JPH10339927A - Silver halide photographic sensitive mateal and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material improved in storage stability by incorporating a specified compound in a silver halide emulsion layer and/or its adjacent hydrophilic colloidal layer and a leuco dye capable of giving a blue dye in a hydrophilic colloidal layer formed on the side of the support opposite to the emulsion layer. SOLUTION: This photographic sensitive material is provided on a support with at least one silver halide emulsion layer and the hydrophilic colloidal layer containing the leuco dye capable of giving a blue dye on the side of the support opposite to this emulsion layer, and this emulsion layer and/or its adjacent hydrophilic colloidal layer contains the compound represented by the formula in which R is an optionally substituted aryl group; and each of R1 -R4 is, independently, an H atom or an optionally substituted alkyl or aralkyl or aryl group, thus permitting the obtained photosensitive material to be improved in storage stability and superior in silver color tone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, not only high sensitivity and high image quality of silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) but also rapid development processing and low replenishment of light-sensitive materials have been required. I'm advancing.

[0003] The use of thin tabular grains for increasing the sensitivity and the reduction in the size of the silver halide grains accompanying the use of the technique for increasing the sensitivity cause the developed silver tone of the silver halide grains to become yellowish. And the impression when observing an image of a black-and-white photographic image, particularly an X-ray photosensitive material, is deteriorated. Therefore, for example, a mercapto compound or the like is used to adjust the color tone of the developed silver of the silver halide grains. However, the use of such a color tone agent is not practical because it causes desensitization. Further, in order to improve the color tone of developed silver, for example, JP-A-3-153
No. 234 describes that a leuco compound giving a blue dye is contained in an emulsion layer of a light-sensitive material.

However, when these leuco compounds are contained in an emulsion layer, the blue coloring efficiency is still insufficient, and the color tone of developed silver after development processing is still insufficient, or when the leuco compound is added to the emulsion layer. There is a problem in that a blue dye is generated during storage of the photosensitive material before or after development processing by addition thereof, thereby increasing the blue density in a low-density portion, and such improvements have been desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having improved storage stability and a method for processing the same.

[0006]

The above objects of the present invention are as follows. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer provided on the opposite side of the silver halide emulsion layer from the support, wherein the silver halide emulsion layer And / or an adjacent hydrophilic colloid layer contains a compound represented by the following general formula (1), and the hydrophilic colloid layer contains a leuco dye capable of giving a blue dye. Silver photographic materials,

[0007]

Embedded image In the general formula (1), R represents a substituted or unsubstituted aryl group, and R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, and are each a hydrogen atom or a substituted or unsubstituted group. Represents a substituted alkyl group, aralkyl group, or aryl group.

[0008] 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer provided on the opposite side of the silver halide emulsion layer from the support, wherein the silver halide emulsion layer And / or the adjacent hydrophilic colloid layer contains a compound represented by the following general formula (2), and the hydrophilic colloid layer contains a leuco dye capable of giving a blue dye. Silver photographic materials,

[0009]

Embedded image In the general formula (2), R ₁ and R ₂ each independently represent a hydroxy group, a —OM group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. M represents an alkali metal atom or an ammonium group, and X represents an atom group necessary for forming a 5- to 6-membered ring together with the two vinyl carbons and carbonyl carbons substituted by R ₁ and R ₂ .

[0010] 3. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer provided on the opposite side of the silver halide emulsion layer from the support, wherein the silver halide emulsion layer And / or wherein the hydrophilic colloid layer contains a compound represented by the following general formula (3), and the hydrophilic colloid layer contains a leuco dye capable of giving a blue dye. Photosensitive material,

[0011]

Embedded image In the general formula (3), R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an alkylcarbonyl group, an arylsulfonyl group, an arylcarbonyl group or a carbamoyl group, or R ₁ and R ₂ are bonded to each other To form a heterocyclic ring. Note that R ₃ , R ₄ ,
R ₅ and R ₆ each represent a hydrogen atom or a substitutable group, and may combine with each other to form a ring.

4. At least one layer of the silver halide emulsion layer contains silver halide grains having parallel (100) major planes having a silver chloride content of 30 mol% or more and at least 50% of the total projected area of the silver halide grains. A silver halide photographic light-sensitive material according to any one of the above 1 to 3,

5. 5. A method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to any one of the above 1 to 4 is processed in a photographic processing step including a development step.

6. 5. A method for processing a silver halide photographic light-sensitive material, comprising processing the silver halide photographic light-sensitive material according to any one of the above 1 to 4 in a photographic processing step including a developing step and a fixing step.

[0015] 7. The silver halide photographic light-sensitive material according to any one of the above 1 to 4, which is processed in a photographic processing step including a developing step and a fixing step using a developer and a fixer obtained by dissolving a solid processing agent. A method for processing a silver halide photographic light-sensitive material,

8. A silver halide photographic light-sensitive material characterized by processing the silver halide photographic light-sensitive material according to any one of the above items 1 to 4 with a photographic processing apparatus having a mechanism for supplying a solid processing agent to a processing tank, particularly an automatic developing machine. Material processing method,
Is achieved by each of

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below. First, the compound represented by the general formula (1) will be described.

[0018]

Embedded image In the general formula (1), R represents an aryl group (for example, a phenyl or naphthyl group). R ₁ , R ₂ , R ₃ , and R ₄ each represent a hydrogen atom, an alkyl group (for example, a lower alkyl group such as methyl, ethyl, propyl, or isopropyl, a higher alkyl group), or an aryl group (for example, phenyl,
Naphthyl group) and aralkyl group (for example, benzyl group).

The above-mentioned alkyl group, aryl group and aralkyl group may each have a substituent. Examples of the substituent include a hydroxy group, an alkoxy group, a hydroxyalkyl group, an amino group, a nitro group, Examples include a sulfo group, a carboxyl group, and a halogen atom.

In the above general formula, R ₁ is preferably an alkyl group or a hydroxyalkyl group substituted with a hydrogen atom or an amino group. R ₄ is preferably a hydrogen atom. More preferably, R ₂ is a hydroxyalkyl group, R ₃ is a hydroxyalkyl group, an alkyl group, or a substituted alkyl group, and R is an aryl or substituted aryl group. The number of carbon atoms in these alkyl groups is preferably 4 or less.

Examples of the compound represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto. A-1 1-phenyl-3-pyrazolidone A-2 1-phenyl-4,4-dihydroxymethyl-
3-pyrazolidone A-3 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidone A-4 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone A-5 1-phenyl-4, 4-dimethyl-3-pyrazolidone A-6 1-phenyl-2-hydroxymethyl-4,4
-Dimethyl-3-pyrazolidone A-7 1-phenyl-2-morpholinomethyl-4,4
-Dimethyl-3-pyrazolidone A-8 1-phenyl-2-morpholinomethyl-4-methyl-3-pyrazolidone A-9 1-phenyl-2-hydroxymethyl-4-methyl-3-pyrazolidone A-10 1-phenyl -5,5-dimethyl-3-pyrazolidone A-11 1-phenyl-5-methyl-3-pyrazolidone A-12 1-p-tolyl-4-methyl-4-dihydroxymethyl-3-pyrazolidone A-13 1- p-Hydroxyphenyl-4,4-dimethyl-3-pyrazolidone A-14 1-o-tolyl-4-methyl-4-dihydroxymethyl-3-pyrazolidone A-15 1-p-methoxyphenyl-4-methyl-4
-Dihydroxymethyl-3-pyrazolidone A-16 1- (3,5-dimethyl) phenyl-4-methyl-4-dihydroxymethyl-3-pyrazolidone

The compound represented by the general formula (1) can be added to a silver halide emulsion layer and / or an adjacent hydrophilic colloid layer, but is preferably added to a silver halide emulsion layer. When the compound represented by the general formula (1) is added to the silver halide emulsion layer, the amount is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻¹ mol, more preferably 3 × 10 ⁻¹ mol per mol of silver halide. ^-6 to 1 x ^10-2 mol is preferred. When the compound represented by the general formula (1) is added to an adjacent hydrophilic colloid layer (non-photosensitive gelatin layer), the amount is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻² mol / m ² , More preferably, it is 3 × 10 ⁻⁷ to 1 × 10 ⁻³ mol / m ² .

Next, the compound represented by formula (2) will be described.

[0024]

Embedded image In the general formula (2), R ₁ and R ₂ each independently represent a hydroxy group, a —OM group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. M represents an alkali metal atom or an ammonium group, and X represents an atom group necessary for forming a 5- to 6-membered ring together with the two vinyl carbons and carbonyl carbons substituted by R ₁ and R ₂ .

In the general formula (2), R ₁ and R ₂ are each independently a hydroxy group, an —OM group (M represents an alkali metal atom or an ammonium group), an amino group (substituent having 1 carbon atom). To 10 alkyl groups such as those having a methyl group, an ethyl group, an n-butyl group, a hydroxyethyl group as a substituent, an acylamino group (such as an acetylamino group or a benzoylamino group), or an alkylsulfonylamino group. (Methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), mercapto group, alkylthio group (methylthio group, ethylthio group And the like, preferably a hydroxy group, a Amino group, an alkylsulfonylamino group, an arylsulfonylamino group. X is -O
_{-, - C (R 3)} (R 4) -, - C (R 5) =, - C
_{(= O) -, - N} (R 6) -, - N = , etc., preferably a carbon atom, an oxygen atom or a nitrogen atom, _{R 1} and _{R 2}
Constitutes a 5- to 6-membered ring together with the two substituted vinyl carbons and carbonyl carbons. Where R ₃ , R ₄ ,
R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent (hydroxy group, carboxy group, sulfo group, etc.), and a substituent (alkyl group, halogen atom, A hydroxy group, a carboxy group, a sulfo group, etc.), an aryl group having 6 to 15 carbon atoms, a hydroxy group, and a carboxy group. Saturated or unsaturated condensed rings may be formed on the constituting 5- to 6-membered ring, and dihydrofuranone, dihydropyrone, pyranone, cyclopentenone, cyclohexenone, pyrrolinone, pyrazolinone, pyridone And a azacyclohexenone ring, a uracil ring and the like, preferably a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, a uracil ring and the like. Hereinafter, specific examples of the compound represented by Formula (2) will be given, but the present invention is not limited thereto.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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The compound represented by formula (2) can be added to a silver halide emulsion layer and / or an adjacent hydrophilic colloid layer, but is preferably added to a silver halide emulsion layer. When the compound represented by the general formula (2) is added to the silver halide emulsion layer, the amount is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻¹ mol, more preferably 3 × 10 ⁻¹ mol, per mol of silver halide. ^-6 to 1 x ^10-2 mol is preferred. When the compound represented by the general formula (2) is added to an adjacent hydrophilic colloid layer (non-photosensitive gelatin layer), it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻² mol / m ² , More preferably, it is 3 × 10 ⁻⁷ to 1 × 10 ⁻³ mol / m ² .

Next, the compound represented by formula (3) will be described.

[0033]

Embedded image In the general formula (3), R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an alkylcarbonyl group, an arylsulfonyl group, an arylcarbonyl group or a carbamoyl group, or R ₁ and R ₂ are bonded to each other To form a heterocyclic ring. Note that R ₃ , R ₄ ,
R ₅ and R ₆ each represent a hydrogen atom or a substitutable group, and may combine with each other to form a ring.

In formula (3), the alkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, arylsulfonyl group, carboxyalkyl group or carbamoyl group represented by R ₁ and R ₂ are all substituted. Alternatively, examples of the heterocyclic group which may be formed by combining unsubstituted R ₁ and R ₂ include groups such as piperidino, pyrrolidino, piperazino, imidazolyl, and morpholino.

The substituent represented by R ₃ , R ₄ , R ₅ and R ₆ includes a halogen atom, an alkyl group having up to 20 carbon atoms,
Monocyclic or bicyclic aryl group, alkoxy group, alkylthio group, acylamino group, alkanoylamino group, alkoxycarbonyl group, alkylsulfonamide group, alkylsulfamoyl group, alkylcarbamoyl group, arylcarbamoyl group, acyloxy group, nitro group Substituted with a cyano group, a carboxyl group, a sulfo group, a ureido group, an alkylureido group, an alkyl group or an aryl group
Tertiary amino group, alkyl carbonate group, alkylsulfonyl group, alkylsulfinyl group, 6 to 20 carbon atoms
Aryloxy group, arylthio group, benzoylamino group, aryloxycarbonyl group, arylsulfonamide group, sulfamoyl group, arylsulfamoyl group, carbamoyl group, arylureido group, amino group,
Examples include an aryl carbonate group, an arylsulfonyl group, an arylsulfinyl group, and an acyl group having 2 to 20 carbon atoms. R _{3 to} R ₆ may be the same or different,
Two adjacent groups may be connected to each other to form a carbon ring.

Specific examples of the compound represented by formula (3) are shown below, but the present invention is not limited thereto.

[0037]

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[0038]

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When the compound represented by the general formula (3) is an acid, it may be a free acid or a salt. Further, it may contain the oxidation product. Usually, the compound of the general formula (3) contains an appropriate amount of an oxidation product for natural oxidation by air or the like. The above compound is dissolved in water or a hydrophilic solvent such as methanol, acetone or ethyl acetate and added to the silver halide emulsion layer and / or the hydrophilic colloid layer. The compound may be added at any position as long as it is a hydrophilic colloid layer. However, when there are a plurality of hydrophilic colloid layers, it is preferable to add the compound to the hydrophilic colloid layer close to the undercoat layer.

When the compound of the general formula (3) is added to the silver halide emulsion layer, 2 × 1
0 ^-6 ~5 × ^{10 -1} mol, more preferably a 1 × ¹⁰ -5 ~5 × ^{10 -2} mol are preferred. Further, the compounds non-light-sensitive hydrophilic colloid layer when added to (a non-photosensitive gelatin ^{layer), 2 × 10 -7 ~5 × 10} -2 mol / ^{m 2} are preferred, more preferably 1 × 10 ^{- 6 to} 5
× 10 ⁻³ mol / m ² .

Next, a leuco dye capable of giving a blue dye will be described. The leuco dye capable of giving a blue dye used in the present invention is a compound which is oxidized to an oxide of a developing agent to give a blue dye during development processing, and is oxidized to an oxide of a black and white developing agent to give a blue dye. Those are preferable, and examples thereof include a compound represented by the general formula (4).

[0042]

Embedded image In the general formula (4), W represents —NR ₁ R ₂ , —OH or —OZ
Wherein 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. 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 each represent a nitrogen atom or ＣC (R ₃ ) —. X represents an atomic group necessary for forming a 5- to 6-membered aromatic heterocyclic ring together with Z ₁ , Z ₂ and carbon atoms adjacent thereto. R ₄ represents a hydrogen atom, an acyl group, 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 is 0-2
Represents an integer. CP represents the following group.

[0043]

Embedded image In the formula, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom, or a substituent that can be substituted on a benzene ring. The _{R 5} and R
₆ and R ₇ and R ₈ may combine with each other to form a 5- to 7-membered ring. R ₉ has the same meaning as R ₄ . R ₁₀ and R
₁₁ represents an alkyl group, an aryl group or a heterocyclic group, respectively. R ₁₂ has the same meaning as R ₄ . R ₁₃ and R
₁₄ has the same meaning as R ₁₀ and R ₁₁ . R ₁₅ is R
Synonymous with ₁₂ . R ₁₆ represents an alkyl group, an aryl group,
Sulfonyl group, trifluoromethyl group, carboxy group,
Represents an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ is R ₄
Is synonymous with R ₁₈ has the same meaning as R ₃ , and m is 1 to 3.
Represents an integer. Y1 represents an atomic group necessary for forming a 5- or 6-membered monocyclic or condensed-ring nitrogen-containing heterocycle 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 have the same meanings as R ₁₉ and R ₂₀ . R
₂₄ has the same meaning as R ₂₁ . R ₂₅ , R ₂₇ and R
₂₈ represents a hydrogen atom or a substituent. R ₂₆ has the same meaning as R ₄ . R ₂₉ , R ₃₁ and R ₃₂ are R ₂₅ , R ₂₇
And R ₂₈ . R ₃₀ has the same meaning as R ₂₆ . R ₃₄ , R ₃₅ and R ₃₆ have the same meaning as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₃ has the same meaning as R ₂₆ .
R ₃₈ , R ₃₉ and R ₄₀ are R ₂₅ , R ₂₇ and R
Synonymous with ₂₈ . R ₃₇ has the same meaning as R ₂₆ . R
₄₁ , R ₄₂ and R ₄₃ are R ₂₅ , R ₂₇ and R
Synonymous with ₂₈ . R ₄₄ has the same meaning as R ₂₆ . The asterisks indicate the bonding points between CP1 and other partial structures in the general formula (4).

The compound represented by the general formula (4) may be a compound represented by the following general formula (5).

[0045]

Embedded image In the general formula (5), R ₁ , R ₂ , R ₃ , R ₄ , CP 1,
n, R and p are R ₁ , R ₂ ,
It is synonymous with R ₃ , R ₄ , CP1, n, R and p.

In the present invention, at least one of the compounds represented by the following general formula (6) and at least one of RSO ₃ H may be contained.

[0047]

Embedded image In the general formula (6), R ₃ , n, R ₄ , W, X, Z ₁ , Z ₂
And CP1 represent R ₃ , n, R ₄ ,
W, _X, same meaning as Z 1, _{Z 2} and CP1.

The compound represented by the general formula (6) may be a compound represented by the following general formula (7).

[0049]

Embedded image In the general formula (7), R ₁ , R ₂ , R ₃ , R ₄ , CP 1 and n represent R ₁ , R ₂ , R ₃ , R ₄ , R ₄ in the general formula (4).
Synonymous with CP1 and n.

In the compounds represented by formulas (4) to (7), R ₄ , R ₉ , R ₁₂ , R ₁₅ , R ₁₇ , R
_At least one of the groups represented by ₂₁ , R ₂₄ , R 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) may be a compound which is substituted with at least one selected from the.

In the general formulas (4) to (7), R ₁
And the alkyl group represented by R _2, preferably a methyl group, an ethyl group, a propyl group, 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.), Alkyl group (for example, cyclopentyl group, cyclohexyl group, etc.),
Aralkyl groups (eg, benzyl group, 2-phenethyl group, etc.), aryl groups (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 (For example, acetylamino group, propionylamino group, etc.),
Alkylthio group (for example, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (for example,
A phenylthio group, a sulfonylamino group (eg, a methanesulfonylamino group, a benzenesulfonylamino group, etc.), a ureido group (eg, a 3-methylureido group,
3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.) ), A sulfamoyl group (eg, an ethylsulfamoyl group, a dimethylsulfamoyl group, etc.), an alkoxycarbonyl group (eg, a methoxycarbonyl group,
Ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl) Group), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group, imide group (for example,
Phthalimide group) and a heterocyclic group (eg, a pyridyl group, a benzimidazolyl group, a benzothiazolyl group, a benzoxazolyl group, etc.).

The acyl group represented by R ₄ is preferably an acetyl group, a trifluoroacetyl group or a benzoyl group. Preferably as a sulfonyl group,
Examples thereof 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,
Triazine ring, tetrazine ring, pyrrole ring, furan ring,
Examples include a thiophene ring, a thiazole ring, an oxazole ring, an imidazole ring, a thiadiazole ring, and an oxadiazole ring. 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 meanings as the monovalent substituent described above for R ₃ . Preferred are an alkyl group and an acylamino group. As the 5- to 7-membered ring formed by combining R ₅ and R ₆ and R ₇ and R ₈ with each other,
Examples thereof include an aromatic carbon ring and a heterocyclic ring, and preferably a benzene ring.

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

[0058] methyl group as the alkyl group represented by _{R 16,} an isopropyl group, a pentyl group, and a t- butyl group and the like are. 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. R ₁₉ and R
Examples of the alkyl group represented by 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. R ₂₅ , R
Examples of the substituent represented by 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. Examples of the aromatic group include p-toluene and dodecylbenzene.

Hereinafter, specific examples of the compounds represented by formulas (4) to (7) will be given, but the present invention is not limited thereto.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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

[0074]

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3.9 g of the above (1) was added to 50 ml of ethyl acetate.
, And 0.5 g of 5% Pd / C was added, and hydrogenation was performed under normal pressure. The blue color of the reaction solution disappeared, and (2) was formed. Next, 1.2 g of triethylamine and 1.5 g of acetyl chloride were added to the reaction solution, 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 obtain 3.8 g (yield: 89%) of the desired Exemplified Compound 8. The structure was confirmed by NMR spectrum and Mass spectrum.

Synthesis Example 2 (Synthesis of Exemplified Compound 9) Reaction Route

[0077]

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3.9 g of Synthesis Example 1 (1) was added to ethyl acetate 5
The mixture was dissolved in 0 ml, and 0.5 g of 5% Pd / C was added to perform normal pressure catalytic hydrogenation. The blue color of the reaction solution disappeared, and (2) was formed. Next, 1.2 g of triethylamine and 4.0 g of trifluoroacetic anhydride were added to the reaction solution, 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 obtain 4.0 g of the desired Exemplified Compound 9 (yield: 85%).
Obtained. The structure was confirmed by NMR spectrum and Mass spectrum.

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

[0080]

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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 stir. Next, the reaction solution was poured into 300 ml of water, and collected by filtration to obtain 4.1 g of the desired Exemplified Compound 58 (yield: 8%).
7%). 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 molar ratio of the compound represented by the general formula (6) or (7) to RSO ₃ H is 1 to ₃ mol of RSO ₃ H per 1 mol of the compound represented by the general formula (6) or (7). It is preferred that

The compounds represented by the general formulas (4) to (7) are compounds which form a blue dye or a blue pigment by reacting with an oxidized form of a representative developing agent. 1 × 10 ^{−6 to} 5 × 10 per mole of silver in the light-sensitive material
^-1 mol is preferred for achieving the effects of the present invention. Below this, the effect of improving the silver tone is small, and
If it exceeds this, the whole image is felt dark, which is not preferable.

The leuco dye used in the present invention is preferably added in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻¹ mol per mol of silver halide, and the addition amount per one side is 5 × 10 6.
^It is preferably from ^{−7 to} 5 × 10 ⁻³ mol / m ² , and more preferably from 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol / m ² .

The method of adding the leuco dye used in the present invention is a method of dispersing by means of a ball mill, colloid mill, or ultrasonic wave and adding as a solid fine particle dispersion, or a conventionally known high boiling solvent and ethyl acetate, cyclohexane. And a method of adding an emulsified dispersion that is dissolved and mechanically emulsified and dispersed by using an auxiliary solvent such as, for example, a method of dissolving in a water-miscible organic solvent (eg, methanol, ethanol, acetone, etc.) and adding the same.

In the present invention, there may be a plurality of hydrophilic colloid layers containing a leuco dye which gives a blue dye, and the hydrophilic colloid layer may contain a non-light-sensitive silver halide emulsion layer or a silver halide emulsion layer. There may be.

The halogen composition of the silver halide grains used in the present invention is arbitrary, and includes silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, silver chloroiodide, and iodide. Any of silver may be used, but the silver chloride content is preferably 30 mol%.
And more preferably 50 mol% or more.

The silver halide grains used in the present invention are:
Normal crystal grains such as cubes, tetradecahedrons, and octahedrons may be used, and spherical particles, plate-like particles, or particles having an aspect ratio of 2
Tabular silver halide grains having two or more parallel (100) planes as main planes are preferred, but may have irregular crystal forms such as potatoes.

The shape of the main plane of the tabular silver halide grain having the (100) plane as the main plane is a shape in which a rectangular parallelogram or a rectangular parallelogram has rounded corners. The adjacent side ratio of the right-angled parallelogram is less than 10, preferably less than 5, and more preferably less than 2. In addition, the length of the side when the corner is rounded, extends the straight line portion of the side,
It is expressed as the distance between the intersection of the straight line portion of the adjacent side and the line extending from the straight line portion.

As a method of obtaining a tabular silver halide emulsion, a method of depositing silver halide on a seed crystal may be used, and a water-soluble silver salt solution and a water-soluble silver salt solution for obtaining a tabular silver halide emulsion may be used. (A) a step of introducing a silver salt and a halide salt into a dispersion medium to form a plate-like nucleus; B) following Ostwald ripening under conditions that maintain the main surface of the tabular grains following nucleation (c) Then, a water-soluble silver salt solution and a water-soluble halide solution and / or halogenated fine particles are added to form seed grains. May be used to provide a step of growing grains so as to obtain a desired particle size and a halogen composition (a grain formation step).

For example, tabular silver halide grains having two parallel (100) planes as main planes are disclosed in US Pat.
No. 0,938, namely, nucleation at low Cl in the presence of iodine ions under conditions that facilitate formation of the (100) plane, followed by Ostwald ripening and / or growth.

Tabular silver halide grains are grains having two opposing parallel main planes, and the aspect ratio is represented by the ratio of the grain size to the grain thickness. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), and is a circle equivalent diameter of a projected area of the tabular silver halide grains (a diameter of a circle having the same projected area as the silver halide grains). ),
Thickness refers to the distance between two parallel main planes forming tabular silver halide grains. The average value of the aspect ratio of the tabular silver halide grains is 2 or more, preferably 2 or more and less than 15, and more preferably 3 or more and less than 10.

The proportion of tabular silver halide grains contained in the emulsion layer is at least 50%, preferably at least 70%, more preferably at least 90% of the total projected area.

The average grain size of the tabular silver halide grains is 0.1.
It is preferably 15 to 5.0 μm, and 0.2 to 3.0 μm.
More preferably, it is 0 μm, most preferably 0.1 μm.
3 to 2.0 μm. The average thickness of the tabular silver halide grains is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.4 μm, even more preferably from 0.02 to 0.3 μm.

The particle size is, for example, 1
It can be obtained by taking an image at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter on the print or the area at the time of photographing (the number of measured particles is indiscriminately 1000 or more).

The tabular silver halide grains are preferably monodisperse emulsions having a narrow grain size distribution, and more specifically, (standard deviation of grain size / average grain size) × 100 = width (%) of grain size distribution. When the area is defined, it is preferably 25% or less, more preferably 20% or less.

It is preferable that the tabular silver halide grains have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is preferably 25% or less, more preferably 20%. These are:

The silver iodide content and the average silver iodide content of each silver halide grain were determined by the EPMA method (Electron).
Probe Micro Analyzer method). According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, an electron beam is irradiated, and X-ray analysis by electron beam excitation is performed. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the silver halide composition of each grain can be determined. EPM for at least 50 particles
If the silver iodide content is determined by the method A, the average silver iodide content is determined from the average thereof.

The silver halide grains preferably have a more uniform halogen composition ratio between the grains. For example,
When the distribution of the halogen content between the grains is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

The distribution of the halogen composition inside the silver halide grains can be determined by pretreating the grains into ultrathin sections, and then observing and analyzing them with a transmission electron microscope while cooling. Specifically, silver halide grains are taken out of the emulsion, embedded in a resin, and cut with a diamond knife to produce a 60-nm-thick section. While cooling this section with liquid nitrogen, observation and point analysis were performed with a transmission electron microscope equipped with an energy dispersive X-ray analyzer,
It can be obtained by quantitative calculation (Inoue, Nagasawa: Abstracts of the 62nd Annual Meeting of the Photographic Society of Japan, 1987 p62).

The tabular silver halide grains may have dislocations. Dislocations are described in F. Hamilton, P
hot. Sci. Eng., 57 (1967); S
hiozawa, J .; Soc. Photo. Sci. Ja
Pan, 35, 213 (1972), which can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to pass therethrough.
Can be observed more clearly using an electron microscope.

The silver halide photographic emulsion is described in JP-A-3-16.
Known silver halide solvents such as ammonia, thioethers, thioureas, thiocyanates, etc. described in No. 8734 can be present and can be substantially rounded as defined above. In the silver halide grain forming step, pA after adding at least 70% of the water-soluble silver salt used for forming the grains of the silver halide emulsion.
g of pAg before adding 70% of the water-soluble silver salt.
By making the size larger, it may be made substantially round as defined above.

In the emulsion thus prepared, an appropriate amount of a halogenated solvent is added to the emulsion at an appropriate time from the time when silver halide grains are formed to the time when chemical ripening starts, at an appropriate time. They may be uniformly mixed and have a substantially rounded shape. After the silver halide emulsion is formed, the silver halide emulsion before the solvent treatment may be desalted (including washing with water).

Conditions for enlarging the produced seed grains in order to obtain silver halide grains are described in JP-A-51-39.
Nos. 027, 55-142329 and 58-1139
Nos. 28, 54-48521 and 58-49938
As can be seen in the issue, the water-soluble silver salt solution and the water-soluble halide solution were added by the double jet method, and the addition rate was gradually increased within the range in which new nucleation did not occur and Ostwald ripening did not occur in accordance with the enlargement of the particles. To change. As another condition for enlarging the seed grains, a method of adding silver halide fine grains, dissolving and recrystallizing the grains, as shown in the 88th Annual Meeting of the Photographic Society of Japan, 1988, may be used.

During growth, an aqueous solution of silver nitrate and an aqueous solution of halide are added by a double jet method, and the addition rate is such that new nuclei are not generated in accordance with the growth of grains, and there is no spread of size distribution due to Ostwald ripening. The speed, ie 30-1 of the speed at which new nuclei are generated
By adding in the range of 00%, particles having a desired particle size and distribution can be obtained.

In preparing the emulsion, ammonia, thioether,
Known silver halide solvents such as thiourea can be present.

The silver halide grains used in the present invention are:
So-called halogen conversion type (conversion type) particles may be used. The halogen conversion amount is 0.1 to silver amount.
The conversion is preferably 2 mol% to 0.5 mol%, and the conversion may be performed either during physical ripening or after completion of physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. The particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

When silver iodide on the outermost surface of silver halide grains is contained, a method for simultaneously adding a silver nitrate solution and a solution containing iodide ions to an emulsion containing silver halide grains as a base is used. A method of adding silver iodide, silver iodobromide or silver chloroiodobromide fine particles of silver halide,
An addition method of potassium iodide or a mixture of potassium iodide and potassium bromide can be applied. Of these, the method of adding fine silver halide grains is preferable. Particularly preferred is the addition of silver iodide fine grains.

The timing of adjusting the silver iodide content on the outermost surface is from the final stage of the silver halide crystal production process to the chemical ripening process, and further to the completion of the solution preparation process immediately before the application of the silver halide emulsion. It is possible to choose between them, but it is preferable to adjust by the end of the chemical ripening step. The chemical ripening step referred to here is a point in time when physical ripening and desalting of the silver halide emulsion of the present invention are completed, when a chemical sensitizer is added, and thereafter, an operation for stopping chemical ripening is performed. Up to. The addition of silver halide fine grains may be carried out several times at intervals, or another chemically-ripened emulsion may be added after the addition of the fine grains.

The temperature of the emulsion of the present invention at the time of adding silver halide fine grains is preferably in the range of 30 to 80 ° C., more preferably in the range of 40 to 65 ° C. Further, the present invention is preferably carried out under the condition that part or all of the silver halide fine grains to be added disappears immediately before coating immediately after the addition, more preferably 20% of the added silver halide fine grains. The above is the disappearance immediately before the application.

The silver iodide content on the outermost surface of a silver halide grain is determined by an XPS method (X-ray Photoselector).
on Spectroscopy: X-ray photoelectron spectroscopy)
Means the silver iodide content of a portion up to a depth of 50 °, which can be determined as follows.

The sample was cooled to −110 ° C. or less in an ultra-high vacuum of 1 × 10 ⁻⁸ torr or less, and MgKα was used as a probe X-ray with an X-ray source voltage of 15 kv and an X-ray source current of 40 mA.
, And measurement is performed for Ag ₃ d _5/2 , Br ₃ d, and I ₃ d _3/2 electrons. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the outermost surface is determined from these intensity ratios.

The purpose of cooling the sample is to eliminate measurement errors caused by destruction of the sample by X-ray irradiation at room temperature (decomposition of silver halide and diffusion of halide (particularly iodine)), and to increase measurement accuracy. By cooling to −110 ° C., sample destruction can be suppressed to a level that does not hinder measurement.

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 per mol of silver, and 3 × 1
It is preferable to add 0 to ² mol or less.

The monodisperse core / shell type silver halide grains used in the present invention are silver halide grains having a grain structure composed of two or more layers having different silver iodide contents. , A core (inner layer) and a shell covering the core, and the shell is formed by one or more layers. The iodine contents of the core and the shell are preferably different from each other, and it is particularly preferable that the iodine content of the core portion is maximized. The core preferably has an iodine content of 5 mol% or more and a solid solution limit or less, more preferably 7 mol% or more and a solid solution limit or less. Preferably, the iodine content of the core is at least 3 mol% higher than the iodine content of the shell. The iodine distribution of the core is usually uniform, but may have a distribution. For example, as the concentration goes from the center to the outside, the concentration may become higher, or the intermediate region may have a maximum or minimum concentration.

The monodisperse core / shell type silver halide grains are prepared by allowing an aqueous solution containing a protective colloid and seed particles to exist in a reaction vessel in advance, and supplying silver ions, halide ions, or silver halide fine particles as needed. It is preferable to obtain the seed particles by crystal growth. In this case, the grain center can have a halogen composition region different from that of the core. The halogen composition of the seed grains is arbitrary, and may be any of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, silver chloroiodide, and silver iodide.

In the present invention, gelatin is preferably used as the dispersion medium for the protective colloid of the silver halide grains. As the gelatin, alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (having a molecular weight of 1,000 to 5,
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (Resea
rc Disclosure. RD)
76 volume No. 17643 (December 1978).

In the preparation of silver halide grains, 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.

Further, the silver halide grains used in the present invention may be used in the course of forming and / or growing grains, in the form of cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts. (Including complex salts) and iron salts (including complex salts) by adding at least one kind of metal ion, so that these metal elements can be contained inside the particles and / or in the particle surface layer. By placing in a reducing atmosphere, a reduction sensitizing nucleus can be provided inside the grain and / or on the grain surface.

[0120] Further, the addition of the action of a reducing agent added at the desired point of particle formation of hydrogen peroxide (water) and an adduct thereof, peroxo salts, ozone, an oxidizing agent such as I ₂ in the desired time It is preferable to deactivate and suppress or stop the reducing agent. The oxidizing agent may be added at any time from when the silver halide grains are formed to before the addition of a gold sensitizer (or a chemical sensitizer if no gold sensitizer is used) in the chemical sensitization step.

In the silver halide photographic emulsion, at the end of the growth of the silver halide grains, unnecessary soluble salts may be removed or may remain contained. The removal of the salts can be carried out according to the method described in RD-17643, Item II, and the silver halide grains of the present invention can be subjected to chemical sensitization. The conditions of the step of chemical ripening or chemical sensitization, for example, pH, pAg, temperature, time and the like are not particularly limited, and they can be carried out under conditions generally used 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 A reduction sensitization method, a gold or other noble metal sensitization method using a noble metal, or the like can be used alone or in combination.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 to 10 per mol of silver halide.
^{About -4} mol is used. Depending on the properties of the selenium compound to be used, the addition may be carried out by dissolving in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent. Further, a method in which the mixture is added in advance with a gelatin solution, or a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent by the method disclosed in JP-A-4-140739 may be used.

The temperature of chemical ripening using a selenium sensitizer is 4
The range is preferably from 0 to 90 ° C, more preferably from 45 ° C to 80 ° C. The pH is 4-9 and the pAg is 6
The range of -9.5 is preferred. The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer. It is also preferable to perform so-called reduction sensitization on the surface of the grains by placing the grains in an appropriate reducing atmosphere.

Preferred examples of the reducing agent include thiourea dioxide, ascorbic acid and derivatives thereof. Other preferable reducing agents include polyamines such as hydrazine and diethylenetriamine, dimethylamineboranes, sulfites and the like.

The amount of the reducing agent added depends on the type of reduction sensitizer, the particle size of silver halide grains, the composition and habit, the temperature of the reaction system,
It is preferable to change the pH depending on environmental conditions such as pH and pAg. For example, in the case of thiourea dioxide, approximately 0.01 to 2 mg per mole of silver halide is used as a rough guide.
Is preferable. In the case of ascorbic acid, the range is preferably about 50 mg to 2 g per mol of silver halide. The conditions for reduction sensitization are as follows:
70 ° C., time is about 10 to 200 minutes, pH is about 5 to 11,
The pAg is preferably in the range of about 1 to 10 (where pAg is used).
The g value is the reciprocal of Ag + ion concentration).

As the water-soluble silver salt, silver nitrate is preferable. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably from 1 to 6, and preferably from 2 to 4. Conditions such as temperature, pH, and time are preferably in the above-described reduction sensitization condition range.

The silver halide grains in the present invention may be spectrally sensitized with methine dyes or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

As these dyes, any of the nuclei generally used can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenin nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye includes pyrazoline- as a nucleus having a ketomethine structure.
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, an aminostilbene compound substituted with a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde condensate (for example, , U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like.

US Pat. Nos. 3,615,613 and 3,6
No. 15,641, No. 3,617,295, No. 3,63
The combination described in US Pat. No. 5,721 or the like is particularly useful.
The sensitizing dye may be added during or during each of the steps of nucleation, growth, desalting, and chemical sensitization, or after the chemical sensitization.

In the light-sensitive material of the present invention, an appropriate amount of a hardener is added in advance in the coating step of the light-sensitive material so as to be suitable for rapid processing, and the water swelling ratio in the developing-fixing-washing step is adjusted. Therefore, it is preferable to reduce the water content in the photosensitive material before the start of drying.

The swelling ratio of the light-sensitive material of the present invention is preferably 150 to 250% during the development processing, and the film thickness after expansion is 70%.
μm or less is preferred. When the water swelling ratio exceeds 250%, poor drying occurs, and for example, conveyance failure also occurs in automatic developing machine processing, particularly in rapid processing.

On the other hand, when the water swelling ratio is less than 150%, there is a tendency that development unevenness and residual color increase upon development. The water swelling ratio as referred to herein means the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, and this is divided by the film thickness before processing and multiplied by 100. .

In the present invention, powder processing agents, tablets, pills,
Solid processing agents such as granules may be used, and those subjected to moisture-proof treatment as needed may be used. The powder in the present invention refers to an aggregate of fine crystals. The term “granules” as used in the present invention refers to granules having a particle diameter of 50 to 5000 μm, which are obtained by adding a granulation step to powder. The tablet referred to in the present invention refers to a tablet obtained by compressing powder or granules into a certain shape.

As a cause of fluctuations in photographic performance, it is effective to reduce the aperture coefficient of a developing solution in an automatic developing machine. In particular, the opening coefficient is preferably 80 cm ² / l or less. That is, when the opening coefficient exceeds 80 cm ² / l, the undissolved solid processing agent or the concentrated liquid immediately after dissolution is apt to be oxidized by air, and as a result, insolubles and scum are generated, and the solid processing machine or the processing is performed. Although problems such as contamination of the light-sensitive material occur, these problems can be solved when the aperture coefficient is 80 m ² / l or less. The opening coefficient referred to here is represented by the area of contact with air per unit volume of the processing solution, and the unit is (cm ² / l). In the present invention, the aperture coefficient is preferably 80 cm ² / l or less, more preferably 50 to ³ cm ² / l, and even more preferably 35 to 10 cm ² / l.

The aperture coefficient can be generally reduced by using a resin or the like that blocks air as a floating lid.
No. 31138, No. 63-216050, No. 63-23
The size can be reduced by the slit type developing device described in No. 5940.

The solid processing agent used in the present invention is a developer,
Although used for photographic processing agents such as fixing agents and rinsing agents, it is the developer that has a great effect of the present invention, especially an effect of stabilizing photographic performance.

In the solid processing agent used in the present invention, only one part of a certain processing agent may be solidified, but preferably, all the components of the processing agent are solidified. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

In the present invention, as a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783, 63-9
There are known methods such as Japanese Patent No. 7522 and Japanese Utility Model Application Laid-Open No. 1-85732, but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is a granule or a powder, the solid processing agent is disclosed in JP-A-62-819.
No. 64, No. 63-84151, JP-A-1-29237
No. 5, the gravity drop method described in the description and Japanese Utility Model Application Laid-open No. 63-105159
And a method using a screw or a screw described in JP-A-63-195345 are known methods, but are not limited thereto.

In the present invention, the place where the solid processing agent is charged may be in the processing tank, but is preferably in communication with the processing section for processing the photosensitive material, and the processing liquid flows between the processing section and the processing section. And a structure in which there is a constant processing solution circulation amount with the processing unit and the dissolved components move to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

In the developer, in addition to dihydroxybenzenes, aminophenols and pyrazolidones described in JP-A-6-138591 (pages 19 to 20), reductones described in JP-A-5-165161 are used as developing agents. Are also preferably used. Among the pyrazolidones to be used, those in which the 4-position is particularly substituted (dimesone, dimesone S, etc.) are particularly preferred since they are less soluble in water and the solid processing agent itself does not change with time.

An organic reducing agent can be used as a preservative in addition to sulfite. In addition, a bisulfite adduct of a chelating agent or a hardening agent can be added.
Also, a silver sludge inhibitor is disclosed in JP-A-5-289255.
JP-A-6-308680 (general formula [4-a] [4
It is also preferable to add the compound described in -b]). It is also preferable to add a cyclodextrin compound.
The compounds described in No. 248543 are particularly preferred. Amine compounds can also be added to the developer, see US Pat.
The compounds described in No. 29 are particularly preferred.

It is necessary to use a buffer for the developer. Examples of the buffer include sodium carbonate, potassium carbonate,
Sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, o-hydroxybenzoic acid Sodium (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like. Can be mentioned.

Examples of the development accelerator include JP-B-37-160.
Nos. 88, 37-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247; No. 50-15554
Quaternary ammonium salts represented by JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429. US Patent 2,61
P-aminophenols described in U.S. Pat. Nos. 0,122 and 4,119,462; U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796 and 3,253. No. 919, JP-B-41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and the like. 42-25201
No. 3,128,183, JP-B-41-11
Nos. 431 and 42-23883 and U.S. Pat.
2,501 or the like, a polyalkylene oxide,
In addition, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be exemplified by 1-phenyl-5-mercaptotetrazole as a typical example.

Further, a methylcellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, and other compounds described in JP-B-47-33378 and JP-B-44-9509 may be added to the developer composition, if necessary. It can be used as an organic solvent for increasing the solubility of the developing agent. Furthermore, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

As the fixing agent, a compound known as a fixing agent can be added. Fixing agents, chelating agents, pH buffers, hardeners,
Preservatives and the like can be added.
2246 (p. 4) and JP-A-5-113632 (2-
4) can be used. In addition, a bisulfite adduct of a hardener and a known fixing accelerator can also be added.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

The present invention relates to black-and-white silver halide photographic light-sensitive materials (for example, medical light-sensitive materials, printing light-sensitive materials, negative films for general photography), and color photographic light-sensitive materials (for example, color negative light-sensitive materials).
Color reversal light-sensitive material, color print light-sensitive material), diffusion transfer photosensitive material, heat-developable photosensitive material, etc.
It can be more preferably applied to a black-and-white silver halide photographic material.

In general, in many cases, hydroquinones are used as a developing agent in a developing solution used for developing a black-and-white photographic light-sensitive material. However, the present invention improves the operational safety and protects the environment. From the viewpoint of being substantially free of hydroquinones, for example, US Pat. No. 5,236,81
A developer using ascorbic acid described in No. 6 may be used. The development time of the black-and-white photographic light-sensitive material of the present invention is 3 to 90 seconds, more preferably 5 to 60 seconds, and the processing time is 15 to 210 seconds, more preferably 15 to 90 seconds, as a dry-to-dry process. .

In the silver halide photographic light-sensitive material of the present invention, various additives can be further added to the silver halide emulsion depending on the purpose. Examples of additives and others used are RD-17643 (December 1978), 1871
6 (November 1979) and 308119 (1989)
December, December). The locations of those descriptions are listed below.

Additive RD-17643 RD-18716 RD-308119 page Classification page Classification page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25 to 26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surface activity Agents 26-7 XI 650 right 1005-6 XI antistatic agent 27 XII 650 right 1006-7 XIII plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26XX I 1003~4 IX support 28 XVII 1009 XVII

The support which can be used in the silver halide photographic material of the present invention includes, for example, the aforementioned RD-1
7643 and RD-308119, page 1009. A suitable support is a plastic film or the like, and the surface of the support is provided with an undercoat layer to improve the adhesion of the coating layer, and the support may be subjected to corona discharge, ultraviolet irradiation or the like.

[0155]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited by these examples. Example 1 (Preparation of Seed Emulsion A) Solution A1 Ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Distilled water 7500 ml B1 solution Silver nitrate 1500 g distilled water 2500 ml C1 solution KI 4 g NaCl 140 g distilled water 684 ml D1 solution 375 g of NaCl 1816 ml with distilled water

At 40 ° C., JP-B-58-58288
A1 in the mixing stirrer shown in the specification, B1
684 ml of the solution and the total amount of the C1 solution were added over 1 minute. The EAg was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the total amount of the remaining solution B1 and the total amount of the solution D5 were reduced to 40.
Added over minutes. During that time, the EAg was controlled at 149 mV.

Immediately after the addition was completed, desalting and washing were performed to obtain a seed emulsion EM-A. Seed emulsion A prepared in this manner has 60% or more of the total projected area of silver halide grains (100).
Electron microscopic observation revealed that the particles consisted of tabular grains having an aspect ratio of 2 or more, having a plane as a main plane, having an average thickness of 0.07 μm, an average diameter of 0.5 μm, and a coefficient of variation of 25%.

(Preparation of Emulsion B) The following four types of solutions were used.
Thus, a tabular silver iodochloride emulsion was prepared. A2 liquid Ossein gelatin 29.4 g HO (CH₂CH₂O) m- (CH (CH (CH₂) CH₂O)₁₇− (CH₂CH ₂ O) nH (m + n ≒ 5.7 molecular weight 1700) (10% methanol solution) 1.25 ml seed emulsion A equivalent to 0.98 mol with distilled water 3000 ml B2 solution 3.5N silver nitrate aqueous solution 2240 ml C2 solution NaCl 455 g with distilled water 2240ml D2 solution 1.75N NaCl aqueous solution The following silver potential control amount

At 40 ° C., JP-B-58-58288
Using a mixing stirrer described in the specification, the total flow rate of the B2 solution and the C2 solution to the A2 solution was doubled by the simultaneous mixing method (double jet method), and the flow rate after the addition was 3 times the flow rate at the start of the addition. , And the addition growth was performed over a period of 110 minutes. During this time, the EAg was 120
Controlled to mV. After completion of the addition, the precipitate was immediately desalted and washed with water to remove excess salts.

When about 3,000 of the obtained emulsions B were observed and measured by electron microscopic observation, and analyzed for their shapes, 80% or more of the total projected area had an aspect ratio of 2 or more with the (100) plane as the main plane. The particles were tabular grains having an average diameter of 1.17 μm and an average thickness of 0.12 μm, and the coefficient of variation was 25%.

(Preparation of Silver Iodide Fine Particles) A3 solution Ossein gelatin 100 g KI 8.5 g with distilled water 2000 ml B3 solution Silver nitrate 360 g with distilled water 605 ml C3 solution KI 352 g with distilled water 605 ml

Solution A3 was added to the reactor, and while stirring at 40 ° C., solution B3 and solution C3 were added at low speed by a simultaneous mixing method over 30 minutes. PAg during the addition is a conventional PAg
It was kept at 13.5 by control means. The formed silver iodide had an average grain size of 0.06 μm. This emulsion is called silver iodide fine grains.

(Preparation of solid fine particle dispersion of spectral sensitizing dye) 5,5'-dichloro-9-ethyl-3,3'-di-
(3-Sulfopropyl) oxacarbocyanine salt anhydride (sensitizing dye A) and 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) Benzimidalocarbocyanine-sodium salt anhydride (sensitizing dye B) was previously added at a ratio of 100: 1 to 27.
C. and water at 3500 rpm with a high-speed stirrer (dissolver). p. m. By stirring for 30 to 120 minutes at, a solid fine particle dispersion of the spectral sensitizing dye was obtained. At this time, it was prepared so that the concentration of the sensitizing dye A was 2% by weight.

(Chemical sensitization) Emulsion B was subjected to spectral sensitization and chemical sensitization in the following manner to obtain a chemically sensitized emulsion. After the emulsion was heated to 60 ° C., sensitizing dye A contained 460 mg /
After the solid fine particle dispersion was added so as to be 1 mol of AgX, ammonium thiocyanate was added to 7 × 10 ^−4.
Mol / AgX1 mol, potassium chloroaurate, sodium thiosulfate, and triphenylphosphine selenide were added at 3 × 10 ⁻⁶ mol / AgX1 mol to perform optimal chemical sensitization. After adding 3 × 10 ⁻³ mol / 1 mol of AgX, 4-hydroxy-6-methyl-
It was stabilized with 1,3,3a, 7-tetrazaindene 1 × 10 ⁻² mol / AgX1 mol. Next, additives described later were added to the emulsion thus sensitized to prepare an emulsion layer coating solution. At the same time, a coating solution for the protective layer was prepared.

(Preparation of support) On both sides of the X-ray polyethylene terephthalate film base (thickness: 175 μm) colored blue with 170 kV
After applying a corona discharge treatment of A · min / m ² , the following (L-1) is dried so that the film thickness of the undercoat latex liquid shown in the following (L-2) becomes 0.2 μm. Is sequentially applied so that the film thickness becomes 0.053 μm.
For 2 minutes to prepare a support.

[0166]

Embedded image

(L-2) n-butyl acrylate 10% by weight, t-butyl acrylate 35% by weight, styrene 2
A copolymer latex solution containing 7% by weight and 28% by weight of 2-hydroxyethyl acrylate (solid content: 30%).

(Preparation of photosensitive material) Next, as shown in Table 1, a leuco dye and a compound represented by the general formula (1)
, And the following coating solution for the crossover cut layer, the coating solution for the emulsion layer and the coating solution for the protective layer were simultaneously coated in the following predetermined coating amounts and dried. Was prepared.

First layer (crossover cut layer) Gelatin 0.2 g / m ² Solid fine particle dispersion dye (AH) (see below) 20 mg / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) (see below) 5 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² Colloidal silica (average particle size 0.014 μm) 10 mg / m ²

[0170]

Embedded image

Second Layer (Emulsion Layer) The following various additives were added to the emulsion obtained above.

Compound represented by general formula (1) Amount added in Table 1 Compound (G) (see below) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,3 5-triazine 5 mg / m ² t-butyl-catechol 5 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 20 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² sodium polystyrene sulfonate 80 mg / m ² tri Methylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 1 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 50 mg / m ² 2-Mercaptobenzimidazole-5-sulfonate sodium 5 mg / ^{m 2} compound (H (See _{^{below) 0.5mg / m 2 n-C}} 4 H 9 OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 20mg / m 2 Compound (M) (see below) 5 mg / ^{m 2} Compound (N (See below) 5 mg / m ² Colloidal silica 0.5 g / m ² Latex (L) (See below) 0.5 g / m ² Sodium styrenesulfonate (molecular weight about 500,000) 7 mg / m ² It was adjusted to 1.0 g / m ² per one side.

[0173]

Embedded image

[0174] The third layer (protective layer lower) Gelatin 0.4 g / ^{m 2} of dioctyl phthalate 195 mg / ^{m 2} Sodium styrene sulfonate (molecular weight: about 500,000) 7 mg / ^{m 2}

[0175] The fourth layer (upper protective layer) Gelatin 0.28 g / ^{m 2} Polymethyl methacrylate consisting matting agent (area average particle diameter 7.0 .mu.m) 27 mg ^/ m 2 2,4-dichloro-6-hydroxy-1,3,5 -Triazine sodium salt 10 mg / m ² latex (L) (see above) 0.2 g / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) (described below) see) 50 mg / ^{m 2} compound (I) (see above) 30 mg / ^{m 2} compound (S-1) (see below) 7 mg / ^{m 2} compound (S-2) (see _{^{below) 5mg / m 2 C 9 F}} 19 —O— (CH ₂ CH ₂ O) ₁₁ —H 3 mg / m ²

[0176]

Embedded image C ₇ F ₁₅ CH ₂ (OCH ₂ CH ₂ ) ₁₃ OH 10 mg / m ^{2 The} amount of the material was one side, and the amount of silver applied was adjusted to 1.5 g / m ² as one side.

[0177]

Embedded image

(Preparation of Tablet for Replenishment of Development) Tablets for replenishment of development were prepared according to the following operations (A, B). Operation (A) 3,000 g of hydroquinone as a developing agent is ground in a commercially available bandan mill until the average particle size becomes 10 μm. In this pulverization, 3000 g of sodium sulfite and 2 parts of potassium sulfite were added.
000 g and Zimezon S1000 g are added in a mill for 30 minutes.
After mixing and granulating by adding 30 ml of water for about 10 minutes at room temperature in a commercially available stirred granulator, the granulated product is dried in a fluidized bed dryer at 40 ° C. for 2 hours. Almost completely removes water from the granules. After 100 g of polyethylene glycol 6000 was uniformly mixed with the granules thus prepared in a room humidified at 25 ° C. and 40% RH or less using a mixer for 10 minutes, the obtained mixture was mixed with Kikusui A tableting machine modified from Tough Press Collect 1527HU manufactured by Seisakusho Co., Ltd. was used to perform compression tableting at a filling amount of 3.84 g per tablet to produce 2500 tablets A for development replenishment.

Operation (B) 100 g of diethylenetriaminepentaacetic acid (DTPA), 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole 7
g, 2-mercaptohypoxanthine 5 g, KOH200
g, 10 g of N-acetyl-D, L-penicillamine are ground and granulated in the same manner as in the operation (A). The amount of water added is 30m
After the granulation, the mixture is dried at 50 ° C. for 30 minutes to almost completely remove the moisture of the granulated product. The mixture thus obtained was filled with the above tableting machine at a filling amount of 1.73 g per tablet.
And compression tableting, and 2,500 development replenishing tablets B
An agent was prepared.

(Preparation of Fixing Supplementary Tablets) Fixing supplementary tablets were prepared by the following procedure. Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in the operation (A), granulation is performed with the addition amount of water being 500 ml. After granulation, the granulated product is
For 30 minutes to remove the moisture of the granules almost completely. 4 g of sodium N-lauroylalanine was added to the granules thus prepared, and the mixture was added at 25 ° C. and 40% RH.
Mix for 3 minutes in a humidified room using a mixer below. Next, the obtained mixture was subjected to compression tableting using the above-mentioned tableting machine at a filling amount per tablet of 6.202 g and a compression tableting of 250%.
Zero fixing replenishing tablets C were prepared.

Operation (D): 1000 g of boric acid, 150 parts of aluminum sulfate / 18 hydrate
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). After adding water to 100 ml and granulating, the granulated material is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. 4 g of sodium N-lauroylalanine was added to the granules thus prepared and mixed for 3 minutes, and the obtained mixture was filled with the above tableting machine at a filling amount of 4.562 g per tablet.
Then, compression tableting was performed to prepare 1250 fixing replenishing tablets D.

(Development of Photosensitive Material) Developer Starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1 liter.

At the start of the processing of the developing solution (start of running), the developing tank was filled with a solution obtained by adding 330 ml of a starter to 16.5 liters of a developing solution prepared by diluting a developing tablet with dilution water. Started processing. The pH of the developer to which the starter was added was 10.45. Further, the fixing start solution is the C agent 298 of the fixing replenishment tablet.
The fixing bath was filled with 11.0 liters of a fixing solution prepared by diluting an equivalent of 149 g of D agent with dilution water. The sample was exposed so that the optical density after the development processing was 1.0, and the sample was run. For the running, an automatic developing machine SRX-502 manufactured by Konica Co., Ltd. equipped with a charging member of a solid processing agent and modified so that the processing speed could be processed in 25 seconds in total was used.

During the running, the photosensitive material contained 0.6 photosensitive material.
The test was carried out by adding ^{two of the} above agents A and B and 76 ml of water per 2 m ² . When each of the agents A and B was dissolved in 38 ml of water, the pH was 10.70. To the fixing solution, ^{2 of the} above-mentioned C agent, 1 of the D agent and 74 ml of water were added per 0.62 m ² of the photosensitive material. The rate of addition of water to each treating agent started almost simultaneously with the addition of the treating agent, and was added at a constant speed for 10 minutes approximately in proportion to the dissolution rate of the treating agent.

Processing conditions Development 35 ° C 8.2 seconds Fixing 33 ° C 5 seconds Rinse at room temperature 4.5 seconds Squeeze 1.6 seconds Drying 40 ° C 5.7 seconds Total 25 seconds

<Evaluation of Blue Density Rise in Low Density Area> A sample was heated at a temperature of 23 ° C. and a humidity of 50% RH (A).
Each sample was stored under the condition (B) of 0 ° C. and a humidity of 80% RH for 5 days, and then subjected to development processing under the above-mentioned 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.
Table 1 shows the obtained results.

<Evaluation of Silver Tone> A sample was cut into half-cut sizes, uniformly exposed to light having a density of 1.2 after development, and then processed according to the above-described processing method. (Light source table) and the following criteria were evaluated with transmitted light. Table 1 shows the obtained results. A: Pure black B: Black that feels very slightly yellow when watched C: Slightly yellowish black D: Yellowish black

[0188]

[Table 1] As is clear from Table 1, the sample of the present invention has good storage stability and excellent silver tone.

Example 2 The procedure of Example 1 was repeated, except that the compound represented by the general formula (2) was added as shown in Table 2 in place of the compound represented by the general formula (1). Samples 12 to 19 were prepared and evaluated in the same manner as in Example 1. Table 2 shows the obtained results.

[0190]

[Table 2]

Example 3 The procedure of Example 1 was repeated, except that the compound represented by the general formula (3) was added as shown in Table 3 in place of the compound represented by the general formula (1). Samples 20 to 29 were prepared and evaluated in the same manner as in Example 1. Table 3 shows the obtained results.

[0192]

[Table 3]

[0193]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having good storage stability and excellent silver tone and a processing method thereof.

Claims (8)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer provided on the opposite side of the silver halide emulsion layer from the support. The silver halide emulsion layer and / or the adjacent hydrophilic colloid layer contains a compound represented by the following general formula (1), and the hydrophilic colloid layer contains a leuco dye capable of giving a blue dye. Characteristic silver halide photographic material. Embedded image In the general formula (1), R represents a substituted or unsubstituted aryl group, and R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, and are each a hydrogen atom or a substituted or unsubstituted group. Represents a substituted alkyl group, aralkyl group, or aryl group. 2. A silver halide photographic material having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer provided on the opposite side of the silver halide emulsion layer from the support. The silver halide emulsion layer and / or the adjacent hydrophilic colloid layer contains a compound represented by the following general formula (2), and the hydrophilic colloid layer contains a leuco dye capable of giving a blue dye. Characteristic silver halide photographic material. Embedded image In the general formula (2), R ₁ and R ₂ each independently represent a hydroxy group, a —OM group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. M represents an alkali metal atom or an ammonium group, and X represents an atom group necessary for forming a 5- to 6-membered ring together with the two vinyl carbons and carbonyl carbons substituted by R ₁ and R ₂ . 3. A silver halide photographic material having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer provided on the opposite side of the silver halide emulsion layer from the support. The silver halide emulsion layer and / or the hydrophilic colloid layer contains a compound represented by the following general formula (3), and the hydrophilic colloid layer contains a leuco dye capable of giving a blue dye. Silver halide photographic light-sensitive material. Embedded image In the general formula (3), R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an alkylcarbonyl group, an arylsulfonyl group, an arylcarbonyl group or a carbamoyl group, or R ₁ and R ₂ are bonded to each other To form a heterocyclic ring. Note that R ₃ , R ₄ ,
R ₅ and R ₆ each represent a hydrogen atom or a substitutable group, and may combine with each other to form a ring. 4. Silver halide grains in which at least one of the silver halide emulsion layers has parallel (100) major planes in which at least 50% of the total projected area of the silver halide grains has a silver chloride content of at least 30 mol%. The silver halide photographic light-sensitive material according to any one of claims 1 to 3, further comprising: 5. A method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 1 is processed in a photographic processing step including a development step. 6. A method for processing a silver halide photographic light-sensitive material, comprising processing the silver halide photographic light-sensitive material according to claim 1 in a photographic processing step including a developing step and a fixing step. . 7. A photographic process comprising a developing step and a fixing step using the silver halide photographic light-sensitive material according to claim 1 and a developing solution and a fixing solution obtained by dissolving a solid processing agent. A method for processing a silver halide photographic material, wherein the method is performed in a processing step. 8. A silver halide photographic material characterized by processing the silver halide photographic material according to claim 1 in a photographic processing apparatus having a mechanism for supplying a solid processing agent to a processing tank. Processing method of photosensitive material.