JP2002244239A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity, rapid processability and improved preservability. SOLUTION: In the silver halide photographic sensitive material having at least one photosensitive layer on the base, the photosensitive layer contains a silver halide emulsion containing a compound of the formula (X)k-(L)m-(A- B)n and silver halide grains containing >=90 mol% silver chloride. Flat platy grains having an average aspect ratio of >=5 and <=0.20 μm average thickness occupy >=90% of the total projected area of the silver halide grains. In the formula, X is a silver halide adsorption group or a light absorbing group having at least one atom selected from N, S, P, Se and Te; L is a divalent linking group having at least one atom selected from C, N, S and O; A is an electron donative group; B is a releasable group or H and forms a radical A* when released or deprotonated after oxidation; (k) and (m) are each an integer of 0-3; and (n) is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to tabular silver chloride or silver chlorobromide, silver chloroiodide or silver chloroiodobromide grains having a high silver chloride content. The present invention relates to a silver halide photographic light-sensitive material containing a silver halide emulsion containing

[0002]

2. Description of the Related Art For the purpose of simple and rapid development processing, so-called high silver chloride grains having a high silver chloride content (a silver chloride content of 9%).
Various techniques have been proposed for utilizing grains of 0 mol% or more (hereinafter referred to as high silver chloride grains). By using high silver chloride particles, advantages such as an increase in development speed and an increase in reusability of the processing solution can be obtained. For this reason, the type of photosensitive material for printing such as color photographic paper, which uses high silver chloride particles, has become the mainstream.

[0003] Under normal production conditions, high silver chloride grains cost $ 10.
Particles having a main plane of 0 ° plane (hereinafter referred to as {100} particles) were also cubic particles that have been used practically. In recent years, specific surface area (ratio of surface area to volume)
Tabular {100} grains have been developed, which have advantages such as large spectral sensitization, and large covering power after development.
Examples are U.S. Patent Nos. 5,320,938 and 5,26.
No. 4,337, 5,292,632 and the like. High spectral sensitization efficiency is particularly important for high silver chloride grains whose light absorption in the blue-sensitive region is small compared to silver iodobromide grains.

However, high silver chloride {100} grains have a problem that they are more easily fogged than ordinary silver bromide grains. In order to overcome this problem, grains of high silver chloride having a {111} plane as a main plane (hereinafter referred to as {111} grains) have been used. This example is disclosed in JP-A-6-138819.

[0005] Special measures are required to produce {111} grains with high silver chloride. Wey is U.S. Pat.
No. 399,215 discloses a method for producing high silver chloride tabular grains using ammonia. When ammonia is used, silver chloride particles having high solubility are produced with higher solubility, and it has been difficult to produce practically useful small-sized particles. In addition, there was a disadvantage that the pH at the time of production was as high as 8 to 10 and fogging easily occurred.
Maskasky in U.S. Pat. No. 5,061,617 discloses high silver chloride {111} grains made using thiocyanate. Thiocyanate, like ammonia, increases the solubility of silver chloride.

In addition, there is known a method of using an additive (crystal phase controlling agent) at the time of grain formation in order to form high silver chloride grains having a {111} plane as a main plane. It is shown below.

Patent No. Crystal habit control agent Inventor US 4,400,463 Azaindenes + Mascasky thioether peptizer US 4,783,398 2-4-Dithiazolidinone Mifune US4,713,323 Aminopyrazolopyrimidine Mascasky US4 983,508 Bispyridinium salt Ishiguro US5,185,239 Triaminopyrimidine Mascasky US5,178,997 7-Azaindole-based compound Masukasky US5,178,998 Xanthine Maskasky JP-A 64-70741 Dye Nishikawa et al 3-212639 Aminothioether Ishiguro JP-A-4-283742 Thiourea derivative Ishiguro JP-A-4-335632 Triazolium salt Ishiguro JP-A-2-32 Bispyridinium salt Ishiguro etc. JP-A-8-227117 Monopyridinium Salt Ozeki and the like.

As a result, particles having a relatively large size and an average equivalent circle diameter (average equivalent circle diameter of the projected area) of about 1 μm can be obtained. However, practically, tabular grains having a high silver chloride and a smaller size and a smaller thickness have been desired. In particular, thin tabular grains having a large specific surface area have been desired. Examples of thin high silver chloride {111} tabular grains are disclosed in U.S. Pat. Nos. 5,217,858 and 5,183,732. However, when the thickness of the tabular grains is reduced, there arises a problem that the grains are easily dissolved during the processing. In actual color processing, the light-sensitive material passes through a developer → fixing / bleaching liquid → wash water.
For this reason, there is a high risk that the fixing / bleaching solution is mixed into the developing solution. As a result, physical dissolution occurs and the photographic properties are impaired (sensitization and high contrast). This phenomenon is also promoted by a reduction in particle size.

Further, when the distribution of the particle thickness and the size is large (polydispersion), particles occupying a thin portion in the distribution and particles in a small size portion are particularly easily dissolved, which causes a problem that the stability of the processing solution is low. Although the above-mentioned patent discloses tabular grains having an average equivalent circle diameter of 0.8 μm or less, the proportion of the tabular grains in the total projected area was 85%. In the case of grains containing silver iodide, the ratio was 70%. When grains having different grain morphologies are mixed, sensitizing dye adsorption or chemical sensitization causes non-uniformity among grains, which causes a problem of deteriorating photographic characteristics. Regarding the above-mentioned problems relating to the tabular grains in the small size region, it can be improved by forming monodisperse tabular grains having a thickness and a circle-equivalent diameter.
-171928.

[0010] Also, recently, US Pat.
35, 5747236, European Patent No. 786,692A
A sensitizing technique using an organic electron-donating compound comprising an electron-donating group and a leaving group as described in JP-A Nos. 1,893731A1, 893732A1, and WO99 / 05570 has been reported. This is an effective sensitization technique.

On the other hand, photosensitive materials using silver halide grains are frequently used after being stored for a long period of time after production. Therefore, there is a demand for a photosensitive material which does not change its performance when used immediately after production and when used after long-term storage. In particular, fluctuations in sensitivity during storage impair the commercial value, and improvements have been desired.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having high sensitivity, rapid processing, and improved storage stability.

[0013]

The object of the present invention has been attained by the following method. 1. In a silver halide photographic light-sensitive material having at least one light-sensitive layer on a support, the light-sensitive layer contains silver halide grains containing a compound of the following general formula (I) and at least 90 mol% or more of silver chloride. A silver halide photographic material comprising a silver halide emulsion containing tabular grains having an average aspect ratio of 5 or more and an average thickness of 0.20 μm or less, wherein 90% or more of the total projected area of the grains is contained. .

In the general formula (I) (X) _k- (L) _m- (AB) _n , X represents at least one atom selected from the group consisting of N, S, P, Se and Te. Represents a silver halide adsorption group or a light absorption group. L is C, N, S and O
Represents a divalent linking group having at least one atom selected from the group consisting of A represents an electron donating group, B represents a leaving group or a hydrogen atom, after oxidation, is disengaged or deprotonated to generate a radical A ^· in. k and m each independently represent an integer of 0 to 3, and n represents 1 or 2.

2. The coefficient of variation of the thickness of the tabular grains is 20.
% Or less, the silver halide photographic light-sensitive material as described in 1 above,

3. 3. The silver halide photographic material as described in 1 or 2 above, wherein the coefficient of variation of the circle equivalent diameter of the tabular grains is 22% or less.

4. 4. The silver halide photographic material as described in 1, 2, or 3, wherein the tabular grains have a {111} main plane.

5. 5. The silver halide photographic material as described in any one of items 1 to 4, wherein the silver halide grains contain silver iodide in an amount of 0.1 mol% to 0.8 mol% based on silver.

6. The silver halide photographic material as described in any one of the above items 1 to 5, wherein the silver halide grains contain silver bromide in an amount of 0.1 mol% to 4 mol% based on silver.

[7] FIG. 7. The silver halide photograph as described in any one of the above items 1 to 6, wherein the silver halide grains are composed of a core and a shell, and the silver iodide content of the shell part is 1 to 13 mol%. Photosensitive material.

8. 8. The silver halide photographic material as described in any one of the above items 1 to 7, wherein the silver halide grains contain a silver bromide localized phase having a silver bromide concentration of 6 mol% or more.

9. The halogen according to the above item ⁸ , wherein the silver bromide localized phase contains 1 × 10 ⁻⁸ mol% to 1 × 10 ⁻⁵ mol% of an Ir compound based on the total silver content of the grains. Silver halide photographic material.

10. The silver halide photographic material as described in any one of 1 to 9 above, wherein the photographic material is processed in a processing time of not more than 60 seconds.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION A grain forming method for an emulsion contained in the silver halide photographic light-sensitive material of the present invention in which 90% or more of the projected area of all grains are tabular grains will be described. First, tabular grains whose principal plane is {111} planes (hereinafter, also referred to as “{111} tabular grains of the present invention”) will be described. The {111} tabular grains of the present invention are basically formed by three stages of nucleation, ripening and growth. When forming ultrafine particles, the growth process can be omitted.

<Nucleation> Tabular grains are obtained by forming two parallel twin planes. The formation of the twin plane depends on the temperature in the reaction vessel, the dispersion medium (gelatin), the halogen concentration, and the like, so that appropriate conditions must be set. When a crystal habit controlling agent is present at the time of nucleation, the gelatin concentration is preferably 0.1% by mass to 10% by mass. The chloride concentration is 0.01 mol / L or more, preferably 0.03 mol / L or more (hereinafter, liter is also referred to as “L”).

It is disclosed in JP-A-8-184931 that it is preferable not to use a crystal habit-controlling agent at the time of nucleation in order to monodisperse the particles. When the crystal habit controlling agent is not used at the time of nucleation, the gelatin concentration is 0.03% by mass to 10% by mass, preferably 0.05% by mass to 1.0% by mass.
% By mass. The chloride concentration is 0.001 mol / L to 1 mol / L, preferably 0.003 mol / L to 0.1 mol / L.
L. The nucleation temperature can be any temperature from 2 ° C to 60 ° C, but is preferably from 5 ° C to 45 ° C, particularly preferably from 5 ° C to 35 ° C.

Gelatin used for nucleation has a molecular weight of 1
High molecular weight gelatin of at least 10,000 is preferred. The pCl is preferably 1.2 to 2.3 for plate nucleation, but is preferably 1.2 to 1.8 for monodispersing the thickness.

<Maturation> Although nuclei of tabular grains are formed at the first nucleation stage, immediately after nucleation, the reaction vessel contains many nuclei other than tabular grains. Therefore, after nucleation, aging is required to leave only tabular grains and to eliminate others. When ordinary Ostwald ripening is performed, the tabular grain nuclei also dissolve and disappear, so that the tabular grain nuclei decrease and the size of the resulting tabular grains increases. To prevent this, a crystal habit controlling agent is added. In particular, the combined use of phthalated gelatin, ambered gelatin, and trimellit gelatin enhances the effect of the crystal habit controlling agent, can prevent the dissolution of tabular grains, and is effective in monodispersing the thickness. At this time, the ratio between the crystal habit controlling agent and the gelatin is important, and it is preferable to use 3 × 10 ⁻⁶ to 6 × 10 ⁻⁶ mol of the crystal habit controlling agent per 1 g of phthalated, ambered or merit gelatin. When used in combination, the crystal habit controlling agent and the gelatin solution may be added at the same time, or may be added with a delay, but it is preferable to add a solution in which both are mixed in advance.

The pAg during ripening is particularly important, and is preferably 60 to 130 mV with respect to the silver-silver chloride electrode. It is efficient that the ripening temperature is higher than the nucleation temperature. In particular, it is preferable to increase the nucleation temperature by at least 15 ° C.

<Growth> Next, the formed nuclei are grown in the presence of a crystal habit controlling agent by physical ripening and addition of a silver salt and a halide. The case will be described. In this case, the chloride concentration is 5 mol / L or less, preferably 0.05 to 1 mol / L.
L. The temperature during grain growth can be selected in the range of 10 ° C to 95 ° C, but is preferably in the range of 30 ° C to 75 ° C.

The total amount of the crystal habit controlling agent used is at least 6 × 10 ^-5 mol, particularly 3 × 10 ⁵ mol per mol of silver halide in the finished emulsion.
It is preferably from 10 ⁻⁴ mol to 6 × 10 ⁻² mol. The phase control agent may be added at any time during the nucleation of silver halide grains, physical ripening, and during grain growth. The crystal habit controlling agent may be added to the reaction vessel in advance, but in the case of forming small-sized tabular grains, it is preferable to add the crystal phase controlling agent to the reaction vessel together with the growth of the grains to increase the concentration.

When the amount of the dispersion medium used at the time of nucleation or growth is insufficient for growth, it is necessary to supplement the amount by addition. Preferably, 10 g / L to 100 g / L of gelatin is present for growth. As the complementary gelatin, phthalated gelatin or trimellit gelatin is preferable. The pH at the time of particle formation is arbitrary, but is preferably in a neutral to acidic range.

As the crystal habit controlling agent used for forming the {111} tabular grains of the present invention, many compounds have been disclosed as described above, but the compounds represented by the general formulas (GI), (GII) and (GIII) The compound of the general formula (G)
Compounds of I) are preferred.

[0034]

Embedded image

In the general formula (GI), R 1 has 1 carbon atom
-20 linear, branched or cyclic alkyl groups (e.g.,
Methyl group, ethyl group, isopropyl group, t-butyl group,
n-octyl group, n-decyl group, n-hexadecyl group,
Cyclopropyl group, cyclopentyl group, cyclohexyl group), alkenyl group having 2 to 20 carbon atoms (for example, allyl group, 2-butenyl group, 3-pentenyl group), carbon number 7
To 20 aralkyl groups (e.g., benzyl group, phenethyl group) are preferred. Each group represented by R1 may be substituted. Examples of the substituent include substitutable groups represented by the following R2 to R6.

R2, R3, R4, R5 and R6 may be the same or different and each represents a hydrogen atom or a group capable of substituting the same. Substitutable groups include the following.

Halogen atom (preferably Cl, B
r) and the following groups having preferably 20 or less carbon atoms: alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group (for example, pyridyl group, furyl group, imidazolyl group, piperidyl group) , Morpholino group, etc.), alkoxy group, aryloxy group, amino group, acylamino group, ureido group, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, acyl group, acyloxy Group, phosphoric amide group, alkylthio group, arylthio group, cyano group, sulfo group,
Carboxy group, hydroxy group, phosphono group, nitro group,
Examples thereof include a sulfino group, an ammonio group (for example, a trimethylammonio group), a phosphonio group, and a hydrazino group.
These groups may be further substituted.

R2 and R3, R3 and R4, R4 and R5, R5 and R6
May be condensed to form a quinoline ring, isoquinoline ring or acridine ring.

[0039] X ^- represents a counter anion. Examples of the counter anion include a halogen ion (a chloride ion and a bromine ion), a nitrate ion, a sulfate ion, a p-toluenesulfonic acid ion, and a trifluoromethanesulfonic acid ion.

In the general formula (GI), R 1 is preferably
Represents an aralkyl group, and R2, R3, R4, R5 and R6
At least one represents an aryl group.

More preferably, in the general formula (GI),
R1 represents an aralkyl group, R4 represents an aryl group, X
^- represents a halogen ion. Examples of these compounds are described in Japanese Unexamined Patent Application Publication No. 8-227117, Crystal habit control agents 1 to 29, but the present invention is not limited thereto.

Next, the compounds of the general formulas (GII) and (GIII) will be described in detail. A1, A2, A3 and A
4 independently represents a nonmetallic element group for completing a nitrogen-containing heterocyclic ring, which may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a benzene ring may be condensed.
The heterocycle composed of A1, A2, A3 and A4 may have a substituent, and each may be the same or different. As the substituent, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxy group, an alkoxy group,
Represents an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an amino group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, and an arylthio group. Preferred examples are A1, A2,
A3 and A4 can be a 5- to 6-membered ring (for example, a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrazine ring, a pyrimidine ring, etc.). A more preferred example is a pyridine ring.

B represents a divalent linking group. Divalent linking groups include alkylene, arylene, alkenylene, and -SO ₂
-, -SO-, -O-, -S-, -CO-, -N
(R ₂ ) — (wherein, R ₂ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B include alkylene and alkenylene. The alkylene, arylene, alkenylene, alkyl group, and aryl group forming the divalent linking group preferably have 20 or less carbon atoms. Further, the alkylene, arylene, alkenylene, alkyl group and aryl group forming these divalent linking groups may have the same substituents as those described above for A1 to A4.

R11 and R12 represent an alkyl group having 1 to 20 carbon atoms. R11 and R12 may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituents are the same as the substituents exemplified as the substituents for A1, A2, A3 and A4. As a preferred example, R11 and R12 each represent an alkyl group having 4 to 10 carbon atoms. A more preferred example is a substituted or unsubstituted aryl-substituted alkyl group.

X represents an anion. For example, they represent chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, and oxalate.
m represents 0 or 1, and in the case of an inner salt, m is 0.

Specific examples of the compound represented by formula (GII) or (GIII) are disclosed in JP-A-2-32 (Compound Examples 1-42), but the present invention is limited to these compounds. It is not something to be done.

Next, tabular grains having a principal plane of {100} plane (hereinafter, also referred to as “{100} tabular grains of the present invention”) will be described. The {100} tabular grains of the present invention are tabular grains having {100} faces as main planes. The shape of the main plane is a right-angled parallelogram or a triangular to pentagonal shape in which one corner of the right-angled parallelogram is missing (the missing shape is a side having the corner as a vertex and the corner forming the corner). A right-angled triangular portion), or a 4- to 8-octagonal shape having two or more and four or less of the missing portions.

Assuming that the right-angled parallelogram shape supplementing the missing portion is a supplementary quadrilateral, the adjacent side ratio (long side length / short side length) of the right-angled parallelogram and the supplementary quadrangle is 1
-6, preferably 1-4, more preferably 1-2.

As a method for forming tabular silver halide emulsion grains having {100} major planes, a silver salt aqueous solution and a halide salt aqueous solution are added to a dispersion medium such as an aqueous gelatin solution with stirring and mixed. At this time, for example, JP-A-6-301129 and JP-A-6-347929.
In JP-A-9-34045 and JP-A-9-96881, silver iodide or iodide ions or silver bromide or bromide ions are present, and nuclei are formed due to the difference in crystal lattice size from silver chloride. There is disclosed a method of introducing a crystal defect that causes distortion and imparts anisotropic growth such as screw dislocation. When the screw dislocations are introduced, the formation of two-dimensional nuclei on the surface is not rate-determining under low supersaturation conditions, so crystallization proceeds on this surface, and tabular grains are formed by introducing the screw dislocations. Is done. Here, the low supersaturation condition is preferably 35% or less at the time of critical addition, more preferably 2 to 2%.
Indicates 0%. Although it is not determined that the crystal defect is a screw dislocation, it is considered that there is a high possibility that the crystal defect is a screw dislocation because the direction in which the dislocation is introduced or the particles are given anisotropic growth. In order to make tabular grains thinner, it is preferable that the introduced dislocations be retained.
Nos. 22954 and 9-189977.

Mixing at the time of nucleation is important. In order to form monodisperse tabular grains having a large thickness, it is necessary to have high stirring efficiency and to mix silver nitrate and a halogen aqueous solution in a short time.
When the mixing apparatus described in JP-A-51-83097 is used, the stirring speed is preferably from 800 to 2,000 rpm, particularly preferably from 1,000 to 2,000 rpm.

In JP-A-6-347928, imidazoles and 3,5-diaminotriazoles are used, and in JP-A-8-339044, polyvinyl alcohols are used. A method of forming {100} tabular grains by addition is disclosed. However, the present invention is not limited to these.

In the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention, 90% or more of the total projected area of the grains in the emulsion, the average aspect ratio is 5 or more, and
Tabular grains having an average thickness of 0.20 μm or less (hereinafter, referred to as
Grains satisfying such requirements of the aspect ratio and the thickness are also referred to as “tabular grains of the present invention”. ). Generally, the form of a tabular grain is a tabular shape having two parallel surfaces, and the two parallel surfaces are referred to as a principal plane, and the distance between the principal planes is referred to as “thickness”.
That. The average thickness is preferably 0.03 μm to 0.18
μm. The uniformity of the grain thickness is important, and the coefficient of variation (standard deviation divided by the average value) of the thickness of the tabular grains of the present invention is preferably 20% or less. The thickness of the particles can be determined from the length of a shadow of an electron micrograph of a carbon replica method using metal evaporation.

The average equivalent circle diameter of the tabular grains of the present invention can be arbitrarily selected from 0.3 μm to 10 μm.
Here, the equivalent circle diameter means the diameter of a circle having an area equal to the projected area of a particle in an electron micrograph. The ratio of the diameter / thickness is called an aspect ratio. The equivalent circle diameter is particularly preferably a small range of 0.3 μm to 1.6 μm for the particles used in the rapid processing light-sensitive material. Further, the distribution of the equivalent circle diameter is preferably monodisperse, and the effect of the present invention is maximized when the variation coefficient of the equivalent circle diameter of the tabular grains is 22% or less. The average aspect ratio of the tabular grains of the present invention is preferably 7 or more and 30 or less.

The silver halide grains contained in the emulsion contained in the silver halide photographic light-sensitive material of the present invention are grains having a silver chloride content of 90 mol% or more, and in particular, 95% or more are silver chloride. preferable.

The tabular grains of the present invention may have a uniform structure, but preferably have a so-called core / shell structure comprising a core and a shell surrounding the core. Preferably, 95% or more of the core is silver chloride. The core portion may be composed of two or more portions having different halogen compositions. The shell portion preferably accounts for 50% or less of the total particle volume, particularly preferably 20% or less.

The tabular grains of the present invention preferably contain silver iodide in an amount of 0.1 mol% to 0.8 mol% based on the total silver. In particular, it is preferable to contain 0.2 mol% to 0.6 mol%. Silver iodide is preferably contained in the shell part (outermost layer). The silver iodide content of the shell part is 1.0 mol%
To 13 mol%, preferably 2 mol% to 1 mol%.
It is particularly preferred that it is 0 mol%. By containing silver iodide, the effect of processing stability by monodispersion of the thickness is promoted.

Also, by containing silver bromide,
The effect of processing stability due to monodispersion of the thickness is promoted.

The silver bromide content is from 0.1 mol% to 4 mol%
Is preferred. The silver bromide content in the grains is preferably higher in the shell part than in the core part. Also, a phase in which the content of silver bromide differs by 6 mol% or more in the grains (the difference in content between the phase having the lowest silver bromide content and the content of the highest phase differs by 6 mol% or more: high content of silver bromide) Phase is referred to as a silver bromide localized phase). Specifically, the shell portion preferably has a silver bromide localized phase having a silver bromide content of 6 mol% or more higher than other portions. It is preferable that the silver bromide localized phase contains 1 × 10 ⁻⁸ mol% to 1 × 10 ⁻⁵ mol% of the Ir compound based on the total silver amount of the grains. As the Ir compound, an Ir complex ion is particularly preferable. As the ligand, for example,
Halogen (preferably Cl, Br), CN, SCN, O
In addition to CN, NO and H ₂ O, organic ligands can be mentioned. The Ir compound stabilizes the morphology of the tabular grains and improves the photographic properties under high illuminance exposure.

If the crystal habit controlling agent is present on the surface of the grains even after the formation of the grains, it affects the adsorption of the sensitizing dye and the development. Therefore, the crystal habit controlling agent is preferably removed after the formation of the particles. However, when the crystal habit controlling agent is removed, it is difficult for the high silver chloride grains to maintain the {111} plane under ordinary conditions. Therefore, it is preferable to maintain the particle form by substituting with a photographically useful compound such as a sensitizing dye. This method is described in JP-A-9-80656 and JP-A-9-1060.
26, US Patent Nos. 5,221,602 and 5,28
6,452, 5,298,387, 5,29
Nos. 8,388 and 5,176,992.

In the silver halide grains of the present invention, the periodic table VI
A group II metal, that is, an ion of a metal selected from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, and iron or a complex ion thereof can be used alone or in combination. Further, a plurality of these metals may be used.

The metal ion-providing compound is added to an aqueous gelatin solution, an aqueous halide solution, an aqueous silver salt solution, or another aqueous solution which serves as a dispersion medium at the time of forming silver halide grains. The silver halide grains of the present invention can be incorporated into the silver halide grains of the present invention by, for example, adding them to the silver halide emulsion in the form of fine silver halide grains and dissolving the emulsion. Further, in order to allow the metal ions to be contained in the particles, before forming the particles,
The addition can be performed either immediately after the formation of the particles or immediately after the formation of the particles. The timing of the addition can be changed depending on where and how much metal ions are contained in the particles.

In the silver halide grains of the present invention, 50 mol% or more, preferably 80 mol% or more, and more preferably 100%, of the metal ion donating compound to be used is 50 mass% or less of the grain volume from the surface of the silver halide grains. % Is preferably localized in the surface layer up to the amount corresponding to not more than 10%. The volume of this surface layer is preferably 30% or less. Localizing metal ions in the surface layer is advantageous for suppressing an increase in internal sensitivity and obtaining high sensitivity. In order to concentrate the metal ion-providing compound in the surface layer of such silver halide grains, for example, after forming the silver halide grains (core) in a portion excluding the surface layer, a water solution for forming the surface layer is formed. It can be carried out by supplying the metal ion providing compound in accordance with the addition of the neutral silver salt solution and the aqueous halide solution.

The silver halide emulsion used in the present invention is:
In addition to the Group VIII metal, various polyvalent metal ion impurities can be introduced during the process of emulsion grain formation or physical ripening. The addition amount of these compounds varies widely depending on the purpose, but is preferably 1 to 1 mol of silver halide.
0 ^-9 to 10 ^-2 mol is preferred.

The silver halide emulsion used in the present invention is
Usually chemically sensitized. As the chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, US Pat. No. 2,448,0
No. 60, No. 3,320,069), a sensitization method using a metal such as iridium, platinum, rhodium, palladium (for example, US Pat. Nos. 2,448,060 and 2,566,2).
No. 45, No. 2,566,263), a sulfur sensitization method using a sulfur-containing compound (for example, US Pat. No. 2,222,264)
No.), selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound or tin salts, thiourea dioxide,
Reduction sensitization method using polyamine or the like (for example, US Pat.
487,850, 2,518,698, 2,5
21,925). These sensitization methods can be used alone or in combination.

The silver halide emulsion used in the present invention is:
Gold sensitized, known in the industry, is preferred
New By applying gold sensitization, laser light etc.
To further reduce fluctuations in photographic performance during scanning exposure
Because it can be. For gold sensitization, chloroauric acid
Or its salts, gold thiocyanates and gold thiosulfates
Compounds can be used. The amount of these compounds added
Depending on the case, 5 × per mole of silver halide
10^-7~ 5 × 10^-2Mol, preferably 1 × 10 ^-6~ 1 ×
10^-3Is a mole. The timing of addition of these compounds
This is performed until the chemical sensitization used for lightening is completed.

In the present invention, gold sensitization is performed by other sensitization methods,
For example, combination with sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a compound other than a gold compound is also preferably performed.

The silver halide emulsion used in the present invention contains various compounds or their precursors for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-21.
No. 5,272, pp. 39-72 are preferably used. The emulsion used in the present invention is preferably a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

Next, the compound represented by formula (I) of the present invention will be described. The compound of the present invention represented by the general formula (I) may be used at any time during the preparation of an emulsion or during the production of a light-sensitive material. For example, at the time of grain formation, at the desalting step, at the time of chemical sensitization, before coating, and the like. Also, it can be added in a plurality of times during these steps. The compounds of the present invention
It is preferable to add it after dissolving in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof.
In the case of dissolving in water, a compound whose solubility increases when the pH is increased or decreased may be dissolved by increasing or decreasing the pH, and then added.

The compound of the present invention represented by the general formula (I)
It is preferably used in an emulsion layer, but it may be added to a protective layer or an intermediate layer together with the emulsion layer and diffused during coating. The compound of the present invention may be added at any time before or after the sensitizing dye, and is preferably 1 × per mol of silver halide.
10 ^{-9 to} 5 × 10 ^-2 mol, more preferably 1 × 10 ^-8 to
It is contained in the silver halide emulsion layer at a ratio of 2 × 10 ⁻³ mol.

The compound of the present invention represented by the general formula (I)
The emulsion may be used at any time during the preparation of the emulsion. For example, at the time of grain formation, at the desalting step, at the time of chemical sensitization, before coating, and the like. Also, it can be added in a plurality of times during these steps. The compound of the present invention is preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. In the case of dissolving in water, a compound whose solubility increases when the pH is increased or decreased may be dissolved by increasing or decreasing the pH, and then added.

The compound of the present invention represented by the general formula (I)
It is preferably used in an emulsion layer, but it may be added to a protective layer or an intermediate layer together with the emulsion layer and diffused during coating. The compound of the present invention may be added at any time before or after the sensitizing dye, and is preferably 1 × per mol of silver halide.
10 ^{-9 to} 5 × 10 ^-2 mol, more preferably 1 × 10 ^-8 to
It is contained in the silver halide emulsion layer at a ratio of 2 × 10 ⁻³ mol.

The compounds used in the present invention will be described in detail. In the general formula (I), the silver halide adsorbing group represented by X has at least one selected from the group consisting of N, S, P, Se and Te, and preferably has a silver ion ligand structure. Things. When k is 2 or more, a plurality of Xs may be the same or different. The following are examples of those having a silver ion ligand structure.

In the general formula (X-1) -G ₁ -Z ₁ -R ₁ , G ₁ is a divalent linking group, which is substituted with a divalent heterocyclic group or a divalent heterocyclic group or Unsubstituted alkylene group, alkenylene group, alkynylene group, arylene group,
It represents a divalent group bonded to any of the SO ₂ groups. Z
₁ represents an S, Se or Te atom. R ₁ is a counter ion necessary when a dissociation of the hydrogen atom or Z _1, represents sodium ion, potassium ion, lithium ion and ammonium ion.

Formulas (X-2a) and (X-2b)

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The general formulas (X-2a) and (X-2b) form a ring, and are in the form of a 5- to 7-membered hetero-saturated ring, hetero-unsaturated ring or unsaturated carbocyclic ring. Z _a is, O, N,
Represents an S, Se or Te atom, and n ₁ represents an integer of 0 to 3. R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. when n ₁ is 2 or more, a plurality of Z _a may be the same or different.

Formula (X-3) -R _3- (Z ₂ ) n ₂ -R _{4 In the} formula, Z ₂ represents an S, Se or Te atom, and n ₂ represents 1 to
Represents an integer of 3. R ₃ is a divalent linking group, and includes an alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, or divalent heterocyclic group and alkylene group, alkenylene group, alkynylene group, arylene group, It represents a divalent group bonded to any of the SO ₂ groups.
R ₄ represents an alkyl group, an aryl group or a heterocyclic group.
When n ₂ is 2 or more, a plurality of Z ₂ may be the same or different.

Formula (X-4)

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In the formula, R ₅ and R ₆ each independently represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

Formulas (X-5a) and (X-5b)

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In the formula, Z ₃ represents an S, Se or Te atom, and E ₁ is a hydrogen atom, NH ₂ , NHR ₁₀ , N
(R ₁₀ ) ₂ , NHN (R ₁₀ ) ₂ , OR ₁₀ or SR ₁₀ . E ₂ is a divalent linking group, NH, NR ₁₀ , NHN
Represents R ₁₀ , O or S. R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R ₈ and R ₉ may combine with each other to form a ring. R ₁₀ is a hydrogen atom, an alkyl group,
Represents an alkenyl group, an aryl group or a heterocyclic group.

Formulas (X-6a) and (X-6b)

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In the formula, R ₁₁ is a divalent linking group, and represents an alkylene group, alkenylene group, alkynylene group, arylene group or divalent heterocyclic group. G ₂ and J are each independently COOR ₁₂ , SO ₂ R ₁₂ , COR ₁₂ , SO
Represents R ₁₂ , CN, CHO or NO ₂ . R ₁₂ represents an alkyl group, an alkenyl group or an aryl group.

The general formula (X-1) will be described in detail. In the formula, as the linking group represented by G ₁ , a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, 3
-Oxapentylene, 2-hydroxytrimethylene),
A substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (eg, cyclopropylene, cyclopentylene, cyclohexylene), a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (eg, ethene, 2-butenylene),
Examples thereof include an alkynylene group having 2 to 10 carbon atoms (eg, ethyne) and a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene, unsubstituted 2,5-naphthylene).

In the formula, as the SO ₂ group represented by G ₁ ,
In addition to the SO ₂ — group, a substituted or unsubstituted linear or branched alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cyclic alkylene group having 3 to 6 carbon atoms, or a carbon atom having 2 carbon atoms
-SO ₂ bound to an alkenylene group of 10 - group.

Further, as the divalent linking group represented by G ₁ , a divalent heterocyclic group, or a divalent heterocyclic group and an alkylene group, alkenylene group, alkynylene group, arylene group or SO ₂ group A divalent group bonded to any of them, or a group obtained by subjecting a heterocyclic portion of these groups to benzo- or naphtho-condensation (for example, 2,3-tetrazolediyl,
1,3-triazoldiyl, 1,2-imidazolediyl, 3,5-oxadiazolediyl, 2,4-thiazoledyl, 1,5-benzimidazolediyl, 2,
5-benzothiazoldiyl, 2,5-benzoxazoldiyl, 2,5-pyrimidinediyl, 3-phenyl-2,5-tetrazolediyl, 2,5-pyridinediyl, 2,4-furandyl, 1,3- Piperidinediyl, 2,4-morpholinediyl).

In the above formula, G ₁ may have a substituent as much as possible. The substituents are shown below, and these substituents are referred to herein as substituents Y.

Examples of the substituent include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, methyl, ethyl, isopropyl, n-propyl, t-butyl) and an alkenyl group (eg, allyl, 2-
Butenyl), alkynyl group (eg, propargyl), aralkyl group (eg, benzyl), aryl group (eg, phenyl, naphthyl, 4-methylphenyl), heterocyclic group (eg, pyridyl, furyl, imidazolyl, piperidinyl, morpholyl), alkoxy group ( For example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy), an aryloxy group (eg, phenoxy, 2-naphthyloxy), an amino group (eg, unsubstituted amino, dimethylamino, diethylamino, dipropylamino, dibutyl) Amino, ethylamino, anilino), acylamino group (eg, acetylamino, benzoylamino), ureido group (eg, unsubstituted ureido, N-methylureido), urethane group (eg, methoxycarbonylamino) Phenoxycarbonylamino), a sulfonylamino group (eg, methylsulfonylamino, phenylsulfonylamino), a sulfamoyl group (eg, unsubstituted sulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), a carbamoyl group (eg, unsubstituted) Carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl), sulfonyl group (eg, mesyl, tosyl), sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxy Carbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, benzoyl, formyl, pivaloyl), acyloxy groups (eg, acetoxy, benzoy) Oxy), phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide), cyano group, sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, phosphono group, nitro group, ammonium group, phosphonio group , A hydrazino group and a thiazolino group. When there are two or more substituents, they may be the same or different, and the substituent may further have a substituent.

Preferred examples of the formula (X-1) are shown below. As a preferable general formula (X-1), G ₁ has 6 to ₁ carbon atoms.
5-7 substituted or unsubstituted arylene group, substituted or unsubstituted alkylene group or arylene group, or benzo- or naphtho-condensed
And a heterocyclic group forming a membered ring. Examples of Z ₁ include S and Se, and examples of R ₁ include a hydrogen atom, a sodium ion, and a potassium ion.

More preferably, G ₁ has 6 to 8 carbon atoms.
Is a heterocyclic group bonded to a substituted or unsubstituted arylene group or forms a 5- or 6-membered benzo-fused ring, and most preferably a 5- or 5-benzo-fused heterocyclic group bonded to an arylene group. It is a heterocyclic group forming a 6-membered ring. More preferred Z ₁ is S, and R ₁ is a hydrogen atom or a sodium ion.

The general formulas (X-2a) and (X-2b) will be described in detail. In the formula, the alkyl group, alkenyl group, and alkynyl group represented by R _{2 have} 1 to 1 carbon atoms.
10 substituted or unsubstituted linear or branched alkyl groups (e.g., methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, n-butoxypropyl, methoxymethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (eg, cyclopropyl, cyclopentyl, cyclohexyl), An alkenyl group having 2 to 10 carbon atoms (e.g., allyl, 2-butenyl, 3-pentenyl);
And alkynyl groups (e.g., propargyl and 3-pentynyl), aralkyl groups having 6 to 12 carbon atoms (e.g., benzyl), and the like. The aryl group has 6 carbon atoms.
To 12 substituted or unsubstituted aryl groups (for example, unsubstituted phenyl and 4-methylphenyl). R ₂ may further have a substituent Y or the like.

Preferred examples of formulas (X-2a) and (X-2b) are shown below. In the formula, preferably, R ₂ is a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms,
Z _a is O, N or S, n ₁ is an integer of 1 to 3.

[0092] More preferably, R ₂ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Z _a is N or S, n ₁ is 2 or 3.

Next, the formula (X-3) will be described in detail. In the formula, as the linking group represented by R ₃ , a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (eg, methylene, ethylene, trimethylene, isopropylene, tetramethylene, hexamethylene, 3-oxapentylene, 2-hydroxytrimethylene), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (e.g., cyclopropylene, cyclopentynylene, cyclohexylene), substituted or unsubstituted having 2 to 20 carbon atoms Substituted alkenylene groups (eg, ethene, 2-butenylene), alkynylene groups having 2 to 10 carbon atoms (eg, ethyne), substituted or unsubstituted arylene groups having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene, unsubstituted 2) , 5-naphthylene), and examples of the heterocyclic group include a substituted or unsubstituted heterocyclic group and Fine alkylene group, an alkenylene group, an arylene group, or even those heterocyclic groups are attached (e.g., 2,5-pyridinediyl, 3-phenyl -
2,5-pyridinediyl, 1,3-piperidindiyl,
2,4-morpholinediyl).

In the formula, as the alkyl group represented by R ₄ , a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, isopropyl, n-propyl, n- Butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl,
2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, methoxymethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (eg, cyclopropyl, cyclopentyl) , Cyclohexyl)
And examples of the aryl group include a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, unsubstituted phenyl and 2-methylphenyl).

Examples of the heterocyclic group include unsubstituted or alkyl, alkenyl, and aryl groups, or those further substituted with a heterocyclic group (eg, pyridyl, 3-phenylpyridyl, piperidyl, morpholyl). R ₄ may further have a substituent Y or the like.

Preferred examples of the formula (X-3) are shown below. In the formula, preferably, R ₃ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and R ₄ is a substituted or unsubstituted arylene group having 1 to 6 carbon atoms. An unsubstituted alkyl group or 6-1 carbon atoms
0 is a substituted or unsubstituted aryl group, and Z ₂ is S
Or Se, and n ₂ is 1-2.

More preferably, R ₃ is an alkylene group having 1 to ₄ carbon atoms, R ₄ is an alkyl group having 1 to ₄ carbon atoms, Z ₂ is S, and n ₂ is 1.

Next, the formula (X-4) will be described in detail. In the formula, as the alkyl group or alkenyl group represented by R ₅ and R ₆ , a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, isopropyl, n-propyl) , N-butyl, t-
Butyl, 2-pentyl, n-hexyl, n-octyl,
t-octyl, 2-ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, n-butoxypropyl, methoxymethyl), substitution of 3 to 6 carbon atoms or Examples include an unsubstituted cyclic alkyl group (eg, cyclopropyl, cyclopentyl, cyclohexyl) and an alkenyl group having 2 to 10 carbon atoms (eg, allyl, 2-butenyl, 3-pentenyl).
Examples of the aryl group include a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, unsubstituted phenyl and 4-methylphenyl). Examples of the heterocyclic group include an unsubstituted or alkylene group, an alkenylene group, an arylene group, Or those further substituted with a heterocyclic group (eg, pyridyl, 3
-Phenylpyridyl, furyl, piperidyl, morpholyl). In the above formula, R ₅ and R ₆ may further have a substituent Y or the like.

Preferred examples of the formula (X-4) are shown below. In the formula, preferably, R ₅ and R ₆ are a substituted or unsubstituted alkyl group having 1 to ₆ carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. More preferably, R ₅ and R ₆ are an aryl group having 6 to 8 carbon atoms.

Next, general formulas (X-5a) and (X-5)
b) will be described in detail. Where E₁Group represented by
As NH_Two, NHCH_Three, NHC_TwoH_Five, NHPh, N
(CH_Three)_Two, N (Ph)_Two, NHNHC_ThreeH₇, NHNH
Ph, OC_FourH₉, OPh, SCH _Three, Etc., and E_Two
As NH, NCH_Three, NC_TwoH_Five, NPh, NHN
C_ThreeH₇, NHNPh, etc. (where Ph = f
Phenyl group (hereinafter the same).

Formulas (X-5a) and (X-5b)
Wherein the alkyl group and alkenyl group represented by R ₇ , R ₈ and R ₉ include a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-
Butyl, 2-pentyl, n-hexyl, n-octyl,
t-octyl, 2-ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, n-butoxypropyl, methoxymethyl), substitution of 3 to 6 carbon atoms or Examples include an unsubstituted cyclic alkyl group (for example, cyclopropyl, cyclopentyl, cyclohexyl) and an alkenyl group having 2 to 10 carbon atoms (for example, allyl, 2-butenyl, 3-pentenyl). As the aryl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, unsubstituted phenyl,
-Methylphenyl), and examples of the heterocyclic group include an unsubstituted or alkylene group, an alkenylene group, an arylene group, or a group further substituted with a heterocyclic group (for example,
Pyridyl, 3-phenylpyridyl, furyl, piperidyl, morpholyl). R ₇ , R ₈ and R ₉ may further have a substituent Y or the like.

Preferred examples of formulas (X-5a) and (X-5b) are shown below. In the formula, preferably, E ₁ is an alkyl-substituted or unsubstituted amino group or an alkoxy group, E ₂ is an alkyl-substituted or unsubstituted amino linking group, and R ₇ , R ₈ and R _{9 each} have 1 to 1 carbon atoms. 6 is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and Z ₃ is S or S
e.

[0103] More preferably, E ₁ is an alkyl substituted or unsubstituted amino group, E ₂ is an amino linking group of the alkyl substituted or unsubstituted, R _7, R ₈ and R
₉ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and Z ₃ is S.

Next, formulas (X-6a) and (X-6)
b) will be described in detail. Where G_TwoAnd represented by J
COOCH_Three, COOC_ThreeH₇, COOC ₆
H₁₃, COOPh, SO_TwoCH_Three, SO_TwoC_FourH₉, COC_Two
H_Five, COPh, SOCH_Three, SOPh, CN, CHO,
NO_TwoAnd the like.

In the formula, the linking group represented by R ₁₁ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene). Methylene, 3-oxapentylene, 2-hydroxytrimethylene), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (eg, cyclopropylene, cyclopentylene, cyclohexylene), substituted with 2 to 20 carbon atoms Alternatively, an unsubstituted alkenylene group (eg, ethene, 2-butenylene), an alkynylene group having 2 to 10 carbon atoms (eg, ethyne), a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene, Substituted 2,5-naphthylene).

Further, as the divalent linking group represented by R ₁₁ , a divalent heterocyclic group, or a divalent heterocyclic group and an alkylene group, alkenylene group, alkynylene group, arylene group or SO ₂ group A divalent group bonded to any of them (eg, 2,5-pyridinediyl, 3-phenyl-2,5-pyridinediyl, 2,4-furandiyl, 1,3-piperidindiyl, 2,4-morpholinediyl) Is mentioned.
In the formula, R ₁₁ may further have a substituent Y or the like.

Preferred examples of formulas (X-6a) and (X-6b) are shown below. In the formula, preferably, G ₂ and J are carboxylic acid esters or carbonyls having 2 to 6 carbon atoms, and R ₁₁ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms or substituted with 6 to 10 carbon atoms. Alternatively, it is an unsubstituted arylene group.

More preferably, G ₂ and J are carboxylic acid esters having 2 to 4 carbon atoms, and R ₁₁ is a carboxylic acid ester having 1 carbon atom.
A substituted or unsubstituted alkylene group having 4 to 4 carbon atoms or a substituted or unsubstituted arylene group having 6 to 8 carbon atoms.

The preferred general formula of the silver halide adsorbing group represented by X is (X-1)>(X-2a)> (X-2
b)>(X-3)>(X-5a)>(X-5b)> (X
-4)>(X-6a)> (X-6b).

Next, the light absorbing group represented by X in the general formula (I) will be described in detail. In the general formula (I), examples of the light absorbing group represented by X include the following. General formula (X-7)

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In the formula, Z ₄ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and L ₂ , L ₃ , L ₄
And L ₅ represents a methine group. p ₁ represents 0 or 1,
n ₃ represents an integer of 0 to 3. M ₁ represents a charge-balancing counter ion, and m ₂ represents 0 to 10 required to neutralize the molecular charge.
Represents an integer. An unsaturated carbocycle such as a benzene ring may be condensed with the nitrogen-containing heterocyclic ring formed by Z ₄ .

In the formula, the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₄ includes a thiazolidine nucleus, a thiazole nucleus, a benzothiazole nucleus, an oxazoline nucleus, an oxazole nucleus,
Benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine),
Imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxalin nucleus , Oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus and the like. The 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₄ may have the substituent Y described above.

In the formula, L ₂ , L ₃ , L ₄ and L ₅ each represent an independent methine group. The methine groups represented by L ₂ , L ₃ , L ₄ and L ₅ may have a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms (eg, methyl , Ethyl, 2-carboxyethyl), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms (eg, phenyl, o-carboxyphenyl), and a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms (eg, N, A monovalent group obtained by removing one hydrogen atom from N-diethylbarbituric acid), a halogen atom (eg, chlorine, bromine, fluorine, iodine), an alkoxy group having 1 to 15 carbon atoms (eg, methoxy, ethoxy) An alkylthio group having 1 to 15 carbon atoms (eg, methylthio, ethylthio), an arylthio group having 6 to 20 carbon atoms (eg, phenylthio), an amino group having 0 to 15 carbon atoms (eg, N, N -Diphenylamino, N-methyl-N-phenylamino, N-
Methylpiperazino) and the like. Further, a ring may be formed with another methine group. Alternatively, a ring can be formed with other parts.

In the formula, M ₁ is included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the light absorbing group. Typical cations include inorganic ions such as hydrogen ion (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion), and ammonium ions (eg, ammonium ion, tetraalkylammonium ion, pyridinium ion). , Ethyl pyridinium ion). The anion may be either an inorganic anion or an organic anion, and may be a halogen anion (eg, a fluorine ion, a chloride ion, an iodine ion), a substituted arylsulfonate ion (eg, a p-toluenesulfonic acid ion, -Chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion,
1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picric acid Ions, acetate ions, and trifluoromethanesulfonate ions. Further, an ionic polymer or a light absorbing group having a reverse charge may be used.

In the present invention, for example, a sulfo group is represented by SO ₃ ⁻ and a carboxy group is represented by CO ₂ ⁻ . However, when a counter ion is a hydrogen ion, they may be represented by SO ₃ H and CO ₂ H, respectively. it can. In the formula, m ₂ represents a number necessary to balance the charges, and is 0 when a salt is formed in the molecule.

Preferred examples of the formula (X-7) are shown below. In a preferred general formula (X-7), Z ₄ is a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus or a quinoline nucleus, and L ₂ , L ₃ , L ₄ and L ₅ are unsubstituted methine groups. , P ₁ is 0, and n ₃ is 1 or 2.

More preferably, Z ₄ is a benzoxazole nucleus or benzothiazole nucleus, and n ₃ is 1.
Particularly preferred Z ₄ is a benzothiazole nucleus.

In the general formula (I), preferred k is 0 or 1.
And more preferably 1.

The specific examples of the X group used in the present invention are shown below, but the compounds used in the present invention are not limited to these.

[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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Next, the linking group represented by L in formula (I) will be described in detail. In the general formula (I), examples of the linking group represented by L include a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, Hexamethylene, 3-oxapentylene, 2-
Hydroxytrimethylene), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (eg, cyclopropylene, cyclopentylene, cyclohexylene), a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (eg, Ethene, 2-butenylene), alkynylene group having 2 to 10 carbon atoms (eg, ethyne), substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene, unsubstituted 2,5-naphthylene) ), A heterocyclic linking group (eg, 2,6-pyridinediyl), a carbonyl group,
Thiocarbonyl group, imide group, sulfonyl group, divalent sulfonic acid group, ester group, thioester group, divalent amide group, ether group, thioether group, divalent amino group,
Examples thereof include a divalent ureido group, a divalent thioureido group, and a thiosulfonyl group. Further, these linking groups may be linked to each other to form a new linking group. When m is 2 or more, a plurality of Ls may be the same or different.

L may further have the aforementioned substituent Y or the like. Preferred examples of the linking group L include an alkylene group having 1 to 10 carbon atoms linked to an unsubstituted alkylene group having 1 to 10 carbon atoms and an amino group, an amide group, a thioether group, a ureido group or a sulfonyl group. Is an alkylene group having 1 to 6 carbon atoms linked to an unsubstituted alkylene group having 1 to 6 carbon atoms and an amino group, an amide group or a thioether group.

In the general formula (I), preferred m is 0 or 1.
And more preferably 1.

Next, the electron donating group A will be described in detail. And generating electrons radical A ^· is generated A-B portion undergoes oxidation and fragmentation to generate electrons more radical A ^· is subjected to oxidation, the following reaction process of high sensitivity.

[0130]

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Since A is an electron donating group, the substituent on the aromatic group in any structure is preferably selected so that A has an excess of electrons. For example, when the aromatic ring is not excessive in electrons, an electron-donating group is introduced. Conversely, when the electron concentration is extremely large as in anthracene, an electron-withdrawing group is introduced to increase the oxidation potential. Adjustment is preferred.

Preferred A groups are those having the following general formula: General formulas (A-1), (A-2), (A-3)

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In the general formulas (A-1) and (A-2), R
₁₂ and R ₁₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkylene group or an arylene group, and R ₁₄ represents an alkyl group, COOH, halogen, N (R ₁₅ ) ₂ , OR _{1 5,} SR _15, CHO, CO
R ₁₅ , COOR ₁₅ , CONHR ₁₅ , CON (R ₁₅ ) ₂ ,
SO ₃ R ₁₅ , SO ₂ NHR ₁₅ , SO ₂ NR ₁₅ , SO ₂ R ₁₅ ,
Represents SOR ₁₅ and CSR ₁₅ . Ar ₁ represents an arylene group or a heterocyclic linking group. R ₁₂ and R _13, or R ₁₂ and Ar ₁ may combine to form a ring. Q ₂ represents O, S, Se or Te; m ₃ and m ₄ represent 0 or 1;
₄ represents an integer of 1 to 3. L ₂ is N—R (where R is
Represents a substituted or unsubstituted alkyl group. ), NA
represents r, O, S, Se. The cyclic form formed by the bonding of R ₁₂ and R ₁₃ and the bonding of R ₁₂ and Ar ₁ each represents a 5- to 7-membered heterocyclic group or unsaturated ring. R ₁₅ represents a hydrogen atom, an alkyl group or an aryl group. The cyclic form of formula (A-3) represents a substituted or unsubstituted 5- to 7-membered unsaturated ring or heterocyclic group.

Formulas (A-1), (A-2) and (A
-3) will be described in detail. Wherein R ₁₂ and R ₁₃
The substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, isopropyl, n-propyl, n-
Butyl, t-butyl, 2-pentyl, n-hexyl, n
-Octyl, t-octyl, 2-ethylhexyl, 2-
Hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, methoxymethyl), and a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (eg, cyclopropyl, cyclopentyl, cyclohexyl). Examples of the aryl group include a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, unsubstituted phenyl and 2-methylphenyl).

Examples of the alkylene group include a substituted or unsubstituted linear or branched alkylene group having 1 to 10 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, methoxyethylene). Examples include substituted or unsubstituted arylene groups represented by Formulas 6 to 12 (for example, unsubstituted phenylene, 2-methylphenylene, and naphthylene).

In the general formulas (A-1) and (A-2), R
_{As the} group represented by ₁₄ , an alkyl group (for example, methyl,
Ethyl, isopropyl, n-propyl, n-butyl, 2
-Pentyl, n-hexyl, n-octyl, 2-ethylhexyl, 2-hydroxyethyl, n-butoxymethyl), a COOH group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom), OH, N (CH ₃ ) ₂ , NP
_{h 2, OCH 3, OPh,} SCH 3, SPh, CHO, C
OCH ₃ , COPh, COOC ₄ H ₉ , COOCH ₃ , CO
NHC ₂ H ₅ , CON (CH ₃ ) ₂ , SO ₃ CH ₃ , SO ₃ C ₃
H ₇ , SO ₂ NHCH ₃ , SO ₂ N (CH ₃ ) ₂ , SO ₂ C ₂ H
₅ , SOCH ₃ , CSPh and CSCH ₃ .

Ar ₁ represented by the general formulas (A-1) and (A-2) is a substituted or unsubstituted arylene group having 6 to 12 carbon atoms (for example, phenylene, 2-methylphenylene, naphthylene) And a divalent or trivalent group in which one or two hydrogen atoms have been removed from a substituted or unsubstituted heterocyclic group (eg, pyridyl, 3-phenylpyridyl, piperidyl, morpholyl).

L ₂ represented by the general formula (A-1) includes NH, NCH ₃ , NC ₄ H ₉ , NC ₃ H ₇ (i), NP
_{h, NPh-CH 3, O} , S, Se, Te and the like.

Examples of the cyclic form of formula (A-3) include an unsaturated 5- to 7-membered carbocyclic ring and a saturated or unsaturated 5- to 7-membered heterocyclic ring (for example, furyl, piperidyl, morpholyl).

R in the general formulas (A-1) and (A-2)
₁₂ , R ₁₃ , R ₁₄ , Ar ₁ , L ₂ , and general formula (A-3)
The above-mentioned substituent Y and the like may further be present on the inner ring.

Formulas (A-1), (A-2) and (A
Preferred examples of -3) are shown below. In the general formulas (A-1) and (A-2), preferably, R ₁₂ and R ₁₃ are a substituted or unsubstituted alkyl group or alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkyl group having 6 to 10 carbon atoms. A substituted aryl group, wherein R ₁₄ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an amino group mono- or disubstituted with an alkyl group having 1 to 4 carbon atoms, a carboxylic acid, a halogen or a carbon atom; A carboxylic acid ester of 1-4, wherein Ar ₁ is a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
Q ₂ is O, S or Se, m ₃ and m ₄ are 0 or 1, n ₄ is 1 to 3, and L ₂ is 0 to 3 carbon atoms.
Is an alkyl-substituted amino group. The general formula (A-
In 3), a preferred cyclic form is a 5- to 7-membered saturated or unsaturated heterocyclic ring.

In the general formulas (A-1) and (A-2), more preferably, R ₁₂ and R ₁₃ are a substituted or unsubstituted alkyl or alkylene group having 1 to 4 carbon atoms;
₁₄ is an unsubstituted alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
Is a monoamino-substituted or diamino-substituted alkyl group, Ar ₁ is a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, Q ₂ is O or S, and m ₃
And m ₄ is 0, n ₄ is 1, and L ₂ has 0 to 0 carbon atoms.
3 alkyl-substituted amino groups. The general formula (A-
In 3), a more preferred cyclic form is a 5- to 6-membered heterocyclic ring.

The portion where the group A is bonded to the group L (the group X when m = 0) is Ar ₁ and R ₁₂ or R ₁₃ .

Specific examples of the group A used in the present invention are shown below, but the compounds used in the present invention are not limited to these.

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Next, the group B will be described in detail. After when B is hydrogen atom oxidation, by intramolecular base is deprotonated to generate a radical A ^·.

Preferred groups B are those having a hydrogen atom and the following general formula: General formulas (B-1), (B-
2), (B-3)

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Formulas (B-1), (B-2) and (B
In -3), W represents Si, Sn or Ge, R ₁₆ each independently represents an alkyl group, and Ar ₂ each independently represents an aryl group.

The formulas (B-2) and (B-3) can be bonded to the adsorbing group X.

Formulas (B-1), (B-2) and (B
-3) will be described in detail. In the formula, as the alkyl group represented by R ₁₆ , a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms (for example, methyl,
Ethyl, isopropyl, n-propyl, n-butyl, t
-Butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, n-butoxyethyl, methoxymethyl), substitution of 6 to 12 carbon atoms or An unsubstituted aryl group (for example, phenyl, 2-methylphenyl) is exemplified.

R in the general formulas (B-2) and (B-3)
₁₆ and Ar ₂ may further have the aforementioned substituent Y or the like.

Formulas (B-1), (B-2) and (B
Preferred examples of -3) are shown below. In formulas (B-2) and (B-3), preferably, R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and Ar ₂ is a substituted or unsubstituted alkyl group having 6 to 10 carbon atoms. Is an aryl group of
W is Si or Sn.

In the general formulas (B-2) and (B-3), more preferably, R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and Ar ₂ is a group having 6 to 8 carbon atoms. It is a substituted or unsubstituted aryl group, and W is Si.

General formulas (B-1), (B-2) and (B
-3) in, most preferred, B-1 of COO ^- and Si- in B-2 (R _{16) 3.}

In the general formula (I), preferred n is 1. In addition, in general formula (I), when n is 2, two (A-
B) may be the same or different.

Hereinafter, examples of the AB group used in the present invention will be described, but the present invention is not limited thereto.

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The counter ions necessary for the charge balance of the compounds AB include sodium ion, potassium ion, triethylammonium ion, diisopropylammonium ion, tetrabutylammonium ion,
And tetramethylguanidinium ion.

The preferred oxidation potential of AB is 0 to 1.5 V
, More preferably 0 to 1.0 V, and still more preferably 0.3 to 1.0 V.

The radical A ^• (E) resulting from the bond cleavage reaction
The preferred oxidation potential of ₂ ) is -0.6 to -2.5 V, more preferably -0.9 to -2 V, and still more preferably -0.9 to -1.6 V.

The measuring method of the oxidation potential is as follows. E
₁ can be performed by cyclic voltammetry. The electron donor A is dissolved in a solution of acetonitrile / 0.1M or 80% / 20% (vol%) of water containing lithium chlorate. A glassy carbon disk is used for the working electrode, a platinum wire is used for the counter electrode, and a saturated calomel electrode (SCE) is used for the reference electrode. 0.1 V /
Measure at a potential scan rate of seconds. The oxidation potential versus SCE is taken at the peak potential of the cyclic voltammetry wave.
The E ₁ values of these AB compounds are described in EP 93,731.
A1.

The measurement of the oxidation potential of radicals is carried out by excessive electrochemical and pulse radiolysis methods. These are described in J.A. Am. Chem. Soc. 1988, 110,.
132, 1974, 96,. 1287, 1974,
96,. 1295.

Specific examples of the compound represented by formula (I) are shown below, but the compounds used in the present invention are not limited to these.

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As a method for synthesizing the compound represented by the general formula (I), US Pat. No. 5,747,235 and US Pat.
35, European Patent 786,692A1, 893,731
A1, 893, 732A1, WO99 / 05570, or the like, or a method analogous thereto can be easily synthesized.

A compound of the general formula (I) as defined in the present invention,
A silver halide emulsion containing silver halide grains containing at least 90 mol% of silver chloride, wherein 90% or more of the projected area of the grains are tabular grains having an average aspect ratio of 5 or more and an average thickness of 0.2 μm or less. (Hereinafter, also referred to as “photosensitive layer of the present invention”) can be provided on the support in one or more layers. Further, the photosensitive layer of the present invention can be used as any of the blue-sensitive layer, the green-sensitive layer, and the red-sensitive layer. Further, the photosensitive layer of the present invention can be provided not only on one side of the support but also on both sides. The photosensitive layer of the present invention includes a black-and-white silver halide photographic light-sensitive material (for example, an X-ray light-sensitive material, a squirrel-type light-sensitive material, a negative film for black-and-white photography) and a color photographic light-sensitive material (for example, a color negative film, a color reversal film, Color paper). Further, it can be used as a photosensitive material for diffusion transfer (for example, a color diffusion transfer element, a silver salt diffusion transfer element), a heat development photosensitive material (black and white, color) and the like. Among these photosensitive materials, printing materials, especially color paper, are preferred. Particularly, the present invention can be applied to a light-sensitive material which is processed rapidly, for example, a light-sensitive material processed in a processing step (time from the development step to the end of the drying step after bleaching / fixing and water washing) of 60 seconds or less. Is effectively exhibited.

Hereinafter, the color photographic light-sensitive material will be described in detail, but is not limited thereto.

The light-sensitive material only needs to have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. There is no particular limitation on the number of layers and the order of the non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having at least one color-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light. The sequence of the red-sensitive layer in order from the support side,
A green color sensitive layer and a blue color sensitive layer are provided in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. Between and above the silver halide photosensitive layer,
A non-photosensitive layer such as an intermediate layer of each layer may be provided as the lowermost layer.

The various additives of the photographic emulsion of the present invention, the layer constitution as a photographic light-sensitive material, the composition of a processing solution such as a developing solution and the like are not particularly limited. For example, refer to the description in the following known examples. Can be done.

Photographic element JP-A-7-104448 JP-A-7-310895 Support 7 column 12 line to 12 column 19 line 5 column 40 line to 9 column 26 line Stabilizer 75 column 9 to 18 line 18 column 11 line Column 31, line 37, antifoggant Chemical sensitizer column 74, line 45 to column 75, line 6, column 81, line 9 to 17 spectral sensitizer column 75, line 19 to column 76, line 45 column 81, line 21 to column 82, line 48 cyan Coupler 12 column 20 line-39 column 49 line 88 column 49 line-89 column 19 line Yellow coupler 87 column 40 line-88 column 3 line 89 column 19 line-30 line Magenta coupler 88 column 4 line-89 column 19 line 32 column Line 34 to column 77, line 44 Emulsification dispersion method Column 71, line 3 to column 72, line 11 Column 87, line 35 to line 48 Color image stabilizer Column 39, line 50 to column 70, line 9 Column 87, line 49 to column 88, line 48 Agent column 70, line 10 to column 71, line 2 Dye column 77, line 42 to column 78, line 41, column 9 line 27 to column 18, line 10 Scanning exposure 76, column 11 line 26 to line 31, column 38 to line 32, line 32 Column 6 line-77 column 41 line 82 column 49 line-83 column 12 line Developer 88 column 19 line-89 column 89 line 22.

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The present invention will be described in more detail with reference to the following examples.

(Example 1) <1. Preparation of {111} high silver chloride tabular grain emulsion (A)>
1.0 g of sodium chloride and 2.5 g of inert gelatin were added to 1.2 L of water, and 75 ml of an aqueous silver nitrate solution (containing 18 g of silver nitrate) and 75 ml of an aqueous sodium chloride solution (containing 6.2 g of sodium and 0.75 g of inert gelatin) were added in one minute by the double jet method (hereinafter, milliliter is also referred to as “mL”). End of addition 1
Minutes later, an aqueous solution 1 containing 0.92 mmol of the crystal habit controlling agent 1
8.6 mL was added. One minute later, 450 mL of a 10% oxidized gelatin solution was added. After the temperature of the reaction vessel was raised to 55 ° C. in the next 28 minutes, aging was performed for 27 minutes.

After aging, 2.35 mg of sodium benzylthiosulfate was added, and an aqueous silver nitrate solution (containing 263 g of silver nitrate) and an aqueous solution of NaCl (96 g of NaCl and 0.016 m ₂ of K ₂ IrCl ₆ ) were added at an accelerated flow rate for 32 minutes.
g) was added. During this time, 2.63 mmol of the crystal habit controlling agent 1 was simultaneously added at an accelerated flow rate (proportional to the added amount of silver nitrate). Next, an aqueous silver nitrate solution (containing 71 g of silver nitrate) and an aqueous NaCl solution (N
aCl, 24.2 g, KI, 1.39 g and yellow blood salt 1
2 mg). After the addition is completed, the temperature is raised to 75 ° C. for 20 minutes, and then at a constant flow rate for one minute, an aqueous silver nitrate solution (containing 2.9 g of silver nitrate) and an aqueous KBr solution (KB
r, including 2.25 g).

After the temperature was lowered to 40 ° C., the product was washed with water by a usual flocculation method. After washing with water, 175 g of inert gelatin, 34 mL of phenoxyethanol (35%) and 700 mL of distilled water were added. Further, the pH was adjusted to 6.2 and the pAg to 7.5 with sodium hydroxide and an aqueous sodium chloride solution. In the obtained grains (A), 99% or more of the total projected area were tabular grains, the average equivalent circle diameter was 0.85 μm, the average thickness was 0.146 μm, and the average aspect ratio was 5.9. The coefficient of variation of the thickness was 16.8%, and the coefficient of variation of the equivalent circle diameter was 19.0%.

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<2. {100} High silver chloride tabular grain emulsion (B)> In a reaction vessel described in JP-A-51-83097, [H ₂ O 1200 mL, gelatin (methionine content is about 40 μm)
Mol / g deionized alkali-treated bone gelatin) 25 g, N
pH 4.5] containing 1 g of aCl and 4.5 mL of a HNO ₃ 1N solution was added thereto, and the temperature was kept at 40 ° C. Ag-1 liquid (AgNO ₃ 0.2g / m while stirring at 1200rpm)
L) and X-1 solution (NaCl 0.069 g / mL) were simultaneously added at 48 mL / min for 15 seconds. Three minutes later, 60 mL of X-2 solution (KBr 0.012 g / mL)
Per minute for 20 seconds. After 3 minutes, the Ag-1 solution (AgNO ₃ 0.
2 g / mL) and the X-1 solution (NaCl 0.069 g / mL) were simultaneously added at 48 mL / min for 45 seconds. The stirring rotation speed was reduced to 750 rpm, and after another minute, an aqueous gelatin solution [H ₂ O 120 mL, gelatin 10 g, NaOH 1N
Solution 7mL, NaCl 1.7g], and after 4 minutes, 75 ℃ in 12 minutes
And aged for 25 minutes. Further, the KI solution (0.01
g / mL) and ripened for 5 minutes.

After the temperature was lowered to 40 ° C., the product was washed with water by a usual flocculation method. After washing with water, gelatin and distilled water were added so that the gelatin became 0.1 g per 1 g of the emulsion. Further, pH 6.2, pA with sodium hydroxide and NaCl.
g was adjusted to 7.5. The obtained emulsion (B) was collected, and an electron microscope photograph image (TEM image) of the particle replica was observed.
According to that, 98% of the projected area meter of all AgX grains are tabular grains with a principal plane of {100} plane, the average of the circle equivalent diameter is 0.66 μm, the coefficient of variation of the circle equivalent diameter is 16.7%, The average thickness is 0.11 μm, and the coefficient of variation of the distance between the main planes is 14.9 μm.
%, And the average aspect ratio was 7.3.

<3. Preparation of Emulsion C containing high silver chloride {100} normal crystal grains; Comparison> Sodium chloride in 1 L of water
8 g of silver nitrate aqueous solution (18 mL of silver nitrate 1.0 g) was added to a container maintained at 45 ° C. while stirring.
8 g) and 18 mL of an aqueous sodium chloride solution (0.389 g of sodium chloride) were added over 3 minutes by the double jet method. After 10 minutes, 270 mL of an aqueous silver nitrate solution (silver nitrate 1
6.2 g) and 270 mL of an aqueous sodium chloride solution (5.832 g of sodium chloride) were added over 18 minutes. After 3 minutes, 595 mL of an aqueous silver nitrate solution (119 silver nitrate) was added.
g) and 595 mL of an aqueous sodium chloride solution (43.0 g of sodium chloride) were added over 41 minutes. During this time, the temperature inside the reaction vessel was raised to 60 ° C. Next, 170 mL of an aqueous silver nitrate solution (34 g of silver nitrate) and an aqueous sodium chloride solution (containing 7.88 g of sodium chloride, 11 mg of yellow blood salt and 1.5 × 10 ⁻⁸ mol of iridium hexachloride) were added.

After the addition was completed, the temperature was lowered to 40 ° C., and then a desalting step was performed by a usual flocculation method. 78 g of gelatin, 80 mL of phenol (5%) and 199 mL of distilled water were added. PH with caustic soda and silver nitrate solution
It adjusted to 6.2 and pAg7.5. Thus, Emulsion C containing high silver chloride grains having an average equivalent spherical diameter of 0.63 μm was obtained.

<4. Chemical sensitization> Emulsions A, B and C
At 0 ° C., sensitizing dyes I and II, sodium benzylthiosulfonate, sodium thiocyanate, 1- (5
-Methylureidophenyl) -5-mercaptotetrazole, sodium thiosulfate and chloroauric acid. Thus, chemically sensitized emulsions A, B and C
I got

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<5. Preparation of coated sample and evaluation of photographic properties and stability> After performing corona discharge treatment on the surface of a support obtained by coating both sides of paper with a polyethylene resin, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was provided. Further, the photographic constitutions of the first to seventh layers were sequentially applied to prepare a coating sample of a silver halide color photographic light-sensitive material having the following layer constitution. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution A coupler, a color image stabilizer and an ultraviolet absorber were dissolved in a solvent and ethyl acetate, and this solution was added to a 10% by mass containing a surfactant.
The resulting mixture was emulsified and dispersed in an aqueous gelatin solution using a high-speed stirring emulsifier (dissolver) to prepare an emulsified dispersion. The emulsified dispersion and the silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution having the following composition.

As the gelatin hardener for each layer, sodium 1-oxy-3,5-dichloro-s-triazine was used.

Further, Ab-1, Ab-2 and A
The total amount of b-3 was 15.0 mg / m ² and 60.0, respectively.
mg / m ² , 5.0 mg / m ² and 10.0 mg / m ²
Was added so that

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The high silver chloride emulsion used for each photosensitive emulsion layer is as follows.

Blue-sensitive emulsion layer (see Table 1)

[Table 1]

Green-sensitive emulsion Silver chlorobromide emulsion (1: 3 mixture (silver molar ratio) of a large cubic emulsion having an average grain size of 0.45 μm (sphere equivalent diameter) and a small cubic emulsion of 0.35 μm. The variation coefficients of the sizes are 10% and 8%, and in each emulsion, 0.4 mol% of silver bromide is locally contained on a part of the surface of a grain based on silver chloride. 3.0 × 10 ^-4 mol for a large-sized emulsion, per mol of silver halide,
3.6 × 10 ^-4 mol was added to the small size emulsion.
Sensitizing dye E was added in an amount of 4.0 × 10 ⁻⁵ mol for a large-sized emulsion and 2.8 × 10 ⁻⁴ mol for a small-sized emulsion per mol of silver halide.

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Red-sensitive emulsion layer Silver chlorobromide emulsion (average grain size 0.40 μm (equivalent to sphere)
Diameter) large cubic emulsion and 0.30 μm small cubic emulsion
1: 1 mixture with silver emulsion (silver molar ratio). Particle size
The coefficients of variation are 0.09 and 0.11. Odor of each size emulsion
Part of the grain surface with 0.5 mol% of silver chloride as the base of silver chloride
Sensitizing dyes G and H, and halogen
Per mole of silver halide, for large emulsions
9.0 × 10 ^-FiveFor mole and small size emulsions respectively
1.2 × 10^-FourMole was added. Further, the following compound I
3.0 × 10 3 per mole of silver halide^-3Mole added
Was.

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Also, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive, green-sensitive and red-sensitive emulsion layers in an amount of 3.3 × 10 ^-4 mol per mol of silver halide. , 1.0 × 10 ^-3 mol and 5.9 × 10 ^-4 mol.

Further, the second layer, the fourth layer, the sixth layer and the seventh layer also have 1- (3-methylureidophenyl) -5-
Mercaptotetrazole was added at 0.2 mg /
m ² , 0.2 mg / m ² , 0.6 mg / m ² and 0.1
mg / m ² . Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol, × 10
^-4 mol was added.

In the red-sensitive emulsion layer, a copolymer of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 2
0000-400,000) was added at 0.05 g / m ² . Catechol-in the second, fourth and sixth layers
Each of disodium 3,5-disulfonate at 6 mg /
m ² , 6 mg / m ² and 18 mg / m ² . To prevent irradiation, the following dyes were added (in parentheses, the coating amount is shown).

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). In the case of an emulsion, the coating amount is expressed in terms of silver.

Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content: 16% by mass, ZnO; content: 4% by mass), fluorescent whitening agent (13 mg / m ^{2 of} 4,4'-bis (5-methylbenzoxazolyl) stilbene), bluish dye (ultramarine)
96 mg / m ² ].

First layer (red-sensitive emulsion layer) Emulsion (red-sensitive emulsion described above) 0.12 Gelatin 0.59 Cyan coupler (ExC-1) 0.13 Cyan coupler (ExC-2) 0.03 Color image stability Agent (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 Solvent (Solv-5) ) 0.09.

Second layer (color mixture prevention layer) Gelatin 0.60 Color mixture prevention agent (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.

Third layer (green-sensitive emulsion layer) Emulsion (green-sensitive emulsion) 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.

Fourth layer (color mixture prevention layer) Gelatin 0.48 Color mixture prevention agent (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.006 Color image stabilizer (Cpd-7) 0.006 UV absorber (UV-C) 0.04 Solvent (Solv-5) 0.09.

Fifth layer (blue-sensitive emulsion layer) Emulsion (see Table 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.

Sixth layer (ultraviolet absorbing layer) Gelatin 0.32 Ultraviolet absorbing agent (UV-C) 0.42 Solvent (Solv-7) 0.08.

Seventh layer (protective layer) Gelatin 0.70 Acrylic modified copolymer of polyvinyl alcohol 0.04 (Modification degree 17%) Liquid paraffin 0.01 Surfactant (Cpd-13) 0.01 Polydimethylsiloxane 0.01 silicon dioxide 0.003.

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Coating samples 1 to 15 were obtained by using the emulsions shown in Table 1 in the blue-sensitive layer of the light-sensitive material having the above layer constitution.

(Exposure) Using the following exposure apparatus, exposure was performed with laser light of three colors, B, G, R, to give a gradation of three colors. At that time, the laser output was corrected for each sample so as to obtain the optimum improvement.

(Exposure apparatus) The light source is a semiconductor laser GaAlAs
(Oscillation wavelength: 808.5nm) YAG solid-state laser with excitation light source
(Oscillation wavelength: 946 nm) with LiNbO ₃ having an inverted domain structure
The SHG crystal of LiNbO ₃ having an inverted domain structure is obtained by using a 473 nm wavelength-converted SHG crystal and a YVO ₄ solid-state laser (oscillation wavelength: 1064 nm) using a semiconductor laser GaAlAs (oscillation wavelength: 808.5 nm) as an excitation light source. 532 nm extracted after wavelength conversion and AlGaInP (oscillation wavelength; 680 nm: type No. LN9R20 manufactured by Matsushita Electric Industrial Co., Ltd.) were used. The laser light of each of the three colors was intensity-modulated by the AOM, moved in the direction perpendicular to the scanning direction by the polygon mirror, and allowed to be sequentially scanned and exposed on color photographic paper. Fluctuations in light intensity due to the temperature of the semiconductor laser are suppressed by using a Peltier element to keep the temperature constant. This scanning exposure is 600dpi
In the light beam diameter measurement using the light beam diameter measuring device [1180GP / manufactured by Beam Scan (USA)], B, G, and R
It was 65 μm (a circular beam having a difference of 1% in the main scanning direction diameter / sub-scanning direction diameter).

(Processing process time: 180 seconds) The sample exposed as described above was subjected to CP-45 of Fuji Photo Film Co., Ltd.
X processing was performed.

The color density of the processed color sample was measured using a TCD type densitometer manufactured by Fuji Photo Film Co., Ltd. The sensitivity was expressed as the logarithm of the exposure required to give a color density 1.0 higher than the fog density. The sensitivity of the blue-sensitive layer is shown in Table 1. In Table 1, the coating samples 1 to 5 are represented by relative values with the sensitivity of the coating sample 1 being 0, and the coating samples 6 to 15 are represented by relative values with the sensitivity of the coating sample 6 being 0. ing. Positive values indicate high sensitivity.

(Storage Stability Test) Further, in order to examine the storage stability of the sample, the sample was stored in an atmosphere of 60 ° C. and 30% RH for 2 days, and then subjected to the above exposure treatment, and was not stored. The sensitivity was compared with the sample. The sensitivity was indicated by a difference in logarithmic value of the exposure amount required to give a density 0.3 higher than the fog density. Positive values indicate sensitization during storage.

From the results shown in Table 1, it was found that the emulsion according to the present invention had high sensitivity, and furthermore sensitization during storage was suppressed and stability was improved. Furthermore, the effect of suppressing sensitization during storage was greater for tabular grains than for cubes.

(Example 2) In the case where the processing time was 60 seconds, the coating samples 1 to 15 of Example 1 were processed in the same manner as in Example 1 except that the processing time of 60 seconds shown below was applied. An evaluation was performed.

Processing Step Temperature Time Replenisher * Tank capacity Color development 45 ° C 13 seconds 35mL 2L Bleach-fix 40 ° C 13 seconds 38mL 1L Rinse 40 ° C 8 seconds --- 1L rinse 40 ° C 8 seconds --- 1L rinse 40 ° C 8 sec 90 mL 1L drying 80 ° C. 10 seconds --- --- (as a tank countercurrent system to rinse →) * replenishment rate per photosensitive material 1 m ^2.

In the above treatment, the rinse water was pumped to the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not pass through the reverse osmosis membrane was returned to the rinse for use. In addition,
In order to reduce the crossover time between the rinses, a blade was installed between the tanks, and the photosensitive material was passed between them. In each step, a circulating treatment liquid was sprayed by using a spraying device described in JP-A-8-314088 with the spraying amount set to 4 to 6 L / min per tank.

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 700 mL 700 mL Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-Dihydroxybenzene-4,6-disulfonate disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 15.8 g --- Potassium bromide 0.04 g --- Potassium carbonate 27.0 g 27.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 18.0 g 18.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 8.0 g 23.0 g sodium-bis- (2,4-disulfonatoethyl, 1,3,5- Triazyl-6) -diaminostilbene-2,2'-disulfonate 5.0 g 6.0 g Water was added to 1000 mL 1000 mL pH (25 ° C) 10.35 12.80.

The bleach-fix solution was prepared by mixing two replenishers as follows. Bleach-fixer tank solution replenishing amount (total per 1 m ² in the following weight 38mL) 1000mL pH (25 ℃) by adding first replenisher 260 mL 18 mL second replenisher 290 mL 20 mL water 5.0.

The composition of the first and second replenishers is as follows. First replenisher Water 150 mL Ethylene bisguanidine nitrate 30 g Ammonium sulfite / monohydrate 226 g Ethylenediaminetetraacetic acid 7.5 g Triazinylaminostilbene-based fluorescent whitening agent 1.0 g (Hakor FWA-SF manufactured by Showa Chemical Co., Ltd.) 30 g Ammonium thiosulfate (700 g / L) 340 mL Add water to 1000 mL pH (25 ° C) 5.82.

Second replenisher Water 140 mL Ethylenediaminetetraacetic acid 11.0 g Ammonium iron (III) ethylenediaminetetraacetate 384 g Acetic acid (50%) 230 mL Water was added to the solution to make 1000 mL pH (25 ° C.) 3.35. Rinse liquid Ion-exchanged water (Ca and Mg each less than 3 ppm).

The results are shown in Table 2. Even in a rapid processing system, the effects of the present invention such as higher sensitivity and improved storage stability were observed. The effect was effective from a smaller amount in the case of rapid processing.

[0253]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/035 G03C 1/035 KL M 1/09 1/09 5/26 5/26

Claims (10)

[Claims] 1. A silver halide photographic material having at least one light-sensitive layer on a support, wherein the light-sensitive layer contains a compound represented by the following general formula (I) and a halogen containing at least 90 mol% of silver chloride. A halide comprising silver halide grains, wherein at least 90% of the total projected area of the grains is a tabular grain having an average aspect ratio of 5 or more and an average thickness of 0.20 μm or less. Silver photographic photosensitive material. Formula (I) (X) _k- (L) _m- (AB) _{n wherein} X is a halogenated atom having at least one atom selected from the group consisting of N, S, P, Se and Te. Represents a silver adsorption group or a light absorption group. L is C, N, S and O
Represents a divalent linking group having at least one atom selected from the group consisting of A represents an electron donating group, B represents a leaving group or a hydrogen atom, after oxidation, is disengaged or deprotonated to generate a radical A ^· in. k and m each independently represent an integer of 0 to 3, and n represents 1 or 2. 2. The coefficient of variation of the thickness of the tabular grains is 20%.
2. The silver halide photographic light-sensitive material according to claim 1, wherein: 3. The silver halide photographic material according to claim 1, wherein the coefficient of variation of the equivalent circle diameter of the tabular grains is 22% or less. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the tabular grains have a {111} major plane. 5. The method according to claim 1, wherein the silver halide grains have a silver content of 0.
5. The silver halide photographic light-sensitive material according to claim 1, comprising 1 mol% to 0.8 mol% of silver iodide. 6. A method according to claim 1, wherein said silver halide grains have a silver content of 0.
The silver halide photographic material according to any one of claims 1 to 5, comprising 1 mol% to 4 mol% of silver bromide. 7. The silver halide grain according to claim 1, wherein the silver halide grains comprise a core and a shell, and the silver iodide content of the shell portion is 1 to 13 mol%. 2. The silver halide photographic light-sensitive material described in 1. above. 8. The halide according to claim 1, wherein the silver halide grains contain a silver bromide localized phase having a silver bromide concentration of 6 mol% or more. Silver photographic photosensitive material. 9. The silver bromide localized phase contains 1 × 10 ⁻⁸ mol% to 1 × 10 ⁻⁵ mol% of an Ir compound based on the total silver content of the grains. Item 8. The silver halide photographic material according to Item 8. 10. The silver halide photographic light-sensitive material according to claim 1, which is processed in a processing time of 60 seconds or less.