JPH0961966A - Silver halide photographic sensitive material and processing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material small in fluctuation of sensitivity and deterioration of dot quality with the lapse of time even in the case of processing reduced in a development replenishing amount, and to provide the photographic sensitive material for forming a printing plate good in dot quality in the case of reproducing minute points <=25μm even at the time of remarkably reducing a processing time. SOLUTION: This silver halide photographic sensitive material having at least one silver halide emulsion layer on a support composed essentially of a syndiotactic polystyrene film contains a silver halide emulsion chemically sensitized with at least one kind of selenium compound and having a >=60mol% silver chloride content.

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 a processing method thereof, and more particularly to a black-and-white silver halide photographic light-sensitive material for printing plate making and a processing method thereof.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials, especially black-and-white light-sensitive materials for printing plate making, are generally coated on a transparent support,
A plastic film base is used as the transparent support. Among them, a transparent support made of polyethylene terephthalate (hereinafter abbreviated as PET) has dimensional stability,
It is often used because of its strength.

Further, the printing plate making operation includes a step of faithfully reproducing the halftone dot image. In order to produce an excellent printed matter, it is necessary that a target halftone dot is faithfully reproduced on a plate-making photosensitive material. In recent years, in the field of printing plate making, improvement in halftone dot quality has been demanded, and for example, 600
The technique called FM screening, which is composed of high-definition printing of lines / inch or more and a random pattern of uniform minimal points, is required to reproduce minute points of 25 μm or less. These are Ar lasers, He-Ne lasers,
When performing exposure with an image output machine equipped with a laser light source such as a semiconductor laser, a so-called plate-making scanner, or exposing a halftone dot image original with a printer, the target minute halftone dot faithfully It needs to be reproduced. Photosensitive materials that faithfully reproduce these halftone dots include
Usually, silver chloride, silver chlorobromide or silver chloroiodobromide containing 60 mol% or more of silver chloride is used.

On the other hand, there are various devices for exposing a printing plate-making photosensitive material, and a photographic emulsion contained in the photosensitive material is used by using a chemical sensitizer in order to have sufficient sensitivity for exposure with each light source. Is usually chemically sensitized. Among them, selenium compounds and tellurium compounds are known to be advantageous in increasing the sensitivity.

After exposure, the black-and-white light-sensitive material for printing plate making is generally processed with an automatic developing machine having at least a developing section, a fixing section, a washing section or a stabilizing bath section, and a drying section.

[0006] In recent years, interest in the environment has been increasing, and attention has been focused on reducing the amount of photographic processing waste liquid. Photographic effluents usually cannot be released to public sewers, and waste liquors are collected and destroyed by cumbersome and costly incineration methods. From these points, it has been strongly desired to reduce the photographic processing waste liquid. As a means for solving such a reduction of the photographic processing waste liquid, it is considered to reduce the replenishment amount of the developing solution, which is usually 300 ml / m ² or more, when the processing is performed by using an automatic developing machine.

[0007]

However, using the above PET support, a silver chloride, silver chlorobromide or silver chloroiodobromide emulsion containing 60 mol% or more of silver chloride is used as a chemical sensitizer as a selenium compound. Alternatively, in the case of a silver halide photographic light-sensitive material chemically sensitized with a tellurium compound, when the processing is carried out by simply reducing the development replenishment amount as described above, there is a large variation in sensitivity over time, and halftone dot quality There were problems such as deterioration and increased fog.

In recent years, there has been an increasing demand for rapid processing. In the conventionally known technology as described above, a phenomenon occurs in which the quality of halftone dots is significantly deteriorated when a small amount of light is exposed, processed rapidly, and a large amount of photosensitive material is subjected to running processing. It's starting to happen.

With respect to the above problems, the object of the present invention is to reduce the replenishment amount of the development and to process the silver halide grains, which are less susceptible to sensitivity fluctuations and deterioration of halftone dot quality over time, and whose fog does not increase. To provide a photographic light-sensitive material.

Another object of the present invention is to obtain good halftone dot quality when reproducing minute points of 25 microns or less in a photosensitive material for printing plate making even when processed in a state where the processing time is greatly shortened. Another object is to provide a novel silver halide photographic light-sensitive material.

[0011]

The above objects of the present invention have been achieved by the following means.

1) A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support comprising a film containing syndiotactic polystyrene as a main component,
A silver halide photographic light-sensitive material characterized in that at least one silver halide emulsion layer is chemically sensitized with at least one selenium compound and contains silver halide grains containing at least 60 mol% of silver chloride.

2) A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support made of a film containing syndiotactic polystyrene as a main component,
A silver halide photographic light-sensitive material characterized in that at least one silver halide emulsion layer is chemically sensitized with at least one tellurium compound and contains silver halide grains containing at least 60 mol% of silver chloride.

3) The silver halide photographic light-sensitive material described in 1 or 2 above is processed by an automatic processor having at least a developing tank, a fixing tank, a washing tank or a stabilizing tank, and a drying section,
Total processing time (dry to dry) from the start of development of the silver halide photographic light-sensitive material to the exit of the drying zone
Is processed for 10 seconds or more and 80 seconds or less, a method for processing a silver halide photographic light-sensitive material.

4) In the method of processing a silver halide photographic light-sensitive material, at least 30 replenishers of development replenisher are added per m ^2.
4. The method for processing a silver halide photographic light-sensitive material as described in 3 above, wherein the development is carried out while replenishing it in an amount of not less than 250 ml and not more than 250 ml.

The specific constitution of the present invention will be described in detail below. In the present invention, a film containing syndiotactic polystyrene (SPS) as a main component means that a stereoregular structure (tacticity) is mainly a syndiotactic structure, that is, a side with respect to a main chain in which a carbon-carbon bond is formed. A phenyl group or a substituted phenyl group that is a chain has a steric structure alternately located in opposite directions, the main chain of the main chain is a styrene polymer that is a racemo chain, or a composition containing the same. If it is a styrene homopolymer, it can be polymerized by the method described in JP-A-62-117708. For other polymers, JP-A-1-46912 and JP-A-1-178 can be used.
It can be obtained by polymerizing by the method described in No. 505 or the like.

The tacticity is quantified by a nuclear magnetic resonance method (13C-NMR method) using isotope carbon. The tacticity measured by 13 C-NMR method is the existence ratio of a plurality of continuous structural units, for example, 2
The number of diads can be represented by triad, the number of triads by 3 and the pentad by 5; however, the styrene-based polymer mainly having a syndiotactic structure referred to in the present invention is usually a racemic diad of 75 % Or more, preferably 85% or more, or racemic triad 60% or more, preferably 75% or more, or racemic pentad 30% or more, preferably 50% or more.

Specific monomers of the polymer constituting the syndiotactic polystyrene composition include alkylstyrene such as styrene and methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, and alkoxystyrene. A single or a mixture containing vinyl benzoate as a main component. In particular, a copolymer of alkyl styrene and styrene has a
This is a preferable combination for obtaining a film having a thickness of at least m.

The polystyrene-based resin having a syndiotactic structure of the present invention uses (a) (a) (a) described in JP-A-5-320448, pages 4 to 10 as a catalyst for polymerization using the above raw material monomers. ) Those containing a transition metal compound and (b) aluminoxane as main components, or (b)
It can be produced by polymerization using a compound containing as a main component a compound capable of reacting with (a) a transition metal compound and (c) a transition metal compound to form an ionic complex.

To produce the styrenic polymer used in the film of the present invention, first, the styrenic monomer is sufficiently purified and then polymerized in the presence of any of the above catalysts. At this time, the polymerization method, the polymerization conditions (polymerization temperature, polymerization time), the solvent and the like may be appropriately selected. Usually from -50
At a temperature of 200 ° C, preferably 30-100 ° C,
Polymerization is carried out for 1 second to 10 hours, preferably 1 minute to 6 hours. As the polymerization method, any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used, and either continuous polymerization or discontinuous polymerization may be used. Here, in solution polymerization, as a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and aliphatic hydrocarbons such as cyclopentane, hexane, heptane, and octane are used alone or in combination of two or more. It can be used in combination. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight and composition of the polymer may be controlled by a commonly used method. The molecular weight can be controlled by, for example, the catalyst, temperature, monomer concentration and the like.

Further, to the extent that the effects of the present invention are not impaired,
It does not matter to copolymerize another monomer copolymerizable therewith.

The polymer used for forming the SPS (syndiotactic polystyrene) film has a weight average molecular weight of 10,000 or more, more preferably 30,000 or more. If the weight average molecular weight is less than 10,000,
The film may not be excellent in strength characteristics and heat resistance. The upper limit of the weight-average molecular weight is not particularly limited. However, if the weight-average molecular weight is 1,500,000 or more, breakage may occur due to an increase in stretching tension.

The molecular weight of the SPS film of the present invention is not limited as long as it is formed, but the weight average molecular weight is preferably 10,000 to 3,000,000, and particularly preferably 30,000 to. It is preferably 1,500,000.

The molecular weight distribution at this time (number average molecular weight /
The weight average molecular weight) is preferably 1.5 to 8. This molecular weight distribution can be adjusted by mixing different molecular weights. Furthermore, the syndiotactic polystyrene-based film of the present invention comprises syndiotactic polystyrene-based pellets at 120 to 180 ° C.
Then, it is dried for 1 to 24 hours under vacuum or under normal pressure under an atmosphere of inert gas such as air or nitrogen. The target moisture content is not particularly limited, but is 0.05% or less, preferably 0.01% or less, and more preferably 0.005% or less from the viewpoint of preventing reduction in mechanical strength and the like due to hydrolysis. . However, these methods are not particularly limited as long as the purpose is achieved.

<< Polymerization Example >> SPS pellets were prepared according to JP-A-3-131843. From the preparation of the catalyst to the polymerization reaction, all were carried out under a dry argon stream. Internal volume 5
Copper sulfate pentahydrate (CuSO ₄ ·
5H ₂ O) 17.8 g (71 mmol) purified benzene 2
The catalyst was adjusted by adding 00 ml and 24 ml of trimethylaluminum and stirring at 40 ° C. for 8 hours. This was placed under an argon gas flow. After filtering through 3 glass filters, the filtrate was freeze-dried. This was taken out, put in a 2 l stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein, and heated to 90 ° C.

Into this, 1 liter of purified styrene was added,
Further, add 70 ml of purified p-methylstyrene,
The polymerization reaction was continued at this temperature for 8 hours. Thereafter, the mixture was cooled to room temperature, 1 l of methylene chloride was added, and a methanol solution of sodium methylate was added to the catalyst to deactivate the catalyst while further stirring. The contents were gradually dropped into 20 l of methanol, filtered through a glass filter, washed with methanol three times, and then dried. The weight average molecular weight of this polymer was 415,000, which was obtained from the results of GPC measurement using standard polystyrene at 135 ° C. using 1,2,4-trichlorobenzene as a solvent. In addition, the melting point of this polymer was 245 ° C., and it was confirmed from the measurement of 13 C-NMR that the polymer obtained also had a syndiotactic structure. This was pelletized with an extruder and then dried at 130 ° C.

The SPS film of the present invention is preferably SPS alone made from styrene, but as a film further containing SPS, a styrene-based polymer having an isotactic structure in which the main chain is meso chain is added to SPS. The crystallization rate can be controlled by mixing the coalescence (IPS), and a stronger film can be obtained.

When SPS and IPS are mixed, the ratio depends on the stereoregularity of each other, but is 30: 7.
0 to 99: 1, preferably 50:50 to 98: 2.

The support contains inorganic fine particles, an antioxidant, a UV absorber, an antistatic agent, a dye, a pigment, a dye, etc. for imparting functionality within a range not to impair the object of the present invention. Is possible.

As a method of extruding at the time of film formation, a known method can be applied.
Syndiotactic polystyrene pellets 280-
An unstretched film is produced by melting and extruding at 350 ° C. and cooling and solidifying while applying static electricity on a casting roll.

Next, this unstretched film is biaxially stretched to obtain 2
Orient the axis. As a stretching method, a known method, for example, a sequential biaxial stretching method in which longitudinal stretching and transverse stretching are sequentially performed, a sequential biaxial stretching method of transverse stretching / longitudinal stretching, a transverse / longitudinal / longitudinal stretching method, a longitudinal / transverse stretching method. -A longitudinal stretching method, a longitudinal-longitudinal-transverse stretching method, a simultaneous biaxial stretching method or the like can be adopted and can be appropriately selected according to various characteristics such as required mechanical strength and dimensional stability. .

In general, a sequential biaxial stretching method in which stretching is carried out first in the longitudinal direction and then in the width direction, is preferred. In this case,
The stretching ratio in the longitudinal and transverse directions is 2.5 to 6 times, and the longitudinal stretching temperature depends on the glass transition temperature (Tg) of the polymer.
Stretching is usually performed in a temperature range of (Tg + 10) ° C. to (Tg + 50) ° C. In the case of a syndiotactic polystyrene film, it is preferably carried out at 110 to 150 ° C. The stretching temperature in the width direction is preferably slightly higher than that in the longitudinal direction and is preferably 115 to 160 ° C. Next, this stretched film is heat-treated. The heat treatment temperature in this case can be appropriately changed depending on the application. A temperature of 150 ° C. or lower is used for shrink-wrapping applications requiring a high shrinkage ratio, and a temperature of 150 to 270 ° C. is appropriately used for photographic, printing or medical applications requiring dimensional stability depending on the purpose.

The heat treatment time is not particularly limited, but is usually 1
About 2 to 2 minutes are adopted. It goes without saying that vertical heat relaxation, horizontal heat relaxation treatment and the like may be performed as necessary. After that, the film may be rapidly cooled and wound, but it is gradually cooled between Tg and the heat treatment temperature for 0.1 minute to 1500 hours, and wound on a large-diameter core, and further -0 between 40 ° C. and Tg. Cooling at an average cooling rate of 0.01 to −20 ° C./min is preferable because it has the effect of making it difficult for the support to be wound. Of course, the heat treatment between 40 ° C and Tg
From the winding of the support to the cutting of the production method after coating the emulsion, 0.
It is preferably carried out by placing it in a constant temperature bath for 1 minute to 1500 hours.

In addition to the above film forming method, slipperiness, adhesiveness,
In order to impart various properties such as antistatic performance, it is also possible to produce an SPS laminated film in which an SPS support having the above-mentioned properties is laminated on at least one surface of the SPS support. The lamination method is such that the resin is melted in a laminar flow and then extruded from a die or cooled and solidified S.
Molten S is added to PS unstretched support or SPS uniaxially stretched support.
It is obtained by extrusion-laminating PS, then stretching in both the longitudinal and transverse directions or in the direction perpendicular to the uniaxial stretching direction and heat setting. Extrusion conditions, stretching temperature, stretching ratio, heat setting temperature, etc. of the SPS resin are slightly different depending on the combination of the SPS laminated support, but may be finely adjusted to select the optimum conditions.
Not a major change.

Needless to say, the laminate is composed of two or more layers, and may be a combination of the same type of polymer (including a combination of copolymerized polymers) or a different type of polymer.

The above-mentioned film forming method can be appropriately changed according to its use and purpose, and the present invention is not limited to these methods for any reason.

The thickness of the thus obtained syndiotactic polystyrene-based stretched film varies depending on the use, but is 0.3 μm for ultra-thin capacitors, 6 μm and 12 μm for ordinary capacitors. There are various thicknesses such as 100 μm for medical and printing sensitive materials and 250 μm for electrical insulating materials (slot liner etc.), but the above film forming conditions are effective for those having a thickness of 0.3 to 500 μm. .

Next, the subbing treatment of the support before the coating of the hydrophilic colloid layer for silver halide photographic light-sensitive materials will be described.

When applying the undercoat layer, chemical treatment, mechanical surface roughening treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
It is preferable to perform laser processing or the like. The surface tension of the surface is preferably 50 dyne / cm or more by these treatments.

The subbing layer may be any of those used in the art. The undercoat layer is
Although it may be a single layer, it is preferably a multi-layer in order to obtain more functionality and increase the adhesive strength. The subbing multilayer method will be described below.

In the multi-layer method, the first subbing layer preferably adheres well to the support, and the raw material is an unsaturated carboxylic acid such as methacrylic acid or acrylic acid or its ester, styrene, vinylidene chloride, or chloride. Examples thereof include polymers or copolymers obtained from monomers such as vinyl, water-dispersed polyesters, polyurethanes, polyethyleneimines, and epoxy resins.

Of these, preferred are copolymers having a water-dispersible polyester and a styrene polymer as constituent elements. The copolymer or composition containing the water-dispersible polyester and the styrene polymer as constituent elements will be described.

The water-dispersible polyester is a substantially linear polymer obtained by a polycondensation reaction of a polybasic acid or its ester-forming derivative with a polyol or its ester-forming derivative. The polybasic acid component of this polymer includes terephthalic acid, isophthalic acid, phthalic acid,
Phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,
Examples thereof include 4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid and dimer acid. Unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and p
A small proportion of hydroxycarboxylic acids such as -hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used.

Further, as the polyol component, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, and triglyceride. Methylolpropane, poly (ethylene oxide) glycol,
Examples thereof include poly (tetramethylene oxide) glycol.

In order to impart water dispersibility and water solubility to the water-dispersible polyester, introduction of a sulfonate, diethylene glycol, polyalkylene ether glycol, etc. is an effective means. In particular, a dicarboxylic acid component having a sulfonic acid salt (a dicarboxylic acid having a sulfonic acid salt and / or
Or an ester-forming derivative thereof) in an amount of from 5 to 15 mol% based on all dicarboxylic acid components in the water-dispersible polyester.

As the dicarboxylic acid having a sulfonic acid salt and / or its ester-forming derivative used in the undercoat layer of the present invention, those having a group of an alkali metal sulfonic acid salt are particularly preferable, for example, 4-sulfoisophthalic acid, 5
-Alkali metal salts such as sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) isophthalic acid or ester-forming derivatives thereof are used. However, 5-sulfoisophthalic acid sodium salt or its ester-forming derivative is particularly preferable. The dicarboxylic acid having a sulfonic acid salt and / or an ester-forming derivative thereof is particularly preferably used in an amount of from 6 to 10 mol% based on all dicarboxylic acid components from the viewpoint of water solubility and water resistance.

As the monomer of the styrene polymer used in the undercoat layer of the present invention, when styrene is used alone or when it is copolymerized, for example, alkyl acrylate or alkyl methacrylate (wherein the alkyl group is a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.); 2-hydroxyethyl acrylate, 2-hydroxy Hydroxy-containing monomers such as ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N-methylolmethacrylamide, N-methylo. Le acrylamide, N, N-
Amido group-containing monomers such as dimethylolacrylamide and N-methoxymethylacrylamide; amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminomethacrylate; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; acrylic acid Monomers containing carboxyl groups or salts thereof such as methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt); styrenesulfonic acid, vinylsulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt) Monomers containing sulfonic acid groups or salts thereof such as; itaconic acid, maleic acid, fumaric acid and salts thereof (sodium salt,
Monomers containing carboxyl groups such as potassium salts and ammonium salts) or salts thereof; monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl isocyanate, allyl isocyanate, vinyl methyl ether, vinyl ethyl ether, acrylonitrile , Vinyl chloride, vinyl acetate, vinylidene chloride and the like.
The above-mentioned monomers can be copolymerized using one kind or two or more kinds.

To modify the water-dispersible polyester into a vinyl-based polymer, an addition-polymerizable group is introduced at the terminal of the water-dispersible polyester and copolymerized with a monomer of the vinyl-based copolymer for grafting. There are methods such as a method of polymerizing a vinyl-based copolymer and introducing a reactive group at the time of polycondensation of a water-dispersible polyester such as a carboxylic acid, a glycidyl group or an amino group as a monomer, and grafting.

The polymerization initiator includes ammonium persulfate, potassium persulfate, sodium persulfate and the like, and ammonium persulfate is preferably used.

Further, regarding the polymerization, a soap is not particularly required and a soap-free reaction is possible. But,
For the purpose of improving the polymerization stability, a surfactant can be used as an emulsifier in the system, and any general nonionic and anionic surfactant can be used.

The ratio of modification of the above water-dispersible polyester and styrene copolymer is 99/1 to 5/95, preferably 97/3 to 50/50, and more preferably 95/5.
~ 80/20 is good.

In order to improve the coating property, it is preferable to add an activator or a cellulose compound such as methyl cellulose in the first subbing layer.

The subbing treatment may be carried out after the film formation, but if the subbing composition can be stretched, before the longitudinal stretching which is in the midst of film formation, between the longitudinal stretching and the transverse stretching, It can be performed at any place such as after transverse stretching and before heat treatment.

When Stretching is not Possible For example, when a polymer having a hydrophilic group is used, it may not be possible to stretch due to the strong interaction between hydrophilic polymers. However, stretching may be performed under steam or as a stretching aid. Stretching is possible by adding polyglycerin or the like.

Preferred among the monomers having a hydrophilic group are unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride. From the viewpoint of water resistance, the content is preferably 1 to 10% by weight,
More preferably 1 to 8% by weight, more preferably 1 to 6
%, Most preferably 1 to 4% by weight. Further, as the fourth component of this copolymer, other copolymerizable monomers may be copolymerized in the range of 0 to 15% by weight, preferably 0 to 10% by weight, if necessary. Examples of this include alkyl-substituted styrenes such as methylstyrene,
Chlorostyrene, chloromethyl styrene and other halogenated styrenes, acrylonitrile and other unsaturated nitrile compounds, methyl acrylate, methyl methacrylate, t-butyl acrylate and other aliphatic compounds, cyclohexyl methacrylate and other alicyclic compounds, and benzyl acrylate. And aromatic (meth) acrylic acid ester compounds, such as butadiene and isoprene, which are rubber-modified compounds.

The method for producing these copolymers is not particularly limited and can be usually obtained by radical polymerization using a generally known radical initiator.

GP of a copolymer composed of these monomers
The standard polystyrene-equivalent weight average molecular weight measured by the C method is preferably 1,500 to 700,000, and more preferably 2,000 to 500,000.

The second subbing layer is preferably a hydrophilic resin layer which adheres well to the photographic emulsion layer. As a binder that constitutes the hydrophilic resin layer, gelatin, a gelatin derivative,
Casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethyl cellulose, water-soluble polymers such as hydroxyethyl cellulose, a combination of a polystyrene sulfonate sodium copolymer and a hydrophobic latex, and the like, Gelatin is preferred.

A hardener is preferably used in these two subbing layers to enhance the film strength. Examples of such hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, and reactive halogen. Having compounds, ketone compounds such as diacetyl, cyclopentanedione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-dichloro-1,3,5-triazine, divinyl sulfone, 5-acetyl-1,3- Diacryloyl hexahydro-1,3,5-triazine, compound having reactive olefin, vinyl sulfone compound, N-hydroxymethylphthalimide, N-methylol compound, isocyanate compound, aziridine compound, acid derivative, carbodiimide compound, epoxy Compounds, isoxazole compounds, mu Halogenoalkoxy carboxaldehyde, such as chlorosulfonic acid, dihydroxy dioxane, organic hardeners and chromium alum and dioxane derivatives such as dichlorodioxane, zirconium sulfate, an inorganic hardeners such as chromium trichloride. As a hardener having a relatively fast hardening effect on gelatin, compounds having a dihydroquinoline skeleton, N-carbamoylpyridinium salts, acylimidazoles, N-acyloxyimidazoles, N
-A compound having two or more acyloxyimino groups in the molecule, a compound having an N-sulfonyloxyimide group, a compound having a phosphorus-halogen bond, a chloroformamidinium compound and the like are known.

The second subbing layer preferably contains, as a slipping agent, inorganic fine particles such as silicon dioxide and titanium dioxide, and an organic matting material (1 to 10 μm) such as polymethylmethacrylate.

In addition to these, various additives such as antistatic agents, antihalation agents, coloring dyes, pigments and coating aids may be contained, if desired.

Among these, it is preferable to include an antistatic agent. Preferred antistatic agents include non-photosensitive conductors and / or semiconductor fine particles.

The non-photosensitive conductor and / or semiconductor fine particles used in the undercoat layer of the present invention are electrically conductive due to charge carriers existing in the particles, such as cations, anions, electrons and holes. As shown, it may be an organic material, an inorganic material, or a composite material of both. Preferably, it is a compound showing electron conductivity, and if it is an organic material, polyaniline,
Examples thereof include polymer fine particles such as polypyrrole and polyacetylene. Oxygen-deficient oxide if inorganic material,
Examples thereof include metal oxide fine particles that easily form a non-stoichiometric compound such as a metal excess oxide, a metal deficient oxide, and an oxygen excess oxide. If it is a charge transfer complex or an organic-inorganic composite material, a phosphazene metal complex or the like can be mentioned.
Among these, the most preferable compound for the undercoat layer of the present invention is metal oxide fine particles which can be manufactured by various methods. Further, the conductor in the undercoat layer of the present invention has a volume resistivity of 10 ³ Ω · cm or less, and the semiconductor has a volume resistivity of 10 ¹² Ω · cm or less.
It is defined as a semiconductor.

A preferred method for producing conductive fine particles will be exemplified below.

(Preparation of semiconductor fine particle solution) 65 g of stannic chloride hydrate was dissolved in 2000 cc of water / ethanol mixed solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The resulting precipitate is removed by decantation, and the precipitate is washed with distilled water many times. Silver nitrate was dropped into distilled water after washing the precipitate, and after confirming that there was no reaction of chlorine ions, 1000 cc of distilled water was added to bring the total amount to 2000.
cc. Further, 40 cc of 30% aqueous ammonia was added and heated in a water bath to obtain a colloidal gel dispersion. This colloidal gel dispersion is designated as dispersion A-1.

(Preparation of Semiconductor Fine Particle Powder) 65 g of stannic chloride hydrate and 1.5 g of antimony trichloride were dissolved in 1000 g of ethanol to obtain a uniform solution. 1N- in this solution
An aqueous solution of sodium hydroxide was added dropwise until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was isolated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. 100 g of the colloidal precipitate from which excess ions were removed was mixed with 50 g of barium sulfate having an average particle size of 0.3 μm and 1000 g of water to obtain 900
A powder mixture A-2 composed of stannic oxide and barium sulfate having a bluish average particle size of 0.1 μm was obtained by spraying in a firing furnace heated to ℃.

The coating liquid concentration of the undercoat layer composition is usually 20% by weight or less, preferably 15% by weight or less. The coating amount is 1 to 30 g by weight of the coating liquid per 1 m ² of the film.
More preferably, it is 5 to 20 g.

As a coating method, various known methods can be applied. For example, a roll coating method, a gravure roll coating method, a spray coating method, an air knife coating method, a bar coating method, an impregnation method, a curtain coating method or the like can be applied alone or in combination.

The silver halide emulsion in the silver halide emulsion used in the present invention is characterized by containing a silver halide emulsion containing 60 mol% or more of silver chloride. In particular,
An emulsion containing a silver halide emulsion having a composition of silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or silver chloroiodobromide containing 60 mol% or more of silver chloride is used.

The average grain size of silver halide is 1.2 μm.
m or less, and particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ccs), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmillan")).

The shape of the silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

As the method of 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 and a combination thereof may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. 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. Gives a silver halide emulsion having a substantially uniform grain size.

As the tabular grains, tabular grains having 60 mol% or more of silver chloride and having a (100) plane as a main plane are preferably used. These are described in US Pat. No. 5,264,33.
7, No. 5,314,798, No. 5,320,958
, Etc., the desired tabular grains can be easily obtained. In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled at specific surface portions. Further, in order to control the photosensitizing nucleus, a transition line can be provided on the surface or inside of the tabular grains. In order to have a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodide ions. The preparation of the particles can be appropriately selected from an acid method, a neutral method, an ammonia method and the like. When doping a metal, it is particularly preferable to form particles under acidic conditions of pH 1 to 5. Ammonia, thioethers, thiourea compounds, thione compounds and the like can be used as a silver halide solvent in order to control grain growth during formation of tabular grains.

During physical aging or chemical aging, metal salts such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can coexist. It is often customary in silver halide emulsions to add iridium in the range of 10 ^-9 to 10 ^-3 mol per mol of silver halide in order to obtain high illuminance characteristics. In the present invention, it is preferable to add rhodium, ruthenium, osmium and / or rhenium to the silver halide emulsion in order to obtain an optimum high-contrast emulsion as a light-sensitive material for printing plate making. As the addition position, there is a method of distributing uniformly in the particles, a method of forming a core-shell structure, and a method of localizing a large amount in the core portion or the shell portion.

When the metal compound is added to the particles,
Metals include halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl,
Phenanthroline or a combination of these compounds can be coordinated. The oxidation state of the metal can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands are described in JP-A No. 2-20.
No. 82, No. 2-20853, No. 2-20854, No. 2-20855, 6-dentate ligands,
Alkali complex salts include common sodium salts, potassium salts, cesium salts, and primary, secondary, and tertiary amine salts. Also, a transition metal complex salt can be formed in the form of an aquo complex. Examples of these are, for example, K ₂ [RuC
l ₆ ], (NH ₄ ) ₂ [RuCl ₆ ], K ₂ [Ru (NO)
Cl ₄ (SCN)], K ₂ [RuCl ₅ (H ₂ O)], and the like. Ru part is Rh, Os, R
e, Ir, Pd, and Pt can be used instead.

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

The silver halide emulsion of the present invention is chemically sensitized, and particularly, it is chemically sensitized with at least one selenium compound. In another embodiment, at least one tellurium compound is chemically sensitized.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
No., JP-A-4-25832, JP-A-4-109240,
It is preferable to use the compounds described in JP-A-4-271341, JP-A-5-40324 and the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg, 2- Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (for example, bis (3-chloro-2,6-
Dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium and the like. The preferred types of labile selenium compounds have been described above, but are not limiting. Those skilled in the art will note that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not important. It is generally understood that the moieties carry selenium and have no role other than to make them present in the emulsion in an unstable manner. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. The non-labile selenium compound used in the present invention is disclosed in
The compounds described in JP-B-6-4553, JP-B-52-34492 and JP-B-52-34491 are used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, and 2-alkyl selenide.
Examples thereof include selenazolidinedione, 2-selenaoxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas (1) and (2) are preferable.

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In the formula, Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (eg, methyl group, ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg, , Vinyl group, propenyl group), aralkyl group (eg, benzyl group, phenethyl group), aryl group (eg, phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoyl) Phenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group), heterocyclic group (for example, pyridyl group, thienyl group,
Furyl group, imidazolal group), -NR _a1 (R _a2 ), -O
Represents R _a3 or -SR _a4 . R _a1 , R _a2 , R _a3 and R
_a4 may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group.
Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R _a1 and R _a2 are each a hydrogen atom or an acyl group (eg, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoro group). Methylbenzoyl group). In the general formula (1), Z ₁ is preferably an alkyl group, an aryl group or —NR _a1 (R
represents _a2), Z ₂ represents -NR _a5 the (R _a6). R _a1 ,
R _a2 , R _a5 and R _{a6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. In the general formula (1), more preferably N, N-
Dialkylselenourea, N, N, N'-trialkyl-
N'-acyl selenourea, tetraalkyl selenourea,
Represents N, N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

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In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR _a7 , -NR _a8 (R _a9 ), _{-SR. a10} , -Se
R _a11 , X and a hydrogen atom. R _a7 , R _a10 and R _a11
Represents an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, R _a8 and R _a9 represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and X represents a halogen atom. In the general formula (2), Z ₃ , Z ₄ , Z ₅ , R _a7 and R
_The aliphatic group represented by _a8 , _Ra9 , _Ra10 and _Ra11 is a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aralkyl group (for example, a methyl group, an ethyl group, an n-propyl group, Isopropyl group, t-butyl group,
n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group,
Allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl). In the general formula (2), Z ₃ , Z ₄ , Z ₅ ,
The aromatic group represented by R _a7 , R _a8 , R _a9 , R _a10 and R _a11 is a monocyclic or condensed aryl group (for example, a phenyl group, a pentafluorophenyl group, a 4-chlorophenyl group, 3-sulfophenyl). Group, α-naphthyl group, 4-methylphenyl group). In the general formula (2), Z ₃ ,
The heterocyclic group represented by Z ₄ , Z ₅ , R _a7 , R _a8 , R _a9 , R _a10 and R _a11 is a saturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom. Alternatively, it represents an unsaturated heterocyclic group (for example, a pyridyl group, a thienyl group, a furyl group, a thiazolyl group, an imidazolyl group, a benzimidazolyl group). In the general formula (2), R _a7 , R
_The cation represented by _a10 and R _a11 represents an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In formula (2), Z ₃ , Z ₄ or Z ₅ preferably represents an aliphatic group, an aromatic group or —OR _a7 , and R
_a7 represents an aliphatic group or an aromatic group. In the general formula (2),
More preferably, it represents trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of the compounds represented by formulas (1) and (2) are shown below, but the invention is not limited thereto.

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[0084]

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[0085]

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[0086]

[Chemical 6]

[0087]

[Chemical 7]

Examples of tellurium sensitizers used in the present invention include US Pat. Nos. 1,623,499, 3,320,069, 3,772,031 and British Patent 235. No. 211, No. 1,121,496
No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.)
635 (1980), ibid 1102 (197)
9), ibid 645 (1979), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin Tra).
ns. ) 1,191 (1980), S.I. Patay (S.
Patai) The Chemistry of Organic Selenium and Tellurium Companies (The Chemistry of Organic)
Selenium and Tellurium co
mounds), Vol 1 (1986), Vol.
2 (1987) is preferably used. Specific tellurium sensitizers include, for example, colloidal tellurium and telluroureas (eg, allyl tellurourea, N,
N-dimethyltellurourea, tetramethyltellurourea, N
-Carboxyethyl-N ', N'-dimethyl tellurourea, N, N'-diphenylethylene tellurourea), interrocyanates (e.g. allylisoterrocyanate), telluroketones (e.g. telluroacetophenone), telluramides (e.g. telluro). Acetamide,
N, N-dimethyl tellurobenzamide), tellurohydrazide (eg N, N ′, N′-trimethyltelulobenzhydrazide), telluroester (eg t-butyl-t)
-Hexyl telluroester), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), diacyl (di) tellurides ( For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, diethylcarbamoyltelluride, bis (ethoxycarbonyl) telluride), (di)
Tellurides, other tellurium compounds (eg British Patent No. 1,
Negatively charged telluride ion-containing gelatin, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, allyl tellurocyanate) described in No. 295,462. Of these tellurium compounds, the following general formulas (3) and (4) are preferable.
And (5).

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In the above general formula (3), R ₁₁ , R ₁₂ and R
₁₃ is an aliphatic group, an aromatic group, a heterocyclic group, OR ₁₄ , NR
₁₅ (R ₁₆ ), SR ₁₇ , OSiR ₁₈ (R ₁₉ ) (R ₂₀ ), X
Or represents a hydrogen atom. R ₁₄ and R ₁₇ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation,
₁₅ and R ₁₆ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, R ₁₈ , R ₁₉ and R ₂₀ represent an aliphatic group, and X represents a halogen atom. Next, the general formula (3) will be described in detail. In the general formula (3), R ₁₁ ,
The aliphatic group represented by R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ preferably has 1 to 30 carbon atoms.
And particularly a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl and 2-butenyl. , 3-pentenyl, propargyl, 3-pentynyl, benzyl and phenethyl. In the general formula (3), R ₁₁ ,
The aromatic group represented by R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed ring having 6 to 20 carbon atoms. Is an aryl group, and examples thereof include phenyl and naphthyl. In the general formula (3), R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆
And the heterocyclic group represented by R ₁₇ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. These may be monocyclic or may form a condensed ring with another aromatic or heterocyclic ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, and examples thereof include pyridyl, furyl, thienyl, thiazolyl, imidazolyl and benzimidazolyl. In the general formula (3), the cation represented by R ₁₄ and R ₁₇ represents an alkali metal or ammonium. The halogen atom represented by X in the general formula (3) is, for example, a fluorine atom, a chlorine atom,
Represents a bromine atom and an iodine atom. Also, this aliphatic group,
The aromatic group and the heterocyclic group may be substituted. The following are mentioned as a substituent. Representative substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, amino groups, acylamino groups, ureido groups,
Urethane group, sulfonylamino group, sulfamoyl group,
Carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, phosphoramide group, diacylamino group, imide group, alkylthio group, arylthio group, halogen atom, cyano group, sulfo group Group, carboxy group, hydroxy group, phosphono group, nitro group and heterocyclic group. These groups may be further substituted. When there are two or more substituents, they may be the same or different. R ₁₁ , R ₁₂ and R ₁₃ may combine with each other to form a ring together with the phosphorus atom, and R ₁₅ and R ₁₆ may combine with each other to form a nitrogen-containing heterocycle. General formula (3)
Of these, preferably R ₁₁ , R ₁₂ and R ₁₃ represent an aliphatic group or an aromatic group, more preferably an alkyl group or an aromatic group.

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In the general formula (4), R ₂₁ represents an aliphatic group, an aromatic group, a heterocyclic group or —NR ₂₃ (R ₂₄ ), and R ₂₂
Represents -NR ₂₅ (R ₂₆ ), -N (R ₂₇ ) N (R ₂₈ ) R ₂₉ or -OR ₃₀ . R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R
₂₈ , R ₂₉ and R ₃₀ are a hydrogen atom, an aliphatic group, an aromatic group,
Represents a heterocyclic group or an acyl group. Where R ₂₁ and R ₂₅ , R
₂₁ and R ₂₇ , R ₂₁ and R ₂₈ , R ₂₁ and R ₃₀ , R ₂₃ and R ₂₅ , R ₂₃
And R ₂₇ , R ₂₃ and R _28, and R ₂₃ and R ₃₀ may combine with each other to form a ring. Next, the general formula (4) will be described in detail. In the general formula (4), R ₂₁ , R ₂₃ , R ₂₄ , R ₂₅ ,
The aliphatic group, aromatic group and heterocyclic group represented by R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ have the same meanings as in formula (1). In the general formula (4), R ₂₃ , R ₂₄ , R ₂₅ ,
The acyl group represented by R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ is preferably one having 1 to 30 carbon atoms, and particularly a straight chain or branched acyl group having 1 to 20 carbon atoms. Examples thereof include acetyl, benzoyl, formyl, pivaloyl and decanoyl. Where R ₂₁ and R ₂₅ , R ₂₁ and R ₂₇ , R
₂₁ and R ₂₈ , R ₂₁ and R ₃₀ , R ₂₃ and R ₂₅ , R ₂₃ and R ₂₇ , R ₂₃
When R ₂₈ and R ₂₃ and R ₂₃ and R ₃₀ combine to form a ring, examples thereof include an alkylene group, an arylene group, an aralkylene group, and an alkenylene group. Further, the aliphatic group, aromatic group and heterocyclic group may be substituted with the substituents given in the general formula (3). In the general formula (4), preferably R ₂₁ represents an aliphatic group, an aromatic group or —NR ₂₃ (R ₂₄ ), and R ₂₂ represents —NR ₂₅ (R ₂₆ ). R ₂₃ , R ₂₄ , R
₂₅ and R ₂₆ represent an aliphatic group or an aromatic group. In formula (4), R ₂₁ is more preferably an aromatic group or —NR.
₂₃ (R ₂₄ ) and R ₂₂ represents -NR ₂₅ (R ₂₆ ). R
₂₃ , R ₂₄ , R ₂₅ and R ₂₆ represent an alkyl group or an aromatic group. Here, it is more preferable that R ₂₁ and R ₂₅ and R ₂₃ and R ₂₅ form a ring via an alkylene group, an arylene group, an aralkylene group or an alkenylene group.

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In the above general formula (5), R₃₁And R₃₂Is the same
Same or different, aliphatic group, aromatic group
Group, heterocyclic group,-(C = Y ')-R₃₃Represents R₃₃Is water
Elementary atom, aliphatic group, aromatic group, heterocyclic group, NR
₃₄(R₃₅), OR₃₆Or SR₃₇And Y'is the oxygen source
Child, sulfur atom or NR₃₈Represents R₃₄, R₃₅, R₃₆,
R₃₇And R₃₈Is a hydrogen atom, an aliphatic group, an aromatic group or
It represents a heterocyclic group, and n represents 1 or 2. Then the general formula
(5) will be described in detail. In general formula (5)
R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇And R₃₈
The aliphatic group, aromatic group or heterocyclic group represented by
It has the same meaning as each of (4). Also, R₃₁, R₃₂,
R₃₃, R₃₄, R₃₅, R₃₆, R₃₇And R₃₈The fat represented by
Aliphatic groups, aromatic groups and heterocyclic groups are listed in general formula (4).
May be substituted with a substituent. Where R₃₁And R₃₂
And R₃₄And R₃₅May combine to form a ring. General
In formula (5), preferably R₃₁And R₃₂Is a heterocyclic group
Is-(C = Y ')-R₃₃Represents R₃₃Is NR₃₄(R₃₅)
Or OR₃₆And Y'represents an oxygen atom. R₃₄, R₃₅
And R₃₆Represents an aliphatic group, aromatic group or heterocyclic group.
You. In the general formula (5), more preferably R ₃₁And R₃₂Is
-(C = Y ')-R₃₃Represents R₃₃Is NR₃₄(R₃₅)
And Y'represents an oxygen atom. R₃₄And R₃₅Is aliphatic
Represents a group, an aromatic group or a heterocyclic group.

Specific examples of the compounds represented by formulas (3), (4) and (5) of the present invention are shown below, but the present invention is not limited thereto.

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[0097]

[Chemical 12]

[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to serve as a sensitizing nucleus on the surface or inside of the silver halide emulsion grain. The following tests can be conducted for the rate of silver telluride formation in a silver halide emulsion. When a large amount is added (for example, 1 × 10 ⁻³ mol / mol Ag), the formed silver telluride has absorption in the visible region. Therefore, for the sulfur sensitizer, E.I. Mois
ar is Journalalof Photographic
Science, 14: 181 (1966)
Alternatively, the method described in the same, Vol. 16, p. 102 (1968) can be applied. The amount of silver sulfide produced in a silver halide emulsion was measured by the infinite reflectance (i) of the emulsion in the visible range (520 nm).
nfinite reflectivity) to Ku
The relative silver telluride formation rate can be easily obtained by the same method as that obtained using the Belka-Munk equation. Since this reaction is apparently close to a first-order reaction, a pseudo-first-order reaction rate constant can also be obtained. For example, a silver bromide octahedral emulsion having an average grain size of 0.5 μm (1 kg
The emulsion contains 0.75 mol of AgBr and 80 g of gelatin) at 50 ° C while maintaining pH = 6.3 and pAg = 8.3.
While keeping the temperature at 1, the tellurium compound dissolved in an organic solvent (such as methanol) is added at 1 × 10 ⁻³ mol / mol Ag. Put the emulsion in a 1 cm thick cell with a spectrophotometer with integrating sphere, reflectivity (R) at 520 nm with reference to the blank emulsion
Is measured over time. Kubelka reflectance
Substitute into the formula (1-R) ² / 2R of -Munk, and obtain the pseudo first-order reaction rate constant k (min ^-1 ) from the change in the value. If you do not produce silver telluride, R = 1 and always Kubel
The value of ka-Munk is the same as that without tellurium compound and is 0.
It remains. A compound having an apparent first-order reaction rate constant k of 1 × 10 ^{−8 to 1} min ⁻¹ under exactly the same conditions as in this test method is preferable. In addition, in a smaller addition region where absorption in the visible region is difficult to detect, the produced silver telluride can be separated from the unreacted tellurium sensitizer and quantified. For example, after separation by immersion in an aqueous solution of a halogen salt or an aqueous solution of a water-soluble mercapto compound, a trace amount of Te is quantitatively analyzed by an atomic absorption method or the like. This reaction rate depends not only on the type of compound but also on the silver halide composition of the emulsion to be tested, the temperature to be tested, the pA.
It fluctuates greatly within a range of several digits depending on g and pH. The tellurium sensitizer preferably used in the present invention is a compound capable of forming silver telluride with respect to a specific silver halide emulsion having a halogen composition and crystal habit to be used. Generally speaking, for a silver bromide emulsion, a temperature of 40 to 95 ° C., p
A compound capable of forming silver telluride in any of H3 to 10 or pAg6 to 11 is preferably used in the present invention, and in this range, the pseudo first-order reaction rate constant k by the above test method is 1 × 10 ^-7 to 1 × 10 ^-1 min ^-1
Compounds falling within the range are more preferable as tellurium sensitizers.

The compounds represented by the general formulas (3), (4) and (5) of the present invention can be synthesized according to known methods. For example, Journal of Chemical Society (J. Chem. Soc.
(A)) 1969, 2927; Journal of Organometallic Chemistry (J. Organome).
t. Chem. ) 4,320 (1965): ibid,
1,200 (1963); ibid, 113, C35.
(1976); Phosphorus Sulfur (Phos)
phorusSulfur) 15, 155 (198)
3); Hemische Berichte (Chem. Ber) 10
9, 2996 (1976); Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.).
635 (1980); ibid, 1102 (197).
9); ibid, 645 (1979); ibid, 82
0 (1987); Journal of Chemical Society Perkin Transactions (J. Chem.
Soc. Perkin. Trans. ) 1,191
(1980); S. Patai, The
Chemistry of Organo Selenium and
Tellurium and Tellurium Campaigns (Th
e Chemistry of Organo Sel
enium and Tellurium Compound
ds) Volume 2 216-267 (1987) Tetrahedron Letters
s) 31, 3587 (1990), Journal of.
Chemical Research, Synopses (J. Chem. R
es. , Synopses) 2, 56 (1990), Bulletin of the Chemical Society of Japan (Bull. Chem. Soc., Japan).
62, 2117 (1989), ibid, 60, 771.
(1987), Journal of Organometallic Chemistry (J. Organometallic).
Chem. ) 338, 9 (1988), ibid, 30
6, C36 (1986), The Chemical Society of Japan, Volume 7, 1475.
(1987), Zeitschrift Chemie 26,17.
9 (1986), Chemistry Letters (Chemi
story Letters) 3,475 (1987),
Indian Journal of Chemistry (In
dian Journol of Chemistr
y, Section A) 25A, 57 (1986),
Angewandte Chemie
Mie, 97, 1051 (1985), Spectrochimica Acta (Spectrochimica Act)
a, Part A) 38A, 185 (1982), Organic Preparation and Prosedia International (Organic Preparat)
ions and Procedures Inter
national) 10,289 (1978), Organometallics (Organometallics)
It can be synthesized by the method described in 1,470 (1982).

The amount of the selenium sensitizer or tellurium sensitizer used in the present invention varies depending on the silver halide grains used, the chemical ripening conditions and the like, but it is generally from 10 ⁻⁸ to 10 ⁸ per mol of silver halide. ^-2 mol, preferably 10 ^-7
About 5 × 10 ⁻³ mol is used.

The conditions for chemical sensitization in the present invention are as follows:
Although there is no particular limitation, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 85 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, palladium, platinum or iridium in combination. It is particularly preferable to use a gold sensitizer, and specific examples thereof include chloroauric acid, potassium chloroauric acid, chloroauric acid thiocyanate and the like.

In the present invention, it is also preferable to use a sulfur sensitizer in combination. As a preferable 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. In the present invention, a reduction sensitizer may also be used in combination.

The light-sensitive material used in 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 such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1
-Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3 , 3a, 7-tetrazaindenes), pentazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like. Can be.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion according to the present invention, 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 hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be.

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

The photographic emulsion 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 (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like 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.

As one method for remarkably exhibiting the effect of the present invention, it is preferable that at least one constituent layer contains a hydrophilic polymer. Preferred hydrophilic polymers include starch, glucose, dextrin, dextran, cyclodextrin, sucrose, maltose, xanthan gum, carrageenan, and the like. The molecular weight of the hydrophilic polymer can be appropriately selected from 600 to 1,000,000. The lower the molecular weight is, the better to elute into the processing solution quickly during the processing, but if it is too low, the film strength of the film is deteriorated. When a hydrophilic polymer is used, the film abrasion resistance deteriorates.
It is preferable to add inorganic colloidal silica, colloidal tin, colloidal zinc, colloidal titanium, colloidal yttrium, colloidal praseodymium, neodymium, zeolite, apatite, and the like. Examples of the zeolite include analsite, erionite, mordenite, shabasite, gmelinite, and levinite, and examples of the synthetic zeolite include zeolite A, X, Y, and L. Examples of apatite include hydroxyapatite, fluorospatite, and chlorapatite. A preferable addition amount is 1% to 200% by weight per hydrophilic binder. By treating the above inorganic compound with a silane coupling agent, the inorganic compound hardly aggregates even when added to an emulsion, and can stabilize a coating solution. Further, cracking due to the inorganic compound can be prevented. As silane coupling agents, triethoxysilanovinyl, trimethoxysilanovinyl, trimethoxypropyl methacrylate, trimethoxysilanopropylglycidyl, 1-mercapto-3-triethoxysilanopropane, 1-amino-3-triethoxysilanopropane, Triethoxysilanophenyl, triethoxymethylsilane and the like. Silane coupling agent, by high temperature treatment with the inorganic compound,
The characteristics can be improved over simple mixing. The mixing ratio is preferably selected in the range of 1: 100 to 100: 1.

In order to bring out the effect of the present invention more remarkably, at least one hydrophilic colloid layer is provided on the opposite side of the silver halide photographic emulsion layer, and at least one hydrophobic polymer layer is provided on the outer side thereof. It is preferable. Here, the hydrophilic colloid layer on the opposite side of the silver halide photographic emulsion layer includes a so-called back layer. In the present invention,
A configuration having at least one hydrophobic polymer layer outside the back layer is preferable. In the present invention, the hydrophobic polymer layer is a layer using a hydrophobic polymer as a binder.
Specific examples of the binder of the polymer layer, polyethylene, polypropylene, polystyrene, polyvinyl chloride,
Polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, tetrafluoroethylene,
Fluorinated resins such as polyvinylidene fluoride, rubbers such as butadiene rubber, chloroprene rubber, and natural rubber; acrylic or methacrylic acid esters such as polymethyl methacrylate and polyethyl acrylate; polyester resins such as polyethylene phthalate; nylon 6; nylon 66
And water-insoluble polymers such as silicone resins and derivatives thereof. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used. Particularly preferred binders are copolymers of alkyl acrylate or alkyl methacrylate with acrylic acid or methacrylic acid (acrylic acid or methacrylic acid is preferably at most 5 mol%), styrene-
Butadiene copolymer, styrene-butadiene-acrylic acid copolymer (acrylic acid is preferably 5 mol% or less), styrene-butadiene-divinylbenzene-methacrylic acid copolymer (methacrylic acid is preferably 5 mol% or less), vinyl acetate-ethylene-acryl Acid copolymers (acrylic acid is 5 mol% or less), vinylidene chloride-acrylonitrile-methyl methacrylate-ethyl acrylate-acrylic acid copolymer (acrylic acid 5 mol% or less), and ethyl acrylate-glycidyl methacrylate-acrylic acid copolymer. These may be used alone or in combination of two or more.

The hydrophobic polymer layer in the present invention may include a matting agent, a surfactant, a dye, a slip agent, a cross-linking agent, a thickener, a UV absorber, and inorganic fine particles such as colloidal silica for photographic use, if necessary. Additives may be added. These additives are also described in Research Disclosure Magazine 17
6, 17646 (December 1978).

The hydrophobic polymer layer in the invention may be one layer or two or more layers. The thickness of the polymer layer of the present invention is not particularly limited. However, if the thickness of the hydrophobic polymer layer is too small, the water resistance of the hydrophobic polymer layer becomes insufficient, and the back layer swells in the treatment liquid, which is inappropriate. Conversely, if the thickness of the hydrophobic polymer layer is too large, the water vapor permeability of the polymer layer becomes insufficient, and the moisture absorption and desorption of the hydrophilic colloid layer of the back layer is inhibited, resulting in poor curl. Of course, the thickness of the hydrophobic polymer layer also depends on the physical properties of the binder used. Therefore, it is necessary to determine the thickness of the polymer layer in consideration of both of them. The preferred thickness of the hydrophobic polymer layer depends on the kind of binder of the hydrophobic polymer layer, but is 0.05 to 10 μm.
m, more preferably 0.1 to 5 μm. When the hydrophobic polymer layer of the present invention comprises two or more layers, the sum of the thicknesses of all the hydrophobic polymer layers is defined as the thickness of the hydrophobic polymer layer of the silver halide photographic light-sensitive material of the present invention.

The method of applying the hydrophobic polymer layer in the present invention is not particularly limited. After applying and drying the back layer, a polymer layer may be applied on the back layer and then dried, or the back layer and the hydrophobic polymer layer may be simultaneously applied,
Thereafter, it may be dried. The hydrophobic polymer layer may be applied in a solvent system by dissolving in a solvent of a binder of the polymer layer, or may be applied in an aqueous system using an aqueous dispersion of the binder polymer.

On the surface opposite to the emulsion layer of the silver halide photographic light-sensitive material of the present invention, an adhesive layer / antistatic layer /
It is preferable to provide a back layer / hydrophobic polymer layer containing a hydrophilic colloid. Further, a protective layer may be provided thereon. As the adhesive layer, a vinylidene chloride copolymer or a styrene-glycidyl acrylate copolymer is applied to a corona-discharged support in a thickness of 0.1 to 1 μm, and then an indium or phosphorus-doped average particle size of 0.01 is applied. ~ 1 μm
And a gelatin layer containing fine particles of tin oxide and vanadium pentoxide. Further, a styrene sulfonic acid / maleic acid copolymer can be formed by forming a film with an epoxy compound, an aziridine compound, or a carbonyl active crosslinking agent. A dye back layer may be provided on these antistatic layers. These layers should contain inorganic fillers such as colloidal silica for dimensional stability, silica or methyl methacrylate matting agent for adhesion prevention, silicon-based slip agent or release agent for transportability control, etc. Can be. The back layer may contain a backing dye, and as the backing dye, a benzylidene dye or an oxonol dye is used. These alkali-soluble or decomposable dyes can be fixed as fine particles. The concentration for preventing halation is preferably 0.1 to 2.0 at each photosensitive wavelength.

An inorganic or organic hardener is added to the photographic emulsion and the non-photosensitive hydrophilic colloid layer of the present invention as a crosslinking agent for hydrophilic colloid such as gelatin. 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 compound (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, etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activating type hardener, etc., alone or in combination. Can be used. These hardeners are available from Research Disclosure.
loss) 176, 17643 (issued in December 1978), page 26, paragraphs A to C. Among them, preferred are carboxyl group-activated hardeners, and compounds represented by formulas (1) to (7) described in JP-A-5-289219, pp. 3-5, are preferred. Is, for example, H- described in pages 6 to 14 of the same specification.
1-H-39.

Various other additives are used in the light-sensitive material used in the present invention. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

In order to improve the curl and curl of the support, it is preferable to perform heat treatment after film formation. Most preferred is after film formation and after emulsion coating, but it may be after emulsion coating. The condition of heat treatment is 45 ° C or higher and glass transition temperature or lower
Preferred is between seconds and 10 days. It is preferable to set the time within one hour from the viewpoint of productivity.

The various photographic additives used in the present invention may be used by dissolving them in an aqueous solution or an organic solvent. However, when they are poorly soluble in water, they are made into a fine-grain crystal state and are made into water, gelatin, hydrophilic or hydrophobic. It can be used by dispersing it in a polymer. In order to disperse the dye, dye, desensitizing dye, hydrazine, redox compound, fogging inhibitor, ultraviolet absorber and the like of the present invention, a known dispersing machine can be used. Specific examples include a ball mill, a sand mill, a colloid mill, an ultrasonic disperser, and a high-speed impeller disperser. These photographic additives dispersed in the present invention are fine particles having an average particle size of 100 μm or less, but usually 0.02 to 10 μm.
Used with an average particle size of. As a dispersing method, a method of mechanically stirring at high speed (Japanese Patent Laid-Open No. 58-105141), heating and dissolving with an organic solvent, and dispersing this by adding gelatin containing a surfactant or defoaming agent and a hydrophilic polymer described above. To remove the organic solvent (JP-A-44-22948).
No.) A method in which crystals dissolved in an acid such as citric acid, acetic acid, sulfuric acid, hydrochloric acid, malic acid, etc. are crystallized and dispersed in a polymer having a pH of 4.5 to 7.5 (JP-A-50-80119), sodium hydroxide. , Dissolving in an alkali such as sodium hydrogen carbonate, sodium carbonate and the like, and crystallizing and dispersing in a polymer such as gelatin having a pH of 4.5 to 7.5 (JP-A-2-1)
No. 5252) can be applied. For example, hydrazine which is hardly soluble in water can be dissolved with reference to JP-A-2-3033, and this method can be applied to other additives. Further, a dye having a carboxyl, a sensitizing dye, an inhibitor and the like can increase the immobilization rate of fine particle crystals by utilizing the chelating ability of the carboxyl group. That is, it is preferable to form a hardly soluble salt by adding 200 to 4000 ppm of a calcium ion, a magnesium ion or the like to the hydrophilic colloid layer. The use of other salts is not limited as long as a hardly soluble salt can be formed. The method of dispersing the fine particles of the photographic additive can be arbitrarily applied to a sensitizer, a dye, an inhibitor, an accelerator, a contrasting agent, a contrasting auxiliary, etc. in accordance with the chemical and physical properties thereof.

To simultaneously coat two to ten constituent layers of the invention at a high speed of 30 to 1000 meters per minute, US Pat. Nos. 3,636,374 and 3,50
8,947, a known slide hopper type,
Alternatively, curtain coating can be used. In order to reduce unevenness during coating, it is preferable to lower the surface tension of the coating solution or to use the above-mentioned hydrophilic polymer which can impart a thixotropic property in which the viscosity is reduced by a shearing force.

The light-sensitive material of the present invention may be provided with a crossover cut layer, an antistatic layer, an antihalation layer and a back coat layer.

Known methods are used for packaging the photographic light-sensitive material comprising the photographic element of the present invention.

Since the silver halide photographic light-sensitive material is vulnerable to heat and humidity, it is preferable to avoid storing it under severe conditions. Generally, it is better to store at 5 ° C to 30 ° C.
The humidity should be between 35% and 60% relative humidity. It is common practice to package in polyethylene of 1-2000μ to protect from humidity. Polyethylene can suppress the permeation of water by improving the regularity of crystals by using a metallocene catalyst. Further, the surface of the polyethylene is 0.1 to 1000
Moisture permeation can be suppressed by coating the silica with a thickness of μ.

Known compounds can be used as the developing agent of the developing solution used in the development processing of the silver halide photographic light-sensitive material according to the present invention. In a preferred embodiment, the silver halide photographic light-sensitive material of the present invention is processed with a developing solution containing ascorbic acid and its derivative as a developing agent.

Ascorbic acid and its derivatives are known as developing agents, and are described, for example, in US Pat.
No. 8,548, No. 2,688,549, No. 3,0
No. 22,168, No. 3,512,981 and No. 4,
Those described in 975,354 and 5,326,816 can be used. Among them, the compound represented by the following general formula (A) can be preferably used.

[0130]

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In the formula, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X
Represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The compound represented by formula (A) will be described.

In the compound represented by the general formula (A), a compound represented by the following general formula [Aa] in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0134]

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In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, Amide group, sulfonamide group, Y ₁ represents O or S, Y ₂ represents O, S or NR
Represents ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in formula (A) or [A-a] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent. Often, the substitutable group includes a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like as a preferable substituent.

Specific examples of the compound represented by the general formula (A) or the general formula [Aa] according to the present invention are shown below.
The present invention is not limited to these.

[0138]

[Chemical 21]

[0139]

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These compounds are typically ascorbic acid, erythorbic acid or derivatives derived from them, and they are available as commercial products or can be easily synthesized by known synthetic methods.

In the present invention, the developing agent of the general formula (A) according to the present invention and 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl). -4,4-Dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-
Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone and the like and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol,
Developers such as 2,4-diaminophenol) and dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate) can be used in combination. When used in combination, the developing agent for 3-pyrazolidones, aminophenols and dihydroxybenzenes is usually 0.01 to 1.
It is preferably used in an amount of 4 mol.

The black-and-white silver halide photographic light-sensitive material according to the present invention is preferably subjected to photographic processing after exposure by an automatic processor having at least four processes including development, fixing, washing (or stabilizing bath) and drying.

In the present invention, the developer contains 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.) are preferably added. The pH buffer is preferably a carbonate, and the amount of the carbonate added is preferably 0.5 mol or more and 2.5 mol or less per liter, more preferably 0.75 mol or more and 1.5 mol or less.
It is in the range of mol or less. If necessary, a solubilizing agent (for example, polyethylene glycols, their esters, alkanolamines, etc.), a sensitizer, a surfactant, a defoaming agent,
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 salts, nitrilotriacetic acid salts, polyphosphate salts, etc., development accelerators (eg US Pat. No. 2,304,025, JP-B-47)
No. -45541), a hardener (for example, glutaraldehyde or its bisulfite adduct), or a defoaming agent.

As a preferred embodiment of the present invention, the silver halide photographic light-sensitive material of the present invention is treated with a developer containing a silver sludge inhibitor in the developer. Various silver sludge inhibitors are known, but preferably contain a compound represented by the following general formula (S).

The developer of the present invention may contain a compound represented by the following general formula (S).

General formula (S) Z ¹ -SM ^{1 In the} formula, Z ¹ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a —SO ₃ M ¹ group or a —COOM.
^At least one selected from the group consisting of ^one group (wherein M ¹ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonio group. Or those substituted with a substituent having at least one selected from this group. M ¹ is a hydrogen atom,
Represents an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate).

Further, in the general formula (S), the alkyl group represented by Z ¹ is preferably one having 1 to 30 carbon atoms, particularly straight chain, branched or cyclic alkyl having 2 to 20 carbon atoms. The group may have a substituent in addition to the above substituents. The aromatic group represented by Z ¹ is preferably a monocyclic or condensed ring having 6 to 32 carbon atoms and may have a substituent in addition to the above substituents. The heterocyclic group represented by Z ¹ is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, and contains 1 to 6 heteroatoms in one ring independently selected from nitrogen, oxygen and sulfur. And may have a substituent in addition to the above. Of the compounds represented by formula (S), Z is preferable.
¹ is a compound in which ¹ is a heterocyclic group having one or more nitrogen atoms.

In the formula, Z ¹ is a hydroxyl group, —SO ₃ M ¹
Group, a —COOM ¹ group (wherein M ¹ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonio group. It is substituted with a substituent having at least one selected or at least one selected from this group. M ¹ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate). The ammonio group preferably has 20 or less carbon atoms and the substituent is a substituted or unsubstituted linear, branched, or cyclic alkyl group (eg, methyl group, ethyl group, benzyl group, ethoxypropyl group, cyclohexyl group). Etc.), a substituted or unsubstituted phenyl group or a naphthyl group.

Further, among the compounds represented by the general formula (S), more preferred are the compounds represented by the following general formula (Sa).

[0150]

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In the formula, Z is an unsaturated 5 member having a nitrogen atom.
Heterocycle or 6-membered heterocycle (eg, pyrrole, a
Midazole, pyrazole, pyrimidine, pyridazine, pi
It is a group necessary to form (eg, radine). Where:
R¹¹, R¹²Is a hydrogen atom, -SM ¹Group, halogen atom,
Alkyl groups (including those with substituents), alkoxy
Group (including those having a substituent), hydroxyl group,-
COOM¹Group, -SO_ThreeM¹Group, alkenyl group (substituent
Those having a substituent), amino groups (having a substituent)
), Carbamoyl group (including those having a substituent)
Mu) and phenyl groups (including those with substituents)
At least one group exposed, R¹¹And R¹²Form a ring with
May be done. The ring that can be formed is a 5-membered ring or 6
A ring having at least one member ring, preferably nitrogen-containing
It is a prime heterocycle. M¹Is represented by the general formula (S) above.
M defined by the compound¹Is the same as. General formula
The compound represented by (S-a) is at least one -S
M¹A compound having a thiol group or a thione group, and
Droxyl group, -COOM¹Group, -SO_ThreeM¹Groups, substitutions
Or unsubstituted amino group, substituted or unsubstituted ammo
At least one substituent selected from the group consisting of nio groups
Having. -SM¹Group or substitution other than thione group
It may have a group, and the substituent may be a halogen atom.
Child (eg, fluorine, chlorine, bromine), lower alkyl group
(Including those having a substituent. Methyl group, ethyl group, etc.
Those having 5 or less carbon atoms are preferable. ), Lower alkoxy groups
(Including those having a substituent. Methoxy, ethoxy, butene
Those having 5 or less carbon atoms such as toxy are preferred. ), Lower
Lucenyl group (including those having a substituent. C5 or less
Are preferred. ), Carbamoyl group, phenyl group, etc.
Is mentioned. Of the compound represented by the general formula (S) below
Specific examples are shown below, but the present invention is not limited to these.
Absent.

[0152]

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[0153]

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[0154]

[Chemical formula 26]

[0155]

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[0156]

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[0157]

[Chemical 29]

The amount of the compound of the general formula (S) used in the present invention is
It is preferably 10 ^-6 to 10 ^-1 mol, and more preferably 10 ^-5 to 10 ^-2 mol in 1 liter of the developing solution.

The sulfite and metabisulfite used as a preservative in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / liter.

The pH of the developer used in the present invention is preferably adjusted to 8 or more and less than 11. More preferably, the pH is at least 8.5 and less than 10.5.

As the fixing liquid, those having a generally used composition can be used. Fixers generally have a pH of 3
~ 8. As a fixing agent, sodium thiosulfate, potassium thiosulfate, thiosulfates such as ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

The fixer contains a water-soluble aluminum salt that acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, and aldehyde compounds (eg, glutaraldehyde and a sulfite adduct of glutaraldehyde).
Etc. can be added.

If desired, the fixer may contain preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid, citric acid, tartaric acid, malic acid, succinic acid, etc. and salts thereof and optical materials thereof. Compounds such as isomers), pH adjusters (for example, sulfuric acid and salts thereof), and chelating agents having the ability to soften water can be included.

After the fixing treatment, it is preferable to perform washing with water and / or treatment with a stabilizing bath. As a stabilizing bath, the film pH is adjusted for the purpose of stabilizing the image (the film surface pH after processing).
3 to 8) and inorganic and organic acids and salts thereof,
Or an alkaline agent and its salt (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide,
Used in combination with sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc.), aldehydes (eg formalin, glyoxal, glutaraldehyde, etc.), chelating agent ( For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate salt, polyphosphate salt, etc., and an antifungal agent (for example, phenol, 4-chlorophenol, cresol, O-phenylphenol, chlorophene, dichlorophene, formaldehyde, P-). Hydroxybenzoic acid ester, 2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride,
N- (fluorodichloromethylthio) phthalimide,
2,4,4'-trichloro-2'-hydroxydiphenyl ether, etc.), a color tone adjusting agent and / or a residual color improving agent (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent; specifically, 2-mercapto). -5 Sodium sulfonate-benzimidazole, 1-phenyl-
5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,4
-Triazole, 2-mercaptohypoxanthine, etc.). Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

In order to reduce the amount of waste liquid, the present invention is processed while supplementing a fixed amount of developing solution and fixing solution proportional to the area of the light-sensitive material. The replenishing amount is 220 ml or less per 1 m ² . Preferably 1m each
It is 30 to 200 ml per ² . The fixing replenishment amount and the development replenishment amount here indicate the amounts to be replenished. Specifically, it is the replenishing amount of each liquid when replenishing the same liquid as the developing mother liquid and the fixing mother liquid, and each concentrating liquid when replenishing with the liquid obtained by diluting the developing concentrated liquid and the fixing concentrated liquid with water. And the total amount of water, the total amount of each solid processing agent and the volume of water when the solid development processing agent and the solid fixing processing agent are replenished with a liquid dissolved in water, and the solid development processing agent. And the total amount of each solid processing agent volume and water volume when the solid fixing processing agent and water are separately replenished. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as or different from the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and the temperature of each may be adjusted separately.

In order to shorten the developing time, the present invention has a total processing time (Dry to Dry) of 80 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. Seconds or less and 10 seconds or more. 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. Time including all process time, that is, Dry to
It is the time of 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 Dry) is 15 to 6
0 seconds. Further, in order to stably process a large amount of photosensitive material of 100 m ² or more, the development time is preferably 22 seconds or less and 2 seconds or more.

In order to bring out the effect of the present invention remarkably, a heat transfer member having a temperature of 60.degree.
~ 130 ° C heat roller etc.) or radiant object above 150 ° C (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc.) Heat energy of copper, stainless steel,
Those which transmit infrared rays by transmitting heat to a radiator such as nickel or various ceramics) and have a zone for drying are preferably used.

As the heat transfer material having a temperature of 60 ° C. or higher,
A heat roller is mentioned as an example. The heat roller preferably has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

Further, it is preferable that a gear is fixed to one end of the heat roller and the gear is rotated in the carrying direction by the driving means and the drive transmitting means. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine.

Further, the temperature controller is connected to a thermistor arranged in contact with the outer peripheral surface of the heat roller, and the temperature controller detects the temperature from the thermistor at 60 ° C to 150 ° C, preferably 70 ° C to 130 ° C. Therefore, it is preferable to control the halogen heater on and off.

The following examples can be given as examples of the radiation object that emits a radiation temperature of 150 ° C. or higher. (Preferably 250 ° C
Tungsten, carbon, tantalum, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, molybdenum disilicide, lanthanum chromate are directly heated and radiated to control the radiation temperature or resistance. There is a method to control by transmitting heat energy from the heating element to the radiator, but copper,
Examples include stainless steel, nickel, and various ceramics.

In the present invention, a heat transfer material having a temperature of 60 ° C. or higher and 150 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

Further, in the present invention, an automatic developing machine having the method and mechanism described below can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column (2) Washing water regeneration purifying agent and apparatus: JP-A-6-2503
No. 52, page 3 (0011) to (8), page 0058 (3) Waste liquid treatment method: JP-A-2-64638 388
(2) Lower left column of page 391 (5) Lower left column of page (4) Rinse bath between developing bath and fixing bath: JP-A-4-31
No. 3749, page 18 [0054] to page (21) [00]
65 "(5) Water replenishment method: JP-A-1-281446 250
(2) Lower left column to lower right column of page (6) Method of detecting outside air temperature and humidity to control drying air of automatic developing machine: JP-A-1-315745, page 496 (2) Lower right column to page 501 (7) Lower right column and JP-A-2-1080
No. 51, lower left column, page 588 (2) to lower left column, page 589 (3) (7) Silver recovery method of fixing waste liquid: JP-A-6-27623, page (0012) to page (0071) to page (0012).

[0176]

【Example】

(Preparation of Support) (SPS Synthesis) SPS pellets were prepared according to JP-A-3-31843. From the preparation of the catalyst to the polymerization reaction, all were carried out under a dry argon stream. Copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) 17.8 g (71 mmol) 200 ml of purified benzene and 24 ml of trimethylaluminum were placed in a glass container having an internal volume of 500 ml and stirred at 40 ° C. for 8 hours to adjust the catalyst. . This was filtered through a No. 3 glass filter under an argon stream, and the filtrate was freeze-dried. This was taken out, put in a 2 l stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein, and heated to 90 ° C.

1 liter of purified styrene was put in this,
Further, add 70 ml of purified p-methylstyrene,
The polymerization reaction was continued at this temperature for 8 hours. Thereafter, the mixture was cooled to room temperature, 1 l of methylene chloride was added, and a methanol solution of sodium methylate was added to the catalyst to deactivate the catalyst while further stirring. The contents were gradually dropped into 20 l of methanol, filtered through a glass filter, washed with methanol three times, and then dried. The weight average molecular weight of this polymer was 415,000, which was determined from the results of GPC measurement using standard polystyrene at 135 ° C. using 1,2,4-trichlorobenzene as a solvent.

The melting point of this polymer was 13 at 245 ° C.
It was confirmed from the C-NMR measurement that the polymer obtained had a syndiotactic structure. This was pelletized with an extruder and then dried at 130 ° C.

(Preparation of SPS film) 330 with extruder
The pellets obtained according to the above polymerization example were melt extruded at 0 ° C. This molten polymer was extruded through a pipe into an extrusion die. Then, an SPS film having a film thickness of 1000 μm was obtained by extruding while being electrostatically applied to the cooled casting drum through the die slit and cooling.

On the obtained SPS film, 23 W / m
After applying a corona discharge of ² · min and further blowing an ion wind, the undercoating processing liquid 1 was provided so as to have a dry film thickness of 1 μm and dried at 140 ° C.

Subbing liquid 1 Styrene-butadiene latex (No619 made by Japan Synthetic Rubber) 40 parts by weight Styrene-butadiene latex (No640 made by Japan Synthetic Rubber) 50 parts by weight Polystyrene matting agent (average particle size 3 μm) 5 parts by weight 2 , 4-dichloro-1,3,5-triazine sodium salt 3 parts by weight Sodium dodecylbenzene sulfonate 2 parts by weight After further corona discharge of 18 W / m ² · min, gelatin 80 parts by weight methyl cellulose 15 parts by weight Sodium dodecylbenzene sulfonate 3 parts by weight 2,4-dichloro-1,3,5-triazine sodium 2 parts by weight A working fluid finished to 100 g with pure water was provided to a dry film thickness of 0.1 μm 140 ° C. And dried further.

Next, a corona discharge of 23 W / m ² · min was applied to this back surface, and further an ionic wind was blown, and then the undercoating processing liquid 2 was provided so that the dry film thickness was 1 μm and 140 ° C.
And dried.

50 parts by weight of styrene-butadiene-based latex (No619 manufactured by Japan Synthetic Rubber) 40 parts by weight of styrene-butadiene-based latex (manufactured by No. 640 Japan Synthetic Rubber) Polystyrene-based matting agent (average particle size 3 μm) 5 parts by weight 2,4-dichloro- Sodium salt of 1,3,5-triazine 3 parts by weight Sodium dodecylbenzenesulfonate 2 parts by weight After further corona discharge of 18 W / m ² · min, gelatin 20 parts by weight methyl cellulose 5 parts by weight Crystalline tin oxide fine particles (Antimony dope) 70 parts by weight Sodium dodecylbenzene sulfonate 3 parts by weight 2,4-dichloro-1,3,5-triazine sodium 2 parts by weight A working liquid finished with 100 g of pure water has a dry film thickness of 0.1 μm. And further dried at 140 ° C.

Further, this undercoated support was subjected to 40c at 50 ° C.
It was wound on an m-diameter core and heat-treated at this temperature for 3 days.

[0185]

[Table 1]

Example 1 An emulsion was prepared by the following method.

(Emulsion A: Inventive) A salt of silver chloride 60 mol%, silver iodide 0.5 mol% and the balance silver bromide having a mean thickness of 0.05 μm and a mean diameter of 0.15 μm, which were obtained by the simultaneous mixing method. A silver iodobromide core grain was prepared. K ₃ R when mixing core particles
2 × 10 ⁻⁸ mol of h (H ₂ O) Br ₅ was added per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added at 3 × 10 ⁻⁷ per mol of silver.
Mole was added. The resulting emulsion had a core / shell type monodisperse (variation coefficient of 10%) silver chloroiodobromide (70 mol% silver chloride, 0.3 mol% silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. , The rest consisting of silver bromide) was a tabular grain emulsion. Further, infrared sensitizing dye d-2 was added so as to be 5 mg per 1 m ² and then adsorbed at 40 ° C. for 15 minutes. Then, a modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, JP-A-2-280139, 287)
Desalting was performed using the exemplified compound G-8) on page (3). The EAg after desalting was 180 mv at 50 ° C.

(Emulsion B: Comparative) An average thickness of 0.05 mol, consisting of 30 mol% of silver chloride and the balance of silver bromide, using the simultaneous mixing method.
Silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. When the core particles were mixed, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 10 ^-8 mol per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆
^Was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion was a tabular grain of silver chlorobromide (30 mol% silver chloride, the rest being silver bromide) of core / shell type monodisperse (variation coefficient 20%) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. It was an emulsion of. Further, infrared sensitizing dye d-2 was added so as to be 5 mg per 1 m ² and then adsorbed at 40 ° C. for 15 minutes. Then, a modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, JP-A-2-280139, 287)
Desalting was performed using the exemplified compound G-8) on page (3). The EAg after desalting was 180 mv at 50 ° C.

(Chemical sensitization 1: The present invention)
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5.6 and EA.
Adjust the G123mv, chemically ripened to maximum sensitivity at selenium compound Se-22 according chloroauric acid 2 × 10 ^-5 mol and the present invention 3 × 10 ^-5 mol per mol to a temperature 60 ° C. is out . After aging, 4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene was added in an amount of 2 × per mole of silver.
10 ⁻³ mol, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and gelatin were added.

(Chemical sensitization 2: comparison)
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ⁻³ mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5.6 and EAg.
After adjusting to 123 mv, 2 × 10 ⁻⁵ mol of chloroauric acid and 2.5 × 10 ⁻⁵ mol of sodium thiosulfate were added, and chemical ripening was performed at a temperature of 60 ° C. until maximum sensitivity was obtained. After aging, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene is 2 × 10 ^-3 mol per mol of silver, 1
-Phenyl-5-mercaptotetrazole in 3 × 10 ^-4
Mole and gelatin were added.

Chemical sensitization of each of emulsions A and B was 1
And a combination of 2 and 2 was used.

(Preparation of Silver Halide Photosensitive Material Containing Hydrazine Derivative for Printing Plate-Making Scanner) On one of the undercoat layers of the present invention and the comparative film, a gelatin undercoat layer of the following Formulation 1 was used in a gelatin amount of so that 0.5 g / m ^2, amount of silver 2 silver halide emulsion layer of formulation 2 thereon.
9 g / m ² , so that the amount of gelatin is 1.0 g / m ² ,
Further, as a lower layer of the emulsion protective layer on the upper layer, a coating solution of the following Formulation 3 is used so that the amount of gelatin is 0.2 g / m ² , and on the upper layer thereof, an upper layer of the emulsion protective layer of Formulation 4 is of the amount of 0.2 g / m 2. Simultaneous multi-layer coating was applied to achieve ² . A backing layer having the following formulation 5 was formed on the undercoat layer on the opposite side so that the amount of gelatin was 0.4 g / m ² , and the following formulation 6
A sample was obtained by coating the above polymer layer (1) and a backing protective layer having the following Formulation 7 on it simultaneously with the emulsion layer side so that the amount of gelatin was 0.4 g / m ² .

Formulation 1 (gelatin undercoat layer composition) Gelatin 0.5 g / m ² Dye AD-1 (ball mill dispersed into powder having a particle size of 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² redox compound RE-1 20 mg / m ² S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² formulation 2 (silver halide emulsion layer composition) silver halide emulsion Table 2 Sensitizing dye d-1 6 mg / m ² hydrazine derivative HY-1 30 mg / m ² compound e 100 mg / m ² latex polymer f 1.0 g / m ² hardening agent g 5 mg / m ² S-1 0.7 mg / m ² 2-mercapto-6-hydroxy purine ^{10mg / m 2 EDTA 50mg / m} 2 formulation 3 (emulsion protective layer underlayer composition) gelatin 0.2 g / m ² amino compound ^{M-1 40mg / m 2 S} -1 2mg / m 2 Formulation 4 (Emulsion protective layer upper compositions) obtained by the powder gelatin 0.2 g / m ² Dye AD-2 (ball mill dispersion to the particle size 0.1μm ) 40 mg / m ² S-1 12 mg / m ² matting agent: monodispersed silica having an average particle size of 3.5 μm 25 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 20 mg / m ² Hardener g 30 mg / m ² Formulation 5 (backing layer composition) Gelatin 0.4 g / m ² S-1 5 mg / m ² Latex polymer f 0.3 g / m ² colloidal silica (average particle size 0.05 .mu.m) 70 mg / ^{m 2} sodium polystyrenesulfonate 20 mg / m ² compound i 100 mg / m ² formulation 6 (polymer layer composition) latex (methylcarbamoyl Methacrylate: acrylic acid = 97: 3) 1.0g / m 2 hardener g 6 mg / m ² formulation 7 (backing protective layer) Gelatin 0.4 g / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² Matting agent: Monodisperse polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² Dye k 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ —OH 50 mg / m ² Hardener K-1 20 mg / m ²

[0194]

Embedded image

[0195]

[Chemical 31]

[0196]

Embedded image

The surface resistivity of the backing side after coating and drying was 5 × 10 ¹¹ Ω at 23 ° C. and 20% RH. The obtained sample was conditioned at 23 ° C. and 48% RH for 1 day, and then packaged in a barrier bag that was shielded from temperature and humidity. After that, heat treatment was performed for 3 days at 55 ° C. as a substitute environmental condition for aging. What was stored in a barrier bag and then stored at 23 ° C. was used as a comparison of aging conditions.

The sample heat-treated under the environmental conditions for the historical period and the sample stored under the comparative conditions were adhered to the step wedge and the wavelength of 670 n was used as a substitute characteristic of the red semiconductor laser light.
After the exposure of m, a developer and a fixer having the following compositions were used and processed under the following conditions with an automatic processor for rapid processing (GR-26SR Konica Corp.). In order to evaluate the quality of minute halftone dots, SG manufactured by Dainippon Screen Co., Ltd.
16μ random pattern halftone dot (FM
The same treatment was carried out after exposure with a screen). Further, 120 m of developing solution and fixing solution per 1 m ^{2 of} film
While replenishing each by 100, 100 sheets of large-size film in which 80% of the area was blackened per day were processed, and this was run for 8 days to process 800 sheets in total. The performance before running and after 800 sheets of running were compared. The surface resistivity of the backing side after treatment is 9 at 23 ° C. and 20% RH.
× 10 ¹¹ Ω.

(Developer Composition) Concentrated Developer Formulation A Diethyltriamine pentaacetic acid / 5 sodium salt 9 g / l Compound of general formula (A) A-17 0.6 mol / l Sodium sulfite 0.45 mol / l 1- Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 7 g / l potassium carbonate 2.4 mol / l 5-methylbenzotriazole 0.75 g / l potassium bromide 22 g / l boric acid 6 g / l diethylene glycol 80 g / l general The compound of formula (S) S-36 1.5 g / l KOH was added in an amount such that the working solution had a pH of 10.0.

At the time of use, 2 parts of water was added to 1 part of the concentrated developer A to prepare a working solution. This used solution was used as a developing mother solution and a developing replenishing solution.

(Fixing solution composition) Concentrated fixing solution A Ammonium thiosulfate (70% aqueous solution) 400 ml / l Sodium sulfite 45 g / l Boric acid 20 g / l Sodium acetate trihydrate 70 g / l Acetic acid (90% aqueous solution) 30 g / l Tartaric acid 6 g / l Glutaraldehyde 6 g / l Aluminum sulfate (27% aqueous solution) 50 ml / l Sulfuric acid was adjusted so that the pH of the used solution was 4.9.

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

(Processing conditions) (Process) (Temperature) (Time) Development 38 ° C. 12 seconds Fixing 35 ° C. 10 seconds Water washing 40 ° C. 10 seconds Drying 50 ° C. 12 seconds Total 44 seconds (Evaluation of sensitivity) Obtained developed sample The PDA-65
(Konica Digital Densitometer). The sensitivities in the table are the material numbers. The relative sensitivity is shown when the sensitivity of 101 at a concentration of 3.0 is 100.

(Evaluation of Fog) The unexposed portion of the obtained developed sample was taken as PDA-65 (Konica Digital Densitometer).
It was measured at. A value of 0.06 or more is a level that cannot be practically used.

(Evaluation method of dot quality (hereinafter abbreviated as DQ))
Exposure with SG-747RU with halftone dots (FM screen) of a 16 μ diameter random pattern.
%) And the dot quality (DQ) was evaluated using a loupe of 100 times. The highest rank is 5, and 4, 3 depending on the dot quality
The rank was lowered to 2, 1 and evaluated. Ranks 1 and 2 are levels that are not practically desirable.

Table 2 shows the evaluation results.

[0207]

[Table 2]

When a silver halide emulsion having a silver chloride content of 60 mol% or more is chemically sensitized with a selenium compound and an SPS support is used, there is little fluctuation in sensitivity and little increase in fog even in aged samples. It can be seen that there is little problem that halftone dot quality deteriorates even when reproducing minute dots. It was also effective when replenishing with a small developer replenishing amount in an automatic processor and rapid processing.

Example 2 A silver halide emulsion was replaced by the following silver halide emulsion C, chemical sensitization was carried out by the following chemical sensitization 3, and hydrazine derivative of the silver halide emulsion layer composition was HY-2. Evaluation was carried out in the same manner as in Example 1.

[0210]

[Chemical 33]

(Silver Halide Emulsion C) 60 mol% of silver chloride, 1 mol% of silver iodide and the balance of silver bromide by the simultaneous mixing method, the average thickness of which is 0.05 μm, and the average diameter of which is 0.15 μm. Silver core particles were prepared. When mixing core particles, K ₂ [O
[s (NO) Cl ₄ (SCN)] 8 × 1 per mol of silver
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The emulsion thus obtained was a core / shell type monodisperse (variation coefficient of 10%) silver chloroiodobromide (65 mol% silver chloride, 0.2 mol% silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.28 μm. , The rest consisting of silver bromide) was a tabular grain emulsion. Further, an infrared sensitizing dye d-2 was added so as to be 5 mg per 1 m ² , and then 40 ° C. 15
Adsorbed for a minute. Then, a modified gelatin described in JP-A-2-280139 (in which an amino group in gelatin is substituted with phenylcarbamyl, for example, as disclosed in JP-A-2-28013)
No. 9, 287 (3) (exemplified compound G-8) and desalted. The EAg after desalting was 190 mv at 50 ° C.

(Chemical Sensitization 3: Inventive) 4 was added to the obtained emulsion.
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5.6 and EA.
g123mv and adjusted to 2 × 10 ⁻⁵ mol of chloroauric acid and 2.5 × 10 ^{5 of the} tellurium compound Te-50 according to the present invention.
^-5 mol was added and chemical ripening was performed at a temperature of 60 ° C. until the maximum sensitivity was obtained. After completion of aging 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 1- (p-carboxy-phenyl)-
4.5 × 10 ⁻⁴ mol of 5-mercaptotetrazole and gelatin were added.

The evaluation results are shown in Table 3.

[0214]

[Table 3]

When a silver halide emulsion having a silver chloride content of 60 mol% or more is chemically sensitized with a tellurium compound and an SPS support is used, there is little fluctuation in sensitivity and little increase in fog even in aged samples. It can be seen that there is little problem that halftone dot quality deteriorates even when reproducing minute dots. It was also effective when replenishing with a small developer replenishing amount in an automatic processor and rapid processing.

[0216]

According to the present invention, there is obtained a silver halide photographic light-sensitive material which is less susceptible to fluctuations in sensitivity and deterioration in halftone dot quality over time and has less fog even when the processing is carried out with a reduced replenishment amount. Further, even when processed in a state where the processing time was greatly shortened, a silver halide photographic light-sensitive material having good halftone dot quality was obtained when reproducing a minute point of 25 microns or less in the light-sensitive material for printing plate making. .

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 5/31 G03C 5/31

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support comprising a film containing syndiotactic polystyrene as a main component, wherein at least one silver halide emulsion layer comprises at least a selenium compound. Chemically sensitized with at least 60% silver chloride
A silver halide photographic light-sensitive material characterized by containing silver halide grains in an amount of at least mol%. 2. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support comprising a film containing syndiotactic polystyrene as a main component, wherein at least one silver halide emulsion layer comprises at least a tellurium compound. Chemically sensitized with at least 60% silver chloride
A silver halide photographic light-sensitive material characterized by containing silver halide grains in an amount of at least mol%. 3. The silver halide photographic light-sensitive material according to claim 1 or 2 is processed by an automatic processor having at least a developing tank, a fixing tank, a washing tank or a stabilizing tank, and a drying section. A processing method for a silver halide photographic light-sensitive material, characterized in that a total processing time (Dry to Dry) from the time the material enters development to the time it leaves the drying zone is 10 seconds or more and 80 seconds or less. 4. In the method of processing a silver halide photographic light-sensitive material, at least 30 ml of a developer replenisher is added per 1 m ^2.
4. The method for processing a silver halide photographic light-sensitive material according to claim 3, wherein the development is performed while replenishing with 250 ml or less.