JPH05134337A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain hard photographic characteristics and to suppress fogging in dot picture images even when the photographic sensitive material is treated with a developer of <pH11, by incorporating a hydrazine compd. and a specified compd. CONSTITUTION:This silver halide photographic sensitive material has at least one layer of silver halide emulsion layer on a supporting body, and at least one layer among the emulsion layer and other structural layers contain a hydrazine compd. This photographic sensitive material contains at least one compd. expressed by formula I. In formula I, R1 and R2 are alkyl groups, alkenyl groups, or alkynyl groups, and R1 and R2 may be linked to form a ring. L1 is a bivalent connecting group, R3 is a group containing a quaternary onium salt. Preferably, R3 is a group having a nitrogen-contg. heterocyclic quaternary onium salt, and more preferably, a group containing a pyrridium ring, quinolium ring, acridinium ring, or isoquinolinium ring. The amt. of the compd. above descrmbed is 5X10<-7>-5xX10<-1>mol per one mol of silver halide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material having a silver halide light-sensitive layer on a support, and more particularly to a silver halide photographic light-sensitive material capable of obtaining high contrast.

[0002]

2. Description of the Related Art A photoengraving process includes a process of converting a continuous-tone original into a halftone dot image. In this step, a technique based on infectious development has been used as a photographic technique capable of reproducing an image in ultrahigh contrast.

The lithographic silver halide photographic light-sensitive material used for infectious development has, for example, an average particle diameter of 0.2 μm, a narrow particle distribution and a uniform particle shape, and a high silver chloride content (at least 50 mol). % Or more) of silver chlorobromide emulsion.
By treating this lith-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, an image having high contrast, high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to aerial oxidation, their preservative properties are extremely poor.
Even in continuous use, it is difficult to keep the development quality constant.

There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as disclosed in U.S. Pat.No. 2,419,975, JP-A-51-16623 and JP-A-51-20921, JP-A-56-106244, a hydrazine derivative is contained in a silver halide light-sensitive material. is there.

According to these methods, the sulfite ion concentration can be kept high in the developing solution, and the processing can be carried out in a state where the homeostasis is enhanced.

However, in these methods, in order to fully exhibit the high contrast of the hydrazine derivative, a pH of 11 or higher is used.
It had to be processed with a developer having a pH. pH11
A developer having a high pH as described above is more stable than a lith developer which is susceptible to oxidation of the developing agent when exposed to air, but oxidation of the developing agent often fails to obtain an ultrahigh contrast image.

In order to make up for this drawback, JP-A-63-29751 and European Patents 333,435 and 345,025 disclose silver halide photographic light-sensitive materials containing a contrast-increasing agent capable of increasing the contrast even in a developer having a relatively low pH. Is disclosed.

However, when a silver halide photographic light-sensitive material containing such a contrast-increasing agent is processed with a developer having a pH of less than 11, the contrast is insufficient and satisfactory halftone dot performance cannot be obtained. The current situation.

On the other hand, European Patent No. 364,166 and Japanese Patent Laid-Open Nos. 62-222241, 60-140340, 62-250439 and 62-
No. 280733 describes nucleation accelerators for promoting high contrast, and by adding these compounds to the emulsion layer, halftone dot performance is improved, but sand-like dots are formed in the halftone dots. It has been found that a pin-shaped fog, that is, a black pin, is generated and the quality of a halftone image is deteriorated.

Therefore, there is a demand for a light-sensitive material using an effective contrast-increasing agent and a nucleation accelerator that solves the above problems.

[0012]

The object of the present invention is to achieve pH 11
It is an object of the present invention to provide a silver halide photographic light-sensitive material which has a photographic characteristic of high contrast even when processed with a developing solution of less than less than that, and which suppresses the fog generated in a halftone image and has a good halftone performance.

[0013]

The above objects of the present invention have been achieved by a silver halide photographic light-sensitive material having the following constitution.

(1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine compound in at least one of the emulsion layer and other constituent layers. And a silver halide photographic light-sensitive material containing at least one compound represented by the following general formula [I].

[0015]

[Chemical 6]

In the formula, R ₁ and R ₂ are each an alkyl group,
It represents an alkenyl group or an alkynyl group, and may be linked with R ₁ and R ₂ to form a ring. L ₁ represents a divalent linking group, and R ₃ represents a group containing a quaternary onium salt.

(2) The silver halide photographic light-sensitive material described in (1), wherein R _{3 in} the general formula [I] in (1) is a group containing a nitrogen-containing heterocyclic quaternary onium salt.

[0018] (3) R ₃ is pyridinium ring of the general formula [I] of (1), quinolinium ring, characterized in that it is a group containing acridinium ring or isoquinolinium ring (1)
The described silver halide photographic light-sensitive material.

(4) The silver halide photographic light-sensitive material according to (1), wherein R _{3 in} the general formula [I] of (1) is a group represented by the following general formula [II] or [III]. material.

[0020]

[Chemical 7]

In the formula, R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Represents a group or an amino group. Y represents a carbonyl group or a sulfonyl group, and L ₂ represents an alkylene group or an alkenylene group. X ⁻ represents an anion. Z represents a group of non-metal atoms necessary for forming a pyridinium ring, a quinolinium ring, an acridinium ring or an isoquinolinium ring.

(5) Having at least one silver halide emulsion layer, and containing at least one compound represented by the following general formula [I] in at least one of the emulsion layers or other constituent layers. And at least one of the emulsion layers or other constituent layers,
A silver halide photographic light-sensitive material comprising at least one hydrazine compound represented by the following general formula [IV].

[0023]

[Chemical 8]

In the formula, R ₁ and R ₂ are each an alkyl group,
It represents an alkenyl group or an alkynyl group, and may be linked with R ₁ and R ₂ to form a ring. L ₁ represents a divalent linking group,
R ₃ represents a group containing a quaternary onium salt.

[0025]

[Chemical 9]

In the formula, R ₆ represents an aryl group or a heterocyclic group, R ₇ represents a —N (R ₈ ) (R ₉ ) group or a —O—R ₁₀ group (wherein R ₈ and R ₉ are Each represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocyclic oxy group, R ₁₀ Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.) A ₁ and A ₂ both represent a hydrogen atom or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group or an oxalyl group. ..

(6) The silver halide photographic light-sensitive material according to (5), wherein R _{3 in} the general formula [I] in (5) is a group containing a nitrogen-containing heterocyclic quaternary onium salt.

(7) R ₃ of the general formula [I] of (5) is a group containing a pyridinium ring, a quinolinium ring, an acridinium ring or an isoquinolinium ring (5)
The described silver halide photographic light-sensitive material.

(8) The silver halide photographic light-sensitive material according to (5), wherein R _{3 in} the general formula [I] of (5) is a group represented by the following general formula [II] or [III]. material.

[0030]

[Chemical 10]

In the formula, R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Represents a group or an amino group. Y represents a carbonyl group or a sulfonyl group, L ₂
Represents an alkylene group or an alkenylene group. X ⁻ represents an anion. Z represents an atomic group necessary for forming a pyridinium ring, a quinolinium ring, an acridinium ring or an isoquinolinium ring.

The present invention will be described in detail below.

In the general formula [I], the groups represented by R ₁ and R ₂ are an alkyl group (eg, methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl, etc.) and an alkenyl group (eg, allyl, Butenyl, etc.), an alkynyl group (eg, propargyl, butynyl, etc.) and the like. These are further substituents (for example, aryl group, alkoxy group, aryloxy group, hydroxyl group, alkylthio group, arylthio group, sulfonamide group, carbonamido group, ureido group, sulfamoyl group, carbamoyl group, amino group, alkoxycarbonyl group, R may be substituted with R)
₁ and R ₂ are linked to form a ring (eg piperidine, piperazine,
Morpholine, pyrrolidine, etc.) may also be formed. As R ₁ and R ₂ , an alkyl group is preferable, and an alkyl group having 2 to 20 carbon atoms is most preferable.

L ₁ represents a divalent linking group, preferably a group having an optionally substituted alkylene group (provided that the alkylene group is bonded to a —N (R ₁ ) (R ₂ ) group).

Among the divalent linking groups represented by L ₁ , more preferred are alkylene groups having 1 to 10 carbon atoms,
Alternatively, a group composed of a combination of an alkylene group having 1 to 10 carbon atoms and a group shown below can be mentioned.

[0036]

[Chemical 11]

In the general formula [I], R ₃ represents a group containing a quaternary onium salt, and examples of the quaternary onium salt include a quaternary onium salt of a nitrogen atom or a phosphorus atom. Onium salts are preferred.

More preferred as R ₃ is a group containing a nitrogen-containing heterocyclic quaternary onium salt (for example, a 5- or 6-membered heterocyclic ring and a condensed ring thereof with benzene, etc.), and more preferably a pyridinium ring. And a group containing a quinolinium ring, an acridinium ring, or an isoquinolinium ring.

The group containing a quaternary onium salt in R ₃ is preferably a monovalent group having a bond by removing one hydrogen atom from the structure represented by the following general formula [V].

[0040]

[Chemical 12]

In the formula, Z represents an atomic group necessary for forming a pyridinium ring, a quinolinium ring, an acridinium ring or an isoquinolinium ring, L ₂ represents an alkylene group or an alkenylene group, and X ⁻ represents an anion. Y'represents a carbonyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a thiocarbonyl group, a thiocarbamoyl group, an oxalyl group, an iminomethylene group, a phosphoryl group or an oxamoyl group, and L ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, Alkynyl group, aryl group, heterocyclic group, hydroxyl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, heterocyclic oxy group, amino group, monosubstituted amino group, disubstituted amino group, hydrazino group, mono It represents a substituted hydrazino group, a di-substituted hydrazino group or a tri-substituted hydrazino group.

Particularly preferred R ₃ represents a group represented by the following general formula [II] or [III].

[0043]

[Chemical 13]

In the general formulas [II] and [III], R ₄ is a hydrogen atom, an alkyl group (eg methyl, ethyl, octyl, benzyl etc.), an alkenyl group (eg allyl, butenyl etc.), an alkynyl group (eg propargyl etc.). ), An aryl group (eg, phenyl, naphthyl, etc.), or a heterocyclic group (eg, pyridyl, etc.). R ₄ is preferably a hydrogen atom, an alkyl group or an aryl group, and most preferably a hydrogen atom.

In the general formulas [II] and [III], Y represents a carbonyl group or a sulfonyl group, L ₂ represents an alkylene group (eg methylene, ethylene, propylene, butylene) or an alkenylene group (eg propenylene, butenylene). Of these, L ₂ is preferably an alkylene group having 1 to 4 carbon atoms, and a methylene group and an ethylene group are most preferable.

Examples of the anion represented by X ⁻ in the general formulas [II] and [III] include halogen ion (eg, chlorine ion, bromine ion, iodine ion), carboxylate ion (eg, acetate, oxalate, Fumarate, benzoate, etc.), sulfonate ion (eg P-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, butanesulfonate,
Benzene sulfonate, etc.), sulfate ion, perchlorate ion, carbonate ion, nitrate ion, boron tetrafluoride ion,
Examples thereof include thiocyan ion.

In the general formula [III], R ₅ is a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 30), an alkenyl group (eg allyl, butynyl etc.), an alkynyl group (eg propargyl, butynyl etc.), aryl. Group (eg phenyl, naphthyl etc.), heterocyclic group (eg pyridyl, 2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl etc.) or amino group (eg dimethylamino,
Dibenzylamino, methylphenylamino, etc.).

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

[0049]

[Chemical 14]

[0050]

[Chemical 15]

[0051]

[Chemical 16]

[0052]

[Chemical 17]

[0053]

[Chemical 18]

[0054]

[Chemical 19]

Next, specific synthesis examples of the compound represented by the general formula [I] will be shown.

Synthesis of Compound I-2 Compound I-2 can be synthesized according to the following synthetic scheme.

[0057]

[Chemical 20]

Synthesis of Compound I-7 Compound I-7 can be synthesized according to the following synthetic scheme.

[0059]

[Chemical 21]

Synthesis of Compound I-15 Compound I-15 can be synthesized according to the following synthetic scheme.

[0061]

[Chemical formula 22]

Synthesis of Compound I-18 Compound I-18 can be synthesized according to the following synthetic scheme.

[0063]

[Chemical formula 23]

The content of the compound represented by the general formula [I] of the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
It is preferably in the molar range.

In the present invention, when the compound represented by the general formula [I] is contained in the photographic light-sensitive material, it is contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

Here, the compound of general formula [I] may be contained in the same layer as the hydrazine compound or in a different layer.

The hydrazine compound used in the present invention is preferably one represented by the following general formula [VI].

[0068]

[Chemical formula 24]

In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, and B represents an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or aryloxycarbonyl group or a sulfamoyl group. Group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, an oxalyl group, or a heterocyclic group,
₁ and A ₂ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group.

However, B, A ₂ and the nitrogen atom to which they bind are a partial structure of hydrazone.

[0071]

[Chemical 25]

May be formed.

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

The aliphatic group represented by A preferably has 1 to 30 carbon atoms, and is particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Examples thereof include a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, and a benzyl group. 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, acylamino group, ureido group, etc.).

The aromatic group represented by A in the general formula [VI] is preferably a monocyclic or condensed-ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A in the general formula [VI] is preferably a monocyclic or condensed ring heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, for example, a pyrrolidine ring, Examples thereof include 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 is an aryl group and a heterocyclic group.

The aryl group and heterocyclic group of A may have a substituent. Representative substituents are an alkyl group (preferably having a carbon number of 1 to 20), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl portion having a carbon number of 1 to 3), an alkoxy group (preferably Alkyl moiety having 1 to 20 carbon atoms, substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms or alkylidene group), acylamino group (preferably having 1 to 40 carbon atoms) ), Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms)
Group), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), a hydroxyl group, a phosphoamide group (preferably having 1 to 40 carbon atoms), and the like.

B is specifically an acyl group (eg formyl, acetyl, propionyl, trifluoroacetyl,
Methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl etc.), alkylsulfonyl group (eg methanesulfonyl, 2-chloroethanesulfonyl etc.), arylsulfonyl group (eg benzenesulfonyl etc.) ), An alkylsulfinyl group (eg methanesulfinyl etc.), an arylsulfinyl group (benzenesulfinyl etc.), a carbamoyl group (eg methylcarbamoyl, phenylcarbamoyl etc.), an alkoxycarbonyl group (eg methoxycarbonyl, methoxyethoxycarbonyl etc.), aryloxy Carbonyl group (eg phenoxycarbonyl etc.), sulfamoyl group (eg dimethylsulfamoyl etc.), sulfinamoyl group (eg methylsulfur) Finamoyl etc.), an alkoxysulfonyl group (eg methoxysulfonyl etc.), a thioacyl group (eg methylthiocarbonyl etc.), a thiocarbamoyl group (eg methylthiocarbamoyl etc.), an oxalyl group (discussed below with respect to general formula [IV]), or a heterocyclic group ( For example, a pyridine ring, a pyridinium ring, etc.) is represented.

B in the general formula [VI] represents A ₂ and the nitrogen atom to which they are attached.

[0081]

[Chemical formula 26]

May be formed.

R'represents an alkyl group, an aryl group or a heterocyclic group, and R "represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

As B, an acyl group or an oxalyl group is particularly preferable.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Etoxaryl etc.).

Among the hydrazine compounds used in the present invention, particularly preferred are the compounds represented by the following general formula [IV].

[0087]

[Chemical 27]

In the formula, R ₆ represents an aryl group or a heterocyclic group, and R ₇ represents —N (R ₈ ) (R ₉ ) or —OR ₁₀ .

R ₈ and R ₉ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Or a heterocyclic oxy group, R ₁₀ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Alternatively, it represents a heterocyclic group. A ₁ and A ₂ are A in the general formula [VI].
₁ and A ₂ each represent the same group.

The general formula [IV] will be described in more detail.

The aryl group represented by R ₆ is preferably a monocyclic or condensed ring, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by R ₆ is preferably a monocyclic or condensed ring 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen. Examples thereof include a ring, a quinoline ring, a pyrimidine ring, a thiophene ring, a furan ring, a thiazole ring and a benzothiazole ring.

Preferred as R ₆ is an aryl group, and a benzene ring is most preferred.

[0094] A ₁ and A ₂ of the general formula (VI) A ₁ and A ₂
And a hydrogen atom are most preferred.

R ₇ represents --N (R ₈ ) (R ₉ ) or --OR ₁₀ , wherein R ₈ and R ₉ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl, etc.), an alkenyl group ( Allyl, butenyl), alkynyl groups (propargyl, butynyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl, quinuclidinyl) , N, N'-diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl, etc.), amino groups (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl groups, alkoxy groups (methoxy, ethoxy, etc.) ), Alkenyloxy group (allyloxy, etc.), alkynyloxy group (propargyloxy, etc.), aryloxy group (phenoxy, etc.), or heterocyclic oxy group (pyridyloxy, etc.) The stands, together with the nitrogen atom by R ₈ and R ₉ may form a ring (piperidine, morpholine). R ₁₀ is a hydrogen atom, an alkyl group (methyl,
Ethyl, methoxyethyl, hydroxyethyl, etc.), alkenyl groups (allyl, butenyl, etc.), alkynyl groups (propargyl, butynyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,2,6,6-tetra) Methylpiperidinyl, N-methylpiperidinyl, pyridyl, etc.).

Specific examples of the compound represented by the general formula [VI] are shown below. However, the present invention is not limited to these.

[0097]

[Chemical 28]

[0098]

[Chemical 29]

[0099]

[Chemical 30]

[0100]

[Chemical 31]

[0101]

[Chemical 32]

The synthetic method of the compound represented by the general formula [VI] used in the present invention is described in JP-A Nos. 62-180361 and 62-178246.
No. 63-234245, No. 63-234246, No. 64-90439, JP-A No. 2-37, No. 2-841, No. 2-947, No. 2-120736, No.
2-230233, 3-125134, U.S. Patent 4,686,167,
4,988,604, 4,994,365, European patent 253,665
No. 333,435, etc. can be referred to.

The content of the compound represented by the general formula [VI] of the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
It is preferably in the molar range.

In the present invention, when the compound represented by the general formula [VI] is contained in the photographic light-sensitive material, it is contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support. The silver halide emulsion can be coated directly on the support or can be coated through another layer such as a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer as a protective layer may be coated on the emulsion layer. Further, the silver halide emulsion layers may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between each silver halide emulsion layer. That is, an intermediate layer made of a hydrophilic colloid may be provided if necessary. or,
A non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer and a backing layer may be provided between the silver halide emulsion layer and the protective layer.

Next, the silver halide used in the silver halide photographic light-sensitive material of the present invention will be described. The silver halide is silver chloroiodobromide or silver iodobromide containing 4 mol% or less of silver iodide, preferably 3 mol% or less. The average grain size of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, but 0.10 to 0.
A thickness of 40 μm is preferable.

The grain size distribution of the silver halide grains used in the present invention is arbitrary, but the monodispersity value defined below is from 1 to 20.
% Is preferable, and more preferably 5 to 15%.

Here, the monodispersity is defined as a value (%) obtained by multiplying a value (variation coefficient) obtained by dividing the standard deviation of particle diameter by the average particle diameter by 100. For the sake of convenience, the grain size of silver halide grains is represented by the edge length in the case of cubic grains, and the other grains (octahedral, tetradecahedron, etc.) are calculated by the square root of the projected area.

When the present invention is carried out, for example, as the grains of silver halide, those of the type having a multi-layered laminated structure of at least two layers can be used. For example, silver iodobromide in the core part and shell part can be used. A silver iodobromide grain having silver bromide can be used. At this time, iodine can be contained in any layer within 5 mol%.

The silver halide grains used in the silver halide emulsion of the present invention include a cadmium salt, a zinc salt, a lead salt, a thallium salt and an iridium salt (including a complex salt) in the process of forming and / or growing the grain. ), A rhodium salt (including a complex salt) and an iron salt (including a complex salt), at least one of which can be added with a metal ion to allow these metal elements to be contained inside and / or on the surface of the particle. Further, the reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere.

Furthermore, the silver halide can be sensitized with various chemical sensitizers. Examples of the sensitizer include active gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiacinate, etc.), selenium sensitizer (N, N-dimethylselenourea,
Selenoureas, etc.), reduction sensitizers (triethylenetetramine, stannous chloride, etc.), potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium Various noble metal sensitizers represented by chloroplatinate, sodium chloroparadite and the like can be used alone or in combination of two or more. When a gold sensitizer is used, rodan ammon can be used as an auxiliary agent.

The silver halide grain used in the present invention can be preferably applied to a grain having a surface sensitivity higher than the internal sensitivity, that is, a silver halide grain giving a so-called negative image, and therefore it should be treated with the above chemical sensitizer. Can improve the performance.

The silver halide emulsion used in the present invention includes mercaptos (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole), benzotriazoles (5-bromobenzotriazole, 5-methylbenzotriazole). ), Benzimidazoles (6-nitrobenzimidazole) and the like can be used to stabilize or suppress fogging.

The photosensitive silver halide emulsion layer or its adjacent layer is provided with Research Disclous for the purpose of increasing sensitivity, increasing contrast or promoting development.
ure) 17463 Nos. ΧΧΙ items B to D can be added.

Further, it is preferable to add a compound represented by the following general formula [P].

[0116] Formula (P) _{R 11 -0- (CH 2 CH 2} O) n H [wherein R ₁₁ represents an aromatic ring having a hydrogen atom or unsubstituted or substituted groups,, n is 10 to 200 Represents an integer up to. Specific examples of the compound represented by the general formula [P] include Japanese Patent Application No.
2-160939, pages 94 to 96, P-1 to P-17. Of these, those having a molecular weight of 1500 or more are preferable,
It is not limited to these. These compounds are commercially available and can be easily obtained. These compounds are preferably added in an amount of 0.01 to 4.0 mol, and more preferably 0.02 to 2 mol, per mol of silver halide.
Also, two or more compounds having different values of n may be included. A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like can be added to the silver halide emulsion used in the present invention.

When the compounds of the general formulas [I] and [VI] according to the present invention are added to the hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer,
Hydrophilic colloids other than gelatin can also be used.
Each of these hydrophilic binders has 10
It is preferable to apply the coating at a rate of g / m ² or less.

Examples of the support usable in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester film such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

To develop the silver halide photographic light-sensitive material of the present invention, the following developing agents are used, for example.

Typical examples of HO- (CH = CH) n-OH type developing agents include hydroquinone, and catechol and pyrogallol.

As the HO- (CH = CH) n-NH ₂ type developer, ortho and para aminophenols or aminopyrazolones are typical ones, and N-methyl-p-aminophenol and N-β are used. -Hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like.

Heterocyclic type developers include 1-phenyl-3
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl
Examples thereof include 3-pyrazolidones such as 3-pyrazolidone.

Others, TH. James The Theory of the Photographic Process 4th Edition (The T
heory of the Photographic Process, Fourth Edition)
Pages 291-334 and Journal of the American
Chemical Society (Journal of the American Chem
The developer described in Vol. 73, p. 3,100 (1951), can be effectively used in the present invention. These developers may be used alone or in combination of two or more kinds, but it is preferable to use two or more kinds in combination.

Further, even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the light-sensitive material of the present invention, the effect of the present invention is not impaired. Further, hydroxylamine or a hydrazide compound may be used as a preservative. In addition, it is possible to adjust the pH with a caustic alkali, an alkali carbonate, an amine or the like as used in a general black and white developer and to have a buffer function.

The developer used in the present invention is characterized in that a developer having a pH of less than 11 can be used. In addition, the developer includes an inorganic development inhibitor such as promkari and an organic development inhibitor such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine, 1-phenyl-5-mercaptotetrazole, and ethylenediamine-4. Metal ion capture agents such as acetic acid, methanol, ethanol,
Benzyl alcohol, development accelerators such as polyalkylene oxides, sodium alkylaryl sulfonates, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, sodium sulfate It is optional to add an ionic strength adjusting agent or the like.

In the developer used in the present invention, alkanolamines such as diethanolamine and triethanolamine and diethylene glycol as organic solvents,
Glycols such as triethylene glycol and alkylamino alcohols such as diethylamino-1,2-propanediol and butylaminopropanol may be contained.

[0127]

EXAMPLES Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

Example 1 (Preparation of Silver Halide Emulsion A) A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by the simultaneous mixing method. During this mixing, K ₂ IrCl ₆ was added at 8 × 10 ^-7 mol per mol of silver. The obtained emulsion was an emulsion composed of cubic monodisperse grains (coefficient of variation 9.5%) having an average grain size of 0.20 μm.
After adding 6.5 ml of 1% potassium iodide aqueous solution per mol of silver to this emulsion, modified gelatin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added to carry out Japanese Patent Application No. 1-180787. It was washed with water and desalted in the same manner as in Example 1. PA at 40 ° C after desalting
g was 8.0. Further, at the time of redispersion, a mixture of the following compounds [A], [B] and [C] was added as an antibacterial agent.

[0129]

[Chemical 33]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) on the undercoat layer, a silver halide emulsion layer gelatin amount 2.0 g / m ² of the following formulation (1) was coated as silver amount is 3.2 g / m ^2, further following formulation thereon ( Apply the emulsion protective layer of 2) so that the amount of gelatin will be 1.0 g / m ² , and
On the other undercoat layer on the opposite side, a backing layer of the following formulation (3) was applied so that the amount of gelatin would be 2.4 g / m ^2, and then a backing of the following formulation (4) was applied. Sample 1 to 28 by coating the protective layer so that the amount of gelatin is 1.0g / m ^2.
It was created.

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.0 g / m ² Silver halide emulsion A (silver amount) 3.2 g / m ² Sensitizing dye: SD-1 8.0 mg / m ² Sensitizing dye : SD-2 0.2 mg / m ² Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: Adenine 10 mg / m ² Surfactant: Saponin 0.1 g / m ² Surfactant: S-1 8.0 mg / m ² Hydrazine derivative according to the present invention [VI] 30 mg / m ² Nucleation promoting compound according to the present invention [I] 100 mg / m ² Latex polymer: LX 1.0 g / m ² Polyethylene glycol (molecular weight 4000) 0.1 g / m ² Hardener: H-1 60 mg / m ² Formulation (2) (Emulsion protective layer composition) Gelatin 1.0 g / m ² Surfactant: S-2 10 mg / m ² matting agent: silica having an average particle size of 3.5 μm 3 mg / m ² hardening agent: formalin 30 mg / m ² surfactant: S-3 10 mg / m ² formulation (3) (backing layer composition) D-1 30 mg / m ² D-2 75mg / m ² D-3 30mg / m ² Gelatin 2.4g / m ² Surfactant: S-1 6.0 mg / m ² Surfactant: Saponin 0.1 g / m ² Formulation (4) (Backing protective layer composition) Gelatin 1 g / m ² Matting agent: Polymethyl with average particle size 3.0-5.0 μm Methacrylate 15 mg / m ² Surfactant: S-2 10 mg / m ² Hardener: Glyoxal 25 mg / m ² Hardener: H-1 35 mg / m ^{2 For} prescription (1), (2) and (3) The compounds that were used are shown below.

[0132]

[Chemical 34]

[0133]

[Chemical 35]

The sample thus obtained was subjected to a halftone dot quality test by the following method.

(Dot quality test method) A stepped wedge was partially provided with a return mesh screen (150 lines / inch) having a dot area of 50%, and a sample was brought into close contact with the screen and exposed for 5 seconds with a xenon light source. This sample was developed with an automatic processor for rapid processing in which the following developer and fixer were added under the following conditions, and the halftone quality of the sample was observed with a magnifying glass of 100 times. The item is ranked as "5", and the following "4",
"3", "2", "1", and the rank is sequentially lowered to 5
Graded. Incidentally, the ranks "1" and "2" are levels that are not practically preferable.

The fog in the halftone dots is also evaluated in the same manner, and the one having no black pin in the halftone dot is set to the highest rank "5", and the black pin occurrence in the halftone dot is determined. The evaluation was performed by sequentially lowering the rank to “4”, “3”, “2”, and “1”.

Incidentally, in the ranks "1" and "2", the black pin is large, which is a level unfavorable for practical use.

Developer Formulation Developer 1 Developer 2 Ethylenediaminetetraacetic acid sodium salt 1g 1g Sodium sulfite 60g 60g Trisodium phosphate (decahydrate) 75g 75g Hydroquinone 22.5g 22.5g Sodium hydroxide 8g 8g Sodium bromide 3g 3g 5 -Methylbenzotriazole 0.25g 0.25g 1-Phenyl-5-mercaptotetrazole 0.08g 0.08g Metol 0.25g 0.25g Add water 1 liter 1 liter Adjust pH with sodium hydroxide pH = 10.8 pH = 10.5 Fixer formulation (Composition A) Ammonium thiosulfate (72.5w / v% aqueous solution) 240ml Sodium sulfite 17g Sodium acetate / trihydrate 6.5g Boric acid 6g Sodium citrate / dihydrate 2g (Composition B) Pure water (ion exchange water) 17ml Sulfuric acid ( 50% w / w aqueous solution) 4.7 g Aluminum sulphate 26.5 g (Aqueous solution having an Al ₂ O ₃ conversion content of 8.1 w / w%) When using the fixer, dissolve the above composition A and composition B in 500 ml of water in this order, and Li It was used after finishing it in torr. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Current image 40 ° C 15 seconds Settlement 35 ° C 15 seconds Water wash 30 ° C 10 seconds Dry 50 ° C 10 seconds Formula (1) The following compounds (a) and (b) were added as comparative compounds of the nucleation promoting compound of the present invention added to the silver halide emulsion layer in the above.

[0140]

[Chemical 36]

The results of the quality test are shown in Table 1.

[0142]

[Table 1]

As is clear from Table 1, the samples according to the present invention have good halftone dot quality and black pins for comparison.

[0144]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having a high contrast and little fog even when it is processed with a low pH developer having a pH of less than 11.

Claims (8)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and containing a hydrazine compound in at least one of said emulsion layers or other constituent layers, wherein ] A silver halide photographic light-sensitive material comprising at least one compound represented by [Chemical 1] [In the formula, R ₁ and R ₂ each represent an alkyl group, an alkenyl group or an alkynyl group, and R ₁ and R ₂ may be linked to form a ring. L ₁ represents a divalent linking group, and R ₃ represents a group containing a quaternary onium salt. ] 2. The silver halide photographic light-sensitive material according to claim 1, wherein R _{3 in} the general formula [I] in claim 1 is a group containing a nitrogen-containing heterocyclic quaternary onium salt. 3. A process according to claim, characterized in that the R ₃ in the general formula of claim 1 (I) a pyridinium ring, quinolinium ring, a group containing acridinium ring or isoquinolinium ring 1
The described silver halide photographic light-sensitive material. 4. The silver halide photographic light-sensitive material according to claim 1, wherein R _{3 in} the general formula [I] is a group represented by the following general formula [II] or [III]. .. [Chemical 2] [In the formula, R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group,
An alkynyl group, an aryl group or a heterocyclic group, R ₅
Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or an amino group. Y represents a carbonyl group or a sulfonyl group, and L ₂ represents an alkylene group or an alkenylene group. X ⁻ represents an anion. Z represents a group of non-metal atoms necessary for forming a pyridinium ring, a quinolinium ring, an acridinium ring or an isoquinolinium ring. ] 5. A method comprising at least one silver halide emulsion layer, wherein at least one of the emulsion layers or other constituent layers contains at least one compound represented by the following general formula [I]. And a silver halide photographic light-sensitive material characterized by containing at least one hydrazine compound represented by the following general formula (IV) in at least one of the emulsion layer and other constituent layers. [Chemical 3] [In the formula, R ₁ and R ₂ each represent an alkyl group, an alkenyl group or an alkynyl group, and R ₁ and R ₂ may be linked to form a ring. L ₁ represents a divalent linking group, and R ₃ represents a group containing a quaternary onium salt. ] [Chemical 4] [In the formula, R ₆ represents an aryl group or a heterocyclic group, R ₇ represents a —N (R ₈ ) (R ₉ ) group or an —O—R ₁₀ group (wherein R ₈ and R ₉ are each hydrogen. Atom, alkyl group, alkenyl group,
An alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocyclic oxy group, R ₁₀ represents a hydrogen atom, an alkyl group, an alkenyl group, It represents an alkynyl group, an aryl group or a heterocyclic group. ) A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is an acyl group, a sulfonyl or an oxalyl group. ] 6. The silver halide photographic light-sensitive material according to claim 5, wherein R _{3 in} the general formula [I] in claim 5 is a group containing a nitrogen-containing heterocyclic quaternary onium salt. 7. The group represented by general formula [I] in claim 5 wherein R ₃ is a group containing a pyridinium ring, a quinolinium ring, an acridinium ring or an isoquinolinium ring.
The described silver halide photographic light-sensitive material. 8. The silver halide photographic light-sensitive material according to claim 5, wherein R _{3 in} the general formula [I] is a group represented by the following general formula [II] or [III]. .. [Chemical 5] [In the formula, R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group,
An alkynyl group, an aryl group or a heterocyclic group, R ₅
Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or an amino group. Y
Represents a carbonyl group or a sulfonyl group, and L ₂ represents an alkylene group or an alkenyl group. X ⁻ represents an anion. Z represents an atomic group necessary for forming a pyridinium ring, a quinolinium ring, an acridinium ring or an isoquinolinium ring. ]