JPH08339046A - Black-and-white silver halide photographic sensitive material and image forming method by using same - Google Patents

Abstract

PURPOSE: To obtain the black-and-white silver halide photographic sensitive material less affected in sensitivity and a dot gradation reproduction region even by the case of processing a large amount of the photosensitive material by incorporating at least one kind of specific compound. CONSTITUTION: The silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer and at least one nonphotosensitive hydrophilic colloidal layer on a support, and it contains at least one kind of compound represented by the formula in which each of R11 -R14 is, undependently, an H or halogen atom or an alkyl or heterocyclic or the like; Y1 is an atomic group necessary to form an aromatic hydrocarbon or heterocyclic group; Z1 is an O or S atom; B1 forms a group capable of adsorbing silver halide alone or together with B1 ; and a ring part to be formed by Y1 is, preferably, an aromatic hydrocarbon ring, especially, a phenyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black-and-white silver halide photographic light-sensitive material and an image forming method using the same, and more specifically, a black-and-white silver halide photographic light-sensitive material for photoengraving in which a developing solution is less deteriorated in a developing process. And an image forming method using the same.

[0002]

2. Description of the Related Art In the field of black-and-white silver halide photographic light-sensitive materials for photoengraving, with the diversification and complexity of printed materials, the reproducibility of the original manuscript in Mincho / Gothic characters, copy dots, and stretching is strongly improved. Is requested.

The photolithography process includes a process of converting a continuous-tone original into a halftone dot image. In this step, a technique capable of reproducing a super-high contrast image is desired, and for example, Japanese Patent Application Laid-Open No. 56-1
A method using a hydrazine derivative as described in No. 06244 is used. According to this method
Although ultra-high contrast and high-sensitivity photographic characteristics can be obtained, its infectious developability is too strong, so when shooting halftone images, it is easy to blacken the areas that would otherwise appear as white background of halftone dots, resulting in very short halftone gradations. Therefore, there was a drawback in image quality that the reproducibility of the original document was poor.

For this reason, it has been attempted to incorporate a compound having a development inhibitory property into a light-sensitive material together with a hydrazine compound.

An example of such an attempt is disclosed in Japanese Laid-Open Patent Publication No.
No. 2-30243, a development inhibitor having a blocking group, a development inhibitor having an adsorption group to silver halide disclosed in JP-A No. 62-237445, and JP-A No. 63-271347. Disclosed structure for releasing development inhibitor upon reduction, JP-A-1-927
The structure having two heterocycles disclosed in JP-A No. 38-38 or the development inhibitor having a hydroxyl group disclosed in JP-A-2-161422 is known. However, with the recent rapid large-scale development processing, these development inhibitors flow out into the developing solution in the course of the development processing and, in addition, retain a strong inhibitory property, so that when the photosensitive material is processed, it is apparently There were problems such as a decrease in sensitivity and a change in halftone gradation.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a black-and-white silver halide photographic light-sensitive material which has little influence on sensitivity and halftone reproduction area even when a large amount of light-sensitive material is processed, and image formation using the same. To provide a method.

[0007]

The above object of the present invention has been achieved by the following constitution.

(1). It has at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, and contains at least one compound represented by the following general formula [1]. Black and white silver halide photographic light-sensitive material.

[0009]

[Chemical 4]

(Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, an alkoxyl group, an aryloxy group, a cyano group. Group, acylamino group,
Alkylthio group, arylthio group, sulfonylamino group, ureido group, sulfamoylamino group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, amino group, hydroxyl group, nitro group, imide group or hetero group Represents a ring group. Y ₁ represents a group of atoms capable of forming an aromatic carbocycle or an aromatic heterocycle. Z ₁ represents an oxygen atom or a sulfur atom, and B ₁ represents a single group or Z ₁ -B ₁ which has a capability of adsorbing silver halide. (2). It has at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, and contains at least one compound represented by the following general formula [2]. Black and white silver halide photographic light-sensitive material.

[0011]

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(In the formula, R ₂₁ represents an alkyl group. Z ₂
Represents an oxygen atom or a sulfur atom, and B ₂ represents a single group or a group of Z ₂ -B ₂ having an adsorptivity for silver halide. ) (3). A support having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer, a hydrazine derivative and the above-mentioned general formula [1]
A black-and-white silver halide photographic light-sensitive material containing a compound represented by:

(4). It has at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, and contains a hydrazine derivative and a compound represented by the above general formula [2]. Black and white silver halide photographic light-sensitive material.

(5). It has at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, and contains a pyridinium salt derivative and a compound represented by the above general formula [1]. Black and white silver halide photographic light sensitive material.

(6). It has at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, and contains a pyridinium salt derivative and a compound represented by the above general formula [2]. Black and white silver halide photographic light sensitive material.

(7). At least one of the light-sensitive silver halide emulsion layers contains silver halide grains having a silver chloride content of 60 mol% or more (1) to
The black-and-white silver halide photographic light-sensitive material according to any one of (6).

(8). The black-and-white silver halide photographic light-sensitive material according to any one of (1) to (7), which contains at least one hardener that acts by activating a carboxyl group.

(9). The black-and-white silver halide photographic light-sensitive material described in (8), wherein the hardener is represented by the following general formula [3].

[0019]

[Chemical 6]

(In the formula, R ₁ and R ₂ each represent an alkyl group or an aryl group, and may form a ring with R ₁ and R _2. R ₃ represents a hydrogen atom or a substituent. L represents L Represents a single bond or a divalent group, X ₁ is a single bond or -O.
Represents —, —N (R ₄ ) —, and R ₄ represents a hydrogen atom, an alkyl group or an aryl group. ) (10). The black-and-white silver halide photographic light-sensitive material according to any one of (1) to (9), which contains a compound that releases a development inhibitor by being oxidized by an oxidized product of a developing agent.

(11). The black-and-white silver halide photographic light-sensitive material according to any one of (1) to (10), wherein at least one conductive layer is provided.

(12). (1) to (11), characterized in that at least one layer in which the dye is substantially fixed is provided between the silver halide emulsion layer closest to the support and the support. The black-and-white silver halide photographic light-sensitive material described in any one of 1.

(13). The hydrophilic colloid is gelatin, and the coating amount of gelatin on each side of the support is 4.0 g / m ² or less per side on both sides (1) to (12) The black-and-white silver halide photographic light-sensitive material described.

(14). The black-and-white halogen, wherein the black-and-white silver halide photographic light-sensitive material described in any one of (1) to (13) above is treated with a developer having a pH of 11.0 or less using dihydroxybenzenes as a developing agent. Image forming method for silver halide photographic light-sensitive material.

(15). The black-and-white silver halide photographic light-sensitive material according to any one of (1) to (14) above, containing at least one selected from ascorbic acid and ascorbic acid derivatives, containing no hydroquinone, and having a pH of 10.8 or less. An image forming method, which comprises processing with the developing solution of.

The present invention will be specifically described below.

The compounds represented by the general formulas [1] and [2] will be described.

In the general formula [1], the ring portion formed by Y ₁ includes an aromatic carbocycle or an aromatic heterocycle, such as a phenyl group, a naphthyl group, a furan group and a thiophene group. An aromatic carbocycle is preferable, and a phenyl group is particularly preferable.

In the general formulas [1] and [2], R ₁₁ ,
Examples of the group represented by R ₁₂ , R ₁₃ , R ₁₄ , and R ₂₁ include a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group,
Isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.) ), An aryl group (for example, a phenyl group, a naphthyl group, a p-tolyl group, a p-chlorophenyl group, etc.),
Alkoxyl group (eg methoxy group, ethoxy group, isopropoxy group, butoxy group etc.), aryloxy group (eg phenoxy group etc.), cyano group, acylamino group (eg acetylamino group, propionylamino group etc.), alkylthio group (Eg, methylthio group, ethylthio group, butylthio group, etc.), arylthio group (eg,
Phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido group,
3,3-dimethylureido group, etc.), sulfamoylamino group (eg, dimethylsulfamoylamino group, etc.),
Carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group) Groups), aryloxycarbonyl groups (eg, phenoxycarbonyl group, p-methoxyphenoxycarbonyl group, naphthoxycarbonyl group, etc.), acyl groups (eg, acetyl group, propanoyl group, butyroyl group, etc.), sulfonyl groups (eg, methane Sulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxyl group, nitro group, imide group (eg phthalimido group, etc.), heterocyclic group ( Examples thereof include a pyridyl group, a benzimidazolyl group, a benzthiazolyl group, a benzoxazolyl group, etc., preferably a hydrogen atom, a substituted or unsubstituted alkyl group or a halogen atom, particularly preferably a hydrogen atom or an unsubstituted atom. It is an alkyl group.

Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, preferably a sulfur atom.

B ₁ , B ₂ alone, or Z ₁ -B ₁ , Z ₂ -B ₂
Examples of the group having the ability to adsorb silver halide represented by the following include a 5-membered to 6-membered nitrogen-containing heterocyclic group, preferably benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole. , Thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, pyrimidine, pyridine, triazine and the like, and particularly preferably tetrazole, benzimidazole, pyrimidine and the like. These may further have a substituent, and examples of the substituent include those mentioned above as examples of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₂₁ .

Of the compounds represented by the general formulas [1] and [2], the compound represented by the general formula [2] is particularly preferable.

The general formula [1] used in the present invention is as follows:
Specific examples of the compound represented by [2] are listed, but the present invention is not limited thereto.

[0034]

[Chemical 7]

[0035]

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[0036]

[Chemical 9]

[0037]

[Chemical 10]

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

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[0042]

[Chemical 15]

[0043]

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[0044]

[Chemical 17]

[0045]

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[0046]

[Chemical 19]

The compounds represented by the general formulas [1] and [2] of the present invention are preferably 1.0 × 10 ⁻⁸ mol / m ² to
1.0 × 10 ^-2 mol / m ² , more preferably 1.0 ×
It is used within the range of 10 ⁻⁷ mol / m ^{2 to} 1.0 × 10 ⁻⁴ mol / m ² . The compounds represented by the general formulas [1] and [2] of the present invention can be used by dissolving in a suitable water-miscible organic solvent such as alcohols, ketones, dimethylsulfoxide, dimethylformamide, methylcellosolve and the like. . It is also possible to add it as an emulsified dispersion using a known oil. Further, the compound powder may be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves according to a method known as a solid dispersion method.

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

[0049]

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[0050] In the formula, E represents represents a heterocycle containing at least one aryl group, or a sulfur atom or an oxygen atom, G is - (CO) _nh - group, a sulfonyl group, a sulfoxy group, -P
(= O) R ₂₃ - represents a group or an iminomethylene group,, n
h represents an integer of 1 or 2, E ₁ and E ₂ both represent a hydrogen atom or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group, and R ₂₂ represents Each represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxyl group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or oxycarbonyl group.

Among the compounds represented by the general formula [H], more preferred are the compounds represented by the following general formula [Ha].

[0052]

[Chemical 21]

In the formula, R ₂₄ is an aliphatic group (eg, octyl group, decyl group, etc.), an aromatic group (eg, phenyl group, 2
-Hydroxyphenyl group, chlorophenyl group, etc.) or a heterocyclic group (eg, pyridyl group, thienyl group, furyl group, etc.), and those groups further substituted with a suitable substituent are preferably used. Further, R ₂₄ preferably contains at least one ballast group (diffusion resistant group) or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in a non-moving photographic additive such as a coupler is preferable, and as the ballast group, an alkyl group or an alkenyl group having 8 or more carbon atoms and relatively inert to photographic properties is preferable. , Alkynyl group, alkoxy group, phenyl group,
Examples thereof include a phenoxy group and an alkylphenoxy group. Examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, and those described in JP-A-64-90439. Examples thereof include adsorption groups.

In the general formula [Ha], Xa represents a group capable of substituting for a phenyl group, ma represents an integer of 0 to 4, and when ma is 2 or more, Xa may be the same or different. .

In the general formula [Ha], E ₃ and E ₄ have the same meanings as E ₁ and E ₂ in the general formula [H], and both are preferably hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ₂₅ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
It represents a carbamoyl group or an oxycarbonyl group. The most preferable R ₂₅ is —COOR ₂₆ group and —CON.
(R ₂₇ ) (R ₂₈ ) group (R ₂₆ represents an alkynyl group or a saturated heterocyclic group, R ₂₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ₂₈ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group or an alkoxyl group).

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

[0059]

[Chemical formula 22]

[0060]

[Chemical formula 23]

[0061]

[Chemical formula 24]

Specific examples of other preferable hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, fourth column to 60th column.

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by the method described in Nos. 29, 248, columns 59 to 80.

In the present invention, the hydrazine compound can be used in any layer on the silver halide emulsion layer side, but is preferably used in the silver halide emulsion layer or its adjacent layer. Further, the addition amount is only required to be an amount for increasing the contrast (contrast adjustment amount), and the optimum amount varies depending on the grain size of the silver halide grain, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc. In particular, the range of 10 ^-6 to 10 ^-1 mol per mol of silver halide is preferable, and 10 mol is particularly preferable.
A range of ^-5 to 10 ^-2 mol is preferred. Further, in the present invention, three or more kinds of hydrazine compounds can be contained in any layer in any state.

In the present invention, it is preferable to use a nucleation accelerator in order to effectively enhance the contrast. Examples of the nucleation accelerator include Japanese Patent Application No. 6-103982, pp. 28-
The compounds described on page 29 are mentioned, and specific examples thereof are described in, for example, Japanese Patent Application No. 6-103982, pages 30 to 35 (N.
a-1) to (Na-22) or (Nb-1) to (N
Examples thereof include, but are not limited to, the compounds described as b-12).

Specific examples of other preferable nucleation promoting compounds are the compounds (2-1) to (2-20) described in JP-A-6-258751 and 6-2587.
The compounds of (3-1) to (3-6) described in No. 51.
Preferred examples of the nucleation accelerator are mentioned here for reference, but the present invention is not limited thereto.

[0067]

[Chemical 25]

In the present invention, the nucleation accelerator can be used in any layer as long as it is on the silver halide emulsion layer side, but it is preferably used in the silver halide emulsion layer or its adjacent layer. The amount of the nucleation accelerator used in the material is 5 × 10 ^{−7 to} 5 × 10 ⁻¹ per mol of silver halide.
It is preferably molar, and particularly 5 × 10 ^{−6 to} 5 × 10
It is preferably in the range of ^-2 mol.

In the present invention, examples of the pyridinium salt derivative include compounds represented by the following general formula [Pa], [Pb] or [Pc].

[0070]

[Chemical formula 26]

In the formula, A ₁ , A ₂ , A ₃ , A ₄ and A ₅ represent a non-metal atom group for completing the nitrogen-containing heterocycle,
It may contain an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. The heterocycle composed of A ₁ , A ₂ , A ₃ , A ₄ and A ₅ may have a substituent and 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 carboxyl group, a hydroxyl group, an alkoxyl group, an aryloxy group. , Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. As preferred examples, A ₁ , A ₂ , A ₃ , A ₄ and A ₅ are 5- or 6-membered rings (for example, pyridine, imidazole, thiazole, oxazole, pyrazine, pyrimidine rings, etc.), and more preferred examples are given. A pyridine ring can be mentioned.

B _p represents a divalent linking group, and the divalent linking group is alkylene, arylene, alkenylene or —SO ₂
-, -SO-, -O-, -S-, -CO-, -N
(R ₂₉ )-, (R ₂₉ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of Bp include alkylene, alkenylene and alkylene oxide.

R ₁ , R ₂ and R ₅ have 1 or more carbon atoms and 20
The following saturated and unsaturated alkyl groups or aryl groups are represented. R ₁ and R ₂ may be the same or different. The substituent has the same meaning as the group mentioned as the substituent of A ₁ , A ₂ , A ₃ , A ₄ and A ₅ . As a preferred example, R ₁ , R ₂ and R ₅ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group. A more preferred example is a substituted alkyl group having 4 to 10 carbon atoms.

[0074] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, and oxalato.

N _p represents the number of counterions 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.

[0077]

[Chemical 27]

[0078]

[Chemical 28]

[0079]

[Chemical 29]

[0080]

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[0081]

[Chemical 31]

The optimum amount of addition varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but generally it is 10 per mole of silver halide.
^It is preferably in the range of ^-6 to 10 ^-1 mol, particularly 10 ^-5 to 10 ^-2.
A molar range is preferred. Further, in the present invention, three or more kinds of pyridinium salt derivatives can be contained in any layer in any state. The pyridinium salt derivative used in the present invention can be used in any layer as long as it is on the silver halide emulsion layer side, but it is preferably used in the silver halide emulsion layer or its adjacent layer.

In the present invention, generally known sulfur sensitization, reduction sensitization and noble metal sensitization methods may be used in combination with chemical sensitization using a compound such as Se or Te.

As the sulfur sensitizer, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, rhodanins and polysulfide compounds can be used.

The gold sensitization method is a typical one of the noble metal sensitization methods, 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 and the like can be used.

In the present invention, the halogen composition of silver halide in the silver halide emulsion is pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or 60 mol% or more in order to realize rapid processing. The silver chloroiodobromide containing silver chloride is preferable.

The average grain size of silver halide is preferably 0.7 μm or less, and more preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. What is particle size?
When the particles are spherical or can be approximated to a sphere, the particle diameter is meant. If the particle is a cube, convert it to a sphere,
Let the diameter of the sphere be the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE Mee).
s & T. H. James: The theory o
f the photographic processes
s), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmillan")).

The shape of silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a tetradecahedral 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 the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

It is also possible to use a method of forming grains in the presence of excess silver ions (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, the crystal form is regular. A silver halide emulsion having a uniform grain size can be obtained.

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

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
search Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978) or cited.

The pyridinium salt derivative and the nucleation accelerator used in the present invention can be used in any layer on the silver halide emulsion layer side, but preferably in the silver halide emulsion layer or its adjacent layer. It is preferable to use.

In the present invention, the black-and-white light-sensitive material is preferably processed by using an automatic developing machine. At that time, processing is performed while replenishing a fixed amount of developing solution and fixing solution proportional to the area of the light-sensitive material. The development replenishment amount and the fixing replenishment amount are 300 ml per 1 m ² to reduce the amount of waste liquid.
It is the following. Preferably 75 to 200 ml per 1 m ²
Is.

In the present invention, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it exits from the drying zone when processing is performed using the automatic developing machine in order to shorten the developing time. Is preferably 10 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 example, developing, fixing, bleaching, washing with water necessary for the processing,
This is the time including all the steps of the stabilization treatment, the drying, etc., that is, the time of Dry to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to D
ry) is 15 to 50 seconds.

In the automatic processor, a heat transfer material at 90 ° C. or higher (for example, a heat roller at 90 ° C. to 130 ° C.) or a radiation object at 150 ° C. or higher (for example, tungsten, carbon, nichrome, zirconium oxide / yttrium oxide /
Infrared rays are emitted from a mixture of thorium oxide, silicon carbide, etc. by directly passing an electric current to generate heat, or by transmitting heat energy from a resistance heating element to a radiator such as copper, stainless steel, nickel or various ceramics to generate heat. ) With a zone to dry.

In the present invention, a redox compound capable of releasing a development inhibitor by being oxidized can be used in combination.

The redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones and the like as redox groups. Preferred redox compounds are compounds having a -NHNH- group as a redox group and compounds represented by the following general formulas [RE-1] to [RE-6].

[0099]

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[0100]

[Chemical 33]

The compound having a --NHNH-- group as a redox group is represented by the following general formula [RE-a] or [RE-a]
-B].

General Formula [RE-a] T-NHNHCOV- (Time) -PUG General Formula [RE-b] T-NHNHCOCOV- (Time) -PUG In General Formula [RE-a] and [RE-b], T and V each represent an optionally substituted aryl group or an optionally substituted alkyl group. Examples of the aryl group represented by T and V include a benzene ring and a naphthalene ring,
These rings may be substituted with various substituents, and preferable substituents are linear or branched alkyl groups (preferably having 2 to 20 carbon atoms such as methyl, ethyl, isopropyl group, dodecyl group, etc.) and alkoxyl groups. Group (preferably having 2 to 21 carbon atoms, for example, methoxy group, ethoxy group, etc.), aliphatic acylamino group (preferably having 2 to 2 carbon atoms)
Having an alkyl group of 1, such as an acetylamino group,
Heptylamino group, etc.), aromatic acylamino group, and the like. In addition to these, for example, the above-mentioned substituted or unsubstituted aromatic ring is —CONH—, —O—, —SO ₂ NH.
Also included are those linked by a linking group such as —, —NHCONH—, and —CH ₂ CHN—. As PUG, 5-nitroindazole, 4-nitroindazole, 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4-nitroimidazole Etc. These development-inhibiting compounds are directly bonded to the CO site of T-NHNH-CO- via a heteroatom such as N or S, or via an alkylene, phenylene, aralkylene, or aryl group and further via a heteroatom such as N or S. Can be connected. In addition, a development inhibitor such as triazole, indazole, imidazole, thiazole or thiadiazole may be introduced into a hydroquinone compound having a ballast group. For example, 2- (dodecylethylene oxide thiopropionamide) -5- (5-nitroindazole-
2-yl) hydroquinone, 2- (stearylamide)
-5- (1-phenyltetrazole-5-thio) hydroquinone, 2- (2,4-di-t-amylphenoxypropionamide) -5- (5-nitrotriazole-
2-yl) hydroquinone, 2-dodecylthio-5-
(2-mercaptothiothiadiazole-5-thio) hydroquinone and the like can be mentioned. The redox compound can be synthesized with reference to the description in US Pat. No. 4,269,929.

The redox compound can be contained in the emulsion layer, in the hydrophilic colloid layer adjacent to the emulsion layer, or in the hydrophilic colloid layer via the intermediate layer.

The above redox compound is added by adding alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ether, dimethylformamide,
It can be added after being dissolved in esters such as dimethyl sulfoxide, tetrahydrofuran and ethyl acetate, and ketones such as acetone and methyl ethyl ketone. Further, those which are difficult to dissolve in water or an organic solvent can be arbitrarily dispersed with an average particle diameter of 0.01 to 6 μm by high speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like. For the dispersion, a surface active agent such as anion or nonion, a thickener, a latex and the like can be added and dispersed. The addition amount of the redox compound is preferably from 10 ^-6 to 10 ^-1 mol, and more preferably from 10 ^-4 to 10 ^-1 mol, per 1 mol of silver halide.
^-In the range of ² moles.

Among the compounds represented by formula [RE-a] or [RE-b], particularly preferable compounds are shown below.

[0106]

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[0107]

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Specific examples of other preferable redox compounds include 236 of JP-A-4-245243.
(8) page “0053” to 250 (22) page “0068”
R-1 to R-50 described in 1.

Further, the above general formulas [RE-1] to [RE-
The redox compound represented by [6] will be described.

In formulas [RE-1] to [RE-6], R ₃₃ represents an alkyl group, an aryl group or a heterocyclic group. R ₃₄ and R ₃₅ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₃₆ represents a hydrogen atom. R ₃₇ and R ₃₈ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r ₁ , r ₂ and r ₃ represent a substituent capable of substituting on the benzene ring. X ₂ and X ₃ are O or N
Represents H. Z ₃ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. W ₂ represents N (R ₄₃ ) R ₄₄ or O, and R ₄₃ and R ₄₄ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. COUP represents a coupler residue capable of causing a coupling reaction with an oxidized product of an aromatic primary amine developing agent, and * represents a coupling site of the coupler. Tm represents a timing group. m ₁ and p ₁ represent an integer of 0 to 3. q ₁ represents an integer of 0 to 4. n is 0
Or represents 1. PUG represents a development inhibitor.

In the above general formulas [RE-1] to [RE-6], alkyl groups represented by R ₃₃ and R _{37 to} R ₄₂ ,
The aryl group and the heterocyclic group are preferably methyl group, p
-Methoxyphenyl group, pyridyl group and the like can be mentioned. R
An acyl group represented by ₃₄ and R ₃₅ , a carbamoyl group,
Among the cyano group, nitro group, sulfonyl group, aryl group, oxalyl group, heterocyclic group, alkoxycarbonyl group and aryloxycarbonyl group, acyl group, carbamoyl group and cyano group are preferable. The total carbon number of these groups is preferably 1-20. R _{33 to} R ₄₄ may further have a substituent, and examples of the substituent include a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group). , Methoxymethyl group, trifluoromethyl group, t-butyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), aralkyl group (eg benzyl group, 2-phenethyl group etc.), aryl group (eg phenyl group) , Naphthyl group, p-tolyl group, p
-Chlorophenyl group etc.), alkoxy group (eg methoxy group, ethoxy group, isopropoxy group, butoxy group etc.), aryloxy group (eg phenoxy group etc.), cyano group, acylamino group (eg acetylamino group, propionylamino group etc.) ), An alkylthio group (eg, methylthio group, ethylthio group, butylthio group, etc.), an arylthio group (eg, phenylthio group, etc.), a sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), an ureido group (eg, 3-methyl). Ureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group) Base etc.) A sulfamoyl group (e.g., ethyl sulfamoyl group, dimethylsulfamoyl group),
Alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group etc.), acyl group (eg acetyl) Group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxyl group, nitro group, imide group (eg phthalimido group etc.), heterocyclic group (eg pyridyl group) , A benzimidazolyl group, a benzthiazolyl group, a benzoxazolyl group and the like).

In the above formulas [RE-1] to [RE-6], examples of the coupler residue represented by COUP include the following. Examples of cyan coupler residues include phenol couplers and naphthol couplers. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, and indazolone couplers. Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler.
Colorless coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic acid diester, imidazolinone, oxazolinone, thiazolinone, etc.). Further, among the coupler residues represented by COUP, those which are preferably used in the present invention are those represented by the general formula (Coup-1) to the general formula (Coup-8).
Can be represented by

[0113]

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In the formula, R ₁₆ represents an acylamido group, anilino group or ureido group, and R ₁₇ represents a phenyl group which may be substituted with one or more halogen atoms, an alkyl group, an alkoxyl group or a cyano group. .

[0115]

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In the formula, R ₁₈ and R _{19 each} represent a halogen atom, an acylamido group, an alkoxycarbonylamido group, a sulfoulide group, an alkoxyl group, an alkylthio group, a hydroxyl group or an aliphatic group, and R ₂₀ and R ₂₁ each represent a fatty acid. Represents a group, an aromatic group or a heterocyclic group. Further, one of R ₂₀ and R ₂₁ may be a hydrogen atom. a is 1 to 4
And the integer b is an integer of 0-5. When a and b are integers of 2 or more, R ₁₈ and R ₁₉ may be the same or different.

[0117]

[Chemical 38]

In the formula, R ₂₂ represents a tertiary alkyl group or an aromatic group, and R ₂₃ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₂₄ represents an acylamide group, an aliphatic group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, a halogen atom or a sulfonamide group.

[0119]

[Chemical Formula 39]

In the formula, R ₂₅ is an aliphatic group, an alkoxyl group,
An acylamino group, a sulfonamide group, a sulfamoyl group, a diacylamino group, R ₂₆ represents a hydrogen atom, a halogen atom or a nitro group.

[0121]

[Chemical 40]

In the formula, R ₂₇ and R ₂₈ are a hydrogen atom, an aliphatic group,
Represents an aromatic group and a heterocyclic group.

In the above general formulas [RE-1] to [RE-6], the 5- or 6-membered heterocycle represented by Z ₃ may be a single ring or a condensed ring, and has O, S, and N atoms. And a 5- or 6-membered heterocycle having at least one of the above in the ring.
These rings may have a substituent, and specific examples thereof include the above-mentioned substituents.

The timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,409,3.
No. 23, or No. 3,674,478, Research
Disclosure 21228 (December 1981)
Month), or JP-A-57-56837 and JP-A-4-43.
Examples thereof include those described in JP-A-8.

Preferred development inhibitors for PUG include, for example, US Pat. No. 4,477,563 and JP-A-60-218.
No. 644, No. 60-221750, No. 60-2336.
No. 50, or the development inhibitor described in No. 61-11743.

The general formula [RE- used in the present invention will be described below.
Specific examples of the compounds represented by 1] to [RE-6] having one timing group are listed, but the present invention is not limited thereto.

[0127]

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[0128]

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[0129]

[Chemical 43]

[0130]

[Chemical 44]

[0131]

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[0132]

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[0133]

[Chemical 47]

[0134]

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[0135]

[Chemical 49]

The general formula [RE which is preferably used in the present invention
-1] to [RE-6] is preferably contained in an amount of 1 x 10 ^-6 to 5 x 10 ^-2 mol, and particularly 1 x 10 ^-4 to 2 mol per mol of silver halide. × 10 ^-2
Molar is preferred.

The compounds represented by the above general formulas [RE-1] to [RE-6] are dissolved in a suitable water-miscible organic solvent such as alcohols, ketones, dimethylsulfoxide, dimethylformamide and methylcellosolve. Can be used. It is also possible to add it as an emulsified dispersion using a known oil. Further, the compound powder may be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves according to a method known as a solid dispersion method.

In the present invention, these redox compounds can be present in the silver halide emulsion layer, in a layer adjacent to the emulsion layer, another layer via the adjacent layer, or the like. Particularly preferred is the emulsion layer and / or the hydrophilic colloid layer adjacent to the emulsion layer. Most preferably, a hydrophilic colloid layer is provided between the emulsion layer and the emulsion layer closest to the support, and the hydrophilic colloid layer is added to the hydrophilic colloid layer. Further, the redox compound may be contained in a plurality of different layers.

In the present invention, the silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus,
Benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus,
A naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanin nucleus,
A 5-6 membered heterocyclic ring such as a thiobarbituric acid nucleus can be applied. Specifically, Research Disclosure Volume 176 RD-17643 (December 1978 issue)
Page 2 and 3, U.S. Pat. Nos. 4,425,425 and 4,4.
Those described in No. 25,426 can be used. The sensitizing dye may be dissolved using ultrasonic vibration described in US Pat. No. 3,485,634. In addition, as a method of dissolving or dispersing the sensitizing dye of the present invention and adding it to an emulsion, US Pat. No. 3,482,981
No. 3,585,195, 3,469,987
No. 3, 3,425,835, 3,342,605
No., British Patent Nos. 1,271,329 and 1,038,0
29, 1,121,174, U.S. Pat. No. 3,66.
The methods described in Nos. 0,101 and 3,658,546 can be used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Re
search Disclosure) Volume 176 176
43 (issued December 1978), page 23, IV, paragraph J.

The light-sensitive material of the present invention may contain various dyes for the purpose of improving safety of safelight. Preferred dyes include those represented by the following general formulas (I) to (VI).

[0141]

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In the formula, A and A ′, which may be the same or different, each represents an acidic nucleus, Q represents an aryl group or a heterocyclic group, B represents a basic nucleus, and Q ′ represents a heterocyclic group. And X ₄ and Y, which may be the same or different, each represents an electron-withdrawing group, and L ₁ , L ₂ and L ₃ each represent a methine group. m ₂ represents 0 or 1, t is 0,
1 or 2, and p ₂ represents 0, 1 or 2. However, the dyes represented by the general formulas (I) to (VI) have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule.

Examples of the aryl group represented by Q in the above general formulas (I) and (IV) include a phenyl group and a naphthyl group. Examples of the heterocyclic group represented by Q include pyridine, quinoline, isoquinoline, pyrrole, pyrazole, imidazole and indole residues.

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

A of the general formulas (I), (II) and (III)
And the acidic nucleus represented by A ′ is preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, Hydroxypyridone,
Examples include pyrazolopyridone. The basic nucleus represented by B in the general formulas (III) and (V) is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole, indole and the like. Is mentioned.

The electron withdrawing groups represented by X ₄ and Y in the general formulas (IV) and (V) may be the same or different,
Examples thereof include a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group and a sulfamoyl group.

The heterocycle represented by Q'in the general formula (VI) is
Examples include pyridine, pyridazine, quinoline, pyrrole, pyrazole, imidazole and indole.

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

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

[0150]

[Chemical 51]

[0151]

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[0152]

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[0153]

[Chemical 54]

These dyes have at least one dissociative proton having a pKa in the range of 4 to 11, preferably 4.5 to 7.0 in a mixed solvent of water-ethanol volume ratio of 1: 1. To have.

Further, in the present invention, immobilization can be achieved by a silver salt and a silver complex formed by the reaction of a dye and silver ion. A preferable dye capable of forming a silver salt of such a dye is, for example, JP-A-5-181230.
The compounds represented by the general formulas [I] to [V], the general formulas [I '] to [V'], and the general formula [VI] described on page 4 to page 28 of the specification. . More specific compounds are I-1 to 37, II-1 to 5, III-1 to 7, IV-1 to 1 described in pages 6 to 46 of the same specification.
6, V-1 to 5, I'-1 to 12, II'-1 to 9, II
I'-1 to 9, IV'-1 to 9, V'-1 to 6, VI-1 to
52 is mentioned.

In the present invention, the above general formulas (I) to (V
The method for dispersing the dye represented by I) is not particularly limited, but a known method such as an acid precipitation method, a ball mill, a jet mill or an impeller dispersion method can be applied.

The average particle size of the finely dispersed dye fine particles of the present invention may be any value, but is preferably 0.01.
˜20 μm, more preferably 0.03 to 2 μm. Further, the coefficient of variation of the particle diameter of the solid dispersed dye fine particles of the present invention is preferably 60% or less, more preferably 40% or less.

In the present invention, the layer containing fine dye particles is preferably provided between the emulsion layer and the support. Preferably, a first subbing layer is provided on the support, on which
A hydrophilic colloid second subbing layer containing the fine dye particles of the present invention is provided. The addition amount of the fine dye particles of the present invention is not particularly limited, but the addition amount is preferably such that the effective transmission density is 0.3 or more and 2 or less.

In the present invention, the hydrophilic colloid layer containing fine dye particles has a coating amount of 0.05 g / m ² or more and a density of 0.
It is less than 5 g / m ² , but preferably 0.18 g / m ² or more and less than 0.42 g / m ² . Further, in order to enhance the effect of the present invention, it is preferable that the ratio of the average particle diameter of the dye fine particles to the film thickness of the dye layer is 0.2 to 2.0.

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

In the present invention, the photographic emulsion and the non-photosensitive hydrophilic colloid may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, 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.), mucohalogen acids (mucochloric acid,
Phenoxymucochloric acid and the like) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination.

The hardener is represented by the following general formula [3]
The compound represented by is particularly preferably used.

[0163]

[Chemical 55]

In the compound represented by the general formula [3],
R ₁ and R ₂ have a linear, branched or cyclic carbon number of 1 to 2
And an alkyl group of 0 (eg, methyl group, ethyl group, butyl group, cyclohexyl group, 2-ethylhexyl group, dodecyl group, etc.). R ₁ and R ₂ may have a substituent, and as an example of the substituent, a substituent for substituting the aryl group represented by Q in the general formulas (I) and (IV) of the dye described above, Further, the above-mentioned examples of the substituent for substituting the heterocycle represented by Q and Q'in the general formulas (I), (IV) and (VI) of the dye can be mentioned. It is also preferable that R ₁ and R ₂ are bonded to form a ring together with a nitrogen atom, and particularly preferable examples are cases where a morpholine ring and a pyrrolidine ring are formed. R ₃ represents a hydrogen atom or a substituent, and examples of the substituent include those enumerated above as the substituents for substituting the aryl group and the heterocycle, and the hydrogen atom is particularly preferable.

L represents a single bond, an alkylene group having 1 to 20 carbon atoms (eg methylene group, ethylene group, trimethylene group, propylene group, propylene group), 6 to 2 carbon atoms.
0 arylene group (for example, phenylene group) and a divalent group (for example, paraxylene group) obtained by combining them, an acylamino group (for example, —NHCOCH ₂ —)
Group), a sulfonamide group (for example, —NHSO ₂ CH ₂ —)
Represents a divalent group such as Of these, preferred are a single bond, an alkylene group such as a methylene group and an ethylene group, and an acylamino group. X ₁ is a single bond or -O-, -N
(R ₄ )-, wherein R ₄ is a hydrogen atom or has 1 to 20 carbon atoms.
Is an alkyl group (eg, methyl group, ethyl group, benzyl group, etc.), an aryl group having 6 to 20 carbon atoms (eg, phenyl group), and an alkoxyl group having 1 to 20 carbon atoms (eg, methoxy group). A hydrogen atom is particularly preferable.

Specific examples of the compound represented by the general formula [3] include, but are not limited to, the compounds (1) to (17) described in Japanese Patent Application No. 6-144823, pp. 11 to 13. Not done.

Specific examples of the compound represented by the general formula [3] include the following.

[0168]

[Chemical 56]

[0169]

[Chemical 57]

In the present invention, the light-sensitive emulsion layer and / or the non-light-sensitive hydrophilic colloid layer are used for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Various known 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-
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

In the present invention, the coating amount of gelatin is 4.0 g / m ² or less per one side from the viewpoint of reducing residual color contamination or preventing drying failure in the drying process in an automatic processor. It is preferable.

As the gelatin, other than lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products can also be used.

In the present invention, the photographic emulsion 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 (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid, Methacrylic acid,
A polymer having a monomer component of a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

In the present invention, various other additives are used in the light-sensitive material. For example, desensitizer, plasticizer,
Examples include slip agents, development accelerators, oils, and the like.

Regarding these additives and the above-mentioned additives, specifically, Research Disclosure 176
Nos. (Ibid.), Pages 22-31, etc. can be used.

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

In the light-sensitive material of the present invention, the photographic 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.

In the present invention, as developing agents, dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromhydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone, etc.), 3-pyrazolidone (Eg 1-phenyl-3-
Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3- Pyrazolidone), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4)
-Diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (for example, 1-
(P-hydroxyphenyl) -3-aminopyrazoline,
1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-
Aminopyrazolin, etc.), transition metal complex salts (Ti, V, C)
It is a complex salt of a transition metal such as r, Mn, Fe, Co, Ni or Cu, and these may be in a form having a reducing power for use as a developing solution, for example, Ti ³⁺ , V ²⁺ , Cr ^2+. , F
It takes the form of a complex salt such as e ²⁺ , and as the ligand, an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof, hexametapolyphosphoric acid, tetrapolyphosphoric acid, etc. Examples thereof include phosphoric acid and salts thereof. ), Etc., can be used alone or in combination, a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid, A combination of aminophenols and ascorbic acid,
It is preferable to use a combination of 3-pyrazolidones and a transition metal complex salt and a combination of an aminophenol and a transition metal complex salt. The developing agent is usually 0.01 to 1.
It is preferably used in an amount of 4 mol / l.

In particular, when dihydroxybenzenes are used as a developing agent in the developing solution, in order to prevent deterioration of the developing solution over time due to oxidation, the silver halide light-sensitive material of the present invention is used in the state where the pH of the developing solution is 11.0 or less. Is preferably treated.

In particular, when the developing solution contains at least one selected from ascorbic acid and ascorbic acid derivatives and does not contain hydroquinone, the pH of the developing solution is set to 10.8 in order to prevent deterioration with time due to oxidation of the developing solution.
The silver halide light-sensitive material of the present invention is preferably processed in the following conditions.

In the present invention, as a silver sludge-preventing agent, JP-B-62-4702, JP-A-3-51844,
No. 4-26838, No. 4-362942, No. 1-3
Examples thereof include compounds described in No. 19031.

A compound represented by the following general formula [8] is particularly preferable.

[0184]

Embedded image

In the formula, R ₅ , R ₆ and R ₇ are each a hydrogen atom,
SM ₁ group, hydroxyl group, lower alkoxyl group, -C
OOM ₂ group, amino group, —SO ₃ M ₃ group or lower alkyl group, and at least one of R ₅ , R ₆ and R ₇ is —S
Represents an M ₁ group. M ₁ , M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different. The lower alkyl group and lower alkoxyl group represented by R ₅ , R ₆ and R ₇ are groups having 1 to 5 carbon atoms, and the amino group represented by R ₅ , R ₆ and R ₇ is substituted or non-substituted. It represents a substituted amino group, and a preferred substituent is a lower alkyl group. In the general formula [8], the ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

Specific examples of the compound represented by the general formula [8] are shown below, but the invention is not limited thereto.

[0187]

Embedded image

The developing waste liquid can be regenerated by energizing it. Specifically, an anion exchange is performed by putting a cathode (for example, an electric conductor or semiconductor such as stainless steel wool) in the developing waste solution and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) in the electrolyte solution. The waste developer tank and the electrolyte solution tank are in contact with each other through the film, and both electrodes are energized for regeneration. It is also possible to process the light-sensitive material according to the present invention while energizing. At that time, various additives added to the developer, for example, preservatives, alkali agents, pH buffers, sensitizers, antifoggants, silver sludge inhibitors, etc., which can be added to the developer, are additionally added. You can do it. Further, there is a method of processing the light-sensitive material while energizing the developing solution, and at that time, an additive which can be added to the developing solution as described above can be additionally added. When the waste developer is regenerated and used, transition metal complex salts are preferable as the developing agent of the developer used.

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and 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.), 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,
No. 025, Japanese Patent Publication No. 47-45541, etc.), a hardener (eg glutaraldehyde or its bisulfite adduct), or an antifoaming agent can be added. Total processing time (Dry to Dry) is 6
The pH of the developer is 8.5 to 10.5 in order to set it to 0 seconds or less.
Is preferably adjusted to

The compounds of the present invention include, as a special form of development processing, a developing agent in a light-sensitive material, for example, an emulsion layer,
You may use it for the activator processing liquid which makes a photosensitive material process in alkaline aqueous solution and develops. 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.
In the case of such rapid processing, the effect of the present invention is particularly great.

As the fixing solution, 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 thereof 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 acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, etc. can be added to the fixing solution.

If desired, the fixer may contain a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid),
A compound such as a pH adjuster (for example, sulfuric acid) and a chelating agent having the ability to soften water can be included.

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

In the development processing of the present invention, the development temperature 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.

[0197]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of silver halide emulsion A1) Using a simultaneous mixing method, silver chloride 70 mol% and the balance silver bromide having an average diameter of 0.0
9 μm silver chlorobromide core particles were prepared. _{K 3 Rh (NO) 4 (} H 2 O) 7 × 10 -8 mol ₂ per mol of silver when silver mole per grain formation ended when the core particle mixture, K ₃ Os
Cl ₆ at 40 ° C. pH 3. in the presence of 8 × 10 ⁻⁶ mol addition.
The silver nitrate aqueous solution and the water-soluble halide solution were simultaneously mixed while keeping the silver potential (EAg) at 165 mV. The core particles were shelled using the double-mix method with EAg lowered to 125 mV with saline. At that time, K ₂ IrC was added to the halide solution.
1 ₆ was added in an amount of 3 × 10 ^-7 mol, and K ₃ RhCl ₆ was added in an amount of 9 × 10 ^-8 mol. Further, KI conversion was performed using silver iodide fine particles, and the obtained emulsion had a core / shell type monodispersion (variation coefficient of 10 with an average diameter of 0.15 μm).
%) Silver chloroiodobromide (70 mol% silver chloride, 0.2% silver iodobromide)
The emulsion was a cubic crystal (mol%, the balance consisting of silver bromide). Then, the modified gelatin described in JP-A-2-280139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, JP-A-2-280139 / 287)
Desalination was carried out using the exemplified compound G-8) on page (3). The EAg after desalting was 190 mv at 50 ° C.

In the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.5 × 10 ^-3 mol per mol of silver, and potassium bromide in an amount of 8.5 × 10 5.
^-4 mol and citric acid added, pH 5.6, EAg12
After adjusting to 3 mv, 1 × 10 ⁻³ mol of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) was added and reacted, and then inorganic sulfur (S
⁸ ) Compound (Seishin Enterprise Co., Ltd .; PM-1200 was added to saponin and dispersed to an average of 0.5 μm)
Also, after adding 1.5 × 10 ⁻⁵ mol of chloroauric acid and performing chemical aging at a temperature of 55 ° C. until maximum sensitivity is obtained, 50
100 mg of sensitizing dye d-1 described later and 5 mg of trihexylamine were added at 0 ° C, and the temperature was further lowered to 40 ° C.
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ^-4 mol, and potassium iodide was added per mol of silver. Was added in an amount of 5 × 10 ⁻³ mol, and the pH was adjusted to 5.1 with citric acid.

(Preparation of silver halide emulsion A2) With respect to silver halide emulsion A1, the reaction temperature was raised to 50 ° C. to make the grain size 0.19 μm, and K ₃ RhCl ₆ in the shell portion was adjusted to 6 × 10.
^-Silver Halide Emulsion A in exactly the same manner except that the amount was changed to ^-8 mol.
2 was prepared. The emulsion of A2 is 40% more sensitive than the emulsion of A1 when subjected to the same chemical sensitization.

(Preparation of a silver halide photographic light-sensitive material containing a hydrazine derivative for a printing plate making scanner) A gelatin subbing layer having the following Formulation 1 was used on a support so that the amount of gelatin was 0.
45 g / m so that the ^2, amount of silver 1.5 g / m ² of silver halide emulsion layers 1 formulation 2 thereon, the amount of gelatin 0.
The silver halide emulsion layer 2 of Formulation 3 was further added thereto so that the amount thereof was 65 g / m ² and the amount of silver was 1.5 g / m ² and the amount of gelatin was 0.65 g / m ^2.
Simultaneous multi-layer coating was performed so that the coating amount of the protective layer coating solution was 0.7 g / m ² . On the other side of the undercoat layer, a backing layer having the following formulation 5 has a gelatin amount of 1.5 g / m ^2, and a backing protective layer having the following formulation 6 has a gelatin amount of 0.8 g / m 2. ^The emulsion layer side and curtain coating method are applied simultaneously so that the number becomes ² , and the emulsion layer side is simultaneously multilayer coated at a speed of 200 m / min. Then, the backing layer side is simultaneously multilayer coated and cooled at -1 ° C. A sample was obtained by simultaneously drying both surfaces.

Formulation 1 (Composition of gelatin subbing layer) Gelatin 0.45 g / m ² saponin 56.5 mg / m ² redox compound (19) (Dissolved in ethyl acetate and dispersed in gelatin solution, ethyl acetate was removed under reduced pressure. 25 mg / m ² Compounds of the general formulas [1] and [2] of the present invention (described in Table 1) (described in Table 1) Solid disperse dye (AD-12) 50 mg / m ² sodium polystyrenesulfonate (average molecular weight 500000) 15 mg / m ² fungicides (z) 0.5 mg / m ² formulation 2 (the composition of the silver halide emulsion layer 1) silver halide emulsion A1 silver amount 1.5 g / m ² equivalent amount Sensitizing dye (d-1) 150 mg / Ag 1 mol Hydrazine compound (H-9) 2 × 10 ⁻³ mol / Ag 1 mol Nucleation accelerator (N-3) 7 mg / m ² General formula of the present invention [1] Compound of [2] (described in Table 1) (described in Table 1) Sodium-di- (3-ethyl-n-butyl) sulphosuccinate 100 mg / m ² polymer latex (L1) (particle size 0.25 μm) 0 25 g / m ² Hardener (K-2) 5 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 0.7 mg / m ² Sodium naphthalenesulfonate 8 mg / m ² Saponin 20 mg / m ² Hydroquinone 20 mg / m ² 2-Mercapto-6-hydroxypurine 2 mg / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² ascorbic acid 20 mg / m ² EDTA · 2Na 25 mg / m ² sodium polystyrene sulfonate 15 mg / m ² coating liquid The pH was 5.2.

Formulation 3 (composition of silver halide emulsion layer 2) Silver halide emulsion A2 Silver amount 1.5 g / m ² equivalent amount Sensitizing dye (d-2) 100 mg / Ag 1 mol Hydrazine compound (H-2) 4 × 10 ^-3 mol / Ag 1 mol Nucleation accelerator (N-3) 7 mg / m ² Sodium-iso-amyl-n-decylsulphosuccinate 1.7 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² Compounds of the general formulas [1] and [2] of the invention (listed in Table 1) (listed in Table 1) gallic acid n-propyl ester 50 mg / m ² EDTA · 2Na 50 mg / m ² styrene-maleic acid copolymer ( molecular weight 70,000) 10 mg / m ² polymer latex (L2) (JP-A 5-665 12 No. example 3 type Lx-3 composition (9)) 0.25g / m ² colloidal silica (average particle size 0.0 μm) 150mg / m ² gelatin coating solution pH using phthalated gelatin 4.8
Met.

Formulation 4 (Emulsion protective layer composition) Gelatin 0.6 g / m ² Compounds of the general formulas [1] and [2] of the present invention (listed in Table 1) (listed in Table 1) Nucleation accelerator (N -3) 14 mg / m ² Sodium-iso-amyl-n-decylsulphosuccinate 12 mg / m ² Matting agent: Spherical poly (methyl methacrylate) with an average particle size of 3.5 μm 25 mg / m ² Average particle size 8 μm Amorphous silica 12.5 mg / m ² surfactant (S-1) 26.5 mg / m ² lubricant (silicone oil) 4 mg / m ² polymer latex (L3) (particle size 0.10 μm) 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² dye (f1) 20 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² hardener (K-2) 30 mg / m ² polystyrene sulfo Sodium acidate 10 mg / m ² Bactericide (z) 0.5 mg / m ² Formulation 5 (backing layer composition) Gelatin 0.6 g / m ² Sodium-iso-amyl-n-decylsulphosuccinate 5 mg / m ² Polymer latex (L3) ) 0.3 g / m ² colloidal silica (average particle size 0.05 μm) 100 mg / m ² sodium polystyrene sulfonate 10 mg / m ² dye (f1) 65 mg / m ² dye (f2) 15 mg / m ² dye (f3) 100 mg / M ² 1-Phenyl-5-mercaptotetrazole 10 mg / m ² Hardener (h2) 100 mg / m ² Zinc hydroxide 50 mg / m ² EDTA · 2Na 50 mg / m ² Formulation 6 (backing protective layer) Gelatin 0.4 g / M ² Matting agent: Monodisperse polymethacrylate having an average particle size of 5 μm 50 mg / m ² Average particle size of 3 μm Undefined Formed silica 12.5 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant (S-1) 1 mg / m ² Dye (f1) 65 mg / m ² Dye (f2) 15 mg / m ² dye (f3) 100 mg / m ² dye (AD-13) (solid dispersion) 20 mg / m ² sodium-di- (3-ethyl-n-butyl) sulfosuccinate 50 mg / m ² hardener (K-2 ) 20 mg / m ² sodium polystyrene sulfonate 10 mg / m ^{2 When a} solid disperse dye is added, a dye (exemplary dye AD-
After dissolving 13) in alkali, 1.2 times the equivalent amount of citric acid was added to the acid groups for acid precipitation. Other dyes (including those after Example 2) were dispersed with ZrO beads to give a particle size of 0.1 μm.
m powder dispersion.

[0205]

Embedded image

[0206]

[Chemical formula 61]

[0207]

Embedded image

Table 1 shows the samples prepared as described above.

<Evaluation> (Evaluation of sensitivity and gamma) An optical wedge was used for the obtained sample, and 633n was used as a substitute for the He-Ne laser light source.
High-speed exposure for 10 ^-5 seconds with a light source equipped with an interference filter of m, and an automatic processor GR for rapid processing made by Konica Corporation GR
A development process was carried out under the following processing conditions with an automatic developing machine in which a pair of transport rollers in the drying zone of -26SR was improved so that it could be heated (processing a). After that, separately, a sample exposed to sunlight (large size 505 mm x 610 mm) is taken as 100
After processing one sheet (that is, with a fatigue-deteriorated developer), an exposed sample was treated under the same conditions as described above (treatment b (that is, the treatment stability when the developer was fatigue-deteriorated). evaluate.)).

The developed sample thus obtained was digitally densitometer P
DA-65 (manufactured by Konica Corporation) was used for sensitivity, fog,
The gradation (γ) was measured. The sensitivities in the table are the material numbers. It was expressed as a relative sensitivity when the sensitivity at a concentration of 2.5 of 1 was 100. Further, the gradation (γ) is expressed by the tangent of the densities of 0.1 and 3.0. When the value of the gradation (γ) in the table is less than 7, it cannot be used, and when it is 7 or more and less than 10, it is still insufficient. is there.
When the gradation (γ) value is 10 or more, a super-high contrast image can be obtained for the first time, indicating that the photosensitive material is sufficiently practical.

(Evaluation of black spots) The obtained developed sample was visually evaluated using a magnifying glass of 100 times, and the number of black spots (pepper fog) was reduced in the order of 5, 4, 3 ,.
It was divided into 5 ranks of 2, 1. Ranks 1 and 2 are practically unfavorable levels.

(Processing conditions) (Process) (Temperature) (Condition A) (Condition B) Development 38 ° C. 12 seconds 7 seconds Fixing 35 ° C. 10 seconds 6 seconds Washing 40 ° C. 10 seconds 6 seconds Drying 50 ° C. 12 seconds 7 seconds Total 44 seconds 26 seconds (Amount of processing agent replenishment) (Condition A) (Condition B) Developing solution Large size All per sheet processing 74cc 35cc Fixing solution Large all size Processing per sheet 120cc 60cc (Developer 1 composition) Per 1 l of used solution Diethyl Triamine pentaacetic acid / 5 sodium salt 1 g Sodium sulfite 42.5 g Potassium sulfite 17.5 g Potassium carbonate 55 g Hydroquinone 20 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.85 g Potassium bromide 4 g 5-methyl Benzotriazole 0.2 g Boric acid 8 g Diethylene glycol 40 g Example of general formula [8] 0.078 g / l KOH of Compound 8-3 was added in an amount such that the working solution had a pH of 10.4.

(Developer 2 composition) Diethyltriamine pentaacetic acid / 5 sodium salt 1 g / l Sodium sulfite 40 g / l Sodium ascorbate 20 g / l 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0 .85 g / l potassium carbonate 45 g / l benzotriazole 0.2 g / l potassium bromide 4 g / l boric acid 8 g / l diethylene glycol 40 g / l 1-phenyl-6-mercaptotetrazole 0.03 g / l hydroxide Potassium 17.5 g / l Compound (3-3) 0.078 g / l Water and potassium hydroxide are added to make 1 liter / pH 9.4.

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) per 1 l working solution 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27% aqueous solution) 25 ml sulfuric acid was used to adjust the pH of the working solution to 4.9.

Table 2 shows the evaluation results.

[0216]

[Table 1]

*: (Replenishment amount of processing agent) (Condition A) (Condition B) Developer solution for all sizes of large size 74 cc 35 cc Fixing solution for all sizes of large size 120 cc 60 cc

[0218]

[Chemical formula 63]

[0219]

[Table 2]

As is clear from Table 2, the silver halide photographic light-sensitive material for a printing plate-making scanner of the present invention has little sensitivity variation and softening, and black spots are suppressed.

Example 2 In place of the hydrazine derivatives H-9 and H-2, 15 mg / m ² of the compound P-1 (pyridinium salt derivative) was used in each of the silver halide emulsion layer 1 and the silver halide emulsion layer 2. Samples shown in Table 3 were prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1, and the results in Table 4 were obtained.

[0222]

[Table 3]

*: (Replenishment amount of the processing agent) (Condition A) (Condition B) Development solution Large size All per sheet processing 74 cc 35 cc Fixer Large size All per sheet processing 120 cc 60 cc

[0224]

[Table 4]

As is clear from Table 4, the silver halide photographic light-sensitive material for a printing plate-making scanner of the present invention has little sensitivity variation and softening, and the generation of black spots is suppressed.

Example 3 In Example 1, the following sensitizing dyes were used instead of d-1 and d-2, and the following d-3, d-4 and d-5 were used, and an addition layer of a solid disperse dye (AD-12) was used. Of 20 mg / m ^{2 for} each of the gelatin undercoat layer and the silver halide emulsion layer 1, and the same undercoat layer as in Example 1 of JP-A-5-66512 was applied to the polyethylene terephthalate support having a thickness of 75 μm. A sample was prepared in the same manner as in Example 1 except that a backing layer and a backing protective layer were provided on the processed surface, and the exposing machine was an infrared semiconductor laser light source recorder M.
The same evaluation as in Example 1 was carried out except that T-R1120 (manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. The silver halide photographic light-sensitive material for a printing plate-making scanner of the present invention showed sensitivity fluctuation and softening. It was found that the black spots were suppressed and the occurrence of black spots was suppressed.

[0227]

[Chemical 64]

[0228]

According to the present invention, it is possible to provide a black-and-white silver halide photographic light-sensitive material and an image forming method using the same which have little influence on sensitivity and halftone reproduction area even when a large amount of light-sensitive material is processed. did it.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 1/43 G03C 1/43 1/83 1/83 1/85 1/85 1/91 1 / 91 5/29 501 5/29 501

Claims (15)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer, and containing at least one compound represented by the following general formula [1]. A black-and-white silver halide photographic light-sensitive material characterized by the above. Embedded image (In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, an alkoxyl group, an aryloxy group, a cyano group or an acylamino group. Group, alkylthio group, arylthio group, sulfonylamino group, ureido group, sulfamoylamino group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, amino group, hydroxyl group,
It represents a nitro group, an imide group or a heterocyclic group. Y ₁ represents a group of atoms capable of forming an aromatic carbocycle or an aromatic heterocycle. Z ₁ represents an oxygen atom or a sulfur atom, and B ₁ represents a single group or Z ₁ -B ₁ which has a capability of adsorbing silver halide. ) 2. A support having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer, and containing at least one compound represented by the following general formula [2]. A black-and-white silver halide photographic light-sensitive material characterized by the above. Embedded image (In the formula, R ₂₁ represents an alkyl group, Z ₂ represents an oxygen atom or a sulfur atom, B ₂ represents a single group or a group of Z ₂ -B ₂ having an adsorptivity for silver halide.) 3. A support having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer, and containing a hydrazine derivative and a compound represented by the above general formula [1]. A black-and-white silver halide photographic light-sensitive material characterized in that 4. A support having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer, containing a hydrazine derivative and a compound represented by the above general formula [2]. A black-and-white silver halide photographic light-sensitive material characterized in that 5. A pyridinium salt derivative and a compound represented by the above general formula [1], which has at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support. A black-and-white silver halide photographic light-sensitive material characterized by containing. 6. A pyridinium salt derivative and a compound represented by the above general formula [2], which has at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support. A black-and-white silver halide photographic light-sensitive material characterized by containing. 7. The photosensitive silver halide emulsion layer according to claim 1, wherein at least one layer contains silver halide grains having a silver chloride content of 60 mol% or more. The black-and-white silver halide photographic light-sensitive material described in. 8. The black-and-white silver halide photographic light-sensitive material according to claim 1, which contains at least one hardener which acts by activating a carboxyl group. . 9. The black-and-white silver halide photographic light-sensitive material according to claim 8, wherein the hardener is represented by the following general formula [3]. Embedded image (In the formula, R ₁ and R ₂ each represent an alkyl group or an aryl group, and R ₁ and R ₂ may form a ring.
R ₃ represents a hydrogen atom or a substituent. L represents a single bond or a divalent group. X ₁ is a single bond or -O-, -N (R ₄ ).
Represents a hydrogen atom, R ₄ represents a hydrogen atom, an alkyl group or an aryl group. ) 10. The black-and-white silver halide photographic light-sensitive material according to claim 1, further comprising a compound which releases a development inhibitor by being oxidized by an oxidant of a developing agent. material. 11. The black-and-white silver halide photographic light-sensitive material according to claim 1, wherein at least one conductive layer is provided. 12. At least one dye-immobilized layer is provided between the support and the silver halide emulsion layer closest to the support. The black-and-white silver halide photographic light-sensitive material according to any one of 1 to 11. 13. The hydrophilic colloid is gelatin, and the coating amount of gelatin on each side of the support is 4.0 g / m ² or less on each side.
13. The black-and-white silver halide photographic light-sensitive material according to any one of 12. 14. The black-and-white silver halide photographic light-sensitive material according to any one of claims 1 to 13 is treated with a developing solution containing dihydroxybenzenes as a developing agent and having a pH of 11.0 or less. An image forming method for a black and white silver halide photographic light-sensitive material. 15. The black-and-white silver halide photographic light-sensitive material according to claim 1, containing at least one selected from ascorbic acid and ascorbic acid derivatives, and containing no hydroquinone and having a pH of 10. An image forming method, which comprises processing with a developing solution of 8 or less.