JPH07311433A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material not shortening halftone gradation and excellent in enlarging characteristics. CONSTITUTION:This silver halide photographic sensitive material with at least one silver halide photosensitive layer contains at least one kind of compd. which suppresses the release of a development inhibitor when oxidized and a hydrazine compd. or a tetrazolium compd. This sensitive material is processed with a developing soln. of <=pH11.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material for printing plate making.

[0002]

2. Description of the Related Art The photolithography process includes a process of converting a continuous-tone original into a halftone dot image. In this process, a technique capable of reproducing a super-high contrast image is desired. For example, Japanese Patent Laid-Open No. 56-106
Method using hydrazine derivative as described in JP-A No. 244, JP-A-56-4140, JP-A-56-62245, JP-A-58-173737
Method using a tetrazolium compound described in JP-A No. 64-72144, during development as described in JP-A No. 61-147250 and the like,
A method is disclosed that includes a redox compound that is oxidized by the oxidation product of a developing agent to release a development inhibitor.

[0003]

However, all of the above techniques have the drawback that the halftone gradation becomes short because the infectious developability is too strong, so that even a portion that should be removed as a white background is easily blackened. I did.

Therefore, it is an object of the present invention to provide a silver halide photographic light-sensitive material which is excellent in stretching characteristics without shortening halftone gradation.

[0005]

The above objects of the present invention can be achieved by the following constitutions.

A silver halide photographic light-sensitive material having at least one silver halide light-sensitive layer contains at least one compound that releases less development inhibitor when oxidized, and contains a hydrazine compound or a tetrazolium compound. A silver halide photographic light-sensitive material characterized by being

The compound whose release of a development inhibitor is reduced by being oxidized is represented by the above general formula [I] or [II], "Chemical formula 1" or "Chemical formula 2". The described silver halide photographic light-sensitive material.

A silver halide photographic light-sensitive material having at least one silver halide light-sensitive layer contains at least one compound that releases a development inhibitor by being oxidized, and contains a hydrazine compound or a tetrazolium compound. A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material with a developer having a pH of 11 or less.

The present invention will be specifically described below.

First, the compound represented by the following general formula [I] or general formula [II], which is particularly preferably used as the compound which reduces the release of the development inhibitor by being oxidized according to the present invention, will be explained.

[0011]

[Chemical 3]

In the formula, R ₁ represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ₂ has 1 carbon atom.
Represents a ~ 3 alkylene group, R _3, R ₄ and R ₅ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
It represents a carbamoyl group, a sulfamoyl group, a sulfonamide group or a thioether group, and R ₄ and R ₅ may form a 5-membered or 6-membered ring. R ₄ is-(R ₂ ) _n -N (R ₁ )-
It may be the same as E- (B) _m -DI.

A and A'represent a hydrogen atom or a group capable of being removed with an alkali, E represents a carbonyl group or a thiocarbonyl group, and B represents DI after the elimination from the hydroquinone nucleus by an intramolecular nucleophilic substitution reaction. Represents a group that emits
Represents a development inhibitor, and m and n each represent 0 or 1.

[0014]

[Chemical 4]

In the formula, E represents a carbonyl group, and Q represents
An alkyl-substituted nitrogen atom, R ₆ represents a methyl group or a benzyl group, R ₇ , R ₈ and R ₉ each represent a hydrogen atom, an alkyl group or an amide group, and ballast which can be immobilized in an alkaline treatment liquid. Has at least one group, B, DI
And m have the same meanings as B, DI and m in the above general formula [I].

Specific examples of the compounds represented by the general formula [I] or [II] used in the present invention are shown below, but the present invention is not limited thereto.

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

The compound represented by the general formula [I] of the present invention is 1.0 × 10 ^{−10 to} 1.0 × 10 ⁻¹ mol / m ² , preferably 1.0 × 1.
It is used within the range of 0 ^{-7 to} 1.0 × 10 ^-3 mol / m ² .

The structure of the hydrazine compound (derivative) used in the present invention is preferably a compound represented by the following general formula [H].

[0024]

[Chemical 10]

[0025]

[Chemical 11]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n = 1, R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Alternatively, it represents a heterocyclic oxy group, and R ₁ and R ₂ may form a ring together with a nitrogen atom. When n = 2, R ₁
And R ₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. Represents a group. However, when n = 2, at least one of R ₁ and R ₂ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. Shall represent a group. R ₃ represents an alkynyl group or a saturated heterocyclic group. General formula [A] or [B]
The compounds represented by include those in which at least one H of -NHNH- in the formula is substituted with a substituent.

More specifically, A is an aryl group (eg, phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (eg, thiophene, furan, benzothiophene, pyran, etc.). Represents

R ₁ and R ₂ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl,
Pentenyl, pentadienyl, etc.), alkynyl group (eg, propargyl, butynyl, pentynyl, etc.), aryl group (eg, phenyl, naphthyl, cyanophenyl,
Methoxyphenyl, etc.), heterocyclic groups (eg, pyridine,
Unsaturated heterocyclic groups such as thiophene and furan and saturated heterocyclic groups such as tetrahydrofuran and sulfolane), hydroxy groups, alkoxy groups (eg, methoxy, ethoxy,
Benzyloxy, cyanomethoxy etc.), alkenyloxy group (eg allyloxy, butenyloxy etc.), alkynyloxy group (eg propargyloxy, butynyloxy etc.), aryloxy group (eg phenoxy, naphthyloxy etc.) or heterocyclic oxy Represents a group (eg, pyridyloxy, pyrimidyloxy, etc.), n
When = 1, R ₁ and R ₂ together with the nitrogen atom may form a ring (eg, piperidine, piperazine, morpholine, etc.).

However, when n = 2, at least one of R ₁ and R ₂ is an alkenyl group, alkynyl group, saturated heterocyclic group, hydroxy group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group or hetero. It represents a ring oxy group.

Specific examples of the alkynyl group and saturated heterocyclic group represented by R ₃ include those mentioned above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group, Acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group,
Examples thereof include a hydroxy group, a carboxy group, a sulfo group, a nitro group and a cyano group. Of these substituents, the sulfonamide group is preferred.

In each general formula, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in non-moving photographic additives such as couplers is preferable. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108 such as thiourea group, thiourethane group, heterocyclic thioamide group, mercapto heterocyclic group and triazole group.

H of --NHNH-- in the general formulas [A] and [B], that is, the hydrogen atom of hydrazine, is a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.), an acyl group (eg, acetyl, trifluoroacetyl, It may be substituted with a substituent such as ethoxycarbonyl) and an oxalyl group (eg, ethoxalyl, pyruvoyl, etc.), and the compounds represented by the general formulas [A] and [B] include such compounds.

More preferred compounds in the present invention are compounds of the general formula [A] when n = 2, and compounds of the general formula [B].
Is a compound of.

In the compound of the general formula [A] with n = 2,
R ₁ and R ₂ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, or an alkoxy group, and R ₁ and R ₂
At least one of them is an alkenyl group, an alkynyl group,
Compounds representing a saturated heterocyclic group, a hydroxy group, or an alkoxy group are more preferable.

Typical compounds represented by the above general formulas [A] and [B] are shown below. However, as a matter of course, the specific compounds of the general formulas [A] and [B] that can be used in the present invention are not limited to these compounds.

Examples of specific compounds

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

[Chemical 14]

The addition amount of the hydrazine derivative in the present invention is 1 × 10 ^{−5 to} 5 × per mol of silver halide.
It is preferably contained in an amount of 10 ^-2 mol, particularly 1 x 10 ^-5 mol-
The preferable addition amount is in the range of 2 × 10 ^-2 mol.

Examples of the nucleation accelerator used in the present invention include amine compounds, hydrazine compounds, quaternary onium salt compounds and carbinol compounds, with amine compounds and carbinol compounds being preferred. Examples of these nucleation accelerators include those described in JP-A-4-56749, JP-A-63-124045 and JP-A-62-187340. These compounds preferably have a diffusion resistance or a silver halide adsorption group in the molecule. Other specific examples include the compounds described in the following patents. Japanese Patent Application 3-29
Compounds described in 5926, 3-293366, 3-286619, 4-33451 and the like.

More specifically, the following nucleation accelerators are listed, but the present invention is not limited to these.

As the compound described in JP-A-4-56949

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17]

These nucleation accelerators are contained at 1.0 × 10 ^{-3 to} 0.5 g /
m ^2, preferably is desirably used in an amount of ^{5.0 × 10 -3 ~0.1g / m 2} .

As the tetrazolium compound used in the present invention, the silver halide photographic light-sensitive material of the present invention preferably contains a tetrazolium compound represented by the following general formula [T] as a contrast adjusting agent.

[0051]

[Chemical 18]

In the general formula [T], preferred examples of the substituent represented by R ₁ to R ₃ include an alkyl group (eg, methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), Amino group, acylamino group (for example, acetylamino), hydroxyl group, alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.), acyloxy group (for example, acetyloxy),
Halogen atom (e.g. fluorine, chlorine, bromine, etc.), carbamoyl group, acylthio group (e.g. acetylthio), alkoxycarbonyl group (e.g. ethoxycarbonyl), carboxyl group, acyl group (e.g. acetyl), cyano group, nitro group, mercapto group, Examples thereof include groups such as a sulfoxy group and an amino sulfoxy group.

Examples of the anion represented by X ⁻ include halogen ions such as chloride ion, bromide ion and iodide ion, acid radicals of inorganic acids such as nitric acid, sulfuric acid and perchloric acid, sulfonic acid and carboxylic acid. Acidic radicals of organic acids, anionic activators, specifically, lower alkylbenzene sulfonate anions such as p-toluene sulfonate anion, higher alkylbenzene sulfonate anions such as p-dodecylbenzene sulfonate anion, lauryl sulfate anion, etc. Higher alkylsulfate anions, borate anions such as tetraphenylboron, di-2-ethylhexylsulfosuccinate anions, dialkylsulfosuccinate anions, cetylpolyethenoxysulfate anions and other polyether alcohol sulfate anions, stearic acid Higher aliphatic anions such as anions, the polymer of polyacrylic acid anion, and the like such as those with a acid radical.

Specific examples of the compound represented by formula [T] used in the present invention are shown below, but the compound of the present invention is not limited thereto.

[0055]

[Chemical 19]

The tetrazolium compound used in the present invention is, for example, a chemical. Review (Chemical Reviews)
It can be easily synthesized according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound represented by the general formula [T] used in the present invention is from about 1 mg to about 10 g, preferably about 10 mg, per mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. The above is used in the range of about 2 g.

The tetrazolium compound used in the present invention can be obtained, for example, from Chemical Reviews
It can be easily synthesized according to the method described in Volume 55, pages 335 to 483.

The tetrazolium compound represented by the general formula [T] of the present invention is about 1 mg to 10 g, preferably about 10 mg or more per mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. It is preferably used in an amount of up to about 2 g, more preferably 100 mg or more and up to 2 g.

The tetrazolium compound represented by the general formula [T] used in the present invention may be used alone or in combination of two or more kinds at an appropriate ratio.

In the present invention, the pH of the developer to be processed is 11.
0 or less, preferably pH 9.5 to 11.0, especially pH 10.2 to 1
A more favorable result is obtained at 0.8.

Next, for the silver halide emulsion used in the light-sensitive material of the present invention, various preparation methods including various sensitizing methods known in the art of silver halide photographic light-sensitive materials and various additives can be used.

In the present invention, a monodisperse emulsion is preferred. As the monodisperse silver halide grains in the monodisperse emulsion, the weight of silver halide contained within the grain size range of ± 20% centering on the average grain size r is 60% or more of the total weight of silver halide grains. Some are preferable, particularly preferably 70% or more, further preferably 80% or more.

The monodisperse emulsion of the present invention has a monodispersity defined by (standard deviation of grain size / average grain size) × 100 = monodispersity of 20 or less, and more preferably 15 or less. is there.

The silver halide photographic light-sensitive material of the present invention comprises at least two silver halide emulsion layers, and the silver chloride content thereof is 60 mol% or more of silver chloride or silver chlorobromide.

Various additives can be used in the light-sensitive material of the present invention depending on the purpose. These additives are described in more detail in Research Disclosure, Vol. 176, Item.
17643 (December 1978) and Volume 187 Item 18716 (November 1979)
Month).

In the present invention, various known flexible supports used for silver halide photographic light-sensitive materials may be coated on one side or both sides. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with emulsion layers and the like.

In the silver halide photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method or the like can be used.

Various known techniques can be used for the treatment in the present invention, but the developing time is preferably within 30 seconds,
The development, fixing, washing and drying steps that are processed within 20 seconds will be described.

A combination of a dihydroxybenzene chain and 1-phenyl-3-pyrazolidones is most preferable for the developing agent used in the black-and-white developing solution used in the present invention because good performance is easily obtained. Of course, in addition to this, a p-aminophenol-based developing agent may be contained.

LFA Meson, "Photographic Processing Chemistry," Focal Press (1966), pages 226-229, US Pat. Nos. 2,193,015 and 2,5.
92,364, JP-A-48-64933 and the like may be used.

In the present invention, the "development time" and the "fixing time" are the time from the immersion of the photosensitive material to be processed in the developing tank solution of the developing machine to the immersion of the next fixing solution, respectively. Next washing tank liquid (stabilizing liquid)
Say the time to soak. What is "washing time"?
It means the time of immersion in the washing tank liquid. In addition, the "drying time" is usually 35 ℃ ~ 100 ℃, preferably 40 ℃ ~ 80 ℃, the drying zone where the hot air is blown is installed in the automatic developing machine, Say.

The development temperature and time are about 25 ° C. to 50 ° C. and 30 seconds or less, preferably 30 ° C. to 40 ° C. and 6 seconds to 20 seconds.

The fixing solution is an aqueous solution containing thiosulfate,
It has a pH of 3.8 or higher, preferably 4.2 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which have thiosulfate ion and ammonium ion as essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 6 mol / l. In addition, various additives commonly used in fixing solutions can be used.

The fixing temperature and time are preferably about 20 ° C. to about 50 ° C. for 6 seconds to 1 minute, more preferably 30 ° C. to 40 ° C. for 6 seconds to 30 seconds, and further preferably 30 ° C. to 40 ° C. for 6 seconds. ~ 15 seconds.

In the present invention, the light-sensitive material is subjected to washing with water or stabilizing treatment after being fixed with the actual solution. For the washing or stabilizing treatment, any method known in the art can be applied, and water containing various additives known in the art can also be used as washing water or a stabilizing solution. Washing or stabilizing bath temperature and time is preferably 0 ° C to 50 ° C for 6 seconds to 1 minute,
6 to 30 seconds at 15 ℃ to 40 ℃ is more preferable, and further 15 ℃
6 to 15 seconds at -40 ° C is preferred.

According to the method of the present invention, the developed, fixed and washed photographic material is dried by squeezing the washing water, that is, the squeeze roller method. Drying is about 40 ℃ ~ 100
The drying time may be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 1 minute, more preferably
It is about 5 to 30 seconds at 40 ° C to 80 ° C.

In the present invention, the line speed is 1000 mm
/ Min or more, preferably 1500 mm / min or more, more preferably
1800 mm / min or more.

According to the method of the present invention, the so-called Dry to Dry processing time until development, fixing, washing and drying is 100 seconds or less, preferably 60 seconds or less, more preferably 50 seconds or less. is there.

Here, "dry to dry" means that from the moment the tip of the photosensitive material to be processed enters the film inserting portion of the automatic developing machine,
It is the time until it is processed and the tip comes out of the machine.

[0081]

EXAMPLES The effects of the present invention will be illustrated by the following examples.

Example 1 On the undercoated polyethylene terephthalate film described in Example 1 of JP-A-59-19941, one side was coated with three layers of a silver halide emulsion layer and a protective layer, and the other side was coated. Was coated with a backing layer.

[Preparation Method of Emulsion (A)] Liquids A and B shown below
Solution and Solution C were used to prepare a silver chlorobromide emulsion.

<Solution A> Ocein gelatin 17 g Polyisopropylene-polyethyleneoxy disuccinate sodium salt 10% aqueous ethanol solution 5 ml Distilled water 1280 ml <Solution B> Silver nitrate 170 g Distilled water 410 ml <Solution C> Sodium chloride 45.0 g Potassium bromide 27.4g 6 Iridium chloride salt 200μg Polyisopropyleneoxydisuccinate sodium salt 10% ethanol solution 3ml ossein gelatin 11g distilled water 407ml After keeping solution A at 40 ℃, add sodium chloride so that the EAg value will be 160mV. Was added. Next, as in JP-A-57-92523
Solution B and solution C were added by the double jet method using the mixing stirrer described in No. 57-92524. As shown below, the addition flow rate was gradually increased over the entire addition time of 80 minutes while the EAg value was kept constant.

The EAg value was 160 mV, and 3 ml 5 minutes after the start of addition.
The EAg value was changed to 120 mV using a 1 / l sodium chloride aqueous solution, and this value was maintained thereafter until the mixing was completed.

In order to keep the EAg value constant, the EAg value was controlled using a 3 mol / l sodium chloride aqueous solution.

[0087] A metal silver electrode and a double junction type saturated Ag / AgCl reference electrode were used to measure the EAg value (the double junction disclosed in JP-A-57-197534 was used for the electrode configuration).

For addition of solutions B and C, a variable flow rate roller tube metering pump was used. During the addition, it was confirmed by observing with an electron microscope that no new grains were found in the system due to sampling of the emulsion. Further, during the addition, the pH value of the system was controlled with a 3% nitric acid aqueous solution so as to keep it constant at 3.0.

After the addition of solutions B and C, the emulsion was ripened for 10 minutes in Ostwald, desalted and washed in a conventional manner, and then 600 ml of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) and a compound [ 15 ml of a 1% aqueous solution of the mixture of A], [B] and [C] was added and dispersed by stirring at 55 ° C. for 30 minutes and then adjusted to 750 ml to obtain emulsion A.

[0090]

[Chemical 20]

The emulsion A thus obtained was sensitized with gold and sulfur, and 4-hydroxy-6-methyl- was added as a stabilizer.
1 g of 1,3,3a, 7-tetrazaindene was added, and sensitizing dye A was added in an amount of 300 mg per mol of silver halide contained in the emulsion, and sensitizing dye B was added in an amount of 1 mol of silver halide contained in the emulsion.
100 mg was added.

Then, the following tetrazolium compound T-14 (tetrazolium exemplified compound T-
14) in an amount of 360 mg, the compound of the general formula [I] of the present invention in the amount shown in Table 1, and p-dodecylbenzenesulfonic acid sodium salt 30.
0 mg, styrene-maleic acid copolymer 2 g, styrene-butyl acrylate-acrylic acid copolymer latex (average particle size about 0.25 μm) 15 g were added, the gelatin amount was emulsion layer 1.8 g / m ² , Ag amount It was coated on the support so that the amount was 4.0 g / m ² . At that time, as a spreading agent, bis - (2-ethylhexyl) Formalin 15 mg / m ² of sulfosuccinate 10 mg / m ^2, as a hardening agent, glyoxal 8 mg / m ²
A protective layer having a gelatin content of 1.0 g / m ² was applied simultaneously in multiple layers.

[0093]

[Chemical 21]

A backing layer described below was provided on the side opposite to the emulsion layer with the support interposed therebetween.

Gelatin 60 g Dyes A to C 100 mg / m ² Saponin 2 g Glyoxal 1 g

[0096]

[Chemical formula 22]

After finishing to 1 liter with pure water, 2 g / m ^{2 of} gelatin was added, and the same protective layer as the emulsion protective layer was coated so that the gelatin content was 1 g / m ² .

(Evaluation of Photographic Performance) The obtained sample was used for 3200
Konica Co., Ltd., into which a developing solution and a fixing solution having the composition shown below was added after being exposed for 5 seconds through an optical wedge or an optical wedge and a contact screen with a tungsten light of ° K.
Processing was carried out under the following conditions with an automatic processor for rapid processing GR-26SR manufactured by the same company. For the developing solution, see p.
The H value was changed and examined, and further, the deterioration of the developing performance with a new solution (immediately) and with time (after being left in a dark room (oxidized) at 25 ° C. for one week) was also examined.

The density of the obtained sample was measured with an optical densitometer, Konica PDA-65, and the gradation (γ) was displayed with the tangent of the densities of 0.1 and 2.5. If the γ value is less than 8.0, the contrast becomes insufficient and it cannot be used. Sensitivity was shown as a relative value when sample No. 13 was set to 100.

(Evaluation of stretchability) Dainippon Screen
Using a scanner SG-808 (II) manufactured by K.K. Co., Ltd. and a photosensitive material RSDII manufactured by Konica Co., Ltd., a transmission image of a person consisting of halftone dots and a step wedge in which halftone% was changed stepwise were prepared. The number of screen lines at this time was 150 lines / inch, and a manuscript was prepared. Using this original, the original was set on a Fine Zoom C-880F manufactured by Dainippon Screen Co., Ltd. so that the stretching magnification was 120%, and the sample was exposed. At this time, the exposure was performed so that 95% of the step wedge of the original became 5%. The evaluation is visually graded in 10 stages, and 10 (excellent) to 1
(Inferior), 6 or above is a level that can be put on the market.

<Development processing conditions> (Process) (Temperature) (Time) Tank capacity (l) Current image 28 ° C 30 seconds 20 Settling 28 ° C 30 seconds 20 Water washing 18 ° C 20 seconds 15 Drying 40 ° C 20 seconds The process includes so-called wading transport time until the next process.
Dry to Dry time is 100 seconds.

<Developer formulation> (Composition A) Pure water (ion exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200mg 1-Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to adjust pH of working solution to 9.0, 10.0, 10.4, 11.0 or 12.0 Potassium bromide 4.5g (Composition B) Pure water (ion exchange water) 3ml Diethylene glycol 50g Ethylenediamine Tetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 700 mg Butylamine Diethanolamine 15 g Dissolve the above composition A and composition B in 500 ml of water in this order when using the developer. It was used after finishing to liter.

<Fixer 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 g Sodium citrate dihydrate 2 g Acetic acid (90% w / w Aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% w / w aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% w / w aqueous solution) 26.5 g Fixer At the time of use, the above composition A and composition B were dissolved in 500 ml of water in this order to make 1 liter and used. Of this fixer
The pH was about 4.3.

The results are shown in Tables 1 and 2.

[0105]

[Table 1]

[0106]

[Chemical formula 23]

[0107]

[Table 2]

From the results shown in Table 1, it can be seen that the present invention has good gamma and good stretchability.
Further, from Table 2, it is preferable that the developer has a pH of 11 to 7. That is, it can be seen that when the pH is 12 or more, the performance in the new solution is good, but the stability with time (storage) deteriorates, and when the pH is 7 or less, the performance does not appear.

Example 2 (Preparation of Silver Halide Emulsion) Emulsion A A silver chlorobromide emulsion (70 mol% of silver chloride per mol of silver) was prepared by the simultaneous mixing method. K ₂ IrCl ₆ in silver 1
8 × 10 ⁻⁷ mol was added per mol. The obtained emulsion was an emulsion composed of cubic monodisperse grains (coefficient of variation 12%) having an average grain size of 0.20 μm. After the sensitizing dye (D) was added to this emulsion, it was washed with water and desalted by a conventional method. Thereafter, a mixture of the compounds [A], [B] and [C] was added, and then sodium thiosulfate and potassium chloroaurate were added for chemical sensitization.

Emulsion B A silver chlorobromide emulsion (65 mol% of silver chloride per mol of silver) was prepared using the simultaneous mixing method. K ₂ IrCl ₆ in silver 1
8 × 10 ^-7 mol per mol and Na ₂ RhCl ₆ were added at 1 × 10 ^-7 mol per mol silver. The obtained emulsion has an average grain size of 0.20.
It was an emulsion composed of cubic monodisperse grains of 10 μm (coefficient of variation 10%). After the sensitizing dye (D) was added to this emulsion, it was washed with water and desalted by a conventional method. Then the compound [A] [B]
After the mixture of [C] was added, inorganic sulfur and potassium chloroaurate were added for chemical sensitization.

[0111]

[Chemical formula 24]

[0112]

[Chemical 25]

(Preparation of silver halide photographic light-sensitive material) Thickness
On a polyethylene terephthalate support having a thickness of 100 μm coated with a 0.1 μm undercoat layer (see Example 1 of JP-A-59-19941), an emulsion B layer, an intermediate layer, an emulsion A layer, in that order from the support side,
A coating solution having the following formulation was prepared in the order of the protective layers, and simultaneous multilayer coating and drying were performed.

(Emulsion B Layer) Gelatin 1.5 g / m ² as emulsion layer Halogenated Emulsion B Silver 3.0 g / m ² 4-Methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² adenine 10 mg / m ² 5-sodium sulfonate-2-mercaptobenzimidazole 5 mg / m ² saponin 0.1 g / m ² surfactant (S-1) 2 mg / m ² hydrazine derivative 20 mg / m ² described in Table 1 m ² Nucleation accelerator (9) 20 mg / m ² (11) 10 mg / m ² Methyl acrylate-2-acrylamido-2-methylpropanesulfonic acid-2-acetoacetoxyethyl methyl acrylate copolymer 1.0 g / m ² polyethylene Glycol (molecular weight 4000) 0.1 g / m ² (intermediate layer) Gelatin 1.0 g / m ² Surfactant (S-1) 4 mg / m ² Methyl acrylate-2-acrylamido-2-methylpropanesulfonic acid-2-acetoacetoxy Ethyl methyl acrylate copolymer 1.0 g / m ² 1,3-Bisvinylsulfonyl-2-propanol 20 mg / m ² (emulsion A layer) Gelatin 0.8 g / m ² as emulsion layer Halogenated emulsion A silver 0.3 g / m ² 4-methyl-6-hydroxy -1,3,3a, 7- tetrazaindene 3 mg / m ² adenine 1 mg / m ² 5-methyl benzotriazole 0.5 mg / m ² surfactant (S-2) 2mg / m 2 colloidal silica (average particle diameter 0.015 μm) 200 mg / m ² Compound of general formula [I] described in Table 1 (Protective layer) Gelatin 0.5 g / m ² as emulsion layer Surfactant (S-2) 10 mg / m ² Surfactant ( S-3) 2 mg / m ² matting agent (monodisperse silica having an average particle diameter of 3.5 μm) 15 mg / m ² 1,3-bisvinylsulfonyl-2-propanol 40 mg / m ²

[0115]

[Chemical formula 26]

(Evaluation of Photographic Performance) The obtained sample was used as 3200
Konica Co., Ltd., into which a developing solution and a fixing solution having the composition shown below was added after being exposed for 5 seconds through an optical wedge or an optical wedge and a contact screen with a tungsten light of ° K.
Processing was carried out under the following conditions with an automatic processor for rapid processing GR-26SR manufactured by the same company. For the developing solution, see p.
The H value was changed and examined, and the deterioration of the developing performance with a new solution (immediately) and with time (after being left in a dark room (oxidized) at 25 ° C. for one week) was also examined.

The density of the obtained sample was measured with an optical densitometer, Konica PDA-65, and the gradation (γ) was displayed with the tangent of the densities of 0.1 and 2.5. If the γ value is less than 8.0, the contrast becomes insufficient and it cannot be used. Sensitivity was shown as a relative value when sample No. 22 was set to 100.

(Evaluation of stretchability) Dainippon Screen
Using a scanner SG-808 (II) manufactured by K.K. Co., Ltd. and a photosensitive material RSDII manufactured by Konica Co., Ltd., a transmission image of a person consisting of halftone dots and a step wedge in which halftone% was changed stepwise were prepared. The number of screen lines at this time was 150 lines / inch, and a manuscript was prepared. Using this original, the original was set on a Fine Zoom C-880F manufactured by Dainippon Screen Co., Ltd. so that the stretching magnification was 120%, and the sample was exposed. At this time, the exposure was performed so that 95% of the step wedge of the original became 5%. The evaluation is visually graded in 10 stages, and 10 (excellent) to 1
(Inferior), 6 or above is a level that can be put on the market.

(Developer Composition) Potassium Sulfite 50.0 g Hydroquinone 20.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g Ethylenediaminetetraacetic acid disodium salt 2.0 g Potassium carbonate 12.0 g Potassium bromide 5.0 g 5-Methylbenzotriazole 0.3 g 5-Mercaptopurine 0.6 g Diethylene glycol 25.0 g Compound (d) 0.1 g Water was added to make 1 liter, and pH was adjusted to 9.0, 10.0, 10.4, 11.0 or 12.0 with potassium hydroxide.

(Fixing solution composition) Ammonium thiosulfate (72.5% W / V aqueous solution) 200 ml Sodium sulfite 17 g Sodium acetate / trihydrate 6.5 g Boric acid 6.0 g Sodium citrate / dihydrate 2.0 g Pure water (ion exchange water) 17 ml Sulfuric acid (50% W / V aqueous solution) 2.0 g Aluminum sulphate (Al ₂ O ₃ converted content is 8.1% W / V aqueous solution) 8.5 g The fixing solution was finished to 1 liter and used. The pH of this fixer was adjusted to 4.8 with acetic acid.

[0121]

[Chemical 27]

(Development processing condition) The time includes the time for wading.

(Process) (Temperature) (Time) Development 38 ° C. 12 seconds Fixing 35 ° C. 10 seconds Washing 30 ° C. 10 seconds Drying 50 ° C. 13 seconds Total 45 seconds The results are shown in Tables 3 and 4.

[0124]

[Table 3]

[0125]

[Chemical 28]

[0126]

[Table 4]

From the results of Table 3, it can be seen that according to the present invention, the gamma is good and the stretchability is also good.
Further, from Table 4, it is preferable that the developer has a pH of 11 to 7. That is, it can be seen that when the pH is 12 or more, the performance in the new solution is good, but the stability with time (storage) deteriorates, and when the pH is 7 or less, the performance does not appear.

[0128]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material excellent in stretchability without shortening halftone gradation.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor ▲ Taka ▼ Yasuhiko Mukai Konica Stock Company, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide light-sensitive layer, which contains at least one compound which reduces the release of a development inhibitor by being oxidized, and a hydrazine compound or a tetrazolium compound. A silver halide photographic light-sensitive material comprising: 2. A silver halide photograph according to claim 1, wherein the compound that reduces the release of the development inhibitor by being oxidized is represented by the following general formula [I] or [II]. Photosensitive material. [Chemical 1] [In the formula, R ₁ represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 20 carbon atoms, R ₂ represents an alkylene group having 1 to 3 carbon atoms, and R ₃ , R ₄ and R ₅ are , A hydrogen atom, a halogen atom,
It represents an alkyl group, an aryl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group or a thioether group, and R ₄ and R ₅ may form a 5-membered or 6-membered ring.
R ₄ may be the same as-(R ₂ ) _n -N (R ₁ ) -E- (B) _m -DI. A and A'represent a hydrogen atom or a group that can be removed with an alkali, E represents a carbonyl group or a thiocarbonyl group, and B represents DI that is released from the hydroquinone nucleus by an intramolecular nucleophilic substitution reaction. Represents a group, DI represents a development inhibitor,
m and n each represent 0 or 1. ] [Chemical 2] [In the formula, E'represents a carbonyl group, Q represents an alkyl-substituted nitrogen atom, R ₆ represents a methyl group or a benzyl group, and R ₇ , R ₈ and R ₉ are each a hydrogen atom or an alkyl group. Group, an amide group, having at least one ballast group capable of being immobilized in an alkaline treatment liquid, B, DI and m have the same meanings as B, DI and m of the above general formula [I]. ] 3. A silver halide photographic light-sensitive material having at least one silver halide light-sensitive layer, which contains at least one compound which releases a development inhibitor by being oxidized and which contains a hydrazine compound or a tetrazolium compound. A method for processing a silver halide photographic light-sensitive material, which comprises processing a silver halide photographic light-sensitive material containing a photographic material with a developer having a pH of 11 or less.