JPH1124193A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material superior in stability and storage stability by incorporating photographic useful compounds microencapsulated with a polymer in hydrophilic colloidal layers. SOLUTION: The silver halide photographic sensitive material is provided on a support with the hydrophilic colloidal layers including a silver halide emulsion layer, and the hydrophilic colloidal layers contain the photographic useful compounds microencapsulated with the polymer. These useful compounds include, for example, photographic couplers including yellow, magenta, and cyan image-forming couplers, colored or masking couplers, a development inhibitor-releasing coupler, a bleach-accelerator-releasing coupler, a dye-releasing coupler, and the like), and an ultraviolet absorber, a reducing agent, a developing agent, a development intensifier, and the like. The ones, among these photographic useful materials, receiving an especially high microencapsulation effect are leuco compounds for forming a blue dye by reaction with the oxidation product of a developing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having excellent stability and storage stability.

[0002]

2. Description of the Related Art Various photographic useful compounds have been added to silver halide photographic light-sensitive materials in view of their constitution and performance.

Conventionally, when preparing a photographic useful compound (photographic additive), preparing a photographic material coating solution, drying after coating, or storing a photographic material, the photographic useful compound is replaced with another compound. And the original function is hindered.

For example, a leuco compound described in JP-A-3-153234, which reacts with an oxidized form of a developing agent to form a blue dye, can be used at times other than development, for example, at the time of preparing a coating solution or storing a film. In addition, there is a problem in that the desired color tone improving performance (low blue density is low in the low density area and high blue density is high in the middle to high density area) is not sufficiently obtained.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material having excellent stability and storage stability.

[0006]

The above object of the present invention has been attained by the following constitutions.

(1). In a silver halide photographic material provided with a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, the hydrophilic colloid layer contains a photographically useful compound microencapsulated by a polymer. A silver halide photographic light-sensitive material, characterized in that:

(2). The silver halide photographic material according to (1), wherein the polymer is an alkali-soluble polymer.

(3). The silver halide photographic material according to (1) or (2), wherein the polymer is soluble at pH = 6 or more.

(4). The silver halide photographic light-sensitive material according to any one of (1) to (3), wherein the photographically useful compound is a leuco compound which forms a blue dye by reacting with an oxidized form of a developing agent.

Hereinafter, the present invention will be described in detail.

The photographically useful compound in the present invention includes, for example, photographic couplers (yellow, magenta and cyan image forming couplers, colored or masking couplers, inhibitor releasing couplers and bleaching accelerator releasing couplers, dye releasing couplers and the like). ), UV absorbers, reducing agents, developing agents, development enhancers, and the like.

Among the photographically useful compounds of the present invention, a leuco compound which forms a blue dye by reacting with an oxidized form of a developing agent is particularly effective for microencapsulation. The following general formulas (1) to form a blue pigment by reacting with the oxidized form of the base drug
Leuco compound represented by (4) (hereinafter also referred to as leuco compound represented by general formulas (1) to (4) of the present invention, or leuco compound represented by general formulas (1) to (4) of the present invention) Is mentioned.

Hereinafter, the leuco compounds represented by formulas (1) to (4) of the present invention will be described.

[0015]

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[Wherein, W represents -NR ₁ R ₂ , -OH or -OZ, R ₁ and R ₂ each represent an alkyl group or an aryl group, and Z represents an alkali metal ion or a quaternary ammonium ion. Represents R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. Z ₁ and Z ₂ are each a nitrogen atom or ＣC
(R ₃ ) —. X represents an atomic group necessary for constructing a 5- to 6-membered aromatic heterocyclic ring together with Z ₁ , Z ₂ and carbon atoms adjacent thereto. R ₄ is a hydrogen atom, an acyl group,
Represents a sulfonyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R represents an aliphatic group or an aromatic group. p represents an integer of 0 to 2. CP1 represents the following groups. ]

[0017]

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[0018]

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[Wherein, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom or a substituent capable of substituting on a benzene ring. R ₅ and R ₆ and R ₇ and R ₈ are bonded to each other to form 5 to 7;
A member ring may be formed. R ₉ has the same meaning as R ₄ . R ₁₀
And R ₁₁ each represents an alkyl group, an aryl group or a heterocyclic group. R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ have the same meaning as R ₁₀ and R ₁₁ . R ₁₅ has the same meaning as R ₁₂ . R ₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ , and m represents an integer of 1 to 3. Y1 represents an atomic group necessary for constructing a 5- or 6-membered monocyclic or condensed nitrogen-containing heterocyclic ring together with two nitrogen atoms. R ₁₉ and R ₂₀ represent an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and R ₂₃ are R
It is synonymous with ₁₉ and R _20. R ₂₄ has the same meaning as R ₂₁ .
R ₂₅ , R ₂₇ and R ₂₈ represent a hydrogen atom or a substituent.
R ₂₆ has the same meaning as R ₄ . R ₂₉ , R ₃₁ and R ₃₂ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₀ has the same meaning as R ₂₆ . R ₃₄ , R ₃₅ and R ₃₆ are R ₂₅ , R ₂₇ and R ₂₈
Is synonymous with R ₃₃ has the same meaning as R ₂₆ . R ₃₈ , R ₃₉ and R ₄₀ have the same meaning as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₇ has the same meaning as R ₂₆ . R ₄₁ , R ₄₂ and R ₄₃ are R ₂₅ , R ₂₇
And R ₂₈ have the same meanings. R ₄₄ has the same meaning as R ₂₆ . ★
Represents a bonding point between CP1 and another partial structure in the general formula (1). ]] It is preferable that the compound represented by the general formula (1) is a compound represented by the following general formula (2).

[0020]

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[Wherein R ₁ , R ₂ , R ₃ , R ₄ , CP 1,
n, R and p are R ₁ , R ₂ ,
It has the same meaning as R ₃ , R ₄ , CP 1, n, R and p. Further, in the present invention, a compound represented by the following general formula (3) is also preferably used. In this case, the compound preferably contains at least one kind of a compound represented by RSO ₃ H,
More preferably, the compound represented by RSO ₃ H is contained in the same layer as the compound represented by the general formula (3).

[0022]

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Wherein R ₃ , n, R ₄ , W, X, Z ₁ ,
Z ₂ and CP1 represent R ₃ , n, R in the general formula (1).
₄ , synonymous with W, X, Z ₁ , Z ₂ and CP1. The compound represented by the general formula (3) is preferably a compound represented by the following general formula (4).

[0024]

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[Wherein R ₁ , R ₂ , R ₃ , R ₄ , CP 1 and n represent R ₁ , R ₂ , R ₃ , R ₄ , CP in the general formula (1).
Synonymous with 1 and n. In the leuco compounds represented by the general formulas (1) to (4), R ₄ , R ₉ , R ₁₂ , R ₁₅ , R ₁₇ , R ₂₁ , R ₂₄ , R
_At least one of the groups represented by ₂₆ , R ₃₀ , R ₃₃ , R ₃₇ and R ₄₄ is —COOM ¹ and —SO ₃ M ² (M ¹ and M
² each represents a hydrogen atom or an alkali metal).

Hereinafter, the leuco compounds represented by the general formulas (1) to (4) will be described in detail.

In the general formulas (1) to (4), the alkyl group represented by R ₁ and R ₂ preferably includes a methyl group, an ethyl group, a propyl group and a butyl group.
These may be further substituted, and preferred substituents include a hydroxy group and a sulfonamide group.

The aryl group represented by R ₁ and R ₂ is preferably a phenyl group.

Examples of the monovalent substituent represented by R ₃ include an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a t-butyl group, etc.), a cycloalkyl group and the like. Group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p
-Tolyl group, p-chlorophenyl group, etc.), alkoxyl group (eg, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), cyano group, acylamino group (eg, acetyl group) Amino group, propionylamino group, etc., alkylthio group (eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.) ), Ureido groups (eg, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino groups (dimethylsulfamoylamino group, etc.),
Carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.) ,
Aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.), sulfonyl group (for example, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.),
Acyl group (for example, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group,
Examples include an imide group (for example, a phthalimido group) and a heterocyclic group (for example, a pyridyl group, a benzimidazolyl group, a benzothiazolyl group, a benzoxazolyl group, and the like).

The acyl group represented by R ₄ is preferably an acetyl group, a trifluoroacetyl group, a benzoyl group or the like. Preferred examples of the sulfonyl group include a methanesulfonyl group and a benzenesulfonyl group. Preferable examples of the carbamoyl group include a diethylcarbamoyl group and a phenylcarbamoyl group. Preferred examples of the sulfamoyl group include a diethylsulfamoyl group. The alkoxycarbonyl group preferably includes a methoxycarbonyloxy group and an ethoxycarbonyloxy group. Preferable examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

Examples of the alkali metal represented by Z include sodium and potassium. Examples of the quaternary ammonium include ammonium having a total carbon number of 8 or more, such as trimethylbenzylammonium, tetrabutylammonium, and tetradecylammonium.

Examples of the 5- or 6-membered aromatic hetero ring composed of X, Z ₁ , Z ₂ and carbon atoms adjacent thereto include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a tetrazine ring, and a pyrrole. Ring, furan ring, thiophene ring, thiazole ring, oxazole ring, imidazole ring, thiadiazole ring, oxadiazole ring and the like. Preferably it is a pyridine ring.

Examples of the substituent capable of substituting on the benzene ring represented by R _{5 to} R ₈ include groups having the same meaning as the above-mentioned monovalent substituent represented by R ₃ . Preferred are an alkyl group and an acylamino group.

The 5- to 7-membered ring formed by combining R ₅ and R ₆ and R ₇ and R ₈ includes an aromatic carbon ring and a heterocyclic ring, preferably a benzene ring. it can.

Examples of the alkyl group represented by R ₁₀ and R ₁₁ include a methyl, ethyl, propyl and butyl group.
Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the heterocyclic group include a 5- to 6-membered aromatic heterocycle having at least one of O, S, and N atoms in the ring (for example, pyridine, pyrazine , A 6-membered ring azine such as a pyrimidine ring and the like, and their benzerogues: pyrrole, thiophene, furan and their benzerogues: imidazole, pyrazole,
5-membered ring azoles such as triazole, tetrazole, thiazole, oxazole, thiadiazole, and oxadiazole, and benzerogue, etc.). R ₁₀ and R ₁₁ preferably include a phenyl group, a pyrazolyl group, a pyridyl group and the like.

Examples of the alkyl group represented by R ₁₆ include a methyl group, an isopropyl group, a pentyl group and a t-butyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the sulfonyl group include a methine sulfonyl group and a benzenesulfonyl group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group. Examples of the alkoxycarbonyl group include an ethoxycarbonyl group. Examples of the carbamoyl group include a diethylaminocarbamoyl group.

Examples of the nitrogen-containing heterocycle represented by Y1 include each of imidazole, triazole, tetrazole and the like, and benzo-fused rings thereof.

Examples of the alkyl group represented by R ₁₉ and R ₂₀ include a methyl group, a pentyl group and a t-butyl group. Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the substituent represented by R ₂₅ , R ₂₇ and R ₂₈ include a phenyl group, a methyl group, a benzoyl group, a phenoxy group and an ethoxy group.

Examples of the aliphatic group represented by R include a hexyl group and a dodecyl group. As the aromatic group, p
-Toluene, dodecylbenzene and the like.

The leuco compounds represented by the general formulas (1) to (4) will be specifically described below, but the invention is not limited thereto.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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Synthesis Example 1 (Synthesis of Exemplified Compound 8) Reaction Route

[0055]

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(1) 3.9 g was dissolved in 50 ml of ethyl acetate, 0.5 g of 5% Pd / C was added, and hydrogenation was carried out at normal pressure. The blue color of the reaction solution disappeared, and (2) was formed.

Next, 1.2 g of triethylamine was added to the reaction solution.
And 1.5 g of acetyl chloride were added, and the mixture was stirred at room temperature for 2 hours. The catalyst and insolubles were separated by filtration, and the residue was recrystallized from ethyl acetate to give 3.8 g of the desired Exemplified Compound 8 (yield: 89).
%)Obtained.

The structure was confirmed by NMR spectrum and Mass spectrum.

Synthesis Example 2 (Synthesis of Exemplified Compound 9)

[0060]

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3.9 g of (1) of Synthesis Example 1 was treated with ethyl acetate 5
The mixture was dissolved in 0 ml, and 0.5 g of 5% Pd / C was added thereto to carry out normal-pressure catalytic hydrogenation. The blue color of the reaction solution disappeared and (2)
Generated.

Next, 1.2 g of triethylamine was added to the reaction solution.
And 4.0 g of trifluoroacetic anhydride were added, followed by stirring at room temperature for 2 hours. The catalyst and insolubles were separated by filtration, and the residue was recrystallized from ethyl acetate to give 4.0 g of the desired Exemplified Compound 9 (yield 8
5%).

The structure was confirmed by NMR spectrum and Mass spectrum.

Synthesis Example 3 (Synthesis of Exemplified Compound 58) Reaction Route

[0065]

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Exemplified Compound 8 was added to 30 ml of methanol.
5 g was dissolved, and p-toluenesulfonic acid monohydrate 2.6
g and stirred.

Next, the reaction mixture was poured into 300 ml of water, and filtered to obtain 4.1 g of the desired Exemplified Compound 58 (yield 87%).
Obtained.

The structure was confirmed by NMR spectrum and Mass spectrum.

Other compounds could be easily synthesized in the same manner as in the above synthesis examples.

The amount of the leuco compound represented by the general formulas (1) to (4) of the present invention is not less than 1 × 10 ^-6 mol and less than 5 × 10 ^-1 mol per mol of silver in a medical light-sensitive material. This is preferable for achieving the effects of the present patent. Below this, the effect of improving the silver tone is small, and above this, the entire image is dark, which is not preferable. More preferably, when it is contained at least 5 × 10 ⁻⁵ mol and less than 5 × 10 ⁻² mol per mol of silver, particularly 5 × 10 ⁻⁴ mol per mol of silver.
More than 1 mol and less than 1 × 10 ^-2 mol is preferable in terms of achieving the effect.

The molar ratio of the leuco compound represented by the general formulas (3) and (4) to RSO ₃ H of the present invention is represented by the general formula (3):
RS0 ₃ H1 to 1 mol of the compound represented by (4)
Preferably it is 3 moles.

The layer to which the leuco compound of the present invention is added is not particularly limited.
It is preferably a layer closer to the emulsion layer, and more preferably contained in the emulsion layer or a layer in contact with the emulsion layer and above the emulsion layer.

Next, the microcapsules according to the present invention will be described.

The microcapsule according to the present invention means that at least one kind of photographic material is used in a solid state, a solution state,
Alternatively, in a suspension state in which the material exists as particles, a reserve type (reservo
(or type) microcapsules,
Monolithic type microcapsules in which the material is uniformly or consciously localized and dispersed in a solid or solution state in a matrix of a polymer substance, so-called microspheres may be used.

The polymer (polymeric substance) of the microcapsules used in the present invention has a pH of 6 or more, preferably 7 or more, for the purpose of preventing the photographically useful compound from being destabilized before the development processing. The polymer which dissolves is good, and the wall material of such an alkali-soluble polymer may or may not dissolve during the development step and elute from the silver halide photographic light-sensitive material.

In the present invention, examples of the polymer that is advantageously used as the wall material of the microcapsules include vinyl polymers having a carboxyl group or a sulfonic acid group in the side chain, condensation polymers, and the like. As a combination, methacrylic acid, acrylic acid, a monomer having a carboxyl group and a sulfonic acid group in a side chain such as vinyl sulfonic acid, and methyl methacrylate, acrylates such as ethyl methacrylate, styrene, Copolymers with styrenes such as methylstyrene and monomers such as vinyl methyl ketone, and the like, and the composition ratio of a monomer having a carboxyl group or a sulfonic acid group in a side chain and other monomers Is 4
0:60 to 70:30 (weight ratio) is preferred. Examples of the condensation polymer include a condensation product of lysine and a polycarboxylic acid chloride such as terephthaloyl chloride, adipic acid chloride, and sebacic acid chloride. In addition to these, a carboxy group-containing cellulose derivative having a carboxyl group in the molecule is exemplified.

In the present invention, the polymer used as the wall material of the microcapsule can be more specifically described as follows:
Methacrylic acid (MAA) -methyl methacrylate (MMA) copolymer (MAA / MMA) which is a vinyl polymer
= 40/60 to 70/30 (% by weight)), and methyl acrylate (MA) -ethyl methacrylate (MAE) copolymer (MA / MAE = 40/60 to 70/30 (% by weight)). A copolymer of acrylic acid or methacrylic acid and an acrylic ester or a methacrylic ester, a vinyl polymer having a carboxyl group or a sulfo group or a salt thereof, such as a vinyl sulfonic acid-methacrylic ester copolymer, Condensation-type polymers having a carboxyl group in the molecule, such as lysine, and acid chlorides such as terephthaloyl chloride, and cellulose derivatives having a carboxyl group in the molecule can be advantageously used.

The thickness of the wall material of the microcapsule of the present invention can be freely changed depending on the solubility of the wall material and the purpose. For example, the film thickness can be arbitrarily selected from the viewpoint of stability during storage of the photographic material included as the core substance and prevention of delay in the development processing time. Further, in order to control the reaction of the core material during the development processing time, the thickness of the wall material can be changed according to the purpose such as changing the thickness of the wall material. In addition, the control of the effects of these core materials in the photographic processing solution can be controlled not only by the wall material film thickness but also by selecting and using polymer materials having different dissolution rates.

The radius particle size of the microcapsule of the present invention is 5
μm or less is preferred. More preferably, it is 1 μm or less, further preferably, 0.5 μm or less.

The production of the microcapsules according to the present invention depends on the form of the photographic material encapsulated or dispersed in the polymer, but may be carried out by a phase separation method, a submerged drying method, a melt dispersion cooling method, a spray drying method, or the like. An interfacial deposition method of depositing a wall material such as a pan coating method or an air suspension coating method at a core material interface may be used, and an interface such as an interfacial polymerization method, an internal polymerization method, an external polymerization method, and a submerged hard coating method. An interface reaction method in which a wall is formed by utilizing the reaction in step (1) may be used.

Next, the silver halide grains used in the present invention will be described.

The silver halide grains used in the present invention are not particularly limited, but tabular silver halide grains having an aspect ratio of 3 or more are preferred. More preferably, it is 3 or more and less than 15. Particularly preferred is 3 or more and less than 8.

In the silver halide grains used in the present invention, silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver iodochloride, silver chloroiodobromide and the like can be used as silver halide. The content of silver iodide is preferably 1.0 mol% or less, more preferably 0.5 mol% or less, as the average silver iodide content in the whole silver halide grains.

The tabular silver halide grains used in the present invention can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to form nuclei with low pCl in the presence of iodine ions under conditions that facilitate formation of the (100) plane. After nucleation, Ostwald ripening and / or growth is performed to obtain tabular silver halide grains having a desired grain size and distribution. The tabular silver halide grains used in the present invention may be so-called halogen conversion type (conversion type) grains. The halogen conversion amount is preferably from 0.2 mol% to 0.5 mol% with respect to the silver amount, and the conversion may be performed during physical ripening or after completion of physical ripening.

During the process of forming and / or growing the silver halide grains, a cadmium salt, a zinc salt,
Lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), ruthenium salts (including complex salts),
It is preferable that a metal ion is added using at least one selected from an osmium salt (including a complex salt) and an iron salt (including a complex salt) to contain these metal elements inside and / or on the surface of the particles.

In the present invention, it is preferable to add a silver halide solvent before the desalting step in order to accelerate the developing speed. For example, a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is used in an amount of 1 × 10 ⁻³ mol or more and 3 × 10 ³ mol or more per mol of silver.
It is preferable to add ^-2 mol or less.

In the present invention, gelatin is preferably used as a dispersion medium for the protective colloid of silver halide grains. As the gelatin, alkali-treated gelatin, acid-treated gelatin, low-molecular-weight gelatin (having a molecular weight of 20,000 to 10
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (Resea
rch Disclosure (hereinafter abbreviated as RD) No. 17
No. 6 No. 17643 (December 1978).

In the present invention, unnecessary soluble salts may be removed during the growth of silver halide grains, or they may be kept contained. When removing the salts, see RD Vol. It can be performed based on the method described in 17643, section II.

The silver halide grains of the present invention can be subjected to chemical sensitization. The conditions of the process of chemical ripening or chemical sensitization,
For example, the pH, pAg, temperature, time and the like are not particularly limited, and the reaction can be performed under conditions generally performed in the art. For chemical sensitization, sulfur sensitization using a compound containing sulfur that can react with silver ions or active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, using a reducing substance Reduction sensitization, gold and other, noble metal sensitization using a noble metal and the like can be used alone or in combination, among which selenium sensitization, tellurium sensitization, reduction sensitization, etc. are preferably used,
In particular, a selenium sensitization method is preferably used.

Regarding the selenium sensitizer, US Pat.
74,944, 1,602,592, 1,62
3,499, JP-A-60-150046, JP-A-4
-25832, 4-109240, 4-147
No. 250, etc.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N,
N-dimethylselenourea, N, N, N'-triethylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), Selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), selenides (diethylselenide) , Diethyl diselenide,
Triphenylphosphine selenide). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenium ketones.

[0092] The amount of the selenium sensitizer selenium compound used, the silver halide grains will vary by the chemical ripening condition and the like, generally per mol of silver halide 10 ^-8 mol to 10
^Use about ^-4 moles. Depending on the properties of the selenium compound to be used, the addition method may be a method of dissolving in water or an organic solvent such as methanol, ethanol or ethyl acetate alone or in a mixed solvent, or a method of preliminarily mixing with a gelatin solution. Also, the method of adding
No. 9, that is, a method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

The silver halide emulsion used in the practice of the present invention may be spectrally sensitized with a cyanine dye or the like. The sensitizing dye may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for supersensitization.

When the light-sensitive material of the present invention is used as a double-sided emulsion X-ray light-sensitive material for medical use, it is preferable to provide a transverse light blocking layer for the purpose of improving image sharpness. The transverse light blocking layer contains a solid fine particle dispersion of a dye for the purpose of absorbing transverse light. Such a dye is not particularly limited as long as it has a structure that is soluble in an alkali having a pH of 9 or more and has a structure that is hardly soluble at a pH of 7 or less. The compound of the general formula (I) described in JP-A-308670 is preferably used.

In the light-sensitive material using the silver halide emulsion of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening of the emulsion.

Compounds that can be used in such a step include, for example, the aforementioned Research Disclosure (R
D) 17643, (RD) 18716 (November 1979) and (RD) 308119 (December 1989)
Month). The types and locations of the compounds described in these three (RD) are described below.

[0097]

[Table 1]

Examples of the support used in the light-sensitive material of the present invention include those described in the above-mentioned RD. A suitable support is a plastic film or the like. In order to improve the performance, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied. Then, the emulsion according to the present invention can be coated on both sides of the support thus treated. The light-sensitive material of the present invention may further include an antihalation layer, an intermediate layer, a filter layer, and the like, if necessary.

In the light-sensitive material of the present invention, a silver halide emulsion layer and other hydrophilic colloid layers can be coated on a support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method, or the like can be used. For details, see Research Disclosure, No. 1.
Vol. 76, p. 27-28, "Coating process"
dures "section.

The processing of the light-sensitive material of the present invention is carried out, for example, in the manner described in RD-17643, pages XX to XXI, pp. 29 to 30 or 3 above.
Treatment with a treatment solution as described in 08119, XX to XXI, pp. 1011 to 1012 may be performed.

Examples of the developer for black-and-white photographic processing include dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), and aminophenols (eg, N-methyl-aminophenol). They can be used alone or in combination. In the developer, a known agent such as a preservative, an alkali agent, a pH buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color tone agent, a water softener, and a dissolution aid can be used. A viscosity imparting agent may be used as necessary.

The fixing solution contains a fixing agent such as thiosulfate and thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. Other preservatives, pH adjusters,
It may contain a water softener or the like.

In the present invention, it is possible to perform ultra-rapid processing with a total processing time (Dry to Dry) of 15 to 60 seconds by an automatic developing machine. "Developing process time" here
Alternatively, the term “development time” refers to the time from when the leading edge of the photosensitive material to be processed is immersed in a developing tank solution of an automatic developing machine (hereinafter referred to as an automatic developing machine) to when it is immersed in the next fixing solution. "
"Washing time" refers to the time from immersion in the fixing tank solution to immersion in the next washing tank solution (stabilizing solution). Also "drying time"
And usually, in the automatic machine, preferably 35 ℃ ~ 100 ℃,
More preferably, a drying zone in which hot air of 40 ° C. to 80 ° C. is blown is provided, and it refers to a time in the drying zone.

In the present invention, in processing such as development and fixing, the processing time is 15 seconds or less, and the processing temperature is preferably 25 seconds.
C. to 50C, more preferably 30C to 40C for 2 seconds to 10 seconds.

In the present invention, the developed, fixed and washed (or stabilized) photosensitive material is dried through a squeeze roller for squeezing the washing water. Washing process is 5-5
It is preferably at 0 ° C. for 2 to 10 seconds.

In the present invention, the photosensitive material which has been developed, fixed and washed with water is dried via a squeeze roller. The drying method is
Either hot air convection drying, radiation drying using a far-infrared heater, or heat transfer drying using a heat roller, or a combination thereof can be used. Drying temperature and time are 4 ~ 15 at 40 ~ 100 ° C
It is preferably done in seconds.

In the present invention, the processing is preferably carried out at a replenishment amount of the developing solution and the fixing solution of 35 to 130 ml per m ^{2 of the} photographic material. As a replenishment method, JP-A-55-12
No. 6243, replenishment by width and feed speed.
No. 0-104946, area replenishment, JP-A-1-149
No. 156, the area replenishment controlled by the number of continuously processed sheets may be used.

[0108]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

(Preparation of Dispersion of Leuco Compound of the Present Invention) << Preparation of Reserve Type Microcapsule Solutions A-1 to A-3 >> The following solutions I and II were emulsified and dispersed using a high-speed stirring type disperser. The pressure in the system was reduced to remove methylene chloride, and the exemplary compound N of the leuco compound of the present invention was removed.
o. A microcapsule solution containing 76 inclusions and having an average particle size of 0.2 μm was obtained. Further, the microcapsule liquid was purified with pure water for 70 minutes.
0 g of the compound No. 1 of the leuco compound of the present invention in the microcapsule liquid. The concentration of No. 76 was adjusted to 0.5% by weight to obtain a reserve type microcapsule solution A-1.

Further, the exemplified compound No. of the leuco compound of the present invention was obtained. No. 76, 79, no. A except for 57
In the same manner as in the preparation of -1, reserve type microcapsule solutions A-2 and A-3 were respectively prepared.

Solution I Methylene chloride 200 g Tricresyl phosphate 10.5 g 1: 2 copolymer of methacrylic acid and methyl methacrylate (dissolved at pH = 7 or more) 3.15 g Exemplary compound of leuco compound of the present invention No. 76 3.50 g II solution Gelatin for photography 52.5 g Surfactant (sodium triisopropyl-β-naphthalenesulfonate) 0.590 g Pure water 297 g << Preparation of reserve type microcapsule solutions B-1 to B-3 >> Methacryl The leuco compound of the present invention having an average particle size of 0.2 μm was prepared in the same manner as in the preparation of the reserve type microcapsule solution A-1 except that the amount of the 1: 2 copolymer of acid and methyl methacrylate was changed to 6.20 g. Exemplified Compound No.
No. 76 having a concentration of 0.5 wt%. A reserve-type microcapsule solution B-1 which is a microcapsule solution containing 76 was obtained.

Further, the exemplified leuco compounds of the present invention, Compound No. No. 76, 79, no. B instead of 57
In the same manner as in the preparation of -1, reserve type microcapsule solutions B-2 and B-3 were prepared.

<< Monolith type microcapsule liquid C-1 ~
Preparation of C-3 >> 1.80 g of a 1: 2 copolymer of methacrylic acid and methyl methacrylate and Exemplified Compound No. 1 of the leuco compound of the present invention. 60.0 g of a methanol solution containing 1.80 g of 76 are mixed with an aqueous 0.1 mmol sodium citrate solution 2,40 under stirring at a stirring blade peripheral speed of 7 m / sec.
0 g was dropped at a rate of 1 g / min, and the average diameter was 0.3 μm.
m of the monolithic microcapsule liquid C was prepared.

Subsequently, the microcapsule solution was concentrated to 360 g by ultrafiltration to give the leuco compound of the present invention. The concentration of 76 is 0.5wt%
Was prepared as a monolithic microcapsule liquid C-1.

Further, the exemplified leuco compounds of the present invention, Compound No. No. 76, 79, no. C instead of 57
Monolithic microcapsule liquids C-2 and C-3 were prepared in the same manner as in the preparation of -1.

<< Monolith Type Microcapsule Liquid D-1 ~
Preparation of D-3 (Comparative Example) >> In the monolith type microcapsule liquid C-1, a methacrylic acid and methyl methacrylate 1: 2 copolymer were converted to methyl methacrylate, butyl methacrylate and dimethylamino methacrylate. Except for using a 2: 1: 1 copolymer of methyl (dissolved at pH = 5 or less), the same procedure as in the monolithic microcapsule liquid C-1 was carried out to obtain the leuco compound of the present invention having an average particle diameter of 0.3 μm. Exemplified Compound No. A monolithic microcapsule solution D-1 having a concentration of 76 of 0.5 wt% was prepared.

Further, the exemplified compound No. No. 76, 79, no. D instead of 57
Monolithic microcapsule solutions D-2 and D-3 were prepared in the same manner as in the preparation of -1.

<< Preparation of Methanol Solutions E-1 to E-3 of the Leuco Compounds of the Present Invention (Comparative Examples) >> 76 was prepared, and a methanol solution E- of the leuco compound of the present invention was prepared.
It was set to 1.

Furthermore, the exemplified compound No. No. 76, 79, no. E instead of 57
-1, methanol solutions E-2 and E-3 of the leuco compound of the present invention were respectively prepared.

Next, the seed emulsion used in the examples and the method of preparing the emulsion will be described.

(Preparation of Seed Emulsion-1) A1 Ossein gelatin 24.2 g Water 9657 ml Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825ml C1 potassium bromide 824g potassium iodide 23.5g Make up to 2825ml with water D1 1.75N potassium bromide aqueous solution The following silver potential control amount 35 ° C, JP-B-58-58288, 58-5828
Using a mixing stirrer described in No. 9, 464.3 ml of each of the solution B1 and the solution C1 was added to the solution A1 by a simultaneous mixing method.
Nucleation was performed by adding over a minute.

After stopping the addition of the solution B1 and the solution C1, it takes 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then again Each of B1 and solution C1 was 55.4 m by a simultaneous mixing method.
It was added at a flow rate of 1 / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 35 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was +8 using the solution D1.
mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH.
Immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.06 μm. Diameter (converted to circle diameter)
Was confirmed to be 0.59 μm by an electron microscope.
The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Em-1) A tabular emulsion having a core / shell structure was prepared using the above seed emulsion-1 and the following four kinds of solutions.

A2 Ossein gelatin 11.7 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous solution of ethanol) 1.4 ml Seed emulsion-1 0.10 mol equivalent Equivalent to 550 ml with water B2 Oscein gelatin 5 9.9 g Potassium bromide 6.2 g Potassium iodide 0.8 g Finish to 145 ml with water C2 Silver nitrate 10.1 g Finish to 145 ml with water D2 Ossein gelatin 6.1 g Potassium bromide 94 g Finish to 304 ml with water E2 137 g with silver nitrate Finish up to 304 ml. Solution B2 and solution C2 were added by double jet method to solution A2 which was vigorously stirred at 67 ° C. in 58 minutes. Next, solution D2 and solution E2 were added to the same solution by a double jet method for 48 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.7.

After completion of the addition, desalting and precipitation were carried out in the same manner as in Seed Emulsion 1 to obtain an emulsion having a pAg of 8.5 and a pH of 5.85 at 40 ° C. and an average silver iodide content of about 0.5 mol%. .

The obtained emulsion was observed with an electron microscope. As a result, 81% of the projected area had a mean grain size of 0.96 μm, the grain size distribution was 19%, and the average aspect ratio was 4.5. It was silver halide particles. The twin plane distance (a)
Is 0.019 μm, and the variation coefficient of (a) is 2
8%.

The temperature of the obtained emulsion Em-1 was raised to 60 ° C.
After adding a predetermined amount of the spectral sensitizing dye as a solid particulate dispersion, adenine, ammonium thiocyanate,
A mixed aqueous solution of chloroauric acid and sodium thiosulfate and a solution obtained by dissolving triphenylphosphine selenide in a mixed solvent of ethyl acetate and methanol were added. After 60 minutes, a silver iodide fine grain emulsion was added, and a total of 2 hours was added. Aged. At the end of ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) is used as a stabilizer.
Was added in a predetermined amount.

The above additives and their amounts (per mole of AgX) are shown below.

Spectral sensitizing dye (A) 120 mg Spectral sensitizing dye (B) 2.0 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Iodide Silver fine particles 280 mg 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 50 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-99.
Prepared according to the method described in No. 437. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) is used for 30 to 12 at 500 rpm.
Obtained by stirring for 0 minutes.

Sensitizing dye (A): 5,5′-dichloro-9-ethyl-
3,3'-di- (sulfopropyl) oxacarbocyanine-sodium salt anhydride Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'- Di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt Anhydrous The following coating solution was applied to both sides of a 175 μm thick polyethylene terephthalate support, which had been subjected to a subbing treatment, and a transverse light-shielding layer from below, An emulsion layer and an emulsion protective layer were simultaneously coated in order and dried.

(Preparation of Sample) First Layer (Transverse Light Shielding Layer) Solid Fine Particle Dispersion Dye (AH) 50 mg / m ² Gelatin 0.2 mg / m ² Sodium Dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / M ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² Potassium polystyrene sulfonate 50 mg / m ² Second layer (emulsion layer) Emulsion obtained above (Em The following various additives were added to -1).

Potassium tetrachloropalladium (2) 100 mg / m ² Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² sodium polystyrene sulfonate 80 mg / m ² trimethylolpropane 50 mg / m ² diethylene glycol 50 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3 ammonium dihydroxybenzene-4-sulfonic acid 100 mg / m ² 2-mercaptobenzimidazole-5-sulfonate sodium 5 mg / m ² compound ^{(H) 0.5mg / m 2 n} -C 4 H 9 OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 35 mg / m ² Compound (M) 5 mg / m ² Compound (N) 5 mg / m ² Colloidal silica (mean particle size 0.014 μm) 500 mg / m ² Latex (L) 500 mg / m ² Dextran (average molecular weight 40,000) 100 mg / m ² Microcapsule solution of the present invention (described in Table 2) Amount described in Table 2 However, the amount of gelatin was adjusted to be 1.2 g / m ² .

Third layer (protective lower layer) Gelatin 0.25 g / m ² Microcapsule solution of the present invention (described in Table 2) Amount shown in Table 2 Sodium polyacrylate (average molecular weight 500000) 30 mg / m ² Compound (K 15 mg / m ² Fourth layer (protective upper layer) Gelatin 0.2 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazindene 50 mg / m ² Polymethyl methacrylate particles (average particle size 4 2.0 μm) 20 mg / m ² polymethyl methacrylate particles (average particle size 1.0 μm) 50 mg / m ² formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonyl methyl ether 36 mg / m ² polyacrylamide (average molecular weight 10,000) 50 mg / m ² poly Siloxane (SI) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² Compound (O) 50 mg / m ² Compound (S-2) 5 mg / m ² compound (F-1) 3 mg / m ² compound (F-2) 2 mg / m ² compound (F-3) 1 mg / m ²

[0135]

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[0136]

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[0137]

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The amount of the material applied was one side, and the amount of silver applied was adjusted to 1.5 g / m ² as one side.

Using the sample prepared as described above, silver tone,
Fog was evaluated in the following manner.

(1) Evaluation of Silver Tone A large-sized sample (35.6 cm × 35.6 cm) was uniformly exposed to X-rays so that the concentration became 1.2, and the following treatment was performed. The developed sample was observed with a Schaukasten, and the silver tone due to transmitted light was visually evaluated according to the following ranks.

4: Pure black with a blue tint 3: Black with a slight blue tint 2: Black with a slight yellow tint 1: Black with a yellow tint << Process >><Automatic developing machine> SRX-501 ( (Konica Co., Ltd.) was modified to increase the transport speed as follows.

<Processing conditions> Developing solution formulation Part-A (for finishing 12 L) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5-mercaptotetrazole 0.2 g Hydroquinone 340 g Add water to make 5000 ml.

Part-B (for finishing 12 L) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1.0 L .

Fixer Formulation Part-A (for 18 liter finishing) Ammonium thiosulfate (70 wt / vol%) 6000 g sodium sulfite 110 g sodium acetate trihydrate 450 g sodium citrate 50 g gluconic acid 70 g 1- (N, N-dimethylamino) -Ethyl-5-mercaptotetrazole 18 g Part-B 800 g of aluminum sulfate To prepare a developer, add Part A and Part B simultaneously to about 5 l of water, add water while stirring and dissolving, and add 12 l to finish. Was adjusted. This is used as a development replenisher.

The starter described above was added to 1 liter of the development replenisher at 20 ml / l to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part A, P
artB was added at the same time, and water was added while stirring and dissolving.
and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This is used as a fixing replenisher.

(2) Evaluation of Blue Density Increase in Unexposed Area Condition (A) at a temperature of 23 ° C. and a relative humidity of 50%;
After storing each sample for 5 days under the condition (B) of 50 ° C. and a relative humidity of 50%, development processing was performed under the above processing conditions without exposure. The spectral absorption spectrum of each sample was measured, and the value at 600 nm of the sample stored under the condition (A) was subtracted from the value at 600 nm of the sample stored under the condition (B) to obtain ΔAbs.

(3) Evaluation of fog Condition (A) at a temperature of 23 ° C. and a relative humidity of 50%, and a temperature of 55
After storing each sample for 5 days under the condition (B) of 50 ° C. and a relative humidity of 50%, development processing was performed under the above processing conditions without exposure. The concentration of each sample was measured, and the value of the sample stored under the condition (A) was subtracted from the value of the sample stored under the condition (B) to obtain Δfog.

Table 2 shows the results.

[0150]

[Table 2]

As is clear from Table 2, the sample of the present invention is a silver halide photographic material having a good silver tone and excellent stability.

[0152]

According to the present invention, a silver halide photographic material excellent in stability and storage stability can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takato Chiba Konica Corporation, 1 Sakuracho, Hino City, Tokyo

Claims (4)

[Claims] 1. A silver halide photographic material comprising a support and a hydrophilic colloid layer comprising at least one silver halide emulsion layer, wherein the hydrophilic colloid layer is microencapsulated with a polymer. A silver halide photographic light-sensitive material comprising a useful compound. 2. The silver halide photographic material according to claim 1, wherein the polymer is an alkali-soluble polymer. 3. The silver halide photographic material according to claim 1, wherein the polymer is soluble at pH = 6 or more. 4. The silver halide photograph according to claim 1, wherein the photographically useful compound is a leuco compound which forms a blue dye by reacting with an oxidized form of a developing agent. Photosensitive material.