JP2003172992A - Photosensitive silver halide grain and silver halide emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide photosensitive silver halide grains for a silver halide emulsion free of desensitization and weakening in tone at a low illuminance side and free of reciprocity law failure over a wide exposure illuminance range. <P>SOLUTION: The photosensitive silver halide grains contain at least one metallic complex having in a ligand a moiety capable of forming a covalent bond, a dative bond, an ionic bond or a band having a form of a mixture of these bonds to an ion, and when the a-, b- and c-axes of a silver halide crystal lattice are set using the central atom of the metallic complex incorporated into the silver halide grains as the origin, the above moiety in the ligand can interact with a silver ion on a lattice point not present on any of the a-, b- and c-axes. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide emulsion used in a silver halide photographic light-sensitive material and a photosensitive silver halide grain used in the silver halide. In particular, the present invention relates to a silver halide photographic light-sensitive material which uses a dopant technique and has high sensitivity, high gradation and no reciprocity law failure.

[0002]

2. Description of the Related Art As one of the techniques for modifying the silver halide grains and improving the performance of the entire silver halide photographic light-sensitive material, the technique of incorporating a substance (dopant) other than silver ions and halide ions. (Dope technology) is available.
In particular, much research has been conducted on the technique of doping transition metal ions. It is generally accepted that when a transition metal ion enters a silver halide grain as a dopant, the photographic performance can be effectively changed even if the addition amount is extremely small.

In order to more effectively improve the photographic characteristics of silver halide emulsions, a technique of doping not only transition metal ions but also transition metal complexes into silver halide grains has been known. The effects obtained by dope technology are 1)
Higher sensitivity, 2) reciprocity law failure improvement, and 3) higher contrast. For the purpose of obtaining a highly sensitized emulsion, a Group VIII metal complex having a cyanide ion as a ligand is used as a dopant as disclosed in JP-A-2-20854 and JP-B-7-113743. Among them, a hexacyano complex having iron or ruthenium as a central metal is an effective sensitizing dopant. In order to obtain a high gradation emulsion, JP-A-63-184740, JP-A-1-285941,
As disclosed in JP-A Nos. 2-20852 and 2-20855, a technique using hexachlororuthenium, hexachlororhodium, and hexachlororhenium, and European Patents 0336642, 0606895, and 061067.
As disclosed in No. 0, there is a technique using nitrosyl or thionitrosyl as a ligand of a transition metal complex.

On the other hand, an iridium complex is used to improve reciprocity law failure, particularly high intensity reciprocity failure failure. Examples in which silver halide grains are doped with an iridium complex are disclosed in JP-A-1-285941 and JP-A-3-118583.
No. 4-213449, 4-278940, 5-66511, 5-313277, 6-82.
No. 947, No. 6-235995, No. 7-72569
No. 7, No. 7-72576, No. 11-202440, No. 11-295841 and the like, and as a ligand of an iridium complex, a fluoride ion, a chloride ion, a bromide ion, H ₂ O, Cyano, nitrosyl and thionitrosyl are used. Furthermore, US Pat.
No. 60,712 discloses a dopant technology using an organic compound as a ligand, and an iridium complex (IrCl ₅ (thia)) having a thiazole as a ligand is disclosed as a dopant for improving high illumination failure. There is.

High-illuminance reciprocity failure is effectively improved by using an iridium complex as a dopant as in these examples, but in any of the above examples, it was attempted to completely improve high-illuminance failure. It was difficult to improve the reciprocity law failure that occurs at high illuminance without changing the photographic characteristics on the low illuminance side, accompanied by desensitization and softening on the low illuminance side.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which is free from reciprocity law failure over a wide range of exposure illuminance without desensitization or softening on the low illuminance side by the dopant technology. And

[0007]

[Means for Solving the Problems]

(1) At least one kind having a site capable of forming a bond of any one of a covalent bond, a donor bond, an ionic bond or a mixture of these bonds with respect to silver ion in the ligand A photosensitive silver halide grain containing a metal complex of, wherein the a-axis, b-axis and c-axis of the silver halide crystal lattice are set with the central metal of the metal complex incorporated in the silver halide grain as the origin. When each is set, the above-mentioned site in the ligand is capable of interacting with a silver ion on a lattice point which is not on any of the a-axis, b-axis and c-axis. Silver halide grains. (2) The ligand has a volume of chloride ion Cl ⁻ of 2
It has a volume of 20% or more and 300% or less, and the distance to the atom in the ligand farthest from the atom in the ligand coordinated to the central metal of the metal complex is 5.1Å or less. The photosensitive silver halide grain of (1), which is a ligand. (3) The ligand has a volume of 220% or more and 265% or less with respect to the volume of chloride ion, and the distance from the atom coordinated to the central metal to the furthest atom is 4.7Å The photosensitive silver halide grain as described in (1) or (2), which is the following ligand. (4) The site where the ligand can interact is at a distance of 2.5Å to 4.0Å with respect to the silver ion on the lattice point that is not on the a-axis, b-axis, or c-axis. The photosensitive silver halide grain according to any one of (1) to (3), characterized in that (5) The metal complex has at least one asymmetric ligand, and a substituent in the ligand occupies a silver ion position adjacent to the asymmetric ligand (1 )
The photosensitive silver halide grain according to any one of to (4). (6) The ionic conductivity of the silver halide grain when the metal complex is incorporated into the silver halide grain in an amount of 1 × 10 ⁻⁴ mol per mol of silver is It is characterized by being less than 50 times the ionic conductivity of particles in which metal complexes are not incorporated (1) ~
The photosensitive silver halide grain according to any one of (5). (7) The ionic conductivity of the silver halide grain when the metal complex is incorporated into the silver halide grain at 1 × 10 ⁻⁴ mol per 1 mol of silver is It is characterized by being less than 30 times as high as the ionic conductivity of particles in which no metal complex is incorporated (1) ~
The silver halide emulsion according to any one of (6). (8) The photosensitive silver halide grain according to any one of (1) to (7), wherein the metal complex incorporated in the silver halide grain has a positive charge of more than -3. (9) The photosensitive silver halide grains as described in (1) to (8), wherein the controlled release time of electrons of the silver halide grains is 5 seconds or less. (10) The photosensitive silver halide grain according to any one of (1) to (9), wherein the metal complex is a transition metal complex. (11) The photosensitive silver halide grain according to any one of (1) to (10), wherein the ligand is an organic compound or an inorganic compound having 3 or less carbon atoms. (12) The photosensitive silver halide grain according to any one of (1) to (11), wherein the metal complex is an iridium complex. (13) The metal complex contains at least one ligand selected from thiadiazoles, thiatriazoles, oxadiazoles and triazoles, (1) to (12) Photosensitive silver halide grains. (14) The photosensitive silver halide grain according to any one of (1) to (13), wherein the ligand of the metal complex contains phosphorus. (15) The photosensitive silver halide grain according to any one of (1) to (14), wherein the ligand of the metal complex has an NCS bond. (16) The photosensitive silver halide grain according to any one of (1) to (15), wherein the silver halide grain contains silver chloride as a main component. (17) The photosensitivity according to any one of (1) to (16), wherein the silver halide grains have a silver bromide layer, and the metal complex is contained in the silver bromide-containing layer. Silver halide grains. (18) The photosensitive silver halide grain as described in (17), wherein the silver bromide-containing layer has a silver bromide content of 5 mol% or more and 50 mol% or less. (19) The silver chloride content of the silver halide grains is 89 mol% to 99.7 mol%, and the silver bromide content is 0.25 mol% to 10 mol%.
Mol% and the silver iodide content is 0.05 mol% to 1 mol%
The photosensitive silver halide grain according to any one of (16) to (18), wherein (20) A silver halide emulsion containing the photosensitive silver halide grain according to any one of (1) to (19) above.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The high-intensity reciprocity failure of a silver halide photographic emulsion occurs when a large amount of photoelectrons are generated in the silver halide grains during high-intensity exposure and latent image dispersion occurs. Therefore, the high illuminance failure is improved by temporarily saving the photoelectrons generated in large amounts by high illuminance exposure from the conduction band, and then having the function in the silver halide grain to release to the conduction band again after staying for a certain period of time. You can do it. This corresponds to recreating the situation inside the silver halide grains at the time of high-illuminance exposure to the same situation as at the time of low-illuminance exposure. The function of temporarily saving the photoelectrons, that is, the function of temporarily trapping the photoelectrons can be realized by doping the transition metal complex (a dopant having such a function is used as an electron sustained release dopant or illuminance conversion). It is called a dopant, and the average time from exposure to the emission of photoelectrons captured by the dopant is called electron sustained release time, and the shortest exposure time that achieves the same photographic performance as low-illuminance exposure is called illuminance conversion time). Hexachloroiridium has been used as a transition metal complex to improve the reciprocity law failure of high illuminance. When hexachloroiridium is used, photoelectrons generated by exposure are trapped in the lowest unoccupied orbital of iridium, which is the central metal, and after staying in this orbit for a certain period of time, they are emitted again to the conduction band. Hexachloroiridium has an excellent function of temporarily saving a large amount of photoelectrons, but since it stays at the electron trap level for a long time, it improves high illumination failure, but it has a sensitivity that depends on the time from exposure to development. Increase (latent image sensitization) occurs and photographic performance becomes unstable. At the same time, it also has a desensitizing effect. On the other hand, IrCl ₅ (thia) of the above-mentioned disclosed examples can improve reciprocity law failure without causing latent image sensitization because it has an appropriate electron sustained release time, but softens at low illuminance exposure. It works and is not perfect as a reciprocity failure improvement dopant.

In order to obtain a preferable reciprocity law characteristic without latent image sensitization, photoelectrons in the conduction band are once captured by the iridium site, and after a "reasonable time" elapses, electrons are emitted again in the conduction band. It is necessary to. In order for the electrons trapped on the central metal of the complex taken in the particles to be released to the conduction band again, there is a path for the electrons to be emitted to the conduction band through one of the ligands bound to the central metal. It must be set, and the electron transfer efficiency at this time determines the reciprocity law characteristic at high illuminance and the latent image storability. Hexachloroiridium is thought to be responsible for the long electron release time due to this poor electron transfer efficiency, and in order to improve this, some of the chloride ions that are ligands have higher electron transfer efficiency than others. It is necessary to change to a ligand. At this time, it is preferable that any atom in the ligand and the silver ion in the particle form some bond, but the silver ion on the extension line of the central metal and the coordination atom in the complex and the silver ion in the ligand When a certain atom forms a bond, the electron-trapping force becomes too strong, resulting in an emulsion with a large desensitization, and thus a ligand that forms such a bond is not preferable. In the present invention, moderate electron capture and slow electron release allow a central metal and a silver ion on a lattice point, which is not on the extension line of the coordination atom, to interact with an atom in the ligand as if forming a very weak bond. Therefore, it was found that good reciprocity law characteristics and good latent image keeping property are realized.

On the other hand, considering only the electronic effect in order to improve the reciprocity law at a wide exposure illuminance, the residence time of the captured photoelectrons on iridium should be set as long as possible without deteriorating the latent image storability. However, longer staying time on iridium causes not only latent image sensitization but also inefficiency such as desensitization and softening. Suppression of desensitization and softening is not sufficient only by improving the electronic effect, and it is necessary to optimize the grain structure near the dopant. This is because the ligands other than halogen used for controlling the reciprocity law properties do not disturb the grain structure of the silver halide grain, and the molecular size and shape are as large as possible with respect to the space in which the ligand is incorporated. This can be achieved by selecting a compatible ligand. As can be seen from the presence of interstitial silver ions, the silver halide grains have many voids in the crystal, and therefore it is necessary to properly fill these voids as a role of the ligand.

These ideas can be realized by using a ligand satisfying the following conditions. In order to realize good reciprocity law / latent image characteristics, the Ir of the central metal is taken as the origin and the coordinates of the asymmetric ligand are taken as the c-axis in the crystal coordinates (1 /
It is preferable that the distance between the silver ion at the 2 1/2 1) position and the atom capable of interacting with the silver ion in the ligand is between 2.5Å and 4.0Å. More preferably, this distance is changed from 2.8Å to 3.6Å. Further, in order to prevent the particle structure near the dopant from becoming unstable, it is necessary to use a bulky ligand as the ligand of the complex to be doped. As the ligand in the complex, a ligand having a size and a shape in which not only Cl ⁻ ion is independently replaced, but also the ligand is replaced with Cl ⁻ ion and Ag ⁺ ion adjacent thereto is preferable. A ligand that satisfies this requirement has a volume of 220% or more and 290% or less with respect to the volume of chloride ions, and the distance from the atom coordinated to the central metal to the farthest atom is 5.1Å The following ligands are preferable, and more preferably, the ligand in the complex has a volume of 220% or more and 265% or less with respect to the volume of Cl ⁻ , and from the coordination atom to the central metal The distance to the furthest atom is less than 4.7Å. If the molecular volume exceeds 300%, or if the atom farthest from the coordinating atom is separated by 5.1 Å or more, the incorporation rate into the silver halide grain decreases, which is not preferable.

The molecular volume can be calculated in various ways. In the present invention, software HyperChem R6 manufactured by Hypercube, Inc.
The structure of the molecule used as the ligand is optimized by molecular force field calculation, and the molecular volume at that time is determined by J. Am. Chem. S.
oc., 1983, 105, 5220-5225. The parameters in the software were used as they were for the calculation of the molecular force field. MO is the structural optimization of the molecule used for the ligand.
It can also be performed with quantum chemical calculations such as PAC and ab initio,
When structural optimization is performed with PM3 or Russian 94, the calculation results and several% of the present invention depend on the calculation method and the basis functions used.
However, it did not result in disturbing the preferable range in the present invention. In these calculations, the distance between silver ion and chloride ion was 2.7751Å.

On the other hand, the ionic conductivity is determined by the Journal of the Photographic Society of Japan, 44
It can be measured by the method described in Volume 81-95 (1981). It is well known that the ionic conductivity changes depending on the amount of dopant and dopant species, and there are some findings regarding the relationship with photographic characteristics. However, the relationship between desensitization and softening on the low illuminance side due to the illuminance conversion dopant and ionic conductivity has not been clarified. In the present invention, a dopant that does not cause a large change from the ionic conductivity of an undoped emulsion when a large amount of dopant is used in a silver chloride emulsion is a desensitization or softening on the low illuminance side, which is an adverse effect on the illuminance conversion dopant. Found to be eliminated (or minimized). That is, the ionic conductivity of the emulsion when the metal complex (dopant) is incorporated into the silver halide grains in an amount of 1 × 10 ⁻⁴ mol per mol of silver is as follows. It has been found that a dopant having a ionic conductivity of 50 times or less, preferably 30 times or less, that of the unincorporated emulsion is suitable for the purpose of the present invention. This is because the use of the ligand of the present invention stabilizes the structure around the dopant and lowers the carrier mobility in ionic conductivity measurement. 0.38 in the present invention
The measurement was performed using a sample in which tetraazaindene was adsorbed on cubic silver chloride cubic particles.

The ligand satisfying these conditions is preferably an organic compound or an inorganic compound having 3 or less carbon atoms in the ligand. Here, the inorganic compound means carbon in the molecule
A compound having no carbon bond, carbon-hydrogen bond, or carbon-nitrogen-hydrogen bond. Since the space occupied by the ligand considered in the present invention is not a sphere but a rectangular parallelepiped, it is not preferable that the ligand has a rectangular space extending in the minor axis direction. An increase in the number of carbon-carbon bonds in the ligand skeleton inevitably leads to the introduction of carbon-hydrogen bonds, which increases the bulk in the direction of the minor axis of the rectangle and gives further distortion to the particles, which is not preferable. Specifically preferred is a compound in which the skeleton of the ligand is thiadiazole, thiatriazole, oxadiazole, or triazole, and the substituent is preferably -F, -Cl, -Br,-.
_{OH, -SH, -CN, -NO 2} , -NH 2, -CH 3,
_{-C 2 H 5, -CH = CH} 2, -CF 3, -CH 2 OH, -
_{CH 2 Cl, -CNHNH 2, -SCN} , -SO 2, -S
_{O 3 H, -OCH 3, -SCH} 3, -SeCH 3, -NH
_{CH 3, -N (CH 3)} 2, -N (CN) 2, -NHSO 3
_{H, -COOH, -COCH 3, -CONH} 2, -CO 2
_{NH 2, -CSCH 3, -OCOCH 3} , -SOCH 3, -
_{SCOCH 3, -SO 2 CH 3,} -SO 2 CF 3, -SO 2
NH _2, a, and among these preferably -F, -Cl, -B
r, -OH, -SH, -CN, -NO 2, -NH 2, -C
_{H 3, -C 2 H 5,} -CHCH 2, -CF 3, -CH 2 OH,
_{-CH 2 Cl, -SCN, -SO 2} , -SO 3 H, -OC
_{H 3, -SCH 3, -SeCH 3} , -NHCH 3, -N (C
_{N) 2, -COOH, -COCH 3} , -CONH 2, -C
_{SCH 3, -SOCH 3, -SO 2} CF 3, -SO 2 NH 2,
Most preferably _{-CH 3, -CF 3, -F,} -Cl, -B
r. These substituents may be the same or different in one ligand. A compound represented by the following general formula (1) or general formula (2) is also a ligand that can be preferably used.

General formula (1): X = Y (R ₁ ) _n General formula (2): R ₂ —X—Y (R ₁ ) _{n In the} formula, X represents oxygen, sulfur, selenium or tellurium,
Y represents carbon, nitrogen, sulfur or phosphorus. R ₁ and R
₂ represents a substituent mentioned above. n is 1, 2 or 3
Represents R ₁ is -F, -Cl, -Br, -OH, -S
_{H, -CN, -NO 2, -NH} 2, -CH 3, -C 2 H 5,
_{-CF 3, -CH 2 OH, -CH} 2 Cl, -SCN, -S
_{O 2, -SO 3 H, -OCH} 3, -SCH 3, -SeC
H _3, -NHCH _3, is preferably -COOH,
Among them, -F, -Cl, -Br, -OH, -SH, -C
_{N, -NO 2, -NH 2,} -CH 3, -CF 3 being preferred.
When n is 2 or 3, R ₁ may be the same substituent or different substituents. R ₂ is -C
_{H 3, -CF 3, -OH,} -SH, -CN, are -NO ₂ or -NH ₂ preferred.

In the present invention, chromium, manganese, rhenium,
Iron, cobalt, nickel, copper, ruthenium, rhodium,
Palladium, rhenium, osmium, iridium or
A platinum complex can be preferably used, but more preferably
Chromium, rhenium, iron, ruthenium, Osmiu
In complexes with aluminum, cobalt, rhodium or iridium
And most preferably a complex with iridium. 1
Use one to six of the above ligands in one complex molecule.
However, the number is preferably 1 or 2. the above
Ligands other than those of
Those that play the role of a car are preferable, specifically F^-,
Cl^-, Br^-, CN^-, NO₂ ^-, OCN^-, SCN^-, N₃
^-, OH^-, H₂O, NH₃, CO, are preferred and most preferred
Or Cl ^-, Br^-, CN^-, SCN^-Is.

Preferred specific examples of the complex according to the present invention are shown below, but the present invention is not limited thereto.

[0020]

[Chemical 1]

[0021]

[Chemical 2]

The illuminance conversion time in the present invention can be determined by comparing the reciprocity law curve of an undoped emulsion and the reciprocity law curve of an emulsion in which a reciprocity law failure improving dopant is incorporated in a silver halide grain. The reciprocity law curve is edited by The Photographic Society of Japan, “Revised Basics of Photographic Engineering-Silver Salt Photography-” P.
Can be drawn as in 297. For ordinary silver halide emulsions, especially silver chloride emulsions, the maximum sensitivity is near the middle illuminance, and desensitization occurs on the low illuminance side and the high illuminance side, and a downward convex curve is drawn. On the other hand, the reciprocity curve in the emulsion in which the high illuminance reciprocity failure is improved by doping the electron sustained release dopant has a flat area where desensitization does not occur in the area on the high illuminance side from a certain exposure illuminance. Different from the reciprocity law curve without doping. The exposure illuminance at which the leveling is started, that is, the exposure time at which there is a difference from the characteristic curve without doping is defined as the illuminance conversion time. The illuminance conversion time is preferably 5 seconds. Considering the distribution of the sustained release time, the illuminance conversion time is 1
More preferably in seconds.

The sustained electron release time in the present invention can be measured by the double pulse photoconductivity method. A microwave photoconductivity method or a radio wave photoconductivity method is used, and after the first short-time exposure, a second short-time exposure is given after a certain period of time has elapsed. Electrons are trapped in the electron trap in the silver halide crystal by the first exposure, and when the second exposure is given immediately after that, the electron trap is clogged and the second photoconductive signal becomes large. If the two exposure intervals are set sufficiently and the electrons trapped in the electron trap have already been emitted in the first exposure, the photoconductive signal in the second exposure returns to the original size. By changing the exposure interval of these two times and examining the change in the photoconductive signal intensity in the second exposure, it was measured that the intensity of the photoconductive signal observed in the second exposure decreased with the increase of the exposure interval. it can. This represents the sustained release time of photoelectrons from the electron trap. Electron sustained release may continue to occur for a certain period of time after exposure, but it is preferable that sustained release is observed between 10 ^-5 and 5 seconds, and between 10 ^-4 and 5 seconds. It is more preferable that sustained release be observed in 10 ^-3 seconds to 1
More preferably, sustained release is observed during the second.

In the present invention, the metal complex can be preferably incorporated inside and / or on the surface of the silver halide grain in the process of forming and / or growing the silver halide grain. When these complexes are incorporated in silver halide grains, it is preferable that they are uniformly present inside the grains, but JP-A-4-208936 and JP-A-2-12524.
5, as disclosed in JP-A-3-188437, it is also preferable that the particles are present only in the particle surface layer,
It is also preferable that the complex is present only inside the particles and a layer not containing the complex is added to the surface of the particles. More preferably, it is incorporated in an area of more than 50% from the center of the particle in the volume of the particle, and 98% from the center so as not to expose the complex on the surface of the particle.
% To stop incorporation, particularly preferred to incorporate in a layer between 80% and 98% of the particle volume. Also, US Pat. Nos. 5,252,451 and 5,
As disclosed in Japanese Patent No. 256,530, it is also preferable to modify the surface phase of particles by physically aging them with fine particles in which a complex is incorporated. Further, these methods can be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the complex is contained, and the complex may be contained in any of silver chloride, silver chlorobromide, silver bromide, silver iodochloride and silver iodobromide. It is particularly preferred to include the complex in the silver bromide layer.

[0025] The above complexes in the present invention, the silver mole per 1 × 10 ^-10 mol 1 × 10 ^{- 4} mol amount that is can be used preferably added, per 1 mol of silver and more preferably × 10 ^-9 It is from 1 to 10 ⁻⁵ mol. These complexes are added directly to the reaction solution at the time of silver halide grain formation, or to an aqueous solution of a halide for forming silver halide grains, or to other solutions, and then added to the grain formation reaction solution. Therefore, it is preferably incorporated into the silver halide grain. Further, it is also preferable to combine these methods to incorporate them in the silver halide grains. When the central metal is an iridium ion, III
The valent one may be used or the valent one may be used, but the valent one is preferable. An iridium trivalent complex having a bromide ion as a ligand is susceptible to oxidation, and it is preferable to add an oxidizing agent to the solution added to the emulsion. As the oxidizing agent to be added, preferably reductones, hydrazines, hydroxylamines, hydroxysemicarbazides, hydroxyurethanes, hydroxyureas, hydroxamic acids, compounds having a vitamin E-like skeleton, phenylenediamines, phenidones, hydrazides, Or phenols. Most preferred are reductones.

The silver halide grains in the silver halide emulsion used in the present invention are preferably cubic or tetradecahedral crystal grains having substantially {100} faces (these grains have rounded vertexes and higher grains). May have the following planes) or octahedral crystal grains, or 50 of the total projected area
A tabular grain having an aspect ratio of 2 or more and having at least 100% of {100} planes or {111} planes is preferable. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of particles. In the present invention, cubic grains or tabular grains having {100} faces as main planes or tabular grains having {111} faces as main planes are preferably applied.

As the silver halide emulsion used in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsion and the like can be used. Specific halogenated silver iodobromochloride is used. Emulsions containing silver particles are preferred. In the above preferred silver iodobromochloride emulsion, the silver chloride content must be 89 mol% to 99.7 mol%, and from the viewpoint of rapid processability, the silver chloride content is 93 mol% to 99.5. Mol% is preferred, 95
More preferably, the mol% to 98.5 mol%. The silver bromide content must be 0.25 mol% to 10 mol%, and the silver bromide content is 0.5 because the hardness is high and a low fog density is obtained.
It is preferably from mol% to 6 mol%, and from 1 mol% to 4
More preferably, it is mol%. The silver iodide content is 0.
It is necessary to be 05 mol% to 1 mol% and 0.05 to 0.6 mol% because it has high sensitivity and high contrast in high illuminance exposure.
Is preferable, and 0.1 to 0.4 mol% is more preferable.

Preferred silver halide grains in the silver halide emulsion of the present invention have a silver bromide-containing layer and / or a silver iodide-containing layer (hereinafter, also referred to as specific silver halide grains). Here, the silver bromide- or silver iodide-containing layer means a portion having a higher content ratio than each grain, and means a portion having a high silver bromide or silver iodide concentration. The halogen composition of the silver bromide-containing layer or silver iodide-containing layer and its surroundings may change continuously or may change sharply. Such a silver bromide- or silver iodide-containing layer may form a layer having a substantially constant concentration in a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing layer is preferably 5 mol% or more, more preferably 5 to 80 mol%, particularly preferably 5 to 50 mol%, 15 Most preferably, it is ˜50 mol%.
The local silver iodide content of the silver iodide-containing layer is preferably 0.2 mol% or more, more preferably 0.5 to 8 mol%, and further preferably 1 to 5 mol%. Most preferred. Further, such a silver bromide- or silver iodide-containing layer is
There may be a plurality of grains in each grain, and the respective silver bromide or silver iodide contents may differ, but it is necessary to have at least one containing layer for each.

The silver bromide-containing layer or silver iodide-containing layer of the silver halide emulsion of the present invention can be layered so as to surround the grains. It is a preferable embodiment that the silver bromide-containing layer or the silver iodide-containing layer formed in a layered manner so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each layer. However, in the silver bromide-containing layer or the silver iodide-containing layer that is layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution May have. For example, when a silver bromide-containing layer or a silver iodide-containing layer is provided in a layered manner so as to surround the grain near the grain surface, the concentration of silver bromide or silver iodide at the corner or edge of the grain will be different from that on the main surface. There are cases. Also, specific parts of particles, such as corners and edges,
It may be a silver bromide-containing layer or a silver iodide-containing layer which is isolated from the grain and does not surround the grain.

The silver bromide-containing layer of the silver halide emulsion of the present invention may be formed in a layered form so as to have a maximum silver bromide concentration inside the grain, or the silver bromide concentration inside the grain. The maximum portion may be formed separately.
Further, one grain may have a plurality of portions having a maximum silver bromide concentration. The silver iodide-containing layer of the silver halide emulsion of the present invention is preferably formed in layers so as to have a maximum silver iodide concentration on the surface of the grain. Such a silver bromide-containing layer or a silver iodide-containing layer is composed of 3% or more and 30% or less of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the amount of silver is 3% or more and 15% or less.

The silver halide emulsion of the present invention must contain both a silver bromide-containing layer and a silver iodide-containing layer. The silver bromide-containing layer may contain silver iodide, and conversely the silver iodide-containing layer may contain silver bromide. The silver bromide-containing layer must be inside the silver iodide-containing layer. The term "inside" means that a part of the silver bromide-containing layer is inside. For example, when there is a continuous silver bromide layer from the inside of the grain to the surface, the silver iodide layer is the silver bromide. It should be outside the beginning of the layer. What is important is that the start of the silver bromide layer is inside the start of the silver iodide layer. Also,
The silver bromide-containing layer is preferably adjacent to the inside of the silver iodide-containing layer in order to enhance the effects of the present invention. The silver bromide concentration maximum may be outside the silver iodide concentration maximum, but it is preferable that the silver bromide concentration maximum is inside the silver iodide concentration maximum in order to obtain the effect of the present invention. Further, another silver bromide-containing layer may be provided further outside the silver iodide-containing phase on the grain surface side, or another silver iodide-containing layer may be provided further inside the silver bromide-containing layer. It may be provided.

The silver bromide content or the silver iodide content necessary for exhibiting the effects of the present invention such as the enhancement of the sensitivity and the increase in the contrast is determined by the silver bromide-containing layer or the silver iodide-containing layer inside the grain. The more it is formed, the more it increases, and the silver chloride content may be unnecessarily reduced to impair the rapid processability. Therefore, it is preferable that the silver bromide-containing layer and the silver iodide-containing layer are adjacent to each other in order to concentrate these functions for controlling the photographic effect near the surface in the grain. From these points, the silver bromide-containing layer measures from 50% to 100% of the grain volume measured from the inside.
It is preferable that the silver iodide-containing layer is formed at any of positions of 85% to 100% of the grain volume. Further, it is preferable that the silver bromide-containing layer is formed at any of 70% to 95% of the grain volume and the silver iodide-containing phase is formed at any of 90% to 100% of the grain volume. preferable.

The introduction of the bromide or iodide ion to contain silver bromide or silver iodide in the silver halide emulsion of the present invention may be carried out by adding a solution of bromide salt or iodide salt alone, or by adding a silver salt. A bromide salt or iodide salt solution may be added together with the addition of the solution and the high chloride salt solution. In the latter case, the bromide salt or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the bromide salt or iodide salt and the high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ion or iodide ion from the organic molecule described in US Pat. No. 5,389,508. Fine silver bromide grains or fine silver iodide grains can also be used as another bromide or iodide ion source.

The addition of the bromide salt or iodide salt solution is
The particle formation may be concentrated in one period, or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fog. When the iodide ion is introduced inside the emulsion grains, the increase in sensitivity is small. Therefore, the addition of the iodide salt solution is preferably performed outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. When the addition of the iodide salt solution is completed slightly inside the grain surface, an emulsion having higher sensitivity and lower fog can be obtained. On the other hand, the bromide salt solution is preferably added to the outside of 50% of the grain volume, more preferably outside of 70%.

The distribution of the bromide or iodide ion concentration in the grain in the depth direction is determined by etching / TOF-SIMS.
(Time of Flight-Secondary
Ion Mass Spectrometry) method, for example, using TRIFTII type TOF-SIMS manufactured by Phi Evans. TOF-SIM
Regarding the S method, specifically, “Surface Analysis Technology Selection Manual, Secondary Ion Mass Spectrometry” edited by Japan Surface Science Society, Maruzen Co., Ltd. (19
Issued in 1999). Etching / TOF-
When the emulsion grains are analyzed by the SIMS method, it can be analyzed that the iodide ions are seeping out toward the grain surface even if the addition of the iodide salt solution is completed inside the grains. The emulsion of the present invention is analyzed by an etching / TOF-SIMS method,
It is preferable that the iodide ion has a maximum concentration on the surface of the grain, and the iodide ion concentration decreases toward the inside, and that the bromide ion has a distribution center of gravity on the inside, and further inside the grain. It is preferable to have a maximum concentration at. The local concentration of silver bromide can also be measured by an X-ray diffraction method if the silver bromide content is high to some extent.

In the present specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. The emulsion of the present invention is required to have a very precise grain structure, and therefore it is preferable that the grain size distribution of the emulsion is monodisperse. The variation coefficient of the spherical equivalent diameter of all particles of the present invention is 20.
% Or less, more preferably 15% or less, still more preferably 10% or less. The coefficient of variation of the sphere-equivalent diameter is expressed as a percentage of the standard deviation of the sphere-equivalent diameter of each particle with respect to the average of the sphere-equivalent diameters. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating.

The equivalent-sphere diameter of the silver halide grains contained in the silver halide emulsion of the present invention is preferably 0.6 μm or less, more preferably 0.5 μm or less, and further 0.4 μm or less. Is most preferred. A particle having a sphere equivalent diameter of 0.6 μm corresponds to a cubic particle having a side length of about 0.48 μm, and a particle having a sphere equivalent diameter of 0.5 μm has a side length of about 0.4 μm.
m cubic particles, and a particle having a spherical equivalent diameter of 0.4 μm corresponds to a cubic particle having a side length of about 0.32 μm. The silver halide emulsion of the present invention may contain silver halide grains other than the silver halide grains contained in the silver halide emulsion defined in the present invention (that is, specific silver halide grains). However, in the silver halide emulsion defined in the present invention, 50% or more of the total projected area of all grains must be silver halide grains defined in the present invention, and preferably 80% or more. , 90% or more is more preferable.

Specific silver halide grains in the silver halide emulsion of the present invention include, in addition to the above-mentioned iridium complex,
All six ligands may additionally contain iridium complexes consisting of Cl, Br or I. In this case, 6
Cl, Br, or I may be mixed in the coordination complex. It is particularly preferable that the iridium complex having Cl, Br or I as a ligand be contained in the silver bromide-containing phase in order to obtain a hard gradation by high-intensity exposure. Below, 6
Specific examples of the iridium complex in which all the individual ligands are Cl, Br, or I are given, but not limited thereto. [IrCl ₆ ] ^2- [IrCl ₆ ] ^3- [IrBr ₆ ] ^2- [IrBr ₆ ] ^3- [IrI ₆ ] ^3-

The effect of improving the reciprocity law can be further enhanced by using the metal complex of the present invention in combination with another iridium complex having a short sustained release time. As a preferred embodiment of another iridium complex used together with the metal complex of the present invention, Ir having at least one ligand other than halogen is used.
A complex is preferable, and a hexacoordinated complex is preferable. As ligands other than halogen, cyanide ion,
Water, hydroxide ion, O ²⁻ , OCN are preferable, and at least one of water, hydroxide ion, O and OCN is used as a ligand, and the remaining ligand is mainly Ir consisting of Cl, Br or I. A hexacoordinated complex with a metal is more preferable. Below, at least one of H ₂ O, OH, O ^{2 −} , or O
Specific examples of the hexacoordinated complex having CN as a ligand and the remaining liligand Cl, Br, or I with Ir as the central metal are given, but not limited thereto.

[IrCl ₅ (H ₂ O)] ^2- [IrCl ₄ (H ₂ O) ₂ ] ^- [IrBr ₅ (H ₂ O)] ^2- [IrBr ₄ (H ₂ O) ₂ ] ^- [IrCl _{5 ^{(OH)] 3- [IrCl 4}} (OH) 2] 3- [IrBr 5 (OH)] 3- [IrBr 4 (OH) 2] 3- [IrCl 5 (O)] 4- [IrCl 4 (O) ₂ ] ^5- [IrBr ₅ (O)] ^4- [IrBr ₄ (O) ₂ ] ^5- [IrCl ₅ (OCN)] ^3- [IrBr ₅ (OCN)] ^3-

When these complexes are incorporated into silver halide grains, they can be present uniformly inside the grains.
JP-A-4-208936, JP-A-2-125245
As disclosed in JP-A No. 3-188437 and Japanese Patent Laid-Open No. 3-188437, it is also preferable that the layer is present only in the particle surface layer, and the complex is present only inside the particle and a layer not containing the complex is added to the particle surface. Is also preferable. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical aging of fine particles in which a complex is incorporated to modify the surface phase of the particles. Is also preferable. Further, these methods may be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the complex is contained is not particularly limited, and it is preferably contained in the pure silver chloride layer or the silver chlorobromide layer. Further, these complexes are added at 1 × per mol of silver during grain formation.
It is preferable to add 10 ^-9 mol to 1 × 10 ^-3 mol, and most preferably 1 × 10 ^-7 mol to 1 × 10 ^-5 mol.

In the present invention, in addition to the above iridium, other metal ions can be doped inside and / or on the surface of the silver halide grain. The metal ion used is preferably iron, ruthenium, osmium, lead, cadmium, or zinc. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol ion It is preferable to use a nitrosyl ion, and the above iron, ruthenium, osmium,
It is also preferable to use it by coordinating it with any metal ion of lead, cadmium, or zinc.
It is also preferred to use it in one complex molecule. Further, an organic compound can be used as the ligand, and preferred organic compounds include a chain compound having a main chain having 5 or less carbon atoms and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compound is a compound having a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom in the molecule as a coordination atom for a metal, and particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazan, pyran, pyridine,
Pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds have a basic skeleton and a substituent is introduced into them are also preferable.

The combination of a metal ion and a ligand is preferably an iron ion or a ruthenium ion and a cyanide ion. The iridium complex in the present invention is also preferably used in combination with these compounds. In these compounds, the cyanide ion preferably occupies the majority of the coordination numbers to the central metal iron or ruthenium, and the remaining coordination sites are thiocyan, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably populated with pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron or hexacyanoruthenium complex. The complex containing these cyanide ions as a ligand is 1 × per 1 mol of silver during grain formation.
It is preferable to add 10 ⁻⁸ mol to 1 × 10 ⁻² mol, and most preferably 1 × 10 ⁻⁶ mol to 5 × 10 ⁻⁴ mol. When ruthenium and osmium are the central metals, it is also preferable to use nitrosyl ion, thionitrosyl ion, or water molecule and chloride ion together as ligands. It is more preferable to form a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex, and it is also preferable to form a hexachloro complex. These complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol, and more preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁶ mol per mol of silver during grain formation. That is.

The silver halide emulsion of the present invention is usually chemically sensitized. In the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used. Of these, gold-sensitized ones are particularly preferable. By performing gold sensitization, it is possible to further reduce fluctuations in photographic performance when scanning and exposing with laser light or the like.

For gold sensitization of the silver halide emulsion of the present invention, various inorganic gold compounds and gold (I) complexes having inorganic ligands and gold (I) compounds having organic ligands are used. can do. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and examples of the gold (I) complex having an inorganic ligand include a gold dithiocyanate compound such as potassium gold (I) dithiocyanate and gold (I) 3 dithiosulfate. Compounds such as sodium dithiosulfate compounds such as sodium can be used.

The silver halide emulsion of the present invention is colloidal.
Gold sulfide or gold complex stability constant log β₂Is 21 or more
And it is preferable that it is gold sensitized with a gold sensitizer of 35 or less.
Good The research method for producing colloidal gold sulfide is
Closure (Research Disclosur)
e, 37154), Solid State Ionics
(Solid State Ionics) No. 79
Vol. 60-66, 1995, Compt. Ren
d. Hebt. Seans Acad. Sci. S
ect. B Vol. 263, p. 1328, published in 1966
Have been described. Various sizes as colloidal gold sulfide
It is possible to use those with a particle size of 50 nm or less.
You can The amount added can vary widely depending on the case
Is 5 × 10 5 as gold atom per mol of silver halide.^-7
~ 5 x 10^-3Mol, preferably 5 × 10 ^-6~ 5 x 10^-Four
It is a mole. In the present invention, gold sensitization is further sensitized.
Methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization
Sensitivity or combination with precious metal sensitization using other than gold compounds
You may let me.

Below, the gold complex stability constant log β ₂ is 2
The gold sensitizer of 1 or more and 35 or less will be described. The complex stability constant log β ₂ of gold is measured by a comprehensive
Coordination Chemistry (Compreh
intensive Coordination Chemis
try, Chapter 55, p.864, 1987), Encyclopedia of Electrochemistry of.
The Elements (Encyclopedia of E
electrochemistry of the El
elements, Chapter IV-3, 1975), Journal of the Royal Chemical Society (Journal of the Roy).
al Netherlands Chemical S
(Vol. 101, 164, 1982), and the measurement methods described in the references thereof, and the measurement temperature is 25 ° C. and pH is potassium dihydrogen phosphate / disodium hydrogen phosphate buffer. The ionic strength was adjusted to 6.0 from the value of the gold potential under the condition of 0.1 M (KBr).
The value of gβ ₂ can be calculated. In this measurement method, the value of log β ₂ of thiocyanate ion is 20.5.
And the literature (Comprehensive Coordination Chemistry (Comprehensive Co
coordination Chemistry, 1987
Year, Chapter 55, page 864, Table 2)) described values, values close to 20 are obtained.

Gold complex stability constant log β in the present invention
The gold sensitizer in which ₂ is 21 or more and 35 or less is preferably represented by the following general formula (I). General formula ^{(I) {(L 1)} x (Au) y (L 2) z · Q q} p

In the general formula (I), L ¹ and L ² each independently represent a compound having a logβ ₂ value of 21 to 35. The compound contained in 22 to 31 is preferable, and the compound contained in 24 to 28 is more preferable.

L ¹ and L ² are, for example, compounds containing at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide, hydantoin compounds,
It represents a thioether compound, a mesoionic compound, -SR ', a heterocyclic compound, a phosphine compound, an amino acid derivative, a sugar derivative, and a thiocyano group, which may be the same or different from each other. Here, R'represents an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, a thiocarbamoyl group, or a sulfonyl group. Q represents a counter anion or counter cation necessary for neutralizing the charge of the compound, x and z represent an integer of 0 to 4, y and p represent 1 or 2, and q represents 0 including a decimal.
Represents a value of ~ 1. However, neither x nor z is 0.

As the compound represented by the general formula (I), L ¹ and L ² preferably have at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide.
A compound, a hydantoin compound, a thioether compound, a mesoionic compound, —SR ′, a heterocyclic compound, or a phosphine compound contained therein, and x, y, and z each represent 1.

More preferably, as the compound represented by formula (I), L ¹ and L ² contain at least one labile sulfur group capable of reacting with silver halide to form silver sulfide. Compound, mesoionic compound, or -S
Represents R ', and x, y, z and p each represent 1.

The gold compound represented by formula (I) will be described in more detail below. In the general formula (I), compounds having an unstable sulfur group capable of reacting with silver halides represented by L ¹ and L ² to produce silver sulfide include thioketones (for example, thioureas, Thioamides or rhodanines), thiophosphates, thiosulfates.

The compound containing at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide is preferably thioketones (preferably thioureas, thioamides, etc.), thiosulfate. Represents a class.

Next, examples of the hydantoin compound represented by L ¹ and L ² in the general formula (I) include unsubstituted hydantoin and N-methylhydantoin.
The thioether compound contains 1 to 8 thio groups, and they are substituted or unsubstituted linear or branched alkylene groups (for example, ethylene, triethylene, etc.), or a chain structure linked by a phenylene group, or Cyclic thioethers (eg, bishydroxyethyl thioether,
3,6-dithia-1,8-octanediol, 1,4
8,11-tetrathiacyclotetradecane) and the like, and the mesoionic compound is mesoionic-3.
-Mercapto-1,2,4-triazoles (e.g.
Mesoionic-1,4,5-trimethyl-3-mercapto-1,2,4-triazole etc.) and the like.

Next, in the general formula (I), L ¹ and L ² are
When SR ′ is represented, the aliphatic hydrocarbon group represented by R ′ is a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl). , N-butyl, t-butyl, 2-
Pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 1,5-dimethylhexyl,
n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, hydroxyethyl, hydroxypropyl,
2,3-dihydroxypropyl, carboxymethyl, carboxyethyl, sodium sulfoethyl, diethylaminoethyl, diethylaminopropyl, butoxypropyl, ethoxyethoxyethyl, n-hexyloxypropyl, etc.), a substituted or unsubstituted cyclic group having 3 to 18 carbon atoms Alkyl groups (eg, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl,
Cyclododecyl etc.), alkenyl group having 2 to 16 carbon atoms (eg allyl, 2-butenyl, 3-pentenyl etc.), alkynyl group having 2 to 10 carbon atoms (eg propargyl, 3-pentynyl etc.), carbon number 6 To 16 aralkyl groups (eg, benzyl, etc.) and the like, and the aryl group includes a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms and a naphthyl group (eg, unsubstituted phenyl, unsubstituted naphthyl, 3,5). -Dimethylphenyl, 4-butoxyphenyl, 4-dimethylaminophenyl, 2-carboxyphenyl, etc.) and the like, and examples of the heterocyclic group include a substituted or unsubstituted nitrogen-containing hetero 5-membered ring (e.g., imidazolyl, 1 , 2,4-triazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, benzimidazolyl, purinyl, etc.) A substituted or unsubstituted nitrogen-containing heterocyclic 6-membered ring (e.g., pyridyl, piperidyl, 1,
3,5-triazino, 4,6-dimercapto-1,3
5-triazino, etc.), a furyl group, or a thienyl group, etc., examples of the acyl group include acetyl, benzoyl, etc., examples of the carbamoyl group include dimethylcarbamoyl, etc., and examples of the thiocarbamoyl group include diethyl. Examples thereof include thiocarbamoyl, and examples of the sulfonyl group include a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms (eg, methanesulfonyl, ethanesulfonyl, etc.), and a substituted or unsubstituted phenylsulfonyl group having 6 to 16 carbon atoms. A group (for example, phenylsulfonyl and the like) can be mentioned.

Further, as —SR ′ represented by L ¹ and L ² , R ′ is preferably an aryl group or a heterocyclic group, more preferably a heterocyclic group, and further preferably 5 or 6 membered. Is a nitrogen-containing heterocyclic group, most preferably a nitrogen-containing heterocyclic group substituted with a water-soluble group (eg, sulfo, carboxy, hydroxy, amino, etc.).

In the general formula (I), the heterocyclic compound represented by L ¹ and L ² is a substituted or unsubstituted nitrogen-containing hetero 5-membered ring (eg, pyrroles, imidazoles, pyrazoles, 1 , 2,3-triazoles, 1,
2,4-triazoles, tetrazoles, oxazoles, isoxazoles, isothiazoles, oxadiazoles, thiadiazoles, pyrrolidines, pyrrolines, imidazolidines, imidazolines, pyrazolidines, pyrazolines, hydantoins Etc.), and 5
Heterocycles containing member rings (indoles, isoindoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraazaindenes, benzothiazoles, indolines, etc.) A substituted or unsubstituted nitrogen-containing hetero 6-membered ring (for example, pyridines, pyrazines, pyrimidines, pyridazines, triazines, thiadiazines, piperidines, piperazines, morpholines, etc.),
And heterocycles containing the 6-membered ring (for example, quinolines, isoquinolines, phthalazines, naphthyridines,
Quinoxalines, quinazolines, pteridines, phenaziridines, acridines, phenanthrolines, phenazines), substituted or unsubstituted furans, substituted or unsubstituted thiophenes, benzothiazolium and the like.

The heterocyclic compound represented by L ¹ and L ² is preferably an unsaturated nitrogen-containing hetero 5- or 6-membered ring, or a heterocycle containing the same, such as pyrroles, Imidazoles, pyrazoles, 1,
2,4-triazoles, oxadiazoles, thiadiazoles, imidazolines, indoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraazaindenes, benzothiazoles , Pyridines, pyrazines, pyrimidines, pyridazines, triazines, quinolines, isoquinolines, phthalazines, and the like. Further, heterocyclic compounds known as antifoggants in the art (for example, indazoles , Benzimidazoles, benzotriazoles, tetraazaindenes, etc.) are preferred.

In the general formula (I), the phosphine compound represented by L ¹ and L ² includes an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heterocyclic group (for example, Pyridyl, etc.), a substituted or unsubstituted amino group (eg, dimethylamino, etc.), and / or an alkyloxy group (eg, methyloxy, ethyloxy, etc.) is substituted, and preferably represents 1 to 1 carbon atoms.
Examples thereof include phosphines substituted with an alkyl group having 10 or an aryl group having 6 to 12 carbon atoms (eg, triphenylphosphine, triethylphosphine, etc.).

Further, the mesoionic compound represented by L ¹ and L ² , -SR ', and the heterocyclic compound are
It is preferable that an unstable sulfur group (for example, thioureido group) capable of reacting with silver halide to produce silver sulfide is substituted.

Further, the compounds represented by L ¹ and L ² in the above general formula (I) may further have a substituent as much as possible, and the substituent is, for example, a halogen atom (eg, , Fluorine atom, chlorine atom, bromine atom, etc.), aliphatic hydrocarbon group (eg, methyl, ethyl, isopropyl, n-
Propyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl etc.), alkenyl group (eg allyl, 2-butenyl, 3-pentenyl etc.), alkynyl group (eg propargyl, 3-pentynyl etc.), aralkyl group (eg , Benzyl, phenethyl, etc.), aryl groups (eg, phenyl, naphthyl, 4-methylphenyl, etc.), heterocyclic groups (eg, pyridyl, furyl, imidazolyl, piperidinyl, morpholyl, etc.), alkyloxy groups (eg, methoxy, ethoxy). , Butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy, etc.), aryloxy groups (eg, phenoxy, 2
-Naphthyloxy etc.), amino group (eg unsubstituted amino, dimethylamino, diethylamino, dipropylamino, dibutylamino, ethylamino, dibenzylamino, anilino etc.), acylamino group (eg acetylamino, benzoylamino etc.) , An ureido group (for example,
Unsubstituted ureido, N-methylureido, N-phenylureido, etc.), thioureido group (eg, unsubstituted thioureido, N-methylthioureido, N-phenylthioureido, etc.), selenourido group (eg, unsubstituted selenouride, etc.), phosphine Selenide group (diphenylphosphine selenide etc.), telluroide group (eg unsubstituted telluroide etc.), urethane group (eg methoxycarbonylamino, phenoxycarbonylamino etc.), sulfonamide group (eg methylsulfonamide, phenylsulfonamide) Etc.), a sulfamoyl group (for example,
Unsubstituted sulfamoyl group, N, N-dimethylsulfamoyl, N-phenylsulfamoyl etc.), carbamoyl group (eg unsubstituted carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl etc.), sulfonyl group (eg , Methanesulfonyl, p-toluenesulfonyl, etc.), sulfinyl group (eg, methylsulfinyl, phenylsulfinyl, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl, etc.), An acyl group (eg, acetyl,
Benzoyl, formyl, pivaloyl etc.), acyloxy group (eg acetoxy, benzoyloxy etc.), phosphoric acid amide group (eg N, N-diethyl phosphoric acid amide etc.), alkylthio group (eg methylthio, ethylthio etc.), arylthio A group (eg, phenylthio etc.),
Cyano group, sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, mercapto group, phosphono group, nitro group, sulfino group, ammonio group (eg, trimethylammonio, etc.), phosphonio group, hydrazino group, thiazolino Group, a silyloxy group (for example, t-
Butyldimethylsilyloxy, t-butyldiphenylsilyloxy) and the like. When there are two or more substituents, they may be the same or different.

Next, regarding Q and q in the general formula (I),
Explain. In the general formula (I), a counter anion represented by Q
Is a halogenium ion (for example, F^-, C
l^-, Br^-, I^-), Tetrafluoroborate ion
(BF_Four ^-), Hexafluorophosphate ion (P
F₆ ^-), Sulfate ion (SO_Four ^2-), Arylsulfone
Salt ion (for example, p-toluenesulfonate ion)
, Naphthalene-2,5-disulfonate ion, etc.),
Carboxy ion (eg acetate ion, trifluoroacetic acid
Acid ion, oxalate ion, benzoate ion, etc.)
The counter cation represented by Q is alkali gold.
Group ions (eg lithium ion, sodium ion
Ion, potassium ion, rubidium ion, cesium ion
Etc.), alkaline earth metal ions (eg magnesium)
(Ion, calcium ion, etc.), substituted or unsubstituted
Ammonium ion (for example, an unsubstituted ammonium ion
On, triethylammonium, tetramethylammoni
Um, etc.), substituted or unsubstituted pyridinium ion
(For example, an unsubstituted pyridinium ion, 4-phenylpyrene
Lydinium ion, etc.)
It Also, q is the number of Q for neutralizing the charge of the compound.
And represents a value from 0 to 1, which is a decimal
Good.

Preferred as the counter anion represented by Q
Is a halogenium ion (eg Cl ^-, Br^-), Te
Trafluoroborate ion, hexafluorophosphate
Cation and sulfate, which are represented by Q
Preferably, the alkali metal ion (for example, sodium
Thorium ion, potassium ion, rubidium ion,
Cesium ion, etc.), substituted or unsubstituted ammonium
Mu ions (eg, unsubstituted ammonium ions, Trier
Til ammonium, tetramethyl ammonium, etc.), or
Is a proton.

Specific examples (L- ^{1 to} L-17) of the compound represented by L ¹ or L ² are shown below, but the present invention is not limited thereto. In addition, the numerical value in parentheses shows a logβ ₂ value.

[0066]

[Chemical 3]

[0067]

[Chemical 4]

The compound represented by the general formula (I) can be prepared by a known method, for example, in Organic and Nuclear Chemistry Letters (INORG.NUCL.
CHEM. LETTERSVOL. 10, 641 pages, 1
974), Transition Metal Chemistry (T
positionMet. Chem. Pages 1,248,
1976), Actor Crystallographica (Act)
a. Cryst. B32, p. 3321, 1976),
JP-A-8-69075, JP-B-45-8831, JP-A-915371A1, JP-A-6-11788,
JP-A-6-501789, JP-A-4-267249
And JP-A-9-118685 and the like.

Next, specific examples (S-1 to S-19) of the compound represented by the general formula (I) are shown, but the present invention is not limited thereto.

[0070]

[Chemical 5]

[0071]

[Chemical 6]

[0072]

[Chemical 7]

The gold sensitization in the present invention is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature (preferably 40 ° C. or higher) for a certain period of time. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 1 × 10 ⁻⁴ mol per mol of silver halide.

In the present invention, as the gold sensitizer, in addition to the above compounds, commonly used gold compounds (eg, chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, Tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichloro gold, etc.) can be used together.

The silver halide emulsion of the present invention can be used in combination with other chemical sensitization besides gold sensitization. As the chemical sensitization method that can be used in combination, sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization other than gold, or reduction sensitization can be used. As the compound used for the chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used.

The silver halide emulsion of the present invention contains various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. It can be added.
Specific examples of these compounds are described in JP-A-62-215272.
Those described on pages 39 to 72 of the publication are preferably used. In addition, 5-described in EP 0447647
An arylamino-1,2,3,4-thiatriazole compound (wherein the aryl residue has at least one electron-withdrawing group) is also preferably used.

Further, in the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A No. 11-109576 and JP-A No. 11-327.
Adjacent to the carbonyl group described in JP-A-094, a cyclic ketone having a double bond in which both ends are substituted with an amino group or a hydroxyl group (particularly represented by the general formula (S1), paragraphs 0036 to 0071 can be incorporated into the specification of the present application.), Sulfo-substituted catechols and hydroquinones described in JP-A No. 11-143011, such as 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2, 5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5
-Dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof, etc.),
General formula (A) of US Pat. No. 5,556,741
Hydroxylamines represented by (US Pat. No. 5,555
No. 6,741 column 4, line 56 to column 11, line 22 is preferably applied to the present application and incorporated as a part of the specification of the present application), JP-A-11-1
The water-soluble reducing agents represented by the general formulas (I) to (III) described in JP-A-02045 are preferably used in the present invention.

Further, the silver halide emulsion of the present invention may contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity, which exhibits photosensitivity in a desired light wavelength region.
Examples of the spectral sensitizing dye used for spectral sensitization in the blue, green and red regions include F.I. M. Harter by Heter
ocyclic compounds-Cyanine
dyes and related compound
ds (John Wiley & Sons [Ne
w York, London] 1964). Examples of specific compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-21.
Those described on page 22, upper right column to page 38 of Japanese Patent No. 5272 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dyes described in JP-A-3-123340 are stable, have strong adsorption, It is very preferable from the viewpoint of temperature dependence and the like.

The amount of these spectral sensitizing dyes added may be in a wide range depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, it is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 0 ⁻³ mol.

[Silver Halide Photosensitive Material] The silver halide photographic material in which the silver halide emulsion of the present invention is used will be described below. The silver halide photographic light-sensitive material of the present invention may be black and white or color, but is preferably
The silver halide emulsion of the present invention is used in a silver halide color photographic light-sensitive material. The silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as "light-sensitive material of the present invention") in which the silver halide emulsion of the present invention is preferably used is
At least one silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a cyan dye-forming coupler are formed on a support. The silver halide color photographic light-sensitive material having the above is characterized in that at least one of the silver halide emulsion layers contains the silver halide emulsion of the present invention. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler as a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler as a magenta coloring layer, and the cyan dye-forming coupler. The silver halide emulsion layer thus prepared functions as a cyan coloring layer. The silver halide emulsion contained in each of the yellow color forming layer, the magenta color forming layer and the cyan color forming layer is sensitive to light in different wavelength regions (for example, light in blue region, green region and red region). It is preferable to have

The light-sensitive material of the present invention may have a hydrophilic colloid layer, an antihalation layer, an intermediate layer and a coloring layer, which will be described later, if desired, in addition to the yellow coloring layer, the magenta coloring layer and the cyan coloring layer. Good.

Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention. For example, a transmissive support or a reflective support can be used as the photographic support. As the transmissive support, a transparent film such as a cellulose nitrate film or polyethylene terephthalate, and further 2,6-naphthalenedicarboxylic acid (NDC)
Polyesters of A) and ethylene glycol (EG), polyesters of NDCA, terephthalic acid and EG, and the like provided with an information recording layer such as a magnetic layer are preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers and containing a white pigment such as titanium oxide in at least one of the water resistant resin layers (laminate layer) is preferable.

Further preferred reflective supports in the present invention include those having a polyolefin layer having fine pores on the paper base on which the silver halide emulsion layer is provided. The polyolefin layer may be composed of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no microvoids (eg polypropylene, polyethylene) and is on a paper substrate. It is more preferable to use a polyolefin (for example, polypropylene or polyethylene) having micropores on the near side. The density of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is 0.40 to 40.
It is preferably 1.0 g / ml, and 0.50 to 0.
70 g / ml is more preferred. The thickness of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is preferably 10 to 100 μm, and 15 to 100 μm.
70 μm is more preferable. The ratio of the thickness of the polyolefin layer to the thickness of the paper substrate is preferably 0.05 to 0.2,
1 to 0.15 is more preferable.

It is also preferable to provide a polyolefin layer on the opposite side (rear surface) to the photographic constituent layers of the paper base from the viewpoint of increasing the rigidity of the reflection support. In this case, the polyolefin layer on the back surface has a matte surface. Preferred are polyethylene or polypropylene, and more preferred is polypropylene. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further has a density of 0.
It is preferably 7 to 1.1 g / ml. Regarding the preferred embodiment of the polyolefin layer provided on the paper substrate in the reflective support of the present invention, see JP-A-10-
No. 333277, No. 10-333278, No. 11-52513, No. 11-65024,
EP0880065 and EP0880066
The examples described in the specification are included.

Further, it is preferable to contain a fluorescent whitening agent in the water resistant resin layer. Also, a hydrophilic colloid layer containing the fluorescent whitening agent dispersed therein may be separately formed. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent can be used, and more preferably, a benzoxazolylnaphthalene-based or benzoxazolyl-stilbene-based fluorescent whitening agent. The amount used is not particularly limited, but preferably 1 to 10
It is 0 mg / m ² . When mixed with a water resistant resin, the mixing ratio is preferably 0.0005 to 3 mass% with respect to the resin.
And more preferably 0.001 to 0.5 mass%.

The reflective type support may be a transmissive type support or the above reflective type support coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular reflective or type II diffuse reflective metal surface.

The support used in the light-sensitive material of the present invention is a support in which a white polyester support or a layer containing a white pigment is provided on the support having a silver halide emulsion layer for display. The body may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. Especially, the transmission density of the support is 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of.

In the light-sensitive material of the present invention, a hydrophilic colloid layer can be decolorized by the treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving the sharpness of an image. Dyes (among others, oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, and dihydric alcohols (e.g. 1 part of titanium oxide surface-treated with trimethylolethane)
It is preferable to contain 2 mass% or more (more preferably 14 mass% or more).

In the light-sensitive material of the present invention, a hydrophilic colloid layer is provided in the European Patent EP0 for the purpose of preventing irradiation and halation and improving safety of safelight.
337490A2, pages 27-76,
Dyes that can be decolorized by treatment (including oxonol dyes,
Cyanine dye) is preferably added. Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes may deteriorate color separation and safelight safety when the amount used is increased. Examples of dyes that can be used without deteriorating the color separation include JP-A-5-127324 and JP-A-5-12
The water-soluble dyes described in JP 7325 and JP 5-216185 are preferable.

In the present invention, instead of the water-soluble dye,
Alternatively, a colored layer that can be decolorized by treatment with a water-soluble dye is used. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to install a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (400 nm for ordinary printer exposure).
It is preferable that the optical density value is 0.2 or more and 3.0 or less at a wavelength having the highest optical density in the visible light region of up to 700 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure). It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, the dyes described in JP-A-2-282244, from page 3, upper right column to page 8,
-7931 gazette, page 3, upper right column to page 11, lower left column, a method of incorporating a hydrophilic colloid layer in the form of solid fine particle dispersion, a method of mordanting an anionic dye with a cationic polymer, a dye A method of adsorbing to a fine particle such as silver halide and fixing it in a layer, JP-A-1-239
A method using colloidal silver as described in Japanese Patent No. 544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at least at pH 6 or less, but is substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Laid-Open No. 2-308244, pages 4-13. Further, for example, a method of mordanting an anionic dye on a cationic polymer is described on pages 18 to 26 of JP-A-2-84637. For the preparation of colloidal silver as a light absorber, see US Pat. No. 2,688,
601 and 3,459,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

The light-sensitive material of the present invention is used as a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc. Among them, the color photographic paper is preferably used. The color photographic paper preferably comprises at least one yellow color forming silver halide emulsion layer, at least one magenta color forming silver halide emulsion layer, and at least one cyan color forming silver halide emulsion layer. The silver halide emulsion layers are a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer in order from the support.

However, a layer structure different from this may be adopted. The silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support, but when the yellow coupler-containing layer contains silver halide tabular grains, the magenta coupler-containing silver halide It is preferably coated at a position farther from the support than at least one of the emulsion layer and the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color due to a sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support as compared with other silver halide emulsion layers. It is preferably provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a central layer of other silver halide emulsion layers, and from the viewpoint of reducing photofading, a cyan coupler-containing silver halide emulsion layer. Is preferably the bottom layer. Further, each of the yellow, magenta and cyan color forming layers may be composed of two layers or three layers. For example, JP-A-4-75055 and 9-1.
As described in 14035, 10-246940, US Pat. No. 5,576,159, etc.,
It is also preferable to provide a coupler layer containing no silver halide emulsion adjacent to the silver halide emulsion layer to form a color forming layer.

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied in the present invention, and the processing method and processing addition applied for processing the light-sensitive material. As the agent, JP-A-62-21
Those described in JP-A-5272, JP-A-2-33144, and European Patent EP0,355,660A2, and particularly those described in European Patent EP0,355,660A2 are preferably used. . Furthermore, JP-A-5-34889 and 4-359249.
No. 4,313753, and No. 4-27034.
4, gazette 5-66527 gazette, and gazette 4-34548.
No. 4, 145,433, No. 2-854, No. 1,158,431, No. 2-90145, No. 3-19439, No. 2-93641, and European Patent Publication No. 0520457A2. The silver halide color photographic light-sensitive material and the processing method therefor described in the specification and the like are also preferable.

In particular, in the present invention, the above-mentioned reflection type support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer for silver halide emulsion or antifoggant. , Chemical sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsion dispersion method, color image storability improving agent (anti-staining agent or anti-fading agent), As for the dye (colored layer), the type of gelatin, the layer structure of the photosensitive material and the coating pH of the photosensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applicable.

[0096]

[Table 1]

Other cyan, magenta and yellow couplers used in the present invention are disclosed in JP-A-62-62.
-215272, page 91, upper right column, fourth line to 121
Page top left column, line 6, page 3 top right column, line 14 to page 18 top left column, end line, page 30 top right column, line 6 to page 35, bottom right column, line 11 of JP-A-2-33144 EP0355,660
Page 4, lines 15 to 27, page 5, lines 30 to 28, end line, page 45, lines 29 to 31, line 47, lines 23 to 63, line 50 of the A2 specification. The couplers described are also useful. In the present invention, compounds represented by the general formulas (II) and (III) of WO-98 / 33760 and the general formula (D) of JP-A-10-221825 may be added, which is preferable.

As a cyan dye-forming coupler usable in the present invention (sometimes referred to simply as "cyan coupler"), a pyrrolotriazole-based coupler is preferably used. Or a coupler represented by (II) and JP-A-6-347960.
The couplers represented by the general formula (I) in JP-A No. 1993-154, and the exemplary couplers described in these patents are particularly preferable.
Phenol-based and naphthol-based cyan couplers are also preferable, and for example, a cyan coupler represented by the general formula (ADF) described in JP-A-10-333297 is preferable. Cyan couplers other than those mentioned above include European Patent Nos. EP 0488248 and EP 0491197A.
1, a pyrroloazole-type cyan coupler,
2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, US Pat.
Pyrazoloazole type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in JP-A-3,183 and JP-A-4,916,051, and particularly, JP-A-8-17
No. 1185, No. 8-311360, No. 8-3
The pyrazoloazole type cyan coupler having a carbamoyl group at the 6-position described in JP-A-39060 is also preferable.

In addition to the diphenylimidazole type cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine type cyan coupler described in European Patent EP 0333185A2 (the couplers listed as specific examples ( 42) A 4-equivalent coupler having a chlorine-eliminating group to make it a 2-equivalent compound, or a coupler (6)
And (9) are particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8 and 3 listed as specific examples among them).
4 is particularly preferred), European Patent EP 0456226A1
, A pyrrolopyrazole-type cyan coupler described in
The pyrroloimidazole type cyan coupler described in European Patent EP 0484909 can also be used.

Among these cyan couplers, the pyrroloazole type cyan coupler represented by the general formula (I) described in JP-A No. 11-28138 is particularly preferable, and paragraphs 0012 to 0059 of the patent are described. Including the exemplified cyan couplers (1) to (47) are directly applied to the present application and are preferably incorporated as part of the specification of the present application.

Magenta dye-forming coupler used in the present invention (sometimes referred to simply as "magenta coupler")
As the 5-
Pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers are used. Among them, secondary or tertiary alkyl groups as described in JP-A-61-65245 in view of hue, image stability, color developability and the like. Is a pyrazolotriazole coupler directly linked to the 2, 3 or 6 position of the pyrazolotriazole ring, a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254 and 6 as described in EP 226,849A and EP 294,785A. It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the position. Particularly, as a magenta coupler, JP-A-8-1
Pyrazoloazole couplers represented by General Formula (M-I) described in JP-A No. 22948 are preferable, and paragraph numbers 0009 to 0026 of the patent are directly applied to the present application and are incorporated as a part of the specification of the present application. In addition to this, a pyrazoloazole coupler having a steric hindrance group at both the 3-position and the 6-position described in European Patent Nos. 854384 and 884640 is also preferably used.

Also, a yellow dye-forming coupler (simply,
(In some cases, referred to as “yellow coupler”), in addition to the compounds listed in the above table, European Patent EP04479
No. 69A1, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group, a malondianilide type yellow coupler having a cyclic structure described in European Patent No. EP 0482552A1, European Patent No. 953870A1. Specification, No. 95387
1A1, No. 953872A1, No. 953873A1, No. 953874A1, No. 953875A1, etc. described in Pyrrole-2 or 3-yl or indole-2 or 3- Ilcarbonylacetic acid anilide coupler, US Pat. No. 5,
The acylacetamide type yellow coupler having a dioxane structure described in 118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

The couplers used in the present invention are loadable latex polymers in the presence (or absence) of the high boiling point organic solvents described in the above table (see, for example, US Pat. No. 4,20,20).
No. 3,716), or dissolved with a water-insoluble polymer soluble in an organic solvent, and then emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers which can be preferably used are described in US Pat. No. 4,857,449, No. 7
Columns to columns 15 and the homopolymers or copolymers described on pages 12 to 30 of International Publication WO88 / 00723 are mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high molecular weight redox compounds described in JP-A-5-333501, WO98 /
No. 33760, U.S. Pat. No. 4,923,787, and other phenidone and hydrazine compounds, JP-A-5-249637 and JP-A-10-28261.
The white couplers described in Japanese Patent No. 5 and German Patent No. 19629142A1 can be used. Further, particularly when the pH of the developing solution is raised to accelerate the development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 84297.
It is also preferable to use the redox compounds described in Japanese Patent No. 5A1, German Patent 1980846A1 and French Patent No. 2760460A1.

In the present invention, it is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient as the ultraviolet absorber. For example, the compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or the non-photosensitive layer. For example, JP-A-46-
3335 gazette, the same 55-152776 gazette, Unexamined-Japanese-Patent No. 5 197074, the same 5-232630 gazette,
No. 5-307232, No. 6-211813, No. 8-53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-15898, and the same. 10-14757
7 gazette, the same 10-182621 gazette, German Patent No. 1
9739797A, European Patent 711804A
The compounds described in JP-A No. 8-501291 and the like can be used.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As preferable gelatin, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably 5 ppm or less,
More preferably, it is 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ²
Or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

In the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the antibacterial and antifungal agents described in JP-A-63-271247 are used. It is preferable to add it. Further, the film pH of the light-sensitive material is preferably 4.0 to 7.0, and more preferably 4.0 to 6.5.

In the present invention, a surfactant can be added to the light-sensitive material from the viewpoints of improving the coating stability of the light-sensitive material, preventing the generation of static electricity, adjusting the charge amount, and the like. Examples of the surfactant include anionic surfactants, cationic surfactants, betaine surfactants and nonionic surfactants, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. Particularly, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but preferably in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , and preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. It is 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The light-sensitive material of the present invention can form an image by an exposure step of irradiating light according to image information and a developing step of developing the light-irradiated light-sensitive material. The light-sensitive material of the present invention is used in a cathode ray (CR) in addition to being used in a printing system using an ordinary negative printer.
It is also suitable for the scanning exposure method using T). A cathode ray tube exposure apparatus is simpler and more compact than an apparatus using a laser, and is low in cost. Moreover, the optical axis and color can be easily adjusted. For the cathode ray tube used for image exposure, various light-emitting bodies that emit light in the spectral region are used as necessary. For example, any one of a red light emitting body, a green light emitting body, and a blue light emitting body, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a fluorescent substance that emits light in a yellow, orange, violet, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

When the light-sensitive material has a plurality of light-sensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor that emits light in a plurality of spectral regions, it exposes a plurality of colors at once, that is, the cathode ray. Image signals of a plurality of colors may be input to the tube to cause the tube surface to emit light. A method of sequentially inputting image signals for each color to sequentially emit light of each color and exposing through a film that cuts colors other than that color (field sequential exposure)
In general, field sequential exposure is preferable for high image quality because a high resolution cathode ray tube can be used.

The light-sensitive material of the present invention comprises a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic emission light source (SHG) in which a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal are combined.
A digital scanning exposure method using monochromatic high-density light such as is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) which is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, it is preferable to use a semiconductor laser in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

The silver halide color photographic light-sensitive material containing the silver halide emulsion of the present invention has an emission wavelength of 420 nm to 46 nm.
Imagewise exposure is preferably carried out with coherent light of a 0 nm blue laser. Among the blue lasers, it is particularly preferable to use a blue semiconductor laser. As a laser light source, specifically, a blue semiconductor laser having a wavelength of 430 to 450 nm (presented by Nichia at the 48th Joint Lecture Meeting on Applied Physics, March 2001) and a semiconductor laser (oscillation wavelength of about 940 nm) in a waveguide shape Wavelength conversion of about 470 nm blue laser and semiconductor laser (oscillation wavelength about 1060 nm) extracted by the LiNbO ₃ SHG crystal having the inversion domain structure of the above is converted by the LiNbO ₃ SHG crystal having the waveguide inversion domain structure. 530nm green laser, wavelength 685nm red semiconductor laser (Hitachi Type No. H
L6738MG), a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG), and the like are preferably used.

When using such a scanning exposure light source,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used.
A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal can halve the oscillation wavelength of the laser, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three wavelength regions of blue, green and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ⁻⁴ seconds or less, more preferably 10 ⁻⁶ seconds or less.

The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known materials. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, and JP-A-2000.
No. 10206, a photosensitive material conveying device, a recording system including the image reading device described in JP-A-11-215312, color images described in JP-A-11-88619 and JP-A-10-202950. Exposure system consisting of recording method, JP-A-10-210206
There is a digital photo printing system including a remote diagnosis system described in Japanese Patent Publication No.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. In the present invention, European patent EP 0789270A
As described in No. 1 specification and EP 0789480 A1 specification, a yellow microdot pattern may be pre-exposed and copy regulation may be applied in advance before image information is added.

Processing of the light-sensitive material of the present invention is described in JP-A-2-
207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 to page 18, lower right column, line 20. The treatment materials and treatment methods of are preferably applicable. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The silver halide light-sensitive material containing the silver halide emulsion of the present invention is preferably applied as a light-sensitive material having suitability for rapid processing. When rapid processing is carried out, the color development time is preferably 30 seconds or less, more preferably 25 seconds or less and 6 seconds or more, and still more preferably 20 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 30 seconds or less, more preferably 25 seconds or less and 6 seconds or more, more preferably 20 seconds or less.
Seconds or less and 6 seconds or more. Also, the washing or stabilization time is
It is preferably 60 seconds or less, more preferably 40 seconds or less and 6 seconds or more. The color developing time means the time from the time when the light-sensitive material enters the color developing solution to the time when it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic developing machine, etc., the time during which the photosensitive material is immersed in the color developing solution (so-called in-liquid time), and the photosensitive material leaves the color developing solution to bleach-fix in the next processing step. The total of the time during which the film is transported in the air toward the bath (so-called air time) is called the color development time. Similarly, the bleach-fixing time refers to the time from when the light-sensitive material enters the bleach-fixing solution until it enters the next washing or stabilizing bath. Also, with washing or stabilization time,
It refers to the time (so-called in-liquid time) during which the light-sensitive material is in the liquid for washing process after entering the washing or stabilizing liquid.

As a method of developing the light-sensitive material of the present invention after exposure, a conventional method of developing with a developer containing an alkali agent and a developing agent, or an alkaline solution containing a developing agent in the light-sensitive material and containing no developing agent is used. In addition to a wet method such as a method of developing with an activator solution such as, a heat development method without using a processing solution can be used. In particular, the activator method is a preferable method because the processing solution does not contain a developing agent, so that the processing solution can be easily managed and handled, and that the load at the time of processing the waste solution is small and the environment can be preserved. In the activator method, the developing agent or its precursor incorporated in the light-sensitive material is, for example, JP-A-8-2343.
88, 9-152686, 9-152.
693, 9-21118, 9-16
The hydrazine type compounds described in Japanese Patent No. 0193 are preferable.

Further, a developing method in which the amount of silver coated on the light-sensitive material is reduced and an image amplification process (enhancing process) using hydrogen peroxide is also preferably used. In particular, it is preferable to use this method as an activator method. Specifically, JP-A-8
Image forming methods using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152695 are preferably used. In the activator method, after the treatment with an activator solution, desilvering is usually carried out.However, in the image amplification processing method using a light-sensitive material having a low silver content, desilvering processing is omitted and washing or stabilization processing is simple. Can be done in any way. Further, in the method of reading image information from a light-sensitive material with a scanner or the like, even when a light-sensitive material having a high silver content such as a light-sensitive material for photographing is used,
A processing mode that does not require desilvering processing can be adopted.

As the activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the present invention, known materials can be used. Preferably, Research Disclosure Item 3654
4 (September 1994) pp. 536 to 541, JP-A-8-234388 can be used.

[0122]

[Example] Example 1 "Emulsion 1-1; Preparation of silver chloride cube sample (1)" (comparison
Example) 1,000 mL of 3% aqueous solution of lime-treated gelatin was added to give a pH of 5.
5, adjusted to pCl 1.7 and containing 2.12 mol of silver nitrate.
Water solution and an aqueous solution containing 2.2 mol of sodium chloride.
The mixture was simultaneously added and mixed at 66 ° C. with vigorous stirring. silver nitrate
Bromide from 80% to 90%
2 moles of potassium per mole of finished silver halide
The amount of 1% is added with vigorous mixing. Of silver nitrate
When the addition is 90% complete, the potassium iodide aqueous solution is discharged.
The amount of I is 0.2 mol per mol of upcoming silver halide.
% Amounts were added with vigorous mixing. Remove at 40 ° C
After salt treatment, 168 g of lime-treated gelatin was added,
The pH was adjusted to 5.5 and pCl 1.8. Obtained grain
Cubic iodine with a spherical equivalent diameter of 0.75 μm and a coefficient of variation of 11%
It was a silver bromochloride emulsion. Melt this emulsion at 40 ° C and
Sodium Osulfonate per mol of silver halide
2 x 10^-FiveMolar added, sodium thiosulfate as sulfur sensitizer
Lithium pentahydrate and gold tetrafluoroborate (I) as a gold sensitizer
Bis (1,4,5-trimethyl-1,2,4-triazo
Optimized at 60 ° C with (3-3-thiolate)
So matured. After cooling to 40 ° C, sensitizing dye A was halogenated.
2 x 10 per mol of silver halide^-FourMole and sensitizing dye B are halo
1 x 10 per mole of silver genide^-FourMole, 1-phenyl-
Warm 5-mercaptotetrazole to 1 mol of silver halide
2 x 10^-FourMolar, 1- (5-methylureidopheni
Ru) -5-mercaptotetrazole to silver halide
2 × 10 per le^-FourMol, potassium bromide to silver halide
2 x 10 per mole ^-3Mol added. In this way
The obtained emulsion was designated as emulsion 1-1.

[0123]

[Chemical 8]

[0124]; the "Emulsion 1-2 [IrCl _6] ^3- Preparation of doped silver cubic samples chloride" (Comparative Example) 92% to 98% of the layer hexachloroiridate from particles central portion in particle volume, the total added 2 × 10 for silver
Emulsion 1-2 was prepared in the same manner as Emulsion 1-1 except that ^-8 mol was added.

"Emulsion 1-3; [IrCl ₅ (thi
a)] ^Preparation of ^2- doped silver chloride cube sample "(comparative example) Pentachloro (thiazole) iridium in a layer of 92 to 98% from the central portion of the grain in a volume of 3 x relative to the total amount of silver added. Emulsion 1-except that 10 ^-7 mol was added
Emulsion 1-3 was prepared in the same manner as 1.

"Emulsion 1-4; [IrCl ₅ (thiou
REA)] ^{2-Preparation} of ^2- doped silver chloride cubic sample "
(Comparative Example) pentachloro a layer of 92% to 98% of the (thiourea) iridium from particles central portion in particle volume, the added total silver amount to the 6 × 10 - ⁷ mol added with it except emulsions 1-1
Emulsion 1-4 was prepared in the same manner as in.

"Emulsion 1-5; [IrCl ₅ (S-Me-
Preparation of silver chloride cube sample doped with ^2- "(invention) Pentachloro (S-methylthiourea) iridium was added to a layer of 92 to 98% from the central part of the particle in terms of particle volume with respect to the total amount of silver added. was an emulsion 1-5 in the same manner as emulsion 1-1 ⁷ except that the molar added - 6 × 10 Te.

[Emulsions 1-6, 1-7; [IrCl ₅ (S
= P (NH ₂ ) ₂ (OH)) ²⁻ , [IrCl ₅ (2,5
_{- (CH 3) 2 -thiadiazole)} ] 2- Preparation of doped silver cubic samples chloride "(present invention) pentachloro (diamino hydroxy thio phosphonic acid) iridium or pentachloro (2,5-dimethyl-1,
3,4 thiadiazole) layer of 92% to 98% from the particle center portion iridium in grain volume, 1 × 10 based on total silver added - ⁶ mol except for adding Emulsions 1-1 Emulsions 1-6 and 1-7 were similarly prepared.

[Emulsions 1-8, 1-9; [IrCl ₅ (5
-Cl-thiatriazole)] ^2- , [IrCl
₅ (2-Cl-5-CH ₃ -thiadiazole)]
^Preparation of ^2- Doped Silver Chloride Cube Samples "(Invention) Pentachloro (5-chloro-1,2,3,4-thiatriazole) iridium or pentachloro (2-chloro-5-methyl-1,3,4) -Thiadiazole) iridium in a layer of 92-98% from the central part of the particle by particle volume,
Emulsions 1-8 and 1-9 were prepared in the same manner as Emulsion 1-1 except that 3 × 10 ^-7 mol was added to the total amount of silver added.

[Emulsions 1-10, 1-11; [IrCl ₅
(2-Cl-5-F-thiadiazole)] ^2- ,
[IrCl ₅ (2-Br-5-F-thiadiazo
le)] ^{2-Preparation} of ^2- doped silver chloride cube samples "(invention) Pentachloro (2-chloro-5-fluoro-1,3,4)
-Thiadiazole) iridium or pentachloro (2
-Bromo-5-fluoro-1,3,4-thiadiazole) iridium in a volume of 92 to 9 from the center of the particle.
8% 6 × the total amount of silver was added to a layer 10 - ^7, except that the addition of molar exactly as Emulsion 1-1 Emulsion 1-1
0, 1-11 were prepared.

Corona discharge treatment was applied to the surface of a support having both sides of paper coated with polyethylene resin, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Samples (101) of a silver halide color photographic light-sensitive material having the layer structure shown below were prepared by sequentially coating the above photographic constituent layers. The coating liquid for each photographic constituent layer was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 57 g, color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
21 g of solvent (Solv-1) and 80 m of ethyl acetate
22 g of a 23.5% by mass gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate.
Emulsified and dispersed in 0 g by a high-speed stirring emulsifying machine (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion 1-1 were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used as a gelatin hardening agent for each layer. Further, Ab-1, Ab-2, Ab-3, and Ab-4 were added to each layer in a total amount of 15.0 mg / m ² , 60.
0 mg / m ² , 5.0 mg / m ² and 10.0 mg / m
^It was added to be ² .

[0134]

[Chemical 9]

[0135]

[Chemical 10]

The silver chlorobromide emulsions of the green and red sensitive emulsion layers include
The following spectral sensitizing dyes were used respectively. Green sensitive emulsion layer

[0137]

[Chemical 11]

(The sensitizing dye D was added per mol of silver halide:
3.0 x 10 for large emulsions ^-FourMole, small size
3.6 × 10 for emulsions^-FourMolar and sensitizing dye E
Per mole of silver halide for large size emulsions
4.0 x 10^-Five7.0 × for moles, small size emulsions
10^-Five1 mole of sensitizing dye F to 1 mole of silver halide
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for Izu emulsion^-FourMol added. ) Red-sensitive emulsion layer

[0139]

[Chemical 12]

(Sensitizing dyes G and H, respectively, per mol of silver halide, 8.0 × 1 for a large-sized emulsion)
0 ^-5 mol, and 10.7 × 10 ^-5 mol was added to the small size emulsion. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide. )

[0141]

[Chemical 13]

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 1.0 × 10 ^-3 mol and 5 mol per mol of silver halide, respectively. 0.9 × 10 ⁻⁴ mol was added. Further, the second layer, the fourth layer, the sixth layer, and the seventh layer also have 0.2 mg / m ² , 0.2 mg / m ² , and
The amount added was 0.6 mg / m ² and 0.1 mg / m ² .

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7 was used.
-Tetrazaindene was added in an amount of 1 x 10 ^-4 mol and 2 x 10 ^-4 mol per mol of silver halide, respectively.

In the red-sensitive emulsion layer, 0.05 g / copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000-400000) was used.
m ² was added.

Also, 6% of catechol-3,5-disulfonic acid disodium was added to each of the second, fourth and sixth layers.
It was added so as to have mg / m ² , 6 mg / m ² , and 18 mg / m ² .

Further, in order to prevent irradiation, the following dyes (the amount in parentheses represents the coating amount) were added.

[0147]

[Chemical 14]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support Polyethylene resin laminated paper [the first layer side contained a white pigment polyethylene resin (TiO _2; content 16 wt%, Z nO; content of 4 mass%) and a fluorescent brightener (4,4 ^'- bis (5 -Methylbenzoxazolyl) stilbene, content 0.03% by mass, containing bluing dye (ultraviolet)] First layer (blue-sensitive emulsion layer) Emulsion 1-1 0.24 Gelatin 1.25 Yellow coupler ( ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

[0149]   Second layer (color mixing prevention layer)     Gelatin 0.99     Color mixing inhibitor (Cpd-4) 0.09     Color image stabilizer (Cpd-5) 0.018     Color image stabilizer (Cpd-6) 0.13     Color image stabilizer (Cpd-7) 0.01     Solvent (Solv-1) 0.06     Solvent (Solv-2) 0.22

[0150]   Third layer (green sensitive emulsion layer)   Silver chlorobromide emulsion Em-1 (gold sulfur sensitized cube, average grain size 0.45μ m large size emulsion and 0.35 μm small size emulsion 1: 3 mixture (silver molar ratio) . Coefficients of variation of particle size distribution are 0.10 and 0.08, respectively. With each size emulsion It contains 0.15 mol% of silver iodide near the surface of the grain and 0.4 mol% of silver bromide on the surface of the grain. Localized in)                                                         0.14     Gelatin 1.36     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.14     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-4) 0.002     Color image stabilizer (Cpd-6) 0.09     Color image stabilizer (Cpd-8) 0.02     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.11     Solvent (Solv-4) 0.22     Solvent (Solv-5) 0.20

[0151]   Fourth layer (color mixing prevention layer)     Gelatin 0.71     Color mixing prevention layer (Cpd-4) 0.06     Color image stabilizer (Cpd-5) 0.013     Color image stabilizer (Cpd-6) 0.10     Color image stabilizer (Cpd-7) 0.007     Solvent (Solv-1) 0.04     Solvent (Solv-2) 0.16

[0152]   Fifth layer (red sensitive emulsion layer)   Silver chlorobromide emulsion Em-2 (cubic sensitized with gold and sulfur, average grain size 0.40μ 5: 5 mixture of a large size emulsion of m and a small size emulsion of 0.30 μm (silver molar ratio) . Coefficients of variation of particle size distribution are 0.09 and 0.11. With each size emulsion Each size emulsion contains 0.1 mol% of silver iodide in the vicinity of the grain surface. % Was localized on the particle surface)                                                           0.12     Gelatin 1.11.     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-1) 0.05     Color image stabilizer (Cpd-6) 0.06     Color image stabilizer (Cpd-7) 0.02     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-14) 0.01     Color image stabilizer (Cpd-15) 0.12     Color image stabilizer (Cpd-16) 0.03     Color image stabilizer (Cpd-17) 0.09     Color image stabilizer (Cpd-18) 0.07     Solvent (Solv-5) 0.15     Solvent (Solv-8) 0.05

[0153] Sixth layer (UV absorption layer)     Gelatin 0.46     UV absorber (UV-B) 0.45     Compound (S1-4) 0.0015     Solvent (Solv-7) 0.25 Seventh layer (protective layer)     Gelatin 1.00     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.02     Surfactant (Cpd-13) 0.01

[0154]

[Chemical 15]

[0155]

[Chemical 16]

[0156]

[Chemical 17]

[0157]

[Chemical 18]

[0158]

[Chemical 19]

[0159]

[Chemical 20]

[0160]

[Chemical 21]

[0161]

[Chemical formula 22]

[0162]

[Chemical formula 23]

[0163]

[Chemical formula 24]

Similarly, the emulsion 1-1 of the sample (101) was changed to the emulsions 1-2 to 1-11, and the samples (102) to (11) were changed.
1) was produced.

The following experiments were conducted to investigate the photographic characteristics of these samples.

Experiment 1: Sensitometry Each coated sample was subjected to gradation exposure for sensitometry using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.). An SP-1 filter was attached and exposure was performed for 10 seconds at low illuminance.

Further, a high-illuminance exposure sensitometer (HIE type manufactured by Yamashita Denso Co., Ltd.) was used to give gradation exposure for sensitometry. An SP-1 filter was attached and exposed to high illuminance for 10 ^-4 seconds. After the exposure, color development processing A shown below was performed.

The processing steps are shown below. [Processing A] The light-sensitive material 101 was processed into a roll having a width of 127 mm, imagewise exposed using a mini-lab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., and then double the color developing tank capacity in the following processing step. Until then, continuous treatment (running test) was performed. The treatment using this running liquid was designated as treatment A. Treatment process Temperature Time Replenishment amount * Color development 38.5 ° C 45 seconds 45mL Bleach fixing 38.0 ° C 45 seconds 35mL Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds-Rinse (3) ** 38.0 ° C 20 seconds-rinse (4) ** 38.0 ° C 30 seconds 121 mL * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. (3) The rinse liquid is taken out from the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the same tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and temperature control circulation was performed for 10 hours a day. (Rinsing was performed from the tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank liquid] [Replenisher]         Water 800mL 800mL Dimethylpolysiloxane surfactant (Silicone KF351A / Shin-Etsu Chemical Co., Ltd. Manufactured by the company) 0.1 g 0.1 g Tri (isopropanol) amine 8.8 g 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 0.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate                                           0.5 g 0.5 g Potassium chloride 10.0 g- Potassium bromide 0.040 g 0.010 g Triazinyl amino stilbene-based optical brightener (HAKCOL FWA-SF / Showa Kaika Gakusha) 2.5 g 5.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                           8.5 g 1.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-ami No-4-aminoaniline / 3/2 sulfuric acid monohydrate                                           5.0 g 15.7 g Potassium carbonate 26.3 g 26.3 g Add water 1000 mL 1000 mL pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid)                                         10.15 12.50

[0170] [Bleach fixer] [Tank solution] [Replenisher]       Water 700 mL 600 mL Ethylenediaminetetraacetate Iron (III) ammonium                                         47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4 g 2.8 g m-carboxybenzene fulphinic acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / l)                                   107.0 mL 214.0 mL Ammonium sulfite 16.0 g 32.0 g Ammonium bisulfite 23.1 g 46.2 g Add water 1000 mL 1000 mL pH (25 ° C / adjusted with acetic acid and ammonia) 6.0 6.0

[0171]         [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02 g 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 mL 1000 mL pH 6.5 6.5

Samples (101) to (1
For 11), the yellow color density was measured. Fog is determined by the minimum color density of the sample, and sensitivity is defined as the reciprocal of the exposure amount required to obtain a color density of fog +1.0.
It was expressed as a relative value when the development-processed sensitivity of the sample (101) was set to 100. Table 2 shows the relative sensitivity of each sample.

[0173]

[Table 2]

It can be seen from Table 2 that the emulsion using the dopant of the present invention has less desensitization after exposure for 10 seconds than the emulsion using the known dopant, and is an emulsion excellent in high illuminance reciprocity law characteristics.

Example 2 "Emulsion 2-1; Preparation of Silver Iodobromochloride Cubic Sample" (Comparative Example) 1000 mL of a 3% aqueous solution of lime-processed gelatin was added to give a pH of 5.
5, pCl was adjusted to 11.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were added and mixed at 45 ° C. at the same time with vigorous stirring. From the time of addition of silver nitrate of 80% to the time of 100%,
Potassium bromide was added with vigorous mixing in an amount of 4.3 mol% per mol of finished silver halide.
From the time when the addition of silver nitrate was 80% to the time when it was 90%, an aqueous K ₄ [Ru (CN) ₆ ] solution was added in such an amount that the amount of Ru was 3 × 10 ^-5 mol per mol of the finished silver halide. Further, when the addition of 90% of silver nitrate was completed, the potassium iodide aqueous solution was added to the finished silver halide 1
An amount of 0.15 mol% per mol I was added with vigorous mixing. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to pH 5.5, pCl 1
Adjusted to 1.8. The obtained particles have an equivalent spherical diameter of 0.35μ.
m was a cubic silver chloride emulsion having a coefficient of variation of 10%. This emulsion was dissolved at 40 ° C., sodium thiosulfonate was added at 2 × 10 ⁻⁵ mol per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S- It was aged at 60 ° C. using 2) so as to be optimum. After cooling to 40 ° C., the sensitizing dye D was 6 × 10 ⁻⁴ mol per mol of silver halide and the 1-phenyl-5-mercaptotetrazole was 2 × 10 ⁻⁴ per mol of silver halide.
8 × 1 mol of 1- (5-methylureidophenyl) -5-mercaptotetrazole per mol of silver halide
0 ^-4 mol, potassium bromide 7 per mol of silver halide
× 10 ⁻³ mol was added. The emulsion thus obtained was designated as emulsion 2-1.

"Emulsion 2-2; [IrCl ₅ (H ₂ O)]
^2- Preparation of Cubic Sample of Silver Iodobromide Chloride Doped ”(Comparative Example) K ₂ [IrCl ₅ (H ₂ O)] Against 5
Emulsion 2-2 was prepared in the same manner as emulsion 2-1 except that x10 ^-7 mol was added.

"Emulsion 2-3; Preparation of Silver Iodobromochloride Cubic Sample Doped with [IrCl ₆ ] ^3- " (Comparative Example) K ₂ [IrCl ₆ ] in terms of grain volume from the grain central portion to 83
~ 88% of the total silver added to the emulsion in layers of 5 x 10
Emulsion 2-3 was prepared in the same manner as Emulsion 2-2 except that ^-8 mol was added.

[Emulsion 2-4; [IrCl ₅ (thi
a)] ^Preparation of ^2- doped silver iodobromochloride cubic sample "
(Comparative Example) Emulsion 2-3 similar to Emulsion 2-3 except that 6 × 10 ⁻⁷ mol was added to the total amount of silver in which pentachloro (thiazole) iridium was added in place of K ₂ [IrCl ₆ ].
4 was prepared.

"Emulsion 2-5; [IrCl ₅ (thiou
rea)] ^2-doped prepared iodobromide cubic silver sample chloride "(Comparative Example) K ₂ [1 × the total amount of silver added pentachloro (S- methylthiourea) iridium instead of IrCl _6] 1
Except for 0 ^-6 mol per mol of the possible in the same manner as Emulsion 2-3 was prepared emulsions 2-5.

[Emulsion 2-6; [IrCl ₅ (S-Me-
Preparation of Silver Iodobromochloride Cubic Samples Doped with ^2-. (Invention) K ₂ [IrCl ₆ ] was replaced by pentachloro (S-methylthiourea) iridium and the total silver amount was 1 × 1.
Except for 0 ^-6 mol per mol of the possible in the same manner as Emulsion 2-3 was prepared emulsions 2-6.

[Emulsion 2-7; [IrCl ₅ (2,5-
_{(CH 3) 2 -thiadiazole)]} 2- Preparation of Doped iodobromide silver cubic samples chloride "(present invention) K ₂ [instead of IrCl _6] pentachloro (diamino hydroxy thio phosphonic acid) iridium or pentachloro (2, 5-dimethyl-1,3,4-thiadiazole)
Emulsion 2-7 was prepared in the same manner as Emulsion 2-3, except that 2 × 10 ⁻⁶ mol was added to the total amount of iridium added.

[Emulsions 2-8, 2-9; [IrCl ₅ (5
-Cl-thiatriazole)] ^2- , [IrCl
₅ (2-Cl-5-CH ₃ -thiadiazol
e)] ^{2-Preparation} of ^2- doped silver iodobromochloride cubic sample "
(Invention) Pentachloro (5-chloro-1,2,3,4-thiatriazole) iridium or pentachloro (2-methyl-5-chloro-1,3,4) in place of K ₂ [IrCl ₆ ].
Emulsions 2-8 and 2-9 were prepared in the same manner as Emulsion 2-3, except that 6 × 10 ⁻⁷ mol was added to the total amount of silver containing (thiadiazole) iridium.

[Emulsions 2-10, 2-11; [IrCl ₅
(2-Cl-5-F-thiadiazole)] ^2- ,
[IrCl ₅ (2-Br-5-F-thiadiazo
le)] ² -doped silver iodobromochloride cubic sample preparation "
(Invention) Pentachloro (2-chloro-5-fluoro-1,3,4-thiadiazole) iridium or pentachloro (2-bromo-5-fluoro-) in place of K ₂ [IrCl ₆ ].
Emulsions 2-10 and 2-11 were prepared in the same manner as emulsion 2-3 except that 1 × 10 ^-6 mol was added to the total amount of silver to which 1,3,4-thiadiazole) iridium was added.

With the completely same layer structure as in Example 1, the emulsion of the third layer was replaced with emulsions 2-1 to 2-11, and the sample (20
1)-(211) were produced. Example 1 for this sample
And the following Experiment 2 was performed

Experiment 2 Latent Image Stability after Exposure For each sample, sensitometry was measured by changing the time from 1/10 second exposure to the treatment A, and the sensitometry was measured after 7 seconds. The sensitivity and the difference in sensitivity when the treatment was applied after 30 minutes were obtained.

The results of these two experiments are shown in Table 3.

[0187]

[Table 3]

The emulsion of the present invention does not cause high illuminance failure between exposure for 10 seconds and exposure for 10 ^-4 seconds, and gives the same sensitivity stably even when the time from exposure to processing is different (latent image stability). It is understood that it is excellent).

Example 3 Samples (301) to (311) were obtained by preparing thin samples by changing the layer structure of each sample of Example 2 as follows. Experiment 1 of Example 1 and Experiment 2 of Example 2 were performed on this sample.
As a result, similar to the result of Example 2, the effect of the present invention was recognized even in the ultra-rapid treatment of the thinned sample, and a good result was obtained. The layer structure is shown in Sample (301), but Samples (302) to (311) are emulsion 2-of Sample (301).
1 was changed to emulsions 2-2 to 2-11.

[0190]   Preparation of sample 301 First layer (blue sensitive emulsion layer)     Emulsion 1-1 0.24     Gelatin 1.25     Yellow coupler (ExY) 0.57     Color image stabilizer (Cpd-1) 0.07     Color image stabilizer (Cpd-2) 0.04     Color image stabilizer (Cpd-3) 0.07     Color image stabilizer (Cpd-8) 0.02     Solvent (Solv-1) 0.21

[0191]   Second layer (color mixing prevention layer)     Gelatin 0.60     Color mixing inhibitor (Cpd-19) 0.09     Color image stabilizer (Cpd-5) 0.007     Color image stabilizer (Cpd-7) 0.007     UV absorber (UV-C) 0.05     Solvent (Solv-5) 0.11

[0192]   Third layer (green sensitive emulsion layer)     Emulsion 2-1 0.14     Gelatin 0.73     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.05     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-7) 0.008     Color image stabilizer (Cpd-8) 0.07     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.009     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.06     Solvent (Solv-4) 0.11     Solvent (Solv-5) 0.06

[0193]   Fourth layer (color mixing prevention layer)     Gelatin 0.48     Color mixing prevention layer (Cpd-4) 0.07     Color image stabilizer (Cpd-5) 0.006     Color image stabilizer (Cpd-7) 0.006     Ultraviolet absorber (UV-C) 0.04     Solvent (Solv-5) 0.09

[0194]   Fifth layer (red sensitive emulsion layer)     Emulsion 2-1 0.12     Gelatin 0.59     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-7) 0.01     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-15) 0.19     Color image stabilizer (Cpd-18) 0.04     Ultraviolet absorber (UV-7) 0.02     Solvent (Solv-5) 0.09

[0195]   Sixth layer (UV absorption layer)     Gelatin 0.32     Ultraviolet absorber (UV-C) 0.42     Solvent (Solv-7) 0.08   Seventh layer (protective layer)     Gelatin 0.70   Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.01     Surfactant (Cpd-13) 0.01     Polydimethylsiloxane 0.01     Silicon dioxide 0.003

Each of the produced samples was exposed in the same manner as in Experiment 1 of Example 1, and the color developing treatment was performed by the developing treatment B shown below.
Ultra-quick treatment was carried out according to.

[Process B] The above-mentioned photosensitive material was processed into a roll having a width of 127 mm, and the processing time and the processing temperature were changed by using an experimental processor in which a mini-lab printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. was modified. Imagewise exposure is performed on a photosensitive material sample from a negative film having an average density, and continuous processing (running test) is carried out until the capacity of the color developing replenisher used in the following processing steps becomes 0.5 times the capacity of the color developing tank. It was

Processing Step Temperature Time Replenishment Amount Color Development 45.0 ° C. 15 seconds 45 mL Bleach-fix 40.0 ° C. 15 seconds 35 mL Rinse 1 40.0 ° C. 8 seconds − Rinse 2 40.0 ° C. 8 seconds − Rinse 3 40.0 ° C. 8 seconds - mounted on rinse 4 38.0 ° C. 8 seconds 121mL dried 80 ° C. 15 seconds (Note) * the replenishing amount per photosensitive material 1 m ² ** manufactured by Fuji Photo Film Co., Ltd. rinse cleaning system RC50D rinsing (3) Then, the rinse liquid is taken out from the rinse (3) and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the same tank is supplied to the rinse (4), and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinse was a 4-tank countercurrent system from (1) to (4).

The composition of each processing solution is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800mL 600mL Optical brightener (FL-1) 5.0 g 8.5 g Triisopropanolamine 8.8g 8.8g Sodium p-toluenesulfonate 20.0 g 20.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10g 0.50g Potassium chloride 10.0g- 4,5-dihydroxybenzene- Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate Ethyl) hydroxylamine 8.5 g 14.5 g 4-amino-3-methyl-N-ethyl-N- (Β-methanesulfonamidoethyl) aniline ・ 3/2 Sulfate ・ Monohydrate 10.0g 22.0g Potassium carbonate 26.3g 26.3g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.35 12.6

[0200] [Bleach fixer] [Tank solution] [Replenisher] Water 800mL 800mL Ammonium thiosulfate (750 g / mL) 107 mL 214 mL Succinic acid 29.5g 59.0g Ethylenediaminetetraammonium iron (III) acetate                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 17.5g 35.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with nitric acid and aqueous ammonia) 6.00 6.00

[0201] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μs / cm or less) 1000mL 1000mL pH (25 ° C) 6.5 6.5

[0202]

[Chemical 25]

Example 4 Using Samples (301) to (311), image formation was performed by laser scanning exposure. As a laser light source,
Semiconductor laser GaAlAs (oscillation wavelength 808.5n
YAG solid-state laser (oscillation wavelength)
LiNbO ₃ having an inverted domain structure of 946 nm)
473nm wavelength converted by SHG crystal of
And semiconductor laser GaAlAs (oscillation wavelength 808.
YVO ₄ solid-state laser (oscillation wavelength 1064 nm) with an excitation light source of 7 nm) is used as Li having an inversion domain structure.
Extracted after wavelength conversion by SHG crystal of NbO ₃ 5
32 nm and AlGaInP (oscillation wavelength about 680 n
m: Type No. manufactured by Matsushita Electric Industrial Co., Ltd. LN9R20) was used. The laser light of each of the three colors was moved in a direction perpendicular to the scanning direction by a polygon mirror so that the sample could be sequentially scanned and exposed. Fluctuations in the amount of light due to the temperature of the semiconductor laser are suppressed by using a Peltier device to keep the temperature constant. Effective beam diameter is 8
0 μm, scanning pitch is 42.3 μm (600 dpi)
And the average exposure time per pixel is 1.7 × 10
^-7 seconds.

After exposure, color development processing B was carried out. As a result, the sample of the present invention showed higher sensitivity than that of the comparative sample, and laser scanning exposure was used. It was found that it was also suitable for image formation.

[0205]

INDUSTRIAL APPLICABILITY In the present invention, by using a bulky ligand in the axial direction of the complex as the ligand of the metal complex, reciprocity law failure is improved over a wide exposure illuminance without desensitization or softening. However, it was possible to obtain an emulsion which did not deteriorate the latent image storability.

Continued front page    (72) Inventor Yu Takasaki             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. (72) Inventor Tadashi Inaba             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F-term (reference) 2H023 BA00 BA01 BA02

Claims (8)

[Claims] 1. At least one metal having a site capable of forming a bond of any one of a covalent bond, a donor bond, an ionic bond or a mixture of these bonds with respect to an ion in a ligand. A photosensitive silver halide grain containing a complex, wherein the a-axis, b-axis and c-axis of the silver halide crystal lattice are set with the central metal of the metal complex incorporated in the silver halide grain as the origin. The photosensitive silver halide is characterized in that the site in the ligand is capable of interacting with silver ions on lattice points that are not on the a-axis, b-axis or c-axis. particle. 2. The atom in the ligand, wherein the ligand has a volume of 220% or more and 300% or less with respect to the volume of chloride ion Cl ⁻ and is coordinated to the central metal of the metal complex. The photosensitive silver halide grain according to claim 1, wherein the distance to the atom in the ligand which is the farthest from is a ligand of 5.1Å or less. 3. The interactable site in the ligand is a
The photosensitive halogenide according to claim 1 or 2, which is at a distance of 2.5Å to 4.0Å with respect to silver ions on a lattice point which is not on any of the axes b, c and c. Silver particles. 4. The silver complex is incorporated into the silver halide grains.
The ionic conductivity of the silver halide grain when 1 × 10 ^-4 mol is incorporated per mol is 50 times the ionic conductivity of the grain in which no metal ion or metal complex is incorporated in the silver halide grain. The photosensitive silver halide grains according to any one of claims 1 to 3, wherein: 5. The sustained electron release time of the silver halide grains is 5
The photosensitive silver halide grain according to any one of claims 1 to 4, wherein the photosensitive silver halide grain is less than or equal to a second. 6. The photosensitive silver halide grain according to claim 1, wherein the ligand is an organic compound or an inorganic compound having 3 or less carbon atoms. 7. The photosensitive silver halide grain according to claim 1, wherein said silver halide grain contains silver chloride as a main component. 8. A silver halide emulsion containing the photosensitive silver halide grains according to claim 1.