JPH07128773A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material capable of obtaining a high-quality image even in the case of a low replenishing rate and rapid processing and superior in dryability and small in sticking of stains and its processing method. CONSTITUTION:The method for processing the silver halide photographic sensitive material having at least one silver halide emulsion layer and an emulsion protective layer on a support is characterized by that this photosensitive material is provided with a layer substantially impermeable to water on the side of the support reverse to the emulsion layer side and it is processed in a developing solution replenishing rate of <=350ml/m<2> of the photosensitive material and in a fixing solution replenishing rate of <=480ml/m<2> of this material, and at least one layer of this photosensitive material contains a hydrazine derivative. It is preferred that the developing solution has a pH of <=11.2 at the time of processing this photosensitive material.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, in the field of printing plate making, it has been desired to speed up development processing in order to process a large amount of a light-sensitive material in a short period of time in order to improve work efficiency. On the other hand, it is desired to reduce the amount of processing waste liquid and the replenishment amount of developing and fixing from the viewpoint of handleability of the processing liquid kit.

When the processing speed is increased while reducing the replenishment amount for development, sludge deposition due to gelatin flowing out from the photosensitive material increases in the developing layer, and the problem that stains adhere to the photosensitive material easily occurs.

When the processing speed is increased while the fixing replenishment rate is reduced, the pH of the fixing solution increases in the developing layer as the running proceeds, and the swelling degree of the light-sensitive material in the washing step increases, which is sufficient in the drying step. It becomes impossible to dry properly. In particular, when the processing speed is increased and rapid processing is performed, the risk of causing jamming in the drying process is increased.

[0005]

In contrast to the problems described above, the object of the present invention is to provide a halogenated product which has high image quality and excellent drying property even in low replenishment and rapid processing, and which has little stain adhesion in the processing step. It is to provide a silver photographic light-sensitive material and a processing method thereof.

[0006]

The above object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and an emulsion protective layer on a support. A silver halide photographic light-sensitive material having a substantially water-impermeable layer on the opposite side of the emulsion layer between the support and a replenishment rate of 350 ml or less and / or a fixing replenishment rate per m ^{2 of the} silver halide photographic light-sensitive material. Is processed with 480 ml or less per 1 m ^{2 of} silver halide photographic light-sensitive material.

In addition, in at least one layer of the above silver halide photographic light-sensitive material, the above-mentioned hydrazine derivative is contained, and in the above method for processing the silver halide photographic light-sensitive material,
In the preferred embodiment, the pH of the developer is less than 11.2.

The present invention will be specifically described below.

The substantially water-impermeable layer in the present invention is different from a hydrophilic colloid binder such as gelatin,
It means a layer using a hydrophobic polymer as a binder.

Even if one such polymer layer is formed,
It may be more than one layer. The preferable thickness of the polymer layer depends on the type of the polymer layer, but is 0.05 to 10 μm, preferably
It is in the range of 0.1 to 5 μm.

The support of the present invention is not particularly limited, but polyethylene terephthalate is preferred. The thickness of the support is preferably 150 to 200 μm.

The polymer layer is a layer containing a hydrophobic polymer as a main binder. The term "hydrophobic" means that this layer does not substantially permeate a developing solution and a non-photosensitive hydrophilic colloid layer (back layer) applied at a position closer to the support than the layer is subjected to a developing step and a water washing step. It means that the water content after the completion is 0.2 g or less per 1 g of the binder. The binder for the polymer layer is not particularly limited as long as the above conditions are satisfied. Specific examples of the binder for the polymer layer include polyethylene,
Polypropylene, polystyronitrile, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin,
Phenol resin, epoxy resin, tetrafluoroethylene, fluororesin such as polyvinylidene fluoride, butadiene rubber, chloropropylene rubber, rubber such as natural rubber, acrylic acid or methacrylic acid ester such as polymethylmethacrylate and polyethylacrylate, polyethylene Examples thereof include polyester resins such as phthalate, polyamide resins such as nylon 6 and nylon 66, cellulose resins such as cellulose triacetate, water-insoluble polymers such as silicone resins, and derivatives thereof. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used. These may be used alone or in combination of two or more. Particularly preferred binders are copolymers of alkyl acrylates or alkyl methacrylates with acrylic acid or methacrylic acid (acrylic acid or methacrylic acid is preferably 5 mol% or less), styrene-butadiene copolymers, styrene-butadiene-acrylic acid copolymers (acrylic acid 5 Mol% or less), styrene-butadiene-divinylbenzene-methacrylic acid copolymer (methacrylic acid is preferably 5 mol% or less), vinyl acetate-ethylene-acrylic acid copolymer (acrylic acid is 5 mol% or less), vinylidene chloride-acrylonitrile. -Methyl methacrylate-ethyl acrylate-acrylic acid copolymer (acrylic acid 5 mol% or less), ethyl acrylate-glycidyl methacrylate-acrylic acid copolymer and the like.

In the polymer layer of the present invention, a photographic additive such as a matting agent, a surfactant, a dye, a slipping agent, a crosslinking agent, a thickener, a UV absorber, and inorganic fine particles such as colloidal silica may be added, if necessary. May be added. Regarding these additives, the description in Research Disclosure Vol. 176, Item 17643 (December 1978) can be referred to.

Next, as the hydrazine derivative used in the present invention, the compound represented by the above general formula [H] is used.

The general formula [H] will be described in detail below.

In the formula, the aliphatic group represented by A is preferably one having 1 to 30 carbon atoms, and particularly a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group,
Examples thereof include a benzyl group and the like, which further include suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfoxy group,
Sulfonamide group, acylamino group, ureido group, etc.).

The aromatic group represented by A in the general formula [H] is preferably a monocyclic or condensed-ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A in the general formula [H] is preferably a monocyclic or condensed ring heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, for example, a pyrrolidine ring, Examples thereof include 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 and a furan ring.

Particularly preferred as A is an aryl group and a heterocyclic group.

The aryl group and heterocyclic group of A may have a substituent. Representative substituents are an alkyl group (preferably having a carbon number of 1 to 20), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl portion having a carbon number of 1 to 3), an alkoxy group (preferably Alkyl moiety having 1 to 20 carbon atoms, substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms or alkylidene group), acylamino group (preferably having 1 to 40 carbon atoms) ), Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms)
Group), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), a hydroxyl group, a phosphoamide group (preferably having 1 to 40 carbon atoms), and the like.

Further, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group has 8 carbon atoms.
Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a phenyl group, a phenoxy group, an alkylphenoxy group and the like, which are relatively inert to the above photographic properties.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

B is specifically an acyl group (eg formyl, acetyl, propionyl, trifluoroacetyl,
Methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc.), alkylsulfonyl groups (eg, methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl groups (eg, benzenesulfonyl, etc.) ), An alkylsulfinyl group (eg methanesulfinyl etc.), an arylsulfinyl group (benzenesulfinyl etc.), a carbamoyl group (eg methylcarbamoyl, phenylcarbamoyl etc.), an alkoxycarbonyl group (eg methoxycarbonyl, methoxyethoxycarbonyl etc.), an aryloxycarbonyl Groups (eg phenoxycarbonyl etc.), sulfamoyl groups (eg dimethylsulfamoyl etc.), sulfinamoyl groups (eg methylsulfur) Finamoyl etc.), an alkoxysulfonyl group (eg methoxysulfonyl etc.), a thioacyl group (eg methylthiocarbonyl etc.), a thiocarbamoyl group (eg methylthiocarbamoyl etc.), an oxalyl group or a heterocyclic group (eg pyridine ring, pyridinium ring etc.) Represent

B in the general formula [H] represents A ₂ and the nitrogen atom to which they are attached.

[0025]

[Chemical 2]

May be formed.

R ₉ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

As B, an acyl group or an oxalyl group is particularly preferable.

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 ( Etoxaryl etc.)

Among the hydrazine compounds used in the present invention, the compounds represented by the following general formula [Ha] are particularly preferable.

[0031]

[Chemical 3]

Where R ₅ is

[0033]

[Chemical 4]

Represents

R ₄ , R ₆ and R ₇ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group,
It represents an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group, and R ₆ and R ₇ may form a ring together with an N atom. R ₈ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. A ₁ and A ₂ A ₁ of formula H
And A ₂ respectively represent the same groups.

The general formula [Ha] will be described in more detail.

[0037] A ₁ and A _2, A ₁ and A ₂ of the formula H
And a hydrogen atom are the most preferable.

R ₅ is

[0039]

[Chemical 5]

Wherein R ₄ , R ₆ and R ₇ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl etc.), an alkenyl group (allyl, butenyl etc.), an alkynyl group (propargyl, butynyl etc.). , Aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl, quinolidinyl, N, N'-diethylpyrazolidinyl, N- Benzylpyrrolidinyl, pyridyl, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy, ethoxy, etc.), alkenyloxy group (allyloxy, etc.), alkynyloxy group ( propargyloxy, etc.), an aryloxy group (phenoxy) or a heterocyclic oxy group (pyridyloxy, etc.), with R ₆ and R ₇ Ring together with atom (piperidine, morpholine) may be formed. R ₈ is a hydrogen atom, an alkyl group (methyl, ethyl, methoxyethyl, hydroxyethyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.), an aryl group (phenyl, naphthyl, etc.), a heterocycle Group (2,2,
6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl and the like).

Specific examples of the compound represented by the general formula [Ha] are shown below. However, the present invention is not limited to these.

[0042]

[Chemical 6]

[0043]

[Chemical 7]

[0044]

[Chemical 8]

[0045]

[Chemical 9]

[0046]

[Chemical 10]

[0047]

[Chemical 11]

[0048]

[Chemical 12]

[0049]

[Chemical 13]

The synthetic method of the compound represented by the general formula [H] used in the present invention is described in JP-A Nos. 62-180361 and 62-178246.
No. 63-234245, No. 63-234246, No. 64-90439, JP-A No. 2-37, No. 2-841, No. 2-947, No. 2-120736, No.
2-230233, 3-125134, U.S. Patent 4,686,167,
4,988,604, 4,994,365, European patent 253,665
No. 333,435, etc. can be referred to.

The amount of the compound represented by the general formula [H] used in the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
It is preferably in the molar range.

In the present invention, when the compound represented by the general formula [H] is contained in the photographic light-sensitive material, it is contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

A so-called nucleation accelerator can be added to the silver halide photographic light-sensitive material of the present invention. Examples of the nucleation accelerator include those represented by the following general formula [Na] or [Nb].

[0054]

[Chemical 14]

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. A ring can be formed by R ₁ , R ₂ and R ₃ . 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 molecular weight of 300 or more is more preferable. Further, preferable adsorption groups include heterocycle, mercapto group, thioether group, thione group, thiourea group and the like.

Specific compounds include those shown below.

[0057]

[Chemical 15]

[0058]

[Chemical 16]

[0059]

[Chemical 17]

[0060]

[Chemical 18]

In the general formula [Nb], Ar represents a substituted or unsubstituted aryl group or heteroaromatic ring. R represents an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have a preferable diffusion resistant group, the molecular weight is preferably 120 or more, particularly preferably 300 or more.

Specific compounds include those shown below.

[0063]

[Chemical 19]

[0064]

[Chemical 20]

In the light-sensitive material of the present invention, it is preferable to provide at least one conductive layer on the support. As a typical method for forming the conductive layer, a water-soluble conductive polymer,
There are a method of forming using a hydrophobic polymer and a curing agent and a method of forming using a metal oxide. For these methods, for example, the methods described in JP-A-3-265842, page [H] to page (15) can be used. The silver halide emulsion used in the present invention includes, for example, silver bromide as silver halide,
Although any of silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride and the like used for ordinary silver halide emulsions can be used, silver chlorobromide and silver bromide are preferable. Alternatively, it is silver iodobromide or silver chloroiodobromide containing 4 mol% or less of silver iodide.

Further, (standard deviation of particle size) / (average value of particle size) × 1
Monodisperse particles having a coefficient of variation represented by 00 of 15% or less are preferable.

In the light-sensitive material of the present invention, the total amount of gelatin on the emulsion layer side is preferably 3.5 g / m ² or less. What is the emulsion layer side?
The side of a layer having a silver halide emulsion with respect to the support, and includes a silver halide emulsion layer, a hydrophilic colloid layer containing a redox compound capable of releasing a development inhibitor compound when oxidized, and other layers. As other layers,
Examples thereof include an emulsion protection layer, an antihalation layer, a UV absorption layer, an intermediate layer, and a conductive layer. Silver halide emulsion layers, although the total amount of gelatin contained in the hydrophilic colloid layer and other layers containing a redox compound is 3.5 g / m ² or less, preferably 0.5~3.3g / m ^2.

The support used in the present invention is not particularly limited, but polyethylene terephthalate and triacetyl cellulose are preferable. The thickness of the support is preferably 150 to 250 μm.

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention. Further, a polymer latex can be contained in the silver halide photographic emulsion and the backing layer of the present invention.

These additives are described in more detail in Research Disclosure (RD) Vol. 176 Item / 7643 (197
December 1988) and Volume 187, Item / 8716 (November 1979), and the relevant parts are summarized below.

Additive type RD / 7643 RD / 8716 Chemical sensitizer page 23, page 648, right column Sensitivity enhancer, same as above, whitening agent, page 24 Antifoggants and stabilizers, pages 24 to 25, page 649, right column Light absorbers, filters Dyes 25-26 pages 649 right column-UV absorbers 650 left column Stain inhibitors 25 pages right column 650 left-right columns Dye image stabilizers 25 pages Hardeners 26 pages 651 left columns Binders 26 pages Same as above Plastics Agents, lubricants page 27, page 650, right column, coating aids, surfactants, pages 26 to 27, same as above, antistatic agent, page 27, same as above The silver halide photographic light-sensitive material according to the present invention can be subjected to various methods after exposure, for example, commonly used methods. Can be developed.

Examples of the developing agent that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromhydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone and 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 (eg o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2 , 4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (tato) If 1
-(p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-
Methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.) alone or Although they can be used in combination, it is preferable to use them in a combination of 3-pyrazolidones and dihydroxybenzenes or a combination of aminophenols and dihydroxybenzenes. The developing agent is usually preferably used in an amount of 0.01 to 1.4 mol / l.

In the present invention, examples of sulfites and metabisulfites used as preservatives include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably 0.25 mol / l or more. It is particularly preferably 0.4 mol / l or more.

In the developer, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a silver sludge inhibitor (for example, JP-B-62-4702, JP-A-03-51844).
No. 04-26838, No. 04-362942, No. 01-319031, etc.), pH buffer (for example, carbonate, phosphate, borate, boric acid, acetic acid, citric acid) , Alkanolamines, etc., dissolution aids (eg polyethylene glycols, their esters, alkanolamines etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.), surface active agents Agents, antifoaming agents, antifoggants (for example, halogens such as potassium bromide, sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example, Ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetate,
Polyphosphate, etc., development accelerator (eg US Pat. No.
2,304,025, compounds described in Japanese Patent Publication No. 47-45541, etc.), hardeners (eg glutaraldehyde or
The bisulfite adduct, etc.), or an antifoaming agent can be added. The pH of the developer is preferably adjusted to 9.5-12.0.

In the present invention, as a special form of development processing, an activator processing solution which contains a developing agent in a light-sensitive material, for example, an emulsion layer, and processes the light-sensitive material in an alkaline aqueous solution to perform development may be used. . Such a development process, in combination with a thiocyanate silver salt stabilization treatment,
It is often used as one of the methods for rapid processing of a light-sensitive material, and the effects of the present invention can be obtained even when rapid processing is performed with such a processing solution.

As the fixing liquid, those having a generally used composition can be used. The fixer is generally an aqueous solution containing a fixer and others, and the pH is usually 3.8 to 5.8. As a fixing agent, sodium thiosulfate, potassium thiosulfate,
Use of thiosulfates such as ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, as well as organic sulfur compounds capable of forming soluble stable silver complex salts, which are known as fixing agents. You can

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

If desired, the fixer may include a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent having a water softening ability. And the like.

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

In the development processing of the present invention, the development temperature is
It can be set to a normal temperature range of 20-30 ° C,
It can also be set to a high temperature treatment range of 30 to 40 ° C.

The black-and-white silver halide photographic light-sensitive material according to the present invention is preferably processed by using an automatic processor.
At that time, processing is performed while replenishing a fixed amount of developing solution and fixing solution proportional to the area of the light-sensitive material. The development replenishment amount is
In order to reduce the amount of waste liquid, the amount of developer is 350 ml or less per 1 m ² . It is preferably 75 ml or more and 280 ml or less per 1 m ² . Particularly preferably, it is 75 ml or more and 150 ml or less per 1 m ² . The fixing replenishing amount is 480 ml or less, preferably 100 to 400 ml.

According to the present invention, in order to shorten the developing time, 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 set when the processing is performed by using the automatic developing machine. It is preferably 20 to 60 seconds. The total processing time referred to here includes all process times required for processing a black and white silver halide photographic light-sensitive material, and specifically includes, for example, development, fixing, bleaching, washing with water, stabilization processing and drying necessary for processing. The time including all process times, that is, Dr
It's y to Dry time. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 30 to 60 seconds.

A compound represented by the following general formula [P] is preferably added to the developing solution which can be used in the present invention.

[0084]

[Chemical 21]

In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom, --S
M ₁ group, hydroxy group, lower alkoxy group, -COOM ₂
Group, an amino group, a —SO ₃ M ₃ group or a lower alkyl group, and at least one of R ₁ , R ₂ and R ₃ represents a —SM ₁ group. M ₁ , M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different.

In the above general formula [P], R ₁ , R ₂ ,
The lower alkyl group and the lower alkoxy group represented by R ₃ are each a group having 1 to 5 carbon atoms, which may further have a substituent, preferably 1 to 5 carbon atoms.
The amino group represented by R ₁ , R ₂ and R ₃ is a group having 3 groups, represents a substituted or unsubstituted amino group, and a preferred substituent is a lower alkyl group.

In the above general formula [P], the ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

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

[0089]

[Chemical formula 22]

[0090]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (Preparation of Silver Halide Emulsion A) A silver chloroiodobromide emulsion containing 70 mol% of silver chloride, 0.2 mol% of silver iodide and the rest of silver bromide was prepared by the simultaneous mixing method. . At the time of simultaneous mixing, K ₃ RhBr ₆ was added at 8.1 × 10 ^-8 mol per mol of silver. The resulting emulsion was a cubic, monodisperse grain with a mean grain size of 0.20 μm (variation coefficient 9
%) Emulsion. Then, the emulsion was desalted with a modified gelatin described in JP-A-2-280139 (wherein the amino group in gelatin was replaced with henylcarbamyl, for example, G-8 in JP-A-2-280139). The EAg after desalting was 190 mv at 50 ° C.

The emulsion thus obtained was adjusted to pH 5.58 and EAg123 mV, and the temperature was adjusted to 60 ° C., and chloroauric acid was added per mol of silver.
After 2.2 × 10 ^-5 mol was added and stirred for 2 minutes, 2.9 × 10 ^-6 mol of S ₈ was added per 1 mol of silver, and chemical ripening was further performed for 78 minutes. At the end of ripening, the following was added per mol of silver.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7.5 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3.5 × 10 ^-4 mol and gelatin 28.4 g An emulsion liquid was added.

(Preparation of silver halide photographic light-sensitive material) The following formulation was prepared on one undercoat layer of a polyethylene terephthalate film having a thickness of 180 μm and subjected to the antistatic treatment described in Example 1 of JP-A-3-92175. The silver halide emulsion of No. 1 was coated so that the amount of silver was 3.3 g / m ² and the amount of gelatin was 1.5 g / m ² .

Furthermore, the following formulation 2 was provided as a protective layer on top of it.
The coating liquid of was coated to a gelatin amount of 0.6 g / m ^2, and the antihalation layer of the following prescription 3 was coated with a gelatin amount of 1.5 g / m 2.
^It was applied so as to be ² . A polymer layer having the following formulation 4 was applied on the undercoat layer on the opposite side.

Formulation 1 (composition of silver halide emulsion layers)

[0097]

[Chemical formula 23]

S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.64 mg / m ² 2-mercapto-6-hydroxypurine 1.7 g / m ² Formulation 2 (emulsion protective layer composition) S-1 12 mg / M ² Matting agent: spherical monodisperse polymethylmethacrylate with an average particle size of 3.0 μm 22 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ²

[0099]

[Chemical formula 24]

[0100] The latex polymer L 0.4 g / m ² formulation 3 (antihalation layer composition) saponin ^{133mg / m 2 S-1 6mg} / m 2 latex polymer L 0.8 mg / ^{m 2}

[0101]

[Chemical 25]

Formulation 4 (hydrophobic polymer layer) Methyl methacrylate: Latex of acrylic acid = 97: 3 1.5 g / m ² Matting agent: 20 mg / m ² of spherical monodisperse polymethyl methacrylate having an average particle size of 8 μm (comparative example) The polymer layer was removed from the constituent layers of the invention, the antihalation layer as the lower emulsion layer was coated on the backing side so that the gelatin was 1.5 g / m ² , and the backing protective layer so that the gelatin was 1 g / m ^{2 on the} upper layer. A sample similar to the above formulation was prepared except that was applied.

An automatic developing machine for rapid processing (GR-26SR Konica) was prepared from these samples using a developing solution and a fixing solution having the following compositions.
(Manufactured by [Co.]) under the following conditions.

(Developer Formulation) Sodium sulfite 55 g / liter Potassium carbonate 40 g / liter Hydroquinone 24 g / liter 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (Dimeson S) 0.9 g / liter Potassium bromide 5 g / Liter 5-methyl-benzotriazole 0.13 g / liter boric acid 2.2 g / liter diethylene glycol 40 g / liter Exemplified P-1 60 mg / liter Add water and potassium hydroxide to make 1 liter / pH 10.5.

(Fixing Solution Formulation) (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g (Composition B) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 26.5 g When using the fixer, add the above in 500 ml of water. The composition A and the composition B were melted in this order and finished to 1 liter before use. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development 38 ° C. 12 seconds Fixing 35 ° C. 10 seconds Washing at room temperature 10 seconds Drying 50 ° C. 13 seconds .

The above samples were evaluated as follows.

(Evaluation of Drying Property and Stain Adhesion Property) The obtained sample was exposed to a blackening rate of 50%, and treated with the above-mentioned treating agent and treating conditions by the above-mentioned rapid processing automatic developing machine for 1000 m ^2. After that, visual evaluation was performed.

Dryability ◯: Completely dry, Δ: There is a part in a dry state, ×: The whole is wet Dirt ◯: No adhesion, Δ: Little adhesion, ×: Large adhesion (image evaluation) A step wedge is attached to the sample. Contact exposure 48
After performing xenon flash exposure through an 8 nm interference filter, processing was performed under the following conditions. The concentration of the obtained sample was measured, and the relative sensitivity was evaluated with γ of 0.1 to 3.0.

The results are shown in Table 1.

[0111]

[Table 1]

As is clear from the table, sample No. 6 of the present invention
To 12 are stains, dryness, and
It can be seen that the result is excellent, and the relative sensitivity and γ are also good.

[0113]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having a high image quality and an excellent drying property even in a low replenishment and rapid processing, and having little stain adhesion in the processing step, and a processing method thereof. .

Claims (6)

[Claims] 1. A method for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and an emulsion protective layer on a support, wherein the opposite side of the silver halide emulsion layer is substantially sandwiched between the supports. A method for processing a silver halide photographic light-sensitive material, which comprises a water-impermeable layer and which is processed in a replenishing amount of 350 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material. 2. A method of processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and an emulsion protective layer on a support, wherein the opposite side of the silver halide emulsion layer is substantially sandwiched between the supports. And a fixing replenishing amount of 480 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material, the processing method of the silver halide photographic light-sensitive material. 3. A method of processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and an emulsion protective layer on a support, wherein the opposite side of the silver halide emulsion layer is substantially sandwiched between the supports. Of a silver halide photographic light-sensitive material characterized by comprising a water-impermeable layer and a development replenishment amount of 350 ml or less and a fixing replenishment amount of 480 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material. Processing method. 4. The silver halide photographic light-sensitive material according to claim 1, wherein at least one layer of the silver halide photographic light-sensitive material according to any one of claims 1 to 3 contains a hydrazine derivative. Processing method. 5. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the pH of the developing solution is less than 11.2. Processing method of silver photographic light-sensitive material. 6. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and an emulsion protective layer on a support, wherein any one layer on the silver halide emulsion surface side has a hydrazine derivative having the following structure. A silver halide photographic light-sensitive material containing the emulsion layer and a substantially water-impermeable layer on the opposite side of the emulsion layer. [Chemical 1] [In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, and B represents an acyl group, an alkyl or arylsulfonyl group, a carbamoyl group, an alkoxy or aryloxycarbonyl group, a sulfamoyl group, a sulfinamoyl group, an alkoxysulfonyl group. , A thioacyl group, a thiocarbamoyl group, an oxalyl group, or a heterocyclic group, and A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is an acyl group, a sulfonyl group, or an oxalyl group. However, B, A ₂ and the nitrogen atom to which they are bonded may form a partial structure —N═C <of hydrazone. ]