JPH1195358A - Silver halide photographic sensitive material and its treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a ultrahigh contrast silver halide photographic sensitive material for plate making which accurately reproduce minute dots, to provide its treating method, and to provide a treating method of the ultrahigh contrast silver halide photographic sensitive material for plate making above described by which the amt. of a developer replenisher can be decreased and rapid treatment is possible. SOLUTION: This material contains a sensitizing dye expressed by the formula in a silver halide emulsion layer and contains a dye in a solid dispersed state in photographic structural layers. In the formula, Z is a 5 to 6-member nitrogen-contg. heterocyclic atomic group, R1 is an alkyl group, R2 is a hydrogen atom, alkyl group, aryl group or heterocyclic group, R3 is a 5-member nitrogen- contg. heterocyclic group or pyrazyl group, L1 and L2 are methine groups, and (n) is an integer of 0, 1, 2, 3 or 4. At least one layer of the structural layers contains a water-soluble dye. The material preferably contains at least one of hydrazine, amine compd. and quaternary onium compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black-and-white silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material for printing plate making and a processing method thereof.

[0002]

2. Description of the Related Art A printing plate making operation includes a step of faithfully reproducing a halftone image. In order to produce excellent printed matter, it is necessary that a desired halftone dot is faithfully reproduced on the photosensitive material.

In recent years, in the field of printing plate making, there has been an increasing demand for improved dot quality. For example, dot quality has been improved by enlarging (expanding) or reducing (shrinking) a halftone photograph in a line drawing process. There is also a strong demand for improvements such as reproducibility of bright dots and reproducibility of fine halftone dots.

Many techniques have been disclosed for obtaining faithful reproducibility. For example, a dye dispersion which is substantially water-soluble at a pH of 8 or more and water-insoluble at a pH of 6 or less is provided between an emulsion layer and a support. The technology for forming an antihalation layer is disclosed in Japanese Patent Application Laid-Open No. 52-92716 or
No. 2,770,045. Further, a technique is also known in which a water-soluble dye is contained in a constituent layer to suppress light scattering.

[0005] However, in these prior arts, the sensitivity and contrast are remarkably reduced, and there is a problem in practical use.

On the other hand, as for the spectral sensitization method of silver halide emulsion for printing plate making, a dimethine merocyanine dye having a thiohydantoin ring substituted with a pyridyl group is used as a spectral sensitizing dye which gives a sharp and sharp halftone image. For example, it is disclosed in JP-A-55-45015. Further, a dimethine merocyanine dye having a thiohydantoin ring substituted with a phenyl group is disclosed in JP-B-54-34532.

However, silver halide photographic materials containing these merocyanine dyes do not have sufficient sensitivity and contrast, and the problem is further increased when a dye dispersion or a water-soluble dye as described above is used. Had the disadvantage that

It is essential to use a super-high contrast agent in a silver halide photographic light-sensitive material for plate making. For example, a light-sensitive material containing a hydrazine derivative disclosed in US Pat. No. 4,269,929. Material or JP-A-4-98
No. 239 and No. 6-102633, photosensitive materials containing an amine compound or a quaternary onium compound are known.

However, the use of these ultra-high contrast agents is effective in reproducing large halftone dots, but has the disadvantage that it is difficult to faithfully reproduce fine halftone dots. In order to do so, further improvements were desired.

[0010] On the other hand, in recent years, with increasing interest in environmental issues, reduction in waste of photographic processing has been required, and among them, the reduction of the development replenisher has a great effect. However, the low replenishment of the developer tends to cause various obstacles from the viewpoint of photographic performance including sensitivity and maximum density from the photosensitive material side.

Conventionally, the replenishing amount of the developing material is usually 350 ml or more per 1 m ² of the area of the photosensitive material to be processed. In recent years, however, it has become necessary to perform low replenishing processing of 250 ml or less per 1 m ^2. On the photosensitive material side, the problem has become even greater.

[0012]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide an ultra-hard silver halide photographic light-sensitive material for printing plate making which faithfully reproduces fine halftone dots and a processing method therefor. . A second object of the present invention is to provide a method for processing the above-described ultra-high contrast silver halide photographic material for printing plate making, which can reduce the replenishment amount of development and can be processed quickly.

[0013]

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

(1) A silver halide photographic light-sensitive material having a photographic component layer comprising at least one silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on one side of a support. The silver emulsion layer contains at least one compound represented by the following general formula (I), and at least one of the photographic constituent layers contains a solid-dispersed dye. Characteristic silver halide photographic material.

[0015]

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(Wherein, Z represents an atom group necessary for forming a 5- to 6-membered nitrogen-containing heterocyclic ring. R ₁ represents an alkyl group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, R ₃ represents a 5-membered nitrogen-containing heterocyclic group or a pyrazyl group, L ₁ and L ₂ each represent a methine group, and n represents an integer of 0, 1, 2, 3, or 4. Represent.

(2) The silver halide photographic material as described in (1) above, wherein at least one of the photographic constituent layers contains a water-soluble dye.

(3) λmax of the dye dispersed in a solid state
(1) or (2), wherein the water-soluble dye has a λmax in the range of 340 to 480 nm.

(4) The halogen according to any one of (1) to (3), wherein at least one photographic component layer on the side of the silver halide emulsion layer contains a hydrazine compound. Silver halide photographic material.

(5) An amine compound and / or a quaternary onium compound are contained in at least one of the photographic constituent layers on the side of the silver halide emulsion layer.
(4) The silver halide photographic material as described in any one of the above items.

(6) Any one of the above items (1) to (5)
Wherein the silver halide photographic light-sensitive material is processed while replenishing a development replenisher within a range of 30 to 250 ml per m ^{2 of the} light-sensitive material. .

(7) When the silver halide photographic light-sensitive material is processed by an automatic developing machine including a developing tank, the entire processing from the insertion of the leading end of the light-sensitive material into the automatic developing machine until it comes out of the drying zone. Time (Dry to Dry) is 10 to 60
(6) The method for processing a silver halide photographic light-sensitive material as described in (6) above,

Hereinafter, the present invention will be described in detail.

In the present invention, the photographic constituent layer refers to a hydrophilic colloid layer constituting a silver halide photographic light-sensitive material,
The photographic constituting layer according to the present invention comprises at least one silver halide emulsion layer and at least one silver halide emulsion layer on one side of the support.
It is composed of at least one non-photosensitive hydrophilic colloid layer. Preferred are silver halide photographic materials having at least two or more silver halide emulsion layers and at least two or more non-photosensitive hydrophilic colloid layers on one surface of a support.
Here, the non-photosensitive layer means a layer having no photosensitivity which substantially contributes to image formation.

In the silver halide emulsion layer according to the present invention,
The dye represented by the general formula (I) is contained. Less than,
The dye represented by formula (I) will be described in detail.

R ₁ is preferably an unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-pentyl). -Hexyl, n
-Octyl, n-decyl, n-dodecyl, n-octadecyl), or a substituted alkyl group.

R ₁ may combine with the methine group in L ₁ and L ₂ to form a ring. Examples of the substituent include a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a hydroxy group, a C2 to C10, preferably a C2 to C8 atom. An alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), an alkoxy group having 1 to 16, preferably 1 to 8 carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), 6 to 1
2, preferably an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, p-tolyloxy);
To 6, preferably an acyloxy group having 2 to 4 carbon atoms (eg, acetyloxy, propionyloxy),
An acyl group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms (eg, acetyl, propionyl, benzoyl, mesyl), 1 to 10 carbon atoms, 1 to 5 carbon atoms
(E.g., carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a sulfamoyl group having 0 to 10 carbon atoms and 0 to 5 carbon atoms (e.g., sulfamoyl, N,
N-dimethylsulfamoyl, morpholinosulfonyl,
Piperidinosulfonyl), aryl groups having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) and the like. Particularly preferred as R ₁ are unsubstituted alkyl groups (eg, methyl, ethyl, n
-Propyl, n-butyl), a carboxyalkyl group (for example, 2-carboxyethyl, carboxymethyl), a sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl),
It is a methanesulfonylcarbamoylmethyl group.

The 5- or 6-membered nitrogen-containing heterocyclic ring completed by Z may be further condensed, may be saturated or unsaturated, and may contain an oxygen atom as a hetero atom other than nitrogen, It may contain a sulfur atom, a selenium atom, and a tellurium atom. Preferred examples include a benzothiazole nucleus, a benzoxazole nucleus, a benzoselenazole nucleus, a benzotellurazole nucleus, a 2-quinoline nucleus, a 4-quinoline nucleus, an isoquinoline nucleus, a pyridine nucleus, an indolenine nucleus, a benzimidazole nucleus, and a naphthothiazole nucleus. , Naphthoxazole nucleus, naphthoselenazole nucleus, naphthotellurazole nucleus, naphthoimidazole nucleus, oxazole nucleus, thiazoline nucleus,
Selenazoline nucleus, indoline nucleus, oxazoline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus,
Examples thereof include a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, an imidazo [4,5-b] quinoxaline nucleus, and a pyrimidine nucleus. More preferably, they are an oxazole nucleus, a benzoxazole nucleus, a naphtho [1,2-d] oxazole nucleus, and a naphtho. [2,1-d] oxazole nucleus, naphtho [2,3-d] oxazole nucleus, oxazoline nucleus and thiazoline nucleus, and particularly preferably benzoxazole nucleus.

These nitrogen-containing heterocycles may have a substituent, and specific examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom) and a carbon atom having 1 to 12 carbon atoms, preferably An unsubstituted alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl), an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (eg, , Methoxy, ethoxy, propoxy, isopropoxy), a hydroxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, preferably 2 to 5 carbon atoms (for example,
Methoxycarbonyl, ethoxycarbonyl), carbon number 2
An alkylcarbonyloxy group having 2 to 5 carbon atoms (for example, acetyloxy, propionyloxy), a phenyl group, a hydroxyphenyl group, a carbon atom having 3 to 15 carbon atoms, preferably having 5 to 10 carbon atoms,
Groups having an amide group and an aromatic ring simultaneously (for example, p-acetylaminophenyl, m-acetylaminophenyl,
-Pyrrolecarboxamide, m-hydroxybenzamide, 2,6-dihydroxybenzamide, 2-furancarboxamide, 2-thiophencarboxamide), a furyl group, a pyrrolyl group, and the like.

R ₂ represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms (eg, allyl, 2-methylallyl), 12 unsubstituted or substituted aryl groups (eg, phenyl, tolyl,
m-cyanophenyl, p-hydroxyphenyl). Preferred examples of the unsubstituted alkyl group include methyl,
Ethyl, propyl, butyl and the like can be mentioned, and more preferably an ethyl group. Examples of the substituted alkyl group include C3 to C12, preferably C3 to C7.
An alkoxycarbonylalkyl group (for example, methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl), a hydroxyalkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (for example, 2
-Hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2,3-dihydroxypropyl),
C2 to C10, preferably C2 to C6 hydroxyalkoxyalkyl group (for example, hydroxymethoxymethyl, 2- (2-hydroxyethoxy) ethyl, 2-hydroxyethoxyethyl), C2 to C12, preferably Is a carbamoylalkyl group having 2 to 8 carbon atoms (N-alkyl substitution, N, N-dialkyl substitution,
N-hydroxyalkyl-substituted, N-alkyl-N-hydroxyalkyl-substituted or N, N-di (hydroxyalkyl) -substituted substituted carbamoylalkyl groups and 5,
Contains a carbamoylalkyl group of a 6-membered cyclic amine.
For example, 2-carbamoylethyl, 2-N- (2-hydroxyethyl) carbamoylethyl, N, N-di (2-
Hydroxyethyl) carbamoylmethyl, N, N-di (2-hydroxyethyl) carbamoylethyl, N, N
Dimethylcarbamoylmethyl, morpholinocarbamoylmethyl, piperidinocarbamoylmethyl), hydroxyphenyl group (for example, o-hydroxyphenyl, p-
Hydroxyphenyl, 2,6-dihydroxyphenyl), a hydroxyalkylphenyl group having 7 to 9 carbon atoms (for example, p- (2-hydroxyethyl) phenyl,
m- (1-hydroxyethyl) phenyl), particularly preferably a hydroxyethyl group, 2
— (2-hydroxyethoxy) ethyl group and 2-hydroxyethoxyethyl group.

L ₁ and L ₂ each independently represent a substituted or unsubstituted methine group. Examples of the substituent include an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms (eg, methyl, ethyl, 2-
Carboxyethyl), a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms (for example, phenyl, o-carboxyphenyl), and having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Alkoxy group (for example, methoxy, ethoxy), halogen atom (for example, chlorine atom, bromine atom, fluorine atom), amino group, having 1 to 20 carbon atoms, preferably 1 to 1 carbon atom
A substituted amino group (e.g., N, N-diphenylamino, N-methyl-N-phenylamino, N-methylpiperazino), a carboxy group, an alkylthio group having 1 to 6, preferably 1 to 3 carbon atoms (e.g., , Methylthio, ethylthio) and the like. Also,
L ₁ and L ₂ can also form a ring with each other or with an auxochrome. Preferred as n are 0, 1, 2 and 3, and particularly preferred are 0, 1 and 2.

The nitrogen-containing 5-membered heterocyclic ring represented by R ₃ may be further condensed, and may contain a saturated or unsaturated hetero atom other than nitrogen, which may contain an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom. It is a nitrogen-containing 5-membered heterocyclic ring. R ₃
Is preferably an unsaturated nitrogen-containing 5-membered heterocyclic group. R ₃
Examples of a substituted or unsubstituted 2-pyrrolyl group, 3
-Pyrrolyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group,
-Isoxazolyl group, 5-isoxazolyl group, 2-
Thiazolyl group, 4-thiazolyl group, 5-thiazolyl group,
3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 3-furazanyl group, 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 3-pyrazolyl group, 4-pyrazolyl group, 5-pyrazolyl group,
1,2,4-triazolyl group, tetrazolyl group, 1,
2,3-thiadiazolyl group, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, 1,2,4-dithiazolyl group, 2,1,3-thiadiazolyl group, 1,
2,4-oxadithiazolyl group, 1,3,4-oxadithiazolyl group, 2-pyrrolidinyl group, 2-imidazolidinyl group, 3-pyrazolidinyl group, 2-oxazolidinyl group, 3-isooxazolidinyl group , A 2-thiazolidinyl group, a 3-isothiazolidinyl group, and the like, preferably a 2-thiazolyl group, a 4-thiazolyl group, a 2-imidazolyl group, a 4-imidazolyl group, a 3-pyrazolyl group, and a 4-pyrazolyl group. , 5-pyrazolyl group, 1,2,4
-Triazolyl group and tetrazolyl group, particularly preferably 2-thiazolyl group, 3-pyrazolyl group, 1,2,4
-A triazolyl group.

The substituent on the nitrogen-containing 5-membered heterocyclic ring may be substituted on any of the carbon atoms and nitrogen atoms forming the heterocyclic ring. Examples of the substituent on the carbon atom include a halogen atom (for example, fluorine, Chlorine, bromine), an unsubstituted alkyl group having 1 to 6, preferably 1 to 3 carbon atoms (eg, methyl, ethyl, propyl), an alkoxy group having 1 to 8, preferably 1 to 4 carbon atoms ( For example, methoxy, ethoxy, propoxy, isopropoxy), a hydroxy group, an alkoxycarbonyl group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl), 2 to 8 carbon atoms, preferably An alkylcarbonyloxy group having 2 to 4 carbon atoms (eg, acetyloxy, propionyloxy), a phenyl group, tolyl , Hydroxyphenyl group, amino group, from 1 to 20 carbon atoms, preferably 1 -C 1
And a substituted amino group (e.g., N, N-dimethylamino group, N-methyl-N-phenylamino group), cyano group, etc., and particularly preferably a halogen atom (e.g., chlorine or bromine). Substituted alkyl groups (eg,
Methyl, ethyl). Examples of the substituent of the nitrogen atom include C1 to C10, preferably C2 to C4.
An unsubstituted alkyl group (eg, methyl, ethyl, propyl, butyl), a carboxyalkyl group having 1 to 10, preferably 2 to 6 carbon atoms (eg, 2-carboxyethyl, carboxymethyl), 1
0, preferably a sulfoalkyl group having 2 to 6 carbon atoms (for example, 2-sulfoethyl, 3-sulfopropyl,
-Sulfobutyl, 3-sulfobutyl), methanesulfonylcarbamoylmethyl group, C1 to C6, preferably C1 to C4 cyanoalkyl group (eg, cyanoethyl, cyanopropyl), C1 to C10, preferably carbon number A halogenated alkyl group of 1 to 6 (eg, trifluoromethyl, 2,2,2-trifluoroethyl), a hydroxyalkyl group of 1 to 10, preferably 1 to 6 carbon atoms (eg, 2-hydroxyethyl , 2-hydroxypropyl), an alkoxycarbonylalkyl group having 3 to 16 carbon atoms, preferably 3 to 8 carbon atoms (for example, methoxycarbonylethyl,
Ethoxycarbonylmethyl), an alkoxyalkyl group having 2 to 16, preferably 2 to 8 carbon atoms (eg, methoxyethyl, ethoxyethyl), an acyl group having 3 to 12, preferably 3 to 8 carbon atoms (eg, , Acetyl, propionyl, benzoyl, mesyl), a carbamoyl group having 1 to 10, preferably 1 to 6 carbon atoms (for example, carbamoyl, N, N-
Dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a sulfamoyl group having 1 to 10, preferably 1 to 6 carbon atoms (for example, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl) And aryl groups having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl), and the like. (For example, methyl and ethyl), a sulfoalkyl group (for example, 3-sulfopropyl and 4-sulfobutyl), and an acetyl group.

When R ₃ is an unsubstituted or substituted pyrazyl group, R ₃ may be further condensed. The substituent on the pyrazine ring may be substituted on any of the ring-forming carbon atom and nitrogen atom. Examples of the substituent on the carbon atom include a halogen atom (eg, fluorine, chlorine, bromine), a carbon number 1 to 6, preferably 1 to 3 carbon atoms
An unsubstituted alkyl group (eg, methyl, ethyl, propyl) having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms
An alkoxy group (e.g., methoxy, ethoxy, propoxy, isopropoxy), a hydroxy group, an alkoxycarbonyl group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl), 8, preferably an alkylcarbonyloxy group having 2 to 4 carbon atoms (eg, acetyloxy, propionyloxy), a phenyl group, a tolyl group,
Hydroxyphenyl group, amino group, 1 to 2 carbon atoms
0, preferably a substituted amino group having 1 to 14 carbon atoms (e.g., N, N-dimethylamino group, N-methyl-N-phenylamino group), cyano group, and the like; A substituted alkyl group (eg, methyl, ethyl) and an alkoxy group (eg, methoxy, ethoxy).

Examples of the substituent of the nitrogen atom include those having 1 carbon atom.
To 10, preferably an unsubstituted alkyl group having 2 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl); a carboxyalkyl group having 1 to 10, preferably 2 to 6 carbon atoms (eg, 2-carboxy) Ethyl, carboxymethyl), a sulfoalkyl group having 1 to 10, preferably 2 to 6 carbon atoms (for example,
2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl), a methanesulfonylcarbamoylmethyl group, having 1 to 6 carbon atoms, preferably 1 carbon atom
To 4 cyanoalkyl groups (eg, cyanoethyl,
Cyanopropyl), a halogenated alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms (eg, trifluoromethyl, 2,2,2-trifluoroethyl),
A hydroxyalkyl group having 1 to 10, preferably 1 to 6 carbon atoms (for example, 2-hydroxyethyl,
2-hydroxypropyl), an alkoxycarbonylalkyl group having 3 to 16 carbon atoms, preferably 3 to 8 carbon atoms (for example, methoxycarbonylethyl, ethoxycarbonylmethyl), and having 2 to 16 carbon atoms, preferably 2 to 8 carbon atoms. An alkoxyalkyl group (eg, methoxyethyl, ethoxyethyl), having 3 to 12 carbon atoms;
Preferably, it is an acyl group having 3 to 8 carbon atoms (eg, acetyl, propionyl, benzoyl, mesyl);
To 10, preferably a carbamoyl group having 1 to 6 carbon atoms (for example, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a sulfamoyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms (Eg, sulfamoyl, N,
N-dimethylsulfamoyl, morpholinosulfonyl,
Piperidinosulfonyl), aryl groups having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl), and the like. ,
Unsubstituted alkyl groups (for example, methyl and ethyl), sulfoalkyl groups (for example, 3-sulfopropyl and 4-sulfobutyl), and acetyl groups. Particularly preferred as R ₃ are a pyrazyl group and a 5-methylpyrazyl group.

In a preferred combination of the substituents represented by R ₁ , R ₂ and R ₃ , the atomic group represented by Z and n, n is 0, 1 and 2, and Z forms a benzoxazole nucleus. It is a combination, among which R ₁ is a sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl), and R ₂ is a hydroxyalkoxyalkyl group (for example, Hydroxymethoxymethyl, 2-hydroxyethoxyethyl) or hydroxyalkyl group (eg, 2-hydroxyethyl, 2-hydroxypropyl)
And particularly preferable are those in which R ₃ is 2
-Thiazolyl group, 3-pyrazolyl group (eg, 3-pyrazolyl, 3- (5-methyl-pyrazolyl), 3- (4-chloro-5-methylpyrazolyl), 3- (1,2,4-triazolyl) unsubstituted Or a 5-methylpyrazyl group.

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

[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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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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In the present invention, the synthesis of the dye represented by the above general formula (I) can be referred to the following literatures and the synthesis examples described in the literatures cited therein.

A) Dokladi Academia Nauk
SSSR (Dokl.Akad.Nauk SSS)
R), 177, 869 (1967).

B) FM Hammer (FM Ha)
Rmer), Heterocyclic Compounds-Cyanine Dye and Related Compounds-Cy
annedyes and related comp
sounds-) "(John Wille & Sons), New York
London, 1964).

C) DM Starmer (DM)
Starmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Communities"
pounds-Specialtopics in h
ethocyclic chemistry) ", 4
82-515 (John Wiley & Sons, Inc., New York London, 1977).

D) JP-B-47-4085, JP-B-46
-549, U.S. Patent 3,625,698, U.S. Patent 3,567,458.

The dye represented by the general formula (I) of the present invention is
It can be present in any layer in the silver halide photographic light-sensitive material, but in the hydrophilic colloid layer containing the photosensitive silver halide particles, it may be present in a state of being adsorbed to the photosensitive silver halide particles. preferable. In order to incorporate the dye represented by formula (I) of the present invention into the silver halide emulsion of the present invention, they may be directly dispersed in the emulsion, or may be dispersed in water, methanol, ethanol, propanol or acetone. , Methylcellosolve, 2,2,3,3-
Tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-
A solvent such as methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide or the like may be dissolved alone or in a mixed solvent and added to the emulsion. Further, as described in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. As described in JP-B-46-24185, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, JP-B-44-23389. As described in JP-B-44-27555 and JP-B-57-22091, a dye is dissolved in an acid, and the solution is added to an emulsion or an aqueous solution is prepared by coexisting an acid or a base. A method of adding to the emulsion,
U.S. Pat. No. 3,822,135, U.S. Pat.
No. 026, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion, as described in JP-A-53-102733 and JP-A-58-105141. As described, a method in which a dye is directly dispersed in a hydrophilic colloid, and the resulting dispersion is added to an emulsion. As described in JP-A-51-74624, the dye is dissolved using a compound that causes a red shift. However, a method of adding the solution to the emulsion may be used. Also,
Ultrasound can also be used for lysis.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention during any step of preparing an emulsion which has been found to be useful. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756.
No. 4,225,666, JP-A-58-18.
No. 4,142, JP-A-60-196749, etc., the start of chemical ripening during the step of forming silver halide grains and / or before desalting, during and / or after desalting. As described in JP-A-58-113920, any time immediately before chemical ripening or during the process, and any time before the emulsion is coated before the emulsion is coated. May be added at the same time.

Further, as disclosed in US Pat. No. 4,225,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, in a particle forming step. It may be divided into medium and during the chemical ripening step or after completion of chemical ripening, or may be divided and added before or during chemical ripening or after completion of the process,
Compounds to be divided and added may be added by changing the kind of the combination of the compounds.

The amount of the dye represented by formula (I) in the present invention varies depending on the shape and size of the silver halide grains, but is preferably 0.1 to 4 mmol, preferably 0.1 to 4 mmol per mol of silver halide. It is 2 to 2.5 mmol, and may be used in combination with another sensitizing dye.

Next, the solid-dispersed dye used in the present invention will be described. Preferred dyes include those represented by the following general formulas (1) to (6).

[0064]

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In the formula, A and A 'may be the same or different and each represents an acidic nucleus, Q represents an aryl group or a heterocyclic group, B represents a basic nucleus, and B' represents a heterocyclic group. X and Y may be the same or different and each represents an electron-withdrawing group, and L ₁ , L ₂ and L ₃ each represent a methine group. m represents 0 or 1, n represents 0, 1 or 2, and p represents 1 or 2. However, the dyes represented by the general formulas (1) to (6) have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule.

The aryl group represented by Q in the general formulas (1) and (4) includes, for example, a phenyl group and a naphthyl group. The heterocyclic group represented by Q includes, for example, pyridine, quinoline, isoquinoline, pyrrole, pyrazole, imidazole, indole residue and the like.

The aryl group and the heterocyclic group include those having a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group,
Carboxy group, cyano group, hydroxy group, mercapto group, amino group, alkoxy group, aryloxy group, acyl group, carbamoyl group, acylamino group, ureido group,
Examples thereof include a sulfamoyl group and a sulfonamide group, and two or more of these substituents may be combined. Preferably,
An alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a butyl group, a 2-hydroxyethyl group), a hydroxyl group, a halogen atom (eg, a fluorine atom, a chlorine atom, etc.), and an alkoxy group (eg, a methoxy group) An ethoxy group, a methylenedioxy group, a 2-hydroxyethoxy group,
n-butoxy group, etc.), substituted amino group (for example, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-
Ethyl-N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc., carboxy group, sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (eg, sulfamoyl group, methyl Sulfamoyl group, phenylsulfamoyl group, etc.), and these substituents may be combined.

The electron-withdrawing groups represented by X and Y in the general formulas (4) and (5) may be the same or different, and the σp value of the substituent constant Hammett (edited by Toshio Fujita,
"Structure-Activity Relationship of Drug No. 122, Special Edition of Chemistry,"
Pp. 103 (1979) in Nankodo and the like. ) Is preferably 0.3 or more, for example, a cyano group,
Alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, 4-hydroxyphenoxycarbonyl group), carbamoyl group (eg, carbamoyl group, dimethyl Carbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group (eg, methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group, 4-ethylsulfonamidocarbonyl group, etc.), alkylsulfonyl group ( For example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, 4-chloro Sulfonyl group, etc.).

The basic nucleus represented by B in the general formulas (3) and (5) is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole,
Thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole, indole and the like.

The heterocyclic ring represented by B 'in the general formula (6) is
Examples include pyridine, pyridazine, quinoline, pyrrole, pyrazole, imidazole, indole and the like.

L ₁ , L ₂ and L _{3 in the} general formulas (1) to (5)
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, isobutyl, etc.),
Aryl group (eg, phenyl, p-tolyl, p-chlorophenyl, etc.), alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenyl group, etc.), aralkyl group (eg, benzyl group, etc.) Groups, phenethyl groups, etc.), heterocyclic groups (eg, pyridyl, furyl, thienyl, etc.), substituted amino groups (eg, dimethylamino, tetramethyleneamino, anilino, etc.), and alkylthio groups (eg, methylthio group, etc.).

In the present invention, among the dyes represented by the general formulas (1) to (6), a dye having at least one carboxyl group in the molecule is preferably used, and more preferably a dye having the general formula (1) And particularly preferably a dye in which Q in the formula (1) is a furyl group.

Next, specific examples of the dye used in the present invention will be described.

[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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Other preferred specific examples of the compounds represented by formulas (1) to (6) include, for example, JP-A-5-18.
Compounds represented by general formulas [I] to [V], general formulas [I '] to [V'], and general formula [VI] described in page 12 to page 28 of JP-A-1230 are mentioned. Can be More specific compounds include I-1 to 37, II-1 to 5, III-1 to 7, and IV-1 described on pages 6 to 46 of the same specification.
-6, V-1-5, I'-1-12, II'-1-9, II
I'-1-9, IV'-1-9, V'-1-6, VI-1
52.

The method for producing the solid fine particle dispersion of the dye according to the present invention is described in JP-A-52-92716, JP-A-52-92716.
5-155350, 55-155351, 63
Nos. 197943, 3-182743, and World Patent WO 88/04794 can be used. Specifically, it can be manufactured using a fine dispersing machine such as a ball mill, a planetary mill, a vibration mill, a sand mill, a roller mill, a jet mill, and a disk impeller mill. When the compound dispersed in solid fine particles is water-insoluble at a relatively low pH and water-soluble at a relatively high pH, after dissolving the compound in a weakly alkaline aqueous solution,
A method of precipitating a particulate solid by lowering the pH to make it weakly acidic, or a method of simultaneously preparing a weakly alkaline solution of the compound and an acidic aqueous solution while adjusting the pH to produce a particulate solid, A dispersion can be obtained. The solid fine particle dispersion of the present invention may be used alone, or may be used as a mixture of two or more kinds, or may be used by mixing with a solid fine particle dispersion other than the present invention. When two or more kinds are used as a mixture, they may be dispersed individually and then mixed, or they may be dispersed simultaneously.

When the solid fine particle dispersion used in the present invention is produced in the presence of an aqueous dispersion medium, it is preferable that a surfactant is present during or after the dispersion.
As such a surfactant, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, but preferably, for example, alkyl sulfonates, alkylbenzene sulfonates Surfactants, alkylnaphthalenesulfonates, alkylsulfates, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, N-acyl-N-alkyltaurines and the like, and saponins and alkylene oxide derivatives, for example. And nonionic surfactants such as alkyl esters of sugars. Particularly preferred are the above-mentioned anionic surfactants. Specific examples of the surfactant include, for example, 1 to 32 described in Japanese Patent Application No. 5-277011, pp. 32-46.
However, the present invention is not limited thereto.

The amount of the anionic activator and / or the nonionic activator to be used is not uniform depending on the kind of the activator or the conditions of the dispersion of the dye.
The amount is preferably 0.1 mg to 2000 mg, more preferably 0.5 mg to 1000 mg, and particularly preferably 1 mg to 500 mg per gram.

The concentration of the dye in the dispersion is 0.01
使用 50% by weight is preferably used,
More preferably, it is 0.1 to 30% by weight. The addition position of the surfactant is preferably added before the start of dispersion of the dye,
If necessary, it may be further added to the dye dispersion after the dispersion is completed. These anionic and / or nonionic activators may be used alone, respectively.
In addition, two or more kinds may be combined, or both activators may be combined.

The solid fine particle dispersion used in the present invention is preferably dispersed such that the average particle size is 0.01 μm to 5 μm, more preferably 0.01 μm.
m to 1 μm, particularly preferably 0.01 μm to 0.1 μm.
5 μm. The dispersion coefficient of the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (average value of particle size) × 100 The solid fine particle dispersion used in the present invention is a hydrophilic colloid used as a binder in a photographic constituent layer before or after the start of dispersion. Can be added.
As the hydrophilic colloid, it is advantageous to use gelatin.In addition, for example, phenylcarbamylated gelatin, acylated gelatin, gelatin derivatives such as phthalated gelatin, and gelatin having a polymerizable ethylene group-containing monomer. Graft polymer, carboxymethylcellulose, hydroxymethylcellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol,
Partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-
Synthetic hydrophilic polymers such as N-vinylpyrrolidone and polymethacrylic acid, agar, gum arabic, alginic acid, albumin, casein and the like can be used. These may be used in combination of two or more. The amount of the hydrophilic colloid added to the solid fine particle dispersion of the present invention is preferably 0.1% to 12% by weight, more preferably 0.5% to 8%. is there.

The solid fine particle dispersion used in the present invention can be used in any layer as long as it is a photographic constituent layer on the side of the silver halide emulsion layer. Preferably, it is used for the silver halide emulsion layer closest to the support and / or the non-photosensitive hydrophilic colloid layer adjacent to the support side of the emulsion layer.

The preferred amount of the solid fine particle dispersion of the dye is not uniform depending on the kind of the dye and the characteristics of the photographic material, but is preferably 1 mg to 1 g per 1 m ^{2 of} the photographic material, and more preferably. 5mg-800m
g, particularly preferably 10 mg to 500 mg.

In the present invention, a photographic component layer containing a dye dispersed in a solid state is provided on the side of the silver halide emulsion layer. It may be contained in any photographic constituent layer. Further, any layer may have a water-soluble dye.

The maximum absorption wavelength of the solid-dispersed dye used in the present invention is preferably from 480 to 620 nm, particularly preferably from 500 to 600 nm.

Next, the water-soluble dye used in the present invention will be described.

The water-soluble dye used in the present invention can be used in any layer on the side of the silver halide emulsion layer.
Further, the photographic constituent layer containing the water-soluble dye is preferably a layer farther from the support than the photographic constituent layer containing the dye dispersed in a solid state.

As the water-soluble dye used in the present invention, dyes generally used for light-sensitive materials can be used. The dye is Research Disclosure (RD) -17643 (25-
26 page) Classification VIII, 18716 (649-650)
Page 308), and -308119 (page 1003).

Particularly preferred is Japanese Patent Application Laid-Open No. 1-293342.
Nos. 1-303434, 1-303433, JP-A-58-83841, 62-103633, 62-291636, JP-A-1-44438, and 1
No. 253735, No. 2-201351, No. 2-20
1352, 2-302752, 7-29513
2. The water-soluble dye according to item 2.

The maximum absorption wavelength of the water-soluble dye used in the present invention is preferably from 300 to 520 nm, more preferably from 340 to 480 nm.

[0100] The preferred amount of water-soluble dye used in the present invention, the type of dye, but not uniform due the characteristics of photographic light-sensitive material, photographic material 1 m ² per 1mg~1
g, more preferably from 10 mg to
500 mg. Water-soluble dye used in the present invention,
A dye that is soluble in pure water at 25 ° C. in an amount of 0.5 wt% or more. In addition, the water-soluble dye used in the present invention has a maximum absorption wavelength of 5% for the solid-dispersed dye used in the present invention.
It is a dye having a maximum absorption wavelength shorter by 0 to 200 nm.
At 50 nm or less, the sensitivity is significantly reduced, and at 200 nm or more, the effect of faithfully reproducing the original is hardly observed.

The photographic constituent layer on the emulsion layer side of the silver halide photographic light-sensitive material of the present invention contains a hydrazine compound. Hereinafter, the hydrazine compound preferably used in the present invention will be described.

As the hydrazine compound used in the present invention, a compound represented by the following general formula [H] is used.

[0103]

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The general formula [H] will be described in detail below.

In the formula, A ₀ represents an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, particularly a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group. Examples include a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, a benzyl group, and the like. These are further suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, Sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed-ring aryl group, such as a benzene ring or a naphthalene ring.

The heterocyclic group represented by A ₀ in the general formula [H] is preferably a monocyclic or condensed heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen. For example, a pyrrolidine ring , An imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, and a furan ring.

Particularly preferred as A ₀ are an aryl group and a heterocyclic group. The aromatic group and heterocyclic group represented by A ₀ preferably have a substituent. Preferred substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups, Alkylthio group, arylthio group, sulfothio group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide Groups, a carboxy group, a phosphoric acid amide group and the like, and these groups may be further substituted. Among these substituents, when a developer having a pH of 10.5 or less and a total processing time (Dry to Dry) of 60 seconds or less are used, the substituent having an acidic group having a pKa of 7 to 11 is used. Preferably, specific examples include a sulfonamide group, a hydroxy group, and a mercapto group, and particularly preferably, a sulfonamide group.

A ₀ preferably contains at least one diffusion-resistant group or silver halide adsorption promoting group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group or an alkenyl group which is relatively inert to photographic properties having 8 or more carbon atoms is preferable. , Alkynyl group, alkoxy group,
Examples include a phenyl group, a phenoxy group, and an alkylphenoxy group.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

B ₀ represents a blocking group, preferably -G ₀ -D ₀ G ₀ represents a -CO- group, -COCO- group, -CS- group, -C
(= NG ₁ D ₁ ) —, —SO—, —SO ₂ —, or —P (O) (G ₁ D ₁ ) —. G ₁ represents a simple bond, —O— group, —S— group or —N (D ₁ ) — group. 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 may be the same or different.

D ₀ represents an aliphatic group, an aromatic group, a heterocyclic group,
Represents an amino group, an alkoxy group, and a mercapto group.

Preferred G ₀ include —CO— group, —C
An OCO- group, particularly preferably a -COCO- group is mentioned.

Preferred D ₀ includes a hydrogen atom, an alkoxy group, an amino group and the like.

A ₁ and A ₂ are both a hydrogen atom, 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).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0117]

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[0118]

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[0119]

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

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 columns 59 to 80 of No. 29,248.

The hydrazine compound of the present invention can be used in any photographic constituent layer on the side of the silver halide emulsion layer. Preferably, it is used for the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer adjacent thereto.

The hydrazine derivative used in the present invention is
One kind may be used, or two or more kinds may be used in combination. The optimal amount varies depending on the particle size of silver halide grains, halogen composition, degree of chemical sensitization, type of inhibitor, etc.
Generally, the range is preferably from 10 ^-6 to 10 ^-1 mol, more preferably from 10 ^-5 to 10 ^-2 mol, per mol of silver halide.

In order to effectively promote hardening by the hydrazine derivative, it is preferable to use an amine compound represented by the following general formula [Na].

[0125]

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In the general formula [Na], R ₁ , R ₂ , R ₃
Represents 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 ₁ , R ₂ and R ₃ 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 more preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group. Particularly preferred as the general formula [Na] is a compound having at least one thioether group as a silver halide adsorptive group in the molecule. Hereinafter, specific examples of the amine compound [Na] will be described.

[0127]

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[0128]

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[0129]

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[0130]

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Specific examples of other preferred amine compounds are described in JP-A-6-258751, page (13), “006”.
2) to (15), “0065” (2-
Compounds 1) to (2-20) and 3-1 to 3-6 described in “0067” on page (15) to “0068” on page (16) of JP-A-6-258751.

The amine compound of the present invention can be used in any photographic constituent layer on the side of the silver halide emulsion layer. Also, two or more kinds may be used in combination. The optimum amount to be added varies depending on the grain size of silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, and the like, but is generally in the range of 10 ^-6 to 10 ^-1 mol per mol of silver halide. It is particularly preferably in the range of 10 ^-5 to 10 ^-2 mol.

The silver halide photographic light-sensitive material of the present invention preferably contains a quaternary onium salt compound.
The quaternary onium salt compound preferably used is a compound having a quaternary cation group of a nitrogen atom or a phosphorus atom in a molecule, and is a compound represented by the following general formula (P).

[0134]

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Further, R _{1 to} R ₄ may be linked to each other to form a ring.

Examples of the substituent represented by R _{1 to} R ₄ include an alkyl group (methyl group, ethyl group, propyl group, butyl group,
Hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (piperidinyl group, piperazinyl group) , Morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group,
Sulfolanyl group), an amino group and the like. R ₁ ~
Examples of the ring which R ₄ can form by connecting to each other include a piperidine ring, a morpholine ring, a piperazine ring, a quinuclidine ring,
Examples include a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring. The groups represented by R _{1 to} R ₄ may have a substituent such as a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group, and an aryl group.

As R ₁ , R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferred.

Examples of the anion represented by X ⁻ include inorganic and organic anions such as a halogen ion, a sulfate ion, a nitrate ion, an acetate ion and a p-toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
b) or a compound represented by (Pc); and a compound represented by the following general formula [T].

[0140]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetal atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include 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, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. A ¹ , A ² ,
Preferred examples of A ³ , A ⁴ and A ⁵ include 5- to 6-membered rings (rings such as pyridine, imidazole, thiazole, oxazole, pyrazine and pyrimidine), and a more preferred example is a pyridine ring. .

_BP represents a divalent linking group, m is 0 or 1
Represents Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, —SO ₂ —, —SO—, and —O
—, —S—, —CO—, and —N (R ⁶ ) — (R ⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. B _p is preferably an alkylene group or an alkenylene group.

R ¹ , R ² and R ⁵ each represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ¹ and R ² may be the same or different. As the substituent,
The substituents are the same as those described as the substituents for A ¹ , A ² , A ³ , A ⁴ and A ⁵ . Preferred examples of R ¹ , R ² and R ⁵ are each an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0144] X _p ^- is a counter ion necessary to balance the charge of the whole molecule, for example chloride, bromide,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate and the like. n _p represents the number of counter ions required to balance the charge of the entire molecule, and n _p is 0 in the case of an internal salt.

[0145]

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The substituents R ₅ and R ₆ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T],
R ₇ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

The Hammett's sigma value at the phenyl group has been described in many literatures, for example, Journal of Medical Chemistry.
Chemistry) 20, vol. 304, p. As a group having a particularly preferable negative sigma value, for example, a methyl group (σP = −0.17 or less, all of which can be seen in reports by C. Hansch et al.)
P value), ethyl group (-0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which has the general formula [T]
Is useful as a substituent of the compound of

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, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

The following are specific examples of the quaternary onium salt compounds, but the invention is not limited thereto.

[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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The above quaternary onium salt compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be obtained from Chemi Abstra. 55 p. 335-4
83 can be referred to.

The quaternary onium compound of the present invention can be used in any photographic constituent layer on the side of the silver halide emulsion layer. Also, two or more kinds may be used in combination.
The optimum amount to be added varies depending on the grain size of silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, and the like, but is generally in the range of 10 ^-6 to 10 ^-1 mol per mol of silver halide. It is particularly preferably in the range of 10 ^-5 to 10 ^-2 mol.

The silver halide photographic light-sensitive material of the present invention may be a silver halide emulsion having a halogen composition of pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or salt containing 60 mol% or more of silver chloride. Preferably, it is silver iodobromide.

The average grain size of the silver halide is preferably 0.7 μm or less, particularly preferably 0.5 to 0.1 μm.

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Also, a narrower particle size distribution is preferable, and 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 particularly preferable.

As a method of reacting a soluble silver salt and a soluble halide in preparing a silver halide emulsion, any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

A method of forming particles in the presence of excess silver ions (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. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

In at least one of the steps of forming or growing the silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, rhodium salts, ruthenium salts, osnium salts, iron salts , Copper salts, platinum salts, palladium salts and the like are preferably added. As a ligand of these complex salts, a halogen atom, a nitrosyl group, a cyano group, an aquo group, an alkyl group, a pseudohalogen group, an alkoxy group, an ammonium group, and any combination thereof can be used.

The surface of silver halide grains can be controlled in halogen composition by using water-soluble halides or silver halide fine grains. This technique is known in the art as conversion and is widely known.

The silver halide grains may be uniform from the inside to the surface, or may be composed of a plurality of layers having different halogen compositions, dopant species and amounts, distribution of lattice defects, and the like.

The silver halide emulsion has a grain size, sensitivity,
A plurality of types of grains differing in crystal habit, photosensitive wavelength, halogen composition, degree of monodispersity, amount and type of doping agent, electric potential, pH, production conditions such as desalting method, surface state, chemical sensitization state, etc. are used in combination. be able to. In that case, these silver halide grains may be contained in the same layer, or may be contained in a plurality of different layers.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (RD).
176: 17643, pp. 22-23 (Dec. 1978
Mon)) or in the literature cited.

The silver halide photographic light-sensitive material of the present invention can be spectrally sensitized to a desired wavelength by a sensitizing dye outside the present invention. Sensitizing dyes that can be used include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl dye, hemioxonol dye, and the like. For the addition of the sensitizing dye, a conventional method of dissolving in a solvent and adding, or an addition method by solid dispersion may be used. The dye may be added by dissolving it using ultrasonic vibration as described in U.S. Pat. No. 3,485,634, for example.

In the present invention, gelatin is advantageously used as a binder or protective colloid of a photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, poly Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as acrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As the 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 poorly-soluble synthetic polymer for the purpose of improving dimensional stability, reducing silver sludge, and the like. For example, alkyl (meth)
Acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination, or acrylic acid, methacrylic acid,
A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like as a monomer component can be used. Further, a monomer having a plurality of ethylenically unsaturated groups may be used as a monomer component. These monomers may have a water-soluble group such as a hydroxyl group, a sulfone group, a carboxyl group, and an amide group, and may have a primary to quaternary amino group, a phosphonium group, an aliphatic group, an aromatic group, -NR ¹ NR ² —R ³ (R ¹ , R ² and R ³ may be different from each other; a hydrogen atom, an aliphatic group, an aromatic group, a sulfinic acid residue, a carbonyl group, an oxalyl group, a carbamoyl group, an amino group, a sulfonyl group , A sulfoxy group, an iminomethylene group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an arbitrary group bonded via an aryloxy group, etc.), a cation group, etc. Is also good. As a synthesis method, in addition to a usual synthesis method, polymerization may be performed in the presence of a water-soluble organic substance such as gelatin or polyvinyl alcohols.
After completion of the synthesis, shelling may be performed with gelatin or a silane coupling agent.

In the silver halide photographic light-sensitive material of the present invention,
The compounds described below can be contained 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) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494 (4) page [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111]
(7) Nucleation accelerator: JP-A-7-114126, page (32) [0158]
(8) Tetrazolium compound JP-A-6-208188, page (8), [0059] to
(10) Compound described on page [0067] (9) Pyridinium compound JP-A-7-110556 (5) page [0028] to
(29) Compound described in [0068] (10) Redox compound JP-A-4-245243, pages 235 (7) to 250
Compound described on page (22) The above-mentioned additives and other known additives are described, for example, in (RD) No. 17643 (December 1978
No.), and No. 18716 (November 1979) and the same No. 308119 (December 1989). The description places of these three (RD) are shown below.

[0178]

[Table 1]

The various photographic additives used in the present invention may be used by dissolving them in an aqueous solution or an organic solvent. However, when they are sparingly soluble in water, they are converted to fine particles of water, gelatin, hydrophilic or hydrophobic polymer. It can be dispersed and used. Dyes, dyes, desensitizing dyes, hydrazines, redox compounds, fog inhibitors, ultraviolet absorbers, and the like can be dispersed with a known disperser. Specific examples include a ball mill, a sand mill, a colloid mill, an ultrasonic disperser, and a high-speed impeller disperser.

In the light-sensitive material of the present invention, the photographic constituent layer is coated on one or both sides of a flexible support usually used for the light-sensitive material. Useful as flexible supports are films of synthetic polymers of cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polyethylene terephthalate (which may contain colored content), or polyethylene or Paper supports and the like coated with a polymer such as polyethylene terephthalate. These supports may have a magnetic recording layer, an antistatic layer, and a release layer.

In the method for processing a silver halide photographic light-sensitive material of the present invention, the developing agents that can be used include:
Dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone, etc.), 3-pyrazolidones (eg, 1-phenyl-3)
-Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3 -Pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4
-Diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (for example, 1-
(P-hydroxyphenyl) -3-aminopyrazoline,
1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-
Aminopyrazoline, etc.), transition metal complex salts (Ti, V, C
Complex salts of transition metals such as r, Mn, Fe, Co, Ni, Cu, etc. These may be in any form having a reducing power for use as a developing solution. For example, Ti ³⁺ , V ²⁺ , Cr ²⁺ , F
In the form of a complex salt such as e.sup.2 ⁺ , the ligands include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof, hexametapolyphosphoric acid, and tetrapolyphosphoric acid. Phosphoric acids and salts thereof. And the like can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid; A combination of aminophenols and ascorbic acid,
It is preferable to use a combination of a 3-pyrazolidone and a transition metal complex, or a combination of an aminophenol and a transition metal complex. The developing agent is usually 0.01 to 1.
It is preferably used in an amount of 4 mol / l.

In the processing method of the present invention, a silver sludge inhibitor is disclosed in JP-B-62-4702, JP-A-3-51844.
No. 4-26838, No. 4-362942, No. 1
Compounds described in JP-A-319031 can be used.

The waste developing solution can be regenerated by energizing. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material according to the present invention can be processed while energizing.

At this time, various additives added to the developer, for example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor which can be added to the developer, etc. Can be added. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. In the case where the waste developer is recycled, the transition agent complex is preferably used as the developing agent of the developer used.

Examples of the preservative include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / liter.

In the developing solution, if necessary, an alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) , Dissolution aids (eg, polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.),
Surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (for example, US Pat.
No. 025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent. The pH of the developer is preferably adjusted to 8 to 12, particularly preferably 9 to 11.

In the method for processing a silver halide photographic light-sensitive material of the present invention, a developer containing substantially no hydroquinones (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, hydroquinone monosulfonate) is used. Can be. The term "substantially not contained" means an amount of less than 0.01 mol per liter of the developer.

In this case, a compound represented by the following general formula (II) is preferably contained.

[0189]

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In the compound represented by the general formula (II),
A compound represented by the following formula (II-a) in which R ¹¹ and R ¹² are bonded to each other to form a ring is preferred.

[0191]

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In the formula, R ¹³ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, Represents an amide group or a sulfonamide group, Y ¹¹ represents O or S, and Y ¹² represents O, S or N
Representing the R ^14. R ¹⁴ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. As the alkyl group,
A lower alkyl group is preferable, for example, an alkyl group having 1 to 5 carbon atoms. As the amino group, an unsubstituted amino group or an amino group substituted with a lower alkyl group is preferable, and as the alkoxy group, a lower alkoxy group is preferable. The aryl group is preferably a phenyl group or a naphthyl group, and these groups may have a substituent. Examples of the substitutable group include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, and a carboxyl group. ,
An amide group, a sulfonamide group and the like are mentioned as preferred substituents.

Specific examples of the compounds represented by formulas (II) and (II-a) are shown below, but the present invention is not limited thereto.

[0194]

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[0195]

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These compounds are typically ascorbic acid or erythorbic acid or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

In the present invention, a developing agent comprising the transition metal complex salt according to the present invention and a 3-pyrazolidone (for example, 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) can be used in combination. When used in combination, the developing agents such as 3-pyrazolidones and aminophenols are usually used in an amount of 0.01 to 1.4 per liter of developer.
It is preferably used in molar amounts.

As a special type of development processing of the light-sensitive material of the present invention, a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is used in an activator processing solution for developing by processing in an aqueous alkali solution. You may. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions. In the case of such rapid processing, the effect of the present invention is particularly large.

As the fixing solution, those having a commonly used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate; and organic sulfur that can form a soluble stable silver complex salt. Compounds known as fixing agents can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum and the like can be added to the fixing solution.

The fixing solution may contain, if desired, a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid),
Compounds such as a pH adjuster (for example, sulfuric acid) and a chelating agent capable of softening water can be included.

In the developing treatment, washing is performed after fixing. The washing layer may be a system in which fresh water is supplied at a rate of several liters per minute according to the treatment, or the washing water may be circulated, a chemical, a filter, ozone may be used. And a method of reusing after treatment with light or the like, or a method of replenishing a small amount of a stabilizing solution in accordance with the amount of treatment by using a washing bath as a stabilizing bath with a stabilizer added. This step is usually at room temperature, but it may be heated to 30 ° C to 50 ° C. In addition, when a stabilizing bath is used, it is possible to perform a pipeless treatment that does not need to be directly connected to the water supply. A rinsing bath can be provided before and after each treatment layer.

As a mother liquor or a replenisher of a developing solution, a fixing solution, or a stabilizing solution, a solution obtained by diluting a working solution or a concentrated solution immediately before is usually supplied. The stock of the mother liquor and replenisher may be in the form of a working liquid, a concentrated liquid, a viscous liquid in a semi-kneaded state having a high viscosity, or a system in which a simple substance or a mixture of solid components is dissolved at the time of use. When a mixture is used, components that are difficult to react with each other are adjacently packed in layers and then vacuum-packed, and are opened and dissolved at the time of use,
A tablet forming method can be used. In particular, the method of adding a tablet formed product to the dissolution layer or the directly treated layer is a method which is extremely excellent in workability, space saving and preservation, and is particularly preferably used.

In the development processing of the present invention, the development temperature can be set in a normal temperature range of 20 to 50 ° C.

The light-sensitive material of the present invention is preferably processed using an automatic processor. At this time, processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photosensitive material.

In the present invention, the amount of replenishment for development is from 30 to 250 ml, preferably from 50 to 200 ml, per m ² in order to reduce the amount of waste liquid. The fixing replenishment amount is preferably 300 ml or less per m ² .

Each treating agent may be replenished in a liquid state or in a solid state.

According to the present invention, the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine to the emergence from the drying zone when processing using the automatic developing machine is 10 because of the demand for shortening the developing time. It is preferably from 60 seconds to 60 seconds. More preferably, it is 15 to 50 seconds.

The term "total processing time" as used herein includes the total processing time required for processing the black-and-white photosensitive material, and includes, for example, the developing, fixing, washing and drying process times (as well as bleaching, stabilization, etc.). ) May be included, ie, a period of Dry to Dry.

In the drying zone of the automatic developing machine, a method of drying using warm air is usually used. However, a heat transfer material of 90 ° C. or more (for example, a heat roller of 90 ° C. to 130 ° C.) or radiation of 150 ° C. or more is used. Objects (for example, tungsten, carbon, nichrome, zirconium oxide, yttrium oxide,
A substance that emits infrared radiation by directly passing an electric current through a mixture of thorium oxide or silicon carbide and causing it to emit heat, or by transferring heat energy from a resistance heating element to a radiator such as copper, stainless steel, nickel, or various ceramics to generate heat and generate heat. ) With drying zone, or dehumidifier,
Those provided with known drying means such as a microwave generator and a water-absorbing resin are included. Further, a control mechanism for a dry state may be provided.

[0211]

EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

Example 1 (Preparation of Silver Halide Emulsion A1) An average diameter of 0.07 mol% of silver chloride and the remainder of silver bromide was obtained by a double jet method.
9 μm silver chlorobromide core particles were prepared. At the time of mixing the core particles, an aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed while maintaining the pH at 36 ° C. and the silver potential (EAg) at 120 mV. The core particles were shelled using a double jet method with EAg reduced to 100 mV with saline. At that time, 38.2 μg of K ₃ RhCl ₆ was added per mole of silver to the halide solution. The obtained emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide having an average diameter of 0.20 μm (silver chloride: 70 mol%, silver iodobromide: 0.2 mol%, the rest being bromide). (Composed of silver).

Thereafter, 70 mg of sensitizing dye d-3 was added per 1 mol of silver. Then, a modified gelatin described in JP-A-2-280139 (in which an amino group in gelatin is substituted with phenylcarbamyl, for example, as disclosed in JP-A-2-28013)
Desalting was carried out using the exemplified compound (G-8) on page 9, 287 (3). Thereafter, at 40 ° C., 90 mg of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) was added per mole of silver.

The EAg of the obtained emulsion was 177 m at 40 ° C.
V and pH were 5.6. The resulting emulsion was reacted with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene at 60 mg per mole of silver and KBr at 100 mg, and then dispersed in a solid to form an inorganic sulfur (S8) compound ( (Seisin Enterprise Co., Ltd .; saponin added to PM-1200 and dispersed to an average of 0.5 μm) and 1.5 × 10 ^-5 mol of chloroauric acid are added to obtain the highest sensitivity at a temperature of 60 ° C. Chemical ripening was carried out until.

Thereafter, 4-hydroxy- / mol of silver was used.
6 methyl-1,3,3a, 7-tetrazaindene is added to 40
0 mg and 100 mg of potassium iodide were added, and the sensitizing dye of the present invention was added at 40 ° C. as shown in Table 1. Then the pH was adjusted to 5.1 by adding citric acid.

(Preparation of Silver Halide Emulsion A2) The reaction temperature was raised to 45 ° C. to give a grain size of 0.30 μm with respect to the silver halide emulsion A1, and K ₃ RhCl ₆ in the shell portion was increased to 10 μg per mole of silver. A silver halide emulsion A2 was prepared in exactly the same manner as described above. When the same chemical sensitization is performed,
The emulsion of A2 is 50% faster than the emulsion of A1.

(Preparation of silver halide photographic light-sensitive material for printing plate making) A silver halide emulsion layer 1 of the following formula 1 was coated on a support with a silver amount of 0.3 g / m ² and a gelatin amount of 0.3 g / m ² . ^Two
The gelatin intermediate layer of Formulation 2 is further provided thereon with a gelatin amount of 0.8 g / m ² , and the silver halide emulsion layer 2 of Formulation 3 is further provided thereon with a silver amount of 3.0 g / m ^2.
Further, the protective layer coating solution having the following formula 4 was further diluted with a gelatin amount of 0.6 g / m ² so that the m ² and the gelatin amount became 1.5 g / m ^2.
2 was applied in multiple layers.

On the other side of the undercoat layer, a backing layer of the following formula 5 was provided so that the amount of gelatin was 1.5 g / m ^2, and a backing protective layer of the following formula 6 was provided thereon so that the amount of gelatin was 1. The emulsion layer side and the emulsion layer side were simultaneously layer-coated at a speed of 200 m / min by a curtain coating method so that the emulsion layer side became 0 g / m ² , and then cooled and set. A sample was obtained by cooling and setting and drying both sides simultaneously.

Formulation 1 (Composition of Silver Halide Emulsion Layer 1) Gelatin 0.3 g / m ² Silver Halide Emulsion A2 Silver Amount 0.3 g / m ² Equivalent Polymer Latex L2 (particle size 0.25 μm) 0.1 g / M ² Saponin 2 mg / m ² Compound T-1 10 mg / m ² Prescription 2 (gelatin intermediate layer composition) Gelatin 0.8 g / m ² Saponin 80 mg / m ² Hydroquinone 0.5 g / m ² Fungicide z 0.5 mg / m ² solid disperse dye Type and amount shown in Table 2 Formulation 3 (Composition of silver halide emulsion layer 2) Silver halide emulsion A1 Silver amount 3.0 g / m ² equivalent Hydrazine compound H-174 4 mg / m ² S- 1 (Sodium - iso - amyl -n- decyl sulfosuccinate) 5mg / m ² 2- mercapto-6-hydroxy purine 1 mg / m ² nicotinamide 1 mg / m ² gallate n- Puropirue Ether 50 mg / m ² mercaptopyrimidine 1 mg / m ² Polymer latex L2 (particle size ^{0.25μm) 0.5g / m 2 EDTA 50mg} / m 2 of sodium polystyrenesulfonate 15 mg / m ² Colloidal silica (average particle size 0.05 .mu.m) 0.5 g / m ² gelatin was phthalated gelatin, and the pH of the coating solution was 5.0.

Formulation 4 (Emulsion protective layer composition) Gelatin 0.6 g / m ² S-1 12 mg / m ² Surfactant b 0.6 mg / m ² Quaternary onium compound P-27 70 g / m ² colloidal silica (average 0.5 g / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener h4 60 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Fungicide z 0.5 mg / m ² (Water-soluble) dye Type and amount shown in Table 2 Formulation 5 (backing layer composition) Gelatin 1.5 g / m ² Polymer latex L3 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 100 mg / m ² dyes f1 40 mg / m ² dye f2 7 mg / m ² dye f3 60mg / m ² 1- phenyl-5-mercaptotetrazole 10 mg / m ² hardener h3 100 mg m ² EDTA 50mg / m ² formulation 6 (backing protective layer) Gelatin 1.0 g / m ² Matting agent: monodisperse mean particle size 5μm polymethylmethacrylate 50 mg / m ² the average particle diameter of 3μm indefinite based silica 12.5 mg / m ² dye f1 40 mg / m ² dye f2 7 mg / m ² dye f3 60 mg / m ² hardener ^{h1 100mg / m 2 S-1} 6mg / m 2 Porisuchireruhon sodium ^{10mg / m 2 KI 15mg / m} 2 amine compound Na- 21 15 mg / m ²

[0221]

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[0222]

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[0223]

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[0224]

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The obtained sample was brought into close contact with a step wedge, exposed to tungsten light at 3200 ° K. for 3 seconds, and an automatic developing machine GR-27 was prepared using a developing solution and a fixing solution having the following compositions.
(Konica Corporation) under the following conditions. The blackening density of the obtained developed sample was measured with a PDA-65 (Konica Digital Densitometer).

In order to evaluate the reproducibility of minute dots of the obtained sample, a manuscript prepared as follows was used.
Fine zoom C-880F manufactured by Dainippon Screen Co., Ltd.
The exposure was performed so that the enlargement magnification became 120% and 95% of the original became 5%. The exposed sample was processed with an automatic developing machine GR-27 using a developing solution and a fixing solution having the following compositions. Regarding the sample after the treatment, the dot percentage was measured by X-Rite361T.

<Preparation of Manuscript> Konica Eco Stage Scanner Film SH-3 was transferred to SelectS made by Agfa.
Small dot (5% halftone dot), middle point (50% halftone dot), large point (9 dots) at 3600 dpi / 300 lpi using et5000.
Exposure was performed by adjusting the amount of light so that solid (5% halftone dot) and solid (100% halftone dot) were faithfully reproduced. The processing was performed at 35 ° C. for 30 seconds with an automatic developing machine GR-27 using a developing solution CDM681 and a fixing solution CFL881.

(Composition of developer) Per liter of working solution Diethyltriamine pentaacetic acid / pentasodium salt 1.45 g Dimezone S 0.85 g Sodium sulfite 42.5 g Potassium sulfite 17.5 g Potassium carbonate 55 g Hydroquinone 20 g 1-phenyl-5- Mercaptotetrazole 0.03 g Potassium bromide 2.67 g Benzotriazole 0.21 g Boric acid 8 g Diethylene glycol 40 g 8-Mercaptoadenine 0.07 g KOH was added in an amount to bring the pH of the working solution to pH 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.

(Evaluation of Sensitivity)
The measurement was performed using DA-65, and the sensitivities shown in Table 2 were obtained. The sensitivities in the table indicate sample No. The sensitivity at a concentration of 3.0 of 11 was 10
It was expressed as a relative sensitivity when 0 was set.

(Evaluation of enlargement) Small point side (highlight part)
Of the treated samples in which the halftone dot% was adjusted to 5%, the five-point evaluation was performed in order from the one with the highest reproducibility (the difficulty of halftone dot collapse) on the middle point and the large point side (shadow portion). 5 is a good level and 1 is a poor level. The practically usable level was set at 3. Table 2 shows the results.

[0232]

[Table 2]

As is clear from Table 2, the sample of the present invention has high sensitivity and good reproducibility of fine halftone dots.

Example 2 (Preparation of Silver Halide Emulsion B1) An average diameter of 0.07 mol% of silver chloride and the remainder of silver bromide was obtained by a double jet method.
9 μm silver chlorobromide core particles were prepared. At the time of mixing the core particles, an aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed while maintaining the pH at 36 ° C. and the silver potential (EAg) at 120 mV. The core particles were shelled using a double jet method with EAg reduced to 90 mV with saline. At this time, K ₂ OsCl ₆ was added to the halide solution in an amount of 4 per mole of silver.
5 μg was added. The resulting emulsion has an average diameter of 0.22 μm
A cubic emulsion of silver / chloroiodobromide (composed of 70 mol% of silver chloride, 0.2 mol% of silver iodobromide and the rest of silver bromide) having a core / shell type monodispersion (coefficient of variation: 10%). Was. Then, desalting is carried out by using a modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, compound G-8 on page 287 (3) of JP-A-2-280139). did. Thereafter, at 40 ° C., 90 mg of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) was added per mole of silver. The EAg of the obtained emulsion was 177 mV at 40 ° C., and the pH was 5.6.

The resulting emulsion was reacted with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene at 60 mg per mole of silver and 100 mg of KBr, and then dispersed in a solid. On the undercoat layer, a backing layer of the following formulation 12 was coated thereon so that the amount of gelatin was 1.0 g / m ^2, and a hydrophobic polymer layer of the following formulation 13 was further placed thereon, and further a backing protective layer of the following formulation 14 The emulsion layer side and the emulsion layer side were coated simultaneously at a rate of 200 m / min by a curtain coating method so that the amount of gelatin became 0.6 g / m ² , cooled and set, and then the backing layer side was coated simultaneously. The sample was obtained by coating, cooling and setting at -1 ° C, and drying both sides simultaneously.

Formulation 7 (Gelatin undercoat composition) Gelatin 0.55 g / m ² Saponin 80 mg / m ² 1-phenyl-5-mercaptotetrazole 2.0 mg / m ² Fungicide z 0.5 mg / m ² Solid disperse dye Type and amount shown in Table 3 Formulation 8 (Composition of silver halide emulsion layer 1) Silver halide emulsion B1 Silver amount equivalent to 3.0 g / m ² Hydrazine compound H-17 5 mg / m ² S-1 5 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² Nicotinamide 20 g / m ² Gallic acid n-propyl ester 50 mg / m ² Mercaptopyrimidine 1 mg / m ² Polymer latex L2 (particle size 0.25 μm) 0.5 g / m ² EDTA 50mg / m ² of sodium polystyrenesulfonate 15 mg / m ² colloidal silica (average particle size 0.05μm) 0.3g / m ² Ze Chin coating solution pH using phthalated gelatin was 5.1.

Formulation 9 (Gelatin middle layer composition) Gelatin 0.8 g / m ² Saponin 80 mg / m ² Hydroquinone 0.5 g / m ² Fungicide z 0.5 mg / m ² Polymer latex L2 (particle size 0.25 μm) 0 0.3 g / m ² amine compound Na-21 10 mg / m ² Prescription 10 (composition of silver halide emulsion layer 2) Silver halide emulsion B2 Silver equivalent 0.3 g / m ² equivalent Polymer latex L2 (particle size 0.25 μm 0.25 g / m ² Saponin 2 mg / m ² Compound T-2 10 mg / m ² Formulation 11 (Emulsion protective layer composition) Gelatin 0.6 g / m ² S-1 12 mg / m ² Surfactant b 0.6 mg / m ² colloidal silica (average particle size 0.05 μm) 0.2 g / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener h4 60 mg / m ² polystyrene sulfone Sodium acid 20 mg / m ² Fungicide z 0.5 mg / m ² Water-soluble dye Type and amount shown in Table 3 Formulation 12 (backing layer composition) Gelatin 1.0 g / m ² Polymer latex L3 0.3 g / m ² colloidal silica (Average particle size 0.05 μm) 100 mg / m ² dye f1 40 mg / m ² dye f2 7 mg / m ² dye f3 60 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² hardener h3 100 mg / m ² EDTA 50 mg / m ² Formula 13 (hydrophobic polymer layer composition) Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² Hardener h1 6 mg / m ² Formula 14 (backing protective layer) Gelatin 0. 6 g / m ² matting agent: monodisperse mean particle size 5μm polymethylmethacrylate 50 mg / m ² the average particle diameter of 3μm indeterminate system silica 12. mg / m ² Dye f1 40 mg / m ² Dye f2 7 mg / m ² Dye f3 60 mg / m ² hardener ^{h1 100mg / m 2 S-1} 6mg / m 2 Sodium polystyrenesulfonate ^{10mg / m 2 KI 15mg / m} 2 Amine compound Na-21 20 mg / m ^{2 The} obtained sample was closely adhered to a step wedge, exposed to tungsten light at 3200 ° K. for 3 seconds, and replenished with 120 ml of developing solution and 120 ml of fixing solution per 1 m ^{2 of} the photosensitive material. The processing was carried out under the same conditions as in Example 1 using the developing solution and the fixing solution.

Further, in order to evaluate the reproducibility of minute halftone dots of the obtained sample, exposure was performed in the same manner as in Example 1, and the above processing was performed.

At the start of running and when the photosensitive material is 200 m ²
The same evaluation as in Example 1 was performed on the running-processed sample (blackening ratio: 80%).

(Developer Composition-Hydroquinone Free) Concentrated Developer A (1 liter formulation) Diethyltriaminepentaacetic acid / pentasodium salt 9 g 8-Mercaptoadenine 0.08 g Sodium sulfite 0.45 mol 1-phenyl-4-methyl- 4-Hydroxymethyl-3-pyrazolidone 7 g Potassium carbonate 2.4 mol 5-Methylbenzotriazole 0.75 g Potassium bromide 22 g Boric acid 6 g Diethylene glycol 80 g Sodium ersorbate 60 g KOH was added in an amount to bring the pH of the working solution to 10.0. At the time of use, 2 parts of water was added to 1 part of the concentrated developer A to obtain a used liquid. This working solution was used as a developing mother liquor and a developing replenisher.

(Fixing solution composition) Concentrated fixing solution A (1 liter formulation) Ammonium thiosulfate (70% aqueous solution) 400 ml Sodium sulfite 45 g Boric acid 20 g Sodium acetate trihydrate 70 g Acetic acid (90% aqueous solution) 30 g Tartaric acid 6 g Glutaraldehyde 6 g Aluminum sulfate (27% aqueous solution) 50 ml sulfuric acid was used to adjust the pH of the used solution to 4.9.

At the time of use, 1 part of water was added to 1 part of the concentrated fixing solution A to prepare a working solution. This working solution was used as a fixing mother liquor and a fixing replenisher. Table 3 shows the obtained results.

[0243]

[Table 3]

[0244] The printing plate making photographic silver halide photographic light-sensitive material 3 from the apparent, such as the present invention Table, even after the photosensitive material was treated in a large amount in the developer replenishing amount of the following photosensitive material 1 m ² per developer 250 ml, high sensitivity It can be seen that the reproducibility of fine dots is good.

Example 3 (Preparation of Silver Halide Emulsion C) An aqueous silver nitrate solution and a mixed aqueous solution of NaCl and KBr were controlled by a double jet so as to obtain a silver halide composition of 70 mol% of silver chloride and 30 mol% of silver bromide. Silver halide grains were grown by mixing. At this time, mixing was performed at 36 ° C., pAg 7.8, and pH 3.0.
During the grain formation, 2 × 10 ⁻⁷ mol of Na ₂ RhCl ₆ was added per mol of silver. After that, desalting was performed with denatured gelatin treated with phenyl isocyanate,
Ossein gelatin was added and redispersed.

The obtained emulsion was an emulsion composed of cubic grains having an average grain size of 0.20 μm and a variation coefficient of 10%. To the emulsion thus obtained was added 50 mer of 4-mercapto-2,3,5,6-tetrafluorobenzoic acid per mole of silver.
g, and 5 mg of chloroauric acid per mole of silver and 0.1 g of silver.
5 mg of sulfur flower was added, and the mixture was chemically ripened at 60 ° C. for 80 minutes under the conditions of pH 5.8 and pAg 7.0. After aging 4-
Methyl-6-hydroxy-1,3,3a, 7-tetrazaindene was added in an amount of 900 mg per mol of silver, and KI was further added.
300 mg was added.

(Preparation of silver halide photographic light-sensitive material for printing plate making) On a support, a gelatin subbing layer of the following formula 15 was prepared so that the amount of gelatin was 0.55 g / m ^2. 16 silver halide emulsion layers having a silver content of 3.4 g / m
^{2. Further} , the coating solution for the lower layer of the protective layer of the following Formulation 17 was prepared so that the amount of gelatin was 0.4 g so that the amount of gelatin became 1.2 g / m ^2.
/ M ^2, and a coating solution for the upper layer of the protective layer having the following formula 18 was further applied thereon so that the amount of gelatin became 0.4 g / m ² .
Coating was applied simultaneously.

On the other side of the undercoat layer, a backing layer of the following formula 19 was formed so that the amount of gelatin was 1.2 g / m ^2, and a backing protective layer of the following formula 20 was formed thereon so that the amount of gelatin was 0.2 g / m ² . The emulsion layer side and the emulsion layer side were simultaneously layer-coated at a speed of 200 m / min by a curtain coating method so that the emulsion layer side became 6 g / m ² , and then cooled and set. , And the sample was obtained by simultaneously drying both sides.

[0249] Formulation 15 (gelatin subbing layer composition) Gelatin 0.55 g / m ² Saponin 56.5 mg / m ² fungicide z 0.5 mg / m ² Solid Disperse Dye table types shown in 4 and quantity Compound T-3 10 mg / m ² formulation 16 (silver halide emulsion layer composition) silver halide emulsion D silver amount 3.4 g / m ² to become as hydrazine compound H-7 7 mg / m ² 4 quaternary onium compound P-54 100 mg / m ² Sensitizing dye Type and amount shown in Table 4 Antifoggant: Adenine 25 mg / m ² Stabilizer: 5-Nitroindazole 10 mg / m ² Polymer latex L1 1.0 g / m ² S-1 1.7 mg / m ² Compound e 45 mg / m ² formulation 17 [emulsion protective layer underlayer composition] gelatin 0.4 g / m ² polymer latex L1 0.5 g / m ² amine compound Na-21 20mg / m ² formulation 18 [emulsion protection Upper Composition] Gelatin 0.4 g / m ² Matting agent: average particle size 3.5μm silica 20 mg / m ² Surfactant b 2 mg / m ² Colloidal silica (average particle size 0.05μm) 0.3g / m ² Hardness Membrane h4 55 mg / m ² Prescription 19 (backing layer composition) Gelatin 1.2 g / m ² Sodium polystyrene sulfonate 20 mg / m ² Colloidal silica (average particle size 0.05 μm) 170 mg / m ² Polymer latex L3 0.3 g / m ² formulation 20 [backing protective layer composition] gelatin 0.6 g / m ² matting agent: polymethyl methacrylate having an average particle size of 4.0 μm 50 mg / m ² dye f1 65 mg / m ² dye f2 15 mg / m ² dye f3 100 mg / m ² hardener h1 100mg / ^{m 2}

[0250]

Embedded image

The obtained sample was brought into close contact with a step wedge,
Exposure to tungsten light of 3200 ° K for 3 seconds, and using a developing solution and a fixing solution having the following composition, under the following conditions (a) and (b), a rapid automatic developing machine GR-26SR (Konica Corporation)
Manufactured).

Further, in order to evaluate the reproducibility of fine halftone dots of the obtained sample, exposure was performed in the same manner as in Example 1, and the above processing was performed. The same evaluation as in Example 1 was performed on the obtained treated sample.

(Developer solution formulation) Working solution 1 liter formulation Diethylenetriaminepentaacetic acid 3.6 g Sodium sulfite 25.0 g Potassium sulfite 38.7 g Potassium bromide 2.5 g Potassium carbonate 40 g 8-Mercaptoadenine 0.07 g Diethylene glycol 50 g 5-methyl -Benzotriazole 0.15 g hydroquinone 23 g 4-methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (dimesone S) 0.8 g 1-phenyl-5-mercaptotetrazole 0.02 g Water and potassium hydroxide were added. Make up to 1 liter / pH 10.4.

(Formulation of fixing solution) Formulation of 1 liter of working solution Ammonium thiosulfate (72.5% W / V aqueous solution) 262 g Water 79 g Sodium sulfite (anhydrous) 22 g Boric acid 9.8 g Sodium acetate trihydrate 38.5 g Tartaric acid 7. 3 g sodium hydroxide 0.25 g aluminum sulfate (aqueous solution having an Al ₂ O ₃ conversion content of 8.1% W / V) 32.9 g glacial acetic acid and sulfuric acid were added to adjust the pH to 4.85, and water was added to add 1 liter. Finished.

Processing conditions (A) Rapid processing (Process) (Temperature) (Time) Development 35 ° C. 15 seconds Fixing 35 ° C. 12 seconds Rinse at room temperature 12 seconds Drying 50 ° C. 17 seconds Total 56 seconds Processing conditions (B) (Process) (Process) (Temperature) (Time) Developing 35 ° C. 30 seconds Fixing 35 ° C. 24 seconds Rinse at room temperature 24 seconds Drying 50 ° C. 34 seconds Total 112 seconds The results obtained are shown in Table 4 below. The photosensitive material is Dry to Dry
It can be seen that even when the rapid processing is performed for 60 seconds or less, the sensitivity is high and the reproducibility of minute halftone dots is good.

[0256]

[Table 4]

Example 4 (Preparation of silver halide emulsion D1) An average thickness of 0.07 mol% of silver chloride and the remainder of silver bromide was obtained by a double jet method.
Silver chlorobromide core particles having a 5 μm average diameter of 0.15 μm were prepared.

At the time of mixing the core particles, K ₃ RuCl ₆ was added in an amount of 8 × 10 ⁻⁸ mol per mol of silver. The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver. The resulting emulsion had a core having an average thickness of 0.10 μm and an average diameter of 0.25 μm /
The emulsion was a shell-type monodisperse (coefficient of variation: 10%) tabular grains of silver chloroiodobromide (80 mol% of silver chloride, 0.2 mol% of silver iodobromide, the balance being silver bromide). Then, Japanese Patent Laid-Open No. 2-2
No. 80139, denatured gelatin (in which the amino group in gelatin is substituted with phenylcarbamyl, for example, Compound G-
Desalting was performed using 8). EAg after desalting is 190 at 50 ° C.
mV.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg to 123 mV, and 5 mg of chloroauric acid and 0.5 mg of sulfur per mole of silver were added, and chemical ripening was performed at a temperature of 60 ° C. until the maximum sensitivity was obtained.

After ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol per mol of silver, and 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ^-4. Mole and gelatin were added.

(Preparation of Silver Halide Emulsion D2) Using a double jet method, silver chloride of 60 mol%, silver iodide of 1.5 mol%, and the balance of silver bromide having an average thickness of 0.05 μm and an average diameter of 0.1 mol.
15 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mole of silver.
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver. The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (70 mol% silver chloride, 0.2 mol% silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. , The remainder being silver bromide). Then, JP-A-2-280139
Described in Japanese Unexamined Patent Publication (Kokai) No. 2-28.
Desalting was performed using Exemplified Compound G-8) described in No. 0139, page 287 (3). The EAg after desalting was 180 mV at 50 ° C.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg was 123 mV, and 7 mg of chloroauric acid and 0.7 mg of sulfur per mole of silver were added, and the mixture was chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained. After aging, 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ⁻⁴ mol, and gelatin was added.

(Preparation of silver halide photographic light-sensitive material for printing plate making) On a PET support, a gelatin subbing layer having the following formulation 21 was coated thereon so that the gelatin amount was 0.55 g / m ^2. The silver halide emulsion layer 1 of the formulation 22 was prepared so that the silver amount was 3.4 g / m ² and the gelatin amount was 1.2 g / m ² , and a gelatin intermediate layer was further formed on the silver halide emulsion layer 1 by the following formulation 2
Coating solution No. 3 so that the gelatin amount becomes 0.6 g / m ^2, and the silver halide emulsion layer 2
Was coated simultaneously so that the amount of silver was 0.3 g / m ² and the amount of gelatin was 0.3 g / m ² , and further a protective layer having the following formulation 25 was formed so that the amount of gelatin was 0.6 g / m ² .

On the other side of the undercoat layer, a backing layer of the following formulation 26 was further coated with a hydrophobic polymer layer of the following formulation 27 so that the amount of gelatin became 1.0 g / m ² , Then, a backing protective layer having the following formulation 28 was coated simultaneously with the emulsion layer so that the amount of gelatin was 0.5 g / m ² , thereby obtaining a sample.

Formulation 21 (Gelatin undercoat layer composition) Gelatin 0.55 g / m ² Solid disperse dye shown in Table 10 Sodium polystyrene sulfonate 10 mg / m ² S-1 (sodium-iso-amyl-n-decyl sulfosuccinate) 0.4 mg / m ² Formulation 22 (Silver halide emulsion layer 1 composition) Silver halide emulsion D1 1.7 mg / m ² sensitizing dye S-1 so that the silver amount becomes 3.4 g / m ^2. Kind and amount Hydrazine compound H-17 10 mg / m ² Amine compound Na-21 10 mg / m ² Compound e 100 mg / m ² Polymer latex L1 5 g / m ² S-1 0.7 mg / m ² 2-mercapto-6-hydroxy purine ^{10mg / m 2 EDTA 50mg / m} 2 formulation 23 (gelatin intermediate layer composition) gelatin ^{0.6g / m 2 S-1 2mg} / m 2 hydroquinone 10 mg / m ² formulation 24 (silver halide emulsion layer 2 composition) Silver halide emulsion D2 compound such that the silver amount ^{0.3g / m 2 T-4 10mg} / m 2 formulation 25 (Emulsion protective layer composition) Gelatin 0 1.6 g / m ² S-1 12 mg / m ² Matting agent: monodisperse silica having an average particle size of 3.5 μm 25 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² surfactant b 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 0.2 g / m ² Hardener h2 130 mg / m ² Formulation 26 (backing layer composition) Gelatin 1.0 g / m ² S-1 5 mg / m ² Polymer latex L30 .3g / m ² colloidal silica (average particle size 0.05 .mu.m) 70 mg / m ² sodium polystyrenesulfonate 20 mg / m ² formulation 27 (hydrophobic polymer layer composition) latex (Mechirume Acrylate: acrylic acid = 97: 3) 1.0g / m 2 hardener h1 6 mg / m ² formulation 28 (backing protective layer) Gelatin 0.5 g / m ² Matting agent: monodisperse polymethylmethacrylate having an average particle diameter of 5μm 50 mg / m ² Sodium di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant b 1 mg / m ² Dye k 40 mg / m ² H (OCH ₂ CH ₂ ) ₆₈ OH 50 mg / m ² Hardener h1 The obtained sample was adhered to a step wedge at 20 mg / m ^{2, and}
Exposed to tungsten light for 3 seconds, and using a developing solution and a fixing solution having the following compositions, an automatic developing machine GR-26 was used to adjust the specific surface area of the developing tank to 8 cm ² / L (the definition of the specific surface area:
No. 77782 (paragraph 0085)) and processed under the following conditions. The tablets were finished after dissolution with a dissolution mixer (1 liter per 25 for both development and fixing). Then, the same evaluation as in Example 1 was performed.

Further, in order to evaluate the reproducibility of minute halftone dots of the obtained sample, exposure was performed in the same manner as in Example 1, and the above processing was performed.

<Processing solution formulation> (1) Starting developer (DS) 224 ml of pure water per liter of working solution DTPA · 5Na 1.00 g (0.002 mol) Sodium sulfite 31.5 g (0.25 mol) Potassium carbonate 41.4 g (0.30 mol) Sodium carbonate 72.4 g (0.70 mol) 8-mercaptoadenine 0.06 g Diethylene glycol 50 g Potassium bromide 4.72 g (0.04 mol) 5-methylbenzotriazole 27 g 1-phenyl-5-mercaptotetrazole 0.03 g Dimezone S 1.1 g Sodium erythorbate (A-1) 35.6 g (0.18 mol) Diethylaminopropanediol 25 g Isoelite P (Shiomizu Port Refining Co., Ltd.) 20 g Using KOH (55% aqueous solution) and pure water, 500 ml (p
H10.45). When using pure water 50
0 ml and 500 ml of the above concentrated liquid are mixed and used. (N
(a ratio: 81.4%) (2) Replenishment developing tablet (D-SR) Preparation of granulated A parts (per liter of liquid used) DTPA · 5Na 1.00 g (0.002 mol) Sulfite 0.25 mol 8-mercaptoadenine 0.06 g 5-methylbenzotriazole 0.27 g potassium bromide 4.72 g (0.04 mol) 1-phenyl-5-mercaptotetrazole 0.03 g dimezone S 1.1 g sodium erysorbate (A-1 35.6 g (0.18 mol) Isoelite P (Saltwater Mineral Refining Co., Ltd.) 20 g D-mannitol (Kao Co., Ltd.) 4 g The above materials were mixed for 30 minutes in a commercially available bantam mill, and then a commercially available stirring product After granulating for 10 minutes at room temperature with a granulator,
The granulated product was dried at 40 ° C. for 2 hours in a fluidized-bed dryer to obtain a granulated product A part.

Preparation of granulated B parts (per liter of liquid used) Carbonate 1.0 mol D-mannitol (Kao Corporation) 5 g Lithium hydroxide 3.4 g The above materials were mixed in a commercially available bantam mill for 30 minutes. After granulating at room temperature for 10 minutes with a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized-bed dryer, and the granulated product B
Got the parts.

The mixture obtained by thoroughly mixing the above-mentioned parts A and B for 10 minutes was used to prepare a mixture of Masina UD ・ DFE30 ・ 4
9. Using a 0 tableting machine (manufactured by Masina Co., Ltd.)
Filling with 83 g, 25 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² .

(3) Starting Fixer (HAF-S) 120 ml of pure water per liter of working solution 140 g ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g sodium sulfite 22 g boric acid 10 g tartaric acid 3 g sodium acetate trihydrate 37. 8 g Acetic acid (90% aqueous solution) 13.5 g Aluminum sulfate / 18-hydrate 18 g Isoelite P (manufactured by Saltwater Port Refining Co., Ltd.) 5 g 500 ml using 50% sulfuric acid aqueous solution and pure water (pH 4.0).
83). When used, 500 ml of pure water and 500 ml of the above concentrated liquid are mixed and used.

(4) Preparation of Replenishment Fixing Tablet Preparation of Granulated A Parts (for 1 L of Working Solution) Ammonium Thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium bisulfite 10 g Sodium acetate 40 g Isoelite P (Salt water refined sugar) 5 g pine flow (trade name: Matsutani Chemical) 8 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator. Granulated material A dried at 40 ° C for 2 hours in a fluidized-bed dryer
Got the parts.

Preparation of granulated B parts (per liter of liquid used) Boric acid 10 g Tartaric acid 3 g Sodium hydrogen sulfate 18 g Aluminum sulfate / 18 hydrate 37 g Pine flow (trade name: Matsutani Chemical) 4 g After mixing for 10 minutes at room temperature with a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized-bed drier to obtain granulated product B.
Got the parts.

The above A parts and B parts were thoroughly mixed for 10 minutes, and the resulting mixture was used as a mixture in Masina UD DFE30.
25 tablets with a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² using a 40 tableting machine at a filling amount of 11.0 g per tablet.

The developers DS and D-SR were sealed in a polyethylene container, stored at 50 ° C. and 80% RH for 7 days, and then opened and used. The oxygen permeability of the container was 30 ml / atm · m ² · day · 25 ° C.

<Automatic developing machine> The automatic developing machine GR-26 was modified so that the specific surface area of the developing tank became 8 cm ² / L (the definition of the specific surface area: described in paragraph No. 0085 of JP-A-7-77782). used. The replenisher should be of the full size (610
× 508 mm) photosensitive material 40 ml of developer per sheet,
40 ml of the fixing solution was replenished. The tablets were replenished after dissolution with a dissolution mixer (finished to 1 liter per 25 for both development and fixing).

Processing Conditions (Step) (Temperature) (Time) Development 35 ° C. for 30 seconds Fixing 34 ° C. for 20 seconds Treatment with swelling agent Room temperature 20 seconds Drying 45 ° C. 20 seconds Line speed (conveying speed) 984 mm / min Result obtained Are shown in Table 5.

[0277]

[Table 5]

As is clear from Table 5, the light-sensitive material of the present invention
Even during the low replenishment process, the sensitivity was high, the reproducibility of fine halftone dots was good, and the enlargement performance was excellent.

[0279]

As has been demonstrated in the examples, according to the present invention, a halogen for printing which is stable in photographic performance even in severe running processing, and has high sensitivity and excellent reproducibility of fine halftone dots in rapid processing. A silver halide photographic material and a processing method thereof were obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03C 5/31 G03C 5/31

Claims (7)

[Claims] 1. A silver halide photographic light-sensitive material having, on one side on a support, a photographic component layer comprising at least one silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer. The emulsion layer contains at least one compound represented by the following general formula (I), and at least one of the photographic constituent layers contains a dye dispersed in a solid state. Silver halide photographic material. Embedded image (Wherein, Z represents an atomic group necessary to form a 5- to 6-membered nitrogen-containing heterocyclic ring. R ₁ represents an alkyl group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic ring. R ₃ represents a 5-membered nitrogen-containing heterocyclic group or a pyrazyl group, L ₁ and L ₂ each represent a methine group, n represents 0,
Represents an integer of 1, 2, 3 or 4. 2. The silver halide photographic light-sensitive material according to claim 1, wherein at least one of the photographic constituent layers contains a water-soluble dye. 3. The dye dispersed in a solid state having a λmax of 5
The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the water-soluble dye has a λmax within a range of 340 to 480 nm. 4. The silver halide photographic light-sensitive material according to claim 1, wherein a hydrazine compound is contained in at least one photographic constituent layer on the side of the silver halide emulsion layer. material. 5. The method according to claim 1, wherein at least one photographic component layer on the side of the silver halide emulsion layer contains an amine compound and / or a quaternary onium compound. The silver halide photographic light-sensitive material as described above. 6. The photosensitive material according to claim 1, which is used for processing the silver halide photographic material according to claim 1.
method for processing a silver halide photographic material, which comprises developing while replenishing the developer replenisher in the range of m ² per 30～250Ml. 7. When a silver halide photographic light-sensitive material is processed by an automatic developing machine including a developing tank, the total processing time from when the leading end of the light-sensitive material is inserted into the automatic developing machine to when it comes out of a drying zone. 7. The method according to claim 6, wherein (Dry to Dry) is from 10 to 60 seconds.