JPH10228073A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obviate the generation of a fluctuation in sensitivity and black dots by lapse of time and contamination with after-colors and to improve safe light resistance by incorporating one kind of specific spectral sensitizing dyestuffs into silver halide emulsion layers and incorporating at least one kind selected from specific nitrogenous heterocyclic compds. into these layers. SOLUTION: This photosensitive material is formed by incorporating at least one kind of the spectral sensitizing dyestuffs expressed by formula I, etc., in the silver halide emulsion layers and at least one kind selected from hydrazine derivatives and/or 5- to 6-membered nitrogenous heterocyclic compds. in the silver halide emulsion layers or hydrophilic colloidal layers. In the formula I, Y denotes an oxygen atom or >N-R group. At least either of R1 and R2 denote lower alkyl groups substd. with a sulfo group or carboxyl group. Z1 to Z5 respectively denote hydrogen atoms or (substd.) atoms or groups. X1 denotes the ions necessary for neutralizing the charge in the molecule and n1 is 0 when the dyestuffs form intra-molecular salt.

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 for plate making printing.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material for plate-making printing, a high-contrast silver image is required to record a dot image and a line image.

Various compounds have been disclosed as a high contrast agent for silver halide emulsions.
I. O. S Final Report No. 252
(PB20,090), FIAT Final Rep
rt No. R known as 360 (PB26,996)
h, Ru described in JP-A-2-20852,
Transition metal complex salts of groups 6 to 10 such as Os have been known for a long time.

In recent years, as a high contrast agent for a photosensitive material for plate making printing, JP-A-53-16623, US Pat.
No. 9,929, the hydrazine derivative disclosed in
-217337, 5-53231 and 6-161
No. 009, etc., a nucleating agent type toning agent comprising a 5- to 6-membered nitrogen-containing heterocycle, or JP-A-57-132137.
And methods using a tetrazolium salt described in JP-A Nos. 58-173737 and 61-270745.

On the other hand, various spectral sensitizing dyes are widely known for increasing the sensitivity of silver halide emulsions. In particular, as a sensitizing dye which imparts high sensitivity to green light, for example, EP-050
6584, JP-A-5-88293, 5-9397
No. 5 discloses a technique using a specific benzimidazolocarbocyanine.

However, when a silver halide photographic light-sensitive material for plate-making printing is prepared by combining the sensitizing dye with the above-mentioned high contrast agent, sensitivity fluctuations over time of the light-sensitive material and spot fog called black spots occur frequently. Had problems. Further, the processed film has many drawbacks such as a large amount of residual color contamination due to dyes and poor safelight resistance in a dark room.

[0007] The residual color contamination of the film not only lowers the commercial value, but also requires a clear silver image from a practical point of view, and further improvement has been desired.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material for plate-making printing which is free from fluctuations in sensitivity over time of the light-sensitive material, generation of black spots and residual color contamination, and safelight resistance. In providing an excellent silver halide photographic light-sensitive material.

[0009]

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

In a silver halide photographic material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, the silver halide emulsion layer contains the following general formula (1) or the following general formula: A hydrazine derivative and / or a 5- to 6-membered nitrogen-containing complex, which contains at least one spectral sensitizing dye represented by (2) and is contained in the silver halide emulsion layer or the hydrophilic colloid layer. A silver halide photographic light-sensitive material comprising at least one selected from cyclic compounds.

[0011]

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In the formula, Y represents an oxygen atom or> NR group. R, R ₁ and R ₂ each represent a lower alkyl group;
At least one of R ₁ and R ₂ represents a lower alkyl group substituted with a sulfo group or a carboxyl group. Z ₁ , Z ₂ ,
Z ₃ , Z ₄ and Z ₅ each represent a hydrogen atom or a substitutable atom or group, and may be respectively bonded between Z ₃ and Z ₄ and between Z ₄ and Z ₅ to form a condensed ring. However, at least one of Z ₁ and Z ₂ represents an electron-withdrawing group. X ₁ represents an ion necessary for neutralizing an intramolecular charge, and n1 is 0 when the dye forms an intramolecular salt.

[0013]

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In the formula, R ₁₁ and R ₁₃ each represent a lower alkyl group or an alkenyl group. However, at least one of R ₁₁ and R ₁₃ represents a vinyl group (—CH ＝ CH ₂ ). R ₁₂ , R ₁₄
Represents a lower alkyl group, and at least one of R ₁₂ and R ₁₄ is a lower alkyl group substituted with a hydrophilic group. Z
₁₁ , Z ₁₂ , Z ₁₃ and Z ₁₄ may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a halogen-substituted alkoxy group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group. An alkylthio group, a halogen-substituted alkylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a hydroxy group, a haloalkyl group, a carboxyl group, a sulfonyl group,
Represents an acylamino group, a heterocyclic group or an aryl group. X ₁₁
Represents an ion necessary for neutralizing an intramolecular charge, and n11 is 0 when the dye forms an intramolecular salt.

In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, the silver halide emulsion layer may contain the above-mentioned general formula (1) or the above-mentioned general formula (1). It contains at least one kind of spectral sensitizing dye represented by the formula (2) and contains at least one kind selected from tetrazolium compounds in the silver halide emulsion layer or the hydrophilic colloid layer. A silver halide photographic light-sensitive material comprising:

Item or The silver halide photographic light-sensitive material according to Item, wherein the silver halide emulsion layer contains at least one transition metal selected from the elements of Groups 6 to 10 of the periodic table.

Hereinafter, the present invention will be described in detail.

The silver halide photographic material of the present invention has at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on one surface of a support,
On the other side, a backing layer containing a dye is provided.

At least one of the light-sensitive silver halide emulsion layers contains the spectral sensitizing dye represented by formula (1) or (2).

In the above formulas (1) and (2), the lower alkyl group represented by R, R ₁ , R ₂ , R ₁₁ -R ₁₄ includes, for example, methyl, ethyl, propyl, isopropyl, butyl , Cyclopentyl, cyclohexyl group and the like.

The substituted lower alkyl group includes
For example, hydroxyethyl, ethoxycarbonylethyl,
Ethoxycarbonylmethyl, benzyl, phenethyl, methoxyethyl, cyanomethyl, 2-cyanoethyl, 2,
2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, carboxymethyl, carboxyethyl, sulfobutyl, sulfoethyl, sulfopropyl, sulfopentyl, 6-sulfo-3-oxahexyl, 4-
Sulfo-3-oxapentyl, 10-sulfo-3,6-
Dioxadecyl, 6-sulfo-3-thiahexyl, o-
Sulfobenzyl, p-sulfobenzyl, p-carboxybenzyl, methanesulfonylaminoethyl, methanesulfonylaminocarbonylmethyl, 3-oxobutyl,
-(N-methylsulfamoyl) ethyl, 2- (trifluoroacetylamino) ethyl group and the like.

Examples of the alkenyl group represented by R ₁₁ and R ₁₃ include a vinyl group, an allyl group and a 1-propenyl group.

As the substitutable group represented by Z ₁ and Z ₂ , any group having a total sum not exceeding 2.4 when adding the Hammett σp value of the substitutable group is preferable, and a halogen atom (For example, a fluorine atom, a chlorine atom, a bromine atom,
Iodine atom, etc.), aryl group (eg, phenyl, 4-bromophenyl group, etc.), alkyl group (eg, methyl, ethyl, t-butyl group, etc.), alkoxy group (eg, methoxy, ethoxy group, etc.), alkylthio Group (eg, methylthio, propylthio group, etc.), trifluoromethyl group, cyano group, carboxy group, alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl group, etc.), acyl group (eg, acetyl, propionyl group, etc.), sulfonyl Groups (eg, methanesulfonyl, trifluoromethanesulfonyl, etc.), carbamoyl groups (eg, carbamoyl, N, N-dimethylcarbamoyl,
Groups such as an N-morpholinocarbonyl group), a sulfamoyl group (eg, a sulfamoyl, N, N-dimethylsulfamoyl group), an acetylamino group, and an acetyloxy group. More preferred are a halogen atom and a trifluoromethyl group.

Z ₃ , Z ₄ and Z ₅ may be any groups, for example, a halogen atom (for example, fluorine, chlorine, bromine, iodine atom, etc.), an aryl group (for example, phenyl, 4-bromophenyl group, etc.), Alkyl groups (eg, methyl, ethyl, t
-Butyl group, etc.), alkoxy group (for example, methoxy, propyloxy group, etc.), alkylthio group (for example, methylthio, ethylthio group, etc.), trifluoromethyl group, cyano group, carboxy group, alkoxycarbonyl group (for example, methoxycarbonyl group) , Ethoxycarbonyl group, etc.),
Acyl group (eg, acetyl, butyryl group, etc.), sulfonyl group (eg, methanesulfonyl, propylsulfonyl group, etc.), carbamoyl group (eg, carbamoyl,
N, N-dimethylcarbamoyl, N-morpholinocarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl group, etc.), and hydroxy group.

Z ₃ and Z ₄ and Z ₄ and Z ₅ each represent a condensed ring which can be formed by bonding to each other, for example, a 6-membered saturated or unsaturated carbocyclic group; And a heterocyclic group, for example, naphtho [2,1
-D] azole, naphtho [1,2-d] azole, naphtho [2,3-d] azole, furano [3,2-e] benzoazole, thieno [3,2-e] benzoazole, thieno [2 , 3-f] benzoazole and the like.

Z ₁₁ , Z ₁₂ , Z ₁₃ and Z ₁₄ may be the same or different, and each represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, iodine atom, etc.), a cyano group, an alkyl group ( For example, methyl, ethyl, t-butyl group, etc.), alkoxy group (eg, methoxy, propyloxy group, etc.), halogen-substituted alkoxy group (eg, trifluoromethoxy, tetrafluoroethyloxy group, etc.),
Aryloxy group (eg, phenyloxy, 4-bromophenyloxy group, etc.), acyl group (eg, acetyl, propionyl group, etc.), acyloxy group (eg, acetyloxy group, propionyloxy group, etc.), alkylthio group (eg, Methylthio, ethylthio, etc.), halogen-substituted alkylthio (eg, trifluoromethylthio, tetrafluoroethylthio, etc.), alkoxycarbonyl (eg, methoxycarbonyl, ethoxycarbonyl, etc.), carbamoyl (eg, carbamoyl, N, N-dimethylcarbamoyl, N-morpholinocarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl group, etc.), hydroxy group, haloalkyl group (eg, trifluoromethyl, pentafluoro A carboxy group, a sulfonyl group (eg, methanesulfonyl, ethanesulfonyl group, etc.), an acylamino group (eg, acetylamino, butyrylamino group, etc.), a heterocyclic group (eg, furanyl, pyrrolyl group, etc.) or an aryl group ( For example, phenyl, 4-
Chlorophenyl group etc.).

The ions represented by X ₁ and X ₁₁ include:
For example, chlorine ion, bromine ion, iodine ion, thiocyanate ion, sulfate ion, perchlorate ion, p-toluenesulfonic acid ion, ethyl sulfate ion, lithium ion, sodium ion, potassium ion, magnesium ion, triethylammonium ion, etc. Can be mentioned.

The Hammett σp value used in the group of the general formula (2) is a substituent constant determined by Hammett et al. From the electronic effect of the substituent on the hydrolysis of ethyl benzoate, and is the journal of Organic Chemistry 23, 420-427 (1958), Experimental Chemistry Course 14 (Maruzen Publishing), Physical Organic Chemistry (McGraw Hill Bo)
ok: 1940), Drag Design VII (Ac)
ademic Press New York: 197
6) and the structure-activity relationship of drugs (Nankodo: 1979).

Hereinafter, the general formulas (1) and (2) of the present invention will be described.
Specific examples of the spectral sensitizing dye represented by are shown below, but the present invention is not limited thereto.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The above-mentioned spectral sensitizing dyes are described, for example, in British Patent No. 95
No. 5,961, U.S. Pat. No. 2,739,149, JP-B-43-10251 and JP-B-43-10252,
The compound can be easily synthesized with reference to the method described in JP-A-88293.

In the present invention, the amount of the sensitizing dye to be added is not uniform depending on the kind of the dye and the structure, composition, ripening condition, purpose and application of the silver halide. The dose may be from 10 to 1000 mg, more preferably from 50 to 500 mg.

The above sensitizing dye may be dissolved by any method and added at any step. As a solvent for the sensitizing dye, a conventionally used water-miscible organic solvent can be used. For example, alcohols, ketones, nitriles, alkoxy alcohols and the like have been used. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, and 2-ethoxyethanol. The sensitizing dye may be added as an acidic solution or a solid fine particle dispersion.

The spectral sensitizing dye of the present invention can be added during the chemical ripening step, particularly preferably at the start of the chemical ripening, and can be added from the nucleation step of the silver halide emulsion to the end of the desalting step. Thus, a high-sensitivity silver halide emulsion having excellent spectral sensitization efficiency can be obtained. However, the above-mentioned step (nucleation) may be performed at any time after the completion of the desalting step, through the chemical ripening step, and immediately before the coating step. The same or a different kind of spectral sensitizing dye according to the present invention may be additionally added to the dye added from the time of the process to the end of the desalting process). The above-mentioned spectral sensitizing dye of the present invention may be used before or after the addition of a later-described high contrast agent or a nucleation accelerator for enhancing the high contrast effect, and preferably the high contrast agent or the high contrast effect is enhanced. To the silver halide emulsion before the addition of a nucleation accelerator or the like.

The silver halide emulsion or hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention contains at least one selected from hydrazine derivatives and / or 5- to 6-membered nitrogen-containing heterocyclic compounds. .

In the present invention, the hydrazine derivative preferably used is a compound represented by the following general formula [H].

[0050]

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In the general formula [H], A ₀ is an aliphatic group,
The aromatic group or the heterocyclic group, the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, particularly 1 to 2 carbon atoms.
A linear, branched or cyclic alkyl group of 0 is preferable, and specific examples include, for example, a methyl group, an ethyl group, a t-butyl group,
Octyl, cyclohexyl, benzyl and the like, which are further substituted with a suitable substituent (for example, aryl, alkoxy, aryloxy, alkylthio, arylthio, sulfoxy, sulfonamide, sulfamoyl, acylamino, ureido, etc.). You may.

[0052] In formula (H), the aromatic group represented by A ₀ is an aryl group preferably a monocyclic or condensed, such as a benzene ring or a naphthalene ring can be mentioned, A ₀
As the heterocyclic group represented by, nitrogen in a single ring or a condensed ring,
Sulfur, a heterocyclic ring containing at least one hetero atom selected from oxygen atoms is preferable, for example, pyrrolidine, imidazole, tetrahydrofuran, morpholine, pyridine,
Pyrimidine, quinoline, thiazole, benzothiazole, thiophene, furan ring and the like. Particularly preferred as A ₀ are an aryl group and a heterocyclic group,
The aromatic group and the heterocyclic group of ₀ may have a substituent. As a particularly preferable group, a substituent having an acidic group having a pKa of 7 or more, specifically, a sulfonamide group,
Examples include a hydroxyl group and a mercapto group.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or a silver halide-adsorbing group. The diffusion-resistant group is commonly used in immobile photographic additives such as couplers. The ballast group is preferably a ballast group. Examples of the ballast group include a photographically inert group having 8 or more carbon atoms, such as an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a phenyl group, a phenoxy group, and an alkylphenoxy group.

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, 64-9
No. 0439, for example.

In the general formula [H], B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group, and G ₀ represents-
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P
(O) A preferred (G ₀ ) representing a (G ₁ D ₁ ) — group is
A CO- group and a -COCO- group are particularly preferably -COCO.
G ₁ is a mere bond, an —O— group, —S
Or a —N (D ₁ ) — group, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they are the same. May or may not be.

In the general formula [H], D ₀ is a hydrogen atom,
Aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, preferably a hydrogen atom as a D _0, an alkoxy group, an amino group, and the like, A ₁ , A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl,
Trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group (ethoxalyl, etc.).

Among the compounds represented by the above general formula [H], more preferred compounds are those represented by the following general formula [H-2]
The compound represented by these is mentioned.

Formula [H-2] R ₀ -SO ₂ NH-Ar-NHNH-G ₀ -D _{0 In the} formula, R ₀ represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group; Represents a substituted or unsubstituted divalent arylene group or heterocyclic group, and G ₀ and D ₀ are represented by the general formula [H]
Is synonymous with Hereinafter, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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Specific examples of other preferred hydrazine derivatives are (1) to (252) described in columns 4 to 60 of US Pat. No. 5,229,248.

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in JP-A-29,248.

Next, the 5- or 6-membered nitrogen-containing heterocyclic compound which can be preferably used in the present invention can be represented by the following general formula [Pa], [Pb] or [Pc].

[0067]

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In the general formulas [Pa], [Pb] or [Pc], A ₁ , A ₂ , A ₃ , A ₄ or A ₅ is a nonmetal for completing a 5- to 6-membered nitrogen-containing heterocyclic ring. Represents a group of atoms, and the hetero ring may contain an oxygen atom, a nitrogen atom and a sulfur atom, and the hetero ring may be condensed with a benzene ring. ₅ to 6 composed of A ₁ , A ₂ , A ₃ , A ₄ or A ₅
The membered nitrogen-containing heterocycle may have a substituent, and the substituent may be an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Sulfo group, carboxy group, hydroxy group, alkoxy group, aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group,
It represents a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, or an arylthio group. A ₁ , A ₂ ,
Examples of the 5- to 6-membered nitrogen-containing heterocyclic ring composed of A ₃ , A ₄ or A ₅ include pyridine, imidazole, thiazole, oxazole, pyrazine, pyrimidine ring and the like, and preferably a pyridine ring. .

In the general formulas [Pa] and [Pb], Bp
Represents a divalent linking group, a divalent linking group is an alkylene,
Arylene, _{alkenylene, -SO 2 -, - SO -} , -
O -, - S -, - CO -, - N (R 6) -, represents what is configured alone or in combination (R ₆ represents an alkyl group, an aryl group, a hydrogen atom). A preferred example is Bp
Represents an alkylene group, alkenylene group, or alkyleneoxy group.

In the general formulas [Pa], [Pb] or [Pc], R ₁ , R ₂ or R ₅ represents a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and R ₁ , R ₂ May be the same or different and the substituents are A ₁ , A ₂ , A
_3, A ₄ or can be given the same as groups given as the substituent of A _5.

Preferred examples of R ₁ , R _{2 and} R ₅ each represent an alkyl group having 4 to 10 carbon atoms, and more preferred examples include a substituted or unsubstituted aryl group and a substituted alkyl group.

In the general formulas [Pa], [Pb] or [Pc], X _p ^- and X each represent a counter ion necessary for balancing the charge of the whole molecule, for example, chloride ion, bromide ion,
Represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate, n _p and n _p ⁻ represent the number of counter ions required to balance the charge of the whole molecule, and in the case of an inner salt, n _p and n _p ^- are zero. Specific examples of the compound represented by the formula [Pa], [Pb] or [Pc] are shown below.

[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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In the present invention, the hydrazine derivative and 5-
The 6-membered nitrogen-containing heterocyclic compound is contained in the hydrophilic colloid layer (including the silver halide emulsion layer) on the side of the silver halide emulsion layer. Preferably, it is contained in a silver halide emulsion layer and / or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

The amount of addition may be any amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 1 per mol of silver halide.
It may be in the range of 0 ^-1 mol, preferably in the range of 10 ^-5 to 10 ^-2 mol.

In the silver halide emulsion layer or the hydrophilic colloid layer of the silver halide photographic material of the present invention, a tetrazolium compound is used.

The preferred tetrazolium compound used in the present invention can be represented by the following general formula [T].

[0082]

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In the formula, R ₁ , R ₂ , and R ₃ are preferably a hydrogen atom or a compound having a negative Hammett sigma value (σp) indicating electron-withdrawing degree.

The Hammett's sigma value for phenyl substitution is described in many literatures, for example, Journal of Medical Chemistry.
Chemistry) Vol. 20, p. 304 (1977)
Year). As a group having a particularly preferable negative sigma value, for example, a methyl group (σp = −0.17 or less, all σp values) and an ethyl group (−0) can be seen in reports by C. Hansch et al. .15), cyclopropyl group (-0.21), n-propyl group (-0.1
3), isopropyl group (-0.15), cyclobutyl group (-0.15), n-butyl group (-0.16), is
o-butyl group (-0.20), n-pentyl group (-0.
15), cyclohexyl group (-0.22), amino group (-0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.22)
7), an ethoxy group (-0.24), a propoxy group (-
0.25), butoxy group (-0.32), pentoxy group (-0.34) and the like, all of which are useful as substituents of the compound of the general formula [T] of the present invention.

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion; and inorganic acids such as nitric acid, sulfuric acid and perchloric acid. Acid radicals, organic acid radicals such as sulfonic acid and carboxylic acid, anionic activators, specifically lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anion and higher alkylbenzenes such as p-dodecylbenzenesulfonic acid anion Sulfonate anion, higher alkyl sulfate anion such as lauryl sulfate anion, borate-based anion such as tetraphenylboron, dialkyl sulfosuccinate anion such as di-2-ethylhexyl sulfosuccinate anion, cetyl polyethenoxy sulfate anion and the like Polyether alcohol Ester anion, higher aliphatic acid such as stearic acid anion anion, those with a acid radical in a polymer of polyacrylic acid anion, and the like.

Hereinafter, specific examples of the compound represented by the general formula [T] are shown below, but it should not be construed that the invention is limited thereto.

[0087]

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The above tetrazolium compound can be easily synthesized, for example, according to the method described in Chemical Reviews, vol. 55, pages 335-483.

The above tetrazolium compounds may be used alone or in combination of two or more at an appropriate ratio.

The above-mentioned tetrazolium salt used in the present invention is preferably used in a silver halide emulsion layer or adjacent thereto, preferably in a silver halide emulsion layer or an adjacent layer thereof.

[0091] The particle size of the added amount of silver halide grains, the halogen composition, the degree of chemical sensitization, although the optimum amount is not uniform due to the type of inhibitor, generally 1 mol of silver halide per 10 ^- The range is preferably from ⁶ to 10 ^-1 mol, particularly preferably from 10 ^-5 mol.
10 ^-2 mol per mol of silver is preferred.

In the present invention, the hydrazine derivative or 5-6
It is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb] in order to effectively promote intensification of the membered heterocyclic compound or tetrazolium compound.

[0093]

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In the general formula [Na], R ₁₁ , R
₁₂ and R ₁₃ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, or a substituted aryl group. R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is particularly preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.

The following are specific examples of these nucleation accelerators [Na].

[0096]

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[0097]

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[0098]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. In the formula, R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group, but Ar and R ₁₄ may be linked by a linking group to form a ring. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by the formula [H].

Specific examples of the compound represented by the general formula [Nb] include the following.

[0101]

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[0102]

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In the present invention, when a nucleation accelerator having a molecular weight of 500 or less was used, the effect of the present invention was great.

The nucleation accelerator used in the present invention includes:
Any layer may be used as long as it is a layer on the side of the silver halide emulsion layer, and is preferably used for the silver halide emulsion layer or a layer adjacent thereto. The optimum amount is not uniform depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like, but is generally 10 ^-6 to 10 per mol of silver halide. A range of ^-1 mol is preferable, and a range of 10 ^-5 to 10 ^-2 mol is particularly preferable.

The silver halide emulsion of the silver halide photographic light-sensitive material of the present invention contains a transition metal complex. As the transition metal complex preferably used in the present invention, a six-coordinate complex represented by the following general formula is preferable.

[ML ₆ ] ^{m In the} formula, M represents a transition metal selected from elements of Groups 6 to 10 of the periodic table, and L represents a bridging ligand. m is 0, -1, -2
Or -3. All L may be the same or different.

Preferred specific examples of the ligand represented by L include halides (fluorides, chlorides, bromides and iodides), cyanides, cyanates, thiocyanates, selenocyanates, tellurocyanates, nitrosyls, and the like. And thionitrosyl, azide and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands.

Particularly preferred examples of M include rhodium (Rh), ruthenium (Ru), and rhenium (R
e), osmium (Os) and iridium (Ir).

The following are specific examples of the transition metal coordination complex, but the present invention is not limited to these.

[0110] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [CrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: _{[Ru (H 2 O) 2 Br} 4 ] ^- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [Rh (H ₂ O) Cl _5] ^2- 11: [Re (NO) Cl _5] ^2- 12: [Re (NO) CN _5] ^2- 13: [Re (NO) ClCN _4] ^2- 14: [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) CN _5] ^2- 17: [Fe (CN) _6] ^3- 18: [Rh (NS ) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN)] ^2- 23 [Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: _{[Os (NS) Cl 4 (SCN} ) 4 ] ^2- 26: [Ir (NO) Cl ₅ ^{2-In order for the} above metal complex to be contained in the silver halide emulsion,
It can be added and contained during the preparation of silver halide grains. The timing of addition may be such that it is uniformly distributed throughout the silver halide grains, or it may be such that it is present in the inner shell of the silver halide grains.

The amount of the metal complex to be added may be 10 ^-9 to 10 ^-3 mol, preferably 10 ^-8 to 10 ^-5 mol, per mol of silver halide in the form of a complex.

The halogen composition of the silver halide emulsion used for the silver halide photographic light-sensitive material of the present invention is particularly preferably a silver halide emulsion having a composition having a limited Salenaiga silver chloride content of 60 mol% or more. The particle size is preferably 0.6 μm or less, especially 0.5 to
0.05 μm is preferred.

The shape of the silver halide grains is not particularly limited, and may be any of tabular, spherical, cubic, tetradecahedral, octahedral, and any other shapes. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

As the tabular grains, tabular grains having a (100) plane having 60 mol% or more of silver chloride as a main plane can be used.

The emulsion may be prepared by any one of a one-side mixing method, a simultaneous mixing method and a combination thereof. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. To obtain a silver halide emulsion having a nearly uniform grain size.

The silver halide emulsion may or may not be chemically sensitized. Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization, and any of these methods may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion according to the present invention.
Other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid or the like as a monomer component can be used.

As one method for remarkably exhibiting the effects of the present invention, it is preferable that at least one constituent layer contains a hydrophilic polymer. Preferred hydrophilic polymers include starch, glucose, dextrin, dextran, cyclodextrin, sucrose, maltose, xanthan gum, carrageenan and the like.

The molecular weight of the hydrophilic polymer is from 600 to 100
Up to ten thousand can be appropriately selected. The lower the molecular weight is, the better to elute into the processing solution quickly during the processing, but if it is too low, the film strength of the film is deteriorated. When a hydrophilic polymer is used, the abrasion resistance of the film deteriorates. Therefore, it is preferable to add inorganic colloidal silica, colloidal tin, colloidal zinc, colloidal titanium, colloidal yttrium, colloidal praseodymium, neodymium, zeolite, apatite, and the like. As zeolites, analsite, erionite, mordenite, shabasite, gmelinite, levinite, and as synthetic zeolites, zeolite A,
X, Y, L and the like. Examples of apatite include hydroxyapatite, fluorospatite, and chlorapatite.

The preferable addition amount is from 1% to 200% by weight per hydrophilic binder. By treating the inorganic compound with a silane coupling agent, the inorganic compound hardly aggregates even when added to the emulsion, and can stabilize the coating solution.

Further, cracking due to the inorganic compound can be prevented. Examples of silane coupling agents include triethoxysilanovinyl, trimethoxysilanovinyl, trimethoxypropyl methacrylate, trimethoxysilanopropylglycidyl, 1-mercapto-3-triethoxysilanopropane, 1-amino-3-triethoxysilanopropane, Triethoxysilanophenyl, triethoxymethylsilane and the like. By treating the silane coupling agent at a high temperature together with the above-mentioned inorganic compound, the characteristics can be improved as compared with the simple mixing. The mixing ratio is preferably selected in the range of 1: 100 to 100: 1.

As one method for remarkably exhibiting the effects of the present invention, it is preferable to have at least two silver halide emulsion layers. The sensitivity of these emulsion layers may be the same or different. These emulsion layers may be adjacent to each other, or may have one or more intermediate layers between each emulsion layer.

In order for the effects of the present invention to be more remarkably exhibited, at least one silver halide photographic emulsion layer is provided on the side opposite to the silver halide photographic emulsion layer.
It is preferred to have a hydrophilic colloid layer as a layer and to have at least one hydrophobic polymer layer outside the layer. Here, the hydrophilic colloid layer on the opposite side of the silver halide photographic emulsion layer includes a so-called backing layer.

A structure having at least one hydrophobic polymer layer outside the backing layer is preferable. The hydrophobic polymer layer is a layer using a hydrophobic polymer as a binder.
Specific examples of the polymer layer binder include polyethylene, polypropylene, polystyrene, polyvinyl chloride,
Polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, tetrafluoroethylene,
Fluorinated resins such as polyvinylidene fluoride, rubbers such as butadiene rubber, chloroprene rubber, and natural rubber; acrylic or methacrylic acid esters such as polymethyl methacrylate and polyethyl acrylate; polyester resins such as polyethylene phthalate; nylon 6; nylon 66
And water-insoluble polymers such as silicone resins and derivatives thereof. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used. Particularly preferred binders are copolymers of alkyl acrylate or alkyl methacrylate with acrylic acid or methacrylic acid (acrylic acid or methacrylic acid is preferably at most 5 mol%), styrene-
Butadiene copolymer, styrene-butadiene-acrylic acid copolymer (acrylic acid is preferably 5 mol% or less), styrene-butadiene-divinylbenzene-methacrylic acid copolymer (methacrylic acid is preferably 5 mol% or less), vinyl acetate-ethylene-acryl Acid copolymers (acrylic acid is 5 mol% or less), vinylidene chloride-acrylonitrile-methyl methacrylate-ethyl acrylate-acrylic acid copolymer (acrylic acid 5 mol% or less), and ethyl acrylate-glycidyl methacrylate-acrylic acid copolymer. These may be used alone or in combination of two or more.

If necessary, a matting agent, a surfactant, a dye, a sliding agent, a crosslinking agent, a thickener,
V absorbers and photographic additives such as inorganic fine particles such as colloidal silica may be added. Regarding these additives, the description in Research Disclosure Magazine, Vol. 176, No. 17646 (December, 1978) can be referred to.

The hydrophobic polymer layer may be a single layer or two or more layers. There is no particular limitation on the thickness of the polymer layer. However, if the thickness of the hydrophobic polymer layer is too small,
The water resistance of the hydrophobic polymer layer becomes insufficient, and the back layer swells in the treatment liquid, which is inappropriate. Conversely, if the thickness of the hydrophobic polymer layer is too large, the water vapor permeability of the polymer layer will be insufficient, and the moisture absorption and desorption of the hydrophilic colloid layer of the back layer will be inhibited, resulting in poor curl. Of course, the thickness of the hydrophobic polymer layer also depends on the physical properties of the binder used. Therefore, the thickness of the polymer layer needs to be determined in consideration of both. The preferred thickness of the hydrophobic polymer layer depends on the binder type of the hydrophobic polymer layer, but is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm.
m. When the hydrophobic polymer layer comprises two or more layers, the sum of the thicknesses of all the hydrophobic polymer layers is defined as the thickness of the hydrophobic polymer layer of the photosensitive material.

There is no particular limitation on the method of applying the hydrophobic polymer layer. After coating and drying the back layer, a polymer layer may be coated on the back layer and then dried, or the back layer and the hydrophobic polymer layer may be simultaneously coated and then dried. The hydrophobic polymer layer may be applied in a solvent system by dissolving in a solvent of a binder of the polymer layer, or may be applied in an aqueous system using an aqueous dispersion of the binder polymer.

On the opposite side of the emulsion layer of the silver halide photographic material, it is preferable to provide an adhesive layer / antistatic layer / back layer containing a hydrophilic colloid / hydrophobic polymer layer on a support. Further, a protective layer may be provided thereon.
As the adhesive layer, a vinylidene chloride copolymer or a styrene-glycidyl acrylate copolymer was applied to a thickness of 0.1 to 1 μm on a corona-discharged support, and then doped with indium or phosphorus to an average particle diameter of 0.01. ~ 1μ tin oxide,
It can be obtained by coating with a gelatin layer containing fine particles of vanadium pentoxide. Further, a styrene sulfonic acid / maleic acid copolymer can be formed by forming a film with an epoxy compound, an aziridine compound, or a carbonyl active crosslinking agent. A dye back layer can be provided on these antistatic layers.
These layers should contain inorganic fillers such as colloidal silica for dimensional stability, silica or methyl methacrylate for preventing adhesion, and silicone-based slipping agents or release agents for controlling transportability. Can be.

The backing layer may contain a dye.
As the backing dye, a benzylidene dye or an oxonol dye is used. These alkali-soluble or decomposable dyes can be fixed as fine particles. The concentration for preventing halation is preferably 0.1 to 2.0 at each photosensitive wavelength.

The support used in the present invention may be either permeable or non-permeable, but is preferably a permeable plastic support. As the plastic support, a support composed of a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), a triacetate compound (eg, triacetate cellulose, etc.), a polystyrene compound, or the like is used.

The thickness of the support is preferably 50 to 2
It is 50 μm, particularly preferably 70 to 200 μm.

In order to further improve the curl and curl of the support, it is preferable to perform a heat treatment after the film formation. Most preferably, after film formation and after emulsion coating, it may be after emulsion coating. The condition of the heat treatment is preferably 45 ° C. or higher and the glass transition temperature or lower, and preferably between 1 second and 10 days. 1 in terms of productivity
It is preferable to be within hours.

The silver halide photographic light-sensitive material according to the present invention may contain the following compounds in the constituent layers of the silver halide photographic light-sensitive material.

(1) Solid Dispersion Fine Particles of Dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Supersensitizer: JP-A-6-347938, page (3) [0011]-
(16) Compound described in [0066] (5) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) The compound described on page.

The above-described additives and other known additives can be used in the silver halide photographic light-sensitive material according to the present invention. These are described in Research Disclosure (RD) Nos. 17643 (December 1978
18716 (November 1979) and 308
119 (Dec. 1989).

The above-mentioned various additives used in the present invention may be used by dissolving them in water or an organic solvent, or may be used by dispersing them in a fine crystal state. As the dispersion method, for example, a ball mill, a sand mill, a colloid mill, an ultrasonic disperser or a high-speed impeller disperser can be used.

In the present invention, for example, JP-A-58-10514
No. 1, the method of mechanically high-speed stirring, or
A method of dissolving by heating after dissolving with an organic solvent described in JP-A-4-2948, removing the solvent and dispersing; dissolving in an acid or alkali described in JP-A-50-80119 or JP-A-2-15252, and then crystallizing out in a polymer; A dispersing method or the like can be applied. In the present invention, the hydrazine derivative which is hardly soluble in water can be dissolved with reference to, for example, the method described in JP-A-2-3033. This method can be applied to other compounds. In addition, a method in which the dye having a carboxy group, the spectral sensitizing dye, an additive, and the like are used to increase the immobilization rate of fine particle crystals by utilizing the chelating ability of the carboxy group.

In the method for processing a silver halide photographic light-sensitive material of the present invention, any known photographic processing agents can be used.

For example, as a developing agent, hydroquinone,
Dihydroxybenzenes such as chlorohydroquinone, methylhydroquinone, potassium hydroquinone monosulfonate, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
3-pyrazolidones such as pyrazolidone, N-methyl-
Aminophenols such as p-aminophenol and the like or a mixture thereof, ascorbic acids such as ascorbic acid, sodium ascorbate, ersorbic acid, etc., or EDTA iron salt as a metal complex salt, DTP
A iron salt, DTPA nickel salt and the like can be used alone or in combination.

Among them, it is preferable to use ascorbic acid and its derivatives in combination with the above-mentioned 3-pyrazolidones or dihydroxybenzenes.

An alkali agent (eg, sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) are added to the developer. Is preferred. As the pH buffering agent, carbonate is preferable, and the amount of addition is preferably 0.5 mol or more and 2.5 mol or less, more preferably 0.75 mol or more and 1.5 mol or less per liter.

If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers, surfactants, defoamers, antifoggants (eg, potassium bromide, sodium bromide, etc.) Halides, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc., chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphates, etc.), Development accelerators (for example, U.S. Pat. No. 2,304,025, JP-B-47-45541)
And the like, a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent.

After exposure, the silver halide photographic light-sensitive material of the present invention is processed with a developer containing the above-mentioned known materials. The developer used in the present invention has a pH of 9.0 to 11 when used.
The developer is processed with the adjusted developer. Particularly preferably pH
9.5 or more and 10.6 or less. This pH is lower than a normal developer pH, and is preferable from the viewpoint of safety during handling or pollution.

As the fixing solution, those having a generally used composition can be used. As fixing agents, thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate can be used. In addition to the thiocyanate, an organic sulfur compound capable of forming a soluble stable silver complex and known as a fixing agent can be used.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum, an aldehyde compound (for example, glutaraldehyde or a sulfurous acid adduct of glutaraldehyde). .

If desired, compounds such as preservatives (for example, sulfites and bisulfites), pH buffering agents (for example, acetic acid and citric acid), pH adjusters (for example, sulfuric acid), and chelating agents capable of softening water can be used. Can be included.

The pH of the fixing solution is preferably 3 or more and less than 8. After the fixing treatment, the sheet is washed with water and / or treated in a stabilizing bath. As a stabilizing bath, for the purpose of stabilizing an image, an inorganic or organic acid and a salt thereof, or an alkali agent and a salt thereof (for example, an inorganic or organic acid and a salt thereof) for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8). Borate, metaborate, borax,
Phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc. are used in combination, and aldehydes (for example, formalin) ,
Glioxal, glutaraldehyde, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and anti-bacterial agents (eg, phenol, 4-chlorophenol, cresol,
O-phenylphenol, chlorophen, dichlorophen, formaldehyde, P-hydroxybenzoate, 2- (4-thiazoline) -benzimidazole, benzoisothiazolin-3-one, dodecyl-benzyl-
Methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, etc.),
Color tone adjuster and / or residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent; specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole , 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine, etc.). Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

[0150] From demands of the processing method of the amount of waste reduction, the developer replenishing amount in 1 m ² per 50 to 150, more preferably 30~130ml per 1 m ^2. Here, the developer replenishment amount indicates the replenishment amount. Specifically, it is the volume of a solution obtained by dissolving a replenisher for granule development in water.

The developing replenisher and the fixing replenisher may be the same or different from the developing starter and the fixing starter in the tank of the automatic developing machine. The development start solution and the fix start solution may be prepared from a granule processing agent, may be prepared from a liquid concentrate, or may be a liquid in use.

The temperature of the developing, fixing, washing and / or stabilizing baths is preferably in the range of 10 to 45 ° C., and each may be separately adjusted.

In the present invention, the total processing time (Dry to Dry) from the insertion of the leading end of the film to the automatic developing machine until it comes out of the drying zone is 10 when the processing is performed using the automatic developing machine because of the demand for shortening the developing time. Processed in ~ 60 seconds.

The term "total processing time" as used herein includes the total processing time required for processing the black-and-white photosensitive material, and specifically includes the processing, development, fixing, water washing, stabilizing processing, drying, etc. necessary for the processing. It is a time that includes all the time. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening.
Preferably, the total processing time (Dry to Dry) is 15
~ 60 seconds. To stably process a large amount of photosensitive material of 100 m ² or more, the development time is 2 hours.
The time is preferably not less than seconds and not more than 22 seconds.

In order to remarkably exert the effects of the present invention, a heat transfer material (for example, 60 to 60 ° C.) is required for an automatic developing machine.
130 ° C heat roller, etc.) or 150 ° C or higher radiant object (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide, yttrium oxide, thorium oxide, silicon carbide, etc.) Those that transmit energy to a radiator such as copper, stainless steel, nickel, and various ceramics to generate heat or emit infrared rays) and have a drying zone are preferably used.

Examples of the heat transfer material having a temperature of 60 ° C. or higher include:
A heat roller is mentioned as an example. The heat roller preferably has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

It is preferable that a gear is fixed to one end of the heat roller, and the heat roller is rotated in the transport direction by a driving unit and a driving transmission unit. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine.

The temperature controller is connected to a thermistor arranged in contact with the outer peripheral surface of the heat roller. The temperature controller controls the temperature detected by the thermistor to be 60 to 150 ° C., preferably 70 to 130 ° C. In addition, it is preferable that the halogen heater be turned on and off.

Examples of radiating objects emitting a radiation temperature of 150 ° C. or higher include the following. (Preferably 250 ° C
Tungsten, carbon, tantalum, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, molybdenum disilicide, lanthanum chromate are directly heated and radiated to control the radiation temperature or resistance. There is a method to control by transmitting heat energy from the heating element to the radiator, but copper,
Examples include stainless steel, nickel, and various ceramics.

In the present invention, a heat transfer body at 60 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

In the present invention, an automatic developing machine having the following method and mechanism can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column (2) Washing water regeneration purifying agent and apparatus: JP-A-6-2503
No. 52, page 3 (0011) to (8), page 0058 (3) Waste liquid treatment method: JP-A-2-64638 388
(2) Bottom left column to 39 (5) Bottom left column (4) Rinse bath between developing bath and fixing bath: JP-A-4-31
No. 3749 (18) “0054” to (21) “006”
5 "(5) Water replenishment method: JP-A-1-281446 250
(2) Lower left column to lower right column of page (6) Method of detecting outside air temperature and humidity to control drying air of automatic developing machine: JP-A-1-315745, page 496 (2) Lower right column to page 501 (7) Lower right column and JP-A-2-1080
No. 51, page 588 (2), lower left column to page 589 (3), lower left column (7) Method for recovering silver of fixing waste liquid: JP-A-6-27623, page (4), "0012" to page (7), "0071".

[0163]

The present invention will be described below with reference to examples.

Example 1 (Preparation of silver halide emulsion A) Aqueous solution of silver nitrate A and Na
Cl, a water-soluble halide solution B, the silver potential consisting of KBr (EAg) 120mV, added AgCl ₇₀ of 0.09 .mu.m 7 minutes in a simultaneous mixing method in C solution at 35 ° C. at pH3.0
A nucleus of Br ₃₀ was formed. Then, the silver potential was increased to 10
0 mV, an aqueous silver nitrate solution D and a water-soluble halide solution E were added again for 15 minutes, and the particle size was 0.20 μm (coefficient of variation 15
%) Silver halide grains of 70 mol% of AgCl and 30 mol% of Br were obtained.

Thereafter, the pH was adjusted to 5.6 with a 1N-NaOH aqueous solution.
S-1 was added at 2 × 10 ^-4 mol per mol of silver and 50
Aged at 10 ° C for 10 minutes. Thereafter, denatured gelatin treated with phenyl isocyanate was added, and the floc was washed with water at pH 4.2. After washing with water, 15 g of gelatin was added per mole of silver, the pH was adjusted to 5.7, and the mixture was dispersed at 55 ° C. for 30 minutes. The silver potential of the resulting emulsion is 190 mV (40 ° C.)
Met.

A: silver nitrate 16 g nitric acid 5% 5.3 ml ion exchange water 48 ml B: NaCl 3.8 g KBr 3.5 g ossein gelatin 1.7 g ion exchange water 48 ml C: NaCl 1.4 g ossein gelatin 7 g nitrate 5% 6.5 ml ion-exchanged water 700 ml D: silver nitrate 154 g nitric acid 5% 4.5 ml ion-exchanged water 200 ml E: NaCl 37 g KBr 33 g ossein gelatin 6 g ion-exchanged water 200 ml 4-hydroxy-6-methyl-1, 3,
3a, 7-tetrazaindene was added in an amount of 1.5 ×
10 ^-3 mol and 8.5 × 10 ^-4 mol of potassium bromide were added to adjust the pH to 5.6 and the EAg to 123 mV. Saponin was added thereto, and 2 × 10 ⁻⁵ mol of sulfur as sulfur atom and 1.5 × 10 ⁻⁵ mol of chloroauric acid were added as sulfur atoms dispersed in fine particles having an average of 0.5 μm by a planetary ball mill.
After 80 minutes of chemical ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver and 1-phenyl-5-mercaptotetrazole. After adding 3 × 10 ^-4 mol and 1.5 × 10 ^-3 mol of potassium iodide, the temperature was lowered to 40 ° C.

(Preparation of photosensitive material) On a subbed support, a silver halide emulsion layer and a protective layer each having the following composition were coated simultaneously from the support side and cooled and set. A backing layer and a backing protective layer were simultaneously coated on the undercoat layer from the support side, cooled and set at -1 ° C, and dried on both sides at the same time. 1-2
7 was obtained.

(Preparation of Coating Solution) Silver halide emulsion layer Silver halide emulsion A Ag amount 3.3 g / m ² Spectral sensitizing dye (shown in Table 1) 2 × 10 ⁻⁴ mol / Ag 1 mol Hardening agent ( (Shown in Table 1) 5 mg / m ² nucleation accelerator Na-12 3 mg / m ² Polymer latex L-1 (particle size: 0.25 μm) 0.25 g / m ² sodium-iso-amyl-n-decyl sulfosuccinate 2 mg / m ² sodium naphthalene sulfonate 8 mg / m ² saponin 20 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² 2-mercaptopyridine 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 150 mg / m ² Ascorbic acid 20 mg / m ² EDTA 25 mg / m ² Sodium polystyrene sulfonate 15 mg / m ^{2 The} coating solution had a pH of 5.2.

Protective Layer Gelatin 0.7 g / m ² Sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² Spherical polymethyl methacrylate (average particle size 3.5 μm) 25 mg / m ² amorphous silica (average particle size) 2.5 mg / m ² Hydroquinone 50 mg / m ² Slip agent (silicone oil) 4 mg / m ² Polymer latex L-2 (particle diameter 0.10 μm) 0.25 g / m ² colloidal silica (average particle diameter of 0. 05μm) 150mg / m ² 1,3- vinylsulfonyl-2-propanol 40 mg / m ² hardener Q-1 30mg / m ² sodium polystyrenesulfonate 10 mg / m ² fungicide Z 0.5 mg / m ² backing layer prescription gelatin 0.6 g / m ² Sodium - iso - amyl -n- decyl sulfosuccinate 5 mg / m ² Porimarate' Scan L-3 0.3g / m ² Colloidal silica (average particle size 0.05μm) 100mg / m ² Sodium polystyrenesulfonate 10 mg / m ² Dye F-1 45mg / m ² Dye ^F-2 25mg / m 2 Dye F -3 30 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² Hardener Q-2 100 mg / m ² Zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² Backing protective layer formulation Gelatin 0.4 g / m ² monodispersed polymethyl methacrylate (average particle size 3 [mu] m) 50 mg / m ² sodium - di-2-ethylhexyl sulfosuccinate 10 mg / m ² sodium polystyrenesulfonate 10 mg / ^{m 2}

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[0171]

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(Developer Composition) Per liter of working solution diethyltriamine pentaacetic acid / 5 sodium salt 1 g sodium sulfite 42.5 g potassium sulfite 17.5 g potassium carbonate 55 g hydroquinone 20 g 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone 0.85 g potassium bromide 4 g 5-methylbenzotriazole 0.2 g boric acid 8 g diethylene glycol 40 g 8-mercaptoadenine 0.07 g KOH was added in such an amount that the working solution pH became 10.4.

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) per liter of working solution 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Sulfuric acid Aluminum (27% aqueous solution) 25 ml sulfuric acid was used to adjust the pH of the working solution to 4.9.

(Processing Conditions) (Process) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Rinse at room temperature 20 seconds Squeeze / Dry 45 ° C. 30 seconds 100 seconds in total (evaluation of sample) <Measurement of sensitivity> The obtained sample was brought into close contact with a step wedge, and exposed to tungsten light of 3200 ° K for 3 seconds,
Automatic developing machine GR- using a developing solution and a fixing solution having the above-mentioned composition.
27 (manufactured by Konica Corporation) under the above conditions. The blackened density of the developed sample thus obtained was measured with a PDA-65 (Konica Digital Densitometer). The reciprocal of the exposure amount at which 1 gives a blackening density of 1.0 is expressed as a relative sensitivity with 100 being the reciprocal.

<Aged Storage Test> The samples were stored for 3 days under the conditions of 55 ° C. and RH 48% as a test for an age, and a forced deterioration test of the photosensitive material was performed. The obtained sample was exposed and developed under the above-mentioned conditions, the sensitivity was measured, and the evaluation was made based on the difference in sensitivity from the sample that was not forcibly deteriorated.
If the sensitivity difference is within ± 20, it is a practically acceptable level.

The blackening density (fog) of the unexposed portion of the forcibly deteriorated sample was measured using a PDA-65 (Konica Digital Densitometer). If the fog density is 0.05 or less, it is a practically acceptable level.

<Safelight Resistance> The obtained sample was covered with a safelight, and the sum of the logarithm of the time until the fogging of the density which is practically problematic and the logarithm of the sensitivity of the sample was determined as Sample No. It was relatively evaluated so that 1 became 4. The smaller the value, the lower the safelight resistance.

<Evaluation of Residual Color Contamination> The unexposed film was developed under the above conditions, and the residual color level when five sheets were superimposed was visually evaluated on a scale of five. Rank 5 is the best level, and rank 3 or higher is a level that can withstand practical use.

<Evaluation of Black Pot> The unexposed sample was developed under the same conditions as in the measurement of the sensitivity, observed with a magnifier of 40 times, and visually evaluated. Rank 5 without black spots
The practical lower limit was ranked 3 and evaluated on a 5-point scale.

<Evaluation of dot quality> The obtained sample was brought into close contact with a contact screen, exposed and processed in the same manner as in the measurement of sensitivity, and the obtained developed sample was observed with a 100-power loupe. The quality of the points was evaluated visually on a five-point scale. Rank 5 is the best level, rank 3 is the practical lower limit, and rank 2 and below are practically problematic levels.

The results obtained are shown in the table below.

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[Table 1]

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[Table 2]

As is clear from the table, the sample containing the sensitizing dye and the high contrast agent of the present invention had high sensitivity, little fluctuation in sensitivity over time, and had a level that was practically acceptable.

Further, it can be seen that there is no generation of fogging and black spots with the passage of time, and the safelight resistance performance is not inferior, and that it has high quality halftone dot performance for plate making printing.

Example 2 (Preparation of Silver Halide Emulsion B) In Emulsion A of Example 1, K ₂ RhCl ₅ (H ₂ O) was added to each of Emulsion A and K ₂ RhCl ₅ (H ₂ O) at 2 × 10 ⁻⁷ mol per mol of Ag. And 1.3 × 1
It was prepared by adding ^0-7 mol, and the other preparations were the same as in emulsion A. Thereafter, chemical sensitization was performed in the same manner as in Emulsion A.

(Preparation of Silver Halide Emulsion C) Additive Solution C
And E were changed to K ₂ Ru (NO) Cl ₅ , except that E was prepared in the same manner as Emulsion B. Thereafter, chemical sensitization was performed in the same manner as in Emulsion A.

(Preparation of Silver Halide Emulsion D) Additive Solution C
E and E were changed to K ₂ Os (NO) Cl ₅ , except that E was changed to Emulsion B. Thereafter, chemical sensitization was performed in the same manner as in Emulsion A.

(Preparation of photosensitive material) Sample N was prepared in the same manner as in Example 1 except that the following formulation was used for the silver halide emulsion layer.
o. 28-37 were obtained.

(Preparation of Coating Solution) Silver halide emulsion layer Silver halide emulsion (shown in Table 3) Ag amount 3.3 g / m ² Spectral sensitizing dye (shown in Table 3) 2 × 10 ^-4 mol / Ag1 Molar contrast agent (shown in Table 3) 5 mg / m ² nucleation accelerator Na-12 3 mg / m
² polymer latex-L-1 (particle size 0.25 μm) 0.25 g / m ² sodium-iso-amyl-n-decylsulfosuccinate 2 mg / m ² sodium naphthalenesulfonate 8 mg / m ² saponin 20 mg / m ² 2 -Mercapto-6-hydroxypurine 2 mg / m ² 2-mercaptopyridine 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 150 mg / m ² Ascorbic acid 20 mg / m ² EDTA 25 mg / m ² Sodium polystyrene sulfonate 15 mg / The pH of the m ² coating solution was 5.2.

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(Evaluation of Sample) The same evaluation as in Example 1 was performed, and the following Tables 3 and 4 were obtained.

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[Table 3]

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[Table 4]

As is clear from Table 4, the samples according to the present invention are excellent in sensitivity and residual color level. In addition, it can be seen that the sample of the present invention when using an emulsion containing a transition metal has a very small change in sensitivity in storage stability over time, and the generation of fog and black spots over time is suppressed to a low level. . Further, according to the present invention, the safelight resistance was also improved, and higher sensitivity and excellent dot quality were obtained.

Claims (3)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the silver halide emulsion layer has the following general formula (1) or A hydrazine derivative and / or a 5- to 6-membered hydrazine derivative in the silver halide emulsion layer or the hydrophilic colloid layer, containing at least one kind of spectral sensitizing dye represented by the general formula (2); A silver halide photographic material comprising at least one selected from nitrogen heterocyclic compounds. Embedded image In the formula, Y represents an oxygen atom or a> NR group. R, R ₁ and R ₂ each represent a lower alkyl group, and at least one of R ₁ and R ₂ represents a lower alkyl group substituted with a sulfo group or a carboxyl group. Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ each represent a hydrogen atom or a substitutable atom or group;
Z ₃ and Z ₄ and Z ₄ and Z ₅ may be bonded to each other to form a condensed ring. However, at least one of Z ₁ and Z ₂ represents an electron-withdrawing group. X ₁ represents an ion necessary for neutralizing the intramolecular charge, and n1 is 0 when the dye forms an inner salt.
It is. Embedded image In the formula, R ₁₁ and R ₁₃ each represent a lower alkyl group or an alkenyl group. However, at least one of R ₁₁ and R ₁₃ represents a vinyl group (—CH ＝ CH ₂ ). R ₁₂ and R ₁₄ each represent a lower alkyl group, and at least one of R ₁₂ and R ₁₄ is a lower alkyl group substituted with a hydrophilic group. Z ₁₁ , Z ₁₂ , Z
₁₃ and Z ₁₄ may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a halogen-substituted alkoxy group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylthio group, or a halogen-substituted group. Represents an alkylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a hydroxy group, a haloalkyl group, a carboxyl group, a sulfonyl group, an acylamino group, a heterocyclic group or an aryl group. X ₁₁ represents an ion necessary to neutralize the molecular charge, when the dye forms an intramolecular salt n11 is 0. 2. A silver halide photographic material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the silver halide emulsion layer contains the compound represented by the above general formula (1) or (2). It contains at least one kind of the spectral sensitizing dye represented by the general formula (2), and contains at least one kind selected from tetrazolium compounds in the silver halide emulsion layer or the hydrophilic colloid layer. A silver halide photographic material. 3. The silver halide emulsion layer according to claim 1, wherein the silver halide emulsion layer contains at least one transition metal selected from the elements of Groups 6 to 10 of the periodic table.
The silver halide photographic light-sensitive material as described above.