction perpendicular to the main plane are determined from the photograph of the grains taken with an electron microscope as described above. Can be. Note that dislocation lines may be visible or invisible depending on the tilt angle of the sample with respect to the electron beam.Therefore, to observe dislocation lines without omission, observe the particle images of the same particle at as many sample tilt angles as possible and observe the dislocation lines. It is necessary to find the location. In the present invention, the same particle is 5 ° using a high-pressure electron microscope.
It is preferable that the inclination angle is changed in steps and five types of particle photographs are taken to determine the location and the number of dislocation lines.
When dislocations are introduced into the tabular silver halide grains in the present invention, their positions can be selected from, for example, those which are limited to the apexes and fringe portions of the grains, or are introduced over the entire main plane portion. In particular, it is preferable to limit to the fringe portion. The fringe portion referred to in the present invention refers to the outer periphery of a 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 entire grain. Outside the point where the average silver iodide content exceeds or falls below the average silver iodide content.

When dislocations are introduced into tabular grains, when the number of dislocation lines is counted by the above-mentioned method using an electron microscope, tabular grains having about 1,000 or less and 10 or more dislocation lines per grain in the fringe portion of the grain are provided. And more preferably 3
The number is 0 or more, particularly preferably 50 or more. When dislocation lines exist in a dense manner or when dislocation lines are observed to intersect 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 about 10, 20 or 30. It is desirable that the distribution of the amount of dislocation between the silver halide grains is uniform. When dislocations are introduced into tabular grains in the present invention, tabular grains having 10 or more dislocation lines per grain in the fringe portion of the grains are 100 to 50% (number) of all grains.
Occupies preferably 100 to 70%, particularly preferably 100 to 90%.

In the present invention, when determining the ratio of dislocation-containing particles and the number of dislocation lines, it is preferable to directly observe dislocation lines for at least 100 particles, more preferably 200 particles or more, particularly preferably 300 particles or more. Observe and determine the above. The tabular silver halide grains are silver halide grains having two opposing parallel main planes. The silver halide tabular grains have one twin plane or two or more parallel twin planes. The twin plane refers to the (111) plane when ions at all lattice points on both sides of the (111) plane are in a mirror image relationship.
The tabular grains, when viewed from above, have a triangular, hexagonal or rounded circular shape,
Each has an outer surface 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 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 to 0.5 μm.
０．３0.3 μm. The aspect ratio of the tabular grains is preferably from 2 to 30, more preferably from 3 to 2.
5

The aspect ratio is a value obtained by dividing a circle equivalent diameter of a projected area of a silver halide grain by a grain thickness. As an example of the method of measuring the aspect ratio, there is a method of taking a transmission electron micrograph by a replica method and obtaining the circle equivalent diameter and the thickness of the projected area of each particle. In this case, the thickness is calculated from the length of the shadow of the replica. It is a preferred embodiment that the outermost shell near the surface of the silver halide grain is prepared using the iodide ion releasing method of the present invention. It is important to form a silver halide phase containing silver iodide in the vicinity of the grain surface in terms of enhancing the dye adsorption power and controlling the developing speed. In the present invention, these can be controlled by selecting the silver iodide content of the outermost silver halide phase near the grain surface according to the purpose. It is desirable that the halogen composition on the surface of the silver halide grains is uniform among the grains, and according to the method of the present invention, it is possible to achieve uniformity between the grains which cannot be achieved by the conventional technique. In this case, the particle surface refers to a region up to a depth of about 50 ° from the surface. The halogen composition in such a region can be determined by XPS (X-ray photoelectron spectroscopy) or ISS.
It can be measured by a surface analysis method such as (ion scattering spectroscopy).

In this embodiment, silver halide grains having a silver iodide content of 0.1 to 15 mol% in a silver halide phase on the grain surface of the emulsion grains measured by these surface analysis methods are preferred, and more preferred. Is from 0.3 to 12 mol%, particularly preferably from 1 to 10 mol%, most preferably from 3 to 8 mol%
It is. According to the present invention, the halogen composition of the whole grains can be made uniform among grains, but in this regard, the present invention also achieves uniformity between grains that could not be attained by conventional techniques. . The coefficient of variation of the silver iodide content distribution among the individual emulsion grains obtained by the method of the present invention is 20%.
~ 3%, more preferably 15% ~
It is 3%, particularly preferably 10% to 3%. The silver iodide content of each of the emulsion grains 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 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 rhodan, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver, may be contained as separate grains or as part of silver halide grains. The silver halide emulsion of the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. A typical example is Japanese Patent Publication No. 43-13162,
Core-shell having a halogen composition in which the inside and the surface of the grains are different from each other as disclosed in JP-A 1-215540, JP-A-60-222845, JP-A-60-143331 and JP-A-61-75337. Type or double structure type particles. Also, it is not a simple double structure.
A triple structure as disclosed in Japanese Patent Application No. 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 grains having the double structure of the shell. In order to give a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonding structure can be produced. Examples of these are disclosed in JP-A-59-133540, JP-A-58-108526, and EP 199,290.
A2, JP-B-58-24772, JP-A-59-16
No. 254, for example. The crystal to be bonded can be formed by bonding to the edge, corner, or surface of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure.

In the case of a joint structure, a combination of silver halides is of course possible, but a silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, can be combined with silver halide to form a joint structure. Further, a non-silver salt compound such as lead oxide may be used as long as the bonding structure is possible. In the case of grains such as silver iodobromide having these structures, it is a preferred embodiment that the core portion has a higher silver iodobromide content than the shell portion. Conversely, grains having a low silver iodide content in the core portion and a high shell portion are sometimes preferred. Similarly, grains having a bonding structure may be grains having a high silver iodide content of the host crystal and relatively low silver iodide content of the bonding crystal, or vice versa. Further, the boundary portions having different halogen compositions of the grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment. In the case of silver halide grains in which two or more silver halides exist as mixed crystals or with 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. 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 having a correlation between the grain size and the halogen composition. As an example, there is a correlation such that the iodine content is higher for larger size particles, while the iodine content is lower for smaller size particles. 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 grains. Increasing the silver iodide content or increasing the silver chloride content in the vicinity of the surface can be selected according to the purpose because the adsorptivity of the dye and the developing speed are changed. When the halogen composition in the vicinity of the surface is changed, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, this is a case where the halogen composition is changed only on one side of a tetrahedral grain composed of the (100) plane and the (111) plane, or one of the main plane and the side face of the tabular grain is changed. The silver halide grains used in the present invention may be normal crystals containing no twin planes, and examples described in the Photographic Society of Japan, Basics of the Photographic Industry, Silver Halide Photography (Corona), p. 163, for example, Select from twin twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, non-parallel multiple twins containing two or more non-parallel twin planes according to the purpose. Can be used.
An example of mixing particles having different shapes is disclosed in U.S. Pat.
Although this method is disclosed in 865,964, this method can be selected as necessary. (100) for normal crystals
Cubes composed of planes, octahedrons composed of (111) planes, and dodecahedral particles composed of (110) planes disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. In addition, the Journal of Imaging Scienc
e, (hl1) plane particles represented by (211) as reported in Vol. 30, page 247, 1986, (3
The (hh1) plane particles represented by (31), the (hk0) plane particles represented by the (210) plane, and the (hk1) plane particles represented by the (321) plane also require some devising method, but depending on the purpose. You can use it selectively. (100) face and (11)
1) a tetrahedral particle whose plane coexists in one particle, (10
Particles in which the (0) plane and the (110) plane coexist, or (11)
Particles in which two surfaces or many surfaces coexist, such as particles in which 1) and (110) surfaces 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; Photographic Science and Engineering (Guto)
ff, Photographic Science and Engineering), 14th
Vol. 248-257 (1970); U.S. Pat.
434,226, 4,414,310, 4,4
It can be prepared by the methods described in Nos. 33,048 and 4,439,520 and British Patent No. 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye.
No. 26 describes this in detail. 8 of the total projected area of the grain
The average aspect ratio of 0% or more is desirably 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 the tabular grains can be selected from triangles, hexagons, and circles. A regular hexagon having almost equal lengths of six sides 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.
m is preferable. The thickness of the tabular grains is 0.
It is preferably from 0.5 to 1.0 μm. The proportion of tabular grains is preferably such that tabular grains having an aspect ratio of 2 or more account for 50% or more, more preferably 80% or more of the total projected area.
%, Particularly preferably 90% or more. When monodisperse tabular grains are used, more preferable results may be obtained. The structure and production method of monodisperse tabular grains are described, for example, in JP-A-63-151618, but the shape is briefly described as follows: 70% or more of the total projected area of silver halide grains is the minimum. The ratio of the length of the side having the maximum length to the length of the side having the length is occupied by tabular silver halide having a hexagonal shape of 2 or less and having two parallel surfaces as outer surfaces. Furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains (the value obtained by dividing the variation (standard deviation) of the grain size represented by the circle-converted diameter of the projected area thereof by the average grain size) Has a monodispersity of 20% to 3%.

It is preferable to use particles having dislocations. In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. Particles containing no dislocation lines at all,
It is preferable to select a particle containing several dislocations or a particle containing many dislocations according to the purpose. It is also possible to select dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grains, to introduce them throughout the grain, or to introduce them only in a specific part of the grain,
For example, dislocations can be introduced only in the fringe portion of the particles. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of normal grains or irregular grains typified by potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle. The silver halide emulsion used in the present invention may be prepared by subjecting grains to a rounding treatment as disclosed in European Patent Nos. 96,727B1 and 64,412B1 or by West German Patent No. 2,306,447C2. The surface may be modified as disclosed in JP-A-60-22130. Although a structure having a flat particle surface is generally used, it is sometimes preferable to form irregularities intentionally. JP-A-58-106532, JP-A-60-2
Examples thereof include a method of making a hole in a part of the crystal described in U.S. Pat. No. 21,320, for example, a vertex or a center of a plane, or a raffle particle described in U.S. 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 sphere diameter of the particle volume calculated from the projected area and the grain thickness, or the equivalent sphere diameter of the volume by the Coulter counter method. It can be used by selecting from ultrafine particles having a sphere equivalent diameter of 0.05 μm or less and coarse particles exceeding 10 μm. Preferably, grains having a size of 0.1 to 3 microns are used as photosensitive silver halide grains. The normal crystal emulsion used in the present invention is a so-called polydisperse emulsion having a wide grain size distribution,
A monodisperse emulsion having a narrow size distribution can be selected and used according to the purpose. As a scale representing the size distribution, a variation coefficient of a circle equivalent diameter of a projected area of a particle or a spherical equivalent diameter of a 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%.

The monodisperse emulsion may be defined as having a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size by number or weight of grains. 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 coated in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture. The emulsion of the present invention and a photographic emulsion used in combination therewith are:
Grafkides, "Physics and Chemistry of Photography", published by Paul Montell (P.Glafkides, Chimie et Physique Photographiqu
e, Paul Montel, 1967), Photographic Emulsion Chemistry by Duffin, Published by Focal Press (GF Duffin, Photogra
phic Emulsion Chemistry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zerikman et al., Focal Press (VL Zelikman et al., Making and Coating).
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 halide may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept 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 nearly uniform grain size can be obtained.

A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion, which is described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is preferred in some cases. These can be used as seed crystals, and are also effective when 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 can be selected from the method of adding the whole amount at a time, adding in a plurality of times or adding continuously. It is also effective in some cases to add particles of various halogen compositions to modify the surface. A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in U.S. Pat. Nos. 3,477,852 and 4,142,
No. 900, European Patent Nos. 273,429 and 273,4
No. 30, No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt. In addition, the method can be selected from a method of performing conversion at a time, a method of performing conversion by dividing into a plurality of times, and a method of performing continuous conversion.

As a method of grain growth, besides a method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate, British Patent No. 1,469,480 and US Pat.
As described in JP-A Nos. 0,757 and 4,242,445, a particle forming method in which the concentration is changed or the flow rate is changed is a preferable method. Increase the concentration,
Alternatively, by increasing the flow rate, the amount of silver halide to be 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 as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is. A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in U.S. Pat. Nos. 2,996,287 and 3,342,6.
05, 3,415,650, 3,785,77
No. 7, West German Patent No. 2,556,885, No. 2,55
The method can be selected from the methods described in US Pat. Silver halide solvents are useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used.
These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, or can be added together with the halide salts, silver salts or peptizers, and added to the reactor. Can also be introduced. As another variant, the ripening agent can be introduced independently during the halide and silver salt addition stage.

Ammonia, thiocyanates (eg, rhodacali, rhodamonium), and organic thioether compounds (eg, US Pat. Nos. 3,574,628 and 3,574)
Nos. 021, 215, 3,057,724, 3,0
38,805, 4,276,374, 4,29
7,439, 3,704,130, 4,78
Compounds described in 2,013, JP-A-57-104926 and the like. ), Thione compounds (for example, JP-A-53-82)
Nos. 408 and 55-77737, U.S. Pat.
No. 1,863), the compounds described in JP-A-53-144319, and the silver halide grains described in JP-A-57-202531. Examples thereof include a mercapto compound and an amine compound which can be accelerated (for example, JP-A-54-100717).

It is advantageous to use gelatin as a protective colloid used in preparing 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 hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan. No. 16.
Enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can 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 for water washing can be selected according to the purpose, but is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. Noodle washing method, dialysis method using a translucent membrane,
It can be selected from centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, 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 can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain and a method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the base grain of the 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 as long as they can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, hexacoordinate complex salts, and tetracoordinate complex salts. 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, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

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

One of the chemical sensitizations which can be preferably carried out in the present invention is a chalcogenide sensitization and a noble metal sensitization, alone or in combination, as described by TH James, The Photographic Process, 4th Edition, Published by Macmillan, 1
977, (TH James, The Theory of the Photogr
aphic Process, 4th ed, Macmillan, 1977) 67-7
It can be performed using active gelatin as described on page 6, and can also be performed using Research Disclosure 120.
Vol. 34, April 1974, 2008; 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, pAg as described in US Pat.
Sulfur, selenium at H5-8 and temperature 30-80 ° C;
It can be tellurium, gold, platinum, palladium, iridium or a combination of a plurality 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 palladium salt or a tetravalent 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 a thiocyanate or a selenocyanate. As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat.
Nos. 7,711, 4,266,018 and 4,05
Sulfur-containing compounds described in US Pat. No. 4,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known as azaindene, azapyridazine, azapyrimidine, which suppress fog in the process of chemical sensitization and increase sensitivity. Chemical sensitizer,
Examples of the modifying agent are described in U.S. Pat. 138-143. The emulsion of the present invention is preferably used in combination with gold sensitization. A preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 / mol of silver halide.
× 10 ⁻⁷ mol, more preferably 1 × 10 ⁻⁵ to
It is 5 × 10 ^-7 mol. The preferred range of the palladium compound is from 1 × 10 ^-3 to 5 × 10 ^-7 per mol of silver halide.
Is a mole. The preferred range of the thiocyan compound or selenocyan compound is from 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 mol.
^-5 to 5 × 10 ^-7 mol.

Selenium sensitization is a preferred sensitization 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 (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization. It is preferred that the silver halide emulsion of the present invention is 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 in a pAg 1 to 7 low pAg atmosphere called silver ripening or a method of ripening, a method of high pH ripening called pH ripening of 8 to 8 or more. Either the method of growing or ripening in a high pH atmosphere of 11 can be selected. Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol 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 at an appropriate time during the particle growth is preferable. Further, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, extremely fine silver grains by-produced during the formation process and the chemical sensitization process of silver halide grains are
Compounds that convert to silver ions are effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, and silver selenide, or may form a silver salt that is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, 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 ), peroxy complex compounds (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 (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O)
₇ ) oxyacid salts such as iodine, bromine and other halogen elements,
Perhalates (eg, potassium periodate), salts of high valent metals (eg, potassium hexacyanoferrate)
And thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds capable of releasing active halogen (eg, N-bromosuccinimide, chloramine T). , Chloramine B). Preferred oxidants used in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidants of thiosulfonates and organic oxidants of quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of coexisting both methods. These methods can be selectively used in both the grain formation step and the chemical sensitization step. The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 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, U.S. Pat.
2,947 and JP-B-52-28660 can be used. One of the preferred compounds is a compound described in JP-A-63-212932.
Antifoggants and stabilizers can be used at various times before, during and 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 according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects when added during emulsion preparation, control the crystal habit of the grains, reduce the grain size, reduce the solubility of the grains, control the 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 by a methine dye or the like to exhibit the effects of the present invention. 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 usually used for cyanine dyes as basic heterocyclic nuclei 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, etc .; A nucleus fused with an aromatic hydrocarbon ring,
That is, an indolenine nucleus, a benzoindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a 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, and a thiazolidine-nucleus.
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 particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, and 3,617. No. 3,293, 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, British Patent No. 1,344,281
No. 1,507,803, JP-B-43-4936
No. 53-12375, JP-A-52-110618
And No. 52-109925.

Along with the sensitizing dye, the dye itself has no spectral sensitizing effect 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 preparation of the emulsion which has been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but as described in US Pat. Nos. 3,628,969 and 4,225,666, a chemical sensitizer is used. At the same time, spectral sensitization can be performed at the same time as chemical sensitization, or can be performed prior to chemical sensitization as described in JP-A-58-113928. Can be added before the completion of the above to start spectral sensitization. Furthermore, U.S. Pat.
It is also possible to add these compounds separately as taught in US Pat. No. 666, that is, to add some of these compounds prior to chemical sensitization and the remainder after chemical sensitization. And U.S. Pat. No. 4,183,756.
And any time during the formation of silver halide grains, including the method disclosed in the above-mentioned publication. The addition amount can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide, and about 5 × when the silver halide grain size is more preferably 0.2 to 1.2 μm. 10 ^{-5 to} 2 × 10 ^-3
Mole is effective.

The light-sensitive material produced by using the silver halide emulsion obtained in the present invention comprises a support, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer. It is sufficient that at least one layer is provided, and there is no particular limitation on the number and layer order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one color-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light. Are sequentially arranged from the support side in the order of a red-sensitive layer, a green-sensitive layer, and a blue-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 silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer is described in JP-A-61-43748 and JP-A-59-11.
No. 3438, No. 59-113440, No. 61-200
The couplers and DIR compounds as described in JP-A Nos. 37 and 61-20038 may be contained, and a color-mixing inhibitor may be contained as usually used.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer constitution of an emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. JP-A-57-112751, JP-A-62-20035
No. 0, 62-206541, 62-206543
As described in Japanese Patent Application Laid-Open No. H10-284, a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on. In addition, Japanese Patent Publication No. 55-34
As described in Japanese Patent No. 932, it is also possible to arrange in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. Japanese Patent Application Laid-Open No. 56-25738
And the blue-sensitive layer / GL / RL from the side farthest from the support as described in JP-A-62-63936.
/ GH / RH in this order.

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. In addition, an arrangement is also possible in which a silver halide emulsion layer having a lower sensitivity is arranged, and an arrangement of three layers having different sensitivities in which the sensitivities are successively decreased toward the support. Even in the case of three layers having different sensitivities, as described in JP-A-59-202264, a medium-sensitivity emulsion from the side farther from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers. In addition, the layers 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. The arrangement may be changed as described above even in the case of four or more layers.

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

The above-mentioned various additives are used in the light-sensitive material according to the present invention, but other various additives 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), and the relevant locations are summarized in the table below.

種類 Additive type RD17643 RD18716 RD308119 ──────── ───────────────────────── 1 Chemical sensitizer Page 23 648 Right column Page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, 23 ~ 24 pages 648 right column ~ 996 right ~ 998 right Supersensitizer 649 page right column 4 Whitening agent 24 page 647 right column 998 right 5 Antifoggant, 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 7 page 25 right column 650 page 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 27 650 page right column 1006 left to 1006 right 12 Coating aid Pp. 26-27 Same as above 1005 left to 1006 left Surfactant 13 Stat P. 27 Same as above 1006 right to 1007 left Inhibitor 14 matting agent 1008 left to 1009 left

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound which can react with formaldehyde described in JP-A-87-87 and JP-A-4,435,503 and can be fixed to the photosensitive material.

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

Examples of the cyan coupler include phenol type and naphthol type couplers.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and 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 and 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
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,
199 and JP-A-61-42658 are preferred. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820, 4,080,
No. 211, No. 4,367,282, No. 4,40
Nos. 9,320, 4,576,910, British Patent 2,102,137, and EP 341,188A.

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

As a coupler which releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,099
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687. 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 and U.S. Pat. Nos. 4,283,472 and 4,338,393.
No. 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950 and JP-A-62-242.
No. 52, etc., DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, European Patent Nos. 173,302A and 31.
No. 3,308A, couplers capable of releasing a dye that recolors after release. D. No. 11449, No. 24241, bleaching accelerator releasing couplers described in JP-A-61-201247 and the like, ligand releasing couplers described in U.S. Pat. No. 4,555,477 and the like, and described in JP-A-63-75747. Couplers releasing leuco dyes, U.S. Pat.
No. 4,181, for example, couplers that release a fluorescent dye.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027, etc. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher 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), benzoates (eg, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide),
N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4
-Di-t-amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (for example, N, N-dibutyl-2-
Butoxy-5-tert-octylaniline) and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

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.
No. 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 and JP-A-63-257747 and JP-A-62-272248 are used.
And 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5- described in JP-A-1-80941.
Dimethylphenol, 2-phenoxyethanol, 2-
It is preferable to add various preservatives or fungicides 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 aforementioned R
D. No. 17643, page 28, and No. 18716, 64
From page 7, right column to page 648, left column, and page 879 of No. 307105.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less,
20 seconds or less are more preferable. The film thickness is 25 ° C and the relative humidity is 5
It means the 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
reen) et al., Photographic Science and Engineering (Photogr. Sci. Eng.), 19
Winding, No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2
Is the saturated film thickness, which is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds.
/ 2 is defined as the time to reach. Film swelling speed T
_{The 1/2} can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 150 to 400
% Is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness−film thickness) / film thickness.
Can be calculated according to The photosensitive 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 a 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 include a binder, a plasticizer, a lubricant, a coating aid, a surfactant, and the like. The swelling ratio of the back layer is preferably from 150 to 500%.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. 17643, pp. 28-29, No. 18
716, pages 880 to 881 of No. 307105. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent.
Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used.
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 include amino-N-ethyl-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among them, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains such a development inhibitor or antifoggant. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, 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, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cycloalkyl 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 salts thereof can be mentioned as typical examples.

When the reversal process is performed, color development is usually performed after black and white development. A known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol is used alone in the black-and-white developer. 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 replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution 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 )] ÷ [capacity of treatment liquid (cm ³ )] The above-mentioned aperture ratio (cm ⁻¹ ) is preferably 0.1 or less, More preferably, it is 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, Japanese Patent Application Laid-Open
And a slit developing method described in JP-A-63-216050. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set to 2 to 5 minutes. However, the processing time can be further shortened by using a high temperature and a 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. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Furthermore, processing in two successive bleach-fixing baths, fixing before bleach-fixing,
Alternatively, bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Representative bleaching agents include organic complexes of iron (III) such as amino diamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex salts such as citric acid, tartaric acid, malic acid and the like can be used. Of these, iron (III) complex salts of aminopolycarboxylate, such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate, are used from the viewpoint of rapid treatment and prevention of environmental pollution. preferable. Further, the iron (III) complex salt of aminopolycarboxylic acid is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8.0, but it is necessary to treat the solution at a lower pH to speed up the processing. Can also.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP Nos. 53-32736, 53-57831, 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
Compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July, 1978); thiazolidine derivatives described in JP-A-50-140129; -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
7,715, JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30;
Polyamine compounds described in JP-A-5-8836; and JP-A-49-40943, JP-A-49-59644 and JP-A-53-96444
No. 94927, No. 54-35727, No. 55-265
Compounds described in JP-A Nos. 06-58 and 163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferred in view of a large accelerating effect, and in particular, U.S. Pat.
Are preferred. Further, U.S. Pat.
Compounds described in 552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids are compounds 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 large amounts of iodides. Is common, and in particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, various aminopolycarboxylic acids or organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, It is preferable to add imidazoles such as methyl imidazole in an amount of 0.1 to 10 mol / l. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 4 ° C.
5 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method described in JP-A-62-183460, is used.
No. 183461, a method of increasing the stirring effect by using the rotating means, and furthermore, by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface to make the emulsion surface turbulent, the stirring effect is further increased. 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 for any of a bleaching solution, a bleach-fixing solution and a 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 increases the desilvering speed. The above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the photosensitive material of the present invention preferably has a photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. As described in Japanese Patent Application Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating.
Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Pictur.
e and Television Engineers Vol. 64, p. 248-
253 (May, 1955). According to the multi-stage countercurrent method described in the literature,
Although the amount of washing water can be greatly reduced, the increase in the residence time of the water in the tank causes a problem that bacteria proliferate and generated floating substances adhere to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, a method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, Japanese Patent Application Laid-Open No.
No. 8542, isothiazolone compounds, thiabendazoles, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles. "Sterilization, Sterilization, and Antifungal Techniques of Microorganisms" (1982) Industrial Association of Japan
986) can also be used.

The pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but are generally at 15 to 45 ° C. for 20 seconds to 10 minutes,
Preferably, a range of 30 seconds to 5 minutes at 25 to 40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, JP-A-57-8543,
All known methods described in JP-A-58-14834 and JP-A-60-220345 can be used. Further, following the water washing treatment, a stabilization treatment may be further 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 photography. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In processing using an automatic developing machine or the like, when each of the above processing solutions is 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 speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. Nos. 3,342,597, 3,342,599, Research Disclosure Nos. 14850 and N
No. 15159, Schiff base type compounds described in No. 1
No. 3924, aldol compounds, US Pat.
Metal salt complexes described in JP-A-19,492, JP-A-53-135
No. 628 can be mentioned. The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339 and JP-A-57-144547.
And No. 58-115438.
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 promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to. The silver halide photographic material of the present invention is disclosed in U.S. Pat. No. 4,500,626.
JP-A-60-133449 and JP-A-59-218443.
No. 61-238056, European Patent 210,660
The invention can also be applied to a photothermographic material described in A2 or the like. The silver halide light-sensitive material of the present invention is disclosed in
When applied to a film unit with a lens described in No. 2615, Japanese Utility Model Publication No. 3-39784 or the like, the effect is more easily exhibited and is effective.

[0079]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 (1) Preparation of emulsion Tabular silver bromide core emulsion 1-A 1200 cc of an aqueous solution containing 8 g of gelatin and 5 g of KBr
Was stirred at 60 ° C., and an aqueous solution of AgNO ₃ (9.7 g) and K
A Br (7 g) aqueous solution was added by a double jet in 45 seconds. (In each of Examples and Comparative Examples, emulsion preparation was performed by the controlled double jet method.) After adding 40 g of gelatin, the temperature was raised to 75 ° C.
Followed by aging for 20 minutes in the presence of H _3. After neutralization with HNO ₃
An aqueous solution of AgNO ₃ (130 g) and an aqueous solution of KBr were added for 80 minutes while accelerating the flow rate (the flow rate at the end was twice that at the start). At this time, the pAg was kept at 8.2. After this,
The emulsion was cooled to 35 ° C. and desalted by a conventional flocculation method. The resulting 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
A was added to 1950 cc of water, keeping the temperature at 55 ° C., the pAg at 8.9 and the pH at 5.6. Thereafter, 126 cc of a 0.32 M KI aqueous solution was added in a fixed amount for 1 minute. Subsequently, an aqueous solution of AgNO ₃ (66 g) and an aqueous solution of KBr were pAg
Was added over 36 minutes to keep it at 8.9. Thereafter, 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 accounted for 95% of the total projected area, and the same applies to the following tabular grain emulsions.

Tabular silver iodobromide emulsion 1-C (comparative emulsion) Except for the following, it was prepared in the same manner as emulsion 1-B. Instead of adding the KI aqueous solution, a separately prepared AgNO ₃
(6.8 g), 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) Except for the following, it was prepared in the same manner as emulsion 1-B. Instead of adding the aqueous KI solution, an equimolar amount of 2-iodopropionic acid to that of KI was added, then a 0.8 M aqueous sodium sulfite solution (60 cc) was added, the pH was raised to 9.0, and the mixture was kept for 8 minutes. 5.6.

Tabular silver iodobromide emulsion 1-E (comparative emulsion) Except for the following, emulsion emulsion 1-E was prepared in the same manner as emulsion 1-D. Instead of adding 2-iodopropionic acid, iodoacetic acid was added in an equimolar amount to KI. Tabular silver iodobromide emulsion 1-F (comparative emulsion) Except for the following, the same preparation was made as in emulsion 1-D. Instead of adding 2-iodopropionic acid, cyanomethane iodide is replaced by K
Equimolar to I was added. Tabular silver iodobromide emulsion 1-G (emulsion of the present invention) Except for the following, it was prepared in the same manner as emulsion 1-D. Instead of adding 2-iodopropionic acid, compound 3 described later was added. Tabular silver iodobromide emulsion 1-H (emulsion of the present invention) Except for the following, emulsion emulsion 1-H was prepared in the same manner as emulsion 1-D. Instead of adding 2-iodopropionic acid, compound 6 described below was added. Tabular silver iodobromide emulsion 1-I (emulsion of the present invention) Except for the following, it was prepared in the same manner as emulsion 1-D. Instead of adding 2-iodopropionic acid, compound 7 described later was added.

(2) Chemical sensitization The emulsions 1-B to 1-I were subjected to gold-sulfur sensitization as follows. The temperature of the emulsion was raised to 64 ° C., and the sensitizing dye ExS-1 described later was mixed with 2.6 × 10 ⁻⁴ mol / mol Ag, ExS-
2 was 1.1 × 10 ⁻⁵ mol / mol Ag, and ExS-3 was 3.
Only 6 × 10 ⁻⁴ mol / mol Ag was added, and then potassium thiocyanate, chloroauric acid and sodium thiosulfate were added for optimal chemical sensitization. Here, "optimally perform chemical sensitization" refers to chemical sensitization in which the sensitivity at the time of 1/100 second exposure becomes highest.

(3) Preparation and Evaluation of Coated Samples On a cellulose triacetate film support provided with an undercoat layer, each of the emulsions and protective materials 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 )

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• 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 allowed to stand at 40 ° C. and 70% relative humidity for 14 hours, and then passed through a continuous wedge.
/ 100 seconds, and color development shown in the following Table B was performed. The concentration of the treated sample was measured with a green filter.

Next, the composition of the processing solution will be described. (Color developing solution) (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 5 mg hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Add water 1.0 liter pH 10.05

(Bleach-fixing solution) (Unit: g) Ferric ethylenediaminetetraacetate 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

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Embedded image Add water 1.0 liter pH 6.0

(Washing solution) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and water through a mixed bed column filled with an OH-type anion exchange resin (Amberlite IR-400) to treat the calcium and magnesium ion concentrations to 3 mg / L or less, followed by isocyanuric dichloride 20 mg / L of sodium and 1.5 g / L of sodium sulfate were added. The pH of this solution is in the range of 6.5-7.5.

(Stabilizing solution) (Unit g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Water was added. 1.0 liters pH 5.0-8.0

The sensitivity was represented by the relative value of the logarithm of the reciprocal of the exposure amount expressed in lux-second giving a density of 0.2 above fog. With respect to the pressure characteristics, a test of the pressure characteristics was performed by the following test method A. Thereafter, 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, apply a load of 4 g with a needle having a diameter of 0.1 mm in the same atmosphere, and scratch the emulsion surface at a speed of 1 cm / sec. .

The density of the developed sample was measured with a measuring slit of 5 μm × 1 mm in a portion where pressure was applied and a portion where no pressure was applied. Increase fog due to pressure by Δ
Fog. Further, in an exposure region equal to or less than 100 times the exposure amount E ₀ that gives a density of fog + 0.2, the density is 0.0% by pressure between a certain exposure amount E ₁ and E _2.
When decremented by 1 or more Pressure desensitization area = ((log E ₂ −log E ₁ ) / 2) × 100
(%). Table 1 shows the obtained results.

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[Table 1]

In Table 1, the sensitivity of Samples 2 to 8 was
Was expressed as a relative value with the sensitivity of 100 as 100. As is clear from Table 1, the present invention was able to obtain an emulsion having low fog, high sensitivity, small increase in pressure fog, and low pressure desensitization.

Example 2 On an undercoated 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 shown below. . (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 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-30. 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-33 0.1 × 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 Speed 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 6th 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 8th layer (medium speed green-sensitive emulsion layer) ) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-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 Sensitive 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 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 speed blue-sensitive 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 (first 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 (second protective layer) Layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-3 0.10 S-1 0.20 Gelatin 1 .20

Further, in order to improve the storability, processability, pressure resistance, fungicidal and bacteriostatic properties, antistatic property and coatability of each layer, W-1 to W-3, B-4 to B -6,
F-1 to F-17 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

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[Table 2]

In Table 2, (1) Emulsions A to F were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples in 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. Have been. (3) For preparing 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 using a high-pressure electron microscope. (5) Emulsions A to G are silver iodobromide.

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The samples 101 to 10 thus obtained were
After exposure of No. 8, the sample was processed by the method described below.

Next, the composition of the processing solution will be described. (Color developing solution) (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 5 mg hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Add water 1.0 liter pH 10.05

(Bleaching solution) (Unit g) Ferric ammonium ethylenediaminetetraacetate 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 ammonia water (27%) 15.0 ml Add water 1.0 liter pH 6.3

(Bleach-fixing solution) (Unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0 Disodium ethylenediaminetetraacetic acid 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia Water (27%) 6.0 ml Add water 1.0 liter pH 7.2 (Wash solution) Tap water is replaced with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas)
And OH type anion exchange resin (Amberlite IR-
400) to treat the calcium and magnesium ion concentrations at 3 mg / L or less, followed by 20 mg of sodium diisocyanurate dichloride.
/ L and 0.15 g / L of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) (Unit g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Water was added. The sensitivity was indicated by the relative value of the fog density and the reciprocal of the exposure amount giving a density 0.2 higher than the fog density for the characteristic curve of the cyan dye, 1.0 liter, pH 5.0-8.0. With respect to the pressure characteristics, a test was conducted using the test method A in the same manner as in Example 1, and after exposure and development, the density of the pressure-applied portion and the non-pressure-applied portion of the characteristic curve of the cyan dye was measured. Fog, and a pressure desensitization region. Table 3 shows the obtained results.
Shown in

[0130]

[Table 3]

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

[0132]

According to the present invention, a silver halide emulsion and a photographic material having high sensitivity, low fog, and improved pressure can be obtained.

Continuation of front page (56) References JP-A-2-68538 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/015 C01G 5/02

Claims (5)

(57) [Claims] 1. A method for forming silver halide grains, comprising using at least one kind of iodide ion releasing compound represented by the following formula (I). ^{_{I-L-S0 3 - M}} + (I) ( wherein, L represents a divalent organic group, M ⁺ represents a hydrogen ion or a monovalent cation.) 2. Silver halide grains containing silver iodide, wherein the silver iodide content inside the silver halide grains is higher than the average silver iodide content of the whole silver halide grains. 2. The method according to claim 1, further comprising a silver iodide region, wherein the high silver iodide region is formed by using the iodide ion releasing compound of the formula (I). 3. The method according to claim 1, wherein an iodide ion releasing compound is used in the presence of an iodide ion release regulator. 4. The method according to claim 1, wherein a group of silver halide grains having a coefficient of variation of a silver iodide content distribution between silver halide grains of 3 to 20% is formed. 5. A silver halide grain is 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 grain is formed on a support. A method for producing a silver halide photographic light-sensitive material, wherein the method is applied as at least one silver halide emulsion layer. ^{_{I-L-S0 3 - M}} + (I) ( wherein, L represents a divalent organic group, M ⁺ represents a hydrogen ion or a monovalent cation.)