JPH0934053A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material reduced in deterioration of dot quality and dot reproducibility in the case of reproducing minute dots by incorporating a specified hydrazine derivative in a photographic constituent layer and syndiotactic polystyrene in a support. SOLUTION: At least one of the photographic constituent layers on the side of a silver halide emulsion layer contains a hydrazine derivative represented by the formula and the support contains syndiotactic polystyrene. In the formula, R1 is an aliphatic or aromatic group and contains a partial structure, such as -(CH2 CH2 O)n -, (n) being an integer of >=1, as a part of substituents or a quaternary ammonium cation; G1 is a -CO- or -COCO- group or the like; G2 is a simple bond or a -O- group or the like; R2 is H atom or an aliphatic or aromatic group; and one of A1 and A2 is H atom and the other is H atom or an acyl or alkyl group or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black and white silver halide photographic light-sensitive material and a processing method thereof, and more particularly to a silver halide photographic light-sensitive material for printing plate making and a processing method thereof.

[0002]

2. Description of the Related Art As a support for a silver halide photographic light-sensitive material, a material comprising a synthetic polymer of cellulose triacetate, polystyrene and polyethylene terephthalate is generally known, and particularly a silver halide photographic light-sensitive material for printing plate making. A polyethylene terephthalate (PET) support has heretofore been used. Further, it is known that a silver halide photographic light-sensitive material using a support containing syndiotactic polystyrene (SPS) as a main component is excellent in drying property and dimensional stability before and after processing or humidity change ( JP-A-3-131843).

In a silver halide photographic light-sensitive material for printing plate making, since a halftone image is usually used, there is known a photographic technique capable of reproducing an image of ultrahigh contrast due to photographic characteristics. Among them, a photographic light-sensitive material containing a hydrazine derivative as shown in US Pat. No. 4,269,929 is known. 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 of halftone dot quality has been demanded.
A technique called FM screening, which is composed of high-definition printing of 0 lines / inch or more and a random pattern of uniform minimal points, needs to reproduce minute points of 25 μm or less. These are Ar laser, HeNe laser,
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.

However, when a silver halide photographic light-sensitive material using a support containing syndiotactic polystyrene (SPS) as a main component, which is excellent in drying property and dimensional stability, is exposed to the light as described above, a fine net is formed. There was a problem that the quality and reproducibility of the dots deteriorated.

On the other hand, as interest in the environment has increased, attention has been focused on reducing the amount of photographic processing waste liquid. The photographic processing waste liquid cannot be discharged directly to the public sewer because the waste liquid contains undesired components, and the waste liquid is collected and destroyed by a troublesome and costly incineration method. From these points, it has been strongly desired to reduce the photographic processing waste liquid.

A black-and-white silver halide photographic light-sensitive material, particularly a silver halide photographic light-sensitive material for printing plate making, is generally an automatic processor having a developing section, a fixing section, a washing section or a stabilizing bath section, and a drying section after exposure. It is processed. As a means for solving the reduction of the photographic processing waste liquid as described above, it is conceivable to reduce the replenishment amount at the time of processing using an automatic processor.

However, when a large amount of silver halide photographic light-sensitive material for printing plate making is processed by reducing the replenishment amount of the processing solution, various problems are apt to occur, and in particular, the quality and reproducibility of the above-mentioned minute halftone dots. Deterioration becomes more remarkable.

Recently, it has been required to shorten the development processing time for black and white silver halide photographic light-sensitive materials. Conventional total processing time (Dry to Dr) from the insertion of the leading edge of the film into the automatic processor to the discharge from the drying section
y) was usually 60 seconds or more, but in recent years it has been 5
It has become necessary to perform rapid processing of 0 seconds or less. However, when performing such rapid processing, it was extremely difficult to faithfully reproduce minute halftone dots.

[0009]

In order to solve the above problems, an object of the present invention is to provide a silver halide photograph for printing plate making using a syndiotactic polystyrene (SPS) support excellent in drying property and dimensional stability. 25 for photosensitive materials
It is an object of the present invention to provide a silver halide photographic light-sensitive material and a method for processing the same, which are less likely to deteriorate the halftone dot quality and the halftone dot reproducibility when reproducing minute halftone dots of μm or less.

[0010]

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

(1). In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one surface on a support, at least one photographic constituent layer on the silver halide emulsion layer side is represented by the following general formula (1). A silver halide photographic light-sensitive material, characterized in that it contains a hydrazine derivative described above, and the support contains syndiotactic polystyrene.

[0012]

[Chemical 7]

[In the formula, R ₁ represents an aliphatic group or an aromatic group, and as a part of the substituent,-(CH ₂ CH ₂ O)
_{n -, - (CH 2 CH} (CH 3) O) n -, - (CH 2 CH
_{(OH) CH 2 O) n} - ( where n contains one or more or containing a partial structure of an integer), or a quaternary ammonium cation group. R ₁ may also contain a silver halide adsorbing group. G ₁ is -CO-, -COCO-, -CS-,-
_{C (= NR 2) -,} - SO -, - SO 2 - or -P (=
_{O) (G 2 R 2)} - represents a group. G ₂ is a mere bond, -O
-, - S- or -N (R ₂₎ - represents a group, R ₂ represents a hydrogen atom or an aliphatic group, an aromatic group. When multiple R _2's are present in the molecule, they may be the same or different.
One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl group or an arylsulfonyl group. (2). The silver halide photographic light-sensitive material according to (1), wherein the hydrazine derivative is represented by the following general formula (2).

[0014]

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[In the formula, R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, which may be substituted. G is -CO -, - COCO -, - SO -, - SO 2 -, thiocarbonyl group, an iminomethylene group or -P (O)
It represents a group - (R ^4). R ² is a carbon atom substituted with G,
It represents a substituted alkyl group substituted with at least one electron withdrawing group. R ⁴ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group. ] (3). The silver halide photographic light-sensitive material according to (1), wherein the hydrazine derivative is represented by the following general formula (3) or (4).

[0016]

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[In the formula, X ¹ represents an alkyl group, an alkoxy group, a substituted amino group or an alkylthio group. Y ¹ represents an alkoxy group, an aryloxy group, a substituted amino group, an alkylthio group or an arylthio group. R ¹ represents an alkylene group. ]

[0018]

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[In the formula, X ² has the same meaning as X ¹ in formula (3). Y ² represents an electron withdrawing group, R ² is a hydrogen atom,
It represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a substituted amino group, an alkylthio group or an arylthio group, and may be further substituted. n represents an integer of 1 to 5, and a plurality of Y ² and R ² existing in the molecule may be the same or different. (4). The silver halide photographic light-sensitive material described in (1), wherein the hydrazine derivative is represented by the following general formula (5).

[0020]

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[Wherein, Ar represents a substituted phenyl group or a substituted or unsubstituted aryl group, and G represents —CO—, —S
_{O -, - SO 2 -,} - PO 2 -, - PO 3 - or C = NR ²
And X ⁺ represents a group containing a cationic group. R, R ',
R ^{2 s} may be the same or different and each is a hydrogen atom, having 1 to 6 carbon atoms.
Alkyl group, A at alkylsulfinyl group having 1 to 6 carbon atoms ^- represents an anionic group. (5). The silver halide photographic light-sensitive material described in (1), wherein the hydrazine derivative is represented by the following general formula (6).

[0022]

[Chemical 12]

[In the formula, R ₁ is an aromatic group and may be substituted. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom, an arylsulfonyl group or a trifluoroacetyl group. G is -CO-, -COCO-, -SO
-, - SO ₂ - or a N- substituted or unsubstituted imino group. X is a cyclization which, in the presence of an oxidized form of a developing agent at pH 9.5 to 12.5, splits the -G-X moiety from the residual molecule to form a cyclic structure containing the atoms of the -G-X moiety. It is the part that causes a reaction. ] (6). Developer replenisher amount and fixing replenisher amount automatic developing machine is replenished in the developer and fixer, respectively ^{50ml / m 2 ~300ml / m 2} , characterized in that it is processed (1) -
The method for processing a silver halide photographic light-sensitive material according to any one of (5).

(7). The total processing time is 15-
The method for processing a silver halide photographic light-sensitive material according to any one of (1) to (6), wherein the processing is performed for 60 seconds. Hereinafter, the present invention will be described in detail.

In the present invention, a support containing syndiotactic polystyrene (SPS) means a stereoregular structure (tacticity) mainly with respect to a syndiotactic structure, that is, a main chain formed by carbon-carbon bonds. A side chain of a phenyl group or a substituted phenyl group having a steric structure alternately positioned in the opposite direction, the main chain of the main chain is a styrene polymer which is a racemo chain, or a composition containing it. 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 1-178505. It can be obtained by polymerizing by the method described in the above.

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 can be indicated by the abundance ratio of a plurality of continuous constitutional units, for example, diad in the case of 2 units, triad in the case of 3 units, and pentad in the case of 5 units. However, the styrene-based polymer mainly having a syndiotactic structure referred to in the present invention usually has a racemic dyad of 75% or more,
Preferably 85% or more, or 6 for racemic triad
It is preferably 0% or more, preferably 75% or more, or racemic pentad is 30% or more, preferably 50% or more.

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 resin having a syndiotactic structure of the present invention contains the above raw material monomers
As a polymerization catalyst, those containing (a) a transition metal compound and (b) an aluminoxane as main components described in JP-A-5-320448, pages 4 to 10, 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 for the support 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, polymerization conditions (polymerization temperature, polymerization time), solvent, etc. 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 the 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 may be used alone or in combination. 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, hydrogen, 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 SPS (syndiotactic polystyrene) has a weight average molecular weight of 1
It is 50,000 or more, more preferably 30,000 or more. If the weight average molecular weight is less than 10,000, the film may not have excellent strength properties 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 15,000,000.

The molecular weight distribution (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. Further, the syndiotactic polystyrene-based film of the present invention contains syndiotactic polystyrene-based pellets at 120 to 180 ° C.
Dry for 1 to 24 hours under vacuum or under normal pressure in 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.

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 obtained 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 measurement of ¹³ C-NMR that the polymer had a syndiotactic structure. After pelletizing this with an extruder,
Dried at 0 ° C.

The SPS support of the present invention is preferably SPS made of styrene alone, but as the support containing SPS, styrene 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 system polymer (IPS), and a stronger support 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, an antioxidant, a UV absorber, an antistatic agent, a dye, a pigment, a dye, etc., in order to impart functionality, within a range not impeding the object of the present invention. Is possible.

A known method can be applied to the method of extrusion during film formation, but it is preferable to extrude using a T die, for example.
Syndiotactic polystyrene pellets 280-3
An unstretched film is produced by melting and extruding at 50 ° 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, but is usually in the 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. Stretching temperature in the width direction should be slightly higher than in the longitudinal direction and should be 1
It is preferably carried out at 15 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. For shrink-wrapping applications that require a high shrinkage rate, 150 ° C or lower, and for photographic, printing, medical applications that require dimensional stability, 1 depending on the purpose.
Temperatures of 50-270 ° C are adopted.

The heat treatment time is not particularly limited, but is usually 1
About 2 to 2 minutes are adopted.

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

After this, the film may be rapidly cooled and wound, but it is 0.1 minute to 1500 at a temperature 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 from 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 and the like 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 may be composed of two or more layers, and may be a combination of the same kind of polymers (including a combination of the copolymerization polymers) or a different kind of polymers.

The above-mentioned film forming method can be appropriately changed depending on 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 stretched film varies depending on the application, but it 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 undercoating 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 subbing layer may be a single layer, but it is desirable that it is a multi-layer in order to obtain more functionality and enhance the adhesive strength.

The subbing overlay 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, acrylic acid, or its ester, 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.

A rubber-like substance may be used as the polymer latex that can be used in the first subbing layer. Rubbery materials generally consist of vinyl monomers-diolefins,
As vinyl monomers, styrene, acrylonitrile,
Methacrylonitrile, methyl methacrylate, methyl acrylate, vinyl acetate and the like are preferably used, and as the diolefin, butadiene, isoprene and chloroprene are preferably used. In addition to these components, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid,
Maleic anhydride or alkyl esters thereof, acrolein, metechlorine, glycidyl acrylate,
Add crosslinkable components such as glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, vinyl isocyanate, allyl isocyanate. Is good. The content of diolefin is preferably about 10 to 60% by weight. As commercially available and easily available ones, styrene-butadiene, styrene-isoprene, styrene-chloroprene, methylmethacrylate-butadiene, acrylonitrile-butadiene and the like can be mentioned, but preferably styrene and its derivative as a monomer constituting the polymer latex. ,
Hydroxy group-containing monomers such as methacrylic acid, acrylic acid, itaconic acid and their esters (alkyl acrylate, alkyl methacrylate, etc.), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. , Acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N-methylolmethacrylamide,
Amide group-containing monomers such as N-methylolacrylamide, N, N-dimethylolacrylamide and N-methoxymethylacrylamide, amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminomethacrylate, glycidyl acrylate and glycidyl Epoxy group-containing monomer such as methacrylate, acrylic acid or methacrylic acid salt (sodium salt,
Monomers containing carboxyl groups or carboxylates such as potassium salts, ammonium salts, etc., styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt,
Monomers containing sulfonic acid groups or sulfonates such as potassium salts, ammonium salts, etc., carboxyl groups or carboxylates such as itaconic acid, maleic acid, fumaric acid salts (sodium salts, potassium salts, ammonium salts) Monomers containing, monomers containing acid anhydrides such as maleic anhydride, itaconic anhydride, vinyl isocyanate,
Allyl isocyanate, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, vinyl acetate and the like can be mentioned, and they can be used by copolymerizing one kind or two or more kinds.

As a method for polymerizing the polymer latex,
An emulsion polymerization method, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, a radiation polymerization method and the like can be mentioned.

In the solution polymerization method, a mixture of monomers having an appropriate concentration in a solvent (usually 40% by weight or less based on the solvent,
Preferably 10 to 25% by weight of the mixture) is polymerized in the presence of an initiator at a temperature of about 10 to 200 ° C, preferably 30 to 120 ° C for about 0.5 to 48 hours, preferably 2 to 20 hours. . The initiator is one that is soluble in the polymerization solvent,
Benzoyl peroxide, azobisisobutyronitrile (AI
BN), an organic solvent-based initiator such as di-tert-butyl peroxide, ammonium persulfate (APS), potassium persulfate, 2,
A water-soluble initiator such as 2'-azobis- (2-aminodipropane) -hydrochloride, or a combination of these with a reducing agent such as a divalent iron salt or sodium bisulfite. Any solvent may be used as long as it dissolves a mixture of monomers, such as water, methanol, ethanol,
Examples thereof include dimethyl sulfoxide, dimethylformamide, dioxane or a mixed solvent thereof.

In the emulsion polymerization method, water is used as a dispersion medium, 10 to 50% by weight of a monomer relative to water and 0.05 to 5% by weight of a polymerization initiator relative to the monomer, and 0.1 to 20% by weight.
About 30 to 100 ° C., preferably 60 to 100 ° C.
Polymerize with stirring at 90 ° C. for 3-8 hours. As the initiator, a water-soluble peroxide (potassium peroxide, ammonium persulfate, etc.), a water-soluble azo compound (2,2′-azobis- (2-aminodipropane) -hydrochloride, etc.), or a divalent thereof A combination of reducing agents such as iron salts and sodium bisulfite may be mentioned. Examples of the dispersant include anionic surfactants, nonionic surfactants, water-soluble polymers and the like.

The molecular weight of the obtained polymer is usually from 500 to 500 in terms of polystyrene or polyethylene oxide.
About 5,000,000, preferably 1,000 to 50
It is 0000.

Regarding the method of synthesizing the hydrophobic polymer latex, US Pat. Nos. 2,852,386 and 2,85
No. 3,457, No. 3,411,911, No. 3,41
1,912, 4,197,127, Belgian Patents 688,882, 691,360, 712.
No. 823, Japanese Patent Publication No. 45-5331, and Japanese Patent Laid-Open No. 60-18.
No. 540, No. 51-130217, No. 58-1378.
31 and 55-50240. The average particle size of the hydrophobic polymer is 0.005-2.0μ
The thickness is about m, preferably 0.01 to 0.8 μm.

A copolymer having a water-dispersible polyester and a styrenic polymer as constituent elements can also be used. 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 an alkali metal sulfonate group 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, 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, etc., 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 modification 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 subbing first 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 lateral 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 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 weight average molecular weight in terms of standard polystyrene measured by the C method is preferably 1500 to 700,000, and more preferably 2000 to 500000.

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 undercoat layers to enhance the film strength. Examples of such hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. 732, 303
No. 3,288,775, British Patent 974,723.
No. 1,167,207, etc., compounds having a reactive halogen, ketone compounds such as diacetyl and 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, U.S. Pat. Nos. 3,232,763 and 3,635.
718, compounds having reactive olefins described in British Patent 994,809, etc., US Pat. No. 3,539,64
No. 4, No. 3,642, 486, Japanese Patent Publication No. 49-1356
No. 8, No. 53-47271, No. 56-48860,
JP-A-53-57257, JP-A-61-128240,
No. 62-4275, No. 63-53541, No. 63-
Vinylsulfone compounds described in No. 264572, N-
Hydroxymethylphthalimide, US Patent 2,732
No. 316, 2,586,168, etc., N-methylol compounds, US Pat. No. 3,103,437, etc., isocyanate compounds, US Pat. No. 2,983,611.
And the aziridine compounds described in U.S. Pat. Nos. 2,725,294 and 2,725,2.
Acid derivatives described in US Pat. No. 3,100,7
No. 04, etc., carbodiimide compounds, U.S. Pat. No. 3,091,537, etc. epoxy compounds, U.S. Pat. Nos. 3,321,313, 3,543,292, etc. isoxazole compounds. , Organic hardeners such as halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride. Further, as a hardener having a relatively fast hardening effect on gelatin, compounds having a dihydroquinoline skeleton described in JP-A-50-38540, JP-A-51-59625 and JP-A-62-26 are mentioned.
No. 2854, No. 62-264044, No. 63-184.
No. 741 N-carbamoylpyridinium salts,
It has two or more acyl-imidazoles described in JP-B-55-38655, N-acyloxyimidazoles described in JP-B-53-22089, and two or more N-acyloxyimino groups described in JP-B-53-22089. Compounds, compounds having an N-sulfonyloxyimide group described in JP-A-52-93470, JP-A-58-113
A compound having a phosphorus-halogen bond described in No. 929,
JP-A-60-225148 and 61-240236.
Nos. 63-41580 and chloroformamidinium compounds 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 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 such as cations, anions, electrons and holes present in the particles. 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 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. 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 separated by centrifugation. Water was added to the precipitate to remove excess ions, and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions.

Colloidal precipitate 10 with excess ions removed
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 A-2 was obtained.

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.

Next, the hydrazine derivatives represented by the general formulas (1) to (6) will be described in detail.

First, the hydrazine derivative represented by the above general formula (1) will be described.

The aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. This alkyl group has a substituent.

The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a fused heterocyclic group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Among them, those containing a benzene ring are preferred. Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group of R ₁ is substituted.

The aliphatic group or aromatic group of R ₁ is substituted, and a typical substituent is, for example, a halogen atom,
Alkyl, aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, ureido, urethane,
Aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl,
Hydroxyl, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl, acyloxy,
Examples of the group include carbonamide, sulfonamide, carboxyl, and phosphoric amide. Preferred substituents are a linear, branched or cyclic alkyl group (preferably having 1 carbon atom).
~ 20) and aralkyl groups (preferably having 7 to 7 carbon atoms).
30), an alkoxy group (preferably having 1 to 3 carbon atoms)
0), a substituted amino group (preferably having 1 to 30 carbon atoms)
An amino group substituted with an alkyl group), an acylamino group (preferably having 2 to 40 carbon atoms), a sulfonamide group (preferably having 1 to 40 carbon atoms), an ureido group (preferably having 1 to 40 carbon atoms). ), A phosphoric acid amide group (preferably having 1 to 40 carbon atoms), and the like.

The aliphatic group, aromatic group or their substituents for R ₁ is-(CH ₂ CH ₂ O) n- or-(CH ₂ CH (C
H ₃₎ O) n- or _{- (CH 2 CH (OH)} CH 2 O) n
It contains-or contains a quaternary ammonium cation. n is preferably an integer of 1 to 15. R
₁ is preferably represented by the following general formula (II), general formula (III), general formula (IV) or general formula (V).

[0096]

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In the above general formula, L ₁ and L ₂ are each -CON.
(R ₇₎ - _{group, -N (R 7) CON (} R 8) - group, -SO ₂
It represents a N (R ₇ )-group or a —N (R ₇ ) SO ₂ N (R ₈ )-group, which may be the same or different. R ₇ and R ₈ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and 6 carbon atoms.
It represents an aryl group of 10 and a hydrogen atom is preferable. m is 0 or 1. R ₃ , R ₄ and R ₅ are each a divalent aliphatic group or an aromatic group, preferably an alkylene group, an arylene group, or -O-, -CO-, -S-,-.
_{SO -, - SO 2 -,} - N (R 9) - (R 9 is the formula (I
I), (III), and (IV) have the same meaning as R ₇ ) and are a divalent group. More preferably, R ₃ is an alkylene group having 1 to 10 carbon atoms, or those and —S—, —
SO -, - SO ₂ - is a bivalent group produced by combining, R ₄ and R ₅ are each an arylene group having 6 to 20 carbon atoms. Particularly, R ₅ is preferably a phenylene group. R ₃ , R
₄ and R ₅ may be substituted, and preferred substituents include those listed as substituents for R ₁ .

In the general formulas (II) and (III), Z ₁ represents an atomic group necessary for forming a nitrogen-containing aromatic ring. Preferred examples of the nitrogen-containing aromatic heterocyclic ring formed by Z ₁ and the nitrogen atom, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, pyrrole ring, oxazole ring, thiazole ring, and their benzo In addition to condensed rings, pteridine rings, naphthyridine rings and the like can be mentioned.

In the general formulas (II), (III) and (IV), X ^- represents a counter anion or a counter anion moiety when forming an inner salt.

In formulas (IV) and (V), R ₆ represents an aliphatic group or an aromatic group. R ₆ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

The three R _{6 s} in the general formula (IV) may be the same or different, and may combine with each other to form a ring. Z ₁ and R ₆ may be substituted, and as the preferable substituents, those enumerated as the substituents of R ₁ are applicable.

In the general formula (V), L ₃ is —CH ₂ CH.
₂ O- _{group, -CH 2 CH (CH 3)} O- group or a -CH ₂ CH
(OH) represents a CH ₂ O- group.

As G ₁ in the general formula (1), --CO
- group, -SO ₂ - groups are preferred, -CO- group is most preferred. A hydrogen atom is preferable as A ₁ and A ₂ .

The alkyl group represented by R ₂ in the general formula (1) is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, benzene). Including rings). G ₁ is-
In the case of a CO— group, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (eg, methyl, trifluoromethyl, 3-hydroxypropyl, 3-methanesulfonamidopropyl, phenylsulfonylmethyl), aralkyl. (Eg, o-hydroxybenzyl), an aryl group (eg, phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, etc., 4-methanesulfonylphenyl, 2-hydroxymethylphenyl, etc.), etc., and a hydrogen atom is particularly preferable. . R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied. Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms, examples Examples thereof include those described in JP-A-63-29751.

R ₁ or R _{2 in} the general formula (1) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and examples thereof include an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from among alkylphenoxy groups and the like.
Further, examples of the polymer include those described in JP-A-1-100530.

Examples of the silver halide adsorbing group which R ₁ can have are --S-- group, --SS-- group, --NHC (=
S) NH- group, 5- or 6-membered nitrogen-containing heterocyclic group (benzotriazole, triazole, imidazole, thiazole,
Oxazole, etc.), and a 5- or 6-membered nitrogen-containing heterocyclic group having a mercapto group or a disulfide bond (2-mercaptothiadiazole, 5-mercaptotetrazole, 2-mercaptobenzoxazole, etc.). In particular, −
5 having S-group, mercapto group or disulfide bond
It is preferable to have a 6-membered nitrogen-containing heterocyclic group.

The compound of the general formula (1) of the present invention is described in, for example, JP-A-61-213847 and JP-A-62-260153.
U.S. Pat. No. 4,684,604, Japanese Patent Application No. 63-98.
803, US Pat. Nos. 3,379,529 and 3,62.
0,746, 4,377,634, 4,33
2,878, JP-A-49-129536, JP-A-56-
153336, 56-153342, U.S. Pat. Nos. 4,988,604, and 4,994,365 can be used for the synthesis.

The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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The amount of the compound of the general formula (1) added is
1 x 10 per mol of silver halide ^-6~ 5 × 10^-2Mole
It is preferably contained, particularly 1 × 10^-Five~ 2 x 10^-2
A molar range is preferred.

The compound of the general formula (1) is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluoroalcohol etc.), ketones (acetone, methyl ethyl ketone etc.), dimethylformamide, dimethyl sulfoxide. , Dissolved in methyl cellosolve and the like. Also, by the well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion. Can be created and used. Alternatively, a redox compound powder can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

Next, the compound represented by formula (2) will be described in more detail. In the general formula (2), R ¹
The aliphatic group represented by is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R ¹ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.
The hetero ring of R ¹ is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, and S atoms, which may be a single ring, A condensed ring may be formed with an aromatic or hetero ring. The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazoline group, and a benzothiazolyl group. Are preferred. Preferred as R ¹ are aromatic groups, nitrogen-containing heterocycles and groups represented by general formula (b).

[0118]

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(In the formula, X _b represents an aromatic group or a nitrogen-containing heterocyclic group, R _b ^{1 to} R _b ⁴ each represent a hydrogen atom, a halogen atom or an alkyl group, and X _b and R _b ¹ to R _b ⁴ may have a substituent if possible, r and s
Represents 0 or 1. ) R ¹ is more preferably an aromatic group, particularly preferably an aryl group. R ¹ may be substituted with a substituent. Examples of the substituent include, for example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group. Groups, hydroxy groups, halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carbonamide groups, sulfonamide groups,
Other than nitro group, alkylthio group, arylthio group, etc.,
Examples thereof include groups represented by general formula (c) below.

[0120]

[Chemical 21]

In the formula (c), Y _C is --CO-- or --SO.
_{2 -, - P (O)} (R C3) - (. Wherein R _C3 represents an alkoxy group or an aryloxy group), or -OP
(O) ( _RC3 )-, L is a single bond, -O-, -S.
-, Or -NR _C4- (in the formula, R _C4 represents a hydrogen atom, an alkyl group, or an aryl group). R _C1 and R _C2 represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group,
They may be the same or different, and may combine with each other to form a ring. R ¹ may include one or more of the general formula (c).

In the general formula (c), the aliphatic group represented by R _C1 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _C1 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocycle of R _C1 is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, which may be a single ring, or other A condensed ring may be formed with the aromatic or heterocyclic ring of. The hetero ring is preferably a 5- to 6-membered aromatic heterocyclic group, for example, pyridine group, imidazolyl group, quinolinyl group, benzimidazolyl group, pyrimidyl group, pyrazolyl group, isoquinolinyl group, thiazolyl group, benzthiazolyl group. Those containing a group are preferred. R _C1 may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted.
For example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group,
Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group and carboxyl group, Alkyl and aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carbonamido groups,
Examples thereof include a sulfonamide group, a nitro group, an alkylthio group and an arylthio group. When possible, these groups may be linked to each other to form a ring.

R in the general formula (c)_C2The fat represented by
Group groups include linear, branched or cyclic alkyl groups, alkenyl
Group or alkynyl group. R_C2Aromatic represented by
The group is a monocyclic or bicyclic aryl group, for example,
A phenyl group is mentioned. R _C2Is substituted with a substituent
May be. Examples of the substituent include those in the general formula (c).
R_C1And those listed as the substituents. Also,
R_C1And R_C2Are linked together to form a ring when possible
May be. R_C2Is more preferably a hydrogen atom. General
Y in formula (c)_CIs -CO-, -SO_Two− Is
Particularly preferably, L is a single bond and -NR_C4− Is preferred
Yes.

The aliphatic group represented by R _C4 in the general formula (c) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _C4 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R _C4 may be substituted with a substituent. Examples of the substituent include R _C1 in the general formula (c).
The substituents listed in are listed. R _C4 is more preferably a hydrogen atom.

Most preferably, G in the general formula (2) is a --CO-- group. R ^{2 in the} general formula (2) represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group, and preferably two electron withdrawing groups,
Particularly preferably, it represents a substituted alkyl group substituted with three electron withdrawing groups. The electron withdrawing group for substituting the carbon atom substituted with G of R ² preferably has a σp value of 0.2 or more and a σm value of 0.3 or more, and examples thereof include halogen, cyano, nitro, nitrosopolyhaloalkyl, and poly. Haloaryl, alkyl or arylcarbonyl group, formyl group, alkyl or aryloxycarbonyl group, alkylcarbonyloxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkyl or arylsulfonyloxy group, sulfamoyl group, phosphino Represents a group, a phosphine oxide group, a phosphonic acid ester group, a phosphonic acid amide group, an arylazo group, an amidino group, an ammonio group, a sulfonio group, and an electron-deficient heterocyclic group. R ^{2 in the} general formula (2) particularly preferably represents a trifluoromethyl group.

R ¹ and R ^{2 in} the general formula (2) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, JP-A-1-100530
The items described in No.

Each of R ¹ and R ^{2 in} the general formula (2) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, triazole group and the like, U.S. Pat. Nos. 4,385,108, 4,459,347, and JP-A-59-195233.
Nos. 59-200231, 59-201045, 59-201046, 59-201047, and 5
9-201048, 59-201049, 61
-170733, 61-270744, 62-
948, 63-234244, 63-2342.
The groups described in No. 45 and No. 63-234246 are mentioned. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0128]

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[0129]

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[0130]

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[0131]

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[0132]

[Chemical formula 26]

[0133]

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[0134]

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[0135]

[Chemical 29]

Next, the hydrazine derivative represented by the above general formulas (3) and (4) will be described.

[0137] In the general formula (3), the alkoxy group represented by an alkyl group and X ¹ is represented by X ^1, the alkyl group contained in the alkylthio group is a linear, branched or cyclic alkyl group, A typical example is an ethyl group,
Examples thereof include a butyl group, an isopropyl group, an isobutyl group, a t-amyl group and a cyclohexyl group. Examples of the substituent of the substituted amino group represented by X ¹ include an alkyl group, an aryl group, an acyl group (R—CO— group, R is alkyl or aryl), an alkoxy or aryloxycarbonyl group, and a substituted or unsubstituted group. It also includes a carbamoyl group, a substituted or unsubstituted hydrazinocarbonyl group, an alkyl or aryl sulfonyl group, a substituted or unsubstituted sulfamoyl group, and the like, and in the latter case, a carbonamido group, a urethane group, a ureido group, a semicarbazide group, a sulfone group. It forms an amide group and the like. X ¹ may be substituted such as 2-methoxyethoxy group and 3,3-bis (2-hydroxyethyl) ureido group. In X ¹ , the total number of carbon atoms including substituents is preferably 1 to 6,
2 to 6 are more preferable. 3 to 6 are particularly preferable.
^Xl is preferably a substituted amino group, and most preferably an amino group substituted so as to form a carbonamido group, a ureido group or a sulfonamide group. The substitution position on the phenyl group of X ¹ may be any of the ortho position, meta position and para position of the hydrazine moiety, but meta position and para position are preferred, and para position is most preferred. The phenylene group connecting X ¹ and the hydrazine moiety may be substituted, but the total number of carbon atoms contained in these substituents and X ¹ is preferably 1 to 6.

In formula (3), the alkoxy group represented by Y ¹ and the alkyl group contained in the alkylthio group are linear, branched or cyclic alkyl groups. Typical examples are methyl group and dodecyl group. Group, isobutyl group, 2-ethylhexyl group and the like. The aryl group contained in the aryloxy group or the arylthio group represented by Y ¹ is preferably a monocyclic or bicyclic unsaturated carbocyclic group or an unsaturated heterocyclic group. Representative examples include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and the like.
Examples of the substituent of the substituted amino group represented by Y ¹ include an alkyl group, an aryl group, an acyl group, (R—CO— group, R is an alkyl group or an aryl group), an alkoxy or aryloxycarbonyl group, a substituted or It also includes an unsubstituted carbamoyl group, a substituted or unsubstituted hydrazinocarbonyl group, an alkyl or aryl sulfonyl group, and a substituted or unsubstituted sulfamoyl group. In the latter case, a carbonamido group, a urethane group, a ureido group, a semicarbazide Form a group, a sulfonamide group, or the like. As Y ¹ , an alkoxy group and an aryloxy group are preferable, and an aryloxy group is most preferable. The group represented by Y ¹ may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group,
Urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, Examples include an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, and an imide group. Preferred substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group. (Preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms), Examples thereof include an ureido group (preferably having 1 to 30 carbon atoms) and a phosphoric acid amide group (preferably having 1 to 30 carbon atoms). These groups may be further substituted.

In the general formula (3), the alkylene group represented by R ¹ may be substituted, and typical examples of the substituent include those listed as examples of the substituent of Y ¹ . R ¹ is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. Most preferably, R ¹ is a substituted or unsubstituted methylene group. The total number of carbon atoms contained in Y ¹ and R ¹ is preferably 6 to 30, particularly preferably 8 to 20.

The group represented by X ² in the general formula (4) has the same definition as the group represented by X ¹ in the general formula (3), and the description of preferred embodiments etc. is the same as that of X ^1. This is true. In the general formula (4), the electron withdrawing group represented by Y ² has a substituent constant value of σm or σp defined by Hammett et al.
It is a group of 2 or more, more preferably 0.3 or more. Y ²
Σm is 0.2 or more (preferably 0.
Groups of 3 or more) are preferably in the meta position with respect to the carbonyl group, and groups having σp of 0.2 or more (preferably 0.3 or more) are preferably in the rose position with respect to the carbonyl group. Further, a group having both σm and σp of 0.2 or more (preferably 0.3 or more) is preferably in the meta position and / or the para position with respect to the carbonyl group. Y
^As typical examples of the group represented by ² , for example, a sulfamoyl group, a carbamoyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group,
Examples thereof include halogen atom, cyano group, alkyl or aryloxycarbonyl group, acyl group, polychloroalkyl or aryl group. Y ² may also be substituted, and as the typical substituents, those enumerated as examples of the substituent for Y ^{1 in} the general formula (3) are applicable. As Y ² , a halogen atom, an alkoxycarbonyl group and a cyano group are particularly preferable.

[0141] Formula (4) in the alkoxy group represented by alkyl group and R ² is represented by R ^2, alkyl groups contained in the alkylthio group is a linear, branched or cyclic alkyl group, representative A typical example is a methyl group,
Examples thereof include dodecyl group, isobutyl group and 2-ethylhexyl group. Aryl group represented by R ² and R ²
The aryl group contained in the aryloxy group and arylthio group represented by is preferably a monocyclic or bicyclic unsaturated carbocyclic group or an unsaturated heterocyclic group. Representative examples include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and the like. Examples of the substituent of the substituted amino group represented by R ² include an alkyl group, an aryl group, and an acyl group (R-CO
-Group, R is alkyl or aryl), alkoxy or aryloxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted hydrazinocarbonyl group, alkyl or arylsulfonyl group, substituted or unsubstituted sulfamoyl group, etc. In the latter case, carbonamide group, urethane group, ureido group,
It forms a semicarbazide group and a sulfonamide group. R
² may be substituted, and as typical substituents, those enumerated as examples of the substituent of Y ¹ in the general formula (3) are applicable. R ² is preferably a hydrogen atom. The total sum of carbon atoms contained in all Y ² and R ² in the general formula (4) is preferably 8 to 30, and particularly preferably 8 to 20. Examples of compounds used in the present invention are shown below, but the invention is not limited thereto.

[0142]

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[0143]

[Chemical 31]

[0144]

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[0145]

[Chemical 33]

[0146]

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[0147]

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[0148]

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[0149]

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The hydrazine compound of the present invention is, for example, JP-A-61-213847, JP-A-62-260153, US Pat. No. 4,684,604 and JP-A-1-26993.
6, U.S. Pat. Nos. 3,379,529 and 3,62.
0,746, 4,377,634, 4,33
2,878, JP-A-49-129536, JP-A-56-
153336, 56-153342, U.S. Pat. Nos. 4,988,604, and 4,994,365.

Next, the hydrazine derivative represented by the above general formula (5) is preferably a compound represented by the following general formula (5-a).

[0152]

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R _{1 to} R ₅ may be the same or different and each is hydrogen, alkyl having 1 to 20 carbon atoms, alkoxy, hydroxyalkyl, haloalkyl, alkylamino, aliphatic. Acylamino or cycloalkyl, each having 6 to 10 carbon atoms, aryl, aryloxy or aromatic acylamino, alkenyl or alkoxy having 1 to 3 carbon atoms in the alkylene chain, or 1 to 10 1-4 substituted by a phenoxy group, which may be substituted on one or more of the alkyl groups having carbon atoms of
Such as an aliphatic acylamino group having carbon atoms,
However, at least one of R _{1 to} R ₅ is not hydrogen,
Q ⁺ is trialkylammonium, pyridinium-1-
Yl, N-alkylpyridinium-m-yl, where m is 2, 3 or 4, thiazolinium-3-yl, or N
-Alkyl thiazolinium-m-yl, where m is 2, 4
Or 5, the heterocycle may be substituted by additional alkyl groups and all the alkyl groups of the group Q ⁺ may be the same or different and / or substituted by hydroxyl or sulphonic acid groups. Each alkyl group does not have more than 12 carbons, and in the case of trialkylammonium two of them may form a 3-12 membered ring with a quaternary nitrogen. .

B is a bridging group composed of 1 to 3 methylene groups, each of which may be substituted with methyl or ethyl, and if Q ⁺ is N ^- alkylpyridinium-m-yl or N-alkylthia. The platform that is zolinium-m-yl may be an oxygen atom or a single bond. A ⁻ represents an anion, but is not necessary when it contains a Q ⁺ sulfo group.

The Ar group represents a substituted phenyl group and may represent a substituted or unsubstituted aryl group such as a naphthyl, anthryl or phenanthryl group.

The substituent on the aromatic ring system of the Ar group has certain characteristics with respect to the hydrazine compound, such as diffusion resistance (ballast group) and adsorptivity to silver halide (adsorption promoting group).
It is preferred to include groups such as those used in the art to provide such as. Examples of such substituents are preferably straight chain, branched chain or cyclic alkyl, alkenyl or alkynyl having 1 to 20 carbon atoms,
It may be further substituted by one of the radicals specified here, which radicals are, for example, 6 to 1 substituted or unsubstituted with halogen atoms, cyano, carboxyl, amino.
Aryl groups having 4 carbon atoms, alkylamino and acylamino groups having 1 to 20 carbon atoms, other groups including thiocarbamide groups and thiocarbonyl groups, alkoxy and aryloxy groups, aliphatic and aromatic groups An acyloxy group, a urethane group, an alkyl- and arylsulfonyl group, an alkyl- and arylsulfonamide group, a 5- to 10-membered nitrogen- or sulfur-containing heterocyclic group such as imidazole, thiazole, benzothiazole, and benzimidazole. is there. Each of the above substituents is
It can be independently attached to the aryl group independently of the others, or it can also be substituted for each other into the chain replacing the hydrogen atom of the aryl. These substituents have the favorable effect of increasing the electron density of the aromatic ring system by the mesomeric or inducing effect.

Q ⁺ is a group with a permanent positive charge such as is found in onium compounds, such as ammonium, phosphonium and oxonium compounds.

The anion A ⁻ is a halide anion such as chloride, bromide, or iodide, or a complex inorganic ion such as sulfate or perchlorate, or also a common inorganic such as toluenesulfonate or trichloroacetate. Can be an organic anion of Strong acid anions are preferred. If the hydrazine compound is replaced by a group bearing an anionic group, this anion disappears by making an internal salt.

Based on the state of the art, it is stated that the compounds according to the invention having a cationic group in the active group will have improved properties, in particular a high development rate at low pH values. It was unexpected for a person skilled in the art.
Rather, in a comparative experiment with hydrazine, Takada et al U.S. Pat. No. 4,224,401 shows that such groups have no effect on contrast during development. US Patent 3,386,8 to Honig et al.
According to No. 31, an aryl hydrazide having no substitution on the aryl group and having a cationic group in the acyl group has a strong fogging effect on a high-sensitivity silver iodobromide emulsion without affecting the contrast. are doing. On the contrary, the element of the present invention showed no increase in fog even after long-term storage, and exhibited super-high contrast property by proper development.

Next, the compound of 5-a will be described.

R _{1 to} R ₅ may be the same or different, but at least one is not hydrogen and they are hydrogen, in each case an alkyl having 1 to 20 carbon atoms, Alkoxy, hydroxyalkyl, haloalkyl, alkylamino, aliphatic acylamino, or cycloalkyl, in each case aryl, aryloxy, or aromatic acylamino having 6 to 10 carbon atoms, 1 in the alkylene chain. 1 to 4 aralkyl or alkoxy having 3 to 3 carbon atoms, or 1 to 4 substituted by a phenoxy group substituted with one or more of alkyl groups having 1 to 10 carbon atoms Q ⁺ is trialkylammonium, pyridinium-1-yl, such as an aliphatic acylamino group having a carbon atom, N-alkylpyridinium-m-yl where m is 2, 3 or 4, thiazolinium-3-yl, N-alkylthiazolinium-m-yl where m is 2, 4 or 5 and the heterocycle is an additional Optionally substituted by alkyl groups, and all alkyl groups of the group Q ⁺ may be the same or different and /
Or may be substituted by hydroxyl or sulfonic acid groups, each alkyl group having no more than 12 carbon atoms and, in the case of trialkylammonium,
Two of them may form a 3- to 12-membered ring with a quaternary nitrogen atom, B is a bridging group composed of 1 to 3 methylene groups, each of which is substituted with methyl or ethyl. If Q ⁺ is N ^- alkylpyridinium-m-yl or N-alkylthiazolinium-m-
When it is yl, it may be an oxygen atom or a single bond, and A ⁻ represents an anion, but is unnecessary when Q ⁺ contains a sulfo group. Hereinafter, specific examples of the compound represented by Formula 5-a will be shown, but the compound is not limited thereto.

[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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The above hydrazine derivative according to the present invention is
It can be synthesized by a known method. The amount added to the silver halide photographic light-sensitive material is not uniform, but is usually preferably in the range of 10 ^-6 to 10 ^-1 mol, and more preferably 10 ^-5 to 10 ^-2 mol per mol of silver halide. Range is good.

Next, the compound represented by formula (6) will be described in more detail.

R ₁ is an aromatic group, generally a monocyclic or bicyclic aromatic group. An example of a monocyclic aromatic group is a phenyl group, and a suitable example of a bicyclic aromatic group is a naphthyl group. Aromatic groups are one or more substituents that are not electron withdrawing groups, such as alkyl groups having 1 to 20 carbon atoms (either straight or branched chain,
For example, methyl, ethyl, propyl, iso-propyl,
n-butyl, iso-butyl, n-octyl, n-hexyl, tert-butyl, n-decyl, n-dodecyl and the like), an aralkyl group having 1 to 3 carbon atoms in the alkyl moiety (for example, Benzyl, phenethyl, etc.), an alkoxy group having 1 to 20 carbon atoms (the alkyl moiety may be linear or branched, and is, for example, methoxy, ethoxy, 2-methylpropoxy, etc.). ), An amino group mono- or di-substituted with an alkyl group having 1 to 20 carbon atoms, an aliphatic acylamino group having 2 to 21 carbon atoms, or an aromatic acylamino group (eg, acetylamino, octyl). Each group such as nylamino, benzoylamino, dimethylamino, etc.) and the like.

As R ₁ , a group represented by general formula (6-a) shown below is preferable.

[0173]

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In the formula, m is 0 or an integer of 1 to 3,
R ₂ is an alkyl group having up to 12 carbon atoms, preferably 1 to 5 carbon atoms, an alkoxy group having up to 12 carbon atoms, a halogen atom or NHCOR.
_{3 where} R ₃ is H, an alkyl group having up to 12 carbon atoms, or an aryl group having up to 12 carbon atoms.

_One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom, an arylsulfonyl group or a trifluoroacetyl group.

G is --CO--, --COCO--, --SO--,
—SO ₂ — or an N-substituted or unsubstituted imino group, and preferably —CO—.

As X, a group represented by general formula (6-b) shown below is preferable.

[0178]

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In the formula, R _{4 to} R ₇ are selected from a hydrogen atom, an alkyl group having up to 12 carbon atoms, or an aryl group having up to 12 carbon atoms. When any of R _{4 to} R ₇ is an alkyl group, the alkyl group may be straight or branched and generally has up to 12 carbon atoms, preferably up to 3 carbon atoms. There is. R ₄
When any of ~ R ₇ is an aryl group, the aryl group generally contains from 5 to 12 carbon atoms and is optionally a substituent such as an alkyl group, an alkoxy group. Etc. may be included. B is an atom necessary for completing a 5-membered ring or 6-membered ring which may have a substituent, and preferably an atom necessary for forming a benzene ring. Y is OH, SH, or NHR ₃ (wherein R ₃ has the same meaning as R ₃ in the general formula (6-a)), p and q are 0 or 1, and (p
+ Q) is 1 or 2.

The -G-X moiety in the general formula (6) is a 5-membered ring or a 6-membered ring derived from the -G-X moiety under basic conditions, generally within the range of pH 9.5 to 12.5. It is possible to produce cyclic structures such as lactones or lactams.

The compound represented by the general formula (6) is preferably represented by the following general formula (6-c).

[0182]

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In the formula, p'and q'are 0 or 1, and (p '+ q') is 1. R ₂ and m are respectively _{R 2} and m synonymous in Formula (6-a). Z is NH ₂ or OH.

Specific examples of the compound represented by formula (6-c) are shown below, but the invention is not limited thereto.

[0185]

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The above hydrazine derivative according to the present invention is
It can be synthesized by a known method. The hydrazine derivative according to the present invention is preferably added in an amount in the range of 10 ^-6 to 10 ^-1 mol, preferably 10 ^-5 to 10 ^-2 mol, per mol of silver halide.

The hydrazine derivative used in the present invention is
It is added to at least one photographic constituent layer on the silver halide emulsion layer side, and preferably to the silver halide emulsion layer and / or its adjacent layer.

Further, the general formula (1) according to the present invention,
Hydrazine derivatives other than the hydrazine derivatives represented by (2), (3), (4), (5) and (6) can be used in combination.

In order to effectively promote the contrast increase by the hydrazine derivative, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb].

[0190]

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In the general formula [Na], R ₁₁ , R ₁₂ , R
₁₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group. Particularly preferred as the general formula [Na] is a compound having at least one thioether group as a silver halide adsorptive group in the molecule.

Specific examples of these nucleation accelerators [Na] will be given below.

[0193]

[Chemical 51]

[0194]

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[0195]

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[0196]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₄ is a hydrogen atom,
Represents an alkyl group, an alkynyl group, or an aryl group;
And R ₁₄ may be linked by a linking group to form a ring. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Examples of the preferable silver halide adsorbing group include the same groups as the silver halide adsorbing group which R _{1 of the} compound represented by the general formula (1) can have.

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

[0199]

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[0200]

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Specific examples of other preferable nucleation-accelerating compounds are described in JP-A-6-258751, page (13), “006”.
2) to (15), “0065” (2-
Compounds 1) to (2-20) and 3-1 to 3-6 described in JP-A-6-2587551, page (15), "0067" to page (16), "0068".

These nucleation-accelerating compounds can be used in any layer as long as they are on the silver halide emulsion layer side, but are preferably used in the silver halide emulsion layer or a layer adjacent thereto.

The average grain size of the silver halide used in the present invention is preferably 0.7 μm or less, particularly 0.5
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 of determining the average particle size, see Mies, James: The Theory of the Photographic Process (by CE Mees & TH James: Th).
e theoryof the photograph
ic process), 3rd edition, pp. 36-43 (19
66 (published by McMillan "Mcmillan").

The shape of silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Also, a narrower particle size distribution is preferable, and 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 particularly preferable.

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

It is also possible to use a method of forming grains in the presence of excess silver ions (so-called reverse mixing method). As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

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

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

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 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.

As the selenium sensitizer, known selenium sensitizers can be used. For example, US Pat.
Nos. 60-71325 and 60-150046.
The compounds described in the publication No. etc. can be preferably used.

As the tellurium sensitizer, known tellurium sensitizers can be used. For example, US Pat. No. 162349.
The compounds described in No. 9, No. 3772031, No. 3320069, etc. can be preferably used.

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

As reduction sensitizers, stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

The black and white silver halide photographic light-sensitive material according to the present invention is preferably processed using an automatic processor.
At this time, processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photosensitive material. The developing replenishing amount and the fixing replenishing amount are 50 ml or more and 300 ml or less per 1 m ² in order to reduce the amount of waste liquid. 50 per 1 m ²
When the replenishing amount is less than or equal to ml, the photographic performance fluctuates greatly, which becomes a problem when a large amount of samples are processed. Preferably 1 m ²
It is 75 to 200 ml per one.

In the present invention, when processing is performed by using an automatic developing machine, 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 10 in order to shorten the developing time. It is preferably -60 seconds. The total processing time referred to here includes the total process time required for processing the black-and-white light-sensitive material, and specifically, for the processing, such as development, fixing, bleaching, washing, stabilizing, and drying. Time including all process time, that is, Dr
It is the time of y to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening.
More preferably, the total processing time (Dry to Dry) is 15 to 50 seconds.

Further, in the automatic processor, a heat transfer material at 90 ° C. or higher (for example, a heat roller at 90 ° C. to 130 ° C.) or a radiation object at 150 ° C. or higher (for example, tungsten, carbon, nichrome, zirconium oxide / yttrium oxide /
A substance that emits infrared rays by directly generating heat through a mixture of thorium oxide or silicon carbide and radiating heat, or transferring heat energy from a resistance heating element to a radiator such as copper, stainless steel, nickel, or various ceramics to generate heat and generate infrared rays ) And those having a zone for drying.

Examples of the developing agent that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone). 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, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol,
Ascorbic acid, 1-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino (Phenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.), transition metal complex salts (T
A complex salt of a transition metal such as i, V, Cr, Mn, Fe, Co, Ni, Cu, etc. These may have a reducing power in order to be used as a developing solution. For example, Ti ³⁺ , V ²⁺ ,
It takes the form of a complex salt such as Cr ²⁺ , Fe ^2+, etc.
Examples include aminopolycarboxylic acids and salts thereof such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), and phosphoric acids and salts thereof such as hexametapolyphosphoric acid and tetrapolyphosphoric acid. ), Etc., can be used alone or in combination, a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid, It is preferable to use a combination of aminophenols and ascorbic acid, a combination of 3-pyrazolidones and transition metal complex salts, and a combination of aminophenols and transition metal complex salts. Further, the developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

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

The developing waste liquid can be regenerated by energizing it. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material according to the present invention can be processed while energizing. At that time, various additives added to the developer, for example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor which can be added to the developer are additionally added. You can do it. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. When the waste developer is regenerated and used, transition metal complex salts are preferable as the developing agent of the developer used.

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

In the developer, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) , Dissolution aids (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.),
Surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (for example, US Pat.
No. 025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent. Total processing time (Dry to Dry) is 6
The pH of the developer is 8.5 to 10.5 in order to set it to 0 seconds or less.
Is preferably adjusted to

The compounds of the present invention, as a special form of development processing, include a developing agent in a light-sensitive material, for example, an emulsion layer,
You may use it for the activator processing liquid which makes a photosensitive material process in alkaline aqueous solution and develops. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions.
In the case of such rapid processing, the effect of the present invention is particularly large.

As the fixing liquid, those having a generally used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, etc. can be added to the fixing solution.

If desired, the fixer may contain preservatives (eg sulfite, bisulfite), pH buffers (eg acetic acid),
Compounds such as a pH adjuster (for example, sulfuric acid) and a chelating agent capable of softening water can be included.

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

In the development processing of the present invention, the development temperature can be set in the usual temperature range of 20 to 30 ° C. or in the high temperature processing range of 30 to 40 ° C.

The silver halide emulsion of the present invention can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, and the like. A benzoxazole 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 be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus,
A 5- to 6-membered heterocyclic ring such as a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied. Specifically, Research Disclosure No. 176
Volume RD-17643 (December 1978 issue) No. 2 and 3
, U.S. Pat. Nos. 4,425,425 and 4,425,4
No. 26 can be used. The sensitizing dye may be dissolved by using ultrasonic vibration described in U.S. Pat. No. 3,485,634. Other methods for dissolving or dispersing the sensitizing dye of the present invention in an emulsion include those described in U.S. Pat. Nos. 3,482,981, 3,585,195, 3,469,987 and 3,469,987. 3,425,835 and 3,342,605, British Patents 1,271,329 and 1,038,029,
No. 1,121,174, U.S. Pat. No. 3,660,101
No. 3,658,546 can be used. These sensitizing dyes may be used alone,
Combinations of these may be used, and combinations of sensitizing dyes are often used particularly for supersensitization. Useful supersensitizing dye combinations and supersensitizing substances are described in Research Disclosure (Research).
h Disclosure) Volume 176 17643 (19
(Issued December, 1978), page 23, IV, J.

The light-sensitive material of the present invention may contain various dyes for the purpose of improving safety of safelight. Preferred dyes include those represented by the following general formulas (7) to (12).

[0230]

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In the formula, A and A ′, which may be the same or different, each represents an acidic nucleus, Q represents an aryl group or a heterocyclic group, B represents a basic nucleus, and B ′ represents a heterocyclic group. X and Y, which may be the same or different, each represents an electron-withdrawing group, and L ₁ , L ₂ and L ₃ each represent a methine group. m represents 0 or 1, n represents 0, 1 or 2, and p represents 1 or 2. However, the dyes represented by the general formulas (7) to (12) have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule.

Examples of the aryl group represented by Q in the above general formulas (7) and (10) include a phenyl group and a naphthyl group. Examples of the heterocyclic group represented by Q include pyridine, quinoline, isoquinoline, pyrrole, pyrazole, imidazole and indole residues.

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

The acidic nuclei represented by A and A'in the general formulas (7), (8) and (9) are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanin, hydantoin and thio. Hydantoin, oxazolone,
Examples thereof include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone and pyrazolopyridone.

The basic nucleus represented by B in the general formulas (9) and (11) is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole. , Indole, etc.

The electron withdrawing groups represented by X and Y in the general formulas (10) and (11) may be the same or different, and for example, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Examples thereof include a carboxy group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group and a sulfamoyl group.

The heterocycle represented by B'in the general formula (12) includes, for example, pyridine, pyridazine, quinoline, pyrrole, pyrazole, imidazole and indole.

L ₁ , L ₂ and L in the general formulas (7) to (11)
_The methine group represented by ₃ includes those having a substituent,
Examples of the substituent include an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, isobutyl, etc.),
Aryl groups (eg phenyl, p-tolyl, p-chlorophenyl etc.), alkoxy groups having 1 to 4 carbon atoms (eg methoxy group, ethoxy group etc.), aryloxy groups (eg phenyl group etc.), aralkyl groups (eg benzyl) Group, phenethyl group, etc.), heterocyclic group (eg, pyridyl, furyl, thienyl, etc.), substituted amino group (eg, dimethylamino, tetramethyleneamino, anilino, etc.), alkylthio group (eg, methylthio group, etc.).

Specific examples of the dyes used in the present invention will be given below.

[0240]

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[0241]

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[0242]

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[0243]

[Chemical formula 61]

[0244]

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[0245]

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[0246]

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[0247]

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[0248]

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[0249]

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These dyes have at least one dissociative proton having a pKa in the range of 4 to 11, preferably 4.5 to 7.0 in a mixed solvent of water-ethanol volume ratio of 1: 1. To have. Further, in the present invention, the immobilization can be achieved by the silver salt and the silver complex formed by the reaction of the dye and the silver ion. Preferred dyes capable of forming silver salts of such dyes are, for example, JP-A-5-18123.
The compounds represented by the general formulas [I] to [V], the general formulas [I '] to [V'], and the general formula [VI] described on page 4 to page 28 of the No. 0 specification are mentioned. To be More specific compounds are I-1 to 37, II-1 to 5, III-1 to 7, IV-1 to 1 described in pages 6 to 46 of the same specification.
6, V-1 to 5, I'-1 to 12, II'-1 to 9, II
I'-1 to 9, IV'-1 to 9, V'-1 to 6, VI-1 to
52 is mentioned.

In the present invention, the above general formulas (7) to (1)
The method of dispersing the dye represented by 2) is not particularly limited, but a known method such as an acid precipitation method, a ball mill, a jet mill or an impeller dispersion method can be applied.

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

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

In the present invention, the coating amount of the hydrophilic colloid layer containing fine dye particles is 0.05 g / m ² or more and 0.1.
It is less than 5 g / m ² , but preferably 0.18 g / m ² or more and less than 0.42 g / m ² . Further, in order to enhance the effect of the present invention, it is preferable that the ratio of the average particle diameter of the dye fine particles to the film thickness of the dye layer is 0.2 to 2.0.

In the present invention, the light-sensitive material may contain various compounds for the purpose of preventing fog during the 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.

In the present invention, the photographic emulsion and the non-photosensitive hydrophilic colloid may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.),
Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β-
(Vinylsulfonyl) propionamide]), an active halogen compound (2,4-dichloro-6-hydroxy-s)
-Triazines, etc.), mucohalic acids (mucochloric acid,
Phenoxymucochloric acid and the like) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination.

In the present invention, the light-sensitive emulsion layer and / or the non-light-sensitive hydrophilic colloid layer are used for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Various known surfactants may be used.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

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

In the present invention, the photographic emulsion may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, Methacrylic acid,
A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like as a monomer component can be used.

Various other additives are used in the light-sensitive material used in the present invention. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, and the like can be used.

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

In the present invention, the emulsion layer and the protective layer in the light-sensitive material may be a single layer or a multi-layer consisting of two or more layers. In the case of a multilayer, an intermediate layer or the like may be provided therebetween.

In the light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one side or both sides of a support containing syndiotactic polystyrene.

[0265]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited thereto.

(Preparation of SPS Support) SPS was synthesized by the method described in << Polymerization Example >>.

Then, the obtained SPS pellets were melt extruded. The molten polymer was extruded through a pipe into an extrusion die. Then, the SPS unstretched sheet having a film thickness of 1000 μm was obtained by extruding while being electrostatically applied to the casting drum cooled through the die slit and cooling.

The prepared sheet was preheated at 115 ° C. and then stretched 3.3 times in the machine direction. After preheating at 100 ° C in a stenter, the film was stretched 3.3 times in the transverse direction at 130 ° C. Heat it at 225 ° C while relaxing it slightly in the lateral direction.
A 0 μm thick SPS film was obtained.

On the obtained SPS film, 23 w / m
After performing a corona discharge for ² minutes 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.

Undercoating liquid 1 Styrene-butadiene latex (No. 619 made by Japan Synthetic Rubber) 40 parts by weight Styrene-butadiene latex (No. 640 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 soda salt 3 parts by weight sodium dodecylbenzenesulfonate 2 parts by weight After further corona discharge for 18 w / m ² minutes, 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 soda 2 parts by weight was finished with 100 g of pure water to obtain a working fluid having a dry film thickness of 0.1.
It was provided to have a thickness of 1 μm and further dried at 140 ° C.

Next, after corona discharge of 23 w / m ² was applied to this back surface and further an ionic wind was blown, the undercoating processing liquid 2 was provided so as to have a dry film thickness of 1 μm and dried at 140 ° C.

Undercoating liquid 2 Styrene butadiene latex (No. 619 made by Japan Synthetic Rubber) 50 parts by weight Styrene butadiene latex (No. 640 made by Japan Synthetic Rubber) 40 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 for 18 w / m ² minutes, 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 Finished solution to 100 g with pure water To a dry film thickness of 0.
It was provided to have a thickness of 1 μm and further dried at 140 ° C.

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

A comparative PET support was made by known techniques.

Example 1 (Preparation of Silver Halide Emulsion A) A controlled double jet of an aqueous silver nitrate solution and a mixed aqueous solution of NaCl and KBr was carried out so that the silver halide composition was 70 mol% silver chloride and 30 mol% silver bromide. Method to mix to grow silver halide grains. At this time, the mixture is 36 ° C, pAg 7.8, pH 3.0.
And 2 × 10 ⁻⁷ mol of Na ₂ RhCl ₆ was added per 1 mol of silver during grain formation. Then desalted with modified gelatin treated with phenyl isocyanate,
Ocein gelatin was added and redispersed. The resulting emulsion was an emulsion composed of cubic grains having an average grain size of 0.20 μm and a coefficient of variation of 10%. The emulsion thus obtained contained 30 mg of S-1 (sodium-isoamyl-n-decylsulfosuccinate) and 4-mercapto-per mole of silver.
50 mg of 2,3,5,6-tetrafluorobenzoic acid was added, and 5 mg of chloroauric acid and 0.5 m were added per 1 mol of silver.
6g under the condition of pH 5.8 and pAg 7.0
Chemical ripening was performed at 0 ° C. for 80 minutes. After the ripening, 900 mg of 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene was added per 1 mol of silver, and KI was further adjusted to 3
00 mg was added.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for Ar laser light source) A silver halide emulsion layer of the following prescription 1 is formed on one undercoat layer of the SPS support of the present invention or the comparative PET support. The amount of gelatin is 2.0 g /
m ² and the amount of silver are 3.2 g / m ² and a protective layer of the following formulation 2 is 1.0 g / m 2 on the protective layer.
² on the other side, and on the other undercoat layer on the other side, a backing layer is coated according to the following prescription 3 so that the amount of gelatin is 2.0 g / m ² , and further on that. A protective layer of the following formulation 4 was applied so that the amount of gelatin would be 0.8 g / m ² , and a sample was obtained.

Formulation (1) (Silver Halide Emulsion Layer Composition) Gelatin 2.0 g / m ² Silver Halide Emulsion A To increase the silver amount to 3.2 mg / m ² Sensitizing dye d-3 6 mg / m ² Sensitizing dye d-4 3 mg / m ² Antifoggant: Adenine 25 mg / m ² Stabilizer: 1-Phenyl-5-mercaptotetrazole 2 mg / m ² 5-Nitroindazole 10 mg / m ² General formula (1) shown in Table 1. 20 mg / m ² nucleation accelerator: Exemplified compound Na-10 50 mg / m ² latex polymer f 1.0 g / m ² S-1 0.7 mg / m ² compound e 45 mg / m ² hardener g 30 mg / m ² formulation (2) [emulsion protective layer composition] gelatin 1.0 g / m ² matting agent: average particle size 3.5μm silica 20 mg / m ² surfactant h 2 mg / ^{m 2} promoter: hydroquinone 50 mg / ² dye (those that have been in the powder particle size 0.1μm is ball dispersed) Exemplified Compound 7-25 20 mg / m ² Hardener g 30 mg / m ² Formulation (3) of the dye (backing layer composition) Gelatin 2 0.0 g / m ² sodium polystyrene sulfonate 20 mg / m ² colloidal silica (average particle size 0.05 μm) 70 mg / m ² latex polymer f 0.3 g / m ² formulation (4) [backing protective layer composition] gelatin 0.8 g / M ² Matting agent: Polymethylmethacrylate having an average particle size of 4.0 μm 50 mg / m ² Surfactant h 1 mg / m ² Dye k 20 mg / m ² Hardener g 15 mg / m ²

[0278]

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[0279]

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The obtained sample was subjected to halftone dot exposure with SG-757 manufactured by Dainippon Screen Co., Ltd. at a number of lines of 700 lines per inch in order to evaluate fine halftone dot quality, and the following composition was obtained. Konica's automatic processor G using developer and fixer
R-27 was processed by modifying it so as to meet the following processing conditions. The halftone quality of the developed sample thus obtained was evaluated.

(Developer composition) Pure water 280 g Sodium sulfite 52 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 850 mg Diethyltriamine 5 acetic acid 1.5 g Boric acid 8 g Potassium bromide 10.0 g Potassium carbonate 50 g Diethylene glycol 40 g Benztriazole 200 mg Hydroquinone 20 g 1-Phenyl-2-mercaptotetrazole 35 mg Potassium hydroxide pH 10.4 The amount was adjusted to 1 liter by adding water at the time of use.

(Fixing liquid composition) Ammonium thiosulfate (72.5% w / v aqueous solution) 200 ml Pure water 140 g Ethylenediaminetetraacetic acid disodium salt 100 mg Sodium sulfite 25 g Boric acid 10.0 g Acetic acid (90% w / v aqueous solution) 15.5 g Sodium acetate / trihydrate 36.5 g Tartaric acid (50% w / v aqueous solution) 6 ml Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% w / v aqueous solution) 25 ml Sodium hydroxide (50% w / v aqueous solution) ) P when used
When the amount of H was set to 4.8, water was added to make 1 liter.

(Development processing conditions) (Process) (Temperature) (Time) Current image 35 ° C 30 seconds Settling 33 ° C 20 seconds Water wash Normal temperature 15 seconds Dry 40 ° C 15 seconds Total 80 seconds (Automatic processor Evaluation of Dryness in Samples) The dryness of the sample discharged through the drying process of the automatic processor was evaluated by feel on a five-point scale. The highest rank was 5, and as the dryness deteriorated, the rank was lowered to 4, 3, 2, 1 and evaluated. Rank 1 and 2
Is a level that is not practically preferable.

(Evaluation method of halftone dot quality) Midpoint (target halftone% 5
0%) was evaluated 100 times with a magnifying glass to evaluate the halftone quality. The highest rank is 5, and 4 according to the halftone dot quality,
The rank was lowered to 3, 2, 1 and evaluated. Ranks 1 and 2 are levels that are not practically desirable.

The evaluation results are shown in Table 1.

[0286]

[Table 1]

[0287]

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As is clear from Table 1, by using the SPS support of the present invention in a silver halide photographic light-sensitive material for a printing plate making scanner for Ar laser light source, the drying property is improved and the hydrazine derivative of the present invention is added. It can be seen that the inclusion of the element suppresses the deterioration of halftone dot quality when reproducing minute halftone dots.

Example 2 (Preparation of Silver Halide Emulsion B) A controlled double jet of an aqueous silver nitrate solution and a mixed aqueous solution of NaCl and KBr was carried out so that the silver halide composition was 65 mol% silver chloride and 35 mol% silver bromide. Method to mix to grow silver halide grains. At this time, mixing was 38 ° C, pAg 8.0, pH 3.5.
Performed under the conditions of, K ₃ RhBr ₆ was per mole silver 2 × 10 ^-7 mol, and K ₃ IrCl ₆ were added 3 × 10 ^-7 mol per mol of silver in the grain formation. After that, desalting was performed with MgSO ₄ and polynaphthalene sulfonic acid, and ossein gelatin was added and redispersed. The resulting emulsion had an average grain size of 0.
The emulsion consisted of cubic grains having a diameter of 2 μm and a coefficient of variation of 10%. The emulsion thus obtained contains 0.12 citric acid.
g, NaCl 0.6 g, pH 5.5, pAg 7.
After adjusting to 0, 14.2 mg of chloroauric acid and 8.5 mg of sodium thiosulfate were added, and chemical ripening was performed at 60 ° C. so that the maximum sensitivity was obtained. After ripening, 14 mg of 4-phenyl-5-mercaptotetrazole and 4-
900 mg of methyl-6-hydroxy-1,3,3a, 7-tetrazaindene was added.

(Preparation of silver halide photographic light-sensitive material for printing plate making scanner for infrared semiconductor laser light source) S of the present invention
On one subbing layer of the PS support or the comparative PET support, a silver halide emulsion layer of the following formulation 5 was prepared so that the amount of gelatin was 1.2 g / m ² and the amount of silver was 3.6 g / m ² . After coating, a protective layer of the following formulation 6 was coated thereon so that the amount of gelatin would be 0.8 g / m ^2, and on the other undercoat layer on the opposite side, a backing according to the following formulation 7 was applied. A layer is coated so that the amount of gelatin is 1.6 g / m ^2, and a protective layer of the following formulation 8 is further applied on the layer so that the amount of gelatin is 0.7 g / m 2.
^A sample was obtained by coating so as to be ² .

Formulation (5) (Silver Halide Emulsion Layer Composition) Gelatin 1.2 g / m ² Silver Halide Emulsion B To increase the amount of silver to 3.6 mg / m ² Sensitizing dye d-2 5 mg / m ² Sensitizing dye d-5 3 mg / m ² Hydrazine derivative of general formula (2) shown in Table 2 30 mg / m ² Accelerator: Hydroquinone 50 mg / m ² Latex polymer f 1.0 g / m ² S-1 0.7 mg / m ² compound e 100 mg / m ² 2-mercapto-6-hydroxypurine 10 mg / m ² hardening agent g 3 mg / m ² formulation (6) [emulsion protective layer composition] gelatin 0.8 g / m ² matting agent: average particle size 3.5 μm silica 25 mg / m ² Surfactant h 2 mg / m ² Nucleation accelerator: Exemplified compound Na-10 50 mg / m ² dye (ball-mill dispersed into powder having a particle size of 0.1 μm): Dye Exemplified Compound 7-2 15 mg / m ² Colloidal silica (average particle size 0.05 .mu.m) 50 mg / m ² Hardener g 30 mg / m ² formulation (7) (Backing layer composition) Gelatin 1.6 g / m ² Sodium polystyrenesulfonate 20 mg / m ² Colloidal silica (average particle size 0.05 μm) 70 mg / m ² latex polymer f 0.3 g / m ² compound i 100 mg / m ² formulation (8) [backing protective layer composition] gelatin 0.7 g / m ² matting agent: average Polymethylmethacrylate having a particle diameter of 4.0 μm 50 mg / m ² Surfactant h 1 mg / m ² Dye k 50 mg / m ² Latex polymer f 0.3 g / m ² Hardener g 20 mg / m ²

[0292]

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The obtained sample was subjected to MTR-110 manufactured by Dainippon Screen Co., Ltd. in order to evaluate fine dot quality.
At 0, halftone dot exposure was performed with 600 lines per inch, the same treatment as in Example 1 was performed, and the same evaluation was performed.

The evaluation results are shown in Table 2.

[0295]

[Table 2]

As is clear from Table 2, by using the SPS support of the present invention in a silver halide photographic light-sensitive material for a printing plate making scanner for infrared semiconductor laser light sources, the drying property is improved and the hydrazine of the present invention is used. It can be seen that the inclusion of the derivative suppresses the deterioration of the halftone dot quality when reproducing minute halftone dots.

Example 3 (Preparation of Silver Halide Emulsion C) In a nitric acid acidic atmosphere having a pH of 3.2, pAg was uncontrolled and a simultaneous mixing method was used.
A rhodium chloride complex was added in an amount of 8 × 10 ^-5 mol per 1 mol of silver and desalted by a conventional method to obtain an emulsion of pure silver chloride cubic grains having an average particle size of 0.09 μm and monodisperse (variation coefficient of 10%). .

To the resulting emulsion, 63 mg of 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added per mol of silver, and sodium thiosulfate was added until the maximum sensitivity was obtained at a temperature of 60 ° C. Chemically aged. After the ripening, 1.5 g of 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added per 1 mol of silver.

(Preparation of light-returning silver halide photographic light-sensitive material) A silver halide emulsion having the following formulation 9 was provided on one undercoat layer of the SPS support of the present invention or a comparative PET support in a silver amount of 3. Simultaneous multi-layer coating was performed so that the amount of gelatin was 3 g / m ² and the amount of gelatin was 1.2 g / m ^2, and a coating solution of the following formulation 10 as a protective layer was further formed on the upper layer thereof so that the amount of gelatin was 1.0 g / m ² . On the opposite undercoat layer, a backing layer having the following formulation 11 was added so that the amount of gelatin would be 1.9 g / m ^2, and a backing protective layer having the following formulation 12 was added to give a gelatin amount of 0.7 g / m ^2. A sample was obtained by performing simultaneous multi-layer coating so as to have m ² .

Formulation 9 (Silver Halide Emulsion Layer Composition) Silver Halide Emulsion C To make the amount of silver 3.3 mg / m ² Gelatin 1.2 g / m ² General formula (3) or (4 shown in Table 3 ) Hydrazine derivative 20 mg / m ² Nucleation accelerator: Exemplified compound Na-10 70 mg / m ² Sodium dodecylbenzene sulfonate 80 mg / m ² Citric acid Adjusted to pH 5.6 Compound m 6 mg / m ² Latex polymer f 0.5 g / M ² S-1 0.7 mg / m ² Styrene-maleic acid copolymer hydrophilic polymer (thickener) 42 mg / m ² EDTA 15 mg / m ² Formulation 10 (emulsion protective layer composition) Gelatin 1.0 g / m ² dye ^{r 14mg / m 2 S-1} 12mg / m 2 matting agent: average particle size 3μm monodisperse silica 15 mg / m ² matting agent: average particle monodisperse silica diameter 8 [mu] m 20 mg / m ² 1 3- vinylsulfonyl-2-propanol 50 mg / m ² Surfactant h 1 mg / m ² Styrene - hydrophilic polymer maleic acid copolymer (thickener) 15.7 mg / m ² Hardener: Formaldehyde 70 mg / m ² Prescription 11 (backing layer composition) Gelatin 1.9 g / m ² Dye r 40 mg / m ² S-1 5 mg / m ² Latex polymer f 0.3 g / m ² 5-Nitroindazole 20 mg / m ² Styrene-maleic acid co Polymeric hydrophilic polymer (thickener) 55 mg / m ² compound i 100 mg / m ² formulation 12 (backing protective layer) gelatin 0.7 g / m ² matting agent: monodisperse polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² surfactant h 1 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² hardener j 40 mg / m ² dye k 14 mg / m ²

[0301]

Embedded image

In order to evaluate the quality of minute halftone dots, the obtained sample was processed No. 1 prepared in Example 1. 14
After making contact (emulsion side to side) exposure with a bright room printer P-627GM (manufactured by Dainippon Screen) as an original, an automatic developing machine G using the developing solution and fixing solution having the following composition
R26SR was processed under the following conditions.

(Processing conditions) (Process) (Temperature) (Time) Development 38 ° C. 20 seconds Fixing 38 ° C. 16 seconds Washing at room temperature 16 seconds Drying 50 ° C. 23 seconds Total 75 seconds (Developer composition) Ammonia water (25%) 40 ml DTPA 0.25 mol sodium sulfite 20g borate 8g potassium bromide 15g potassium carbonate 40 g 2-mercapto-6-hydroxy purine 60mg diethylene 40 g 5-methylbenzotriazole 0.2g FeSO ₄ · 7H ₂ O 0.2 moles of 1-phenyl - 3-Pyrazolidone 0.9 g Water is added to make 1 liter The pH is adjusted to 9.2 with an aqueous potassium hydroxide solution.

(Fixing liquid composition) Amount used per liter Fixing liquid (c) Sodium thiosulfate 100 g / l Sodium sulfite 22 g / l Boric acid 10 g / l Sodium acetate trihydrate 34 g / l Tartaric acid 3.0 g / Lithium sulfate (27% aqueous solution) 10 ml / liter Glutaraldehyde 3 g / liter Acetic acid was adjusted to pH 5.0.

The samples thus obtained were evaluated as follows.

(Evaluation of reproducibility of minute halftone dots) Halftone dot% of a negative image corresponding to a small dot (5%) at an exposure amount giving a solid density of 5.0 on a document. The closer to 95%, the better.

(Evaluation of halftone dot quality) The halftone dot quality (sharpness) of a negative image for a small dot (5%) of a document was evaluated with a magnifying glass 100 times. The highest rank was set to 5, and the rank was lowered to 4, 3, 2, and 1 according to the halftone dot quality and evaluated. Rank 1 and 2
Is a level that is not practically preferable.

(Dimensional stability) The sample is 30 cm × 60 cm.
The image was exposed to light using a bright room printer P-627GM (manufactured by Dainippon Screen Co., Ltd.) at a distance of 60 cm, and developed. This original, evaluation sample (same size as original), printer and automatic processor were conditioned at 23 ° C and 20% RH for 2 hours, then exposed to unexposed sample (emulsion side) and exposed automatically. Machine processed. Develop processed sample at 23 ℃ 20% R
After humidity conditioning for 2 hours at H, the original was overlaid and the distance between the fine lines was measured with a loupe with a scale. The smaller the distance, the better.

The results are shown in Table 3.

[0310]

[Table 3]

As is clear from Table 3, when the SPS support of the present invention is used in a silver halide photographic light-sensitive material for printing plate-making bright room return, the dimensional stability is improved and the hydrazine derivative of the present invention is contained. It can be seen that there are few problems that the quality of the halftone dots deteriorates or the reproducibility of the halftone dots deteriorates even when reproducing the minute halftone dots.

Example 4 (Preparation of silver halide emulsion D) 80 mol% of silver chloride, bromide
Aqueous silver nitrate solution to obtain a silver halide composition of 20 mol% silver
Solution and mixed aqueous solution of NaCl and KBr are controlled.
Mixed by double jet method to grow silver halide grains.
I let you. At this time, the mixture is 36 ° C, pAg 7.8, pH 3.0.
Under the conditions of K_ThreeRuCl₆1 mole of silver
8 × 10 per^-8Mole and K_TwoIrCl₆Per mole of silver
3 x 10^-7Mole was added. Then phenyl isocyanate
Desalted with modified gelatin treated with
Gelatin was added and redispersed. The resulting emulsion has an average grain size
Milk consisting of cubic particles with a coefficient of variation of 10% and 0.18 μm
It was a drug. The emulsion thus obtained was
Xy-6-methyl-1,3,3a7-tetrazaindene
1 x 10 per mole of silver ^-3Add moles and add potassium bromide
PH and 5.6 by adding sodium and citric acid, EAg123
Adjust to mv and add 2 × 10 chloroauric acid^-FiveAfter adding moles,
N, N, N'-trimethyl-N'heptafluoroseleno
2 x 10 urea^-6The highest sensitivity is obtained at a temperature of 60 ° C by adding a mole.
It was chemically aged until it appeared.

After completion of aging, 4-methyl-6-hydroxy-
1,3,3a, 7-Tetrazaindene was added in an amount of 3 × 10 ^-3 mol per mol of silver.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for He-Ne laser light source) S of the present invention
On one subbing layer of the PS support or the comparative PET support, a gelatin subbing layer of the following Formulation 13 was formed thereon so that the amount of gelatin was 1.0 g / m ^2, and silver halide of the Formulation 14 was prepared. Simultaneous multilayer coating was applied to the emulsion layer such that the silver amount was 3.5 g / m ² and the gelatin amount was 1.5 g / m ^2, and the coating solution of the following formulation 15 was 0.6 g / m ² . . On the opposite undercoat layer, a backing layer having the following formulation 16 was used so that the amount of gelatin was 2.0 g / m ^2, and a backing protective layer having the following formulation 17 was used at a gelatin amount of 1.0 g / m ^2. A sample was obtained by simultaneous multi-layer coating with the emulsion layer side so as to obtain m ² .

Formulation 13 (gelatin undercoat layer composition) Gelatin 1.0 g / m ² 1-phenyl-5-mercaptotetrazole 1 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (sodium-iso-amyl-n) -Decyl sulfosuccinate) 0.4 mg / m ² Formulation 14 (silver halide emulsion layer composition) Silver halide emulsion D Increase sensitizing dye d-1 3 mg / m ² so that the silver amount becomes 3.5 g / m ^2. Sensitizing dye d-2 3 mg / m ² Hydrazine derivative of general formula (5) shown in Table 4 10 mg / m ² Compound e 100 mg / m ² Latex polymer f 0.5 g / m ² Hardener g 5 mg / m ² S- 1 0.7mg / m ² 2- mercapto-6-hydroxy-purine 5 mg / m ² styrene - hydrophilic polymer (thickener) of maleic acid copolymer 15mg / m ² EDTA 30m / M ² formulation 15 (Emulsion protective layer composition) Gelatin 0.6 g / m ² S-1 12 mg / m ² Matting agent: average particle size 3.5μm monodisperse silica 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 Nucleation accelerator: Exemplified compound Na-21 20 mg / m ² Hardener j 30 mg / m ² Formulation 16 (backing layer composition) Gelatin 2.0 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 Sodium polystyrene sulfonate 20 mg / m ² compound i 100 mg / m ² formulation 17 (backing protective layer) gelatin 1.0 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 Hard Membrane agent g 20 mg / m ²

[0316]

Embedded image

In order to evaluate the reproducibility of minute halftone dots of the sample thus obtained, Select manufactured by Agfa Co.
3600 dpi / 300 lpi using Set5000
Set to output small dots (5% halftone dots), middle dots (50% halftone dots), and solid dots (100% halftone dots), expose while changing the light intensity, and develop with the following composition The solution and the fixing solution were used and processed with an automatic processor GR-27 (manufactured by Konica Corp.) under the following conditions. About the obtained developed sample X
Halftone% was measured with Rite 361T. The quality of the dots was also evaluated.

(Developer composition) Concentrated developer formulation A (amount per liter) Diethyltriamine pentaacetic acid / 5-sodium salt 9 g / l Sodium sulfite 0.45 mol / l Hydroquinone 18 g / 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 KOH used pH 10 An amount of 0.0 was added.

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

(Fixing solution composition) Concentrated fixing solution A (amount per liter) 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 working 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 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Washing at room temperature 20 seconds Drying 50 ° C. 30 seconds Total 100 seconds (Evaluation of dryness in automatic developing machine) Automatic The dryness of the sample discharged through the developing process of the developing machine was evaluated by feeling on a five-point scale. The highest rank was 5, and as the dryness deteriorated, the rank was lowered to 4, 3, 2, 1 and evaluated.

(Evaluation method of dot reproducibility of small dots) Small dots at the exposure amount giving a solid density of 5.0 (target dot% 5%)
The net% actually reproduced on the sample. The closer to 5%, the better.

(Evaluation Method of Halftone Dot Reproducibility) Midpoint at the exposure amount giving a solid density of 5.0 (target halftone% 50
%) The net% actually reproduced on the sample. The closer to 50%, the better.

(Evaluation method of dot quality) Solid density is 5.0
The midpoint (target halftone dot 50%) in the exposure amount that gives 10
The halftone dot quality (sharpness) was evaluated using a magnifying glass of 0 times. The highest rank was set to 5, and the rank was lowered to 4, 3, 2, and 1 according to the halftone dot quality and evaluated. Ranks 1 and 2 are levels that are not practically desirable.

Table 4 shows the evaluation results.

[0327]

[Table 4]

As is clear from Table 4, the use of the SPS support of the present invention in a silver halide photographic light-sensitive material for a printing plate-making scanner for a He-Ne laser light source improves the drying property and allows the hydrazine of the present invention to be used. By including the derivative, the deterioration of the halftone dot quality and the deterioration of the halftone dot reproducibility in the case of reproducing minute halftone dots are suppressed.

Example 5 (Preparation of silver halide emulsion E) Water-soluble iridium 2 × 1
EAg of 120 mV, p in the presence of 0 ^-6 mol / silver 1 mol
It was adjusted while controlling H to 3.0, desalted and washed with water by a conventional method to obtain silver chlorobromide grains containing 35 mol% of silver bromide. This particle was a cubic particle having an average particle size of 0.24 μm, and the distribution width was 11%. Chloroauric acid (5 mg) and sulfur flower (1.5 mg) were added to each mole of silver halide for chemical sensitization, and then sensitizing dye d- was used as a sensitizing dye.
300 mg was added per mol of silver halide, and 1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer per mol of silver halide.

(Preparation of silver halide photographic light-sensitive material for printing plate making scanner for Ar laser light source) On one undercoat layer of the SPS support of the present invention or the comparative PET support, a gelatin undercoat layer of the following Formulation 18 was prepared. The amount of gelatin is 0.6 g /
such that m ^2, amount of silver 3.5 g / m ² of silver halide emulsion layers of the formulation 19 thereon, gelatin amount 1.7 g / m ²
Further, a coating solution of the following formulation 20 was simultaneously multilayer coated so that the amount of gelatin would be 1.0 g / m ² . Further, on the undercoat layer on the opposite side, a backing layer having the following formulation 21 had a gelatin content of 2.2 g / m ^2, and a backing protective layer having the following formulation 22 having a gelatin content of 1.
A sample was obtained by simultaneous multi-layer coating on the emulsion layer side so as to obtain 0 g / m ² .

Formulation 18 (gelatin undercoat layer composition) Gelatin 0.6 g / m ² 1-phenyl-5-mercaptotetrazole 1 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (sodium-iso-amyl-n) -Decyl sulfosuccinate) 0.4 mg / m ² Formulation 19 (silver halide emulsion layer composition) Silver halide emulsion E To obtain a silver amount of 3.5 g / m ² Sensitizing dye d-4 3 mg / m ² Table The hydrazine derivative of the general formula (6) shown in 5 is 15 mg / m ² sodium n-dodecylbenzenesulfonate 0.6 g / m ² compound e 100 mg / m ² Styrene-maleic acid copolymer latex (average particle size 0.25 μm) ^{0.25g / m 2 S-1 0.7mg} / m 2 2- mercapto-6-hydroxy-purine 5 mg / m ² styrene - parent maleic acid copolymer Sex polymer ^{(thickener) 15mg / m 2 EDTA 30mg /} m 2 formulation 20 (Emulsion protective layer composition) Gelatin ^{1.0g / m 2 S-1 12mg} / m 2 Matting agent: average particle size 3.5μm monodisperse Silica 25 mg / m ² 1-Phenyl-3-pyrazolidone 2.5 mg / m ² 5-nitroindazole 5 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 Nucleation accelerator: Exemplified compound Na-21 17 mg / m ² Hardener: Formalin 20 mg / m ² Formulation 21 (Backing layer composition) Gelatin 2.2 g / m ² S -1 5 mg / m ² latex polymer f 0.3 g / m ² colloidal silica (average particle size 0.05μm) 70mg / m ² sodium polystyrenesulfonate 0 mg / m ² sodium dodecylbenzenesulfonate 10 mg / m ² Hardener: glyoxal 10 mg / m ² formulation 22 (backing protective layer composition) Gelatin 1.0 g / m ² Matting agent: average particle size 3.0~5.0μm Polymethylmethacrylate 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: Glyoxal 25 mg / m ^{2 In} order to evaluate reproducibility of minute halftone dots of the sample thus obtained, SG-75 manufactured by Dainippon Screen Co., Ltd.
7, with 700 lines per inch, small dots (5% halftone dots), medium dots (50% halftone dots), solid dots (100% halftone dots)
Was set, the exposure was performed while changing the light amount, and the same processing and evaluation as in Example 4 were performed.

The evaluation results are shown in Table 5.

[0333]

[Table 5]

As is clear from Table 5, the use of the SPS support of the present invention in a silver halide photographic light-sensitive material for a printing plate making scanner for an Ar laser light source improves the drying property and improves the hydrazine derivative of the present invention. By including it, the deterioration of halftone dot quality and the deterioration of halftone dot reproducibility when reproducing minute halftone dots are suppressed.

Example 6 (Preparation of Silver Halide Emulsion F) Using a simultaneous mixing method, silver chloride 70 mol% and the rest silver bromide having an average thickness of 0.05.
Silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. When the core particles were mixed, K ₃ RhBr ₆ was added in an amount of 8 × 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 had a core / shell type monodisperse (variation coefficient of 10%) silver chloroiodobromide (silver chloride 90) with an average thickness of 0.10 μm and an average diameter of 0.29 μm.
Mol%, silver iodobromide 0.2 mol% and the rest silver bromide). Then, JP-A-2-280
Modified gelatin described in JP-A-139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, Japanese Patent Laid-Open No. 2-53967).
-280139, Exemplified compound G-8 on page 287 (3))
It was desalted using. EAg after desalting is 190 mv at 50 ° C
Met.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were added. PH of 5.6 and EAg of 123 mv, chloroauric acid was added in an amount of 2 × 10 ^-5 mol, and then inorganic sulfur was added in an amount of 3 × 10 ^-6 mol, and chemical aging was performed at a temperature of 60 ° C. until maximum sensitivity was obtained. . After aging, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and gelatin were added.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for He-Ne laser light source) S of the present invention
On one subbing layer of the PS support or the comparative PET support, a gelatin subbing layer of the following formulation 23 was further formulated so that the amount of gelatin would be 0.5 g / m ^2.
Of the silver halide emulsion layer of 3.3 g / m ² and the gelatin amount of 1.5 g / m ^2, and a coating solution of the following formulation 25 as a protective layer on the upper layer of which the gelatin amount was 0.8 g.
Simultaneous multi-layer coating was applied so as to obtain g / m ² . A backing layer of the following formulation 26 is provided on the opposite undercoat layer so that the amount of gelatin is 0.6 g / m ^2, and a hydrophobic polymer layer of the following formulation 27 is further provided thereon, and the following formulation is further provided thereon. A sample was obtained by simultaneous multilayer coating of 28 backing protective layers so that the amount of gelatin was 0.4 g / m ² .

Formulation 23 (gelatin undercoat layer composition) Gelatin 0.5 g / m ² Dye (ball-mill dispersed into powder having a particle size of 0.1 μm): Dye Exemplified Compound 7-25 20 mg / m ² S -1 (Sodium-isoamyl-n-decylsulfosuccinate) 0.4 mg / m ² Styrene-maleic acid copolymer hydrophilic polymer (thickener) 10 mg / m ² Formulation 24 (silver halide emulsion layer composition) Silver halide emulsion A Sensitizing dye d-1 1.0 mg / m ² so that the amount of silver is 3.3 mg / m ² Hydrazine derivative shown in Table 6 20 mg / m ² Nucleation accelerator: Exemplified compound Na-21 50 mg / M ² compound e 100 mg / m ² latex polymer f 1.0 g / m ² hardener g 30 mg / m ² S-1 (sodium-isoamyl-n-decylsulfosuccinate) 0.7 mg / m ² 2 - mercapto-6-hydroxy purine ^{5mg / m 2 EDTA 30mg / m} 2 formulation 25 (Emulsion protective layer composition) Gelatin 0.8 g / m ² Dye (obtained by the powder of a ball mill dispersion to the particle size 0.1 [mu] m): Dye Exemplified Compound 7-26 20 mg / m ² S-1 12 mg / m ² Matting agent: Monodispersed silica with an average particle size of 3.5 μm 25 mg / m ² Hardener g 30 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ^2, 1,3-vinylsulfonyl-2-propanol 50 mg / m ² Formulation 26 (backing layer composition) Gelatin 0.6 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 sodium polystyrene sulfonate 20 mg / m ² compound i 100 mg / M ² Dye (ball mill-dispersed powder having a particle size of 0.1 μm): Dye Exemplified Compound 7-25 20 mg / m ² Formulation 27 (hydrophobic polymer layer composition) Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² hardener g 6 mg / m ² formulation 28 (backing protective layer) gelatin 0.4 g / m ² matting agent: monodisperse polymethylmethacrylate 50 mg / m ² sodium having an average particle size of 5 μm -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 g 15 mg / M ² polysiloxane 0.7 g / m ^{2 A} 16 μ random pattern was applied to the obtained sample with SG-747RU manufactured by Dainippon Screen Co., Ltd. in order to evaluate fine dot quality. Exposure with a halftone dot (FM screen), and using the developer and fixer of the following composition, the automatic processor S
RX-1001 (manufactured by Konica Corp.) was modified to change the line speed to obtain the total processing time (Dry to
Dry) was treated in 40 seconds. The halftone quality of the developed sample thus obtained was evaluated. While replenishing 150 ml of developer and fixer per 1 m ^{2 of} film, 1
100 sheets of large size film with 70% blackened area per day are processed and run for 8 days for a total of 800
One sheet was processed. The performance before running and after 800 sheets of running were compared.

(Developer composition) Amount per 1 liter of used solution Diethyltriamine pentaacetic acid / 5 sodium salt 3 g / liter Sodium sulfite 50 g / liter Potassium carbonate 40 g / liter Hydroquinone 21 g / liter 4-Methyl-4-hydroxymethyl- 1-phenyl-3-hydrazolidone (dimesone S) 0.9 g / liter potassium bromide 5 g / liter benzotriazole 0.2 g / liter 5-methyl-benzotriazole 0.13 g / liter boric acid 8 g / liter diethylene glycol 40 g / liter 2- Mercapto-6-hydroxypurine 0.06 g / liter Water and potassium hydroxide were added to 1 liter / pH 10.2
To

(Fixing liquid composition) Amount used per liter Ammonium thiosulfate (70% aqueous solution) 200 ml / liter Sodium sulfite 22 g / liter Boric acid 9.8 g / liter Sodium acetate trihydrate 34 g / liter Acetic acid (90% Aqueous solution) 14.5 g / liter Tartaric acid 3.0 g / liter Aluminum sulfate (27% aqueous solution) 25 ml / liter The pH of the used liquid was 4.9.

(Evaluation of Drying Property in Automatic Developing Machine) The dryness of the sample discharged through the drying process of the automatic developing machine was evaluated by feeling on a 5-point scale. The highest rank was 5, and as the dryness deteriorated, the rank was lowered to 4, 3, 2, 1 and evaluated.

(Evaluation method of halftone dot quality) Midpoint (target 50
%) Was evaluated with a magnifying glass 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 6 shows the evaluation results.

[0344]

[Table 6]

As is apparent from Table 6, when the SPS support of the present invention was used in a silver halide photographic light-sensitive material for a printing plate-making scanner for a He-Ne laser light source and the hydrazine derivative of the present invention was incorporated, an automatic developing machine was used. Even if the developer replenishment amount and the fixer replenishment amount are reduced by replenishing and a large amount of processing is performed, the dryness of the processed light-sensitive material is not deteriorated and minute halftone dots of 25 μm or less are reproduced. In this case, it can be seen that there are few problems that the quality of halftone dots deteriorates.

Example 7 (Preparation of Silver Halide Emulsion G) At the time of mixing using the simultaneous mixing method, 8 × 10 ⁻⁵ mol of rhodium hexachloride complex was added per 1 mol of silver, and after desalting by a conventional method, the average grain size was changed. An emulsion of monodisperse (variation coefficient: 10%) cubic chloroiodobromide (99 mol% silver chloride, the rest consisting of silver bromide) cubic grains having a diameter of 0.10 μm was obtained.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene, potassium bromide and citric acid were added to the resulting emulsion to add inorganic sulfur to 3 mol per silver mol.
Chemical aging was performed at a temperature of 60 ° C. until the maximum sensitivity was obtained by adding × 10 ^-6 mol. After completion of the ripening, 3 × 10 ^-4 mol of 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene and 1-phenyl-5-mercaptotetrazole and gelatin were added.

(Preparation of silver halide photographic light-sensitive material for bright room reversal) On one undercoat layer of the SPS support of the present invention or the comparative PET support, a gelatin undercoat layer of the following Formulation 29 was used in the amount of gelatin. so that 0.5 g / m ^2, protects thereon formulation 30 silver halide emulsion of the silver amount 2.8 g / m ^2, so that the amount of gelatin is 1.0 g / m ^2, further on the upper layer thereof As a layer, a coating solution having the following formulation 31 was simultaneously multilayer-coated so that the amount of gelatin was 0.5 g / m ² . On the opposite undercoat layer, a backing layer of the following formulation 32 was prepared so that the amount of gelatin was 0.4 g / m ^2, and a hydrophobic polymer layer of the following formulation 33 was further formed on the backing layer of the following formulation 32. Three
A sample was obtained by simultaneous multilayer coating of the backing protective layer of No. 4 so that the amount of gelatin was 0.4 g / m ² .

Formulation 29 (gelatin undercoat layer composition) Gelatin 0.5 g / m ² Hydrophilic polymer of styrene-maleic acid copolymer (thickener) 10 mg / m ² S-1 (sodium-iso-amyl-n) -Decylsulfosuccinate) 0.4 mg / m ² Formulation 30 (silver halide emulsion layer composition) Silver halide emulsion G Hydrazine derivative shown in Table 7 so that the silver amount is 2.8 mg / m ² 30 mg / m ² Nucleation accelerator: Exemplified compound Na-21 30 mg / m ² sodium dodecylbenzenesulfonate 10 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound m 6 mg / m ² latex polymer f 1.0 g / m ² hardener j 40 mg / m ² S-1 0.7 mg / m ² Styrene-maleic acid copolymer hydrophilic polymer (thickener) 20 mg / m ² Formulation 31 (emulsion protective layer composition) Gelatin 0.5 g / m ² S-1 12 mg / m ² Matting agent: Monodisperse silica having an average particle size of 3 μm 15 mg / m ² Matting agent: Monodisperse silica having an average particle size of 8 μm 20 mg / m ² 1,3-vinylsulfonyl 2-Propanol 50 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 20 mg / m ² Hardener j 50 mg / m ² Formulation 32 (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 hydrophilic polymer of styrene-maleic acid copolymer (thickener) 20 mg / m ² compound i 100 mg / m ² formulation 33 (hydrophobic polymer layer composition) latex (styrene: butadiene: acrylic acid = 30: 65: 5) 1.0g / m 2 hardener 10 mg / m ² formulation 34 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: monodispersed polymethylmethacrylate 50 mg / m ² Sodium an average particle diameter of 5 [mu] m - di - (2-ethylhexyl) sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Dye k 40 mg / m ² Hardener j 40 mg / m ² Obtained in order to evaluate fine dot quality. The processed sample is the processed sample No. Bright room printer P-627GM (manufactured by Dainippon Screen) with 66 as the manuscript
After contact exposure (between emulsion surfaces) was performed with an automatic developing machine GR26SR or GR27 (both manufactured by Konica Corporation) under the following conditions using a developing solution and a fixing solution having the following compositions.

Processing conditions (a) GR27 (step) (temperature) (time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Washing at room temperature 20 seconds Drying 50 ° C. 30 seconds Total 100 seconds Processing conditions (b) GR26SR (step) ( Temperature) (Time) Development 38 ° C. 12 seconds Fixing 38 ° C. 10 seconds Water washing 10 seconds Normal temperature 10 seconds Drying 50 ° C. 13 seconds Total 45 seconds (Developer formulation) Diethylenetriamine pentaacetic acid 3.6 g / liter Sodium sulfite 14.7 g / liter Potassium sulfite 38 0.7 g / liter Potassium bromide 2.5 g / liter Potassium carbonate 40 g / liter 2-mercapto-hypoxanthine 0.06 g / liter Diethylene glycol 50 g / liter 5-methyl-benzotriazole 0.5 g / liter Hydroquinone 14 g / liter 4-methyl -4-hydroxy Methyl-1-phenyl-3-Hidorazoridon (Dimezone S) 1.4 g / l 1-phenyl-5-mercaptotetrazole 0.02 g / l Water and potassium along with one liter of hydroxide /pH10.4
To

(Fixing Solution Formulation) Ammonium thiosulfate (72.5% W / V aqueous solution) 262 g / liter water 79 g / liter sodium sulfite (anhydrous) 22 g / liter boric acid 9.8 g / liter sodium acetate trihydrate 38.5 g / Liter Tartaric acid 7.3 g / liter Sodium hydroxide 0.25 g / liter Aluminum sulfate (aqueous solution having an Al ₂ O ₃ conversion content of 8.1% W / V) 32.9 g / liter Glacial acetic acid and sulfuric acid are added to pH 4. It was adjusted to 85 and water was added to make 1 L.

The sample thus obtained was evaluated in the same manner as in Example 3.

The results are shown in Table 7.

[0354]

[Table 7]

As is apparent from Table 7, when the SPS support of the present invention was used in the silver halide photographic light-sensitive material for printing plate-making light room reversal and the hydrazine derivative of the present invention was contained, the entire processing in the automatic processor was carried out. It can be seen that even if the time is 60 seconds or less, there are few problems that the dimension is stable and that the dot quality is deteriorated and the dot reproducibility is deteriorated even when reproducing minute dots.

[0356]

INDUSTRIAL APPLICABILITY According to the present invention, fine halftone dots of 25 μm or less are reproduced in a silver halide photographic light-sensitive material for printing plate making using a syndiotactic polystyrene (SPS) support excellent in drying property and dimensional stability. In this case, it was possible to provide a silver halide photographic light-sensitive material and a processing method thereof in which the quality of halftone dots and the reproducibility of halftone dots are less likely to occur.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication G03C 5/395 G03C 5/395

Claims (7)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one surface of a support, wherein at least one photographic constituent layer on the silver halide emulsion layer side has the following general formula: A silver halide photographic light-sensitive material comprising the hydrazine derivative represented by (1), and the support containing syndiotactic polystyrene. Embedded image [In the formula, R ₁ represents an aliphatic group or an aromatic group, and as a part of the substituent, — (CH ₂ CH ₂ O) _n —, — (C
_{H 2 CH (CH 3) O} ) n -, - (CH 2 CH (OH) CH
₂ O) _n- (where n is an integer of 1 or more) or a quaternary ammonium cation group.
R ₁ may also contain a silver halide adsorbing group. G ₁ is -CO -, - COCO -, - CS -, - C (= NR 2)
-, - SO -, - SO 2 - or _{-P (= O) (G 2} R 2)
Represents a group. G ₂ represents a simple bond, —O—, —S— or —N (R ₂ ) — group, R ₂ is a hydrogen atom or an aliphatic group,
Represents an aromatic group. When multiple R _2's are present in the molecule,
They may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl group or an arylsulfonyl group. ] 2. The silver halide photographic light-sensitive material according to claim 1, wherein the hydrazine derivative is represented by the following general formula (2). Embedded image [In the formula, R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, and these may be substituted. G is -CO-,-
COCO -, - SO -, - SO 2 -, thiocarbonyl group, an iminomethylene group or ^{-P (O) (R 4)} - represents a group. R ² represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group. R ⁴
Represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group. ] 3. The silver halide photographic light-sensitive material according to claim 1, wherein the hydrazine derivative is represented by the following general formula (3) or (4). Embedded image [In the formula, X ¹ represents an alkyl group, an alkoxy group, a substituted amino group or an alkylthio group. Y ¹ is an alkoxy group,
It represents an aryloxy group, a substituted amino group, an alkylthio group or an arylthio group. R ¹ represents an alkylene group. [Formula 4] [In formula, X < ² > is synonymous with X < ¹ > in General formula (3).
Y ² represents an electron withdrawing group, R ² is a hydrogen atom, an alkyl group,
It represents an aryl group, an alkoxy group, an aryloxy group, a substituted amino group, an alkylthio group or an arylthio group, and may be further substituted. n represents an integer from 1 to 5,
A plurality of Y ² and R ² present in the molecule may be the same or different. ] 4. The silver halide photographic light-sensitive material according to claim 1, wherein the hydrazine derivative is represented by the following general formula (5). Embedded image [In the formula, Ar represents a substituted phenyl group or a substituted or unsubstituted aryl group, and G represents -CO-, -SO-, -SO.
_{2 -, - PO 2 -,} - PO 3 - in or C = NR ^2, X ⁺ represents a group comprising a cationic group. R, R ′ and R ² may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkylsulfinyl group having 1 to 6 carbon atoms and A ⁻ represents an anionic group. ] 5. The silver halide photographic light-sensitive material according to claim 1, wherein the hydrazine derivative is represented by the following general formula (6). [Chemical 6] [In the formula, R ₁ is an aromatic group which may be substituted.
One of A ₁ and A ₂ is a hydrogen atom, the other is a hydrogen atom,
It represents an arylsulfonyl group or a trifluoroacetyl group. G is -CO -, - COCO -, - SO -, - SO 2
-Or an N-substituted or unsubstituted imino group. X
At a pH of 9.5 to 12.5, in the presence of an oxidized form of a developing agent, a cyclization reaction in which a -G-X moiety is cleaved from a residual molecule to form a cyclic structure containing an atom of the -G-X moiety. Is the part that causes ] 6. The method of claim Replenisher amount automatic developing machine and the fixing replenisher amount is replenished to the developer and fixer, respectively ^{50ml / m 2 ~300ml / m 2} , characterized in that it is processed 1 6. The method for processing a silver halide photographic light-sensitive material according to any one of items 1 to 5. 7. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the total processing time is 15 to 60 seconds in an automatic processor.