JP2873854B2 - Processing method of silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a photographic light-sensitive material having a silver halide light-sensitive layer on a support, and more particularly to a silver halide photographic light-sensitive material capable of obtaining high contrast. The present invention relates to a material processing method.

[Background of the Invention]

Generally, in the photoengraving process, a photographic image in which characters and halftones are decomposed, and in the ultra-precision photoengraving process, a photographic image having a high contrast is used for forming a fine line image.

In some kinds of silver halide photographic materials for this purpose,
It is known that photographic images with extremely high contrast can be formed.

Conventionally, for example, a light-sensitive material comprising a silver chlorobromide emulsion having an average particle diameter of 0.2 μm, a narrow particle distribution, a uniform particle shape, and a high silver chloride content (at least 50 mol% or more) was prepared using a sulfite ion concentration A high contrast, high sharpness, and high resolution image, for example, a halftone image or a fine line image is obtained by processing with an alkaline hydroquinone developer having a low image density.

This type of silver halide photosensitive material is known as a lith type photosensitive material.

The photoengraving process includes a step of converting a continuous tone original into a halftone image, that is, a step of converting a continuous tone density change of the original into a set of halftone dots having an area proportional to the density. I have.

For this purpose, a document is photographed through the intersecting screen or the contact screen using the lith-type photosensitive material, and then subjected to a development process to form a halftone image.

For this purpose, silver halide photographic light-sensitive materials containing silver halide emulsions of fine grains and having a uniform grain size and shape are used. In the case of processing with a developing solution for use, it is inferior to the case of developing with a lith type developing solution in dot image formation and the like. Therefore, the sulphite ion concentration is extremely low, and processing is carried out with a developing solution called a lith-type developing solution which is a hydroquinone monopharmaceutical as a developing agent.

However, since the squirrel-type developer is very susceptible to auto-oxidation and has extremely poor preservation, a control method for keeping the development quality constant even during continuous use is required as much as possible. Great efforts have been made to improve sex.

As a method of improving the replenishment, a replenisher (replenishment of processing fatigue) for compensating for the deterioration of the activity due to the development process and a replenisher (for replenishing the oxidation deterioration due to aging) in order to maintain the preservation of the squirrel-type developer. The so-called two-liquid separation replenishment method, in which replenishment over time (fatigue replenishment over time) is carried out using separate replenishers, is generally widely used in automatic developing machines for photolithography.

However, the above method has a drawback that the control of the replenishment balance of the two liquids needs to be controlled, which complicates the apparatus and the operation.

Also, in lith-type development, an image cannot be obtained quickly because the time (induction period) until an image appears by development is long.

On the other hand, there is known a method of obtaining an image with high contrast quickly without using the lithographic developer. For example, U.S. Patent No. 2,419,975, JP-A-51-16623 and
As disclosed in JP-A-51-20921 and JP-A-56-106244, a hydrazine derivative is contained in a silver halide photosensitive material.

According to these methods, the sulfite ion concentration in the developer can be kept high, and the processing can be performed in a state where the preservation property is enhanced.

However, in these methods, the hydrazine derivative must be treated with a developer having a pH of 11 or more in order to sufficiently exhibit the high contrast. pH 11 or higher
When a developer having a pH is exposed to air, the developing agent is easily oxidized. Although it is more stable than the squirrel developing solution, an ultra-high contrast image is often not obtained due to oxidation of the developing agent.

To compensate for this drawback, JP-A-63-29751 and EP-A-333435 disclose silver halide photographic materials containing a high contrast agent which makes high contrast even with a developer having a relatively low pH.

However, when a silver halide photographic light-sensitive material containing such a high contrast agent is processed with a developer having a pH of less than 11, the high contrast is insufficient and satisfactory dot performance cannot be obtained at present. .

[Object of the invention]

In view of the above problems, an object of the present invention is to provide a processing method which has high stability against air oxidation and can obtain an image having a super-high contrast.

[Configuration of the invention]

The object of the present invention is to provide a support having at least one silver halide photographic emulsion layer on a support and containing a hydrazine derivative in the silver halide emulsion layer and / or an adjacent layer thereof.
And the surface pH of the surface on which the photographic emulsion layer is coated
Is achieved by processing a silver halide photographic material having a pH of 6.0 or more with a developer having a pH of less than 11.

The hydrazine derivative used in the present invention is preferably represented by the following general formula [I] or general formula [II].

General formula [I] In the formula, R ₁₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₂ represents a hydrogen atom or a block group. Ar represents an arylene group or a heterocyclic group, one of A ₁ and A ₂ are the other is a hydrogen atom and a hydrogen atom, an acyl group, a sulfonyl group or an oxalyl group.

General formula (II) In the formula, R ₂₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, R ₂₂ represents an alkylene group or an alkenylene group, and R ₂₃ represents a hydrogen atom or an alkyl group. , R represents a hydrogen atom or a block group, Ar represents an arylene group or a heterocyclic group,
One of A ₁ and A ₂ represents a hydrogen atom, and the other represents a hydrogen atom, an acyl group, a sulfonyl group, or an oxalyl group.

Hereinafter, the specific configuration of the present invention will be described in more detail.

The general formula [I] will be described in more detail. R ₁₁ represents an alkyl group (for example, a group such as octyl, t-octyl, decyl, dodecyl, or tetradecyl), an aryl group (for example, a group such as phenyl, p-propyl, phenyl, or naphthyl);
Represents a heterocyclic group (for example, a group such as pyridyl, tetrazoline, oxazolyl, benzolooxazolyl, benzothiazolyl, and benzoimidazolyl). Preferred as the alkyl group for R _{11 is} a group having 6 to 20 carbon atoms.

Preferred as the aryl group for R ₁₁ are It is represented by

X represents a substituted or unsubstituted alkyl group (for example, a group such as methyl, ethyl, methoxy, i-propyl), an acylamino (for example, a group such as octaneamide, tetradecaneamide), or a ureide (for example, hexylureide, δ- (2,4
-Di-t-acylphenoxy) butylureido, etc.), hydrazinocarbonylamino (eg, 2,2-dibutylhydrazinocarbonylamino, 2-phenyl-2-
Groups such as methylhydrazinocarbonylamino), sulfonamides (eg, groups such as hexadecanesulfonamide, 4-butoxybenzenesulfonamide, and morpholinosulfonamide), and aminosulfonamides (eg, N, N-dibutylsulfamoylamino, N, N- dimethylsulfamoyl group amino, etc.), aryloxycarbonylamino (e.g. octyloxycarbonylamino, groups such as benzyloxycarbonyl amino), - S- carbonylamino (e.g. _{C 8 H 17 SCONH-, C 6} H 5 SCONH -Group etc.) Represents each group.

R ₁ and R ₂ each represent a hydrogen atom, an alkyl (for example, a group such as methyl, ethyl, propyl, butyl, or cyclohexyl), an aryl (for example, a group such as phenyl or naphthyl),
Representing each group of a heterocyclic ring (for example, a group such as pyridyl, thienyl, piperidino, and morpholino), R ₁ and R ₂ may form a ring together with a nitrogen atom (for example, a ring such as piperidino, piperazino, and morpholino), May be formed.

R ₄ and R ₅ are each a hydrogen atom or a substitutable group (eg, an alkyl, aryl, heterocyclic group, etc.) and a ring (eg, cyclohexane, thiazole, oxazole,
A ring such as benzothiazole may be formed.

R ₃ represents a hydrogen atom, aryl (for example, a group such as phenyl or naphthyl), or a heterocyclic group (for example, a group such as piperidino, monophorino, tetrahydropranyl, pyridyl, or thienyl).

Z ₁ is a substitutable group (eg, alkyl, aryl, heterocycle, hydroxy, alkoxy, amino, acylamino,
Ureido, hydrazinocarbonylamino, sulfonamide, aminosulfonamide, oxycarbonylamino,
-S-carbonylamino, Carbamoyl, sulfamoyl, halogen and the like).

A ₁ and A ₂ are both a hydrogen atom, or one is a hydrogen atom and the other is an acyl (for example, a group such as acetyl or trifluoroacetyl), a sulfonyl (for example, a group such as metasulfonyl or toluenesulfonyl), an oxalyl (for example, ethoxalyl or the like). It represents the name of the radical), and most preferably a ₁ and a ₂ are both hydrogen atoms. R ₁₂ is a hydrogen atom, or an alkyl (for example, a group such as methyl, ethyl, benzyl, methoxymethyl, trifluoromethyl, phenoxymethyl, hydroxymethyl, methylthiomethyl, or phenylthiomethyl), or an aryl (for example, phenyl, Groups such as chlorophenyl), heterocycles (eg, groups such as pyridyl, thienyl, furyl), Are preferred.

R ₆ and R ₇ are a hydrogen atom, an alkyl (for example, a group such as methyl, ethyl, or benzyl), an alkenyl (for example, a group such as allyl or butenyl), an alkynyl (for example, a group such as propargyl or butynyl), or an aryl (for example, phenyl or naphthyl) A heterocycle (e.g., 2,2,6,6-tetramethylpiperidinyl, N-ethyl-N'-ethylpyrazolidinyl,
Groups such as pyridinyl), hydroxy, alkoxy (for example, groups such as methoxy and ethoxy), amino (for example, amino,
Represent each group of methyl groups for amino, etc.), it may form a ring together with the nitrogen atom in R ₆ and R ₇ (e.g. piperidino, ring morpholino).

R ₈ is a hydrogen atom, an alkyl (eg, a group such as methyl, ethyl, hydroxyethyl), an alkenyl (eg, allyl,
Groups such as butenyl), alkynyl (eg, propargyl,
Name groups of groups such as butynyl), aryls (eg, groups such as phenyl and naphthyl), and heterocycles (groups such as 2,2,6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl) Represents

 The following are specific examples of the compounds.

Specific compound examples Next, the general formula [II] will be described in more detail.

R ₂₁ is a hydrogen atom, an alkyl group (for example, a group such as methyl, ethyl, i-propyl, butyl, t-butyl, hexyl, octyl, t-octyl, decyl, dodecyl, tetradecyl, cyclohexylmethyl, benzyl, etc.), and a cycloalkyl group (For example, groups such as cyclohexyl and 4-chlorocyclohexyl), alkenyl groups (for example, allyl, 1-
Propenyl, 1,3-butadienyl, 2-butenyl, 2-
Pentenyl, cinnamyl, etc.), alkynyl group (eg, propargyl, 2-butynyl, etc.), aryl group (eg, phenyl, pt-butylphenyl, naphthyl, etc.), heterocyclic group (eg, pyridyl, tetrazolyl, Oxazolyl, benzoxazolyl, benzothiazolyl, benzoimidazolyl, etc.), but the heterocyclic group preferably does not contain a mercapto group.

R ₂₂ is an alkylene group (for example, methylene, ethylene, trimethylene, methylmethylene, ethylmethylene, butylmethylene, hexylmethylene, decylmethylene, etc.)
Or an alkenylene group (for example, a group such as propenylene and butenylene).

R ₂₃ represents a hydrogen atom or an alkyl group (for example, a group such as methyl, ethyl and benzyl).

Ar represents an arylene group (for example, a group such as phenylene or naphthylene) or a heterocyclic group (for example, pyridine, thiophene,
(A bivalent group such as furan).

The arylene group or heterocyclic group represented by Ar includes those having a substituent such as alkyl, alkoxy, hydroxyl, halogen, amino, acylamino, sulfonamide, and ureide.

R represents a hydrogen atom or an alkyl group (for example, a group such as methyl, ethyl, benzyl, methoxymethyl, trifluoromethyl, phenoxymethyl, hydroxymethyl, methylthiomethyl, phenylthiomethyl) as a blocking group, or an aryl group (for example, phenyl, Groups such as chlorophenyl), heterocyclic groups (eg, groups such as pyridyl, thienyl, furyl), And the like.

R ₂₄ and R ₂₅ represent a hydrogen atom, an alkyl group (eg, methyl,
Groups such as ethyl and benzyl), alkenyl groups (such as allyl and butenyl), alkynyl groups (such as propargyl and butynyl), aryl groups (such as phenyl and naphthyl) and heterocyclic groups (such as 2 , 2,6,6-
Groups such as tetramethylpiperidinyl, N-ethyl-N'-ethylpyrazolidinyl, pyridyl), a hydroxyl group,
Represents an alkoxy group (for example, a group such as methoxy or ethoxy), an amino group (for example, a group such as amino or methylamino),
R ₂₄ and R ₂₅ may form a ring together with the nitrogen atom (for example, a ring such as piperidino and morpholino may be formed).

R ₂₆ is a hydrogen atom, an alkyl group (for example, a group such as methyl, ethyl, methoxymethyl, or hydroxyethyl), an alkenyl group (for example, a group such as allyl or butenyl), an alkynyl group (for example, a group such as propargyl or butynyl), or an aryl group (For example, groups such as phenyl and naphthyl) and a heterocyclic group (for example, groups such as 2,2,6,6-tetramethylpiperidinyl, N-methylpiperidinyl, and pyridyl).

One of A ₁ and A ₂ is a hydrogen atom, the other is a hydrogen atom, an acyl group (for example, a group such as acetyl and trifluoroacetyl), a sulfonyl group (for example, a group such as methanesulfonyl and toluenesulfonyl), and an oxalyl group (for example, ethoxalyl) And A ₁ and A ₂ are most preferably both hydrogen atoms.

Representative specific compounds represented by the above general formula [II] are shown below, but the compounds that can be used in the present invention are not limited thereto.

Next, a method for synthesizing the compound of the present invention will be described. For example, compound (II-1) can be synthesized from the intermediate described in EP 330,109 according to the following synthesis method.

Compound (II-32) can be synthesized from the intermediate described in Japanese Patent Application No. 62-336565 according to the following synthesis method.

Other compounds can be synthesized by the same synthesis method.

Next, a preferred embodiment in which the silver halide photosensitive material of the present invention is applied to a photosensitive material exhibiting photographic characteristics with high contrast will be described.

In a silver halide photographic light-sensitive material capable of obtaining a high-contrast image to which the present invention is applied, at least one of the compounds represented by the above general formulas (I) and (II) functions as a high contrast agent Although contained as a substance, the amount of the compounds of the general formulas [I] and [II] contained in the photographic light-sensitive material is from 5 × 10 ^-7 mol to 1 mol of silver halide contained in the photographic light-sensitive material. It is preferably 5 × 10 ^-1 mol.

In particular, it is preferably in the range of 5 × 10 ^-6 mol to 1 × 10 ^-2 mol.

The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support. The silver halide emulsion can be coated directly on the support or can be coated via another layer such as a hydrophilic colloid layer containing no silver halide emulsion. A hydrophilic colloid layer as a protective layer may be provided on the emulsion layer. Further, the silver halide emulsion layer may be separately applied to silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between the silver halide emulsion layers. That is, an intermediate layer made of a hydrophilic colloid may be provided as necessary. Further, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer, and a backing layer may be provided between the silver halide emulsion layer and the protective layer.

In the present invention, it is necessary that the surface pH of the surface on the side on which the emulsion layer is provided be 6.0 or more. Preferably the pH is in the range of 6.0 to 7.5, more preferably pH 6.0 to
It is in the range of 6.8. If the pH is less than 6.0, the contrast is not sufficient, and if the pH exceeds 7.5, fog may occur during storage of the raw sample.

Here, the film surface pH in the present invention is a value measured using a silver chloride flat electrode after adding 0.05 cc of water to 1 cm ² photographic light-sensitive material, leaving it for 10 minutes in an atmosphere of 90% RH or more. is there. Specific examples of the flat electrode include a flat electrode GST-5313F manufactured by Toa Denpa Kogyo Co., Ltd.

The compounds represented by the general formulas [I] and [II] are contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention.

Next, the silver halide used in the silver halide photographic light-sensitive material of the present invention will be described.

Any composition can be used as the silver halide. For example, there are silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide and silver iodobromide. The average grain size of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, and more preferably 0.10 to 0.40 μm.

The particle size distribution of the silver halide grains used in the present invention is arbitrary, but is preferably adjusted so that the value of the monodispersity defined below is from 1 to 30, and more preferably from 5 to 20.

Here, the monodispersity is defined as a value obtained by multiplying the value obtained by dividing the standard deviation of the particle size by the average particle size by 100. For convenience, the grain size of silver halide grains is represented by a ridge length in the case of cubic grains, and other grains (octahedral, tetrahedral, etc.)
Is calculated by the square root of the projected area.

In practicing the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used, for example, silver iodobromide in the core and bromide in the shell. What consists of silver iodobromide grains which are silver can be used. At this time, iodine can be contained in any layer within 5 mol%.

The silver halide grains used in the silver halide emulsion of the present invention can be formed by a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including complex salts), and a rhodium during the process of forming and / or growing the grains. A metal ion is added using at least one selected from a salt (including complex salt) and an iron salt (including complex salt), and these metal elements can be contained inside the particles and / or on the surface of the particles; By arranging in an appropriate reducing atmosphere, reduction sensitization can be imparted to the inside and / or the surface of the grains.

Furthermore, silver halide can be sensitized by various chemical sensitizers. As the sensitizer, for example,
Active gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, etc.), selenium sensitizer (N, N-dimethylselenourea, selenourea, etc.), reduction sensitizer (tri- Ethylene tetramine, stannous silver chloride, etc.) such as potassium chloroaulite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc. The representative various noble metal sensitizers can be used alone or in combination of two or more. When a gold sensitizer is used, rhodamonmon can also be used as an auxiliary agent.

The silver halide grains used in the present invention can be preferably applied to grains having a surface sensitivity higher than the internal sensitivity, that is, silver halide grains giving a so-called negative image. Can be enhanced.

The silver halide emulsion used in the present invention may be a mercapto (1-phenyl-5-mercaptotetrazole,
Stabilized using 2-mercaptobenzthiazole), benzotriazoles (5-bromobenzotriazole-5-methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole), indazoles (5-nitroindazole), or the like. Fog suppression can be performed.

In the photosensitive silver halide emulsion layer or its adjacent layer, Research Disclosure 1746 is used for the purpose of increasing sensitivity, increasing contrast, or accelerating development.
Compounds described in No. 3 in the paragraphs XXI BD can be added.

The silver halide emulsion used in the present invention may contain a sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener, and the like. When the compound of the general formula according to the present invention is added to a hydrophilic colloid layer, gelatin is suitable as a binder for the hydrophilic colloid layer, but a hydrophilic colloid other than gelatin can also be used. These hydrophilic binders are preferably applied on both sides of the support at 10 g / m ² or less.

Examples of the support used in the practice of the present invention include polyester films such as baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, for example, polyethylene terephthalate. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material.

For the development processing of the silver halide photographic light-sensitive material of the present invention, for example, the following developing agents are used.

Representative HO- (CH = CH) n-OH type developing agents include hydroquinone, and catechol, pyrogallol and the like.

Also, HO- (CH = CH) The n-NH ₂ type developer, the ortho and para-aminophenol or aminopyrazolone those typical, N- methyl -p- aminophenol, N-beta-hydroxyethyl -P-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like.

Heterocyclic developers include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl -4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
And pyrazolidones.

In addition, The James of the Theory of the James
Photographic Process 4th Edition (The Theory of th
e Photographic Process, Fourth Edition) 291-334
Pages and Journal of the American Chemical
Society (Journal of the American Chemical Socie
ty) Developers described in Vol. 73, page 3, 100 (1951) can be used effectively in the present invention. These developers may be used alone or in combination of two or more, but it is preferable to use two or more in combination.

Further, even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the light-sensitive material of the present invention, the effects of the present invention are not impaired. Also, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, it can have a pH adjustment and buffer function with caustic alkali, alkali carbonate, amine or the like as used in general black and white developers.

The present invention is characterized in that a developer having a pH of less than 11 can be used. Preferably, the pH is 10.0 to 10.9. Further, the developer may include an inorganic development inhibitor such as bromkari, an organic development inhibitor such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine, 1-phenyl-5-mercaptotetrazole, ethylenediamine. Metal ion scavengers such as tetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol and polyalkylene oxide; surfactants such as sodium alkylarylsulfonate, natural saponins, sugars and alkylesters of the above compounds, glutar It is optional to add a hardening agent such as aldehyde, formalin and glyoxal, and an ionic strength adjusting agent such as sodium sulfate.

The developer used in the present invention may contain alkanolamines such as diethanolamine and triethanolamine and glycols such as diethylene glycol and triethylene glycol as organic solvents. Alkylamino alcohols such as diethylamino-1,2-propanediol and butylaminopropanol can be particularly preferably used.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of silver halide photographic emulsion A) A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by a double jet method. During this mixing, 8 × 10 ^-7 mol of K ₂ IrCl ₆ was added per mol of silver. The resulting emulsion was an emulsion composed of monodisperse (monodispersity: 10) cubic grains having an average grain size of 0.24 μm. After adding 6.5 cc of 1% aqueous solution of potassium iodide per mol of silver to this emulsion, modified gelatin (exemplary compound G-8 of Japanese Patent Application No. 1-180787) was added, and the process of Japanese Patent Application No. 1-180787 was carried out. Washing and desalting were carried out in the same manner as in the example. The pAg at 40 ° C. after desalting was 8.0.

Further, at the time of redispersion, a mixture of the following compounds [A], [B] and [C] was added.

Compound [A] + [B] + [C] (Preparation of silver halide photographic light-sensitive material) One undercoat layer of a 100 μm-thick polyethylene terephthalate film having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) On top, a silver halide emulsion layer having the following formula (1) was prepared with a gelatin amount of 2.0 g / m ² ,
Coating is performed so that the amount of silver becomes 3.2 g / m ^2, and a protective layer having the following formulation (2) is further coated thereon so that the amount of gelatin becomes 1.0 g / m ^2, and the other side is further coated. On the undercoat layer, a backing layer was coated according to the following formula (3) so that the amount of gelatin became 2.4 g / m ^2, and a protective layer having the following formula (4) was further coated thereon with a gelatin amount of 1 g. / m ² to become like to be coated sample No.1~1
8 got.

Compound according to the present invention or comparative compound Amount shown in Table 1 Formulation (4) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: Polymethyl methacrylate 50 mg / m ² having an average particle size of 3.0 to 5.0 μm Surfactant: S-2 10 mg / m ² Hardening agent: Glyoxal 25 mg / m ² : H-1 35 mg / m ^{2 The} obtained sample was brought into close contact with a step wedge, exposed to tungsten light of 3200K for 5 seconds, and then rapidly developed with a developer and a fixer having the composition shown in Table 1. Was processed under the following conditions. The above-described method was used for measuring the membrane surface pH.

Fixer formulation (Composition A) Ammonium thia sulfate (72.5% w / v aqueous solution) 240ml Sodium sulfite 17g Sodium sulfate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g (Composition B) Pure water (ion exchange water) 17ml sulfate (50% w / w aqueous solution of) 4.7 g aluminum sulfate (Al ₂ O ₃ in terms of content of 8.1% w / w aqueous solution) 26.5 g fixer above composition a in water 500ml when using, in the order of composition B Melted and finished to 1 for use. The pH of the fixing solution was adjusted to 4.8 with acetic acid.

(Processing conditions) (Process) (Temperature) (Time) Current image 40 ° C 15 seconds Fixed 35 ° C 15 seconds Rinse 30 ° C 10 seconds Dry 50 ° C 10 seconds The obtained sample is subjected to Konica digital densitometer. The measurement was performed using PDP-65, and the relative sensitivity was represented by setting the sensitivity of Sample No. 1 at a density of 3.0 as 100, and gamma was indicated by the tangent of the density of 0.3 and 3.0. Unavailable with gamma values less than 6,
A gamma value of 6 or more and less than 10 still has insufficient high contrast performance. When the gamma value is 10 or more, the image becomes a super-high contrast image, and is sufficiently practical.

In order to further examine the stability against air oxidation, the prepared developer was allowed to stand at room temperature for one week, and the photographic performance was similarly examined.

 The results are shown in Table 2.

As is clear from the results in Table 2, the sample N according to the present invention
o.10 to 13 and 16 to 18 show that the contrast is high and the stability of the developer to air oxidation is good.

[Effects of the Invention] According to the present invention, a method for processing a silver halide photographic light-sensitive material having high stability against air oxidation and capable of obtaining a super-hard image can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 5/29 G03C 1/06 501 G03C 1/76 501

Claims (3)

(57) [Claims] 1. A support comprising at least one silver halide photographic emulsion layer on a support, a hydrazine derivative in the silver halide emulsion layer and / or a layer adjacent thereto, and the photographic emulsion layer is A method for processing a silver halide photographic light-sensitive material, wherein a silver halide photographic light-sensitive material having a coating surface pH of 6.0 or more is processed with a developer having a pH of less than 11. 2. The method for processing a silver halide photographic material according to claim 1, wherein the hydrazine derivative is represented by the following general formula [I]. 3. The method for processing a silver halide photographic material according to claim 1, wherein the hydrazine derivative is represented by the following general formula [II]. General formula [I] [In the formula, R ₁₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₂ represents a hydrogen atom or a block group. Ar is an arylene group or a heterocyclic group, one of A ₁ and A ₂ are a hydrogen atom and the other represents a hydrogen atom, an acyl group, a sulfonyl group or an oxalyl group. General formula [II] (In the formula, R ₂₁ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, R ₂₂ is an alkylene group or an alkenylene group, and R ₂₃ is a hydrogen atom or an alkyl group. R represents a hydrogen atom or a block group, Ar represents an arylene group or a heterocyclic group,
One of A ₁ and A ₂ represents a hydrogen atom, and the other represents a hydrogen atom, an acyl group, a sulfonyl group, or an oxalyl group.