JPH07159917A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance dot gradation and enlargeability and to prevent occurrence of uneven development by forming a silver halide emulsion layer containing a specified compound on a support and incorporating a tetrazolium compound. CONSTITUTION:This photosensitive material contains the tetrazolium lium compound and has a silver halide emulsion layer containing at least one of the compounds represented by formulae I and II in which R1 is (R3)(R5)>N-C(= S)-N(R4)-, (R4)-C(=S)=N(R4)-, (R3)O-C(=S)-N(R4)-, or the like: R3 is alkyl, aryl, or the like; each of R4-R6 is H or the like; R. is a substituent except R7 is an aliphatic group or the like; L1 is -CONR9-,-NR10CONR9-, or the like; L2 is a divalent bonding group; each of R9-R11 is H or the like; R8 is a group except H; B is a group releasing DI; and each of A and A' is H or a group releasable by alkali.

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 silver halide photographic light-sensitive material for printing plate making which has improved running stability and stretchability.

[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 step, a technique capable of achieving super-high contrast image reproduction is desired, and for example, a method using a tetrazolium compound is used. According to this method, although photographic characteristics with high sensitivity in ultra-high contrast can be obtained, its infectious developability is too strong, so in the halftone image shooting, it is easy to blacken even the part that falls out as a white background of halftone dots, resulting in It had a drawback in image quality that halftone gradation became very short.

In order to improve this, JP-A-4-438 and JP-A-4-438
-5653, 4-6548, 4-6551 and the like, the technology of using a hydroquinone derivative that releases a development inhibitor by oxidizing is disclosed, but there was a problem that uneven development occurs .

On the other hand, in the line drawing photographing process of printing plate making, characters,
Various originals with different densities and line widths such as illustrations and halftone dots are pasted. Therefore, images having different densities and line widths are mixed in the original document, and there is a strong demand for a plate-making camera, a photographic light-sensitive material, or an image forming method for finishing these original documents with good reproduction. Further, in catalogs and posters, so-called expansion and contraction of halftone pictures, such as enlargement and reduction, are performed, and in plate making using enlarged halftone dots, the number of lines becomes rough and blurred points are taken. Therefore, in order to enhance the reproducibility of halftone, a photosensitive material having a wide exposure latitude is required.

[0005]

SUMMARY OF THE INVENTION The present invention has been made under the above circumstances and is suitable for use in a photomechanical process. It is excellent in halftone gradation and stretchability and does not cause uneven development. It is an object of the present invention to provide a photographic light-sensitive material.

[0006]

The above object of the present invention is to provide at least one compound selected from the compound represented by the following general formula [I] and the compound represented by the following general formula [II] on a support. Having a silver halide emulsion layer containing, a silver halide photographic light-sensitive material containing a tetrazolium compound,

[0007]

[Chemical 3]

[Wherein R ₁ is (R ₃ ) (R ₅ )> N-C (= S) -N
(R ₄ ) −, (R ₃ ) −C (= S) −N (R ₄ ) −, (R ₃ ) O−C (= S) −N
_{(R 4) -, (R} 3) S-C (= S) -N (R 4) -, (R 3) S-C (= O) -N (R
_{4) -, (R 3)} -C (= O) -C (= O) -N (R 4) -, (R 3) O-C (= O)
-C (= O) -N (R 4) -, (R 3) (R 5)> N-C (= O) -C (= O) -N
(R ₄ )-and (R ₃ ) (R ₆ )> N-N (R ₅ ) -C (= O) -N (R ₄ )-, wherein R ₃ is an alkyl group, an aryl group or a heterocyclic group. R ₄ , R ₅ and R ₆ represent a hydrogen atom, an alkyl group or an aryl group, and R ₂ represents a substituent other than a hydrogen atom. B represents a group that releases DI after leaving the hydroquinone mother nucleic acid product, DI represents a development inhibitor, m and n represent integers, and A and A'represent a hydrogen atom or a group capable of being removed by an alkali. . R ₁ and R ₂ and two R ₂ may combine together to form a ring. ]

[0009]

[Chemical 4]

[0010] wherein, R ₇ represents an aliphatic group or an aromatic group, L ₁ is _{-CONR 9 -, - NR 10 CONR} 9 -, - OCONR 9 -, - C
ONR ₁₁ NR ₁₀ CONR ₉ −, −SO ₂ NR ₉ −, −NR ₁₀ SO ₂ NR ₉ −, −CO
_{CONR 9 -, - NR 10 COCONR} 9 - represents a group, L ₂ represents a divalent linking group having a repeating unit of ethylene oxide 3 or more, R _9, R ₁₀ and R ₁₁ are a hydrogen atom, an alkyl group or Represents an aryl group. R ₈ represents a substituent other than a hydrogen atom,
B represents a group that releases DI after being separated from the hydroquinone mother nucleic acid product, represents a DI mother development inhibitor, o, p, and q represent integers, r and s are 0 or 1, but at the same time, 0 or 1
Never be. A and A'represent a hydrogen atom or a group which can be removed with an alkali. ] And the amount of the hydrophilic binder on the side having the silver halide emulsion layer in the photographic light-sensitive material is 4.5 g / m ² or less, and the swelling rate during development processing is 200% or less. To be achieved.

The present invention will be specifically described below.

First, the compound represented by the general formula [I] will be described.

R ₃ is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and pyridyl, furyl, thiophenyl and the like as the heterocyclic group. Can be mentioned. Examples of the substituent on R ₃ include an alkyl group, an alkoxy group, an alkylthio group, an acylamino group, a sulfonic acid amide group, and a halogen atom. R ₄ , R ₅ and R ₆ are
They may be the same or different, and represent a hydrogen atom or a substituent represented by R ₃ , and preferably a hydrogen atom.
R ₂ represents, for example, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a sulfonic acid amide group or a halogen atom. R ₁ and R ₂ , and two R ₂ may combine with each other to form a ring, in which case the number of ring members is 5
To 7 are preferred. m and n are preferably 0, 1 or 2
Represents A and A'represent a hydrogen atom or a group which can be removed with an alkali. In that case, a hydrolyzable group such as an acyl group, an alkoxycarbonyl group and a sulfonyl group is preferable, and a hydrogen atom is particularly preferable. The group represented by B is a divalent divalent group capable of releasing-(B) n-DI after the hydroquinone mother nucleus is oxidized by the developing agent oxidant during development to form a quinone, and then DI. It may represent a group and have a timing adjusting function, or may be a redox group which reacts with another molecule of an oxidized product of a developing agent to release DI. Here, when n is 0, D
I means a case where I is directly bonded to the hydroquinone mother nucleus, and when n is 2, it represents a combination of two or more of the same or different B, but n is preferably 0.

When B is a divalent linking group having a timing adjusting function, examples thereof include formulas (T-1) to (T-6) and (R) described in JP-A-4-438. -1) ~
Examples thereof include those having a structure represented by (R3).

A preferred development inhibitor for DI is a compound having a development inhibitory property when cleaved, but is decomposed into a compound which does not substantially affect the photographic performance after it is dissolved in a developing solution. It has (or changes) properties, and is described in, for example, U.S. Pat. No. 4,477,563, JP-A-60-218644, 60-221750, 60-233650, or 61-11743. Development inhibitors may be mentioned.

Specific examples of the compounds used in the present invention are listed below, but the present invention is not limited to these.

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

Specific examples of synthesizing the compound represented by the general formula [I] are shown below, but the compound used in the present invention can be easily synthesized by the same method.

[0023]

[Chemical 10]

1) Synthesis of 1-A 400 g of acetonitrile in 50 g of 2,5-dimethoxyaniline,
Add 26 ml of pyridine and add ethyl isothiocyanate.
28.5 g was added and the mixture was heated under reflux for 5 hours. After the reaction,
Aqueous hydrochloric acid was added to the reaction mixture, which was extracted with ethyl acetate,
It was washed with water, concentrated and dried to obtain 47 g of the title compound.

2) Synthesis of 1-B To 30 g of 1-A obtained above was added 500 ml of 47% hydrobromic acid, and the mixture was heated under reflux for 4 hours. After completion of the reaction, water was added to the reaction mixture, the mixture was extracted with ethyl acetate, washed with water, concentrated and dried to obtain 13 g of the title compound.

3) Synthesis of 1-C To 10 g of 1-B obtained above, 400 ml of ethanol and 11 g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone were added and stirred at room temperature for 2 hours. . After the reaction was completed, the precipitated crystals were separated by filtration, washed with ethanol and dried to obtain 8 g of the title compound.

4) Synthesis of Exemplified Compound (1) To 1-C4g obtained above, 400 ml of ethyl acetate, 5 g of 5-mercapto-1- (4-nitrophenyl) tetrazole, p-
0.1 g of toluenesulfonic acid monohydrate was added, and the mixture was stirred at 50 ° C for 2 hours. After completion of the reaction, water was added, the mixture was extracted with methylene chloride, washed with water, concentrated and dried to obtain 3.5 g of the title compound.

The compound represented by the general formula [I] of the present invention is 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻² mol / m ² , preferably 1.0 × 10 8.
Used in the range of ^{-7 to} 1.0 x 10 ^-4 mol / m ² .

Next, the compound of the general formula [II] will be described.

The aliphatic group of R ₇ and R ₈ has 1 carbon atom.
To 30 substituted or unsubstituted alkyl group, cycloalkyl group or heterocyclic group are preferred, and the aromatic group is a monocyclic or bicyclic substituted or unsubstituted aryl group or unsaturated heterocyclic group. Examples of the substituents include an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, an arylthio group, an aralkylthio group, an alkylamino group, an arylamino group and an alkylsulfonic acid amide group. , An aryl sulfonic acid amide group or a halogen atom.

R ₉ , R ₁₀ and R ₁₁ may be the same or different and are the same as hydrogen atom or R ₇ ,
It is preferably a hydrogen atom. o and p are preferably 0, 1
Or 2, and q is an integer of 1 to 6.

The alkali-removable group of A and A ′ is preferably a hydrolyzable group such as an acyl group, an alkoxycarbonyl group or a sulfonyl group.
As', a hydrogen atom is particularly preferable.

B is-after the hydroquinone mother nucleus is oxidized by the oxidized form of the developing agent during development to form a quinone form,
(B) Represents a divalent group capable of releasing o-DI and then DI, and may have a timing adjusting function, and releases DI by reacting with another molecule of an oxidized developing agent. It may be a redox group. Here, when o is 0, DI is directly bonded to the hydroquinone mother nucleus and o is 2
In the case of, the same or different combinations of B are represented, and o is preferably 0.

When B is a divalent linking group having a timing adjusting function, examples thereof include formulas (T-1) to (T-6) and (R-6) described in JP-A-4-438. -1) ~
The thing of the structure represented by (R-3) is mentioned.

A preferred development inhibitor as DI is a compound having a development inhibitory property when cleaved, but is decomposed into a compound having substantially no influence on photographic performance after it is eluted in a developing solution. (Or change) properties, for example, US Pat. No. 4,477,563, JP-A-60-218644, JP-A-60-221750, and JP-A-60-233650.
And the development inhibitors described in JP-A Nos. 60-11743.

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

[0037]

[Chemical 11]

[0038]

[Chemical 12]

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

The synthetic examples of the compounds are shown below, but the compounds used in the present invention can be easily synthesized by the same method.

[0043]

[Chemical 16]

1) Synthesis of 2-A 11.2 g of 2,5-dimethoxyaniline and 200 m of acetonitrile
l, 13 ml of pyridine were added, and chloroacetic acid chloride was added.
8.3 g was added and the mixture was heated under reflux for 5 hours. After the reaction,
Aqueous hydrochloric acid was added to the reaction mixture, which was extracted with ethyl acetate,
After washing with water, concentration, and drying, 13.3 g of the title compound was obtained.

2) Synthesis of 2-B 8.0 ml of tribromic acid boric acid was added to 13.1 g of 2-A obtained above under ice cooling.
Was added, and the mixture was stirred under ice cooling for 2 hours. After completion of the reaction, water was added to the reaction mixture, extracted with ethyl acetate, washed with water, concentrated,
After drying, 6.9 g of the title compound was obtained.

3) Synthesis of 2-C 300 ml of ethanol and 7.5 g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone were added to 6.7 g of 2-B obtained above.
The mixture was stirred at room temperature for 2 hours. After the reaction was completed, the precipitated crystals were separated by filtration, washed with ethanol and dried to give 4.6 g of the title compound.
Got

4) Synthesis of 2-D Tetrahydrofuran 200 m was added to the 2-C 4.4 g obtained above.
1, sodium hydride (0.6 g) and octyltetraethyleneoxythiol (which can be synthesized, for example, according to the method described in US Pat. No. 4,988,604) (9.1 g) were added, and the mixture was stirred at 0 ° C. for 10 hours. After the reaction was completed, ice water was added,
After extraction with ethyl acetate, washing with water, concentration, and drying, the title compound
6.3 g was obtained.

5) Synthesis of Exemplified Compound (2) To 2-D 5.7 g obtained above, 400 ml of ethyl acetate, 1.6 g of 2-mercapto-5-methylthio-1,3,4-thiadiazole, p-
Toluenesulfonic acid monohydrate 0.1 g was added, extracted with methylene chloride, washed with water, concentrated and dried to give 3.7 g of the title compound.
Got

In the present invention, L of the general formula [II]
₁ is -CONR ₁₁ NR ₁₀ CONR ₉ - when the most preferred results are obtained.

In the present invention, the compound of the general formula [II] is
1.0 × 10 ^{-8 to} 1.0 × 10 ^-2 mol / m ² , preferably 1.0 × 10 ^-7
It is used in the range of up to 1.0 × 10 ⁻⁴ mol / m ² .

The tetrazolium compound contained in the silver halide photographic light-sensitive material of the present invention is represented by the following general formula [II
I] can be mentioned.

[0052]

[Chemical 17]

In the general formula [III], preferred examples of the substituent represented by R ₁₂ , R ₁₃ to R ₁₄ are alkyl groups (eg, methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl). Etc.), amino group, acylamino group
(E.g. acetylamino), hydroxyl group, alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy, pentoxy etc.), acyloxy group (e.g. acetyloxy), halogen atom (e.g. fluorine, chlorine, bromine etc.),
A carbamoyl group, an acylthio group (for example, acetylthio),
Examples thereof include groups such as an alkoxycarbonyl group (eg ethoxycarbonyl), a carboxyl group, an acyl group (eg acetyl), a cyano group, a nitro group, a mercapto group, a sulfooxy group and an aminosulfoxy group.

Examples of the anion represented by X ⁻ include halogen ions such as chloride ions, bromide ions and iodide ions, acid radicals of inorganic acids such as nitric acid, sulfuric acid and perchloric acid,
Acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically, lower alkylbenzene sulfonate anions such as p-toluene sulfonate anion and higher alkylbenzene sulfonate anions such as p-dodecylbenzene sulfonate anion , Higher alkyl sulfate anions such as lauryl sulfate anion, borate anions such as tetraphenylboron, dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anion, and polyether alcohols such as cetyl polyethenoxy sulfate anion Examples thereof include higher aliphatic anions such as sulfate anion and stearic acid anion, and polymers such as polyacrylic acid anion having an acid radical.

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

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

[0059]

[Chemical 21]

[0060]

[Chemical formula 22]

The tetrazolium compound used in the present invention can be obtained, for example, from Chemical Reviews No. 55.
Vol., Pp. 335-483, and can be easily synthesized.

In the present invention, the tetrazolium compound is
The silver halide photographic light-sensitive material of the present invention contains about 1 mg to 10 g, preferably about 1 mg, per mol of silver halide.
It is preferably used in the range of 10 mg to about 2 g.

The compound of the present invention can be used by dissolving it in a suitable water-miscible organic solvent such as alcohols, ketones, dimethylsulfoxide, dimethylformamide, methylcellosolve and the like.

It is also possible to add it as an emulsified dispersion using an already known oil.

Alternatively, the compound powder may be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves according to a method known as a solid dispersion method.

The layer containing the tetrazolium compound and the silver halide emulsion layer containing the compound of the general formula may be coated on the support in any order, and may be in the same layer or in different layers. Another hydrophilic colloid layer may be provided, but preferably, a silver halide emulsion layer containing a tetrazolium compound and a silver halide emulsion layer containing a compound of the general formula are separately provided.

More preferably, an emulsion layer containing a compound of the general formula is provided on the exposed surface side, an emulsion layer containing a tetrazolium compound is provided on the support side, and the amount of the emulsion and the like are adjusted to adjust the amount on the support side. The emulsion layer is set so as to mainly contribute to the image so that the edge of the image on the support side is suppressed by the diffusion of DI from the exposed surface side.

Between both emulsion layers, the timing function or D
A hydrophilic colloid layer having a diffusion control function of I may be provided.

The emulsion layer containing the tetrazolium compound preferably has a coated silver amount of 0.5 to 6.0 g / m ² , and more preferably 1.0 to 5.0 g / m ² . The emulsion layer containing the compound of the general formula preferably has a coated silver amount of 0.01 to 2.0 g / m ² , and more preferably 0.05 to 1.0 g / m ² .

In the present invention, the film is hardened so that the amount of the hydrophilic binder on the side having the silver halide emulsion layer is 4.5 g / m ² or less and the swelling rate during development processing is 200% or less. preferable.

When the amount of the binder is large, the balance between the penetration of the developing agent and the diffusibility of DI is deviated, and good halftone dot quality may not be obtained. When the swelling ratio is more than 200%, DI is unnecessarily diffused at the time of development, the edge enhancement of the image becomes insufficient, and uneven development easily occurs.

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.

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

The silver halide photographic light-sensitive material of the present invention preferably 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.

When the silver halide photographic light-sensitive material of the present invention contains a dye, it can be fixed by a silver salt and a silver complex formed by a reaction with silver ions.

Instead of the above-mentioned silver salt dye form, the dye itself may be dispersed and added as a fine particle solid.

Such a fixed dye layer can be formed on the support side of the silver halide emulsion layer.

In the present invention, various known flexible supports used for silver halide photographic light-sensitive materials can 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 on 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 additives can be used in the light-sensitive material of the present invention depending on the purpose. More specifically, these additives are described in Research Disclosure Vol. 176, Item 17643 (December 1978).
And 187, Item 18716 (November 1979).

[0081]

【Example】

Example 1 (Preparation of silver halide emulsion) Emulsion A A silver chlorobromide emulsion (70 mol% of silver chloride) was prepared by using the simultaneous mixing method. During this mixing, K ₂ IrCl ₆ was added at 8 × 1 per mol of silver.
^0-7 mol was added. The obtained emulsion was an emulsion composed of cubic monodisperse grains (variation coefficient: 15%) having an average grain size of 0.30 μm. Washing with water, desalting, and gold-sulfur sensitization by a conventional method, 4-hydroxy-6-methyl-1,3,3a-tetrazaindene as a stabilizer was added at 0.7 g per 1 mol of silver, and sensitizing dye A was added. 200 mg was added per mol of silver halide. Further compound (C)
150 mg of the mixture of (D) and (E) was added.

Emulsion B Same as Emulsion A except that 300 mg of sensitizing dye A and 100 mg of sensitizing dye B were added per mol of silver halide.

[0083]

[Chemical formula 23]

(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 coating amount as shown in Table 1 for emulsion layer Halogenated emulsion B silver amount 3 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 tetrazolium compound 20 mg / m ² methyl acrylate -2-Acrylamido-2-methylpropanesulfonic acid-2-acetoacetoxyethylmethyl acrylate copolymer 1.0 g / m ² polyethylene glycol (molecular weight 4000) 0.1 g / m ² (intermediate layer) Gelatin The coating amount is shown as an emulsion layer. the amount surfactant becomes 1 (S-2) 20mg / m 2 methyl acrylate-2-acrylamido-2-methylpropane sulfonic acid-2-acetoacetoxyethyl methyl acrylate copolymer 1.0 g / m ² formalin coating Amount that the swelling ratio of Table 1 (Emulsion A layer) Gelatin coated amount is shown in Table 1 as an emulsion layer amounts halide emulsion A silver amount 0.3 g / m ² 4-methyl-6-hydroxy -1,3,3a , 7-Tetrazaindene 3mg / m ² Adenine 1mg / m ² 5-Methylbenztriazole 0.5mg / m ² Surfactant (S-2) 2mg / m ² Colloidal silica (average particle size 0.015μm) 200mg / m ² Compound of general formula [I] Described in Table 1 (Protective layer) Gelatin Coating amount as shown in Table 1 for emulsion layer Surfactant (S-2) 10 mg / m ² Surfactant (S-3) 2 mg / m ² matting agent (monodisperse silica with an average particle diameter of 3.5 μm) 15 mg / m ² 1,3-bisvinylsulfonyl-2-propanol The coating amount is the amount shown in Table 1

[0086]

[Chemical formula 24]

[0087]

[Chemical 25]

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

Gelatin 50 g Dyes A to C 100 mg / m ² Saponin 2 g Glyoxal 1 g

[0090]

[Chemical formula 26]

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

(Measurement of swelling rate) The film thickness of each sample was set to 23 ° C. and 50
After measuring under the condition of% RH, distilled water was dropped, and after standing for 1 minute, the film thickness was measured again to obtain the swelling ratio. The film thickness was measured using an electronic micrometer manufactured by Anritsu Electric Co., Ltd.

(Measurement of development unevenness) The obtained sample was measured at 3200
After half-tone exposure with a tungsten light of ° K through a contact screen to a density of 1.0, a developer and a fixer having the composition shown below were added and an automatic processor GR- for rapid processing manufactured by Konica Corporation After processing with 26SR under the following conditions, development unevenness was visually evaluated in 10 levels.

(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 10.4 with potassium hydroxide.

(Fixing liquid 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.

[0096]

[Chemical 27]

(Development processing conditions) 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 (Evaluation of stretchability) Scanner manufactured by Dainippon Screen Co., Ltd. SG-808 (II) and photosensitive material RSDII manufactured by Konica Corporation
Using, a transparent image of a person consisting of halftone dots and a step wedge in which halftone% was changed stepwise were created. 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 filter of the present invention was installed between the original and the light source.

The exposed sample was processed in an automatic developing machine using the developing solution and fixing solution according to the above formulation.

Gradation reproducibility of the sample was obtained by adjusting the exposure amount and the dot% on the small dot side (highlight part) was combined. The 10-point evaluation was carried out in order from the best one. The case where the stretchability was excellent was set to 10, and the case where it was very inferior was set to 1. 5 is the practical lower limit.

(Evaluation of halftone dot quality) 50% halftone dots were visually evaluated in 10 grades with a 100 times magnifying glass. 10 is good, 1 is poor, and the lower limit of what can be put on the market is 5.

The results are shown in Table 1.

[0103]

[Table 1]

[0104]

As demonstrated in the examples, the silver halide photographic light-sensitive material of the present invention is excellent in halftone gradation and spreadability, and uneven development can be eliminated by the amount of the binder and the degree of hardening.

Claims (2)

[Claims] 1. A silver halide emulsion layer containing at least one compound selected from a compound represented by the following general formula [I] and a compound represented by the following general formula [II] on a support. , A silver halide photographic light-sensitive material containing a tetrazolium compound. [Chemical 1] [In the formula, R ₁ is (R ₃ ) (R ₅ )> N-C (= S) -N (R ₄ )-, (R ₃ ) -C
_{(= S) -N (R 4} ) -, (R 3) O-C (= S) -N (R 4) -, (R 3) S-C
_{(= S) -N (R 4} ) -, (R 3) S-C (= O) -N (R 4) -, (R 3) -C (=
O) -C (= O) -N (R 4) -, (R 3) O-C (= O) -C (= O) -N (R 4)
−, (R ₃ ) (R ₅ )> N−C (= O) −C (= O) −N (R ₄ ) − and (R ₃ ) (R
_{6)> N-N (R} 5) -C (= O) -N (R 4) - represents, R ₃ represents an alkyl group, an aryl group or a heterocyclic group, R _4, R ₅ and R ₆ It represents a hydrogen atom, an alkyl group or an aryl group, and R ₂ represents a substituent other than a hydrogen atom. B represents a group that releases DI after withdrawing from the hydroquinone mother nucleic acid product,
DI represents a development inhibitor, m and n represent integers, and A and A'represent a hydrogen atom or a group removable by an alkali. R ₁ and R ₂ and two R ₂ may combine together to form a ring. ] [Chemical 2] [In the formula, R ₇ represents an aliphatic group or an aromatic group, and L ₁ represents -CO
NR ₉ −, −NR ₁₀ CONR ₉ −, −OCONR ₉ −, −CONR ₁₁ NR ₁₀ CONR
₉ −, −SO ₂ NR ₉ −, −NR ₁₀ SO ₂ NR ₉ −, −COCONR ₉ −, −NR
₁₀ COCONR ₉ -group, L ₂ represents a divalent linking group having 3 or more repeating units of ethylene oxide, R ₉
R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or an aryl group. R ₈ represents a substituent other than a hydrogen atom, B represents a group that releases DI after leaving from the hydroquinone mother nucleic acid product, represents a DI mother development inhibitor, o, p, and q represent integers, r, s is 0 or 1, but never 0 or 1 at the same time. A and A'represent a hydrogen atom or a group which can be removed with an alkali. ] 2. The film is hardened so that the amount of the hydrophilic binder on the side having the silver halide emulsion layer is 4.5 g / m ² or less and the swelling rate during development processing is 200% or less. The silver halide photographic light-sensitive material according to claim 1.