JPH0980664A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the sensitivity change or the dot quality deterioration produced with the lapse of time, even if doing the processing with the reduction in the replenishment quantity of developer, and eliminate the increase in fogging by providing a silver halide emulsion layer containing a specified silver halide grain on a film support body. SOLUTION: Silver halide emulsion layers at least one of which contains a silver halide grain having an average grain size less than 0.1μm is provided on a film base body mainly containing syndiotactic polystyrene. The halogen composition of the silver halide in the used silver halide emulsion is not particularly limited, and silver chloride, silver chloride bromide, silver bromide, silver iodide bromide, and silver chloride iodide bromide are used. The average grain size is a term which is generally used by experts in the field of photographic science and can be easily understood thereby, Further, the particle grain means a grain diameter when the grain is spherical or approximate to sphere. When the grain is cubic, it is converted into sphere to take its diameter as the grain size.

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 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.

On the other hand, silver halide grains having various grain sizes are used as the silver halide emulsion. Among them, in order to faithfully reproduce a high resolution image, for example, the above-mentioned minute halftone dots, the average is used. Fine particles having a particle size of 0.1 μm or less are preferably used.

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.

However, in the silver halide photographic light-sensitive material containing the above-mentioned PET support and containing a silver halide emulsion having an average grain size of 0.1 μm or less, the development replenishment amount is simply reduced as described above. In the case of the treatment, there were problems such as a large sensitivity variation with time, deterioration of halftone dot quality, and increase of 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.

[0009]

In view of the above problems, the object of the present invention is to reduce fog and sensitivity deterioration over time even if processing is performed with a reduced developer replenishment amount, and fog is reduced. The object is to provide a silver halide photographic light-sensitive material that does not increase

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 object of the present invention can be achieved by the following constitutions.

1) At least one silver halide emulsion layer containing silver halide grains having an average grain size of 0.1 μm or less is provided on a film support containing syndiotactic polystyrene as a main component. A silver halide photographic light-sensitive material.

2) The silver halide photographic light-sensitive material described in 1 above is processed by an automatic processor having at least a developing tank, a fixing tank, a water washing tank or a stabilizing tank, and a drying section to obtain the silver halide photographic light-sensitive material. Processing time (Dry to Dry) from the start of development to the exit of the drying zone is 1
A processing method of a silver halide photographic light-sensitive material, wherein the processing is carried out for 0 second or more and 80 seconds or less.

3) In a method of processing a silver halide photographic light-sensitive material in which development is performed with an automatic processor while replenishing at least a development replenisher, the amount of the development replenisher is 30 ml or more and 250 ml or less per 1 m ^{2 of the} silver halide light-sensitive material. 3. The method for processing a silver halide photographic light-sensitive material as described in 2 above, wherein

A so-called Lippmann emulsion can be used as the silver halide emulsion having an average grain size of 0.1 μm or less used in the present invention. As the Lippmann emulsion, emulsions described in GB-1139062, US-3573057 and JP-B-49-8333 can be used. Particularly preferred emulsions are JP-A-58-160948 and JP-A-60-1254.
It is preferable to use the emulsion described in No. 0. A preferable average particle size is 0.005 to 0.09 μm.

The halogen composition of silver halide in the silver halide emulsion used in the present invention is not particularly limited, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide are used. To be The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. What is particle size?
In the case where the particles are spherical or particles that can be approximated to spheres, this means particle diameter. If the particle is a cube, convert it to a sphere,
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 Mee).
s & T. H. By James: The theory o
f the photographic processes
s), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

The shape of the silver halide grains is not limited,
It may have any shape such as a tabular shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedron shape, and cubic particles are preferable.

The silver halide grains of the present invention are preferably monodisperse emulsions having a narrow grain size distribution, specifically, (standard deviation of grain size / average grain size) × 100 = width of grain size distribution (%) When the breadth of the distribution is defined, it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used. 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.

During physical ripening or chemical ripening, 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.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (RD).
176, 17643, 22-23 (December 1978)
Mon)) or in the literature cited.

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 carbon-carbon bond to a main chain formed. On the other hand, a phenyl group or a substituted phenyl group, which is a side chain, has a steric structure in which they are alternately located in opposite directions, and the main chain of the main chain is a styrene polymer which 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, and as for other polymers, JP-A-1-46912 and 1-178.
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 ( ¹³ C-NMR method) using isotope carbon.

The tacticity measured by the ¹³ C-NMR method is represented by the abundance ratio of a plurality of continuous constitutional units, for example, two diads, three triads, and five pentads. However, the styrene-based polymer having a predominantly syndiotactic structure as referred to in the present invention is usually a racemic diad of 75% or more, preferably 85% or more, or a racemic triad of 60% or more, preferably 75% or more, Alternatively, it is preferably 30% or more, more preferably 50% or more, of racemic pentad.

Specific monomers of the polymer constituting the syndiotactic polystyrene-based composition include styrene, alkylstyrene such as methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, 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 thoroughly 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, for example, by the temperature and the monomer concentration.

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 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 (number average molecular weight / weight average molecular weight) at this time 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 of 120 to 180.
Drying is performed under vacuum or at atmospheric pressure in an inert gas atmosphere such as air or nitrogen at 1 ° C. for 1 to 24 hours. 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 and put in a 2 l stainless steel container, and tributylaluminum and pentacyclomethyl-pentadiethyltitanium-trimethoxide were further mixed therein and heated to 90 ° C.

1 liter of purified styrene was added to 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 245 ° C., and it was confirmed from the ¹³ C-NMR measurement that the polymer 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 a 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 may contain inorganic fine particles, antioxidants, UV absorbers, antistatic agents, dyes, pigments, dyes, etc., for the purpose of imparting functionality, within a range not impairing the object of the present invention. Is possible.

A known method can be applied as a method of extruding at the time of film formation, but it is preferable to extrude with a T-die, for example.
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 was 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
Although not particularly limited, it is usually about 1 second to 2 minutes.

It goes without saying that longitudinal heat relaxation, horizontal heat relaxation treatment and the like may be carried out if necessary.

After this, the film may be rapidly cooled and wound up, but it is 0.1 min-1500 between Tg and the heat treatment temperature.
Slowly cool over time and wind up into a large diameter core 40 ° C to Tg
Further, it is preferable to cool the support at an average cooling rate of −0.01 to −20 ° C./minute because it has an effect of making it difficult to wind the support. Of course, it is preferable that the heat treatment at 40 ° C. to Tg is carried out in a constant temperature bath for 0.1 minutes to 1500 hours after winding the support to cutting the product after coating the emulsion.

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 homopolymers (including a combination of copolymers) or different polymers.

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 application, 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 liners, 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 coating 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 layer method will be described below. In the multi-layer method, the first subbing layer preferably adheres well to the support, and the materials include unsaturated carboxylic acids such as methacrylic acid and acrylic acid, or their esters, styrene, vinylidene chloride, vinyl chloride, Polymers or copolymers obtained from such monomers as above, water-dispersed polyesters, polyurethanes, polyethyleneimines, epoxy resins and the like can be mentioned.

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 are used. 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 or the like 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 alone is used or when it is copolymerized, for example, alkyl acrylate, 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.

In order to modify the water-dispersible polyester into a vinyl polymer, an addition-polymerizable group is introduced at the terminal of the water-dispersible polyester and copolymerized with a monomer of the vinyl 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 condensation polymerization 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 the reaction can be carried out soap-free. 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 modifying ratio 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 coatability, it is preferable to add an activator or a cellulose compound such as methylcellulose to 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, the interaction between hydrophilic macromolecules may be strong and thus stretching may not be possible. 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.

The copolymer of these monomers, GP
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 the 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- Diacryloylhexahydro-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 inorganic fine particles such as silicon dioxide and titanium oxide as a slip agent, and an organic matting material (1 to 10 μm) such as polymethylmethacrylate.

In addition to these, various additives such as an antistatic agent, an antihalation agent, a coloring dye, a pigment, and a coating aid can be contained, if necessary.

Among these, it is preferable to contain 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 illustrated below.

(Preparation of Semiconductor Fine Particle Solution) 65 g of stannic chloride hydrate was dissolved in 2000 cc of a 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.

(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 separated 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.

Colloidal precipitate from which excess ions have been removed 10
0 g was mixed with 50 g of barium sulfate having an average particle size of 0.3 μm and 1000 g of water and sprayed in a firing furnace heated to 900 ° C., and a bluish powder mixture of stannic oxide and barium sulfate having an average particle size of 0.1 μm Got

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.

In the present invention, gelatin is preferably used as the dispersion medium for the protective colloid of silver halide grains, and as the gelatin, ossein gelatin, pigskin gelatin or the like is used. In addition, modified gelatin such as alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 100,000), and phthalated gelatin are used. Other hydrophilic colloids can also be used.

In the production of the silver halide grains of the present invention, unnecessary soluble salts may be removed during the growth of the silver halide grains, or they may be contained therein. When removing the salts, see RD Vol. 17643
The method can be carried out based on the method described in section II. Noodle washing with water and ultrafiltration are preferable. A commonly used polymer flocculant (for example, Demol N manufactured by Kao Corporation)
Etc.) may be used.

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

The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

These dyes can be applied to any of the commonly used nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenin nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethine structure, pyrazoline-
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.
Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (RD) 17
Volume 6, 17643 (published December 1978), page 23, IV, section J.

As the polymer latex used in the present invention, the polymer latex generally used in silver halide photographic light-sensitive materials can be used. That is, it is a polymerizable ethylene-based compound or a polymerizable diolefin-based compound and is roughly classified into a hydrophobic monomer and a hydrophilic monomer.
Examples of the hydrophobic monomer include alkyl acrylates, alkyl methacrylates, glycidyl esters, alkenylbenzenes, vinyl esters, vinyl ethers, vinyl halides, and diene monomers. Further, as the hydrophilic monomer,
Examples thereof include acrylic acid hydroxyalkyl esters, methacrylic acid hydroxyalkyl esters, (meth) acrylic acid ethylene glycols, and ionic monomers.
These monomers may be used alone or in combination of two or more kinds, but when a hydrophilic monomer is used, it is preferable to use it in combination with a hydrophobic monomer to obtain a stable latex. In order to obtain it, it is better not to use hydrophilic monomers so much.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitro Benzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, azaindenes, tetrazaindenes,
Many compounds known as antifoggants or stabilizers can be added, such as pentazaindenes, benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amides and the like. It is preferable to use a mercapto compound.

Examples of the binder or protective colloid of the photographic emulsion according to the present invention include gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives, sugar derivatives, single or A wide variety of synthetic hydrophilic polymeric materials such as polymers can be used.

In the present invention, as a matting agent, US Pat. Nos. 2,992,101 and 2,701,245 are used.
No. 4,142,894, No. 4,396,70
A homopolymer of polymethylmethacrylate as described in No. 6 or a polymer of methylmethacrylate and methacrylic acid, an organic compound such as starch, and fine particles of an inorganic compound such as silica, titanium dioxide, strontium sulfate, and barium sulfate may be used in combination. it can. The particle size is preferably 0.6 to 10 μm, particularly preferably 1 to 5 μm.

The surface layer of the photographic element of the present invention can be used as a slip agent in US Pat. Nos. 3,489,576 and 4,047.
958 and other silicone compounds, Japanese Examined Patent Publication No. 56-2
In addition to the colloidal silica described in JP-A-3139, paraffin wax, higher fatty acid esters, starch derivatives and the like can be used.

The hardener of the present invention includes chromium salts, aldehydes, N-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds, mucohalogen acids,
Isoxazoles, dialdehyde starch, 2-chloro-
6-Hydroxytriazinylated gelatin, a carboxyl group-activating type hardener and the like can be used alone or in combination.

In the light-sensitive material used in the present invention, various other additives such as surfactants, desensitizers, plasticizers, slip agents, development accelerators and oils are used.

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.

In the present invention, the compounds described below are preferably contained in the constituent layers of the silver halide photographic light-sensitive material.

(1) Solid Dispersion Fine Particles of Dye JP-A-7-5629, page (3), pages [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
Compounds described on page (34), page [0056], JP-A-6-337494, page (4), page [0013] to
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111]
(7) Nucleation accelerator: JP-A-7-114126, page (32) [0158]
(8) Tetrazolium compound JP-A-6-208188, page (8), [0059] to
(10) Compound described on page [0067] (9) Pyridinium compound JP-A-7-110556 (5) page [0028] to
(29) Compound described in [0068] (10) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) The compound described on page.

Regarding the above-mentioned additives and other known additives, for example, Research Disclosure No. No. 17643 (December 1978); 1
8716 (November 1979) and the same No. 30811
9 (December 1989). The types of compounds and the locations described in these three research disclosures are listed below.

[0097]

[Table 1]

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. To disperse dyes, pigments, desensitizing dyes, hydrazine, redox compounds, antifoggants, UV absorbers, etc.,
It can be dispersed by a known disperser. Specifically, a ball mill,
Examples include a sand mill, a colloid mill, an ultrasonic disperser, and a high speed impeller disperser.

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
A known slide hopper type described in JP-A-8,947 or curtain coating can be used.

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 sensitive 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 developer used in the development processing of the silver halide photographic light-sensitive material according to the present invention, but ascorbic acid and its derivatives are preferably used as the 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.

[0104]

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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.

[0108]

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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 the general formula (A) or [Aa] 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.

[0112]

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[0113]

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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 formula (A) and 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4) are used. -Dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (eg o-aminophenol, p-)
Aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) and dihydroxybenzenes (eg hydroquinone, hydroquinone monosulfonate, etc.)
The developing agents can be used in combination. When used in combination, the developing agents such as 3-pyrazolidones, aminophenols and dihydroxybenzenes are usually preferably used in an amount of 0.01 to 1.4 mol per liter of the developing solution.

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 of 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.

In the present invention, it is preferable that the developer contains a silver sludge inhibitor. Various silver sludge inhibitors are known, but preferably contain a compound represented by the following general formula (S).

As a preferred embodiment of the present invention, the silver halide photographic light-sensitive material of the present invention is treated with a developing solution containing a silver sludge inhibitor in the developing solution. 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 an alkyl group having 1 to 30 carbon atoms, particularly a straight chain, branched or cyclic alkyl group 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).

[0125]

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In the formula, Z is a group necessary for forming an unsaturated 5-membered heterocycle having a nitrogen atom or a 6-membered heterocycle (eg, pyrrole, imidazole, pyrazole, pyrimidine, pyridazine, pyrazine, etc.). is there. Where:
R ¹¹ and R ¹² are a hydrogen atom, a —SM ¹ group, a halogen atom,
Alkyl group (including those having a substituent), alkoxy group (including those having a substituent), hydroxyl group,-
COOM ¹ group, —SO ₃ M ¹ group, alkenyl group (including those having a substituent), amino group (including those having a substituent), carbamoyl group (including those having a substituent), phenyl group ( At least one group selected from (including those having a substituent), and R ¹¹ and R ¹² may form a ring. The ring that can be formed is a 5-membered ring or 6
A ring having at least one member ring, preferably a nitrogen-containing heterocycle. M ¹ is the same as M ¹ defined for the compound represented by formula (S). In the formula, the compound represented by the general formula (S-a) is at least one -S
A compound having a M ¹ group or a thione group, which is selected from the group consisting of a hydroxyl group, a —COOM ¹ group, a —SO ₃ M ¹ group, a substituted or unsubstituted amino group, and a substituted or unsubstituted ammonio group. And has at least one substituent. It may have a substituent other than the aforementioned -SM ¹ group or thione group, and the substituent includes a halogen atom (for example, fluorine, chlorine, bromine), a lower alkyl group (having a substituent). A methyl group, an ethyl group or the like having a carbon number of 5 or less is preferable), a lower alkoxy group (including a group having a substituent, methoxy, ethoxy, butoxy or the like having a carbon number of 5 or less is preferable), a lower alkenyl Examples thereof include groups (including those having a substituent, those having 5 or less carbon atoms are preferable), carbamoyl groups, phenyl groups and the like. Specific examples of the compound represented by formula (S) are shown below, but the invention is not limited thereto.

[0127]

[Chemical 6]

[0128]

[Chemical 7]

[0129]

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[0130]

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[0131]

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[0132]

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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.

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably 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 fixing solution contains a water-soluble aluminum salt which 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, ammonia water, 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, nitrilotriacetic acid salt, polyphosphate salt, etc., and an antifungal agent (for example, phenol, 4-chlorophenol, cresol, 2-phenylphenol, chlorophene, dichlorophene, formaldehyde, 4- 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 replenishing a fixed amount of developing liquid proportional to the area of the light-sensitive material. The replenishment amount is 30 to 250 ml per 1 m ² .
It is. Preferably, it is 30 to 200 ml per 1 m ² . The development replenishment amount here indicates the amount replenished. Specifically, it is the replenishing amount of the liquid when replenishing the same liquid as the developing mother liquor, and the total amount of the concentrated liquid and the water when replenishing the developing concentrated liquid with a liquid diluted with water. The total amount of the solid processing agent volume and the volume of water when the developer is replenished with a liquid dissolved in water, and the respective solid processing when the developer and the water after the solid development processing agent are replenished separately. It is the total volume of the developer and water after the agent is dissolved. The developing replenisher may be the same as the developing mother liquor in the tank of the automatic processor, or may be a different liquid or a solid processing agent.

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.

According to the present invention, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone is 80 when the processing is performed by using the automatic developing machine in order to shorten the developing time. 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 run a large amount of a light-sensitive material of 100 m ² or more, the development time is preferably 40 seconds or less and 2 seconds or more.

In order to bring out the effect of the present invention remarkably, the automatic processor should be equipped with a heat transfer material at a temperature of 60 ° C. or higher (for example, 60 ° C.).
~ 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 drive means and the drive transmission 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, the 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 (6) Method of controlling the drying air of the automatic processor by detecting the outside temperature and humidity: JP-A-1-3157
No. 45, lower right column, page 496 (2) to lower right column, page 501 (7) and lower left column, page 588 (2) of JP-A-2-108051.
589 (3) page, lower left column (7) Method for recovering silver from fixing waste liquid: JP-A-6-27623, (4) page, “0012” to (7) page, “0071”.

[0151]

【Example】

(Preparation of support) (SPS synthesis) S according to JP-A-3-131843
PS pellets were prepared. From the preparation of the catalyst to the polymerization reaction, all were carried out under a dry argon stream. Internal volume 500m
l copper sulfate glass container pentahydrate (CuSO ₄ · 5H
₂ O) 17.8 g (71 mmol) purified benzene 200
ml and trimethylaluminum 24 ml, add 4
The catalyst was adjusted by stirring at 0 ° 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 and put in a 2 l stainless steel container, and tributylaluminum and pentacyclomethyl-pentadiethyltitanium-trimethoxide 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 C at 245 ° C.
It was confirmed from the 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 by 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 100 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.

Undercoat processing 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 ion wind was blown, and then the undercoating working liquid 2 was provided so that the dry film thickness was 1 μm, and the temperature was 140 ° C.
And dried.

Styrene-butadiene-based latex (No619 made by Japan Synthetic Rubber) 50 parts by weight Styrene-butadiene-based latex (No640 made by Japan Synthetic Rubber) 40 parts by weight Polystyrene 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. For comparison, a polyethylene phthalate (P
ET) film subjected to the same undercoating process was used.

Example 1 An emulsion was prepared by the following method.

(Emulsion A: Present Invention) Liquid A Pure water 1000 cc Gelatin 120 g KBr 1 g Liquid B Silver nitrate 100 g Pure water 700 cc Ammonia water 25 cc Liquid C KBr 70 g KI 4.8 g K ₂ IrCl ₆ 2 × 10 ⁻⁷ mol Pure water 700 cc Liquid A was put in a mixing pot, and liquid B and liquid C were mixed for 70 seconds to simultaneously mix them. 10 seconds after the addition was completed, citric acid (40%) 1
The pH was adjusted by adding 0 cc. The obtained emulsion was desalted by ultrafiltration. The average grain size of the obtained emulsion was 0.03 μm,
The breadth of the particle distribution was 10%. Next, selenourea and chloroauric acid were added, and chemical aging was performed at 60 ° C. so that maximum sensitivity was obtained.

(Emulsion B: Comparative) The mixing time of the liquids B and C was adjusted to obtain particles having an average particle size of 0.15 μm. Emulsion A
Chemical ripening was carried out in the same manner as in.

(Preparation of silver halide photographic light-sensitive material 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 added at a gelatin content of 0.5 g / m 2. ² and the silver halide emulsion layer of Formulation 2 thereon so that the amount of silver is 2.9 g / m ² and the amount of gelatin is 1.0 g / m ² , and as an emulsion protective layer lower layer thereabove. The coating solution of the following prescription 3 has a gelatin content of 0.
So that 2 g / m ^2, the amount of gelatin of the emulsion protective layer layer of Formulation 4 in the upper layer was simultaneously coated so as to be 0.2 g / m ² more. On the other side of the undercoat layer, a backing layer of the following formulation 5 was further coated with a polymer layer of the following formulation 6 so that the amount of gelatin was 0.4 g / m ² , and further a polymer layer of the following formulation 7 was further formed thereon. A sample was obtained by simultaneously coating the backing protective layer with the emulsion layer 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 Recipe 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 Lower Layer Composition) Gelatin 0.2 g / m ² Amino Compound AM-1 40 mg / m ² S-1 2 mg / m ² Formulation 4 (Emulsion Protective Layer Upper Layer Composition) Gelatin 0.2 g / m ² Dye AD-2 (ball mill dispersed into powder with a particle size of 0.1 μm) 40 mg / m ² S-1 12 mg / m ² Matting agent: monodisperse silica with 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 1 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 μm) 70 mg / m ² Polystyrene sulfonic acid Sodium 20 mg / m ² Compound i 100 mg / m ² Formulation 6 (polymer layer composition) Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / 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) -sulfosuccin sulfonate 10 mg / m ² surfactant h 1 mg / m ² dye ^{k 20mg / m 2 H- (OCH} 2 CH 2) 68 -OH 0mg / m ² hardener l 20mg / ^{m 2}

[0167]

[Chemical 12]

[0168]

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[0169]

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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.

A sample heat-treated under the environmental conditions for the historical period and a sample stored under the comparative conditions were in close contact with 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 the formula (S) S-36 1.5 g / l KOH was added in an amount such that the working solution had a pH of 9.9.

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

(Fixing solution composition) Concentrating 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 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 halftone 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.

[0180]

[Table 2]

When a silver halide emulsion having an average grain size of 0.1 μm or less is used and an SPS support is used, even in an aged sample, there is little fluctuation in sensitivity, little increase in fog, and reproduction of minute points. It can be seen that there is little problem that the quality of the halftone dots is deteriorated even when it is performed. Further, it can be seen that the effect is also obtained when the developer replenishing amount is reduced and replenished by an automatic developing machine, and rapid processing is performed.

Example 2 An emulsion was prepared by the following method.

[0183] The liquid A was put in a mixing pot, and the pH was adjusted to 2 with nitric acid, and then the liquid B and the liquid C were mixed while controlling the flow rate by the simultaneous mixing method. When the addition is complete, adjust the pH to 6 with aqueous sodium carbonate solution.
Adjusted to. The resulting emulsion was desalted by vacuum ultrafiltration.
The emulsion thus obtained had an average grain size of 0.07 μm and a grain distribution of 10%. Next, inorganic sulfur was added and chemically aged at 60 ° C. so that the maximum sensitivity was obtained.

Gelatin was added to the obtained silver halide emulsion so that the amount of gelatin would be 1.2 g / m ^2, and then the following additives were added to prepare Emulsion Coating Solution E-0. Coating solution P-0, backing layer coating solution B-0, and backing protective layer coating solution BP-0 were prepared with the following compositions.

(Preparation of Emulsion Coating Solution E-0) Silver Halide Emulsion NaOH (0.5N) shown in Table 3 adjusted to pH 5.6 tetrazolium compound (T-1) 30 mg / m ² saponin (20%) 5 cc / m ² sodium dodecylbenzene sulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound (b) 2 mg / m ² compound (c) 6 mg / m ² latex La 1.0 g / m ² styrene-maleic acid Copolymer polymer (thickener) 90 mg / m ²

[0186]

[Chemical 15]

(Emulsion Protective Layer Coating Solution P-0) Gelatin 1.1 g / m ² compound (d) (1%) 25 cc / m ² compound (e) 20 mg / m ² p-perfluoro-4-nonenyl-benzenesulfone Acid soda 2 mg / m ² Spherical monodisperse silica (8 μm) 20 mg / m ² 〃 (3 μm) 10 mg / m ² Compound (f) 100 mg / m ² Citric acid Adjusted to pH 6.0 Styrene-maleic acid copolymer polymer (increased Sticky agent) 100 mg / m ² (backing layer coating solution B-0) Gelatin 1.0 g / m ² compound (g) 100 mg / m ² compound (h) 18 mg / m ² compound (i) 100 mg / m ² saponin (20 %) 0.6cc / m ² latex (j) 300mg / m ² 5- nitroindazole 20 mg / m ² styrene - maleic acid copolymer polymer (thickener) 45 mg / m ² Riokizaru 4 mg / m ² Compound (k) 10mg / m ² Compound (l) 10mg / m ² 5- methyl benzotriazole 20 mg / m ² (Backing protective layer coating solution BP-0) Gelatin 0.5 g / m ² Compound (d ) (1%) ² cc / m ² spherical polymethylmethacrylate (4μ) 25 mg / m ² sodium chloride 70 mg / m ² glyoxal 22 mg / m ²

[0188]

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[0189]

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[0190]

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On a support provided with an undercoat layer in Example 1, first, as an emulsion surface side, the emulsion layer and the emulsion protective layer were sequentially placed from the side closer to the support at 35 ° C. in this order as a hardener by a slide hopper method. The hardener 1 used in Example 1 was simultaneously multilayer coated while adding 30 mg per 1 g of gelatin. A backing layer and a backing protective layer were applied in multiple layers on the opposite surface of the support while adding a hardener with a slide hopper.

The obtained sample was evaluated in the same manner as in Example 1 except that the exposure was carried out by a bright room printer manufactured by Dainippon Screen Co., Ltd., and the results are shown in Table 3.

[0193]

[Table 3]

When a silver halide emulsion having an average grain size of 0.1 μm or less is used and an SPS support is used, even aged samples show little change in sensitivity, little increase in fog, and reproduction of minute points. It can be seen that there is little problem that the quality of the halftone dots is deteriorated even when it is performed. Further, it can be seen that the effect is also obtained when the developer replenishing amount is reduced and replenished by an automatic developing machine, and rapid processing is performed.

[0195]

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. .

Claims (3)

[Claims] 1. A silver halide emulsion layer containing at least one silver halide grain having an average grain size of 0.1 μm or less on a film support containing syndiotactic polystyrene as a main component. A silver halide photographic light-sensitive material. 2. The silver halide photographic light-sensitive material according to claim 1 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, and the silver halide photographic light-sensitive material is processed. The total processing time (Dry to Dry) from the start of development of the material to the exit of the drying zone is 10
A method for processing a silver halide photographic light-sensitive material, characterized in that the processing is carried out for at least 2 seconds and at most 80 seconds. 3. A method of processing a silver halide photographic light-sensitive material, which is developed while replenishing at least a development replenisher with an automatic processor, wherein the amount of the development replenisher is 30 ml or more and 250 ml or less per 1 m ^{2 of the} silver halide light-sensitive material. 3. The method for processing a silver halide photographic light-sensitive material according to claim 2, wherein the processing is carried out by