JP3041735B2 - Silver halide photographic material - Google Patents

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 image. In this process, a technique based on infectious development has been used as a photographic technique capable of reproducing an image having a super-high contrast.

A 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, uniform particle shape, and a high silver chloride content (at least 50 mol. % Or more) silver chlorobromide emulsion.
By processing this lithographic silver halide photographic material with an alkaline hydroquinone developer having a low sulfite ion concentration, an image with high contrast, high sharpness and high resolution can be obtained.

However, since these squirrel-type developers are susceptible to air oxidation, they have extremely poor preservative properties.
Even during continuous use, it is difficult to keep development quality constant.

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

According to these methods, the sulfite ion concentration in the developing solution can be kept high, and the processing can be performed with the preservation enhanced.

However, in these methods, the hydrazine derivative is required to have a pH of 11 or more in order to sufficiently exhibit high contrast.
It had to be processed with a developer having a pH. pH11
A developer having the above-mentioned high pH is more stable than a squirrel-type developer in which the developing agent is easily oxidized when exposed to air. However, due to oxidation of the developing agent, a super-high contrast image is often not obtained.

In order to make up for this disadvantage, JP-A-63-29751 and EP-A-333,435 and EP-A-345,025 disclose a silver halide photographic light-sensitive material containing a high contrast agent which makes high contrast even in a developer having a relatively low pH. Is disclosed.

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

On the other hand, European Patent Nos. 364,166 and JP-A Nos. 62-222241, 60-140340, 62-250439, 62-222
280733 and the like describe a nucleation accelerator for accelerating the contrast enhancement, and by adding these compounds to the emulsion layer, the dot performance is improved, but the It has been found that a pin-shaped fog, a so-called black pin, is generated, which deteriorates the quality of a halftone dot image.

Therefore, there is a demand for a light-sensitive material using an effective high contrast agent and a nucleation accelerator which has solved the above problems.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to adjust the pH to 11
An object of the present invention is to provide a silver halide photographic light-sensitive material which has high photographic characteristics even when processed with a developing solution of less than 1, and has good halftone performance by suppressing fog generated in a halftone image.

[0013]

The above object of the present invention has been attained by a silver halide photographic 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 above-mentioned emulsion layers or other constituent layers. A silver halide photographic material comprising at least one compound represented by the formula [I].

[0015]

Embedded image

Wherein R ₁ and R ₂ are each an alkyl group,
It represents an alkenyl group or an alkynyl group, and R ₁ and R ₂ may form a ring. R ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. L ₁ represents a divalent linking group, and X is

[0017]

Embedded image

## EQU1 ##

L ₂ represents an alkylene group or an alkenylene group, and Y represents a carbonyl group, a sulfonyl group, a sulfoxy group, or a phosphoryl group. L ₃ is

[0020]

Embedded image

Represents the following.

Z ₁ , Z ₂ and Z ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. n represents 0 or 1.

(2) The silver halide photographic material as described in (1), wherein the hydrazine compound as described in (1) is a compound represented by the following general formula [II].

[0024]

Embedded image

In the formula, R ₄ represents an aryl group or a heterocyclic group, and R ₅ is

[0026]

Embedded image

Represents the following. R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Represents 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, and R ₈ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group. Or a heterocyclic group. A ₁ and A _{2 each} represent a hydrogen atom or one of them represents a hydrogen atom and the other represents an acyl group, a sulfonyl group or an oxalyl group.

Hereinafter, the present invention will be described in detail.

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), alkynyl group (eg, propargyl, butynyl, etc.)
And the like. These further have a substituent (for example, an aryl group, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group, a sulfonamide group, a carbonamide group, a ureido group, a sulfamoyl group, a carbamoyl group, an amino group, an alkoxycarbonyl group, Carboxyl group), and R ₁
And a ring linked by R ₂ (eg, piperidine, piperazine,
Morpholine, pyrrolidine, etc.). As R ₁ and R ₂ , an alkyl group is preferable, and an alkyl group having 2 to 20 carbon atoms is most preferable.

Examples of the group represented by R ₃ include an alkyl group (eg, methyl, ethyl, propyl, t-butyl, octyl, dodecyl, etc.), an alkenyl group (eg, allyl, butenyl, etc.), and an alkynyl group (eg, propargyl, butynyl, etc.). ), An aryl group (eg, phenyl, naphthyl, etc.), or a heterocyclic group (eg, thienyl, furyl, pyridyl, etc.)
And the like.

These may be further substituted with the same substituents as those described for R ₁ and R ₂ .

L ₁ is a divalent linking group, preferably a group having an optionally substituted alkylene group (provided that the alkylene group is

[0033]

Embedded image

Which is combined with

Of the divalent linking groups represented by L ₁ , more preferred are alkylene groups having 1 to 10 carbon atoms,
Alternatively, a group consisting of a combination of an alkylene group having 1 to 10 carbon atoms and the following groups may be mentioned.

[0036]

Embedded image

X is

[0038]

Embedded image

Represents

L ₂ represents an alkylene group (eg, methylene, ethylene, propylene, butylene, etc.) or an alkenylene group (eg, propenylene, butenylene, etc.), preferably an alkylene group having 1 to 4 carbon atoms, more preferably a methylene group And an ethylene group. Y represents a carbonyl group, a sulfonyl group, a sulfoxy group, or a phosphoryl group, preferably a carbonyl group or a sulfonyl group. L ₃ is

[0041]

Embedded image

Represents the following.

Z ₁ , Z ₂ and Z ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Z ₁ , Z ₂ and Z ₃ are each preferably a hydrogen atom, an alkyl group or an aryl group.

N represents 0 or 1.

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

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

Next, a method for obtaining the compound represented by the general formula [I] and specific synthesis examples will be described.

Method for Obtaining Compound I-2 Compound I-2 was commercially available from BADER (catalog number:
S42233-9).

Method for Obtaining Compound I-4 Compound I-4 was commercially available from BADER (catalog number:
S42128-6).

Synthesis of Compound I-3 Compound I-3 can be synthesized according to the following synthesis method.

[0060]

Embedded image

7 g of 1-naphthylamine and 280 ml of acetic acid were mixed, and 4.64 g of pyridine was added thereto. While cooling this solution in an ice water bath, 7.21 g of chloroacetyl chloride was added dropwise, and the mixture was stirred at room temperature for 30 minutes. After adding 200 ml of water and stirring for 5 minutes, the precipitated crystals were collected by filtration. The crude crystals were dispersed in 100 ml of isopropyl ether for 10 minutes and then filtered to obtain a compound (A).

6.14 g (57% yield) White crystals 3.87 g of diethylaminoethanethiol monohydrochloride and 100 ml of ethanol were mixed, 1.82 g of sodium hydroxide was added with stirring at room temperature, and the mixture was stirred for 20 minutes. To this was added 5 g of (A) synthesized above, and the mixture was stirred at an internal temperature of 50 ° C. for 2 hours. To this was added 100 ml of an aqueous solution of sodium hydroxide having a pH of 13, and the mixture was extracted three times with 50 ml of isopropyl ether. The obtained organic layer was extracted four times with 200 ml of an aqueous hydrochloric acid solution of pH = 1,
The aqueous layer was adjusted to pH = 13 with sodium hydroxide and extracted four times with 200 ml of isopropyl ether. Organic layer with water 500
After washing twice with ml, the solvent was distilled off, and the obtained oily substance was subjected to silica gel column chromatography (Wakogel C-200,
Purification with chloroform-methanol (10/1) yielded compound I-3.

Yield: 5.59 g (77% yield) Synthesis of white amorphous solid compound I-11 Compound I-11 can be synthesized according to the following synthesis scheme.

[0064]

Embedded image

Synthesis of Compound I-12 Compound I-12 can be synthesized according to the following synthesis scheme.

[0066]

Embedded image

Synthesis of Compound I-17 Compound I-17 can be synthesized according to the following synthesis scheme.

[0068]

Embedded image

Synthesis of Compound I-20 Compound I-20 can be synthesized according to the following synthesis scheme.

[0070]

Embedded image

Synthesis of Compound I-22 Compound I-22 can be synthesized according to the following synthesis scheme.

[0072]

Embedded image

Synthesis of Compound I-34 Compound I-34 can be synthesized according to the following synthesis scheme.

[0074]

Embedded image

Synthesis of Compound I-44 Compound I-44 can be synthesized according to the following synthesis scheme.

[0076]

Embedded image

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

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

Here, the compound of the 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 a compound represented by the following general formula [III].

[0081]

Embedded image

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, a sulfamoyl group. A 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 and A ₂ and the nitrogen atom to which they are bonded are a hydrazone partial structure.

[0084]

Embedded image

May be formed.

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

The aliphatic group represented by A preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. 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, A sulfoxy group, a sulfonamide group, an acylamino group, a ureido group, etc.).

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

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

Particularly preferred as A are an aryl group and a heterocyclic group.

The aryl group and heterocyclic group of A may have a substituent. Representative substituents include an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or condensed ring having 1 to 3 carbon atoms in the alkyl moiety), and an alkoxy group (preferably An alkyl moiety having 1 to 20 carbon atoms, a substituted amino group (preferably an amino group substituted with an alkyl group or an alkylidene group having 1 to 20 carbon atoms), an acylamino group (preferably having 1 to 40 carbon atoms) ), A sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 to 40 carbon atoms)
), 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 arylsulfinyl group (eg, methanesulfinyl), an arylsulfinyl group (eg, benzenesulfinyl), a carbamoyl group (eg, methylcarbamoyl, phenylcarbamoyl, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl, methoxyethoxycarbonyl, etc.), aryloxy A carbonyl group (eg, phenoxycarbonyl), a sulfamoyl group (eg, dimethylsulfamoyl), a sulfinamoyl group (eg, methylsulfo) Finamoyl), an alkoxysulfonyl group (eg, methoxysulfonyl), a thioacyl group (eg, methylthiocarbonyl), a thiocarbamoyl group (eg, methylthiocarbamoyl), an oxalyl group (described later with respect to the general formula [II]), or a heterocyclic group ( For example, a pyridine ring or a pyridinium ring).

B in the general formula [III] represents A ₂ together with the nitrogen atom to which they are bonded.

[0094]

Embedded image

May be formed.

R ₉ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₀ 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 preferred.

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 ( Ethoxalyl).

Particularly preferred among the hydrazine compounds used in the present invention are compounds represented by the following general formula [II].

[0100]

Embedded image

In the formula, R ₄ represents an aryl group or a heterocyclic group, and R ₅ is

[0102]

Embedded image

Represents the following.

R ₆ and R ₇ each represent 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 ₈ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Or a heterocyclic group. A ₁ and A ₂ of the general formula represents an A ₁ and A ₂ respectively synonymous groups [III].

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

The aryl group represented by R ₄ is preferably a single ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by R ₄ is preferably a monocyclic or condensed 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen. Ring, quinoline ring, pyrimidine ring, thiophene ring, furan ring, thiazole ring or benzothiazole ring.

Preferred as R ₄ is an aryl group, most preferably a benzene ring.

[0109] A ₁ and A _2, A ₁ and A in the formula [III]
Represents a group having the same meaning as _2, and most preferably both are hydrogen atoms.

R ₅ is

[0111]

Embedded image

Wherein R ₆ and R ₇ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, benzyl),
Alkenyl group (allyl, butenyl, etc.), alkynyl group (propargyl, butynyl, etc.), aryl group (phenyl, naphthyl, etc.), heterocyclic group (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidyl Nyl, quinuclidinyl, N, N'-diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy , Ethoxy, etc.), an alkenyloxy group (such as allyloxy), an alkynyloxy group (such as propargyloxy), an aryloxy group (such as phenoxy), or a heterocyclic oxy group (such as pyridyloxy), wherein R ₆ and R ₇ represent nitrogen. A ring (piperidine, morpholine, etc.) may be formed together with the atom. R ₈ represents a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, hydroxyethyl), an alkenyl group (eg, allyl, butenyl), an alkynyl group (eg, propargyl, butynyl), an aryl group (eg, phenyl, naphthyl), and a heterocyclic ring. Group (2,2,
6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl, etc.).

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

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

The method for synthesizing the compound represented by the general formula [III] used in the present invention is described in JP-A Nos. 62-180361 and 62-1782.
No. 46, No. 63-234245, No. 63-234246, No. 64-90439,
JP-A-2-37, JP-A-2-841, JP-A-2-947, JP-A-2-120736,
2-230233, 3-125134, U.S. Patent 4,686,167,
4,988,604 and 4,994,365, European Patent 253,66
Nos. 5, 333,435 and the like can be referred to.

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

In the present invention, when the compound represented by the general formula [III] is contained in a photographic material, it is contained in a silver halide emulsion layer or a 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 via another layer such as a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer as a protective layer may be provided on the emulsion layer. Further, the silver halide emulsion layers may be separately applied to silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between the silver halide emulsion layers. That is, an intermediate layer made of a hydrophilic colloid may be provided as 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 iodobromide or silver iodobromide containing 4 mol% or less, preferably 3 mol% or less of silver iodide. The average diameter of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, and particularly preferably 0.10 to 0.
40 μm is preferred.

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

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

In the practice of the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used as the silver halide grains. Consisting of silver iodobromide grains, which is silver bromide. 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 may be formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt) during the step of forming and / or growing the grains. ), A rhodium salt (including a complex salt) and an iron salt (including a complex salt) to add metal ions using at least one selected from the group consisting of these metal elements inside and / or on the particle surface. Further, by placing the particles in an appropriate reducing atmosphere, a reduction sensitizing nucleus can be provided inside the grains and / or on the surface of the grains.

Further, silver halide can be sensitized by various chemical sensitizers. As the sensitizer, for example, active gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, etc.), selenium sensitizer (N, N-dimethylselenourea, selenourea, etc.) ), Reduction sensitizers (triethylenetetramine, stannous chloride, etc.), potassium chloroaulite, potassium aurithiocyanate, potassium chloroaurate, 2-
Various noble metal sensitizers represented by aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite and the like can be used alone or in combination of two or more. When a gold sensitizer is used, rhodamonmon can be used as an auxiliary agent.

The silver halide grains used in the present invention can be preferably applied to grains having higher surface sensitivity than internal sensitivity, that is, silver halide grains giving a so-called negative image. Performance can be enhanced.

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

The photosensitive silver halide emulsion layer or an adjacent layer is provided with a Research Disclosure (Research Disclosure) for the purpose of increasing the sensitivity, increasing the contrast or accelerating the development.
ure) No. 17463, paragraphs (B) to (D) can be added.

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

[0133] Formula (P) _{R 11 -0- (CH 2 CH 2} O) nH [wherein R ₁₁ represents an aromatic ring having a hydrogen atom or unsubstituted or substituted groups,, n until 10-200 Represents an integer. Specific examples of the compound represented by the general formula [P] include Japanese Patent Application No.
P-1 to P-17 described on pages 94 to 96 of 2-160939. Of these, those having a molecular weight of 1500 or more are preferred,
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 per mol of silver halide,
2-2 mol is more preferred. Further, two or more compounds having different values of n may be included.

The silver halide emulsion used in the present invention may contain a sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like.

When the compounds of the general formulas [I] and [III] according to the present invention are added to a hydrophilic colloid layer, gelatin is preferred as a binder for the hydrophilic colloid layer.
Hydrophilic colloids other than gelatin can also be used.
These hydrophilic binders are applied on both sides of the support, respectively.
It is preferable to apply the coating at g / m ² or less.

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

In the development processing of the silver halide photographic material of the present invention, for example, the following developing agents are used.

Representative 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, and N-methyl-p-aminophenol, N-β -Hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like.

Examples of the heterocyclic developer 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.

In addition, 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)
ical society), 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, but it is preferable to use two or more in combination.

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

The developer used in the present invention is characterized in that a developer having a pH of less than 11 can be used. In the developing solution, an inorganic development inhibitor such as promcali, an organic development inhibitor such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine, 1-phenyl-5-mercaptotetrazole, ethylenediamine Metal ion scavengers such as acetic acid, methanol, ethanol,
Development accelerators such as benzyl alcohol and polyalkylene oxide, sodium alkylaryl sulfonates, surfactants such as natural saponins, saccharides or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, sodium sulfate It is optional to add an ionic strength regulator or the like.

In the developer used in the present invention, alkanolamines such as diethanolamine and triethanolamine, diethylene glycol,
A glycol such as triethylene glycol or an alkylamino alcohol such as diethylamino-1,2-propanediol or butylaminopropanol may be contained.

[0146]

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

Example 1 (Preparation of Silver Halide Emulsion A) A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by a double jet method. During this mixing, 8 × 10 ^-7 mol of K ₂ IrCl ₆ was added per mol of silver. The resulting emulsion was an emulsion composed of cubic monodisperse particles (average coefficient of variation: 9.5%) having an average particle size of 0.20 μm.
After adding 6.5 ml of a 1% aqueous solution of potassium iodide per mol of silver to this emulsion, modified gelatin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added. Water washing and desalting were performed 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.

[0148]

Embedded image

(Preparation of silver halide photographic light-sensitive material) One side of a 100 μm-thick polyethylene terephthalate film having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) A silver halide emulsion layer of the following formula (1) was coated on the undercoat layer so that the amount of gelatin was 2.0 g / m ² and the amount of silver was 3.2 g / m ^2. (2) coating the emulsion protective layer so that the amount of gelatin is 1.0 g / m ² ;
On the other undercoat layer on the opposite side, a backing layer of the following formula (3) was applied so that the amount of gelatin was 2.4 g / m ² ,
Further, a backing protective layer having the following formulation (4) was further applied thereon so that the amount of gelatin became 1.0 g / m ² , thereby obtaining Samples 1 to 30.

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.0 g / m ² silver halide emulsion A (silver content) 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 [III] 30 mg / m ² nucleation promoting compound [I] according to the present invention 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 30m
g / m ² gelatin 2.4 g / 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 methacrylate having an average particle size of 3.0 to 5.0 μm 15 mg / m ² Surfactant: S-2 10 mg / m ² Hardener: Glyoxal 25 mg / m ² Hardener: H-1 35 mg / m ² Formulation (1) The compounds used in (2) and (3) are shown below.

[0151]

Embedded image

[0152]

Embedded image

The obtained samples were subjected to a dot quality test by the following method.

(Dot Quality Test Method) A halftone screen (150 lines / inch) having a halftone dot area of 50% was partially attached to the step wedge, and the sample was brought into close contact with the screen and exposed for 5 seconds with a xenon light source. This sample was subjected to development processing under the following conditions in a rapid processing automatic developing machine into which the following developing solution and the following fixing solution were charged, and the dot quality of the sample was observed with a loupe of 100 times, and the dot quality was high. The items are given a "5" rank, and the following "4",
"3", "2", "1", the rank is sequentially lowered to 5
It was rated on a scale. Note that the ranks “1” and “2” are levels that are not preferable for practical use.

Fog in halftone dots was evaluated in the same manner, and those having no black pin in the halftone dot were assigned the highest rank of "5". The ranks "4", "3", "2", and "1" were sequentially reduced and evaluated.

In the ranks "1" and "2", the black pins are large, which is not practically preferable.

Developer Formulation Developer 1 Developer 2 Sodium ethylenediaminetetraacetate 1 g 1 g Sodium sulfite 60 g 60 g Trisodium phosphate (decahydrate) 75 g 75 g Hydroquinone 22.5 g 22.5 g Sodium hydroxide 8 g 8 g Sodium bromide 3 g 3 g 5 -Methylbenzotriazole 0.25g 0.25g 1-phenyl-5-mercaptotetrazole 0.08g 0.08g Methol 0.25g 0.25g Add water 1 liter 1 liter Adjust pH with sodium hydroxide pH = 10.8 pH = 10.5 Formulation of fixer (Composition A) Ammonium thiosulfate (72.5 w / v% aqueous solution) 240
ml 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) 4.7g Aluminum sulfate 26.5g (Aqueous solution whose content in terms of Al ₂ O ₃ is 8.1 w / w%) At the time of use of the fixing solution, the above composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 liter. This fixer
The pH was adjusted to 4.8 with acetic acid.

(Processing conditions) (Process) (Temperature) (Time) Current image 40 ° C. 15 seconds Fixed 35 ° C. 15 seconds Rinse 30 ° C. 10 seconds Dry 50 ° C. 10 seconds In addition, prescription (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 Example 1.

[0159]

Embedded image

Table 1 shows the results of the quality test.

[0161]

[Table 1]

As is clear from Table 1, the sample according to the present invention has better dot quality and black pin compared to the comparison.

[0163]

According to the present invention, a silver halide photographic light-sensitive material having high contrast, low fog and good halftone dot performance even when processed with a developing solution having a low pH of less than 11 can be provided.

Claims (2)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support and containing a hydrazine compound in at least one of said emulsion layers and other constituent layers, has the following general formula: A silver halide photographic material comprising at least one compound represented by [I]. Embedded image [Wherein, R ₁ and R ₂ each represent an alkyl group, an alkenyl group, or an alkynyl group, and R ₁ and R ₂ may form a ring. R ₃ is a hydrogen atom, an alkyl group, an alkenyl group,
Represents an alkynyl group, an aryl group, or a heterocyclic group. L
₁ represents a divalent linking group, and X represents Represents L ₂ represents an alkylene group or an alkenylene group, Y represents a carbonyl group, a sulfonyl group, a sulfoxy group,
Represents a phosphoryl group. L ₃ is Represents Z ₁ , Z ₂ and Z ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. n represents 0 or 1. ] 2. The silver halide photographic material according to claim 1, wherein the hydrazine compound according to claim 1 is a compound represented by the following general formula [II]. Embedded image [Wherein, R ₄ represents an aryl group or a heterocyclic group, and R ₅ represents Represents R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
Represents an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group, and R ₈ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Represents a group. A ₁ and A _{2 each} represent a hydrogen atom or one of them represents a hydrogen atom and the other represents an acyl group, a sulfonyl group or an oxalyl group. ]