JPH11119383A - Production of solid treating agent for silver halide photography, and treating method of silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make reducible the residual atm. of a treating agent in a packaging material when it is opened, by production a raw material having a specified bulk density by a specified method. SOLUTION: A raw material having a bulk density ρ satisfying ρ<=1.0 g/ml is produced by a method for mixing it with another raw material having a larger bulk density to increase the bulk density ρ after being mixed to be larger than 1.0 g/ml. Or, the raw material in a single state or after being mixed with the other raw material is produced by a method for forming particles having 0.1 to 10 mm particle size. As for the forming method, for example, a rolling granulation method, an extrusion granulation method, a compressive granulation method, an agitation granulation method, a spray-dry method and a dissolution aggregation method or the like can be used and especially, the compressive granulation method is preferably used. The average particle size of the molding is more preferably 0.5 to 7 mm. The raw material may be preliminarily performed by a pretreatment such as pulverization or grain size regulation. Even when as for the bulk density of the raw material mixture, one or more kinds of the single raw material to be mixed has >=1.0 g/ml bulk density and in the case that the bulk density after being mixed is <=1.0 g/ml, the mixture is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid processing agent for silver halide photography, and more particularly, to a solid processing agent in which a raw material (material) is less attached to a packaging material (hereinafter, also referred to as a packaging material).

[0002]

2. Description of the Related Art Conventionally, a liquid agent kit has often been used as a developing agent for a silver halide photographic light-sensitive material.
Was slight. However, in recent years, since the treatment agent has been converted into a solid treatment agent, the so-called “remaining packaging material” that remains on the packaging material when the treatment agent is opened is an obstacle to obtaining stable processing performance. Further, the residual drug is not preferable from the viewpoint of pollution.

In recent years, there have been many reports on solid processing agents whose filling efficiency has been increased by solidifying the processing agents.
However, there is no report disclosing a technique corresponding to the above-mentioned remaining packaging material, and improvement thereof has been strongly desired.

[0004]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a solid processing agent for a silver halide photographic light-sensitive material capable of reducing the residual amount of the processing agent in a packaging material at the time of opening. An object of the present invention is to provide a method for producing a solid processing agent. A second object of the present invention is to provide a method for processing a silver halide photographic material using the solid processing agent.

[0005]

The object of the present invention has been attained by the following constitutions.

In a method for producing a solid processing agent for silver halide photography, a raw material having a bulk density ρ of ρ ≦ 1.0 g / ml is produced by the following method (1) or (2). A method for producing a solid processing agent for silver halide photography.

(1) By mixing with other raw materials having a large bulk density, the bulk density ρ after mixing is set to 1.0 g / m 2.
greater than l.

(2) alone or after mixing with other raw materials,
It is formed to a particle size of 0.1 to 10 mm.

[0009] In a solid processing agent for silver halide photography, which has been subjected to lamination filling of at least two or more layers, a particle size of 0.1
Filling the top layer with a molded product of 10 mm to 10 mm, and describing the vertical direction on the packaging material of the packaged solid processing agent or the material for packaging a plurality of them at the time of transportation, storage, and opening the packaging material The method for producing a solid processing agent for silver halide photography according to the above item, wherein the regulation of the vertical direction is specified.

[0010] In a silver halide photographic solid processing agent having at least two or more layers filled therein, a raw material having a minimum bulk density ρ or a mixture with the raw material is filled in the uppermost layer, and the packaged solid processing agent is used. Silver halide as described in the paragraph, in which the vertical direction is described in the packaging material of the agent or the material for packaging a plurality of them in a lump and the vertical direction is specified when transporting, storing, and opening the packaging material. A method for producing a photographic solid processing agent.

A process for producing a solid processing agent for silver halide photography, wherein the packaging material is in the form of a standing pouch.

Any one of the above-mentioned items, characterized by containing reductones as a silver halide photographic developer.
13. The method for producing a solid processing agent for silver halide photography according to the above item.

A method for processing a silver halide photographic light-sensitive material, comprising processing a silver halide photographic light-sensitive material containing a hydrazine compound with the solid processing agent according to any one of the above.

Hereinafter, the present invention will be described in detail.

The solid processing agent of the present invention has a bulk density ρ ≦ 1.
0 g / ml. The bulk density referred to in the present invention refers to the density of the raw material for processing or a mixture of the raw material and the space including the filling space of powder, granules, fibrous bodies, and the like. A densitometer was used.

The method for producing the photographic solid processing agent of the present invention comprises:
(1) Raw materials having a bulk density ρ of 1.0 g / ml or less
A manufacturing method in which the bulk density after mixing is adjusted to 1.0 g / ml or more by mixing with other raw materials having a large bulk density, or (2) the raw material alone or after mixing with other raw materials,
This is a production method in which an average particle diameter is formed to be 0.1 to 10 mm.

As a molding method, a tumbling granulation method, an extrusion granulation method, a compression granulation method, a stirring granulation method, a spray drying method, a dissolution solidification method and the like can be used, and the compression granulation method is particularly preferable. .

The average particle size of the molded article of the present invention is 0.1 to 1
0 mm, more preferably 0.5 to 7 mm.
Here, the average particle size of the molded body is used in terms of the diameter of a sphere having the same volume when the object is not spherical.

Regarding the particle size and shape of the molded article desired in the present invention, the molded article is required to have the following properties:
Alternatively, when considering the solubility at the time of liquid preparation and remaining in the waste packaging material, the average particle size is 0.1 to 10 mm, and the shape is cylindrical, spherical, cubic, rectangular, and the like. Preferably, a spherical or cylindrical shaped body is used.

In the present invention, the raw material may be subjected to pretreatment such as pulverization or sizing in advance, and the bulk density in that case uses a value measured after the pretreatment. In addition, the bulk density of the mixture of raw materials is such that the bulk density after mixing is 1.0 g / ml or less even if the bulk density of one or more of the raw materials to be mixed is 1.0 g / ml or more. Need to be molded.

In the present invention, as a method for mixing the raw materials, a commercially available mixer can be used, for example, a cross rotary mixer, a V mixer, or the like. In the mixing, from the viewpoint of preventing the segregation of the raw materials in the molded article, it is preferable that the raw materials are uniformly mixed so that the degree of segregation is within ± 5%.

In the present invention, even if the bulk density of the raw material alone is 1.0 g / ml or less, the bulk density after mixing can be 1.0 g / ml by mixing with another material.
If larger, there is no need to mold. The same applies when the bulk density becomes 1.0 g / ml or more due to pretreatment such as pulverization or sizing.

Next, the lamination filling in the present invention will be described. In the present invention, the term “stacked packing” refers to stacking raw materials having different components, a mixture of raw materials, and a molded body in layers.

As a laminating method, each layer is filled in order when filling the packaging material, and finally, a raw material having the smallest apparent bulk density, a mixture of raw materials, or a molded body may be filled. In the present invention, not all the layers to be stacked and filled need to reach the horizontal cross-sectional area of the packaging material.

The effect of the present invention can be achieved if the top layer reaches the cross-sectional area of the packaging material. That is, in filling as a layer, the fact that the layer does not reach the cross-sectional area of the package other than the uppermost layer due to the small absolute amount of the layer does not impair the effects of the present invention.

In the present invention, in order to maintain the effect, that is, in order not to break the layer structure of the lamination and filling, the display for regulating the up and down direction of the packaging material at the time of transportation, storage or opening of the packaging material is displayed on the packaging body. The package is described in an outer box or the like in which a plurality of the packages are collectively packaged.

As a display method for regulating the vertical direction, a generally used method may be used.
Or an arrow or the like.

In the present invention, the packaging material is in the form of a standing pouch. Here, the standing pouch form is a packaging bag having the form shown in FIGS. 2 and 3 of the present invention.

When the solid processing agent of the present invention is transported and stored, vibrations applied to the processing agent, for example, vibrations in truck transportation, unloading with a forklift, or vibrations applied when a person carries the solid processing agent, etc. It was confirmed that the laminated structure of the present invention did not collapse (see FIGS. 4 and 5).

The solid processing composition according to the present invention can be used as a processing and development processing composition for black-and-white silver halide photographic materials.

The silver halide photographic light-sensitive material to which the solid processing agent of the present invention can be applied includes a light-sensitive material for printing. The silver halide photographic material contains a hydrazine compound as a high contrast agent.

As the hydrazine compound preferably used in the present invention, a compound represented by the following general formula [H] is used.

[0033]

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The general formula [H] will be described.

In the formula, A ₀ represents an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, particularly a straight chain having 1 to 20 carbon atoms,
A branched or cyclic alkyl group such as methyl, ethyl,
t-butyl, octyl, cyclohexyl, benzyl group and the like, which are further substituted with a suitable substituent (for example, aryl, alkoxy, aryloxy, alkylthio, arylthio, sulfoxy, sulfonamide, sulfamoyl, acylamino, ureido group, etc.). May be done.

The aromatic group represented by A ₀ in the general formula [H] is preferably a monocyclic or condensed-ring aryl group, such as a benzene ring or a naphthalene ring.

The heterocyclic group represented by A ₀ in the general formula [H] is preferably a monocyclic or condensed heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen. , An imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, a furan ring and the like.

Particularly preferred as A ₀ are an aryl group and a heterocyclic group. The aromatic group and heterocyclic group represented by A ₀ preferably have a substituent. Preferred substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups, Alkylthio group, arylthio group, sulfothio group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide Groups, a carboxy group, a phosphoric acid amide group and the like, and these groups may be further substituted.

Among these substituents, using a developer having a pH of 10.5 or less, the total processing time (Dry to Dry)
In the case of the image forming method of the present invention, wherein the pKa has a substituent having an acidic group having a pKa of 7 to 11, specifically, a sulfonamide group, a hydroxy group, a mercapto group And particularly preferably a sulfonamide group.

A ₀ preferably contains at least one diffusion-resistant group or silver halide adsorption promoting group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group or an alkenyl group which is relatively inert to photographic properties having 8 or more carbon atoms is preferable. , Alkynyl group, alkoxy group,
Examples include a phenyl group, a phenoxy group, and an alkylphenoxy group.

The silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

B ₀ represents a blocking group, preferably -G ₀ -D ₀ G ₀ represents a -CO- group, -COCO- group, -CS- group, -C
(= NG ₁ D ₁ ) —, —SO—, —SO ₂ —, or —P (O) (G ₁ D ₁ ) —. G ₁ represents a simple bond, —O— group, —S— group or —N (D ₁ ) — group. D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they may be the same or different.

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

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Ethoxalyl).

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

[0046]

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[0047]

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[0048]

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Specific examples of other preferred hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The hydrazine derivative preferably used in the present invention can be synthesized by a known method, for example, by the methods described in US Pat. No. 5,229,248, columns 59 to 80. .

The hydrazine derivative preferably used in the present invention can be used in any of the photographic constituent layers on the side of the silver halide emulsion layer. Preferably, the hydrazine derivative is a silver halide emulsion layer and / or a hydrophilic layer adjacent thereto. It is used for at least two or more of the sexual colloid layers.

Further, the amount of addition depends on the particle size of the silver halide grains,
Although the optimum amount varies depending on the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., it is generally preferably in the range of 10 ^-6 to 10 ^-1 mol, particularly preferably 10 ^-5 to 1 mol per mol of silver halide.
A range of 10 ^-2 mol is preferred. The amount of the hydrazine derivative contained in the photographic component layer closest to the support among the hydrazine derivative-containing photographic component layers is 0% of the total amount of the hydrazine derivative contained in the photographic component layer farther from the support. 0.2 to 0.8 times molar equivalent. Preferably, it is 0.4 to 0.6 times molar equivalent.

The hydrazine derivatives preferably used in the present invention may be used alone or in combination of two or more.

In order to effectively promote hardening by the hydrazine derivative, it is preferable to use an amine compound represented by the following general formula [Na] or [Nb].

[0055]

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In the general formula [Na], R ₁ , R ₂ , R ₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, or a substituted aryl group. R ₁ , R ₂ and R ₃ 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 silver halide adsorptive groups include heterocyclic group-containing compounds, mercapto groups, thioether groups, thione groups and thiourea groups. General formula [Na]
Particularly preferred are compounds having at least one thioether group as a silver halide adsorptive group in the molecule.

Hereinafter, specific examples of these amine compounds [Na] will be described.

[0059]

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[0060]

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[0061]

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[0062]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₄ is a hydrogen atom,
Represents an alkyl group, an alkynyl group, or an aryl group;
And R ₄ 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. Specific compounds of the general formula [Nb] include the following.

[0064]

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[0065]

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Specific examples of other preferred amine 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".

The above amine compound preferably used in the present invention may be any of the following photographic constituent layers on the silver halide emulsion layer side:
It may be used for any layer and can be used in the same manner as the hydrazine derivative described above. Also, two or more kinds may be used in combination.

The optimum amount to be added varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 per mol of silver halide.
The range is preferably 10 to 10 ^-1 mol, particularly preferably 10 ^-5 to 10 ^-2 mol.

In the silver halide photographic light-sensitive material of the present invention, the silver halide emulsion contains pure silver chloride or
It is preferably silver chlorobromide or silver chloroiodobromide having a silver chloride content of 60 mol% or more.

The average grain size of the silver halide is preferably 0.7 μm or less, particularly preferably 0.5 to 0.1 μm. The shape of the silver halide grains is not particularly limited, and may be any of a tabular shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedral shape and the like. Further, it is preferable that the particle size distribution is narrow, and in particular, the total number of particles is 9% within a particle size range of ± 40% of the average particle size.
So-called monodisperse emulsions containing 0%, preferably 95% are preferred.

The method of reacting the soluble silver salt and the soluble halogen salt in the emulsion production method may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. 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 emulsion is formed in at least one of the steps of forming or growing grains, and includes cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, ruthenium salt, osnium salt, iron salt. , Copper salts, platinum salts, palladium salts and the like are preferably added. As a ligand of these complex salts, a halogen atom, a nitrosyl group, a cyano group, an aquo group, an alkyl group, a pseudohalogen group, an alkoxy group, an ammonium group, and any combination thereof can be used.

The surface of the silver halide grains can be controlled in halogen composition by using water-soluble halides or silver halide fine grains. This technique is known in the art as conversion and is widely known.

The silver halide grains may be uniform from the inside to the surface, or may be composed of a plurality of layers having different halogen compositions, dopant species and amounts, distribution of lattice defects, and the like.

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 photographic light-sensitive material of the present invention can be prepared by using generally known sulfur sensitization, selenium or tellurium sensitization,
Chemical sensitization methods such as reduction sensitization and noble metal sensitization may be appropriately selected and used together. Further, these chemical sensitizations may not be performed.

The silver halide photographic material of the present invention can be spectrally sensitized to a desired wavelength by a sensitizing dye. Sensitizing dyes that can be used include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl dye, hemioxonol dye, and the like. Any of nuclei generally used as basic heterocyclic nuclei in cyanine dyes can be applied to these dyes. That is, a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, such as a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, and an nucleus of these, A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, that is, indolenine nucleus, benzindolenine nucleus,
Indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine or the complex merocyanine includes a pyrazolin-5-one nucleus, a thiohydantoin nucleus and a 2-thiooxazolidine-nucleus as nuclei having a ketomethylene structure.
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic ring such as a rhodanine nucleus and a thiobarbituric acid nucleus can be applied. Specifically, research and
Disclosure (RD) 17643 (1978/1
February issue) page 2-3, U.S. Pat. No. 4,425,425,
No. 4,425,426 can be used. The sensitizing dye is disclosed in U.S. Pat.
The dissolution may be performed by using ultrasonic vibration described in No. 34.

The silver halide photographic light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. it can. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole)
Mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3
a, 7-tetrazaindenes), pentazaindenes and the like; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers, such as benzenesulfonamide, potassium bromide and the like, can be added. Particularly preferably, N, O, S, Se
Or a substituted or unsubstituted heterocyclic or fused heterocyclic ring, or a water-soluble halide.

The photographic emulsion layer and the non-photosensitive hydrophilic colloid may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'- Methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.) isoxazole , Dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, isocyanates, carboxyl group-activated hardeners and the like can be used alone or in combination.

The emulsion layer and / or the non-photosensitive hydrophilic colloid layer may contain various known surfactants for various purposes such as coating aids, antistatic, slipperiness improvement, emulsification dispersion, adhesion prevention and photographic property improvement. An agent may be used.

The photosensitive material used in the present invention contains various other additives. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, colloidal silica, and the like can be used.

These additives and the above-mentioned additives are specifically described in (RD) No. 17643 (supra), 22 to 3
One described on page 1, etc. can be used.

In the light-sensitive material of the present invention, the photographic constituent layer is coated on one or both sides of a flexible support usually used for the light-sensitive material. Useful as flexible supports are films of synthetic polymers of cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polyethylene terephthalate (which may contain colored content), or polyethylene or Paper supports and the like coated with a polymer such as polyethylene terephthalate. These supports may have a magnetic recording layer, an antistatic layer, and a release layer.

When the processing agent of the present invention is applied to a silver halide photographic light-sensitive material for plate-making printing, it is preferable to include the following compounds in the constituent layers of the silver halide photographic light-sensitive material.

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

The developing agents which can be used in the solid processing agent of the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethyl Hydroquinone), 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 (eg, o-
Aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc., pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (for example, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-
Aminopyrazoline, 1- (p-aminophenyl) -3-
Aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.) and transition metal complexes (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, etc.) Complex salts, which may be in any form having a reducing power to be used as a developer, for example, Ti ³⁺ , V
^In the form of complex salts such as ²⁺ , Cr ²⁺ and Fe ²⁺ , the ligands are aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof, and hexametapolyline. Acids, phosphoric acids such as tetrapolyphosphoric acid, and salts thereof. And the like can be used alone or in combination, but 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 an aminophenol and ascorbic acid, a combination of a 3-pyrazolidone and a transition metal complex, or a combination of an aminophenol and a transition metal complex. Further, the developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

For the solid processing agent of the present invention, a developer substantially free of hydroquinones (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, hydroquinone monosulfonate) can be used as a developing agent. . The term "substantially not contained" means an amount of less than 0.01 mol per liter of the developer. When substantially no hydroquinones are contained, reductones represented by the following general formula (I) are contained.

[0090]

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In the compound represented by the general formula (I),
A compound represented by the following formula (Ia) in which R ¹¹ and R ¹² are bonded to each other to form a ring is preferred. X ¹¹ is -CO
In the — and —CS— groups, k represents 0 to 1.

[0092]

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In the formula, R ¹³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group , An amide group or a sulfonamide group, Y ¹¹ represents O or S, and Y ¹² represents O, S or NR ¹⁴ . R ¹⁴ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

The alkyl group in the formula (I) or (Ia) is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group, and these groups may have a substituent. Preferred examples of the substitutable group include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (I) or (Ia) are shown below, but the present invention is not limited thereto.

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[0097]

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The compounds of these reductones include:
Typically, it is ascorbic acid or erythorbic acid or a derivative derived therefrom, and is commercially available or can be easily synthesized by a known synthesis method.

In the present invention, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), p
H buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.), dissolution aid (eg, polyethylene glycols, their esters, alkanolamines, etc.), sensitizer (eg, Nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc., surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenz) Imidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc., chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetates, polyphosphates, etc.), development accelerators (eg, US Pat. No. 304,025, compounds described in JP-B-47-45541), hardeners For example glutaraldehyde or can bisulfite adduct), or the addition of antifoaming agents.

The pH of the developing solution is adjusted to 7.5 to 11.5, preferably to 8.0 to 11.0.

As the solid processing agent of the present invention, those having a general composition as a fixing agent can be used. 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 that can form a soluble stable silver complex salt. Compounds known as fixing agents can be used.

The fixing agent may contain a water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum and the like. The fixing solution optionally contains compounds such as a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent capable of softening water. be able to.

[0103]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 The bulk density of each of the following developing materials was measured.
The measurement was carried out using a bulk density measuring instrument manufactured by Tsutsui Chemical Chemical Instruments Co., Ltd.

The materials 1) to 4) were filled in a packaging material (standing pouch) shown in FIG. In addition, in order to make the contact area with the packaging material the same, the materials of 1) to 10) were laminated as shown in FIG. 3 so as to have a thickness of 2 cm to prepare a sample.
The material inside the packaging material was discharged by cutting off the bottom surface of the packaging material, and the remaining amount of the material remaining inside the packaging material was measured.

Measurement method: [weight of packaging material with raw material (raw material) attached] − [weight of packaging material after washing and drying] =
[Residual amount of raw material (raw material)] The obtained bulk density and residual amount are shown in Table 1 below.

[0107]

[Table 1]

As is clear from Table 1, a material having a bulk density of less than 1 indicates that the amount remaining in the packaging material is large.

Example 2 Preparation of solid developer kit (for use in 10 liters of solution) <Pretreatment of material> Hydroquinone was replaced with MIKURO-PULVERIZER AP- manufactured by Hosokawa Micron Corporation.
The mixture was crushed with a B crusher at a mesh of 8 mm and a rotation speed of 25 Hz. Also, 8-mercaptoadenine and KBr are mesh 8
mm, and crushed at a rotation speed of 50 Hz.

<Mixing of Materials> A commercially available V-type mixer (capacity 2
00 liters) was mixed for 10 minutes.

Hydroquinone (the above-mentioned pulverized material) 65 kg Sodium erythorbate 16 kg Dimezone S 3.5 kg 8-mercaptoadenine (the above-mentioned pulverized substance) 0.3 kg DTPA · 5H 11 kg KBr (the above-mentioned pulverized substance) 6.5 kg 5 kg of sorbitol The apparent bulk density of the body is 0.75 g / ml
Met. When 50 g of each component was sampled and analyzed from arbitrary points (5 places), the concentration of each component was within ± 5% of the above prescribed value, and the components were sufficiently homogeneously mixed.

<Molding> Using a compression granulator Briquetter BSS-IH type (manufactured by Shinto Kogyo Co., Ltd.), the above mixture was used to form a pocket having a pocket shape of 5.0 mmФ × 1.2 mm (Depth).
Roller rotation speed 20 rpm, feeder rotation speed 50 rpm
m and a roll gab of 1 to 1.5 mm. The obtained plate-like molded product was crushed by a classifier, and was 2.4 to 7.0 mm.
And granules of 2.4 mm or less. (7.0mm
The above powder is crushed.) Fine powder having a size of 2.4 mm or less was mixed with the above-mentioned mixture and returned to the compression molding machine again to be molded.

Thus, about 95 kg of granules DA was obtained. The granules DA are the compacts shown in FIG.

<Preparation of Raw Materials> The following raw materials were prepared.
The following pretreatment was performed.

(Sodium sulfite / 1-phenyl-5-
Mercaptotetrazole / benzotriazole mixture)
18 g of 1-phenyl-5-mercaptotetrazole and 78 g of benzotriazole in 400 ml of ethyl alcohol
g was dissolved. The obtained solution was added dropwise to 20 kg of sodium sulfite being rotated by a mixer in small amounts, and the rotation was continued until the solution was sufficiently dried. The apparent sodium density of the obtained mixture M-1 of sodium sulfite / 1-phenyl-5-mercaptotetrazole / benzotriazole was 1.
43 g / ml. In addition, it is 1 from arbitrary points (5 places)
When 0 g was sampled and analyzed at a time, 1-phenyl-5-mercaptotetrazole and benzotriazole were sufficiently homogeneously mixed.

(Potassium carbonate / sodium carbonate / anhydrous /
Mixing of lithium hydroxide and 1H ₂ O) Using a commercially available V-type mixer (capacity 200 liters), potassium carbonate 56k
g, sodium carbonate 42 kg, lithium hydroxide 1H ₂
22 kg of O was mixed for 10 minutes. The resulting mixture M-2
Had a bulk density of 1.16 g / ml.

<Packaging> The packaging material in the form of the standing pouch shown in FIG. 2 was filled with the raw material mixture and the molded article in the following order. This package is designated as K-1. The standing pouch has a water vapor transmission rate of 0.1 g / m ² · at
m · 24Hr or less, and the oxygen permeability is 1 ml / m
^{It was 2} · atm · 24Hr or less.

Mixture M-2 600 g (bottom layer) bulk density 1.16 g / m ² Mixture M-1 663.2 g (middle layer) bulk density 1.43 g / m ² granule DA 399 g (top layer) <Comparison Preparation of packaging material for use> A mixture obtained by mixing granules DA without molding is referred to as a mixture DA (bulk density: 0.75 g / ml). A mixture of the mixture DA and M-1363.2 g is referred to as a mixture DA '. The bulk density is 1.05 g / ml
Met. K- except that the stacking order was changed as shown in Table 2.
This was packaged in the same manner as in No. 1 and was designated as K-2 to K-9. Of those, the mixture using the mixture DA 'had a filling amount of 300 g for the M-1 layer.

(Evaluation) The developing kit obtained by the above method was filled into a cardboard box in the transport form shown in FIG. 4 with four partitions interposed between partitions, and a display indicating that the container was not upside down was placed in order to regulate the vertical direction. The following routes were transported by truck.

<Route> Konica Tokyo Office in Hino City, Tokyo-Konica Distribution Center Takashimadaira, Itabashi-ku, Tokyo-Konica Kyushu Branch in Fukuoka City, Konica-Konica Tokyo Office in Hino City, Tokyo.

In the Konica distribution center, the pallets were loaded and unloaded with a forklift. At the Konica Kyushu branch, they were manually unloaded. After transporting in this manner, when the kit was opened, it was confirmed that the laminated structure was not collapsed.

The bottom of the above kit was cut off with a cutter, the material inside was taken out by natural fall, the weight of the packaging material (with residual material) was measured, and then the packaging material was thoroughly washed with water and dried. The weight was measured again, and the residual weight remaining in the packaging material was determined from the difference in weight. The results obtained are shown in Table 2 below.

[0123]

[Table 2]

As can be seen from Table 2, in the sample of the present invention,
It can be seen that the residual amount remaining in the packaging material is small, which is superior to the comparative packaging material.

Example 3 (Preparation of Silver Halide Emulsion A1) Silver chlorobromide core particles having a silver chloride content of 70 mol% and a balance of silver bromide having an average particle size of 0.09 μm by a double jet method. Was prepared. K ₃ Rh (NO) per mole of silver at the end of the core particle formation
₄ (H ₂ O) ₂ is 7 × 10 ⁻⁸ mol, and K ₃ OsCl ₆ is 8 × 1
0 ^-6 mol was added, at 40 ° C. pH 3.0, the silver potential (EA
g) An aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed while maintaining the temperature at 165 mV.

EAg was added to the core particles with a salt solution for 125 m.
V and shelled using a double jet method. At that time, 3 × 10 ⁻⁷ K ₂ IrCl ₆ per mole of silver was added to the halide solution.
And 9 × 10 ⁻⁸ mol of K ₃ RhCl ₆ . Further, KI conversion was performed using silver iodide fine grains.

The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (silver chloride content: 70 mol%, silver iodobromide content: 0.15 μm). 2 mol%, the balance being silver bromide).

Next, modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, JP-A-2-280139-2)
The salt was desalted using the exemplified compound (G-8) on page 87 (3). The EAg after desalting was 190 mV at 50 ° C.

The obtained emulsion was mixed with 1.5 × 10 ⁻³ mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (hereinafter referred to as TAI) per mol of silver, The pH was adjusted to 5.6 and the EAg was adjusted to 123 mV by adding 8.5 × 10 ^-4 mol of potassium chloride and citric acid, and p-
After adding 1 × 10 ⁻³ mol of toluenesulfonylchloramide sodium trihydrate (chloramine T) and reacting, an inorganic sulfur (S8) compound dispersed in a solid [Seisin Corporation; PM-1200 And saponin was added and dispersed to an average of 0.5 μm], and 1.5 × 10 ⁻⁵ mol of chloroauric acid was added, and the mixture was chemically ripened at 55 ° C. until the maximum sensitivity was obtained. 100 mg of sensitizing dye d-1 and 5 mg of trihexylamine were added, and after further lowering the temperature to 40 ° C., 2 × 10 ⁻³ mol of TAI, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole, iodide After adding 5 × 10 ⁻³ mol of potassium, the pH was adjusted to 5.1 with citric acid.

(Preparation of Silver Halide Emulsion A2) The reaction temperature was raised to 50 ° C. to give a grain size of 0.30 μm with respect to the silver halide emulsion A1, and K ₃ RhCl ₆ in the shell portion was added to the silver halide emulsion at a concentration of 6 × per mole of silver. A silver halide emulsion A2 was prepared in exactly the same manner as in A1 except that the amount was 10 ^-8 mol. When the same chemical sensitization was performed, the emulsion of A2 was 40% higher than the emulsion of A1.
High sensitivity.

(Preparation of silver halide photographic light-sensitive material for printing plate making scanner for He-Ne laser light source) A silver halide emulsion layer 1 of the following formula 1 was coated on a support at a silver amount of 0.3 g /
m ^2, so that the amount of gelatin is 0.3 g / m ^2, more amount of gelatin gelatin intermediate layer of Formulation 2 thereon 0.
Further, the silver halide emulsion layer 2 of Formulation 3 was adjusted so that the silver amount was 8 g / m ² and the silver amount was 1.5 g / m ² , and the gelatin amount was 1.4 g.
/ M ^2, and a protective layer coating solution of the following formulation 4 was simultaneously coated in a multilayer so that the amount of gelatin became 0.7 g / m ² .

On the other side of the undercoat layer, a backing layer of the following formula 5 was provided so that the amount of gelatin was 1.5 g / m ^2, and a backing protective layer of the following formula 6 was provided thereon so that the amount of gelatin was 0.1 g / m ² . The emulsion layer side and the emulsion layer side were simultaneously layer-coated at a speed of 200 m / min by a curtain coating method so that the emulsion layer side became 8 g / m ² , and cooled and set. , And the sample was obtained by simultaneously drying both sides.

Formulation 1 (Composition of Silver Halide Emulsion Layer 1) Gelatin 0.3 g / m ² Silver halide emulsion A2 Amount of silver 0.3 g / m ² equivalent Sensitizing dye d-1 150 mg / Ag 1 mol Hydrazine compound: Illustrative H-17 3 mg / m ² amine compound: Illustrative Na-21 7 mg / m ² Compound a 100 mg / m ² 2-pyridinol 1 mg / m ² Polymer latex (L1) (particle size 0.25 μm) 0.25 g / m ² Hardener h1 5 mg / m ² (S-1) Sodium-iso-amyl-n-decylsulfosuccinate 0.7 mg / m ² Sodium naphthalenesulfonate 8 mg / m ² Saponin 20 mg / m ² Hydroquinone 20 mg / m ² 2 -Mercapto-6-hydroxypurine 2 mg / m ² 2-mercaptopyridine 1 mg / m ² ascorbic acid 20 mg / m ² EDTA 25 mg / m ² Sodium polystyrene sulfonate 15 mg / m ² Compound n-1 0.2 mmol / Ag 1 mol The coating solution pH was 5.2.

Formulation 2 (Composition of gelatin intermediate layer) Gelatin 1.0 g / m ² Saponin 80 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500,000) 15 mg / m ² Fungicide z 0.5 mg / m ² Solid disperse dye b 50 mg / m ² Formula 3 (composition of silver halide emulsion layer 2) Silver halide emulsion A1 equivalent to 1.5 g / m ^{2 of} silver Amount of sensitizing dye d-2 150 mg / Ag 1 mol Hydrazine compound: Exemplified H-17 30 mmol / Ag 1 mol Amine compound: Exemplified Na-21 1.3 mmol mmol / Ag 1 mol (S-1) 1.7 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² Nicotinamide 1 mg / m ² Gallic acid n - propyl ester 50 mg / m ² mercaptopyrimidine ^{1mg / m 2 EDTA 50mg / m} 2 styrene - maleic acid Polymer (molecular weight 70,000) 10 mg / m ² Polymer latex (L2) 0.25g / m ² colloidal silica coating solution pH using a (average particle size 0.05μm) 150mg / m ² gelatin phthalated gelatin 4.8
Met.

Formulation 4 (Emulsion protective layer composition) Gelatin 0.7 g / m ² (S-1) 12 mg / m ² Matting agent: spherical polymethyl methacrylate having an average particle size of 3.5 μm 25 mg / m ² Average particle size 8 μm Silica 12.5 mg / m ² Slip agent (silicone oil) 4 mg / m ² Compound a 50 mg / m ² Polymer latex (L3) (particle size 0.10 μm) 0.25 g / m ² colloidal silica (average particle size of 0. 05μm) 150mg / m ² 1,3- vinylsulfonyl-2-propanol 40 mg / m ² hardener h2 30 mg / m ² sodium polystyrenesulfonate 10 mg / m ² fungicide z 0.5 mg / m ² formulation 5 (backing layer composition) gelatin ^{1.5g / m 2 (S-1} ) 5mg / m 2 polymer latex (L3) 0.3 g / m ² colloidal silica (average particle diameter 0 05μm) 100mg / m ² Sodium polystyrenesulfonate 10 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100mg / m ² 1- phenyl-5-mercaptotetrazole 10 mg / ^{m 2} hardener h3 100 mg / m ² zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² prescription 6 (backing protective layer) gelatin 0.8 g / m ² matting agent: monodisperse polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² average particle size 3 μm Silica 2.5 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² (S1) 1 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² compound a 50 mg / m ² hardener h2 20 mg / m ² sodium polystyrenesulfonate 0mg / ^{m 2}

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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The sample thus obtained was cut into a size of 40 inches × 30 inches, and 20% of the sample was blackened, and a developing solution and a fixing solution having the following compositions as starting solutions and a developing replenisher as described in Example 2 were used. Each of the used solid developers K-1 to 9 was dissolved in water and finished to 10 liters, and a replenisher for fixing was prepared by dissolving a solid fixing agent in water with the following composition and finishing to 10 liters. used. The replenishing rate was 100 ml / m ² for both the developing solution and the fixing solution, and the processing was continued under the following conditions until the developing replenisher was replenished three times the capacity of the developing tank.

Separately, the sample prepared here was subjected to step exposure with a laser sensitometer using a 633 nm He-Ne laser as a light source while changing the light amount in 1.5 × 10 ⁻⁷ seconds. did. The blackening density of the obtained developed sample was measured with a densitometer PDA-65 (manufactured by Konica Corporation).

In order to evaluate the reproducibility of the fine halftone dots of the sample prepared here, SelectS by Agfa was used.
Small dot (5% halftone dot), middle point (50% halftone dot), large point (9 dots) at 3600 dpi / 300 lpi using et5000.
Exposure was performed while setting the output so as to output 5% of halftone dots) and solid (100% halftone dots). The obtained developed sample was subjected to X-Rite3
The net% was measured at 61T.

(Composition of developer used (starting solution)) Diethylenetriaminepentaacetic acid / pentasodium salt 1.45 g Dimezone S 0.85 g Sodium sulfite 42.5 g Potassium sulfite 17.5 g Potassium carbonate 55 g Hydroquinone 20 g 1 per liter of used solution -Phenyl-5-mercaptotetrazole 0.03 g Potassium bromide 2.67 g Benzotriazole 0.21 g Boric acid 8 g Diethylene glycol 40 g 8-Mercaptoadenine 0.07 g KOH was added in an amount to bring the pH of the working solution to pH 10.4.

(Preparation of used replenisher for fixing) Preparation of solid fixing agent kit (10 liters of used solution) <Pretreatment of material> Sodium 1-octanesulfonate was added to MIKURO-PULVER manufactured by Hosokawa Micron Corp.
4 mm mesh, 6 revolutions with IZER AP-B crusher
Milled at 0 Hz. 8-mercaptoadenine and KB
r was crushed at a mesh of 8 mm and a rotation speed of 50 Hz.

<Mixing of Materials> A commercially available V-type mixer (capacity 2
00 liters) was mixed for 10 minutes.

91 kg of ammonium thiosulfate (10% sodium salt) 1 kg of sodium sulfite 1 kg 9 kg of sodium metabisulfite 1 kg of sodium 1-octanesulfonate (the above-mentioned ground product) was added to the obtained mixture, and the mixture was further mixed for 5 minutes. The bulk density of the obtained mixture was 0.84 g / ml.

<Molding> Using a compression granulator Briquetta BSS-IH type (manufactured by Shinto Kogyo Co., Ltd.), the above mixture was used to form a pocket of 5.0 mm 形状 × 1.2 mm (Depth).
Roller rotation speed 30 rpm, feeder rotation speed 67 rpm
Molded at The obtained plate-like molded product was pulverized with a classifier and divided into 2.4 to 7.0 mm granules FA and 2.4 mm or less fine powder. (A fine powder having a size of 7.0 mm or more is crushed.) A fine powder having a size of 2.4 mm or less was mixed with the above-mentioned mixture and returned to a compression molding machine to be molded again. Thus, about 95 kg of granule FA was obtained.

<Mixing of Materials> A commercially available V-type mixer (capacity 2
00 liters) was mixed for 10 minutes. The bulk density of the obtained mixture was 0.82 g / ml.

Sodium acetate / anhydrous 45 kg dehydrated aluminum sulfate 19 kg boric acid 10 kg tartaric acid 5 kg succinic acid 21 kg <Molding> The above mixture is subjected to a compression granulator Briquetta BSS-
Using an IH type [manufactured by Shinto Kogyo Co., Ltd.], molding was performed at a pocket shape of 5.0 mmФ × 1.2 mm (Depth), a roller rotation speed of 30 rpm, and a feeder rotation speed of 67 rpm. The obtained plate-like molded product is pulverized with a classifier, and
It was divided into granules FA of 7.0 mm and fine powder of 2.4 mm or less. (Those with a size of 7.0 mm or more are crushed.)
The fine powder having a particle size of m or less was mixed with the above mixture and returned to the compression molding machine again to be molded. From above, granule FA is about 95kg
Obtained.

<Packaging> A packaging material in the form of a standing pouch shown in FIG. 2 was filled with the raw material mixture and the molded article in the following order.

Granular FB 620 g (bottom layer) Granular FA 1610 g (top layer) (Fixing solution (starting solution) composition used) Ammonium thiosulfate (70% aqueous solution) per liter of working solution 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate -Trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27% aqueous solution) 25 ml Sulfuric acid was used to adjust the pH of the working solution to 4.85.

(Processing conditions) (Process) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Rinse at room temperature 20 seconds Squeeze / dry 50 ° C. 30 seconds Total 100 seconds (Evaluation of gamma) It is represented by the tangent of 1 and 3.0, and indicates that a super-high contrast image is obtained only when the gamma value in the table is 10 or more.

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

(Evaluation Method of Reproducibility of Halftone Halftone) The halftone point (target halftone 50%) at an exposure amount giving a solid density of 5.0
%) Actually shows the halftone dot reproduced on the sample. The closer to 50%, the better. Table 3 shows the obtained results.

[0158]

[Table 3]

As is clear from Table 3, the solid processing agent for a silver halide photographic light-sensitive material of the present invention had a high gamma and good reproducibility of fine halftone dots.

Example 4 (Preparation of Silver Halide Emulsion B1) Using a double jet method, 70 mol% of silver chloride and the balance of silver bromide having an average diameter of 0.0
9 μm silver chlorobromide core particles were prepared. At the time of mixing the core particles, an aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed while maintaining the pH at 36 ° C. and the silver potential (EAg) at 120 mV. The core particles were shelled using a double jet method with EAg reduced to 100 mV with saline. At that time, 38.2 μg of K ₃ RhCl ₆ was added per mole of silver to the halide solution. The resulting emulsion was a core / shell type monodispersed silver chloroiodobromide (coefficient of variation: 10%) having an average diameter of 0.20 μm (silver chloride content: 70 mol%, silver iodide content: 0.2 mol%, remaining (A silver bromide) was a cubic emulsion.

Thereafter, sensitizing dye d-3 was added in an amount of 70 mg per mol of silver. Then, a modified gelatin described in JP-A-2-280139 (in which an amino group in gelatin is substituted with phenylcarbamyl, for example, as disclosed in JP-A-2-28013)
No. 9, 287 (3) (exemplified compound G-8) and desalted. Thereafter, at 40 ° C., 30 mg of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) was added per 1 mol of silver. The EAg of the obtained emulsion was 177 mV at 40 ° C., and the pH was 5.6.

Next, TAI was added to the emulsion at 60 / mol silver.
After reacting 35 mg of KBr and KBr, the inorganic sulfur S8 compound dispersed in a solid (manufactured by Seishin Enterprise Co., Ltd .; PM-1)
200, and saponin was added and dispersed to an average of 0.5 μm), and 1.5 × 10 −5 mol of chloroauric acid was added, followed by chemical ripening at a temperature of 60 ° C. until the maximum sensitivity was obtained. Thereafter, 400 mg of TAI and 30 mg of potassium iodide were added per mol of silver, and 255 mg of sensitizing dye d-5 was added per mol of silver at 40 ° C. Then, the pH was adjusted to 5.1 by adding citric acid.

(Preparation of Silver Halide Emulsion B2) The reaction temperature was raised to 45 ° C. to give a grain size of 0.30 μm with respect to the silver halide emulsion B1, and K ₃ RhCl ₆ in the shell portion was 26.7.
silver halide emulsion B2
Was prepared. With the same chemical sensitization, the emulsion of B2 is 35% faster than the emulsion of B1.

(Preparation of silver halide photographic light-sensitive material for printing plate making) On a support, a gelatin subbing layer of the following formula 7 was prepared so that the amount of gelatin was 0.5 g / m ^2. No. 8 silver halide emulsion layer 1 having a silver amount of 3.0 g / m ² ,
Further, a gelatin intermediate layer of formula 9 is further placed on the upper layer so that the amount of gelatin is 1.5 g / m ² , and the amount of gelatin is 0.8 g / m ^2.
/ M at ^2, further following formulation 10 silver halide emulsion layer 2 of silver amount 0.3g / m ^2, the amount of gelatin 0.3g
/ M ^2, and a protective layer coating solution of the following formula 11 was further simultaneously coated in a multilayer so that the amount of gelatin became 0.3 g / m ² . On the other side of the undercoat layer, a backing layer having the following formulation 12 was prepared so that the amount of gelatin was 2.0 g / m ² .
Then, a backing protective layer of the following formula 13 was simultaneously coated on the emulsion layer side and the emulsion layer side at a speed of 200 m / min by a curtain coating method so that the amount of gelatin became 1.0 g / m ² , and then cooled and set. After that, the backing layer side was simultaneously coated in a multi-layer manner, cooled and set at -1 ° C, and both sides were simultaneously dried to obtain a sample.

Formulation 7 (Gelatin undercoat layer composition) Gelatin 0.5 g / m ² Saponin 80 mg / m ² Hydroquinone 0.5 g / m ² 1-phenyl-5-mercaptotetrazole 2.0 mg / m ² Fungicide z 0. 5 mg / m ² solid disperse dye C 15 mg / m ² Prescription 8 (composition of silver halide emulsion layer 1) Silver halide emulsion B1 Silver amount 3.0 g / m ² equivalent Hydrazine compound: Exemplified H-17 0.30 mg / m ² (S-1) 5 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² Nicotinamide 1 mg / m ² Gallic acid n-propyl ester 50 mg / m ² Mercaptopyrimidine 1 mg / m ² Polymer latex (L2 ) (Particle size 0.25 μm) 0.5 g / m ² EDTA 50 mg / m ² Sodium polystyrene sulfonate 15 mg / m ² Colloidal silicide Mosquito (average particle size: 0.05 μm) 150 mg / m ² gelatin is phthalated gelatin and the coating solution pH is 4.8.
Met.

Formulation 9 (Composition of gelatin intermediate layer) Gelatin 0.8 g / m ² Saponin 80 mg / m ² Hydroquinone 0.5 g / m ² Polymer latex (L2) (particle size 0.25 μm) 0.5 g / m ² Fungicide z 0.5 mg / m ² Prescription 10 (composition of silver halide emulsion layer 2) Silver halide emulsion B2 Silver equivalent 0.3 g / m ² equivalent 2-pyridinol 1 mg / m ² Polymer latex (L2) (particle size 0 0.25 g / m ² (S-1) 3 mg / m ² saponin 2 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² 2-mercaptopyridine 1 mg / m ² Sodium polystyrene sulfonate 15 mg / m ^Two compounds n-2 0.2 mmol / Ag1 mol The coating solution pH was 5.2.

Formulation 11 (Emulsion protective layer composition) Gelatin 0.3 g / m ² (S-1) 12 mg / m ² Activator b 0.6 mg / m ² Quaternary onium compound P-1 0.9 mmol / Ag 1 mol Colloidal silica (Average particle size 0.05 μm) 0.7 g / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener h2 160 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Disinfectant z 0.5 mg / m ² formulation 12 (backing layer composition) gelatin 2.0 g / m ² polymer latex L3 0.3 g / m ² colloidal silica (average particle size 0.05 .mu.m) 100 mg / ^{m 2} dye f1 40 mg / m ² dye f2 7 mg / m ² dye f3 60 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² Hardener h3 100 mg / m ² EDTA 50 mg / m ² formulation 13 (backing protective layer) Gelatin 1.0 g / m ² Matting agent: monodisperse mean particle size 5μm polymethylmethacrylate 50 mg / m ² Hiratsubu径3μm indefinite based silica 12.5 mg / m ² Dye f1 40 mg / m ² Dye f2 7 mg / m ² Dye f3 60 mg / m ² Hardener h1 100 mg / m ² (S-1) 6 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² KI 15 mg / m ² Amine compound Na- 21 15 mg / m ² After continuous treatment in the same manner as in Example 3, the obtained sample was adhered to a step wedge, exposed to tungsten light at 3200 ° K for 3 seconds, and subjected to the same treatment and evaluation as in Example 3. went.

In order to evaluate the reproducibility of minute halftone dots of the obtained sample, No. 3 of Example 3 was evaluated. Using the sample processed in 3-1 as a manuscript, with a fine zoom C-880F (manufactured by Dainippon Screen Co., Ltd.), the enlargement magnification is 120.
% And 95% of the original step wedge
Exposure was performed so that the% portion became 5%. The exposed sample was processed under the same conditions as in Example 3 by using an automatic developing machine GR-27 (manufactured by Konica Corporation) using the developing solution and fixing solution used in Example 3. X-Rite for sample after treatment
The net% was measured at 361T.

(Evaluation of enlargement) The reproducibility of the large dot side (shadow part) of the treated sample in which the dot percentage on the small dot side (highlight part) was adjusted to 5% (the difficulty of halftone dot collapse) ) Were evaluated in five steps in order from the best one. 5 is a good level and 1 is a poor level. The practically usable level was set at 3. Table 4 shows the obtained results.

[0170]

[Table 4]

As is clear from Table 4, the solid processing agent for a silver halide photographic light-sensitive material of the present invention has an ultra-high contrast property (high gamma value) and a good enlargement (reproducibility on the large point side). It was good.

[0172] Example _{5 K 3 Os (H 2 O} ) a Cl ₅ per mol of silver 8 × 10 during mixing with (silver Preparation of Halide Emulsion C) simultaneously mixing method
^-5 moles and K ₂ IrCl ₆ at 3 × 10 ^-7 per mole of silver
Mol, and after desalting by a conventional method, average particle size 0.10 μm
Of cubic silver chlorobromide (99 mol% of silver chloride, the balance being silver bromide) having a monodispersion (coefficient of variation: 10%).

After adding appropriate amounts of TAI, potassium bromide and citric acid to the obtained emulsion, sodium thiosulfate was added in an amount of 70 mg per mol of silver, and chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained. . After aging, 3 × 10 5 TAI and 1-phenyl-5-mercaptotetrazole were added.
^-4 moles and gelatin were added.

(Preparation of a silver halide photographic light-sensitive material for use in a printing plate turning room) A silver halide emulsion layer having the following formulation 14 was provided on a support with a silver content of 2.8 g / m ² and a gelatin content of 1.4 g.
/ M ² , a coating solution of the following formulation 15 was further formed as a lower layer of a protective layer on the upper layer, and the amount of gelatin was 0.5 g / m ^2.
Then, a coating solution of the following formulation 16 was simultaneously applied as a protective layer on the upper layer so that the amount of gelatin became 0.5 g / m ² . After the conductive layer described in Example 1 of JP-A-5-188518 was coated on the undercoat layer on the opposite side, the backing layer of the following formulation 17 was coated so that the amount of gelatin was 1.4 g / m ² . A backing protective layer having the following formulation 18 was further simultaneously coated thereon so that the amount of gelatin became 1.0 g / m ² to obtain a sample.

Formulation 14 (Silver Halide Emulsion Layer Composition) Silver Halide Emulsion C Quaternary onium compound P-1 0.9 mmol / Ag 1 mol Sodium dodecylbenzenesulfonate 10 mg / m so that the silver amount becomes 2.8 g / m ^{2. 2} 5-methyl-benzotriazole 10 mg / m ² compound m 6 mg / m ² latex polymer (L4) 1.0g / m ² hardener ^{h1 40mg / m 2 (S-} 1) 0.7mg / m 2 styrene - maleic acid Copolymer hydrophilic polymer 20 mg / m ² Formula 15 (Emulsion protective layer lower layer composition) Gelatin 0.5 g / m ² (S-1) 12 mg / m ² 1,3-vinylsulfonyl-2-propanol 50 mg / m ² active agent b 1 mg / m ² latex polymer (L4) 0.5 g / m ² formulation 16 (emulsion protective layer upper composition) gelatin 0.5 g / m ² solid disperse dye 100 mg / m ² Compound n-2 0.9mmol / Ag1mol (S -1) 12mg / m 2 Matting agent: monodisperse silica 15 mg / m ² Matting agent having an average particle diameter of 3 [mu] m: monodisperse silica having an average particle size of 8 [mu] m 20 mg / m ² 1,3-vinylsulfonyl-2-propanol 50 mg / m ² activator b 1 mg / m ² colloidal silica (mean particle size 0.05 μm) 20 mg / m ² prescription 17 (backing layer composition) gelatin 1.4 g / m ² dye f1 65 mg / m ² dye f6 150 mg / m ² dye f7 70 mg / m ² (S-1) 5 mg / m ² latex polymer (L3) 0.3 g / m ² colloidal silica (average particle size 0.05 μm) 70 mg / m ² styrene - hydrophilic maleic acid copolymer polymer 20 mg / m ² hardener h3 100 mg / m ² formulation 18 (backing protective layer) Zera Down 1.0 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 active agent b 1mg / m ² HO ( CH ₂ CH ₂ O) ₆₈ H 50 mg / m ² Hardener h2 40 mg / m ² A sample obtained in this manner was sent to a bright room printer P-6.
After performing step wedge and close contact (emulsion surfaces) exposure at 27 GM (manufactured by Dainippon Screen), continuous processing was performed in the same manner as in Example 3. However, the processing conditions were as follows (a), and the automatic developing machine was processed with GX-960 (manufactured by Konica Corporation). The same evaluation as in Example 3 was performed on the obtained developed sample.

Further, in order to evaluate the reproducibility of the minute halftone dots, the processed sample obtained in Example 4 was used as a document, and was closely adhered to a light room printer P-627GM (manufactured by Dainippon Screen). (Emulsion surfaces) After exposure, processing was carried out under the following conditions (a) or (b).

Processing conditions (a) Rapid processing (step (temperature) (time) Development 35 ° C. 15 seconds Fixing 35 ° C. 12 seconds Rinse at room temperature 12 seconds Drying 50 ° C. 17 seconds 56 seconds in total Processing conditions (b) Normal processing (step) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 24 seconds Water washing Room temperature 24 seconds Drying 50 ° C. 34 seconds Total 112 seconds The results obtained are shown in Table 5 below.

[0178]

[Table 5]

As is clear from Table 5, the solid processing agent for a silver halide photographic light-sensitive material of the present invention had a high gamma and excellent dot reproducibility at a large point even during ultra-rapid processing.

Example 6 (Preparation of Silver Halide Emulsion D) An aqueous solution of silver nitrate and a mixed aqueous solution of NaCl and KBr were prepared so that a silver halide composition having a silver chloride content of 70 mol% and a silver bromide content of 30 mol% was obtained. Were mixed by a controlled double jet method to grow silver halide grains. At this time, mixing was performed at 36 ° C.
g7.8, pH 3.0, and N during particle formation.
a ₂ RhCl ₆ was added in an amount of 2 × 10 ⁻⁷ mol per mol of silver. Thereafter, desalting was carried out using denatured gelatin treated with phenyl isocyanate, and ossein gelatin was added and redispersed.

The obtained 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 was added with 50-mercapto-2,3,5,6-tetrafluorobenzoic acid per mole of silver.
mg and then 5 mg of chloroauric acid and 0.5 mg of sulfur per mole of silver were added, and the pH and pAg were adjusted to 5.8 and 7.0, respectively.
Was chemically ripened at 60 ° C. for 80 minutes. After ripening, add 900 mg of TAI per mole of silver and add K
300 mg of I was added.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for Ar laser light source) On a support, a gelatin undercoat layer of the following formulation 19 was prepared with a gelatin amount of 0.6 g / g.
m ² , a silver halide emulsion layer of formula 20 was further coated thereon with a silver amount of 3.5 g / m ² and a gelatin amount of 1.7 g / m ^2.
Further, a coating solution for a protective layer having the following formulation 21 was simultaneously and multi-layer coated so that the amount of gelatin became 0.9 g / m ² . On the other side of the undercoat layer, a backing layer of the following formulation 22 was provided with a gelatin amount of 2.0 g / m ^2, and a backing protective layer of the following formulation 23 was provided thereon with a gelatin amount of 1.0 g / m 2. ² was applied. The coating method is simultaneous coating with a curtain coating method at a speed of 200 m / min, followed by simultaneous cooling and setting. Subsequently, simultaneous coating with the backing layer and simultaneous cooling and setting at -1 ° C. Obtained.

[0183] Formulation 19 (gelatin subbing layer composition) Gelatin 0.6 g / m ² Saponin 56.5 mg / m ² sodium polystyrenesulfonate (average molecular weight 500,000) 15 mg / m ² fungicide z 5 mg / m ² Solid Disperse Dye e 50 mg / m ² Compound n-3 0.2 mmol / Ag 1 mol Formulation 20 (Silver halide emulsion layer composition) Silver halide emulsion D A hydrazine compound: Exemplified H-7 so that the silver amount becomes 3.5 g / m ² . 3 mmol / Ag 1 mol Quaternary onium compound P-2 0.5 mmol / Ag 1 mol Sensitizing dye d-3 6 mg / m ² Sensitizing dye d-4 3 mg / m ² Antifoggant: Adenine 25 mg / m ² Stabilizer: 5-nitro indazole 10 mg / m ² polymer latex ^{(L1) 1.0g / m 2 (} S-1) 0.7mg / m 2 compound e 45 mg / m ² formulation 1 (Emulsion protective layer composition) Gelatin 0.9 g / m ² Matting agent: average particle size 3.5μm silica 20 mg / m ² active agent b 2 mg / m ² promoter: hydroquinone 50 mg / m ² hardener h2 150 mg / m ² amine compound: Exemplified Na-3 0.7 mmol / Ag 1 mol Formulation 22 (composition of backing layer) Gelatin 2.0 g / m ² Sodium polystyrene sulfonate 0 mg / m ² Colloidal silica (average particle size 0.05 μm) 170 mg / m ² Polymer latex (L3) 0.3 g / m ² Formulation 23 (composition of backing protective layer) Gelatin 1.0 g / m ² Matting agent: polymethyl methacrylate having an average particle size of 4.0 μm 50 mg / m ² dye f1 65 mg / m ² dye the samples obtained f2 15 mg / m ² dye f3 100 mg / m ² hardener h1 100 mg / m ² Thus,施例3 and performs the step exposure while light amount change by 1.5 × 10 ^-7 seconds with a laser sensitometer using Ar laser of 488nm as a light source from continuously treated in the same manner, the same evaluation as in Example 3 went.

In order to evaluate the reproducibility of minute halftone dots, a small dot (5% halftone dot) with a line number of 700 lines per inch by SG-757 [manufactured by Dainippon Screen Co., Ltd.] The medium point (50% halftone dot) was set to be output, halftone exposure was performed while changing the amount of light, and the same processing was performed using the same developing solution and fixing solution as described above.

[0185] Table 6 shows the obtained results.

[0186]

[Table 6]

As is clear from Table 6, the solid processing agent for a silver halide photographic light-sensitive material of the present invention had an ultra-high contrast and a good reproducibility of fine halftone dots.

Example 7 (Preparation of Silver Halide Emulsion E1) Chlorobromide having a silver chloride content of 70 mol% and a balance of silver bromide having an average thickness of 0.05 μm and an average diameter of 0.15 μm using a double jet method. Silver core particles were prepared. At the time of mixing the core particles, K ₃ RuCl 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, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver. The resulting emulsion had a core having an average thickness of 0.10 μm and an average diameter of 0.25 μm /
It is an emulsion of shell-type monodisperse (coefficient of variation: 10%) tabular grains of silver chloroiodobromide (silver chloride content: 90 mol%, silver iodide content: 0.2 mol%, balance: silver bromide). Was.

Then, the modified gelatin described in JP-A-2-280139 (Example in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, compound G-8 on page 287 (3) of JP-A-2-280139) is used. Use desalted.
The EAg after desalting was 190 mV at 50 ° C.

The obtained emulsion was added with TAI in an amount of 1 / mol of silver.
× 10 ^-3 mol, potassium bromide and citric acid were further added to adjust the pH to 5.6 and the EAg to 123 mV, and 5 mg of chloroauric acid and 0.5 mg of sulfur white per mol of silver were added. Chemical ripening was performed at 60 ° C. until the maximum sensitivity was obtained. After ripening, TAI was added at 2 × 10 ^-3 per mole of silver.
Mole, 1-phenyl-5-mercaptotetrazole
× 10 ^-4 mol and gelatin were added.

(Preparation of Silver Halide Emulsion E2) The silver chloride content was 60 mol% and the silver iodide content was 1.
5 mol%, the balance is made of silver bromide.
Silver chloroiodobromide core grains having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, 2 × 10 ⁻⁸ mol of K ₃ Rh (H ₂ O) Br ₅ was added per mol of silver. The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver. The resulting emulsion had a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (silver chloride content: 90 mol%, silver iodide content: 0,10 μm, average diameter: 0.42 μm). .2 mol%, the balance being silver bromide). Then, desalting is carried out by using a modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, compound G-8 on page 287 (3) of JP-A-2-280139). did. EAg after desalination is 5
It was 180 mV at 0 ° C.

The obtained emulsion was mixed with TAI per mole of silver.
10 ^-3 mol was added, and further, potassium bromide and citric acid were added to adjust the pH to 5.6 and the EAg to 123 mV.
7 mg of chloroauric acid and 0.7 mg of sulfur flower were added per mole, and the mixture was chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained. After ripening, TAI was added in an amount of 2 × 10 ⁻³ mol per mol of silver and 1-phenyl-5-mercaptotetrazole in 3 ×
10 ^-4 mol and gelatin were added.

(Preparation of silver halide photographic light-sensitive material for printing plate making scanner for red semiconductor laser light source) On a polyethylene terephthalate support, a gelatin subbing layer having the following formulation 24 was prepared so that the gelatin amount was 0.3 g / m ^2. In addition, a silver halide emulsion layer 1 having a formulation of 25 was added thereto in an amount of 0.3 g of silver.
/ M ² and a gelatin solution of 0.3 g / m ^2, and a coating solution of the following formulation 26 as a gelatin intermediate layer was further added thereon so that the gelatin amount was 0.6 g / m ^2. In the upper layer, the silver halide emulsion layer 2 of the prescription 27 was adjusted so that the silver amount was 2.9 g / m ² and the gelatin amount was 1.5 g / m ^2.
g / m ² . On the other side of the undercoat layer, a backing layer of the following formulation 29 was further provided with a polymer layer of the following formulation 30 so that the amount of gelatin was 0.6 g / m ² , and further a further polymer layer of the following formulation 31 was further provided thereon. A sample was obtained by simultaneously coating the backing protective layer with the emulsion layer so that the amount of gelatin was 0.4 g / m ² .

Formulation 24 (Gelatin undercoat layer composition) Gelatin 0.3 g / m ² solid disperse dye b 50 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² (S-1) 0.4 mg / m ² Formula 25 (halogen Silver halide emulsion layer 1 composition) Silver halide emulsion E2 Compound n-4 0.2 mmol / Ag 1 mol (S-1) 1.7 mg / m ² Formulation 26 (gelatin intermediate layer) so that the silver amount becomes 0.3 g / m ^2. Composition) Gelatin 0.6 g / m ² (S-1) 2 mg / m ² Hydroquinone 50 mg / m ² Prescription 27 (Silver halide emulsion layer 2 composition) Silver halide emulsion E1 The silver content was 2.9 g / m ^2. sensitizing dye d-5 6mg / m ² sensitizing dye ^d-2 3mg / m 2 hydrazine compound: exemplary H-7 0.28mmol / Ag1mol amine compound: exemplary 21 1.50 mmol / a 1mol compound e 100 mg / m ² latex polymer ^{(L1) 0.5g / m 2 (} S-1) 0.7mg / m 2 2- mercapto-6-hydroxy purine ^{10mg / m 2 EDTA 50mg / m} 2 formulation 28 (Emulsion Protective layer composition) Gelatin 0.6 g / m ² (S-1) 12 mg / m ² Matting agent: monodisperse silica having an average particle size of 3.5 μm 25 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Surfactant b 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 20 mg / m ² Hardener h2 130 mg / m ² Formulation 29 (backing layer composition) Gelatin 0.6 g / m ² (S-1) 5 mg / m ² latex polymer (L3) 0.3g / m ² colloidal silica (average particle size 0.05μm) 70mg / m ² sodium polystyrenesulfonate 20 g / m ² formulation 30 (hydrophobic polymer layer composition) latex (methyl methacrylate: acrylic acid = 97: 3) 1.0g / m 2 hardener h1 6 mg / m ² formulation 31 (backing protective layer) Gelatin 0.4g / M ² matting agent: monodispersed polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² activator b 1 mg / m ² dye k 40 mg / m ² HO (CH ₂ CH ₂ O) ₆₈ H 50 mg / m ² Hardener h1 20 mg / m ² The sample thus obtained was continuously treated in the same manner as in Example 3, and then an infrared semiconductor laser was used as a light source. Using the laser sensitometer used, step exposure was performed while changing the light amount at 1.5 × 10 ⁻⁷ seconds, and evaluation was performed in the same manner as in Example 3.

Further, in order to evaluate the reproducibility of minute halftone dots, a small dot (5% halftone dot) with 700 lines per inch by MTR-1100 (manufactured by Dainippon Screen Co., Ltd.)
The medium point (50% halftone dot) was set to be output, halftone exposure was performed while changing the amount of light, and the same processing was performed as described above to obtain Table 7 below.

[0196]

[Table 7]

[0197]

As has been demonstrated in the examples, according to the present invention, a solid processing agent for a silver halide photographic light-sensitive material for printing plate making, which has a high gamma and excellent reproducibility of fine halftone dots even when subjected to rapid processing. And the processing method by it was obtained.

[Brief description of the drawings]

FIG. 1 is a side view and a front view of a granulated product.

FIG. 2 is a side view, a front view, and a bottom view of a standing pouch.

FIG. 3 is a stacking diagram (perspective view).

FIG. 4 is a view showing a standing pouch transportation mode.

FIG. 5 is a standing pouch transportation mode diagram (loading method).

[Explanation of symbols]

 A Standing Pouch Front B Standing Pouch Side C Standing Pouch Bottom d Top Layer Stack e Middle Layer Stack f Bottom Layer Stack 1 Cardboard 2 Cardboard Partition

Claims (6)

[Claims] 1. A method for producing a solid processing agent for silver halide photography, wherein a raw material having a bulk density ρ ≦ 1.0 g / ml is produced by the following method (1) or (2). For producing a solid processing agent for silver halide photography. (1) By mixing with another raw material having a large bulk density, the bulk density ρ after mixing is made larger than 1.0 g / ml. (2) Particle size 0.1 to 0.1 or after mixing with other raw materials
Mold to 10 mm. 2. A silver halide photographic solid processing agent which has been subjected to lamination filling of at least two layers and has a particle size of 0.1.
Filling the top layer with a molded product of 10 mm to 10 mm, and describing the vertical direction on the packaging material of the packaged solid processing agent or the material for packaging a plurality of them at the time of transportation, storage, and opening the packaging material 2. The method for producing a solid processing agent for silver halide photography according to claim 1, wherein the regulation of the vertical direction is specified. 3. A silver halide photographic solid processing composition having at least two or more layers filled therein, wherein the top layer is filled with a raw material having the lowest bulk density ρ or a mixture with the raw material, and 2. The vertical direction is described on a packaging material of the solid processing agent or a material for packaging a plurality of them in a lump, and a vertical direction is specified when transporting, storing, and opening the packaging material. For producing a solid processing agent for silver halide photography. 4. The method according to claim 2, wherein the packaging material is in the form of a standing pouch. 5. The method for producing a solid processing agent for silver halide photography according to claim 1, wherein the developer for silver halide photography contains reductones. 6. A silver halide photographic light-sensitive material characterized by processing a silver halide photographic light-sensitive material containing a hydrazine compound with the solid processing agent according to any one of claims 1 to 5. Processing method.