JPH07306490A - Silver halide photographic sensitive material and its image forming method - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material for plate making which is improved in image reproducibility and ultra-high contrast characteristic and its image forming method. CONSTITUTION:(1) The silver/binder ratio of silver halide emulsion layers for forming the images is >=0.7 to <=1.3, the thickness of a protective layer is >=0.6 to <=2.0mum and at least one kind of a nucleating agent consisting of a hydrazine deriv. and nucleation accelerating agent are contained in the constituting layers of the silver halide photographic sensitive material. (2) The silver/binder ratio of the silver halide emulsion layers for forming the images is deg.0.7 to <=1.3, the thickness of the protective layer is >=0.6 to <=2.0mum and at least one kind of the nucleus footing agents consisting a pyridinium salt deriv. are contained in the constituting layers of the silver halide photographic sensitive material. (3) The images of the silver halide photographic sensitive material stated in the term (1) or (2) are formed by using a light source for sensitizing the photosensitive material, which light source has a spread of >=30nm in the half- amplitude value of the light source.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive material using a hydrazine derivative and a nucleation accelerator as a nucleating agent or a light-sensitive material using a pyridinium salt derivative as a nucleating agent. The present invention relates to a silver halide photographic light-sensitive material having improved and improved image reproducibility and super-high contrast for plate making, and an image forming method thereof.

[0002]

2. Description of the Related Art Conventionally, lithographic silver halide photographic light-sensitive materials have been well known for obtaining high-contrast photographic images. It had the disadvantage of being unstable.

Therefore, as a new image forming system replacing the lith system, for example, US Pat. Nos. 4,166,742 and 4,16.
No. 8,977, No. 4,221,857, No. 4,224,401, No. 4,311,781
The surface latent image type silver halide photographic light-sensitive material to which a specific hydrazine derivative is added as disclosed in Japanese Patent Publication No. 1994-126, containing 0.15 mol / liter or more of sulfite ion and having a pH of 11.0.
~ 12.3 with a relatively storage-stable developer,
A system for forming a super-high contrast negative image having a (gamma) of more than 10 has been proposed.

However, this system has a drawback that a faithful image cannot be reproduced because the hydrazine derivative has a remarkable nucleating action and the nucleating action extends to the unexposed portion to enlarge the image.

Further, in the system, the pH of the developing solution is 11.
Although it is more stable than the lith method because it is relatively high at 0 to 12.3, it is still susceptible to air oxidation and the storability of the developer was not sufficient. Therefore, there is known a method of adding a highly active hydrazine derivative which makes a high contrast even in a developer having a pH of 11.0 or less and a compound (nucleation accelerator) which promotes a nucleation reaction to a light-sensitive material. As such a highly active hydrazine derivative, for example, European Patent 0333435, U.S. Pat.
8,604, 4,994,346, JP-A-63-234244, JP-A-63-
No. 249838 is disclosed. Further, examples of the nucleation accelerator include JP-A-60-140340, 63-124045 and 63-13314.
5, U.S. Pat. Nos. 4,975,354 and 4,963,956.

However, when these highly active hydrazine derivatives or nucleation accelerators are used, the nucleation action is larger than that of the conventional system, and thus the faithful image reproducibility is inferior to that of the conventional system. . Therefore, for example, the quality of enlargement (expansion) and reduction (expansion) of halftone pictures in the line drawing process, the reproducibility of bright dots, the quality of blank characters in the return process, or the scanner process has attracted attention in recent years.
High-definition output exceeding 0 lines / inch and methods that output with minute Dots such as the FM screen method require particularly severe quality. Therefore, it was not sufficient for image reproduction compared with the conventional system.

Further, as a nucleating agent other than the hydrazine derivative, a method using a pyridinium salt derivative disclosed in, for example, JP-A 1-217339 and 5-53231 is known. In this image forming system, Similar to the case where the hydrazine derivative is used, it is insufficient in image reproduction, and further improvement has been desired.

[0008]

Therefore, an object of the present invention is to provide a light-sensitive material using a hydrazine derivative and a nucleation accelerator as a nucleating agent, or a light-sensitive material using a pyridinium salt derivative as a nucleating agent. An object of the present invention is to provide an ultrahigh contrast silver halide photographic light-sensitive material having improved reproducibility and an image forming method thereof.

[0009]

The above objects have been solved by the present invention described below.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver / binder ratio of the silver halide emulsion layer for image formation is 0.7 or more and 1.3 or less. And the thickness of the protective layer coated on the emulsion layer is 0.6 μm or more and 2.0 μm or less,
A silver halide photographic light-sensitive material comprising at least one of a nucleating agent composed of a hydrazine derivative and a nucleation accelerator in at least one of the layers constituting the silver halide photographic light-sensitive material.

(2) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver / binder ratio of the silver halide emulsion layer for image formation is 0.7 or more and 1.3 or less. And the thickness of the protective layer coated on the emulsion layer is 0.6 μm or more and 2.0 μm or less,
A silver halide photographic light-sensitive material, characterized in that at least one of the constituent layers of the silver halide photographic light-sensitive material contains at least one nucleating agent composed of a pyridinium salt derivative.

(3) The full width at half maximum of the light source for exposing the photosensitive material is 3
Characterized by a light source with a spread of 0 nm or more
(1) or the image forming method of the silver halide photographic light-sensitive material according to (2).

The present invention will be described in detail below.

The term "silver halide emulsion layer for image formation" as used in the present invention refers to a photosensitive silver halide emulsion layer according to the present invention described later. The term "silver / binder ratio" as used in the present invention refers to the weight of silver atoms per unit area divided by the weight of the binder, and the binder means a solid content other than the silver halide grains contained in the emulsion layer. Specifically, it represents the total solid content of gelatin, latex, and other various additives contained in the emulsion layer. The silver / binder ratio is preferably 0.7 or more and 1.3 or less, particularly 0.8
More preferably, it is 1.2.

The protective layer coated on the emulsion layer forming an image is a hydrophilic colloid layer having substantially no photosensitivity and is usually re-surfaced for the purpose of protecting the photosensitive emulsion layer. It is to be placed in layers. According to the study by the present inventors, it was surprising that the film thickness of this protective layer and the silver / binder ratio of the emulsion layer to be imaged have a great influence on the image reproducibility. It has been found that this effect is remarkable especially in the case of a light source having a continuous wavelength as compared with a light source having excellent monochromaticity such as laser light.

In the present invention, for example, when an Xe light source, a yosso light source, a quartz light source, a mercury lamp, etc. are used as a light source, and an image is formed by a light source having a half width of 30 nm or more, preferably 50 nm or more. The effect of the present invention is excellently exhibited.

In the light-sensitive material according to the present invention, each of the emulsion layer and the protective layer may be a single layer or a multi-layer composed of two or more layers. In the case of multiple layers, an intermediate layer or the like may be provided between them. When the number of emulsion layers is two or more, the silver / binder ratio of the present invention is at least 1 of the emulsion layers substantially contributing to image formation.
It is necessary that the layers have a silver / binder ratio that is within the range of the present invention, and it is particularly preferable that all layers satisfy the conditions of the present invention.

When there are two or more emulsion layers, the protective layer indicates the thickness from the uppermost emulsion layer. An emulsion layer, which is a non-photosensitive layer and does not substantially contribute to image formation, can be coated for various purposes.

Next, in at least one layer of the silver halide photographic light-sensitive material according to the present invention, at least one of a nucleating agent consisting of a hydrazine derivative and a nucleation accelerator or a pyridinium salt derivative is contained.

The silver halide photographic light-sensitive material constituent layer referred to herein is, for example, a light-sensitive silver halide emulsion layer, a silver halide emulsion layer having substantially no photosensitivity, an intermediate layer, an undercoat layer, a protective layer or a charge layer. Examples of the protective layer include a hydrophilic layer constituting a silver halide photographic light-sensitive material. Preferably, it is contained in at least one of the light-sensitive silver halide emulsion layer and the protective layer adjacent thereto.

The hydrazine compound preferably used in the present invention can be represented by the following general formula [H].

[0022]

[Chemical 1]

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, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples include, for example, methyl, ethyl, t-butyl, octyl, cyclohexyl, benzyl group and the like, and these are further suitable substituents (for example, aryl, alkoxy, aryloxy,
(Alkylthio, arylthio, sulfoxy, sulfonamide, sulfamoyl, acylamino, ureido groups, etc.)
May be replaced with.

The aromatic group represented by A ₀ 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 ₀ is preferably a monocycle or a condensed ring containing at least one hetero atom selected from nitrogen, sulfur and oxygen atoms, and examples thereof include pyrrolidine, imidazole, tetrahydrofuran, morpholine and pyridine. Pyrimidine, quinoline,
Examples thereof include thiazole, benzothiazole, thiophene and furan ring. Particularly preferred as A ₀ are an aryl group and a heterocyclic group. The aromatic group and heterocyclic group of A ₀ may have a substituent. Particularly preferred groups include a substituent having an acidic group having a pKa of 7 or more and 11 or less, and specific examples thereof include a sulfonamide group, a hydroxyl group, and a mercapto group.

Further, A ₀ preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group is a photographically inactive group having 8 or more carbon atoms, such as an alkyl group, an alkenyl group or an alkynyl group, Alkoxy group, phenyl group,
Examples thereof include a phenoxy group and an alkylphenoxy group.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group.

G ₀ is a --CO-- group, --COCO-- group, --CS-- group,
_{-C (= NG 1 D 1)} - group, -SO- group, -SO ₂ - group or -P
_{(O) (G 1 D 1} ) - represents a group. G ₁ is just a bond, −
It represents an O-group, a -S- group or a -N (D ₁ )-group. D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when plural D ₁ are present in the molecule, they may be the same or different.

D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group. Preferable G ₀ is —CO— group, and —COCO— group, and particularly preferably —COCO—
Groups. Preferred D ₀ includes a hydrogen atom, an alkoxy group, an amino group and the like.

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). Etc.).

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

[0032]

[Chemical 2]

[0033]

[Chemical 3]

[0034]

[Chemical 4]

[0035]

[Chemical 5]

[0036]

[Chemical 6]

Next, the pyridinium salt derivative used in the present invention is represented by the following general formula [Pa], [Pb] or [Pc].

[0038]

[Chemical 7]

In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a non-metal atom group for completing a nitrogen-containing heterocycle,
It may contain an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴
And the heterocycle composed of A ⁵ may have a substituent, and they may be the same or different. As the substituent, 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 hydroxy group, an alkoxy group, an aryloxy group. , Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group,
It represents a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, or an arylthio group. Preferred examples include A ¹ , A ² , A ³ , A ⁴ and A ^{5 which} are 5- or 6-membered rings (for example, pyridine, imidazole, thiozole, oxazole, pyrazine, pyrimidine rings, etc.). A pyridine ring can be mentioned.

B _P represents a divalent linking group, and the divalent linking group is alkylene, arylene, alkenylene, --SO _2- ,
-SO -, - O -, - S -, - CO -, - N (R 6) -, represents what is configured alone or in combination (R ⁶ is an alkyl group, an aryl group, a hydrogen atom) . As a preferred example, B
Examples of _p include alkylene, alkenylene, and alkylene oxide.

R ¹ , R ² and R ⁵ represent a saturated or unsaturated alkyl group having 1 to 20 carbon atoms. R ¹ and R ² may be the same or different. As the substituents, A ¹ , A ² ,
It has the same meaning as the groups mentioned as the substituents for A ³ , A ⁴ and A ⁵ .

As a preferred example, R ¹ , R ² and R ⁵ each represent an alkyl group having 4 to 10 carbon atoms. Further preferable examples are a substituted or unsubstituted aryl group and a substituted alkyl group. X _p represents a counter ion required to balance the charge of the entire molecule, and represents, for example, chloride ion, bromine ion, iodide ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an intramolecular salt. Specific compound examples are shown below.

[0043]

[Chemical 8]

[0044]

[Chemical 9]

[0045]

[Chemical 10]

[0046]

[Chemical 11]

[0047]

[Chemical 12]

In the present invention, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb] in order to effectively accelerate the contrast increase by the hydrazine and pyridinium compounds.

[0049]

[Chemical 13]

In the general formula [Na], R ₁₁ , R ₁₂ , and R ₁₃
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. A ring can be formed by R ₁₁ , R ₁₂ , and R ₁₃ . 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 molecular weight of 300 or more is particularly preferable. Further, preferable adsorption groups include heterocycle, mercapto group, thioether group, thione group, thiourea group and the like.

Specific examples of compounds of these nucleation accelerators [Na] are shown below.

[0052]

[Chemical 14]

[0053]

[Chemical 15]

[0054]

[Chemical 16]

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

Specific examples of the compound of the general formula [Nb] include those shown below.

[0057]

[Chemical 17]

[0058]

[Chemical 18]

In the present invention, the effect of the present invention was great when a nucleation accelerator having a molecular weight of 500 or less was used. The hydrazine derivative or pyridinium salt derivative and the nucleation accelerator used in the present invention may be used in any layer on the silver halide emulsion layer side, preferably in the silver halide emulsion layer or its adjacent layer. Is preferred.

The optimum amount of addition is not uniform depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, etc., but generally 10 moles per mol of silver halide. ^-6 mol to 10 ^-1 mol range is preferred, especially 10
A range of ^-5 mol to 10 ^-2 mol is preferred.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited in halogen composition, but is preferably silver chloride, silver chlorobromide or silver chloroiodobromide. The average grain size of the silver halide grains is preferably 0.7 μm or less, and particularly preferably 0.5 μm to 0.1 μm.
The average particle diameter as used herein means the particle diameter when the particles are spherical or can approximate a sphere. When the particle is a cube, it is converted into a sphere, and the diameter of the sphere is taken as the particle size.
See CEK Mees & T. For details on how to determine the average particle size.
By H. James. The theory of the photographic process.
The third edition, pages 36 to 43 (1966. Published by Macmillan) can be referred to.

There is no limitation on the shape of the silver halide grains,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a 14-sided shape, a regular octahedron shape or the like may be used. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within a grain size range of ± 40% of the average grain size is particularly preferable. As a method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

For the silver halide emulsion, a method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can be used. As one type of simultaneous mixing method, a method of keeping pAg constant in the liquid phase where silver halide is formed, that is, a controlled double jet method can be used. A silver halide emulsion having a substantially uniform grain size can be obtained.

The silver halide grains used in the silver halide emulsion may be cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, or any of these in at least one of the grain forming process and the growing process. It is preferable to add a complex salt containing the element.

For the silver halide emulsion and its preparation method, see Research Disclosure (RD) 17643.22-23 (1978.
You can refer to the method described in (December).

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these may be used alone or in combination. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanins and polysulfide compounds can be used in addition to the sulfur compounds contained in gelatin.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, platinum, palladium, rhodium and other complex salts may be contained. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound, ascorbic acid and the like can be used.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptotetrazole), etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7 -Tetrazaindenes), pentazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added.

The silver halide emulsion layer and the protective layer according to the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-
Hydroxy-s-triazine, etc.), mucohalogenates (mucochloric acid, phenoxymucochloric acid, etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, etc. may be used alone or in combination. it can.

The photosensitive emulsion layer, protective layer and other non-photosensitive hydrophilic colloid layers according to the present invention have improved coating properties, antistatic properties, slipperiness, emulsion dispersibility, anti-adhesion properties and photographic properties. For the purpose of, various surfactants may be used.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,
A wide variety of synthetic hydrophilic polymeric substances such as polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products can also be used.

The light-sensitive material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (eg vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination,
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

The silver halide emulsion is preferably spectrally sensitized with various spectral sensitizing dyes. Preferred sensitizing dyes include (RD) 17643.23 to 24 (December 1978) and (R
D) 34685 (1993) can be used.

Various other additives are used in the light-sensitive material according to the present invention. For example, desensitizer, plasticizer, slip agent,
Development accelerators, oils, dyes, etc. These are (RD) 17643.23
The materials described on page 31 can be used.

The emulsion layer and the protective layer of the light-sensitive material according to the present invention may each be a single layer or a multilayer composed of two or more layers. In the case of multiple layers, an intermediate layer or the like may be provided between them.

The emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials. Useful as the flexible support are films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene and polyethylene terephthalate.

Examples of the developing agent that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromhydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone, etc.), 3-pyrazolidones (eg 1-phenyl-3
-Pyrazolidone, 1-phenyl-4-hydroxymethyl-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 (eg o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diamino) Phenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1
-(p-Methylaminophenyl) -3-aminopyrazoline, 1- (p
-Aminophenyl) -3-aminopyrazoline, 1- (p-amino-N
-Methylphenyl) -3-aminopyrazoline etc.) can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes or a combination of aminophenols and dihydroxybenzenes or It is preferable to use a combination of 3-pyrazolidones and ascorbic acid and a combination of aminophenols and ascorbic acid. The developing agent is usually 0.01 to 1.4
It is preferably used in an amount of mol / l.

As a silver sludge preventive agent, Japanese Patent Publication No. 62-4702
No. 3, JP-A-51844, No. 4-26838, No. 4-362942,
Examples thereof include the compounds described in 1-319031. Further, as sulfites and metabisulfites used as preservatives, sodium sulfite, potassium sulfite, ammonium sulfite,
For example, sodium metabisulfite. The sulfite is preferably 0.25 mol / liter or more. It is particularly preferably 0.4 mol / liter or more.

In the developer, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) , Solubilizers (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.),
Surfactants, antifoaming agents, antifoggants (for example, 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.), development accelerator (for example, US Pat. No. 2,304,025)
Nos. 4,047,456 and Japanese Patent Publication No. 47-45541), a hardener (eg, glutaraldehyde or its bisulfite adduct), or a defoaming agent. The pH of the developer is preferably adjusted to 9.5-10.5.

The light-sensitive material of the present invention is used as an activator processing solution containing a developing agent in a light-sensitive material, for example, an emulsion layer, as a special form of development processing, and processing the light-sensitive material in an alkaline aqueous solution to perform development. May be. Such a developing treatment is often used as one of the rapid processing methods for a light-sensitive material in combination with a silver salt stabilizing treatment with a thiocyanate, and can be applied to such a processing solution.

As the fixing solution for the development processing of the light-sensitive material of the present invention, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and others, and the pH is 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 capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used. A water-soluble aluminum salt that acts as a hardening agent, such as aluminum chloride, aluminum sulfate, and potassium alum, can be added to the fixing solution. If desired, the fixer may contain a compound such as a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent having a water softening ability. You can

The developer may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid with a high viscosity in a semi-kneaded state. Further, it may be diluted before use, or may be used as it is.

The development temperature of the silver halide photographic light-sensitive material of the present invention can be set in the usual temperature range of 20 to 30 ° C. or in the high temperature processing range of 30 to 40 ° C. You can also

The silver halide photographic light-sensitive material of the present invention is preferably processed by using an automatic processor. At that time, the processing is performed while replenishing a fixed amount of developing solution proportional to the area of the photosensitive material. The developer replenishment amount is preferably 300 ml or less per 1 m ² in order to reduce the amount of waste liquid, and particularly preferably 75 to 200 ml per 1 m ² .

The development time is the total processing time (Dr from the time when the leading edge of the film is inserted into the automatic developing machine to the time when it comes out of the drying zone when the processing is performed by using the automatic developing machine due to the demand for reduction.
y to Dry) is preferably 20 to 60 seconds. The total processing time referred to here includes all process times required for processing the black-and-white light-sensitive material, and specifically, for processing, for example, developing, fixing, bleaching, washing, stabilizing, drying, etc. It is the time that includes all the process time, that is, the time to Dry to Dry.
More preferably, the total processing time (Dry to Dry) is 30 to 60 seconds.

[0087]

EXAMPLES The effects of the present invention will be specifically illustrated by the following examples.

Example 1 (Preparation of silver halide emulsion) 70 mol% of silver chloride, 30 silver bromide
A silver nitrate aqueous solution and a mixed aqueous solution of NaCl and KBr were mixed by a controlled double jet method to grow a silver halide grain so as to have a mol% silver halide composition. At this time, the mixing was carried out under the conditions of 36 ° C., pAg 7.8 and pH 3.0, and 2 × 10 ⁻⁷ mol of Na ₃ RhCl ₆ was added per 1 mol of silver during grain formation. After the completion of mixing, 80 mg of the following S-1 was added per mol of silver. After that, desalting was carried out with a modified gelatin treated with phenyl isocyanate, and the following compounds [A] [B]
A bactericide consisting of the mixture of [C] and ossein gelatin were added and redispersed. The obtained emulsion was cubic grains having an average grain size of 0.2 μm and a coefficient of variation of 10%. The emulsion thus obtained contains 4-hydroxy-6 per mole of silver.
-Methyl-1,3,3a, 7-tetrazaindene (60 mg) was added, and 5 mg chloroauric acid and 0.5 mg sulfur flower were added to 1 mol of silver, and the pH was adjusted to 5.8 and pAg 6.5 at 60 ° C, 80 ° C. Chemical aging was performed for a minute. After ripening, add 900 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per 1 mol of silver, and add KI300
mg, S-2 350 ml were added.

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate films having a 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 of the following formula (1) was coated so that the amount of silver was 3.3 g / m ^2, and a protective layer of the following formula (2) was further coated thereon. . The thickness of the protective layer and the silver / binder ratio of the emulsion layer were adjusted by changing the amount of gelatin. The thickness of the protective layer is
An SEM photograph was taken at 6000 times and measured. On the other undercoat layer on the opposite side, a backing layer was applied according to the following prescription (3) so that the amount of gelatin would be 3.1 g / m ^2, and a protective layer of the following prescription (4) was further applied thereon. The amount of gelatin is 1 g /
A sample was obtained by coating so as to be m ² .

Formulation (1) [Silver halide emulsion layer composition] Gelatin Amount described in Table 1 Silver halide emulsion Silver amount 3.3 g / m ² Antifoggant: 4-mercaptobenzoic acid 2 mg / m ² : 5-nitro Indazole 10 mg / m ² nucleating agent: compound of Table 1 3 × 10 ⁻⁵ mol / m ² nucleating accelerator: compound of Table 1
1 × 10 ⁻⁴ mol / m ² polymer latex 1 0.7 g / m ² colloidal silica 0.5 g / m ² compound K 45 mg / m ² water-soluble polymer V-1 20 mg / m ² surfactant: saponin 0.1 g / m ² : Sodium sulfosuccinate Isopentyl normal decyl ester 8 mg / m ² Formulation (2) [Emulsion protective layer composition] Gelatin Amount shown in Table 1 Polymer latex 2 0.3 g / m ² Matting agent: Silica 20 mg / average particle diameter 3.5 μm m ² surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² surfactant F-1 2 mg / m ² accelerator: hydroquinone 50 mg / m ² : 1-phenyl-4-hydroxymethyl-4 ′ -Methyl-3-pyrazolidone 5 mg / m ² Hardener: Formalin 30 mg / m ²

[0091]

[Chemical 19]

[0092]

[Chemical 20]

Formulation (3) [Backing layer composition]

[0094]

[Chemical 21]

Gelatin 3.1 g / m ² Surfactant: Sodium dodecylbenzenesulfonate 50 mg / m ² Colloidal silica 0.5 g / m ² (4) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: Average particle size 4.0 μm Polymethylmethacrylate 50 mg / m ² Surfactant: Sodium sulfosuccinate: Di (2-ethylhexyl) ester 10 mg / m ² Hardener: Glyoxal 25 mg / m ² 2-Hydroxy-4,6-dichloro-1,3 35 mg / m ^{2 of} 5,5-triazine The obtained sample was evaluated by the following method.

Evaluation of Sample (Sensitivity and Gamma) The obtained sample was brought into close contact with a step wedge, exposed to a tungsten light of 3200 ° K for 3 seconds, and developed and fixed to determine the sensitivity. Note that the sensitivity is the reciprocal of the exposure dose that gives the fog density +3.0 transmission density, and is sample No.
The sensitivity was calculated as a relative value under each condition with the sensitivity of 100 as 100. Further, gamma was obtained from the slope of the characteristic curve in transmission densities 1 to 3. Gamma needs to be 10 or more for practical use.

(Eye enlargement) Manuscript preparation Using a scanner SG-747 manufactured by Dainippon Screen Co., Ltd. and a new RST system scanner film RSP-3 manufactured by Konica Corporation, a transparent image and a dot% of a person consisting of halftone dots. We made a step wedge that changed step by step. The screen frequency at this time was 150 lines / inch.

Photographing The above document was set and exposed on a Fine Zoom C-880F manufactured by Dainippon Screen Co., Ltd. so that the stretching magnification was 120%. At this time, 95% of the step wedge of the manuscript is 5
It was exposed so that it became%. Further, the light source was changed by installing an interference filter having the following full width at half maximum and transmission maximum in the light source section.

Filter (1) Transmission maximum 530 nm, half width 10
nm filter (2) Transmission maximum 530 nm Half-value width 30 nm The exposed sample was developed by the method for determining the sensitivity and gamma.

Evaluation method Good gradation reproducibility (difficulty of dot collapse) in the shadow part of the sample obtained by adjusting the exposure amount and combining the dot% on the small dot side (highlight part). Five-level evaluation was performed in order from the thing. 5 is good and 1 is inferior. The practically usable level was set to 3.

(Processing conditions) Developer formulation Sodium sulfite 50g 1-phenyl-4-methyl, 4'-hydroxymethyl-3-pyrazolidone 0.85mg Diethylenetriamine 5 acetic acid 1.5g Boric acid 8g Potassium bromide 4g Potassium carbonate 55g 5-Methylbenz Triazole 200 mg Hydroquinone 20 g Potassium hydroxide pH 10.4 At the time of use, water was added to make 1 liter.

Fixer formulation Ammonium thiosulfate (59.5% w / v aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% w / v aqueous solution) 82 g Citric acid (50% w / v aqueous solution) 15.7 g Gluconic acid (50% w / w aqueous solution) 8.55 g Aluminum sulphate (48% aqueous solution) 13 ml Glutaraldehyde 3 g Sulfuric acid Amount to bring the pH to 4.6 when using Water was added to make 1 liter.

(Development processing conditions) (Process) (Temperature) (Time) Current image 35 ℃ 30 seconds Settling 33 ℃ 20 seconds Water wash 15 ℃ Room temperature 15 s Dry 40 ℃ 15 s (Evaluation of black spots) No Film for exposure The film was processed under the above-mentioned developing and fixing processing conditions, and the film after processing was observed with a magnifying power of 50 to evaluate the degree of occurrence of black spots. The highest rank is "5" when there are no black spots in the halftone dots, and the rank is "4" according to the degree of occurrence of black spots in 2mm x 2mm.
The evaluation was made in order of "3", "2" and "1". Incidentally, in the ranks "1" and "2", black spots are large, which is a level unfavorable for practical use.

The results are shown in Table 1.

[0105]

[Table 1]

From the results shown in Table 1, it can be seen that the sample of the present invention is excellent in halftone dot reproducibility such as stretching.

Example 2 Preparation of Silver Halide Emulsion An emulsion of the present invention and a comparative emulsion were prepared using the solutions shown below.

(Solution A) Gelatin 5.6 g Polyisopropylene polyethyleneoxy disuccinate 0.56 ml Sodium salt (10% ethanol solution) Sodium chloride 0.11 g Concentrated nitric acid 0.43 ml Distilled water 440 ml (Solution B) Silver nitrate 60 g Concentrated nitric acid 0.21 ml Distilled water 96 ml (Solution C) Gelatin 2.0 g Polyisopropylene polyethyleneoxy disuccinate 0.3 ml Sodium salt (10% ethanol solution) Sodium chloride 23.07 g Na ₃ RhCl ₆ 1% aqueous solution 0.96 ml Distilled water 98.6 ml pH 3.2 (Solution B) and (Solution C) were added to the above (Solution A) by a controlled double jet method under a nitric acid acidic atmosphere. During this time, EAg changed from 170 mV to 125 mV. After mixing silver and halide, 4-hydroxy-6-methyl-
600 mg of 1,3,3a, 7-tetrazaindene was added per mol of silver halide, followed by washing with water and desalting.

The obtained emulsion was a cubic crystal having an average grain size of 0.09 μm and the amount of gelatin was 30 g per mol of silver. Then 63 mg of 4-hydroxy-6-methyl-per mole of silver halide
After adding 1,3,3a, 7-tetrazaindene, sodium thiosulfate was added and chemically sensitized at 60 ° C. After the chemical sensitization, 1500 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 50 mg of 2-mercaptobenzoic acid were added per mol of silver halide as stabilizers.

Further, the following additives were added in the following amounts to prepare a coating solution for emulsion. The emulsion layer was prepared by the method of Example 1 described in JP-A-59-19941, and the backing layer was prepared by JP-A-3-293656. 1
The thickness of the backing layer and backing protective layer having the following composition, which have been subjected to the latex undercoating treatment described above
A 100 μm polyethylene terephthalate film was simultaneously multilayer coated with an emulsion protective layer having the following composition.

(Emulsion coating solution composition) Silver amount 2.8 g / m ² gelatin Amount shown in Table 1 1-Phenyl-5-mercaptotetrazole 2.2 mg / m ² Potassium bromide 4.1 mg / m ² saponin (20%) 100 mg / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Citric acid pH 5.6 adjusted Nucleating agent 3 × 10 ^-5 mol / m ² Nucleation accelerator 1 × 10 ^-4 mol / m ² Hydroquinone 160 mg / m ² Polymer below Latex (P) 0.6 g / m ² Polystyrene sulfonic acid and maleic acid copolymerizable polymer 4.2 mg / m ² (composition of emulsion protective layer coating solution) Gelatin Amount shown in Table 2 Compound (Q) 14 mg / m ² Compound below (R) 170 mg / m ² spherical monodisperse silica (8 μm) 20 mg / m ² spherical monodisperse silica (3 μm) 12 mg / m ^{2 The following} compound (S) 30 mg / m ² citric acid adjusted to pH 5.8 styrene-maleic acid co- polymerized polymer 15.7 mg / m ² The following polymer latex (P) 0.5g / m ² Horumuaru Hydrate (curing agent) 70 mg / m ² (Backing layer coating solution composition) Gelatin 1.9 g / m ² the following compound (T) 38.7 mg / m ² the following compound (R) 22 mg / m ² the following compound (U) 146 mg / m ² Calcium chloride 3 mg / m ² Saponin (20%) 120 mg / m ² Citric acid Adjusted to pH 5.5 Polymer latex (V) 370 g / m ² 5-Nitroindazole 20 mg / m ² Polyethylene glycol (Molecular weight 1540) 10 mg / m ² Styrene-maleic acid copolymer 53 mg / m ² glyoxal 10 mg / m ² (backing protection coating solution composition) Gelatin 0.7 g / m ² Compound (Q) 5 mg / m ² Compound (T) 14 mg / m ² Compound ( R) 8 mg / m ² Compound (U) 51 mg / m ² Spherical polymethylmethacrylate (4 μm) 40 mg / m ² Sodium chloride 3 mg / m ² Glyoxal 10 mg / m ² Compound (W) 80 mg / m ²

[0112]

[Chemical formula 22]

[0113]

[Chemical formula 23]

The processing was performed using the same developing solution and fixing solution as in Example 1.

Development Process Conditions Process Temperature (° C.) Time (sec) Development 38 15 Fixing 38 10 Washing 20 10 Drying 50 15 Total 50 Sample Evaluation Sensitivity Performed in the same manner as in Example 1 and using Sample No. 2-1. 100 sensitivity
Is shown as relative sensitivity.

The gamma sample film was processed using the above-mentioned processing agent with an automatic processor GR-27 (manufactured by Konica Corporation). When the exposure amount A required to give the blackened density 2.5 after development and the exposure amount required to give the blackened density 1.0 are B, gamma is given by the following formula.

Gamma (γ) =-(2.5-0.1) / IogA-IogB Dmax (1: 1) Scanner SG747 and New R manufactured by Dainippon Screen Co., Ltd.
ST system scanner film RSP-3 (manufactured by Konica Corporation)
Was used to create a halftone dot original with a screen ruling of 700 lines / inch and 50%. When this is attached to the base and adhered to each sample film face-to-face, the sample is exposed so that it is converted into 50% halftone dots, and the same development process as above is performed. The maximum blackening density is Dmax (1:
1).

[0118] The mark of sticking and the mark of the sticking base at this time were visually evaluated on a scale of 5, and the highest level was evaluated as 5, the practically marginal level was 3 and the lowest level was 1. did. The obtained results are shown in Table 2.

[0119]

[Table 2]

As is clear from Table 2, since the sample according to the present invention has a small halftone dot thickening in the returning step, a sufficient exposure amount can be given, and therefore an image having a high practical density can be obtained. ing. Further, it can be seen that the sample of the present invention can obtain an image with few sticking marks.

[0121]

【The invention's effect】

According to the present invention, in a light-sensitive material using a hydrazine derivative and a nucleation accelerator as a nucleating agent, or a light-sensitive material using a pyridinium salt derivative as a nucleating agent, image reproducibility (sensitivity for plate making, gamma , A silver halide photographic light-sensitive material for plate-making and an image forming method thereof, in which the reproducibility of halftone dots, traces of sticking, and improvement of black spots) were improved.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
When the silver / binder ratio of the silver halide emulsion layer for image formation is 0.7 or more and 1.3 or less, and the thickness of the protective layer coated on the emulsion layer is 0.6 μm or more and 2.0 μm or less, the silver halide is In at least one of the constituent layers of the photographic light-sensitive material,
A silver halide photographic light-sensitive material containing at least one of a nucleating agent and a nucleating accelerator composed of a hydrazine derivative. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
When the silver / binder ratio of the silver halide emulsion layer for image formation is 0.7 or more and 1.3 or less, and the thickness of the protective layer coated on the emulsion layer is 0.6 μm or more and 2.0 μm or less, the silver halide is In at least one of the constituent layers of the photographic light-sensitive material,
A silver halide photographic light-sensitive material comprising at least one nucleating agent consisting of a pyridinium salt derivative. 3. The half width of the light source for exposing the photosensitive material to light is 30.
An image forming method for a silver halide photographic light-sensitive material according to claim 1 or 2, which is a light source having a spread of not less than nm.